Foamed items and methods for manufacturing foamed items

Abstract

Foamed articles comprising foamed thermoplastic elastomer materials are provided, methods for manufacturing foamed articles, and methods for manufacturing footwear, apparel, and sports equipment articles incorporating such foamed articles. In one aspect, the method for manufacturing foamed articles includes placing an article comprising a foamable material and carbon dioxide in a container; maintaining the container at a first pressure and a first temperature, wherein the carbon dioxide is liquid and soluble in the foamable material; optionally exposing the injected article to a second temperature and a second pressure; and subjecting the article to a third pressure and a third temperature, wherein the injected carbon dioxide phases into a gas, thereby causing the foamable material to expand into a foamed material and form a foamed article.

Description

[0007] Cross - reference to related applications

[0002] This application claims the benefit of U.S. Provisional Application No. 63 / 153,238, filed Feb. 24, 2021, which is incorporated herein by reference in its entirety. Technical Field

[0003] The present disclosure relates to foamed articles. More specifically, the present disclosure relates to foamed articles comprising a foamed thermoplastic elastomeric material, methods of making such foamed articles, and methods of making footwear articles comprising such foamed articles.

[0004] Background

[0005] The design of sports equipment, clothing, and footwear involves multiple factors ranging from aesthetics to comfort and feel, to performance and durability. While designs and fashions may change rapidly, the demand for enhanced performance in the market remains constant. To balance these demands, designers employ a variety of materials and designs for the various components that make up sports equipment, clothing, and footwear. Summary of the Invention<000,0012>

[0006] The present disclosure provides the following items:

[0007] 1. A method for manufacturing a foamed article, the method comprising:

[0008] Placing an article and carbon dioxide in a container, wherein the article comprises a solid foamable material, the solid foamable material being a thermoplastic elastomeric material comprising one or more first thermoplastic elastomers;[[ID=2,7]]

[0009] After the placing step, maintaining the container at a first pressure and a first temperature, wherein the first pressure and the first temperature are the pressure and temperature at which the carbon dioxide is liquid and the liquid carbon dioxide is soluble in the solid foamable material, and wherein the maintaining comprises holding the article and the liquid carbon dioxide in the container for a duration sufficient for at least a portion of the liquid carbon dioxide to be injected into the solid foamable material of the article;

[0010] After the maintaining and holding step, optionally exposing the injected article to a second pressure and a second temperature, at which the carbon dioxide remains injected into at least a portion of the solid foamable material;

[0011] Following the maintenance and holding steps and the optional exposure step, the article is subjected to a third pressure and a third temperature, at which the liquid carbon dioxide injected into the solid foamable material phases into a gas, thereby causing the solid foamable material to expand into a foamed material and form the foamed article; and

[0012] The article is configured as a series of two or more regions, the series of two or more regions including a first region containing a first region material and a second region containing a second region material, wherein the first region material or the second region material, or both the first region material and the second region material, are solid foamable materials.

[0013] 2. The method according to item 1, wherein the first region or the second region forms the outermost surface of the article, or wherein both the first region and the second region form the outermost surface of the article individually or jointly.

[0014] 3. The method according to item 1 or 2, wherein the one or more first thermoplastic elastomers comprise one or more thermoplastic elastomer polyolefin homopolymers or copolymers, one or more thermoplastic elastomer polyamide homopolymers or copolymers, one or more thermoplastic elastomer polyester homopolymers or copolymers, one or more thermoplastic elastomer polyurethane homopolymers or copolymers, one or more thermoplastic elastomer styrene homopolymers or copolymers, or any combination thereof.

[0015] 4. The method according to any one of items 1-3, wherein in the article, the first region forms the outermost surface of the article, and the second region forms the inner layer of the article.

[0016] 5. The method according to any one of items 1-3, wherein in the article, the first region comprises or is substantially composed of the solid foamable material, the solid foamable material of the first region is the first region solid foamable material, and during the step of undergoing and expanding, the first region solid foamable material remains the first region solid foamable material.

[0017] 6. The method according to any one of items 1-3, wherein in the article, the first region comprises or is substantially composed of the solid foamable material, the solid foamable material of the first region being the solid foamable material of the first region, and in the step of undergoing and expanding, the solid foamable material of the first region expands into the foamed material, wherein the foamed material of the first region is the foamed material of the first region.

[0018] 7. The method according to any one of items 1-6, wherein in the article, the second region comprises or is substantially composed of the solid foamable material, the solid foamable material of the second region is the solid foamable material of the second region, and during the step of undergoing and expanding, the solid foamable material of the second region remains the solid foamable material of the second region.

[0019] 8. The method according to any one of items 1-6, wherein in the article, the second region comprises or is substantially composed of the solid foamable material, the solid foamable material of the second region being the solid foamable material of the second region, and in the step of undergoing and expanding, the solid foamable material of the second region expands into the foamed material, wherein the foamed material of the second region is the foamed material of the second region.

[0020] 9. The method according to any one of items 1-8, wherein the first region material or the second region material comprises or is substantially composed of a barrier material.

[0021] 10. The method according to any one of items 1-9, wherein

[0022] The first region comprises or is substantially composed of a first region solid foamable material.

[0023] The maintaining and holding steps include holding the article and the liquid carbon dioxide in the container for a duration sufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of the solid foamable material in the first region, and

[0024] The process of undergoing and expanding includes expanding at least a portion of the solid foamable material in the first region into the foamed material, wherein the foamed material in the first region includes the foamed material in the first region.

[0025] 11. The method according to any one of items 1-10, wherein

[0026] The maintaining and holding step includes holding the article and the liquid carbon dioxide in the container for a duration sufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of the first region, wherein the duration is insufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of the second region;

[0027] Furthermore, the process of undergoing and expanding includes expanding at least a portion of the solid foamable material in the first region into the foamed material of the first region without expanding the material in the second region.

[0028] 12. The method according to any one of items 1-11, wherein

[0029] The maintaining and holding steps include holding the article and the liquid carbon dioxide in the container for a duration sufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of the first region and into at least a portion of the second region, and the method further includes the steps of: exposing the injected article to the second pressure and the second temperature for a period of time, such that at least a portion of the carbon dioxide injected into the at least a portion of the second region diffuses out of the at least a portion of the second region, while at least a portion of the injected carbon dioxide injected into the first region remains injected into the at least a portion of the first region after the exposure; and

[0030] The process of undergoing and expanding includes expanding at least a portion of the solid foamable material in the first region into foamable material in the first region without expanding the material in the second region, thereby forming a foamed first region, while maintaining the second region in a solid, unfoamed state.

[0031] 13. The method according to any one of items 1-12, wherein immediately prior to the said undergoing and expansion step, the second region is substantially free of injected carbon dioxide.

[0032] 14. The method according to any one of items 1-13, wherein

[0033] The second region includes or is substantially composed of the solid foamable material.

[0034] The maintaining and holding step includes holding the article and the liquid carbon dioxide in the container for a duration sufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of the solid foamable material in the second region, and

[0035] The process of undergoing and expanding includes expanding at least a portion of the solid foamable material in the second region into the foamed material, wherein the foamed material in the second region includes the foamed material in the second region.

[0036] 15. According to the method described in Project 14, wherein

[0037] The maintaining and holding step includes holding the article and the liquid carbon dioxide in the container for a duration sufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of the second region, wherein the duration is insufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of the first region; and

[0038] The process of undergoing and expanding includes expanding at least a portion of the solid foamable material in the second region into foamable material in the second region without expanding the material in the first region, thereby forming a foamed second region, while maintaining the first region in a solid, unfoamed state.

[0039] 16. According to the method described in Item 14, wherein

[0040] The maintaining and holding steps include holding the article and the liquid carbon dioxide in the container for a duration sufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of the first region and into at least a portion of the second region, and the method further includes the steps of: exposing the injected article to the second pressure and the second temperature for a period of time, such that at least a portion of the carbon dioxide injected into the at least a portion of the first region diffuses out of the at least a portion of the first region, while at least a portion of the injected carbon dioxide injected into the second region remains injected into the at least a portion of the second region after the exposure; and

[0041] The process of undergoing and expanding includes expanding at least a portion of the solid foamable material in the second region into foamable material in the second region without expanding the material in the first region.

[0042] 17. The method according to any one of items 1-16, wherein

[0043] The first region includes or is composed of the solid foamable material, wherein the solid foamable material in the first region is the solid foamable material of the first region;

[0044] The second region includes or is substantially composed of the solid foamable material, wherein the solid foamable material in the second region is the solid foamable material of the second region;

[0045] The steps of maintaining and holding include maintaining the article and the liquid carbon dioxide in the container for a duration sufficient to inject at least a portion of the liquid carbon dioxide into at least a portion of the first region and into at least a portion of the second region; and

[0046] The steps of experiencing and expanding cause at least a portion of the solid foamable material in the first region to expand into foamed material of the first region and cause at least a portion of the solid foamable material in the second region to expand into foamed material of the second region.

[0047] 18. A foamed article comprising a first region and a second region, the first region comprising a first region material or consisting essentially of a first region material, the second region comprising a second region material or consisting essentially of a second region material, wherein:

[0048] At least one of the first region material or the second region material is a foamed material, the foamed material being a physically expanded foam formed from a thermoplastic elastomer material comprising one or more first thermoplastic elastomers; and

[0049] wherein the foamed material is the product of placing an unfoamed article comprising a solid foamable material in liquid carbon dioxide, injecting the solid foamable material with the liquid carbon dioxide, and expanding the injected solid foamable material by causing the injected carbon dioxide to phase change into a gas under conditions that do not soften the solid foamable material, thereby forming the foamed material of the foamed article.

[0050] 19. The foamed article according to item 18, wherein the first region material is the foamed material, or wherein the second region material is the foamed material, or wherein both the first region material and the second region material are foamed materials.

[0051] 20. The foamed article according to item 18 or 19, wherein the foamed article is an article of clothing, an article of footwear or an article of sports equipment, or a component of an article of clothing, an article of footwear or an article of sports equipment. Brief Description of the Drawings

[0053] Additional aspects of the present disclosure will be readily understood upon review of the detailed description described below when taken in conjunction with the accompanying drawings.

[0054] Figures 1A-1MThe illustrations depict various footwear, apparel, and sports equipment items according to this disclosure, including containers, electronic equipment, and vision wear, which are foamed or comprise foamed articles. Figure 1N(a)-Figure 1Q(e) The diagram illustrates additional details about different types of footwear.

[0055] Figure 2 A side view illustration shows a thermoplastic elastomer material for forming a foamed thermoplastic elastomer material during an early manufacturing stage, according to an exemplary embodiment.

[0056] Figure 3 The cross-sectional view shows the figure in Figure 2 The thermoplastic elastomer material is depicted along line 202-202.

[0057] Figure 4 A partial cross-sectional side view illustrates a thermoplastic elastomer material in a container for forming a foamed thermoplastic elastomer material during an intermediate manufacturing stage, according to an exemplary embodiment.

[0058] Figure 5 A partial cross-sectional side view illustrates a foamable article injected with carbon dioxide during exposure to a second temperature and a second pressure, according to an exemplary embodiment.

[0059] Figure 6 A partial cross-sectional side view illustrates, according to an exemplary embodiment, the introduction of a carbon dioxide-injected foamable article into a water bath during a process to form a foamed article.

[0060] Figure 7 The figure illustrates a flowchart of a method for manufacturing foamed articles according to an exemplary embodiment.

[0061] Figure 8A The figure illustrates the construction of a foamable article comprising multiple regions according to an exemplary embodiment. Figures 8B-8C The figures illustrate various schemes for selectively foaming areas of a foamable article according to other exemplary embodiments.

[0062] Figures 9A-9F It is a multi-layered article according to an exemplary embodiment before foaming ( Figure 9A , Figure 9C and Figure 9E ) and after foaming ( Figure 9B , Figure 9D and Figure 9F A schematic diagram of ).

[0063] Figures 10A-10KSchematic diagram of a foamable article according to an exemplary embodiment, where a selected portion of the foamable article can be foamed by controllably injecting and diffusing carbon dioxide into and / or out of all or part of the article and leaving other parts of the article unfoamed prior to performing the expansion step disclosed herein.

[0064] Description

[0065] New foamable articles comprising a foamed thermoplastic elastomer material have been identified, as well as methods for manufacturing such foamable articles. The methods described herein include the step of injecting carbon dioxide into a solid foamable material of an article (i.e., a solid article). After injection, the injected solid foamable material is foamed by expanding the injected carbon dioxide, for example by phase-changing the injected carbon dioxide into carbon dioxide gas, without thermally softening the solid foamable material, which in turn expands the solid foamable material into a foamed material, forming a foam, e.g., a foam having a porous foam structure. In this way, the solid foamable material is physically foamed in the process without being melted. The foamable articles described herein include one or more foamed materials, which are physically foamed materials. It has been found that these physically foamed materials comprising a thermoplastic elastomer material as described herein have low density, a uniform porous foam structure, and / or other beneficial properties, making the foamed materials suitable for use in many mass-produced consumer products, including clothing articles, footwear articles, and sports equipment articles. Figures 1A-1M Illustrations show various footwear articles, clothing articles, and sports equipment articles according to the present disclosure, including containers, electronic equipment, and visual protectors, which are foamable articles or include foamable articles, and Figure 1N(a)-Figure 1Q(e) Illustrations show additional details regarding different types of footwear.

[0066] It has also been found that the multi-step foaming processes described herein can be readily adapted for conventional materials and production lines because they utilize simpler, cheaper, and more energy-efficient equipment and processes than other physical foaming processes. For example, maintaining carbon dioxide as a liquid and holding a solid foamable material in liquid carbon dioxide requires maintaining lower extreme temperatures and pressures than using supercritical carbon dioxide to inject the solid foamable material (and therefore requires cheaper, more energy-efficient equipment). In many respects, the step of expanding the solid foamable material into a foamed material can be carried out at or near atmospheric pressure and at relatively low temperatures well below the melting temperature of the foamable material, and therefore can be carried out using simple, inexpensive heating methods and equipment, making the entire foaming process efficient and cost-effective. Furthermore, this disclosure is applicable to a wide range of solid foamable materials, as well as to articles having many different geometries, including but not limited to sheets of solid foamable materials. Furthermore, by using articles comprising two or more types of solid foamable materials, articles comprising two or more portions or regions of solid foamable materials, and articles comprising a combination of one or more solid foamable materials and one or more solid non-foamable materials, and / or by changing processing conditions, the process described herein for foaming solid articles can be adapted to selectively foam portions or regions of articles without requiring additional tools or equipment.

[0067] Compared to articles without foamed materials, i.e., articles containing only solid materials, the use of foamed thermoplastic elastomer materials in the foamed articles disclosed herein can reduce the weight or density of the articles. Additionally or alternatively, by using foamed material instead of unfoamed material, the total amount of material required to provide the same volume is reduced, lowering material costs and making the foamed articles more sustainable compared to comparable articles without foamed materials. Furthermore, by forming the foamed articles using foamed thermoplastic elastomer materials alone or in combination with one or more other thermoplastic materials, the components of the foamed article or the entire foamed article may include recycled thermoplastic material, and consequently, the component or the entire foamed article itself may be recycled. In some aspects, by controlling the foaming conditions and optionally controlling an optional stabilization process, the overall volume of the foamed article can increase within a predicted or predetermined range. The increase in volume can be relatively small compared to the total volume of the article before undergoing the foaming process, for example, less than 10% or less than 5%. Alternatively, the increase in volume can be relatively large compared to the total volume of the article before undergoing the foaming process, for example, an increase in volume greater than 20% or greater than 40%.

[0068] In some aspects, the foaming material of the foamed article is a stabilized foam material that has undergone a stabilization process. In some aspects, the foamed article includes a layer or region of foamed material adjacent to a layer or region of solid (i.e., unfoamed) material. In some aspects, the foamed article can be a cushioning element, such as a fluid-filled bladder. In some aspects, the thermoplastic elastomer material can include one or more thermoplastic polyurethanes. In some aspects, in addition to the thermoplastic elastomer material, the foamed article may also include a second material, such as a second thermoplastic material, including a second thermoplastic material that does not foam during the foaming process.

[0069] In one aspect, this disclosure relates to a method for manufacturing foamed articles. As disclosed herein, the foaming process is a multi-step process comprising first injecting a solid foamable material with carbon dioxide, and then exposing the injected article to conditions that cause the carbon dioxide injected into the solid foamable material to undergo a phase change, causing the solid foamable material to expand and foam into a foamed material. Optionally, prior to the foaming step, the injected article may be exposed to a pressure and temperature and held (e.g., stored) at said pressure and temperature, whereby the injected carbon dioxide remains injected into the article, allowing the injected article to be foamed at a later time. Alternatively, the injected article may be exposed to conditions in which a portion of the injected carbon dioxide diffuses out of the injected article and said conditions are maintained for a duration to allow the carbon dioxide to diffuse out from selected portions of the injected article. In this way, the injected carbon dioxide can be removed from selected areas or portions of the article prior to foaming, resulting in only selected areas or portions of the article foaming when exposed to foaming conditions. Optionally, after foaming, the foamed article can be stabilized to release residual carbon dioxide and / or release residual stress in the article.

[0070] In another aspect, this disclosure relates to foamed articles. Foamed articles include or are substantially composed of foamed materials, wherein the foamed material is a physically expanded foam formed from a thermoplastic elastomer material comprising one or more first thermoplastic elastomers. The foamed material is the product of injecting carbon dioxide into a solid foamable material comprising a thermoplastic elastomer material, and generating a phase change that causes the injected carbon dioxide to expand, thereby foaming the solid foamable material into a foamed material without thermally softening the solid foamable material. Optionally, the foamed article may include additional foamed material or additional unfoamed material. Optionally, the foamed article may be a stabilized foamed article from which residual carbon dioxide has been removed, or from which residual stress generated during the foaming process has been reduced or removed.

[0071] In one aspect, methods for manufacturing foamed articles are disclosed herein, the methods comprising: placing an article and carbon dioxide in a container, wherein the article comprises a solid foamable material, the solid foamable material being a thermoplastic elastomeric material comprising one or more first thermoplastic elastomers; after placement, maintaining the container at a first pressure and a first temperature, wherein the first pressure and the first temperature are the pressure and temperature at which carbon dioxide is a liquid and the liquid carbon dioxide is soluble in the solid foamable material, and wherein maintaining comprises holding the article and the liquid carbon dioxide in the container for a duration sufficient for at least a portion of the liquid carbon dioxide to be injected into the solid foamable material of the article; after maintaining and holding, optionally exposing the injected article to a second pressure and a second temperature, at which the carbon dioxide remains injected into at least a portion of the solid foamable material; after maintaining and holding and the optional exposure, subjecting the article to a third pressure and a third temperature, at which the carbon dioxide injected into the solid foamable material phase changes to a gas, thereby causing the solid foamable material to expand into a foamed material and form a foamed article; and wherein the article is configured as a series of two or more regions, the series of two or more regions comprising a first region comprising a first region material and a second region comprising a second region material, wherein the first region material or the second region material or both the first region material and the second region material are solid foamable materials.

[0072] The following list of exemplary aspects supports and is supported by the disclosure provided herein.

[0073] According to aspect 1, the present disclosure relates to a method for manufacturing a foamed article, the method comprising:

[0074] placing an article and carbon dioxide (CO2) in a container, wherein the article comprises a solid foamable material, the solid foamable material being a thermoplastic elastomeric material comprising one or more first thermoplastic elastomers;

[0075] after placement, maintaining the container at a first pressure and a first temperature, wherein the first pressure and the first temperature are the pressure and temperature at which carbon dioxide is a liquid and the liquid carbon dioxide is soluble in the solid foamable material, and wherein maintaining comprises holding the article and the liquid carbon dioxide in the container for a duration sufficient for at least a portion of the liquid carbon dioxide to be injected into the solid foamable material of the article;

[0076] after maintaining and holding, optionally exposing the injected article to a second pressure and a second temperature, at which the carbon dioxide remains injected into at least a portion of the solid foamable material;

[0077] After being maintained and held, and optionally exposed, the article is subjected to a third pressure and a third temperature, at which carbon dioxide injected into the solid foamable material is phase-changed into a gas, thereby causing the solid foamable material to expand into a foamed material and form a foamed article.

[0078] According to aspect 2, this disclosure relates to the method of aspect 1, further comprising, after experiencing and expanding, bringing the foamed article to a fourth temperature and a fourth pressure, and maintaining the foamed article at or below the fourth temperature, fourth pressure, or both for a period of time.

[0079] According to aspect 3, this disclosure relates to the method of aspect 1 or 2, further comprising, after experiencing and expanding or optionally reaching, stabilizing the foamed article at a fifth pressure and a fifth temperature, wherein carbon dioxide diffuses from the foamed material of the foamed article while maintaining the foamed material in a foam structure, forming a stabilized foamed article.

[0080] According to aspect 4, this disclosure relates to the method of aspect 3, wherein stabilization includes maintaining the foamed article at a fifth pressure and a fifth temperature for a duration sufficient to remove substantially all carbon dioxide from the foamed material.

[0081] According to aspect 5, this disclosure relates to a method according to any one of the foregoing aspects, wherein liquid carbon dioxide is soluble in a solid foamable material at a concentration from about 1 wt% to about 30 wt%, optionally from about 5 wt% to about 20 wt%, at a first pressure and a first temperature.

[0082] According to aspect 6, this disclosure relates to the method of any one of the foregoing aspects, wherein the foaming material of the foamed article is substantially opaque.

[0083] According to aspect 7, this disclosure relates to a method according to any one of the foregoing aspects, wherein the foamed material has a split-tear value from about 2.5 kg / cm to about 3.0 kg / cm.

[0084] According to aspect 8, this disclosure relates to a method according to any one of the foregoing aspects, wherein the foamed material has an Asker C hardness of about 10 to about 50.

[0085] According to aspect 9, this disclosure relates to a method according to any one of the foregoing aspects, wherein the foamable material comprises a polymeric component containing all polymers present in the foamable material, and the polymeric component consists of one or more first thermoplastic elastomers.

[0086] According to aspect 10, this disclosure relates to the method of aspect 9, wherein one or more first thermoplastic elastomers comprise one or more thermoplastic elastomer polyolefin homopolymers or copolymers, one or more thermoplastic elastomer polyamide homopolymers or copolymers, one or more thermoplastic elastomer polyester homopolymers or copolymers, one or more thermoplastic elastomer polyurethane homopolymers or copolymers, one or more thermoplastic elastomer styrene homopolymers or copolymers, or any combination thereof.

[0087] According to aspect 11, this disclosure relates to the methods of aspect 9 or 10, wherein one or more first thermoplastic elastomers comprise one or more thermoplastic elastomer polyamide homopolymers or copolymers or are substantially composed of one or more thermoplastic elastomer polyamide homopolymers or copolymers.

[0088] According to aspect 12, this disclosure relates to the method of any one of aspects 9-11, wherein one or more first thermoplastic elastomers comprise or are substantially composed of polyether block polyamide (PEBA) copolymer elastomers.

[0089] According to aspect 13, this disclosure relates to the method of any one of aspects 9-12, wherein one or more first thermoplastic elastomers comprise one or more thermoplastic elastomer styrene homopolymers or copolymers or are substantially composed of one or more thermoplastic elastomer styrene homopolymers or copolymers.

[0090] According to aspect 14, this disclosure relates to the method of any one of aspects 9-13, wherein one or more first thermoplastic elastomers comprise or are substantially composed of: styrene-butadiene-styrene (SBS) block copolymer elastomers, styrene-ethylene-butadiene-styrene (SEBS) copolymer elastomers, styrene-acrylonitrile (SAN) copolymer elastomers, or any combination thereof.

[0091] According to aspect 15, this disclosure relates to the method of any one of aspects 9-14, wherein one or more first thermoplastic elastomers comprise one or more thermoplastic polyurethane elastomer homopolymers or copolymers or are substantially composed of one or more thermoplastic polyurethane elastomer homopolymers or copolymers.

[0092] According to aspect 16, this disclosure relates to the method of any one of aspects 9-15, wherein one or more first thermoplastic elastomers comprise or are substantially composed of: thermoplastic polyester-polyurethane elastomers, polyether-polyurethane elastomers, polycarbonate-polyurethane elastomers, or combinations thereof.

[0093] According to aspect 17, this disclosure relates to the method of any one of aspects 9-16, wherein one or more first thermoplastic elastomers of the foamable material comprise one or more thermoplastic polyester-polyurethane elastomers or are substantially composed of one or more thermoplastic polyester-polyurethane elastomers, optionally wherein the polymer component of the foamable material is composed of one or more thermoplastic polyester-polyurethane elastomers.

[0094] According to aspect 18, this disclosure relates to the method of any one of aspects 9-16, wherein one or more first thermoplastic elastomers comprise one or more thermoplastic polyolefin elastomer homopolymers or copolymers or are substantially composed of one or more thermoplastic polyolefin elastomer homopolymers or copolymers.

[0095] According to aspect 19, this disclosure relates to the method of any one of aspects 9-18, wherein one or more first thermoplastic elastomers comprise or are substantially composed of: thermoplastic elastomer polypropylene homopolymer or copolymer, thermoplastic elastomer polyethylene homopolymer or copolymer, thermoplastic elastomer polybutene homopolymer or copolymer, or any combination thereof.

[0096] According to aspect 20, this disclosure relates to the method of any one of aspects 9-18, wherein one or more first thermoplastic elastomers comprise or are substantially composed of thermoplastic elastomers ethylene-vinyl acetate copolymers.

[0097] According to aspect 21, this disclosure relates to the method of aspect 20, wherein the thermoplastic elastomer ethylene-vinyl acetate copolymer comprises a vinyl acetate content from about 25% by weight to about 50% by weight.

[0098] According to aspect 22, this disclosure relates to a method according to any one of aspects 9-21, wherein the foamable material comprises a polymeric component and a mixture of a nonpolymeric component consisting of one or more nonpolymeric additives, optionally wherein the foamable material comprises, by weight, from about 0.005% to about 20% of the nonpolymeric component based on the total weight of the foamable material, or by weight, from about 0.5% to about 10% of the nonpolymeric additives based on the total weight of the foamable material.

[0099] According to aspect 23, this disclosure relates to the method of any one of aspects 9-22, wherein one or more first thermoplastic elastomers comprise one or more recycled first thermoplastic elastomers or are substantially composed of one or more recycled first thermoplastic elastomers.

[0100] According to aspect 24, this disclosure relates to the method of any one of aspects 9-20, wherein the foamable material comprises or consists of a blend of one or more first thermoplastic elastomers and a second material, or is substantially composed of a blend of one or more first thermoplastic elastomers and a second material, optionally wherein the second material comprises or consists of one or more second polymers, or is substantially composed of one or more second polymers, optionally wherein the one or more second polymers comprises or consists of one or more second thermoplastics, or is substantially composed of one or more second thermoplastics.

[0101] According to aspect 25, this disclosure relates to the method of any one of aspects 9-24, wherein the polymer component of the foamable material comprises a blend of one or more first thermoplastic elastomers and one or more second thermoplastics, optionally wherein the blend foams during the steps of undergoing and expanding.

[0102] According to aspect 26, this disclosure relates to the method described in aspect 25, wherein one or more second thermoplastics comprise one or more thermoplastic polyolefin homopolymers or copolymers, one or more thermoplastic polyamide homopolymers or copolymers, one or more thermoplastic polyester homopolymers or copolymers, one or more thermoplastic polyurethane homopolymers or copolymers, one or more thermoplastic styrene homopolymers or copolymers, or any combination thereof.

[0103] According to aspect 27, this disclosure relates to the methods described in aspect 25 or 26, wherein one or more second thermoplastics comprise or are substantially composed of: thermoplastic polypropylene homopolymers or copolymers, thermoplastic polyethylene homopolymers or copolymers, thermoplastic polybutene homopolymers or copolymers, or any combination thereof.

[0104] According to aspect 28, this disclosure relates to the method of any one of aspects 24-27, wherein one or more second thermoplastics comprise one or more thermoplastic polyethylene copolymers or are substantially composed of one or more thermoplastic polyethylene copolymers.

[0105] According to aspect 29, this disclosure relates to the method of any one of aspects 24-28, wherein one or more second thermoplastics comprise one or more thermoplastic ethylene-vinyl alcohol copolymers or are substantially composed of one or more thermoplastic ethylene-vinyl alcohol copolymers.

[0106] According to aspect 30, this disclosure relates to the method of aspect 24, wherein the polymeric component of the foamable material comprises one or more first thermoplastic elastomer polyurethane homopolymers or copolymers and one or more second thermoplastic ethylene-vinyl alcohol copolymers.

[0107] According to aspect 31, this disclosure relates to the method of aspect 30, wherein the polymer component comprises one or more first thermoplastic elastomer polyester-polyurethane copolymers and one or more second thermoplastic ethylene-vinyl alcohol copolymers.

[0108] According to aspect 32, this disclosure relates to the method of any one of aspects 24-31, wherein the blend comprises one or more recycled first thermoplastic elastomers, or one or more recycled second thermoplastics, or both.

[0109] According to aspect 33, this disclosure relates to the method of aspect 32, wherein the blend is a phase-separated blend of one or more first thermoplastic elastomers and one or more second thermoplastics.

[0110] According to aspect 34, this disclosure relates to the method of aspect 33, wherein the phase-separated blend includes one or more phase-separated regions, the one or more phase-separated regions being included at the interface between one or more first thermoplastic elastomers and one or more second thermoplastics.

