PTFE and Active Particle Composition

Abstract

Compositions including a matrix, methods of making such compositions, structures including such compositions, and methods of disposing such compositions on a substrate, wherein the matrix includes a plurality of polytetrafluoroethylene fibrils formed from a PTFE resin and a plurality of active particles.

Description

[Technical Field]

[0001] This application claims the benefit of U.S. Provisional Patent Application No. 63 / 429,963, filed December 2, 2022, the entire contents of which are incorporated herein by reference. [Background technology]

[0002] Catalysts and sorbents (adsorbents and absorbents) can be used to remove undesirable chemicals from fluids (e.g., gases or liquids). For example, catalysts can be used to destroy chemicals such as ozone. Adsorbents can be used to isolate or remove acidic molecules, basic molecules, ozone, or various other organic or inorganic compounds from a fluid. Catalysts and sorbents can be difficult to handle when in powder or particulate form. Therefore, catalysts and sorbents are often fixed to a support. Fixing the catalyst or sorbent to a support makes it easier to handle the catalyst or sorbent. Summary of the Invention [Problem to be solved by the invention]

[0003] However, immobilizing a catalyst or adsorbent on a support can reduce the surface area of ​​the catalyst or adsorbent available for removing undesirable chemicals from a fluid. The physical and chemical properties of the support can also affect the functionality of the catalyst (e.g., catalytic efficiency) or adsorbent. Furthermore, the physical and chemical properties of the support can affect the final configuration of a product (e.g., a filter) that includes the catalyst or adsorbent-functionalized support. Ideally, a catalyst or adsorbent-functionalized support has one or more of the following properties: a shape that is easy to design, a configuration in which the catalyst or adsorbent is immobilized that presents a large surface area of ​​the catalyst or adsorbent, and resistance to mechanical and chemical degradation. [Means for solving the problem]

[0004] In one aspect, the present disclosure provides a composition comprising a matrix having a plurality of polytetrafluoroethylene (PTFE) fibrils and a plurality of active particles. In some embodiments, the plurality of PTFE fibrils comprises short-strand PTFE fibrils and long-strand PTFE fibrils.

[0005] In certain embodiments, when the composition is in an unexpanded state, at least a portion of the plurality of active particles and at least a portion of the plurality of PTFE fibrils adopt a catenated structure, an aggregated structure, or both.

[0006] In some embodiments, the plurality of active particles comprises a catalyst, an adsorbent, a growth seed, a metal-organic framework (MOF), or any combination thereof.

[0007] In another aspect, the present disclosure provides a putty, tape, honeycomb structure, web structure, or cast film comprising the composition of any one of the preceding aspects or embodiments.

[0008] In another aspect, the present disclosure provides a substrate comprising an exterior surface, wherein the composition of any one of the preceding aspects or embodiments is disposed on at least a portion of said exterior surface.

[0009] In another aspect, the present disclosure provides a method of making the composition of any one of the preceding aspects or embodiments.

[0010] In another aspect, the present disclosure provides a method of disposing a composition of any one of the preceding aspects or embodiments on at least a portion of an exterior surface of a substrate.

[0011] The terms "short-strand PTFE fibrils" and "long-strand PTFE fibrils" are used in conjunction with one another. A short-strand PTFE fibril has a shorter length than a long-strand PTFE fibril as measured by dimensional analysis test methods. A plurality of short-strand PTFE fibrils has an average length that is shorter than the average length of a plurality of long-strand PTFE fibrils as measured by dimensional analysis test methods. The fibril length is the largest dimension of the fibril. The short-strand PTFE fibrils and long-strand PTFE fibrils are formed from PTFE starting materials having different average PTFE resin sizes.

[0012] As used herein, the term "active particles" refers to particles that include at least one component that can participate in a chemical reaction (e.g., as a catalyst) and / or act as an adsorbent and / or absorbent.

[0013] As used herein, the term "comprising" and variations thereof do not have a limiting meaning when these terms appear in the description and claims. Such terms are understood to mean the inclusion of the recited step or element, or group of steps or elements, but not the exclusion of other steps or elements, or group of steps or elements. The term "consisting of" means inclusive of and limited to what follows the term "consisting of." Thus, the term "consisting of" indicates that the recited elements are required or mandatory, and that no other elements may be present. The term "essentially consisting of" means inclusive of any elements listed after the term, and is limited to other elements that do not interfere with or contribute to the activity or operation specified in the disclosure of the recited elements. Thus, the term "essentially consisting of" indicates that the recited elements are necessary or mandatory, but that other elements are optional and may or may not be present depending on whether they substantially affect the activity or operation of the recited elements. In this application, any element or combination of elements recited in open-ended language (e.g., comprise and its derivatives) is considered to be further recited in closed-ended language (e.g., consist and its derivatives) and partially closed-ended language (e.g., consist essentially and its derivatives). The terms "preferred" and "preferably" refer to embodiments of the disclosure that may offer certain benefits, under particular circumstances. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the present disclosure.

[0014] In this application, terms such as "a," "an," and "the" are not intended to represent only a single entity, but include general classes for which specific examples may be used for illustration. The terms "a," "an," and "the" are used interchangeably with the term "at least one." The phrases "at least one of" and "including at least one of," when followed by a list, refer to any one item in the list, and any combination of two or more items in the list.

[0015] As used herein, the term "or" is generally used in its ordinary sense, including "and / or," unless the content clearly dictates otherwise.

[0016] The term "and / or" means one or all of the listed elements or a combination of any two or more of the listed elements.