[0111] According to aspect 35, this disclosure relates to the method of any one of aspects 24-34, wherein the blend comprises about 95% by weight of one or more first thermoplastic elastomers and about 5% by weight of one or more second thermoplastics based on the total weight of the blend.

[0112] According to aspect 36, this disclosure relates to a method according to any one of aspects 24-35, wherein liquid carbon dioxide is soluble in one or more first thermoplastic elastomers at a concentration of from about 1% to about 30% by weight, optionally from about 5% to about 20% by weight, based on the total weight of one or more first thermoplastic elastomers present in the foamable material, and wherein liquid carbon dioxide is soluble in one or more second thermoplastics at a concentration of less than 1% by weight, optionally less than 0.1% by weight, based on the total weight of one or more second thermoplastics present in the foamable material, or optionally wherein liquid carbon dioxide is substantially insoluble in one or more second thermoplastics.

[0113] According to aspect 37, this disclosure relates to a method according to any one of the foregoing aspects, wherein the article includes an additional material, wherein the additional material is a material separate from the foamable material, wherein the additional material includes one or more polymers or is substantially composed of one or more polymers, and includes an additional material polymer component consisting of all polymers present in the additional material; optionally, wherein the additional material includes a second material or is substantially composed of a second material, optionally wherein the second material is a thermoplastic material, optionally wherein the additional material includes an additional material polymer component mixed with an additional material non-polymer component, the additional material non-polymer component consisting of all non-polymer components present in the additional material.

[0114] According to aspect 38, this disclosure relates to a method according to any one of the foregoing aspects, wherein the article comprises one or more first portions of a foamable material and one or more second portions of an additional material, and one or more of the first portions differ from one or more of the second portions.

[0115] According to aspect 39, this disclosure relates to the methods of aspect 37 or 38, wherein the additional material includes a barrier material comprising one or more barrier polymers, the barrier material comprising a barrier polymer component consisting of all polymers present in the barrier material.

[0116] According to aspect 40, this disclosure relates to the method of any one of aspects 37-39, wherein the additional material includes a plasticizer.

[0117] According to aspect 41, this disclosure relates to the method described in aspect 39 or 40, wherein during the expansion step, additional material remains substantially unfoamed.

[0118] According to aspect 42, this disclosure relates to the method of aspect 41, wherein the barrier material has a hardness that is at least 10 Shore A units greater than that of the foamable material, or optionally at least 20 Shore A units, at least 30 Shore A units, or at least 40 Shore A units greater than that of the foamable material.

[0119] According to aspect 43, this disclosure relates to the method of any one of aspects 37-42, wherein the barrier material has a nitrogen permeability that is at least 50% lower than that of the foamable material, optionally less than or equal to 10 cubic centimeters per square meter per 24 hours, or less than or equal to 1 cubic centimeter per square meter per 24 hours.

[0120] According to aspect 44, this disclosure relates to the method of any one of aspects 37-43, wherein the barrier polymer component of the barrier material consists of one or more barrier polymers, each barrier polymer individually having a nitrogen permeability of less than or equal to 30 cubic centimeters per square meter per 24 hours, or less than or equal to 10 cubic centimeters per square meter per 24 hours, or less than or equal to 1 cubic centimeter per square meter per 24 hours.

[0121] According to aspect 45, this disclosure relates to the method of aspect 44, wherein one or more barrier polymers comprise or are substantially composed of: one or more vinylidene chloride polymers, one or more acrylonitrile polymers or copolymers, one or more polyamides, one or more epoxy resins, one or more amine polymers or copolymers, or one or more thermoplastic polyolefin homopolymers or copolymers, optionally wherein one or more thermoplastic polyolefin homopolymers or copolymers comprise or are substantially composed of: one or more thermoplastic polyethylene copolymers, one or more thermoplastic ethylene-vinyl alcohol copolymers, or one or more thermoplastic elastomer ethylene-vinyl alcohol copolymers.

[0122] According to aspect 46, this disclosure relates to the method of any one of aspects 37-43, wherein at a first temperature and a first pressure, liquid carbon dioxide is soluble in a foamable material at a first concentration, liquid carbon dioxide is soluble in a barrier material at a second concentration, and the first concentration is at least 20% greater than the second concentration, optionally wherein the first concentration is at least 50% greater than the second concentration, or at least 70% greater than the second concentration.

[0123] According to aspect 47, this disclosure relates to the method of aspect 46, wherein the second concentration is less than 1 weight percentage, optionally less than 0.1 weight percentage, or optionally wherein the liquid carbon dioxide is substantially insoluble in the barrier material.

[0124] According to aspect 48, this disclosure relates to the method of any one of aspects 37-47, wherein the barrier material comprises one or more ethylene-vinyl alcohol copolymers, optionally one or more ethylene-vinyl alcohol copolymers are thermoplastic, optionally one or more ethylene-vinyl alcohol thermoplastic copolymers comprise one or more thermoplastic elastomer copolymers; optionally the barrier polymer component consists of one or more ethylene-vinyl alcohol copolymers, optionally one or more ethylene-vinyl alcohol copolymers are thermoplastic, optionally one or more ethylene-vinyl alcohol thermoplastic copolymers comprise one or more thermoplastic elastomer copolymers.

[0125] According to aspect 49, this disclosure relates to the methods of aspect 37 or 38, wherein the additional material is a thermoplastic material, optionally wherein the additional material is an additional thermoplastic elastomer material, and optionally wherein the additional thermoplastic elastomer material is an additional foamable material.

[0126] According to aspect 50, this disclosure relates to the method of aspect 49, wherein the additional material is a further foamable material, and during the expansion step, the further foamable material expands into a further foamable material.

[0127] According to aspect 51, this disclosure relates to the method of aspect 50, wherein in the foamed article, the density of the first foamed material differs from the density of the other foamed material by at least 5%, or at least 10%, or at least 20%.

[0128] According to aspect 52, this disclosure relates to the method of aspect 49, wherein the article comprises a first foamable material, the first foamable material comprising a solid foamable material or substantially composed of a solid foamable material, and further comprises an additional material, wherein the additional material is an additional foamable material, the maintaining and holding step comprising holding the article and liquid carbon dioxide in a container for a duration sufficient to inject at least a portion of the liquid carbon dioxide into the first foamable material but not into the additional foamable material, and the undergoing and expanding step comprising expanding the first foamable material into the first foamable material while maintaining the additional foamable material as a substantially unfoamed additional foamable material.

[0129] According to aspect 53, this disclosure relates to the method of aspect 49, wherein the article comprises a solid first foamable material and further comprises an additional material, wherein the additional material is an additional foamable material, the maintaining and holding steps comprising holding the article and liquid carbon dioxide in a container for a duration sufficient to inject at least a portion of the liquid carbon dioxide into the solid first foamable material and into the solid additional foamable material, the method comprising an optional exposure step, and the exposure comprising exposing the article to a second pressure and a second temperature, wherein carbon dioxide is retained injected into the solid additional foamable material, but at the second pressure and the second temperature, carbon dioxide diffuses out of the solid first foamable material, and the undergoing and expanding steps comprise expanding the additional foamable material into the additional foamable material, while maintaining the solid first foamable material as a substantially unfoamed first foamable material.

[0130] According to aspect 54, this disclosure relates to the method of aspect 49, wherein the additional material is a recycled material comprising one or more recycled polymers, optionally wherein the one or more recycled polymers comprise one or more recycled thermoplastics, optionally wherein the one or more recycled thermoplastics comprise one or more recycled thermoplastic elastomers; optionally wherein the recycled material comprises a recycled material polymer component consisting of one or more recycled thermoplastics, optionally wherein the recycled material polymer component comprises one or more recycled thermoplastic elastomers or is substantially composed of one or more recycled thermoplastic elastomers.

[0131] According to aspect 55, this disclosure relates to the method of aspect 54, wherein the recycled material comprises one or more recycled first thermoplastic elastomers, optionally one or more recycled first thermoplastic elastomers comprises one or more re-milled first thermoplastic elastomers, optionally one or more recycled first thermoplastic elastomers or re-milled first thermoplastic elastomers comprises a thermoplastic elastomer according to any one of aspects 9-23 or 24-36.

[0132] According to aspect 56, this disclosure relates to the method of aspect 54 or 55, wherein the recycled material further comprises one or more recycled second thermoplastics, optionally one or more recycled second thermoplastics comprising one or more re-milled second thermoplastics, optionally one or more recycled second thermoplastics or re-milled second thermoplastics comprising a thermoplastic according to any one of aspects 26-29.

[0133] According to aspect 57, this disclosure relates to the method of aspect 56, wherein the recycled material comprises one or more recycled thermoplastic polyurethane elastomers or re-milled thermoplastic polyurethane elastomers or one or more recycled thermoplastic ethylene-vinyl alcohol copolymers or re-milled thermoplastic ethylene-vinyl alcohol copolymers or both.

[0134] According to aspect 58, this disclosure relates to the methods of aspect 56 or 57, wherein the recycled material comprises a blend of one or more recycled thermoplastic elastomers or re-milled thermoplastic elastomers and one or more second thermoplastics, or wherein the recycled material comprises a blend of one or more thermoplastic elastomers and one or more recycled thermoplastics or one or more recycled second thermoplastics, optionally wherein the blend is a phase-separated blend, and optionally wherein the phase-separated blend includes one or more interfaces between one or more first thermoplastic elastomers and one or more second thermoplastics.

[0135] According to aspect 59, this disclosure relates to the method of any one of aspects 56-58, wherein the recycled material comprises about 99% to about 90% by weight of one or more first thermoplastic elastomers and about 1% to about 10% by weight of a second thermoplastic, based on the total weight of the recycled material, optionally wherein the recycled material comprises about 99% to about 93% by weight of one or more first thermoplastic elastomers and about 1% to about 7% by weight of one or more second thermoplastics, or about 99% to about 95% by weight of one or more first thermoplastic elastomers and about 1% to about 5% by weight of one or more second thermoplastics.

[0136] According to aspect 60, this disclosure relates to a method according to any one of aspects 54-59, wherein the recycled material comprises about 99% to about 50% by weight of a recycled polymer or a re-milled polymer based on the total weight of the recycled material, optionally from about 99% to about 75% by weight of a recycled polymer or a re-milled polymer.

[0137] According to aspect 61, this disclosure relates to a method according to any one of aspects 54-60, wherein liquid carbon dioxide is soluble in the recycled material at a concentration from about 1% to about 30% by weight, optionally from about 5% to about 20% by weight, based on the total weight of the recycled material.

[0138] According to aspect 62, this disclosure relates to the method of any one of aspects 54-59, wherein liquid carbon dioxide is soluble in one or more recycled or re-ground thermoplastic elastomers at a concentration of from about 1% to about 30% by weight, optionally from about 5% to about 20% by weight, based on the total weight of one or more recycled or re-ground thermoplastic elastomers.

[0139] According to aspect 63, this disclosure relates to the method of any one of aspects 54-62, wherein liquid carbon dioxide is soluble in one or more recycled second thermoplastics or re-ground second thermoplastics at less than 1 weight percentage, optionally less than 0.1 weight percentage, based on the total weight of one or more recycled second thermoplastics or re-ground second thermoplastics, or optionally the liquid carbon dioxide is substantially insoluble in one or more recycled second thermoplastics or re-ground second thermoplastics.

[0140] According to aspect 64, this disclosure relates to the method of any one of aspects 55-63, wherein the recycled material comprises a recycled foamed article produced by the method of any one of aspects 1-54, optionally wherein the recycled foamed article is a re-milled foamed article.

[0141] According to aspect 65, this disclosure relates to the method of any one of aspects 55-63, wherein the recycled material comprises a foamable material, wherein the foamable material is an unfoamed material.

[0142] According to aspect 66, this disclosure relates to the method of any one of aspects 55-65, wherein the recycled material further comprises one or more original first thermoplastic elastomers, optionally including one or more original thermoplastic polyurethane elastomers.

[0143] According to aspect 67, this disclosure relates to a method according to any one of aspects 58-66, wherein the recycled material includes one or more nucleating agents or nucleation sites for foaming the recycled material, optionally wherein one or more nucleation sites are included at one or more interfaces between phase-separated polymers.

[0144] According to aspect 68, this disclosure relates to the method of any one of aspects 55-67, wherein the solid foamable material is a recycled material.

[0145] According to aspect 69, this disclosure relates to a method according to any one of aspects 55-67, wherein the article comprises a first solid foamable material and a further solid foamable material, and the first solid foamable material is a recycled material, or the further solid foamable material is a recycled material, or both the first solid foamable material and the further solid foamable material are recycled materials.

[0146] According to aspect 70, this disclosure relates to a method according to any one of the foregoing aspects, wherein the article includes a barrier layer comprising or substantially consisting of a barrier material.

[0147] According to aspect 71, this disclosure relates to the method of aspect 70, wherein the barrier material is another material according to any one of aspects 37-67.

[0148] According to aspect 72, this disclosure relates to a method according to any one of the foregoing aspects, wherein the article includes a structural layer comprising or substantially composed of structural material.

[0149] According to aspect 73, this disclosure relates to the method of aspect 72, wherein the structural material is another material according to any one of aspects 37-67, optionally wherein the structural material comprises a blend of two or more other materials, optionally wherein at least one of the two or more other materials is a recycled material.

[0150] According to aspect 74, this disclosure relates to a method according to any one of the preceding aspects, wherein the article comprises one or more connecting layers, each of the one or more connecting layers individually comprising or substantially consisting of a connecting material, each of the one or more connecting layers increasing the bonding strength between two adjacent layers, optionally wherein the connecting material is a solid foamable material according to any one of aspects 1-73, optionally wherein the solid foamable material is a recycled material.

[0151] According to aspect 75, this disclosure relates to a method according to any one of the preceding aspects, wherein the article comprises one or more protective layers, each of the one or more protective layers individually comprising or substantially consisting of a protective material, each of the one or more protective layers being adjacent to a core layer and having a protective layer thickness, the combination of the one or more protective layers and the adjacent core layer having a minimum radius of curvature greater than the minimum radius of curvature that causes cracking of the core layer or cracking of one or more individual layers within the core layer, optionally wherein the protective material is a solid foamable material according to any one of aspects 1-73, optionally wherein the solid foamable material is a recycled material.

[0152] According to aspect 76, this disclosure relates to a method according to any one of aspects 34-36, wherein the maintaining and expanding steps include nucleation and foaming at one or more interfaces of a foamable material.

[0153] According to aspect 77, this disclosure relates to a method according to any one of the foregoing aspects, wherein the steps of maintaining and sustaining include maintaining a first pressure from about 0.05 psi (0.345 kPa) to about 6,000 psi (41,300 kPa), optionally from about 15 psi (103.4 kPa) to about 5,500 psi (37,900 kPa), from about 100 psi (689.5 kPa) to about 5,000 psi (34,500 kPa), from about 500 psi (3,450 kPa) to about 2,000 psi (13,790 kPa), or from about 1,000 psi (6,895 kPa) to about 1,500 psi (10,300 kPa).

[0154] According to aspect 78, this disclosure relates to a method according to any one of the foregoing aspects, wherein the steps of maintaining and holding include maintaining a first temperature from about -57 degrees Celsius to about 31 degrees Celsius.

[0155] According to aspect 79, this disclosure relates to a method according to any one of the foregoing aspects, wherein the steps of maintaining and holding include holding the article at a first pressure and a first temperature for a duration from about 20 seconds to about 72 hours.

[0156] According to aspect 80, this disclosure relates to a method according to any one of the foregoing aspects, wherein an optional exposure step includes exposing the article to a second pressure from about 1 atmosphere (101 kPa) to about 85 atmospheres (8613 kPa).

[0157] According to aspect 81, this disclosure relates to a method according to any one of the foregoing aspects, wherein an optional exposure step includes exposing the article to a second temperature more than 30 degrees below the softening point of the solid foamable material, or more than 50 degrees below the softening point of the solid foamable material, or optionally more than 100 degrees below the softening point of the solid foamable material.

[0158] According to aspect 82, this disclosure relates to a method according to any one of the foregoing aspects, wherein an optional exposure step includes exposing the article to a second pressure and a second temperature for a duration from about 30 minutes to about 4 weeks.

[0159] According to aspect 83, this disclosure relates to a method according to any one of the foregoing aspects, wherein the steps of experiencing and expanding include subjecting the article to a third pressure from about 13 pounds per square inch (89.6 kPa) to about 16 pounds per square inch (110.3 kPa).

[0160] According to aspect 84, this disclosure relates to a method according to any one of the foregoing aspects, wherein the steps of experiencing and expanding include subjecting the article to a third temperature from about 20 degrees Celsius to about 150 degrees Celsius.

[0161] According to aspect 85, this disclosure relates to a method according to any one of the foregoing aspects, wherein the steps of experiencing and expanding include subjecting the article to a third pressure and a third temperature for a duration from about 2 seconds to about 5 minutes.

[0162] According to aspect 86, this disclosure relates to a method according to any one of the foregoing aspects, wherein an optional step of achieving the foamed article includes bringing the foamed article to a fourth pressure from about 0.03 atmospheres (3.04 kPa) to about 2 atmospheres (202.65 kPa).

[0163] According to aspect 87, this disclosure relates to a method according to any one of the foregoing aspects, wherein the optional step of achieving the foamed article includes bringing the foamed article to a fourth temperature from about 30 degrees Celsius to about 70 degrees Celsius.

[0164] According to aspect 88, this disclosure relates to a method according to any one of the foregoing aspects, wherein the optional achieving step includes subjecting the foamed article to a fourth pressure and a fourth temperature for a duration from about 15 minutes to about 1 hour.

[0165] According to aspect 89, this disclosure relates to the method of any one of aspects 2-88, wherein in an optional reaching step, the fourth temperature is at or below the glass transition temperature of the solid foamable material.

[0166] According to aspect 90, this disclosure relates to the method of any one of aspects 2-88, wherein in an optional reaching step, the fourth temperature is from about 10 degrees Celsius less than the glass transition temperature of the solid foamable material to about 10 degrees Celsius less than the glass transition temperature of the solid foamable material.

[0167] According to aspect 91, this disclosure relates to a method according to any one of the foregoing aspects, wherein in the foamed article, the foamed material has a density from about 0.01 g / cm³ to about 3.0 g / cm³, optionally from about 0.01 g / cm³ to about 0.1 g / cm³, from about 0.01 g / cm³ to about 0.05 g / cm³, from about 0.01 g / cm³ to about 0.025 g / cm³, from about 0.05 g / cm³ to about 0.1 g / cm³, from about 0.1 g / cm³ to about 3.0 g / cm³, from about 0.2 g / cm³ to about 2.0 g / cm³, from about 0.3 g / cm³ to about 1.5 g / cm³, from about 0.3 g / cm³ to about 1.2 g / cm³, or from about 0.4 g / cm³ to about 1.0 g / cm³.

[0168] According to aspect 92, this disclosure relates to a method according to any one of the foregoing aspects, wherein in the foamed article, the foamed material has a volume greater than or less than 10%, optionally less than 5%, of the foamable material prior to foaming, and optionally wherein the foamed article is a stabilized foamed article.

[0169] According to aspect 93, this disclosure relates to the method of any one of aspects 1-91, wherein in the foamed article, the foamed material has a volume that is more than 20%, optionally more than 30%, or more than 40% larger than the foamable material prior to foaming, and optionally wherein the foamed article is a stabilized foamed article.

[0170] According to aspect 94, this disclosure relates to a method according to any one of the foregoing aspects, wherein the steps of undergoing and expanding include expanding a foamable material into a foamed material until the foamed material has a density from about 0.01 g / cm³ to about 3.0 g / cm³.

[0171] According to aspect 95, this disclosure relates to a method according to any one of the foregoing aspects, wherein after undergoing and expanding steps, the foamed material has an expansion ratio of about 3:1 to about 120:1 relative to the solid foamable material before undergoing and expanding.

[0172] According to aspect 96, this disclosure relates to a method according to any one of the foregoing aspects, wherein the solid foamable material has a Shore A hardness from about 35A to about 95A, optionally from about 55A to about 90A.

[0173] According to aspect 97, this disclosure relates to a method according to any one of the foregoing aspects, wherein the foamed material of the foamed article has a Shore A hardness from about 35A to about 95A, optionally from about 55A to about 90A.

[0174] According to aspect 98, this disclosure relates to the method of any one of the foregoing aspects, further comprising forming a solid foamable material using an extrusion process prior to the placement step.

[0175] According to aspect 99, this disclosure relates to the method of any one of the foregoing aspects, further comprising forming a solid foamable material using an injection molding process prior to the placement step.

[0176] According to aspect 100, this disclosure relates to the method of any one of the foregoing aspects, further comprising forming a solid foamable material using a thermoforming process and / or a vacuum forming process prior to the placement step.

[0177] According to aspect 101, this disclosure relates to the method of any one of the foregoing aspects, further comprising forming a solid foamable material using an additive manufacturing process prior to the placement step.

[0178] According to aspect 102, this disclosure relates to a method according to any one of the foregoing aspects, wherein an optional exposure step occurs in a container.

[0179] According to aspect 103, this disclosure relates to a method according to any one of the foregoing aspects, wherein the steps of experiencing and expanding occur in a container.

[0180] According to aspect 104, this disclosure relates to the method of any one of aspects 1-101, wherein the optional exposure step further includes removing the article injected with liquid carbon dioxide from the container before exposing the article to an optional second pressure and a second temperature.

[0181] According to aspect 105, this disclosure relates to a method according to any one of aspects 1-101, wherein the steps further include removing the article injected with liquid carbon dioxide from the container before subjecting the article to a third pressure and a third temperature.

[0182] According to aspect 106, this disclosure relates to the method of aspect 105, wherein the step of placing carbon dioxide in a container includes introducing carbon dioxide vapor into the container prior to the steps of maintaining and holding.

[0183] According to aspect 107, this disclosure relates to the method of aspect 106, wherein introducing carbon dioxide vapor includes loading a container with carbon dioxide vapor under pressure and temperature conditions that are in liquid / vapor equilibrium of carbon dioxide.

[0184] According to aspect 108, this disclosure relates to a method according to any one of aspects 105-107, wherein the method further includes discharging liquid carbon dioxide from a container after a sustaining and holding step, before an optional exposure step, or before an experience and expansion step.

[0185] According to aspect 109, this disclosure relates to the method of aspect 108, wherein discharging liquid carbon dioxide from a container includes converting the liquid carbon dioxide into carbon dioxide vapor before or during the discharge.

[0186] According to aspect 110, this disclosure relates to a method according to any one of the foregoing aspects, wherein the step of subjecting the article to a third temperature and a third pressure includes introducing the article into a fluid bath, optionally wherein the fluid bath is a water bath.

[0187] According to aspect 111, this disclosure relates to the method of aspect 110, wherein the fluid bath has a temperature from about 20 degrees Celsius to about 90 degrees Celsius.

[0188] According to aspect 112, this disclosure relates to the method of aspect 110 or 111, wherein during the process, the article is held in a fluid bath for a duration of from about 15 seconds to about 5 minutes.

[0189] According to aspect 113, this disclosure relates to a method according to any one of aspects 1-109, wherein the steps include subjecting the article to an energy source or heat source, optionally wherein the energy source or heat source includes steam, microwave energy, infrared (IR) energy, radio frequency (RF) energy, or any combination thereof.

[0190] According to aspect 114, this disclosure relates to the method of aspect 113, wherein the step of subjecting the article to an energy source or heat source raises the temperature of at least a portion of the foamable material of the article to a temperature from about 60 degrees Celsius to about 150 degrees Celsius, optionally wherein the subjecting lasts for a duration from about 2 seconds to about 5 minutes.

[0191] According to aspect 115, this disclosure relates to the method of any one of aspects 3-114, wherein the optional step of stabilizing at a fifth pressure and a fifth temperature includes placing the foamed article in an oven.

[0192] According to aspect 116, this disclosure relates to the method of any one of aspects 3-115, wherein the optional stabilization step includes stabilization at a fifth pressure of about atmospheric pressure.

[0193] According to aspect 117, this disclosure relates to the method of any one of aspects 3-116, wherein the optional stabilization step includes stabilization at a fifth temperature greater than the glass transition temperature of the solid foamable material.

[0194] According to aspect 118, this disclosure relates to the method of any one of aspects 3-117, wherein the optional stabilization step includes stabilization at a fifth temperature from about 30 degrees Celsius to about 70 degrees Celsius, optionally about 50 degrees Celsius.

[0195] According to aspect 119, this disclosure relates to the method of any one of aspects 3-118, wherein the optional stabilization step includes stabilizing the foamed article at a fifth temperature for a period of about 15 minutes to about 60 minutes, optionally for a period of about 30 minutes to about 45 minutes.

[0196] According to aspect 120, this disclosure relates to a method according to any one of the foregoing aspects, wherein an article is configured as a roll, and wherein the placement step includes setting the roll into a container, and wherein the experiencing and expanding steps include unfolding the article before or during the experiencing, or before or during the expanding.

[0197] According to aspect 121, this disclosure relates to the method of aspect 120, wherein the placement step further includes disposing a porous spacer between adjacent portions of the article before or during placement, and wherein the maintaining and holding step includes flowing liquid carbon dioxide through the porous spacer to the adjacent portions of the article.

[0198] According to aspect 122, this disclosure relates to a method according to any one of the foregoing aspects, wherein during expansion, at least a portion of an article comprising a solid foamable material expands in length, width, and height as the solid foamable material expands into a foamable material.

[0199] According to aspect 123, this disclosure relates to the method of aspect 122, wherein after expansion, the size of the foamed article is larger in at least one dimension than the size of the article before placement, optionally wherein the foamed article is at least 5%, or at least 10%, or at least 15%, or at least 20% larger in one or more of the dimensions of length, width, and height.

[0200] According to aspect 124, this disclosure relates to the method of aspect 122 or 123, wherein the article is a layered sheet, undergoes a step of foaming at least one layer of the sheet, and after undergoing and expanding, the thickness of the foamed layered sheet is at least 5%, or at least 10%, or at least 15%, or at least 20% greater than the thickness of the layered sheet in its unfoamed state.

[0201] According to aspect 125, this disclosure relates to a method according to any one of aspects 122-124, wherein the method includes a stabilization step, and after stabilization, the stabilized foam article is larger in at least one dimension than the size of the article before placement, optionally wherein the stabilized foam article is at least 5%, or at least 10%, or at least 15%, or at least 20% larger in one or more of the dimensions of length, width, and height.

[0202] According to aspect 126, this disclosure relates to the method described in any of the foregoing aspects, further comprising thermoforming the foamed article, optionally wherein the foamed article is a stabilized foamed article.

[0203] According to aspect 127, this disclosure relates to the method of aspect 126, wherein the foamed article is a sheet, optionally wherein the sheet is a layered sheet, optionally wherein the layered sheet includes at least one unfoamed capping layer, optionally wherein the layered sheet includes one or more foamed inner layers and two unfoamed capping layers.

[0204] According to aspect 128, this disclosure relates to a method according to any one of the foregoing aspects, wherein the article is a thermoformed article, and optionally the method further includes a step of thermoforming the article prior to the placement step.

[0205] According to aspect 129, this disclosure relates to the method described in any one of the foregoing aspects, wherein the foamed article is a component of clothing, footwear, or sports equipment.

[0206] According to aspect 130, this disclosure relates to a method according to any one of the foregoing aspects, wherein an article is configured as a series of two or more regions, the series of two or more regions including a first region comprising a first region material and a second region comprising a second region material, wherein the first region material or the second region material or both the first region material and the second region material are solid foamable materials; optionally wherein the first region or the second region forms the outermost surface of the article, or wherein both the first region and the second region, individually or jointly, form the outermost surface of the article.

[0207] According to aspect 131, this disclosure relates to the method of aspect 130, wherein the region includes a layer, and wherein a first region or a second region forms an inner layer of an article, or both the first region and the second region separately form separate inner layers of an article, optionally wherein the article is a layered sheet.

[0208] According to aspect 132, this disclosure relates to the method of aspect 130 or 131, wherein in an article, a first region forms the outermost surface of the article, and a second region forms the inner layer of the article.

[0209] According to aspect 133, this disclosure relates to a method according to any one of aspects 130-132, wherein in the article, a first region comprises or is substantially composed of a solid foamable material, the solid foamable material of the first region being a first region solid foamable material, and during the steps of undergoing and expanding, the solid foamable material of the first region remains as a first region solid foamable material or expands into a foamed material, wherein the foamed material of the first region is a first region foamed material.

[0210] According to aspect 134, this disclosure relates to a method according to any one of aspects 130-133, wherein in the article, the second region comprises or is substantially composed of a solid foamable material, the solid foamable material of the second region being a solid foamable material of the second region, and during the steps of undergoing and expanding, the solid foamable material of the second region remains as a solid foamable material of the second region or expands into a foamed material, wherein the foamed material of the second region is a foamed material of the second region.

[0211] According to aspect 135, this disclosure relates to the method of any one of aspects 130-134, wherein the first region solid foamable material, or the second region solid foamable material, or both individually, are solid foamable materials according to any one of aspects 1, 5, 9-36, 54-69, or 92-101.

[0212] According to aspect 136, this disclosure relates to the method of any one of aspects 130-135, wherein the material foamed in the first region, or the material foamed in the second region, or both individually, is the material foamed according to any one of aspects 6-8, 50, 51, or 165-170.