[0017] It is also assumed herein that all numbers are modified by the term "about," and in certain embodiments, preferably by the term "exactly." When used herein in connection with a measured quantity, the term "about" accounts for the variation of the measured quantity that would be expected by a skilled artisan making the measurement and exercising a level of care commensurate with the purpose of the measurement and the precision of the measuring equipment used. At the very least, and not as an attempt to limit the doctrine of equivalents to the scope of the claims, each numerical parameter should, at the very least, be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0018] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values ​​set forth in the specific examples are reported as precisely as possible, however, all numerical values ​​inherently contain ranges necessarily resulting from the standard deviation found in their respective testing measurements.

[0019] Here, a number "up to" (e.g., up to 50) is inclusive of the number (e.g., 50). Here, a number "at least" (e.g., at least 50) is inclusive of the number (e.g., 50). Here, a number "equal to or less than" (e.g., 50 or less) is inclusive of the number (e.g., 50).

[0020] Also herein, the recitations of numerical ranges by endpoints include all numbers subsumed within that range, as well as the endpoints (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.).

[0021] As used herein, the term "room temperature" or "ambient temperature" refers to a temperature between 20°C and 25°C.

[0022] The terms "in the range" or "within the range" (and similar descriptions) include the endpoints of the stated range.

[0023] Throughout this application, references to "one aspect," "one aspect," "aspect," "one embodiment," "one embodiment," "particular embodiments," "some embodiments," or "one or more embodiments" mean that a particular feature, configuration, composition, or characteristic described in connection with an embodiment or aspect is included in at least one embodiment or aspect of the disclosure. Thus, the appearances of such phrases in various places throughout this application do not necessarily refer to the same embodiment or aspect of the disclosure. Furthermore, particular features, configurations, compositions, or characteristics may be combined in any suitable manner in one or more embodiments or aspects.

[0024] The term "on," when used in reference to a composition or hydrated solid disposed on a surface or substrate, includes both compositions or hydrated solids disposed (e.g., applied) to the surface or substrate, directly or indirectly (e.g., on a primer layer). Thus, for example, a composition or hydrated solid disposed on a pretreatment or primer layer covering a substrate constitutes a composition or hydrated solid disposed on the substrate.

[0025] The above summary of the present disclosure is not intended to describe each illustrated embodiment or every implementation of the present disclosure. In the following description, exemplary embodiments are more particularly presented. In several places throughout this disclosure, a summary is provided via a list of examples, which examples may be used in various combinations. In each instance, the recited list serves merely as a representative group and should not be interpreted as an exclusive or exhaustive list. Thus, the scope of the present disclosure should not be limited to the specific exemplary structures described herein, but should extend at least to the structures described by the language of the claims and equivalents of those structures. Any elements positively described herein as alternatives may be expressly included in or excluded from the claims in any combination desired. While various theories and possible mechanisms are discussed herein, such discussions should not be used to limit the claimable subject matter in any manner.

[0026] The complete disclosures of all patents, patent applications, publications, and electronically available materials cited in this application are incorporated by reference in their entirety. In the event of a conflict between this disclosure and the disclosure of any document incorporated by reference into this application, the present disclosure shall control. The foregoing detailed description and embodiments are set forth solely for clarity of understanding. No unnecessary limitations should be understood therefrom. The invention is not limited to the exact details shown and described, since variations obvious to those skilled in the art are included within the invention, which is defined by the claims.

[0027] All headings are for the convenience of the reader and should not be used to limit the meaning of the text that follows the heading, unless specifically stated. [Brief explanation of the drawings]