[0213] According to aspect 137, this disclosure relates to the method of any one of aspects 130-136, wherein the first region material or the second region material is a barrier material according to any one of aspects 39-48, 54-67, 70, 71 or 203-212.

[0214] According to aspect 138, this disclosure relates to the method described in any one of aspects 130-137, wherein

[0215] The steps of maintaining and holding include keeping the articles and liquid carbon dioxide in the container for a duration sufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of the first area, or

[0216] The duration is sufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of the second region, or

[0217] The duration is sufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of the first region and at least a portion of the second region;

[0218] Optionally, the duration is sufficient to allow at least a portion of the liquid carbon dioxide to be injected into substantially all of the first region or substantially all of the second region, or into substantially all of the first region and the second region.

[0219] According to aspect 139, this disclosure relates to the method described in aspect 138, wherein

[0220] The first region includes or is substantially composed of a solid foamable material in the first region.

[0221] The maintenance and holding steps include holding the article and liquid carbon dioxide in the container for a duration sufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of the solid expandable material in the first region, and

[0222] The process of undergoing and expanding includes expanding at least a portion of the solid foamable material in the first region into a foamed material, wherein the foamed material in the first region includes the foamed material in the first region.

[0223] Optionally, the expansion includes expanding substantially all of the solid foamable material in the first region into foamed material in the first region.

[0224] According to aspect 140, this disclosure relates to the method described in aspect 138, wherein

[0225] The maintenance and holding steps include holding the article and liquid carbon dioxide in the container for a duration sufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of the first region, wherein the duration is insufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of the second region.

[0226] The process of undergoing and expanding includes expanding at least a portion of the solid foamable material in the first region into foamable material in the first region without expanding the material in the second region.

[0227] Optionally, after the maintenance and holding steps, the second region is substantially free of injected carbon dioxide, and

[0228] Optionally, the second region may include or consist primarily of barrier material.

[0229] According to aspect 141, this disclosure relates to the method described in aspect 138, wherein

[0230] The maintaining and holding steps include holding the article and liquid carbon dioxide in a container for a duration sufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of a first region and into at least a portion of a second region, and the method further includes the steps of: exposing the injected article to a second pressure and a second temperature for a period of time, such that at least a portion of the carbon dioxide injected into at least a portion of the second region diffuses out of at least a portion of the second region, while at least a portion of the injected carbon dioxide injected into the first region remains injected into at least a portion of the first region after the exposure;

[0231] The process of undergoing and expanding includes expanding at least a portion of the solid foamable material in the first region into foamable material in the first region without expanding the material in the second region, thereby forming a foamed first region, while maintaining the second region in a solid, unfoamed state.

[0232] Optionally, after the exposure step, the second area is substantially free of injected carbon dioxide, and

[0233] Optionally, the second region may include or consist primarily of barrier material.

[0234] According to aspect 142, this disclosure relates to a method according to any one of aspects 130-137, wherein the placement step includes placing the article in liquid carbon dioxide in a container such that the article is not completely immersed in the liquid carbon dioxide.

[0235] According to aspect 143, this disclosure relates to the method of aspect 142, wherein a first region is immersed in liquid carbon dioxide and a second region is not immersed in liquid carbon dioxide, and wherein, after the exposure step, the second region is substantially free of injected carbon dioxide.

[0236] According to aspect 144, this disclosure relates to the method described in any one of aspects 130-137, wherein

[0237] The steps of maintaining and holding include keeping the articles and liquid carbon dioxide in the container for a duration sufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of the second area, or

[0238] The duration is sufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of the first region and at least a portion of the second region;

[0239] Optionally, the duration is sufficient to allow at least a portion of the liquid carbon dioxide to be injected into substantially all of the first region or substantially all of the second region, or into substantially all of the first region and the second region.

[0240] According to aspect 145, this disclosure relates to the method described in aspect 144, wherein

[0241] The second region includes solid foamable materials or is essentially composed of solid foamable materials.

[0242] The maintenance and holding steps include keeping the article and liquid carbon dioxide in the container for a duration sufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of the solid expandable material in the second region, and

[0243] The process of undergoing and expanding includes expanding at least a portion of the solid foamable material in the second region into a foamed material, wherein the foamed material in the second region includes the foamed material in the second region.

[0244] Optionally, the expansion includes expanding substantially all of the second-region solid foamable material into a second-region foamed material.

[0245] According to aspect 146, this disclosure relates to the method described in aspect 144, wherein

[0246] The maintenance and holding steps include holding the article and liquid carbon dioxide in the container for a duration sufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of the second region, wherein the duration is insufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of the first region.

[0247] The process of undergoing and expanding includes expanding at least a portion of the solid foamable material in the second region into foamable material in the second region without expanding the material in the first region, thereby forming a foamed second region, while maintaining the first region in a solid, unfoamed state.

[0248] Optionally, after the maintenance and holding steps, the first region is substantially free of injected carbon dioxide, and

[0249] Optionally, the first region may include or consist primarily of barrier material.

[0250] According to aspect 147, this disclosure relates to the method described in aspect 144, wherein

[0251] The maintaining and holding steps include holding the article and liquid carbon dioxide in a container for a duration sufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of a first region and into at least a portion of a second region, and the method further includes the steps of: exposing the injected article to a second pressure and a second temperature for a period of time, such that at least a portion of the carbon dioxide injected into at least a portion of the first region diffuses out of at least a portion of the first region, while at least a portion of the injected carbon dioxide injected into the second region remains injected into at least a portion of the second region after the exposure;

[0252] The process of undergoing and expanding includes expanding at least a portion of the solid foamable material in the second region into a foamed material in the second region without expanding the material in the first region.

[0253] Optionally, after the exposure step, the first area is substantially free of injected carbon dioxide, and

[0254] Optionally, the first region may include or consist primarily of barrier material.

[0255] According to aspect 148, this disclosure relates to the method described in any one of aspects 130-137, wherein

[0256] The first region includes or is composed of a solid foamable material, and the solid foamable material in the first region is the solid foamable material in the first region.

[0257] The second region includes solid foamable materials or is essentially composed of solid foamable materials, and the solid foamable materials in the second region are the solid foamable materials in the second region.

[0258] The maintaining and holding steps include holding the article and liquid carbon dioxide in the container for a duration sufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of the first region and into at least a portion of the second region; and

[0259] The process of undergoing expansion causes at least a portion of the first region of solid foamable material to expand into a first region of foamed material, and at least a portion of the second region of solid foamable material to expand into a second region of foamed material.

[0260] Optionally, the expansion includes expanding substantially all of the first-region solid foamable material or substantially all of the second-region solid foamable material, or expanding substantially all of the first-region solid foamable material and substantially all of the second-region solid foamable material.

[0261] According to aspect 149, this disclosure relates to the method of aspect 148, wherein in a foamed article, materials foamed in a first region and materials foamed in a second region are in contact with each other.

[0262] According to aspect 150, this disclosure relates to the method of aspect 148, wherein in the foamed article, the material of the first region foamed and the material of the second region foamed do not come into contact with each other.

[0263] According to aspect 151, this disclosure relates to the method described in any one of aspects 130-148, wherein

[0264] The first region includes or is substantially composed of a solid foamable material, and the second region includes or is substantially composed of a barrier material, or wherein the first region includes or is substantially composed of a barrier material, and the second region includes or is substantially composed of a solid foamable material.

[0265] The maintenance and holding steps include holding the article and liquid carbon dioxide in a container for a duration sufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of the solid foamable material, wherein the duration is insufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of the barrier material.

[0266] The process of expansion includes expanding a solid foamable material into a foamed material without expanding the barrier material;

[0267] Optionally, in the foamed article, the foamed material and the barrier material are in contact with each other, or the foamed material and the barrier material are not in contact with each other.

[0268] According to aspect 152, this disclosure relates to a method as described in any one of aspects 130-151, wherein an article is configured as a series of three or more regions, the series of three or more regions further comprising a third region, the third region comprising or substantially consisting of a third region material.

[0269] Optionally, the material in the third region includes or is substantially composed of a barrier material, or includes or is substantially composed of a solid foamable material in the third region, or

[0270] Optionally, the third region is positioned between the first and second regions.

[0271] According to aspect 153, this disclosure relates to the method of aspect 152, wherein the maintaining and holding steps include holding the article and liquid carbon dioxide in a container for a duration sufficient to allow at least a portion of the liquid carbon dioxide to be injected into a first region, or into a first region and a second region, or into a second region, or into a second region and a third region, or into a third region, or into a third region and a first region.

[0272] According to aspect 154, this disclosure relates to the method of aspect 152 or 153, wherein the maintaining and holding step includes holding the article and liquid carbon dioxide in a container for a duration sufficient to allow the liquid carbon dioxide to be injected into one or two of the three zones, but not into the other three zones.

[0273] Optionally, carbon dioxide is injected into the first region but substantially not into the second region, or injected into the first region but substantially not into the third region, or injected into the second region but substantially not into the first region, or injected into the second region but substantially not into the third region, or injected into the third region but substantially not into the first region, or injected into the third region but substantially not into the second region; or

[0274] Optionally, carbon dioxide is injected into the first region and the second region but not substantially into the third region, or into the first region and the third region but not substantially into the second region, or into the second region and the third region but not substantially into the first region.

[0275] According to aspect 155, this disclosure relates to a method according to any one of aspects 152-154, wherein the method includes an exposure step, and the exposure step includes exposing an article to a second pressure and a second temperature, wherein carbon dioxide is continuously injected into one or two of three zones while carbon dioxide diffuses out from the other zones of the three zones.

[0276] Optionally, carbon dioxide is injected into the first region but substantially not into the second region, or injected into the first region but substantially not into the third region, or injected into the second region but substantially not into the first region, or injected into the second region but substantially not into the third region, or injected into the third region but substantially not into the first region, or injected into the third region but substantially not into the second region; or

[0277] Optionally, carbon dioxide is maintained injected into the first and second regions and diffuses substantially out of the third region, or is maintained injected into both the first and third regions and diffuses substantially out of the second region, or is maintained injected into both the second and third regions and diffuses substantially out of the first region; or

[0278] Optionally, carbon dioxide diffuses substantially from the first and second regions and remains injected into the third region, or diffuses substantially from the first and third regions and remains injected into the second region, or diffuses substantially from the second and third regions and remains injected into the first region.

[0279] According to aspect 156, this disclosure relates to a method according to any one of aspects 152-155, wherein the steps of undergoing expansion cause the material of one or two of the three regions to expand into a foamed material, while maintaining the other regions of the three regions in a solid, unfoamed state.

[0280] Optionally, the steps of undergoing expansion cause at least a portion of the material in the first region to expand into a material foamed in the first region, or at least a portion of the material in the second region to expand into a material foamed in the second region, or at least a portion of the material in the third region to expand into a material foamed in the third region, or any combination thereof; or

[0281] Optionally, the steps of expansion cause the material in the first region to expand into a foamed material in the first region and the material in the second region to expand into a foamed material in the second region, or cause the material in the first region to expand into a foamed material in the first region and the material in the third region to expand into a foamed material in the third region, or cause the material in the second region to expand into a foamed material in the second region and the material in the third region to expand into a foamed material in the third region; or

[0282] Optionally, after undergoing the expansion step, the material in the first region remains as a solid, unfoamed material in the first region, or the material in the second region remains as a solid, unfoamed material in the second region, or the material in the third region remains as a solid, unfoamed material in the third region, or both the material in the first and second regions remain as solid, unfoamed materials in the first and second regions, or both the material in the first and third regions remain as solid, unfoamed materials in the first and third regions, or both the material in the second and third regions remain as solid, unfoamed materials in the second and third regions.

[0283] According to aspect 157, this disclosure relates to the method of any one of aspects 152-156, wherein the article is configured as a series of four or more regions, the fourth region comprising or substantially consisting of a fourth region material, optionally wherein the fourth region material comprises or substantially consists of a barrier material, or comprises or substantially consists of a solid foamable material.

[0284] Optionally, the maintaining and holding steps include holding the articles and liquid carbon dioxide in the container for a duration sufficient to allow at least a portion of the liquid carbon dioxide to be injected into the fourth region; or

[0285] Optionally, the maintaining and holding steps include holding the article and liquid carbon dioxide in the container for a duration sufficient to allow the liquid carbon dioxide to be injected into one or more of the first, second, and third zones but not into the fourth zone; or

[0286] Optionally, the method includes an exposure step, and the exposure step includes exposing the article to a second pressure and a second temperature, wherein carbon dioxide is continuously injected into one or more of a first region, a second region, and a third region, while carbon dioxide diffuses out from a fourth region; or

[0287] Optionally, the method includes an exposure step, and the exposure step includes exposing the article to a second pressure and a second temperature, wherein carbon dioxide is continuously injected into a fourth region.

[0288] According to aspect 158, this disclosure relates to the method of aspect 157, wherein after undergoing the expansion step, the fourth region material remains as a fourth region solid unfoamed material, or the fourth region material expands into a fourth region foamed material.

[0289] According to aspect 159, this disclosure relates to a method of manufacturing an article, said method comprising:

[0290] The first component is attached to the second component, wherein the first component is a foamed article manufactured by any one of aspects 1-158.

[0291] According to aspect 160, this disclosure relates to the method of aspect 159, wherein the first component is a first component of a garment article, the second component is a second component of a garment article, and the article is a garment article.

[0292] According to aspect 161, this disclosure relates to the method of aspect 159, wherein the first component is a first component of a footwear article, the second component is a second component of a footwear article, and the article is a footwear article.

[0293] According to aspect 162, this disclosure relates to the method of aspect 161, wherein the first component is a cushioning element and the second component is a sole component or an upper component.

[0294] According to aspect 163, this disclosure relates to the method described in aspect 159, wherein the first component is a first component of a sports equipment article, the second component is a second component of a sports equipment article, and the article is a sports equipment article.

[0295] According to aspect 164, this disclosure relates to a foamed article manufactured by any one of aspects 1-163.

[0296] According to aspect 165, this disclosure relates to a foamed article comprising:

[0297] Foamed materials are physically expanded foams formed from thermoplastic elastomer materials containing one or more first thermoplastic elastomers.

[0298] According to aspect 166, this disclosure relates to the foamed article described in aspect 165, wherein the foamed material is a product of: placing an unfoamed article containing a solid foamable material in liquid carbon dioxide, injecting the solid foamable material with liquid carbon dioxide, and expanding the injected solid foamable material by causing the injected carbon dioxide to phase into a gas without softening the solid foamable material, thereby forming a foamed article.

[0299] According to aspect 167, this disclosure relates to the foamed articles described in aspect 165 or 166, wherein the foamed articles are stabilized foamed articles comprising stabilized foamed materials, wherein the stabilized foamed materials contain no or substantially no injected carbon dioxide.

[0300] According to aspect 168, this disclosure relates to a foamed article as described in any one of aspects 165-167, wherein, at a first pressure of about 0.05 psi (0.345 kPa) to about 6,000 psi (41,300 kPa) and a first temperature of about -57°C to about 31°C, liquid carbon dioxide is soluble in the foamed material, or a solid foamable material, or both, at a concentration of about 1 wt% to about 30 wt%, optionally from about 5 wt% to about 20 wt%.

[0301] According to aspect 169, this disclosure relates to a foamed article as described in any one of aspects 165-168, wherein the foaming material of the foamed article is substantially opaque.

[0302] According to aspect 170, this disclosure relates to a foamed article as described in any one of aspects 165-169, wherein the foamed material has a tear value from about 2.5 kg / cm to about 3.0 kg / cm.

[0303] According to aspect 171, this disclosure relates to a foamed article as described in any one of aspects 165-170, wherein the foamed material has an Asker C hardness of about 10 to about 50.

[0304] According to aspect 172, this disclosure relates to a foamed article according to any one of aspects 165-171, wherein the thermoplastic elastomer material includes a polymer component comprising all polymers present in the thermoplastic elastomer material, and the polymer component consists of one or more first thermoplastic elastomers.

[0305] According to aspect 173, this disclosure relates to foamed articles according to any one of aspects 165-172, wherein one or more first thermoplastic elastomers comprise one or more thermoplastic elastomer polyolefin homopolymers or copolymers, one or more thermoplastic elastomer polyamide homopolymers or copolymers, one or more thermoplastic elastomer polyester homopolymers or copolymers, one or more thermoplastic elastomer polyurethane homopolymers or copolymers, one or more thermoplastic elastomer styrene homopolymers or copolymers, or any combination thereof.

[0306] According to aspect 174, this disclosure relates to foamed articles according to any one of aspects 165-173, wherein one or more first thermoplastic elastomers comprise one or more thermoplastic elastomer polyamide homopolymers or copolymers or are substantially composed of one or more thermoplastic elastomer polyamide homopolymers or copolymers.

[0307] According to aspect 175, this disclosure relates to foamed articles according to any one of aspects 165-174, wherein one or more first thermoplastic elastomers comprise or are substantially composed of polyether block polyamide (PEBA) copolymer elastomers.

[0308] According to aspect 176, this disclosure relates to foamed articles according to any one of aspects 165-175, wherein one or more first thermoplastic elastomers comprise one or more thermoplastic elastomer styrene homopolymers or copolymers or are substantially composed of one or more thermoplastic elastomer styrene homopolymers or copolymers.

[0309] According to aspect 177, this disclosure relates to foamed articles according to any one of aspects 165-176, wherein one or more first thermoplastic elastomers comprise or are substantially composed of: styrene-butadiene-styrene (SBS) block copolymer elastomers, styrene-ethylene-butadiene-styrene (SEBS) copolymer elastomers, styrene-acrylonitrile (SAN) copolymer elastomers, or any combination thereof.

[0310] According to aspect 178, this disclosure relates to foamed articles according to any one of aspects 165-177, wherein one or more first thermoplastic elastomers comprise one or more thermoplastic polyurethane elastomer homopolymers or copolymers or are substantially composed of one or more thermoplastic polyurethane elastomer homopolymers or copolymers.

[0311] According to aspect 179, this disclosure relates to foamed articles as described in any one of aspects 165-178, wherein one or more first thermoplastic elastomers comprise or are substantially composed of: thermoplastic polyester-polyurethane elastomers, polyether-polyurethane elastomers, polycarbonate-polyurethane elastomers, or any combination thereof.

[0312] According to aspect 180, this disclosure relates to foamed articles as described in any one of aspects 165-179, wherein one or more first thermoplastic elastomers comprise one or more thermoplastic polyester-polyurethane elastomers or are substantially composed of one or more thermoplastic polyester-polyurethane elastomers.

[0313] According to aspect 181, this disclosure relates to a foamed article as described in any one of aspects 165-180, wherein the polymer component of the thermoplastic elastomer material consists of one or more thermoplastic polyester-polyurethane elastomers.

[0314] According to aspect 182, this disclosure relates to foamed articles according to any one of aspects 165-181, wherein one or more first thermoplastic elastomers comprise one or more thermoplastic polyolefin elastomer homopolymers or copolymers or are substantially composed of one or more thermoplastic polyolefin elastomer homopolymers or copolymers.

[0315] According to aspect 183, this disclosure relates to foamed articles according to any one of aspects 165-182, wherein one or more first thermoplastic elastomers comprise or are substantially composed of: thermoplastic elastomer polypropylene homopolymer or copolymer, thermoplastic elastomer polyethylene homopolymer or copolymer, thermoplastic elastomer polybutene homopolymer or copolymer, or any combination thereof.

[0316] According to aspect 184, this disclosure relates to foamed articles according to any one of aspects 165-183, wherein one or more first thermoplastic elastomers comprise or are substantially composed of thermoplastic elastomers ethylene-vinyl acetate copolymers.

[0317] According to aspect 185, this disclosure relates to the foamed articles described in aspect 184, wherein the thermoplastic elastomer ethylene-vinyl acetate copolymer comprises a vinyl acetate content from about 25% by weight to about 50% by weight.

[0318] According to aspect 186, this disclosure relates to a foamed article as described in any one of aspects 165-185, wherein the thermoplastic elastomer material comprises a polymeric component and a mixture of a nonpolymeric component consisting of one or more nonpolymeric additives, optionally wherein the foamable material comprises, by weight, from about 0.005% to about 20% of the nonpolymeric component based on the total weight of the foamable material, or by weight, from about 0.5% to about 10% of the nonpolymeric additives based on the total weight of the foamable material.

[0319] According to aspect 187, this disclosure relates to foamed articles as described in any one of aspects 165-186, wherein one or more first thermoplastic elastomers comprise one or more recycled first thermoplastic elastomers or are substantially composed of one or more recycled first thermoplastic elastomers.

[0320] According to aspect 188, this disclosure relates to foamed articles according to any one of aspects 165-187, wherein the thermoplastic elastomer material comprises or consists substantially of a blend of one or more first thermoplastic elastomers and a second material, optionally wherein the second material comprises or consists substantially of one or more second polymers, optionally wherein the one or more second polymers comprises or consists substantially of one or more second thermoplastic plastics.

[0321] According to aspect 189, this disclosure relates to the foamed articles described in aspect 188, wherein the polymer component of the thermoplastic elastomer material comprises a blend of one or more first thermoplastic elastomers and one or more second thermoplastics.

[0322] According to aspect 190, this disclosure relates to the foamed articles described in aspects 188 or 189, wherein one or more second thermoplastics include one or more thermoplastic polyolefin homopolymers or copolymers, one or more thermoplastic polyamide homopolymers or copolymers, one or more thermoplastic polyester homopolymers or copolymers, one or more thermoplastic polyurethane homopolymers or copolymers, one or more thermoplastic styrene homopolymers or copolymers, or any combination thereof.

[0323] According to aspect 191, this disclosure relates to foamed articles as described in any one of aspects 188-190, wherein one or more second thermoplastics comprise or are substantially composed of: thermoplastic polypropylene homopolymers or copolymers, thermoplastic polyethylene homopolymers or copolymers, thermoplastic polybutene homopolymers or copolymers, or any combination thereof.

[0324] According to aspect 192, this disclosure relates to foamed articles as described in any one of aspects 188-191, wherein one or more second thermoplastics comprise one or more thermoplastic polyethylene copolymers or are substantially composed of one or more thermoplastic polyethylene copolymers.

[0325] According to aspect 193, this disclosure relates to foamed articles as described in any one of aspects 188-192, wherein one or more second thermoplastics comprise one or more thermoplastic ethylene-vinyl alcohol copolymers or are substantially composed of one or more thermoplastic ethylene-vinyl alcohol copolymers.

[0326] According to aspect 194, this disclosure relates to a foamed article as described in any one of aspects 188-193, wherein the polymer component of the thermoplastic elastomer material consists of one or more first thermoplastic elastomer polyurethane homopolymers or copolymers and one or more second thermoplastic ethylene-vinyl alcohol copolymers.

[0327] According to aspect 195, this disclosure relates to a foamed article as described in any one of aspects 188-194, wherein the polymer component of the thermoplastic elastomer material comprises one or more first thermoplastic elastomer polyester-polyurethane copolymers and one or more second thermoplastic ethylene-vinyl alcohol copolymers.

[0328] According to aspect 196, this disclosure relates to foamed articles as described in any one of aspects 188-195, wherein the blend comprises one or more recycled first thermoplastic elastomers, or one or more recycled second thermoplastics, or both.

[0329] According to aspect 197, this disclosure relates to foamed articles as described in any one of aspects 188-196, wherein the blend is a phase-separated blend of one or more first thermoplastic elastomers and one or more second thermoplastics.

[0330] According to aspect 198, this disclosure relates to the foamed articles described in aspect 197, wherein the phase-separated blends include one or more phase-separated regions, the one or more phase-separated regions being included at the interface between one or more first thermoplastic elastomers and one or more second thermoplastics.

[0331] According to aspect 199, this disclosure relates to a foamed article as described in any one of aspects 188-198, wherein the blend comprises about 95% by weight of one or more first thermoplastic elastomers and about 5% by weight of one or more second thermoplastics based on the total weight of the blend.

[0332] According to aspect 200, this disclosure relates to a foamed article as described in any one of aspects 188-199, wherein, at a first pressure of about 0.05 psi (0.345 kPa) to about 6000 psi (41,300 kPa) and a first temperature of about -57°C to about 31°C, liquid carbon dioxide is soluble in one or more first thermoplastic elastomers at a concentration of about 1% to about 30% by weight, optionally from about 5% to about 20% by weight, based on the total weight of one or more first thermoplastic elastomers present in the thermoplastic elastomer material, and wherein the liquid carbon dioxide is soluble in one or more second thermoplastics at a concentration of less than 1% by weight, optionally less than 0.1% by weight, based on the total weight of one or more second thermoplastics present in the thermoplastic elastomer material, or optionally wherein the liquid carbon dioxide is substantially insoluble in one or more second thermoplastics.

[0333] According to aspect 201, this disclosure relates to a foamed article as described in any one of aspects 165-200, wherein the foamed article includes an additional material, wherein the additional material is a material separate from the foamed material, wherein the additional material comprises one or more polymers or is substantially composed of one or more polymers, and includes an additional material polymer component consisting of all polymers present in the additional material; optionally, wherein the additional material includes a second material or is substantially composed of a second material, optionally wherein the second material is a thermoplastic material, optionally wherein the additional material includes an additional material polymer component mixed with an additional material non-polymer component, the additional material non-polymer component consisting of all non-polymer components present in the additional material.

[0334] According to aspect 202, this disclosure relates to a foamed article as described in any one of aspects 165-201, wherein the foamed article comprises one or more first portions of foamed material and one or more second portions of additional material, and one or more of the first portions differ from one or more of the second portions.

[0335] According to aspect 203, this disclosure relates to the foamed articles described in aspect 201 or 202, wherein the additional material includes a barrier material comprising one or more barrier polymers, the barrier material comprising a barrier polymer component consisting of all polymers present in the barrier material.

[0336] According to aspect 204, this disclosure relates to foamed articles as described in any one of aspects 201-203, wherein the additional material includes a plasticizer.

[0337] According to aspect 205, this disclosure relates to foamed articles as described in aspects 203 or 204, wherein in the foamed articles, the other materials are substantially unfoamed.

[0338] According to aspect 206, this disclosure relates to a foamed article as described in any one of aspects 203-205, wherein the barrier material has a hardness at least 10 Shore A units greater than that of a thermoplastic elastomer material in solid form, or optionally at least 20 Shore A units, at least 30 Shore A units, or at least 40 Shore A units greater than that of a thermoplastic elastomer material in solid form.

[0339] According to aspect 207, this disclosure relates to a foamed article according to any one of aspects 203-206, wherein the barrier material has a nitrogen permeability that is at least 50% lower than that of a thermoplastic elastomer material in solid form, optionally less than or equal to 10 cubic centimeters per square meter per 24 hours, or less than or equal to 1 cubic centimeter per square meter per 24 hours.

[0340] According to aspect 208, this disclosure relates to a foamed article as described in any one of aspects 203-207, wherein the barrier polymer component of the barrier material consists of one or more barrier polymers, each barrier polymer individually having a nitrogen permeability of less than or equal to 30 cubic centimeters per square meter per 24 hours, or less than or equal to 10 cubic centimeters per square meter per 24 hours, or less than or equal to 1 cubic centimeter per square meter per 24 hours.

[0341] According to aspect 209, this disclosure relates to foamed articles according to any one of aspects 203-208, wherein one or more barrier polymers comprise or are substantially composed of: one or more vinylidene chloride polymers, one or more acrylonitrile polymers or copolymers, one or more polyamides, one or more epoxy resins, one or more amine polymers or copolymers, or one or more thermoplastic polyolefin homopolymers or copolymers, optionally wherein one or more thermoplastic polyolefin homopolymers or copolymers comprise or are substantially composed of: one or more thermoplastic polyethylene copolymers, one or more thermoplastic ethylene-vinyl alcohol copolymers, or one or more thermoplastic elastomer ethylene-vinyl alcohol copolymers.

[0342] According to aspect 210, this disclosure relates to a foamed article as described in any one of aspects 203-209, wherein, under a first pressure of about 0.05 psi (0.345 kPa) to about 6000 psi (41,300 kPa) and a first temperature of about -57°C to about 31°C, liquid carbon dioxide is soluble in a thermoplastic elastomer material at a first concentration, liquid carbon dioxide is soluble in a barrier material at a second concentration, and the first concentration is at least 20% greater than the second concentration, optionally wherein the first concentration is at least 50% greater than the second concentration, or at least 70% greater than the second concentration.

[0343] According to aspect 211, this disclosure relates to the foamed article described in aspect 210, wherein the second concentration is less than 1 weight percentage, optionally less than 0.1 weight percentage, or optionally wherein liquid carbon dioxide is substantially insoluble in the barrier material at a first pressure from about 0.05 pounds per square inch (0.345 kPa) to about 6,000 pounds per square inch (41,300 kPa) and a first temperature from about -57 degrees Celsius to about 31 degrees Celsius.

[0344] According to aspect 212, this disclosure relates to a foamed article according to any one of aspects 203-211, wherein the barrier material comprises one or more ethylene-vinyl alcohol copolymers, optionally wherein one or more ethylene-vinyl alcohol copolymers are thermoplastic, optionally wherein one or more ethylene-vinyl alcohol thermoplastic copolymers comprise one or more thermoplastic elastomer copolymers; optionally wherein the barrier polymer component consists of one or more ethylene-vinyl alcohol copolymers, optionally wherein one or more ethylene-vinyl alcohol copolymers are thermoplastic, optionally wherein one or more ethylene-vinyl alcohol thermoplastic copolymers comprise one or more thermoplastic elastomer copolymers.

[0345] According to aspect 213, this disclosure relates to foamed articles according to any one of aspects 204-212, wherein the additional material is a thermoplastic material, optionally wherein the additional material is another thermoplastic elastomer material.

[0346] According to aspect 214, this disclosure relates to a foamed article as described in any one of aspects 204-212, wherein the foamed article includes a foamed material, wherein the foamed material is a first foamed material, and the foamed article further includes a second foamed material, wherein the second foamed material includes or is substantially composed of another material.

[0347] According to aspect 215, this disclosure relates to the foamed article described in aspect 214, wherein in the foamed article, the density of the first foamed material differs from the density of the second foamed material by at least 5%, at least 10%, or at least 20%.

[0348] According to aspect 216, this disclosure relates to a foamed article as described in any one of aspects 214 or 215, wherein the second foamed material is a second physically expanded foam.

[0349] According to aspect 217, this disclosure relates to a foamed article according to any one of aspects 214-216, wherein the second physically expanded foam is a product of: placing an unfoamed article containing a solid additional material in liquid carbon dioxide, injecting the solid additional material with liquid carbon dioxide, and expanding the injected solid additional material by causing the injected carbon dioxide to phase into a gas without softening the solid additional material, thereby forming a foamed additional material of the foamed article.

[0350] According to aspect 218, this disclosure relates to a foamed article as described in any one of aspects 204-217, wherein the additional material is a recycled material comprising one or more recycled polymers, optionally wherein the one or more recycled polymers comprise one or more recycled thermoplastics, optionally wherein the one or more recycled thermoplastics comprise one or more recycled thermoplastic elastomers; optionally wherein the recycled material comprises a recycled material polymer component consisting of one or more recycled thermoplastics, optionally wherein the recycled material polymer component consists of one or more recycled thermoplastic elastomers.

[0351] According to aspect 219, this disclosure relates to the foamed articles described in aspect 218, wherein the recycled material comprises one or more recycled first thermoplastic elastomers, optionally one or more recycled first thermoplastic elastomers comprises one or more re-milled first thermoplastic elastomers, optionally one or more recycled first thermoplastic elastomers or re-milled first thermoplastic elastomers comprises a thermoplastic elastomer according to any one of aspects 165-218.

[0352] According to aspect 220, this disclosure relates to the foamed articles described in aspect 218 or 219, wherein the recycled material further comprises one or more recycled second thermoplastics, optionally one or more of the recycled second thermoplastics comprising one or more re-milled second thermoplastics, optionally one or more of the recycled second thermoplastics or re-milled second thermoplastics comprising the thermoplastic according to any one of aspects 165-219.

[0353] According to aspect 221, this disclosure relates to the foamed articles described in aspect 220, wherein the recycled material comprises one or more recycled thermoplastic polyurethane elastomers or re-milled thermoplastic polyurethane elastomers, one or more recycled thermoplastic ethylene-vinyl alcohol copolymers or re-milled thermoplastic ethylene-vinyl alcohol copolymers, or both.

[0354] According to aspect 222, this disclosure relates to foamed articles as described in aspects 220 or 221, wherein the recycled material comprises a blend of one or more recycled thermoplastic elastomers or re-milled thermoplastic elastomers and one or more second thermoplastics, or wherein the recycled material comprises a blend of one or more thermoplastic elastomers and one or more recycled thermoplastics or one or more recycled second thermoplastics, optionally wherein the blend is a phase-separated blend, and optionally wherein the phase-separated blend includes one or more interfaces between one or more first thermoplastic elastomers and one or more second thermoplastics.

[0355] According to aspect 223, this disclosure relates to a foamed article according to any one of aspects 220-222, wherein the recycled material comprises about 99% to about 90% by weight of one or more first thermoplastic elastomers and about 1% to about 10% by weight of a second thermoplastic plastic based on the total weight of the recycled material, optionally wherein the recycled material comprises about 99% to about 93% by weight of one or more first thermoplastic elastomers and about 1% to about 7% by weight of one or more second thermoplastic plastics, or about 99% to about 95% by weight of one or more first thermoplastic elastomers and about 1% to about 5% by weight of one or more second thermoplastic plastics.

[0356] According to aspect 224, this disclosure relates to a foamed article according to any one of aspects 218-223, wherein the recycled material comprises about 99% to about 50% by weight of a recycled polymer or a re-milled polymer based on the total weight of the recycled material, optionally from about 99% to about 75% by weight of a recycled polymer or a re-milled polymer.

[0357] According to aspect 225, this disclosure relates to a foamed article as described in any one of aspects 218-222, wherein, at a first pressure of about 0.05 psi (0.345 kPa) to about 6,000 psi (41,300 kPa) and a first temperature of about -57°C to about 31°C, liquid carbon dioxide is soluble in the recycled material at a concentration of about 1% to about 30% by weight, optionally from about 5% to about 20% by weight, based on the total weight of the recycled material.

[0358] According to aspect 226, this disclosure relates to a foamed article as described in any one of aspects 218-225, wherein, at a first pressure of about 0.05 psi (0.345 kPa) to about 6,000 psi (41,300 kPa) and a first temperature of about -57°C to about 31°C, liquid carbon dioxide is soluble in one or more recycled or re-milled thermoplastic elastomers at a concentration of about 1% to about 30% by weight, optionally from about 5% to about 20% by weight, based on the total weight of the one or more recycled or re-milled thermoplastic elastomers.

[0359] According to aspect 227, this disclosure relates to foamed articles according to any one of aspects 218-226, wherein, at a first pressure of about 0.05 psi (0.345 kPa) to about 6000 psi (41,300 kPa) and a first temperature of about -57°C to about 31°C, liquid carbon dioxide is soluble in one or more recycled or re-ground thermoplastics at less than 1% by weight, optionally less than 0.1% by weight, based on the total weight of one or more recycled or re-ground thermoplastics, or optionally wherein the liquid carbon dioxide is substantially insoluble in one or more recycled or re-ground thermoplastics.

[0360] According to aspect 228, this disclosure relates to a foamed article as described in any one of aspects 218-227, wherein recycled material constitutes a recycled foamed article, optionally wherein the recycled foamed article is a re-ground foamed article, optionally wherein the recycled foamed article is a foamed article as described in any one of aspects 165-227.

[0361] According to aspect 229, this disclosure relates to a foamed article as described in any one of aspects 218-227, wherein the recycled material comprises a solid material, wherein the solid material is a thermoplastic elastomer material.

[0362] According to aspect 230, this disclosure relates to a foamed article as described in any one of aspects 218-229, wherein the recycled material further comprises one or more original first thermoplastic elastomers, optionally including one or more original thermoplastic polyurethane elastomers.

[0363] According to aspect 231, this disclosure relates to foamed articles according to any one of aspects 222-230, wherein the recycled material comprises one or more nucleating agents or one or more interfaces between phase-separated polymers.

[0364] According to aspect 232, this disclosure relates to foamed articles according to any one of aspects 218-231, wherein the thermoplastic elastomer material is a recycled material, or includes recycled material, or is substantially composed of recycled material.

[0365] According to aspect 233, this disclosure relates to a foamed article as described in any one of aspects 218-232, wherein the foamed material is a first foamed material, the foamed article includes a second foamed material, the second foamed material is another material, and the thermoplastic elastomer material of the first foamed material is a recycled material, or the other material of the second foamed material is a recycled material, or both the thermoplastic elastomer material and the other material are recycled materials.

[0366] According to aspect 234, this disclosure relates to a foamed article as described in any one of aspects 218-233, wherein the foamed article includes a barrier layer or barrier region, and the barrier layer or barrier region includes or is substantially composed of a barrier material.

[0367] According to aspect 235, this disclosure relates to the foamed articles described in aspect 234, wherein the barrier material is another material according to any one of aspects 201-231.

[0368] According to aspect 236, this disclosure relates to a foamed article as described in any one of aspects 165-235, wherein the foamed article includes a structural layer or structural region, and the structural layer or structural region includes or is substantially composed of structural material.

[0369] According to aspect 237, this disclosure relates to the foamed articles described in aspect 236, wherein the structural material is another material according to any one of aspects 201-231, optionally wherein the structural material comprises a blend of two or more other materials, optionally wherein at least one of the two or more other materials is a recycled material.

[0370] According to aspect 238, this disclosure relates to a foamed article as described in any one of aspects 165-237, wherein the foamed article comprises one or more connecting layers or connecting regions, each of the one or more connecting layers or connecting regions individually comprising or substantially consisting of a connecting material, each of the one or more connecting layers or connecting regions increasing the bonding strength between two adjacent layers or regions, optionally wherein the connecting material is a thermoplastic elastomer material as described in any one of aspects 165-237, optionally wherein the thermoplastic elastomer material is a recycled material.

[0371] According to aspect 239, this disclosure relates to a foamed article according to any one of aspects 165-238, wherein the foamed article comprises one or more protective layers, each of the one or more protective layers individually comprising or substantially consisting of a protective material, each of the one or more protective layers being adjacent to a core layer and having a protective layer thickness, the combination of the one or more protective layers and the adjacent core layer having a minimum radius of curvature greater than the minimum radius of curvature that causes cracking of the core layer or cracking of one or more individual layers within the core layer, optionally wherein the protective material is a solid foamable material according to any one of aspects 165-237, optionally wherein the solid foamable material is a recycled material.

[0372] According to aspect 240, this disclosure relates to a foamed article as described in any one of aspects 165-239, wherein the foamed material has a density from about 0.01 g / cm³ to about 3.0 g / cm³, optionally wherein the foamed material is a stabilized foamed material having a density from about 0.01 g / cm³ to about 3.0 g / cm³.

[0373] According to aspect 241, this disclosure relates to a foamed article as described in any one of aspects 165-240, wherein the foamed material has a volume greater than or less than 10%, optionally less than 5%, of the foamable material prior to foaming, and optionally wherein the foamed article is a stabilized foamed article.

[0374] According to aspect 242, this disclosure relates to a foamed article as described in any one of aspects 165-240, wherein the foamed material has a volume that is more than 20%, optionally more than 30%, or more than 40% larger than the foamable material prior to foaming, and optionally wherein the foamed article is a stabilized foamed article.

[0375] According to aspect 243, this disclosure relates to a foamed article as described in any one of aspects 165-242, wherein the foamed material has a Shore A hardness of from about 35A to about 95A, optionally from about 55A to about 90A.

[0376] According to aspect 244, this disclosure relates to a foamed article as described in any one of aspects 165-243, wherein the foamed article is configured as a roll, the roll optionally including spacers or protective layers between adjacent portions of the foamed article.

[0377] According to aspect 245, this disclosure relates to a foamed article as described in any one of aspects 165-244, wherein the article is a layered sheet comprising one or more foamed layers.

[0378] According to aspect 246, this disclosure relates to a foamed article as described in any one of aspects 165-245, wherein the foamed article is configured as a series of two or more regions, the series of two or more regions including a first region comprising a material comprising a first region foamed and a second region comprising a second region material, optionally wherein the second region material is a material comprising a second region foamed; optionally wherein the first region or the second region forms the outermost surface of the article, or wherein both the first region and the second region, individually or jointly, form the outermost surface of the article.

[0379] According to aspect 247, this disclosure relates to the foamed article described in aspect 246, wherein the region includes layers, and wherein a first region or a second region forms an inner layer of the foamed article, or both the first region and the second region separately form separate inner layers of the foamed article, optionally wherein the foamed article is a layered sheet comprising one or more foamed layers.

[0380] According to aspect 248, this disclosure relates to the foamed article described in aspect 246 or 247, wherein in the foamed article, a first region forms the outermost surface of the foamed article, and a second region forms the inner layer of the foamed article.

[0381] According to aspect 249, this disclosure relates to the foamed article described in aspect 246 or 247, wherein in the foamed article, a first region forms the inner layer of the foamed article, and a second region forms the outermost surface of the foamed article.

[0382] According to aspect 250, this disclosure relates to a foamed article as described in any one of aspects 246-249, wherein the first region comprises or is substantially composed of a first region material, and the first region material is a solid material.

[0383] According to aspect 251, this disclosure relates to a foamed article as described in any one of aspects 246-249, wherein the first region comprises or is substantially composed of a first region material, and the first region material is a foamed material.

[0384] According to aspect 252, this disclosure relates to a foamed article as described in any one of aspects 246-249, wherein the second region comprises or is substantially composed of a second region material, and the second region material is a solid material.

[0385] According to aspect 253, this disclosure relates to a foamed article as described in any one of aspects 246-249, wherein the second region comprises or is substantially composed of a second region material, and the second region material is a foamed material.

[0386] According to aspect 254, this disclosure relates to a foamed article as described in any one of aspects 246-249, wherein a first region comprises or is substantially composed of a foamed material, and a second region comprises or is substantially composed of a solid material.

[0387] According to aspect 255, this disclosure relates to a foamed article as described in any one of aspects 246-249, wherein a first region comprises or is substantially composed of a solid material, and a second region comprises or is substantially composed of a foamed material.

[0388] According to aspect 256, this disclosure relates to a foamed article as described in any one of aspects 246-249, wherein both the first region and the second region comprise or are substantially composed of a foamed material.

[0389] According to aspect 257, this disclosure relates to foamed articles according to any one of aspects 246-256, wherein the first region material, the second region material, or both are individually thermoplastic elastomer materials according to any one of aspects 9-23 or 172-184.

[0390] According to aspect 258, this disclosure relates to a foamed article as described in any one of aspects 246-257, wherein the first region material, the second region material, or both are individually foamed materials according to any one of aspects 6-8, 50, 51, or 165-171.

[0391] According to aspect 259, this disclosure relates to a foamed article according to any one of aspects 246-258, wherein the first region material or the second region material is a second material according to any one of aspects 24-67, 70, 71 or 203-212.

[0392] According to aspect 260, this disclosure relates to a foamed article as described in any one of aspects 246-258, wherein a first region comprises or is substantially composed of a foamed material, and a second region comprises or is substantially composed of a barrier material.

[0393] According to aspect 261, this disclosure relates to a foamed article as described in any one of aspects 246-258, wherein a first region comprises or is substantially composed of a barrier material, and a second region comprises or is substantially composed of a foamed material.

[0394] According to aspect 262, this disclosure relates to a foamed article as described in any one of aspects 246-261, wherein the foamed article is configured as a series of three or more regions and includes a third region comprising or substantially composed of a third region material, optionally wherein the third region is positioned between the first and second regions.

[0395] According to aspect 263, this disclosure relates to a foamed article as described in any one of aspects 246-261, wherein the material of the third region is a material foamed in the third region, optionally wherein the material foamed in the third region is another foamed material, optionally wherein the material foamed in the third region is a foamed material.

[0396] According to aspect 264, this disclosure relates to a foamed article as described in any one of aspects 246-261, wherein the third region material is a third region solid material, optionally wherein the third region material is another solid material, optionally wherein the other solid material is a barrier material.

[0397] According to aspect 265, this disclosure relates to a foamed article as described in any one of aspects 246-264, wherein the foamed article is configured as a series of four or more regions and includes a fourth region comprising or substantially consisting of a fourth region material, optionally wherein the fourth region is positioned between the third and second regions.

[0398] According to aspect 266, this disclosure relates to a foamed article as described in any one of aspects 246-264, wherein the fourth region material is a fourth region foamed material, optionally wherein the fourth region foamed material is another foamed material, optionally wherein the fourth region foamed material is a foamed material.

[0399] According to aspect 267, this disclosure relates to a foamed article according to any one of aspects 246-264, wherein the fourth region material is a fourth region solid material, optionally wherein the fourth region material is another solid material, optionally wherein the other solid material is a barrier material.

[0400] According to aspect 268, this disclosure relates to a method of manufacturing an article, the method comprising:

[0401] The first component is attached to the second component, wherein the first component is a foamed article according to any one of aspects 165-267.

[0402] According to aspect 269, this disclosure relates to foamed articles manufactured by any one of aspects 1-163, optionally wherein the foamed articles are foamed articles according to any one of aspects 165-267.

[0403] Methods for manufacturing foamed articles

[0404] In one aspect, this document provides a method for manufacturing a foamed article. The method includes placing the article and carbon dioxide in a container, wherein the article comprises a solid foamable material, and wherein the foamable material is a thermoplastic elastomer material comprising one or more thermoplastic elastomers. After placement, the method further includes maintaining the container at a first pressure and a first temperature, wherein the first pressure and the first temperature are the pressure and temperature at which the carbon dioxide is liquid and the liquid carbon dioxide is soluble in the solid foamable material, and wherein maintenance includes holding the article and the liquid carbon dioxide in the container for a duration sufficient to inject at least a portion of the liquid carbon dioxide into the solid foamable material of the article. As used herein, “injected” and “injected” carbon dioxide are understood to mean carbon dioxide dissolved in, contained in, or otherwise adsorbed and / or absorbed in the solid foamable material. In some aspects, after maintenance and holding, the method optionally includes exposing the article to a second pressure and a second temperature, at which the carbon dioxide remains injected into at least a portion of the solid foamable material. In any of these aspects, after the maintenance and holding of the article and optional exposure, the method includes subjecting the article to a third pressure and a third temperature, at which carbon dioxide injected into a solid foamable material undergoes a phase change to gas, thereby causing the solid foamable material to expand into a foamed material and form a foamed article. The foamed material has a porous foam structure. In one aspect, the foamed material has a porous closed-cell structure. In another aspect, the foamed material has a porous open-cell structure. In some aspects, subjecting the article to a third temperature and a third pressure and causing the carbon dioxide to undergo a phase change to gas also serves to cool the foamable material and / or the foamed material.

[0405] Place it in a container. In one aspect, the step of placing carbon dioxide in a container includes introducing carbon dioxide, in the form of a solid, liquid, gas, or supercritical fluid, into the container prior to the step of maintaining and retaining carbon dioxide in liquid form. In another aspect, introducing carbon dioxide includes loading the container with carbon dioxide gas under pressure and temperature conditions that represent a liquid / vapor equilibrium of carbon dioxide.

[0406] In one aspect, when the article is a sheet, it can be configured as a roll, which optionally includes spacers or protective layers between adjacent portions of the foamed article. In some aspects, the article can be a layered sheet comprising one or more foamed layers. Furthermore, in this aspect, the placement step includes setting the roll into a container, and the experiencing and expanding steps include unrolling the article before or during the experiencing, or before or during the expanding. In some aspects, the placement step further includes setting porous spacers between adjacent portions of the article before or during placement, and the maintaining and retaining step includes allowing carbon dioxide to flow through the porous spacers to the adjacent portions of the article. In other aspects, the article or sheet is not configured as a roll, but can be a sheet, yarn or fibril, fabric, bladder, or any other foamable structure such as those disclosed herein.

[0407] In some aspects, the foamable article can be a foamable bladder or a component of a foamable bladder. In other words, the foamable articles disclosed herein can be used to form bladders or bladder components, and these bladders or bladder components can be foamed using the foaming process disclosed herein. In other aspects, the foamable article can be a foamable bladder or a component of a foamable bladder, wherein the bladder or bladder component is foamed using the foaming process disclosed herein before, during, or after the formation of the bladder or bladder component.

[0408] Maintain and keep at the first temperature and the first pressure.Following the step of placing the article and carbon dioxide in a container, the article and carbon dioxide in the container are maintained at a first pressure and a first temperature. The first pressure and the first temperature are the pressure and temperature at which the carbon dioxide is liquid and the liquid carbon dioxide is soluble in the solid foamable material. This step includes holding the article and liquid carbon dioxide in the container for a duration sufficient to allow at least a portion of the liquid carbon dioxide to be injected into the solid foamable material. During this step, the liquid carbon dioxide contacts the article and is injected into one or more materials (including the solid foamable material) present in the article. For carbon dioxide to be injected into the solid foamable material of the article, the carbon dioxide in contact with the article must be in a form soluble in the solid foamable material and to be injected into the solid foamable material. After being injected into the solid foamable material, the injected carbon dioxide also needs to be present in a phase capable of changing to a gas during the foaming process, and must also be present in the solid foamable material at a sufficient concentration to expand at least a portion of the solid foamable material into a foam with a porous structure. Although solid carbon dioxide expands directly from a solid to a gas under certain conditions, under most conditions, when solid carbon dioxide is placed in contact with the solid expandable materials disclosed herein, it is not injected into the solid expandable materials at a rate sufficient for its use as a physical blowing agent for large-scale manufacturing, nor at a concentration sufficient for its use as a physical blowing agent for large-scale manufacturing. While supercritical carbon dioxide can also undergo phase change and expand into a gas, and is generally highly soluble in many polymer materials, the extreme temperatures and pressures required to maintain carbon dioxide in a supercritical state significantly increase the equipment and energy demands of the process. However, liquid carbon dioxide has been found to be soluble in the solid expandable materials disclosed herein at a concentration sufficient to act as a physical blowing agent.

[0409] In one aspect, the method further includes venting any remaining carbon dioxide from the container after the sustaining and holding step, before the optional exposure step, or before the undergoing and expanding step. Furthermore, in this aspect, venting carbon dioxide from the container includes converting liquid carbon dioxide into carbon dioxide gas before or during venting.

[0410] In one aspect, at a first pressure and a first temperature, carbon dioxide is soluble in the solid foamable material at a concentration ranging from about 1 wt% to about 30 wt%, optionally from about 5 wt% to about 20 wt%, from about 5 wt% to about 10 wt%, or from about 10 wt% to about 20 wt%.

[0411] In another aspect, the steps of maintaining and sustaining include maintaining the first pressure at a range from about 0.05 pounds per square inch (about 0.345 kPa) to about 6,000 pounds per square inch (about 41,300 kPa). In another aspect, the first pressure is from about 15 pounds per square inch (103.4 kPa) to about 5,500 pounds per square inch (37,900 kPa), optionally from about 100 pounds per square inch (689.5 kPa) to about 5,000 pounds per square inch (34,500 kPa), from about 500 pounds per square inch (3,450 kPa) to about 2,000 pounds per square inch (about 13,790 kPa), or from about 1,000 pounds per square inch (6,895 kPa) to about 1,500 pounds per square inch (10,300 kPa).

[0412] In yet another aspect, the maintaining and holding step may include maintaining a first temperature from about -57 degrees Celsius to about 31 degrees Celsius, optionally from about -40 degrees Celsius to about 25 degrees Celsius, or from about -40 degrees Celsius to about 0 degrees Celsius. In one aspect, the maintaining and holding step includes maintaining the article at a first pressure and a first temperature for a duration from about 20 seconds to about 72 hours, optionally from about 20 seconds to about 24 hours, from about 1 minute to about 24 hours, or from about 1 minute to about 1 hour.

[0413] Optionally, in any of these aspects, during the maintenance and holding steps and the undergoing and expanding steps of the methods disclosed herein, the temperature of the foamable material is maintained at a temperature below the softening temperature of the foamable material. For example, thermoplastic elastomer materials may be maintained at a temperature at least 10 degrees Celsius or at least 20 degrees Celsius below the Vicat softening temperature of the foamable material. Although additional processing steps may be performed on the foamed article that can thermally soften the solid foamable material or portions or areas of the foamed material, in these aspects, these steps involving thermally softening the solid foamable material or melting the foamed material are performed before the maintenance and holding steps or after the undergoing and expanding steps. Avoiding thermal softening of the foamable material can reduce or prevent thermal degradation of the foamable material.

[0414] In this aspect, the article comprises a solid first expandable material and a second material, wherein the second material is a second expandable material. Furthermore, in this aspect, the maintaining and holding step includes holding the article and liquid carbon dioxide in a container for a duration sufficient to allow at least a portion of the liquid carbon dioxide to be injected into the solid first expandable material but not into the solid second expandable material. Furthermore, in this aspect, the undergoing and expanding step includes expanding the first expandable material into a first expandable material while maintaining the solid second expandable material as a substantially unfoamed second expandable material.

[0415] In some aspects, a foamable article may include a foamable region or a foamable layer comprising a first foamable material. In some aspects, the foamable article may also include a second region or layer comprising a second material (the foamable region or layer comprising the foamable material is the first foamable region or the first foamable layer). The second material may be a second foamable material as disclosed herein, or it may be a second non-foamable material. In another aspect, as disclosed herein, a foamed article may include a foamed region or a foamed layer comprising a foamable material, and in some aspects, a foamed article may include a second foamed region or a second foamed layer comprising a second foamable material, or it may include a second unfoamed region or a second unfoamed layer comprising a second unfoamed material.

[0416] In another aspect, the article comprises a solid first expandable material and further comprises an additional material, wherein the additional material is another expandable material. Furthermore, in this aspect, the holding and maintaining step comprises holding the article and liquid carbon dioxide in a container for a duration sufficient to allow at least a portion of the liquid carbon dioxide to be injected into the solid first expandable material and into the solid additional expandable material. In another aspect, the method includes an optional exposure step, and the exposure comprises exposing the article to a second pressure and a second temperature, at which carbon dioxide is retained injected into the solid additional expandable material, but at which the carbon dioxide diffuses out of the solid first expandable material. Furthermore, in this aspect, the undergoing and expanding step comprises expanding the solid expandable material into a second expandable material while maintaining the solid first expandable material as a substantially unfoamed first expandable material.

[0417] Optional exposure to a second pressure and a second temperature.In some aspects, after holding and maintaining, the method optionally includes exposing the article to a second pressure and a second temperature, at which carbon dioxide is maintained injected into at least a portion of the solid foamable material. In some aspects, this optional step may involve raising or lowering the temperature of the foamed article, for example, to bring the foamed article to a higher or lower temperature. In other aspects, this optional step may involve increasing or decreasing the pressure holding the foamed article, for example, to expose the foamed article to a higher or lower pressure. In still other aspects, this optional exposure step may include exposing the injected article to a pressure that is increased or decreased compared to a first pressure, and / or a temperature that is increased or decreased compared to a first temperature. Optional exposure steps may include exposing the injected article to a second pressure and a second temperature, at which the injected carbon dioxide is substantially maintained injected into the injected article. For example, the second pressure and second temperature may be the pressure and temperature at which very little (if any) carbon dioxide diffuses from the injected article during the duration of exposure to the second pressure and / or the second temperature. In one aspect, exposure may include storing the injected article in a conventional freezer at atmospheric pressure and a temperature at which injected carbon dioxide diffuses out of the injected article at a low rate. Alternatively, the optional exposure step may include exposing the injected article to a second pressure and a second temperature at which a certain amount of injected carbon dioxide diffuses out of the injected article. For example, when the rate of carbon dioxide diffusion from the thermoplastic material is known for a particular second pressure and second temperature, the duration required for a certain amount of carbon dioxide to diffuse out from a specific portion of the injected article can be determined, and the injected article can be maintained at the second pressure and second temperature for a determined duration to reduce the concentration of carbon dioxide in a portion or region of the injected article. For example, based on allowing some or all of the carbon dioxide to diffuse out from a first region or portion, the exposure step may be used to first create a region or portion of the injected article that will expand into a relatively denser foam compared to other regions or portions of the injected article, or will remain substantially unfoamed during the foaming step. In this way, it has been found that good control over the degree to which an article is foamed can be achieved without the need for expensive, complex equipment or tools.

[0418] In one aspect, optional exposure steps include exposing the article to a second pressure ranging from about 1 atmosphere (101 kPa) to about 85 atmospheres (8613 kPa), optionally from about 1 atmosphere (101 kPa) to about 40 atmospheres (4053 kPa) or from about 1 atmosphere (101 kPa) to about 20 atmospheres (2026.5 kPa).

[0419] In some aspects, optional exposure steps include exposing the article to a second temperature more than 30 degrees Celsius below the softening point of the solid foamable material, optionally more than 50 degrees Celsius below the softening point of the solid foamable material, or more than 100 degrees Celsius below the softening point of the solid foamable material.

[0420] In any of these aspects, optional exposure steps include exposing the article to a second pressure and a second temperature for a duration ranging from about 30 minutes to about 4 weeks, optionally from about 1 hour to about 1 week, or from about 1 hour to about 24 hours.

[0421] In some aspects, the optional exposure step may occur within the container. In other aspects, the optional exposure step also includes removing the article injected with carbon dioxide from the container before exposing the article to an optional second pressure and second temperature.

[0422] The solid foamable material expands after being subjected to a third pressure and a third temperature. As stated above, the method includes subjecting the article to a third pressure and a third temperature, at which carbon dioxide injected into the solid expandable material phases into a gas, thereby causing the solid expandable material to expand into a foamed material and form a foamed article. The third pressure can be a pressure higher or lower than the first pressure or optionally a second pressure, and the third temperature can be a temperature higher or lower than the first temperature or optionally a second temperature, provided that the third pressure and third temperature are conditions under which the injected carbon dioxide present in the injected article phases into a gas and phases into a gas at a rate sufficient to cause at least a portion of the solid expandable material of the article to expand. In many aspects, the third pressure can be at or near atmospheric pressure, and the third temperature can be at or near room temperature, or a high temperature below the softening temperature of the solid expandable material, i.e., conditions achievable with inexpensive equipment and low energy consumption.