[0028] [Figure 1] 1A-1C are schematic diagrams of an exemplary matrix at two magnifications consistent with embodiments of the present disclosure. [Figure 2A]FIG. 1 is a schematic diagram of a short-strand PTFE fibril. [Figure 2B] FIG. 1 is a schematic diagram of a long-strand PTFE fibril. [Figure 3A] 2 is a schematic diagram of a catenated structure of multiple active particles around a PTFE fibril of the matrix of FIG. 1. FIG. [Figure 3B] FIG. 2 is a schematic diagram of an aggregate structure including a portion of a plurality of active particles and a portion of a plurality of PTFE fibrils of the matrix of FIG. 1. [Figure 4] FIG. 1 is a flow diagram outlining a first method of making a composition and / or disposing a composition on a substrate, according to an embodiment of the present disclosure. [Figure 5] FIG. 2 is a flow diagram outlining a second method of making a composition and / or disposing a composition on a substrate, according to an embodiment of the present disclosure. [Figure 6] FIG. 1 is a flow diagram outlining a method for drying a hydrated solid to form a matrix, consistent with an embodiment of the present disclosure. [Figure 7] 1 is a first scanning electron micrograph of a matrix according to the present disclosure. The matrix contains 40 wt% K2CO3, 8.6 wt% PTFE-12, and 51.4 wt% PTFE-E. Image information: working distance (WD) = 4.0 mm, 5.0 kV LED, x11,000. [Figure 8] 1 is a second scanning electron micrograph of a matrix according to the present disclosure. The matrix contains 68.9 wt% CARULITE, 15.5 wt% PTFE-E, and 15.5 wt% PTFE-12. Image information: WD=4.9 mm, 5.0 kV LED, x370. [Figure 9] 12 is a third scanning electron micrograph of a matrix according to the present disclosure. The matrix contains 68.9 wt% CARULITE, 15.5 wt% PTFE-E, and 15.5 wt% PTFE-12. Image information: WD=7.5 mm, 5.0 kV LED, x1,100. [Figure 10]4 is a fourth scanning electron micrograph of a matrix according to the present disclosure. The matrix contains 68.9 wt% CARULITE, 15.5 wt% PTFE-E, and 15.5 wt% PTFE-12. Image information: WD=7.2 mm, 5.0 kV LED, x3,500. [Figure 11] Scanning electron micrographs of macroscopic coating images (11A, 11C) and microscopic particle distributions (11B, 11D) for PTFE-10g* (11A, 11B) and PTFE-10 (11C, 11D) media after calcination at 330°C for 3 hours (11A and 11B) and hot pressing at 300°F (148.9°C) for 1 hour (11C and 11D). Image information for 11B: Operating WD=7.0 mm, 7.5 kV LED, x15,000. Image information for 11D: WD=6.9 mm, 7.0 kV LED, x9,000. [Figure 12] 1 is a plot showing ozone depletion rate as a function of downstream bed temperature for different PTFE composites under hot pressing and calcination post-treatment conditions. [Figure 13] Scanning electron micrographs of (13A) PTFE-10g and (13B) CARULTIE-CeO2 / PTFE-10µm after hot pressing at 300°F (148.9°C). Image information for 13A: WD=4.0mm, 5.0kV LED, x6,500. Image information for 13B: WD=4.8mm, 5.0kV LED, x5,000. [Figure 14] 14A-14C show scanning electron micrographs of (14A) surface, (14B) K2CO3-embedded particles, and (14C) K2CO3-aggregated particles within a composition containing long-strand and short-strand PTFE fibrils after vacuum drying. Image information for 14A: WD=3.9 mm, 5.0 kV LED, x1.00. Image information for 14B: WD=3.9 mm, 5.0 kV LED, x9,000. Image information for 14C: WD=4.0 mm, 5.0 kV LED, x11,000. [Figure 15]Scanning electron micrograph of the dehydrated cast membrane surface. 14C image information: WD=6.6 mm, 7.0 kV LED, x1,000. DETAILED DESCRIPTION OF THE INVENTION

[0029] The present disclosure provides compositions comprising a matrix; substrates comprised of such compositions; substrates having such compositions disposed thereon; methods for making such compositions; and methods for disposing such compositions on a substrate. As used herein, the term "composition" includes the matrix alone or the matrix together with one or more additional components of the composition.

[0030] The composition of the present disclosure includes a matrix. The matrix of the present disclosure includes a plurality of PTFE fibrils and a plurality of active particles. The composition after formation is understood to be in an unexpanded state as a whole unless otherwise specified. One or more components of the composition may be expanded before or during the formation of the composition. Expanding typically requires subjecting the composition to a shear force sufficient to increase the surface area of ​​the material by two or more times. As used herein, "shear force" refers to a non-aligning force acting on a material in different directions (e.g., compression, torsion, tension, etc.). A matrix in an unexpanded state is not expanded.

[0031] Multiple polytetrafluoroethylene (PTFE) fibrils The matrix of the present disclosure comprises a plurality of PTFE fibrils. The fibrils may have a single strand of PTFE or multiple strands of PTFE. In some embodiments, the fibrils are arranged in a fibrous configuration, i.e., multiple ordered PTFE strands are aligned generally in the same direction.

[0032] The PTFE fibrils are formed from PTFE resin. The PTFE resin may comprise a PTFE polymer, oligomer, monomer, or any combination thereof. The PTFE resin may be solid or liquid. The PTFE resin may be an emulsion. The PTFE resin comprises particles comprising a PTFE polymer, oligomer, monomer, or any combination thereof. Each particle of the PTFE resin has a resin particle size. The resin particle size is defined as the maximum distance across the resin particle.

[0033] In some embodiments, the plurality of PTFE fibrils is a single type of PTFE fibrils, such as short-strand PTFE fibrils or long-strand PTFE fibrils. In some embodiments, the matrix of the present disclosure comprises short-strand PTFE fibrils (formed from short-strand PTFE resin) and long-strand PTFE fibrils (formed from long-strand PTFE resin).

[0034] Figure 2A shows a schematic diagram of a short-strand PTFE fibril 30. The short-strand PTFE fibril has a length 31 and a diameter 32. The length of a PTFE fibril (short-strand or long-strand) is the distance spanning the largest dimension of the fibril. The diameter of a PTFE fibril (short-strand or long-strand) is the greatest distance spanning the smallest dimension of the fibril.

[0035] Short-strand PTFE fibrils are formed from short-strand PTFE resin. The short-strand PTFE resin can be obtained or formed as an emulsion with a dispersant (e.g., water and / or organic solvent) and / or surfactant. As used herein, the use of short-strand PTFE resin includes the use of resin and / or short-strand PTFE emulsion with a dispersant and / or surfactant. In some embodiments, short-strand PTFE resin, such as the PTFE resin used to form the short-strand PTFE fibrils of the matrix of the present disclosure, has an average resin particle size of 1 μm to 9 μm, preferably 3 μm to 5 μm, as measured according to a dimensional analysis test method. When the short-strand PTFE resin is incorporated into the matrix of the present disclosure (e.g., using the method of the present disclosure), the resin particles of the short-strand PTFE resin elongate (e.g., fibrillate) to form short-strand PTFE fibrils.