[0423] In one aspect, the process of experiencing and inflating includes subjecting the article to a third pressure ranging from about 13 pounds per square inch (89.6 kPa) to about 16 pounds per square inch (110.3 kPa), optionally from about 13 pounds per square inch (89.6 kPa) to about 15 pounds per square inch (103.4 kPa), or from about 14 pounds per square inch (96.5 kPa) to about 15 pounds per square inch (103.4 kPa).

[0424] In some aspects, the process of experiencing and expanding includes subjecting the article to a third temperature ranging from about 20 degrees Celsius to about 150 degrees Celsius, optionally from about 20 degrees Celsius to about 100 degrees Celsius, from about 25 degrees Celsius to about 70 degrees Celsius, from about 50 degrees Celsius to about 70 degrees Celsius, or about 60 degrees Celsius.

[0425] In any of these aspects, the process of experiencing and expanding includes subjecting the article to a third pressure and a third temperature for a duration ranging from about 2 seconds to about 5 minutes, optionally from about 5 seconds to about 2 minutes or from about 30 seconds to about 1 minute.

[0426] In some respects, the process of undergoing and expanding can occur within the container. In other respects, the process of undergoing includes removing the injected carbon dioxide from the container before subjecting the article to a third pressure and a third temperature.

[0427] In one aspect, the step of subjecting the article to a third temperature and a third pressure includes introducing the article into a fluid bath, optionally wherein the fluid bath is a water bath. In some aspects, the fluid bath has a temperature from about 20 degrees Celsius to about 90 degrees Celsius, optionally from about 40 degrees Celsius to about 80 degrees Celsius, or from about 50 degrees Celsius to about 70 degrees Celsius. In another aspect, during the experience, the article is held in the fluid bath for a duration from about 15 seconds to about 5 minutes, optionally from about 30 seconds to about 3 minutes, or from about 1 minute to about 2 minutes.

[0428] In an alternative aspect, the process includes subjecting the article to an energy source or heat source, optionally including steam, microwave energy, infrared (IR) energy, or radio frequency (RF) energy. Furthermore, in this aspect, subjecting the article to the energy source or heat source raises the temperature of at least a portion of the foamable material of the article to a temperature from about 60 degrees Celsius to about 150 degrees Celsius, optionally from about 70 degrees Celsius to about 100 degrees Celsius, or from about 75 degrees Celsius to about 90 degrees Celsius. In one aspect, the process lasts for a duration from about 2 seconds to about 5 minutes, optionally from about 15 seconds to about 3 minutes, or from about 1 minute to about 2 minutes.

[0429] In another aspect, the process of undergoing and expanding includes expanding the foamable material into a foamed material until the foamed material has a density from about 0.01 g / cm³ to about 3.0 g / cm³, optionally from about 0.01 g / cm³ to about 0.1 g / cm³, from about 0.01 g / cm³ to about 0.05 g / cm³, from about 0.01 g / cm³ to about 0.025 g / cm³, from about 0.05 g / cm³ to about 0.1 g / cm³, from about 0.1 g / cm³ to about 3.0 g / cm³, from about 0.2 g / cm³ to about 2.0 g / cm³, from about 0.3 g / cm³ to about 1.5 g / cm³, from about 0.3 g / cm³ to about 1.2 g / cm³, or from about 0.4 g / cm³ to about 1.0 g / cm³.

[0430] In another aspect, after the expansion step, the foamed material has an expansion ratio of about 3:1 to about 120:1 relative to the solid foamable material before the expansion, and optionally has an expansion ratio of about 3:1 to about 100:1, or from 3:1 to about 50:1, or from about 5:1 to about 10:1 relative to the thermoplastic elastomer material in unfoamed conditions. In one aspect, during expansion, at least a portion of the article comprising the solid foamable material expands in length, width, and height as the solid foamable material expands into the foamed material.

[0431] In one aspect, after expansion, the size of the foamed item is larger in at least one dimension than the size of the item before placement, optionally wherein the foamed item is at least 5% larger in one or more of the dimensions of length, width, and height, optionally at least 10%, at least 15%, or at least 20% larger.

[0432] In some aspects, the article is a layered sheet, and at least one layer of the sheet undergoes a foaming and expanding step. Furthermore, in this aspect, after the foaming and expanding process, the thickness of the foamed layered sheet is at least 5% greater than the thickness of the layered sheet in its unfoamed state, optionally at least 10%, at least 15%, or at least 20% greater.

[0433] Optional exposure to a fourth temperature and a fourth pressure. In some aspects, the method further includes the optional step of bringing the foamed article to a fourth temperature and a fourth pressure after experiencing and expanding, and holding the foamed article at or below the fourth temperature, fourth pressure, or both for a period of time. This optional step may involve raising or lowering the temperature of the foamed article, for example, to bring the foamed article to room temperature. Similarly, in some aspects, this optional step may involve increasing or decreasing the pressure at which the foamed article is held, for example, to bring the foamed article to atmospheric pressure and / or room temperature.

[0434] In one aspect, the optional reaching step includes bringing the foamed article to a pressure ranging from about 0.03 atmospheres (3.04 kPa) to about 2 atmospheres (202.65 kPa), optionally from about 0.5 atmospheres (50.7 kPa) to about 1.5 atmospheres (152 kPa) or a fourth pressure of about 1 atmosphere (101.3 kPa).

[0435] In another aspect, the optional reaching step includes bringing the foamed article to a fourth temperature ranging from about 30 degrees Celsius to about 70 degrees Celsius, optionally from about 40 degrees Celsius to about 60 degrees Celsius, or from about 45 degrees Celsius to about 55 degrees Celsius. In some aspects, in the optional reaching step, the fourth temperature is at or below the glass transition temperature of the solid foamable material, or from about 10 degrees Celsius less than the glass transition temperature of the solid foamable material to about 10 degrees Celsius more than the glass transition temperature of the solid foamable material, as measured by a melting temperature, glass transition temperature, and enthalpy of fusion test scheme. In one aspect, the glass transition temperature of the solid foamable material is less than 0 degrees Celsius, optionally less than -10 degrees Celsius, less than -20 degrees Celsius, less than -30 degrees Celsius, or less than -40 degrees Celsius.

[0436] In any of these aspects, the optional steps include bringing the foamed article to a fourth pressure and a fourth temperature for a duration ranging from about 15 minutes to about 1 hour, optionally from about 20 minutes to about 45 minutes, or from about 20 minutes to about 30 minutes.

[0437] Optional stabilization at the fifth temperature and the fifth pressure.In other aspects, the method further includes stabilizing the foamed article at a fifth pressure and a fifth temperature after experiencing and expanding, or optionally after reaching. The fifth pressure and fifth temperature can be such that carbon dioxide diffuses from the foamed material of the foamed article while maintaining the foamed material within the foam structure, thereby forming a stabilized foamed article. In some aspects, stabilization includes maintaining the foamed article at the fifth pressure and fifth temperature for a duration sufficient to remove substantially all carbon dioxide from the foamed material. The fifth pressure can be at or near atmospheric pressure, or at a pressure where the rate of air diffusion into the foam and / or the rate of carbon dioxide diffusion out of the foam is greater than at atmospheric pressure. The fifth temperature can be at or near room temperature, or at a temperature where the rate of air diffusion into the foam and / or the rate of carbon dioxide diffusion out of the foam is greater than at room temperature. Stabilizing foamed articles can also include releasing stresses in the foamed article, such as stresses in the foamed thermoplastic elastomer material or stresses present in the solid material within the foamed article. In such an aspect, the fifth pressure and / or fifth temperature can be atmospheric pressure and / or room temperature, or it can be a pressure and / or temperature at which stresses in the foamed article are released at a rate faster than at atmospheric pressure or room temperature. In one example, stabilization can be performed at atmospheric pressure and at a temperature at least 5 degrees Celsius above room temperature and below the softening temperature of the foamed material. Stabilization can be performed using conventional heating equipment such as convection ovens, microwave ovens, or infrared ovens, or heating tunnels. Stabilization can be particularly useful when the foamed material is in sheet form, and / or when the foamed article comprises a layered structure containing layers of foamed material adjacent to layers of solid (unfoamed) material, because the foamed material can release stresses in the solid material generated during the foaming process.

[0438] In one aspect, the optional stabilization step includes fifth pressure stabilization at approximately atmospheric pressure. In another aspect, the optional stabilization step includes fifth temperature stabilization at a temperature greater than the glass transition temperature of the foamed material, as measured by a melting temperature, glass transition temperature, and enthalpy of fusion test scheme. Furthermore, in this aspect, the optional stabilization step includes fifth temperature stabilization from about 30 degrees Celsius to about 70 degrees Celsius, optionally from about 40 degrees Celsius to about 60 degrees Celsius, or about 50 degrees Celsius. In one aspect, the optional stabilization step includes stabilizing the foamed article at the fifth temperature for a duration from about 15 minutes to about 60 minutes, optionally from about 30 minutes to about 45 minutes.

[0439] In one aspect, the optional step of stabilizing at a fifth pressure and a fifth temperature includes placing the foamed article in an oven. In some aspects, stabilizing the foamed article at a fifth pressure and a fifth temperature releases stress in the foamed article. In another aspect, stabilizing the foamed article at a fifth pressure and a fifth temperature removes substantially all residual carbon dioxide from the foamed article. In yet another aspect, stabilization can remove carbon dioxide gas if it is retained in individual foam pores. In yet another aspect, stabilization can remove injected carbon dioxide if it is retained in either the foamed or unfoamed material. In yet another aspect, stress can be introduced when a foamable material is transformed into a foamed material while remaining bonded to an unfoamed material; furthermore, in this aspect, stabilization can release these stresses.

[0440] In some respects, the shrinkage rate of foamed articles can be a concern or it can be desirable. The step of stabilizing the foamed article at a fifth pressure and a fifth temperature can be used to reduce or control the shrinkage level of the foamed article after foaming. For example, the shrinkage rate under specific conditions can be used to determine time, temperature, and pressure to obtain the desired shrinkage level of the foamed article. In some respects, stabilization can reduce or release stress that would otherwise lead to an undesirable level of shrinkage.

[0441] In any of these aspects, the method may include a stabilization step, and after stabilization, the size of the stabilized foamed article is larger in at least one dimension than the size of the article before placement, optionally wherein the stabilized foamed article is at least 5%, at least 10%, at least 15%, or at least 20% larger in one or more of the length, width, and height.

[0442] Foamable materials and foamed materials, as well as further processing of articles.In this aspect, the foamable material can optionally be formed using a variety of processes. In one aspect, the solid foamable material can be formed using an extrusion process prior to the placement step. In one aspect, the solid foamable material can be formed using an injection molding process prior to the placement step. In another aspect, the solid foamable material can be formed using a thermoforming process and / or a vacuum forming process prior to the placement step. In one aspect, the thermoforming process and / or vacuum forming process can use pressure and / or heat to conform the foamable material to the shape of a mold. In one aspect, the mold may include one or more curved surfaces. In another aspect, the mold may be an open mold or a closed mold. In some aspects, the mold may be configured to form a single surface or multiple surfaces of the foamable material. Optionally or additionally, additive manufacturing processes such as extrusion, deposition printing, and / or selective sintering may be used to form the foamable material and / or shape the foamable material prior to the placement step.

[0443] In one aspect, the method further includes thermoforming the foamed article, optionally wherein the foamed article is a stabilized foamed article. In some aspects, the foamed article is a sheet, optionally a layered sheet, optionally wherein the layered sheet includes at least one unfoamed capping layer, and optionally wherein the layered sheet includes one or more foamed inner layers and two unfoamed capping layers. In some aspects, the article may be a thermoformed article. In any of these aspects, the foamed article may be a component of clothing, footwear, or sports equipment.

[0444] Make a selected area of ​​the item foam. In one aspect, in the method disclosed herein, the foamable article comprises one or more regions, the one or more regions comprising at least a first region and a second region, and the maintaining and holding steps comprise holding the article and liquid carbon dioxide in a container for a duration sufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of the first region, or said duration sufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of the second region, or said duration sufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of the first region and into at least a portion of the second region, optionally said duration sufficient to allow at least a portion of the liquid carbon dioxide to be injected into substantially all of the first region, substantially all of the second region, or both.

[0445] In another aspect, in the method disclosed herein, the first region comprises a first region solid foamable material or is substantially composed of a first region solid foamable material, the maintaining and holding steps include holding the article and liquid carbon dioxide in a container for a duration sufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of the first region solid foamable material, and the undergoing and expanding steps include expanding at least a portion of the first region solid foamable material into a foamed material, wherein the foamed material of the first region comprises a first region foamed material, optionally wherein said expansion comprises expanding substantially all of the first region solid foamable material into a first region foamed material.

[0446] In another aspect, in the method disclosed herein, the maintaining and holding step includes holding the article and liquid carbon dioxide in a container for a duration sufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of a first region, wherein the duration is insufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of a second region; the undergoing and expanding step includes expanding at least a portion of the solid foamable material of the first region into the foamable material of the first region without expanding the material of the second region; optionally, wherein after the maintaining and holding step, the second region is substantially free of carbon dioxide, and optionally, wherein the second region comprises or is substantially composed of a barrier material as described herein.

[0447] In another aspect, the maintaining and holding step may include holding the article and liquid carbon dioxide in a container for a duration sufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of a first region and into at least a portion of a second region, and the method further includes the steps of: exposing the injected article to a second pressure and a second temperature for a period of time, such that at least a portion of the carbon dioxide injected into at least a portion of the second region diffuses out of at least a portion of the second region, while at least a portion of the injected carbon dioxide injected into the first region remains injected into at least a portion of the first region after the exposure; and the undergoing and expanding step includes expanding at least a portion of the solid foamable material of the first region into a foamable material of the first region without expanding the material of the second region, thereby forming a foamed first region, while maintaining the second region in a solid, unfoamed state; optionally, wherein after the exposure step, the second region is substantially free of injected carbon dioxide; and optionally, wherein the second region comprises or is substantially composed of a barrier material as described herein.

[0448] Now go to Figure 8BIn any of these aspects, carbon dioxide may be filled into container 480 to level 482, wherein the first region 464, the second region 460, and optionally the third region 462 are completely immersed in carbon dioxide. Furthermore, in this aspect, any one of the first region 464, the second region 460, and / or the third region 462 may comprise or be substantially composed of a foamable material as described herein, and may become filled with carbon dioxide. In an alternative aspect, one or more of the second region 460 and / or the third region 462 may comprise or be substantially composed of a barrier material, and may not become filled with carbon dioxide despite being completely immersed in carbon dioxide in container 480. In one aspect, when two or more of the first region 464, the second region 460, and / or the third region 462 comprise or are substantially composed of a solid foamable material, at least one of the first region 464, the second region 460, and / or the third region 462 remains in an unfoamed state during the undergoing and expansion steps. In one aspect, the first region 464 expands into a foamed state, while the second region 460 and the third region 462 remain unfoamed. In an alternative aspect, the first region 464 and the second region 460 expand into a foamed state, while the third region 462 remains unfoamed. In yet another aspect, the first region 464 and the third region 462 expand into a foamed state, while the second region 460 remains unfoamed. In still another aspect, each of the first region 464, the second region 460, and the third region 462 expands into a foamed state. In one aspect, when the first region 464, the second region 460, and / or the third region 462 comprise different solid foamable materials or are substantially composed of different solid foamable materials, the three regions can expand into a foamed state with different region volumes and / or densities.

[0449] Among the optional aspects, such as Figure 8CAs shown, carbon dioxide can fill container 480 to level 484, wherein a portion of the first region 464 and optionally the third region 462 are immersed in carbon dioxide, but the second region 460 is not immersed in carbon dioxide. Furthermore, in this aspect, even if the second region 460 comprises or is substantially composed of a solid foamable material as described herein, because the second region 460 is not immersed in carbon dioxide, the second region 460 does not become infused with carbon dioxide and cannot expand into a foamed state during the execution of the disclosed method. Alternatively, in this aspect, the first region 464 is wholly or partially immersed in carbon dioxide and becomes infused with carbon dioxide, allowing the first region 464 to expand during the expansion steps. Additionally, in this aspect, the third region 462 is partially immersed in carbon dioxide in container 480 and can become partially infused with carbon dioxide and partially expand into a foamed state during the expansion steps. Alternatively, the third region 462 may comprise or be substantially composed of a barrier material and does not become infused with carbon dioxide during the execution of the method described herein. In one respect, although Figure 8B and Figure 8C In this context, foamable articles are described as components of footwear, but any foamable article as described herein can be fully or partially immersed in carbon dioxide in container 480 in any possible direction.

[0450] Second area. In one aspect, the maintaining and holding steps may include holding the article and liquid carbon dioxide in a container for a duration sufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of the second region, or said duration sufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of the first region and into at least a portion of the second region; optionally said duration sufficient to allow at least a portion of the liquid carbon dioxide to be injected into substantially all of the first region, or substantially all of the second region, or both.

[0451] In another aspect, the maintaining and holding step includes holding the article and liquid carbon dioxide in a container for a duration sufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of the second region, said duration being insufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of the first region; and the undergoing and expanding step includes expanding at least a portion of the solid foamable material of the second region into a foamable material of the second region without expanding the material of the first region, thereby forming a foamed second region, while maintaining the first region in a solid, unfoamed state; optionally, after the maintaining and holding step, the first region is substantially free of injected carbon dioxide, and optionally, the first region comprises or is substantially composed of a barrier material as described herein.

[0452] In one aspect, the maintaining and holding step may include holding the article and liquid carbon dioxide in a container for a duration sufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of a first region and into at least a portion of a second region, and the method further includes the steps of: exposing the injected article to a second pressure and a second temperature for a period of time, such that at least a portion of the carbon dioxide injected into at least a portion of the first region diffuses out of at least a portion of the first region, while at least a portion of the injected carbon dioxide injected into the second region remains injected into at least a portion of the second region after the exposure; and the undergoing and expanding step includes expanding at least a portion of the solid foamable material of the second region into a foamable material of the second region without expanding the material of the first region; optionally wherein, after the exposure step, the first region is substantially free of injected carbon dioxide, and optionally wherein the first region comprises or is substantially composed of a barrier material as described herein.

[0453] In another aspect, the article also includes a third region, and the steps of maintaining and holding may include holding the article and liquid carbon dioxide in a container for a duration sufficient to allow at least a portion of the liquid carbon dioxide to be injected into the first region, or into the first and second regions, or into the second region, or into both the second and third regions, or into the third region, or into both the third and first regions.

[0454] In this aspect, the steps of maintaining and holding include keeping the article and liquid carbon dioxide in the container for a duration sufficient to allow the liquid carbon dioxide to be injected into one or two of the three zones, but not into the other three zones, optionally wherein carbon dioxide is injected into the first zone but not substantially into the second zone, or injected into the first zone but not substantially into the third zone, or injected into the second zone but not substantially into the first zone, or injected into the second zone but not substantially into the third zone, or injected into the third zone but not substantially into the first zone, or injected into the third zone but not substantially into the second zone, or optionally wherein carbon dioxide is injected into the first and second zones but not substantially into the third zone, or injected into the first and third zones but not substantially into the second zone, or injected into the second and third zones but not substantially into the first zone.

[0455] In one aspect, the method disclosed herein includes an exposure step, which includes exposing an article to a second pressure and a second temperature, wherein carbon dioxide is maintained injected into one or two of three zones while diffused out from the other zones, optionally wherein carbon dioxide is maintained injected into a first zone but substantially not into a second zone, or injected into a first zone but substantially not into a third zone, or injected into a second zone but substantially not into a first zone, or injected into a second zone but substantially not into a third zone, or injected into a third zone but substantially not into a first zone, or The carbon dioxide is injected into the third region but not substantially into the second region, or optionally, the carbon dioxide is injected into the first and second regions and substantially diffuses out of the third region, or is injected into the first and third regions and substantially diffuses out of the second region, or is injected into the second and third regions and substantially diffuses out of the first region, or optionally, the carbon dioxide substantially diffuses out of the first and second regions and is injected into the third region, or substantially diffuses out of the first and third regions and is injected into the second region, or substantially diffuses out of the second and third regions and is injected into the first region.

[0456] In one aspect, the process of undergoing and expanding causes the material in one or two of the three regions to expand into a foamed material, while maintaining the other regions in a solid, unfoamed state; optionally, the process of undergoing and expanding causes at least a portion of the material in the first region to expand into a foamed material in the first region, or at least a portion of the material in the third region to expand into a foamed material in the third region, or any combination thereof; or optionally, the process of undergoing and expanding causes the material in the first region to expand into a foamed material in the first region and the material in the third region to expand into a foamed material in the third region, or the material in the second region to expand into a foamed material in the second region and the material in the third region to expand into a foamed material in the third region; or optionally, after the process of undergoing and expanding, the material in the first region remains as a solid, unfoamed material in the first region, or the material in the second region remains as a solid, unfoamed material in the second region, or the material in the third region remains as a solid, unfoamed material in the third region, or both the material in the first and second regions remain as solid, unfoamed materials, or both the material in the first and third regions remain as solid, unfoamed materials, or both the material in the second and third regions remain as solid, unfoamed materials.

[0457] In one aspect, the article may include a fourth region, and optionally the maintaining and holding steps include holding the article and liquid carbon dioxide in a container for a duration sufficient to allow at least a portion of the liquid carbon dioxide to be injected into the fourth region, or optionally the maintaining and holding steps include holding the article and liquid carbon dioxide in a container for a duration sufficient to allow the liquid carbon dioxide to be injected into one or more of the first, second, and third regions but not into the fourth region, or optionally the method includes an exposure step, and the exposure step includes exposing the article to a second pressure and a second temperature, at which carbon dioxide is kept injected into one or more of the first, second, and third regions while carbon dioxide diffuses out of the fourth region, or optionally the method includes an exposure step, and the exposure step includes exposing the article to a second pressure and a second temperature, at which carbon dioxide is kept injected into the fourth region.

[0458] Furthermore, in this respect, after undergoing the expansion steps, the fourth region material remains as a fourth region solid unfoamed material, or the fourth region material expands into a fourth region foamed material.

[0459] Foamed items

[0460] In one aspect, this document discloses a foamed article comprising a foamed material, the foamed material being a physically expanded foam formed from a thermoplastic elastomer material comprising one or more first thermoplastic elastomers. In another aspect, the foamed material is a product of placing an unfoamed article comprising a solid foamable material in liquid carbon dioxide, injecting the solid foamable material with carbon dioxide, and expanding the injected carbon dioxide without thermally softening the solid foamable material, for example by converting the injected carbon dioxide into a gas without softening the solid foamable material, thereby expanding the injected solid foamable material into a foamed article. In some aspects, the foamed article is a stabilized foamed article comprising a stabilized foamed material, wherein the stabilized foamed material contains no or substantially no injected carbon dioxide.

[0461] In another aspect, in the foamed articles described herein, the foamed material is a first foamed material, the foamed articles include a second foamed material, the second foamed material is another material as disclosed herein, and the thermoplastic elastomer material of the first foamed material is a recycled material, or the other material of the second foamed material is a recycled material, or both the thermoplastic elastomer material and the other material are recycled materials.

[0462] In another aspect, when the initial pressure is from about 0.05 psi (0.345 kPa) to about 6000 psi (about 41,300 kPa), optionally from about 15 psi (103.4 kPa) to about 5500 psi (37,900 kPa), from about 100 psi (689.5 kPa) to about 5000 psi (34,500 kPa), from about 500 psi (3,450 kPa) to about 2000 psi (about 13,790 kPa), or from about 1000 psi (0.05 kPa) to about 6000 psi (about 41,300 kPa), optionally from about 15 psi (103.4 kPa) to about 5500 psi (37,900 kPa), optionally from about 10 ... The concentration of carbon dioxide is from about 1 wt% to about 30 wt%, optionally from about -57 degrees Celsius to about 31 degrees Celsius, or from about -40 degrees Celsius to about 25 degrees Celsius, or from about -40 degrees Celsius to about 0 degrees Celsius, and the first temperature can be from about -57 degrees Celsius to about 31 degrees Celsius, optionally from about -40 degrees Celsius to about 25 degrees Celsius, or from about -40 degrees Celsius to about 0 degrees Celsius, at a concentration from about 1 wt% to about 30 wt%, optionally from about 5 wt% to about 20 wt%, from about 5 wt% to about 10 wt%, or from about 10 wt% to about 20 wt%, soluble in the foaming material, or solid foamable material, or both.

[0463] In one aspect, the foamed material of the foamed article is substantially opaque. In another aspect, the foamed material has a tear value of about 2.5 kg / cm to about 3.0 kg / cm, optionally from about 2.5 kg / cm to about 2.8 kg / cm, from about 2.5 kg / cm to about 2.75 kg / cm, or from about 2.75 kg / cm to about 3.0 kg / cm, as measured using a plyometric tear test protocol. In another example, a foamed article is formed having an Asker C hardness of about 10 to about 50, or from about 15 to about 50, from about 15 to about 45, from about 20 to 45, or from about 20 to about 40, as measured using an Asker C hardness test protocol.

[0464] The area and arrangement of foamed materials and foamed items.

[0465] Two areas In one aspect, an article may be configured as a series of two or more regions, the series of two or more regions comprising a first region containing a first region material and a second region containing a second region material, wherein the first region material, the second region material, or both the first region material and the second region material may be solid foamable materials, optionally wherein the first region or the second region or both form the outermost surface of the article, or wherein the first region and the second region, individually or jointly, form the outermost surface of the article. In another aspect, after the foaming process disclosed herein, the first region material becomes a first region foamed material, and when the second region is a solid foamable material, the second region material becomes a second region foamed material.

[0466] In another aspect, the region may include a layer, and either the first region or the second region may form an inner layer of the article, or both the first region and the second region may separately form separate inner layers of the article. In either of these aspects, the article may optionally be a layered sheet. In yet another aspect, the first region may form the outermost surface of the article, and the second region may form an inner layer of the article.

[0467] In another aspect, in the article, the first region comprises or is substantially composed of a solid foamable material, the solid foamable material of the first region being a solid foamable material of the first region, and in the process of undergoing and expanding, the first solid foamable material remains as a solid foamable material of the first region or expands into a foamed material, wherein the foamed material of the first region is a foamed material of the first region.

[0468] In another aspect, in the article, the second region comprises or is substantially composed of a solid foamable material, the solid foamable material of the second region being a solid foamable material of the second region, and during the steps of undergoing and expanding, the second solid foamable material remains as a solid foamable material of the second region or expands into a foamed material, wherein the foamed material of the second region is a foamed material of the second region.

[0469] In any of these aspects, the first-region solid foamable material, the second-region solid foamable material, or both may individually be solid foamable materials as described herein. In another aspect, the first foamed material, the second foamed material, or both may individually be foamed materials as described herein. In some aspects, the first-region material or the second-region material may be barrier materials as described herein.

[0470] In one aspect, in the foamed article, the first region comprises or is substantially composed of a foamed material, and the second region comprises or is substantially composed of a solid material. In an alternative aspect, the first region comprises or is substantially composed of a solid material, and the second region comprises or is substantially composed of a foamed material. In another aspect, both the first and second regions comprise or are substantially composed of a foamed material.

[0471] In one aspect, the first region material, the second region material, or both individually are thermoplastic elastomer materials as disclosed herein. In another aspect, the first region material, the second region material, or both individually are foamed materials as disclosed herein. In an alternative aspect, the first region material or the second region material may be a second material as described herein.

[0472] In one aspect, in a foamed article, a first region comprises or is substantially composed of a foamed material, and a second region comprises or is substantially composed of a barrier material. In another aspect, the first region may comprise or is substantially composed of a barrier material, and the second region may comprise or is substantially composed of a foamed material.

[0473] In another aspect, the second region may comprise or consist substantially of a second region solid foamable material, the maintaining and holding steps include holding the article and liquid carbon dioxide in the container for a duration sufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of the second region solid foamable material, and the undergoing and expanding steps include expanding at least a portion of the second region solid foamable material into the second region foamable material, wherein the foamed material of the second region comprises the second region foamed material, optionally wherein said expansion includes expanding substantially all of the second region solid foamable material into the second region foamed material.

[0474] In some aspects, the first region comprises or is substantially composed of a first region solid foamable material, the first region solid foamable material being a first solid foamable material; the second region comprises or is substantially composed of a second region solid foamable material, the second region solid foamable material being a second solid foamable material; the maintaining and holding steps include holding the article and liquid carbon dioxide in a container for a duration sufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of the first region and into at least a portion of the second region; and undergoing the expansion steps to expand at least a portion of the first region solid foamable material into the first region foamable material, and to expand at least a portion of the second region solid foamable material into the second region foamable material, optionally said expansion includes expanding substantially all of the first region solid foamable material or substantially all of the second region solid foamable material, or expanding substantially all of the first region solid foamable material and substantially all of the second region solid foamable material.

[0475] In one aspect, in the disclosed method, in the foamed article, the materials foamed in the first region and the materials foamed in the second region are in contact with each other. In an alternative aspect, the materials foamed in the first region and the materials foamed in the second region are not in contact with each other.

[0476] Barrier area.In one aspect, in the method disclosed herein, a first region comprises or is substantially composed of a solid foamable material, and a second region comprises or is substantially composed of a barrier material, or wherein the first region comprises or is substantially composed of a barrier material, and the second region comprises or is substantially composed of a solid foamable material, and the maintaining and holding step comprises holding the article and liquid carbon dioxide in a container for a duration sufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of the solid foamable material, wherein the duration is insufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of the barrier material; the undergoing and expanding step comprises expanding the solid foamable material into a foamed material without expanding the barrier material; and optionally wherein in the foamed article, the foamed material and the barrier material are in contact with each other, or the foamed material and the barrier material are not in contact with each other.

[0477] Three regions. In one aspect, in the disclosed method, an article may be configured as a series of three or more regions, the series of three or more regions further comprising a third region comprising or substantially composed of a third region material, optionally wherein the third region material comprises or substantially composed of a barrier material, or comprises or substantially composed of a third region solid foamable material, or optionally wherein the third region is positioned between the first and second regions.

[0478] In another aspect, in the foamed article, the third-region material can be a third-region foamed material. Optionally, the third-region foamed material can be another foamed material as defined herein, or it can be a foamed material as disclosed herein. In an alternative aspect, the third-region material is a third-region solid material, optionally another solid material. In some aspects, the other solid material can be a barrier material.

[0479] Now go to Figure 8AIn an exemplary embodiment, the foamable article may include three regions. In one aspect, when the foamable article is the outsole of a footwear article, the heel region 451 may include region 464, which may include or be substantially composed of a first region material, wherein the first region material may be a first region foamable material. Furthermore, in this aspect, the toe region 450 may include region 460, which may include or be substantially composed of a second region material, wherein the second region material may be a second region foamable material, or in some aspects, a barrier material. Still additionally, in this aspect, the foamable article may include a third region 462, which may include or be substantially composed of a third region material, wherein the third region material may be a third region foamable material, or in some aspects, a barrier material. In any of these aspects, at least one of the first, second, and / or third regions includes or is substantially composed of a solid foamable material.

[0480] In this context, when a foamable item comprises two or more zones, interfaces will also exist between and within the zones. Therefore, in situations such as... Figure 8A In one exemplary aspect depicted, a foamable article may include an interface 474 between a first region 464 and a second region 460, and / or may include an interface 470 between a second region 460 and a third region 462, and / or may include an interface 472 between a first region 464 and a third region 462.

[0481] Four regions. In another aspect, the article can be configured as a series of four or more regions, wherein the fourth region comprises or is substantially composed of a fourth region material, optionally wherein the fourth region is positioned between the third and second regions. In some aspects, the fourth region material can be a fourth region foamed material, and optionally the fourth region foamed material can be another foamed material, or it can be a foamed material as disclosed herein. In alternative aspects, the fourth region material is a fourth region solid material, optionally another solid material. In some aspects, the other solid material can be a barrier material.

[0482] The properties of foamed materials and foamed items

[0483] In one aspect, in the foamed article, the foamed material has a density from about 0.01 g / cm³ to about 3.0 g / cm³, optionally from about 0.01 g / cm³ to about 0.1 g / cm³, from about 0.01 g / cm³ to about 0.05 g / cm³, from about 0.01 g / cm³ to about 0.025 g / cm³, from about 0.05 g / cm³ to about 0.1 g / cm³, from about 0.1 g / cm³ to about 3.0 g / cm³, from about 0.2 g / cm³ to about 2.0 g / cm³, from about 0.3 g / cm³ to about 1.5 g / cm³, from about 0.3 g / cm³ to about 1.2 g / cm³, or from about 0.4 g / cm³ to about 1.0 g / cm³.

[0484] In one respect, foamed articles are generally opaque after foaming. In another respect, the opacity of foamed articles eliminates the need to add pigments to thermoplastic elastomer materials to make them whiter.

[0485] In one aspect, the foamed material, the foamed article, or both have a plyometric tear value of about 2.5 kg / cm to about 3.0 kg / cm, optionally about 2.5 kg / cm to about 2.7 kg / cm, about 2.5 kg / cm to about 2.6 kg / cm, about 2.7 kg / cm to about 3.0 kg / cm, or about 2.8 kg / cm to about 3.0 kg / cm, as measured using a plyometric tear test protocol.

[0486] Methods for manufacturing items that include foaming

[0487] In one aspect, this document discloses a method for manufacturing an article, the method comprising attaching a first component to a second component, wherein the first component is a foamed article manufactured by the method disclosed herein. In some aspects, the first component may be a first component of a garment article, the second component may be a second component of a garment article, and the article to be manufactured is a garment article.

[0488] In other aspects, the first component can be a first component of a footwear article, the second component can be a second component of a footwear article, and the article to be manufactured is a footwear article. Furthermore, in these aspects, the first component can be a cushioning element, and the second component can be a sole component or an upper component.

[0489] In other respects, the first component can be a first component of a sports equipment item, the second component can be a second component of a sports equipment item, and the item to be manufactured is a sports equipment item.

[0490] Foamable materials

[0491] The solid foamable material of the articles described herein is a thermoplastic elastomer material, meaning that the material is a polymer material having both thermoplastic and elastomer properties. A solid foamable material is a polymer material comprising one or more first thermoplastic elastomers or substantially composed of one or more first thermoplastic elastomers. In some aspects, a solid foamable material includes one or more additional thermoplastic polymers, wherein the one or more additional thermoplastic polymers may be thermoplastic elastomers, or may be thermoplastic but not elastomers. In some aspects, a solid foamable material includes additional non-polymer components. In many of the disclosed foamed articles described herein, the foamed material is a thermoplastic elastomer material, meaning that after expansion, the foamed material retains both thermoplastic and elastomer properties.

[0492] In any of the disclosed aspects, the foamable material can be described as comprising a polymer component, wherein the polymer component includes all polymers present in the foamable material. In this respect, the polymer component may consist substantially of one or more first thermoplastic elastomers, meaning that in such an aspect, substantially all polymers present in the foamable material are thermoplastic elastomers. In one aspect, one or more first thermoplastic elastomers of the foamable material include one or more thermoplastic elastomer polyolefin homopolymers or copolymers, one or more thermoplastic elastomer polyamide homopolymers or copolymers, one or more thermoplastic elastomer polyester homopolymers or copolymers, one or more thermoplastic elastomer polyether homopolymers or copolymers, one or more thermoplastic elastomer polycarbonate homopolymers or copolymers, one or more thermoplastic elastomer polyacrylate homopolymers or copolymers, one or more thermoplastic elastomer polyurethane homopolymers or copolymers, one or more thermoplastic elastomer styrene homopolymers or copolymers, or any combination thereof. Similarly, the polymeric component of a foamable material may consist essentially of one or more thermoplastic elastomer polyolefin homopolymers or copolymers, one or more thermoplastic elastomer polyamide homopolymers or copolymers, one or more thermoplastic elastomer polyester homopolymers or copolymers, one or more thermoplastic elastomer polyether homopolymers or copolymers, one or more thermoplastic elastomer polycarbonate homopolymers or copolymers, one or more thermoplastic elastomer polyacrylate homopolymers or copolymers, one or more thermoplastic elastomer polyurethane homopolymers or copolymers, one or more thermoplastic elastomer styrene homopolymers or copolymers, or any combination thereof.

[0493] In one aspect, one or more first thermoplastic elastomers of the foamable material include one or more thermoplastic elastomer polyolefin homopolymers or copolymers, one or more thermoplastic elastomer polyamide homopolymers or copolymers, one or more thermoplastic elastomer polyester homopolymers or copolymers, one or more thermoplastic elastomer polyurethane homopolymers or copolymers, one or more thermoplastic elastomer styrene homopolymers or copolymers, or any combination thereof. Similarly, the polymeric component of the foamable material may consist substantially of one or more thermoplastic elastomer polyolefin homopolymers or copolymers, one or more thermoplastic elastomer polyamide homopolymers or copolymers, one or more thermoplastic elastomer polyester homopolymers or copolymers, one or more thermoplastic elastomer polyurethane homopolymers or copolymers, one or more thermoplastic elastomer styrene homopolymers or copolymers, or any combination thereof.

[0494] In one aspect, thermoplastic materials, including thermoplastic elastomers, are advantageous for use in the articles described herein because they can be recycled and reformed into new articles, thus reducing waste and promoting recycling. In another aspect, both foamed and unfoamed thermoplastic materials can be recycled for use in the articles and methods described herein.

[0495] In one aspect, when one or more first thermoplastic elastomers comprise or are substantially composed of one or more thermoplastic elastomer polyolefin homopolymers or copolymers, the one or more first thermoplastic elastomers comprise or are substantially composed of: thermoplastic elastomer polypropylene homopolymers or copolymers; thermoplastic polyethylene homopolymers or copolymers, including thermoplastic elastomer ethylene-vinyl acetate copolymers; thermoplastic elastomer polybutene homopolymers or copolymers; or any combination thereof. The polymeric component of the foamable material may consist substantially of one or more thermoplastic elastomer polyolefin homopolymers or copolymers.

[0496] In one aspect, one or more thermoplastic elastomer polyolefin homopolymers or copolymers may comprise one or more thermoplastic elastomer ethylene-vinyl acetate copolymers or be substantially composed of one or more thermoplastic elastomer ethylene-vinyl acetate copolymers. The polymer component of the foamable material may be substantially composed of one or more thermoplastic elastomer ethylene-vinyl acetate copolymers. Furthermore, in this aspect, the thermoplastic ethylene-vinyl acetate copolymer may comprise a vinyl acetate content from about 25 weight percent to about 50 weight percent, optionally from about 25 weight percent to about 40 weight percent, from about 25 weight percent to about 30 weight percent, or from about 35 weight percent to about 50 weight percent.

[0497] In another aspect, the foamable material may include one or more thermoplastic ethylene-vinyl alcohol copolymers. The polymer component of the foamable material may include one or more thermoplastic ethylene-vinyl alcohol copolymers. Furthermore, in this aspect, the thermoplastic ethylene-vinyl alcohol copolymer may include an ethylene alcohol content of from about 25 weight percent to about 50 weight percent, optionally from about 25 weight percent to about 40 weight percent, from about 25 weight percent to about 30 weight percent, or from about 35 weight percent to about 50 weight percent.

[0498] In another aspect, one or more first thermoplastic elastomers of the foamable material comprise one or more thermoplastic elastomer polyamide homopolymers or copolymers, or are substantially composed of one or more thermoplastic elastomer polyamide homopolymers or copolymers. The polymeric component of the foamable material may consist substantially of one or more thermoplastic elastomer polyamide homopolymers or copolymers. One or more thermoplastic elastomer polyamide homopolymers or copolymers may include thermoplastic elastomer polyether block polyamide (PEBA) copolymer elastomers, or are substantially composed of thermoplastic elastomer polyether block polyamide (PEBA) copolymer elastomers.

[0499] One or more first thermoplastic elastomers may comprise one or more thermoplastic elastomer polyester homopolymers or copolymers, or be substantially composed of one or more thermoplastic elastomer polyester homopolymers or copolymers. The polymer component of the foamable material may be substantially composed of one or more thermoplastic elastomer polyester homopolymers or copolymers. The thermoplastic elastomer polyester homopolymer may comprise one or more polyester terephthalates, or be substantially composed of one or more polyester terephthalates. The thermoplastic elastomer polyester homopolymer or copolymer may comprise one or more thermoplastic elastomer copolyesters, or be substantially composed of one or more thermoplastic elastomer copolyesters.

[0500] One or more first thermoplastic elastomers may comprise one or more thermoplastic elastomer polyether homopolymers or copolymers, or be substantially composed of one or more thermoplastic elastomer polyether homopolymers or copolymers. The polymer component of a foamable material may be substantially composed of one or more thermoplastic elastomer polyether homopolymers or copolymers.

[0501] One or more first thermoplastic elastomers may comprise one or more thermoplastic elastomer polyether homopolymers or copolymers, or be substantially composed of one or more thermoplastic elastomer polyether homopolymers or copolymers. The polymer component of a foamable material may be substantially composed of one or more thermoplastic elastomer polyether homopolymers or copolymers.

[0502] One or more first thermoplastic elastomers may comprise one or more thermoplastic elastomer polycarbonate homopolymers or copolymers, or be substantially composed of one or more thermoplastic elastomer polycarbonate homopolymers or copolymers. The polymer component of a foamable material may be substantially composed of one or more thermoplastic elastomer polycarbonate homopolymers or copolymers.

[0503] One or more first thermoplastic elastomers may include, or are substantially composed of, one or more thermoplastic elastomer polyacrylate homopolymers or copolymers, including polyacrylic acid, polymethacrylate, and the like. The polymeric component of the foamable material may consist substantially of one or more thermoplastic elastomer polyacrylate homopolymers or copolymers.

[0504] Thermoplastic elastomer polyurethane homopolymers and copolymers have been found to be particularly useful in the methods and articles described herein. In this aspect, one or more first thermoplastic elastomers comprise or consist of one or more thermoplastic elastomer polyurethane homopolymers or copolymers, wherein a thermoplastic polyurethane homopolymer is understood to mean a polymer chain comprising only urethane segments, and a polyurethane copolymer is understood to mean a polymer chain comprising urethane segments as well as other types of segments, such as ester segments or ether segments or the like, and combinations thereof. When one or more first thermoplastic elastomers comprise one or more thermoplastic elastomer polyurethane homopolymers or copolymers, the one or more thermoplastic elastomers may comprise or consist substantially of: thermoplastic elastomer polyester-polyurethane copolymers, thermoplastic elastomer polyether-polyurethane copolymers, thermoplastic elastomer polycarbonate-polyurethane copolymers, or combinations thereof. In some aspects, one or more first thermoplastic elastomers of the foamable material comprise one or more thermoplastic elastomer polyester-polyurethane copolymers or are substantially composed of one or more thermoplastic elastomer polyester-polyurethane copolymers, optionally wherein the polymeric component of the foamable material comprises one or more thermoplastic elastomer polyester-polyurethane copolymers.

[0505] Thermoplastic polyurethanes can be produced by reacting diisocyanates with difunctional compounds that are reactive to isocyanates. Typically, the difunctional compounds have two hydroxyl groups (diols) and can have molar masses from about 62 Daltons (molar mass of ethylene glycol) to about 10,000 Daltons, or from about 100 Daltons to about 5,000 Daltons, or from about 500 Daltons to about 5,000 Daltons, or from about 500 Daltons to about 2,500 Daltons, or from about 2,500 Daltons to about 10,000 Daltons, or from about 5,000 Daltons to about 10,000 Daltons, or from about 5,000 Daltons to about 7,500 Daltons, or from about 7,500 Daltons to about 10,000 Daltons. Although difunctional compounds with other isocyanate-reactive groups (e.g., secondary amines) can generally be used in small amounts, and trifunctional and monofunctional isocyanate-reactive compounds can be used in limited molar fractions. In one example, the polyurethane is linear. Including a bifunctional compound having a molar mass of about 400 Daltons or greater introduces soft segments into the polyurethane. The increased ratio of soft to hard segments in the polyurethane can cause the polyurethane to become increasingly flexible and eventually become an elastomer. In one example, one or more thermoplastic elastomer materials comprise thermoplastic polyurethane elastomers or combinations of thermoplastic polyurethane elastomers.

[0506] Suitable thermoplastic polyurethane elastomers include thermoplastic polyester-polyurethane, polyether-polyurethane, and polycarbonate-polyurethane. Non-limiting examples of these include polyurethanes polymerized using the following as diol reactants: polyester diols prepared from diols and dicarboxylic acids or anhydrides; polylactone polyester diols (e.g., polycaprolactone diol); polyester diols prepared from hydroxy acids, which are monocarboxylic acids containing a hydroxyl group; polytetrahydrofuran diol; polyether diols prepared from ethylene oxide or combinations thereof; and polycarbonate diols such as polyhexamethylene carbonate diol and poly(hexamethylene-co-pentamethylene) carbonate diol. Thermoplastic polyurethane elastomers can be prepared by reacting one or more of these polymeric diols (polyester diol, polyether diol, polylactone diol, polytetrahydrofuran diol, or polycarbonate diol) with one or more polyisocyanates and optionally one or more monomeric chain extenders. The chain extender is a compound having two or more functional groups reactive with the isocyanate group, for example, two functional groups. In one instance, the thermoplastic polyurethane elastomer is substantially linear (i.e., all or substantially all of the reactants are bifunctional).

[0507] In another aspect, one or more first thermoplastic elastomers comprise one or more thermoplastic elastomer styrene homopolymers or copolymers, or are substantially composed of one or more thermoplastic elastomer styrene homopolymers or copolymers. The polymeric component of the foamable material may be substantially composed of one or more thermoplastic elastomer styrene homopolymers or copolymers. One or more thermoplastic elastomer styrene homopolymers or copolymers may include, or are substantially composed of, one or more styrene-butadiene-styrene (SBS) block copolymer elastomers, one or more styrene-ethylene-butene-styrene (SEBS) copolymer elastomers, one or more styrene-acrylonitrile (SAN) copolymer elastomers, or any combination thereof.

[0508] In any of these aspects, one or more first thermoplastic elastomers comprise one or more recycled first thermoplastic elastomers or are substantially composed of one or more recycled first thermoplastic elastomers. Similarly, the polymeric component of the foamable material may comprise a recycled thermoplastic polymer or be substantially composed of a recycled thermoplastic polymer. In one aspect, the polymeric component of the foamable material comprises one or more recycled thermoplastic elastomer polymers or is substantially composed of one or more recycled thermoplastic elastomer polymers. In another aspect, the polymeric component of the foamable material comprises one or more recycled thermoplastic polymers. In yet another aspect, the polymeric component of the foamable material comprises one or more recycled thermoplastic elastomer polymers and one or more thermoplastic non-elastic polymers, or is substantially composed of one or more recycled thermoplastic elastomer polymers and one or more thermoplastic non-elastic polymers. In yet another aspect, the polymeric component of the foam is substantially composed of one or more thermoplastic elastomer polyurethanes and one or more thermoplastic polyolefins.

[0509] In one aspect, the foamable material comprises a polymeric component and a mixture of a nonpolymeric component consisting of one or more nonpolymeric additives, optionally wherein the foamable material comprises a nonpolymeric component of about 0.005% to about 20% by weight based on the total weight of the foamable material, and optionally a nonpolymeric additive of about 0.5% to about 10%, about 1% to about 5%, or about 1% to about 2% by weight based on the total weight of the foamable material.

[0510] Other materials that can be used as part of a composition forming a foamable material include, but are not limited to: colorants, including pigments and dyes; fillers such as clay, including nanoclay and halloysite clay; nanotubes; nucleating agents; emulsifiers; release agents, including surfactant-based release agents; antioxidants; stabilizers; crosslinking agents; and / or the like.

[0511] Foamable materials can be relatively soft. In some instances, foamable materials have a Shore A hardness of about 35A to about 95A. In other instances, foamable materials have a Shore A hardness of about 70A to about 95A, optionally about 35A to about 70A, about 50A to about 70A, or about 55A to about 90A, as measured using the Shore A hardness testing protocol.

[0512] In any of these aspects, the expandable material does not melt and / or is not melted during the maintenance and holding steps or the undergoing and expansion steps of the methods disclosed herein. According to this disclosure, carbon dioxide is used to inject at least a portion of the solid expandable material of the article, and the solid expandable material remains solid during injection. The injected solid expandable material of the article remains in a solid state until it expands by the phase transformation of the injected carbon dioxide into a gas, at a point during which the expandable material acquires a porous structure without melting or being in a molten state. While additional processing steps may be performed on the foamed article that could melt the solid expandable material or portions or areas of the foamed material, it should be understood that any step involving melting the solid expandable material or the foamed material is performed before the maintenance and holding step or after the undergoing and expansion step. In some aspects, the foamed material of the foamed article is a physically expanded solid material formed without melting the solid material. Avoiding melting of thermoplastic elastomer materials during the foaming process reduces the "thermal history" of the thermoplastic elastomer material, which is the number of heating and cooling cycles to which the thermoplastic elastomer material is exposed. This reduces or prevents the thermal degradation of the thermoplastic elastomer material.

[0513] Blends.In one aspect, the foamable material may comprise a blend of one or more first thermoplastic elastomers and a second material, or substantially consist of a blend of one or more first thermoplastic elastomers and a second material. In some aspects, the second material comprises one or more second polymers, or substantially consists of one or more second polymers, optionally comprising one or more second thermoplastic plastics, or substantially consists of one or more second thermoplastic plastics. In such aspects, the polymeric component of the foamable material comprises one or more first thermoplastic elastomers and one or more second thermoplastic plastics, or substantially consists of one or more first thermoplastic elastomers and one or more second thermoplastic plastics.

[0514] In another aspect, one or more second thermoplastic plastics may comprise or consist essentially of: one or more thermoplastic polyolefin homopolymers or copolymers, one or more thermoplastic polyamide homopolymers or copolymers, one or more thermoplastic polyester homopolymers or copolymers, one or more thermoplastic polyether homopolymers or copolymers, one or more thermoplastic polycarbonate homopolymers or copolymers, one or more thermoplastic polyacrylate homopolymers or copolymers, one or more thermoplastic polyurethane homopolymers or copolymers, one or more thermoplastic styrene homopolymers or copolymers, or any combination thereof. In some aspects, one or more second thermoplastic polyolefin homopolymers or copolymers comprise or consist essentially of: thermoplastic polypropylene homopolymers or copolymers, thermoplastic polyethylene homopolymers or copolymers, thermoplastic polybutene homopolymers or copolymers, or any combination thereof. In one aspect, one or more second thermoplastics comprise or are substantially composed of one or more thermoplastic polyethylene copolymers, including one or more thermoplastic ethylene-vinyl alcohol copolymers or one or more thermoplastic ethylene-vinyl acetate copolymers. In one aspect, the polymeric component of the foamable material is substantially composed of a blend of one or more first thermoplastic elastomers and one or more second thermoplastics, optionally wherein the blend foams during the undergoing and expansion steps. In such an aspect, one or more second thermoplastics may comprise one or more thermoplastic polyolefin homopolymers or copolymers. In another aspect, the polymeric component of the foamable material is substantially composed of a blend of one or more first thermoplastic elastomer polyurethane homopolymers or copolymers and one or more second thermoplastic ethylene-vinyl alcohol copolymers. Furthermore, in this aspect, the polymeric component may substantially consist of one or more first thermoplastic elastomer polyester-polyurethane homopolymers or copolymers and one or more second thermoplastic ethylene-vinyl alcohol copolymers.

[0515] In one aspect, the blend may include one or more recycled first thermoplastic elastomers, one or more recycled second thermoplastics, or both. The one or more recycled first thermoplastic elastomers may include one or more recycled thermoplastic elastomer polyurethane copolymers, such as one or more recycled thermoplastic elastomer polyurethane-polyester copolymers or one or more recycled thermoplastic elastomer polyurethane-polyether copolymers. The one or more recycled second thermoplastics may include one or more recycled thermoplastic polyolefins, such as one or more recycled polyethylene copolymers.

[0516] Recycled materials. In one aspect, the recycled material that can be used in the methods disclosed herein may include a foamable material that is unfoamed (i.e., a foamable material that has not been previously foamed). For example, recycled material can be obtained by recycling unfoamed foamable material, such as waste or scrap material (e.g., by regrinding or another method). In another aspect, recycled foamable material can be obtained by recycling an article containing foamable material before the article has been foamed (e.g., by recycling a defective article that has been discarded before foaming).

[0517] In one aspect, the blend comprises a phase-separated blend of one or more first thermoplastic elastomers and one or more second thermoplastics. In some aspects, the phase-separated blend comprises one or more phase-separated regions at the interface between one or more first thermoplastic elastomers and one or more second thermoplastics. Without being bound by theory, one or more first thermoplastic elastomers and one or more second thermoplastics may be phase-separated, or when one or more first thermoplastic elastomers comprise at least one copolymer having hard and / or soft segments, the hard and / or soft segments may have an affinity for the second thermoplastic; thus, in some aspects, the phase-separated blend may include polymer entanglements in addition to the interface between portions of one or more first thermoplastic elastomers and one or more second thermoplastics. During the process of expansion, the presence of one or more interfaces, such as between phase-separated regions or between different polymeric materials within an article, can act as nucleation sites for the formation of bubbles, and thus the presence of such nucleation sites in the article can increase the uniformity of the pore structure in the foamed material.

[0518] The blend may comprise at least 50% by weight of one or more first thermoplastic elastomers and less than 50% by weight of one or more second thermoplastics based on the total weight of the blend. The blend may comprise at least 70% by weight of one or more first thermoplastic elastomers and less than 30% by weight of one or more second thermoplastics based on the total weight of the blend. The blend may comprise at least 80% by weight of one or more first thermoplastic elastomers and less than 20% by weight of one or more second thermoplastics based on the total weight of the blend. In an exemplary aspect, the blend comprises about 95% by weight of one or more first thermoplastic elastomers and about 5% by weight of one or more second thermoplastics based on the total weight of the blend.

[0519] In some aspects, the solubility of carbon dioxide can vary among different polymeric materials constituting the foamable material because the retolded material and the virgin material have different thermal histories, such as when the foamable material is a blend of a first thermoplastic elastomer and a second non-elastomeric thermoplastic material, or a blend of the retolded material and the virgin material. In some aspects, the solubility of carbon dioxide is greater in one or more thermoplastic elastomers than in one or more non-elastomeric thermoplastics. In one aspect, carbon dioxide is soluble in one or more first thermoplastic elastomers at a concentration from about 1% to about 30% by weight, optionally from about 5% to about 20% by weight, from about 5% to about 10% by weight, or from about 10% to about 20% by weight, based on the total weight of the one or more first thermoplastic elastomers present in the foamable material. In another aspect, carbon dioxide is soluble in one or more second thermoplastics at a concentration of less than 1 wt%, optionally less than 0.5 wt%, less than 0.25 wt%, or less than 0.1 wt%, based on the total weight of the one or more second thermoplastics present in the foamable material. In some aspects, carbon dioxide is substantially insoluble in one or more second thermoplastics. The solubility of carbon dioxide in one or more first thermoplastic elastomers and one or more second thermoplastics can be determined by gravimetric analysis by injecting carbon dioxide into separate samples of the first thermoplastic elastomer and the second thermoplastics at a first temperature.

[0520] foamed materials

[0521] In this document, foamed materials are disclosed. In one aspect, the foamed material can be a product that expands any of the foamable materials described above. In another aspect, the foamed material can be a thermoplastic material. In yet another aspect, the foamed material can be partially or completely crosslinked. In one aspect, when the foamed material is crosslinked, the crosslinking can make the foamed material completely or partially crosslinked. In some aspects, when the foamed material is partially crosslinked, it can retain some thermoplastic properties, allowing the foam to soften with heat. In an alternative aspect, the foamed material can be crosslinked to the point where it becomes a thermosetting foamed material.

[0522] In one aspect, the foamed material may be crosslinked during or after the expansion and swelling steps. In another aspect, crosslinking may be photochemically initiated. In an exemplary aspect, crosslinking may be initiated using thermal radiation, light (e.g., UV radiation), electron beams, or any combination thereof.

[0523] In some respects, foamable materials also include crosslinking agents, such as thermally initiated or photoinitiated crosslinking agents.

[0524] In one aspect, the foamed material has a Shore A hardness of about 35A to about 95A. In other examples, the foamed material has a Shore A hardness of about 70A to about 95A, optionally about 35A to about 70A, about 50A to about 70A, or about 55A to about 90A, as measured using the Shore A hardness testing protocol.

[0525] In another aspect, the foamed material may have an Asker C hardness of about 10 to about 50, optionally about 15 to about 50, about 15 to about 45, about 20 to about 45 or about 20 to about 40, as measured using the Asker C hardness testing protocol.

[0526] In some respects, an item before foaming can be optically transparent and colorless. After foaming, the item can be opaque, depending on the placement and thickness of the foaming material.

[0527] Other materials

[0528] In one aspect, the article includes an additional material, i.e., a material other than a solid foamable material. Optionally, the additional material may be an additional thermoplastic material, optionally an additional thermoplastic elastomer material, optionally wherein the additional thermoplastic elastomer material is an additional (i.e., second) foamable material. In another aspect, the additional material may be an additional foamable material, and during the expansion step, the additional foamable material expands into an additional foamed material. In yet another aspect, in the foamed article, the density of the first foamed material differs from the density of the additional foamed material by at least 5%, optionally at least 10%, or at least 20%.

[0529] In one aspect, the article includes an additional material, wherein the additional material is separate from the foamable material. In one aspect, the additional material and the foamable material may be bonded to each other or may be connected to each other. In another aspect, the additional material and the foamable material may have some polymer chains mixed at the interface (e.g., if the foamable material and the additional material are thermally bonded). In another aspect, the additional material comprises one or more polymers or is substantially composed of one or more polymers, and includes an additional material polymer component consisting of all the polymers present in the additional material. In an optional aspect, the additional material includes or is substantially composed of a second material, optionally wherein the second material is a thermoplastic material. Still additionally, in this aspect, the additional material may optionally include an additional material polymer component mixed with a non-polymer component of the additional material, which consists of all the non-polymer components present in the additional material.

[0530] In some respects, an article comprises one or more first parts of a foamable material and one or more second parts of another material, wherein one or more first parts are different from one or more second parts.

[0531] In one aspect, the additional material is separate from and / or is not a component of the foamable material. Furthermore, in this aspect, the additional material may exist in the article as a different element separate from the foamable material but capable of contacting at least a portion of the foamable material. In other aspects, the additional material may be a component of the foamable material, for example, as part of a blend that also comprises the first material.

[0532] In one aspect, the additional material includes a barrier material comprising one or more barrier polymers, the barrier material comprising a barrier polymer component consisting of all the polymers present in the barrier material. In some aspects, the additional material remains substantially non-foamed during the expansion step.