[0036] In certain embodiments, the short-strand PTFE fibrils of the matrix have an average length of 30 μm or less (1 μm or more), preferably 20 μm or less (1 μm or more), 10 μm or less (1 μm or more), or 5 μm or less (1 μm or more), as measured according to the Dimensional Analysis Test Method. In some embodiments, the short-strand PTFE fibrils of the matrix have an average length of 30 μm or less (1 μm or more), preferably 20 μm or less (1 μm or more), 10 μm or less (1 μm or more), or 5 μm or less (1 μm or more), as measured according to the Dimensional Analysis Test Method. In certain embodiments, the short-strand PTFE fibrils of the matrix have an average diameter of 0.01 μm or more, 0.05 μm or more, 0.3 μm or more, or 0.5 μm or more, as measured according to the Dimensional Analysis Test Method. In certain embodiments, the matrix has an average diameter of 1 μm or less, 0.5 μm or less, or 0.3 μm or less, as measured according to the Dimensional Analysis Test Method.

[0037] The short-strand PTFE fibrils of the matrix are usually not arranged in a regular manner (see, eg, FIG. 8 and elsewhere).

[0038] FIG. 2B shows a schematic diagram of a long-strand PTFE fibril 20. The long-strand PTFE fibril 20 has a diameter 23 and a length 24. In some embodiments, the long-strand PTFE fibril 20 is composed of multiple constituent PTFE fibrils 22. The multiple constituent PTFE fibrils 22 are generally aligned in the same direction to form the long-strand PTFE fibril structure. In this manner, the long-strand PTFE fibril can be considered a fiber composed of constituent fibrils generally aligned in a single direction. The multiple constituent PTFE fibrils 22 differ from short-strand PTFE fibrils at least because the constituent PTFE fibrils 22 have an average fibril length that is longer than the average fibril length of the short-strand PTFE fibrils. In certain embodiments, the long-strand PTFE fibrils (and thus the constituent PTFE fibrils) have an average length of 40 μm or more, 100 μm or more, 150 μm or more, 250 μm or more, 500 μm or more, 700 μm or more, or 1000 μm or more, as measured according to the Dimensional Analysis Test Method. In some embodiments, the long-strand PTFE fibrils have an average length of 2000 μm or less, 1000 μm or less, 700 μm or less, 500 μm or less, 250 μm or less, 150 μm or less, or 100 μm or less, as measured according to the Dimensional Analysis Test Method. The constituent PTFE fibrils 22 need not directly interact; i.e., there may be spaces separating two or more constituent PTFE fibrils. Each constituent PTFE fibril of the plurality of constituent PTFE fibrils 22 has a fibril diameter smaller than the diameter of the long-strand PTFE fibril 20. The diameter 23 of the long-strand PTFE fibrils is the sum of the thickness of each constituent PTFE fibril and the spaces between the constituent PTFE fibrils, if present. In some embodiments, the average diameter of the long-strand PTFE fibrils is 0.5 μm or more, 1 μm or more, 10 μm or more, or 50 μm or more. In certain embodiments, the average diameter of the long-strand PTFE fibrils is 100 μm or less, 50 μm or less, 10 μm or less, or 1 μm or less, as measured by a dimensional analysis test method.In one embodiment, the average diameter of the long-strand PTFE fibrils is from 0.5 μm to 50 μm, preferably from 1 μm to 50 μm, and more preferably from 10 μm to 50 μm, as measured according to the Dimensional Analysis Test Method.

[0039] Long-strand PTFE fibrils are formed from long-strand PTFE resin. In some embodiments, the long-strand PTFE resin has an average resin particle size of 10 μm or more, 25 μm or more, 50 μm or more, 100 μm or more, 200 μm or more, 200 μm or more, and 1000 μm or less, as measured according to the Dimensional Analysis Test Method. When the long-strand PTFE resin is incorporated into a matrix of the present disclosure (e.g., using the methods of the present disclosure), the particles of the long-strand PTFE resin elongate (e.g., fibrillate) to form long-strand PTFE fibrils.

[0040] Some examples of long-strand PTFE fibrils in the matrices of the present disclosure are shown in box 30 of Figure 9. Without wishing to be bound by theory, it is believed that the long-strand PTFE fibrils impart a degree of mechanical rigidity to the matrix, resulting in a membrane-like matrix.

[0041] Without wishing to be bound by theory, it is believed that particles of short-strand PTFE resin and particles of long-strand PTFE resin do not coalesce to form PTFE fibrils. That is, it is believed that particles of long-strand PTFE resin form long-strand PTFE fibrils, and particles of short-strand PTFE resin form short-strand PTFE fibrils. The short-strand PTFE fibrils may be disposed within the long-strand PTFE fibrils, although they are believed to be separate entities.

[0042] The average PTFE fibril diameter, average PTFE fibril length, and average resin particle size may be determined using a variety of methods, including microscopy such as scanning electron microscopy (SEM; see Dimensional Analysis Test Methods) or transmission electron microscopy (TEM).

[0043] In some embodiments, the compositions of the present disclosure comprise 5% or more, 15% or more, 25% or more, 45% or more, 55% or more, 65% or more, or 80% or more by weight of a plurality of PTFE fibrils, calculated by Compositional Analysis Test Method, based on the total weight of the composition. In certain embodiments, the compositions comprise 95% or less, 80% or less, 65% or less, 55% or less, 45% or less, 25% or less, 15% or less, or 5% or less by weight of a plurality of PTFE fibrils, calculated by Compositional Analysis Test Method, based on the total weight of the composition.