[0533] In some aspects, the additional material may be a recycled material comprising one or more recycled polymers, optionally including one or more recycled thermoplastics, optionally including one or more recycled thermoplastic elastomers, optionally including a recycled thermoplastic elastomer, optionally including a recycled material polymer component composed of one or more recycled thermoplastics, optionally including a recycled material polymer component composed of one or more recycled thermoplastic elastomers. In some aspects, the recycled material comprises one or more recycled first thermoplastic elastomers. Optionally, in another aspect, one or more recycled first thermoplastic elastomers comprise one or more re-ground first thermoplastic elastomers. Optionally, further in this aspect, one or more recycled first thermoplastic elastomers or re-ground first thermoplastic elastomers comprise thermoplastic elastomers as described herein.

[0534] In another aspect, the recycled material further includes one or more recycled second thermoplastics. Optionally, in this aspect, the one or more recycled second thermoplastics include one or more re-milled second thermoplastics. Optionally, furthermore, in this aspect, the one or more recycled second thermoplastics or re-milled second thermoplastics include thermoplastics according to any one of the foregoing aspects. In some aspects, the recycled material includes one or more recycled thermoplastic polyurethane elastomers or re-milled thermoplastic polyurethane elastomers or one or more recycled thermoplastic ethylene-vinyl alcohol copolymers or both.

[0535] In one aspect, the recycled material may comprise a blend of one or more recycled thermoplastic elastomers or re-milled thermoplastic elastomers and one or more second thermoplastics, or may comprise a blend of one or more thermoplastic elastomers and one or more recycled thermoplastics or one or more recycled second thermoplastics. Optionally, in one aspect, the blend may be a phase-separated blend, optionally wherein the phase-separated blend includes one or more interfaces between one or more first thermoplastic elastomers and one or more second thermoplastics.

[0536] In another aspect, the recycled material may comprise, by weight, one or more first thermoplastic elastomers from about 99% to about 90% and second thermoplastics from about 1% to about 10% of the total weight of the recycled material, optionally, one or more first thermoplastic elastomers from about 99% to about 93% and second thermoplastics from about 1% to about 7% of the total weight, or one or more first thermoplastic elastomers from about 99% to about 95% and second thermoplastics from about 1% to about 5% of the total weight.

[0537] In some aspects, the recycled material comprises about 99% to about 50% by weight of a recycled polymer or a re-milled polymer based on the total weight of the recycled material, optionally from about 99% to about 75% by weight of a recycled polymer or a re-milled polymer.

[0538] In any of these aspects, carbon dioxide is soluble in the recycled material at a concentration of from about 1% to about 30% by weight, optionally from about 5% to about 20% by weight, based on the total weight of the recycled material. In another aspect, carbon dioxide is soluble in one or more recycled or re-ground thermoplastic elastomers at a concentration of from about 1% to about 30% by weight, optionally from about 5% to about 20% by weight, based on the total weight of one or more recycled or re-ground thermoplastic elastomers. In yet another aspect, carbon dioxide may be soluble in one or more recycled or re-ground thermoplastic elastomers at a concentration of less than 1% by weight, optionally less than 0.5% by weight, less than 0.25% by weight, or less than 0.1% by weight, based on the total weight of one or more recycled or re-ground thermoplastic elastomers, or optionally wherein carbon dioxide is substantially insoluble in one or more recycled or re-ground thermoplastic elastomers.

[0539] In some aspects, the recycled material includes recycled foamed articles produced by the methods disclosed herein, optionally wherein the recycled foamed articles are refurbished foamed articles. In some aspects, the recycled material includes foamable materials, wherein the foamable materials are unfoamed materials. In another aspect, the recycled material also includes one or more original first thermoplastic elastomers, optionally wherein one or more original first thermoplastic elastomers include one or more original thermoplastic polyurethane elastomers. In yet another aspect, the recycled material includes one or more nucleating agents or nucleation sites for foaming the recycled material, optionally wherein one or more nucleation sites are located at one or more interfaces between phase-separated polymers.

[0540] In one aspect, the barrier material has a hardness that is at least 10 Shore A units greater than that of the foamable material, or optionally at least 20 Shore A units, 30 Shore A units, or 40 Shore A units greater than that of the foamable material, as measured using the Shore A hardness testing scheme.

[0541] In any of these aspects, the additional material may be a barrier material having a nitrogen permeability of less than or equal to 10 cubic centimeters per square meter per 24 hours, or less than or equal to 1 cubic centimeter per square meter per 24 hours. In some aspects, although the second material may be slightly stretched or deformed during the foaming process, the gas permeability, gas barrier properties, and durability of the layer remain substantially unchanged after foaming.

[0542] In another aspect, the barrier material has a nitrogen permeability that is at least 50% lower than that of the foamable material, optionally less than or equal to 10 cubic centimeters per square meter per 24 hours, or less than or equal to 1 cubic centimeter per square meter per 24 hours.

[0543] In some aspects, the barrier polymer component of the barrier material consists of one or more barrier polymers, each of which individually has a nitrogen permeability of less than or equal to 30 cubic centimeters per square meter per 24 hours, or less than or equal to 10 cubic centimeters per square meter per 24 hours, or less than or equal to 1 cubic centimeter per square meter per 24 hours.

[0544] In one aspect, at a first temperature and a first pressure, carbon dioxide is soluble in the foamable material at a first concentration, and carbon dioxide is soluble in the barrier material at a second concentration, wherein the first concentration is at least 20% greater than the second concentration, optionally at least 50% greater, or at least 70% greater. In another aspect, the second concentration is less than 1 wt%, optionally less than 0.5 wt%, less than 0.25 wt%, or less than 0.1 wt%, or optionally carbon dioxide is substantially insoluble in the barrier material.

[0545] In one aspect, the barrier material comprises one or more ethylene-vinyl alcohol copolymers, optionally one or more of which are thermoplastic, and optionally one or more of which are thermoplastic elastomer copolymers. In another aspect, the barrier polymer component consists of one or more ethylene-vinyl alcohol copolymers, optionally one or more of which are thermoplastic, and optionally one or more of which are thermoplastic elastomer copolymers. In some aspects, the barrier polymer component optionally comprises: one or more thermoplastic polyolefin homopolymers or copolymers, optionally one or more thermoplastic polyolefin copolymers, or one or more thermoplastic polyethylene copolymers.

[0546] In one aspect, the additional material has a higher degree of crystallinity than the foamable material. In another aspect, the additional material comprises one or more barrier polymers including or substantially composed of: one or more vinylidene chloride polymers, one or more acrylonitrile polymers or copolymers, one or more polyamides, one or more epoxy resins, one or more amine polymers or copolymers, one or more thermoplastic polyolefin homopolymers or copolymers, one or more thermoplastic polyolefin copolymers, or one or more thermoplastic polyethylene copolymers, or one or more thermoplastic ethylene-vinyl alcohol copolymers, or one or more thermoplastic elastomer ethylene-vinyl alcohol copolymers.

[0547] In some aspects, other materials also include plasticizers.

[0548] Third material

[0549] In some aspects, the article also includes a third material. In other aspects, the third material may optionally be a recycled material. In one aspect, the recycled material includes a refurbished thermoplastic elastomer material. In some aspects, the recycled material also includes a refurbished second thermoplastic material. In one aspect, the refurbished thermoplastic elastomer material includes one or more thermoplastic polyurethanes, and the refurbished second thermoplastic material includes one or more ethylene-vinyl alcohol copolymers.

[0550] In some aspects, the recycled material comprises a phase-separated blend of one or more refurbished thermoplastic elastomer materials and one or more refurbished second thermoplastics. Furthermore, in this aspect, the phase-separated blend comprises one or more phase-separated regions located at the interface between one or more first thermoplastic elastomers and one or more second thermoplastics. In one aspect, the recycled material comprises about 95% by weight of refurbished thermoplastic elastomer material and about 5% by weight of second thermoplastic.

[0551] In some aspects, carbon dioxide has different solubilities in the re-milled thermoplastic elastomer material and the re-milled second thermoplastic material. In one aspect, carbon dioxide is soluble in the re-milled thermoplastic elastomer material at a concentration from about 1 wt% to about 30 wt%, optionally from about 5 wt% to about 20 wt%, from about 5 wt% to about 10 wt%, or from about 10 wt% to about 20 wt%. In another aspect, carbon dioxide is soluble in the re-milled second thermoplastic material at a concentration of less than 1 wt%, optionally less than 0.5 wt%, less than 0.25 wt%, or less than 0.1 wt%. In some aspects, carbon dioxide is substantially insoluble in the re-milled second thermoplastic material.

[0552] In one aspect, the recycled material includes refurbished foamed articles produced by the methods disclosed herein. In an alternative aspect, the recycled material includes articles comprising foamable material that has not previously been foamed. In some aspects, the recycled material also includes virgin or pristine thermoplastic polyurethane elastomers.

[0553] In any of these aspects, one or more interfaces serve as nucleation sites for foaming in thermoplastic elastomer materials.

[0554] Barrier materials

[0555] In some aspects, the additional material includes a barrier material comprising one or more barrier polymers, the barrier material comprising a barrier polymer component consisting of all the polymers present in the barrier material. In some aspects, the additional material includes a plasticizer. In one aspect, in the foamed article, the additional material is substantially unfoamed.

[0556] In one aspect, in the foamed article, the barrier material has a hardness that is at least 10 Shore A units greater than that of the thermoplastic elastomer material in solid form, or optionally at least 20 Shore A units, at least 30 Shore A units, or at least 40 Shore A units greater than that of the thermoplastic elastomer material in solid form, as measured using the Shore A hardness testing scheme.

[0557] In one aspect, the barrier material has a nitrogen permeability at least 50% lower than that of a thermoplastic elastomer material in solid form, optionally less than or equal to 10 cubic centimeters per square meter per 24 hours, or less than or equal to 1 cubic centimeter per square meter per 24 hours. In another aspect, the barrier polymer component of the barrier material consists of one or more barrier polymers, each barrier polymer individually having a nitrogen permeability of less than or equal to 30 cubic centimeters per square meter per 24 hours, or less than or equal to 10 cubic centimeters per square meter per 24 hours, or less than or equal to 1 cubic centimeter per square meter per 24 hours.

[0558] In any of these aspects, one or more barrier polymers comprise or are substantially composed of: one or more vinylidene chloride polymers, one or more acrylonitrile polymers or copolymers, one or more polyamides, one or more epoxy resins, one or more amine polymers or copolymers, one or more thermoplastic polyolefin homopolymers or copolymers, one or more thermoplastic polyolefin copolymers, or one or more thermoplastic polyethylene copolymers, one or more thermoplastic ethylene-vinyl alcohol copolymers, or one or more thermoplastic elastomer ethylene-vinyl alcohol copolymers.

[0559] In another aspect, carbon dioxide is soluble in the thermoplastic elastomer material at a first concentration and in the barrier material at a first pressure from about 0.05 psi (0.345 kPa) to about 6000 psi (41,300 kPa) and a first temperature from about -57°C to about 31°C. In one aspect, the first concentration is at least 20% greater than the second concentration, optionally at least 50% greater or at least 70% greater than the second concentration. In another aspect, the second concentration is less than 1% by weight, optionally less than 0.5%, less than 0.25%, or less than 0.1% by weight, based on the total weight of one or more second thermoplastics present in the foamable material, or optionally at a first pressure from about 0.05 psi (0.345 kPa) to about 6,000 psi (41,300 kPa) and a first temperature from about -57°C to about 31°C, where carbon dioxide is substantially insoluble in the barrier material.

[0560] In this aspect, the barrier material comprises one or more ethylene-vinyl alcohol copolymers, optionally one or more of which are thermoplastic, optionally one or more of which comprise one or more thermoplastic elastomer copolymers, optionally the barrier polymer component consists of one or more ethylene-vinyl alcohol copolymers, optionally one or more of which are thermoplastic, optionally one or more of which are thermoplastic elastomer copolymers.

[0561] The material for the second foaming

[0562] In one aspect, the foamed articles disclosed herein include foamed materials, wherein the foamed materials are first foamed materials, and the foamed articles also include second foamed materials, wherein the second foamed materials comprise or are substantially composed of other materials. In one aspect, the density of the first foamed material may differ from the density of the second foamed material by at least 5%, at least 10%, or at least 20%. In another aspect, the second foamed material may be a second physically expanded foam.

[0563] In one aspect, the second physical expansion foam is the product of placing an unfoamed article containing a solid additional material in carbon dioxide, injecting the solid additional material with carbon dioxide, and expanding the injected solid additional material by causing the injected carbon dioxide to phase into a gas without softening the solid additional material, thereby forming a foamed article.

[0564] Recycled materials

[0565] In another aspect, the foamable materials and foamable articles disclosed herein may include recycled materials or be substantially composed of recycled materials. In another aspect, the other materials disclosed herein may be recycled materials. In any of these aspects, the recycled material includes one or more recycled polymers, optionally including one or more recycled thermoplastics, optionally including one or more recycled thermoplastic elastomers, optionally including a recycled material polymer component composed of one or more recycled thermoplastics, optionally including a recycled material polymer component composed of one or more recycled thermoplastics, optionally including a recycled material polymer component composed of one or more recycled thermoplastic elastomers. In another aspect, the recycled material includes one or more recycled first thermoplastic elastomers, optionally including one or more recycled first thermoplastic elastomers as one or more re-milled first thermoplastic elastomers. In another aspect, one or more recycled first thermoplastic elastomers or re-milled first thermoplastic elastomers include thermoplastic elastomers as disclosed herein.

[0566] In another aspect, the recycled material may also include one or more recycled second thermoplastics, optionally including one or more re-milled second thermoplastics, optionally including thermoplastics as disclosed herein.

[0567] In another aspect, among the foamed articles disclosed herein, the recycled material includes one or more recycled thermoplastic polyurethane elastomers or re-milled thermoplastic polyurethane elastomers, one or more recycled thermoplastic ethylene-vinyl alcohol copolymers or re-milled thermoplastic ethylene-vinyl alcohol copolymers, or both.

[0568] In another aspect, the recycled material may include a blend of one or more recycled thermoplastic elastomers or re-milled thermoplastic elastomers and one or more second thermoplastics, or may include a blend of one or more thermoplastic elastomers and one or more recycled thermoplastics or one or more recycled second thermoplastics. Optionally, in this aspect, the blend may be a phase-separated blend, optionally wherein the phase-separated blend includes one or more interfaces between one or more first thermoplastic elastomers and one or more second thermoplastics.

[0569] In any of these aspects, the recycled material may comprise, by weight, one or more first thermoplastic elastomers from about 99% to about 90% and second thermoplastics from about 1% to about 10% of the total weight of the recycled material, optionally wherein the recycled material comprises, by weight, one or more first thermoplastic elastomers from about 99% to about 93% and second thermoplastics from about 1% to about 7% of the total weight, or one or more first thermoplastic elastomers from about 99% to about 95% and second thermoplastics from about 1% to about 5% of the total weight.

[0570] In some aspects, the recycled material may comprise, by weight, from about 99% to about 50% of a recycled polymer or a re-milled polymer, based on the total weight of the recycled material, and optionally from about 99% to about 75% of a recycled polymer or a re-milled polymer.

[0571] In any of these aspects, at a first pressure of about 0.05 pounds per square inch (0.345 kPa) to about 6,000 pounds per square inch (41,300 kPa) and a first temperature of about -57 degrees Celsius to about 31 degrees Celsius, carbon dioxide is soluble in the recycled material at a concentration of about 1% to about 30% by weight, optionally from about 5% to about 20% by weight, based on the total weight of the recycled material.

[0572] In another aspect, the range is from about 0.05 pounds per square inch (0.345 kPa) to about 6,000 pounds per square inch (41,300 kPa), optionally from about 15 pounds per square inch (103.4 kPa) to about 5,500 pounds per square inch (37,900 kPa), from about 100 pounds per square inch (689.5 kPa) to about 5,000 pounds per square inch (34,500 kPa), from about 500 pounds per square inch (3,450 kPa) to about 2,000 pounds per square inch (13,790 kPa), or from about 1,000 pounds per square inch (... A first pressure of about 6895 kPa to about 1500 psi (10,300 kPa) and a first temperature of about -57°C to about 31°C, optionally from about -40°C to about 25°C or from about -40°C to about 0°C, with carbon dioxide soluble in a foaming material, or a solid foamable material, or both, at a concentration of about 1 wt% to about 30 wt%, optionally from about 5 wt% to about 20 wt%, from about 5 wt% to about 10 wt%, or from about 10 wt% to about 20 wt%.

[0573] In another aspect, at a first pressure of about 0.05 psi (0.345 kPa) to about 6,000 psi (41,300 kPa) and a first temperature of about -57°C to about 31°C, carbon dioxide is soluble in one or more recycled or re-ground thermoplastics at a weight percentage of less than 1%, optionally less than 0.5%, less than 0.25%, or less than 0.1%, based on the total weight of one or more recycled or re-ground thermoplastics, or optionally wherein carbon dioxide is substantially insoluble in one or more recycled or re-ground thermoplastics.

[0574] In another aspect, the range is from about 0.05 pounds per square inch (0.345 kPa) to about 6,000 pounds per square inch (41,300 kPa), optionally from about 15 pounds per square inch (103.4 kPa) to about 5,500 pounds per square inch (37,900 kPa), from about 100 pounds per square inch (689.5 kPa) to about 5,000 pounds per square inch (34,500 kPa), from about 500 pounds per square inch (3,450 kPa) to about 2,000 pounds per square inch (13,790 kPa), or from about 1,000 pounds per square inch (... A first pressure of about 6895 kPa to about 1500 psi (10,300 kPa) and a first temperature of about -57°C to about 31°C, optionally from about -40°C to about 25°C or from about -40°C to about 0°C, with carbon dioxide soluble in a foaming material, or a solid foamable material, or both, at a concentration of about 1 wt% to about 30 wt%, optionally from about 5 wt% to about 20 wt%, from about 5 wt% to about 10 wt%, or from about 10 wt% to about 20 wt%.

[0575] In any of these aspects, the recycled material may be a recycled foamed article, optionally wherein the recycled foamed article is a re-milled foamed article as disclosed herein. In some aspects, the recycled material may include a solid material, wherein the solid material may be a thermoplastic elastomer material. In another aspect, the recycled material may also include one or more original first thermoplastic elastomers, optionally wherein one or more original first thermoplastic elastomers include one or more original thermoplastic polyurethane elastomers.

[0576] In one aspect, the recycled material may include one or more nucleating agents and / or one or more interfaces between phase-separated polymers. In another aspect, in the foamed articles disclosed herein, the thermoplastic elastomer material may be recycled material, or include recycled material, or consist substantially of recycled material.

[0577] Exemplary aspects of footwear, apparel, and sports equipment.

[0578] Figures 1A-1M The illustrations depict footwear, apparel, sports equipment, containers, electronic devices, and visual protection devices that incorporate structures (e.g., foamed articles) that include the contents of this disclosure.

[0579] Figure 1N(a)-Figure 1N(b) The figures show perspective and side views of a footwear article 100 including a sole structure 104 and an upper 102. The sole structure 104 is attached to the upper 102 and extends between the foot and the ground when the footwear article 100 is worn. The main components of the sole structure 104 are a midsole 114 and an outsole 112. The midsole 114 is attached to the lower region of the upper 102 and may be formed of polymer foam or another suitable material. In other constructions, the midsole 114 may incorporate fluid-filled chambers, plates, adjusters, and / or other elements to further reduce force, enhance stability, or influence foot movement. The outsole 112 is attached to the lower surface of the midsole 114 and may be formed of, for example, an abrasion-resistant rubber material textured to impart adhesive friction. The upper 102 may be formed of various elements (e.g., laces, tongue, collar) that combine to provide a structure for securely and comfortably receiving the foot. Although the construction of the upper 102 can vary significantly, various elements typically define a cavity within the upper 102 for receiving and securing the foot relative to the sole structure 104. The surface of the cavity within the upper 102 is shaped to accommodate the foot and can extend over the instep and toe areas of the foot, along the medial and lateral sides of the foot, under the foot, and around the heel area. The upper 102 can be made of one or more materials stitched or combined together, such as textiles, polymer foams, natural leather, synthetic leather, and the like. While this construction of the sole structure 104 and the upper 102 provides an example of a sole structure that can be used in conjunction with an upper, a variety of other conventional or unconventional constructions of the sole structure 104 and / or the upper 102 can also be utilized. Therefore, the construction and characteristics of the sole structure 104 and / or the upper 102 can vary significantly.

[0580] Figure 1O(a)-Figure 1O(b)The figures illustrate perspective and side views of a footwear article 130 including a sole structure 134 and an upper 132. The sole structure 134 is attached to the upper 132 and extends between the foot and the ground when the footwear article 130 is worn. The upper 132 may be formed of various elements (e.g., laces, tongue, collar) that combine to provide a structure for securely and comfortably receiving the foot. Although the construction of the upper 132 can vary significantly, various elements generally define cavities within the upper 132 for receiving and securing the foot relative to the sole structure 134. The surfaces of the cavities within the upper 132 are shaped to accommodate the foot and may extend over the instep and toe areas of the foot, along the medial and lateral sides of the foot, under the foot, and around the heel area of ​​the foot. The upper 132 may be made of one or more materials stitched or bonded together, such as textiles including natural and synthetic leather, molded polymer components, polymer foams, and similar materials.

[0581] The main components of the sole structure 134 are the forefoot component 142, the heel component 144, and the outsole 146. Each of the forefoot component 142 and the heel component 144 is directly or indirectly attached to the lower region of the upper 132 and is formed of a polymeric material encapsulating a fluid, which may be a gas, liquid, or gel. For example, during walking and running, the forefoot component 142 and the heel component 144 are compressed between the foot and the ground, thereby reducing ground reaction forces. That is, the forefoot component 142 and the heel component 144 are inflated and can be pressurized with fluid to cushion the foot. The outsole 146 is attached to the lower region of the forefoot component 142 and the heel component 144 and may be formed of an abrasion-resistant rubber material that is textured to impart adhesion friction. The forefoot component 142 may be made of one or more polymers (e.g., layers of one or more polymer films) that form more than one chamber containing a fluid such as a gas. The multiple chambers can be independent or fluidly interconnected. Similarly, the heel component 144 can be made of one or more polymers (e.g., layers of one or more polymer films) forming multiple chambers containing fluids such as gases and can also be independent or fluidly interconnected. In some configurations, the sole structure 134 may include a foam layer, for example, extending between one or both of the upper 132 and the forefoot component 142 and the heel component 144, or foam elements may be located within indentations in the lower regions of the forefoot component 142 and the heel component 144. In other configurations, the sole structure 134 may incorporate, for example, plates, adjusters, lasting elements, or motion control components that further dampen forces, enhance stability, or influence foot movement. While the depicted constructions of sole structure 134 and upper 132 provide examples of sole structures that can be used in conjunction with an upper, a variety of other conventional or unconventional constructions of sole structure 134 and / or upper 132 can also be utilized. Therefore, the construction and features of sole structure 134 and / or upper 132 can vary significantly.

[0582] Figure 1O(c) is a cross-sectional view of AA depicting the upper 132 and the heel component 144.

[0583] Figure 1P(a)-Figure 1P(b)The figures show a perspective and side view of a footwear article 160 including an adhesive friction element 168. The footwear article 160 includes an upper 162 and a sole structure 164, wherein the upper 162 is attached to the sole structure 164. The sole structure 164 may include one or more of a toe plate 166a, a midsole plate 166b, and a heel plate 166c. The plates may include one or more adhesive friction elements 168, or the adhesive friction elements may be applied directly to the ground-facing surface of the footwear article. Figure 1P(a)-Figure 1P(b) As shown, the adhesion friction element 168 is an anti-slip element, but adhesion friction elements may include lugs, anti-slip elements, cleats and spikes, and tread patterns to provide adhesion friction on soft and smooth surfaces. Typically, anti-slip elements, cleats and spikes are commonly included in footwear designed for sports such as international football / football, golf, American football, rugby, baseball, and similar sports, while lugs and / or reinforced tread patterns are commonly included in footwear (not shown) including boots designed for use in harsh outdoor conditions such as cross-country running, hiking, and military applications. The sole structure 164 is attached to the upper 162 and extends between the foot and the ground when the footwear article 160 is worn. The upper 162 may be formed from a variety of elements (e.g., laces, tongue, collar) that combine to provide a structure for securely and comfortably receiving the foot. Although the construction of the upper 162 can vary significantly, various elements typically define cavities within the upper 162 for receiving and securing the foot relative to the sole structure 164. The surfaces of the cavities within the upper 162 are shaped to accommodate the foot and extend over the instep and toe areas of the foot, along the medial and lateral sides of the foot, under the foot, and around the heel area of ​​the foot. The upper 162 can be made of one or more materials stitched or bonded together, such as textiles including natural and synthetic leather, molded polymer components, polymer foams, and the like. In other aspects not depicted, the sole component 164 may incorporate foams, one or more fluid-filled chambers, plates, adjusters, or other elements for further force reduction, enhanced stability, or influencing foot movement. While the depicted constructions of the sole structure 164 and the upper 162 provide examples of sole structures that can be used in conjunction with an upper, a variety of other conventional or unconventional constructions of the sole structure 164 and / or the upper 162 can also be utilized. Therefore, the construction and features of the sole structure 164 and / or the upper 162 can vary significantly.

[0584] Figure 1Q(a)-Figure 1Q(e)Further views of exemplary athletic footwear articles including an upper 176 are illustrated. Figure 1Q(a) is an exploded perspective view of an exemplary athletic footwear article showing an insole 174, an upper 176, a midsole or optional last 177, and an outsole 178. Figure 1Q(b) is a top view of an exemplary athletic footwear article, indicating an opening 183 configured to receive the wearer's foot and cushioning material 181 surrounding the wearer's ankle. The outer side 180 and inner side 179 of the exemplary athletic footwear article are also illustrated. Figure 1Q(c) is a rear view of the footwear article depicted in Figure 1Q(b), showing a heel clip 184. Figure 1Q(d) shows a side view of an exemplary athletic footwear article that may optionally include a tongue 186, laces 188, a toe cap 189, a heel stabilizer 190, decorative elements such as a logo 191, and / or eyelets 192 for the laces. The toe area 193a, heel area 193b, and upper 193c are also shown. In some aspects, the heel stabilizer 190 may be covered by a layer of knitted fabric, woven fabric, or non-woven fabric, natural leather, synthetic leather, or other shoe upper material. In some aspects, the eyelets 192 are formed as a continuous piece; however, they may also include several separate pieces surrounding a single eyelet or more than one eyelet. Although not depicted, foamed articles may be present on the eyelets 192 and / or the laces 188. In some constructions, the sole structure may include a sole interlayer with foam or air bladders in part or substantially all of the sole interlayer, and foamed articles may be disposed on the sole interlayer foam or air bladders. Figure 1Q(e) is a side view of another exemplary athletic footwear article. In some aspects, the upper may include receiving elements 194, such as mag wire or molded plastic pieces extending from lacing structures on portions of the medial and lateral sides of an exemplary athletic footwear article to the top of the sole structure, to provide a foot-to-sole lock, wherein the receiving elements may have foamed articles (not shown) disposed thereon. Engagement lines 195 between the upper and sole structures are also depicted.

[0585] Exemplary aspects of the disclosed method for manufacturing foamed articles

[0586] In one aspect, referring to the figure, Figure 2 The figure shows a side view of an article comprising a solid foamable material as described herein. In one aspect, the solid foamable material includes one or more thermoplastic elastomer polyurethane copolymers.

[0587] Figure 7 The diagram illustrates a flowchart of a method 300 for manufacturing foamed articles as disclosed herein. (Reference) Figure 2 and Figure 7Optionally, in one aspect, the foamable material 210 is formed (optional step 302) into an article 214. In another aspect, the article 214 may optionally be configured to have a generally two-dimensional (2-D) shape, or alternatively, the article 214 may be configured to have a generally three-dimensional (3-D) shape or a combination of 2-D and 3-D shapes.

[0588] Articles containing the disclosed foamable material can take many forms. In one non-limiting aspect, as illustrated, article 214 can be configured as a sheet 216 that has been rolled or otherwise folded into a roll 218, or the article may not be a sheet but may be configured as a roll in some aspects. In one example, sheet 216 has a thickness from about 0.5 mm to about 2 cm, or from about 0.5 mm to about 1 cm, or from about 0.5 mm to about 100 mm, optionally from about 0.5 mm to about 5 mm, such as about 1.5 mm.

[0589] Also refer to Figure 3When the article is configured as a roll, an optional porous spacer 220 may be arranged in roll 218 between segments 222, 224, 226, and 228 of adjacent rolls of the article 214 comprising the foamable material 210. In one aspect, as will be described in further detail below, the optional porous spacer 220 is porous enough to allow carbon dioxide to travel through or through the porous spacer 220 (e.g., through or through the porous structure and / or along the porous channels) for contact with the foamable material 210. In one aspect, the optional porous spacer 220 is formed of a thermoplastic material, such as, for example, a polyolefin (e.g., meltblown polyethylene) or the like. In an alternative aspect, the optional porous spacer 220 may be formed of a non-thermoplastic material, such as, for example, paper or cellulose products, fibrous products (e.g., natural or synthetic fiber products), fabric products, or the like. In one example, the optional porous spacer 220 is formed of a recyclable material. In another aspect, for example, article 214 and optional porous spacer 220 can be of any desired thickness, such that sheet 216 and / or roll 218 can be arranged in container 234, as discussed further in detail below. Optional porous spacer 220 can have a thickness from about 0.1 mm to about 2 mm, or from about 0.1 mm to about 1 mm, or from about 0.1 mm to about 0.5 mm, for example, about 0.25 mm. In one example, optional porous spacer 220 has a porosity such that the diffusion rate of carbon dioxide (e.g., liquid phase) through spacer 220 is higher than or greater than the diffusion rate of carbon dioxide (e.g., liquid phase) through foamable material 210. In other aspects, the article can be folded, and optional porous spacers are placed between folded sections of the article, or porous spacers can be incorporated between more than one discrete article (e.g., multiple sheets of a single article or bundles or stacks of single articles, and the like).

[0590] exist Figures 2-4 and Figure 7 In one exemplary embodiment, as illustrated, a roll 218 comprising a solid expandable material 210 is vertically arranged on a base 230, which is operatively coupled to a rod 232. The roll 218 is positioned in a container 234 by manipulating the rod 232 to lower the base 230 through an opening 236 and into the container 234. The opening 236 of the container 234 is then covered and sealed with a cover 238 (e.g., a clamshell or other pressure-sealing cap). In other aspects (not shown), expandable articles of any suitable shape can be arranged on a base operatively coupled to a rod, wherein the rod can be manipulated to lower the base through an opening and into the container. Furthermore, in this aspect, the opening of the container can then be covered and sealed with a cover.

[0591] Carbon dioxide 240 is supplied or received in container 234 (step 304) for contact with the expandable material 210. In one example, during the placement step, liquid carbon dioxide 240 is present in container 234 before the roll 218, article, or bundle of articles of the expandable material 210 is positioned in container 234. In another example, during the placement step, after the roll 218, article, or bundle of articles of the expandable material 210 is positioned in container 234, liquid or gaseous carbon dioxide 240 from liquid or gaseous carbon dioxide source 242 is introduced into container 234 through control valve 244.

[0592] In another example, during the placement step, a roll 218 of a sheet 210 of foamable material 210, or alternatively, an article, bundle of articles, or the like, is positioned in container 234 and sealed with a lid 238. Liquid and / or gaseous carbon dioxide 246 from a liquid and / or gaseous carbon dioxide source 248 passes through a control valve 250 and is introduced into container 234. In one aspect, container 234 is loaded with liquid and / or gaseous carbon dioxide 246 to a pressure and temperature condition, such as a liquid / vapor equilibrium condition for carbon dioxide. The pressure and temperature of container 234 can be monitored via a pressure measuring device 252 and a temperature measuring device 254, respectively. In one example, after being loaded with liquid and / or gaseous carbon dioxide 246, container 234 has a capacitance ranging from about 0.05 psi (0.345 kPa) to about 6,000 psi (41,300 kPa), optionally from about 15 psi (103.4 kPa) to about 5,500 psi (37,900 kPa), and from about 100 psi (689.5 kPa) to about 5,000 psi (34,500 kPa). The pressure can be from about 500 psi (3450 kPa) to about 2000 psi (13,790 kPa) or from about 1000 psi (6895 kPa) to about 1500 psi (10,300 kPa), and the temperature can be from about -57 degrees Celsius to about 31 degrees Celsius, optionally from about 0 degrees Celsius to about 23 degrees Celsius, or as needed, about ambient temperature (e.g., from about 18 degrees Celsius to about 23 degrees Celsius) or higher. After container 234 is filled with liquid and / or gaseous carbon dioxide, liquid carbon dioxide 240 is introduced into container 234 as described above.

[0593] As illustrated, container 234 may be adequately filled with liquid carbon dioxide 240 such that rolls 218 comprising foamable material 210 and / or articles or bundles thereof are substantially or completely immersed in the liquid carbon dioxide 240. As briefly mentioned above, the liquid carbon dioxide 240 travels through optional porous spacers 220 for contacting sections 222, 224, 226, and 228 of adjacent rolls of sheet 216 of foamable material 210, or for contacting sections (not shown) of adjacent discrete or folded articles. Upon contact with the liquid carbon dioxide 240, the foamable material 210 adsorbs and / or otherwise absorbs the liquid carbon dioxide 240 (e.g., via diffusion step 305) to form carbon dioxide-injected articles 256. In one example, during the steps of maintaining and holding the first pressure and the first temperature, the foamable material 210 is contacted with carbon dioxide 240 for a duration ranging from about 20 seconds to about 72 hours, optionally from about 30 minutes to about 30 hours, from about 1 hour to about 24 hours, from about 6 hours to about 12 hours, or from about 20 seconds to about 1 hour, to form a carbon dioxide-infused article 256. Without being theoretically limited, it is believed that during contact with carbon dioxide 240, the foamable material 210 is solvated by carbon dioxide 240 to form the carbon dioxide-infused article 256.

[0594] In one exemplary aspect, the process continues by discharging liquid and / or gaseous carbon dioxide 246 from container 234 via control valve 250 and line 258. Preferably, container 234 discharges liquid and / or gaseous carbon dioxide 246 at a temperature sufficient to substantially prevent foaming of the foamable material 210 containing liquid carbon dioxide. In one example, the temperature in container 234 during discharge is from about -60 degrees Celsius to about -20 degrees Celsius, or from about -50 degrees Celsius to about -30 degrees Celsius, or from about -45 degrees Celsius to about -38 degrees Celsius. In another aspect, liquid carbon dioxide 240 may be removed from container 234 via pump 260 and line 262 before, during, or after discharging liquid and / or gaseous carbon dioxide 246 from container 234.

[0595] For example, by removing the cap 238 and lifting the base 230 through the opening 236 using the lever 232, the carbon dioxide-injected item 256 or other carbon dioxide-injected items or bundles of items in a roll 218 are removed from the container 234. Optionally and as... Figure 5As illustrated, prior to heating and foaming the material 210, the carbon dioxide-injected article 256 or other carbon dioxide-injected articles or bundles of articles 218 may be temporarily exposed to a second pressure and a second temperature in cooling zone 308 (step 306). As used herein, the term "zone" refers to an area comprising one or more equipment items and / or one or more subzones. Equipment items may include, for example, one or more containers, chambers, heaters, exchangers, chillers, pipes, pumps, compressors, controllers, and similar equipment items. Additionally, an equipment item may also comprise one or more zones or subzones. In one example, the carbon dioxide-injected article 256 bundle 218 is stored in cooling zone 308 at a temperature from about -100 degrees Celsius to about -20 degrees Celsius, optionally from about -60 degrees Celsius to about -20 degrees Celsius, or from -40 degrees Celsius to about -20 degrees Celsius.

[0596] refer to Figure 6 and Figure 7 The process continues by subjecting an article comprising the foamable material 210 to a third temperature and a third pressure (step 310) to induce expansion of the injected carbon dioxide, for example, by causing a phase change in the carbon dioxide 240 injected into the foamable material. As the carbon dioxide expands, this expansion causes the foamable material 210 to foam into a foamed material, such as a foamed material with a porous foam structure. In some aspects, nucleation sites within the article promote the formation of bubbles that expand and form foam pores. In one aspect, when the article comprises recycled material in the form of a phase-separated blend, the nucleation site may be a phase-separated interface between one or more first thermoplastic elastomers and one or more second thermoplastics in the blend. Other nucleation sites and / or nucleating agents are also contemplated and should be considered disclosed. In one example, an article 255 infused with carbon dioxide is subjected to a temperature ranging from about 20 degrees Celsius to about 150 degrees Celsius, optionally from about 20 degrees Celsius to about 100 degrees Celsius, from about 40 degrees Celsius to about 80 degrees Celsius, from about 50 degrees Celsius to about 70 degrees Celsius, or at a third temperature of about 60 degrees Celsius, and independently sustained for a period of time ranging from about 1 second to about 5 minutes, optionally from about 10 seconds to about 2 minutes, from about 30 seconds to about 90 seconds, or from about 45 seconds to about 60 seconds, to cause the foamable material 210 to expand and foam and form a foamed article 265. In some aspects, after the exposure and expansion, the article retains carbon dioxide gas in the pores of the foamed material, or retains solubilized carbon dioxide in the foamed article 265, or retains solubilized carbon dioxide in another polymeric material of the article.

[0597] In one instance, during the process, the carbon dioxide-injected article 255 is heated by introducing the carbon dioxide-injected article 255 into a water bath 266. Figure 6 The illustration for the rolled article shows the case where the roll 219 of the carbon dioxide-injected article 255 is unrolled and the porous spacer 220 is removed to expose the carbon dioxide-injected article 255 for introduction into the water bath 266. Other methods of introducing articles, including unrolled articles, are also contemplated and should be considered public. In the water bath 266, the carbon dioxide-injected article 255 comes into contact with water at a higher temperature than the carbon dioxide-injected article 255. Therefore, heat is transferred from the water bath 266 to the carbon dioxide-injected article 255 to cause a phase change in the carbon dioxide 240, thereby causing the foamable material 210 to expand and foam to form the foamed article 265. In one example, the water bath 266 is at a third temperature ranging from about 20 degrees Celsius to about 90 degrees Celsius, or from about 50 degrees Celsius to about 70 degrees Celsius, or about 60 degrees Celsius, and independently, the carbon dioxide-infused article 255 is immersed in the water bath 266 for a duration ranging from about 2 seconds to about 30 minutes, optionally from about 10 seconds to about 30 minutes, from about 30 seconds to about 20 minutes, from about 30 seconds to about 10 minutes, or from about 30 seconds to about 5 minutes, to form a foamed article 265. In an alternative example, water in the form of steam is used to heat the carbon dioxide-infused article 255. In particular, the temperature of the carbon dioxide-infused article 255 is increased by subjecting the carbon dioxide-infused article 255 to steam. In one example, steam is used to heat the carbon dioxide-injected article 255 to a third temperature ranging from about 60 degrees Celsius to about 150 degrees Celsius, optionally from about 60 degrees Celsius to about 100 degrees Celsius, or from about 75 degrees Celsius to about 90 degrees Celsius, to induce a phase change of carbon dioxide 240 to carbon dioxide gas, thereby causing the foamable material 210 to expand and foam to form a foamed article 265.

[0598] In another example, the carbon dioxide-injected article 255 can be subjected to microwave energy using a microwave generator or an RF generator 268 (in... Figure 7(Illustrated in the diagram) The article 255 injected with carbon dioxide is heated by subjecting it to radio frequency (RF) energy. Specifically, heat is generated in the article 255 by adsorbing microwave or RF energy to induce a phase change in carbon dioxide 240, thereby causing the foamable material 210 to expand and foam to form a foamed article 265. In one example, the article 255 injected with carbon dioxide is heated by microwave or RF energy to a third temperature ranging from about 60 degrees Celsius to about 150 degrees Celsius, optionally from about 60 degrees Celsius to about 100 degrees Celsius, or from about 75 degrees Celsius to about 90 degrees Celsius, and independently sustained for a period of time ranging from about 2 seconds to about 5 minutes, optionally from about 10 seconds to about 2 minutes, or from about 30 seconds to about 1 minute to form the foamed article 265.

[0599] refer to Figure 7 The process continues by optionally bringing the foamed article 265 to a fourth temperature and a fourth pressure (step 311) and holding the foamed article at or below the fourth temperature, fourth pressure, or both to form a stabilized foamed thermoplastic article. The stabilized foamed article may be formed into a net shape, or may be trimmed, machined, or otherwise shaped to a desired form to define the shape of the foamed article. Residual carbon dioxide removal (step 312) is achieved by optionally holding the foamed article at a fifth temperature and a fifth pressure, for example, in an oven 314. After the residual carbon dioxide is removed, the foamed article may be cooled to room temperature by any means (step 316), including but not limited to removing the foamed article from the oven 314 and allowing it to equilibrate with room temperature air.

[0600] refer to Figure 7 In one aspect, the foamed article can be used to manufacture articles such as sports equipment articles, clothing articles, or footwear articles (optional step 318). In one aspect, the foamed article 319 can be combined with a second component (e.g., attached, step 318) to form a finished article 317. In some aspects, the foamed article as described above can be a foamed footwear component. Furthermore, in this aspect, the foamed footwear component and footwear upper and / or footwear outsole can be attached (step 318) to manufacture a finished footwear article.

[0601] In any of the above aspects in which a core layer exists, the core layer may include more than one microlayer (not shown) as described and disclosed herein.

[0602] Property analysis and characterization procedures

[0603] Specific gravity / density testing procedure.Measure the specific gravity (SG) or density of the samples obtained using the component sampling procedure described herein using a digital balance or a Densicom tester (Qualitest, Plantation, Florida, USA). Weigh each sample and then immerse it in a distilled water bath (at 22 degrees Celsius plus or minus 2 degrees Celsius). To avoid errors, remove air bubbles from the surface of the sample, for example, by wiping the sample with isopropanol before immersion in water or by brushing the sample after immersion. Record the weight of the sample in distilled water. Calculate the specific gravity using the following formula:

[0604]

[0605] Test procedures for melting temperature, glass transition temperature, and enthalpy of melting. According to ASTM D3418-97, the melting temperature and glass transition temperature are determined using a commercially available differential scanning calorimeter (“DSC”) with samples prepared using a material sampling procedure. Briefly, 10-15 g of sample is placed in an aluminum DSC pan and the pan is then sealed with a tablet press. The DSC is configured to scan from -100°C to 225°C at a heating rate of 20°C per minute, held at 225°C for 2 minutes, and then cooled to 25°C at a rate of -10°C per minute. The DSC curves generated from this scan are then analyzed using standard techniques to determine the glass transition temperature and melting temperature. The enthalpy of fusion is calculated by integrating the area of ​​the endothermic melting peak and normalizing by the sample mass.

[0606] Alternatively, the glass transition temperature can be determined using dynamic mechanical analysis (DMA). In this technique, a foamable sheet of material, in the form of a film approximately 1 mm thick, approximately 5 mm to approximately 10 mm wide, and approximately 20 mm long, is mounted on a film tension fixture of a DMA device. The sample is heated at a fixed rate, for example, approximately 1°C to approximately 5°C per minute, within a predetermined temperature range. During heating, the sample is tested at a fixed frequency (e.g., approximately 1 Hz) and a small oscillation amplitude (e.g., approximately 0.05% strain). The storage modulus (or complex shear) is recorded. In the DMA plot, G′ is the storage modulus, and G″ is the loss modulus. G′ measures the stored energy, and G″ measures the energy lost / dissipated as heat. tanδ is the ratio of G″ / G′, and the peak region in the tanδ curve indicates the glass transition temperature of the sample.

[0607] Shore A hardness test scheme. The hardness of a material is determined using the Shore A scale, according to the test protocol detailed in ASTM D-2240 hardness tester specifications. Samples are prepared using material sampling procedures and / or component sampling procedures.

[0608] Asker C hardness testing solution. For flat foam, the sample thickness for Asker C hardness testing should be at least 6 mm. If necessary, foam samples should be stacked to achieve the minimum thickness. The foam sample should be large enough to allow all measurements to be taken at least 12 mm from the edge of the sample and at least 12 mm from any other measurement. The tested area should be flat and parallel to an area at least 6 mm in diameter. The standard sample has dimensions of approximately 35 cm × 13 cm × 1.8 cm and undergoes at least 5 hardness measurements using a 1 kg head weight. Samples should be prepared using material sampling procedures and / or component sampling procedures.

[0609] Layer tear test protocol. The test protocol for obtaining the ply tear value of foam articles is as follows. Samples are prepared using a material sampling procedure and / or a component sampling procedure. Four punched rectangular sheets or molded foam samples are prepared, each measured to be 2.54 cm × 15.24 cm × 10 ± 1 mm (thickness). If the foam material to be tested has a surface or barrier layer, remove the surface or barrier layer before preparing the four samples. A 3 cm long cut is made at the center of one end of the sample. Five consecutive 2 cm sections are then marked on the sample.

[0610] The crosshead speed of the tensile testing equipment is set to 50 mm per minute. Each separated end of the sample is clamped in the upper and lower clamps of the testing equipment. The separation is placed in the middle between the two clamps. Each segment of the sample is held in the clamps in such a way that the original adjacent cut edges form a straight line connecting the center of the clamps.

[0611] If necessary, use a sharp knife to assist in cutting to keep the foam material in the center of the sample separate. Readings obtained by cutting with a knife are discarded. The lowest value of each of the five sections of each sample is recorded in kilograms per centimeter. For each sample, five values ​​are recorded, and then the average of the five values ​​is obtained and reported. If a section of the sample includes a portion with a bubble diameter greater than 2 mm, the value of that portion is not included in the average. If more than one section of the sample is found to contain bubbles with a diameter greater than 2 mm, then another sample is tested.

[0612] Sampling procedure

[0613] Using the test scheme described above, a variety of properties of the materials disclosed herein and articles formed therefrom can be characterized using samples prepared with the following sampling procedure.

[0614] Material sampling procedure.Material sampling procedures can be used to obtain pure samples of polymeric materials or polymers, or in some cases, samples of materials used to form polymeric materials or polymers. The material is provided in the form of a medium, such as flakes, granules, powders, pellets, or the like. If the source of the polymeric material or polymer is not available in pure form, a sample can be cut from a part or component containing the polymeric material or polymer (such as a composite element or sole structure) to separate a sample of the material.

[0615] Component sampling procedure. This procedure can be used to obtain samples of material from components of footwear, apparel, sports equipment, or other sports equipment. A blade is used to cut the sample from the article or component, containing material in a non-wet state (e.g., at 25 degrees Celsius and 20% relative humidity). If the material is bonded to one or more other materials, the procedure may include separating the other materials from the material being tested.

[0616] Samples are taken at locations along the article or component where the material present provides a substantially constant thickness (within 10% of the average material thickness). For many of the test protocols described above, samples with a surface area of ​​4 square centimeters are used. The samples are cut to a specific size and shape (e.g., dog bone-shaped samples) for assembly into the test apparatus. Where the material is not present on any section of the article or component with a surface area of ​​4 square centimeters and / or where the material thickness for sections with a surface area of ​​4 square centimeters is not substantially constant, sample sizes with smaller cross-sectional surface areas can be obtained, and the measurements of specific areas are adjusted accordingly.

[0617] definition

[0618] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure pertains. It will also be understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having the meaning consistent with their meaning in the context of the specification and in the relevant field, and should not be interpreted in an idealized or overly formal sense unless expressly defined herein.

[0619] All publications, patents, and patent applications referenced in this specification are cited to disclose and describe methods and / or materials associated with the cited publications. All such publications, patents, and patent applications are incorporated herein by reference as if each individual publication or patent were specifically and individually indicated as incorporated by reference. Such incorporation by reference is expressly limited to the methods and / or materials described in the cited publications, patents, and patent applications and does not extend to any dictionary definitions derived from the cited publications, patents, and patent applications. Any dictionary definitions in the cited publications, patents, and patent applications that are not expressly repeated in this specification should not be considered such dictionary definitions and should not be construed as defining any terms appearing in the appended claims.

[0620] This disclosure is not limited to the specific aspects, embodiments, or examples described, and therefore is subject to variation. The terminology used herein is for the purpose of describing specific aspects, embodiments, and examples only, and is not intended to be restrictive, as the scope of this disclosure will be limited only by the appended claims.

[0621] Where a range of values ​​is provided, every intermediate value between the upper and lower limits of that range (in units of one-tenth of the lower limit, unless the context explicitly indicates otherwise) and any other stated value or intermediate value within that range are included in this disclosure. The upper and lower limits of these smaller ranges may be independently included in the smaller ranges and are also included in this disclosure, subject to any specific excluded limit value within the stated range. Where a stated range includes one or both of the included limit values, the range excluding any one or both of those included limit values ​​is also included in this disclosure.

[0622] Upon reading this disclosure, it will be apparent to those skilled in the art that each of the various aspects, embodiments, and examples described and illustrated herein has discrete components and features that can be readily separated from or combined with any of the other aspects, embodiments, and examples without departing from the scope or spirit of this disclosure. Any enumerated method may be implemented in the order of the enumerated events or in any other logically possible order.

[0623] Although any methods and materials similar to or equivalent to those described herein may be used in the practice or testing of this disclosure, preferred methods and materials are described hereafter. For brevity and / or clarity, well-known functions or constructions may not be described in detail. Unless otherwise indicated, aspects of this disclosure will employ techniques such as nanotechnology, organic chemistry, materials science, and engineering, which are well-explained in the literature.

[0624] It should be noted that ratios, concentrations, amounts, and other numerical data may be expressed in range format herein. Where a stated range contains one or both extreme values, the range excluding any one or both of those extreme values ​​is also included in this disclosure; for example, the phrase “x to y” includes the range from 'x' to 'y' as well as the range greater than 'x' and less than 'y'. Ranges may also be expressed as upper limits, such as 'about x, y, z, or less', and should be interpreted as including the specific ranges of 'about x', 'about y', and 'about z', as well as the ranges of 'less than x', 'less than y', and 'less than z'. Similarly, the phrase 'about x, y, z, or greater' should be interpreted as including the specific ranges of 'about x', 'about y', and 'about z', as well as the ranges of 'greater than x', 'greater than y', and 'greater than z'. Furthermore, the phrase “about 'x' to 'y'”, where 'x' and 'y' are numerical values, includes “about 'x' to about 'y'”. It should ...

Claims

1. A method for manufacturing foamed articles, the method comprising: The article and carbon dioxide are placed in a container, wherein the article comprises a solid foamable material, the solid foamable material being a thermoplastic elastomer material containing one or more first thermoplastic elastomers; After the placement step, the container is maintained at a first pressure and a first temperature, wherein the first pressure and the first temperature are the pressure and temperature at which the carbon dioxide is liquid and the liquid carbon dioxide is soluble in the solid foamable material, and wherein the maintenance includes holding the article and the liquid carbon dioxide in the container for a duration sufficient to allow at least a portion of the liquid carbon dioxide to be injected into the solid foamable material of the article. Following the maintenance and holding steps, the injected article is optionally exposed to a second pressure and a second temperature, at which the carbon dioxide is maintained injected into at least a portion of the solid foamable material; Following the maintenance and holding steps and the optional exposure step, the article is subjected to a third pressure and a third temperature, at which the liquid carbon dioxide injected into the solid foamable material phases into a gas, thereby causing the solid foamable material to expand into a foamed material and form the foamed article; and The article is configured as a series of two or more regions, the series of two or more regions including a first region containing a first region material and a second region containing a second region material, wherein both the first region material and the second region material are solid foamable materials.

2. The method of claim 1, wherein the first region or the second region forms the outermost surface of the article, or wherein both the first region and the second region together form the outermost surface of the article.

3. The method according to claim 1 or 2, wherein the one or more first thermoplastic elastomers comprise one or more thermoplastic elastomer polyolefin homopolymers or copolymers, one or more thermoplastic elastomer polyamide homopolymers or copolymers, one or more thermoplastic elastomer polyester homopolymers or copolymers, one or more thermoplastic elastomer polyurethane homopolymers or copolymers, one or more thermoplastic elastomer styrene homopolymers or copolymers, or any combination thereof.

4. The method according to claim 1 or 3, wherein in the article, the first region forms the outermost surface of the article, and the second region forms the inner layer of the article.

5. The method according to any one of claims 1-3, wherein in the article, the first region comprises the solid foamable material, the solid foamable material of the first region is the solid foamable material of the first region, and during the step of undergoing and expanding, the solid foamable material of the first region remains the solid foamable material of the first region.

6. The method according to any one of claims 1-3, wherein in the article, the first region comprises the solid foamable material, the solid foamable material of the first region is the solid foamable material of the first region, and in the step of undergoing and expanding, the solid foamable material of the first region expands into the foamed material, wherein the foamed material of the first region is the foamed material of the first region.

7. The method according to any one of claims 1-4 and 6, wherein in the article, the second region comprises the solid foamable material, the solid foamable material of the second region is the solid foamable material of the second region, and during the step of undergoing and expanding, the solid foamable material of the second region remains the solid foamable material of the second region.

8. The method according to any one of claims 1-6, wherein in the article, the second region comprises the solid foamable material, the solid foamable material of the second region is the solid foamable material of the second region, and in the step of undergoing and expanding, the solid foamable material of the second region expands into the foamed material, wherein the foamed material of the second region is the foamed material of the second region.

9. The method according to any one of claims 1-8, wherein the first region material or the second region material comprises a barrier material.

10. The method according to any one of claims 1-4, wherein The first region includes a first region solid foamable material. The maintaining and holding steps include holding the article and the liquid carbon dioxide in the container for a duration sufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of the solid foamable material in the first region, and The process of undergoing and expanding includes expanding at least a portion of the solid foamable material in the first region into the foamed material, wherein the foamed material in the first region includes the foamed material in the first region.

11. The method according to any one of claims 1-4, wherein The maintaining and holding step includes holding the article and the liquid carbon dioxide in the container for a duration sufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of the first region, wherein the duration is insufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of the second region; Furthermore, the process of undergoing and expanding includes expanding at least a portion of the solid foamable material in the first region into the foamed material of the first region without expanding the material in the second region.

12. The method according to any one of claims 1-4, wherein The maintaining and holding step includes holding the article and the liquid carbon dioxide in the container for a duration sufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of the first region and into at least a portion of the second region, and the method further includes the following steps: The injected article is exposed to the second pressure and the second temperature for a period of time, such that at least a portion of the carbon dioxide injected into the at least portion of the second region diffuses out of the at least portion of the second region, while at least a portion of the injected carbon dioxide injected into the first region remains injected into the at least portion of the first region after the exposure; and The process of undergoing and expanding includes expanding at least a portion of the solid foamable material in the first region into foamable material in the first region without expanding the material in the second region, thereby forming a foamed first region, while maintaining the second region in a solid, unfoamed state.

13. The method according to any one of claims 1-4, 6-7 and 10-11, wherein immediately prior to the undergoing and expansion step, the second region is substantially free of injected carbon dioxide.

14. The method according to any one of claims 1-4, wherein The second region includes the solid foamable material. The maintaining and holding step includes holding the article and the liquid carbon dioxide in the container for a duration sufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of the solid foamable material in the second region, and The process of undergoing and expanding includes expanding at least a portion of the solid foamable material in the second region into the foamed material, wherein the foamed material in the second region includes the foamed material in the second region.

15. The method according to any one of claims 1-4, wherein The maintaining and holding step includes holding the article and the liquid carbon dioxide in the container for a duration sufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of the second region, wherein the duration is insufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of the first region; and The process of undergoing and expanding includes expanding at least a portion of the solid foamable material in the second region into foamable material in the second region without expanding the material in the first region, thereby forming a foamed second region, while maintaining the first region in a solid, unfoamed state.

16. The method according to any one of claims 1-4, wherein The maintaining and holding step includes holding the article and the liquid carbon dioxide in the container for a duration sufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of the first region and into at least a portion of the second region, and the method further includes the following steps: The injected article is exposed to the second pressure and the second temperature for a period of time, such that at least a portion of the carbon dioxide injected into the at least portion of the first region diffuses out of the at least portion of the first region, while at least a portion of the injected carbon dioxide injected into the second region remains injected into the at least portion of the second region after the exposure; and The process of undergoing and expanding includes expanding at least a portion of the solid foamable material in the second region into foamable material in the second region without expanding the material in the first region.

17. The method according to any one of claims 1-4, wherein The first region includes the solid foamable material, and the solid foamable material in the first region is the solid foamable material of the first region; The second region includes the solid foamable material, and the solid foamable material in the second region is the solid foamable material in the second region; The maintaining and holding steps include holding the article and the liquid carbon dioxide in the container for a duration sufficient to allow at least a portion of the liquid carbon dioxide to be injected into at least a portion of the first region and into at least a portion of the second region; and The process of undergoing and expanding causes at least a portion of the solid foamable material in the first region to expand into a foamed material in the first region, and at least a portion of the solid foamable material in the second region to expand into a foamed material in the second region.

18. The method according to any one of claims 1-17, wherein the solid foamable material has a Shore A hardness from 35 A to 95 A.

19. A foamed article comprising a first region and a second region, the first region comprising a first region material, and the second region comprising a second region material, wherein: At least one of the first region material or the second region material is a foamed material, said foamed material being a physically expanded foam formed from a thermoplastic elastomer material comprising one or more first thermoplastic elastomers; and The foamed material is a product of placing an unfoamed article containing a solid foamable material in liquid carbon dioxide, injecting the solid foamable material with the liquid carbon dioxide, and expanding the injected solid foamable material by causing the injected carbon dioxide to phase into a gas without softening the solid foamable material, thereby forming the foamed material of the foamed article, wherein the unfoamed article comprises a first region containing an unfoamed first region material and a second region containing an unfoamed second region material, and wherein both the unfoamed first region material and the unfoamed second region material are solid foamable materials, the solid foamable material being a thermoplastic elastomer material containing one or more first thermoplastic elastomers.

20. The foamed article of claim 19, wherein the first region material is the foamed material, or wherein the second region material is the foamed material, or wherein both the first region material and the second region material are foamed materials.

21. The foamed article according to claim 19 or 20, wherein the foamed article is a garment article, footwear article or sports equipment article, or a component of a garment article, footwear article or sports equipment article.

22. The foamed article according to any one of claims 19-21, wherein the foamed material has a Shore A hardness of 35 A to 95 A.

Images