[0044] The ratio of short-strand PTFE fibrils to long-strand PTFE fibrils in the composition can vary depending on the desired end use of the composition. The ratio and weight percentage of short-strand PTFE fibrils to long-strand PTFE fibrils in the composition is defined as the mass of short-strand PTFE resin and the mass of long-strand PTFE resin used in forming the matrix. In one embodiment, the weight ratio of short-strand PTFE fibrils to long-strand PTFE fibrils can be 5 parts to 1 part short-strand PTFE fibrils per 0.1 part long-strand PTFE fibrils, and preferably 3 parts to 1 part short-strand PTFE fibrils per 0.1 part long-strand PTFE fibrils.

[0045] In other words, the total amount of PTFE in the matrix (i.e., the sum of short-strand PTFE fibrils and long-strand PTFE fibrils) may include various weight percentages of short-strand PTFE fibrils and long-strand PTFE fibrils. In some embodiments, the composition contains 0.1% or more, 1% or more, 5% or more, 15% or more, 25% or more, 45% or more, 55% or more, 65% or more, or 80% or more short-strand PTFE fibrils by weight, based on the total weight of the composition, as calculated by Compositional Analysis Test Methods. In some embodiments, the composition contains 95% or less, 80% or less, 65% or less, 55% or less, 45% or less, 25% or less, 15% or less, 5% or less, or 1% or less short-strand PTFE fibrils by weight, based on the total weight of the composition, as calculated by Compositional Analysis Test Methods. In some embodiments, the composition contains at least 0.01%, at least 1%, at least 5%, at least 10%, at least 15%, at least 20%, at least 30%, or at least 40% by weight of long-strand PTFE fibrils, calculated by Compositional Analysis Test Method, based on the total weight of the composition. In some embodiments, the composition contains no more than 50%, no more than 40%, no more than 30%, no more than 20%, no more than 15%, no more than 10%, no more than 5%, or no more than 1% by weight of long-strand PTFE fibrils, calculated by Compositional Analysis Test Method, based on the total weight of the composition.

[0046] The PTFE fibrils, or short-strand and long-strand PTFE fibrils, may have various forms of PTFE, such as C3-PTFE, C2-PTFE, C1-PTFE, or any combination thereof. C1-PTFE is a polytetrafluoroethylene polymer containing a -(CF2-C(F)(CF3))- repeating group. C2-PTFE is a polytetrafluoroethylene polymer containing a -(CF2-C(F)(CF2-CF3))- repeating group. C3-PTFE is a polytetrafluoroethylene polymer containing a -(CF2-C(F)(CF2-CF2-CF3))- repeating group. In some cases, it may be desirable to reduce the amount of fluorine in the final composition and / or reduce the amount of fluorine-carbon bonds used in making the PTFE. In some embodiments, the PTFE resin used in forming the PTFE fibrils, and therefore the PTFE fibrils in the matrix, may comprise any combination of C1 short-strand PTFE, C2 short-strand PTFE, C3 short-strand PTFE, C1 long-strand PTFE, C2 long-strand PTFE, or C3 long-strand PTFE.

[0047] Multiple active particles The matrix of the present disclosure includes a plurality of active particles. The physical and / or chemical function of the particles comprising the plurality of active particles may vary based on the intended use of a given matrix or composition including such a matrix. The plurality of active particles may include catalysts, adsorbents (e.g., adsorbents, absorbents, or both), growth seeds, metal-organic frameworks, electroactive materials, or any combination thereof.

[0048] In some embodiments, the plurality of active particles comprises a catalyst. A catalyst is a chemical species that is not consumed but alters the rate of one or more reactions. The matrix may include any suitable catalyst, or combination of catalysts, to promote any desired reaction. In some embodiments, the desired reactions are nitrobenzene reduction, nitrogen oxides (NO x) compound reduction, hydrogenation, or any combination thereof. Catalysts that can remove, suppress, and / or reduce harmful gas emissions into the atmosphere may be of particular interest. For example, a plurality of active particles may be used to remove one or more nitrogen oxides (NO x The catalyst may include a catalyst capable of reducing and / or converting diatomic nitrogen compounds (e.g., nitric oxide, nitrogen dioxide, dinitrogen trioxide, and / or nitrates) to diatomic nitrogen. The catalyst may be grafted onto a support such as an adsorbent (described elsewhere in this application).

[0049] In some embodiments, the catalyst can destroy ozone (O), i.e., the catalyst can convert ozone (O) to oxygen (O) through bond rearrangement. Examples of catalysts capable of ozone destruction include silicates such as iron silicate, iron manganese silicate, zinc iron silicate, or any combination thereof; transition metal oxides such as zinc oxide, manganese oxide, copper oxide, cerium dioxide, or any combination thereof; metals such as reduced metals (i.e., zero-valent metals) including titanium, lead, iron, copper, zinc, chromium, cobalt, nickel, manganese, gold, silver, platinum, palladium, rhodium, tungsten, molybdenum, vanadium, zirconium, silicon, ruthenium, or any combination thereof; carbonates such as barium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, or any combination thereof; zeolites; or any combination thereof. Zeolites are aluminosilicate compounds composed of aluminum, oxygen, silicon, and one or more counterions.

[0050] In certain embodiments, the catalyst can perform hydrogenation and / or cross-coupling reactions. Such chemical transformations can be useful in small molecule synthesis. Examples of catalysts capable of initiating such reactions include platinum, palladium, rhodium, iridium, PdCl, iron, iron oxide, gold, silver, copper, copper oxide, compounds containing these, and any combination thereof.

[0051] In some embodiments, the plurality of active particles comprises a catalyst capable of ozone depletion comprising manganese oxide (e.g., amorphous manganese oxide), copper oxide, or both. Amorphous materials have little or no crystallinity and are contrasted with polymorphic materials. An example of an ozone depletion catalyst comprising amorphous manganese oxide is available from Carus LLC (LaSalle, Illinois) under the trade name CARULITE 400. In certain embodiments, the plurality of active particles comprises a catalyst capable of ozone depletion comprising cerium dioxide. In some embodiments, the plurality of active particles comprises a catalyst capable of ozone depletion comprising manganese oxide, copper oxide, cerium dioxide, or any combination thereof.

[0052] In some embodiments, the active particles include an adsorbent. In certain embodiments, the adsorbent is an adsorbent, an absorbent, or both. Examples of absorbents include cellulose, fumed silica, cotton, natural or synthetic sponge, clay, sodium polyacrylate, sodium alginate, gelatin, and wool.

[0053] In some embodiments, the plurality of active particles comprises an adsorbent, such as a physisorbent, a chemisorbent, a physisorbent-chemisorbent hybrid, or any combination thereof. In some embodiments, the adsorbent is a chemisorbent-physisorbent hybrid. Chemisorbent-physisorbent hybrids include grafted hybrids and impregnated hybrids. Grafted hybrids are chemisorbents grafted onto physisorbents or physisorbents grafted onto chemisorbents. Impregnated hybrids are physisorbents impregnated with chemisorbents or chemisorbents impregnated with physisorbents. Grafted hybrids are characterized as chemisorbents covalently bonded to physisorbents. Impregnated hybrids are characterized as chemisorbents disposed within the pores of a physisorbent. In impregnated hybrids, the chemisorbents are held within the pores via non-covalent interactions (e.g., van der Waals forces). In some embodiments, the grafted or impregnated hybrid comprises one or more of the following: a physisorbent, activated carbon, a zeolite, a silicate, a metal-organic framework (MOF), or a mesoporous transition metal oxide.

[0054] Adsorbents are materials that can adsorb chemicals, i.e., the material can separate chemicals over at least a portion of its surface area. Physisorbents are adsorbents that separate chemicals through the formation of weak interactions (e.g., van der Waals and / or electrostatic forces) between the physisorbent and the adsorbed chemical. Chemisorbents are adsorbents that separate chemicals through the formation of ionic or covalent bonds between the chemisorbent and the adsorbed chemical.

[0055] The identity of the adsorbent will depend, at least in part, on the intended use of the composition. Adsorbents capable of adsorbing basic compounds, acidic compounds, organic compounds, inorganic compounds, or any combination thereof may be included. Such adsorbents may be physisorbents, chemisorbents, or physisorbent-chemisorbent hybrids. The acidic compounds, basic compounds, organic compounds, inorganic compounds, or any combination thereof may be in a liquid state, a gaseous state, and / or a vapor state (preferably), or any combination thereof.

[0056] In certain embodiments, the adsorbent is capable of adsorbing organic compounds in the liquid state, the gaseous state and / or the vapor state (preferably), or both. Organic compounds are compounds that contain at least one carbon-hydrogen covalent bond. Examples of organic compounds that the adsorbent can adsorb include aromatic hydrocarbons such as toluene, benzene, xylene, and ethylbenzene; siloxanes; polycyclic aromatic hydrocarbons, such as the 16 polycyclic aromatic hydrocarbons classified as priority pollutants by the U.S. Environmental Protection Agency in 2005 (i.e., naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo(a)anthracene, chrysene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(a)fluoranthene, dibenzo(a,h)anthracene, benzo(ghi)perylene, and indeno(1,2,3-cd)pyrene); n-alkanes, such as methane, ethane, and n-propane, n-butane, n-pentane, and n-hexane; n-alkenes, such as methylene, ethylene, and propylene; various alcohols; aldehydes, such as formaldehyde; siloxanes; or any combination thereof. Examples of adsorbents capable of adsorbing organic compounds include activated carbon, zeolites (e.g., zeolite X, zeolite A, zeolite Y, zeolite beta, and zeolite ZSM-5), silicates, metal-organic frameworks (MOFs), mesoporous transition metal oxides, or any combination thereof.

[0057] In some embodiments, the sorbent can adsorb inorganic compounds in a liquid state, a gaseous state, and / or a vapor state (preferably), or both. An inorganic compound is a compound that does not contain at least one carbon-hydrogen bond. Examples of inorganic compounds that the sorbent can adsorb include carbon dioxide, carbon monoxide, hydrogen sulfide, water, perfluorocarbons such as tetrafluoromethane and hexafluoroethane, nitrogen oxides, sulfur oxides, sulfur hexafluoride, ozone, and any combination thereof. Examples of sorbents that can adsorb one or more inorganic compounds include activated carbon, zeolites (e.g., zeolite X, zeolite A, zeolite Y, zeolite beta, and zeolite ZsM-5), silicates, metal-organic frameworks (MOFs), mesoporous transition metal oxides, or any combination thereof. Zeolite physisorbents are one example of an sorbent that can adsorb ozone.

[0058] In certain embodiments, the sorbent is capable of adsorbing acidic compounds in a liquid state, a gaseous state and / or a vapor state (preferably), or both. An acidic compound is a compound that, when mixed with water at a pH of 7, acidifies the water such that the pH of the resulting solution is less than 7. The acidic compound may be an organic or inorganic compound. Examples of acidic compounds that the sorbent can adsorb include sulfur dioxide, nitrogen dioxide, hydrogen sulfide, sulfur trioxide, nitric oxide, or any combination thereof. Examples of adsorbents capable of adsorbing acidic compounds include chemisorbents, including carbonates of Group I metals (Li, Na, K, Rb, Cs, Fr); metal oxides; Group I (Li, Na, K, Rb, Cs, Fr) metal hydroxides; Group II metal (Be, Mg, Ca, Sr, Ba, Ra) hydroxides; Group II metal (Be, Mg, Ca, Sr, Ba, Ra) oxides; N-containing compounds such as amines (e.g., tetraethylenepentamine, ethylenediamine, 3-aminopropyltriethoxysilane), imines (e.g., polyethyleneimine), ammonium salts (e.g., ammonium persulfate); or any combination thereof. In certain embodiments, the selected chemisorbent may be grafted onto or impregnated within a physisorbent (e.g., activated carbon; zeolite; silicate; or any combination thereof).

[0059] In certain embodiments, the sorbent can adsorb basic compounds in a liquid state, a gaseous state, and / or a vapor state (preferably), or both. A basic compound is a compound that, when mixed with water at pH 7, renders the water basic such that the pH of the resulting solution is greater than 7. The basic compound can be an inorganic or organic compound. Examples of basic compounds that the sorbent can adsorb include ammonia, nitrogen trifluoride, and the like. Examples of sorbents that can adsorb basic compounds include physisorbents, such as activated carbon, zeolites, silicates, or any combination thereof. Another example of an sorbent that can adsorb basic compounds includes chemisorbents with carboxylic acid (COOH) functional groups. Examples of chemisorbent compounds with carboxylic acid functional groups include citric acid, terephthalic acid, trimesic acid, tartaric acid, maleic acid, benzoic acid, oxalic acid, or any combination thereof. Chemisorbents capable of adsorbing basic compounds include inorganic acids such as boric acid, nitric acid, sulfuric acid, hydrochloric acid, hydrogen chloride, hydrogen fluoride, hydrogen bromide, phosphoric acid, perchloric acid, periodic acid, and any combination thereof. Such chemisorbents may be grafted onto or impregnated within a physisorbent such as activated carbon, zeolite, silicate, or any combination thereof.

[0060] In some embodiments, the plurality of active particles comprises a metal-organic framework (MOF). A metal-organic framework (MOF) is a compound comprising clusters of metal ions coordinated to organic ligands that form a two- or three-dimensional structure. MOFs can be adsorbents (e.g., physisorbents, chemisorbents, or both), catalysts, or both. Examples of MOF adsorbents include copper benzene-1,3,5-tricarboxylic acid (C, also known as HKUST-1, Cu-BTC MOF, or MOF-199). 18 H6Cu3O 12available from NOVOMOF, Sofingen, Aargau, Switzerland; zirconium 1,4-dicarboxyene MOF (Zr6O4(OH)4(dicarboxylate)6), also known as UiO-66; available from NOVOMOF, Switzerland; zirconium 4,4'-biphenyldicarboxylic acid MOF (Zr6O4(OH)4(4,4'-biphenyldicarboxylic acid)6), also known as UiO-67; available from NOVOMOF, Switzerland; or any combination thereof.

[0061] In certain embodiments, the plurality of active particles includes growth seeds. The growth seeds may serve as nucleation points for compounds such as metal-organic frameworks (MOFs). In some such embodiments, the growth seeds include copper nitrate as growth seeds for copper-based MOFs, such as copper benzene-1,3,5-tricarboxylate. In certain embodiments, the growth seeds include trimesic acid as growth seeds for copper-based MOFs, such as copper benzene-1,3,5-tricarboxylate. The growth seeds may be reacted with one or more additional chemicals before, during, or after matrix formation to form the MOF.

[0062] In certain embodiments, the active particles comprise an electroactive material. In some embodiments, the electroactive material comprises lithium. In some embodiments, the electroactive material comprises lithium and one or more metals. Examples of cathode active electroactive materials include LiCoO, LiFePO, LiMnO, LiNiO, Li(Ni x Mn y Co z )O2, and Li(Ni x Al y Co z )O2, where x+y+z=1. In some embodiments, the cathode electroactive material is LiCoO2. In some embodiments, the cathode electroactive material is LiNiO2.

[0063] In some embodiments, the electroactive material is an anode active compound species. Examples of anode electroactive materials include Co3O4, Cu2O, Li4Ti5O 12 Examples of anode electroactive species include lithium titanate (lithium titanate), SiO2, Fe2O3, Al3Ni, CuCo2O4, PdNiBi, TiO, Sn4P3, NiO, carbides thereof, and any combination thereof. Examples of metal anode materials include Li metal, alkaline earth metals such as Mg or Ca, and Si-based compounds. Si-based compounds may be in the form of Si fibers. Other examples of anode electroactive species include LiAl alloys, LiSi alloys, LiBi alloys, LiCd alloys, AlMg alloys, LiMg alloys, LiSn alloys, LiSb alloys, FeSn alloys, SnSb alloys, SnCu alloys, LiGe alloys, LiPb alloys, oxides thereof, sulfides thereof, phosphides thereof, carbides thereof, nitrides thereof, and any combination thereof. The molecular formula of the anode electroactive material may not reflect an empirical formula. Additional examples of anode electroactive species include nitrides, oxides, and carbides of metal or metalloid elements, including Li, Co, Pd, Pt, W, Mo, Zr, Fe, Al, Ni, Ti, Sn, or any combination thereof. In some embodiments, the anode electroactive material is silicon. In some embodiments, the electroactive material is silicon, and the silicon is a silicon fiber construction. In some embodiments, the anode electroactive material is Li4Ti5O 12 is.

[0064] Each particle of the plurality of active particles has a particle size. The particle size is the maximum distance across the particle. The average particle size of the plurality of active particles may vary based on the intended use of the composition and / or the chemical or physical properties of the active particles. The plurality of active particles may have an average particle size of 0.001 μm or more, 0.01 μm or more, 0.1 μm or more, 1 μm or more, 5 μm or more, 10 μm or more, or 100 μm or more, as measured by dimensional analysis testing. The plurality of active particles may have an average particle size of 500 μm or less, 100 μm or less, 10 μm or less, or 1 μm or less, as measured by dimensional analysis testing.

[0065] Generally, smaller particle sizes are preferred for catalyst-containing particles because they provide greater surface area and a higher density of active sites available for catalytic reactions. Thus, in some embodiments where the plurality of active particles comprises a catalyst, the average particle size of the plurality of active particles is 0.001 μm to 5 μm, 0.001 μm to 1 μm, or 0.001 μm to 0.1 μm, as measured by dimensional analysis testing. Generally, active particles comprising an adsorbent having a small particle size are preferred because smaller particle sizes allow for greater surface area and greater diffusion. In some embodiments, when the plurality of active particles comprises an adsorbent, the average particle size of the particles in the plurality of active particles is 0.001 μm to 100 μm, 1 μm to 100 μm, or 0.001 μm to 0.1 μm, as measured by dimensional analysis testing.

[0066] The compositions and / or matrices of the present disclosure may have various amounts of active particles. The weight percent of the active particles (or any individual components of the active particles) in the composition and / or matrix may be calculated according to the Compositional Analysis Test Method.

[0067] The sum of the weight percents for each component of an active particle is considered to be the weight percent of the active particle including the components of the active particle. For example, if an active particle includes activated carbon, the amount of activated carbon is the weight percent of the active particle including activated carbon. If an active particle includes manganese oxide and copper oxide, the weight percent of the active particle including manganese oxide and copper oxide is the sum of the weight percent of manganese oxide and the weight percent of copper oxide.

[0068] The total active particle amount is the sum of the weight percent of one or more components comprising the active particles in the composition and / or matrix. For example, in an embodiment in which the active particles include manganese oxide and copper oxide, the weight percent of the total active particles in the matrix is ​​the sum of the weight percent of the manganese oxide and the weight percent of the copper oxide. In some embodiments, the weight percent of the total active particles in the composition and / or matrix, as determined by the Composition Analysis Test Method, is 50% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more of the composition and / or matrix. In some embodiments, the weight percent of the total active particles in the composition and / or matrix, as determined by the Composition Analysis Test Method, is 95% by weight or less, 90% by weight or less, 80% by weight or less, or 70% by weight or less of the composition and / or matrix. In other words, in some embodiments, the composition and / or matrix contains 50% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more of the active particles, as determined by the Composition Analysis Test Method. In certain embodiments, the composition and / or matrix comprises 95% or less, 90% or less, 80% or less, or 70% or less by weight of active particles, based on the weight of the composition and / or matrix, according to the Composition Analysis Test Method.

[0069] In some applications of the composition and / or matrix, a low amount of active particles in the composition and / or matrix can be beneficial. In some embodiments, the weight percent of total active particles in the composition and / or matrix is ​​0% by weight or more, 0.001% by weight or more, 0.01% by weight or more, 0.1% by weight or more, 1% by weight or more, 2% by weight or more, 3% by weight or more, 4% by weight or more, 5% by weight or more, 10% by weight or more, or 15% by weight or more, based on the weight of the composition and / or matrix, as determined by the Composition Analysis Test Method. In some embodiments, the weight percent of total active particles in the composition and / or matrix is ​​less than 20% by weight, 15% by weight or less, 10% by weight or less, 5% by weight or less, 4% by weight or less, 3% by weight or less, 2% by weight or less, 1% by weight or less, 0.1% by weight or less, 0.01% by weight or less, or 0.001% by weight or less, based on the weight of the composition and / or matrix, as determined by the Composition Analysis Test Method. In other words, in some embodiments, the composition and / or matrix comprises at least 0%, at least 0.001%, at least 0.01%, at least 0.1%, at least 1%, at least 2%, at least 3%, at least 4%, at least 5%, at least 10%, or at least 15% by weight of active particles, based on the weight of the composition and / or matrix, as determined by the Composition Analysis Test Method. In some embodiments, the composition and / or matrix comprises no more than 20%, no more than 15%, no more than 10%, no more than 5%, no more than 4%, no more than 3%, no more than 2%, no more than 1%, no more than 0.1%, no more than 0.01%, or no more than 0.001% by weight of active particles, based on the weight of the composition and / or matrix, as determined by the Composition Analysis Test Method.

[0070] Matrix The composition of the present disclosure includes a matrix. The matrix includes a plurality of PTFE fibrils and a plurality of active particles. In some embodiments, the plurality of PTFE fibrils includes short-strand PTFE fibrils and long-strand PTFE fibrils. The plurality of PTFE fibrils may have any chemical and / or physical properties described herein. The plurality of active particles may have any chemical and / or physical properties described herein.

[0071] FIG. 1 shows a schematic diagram of a matrix according to an embodiment of the present disclosure. The matrix 10 includes long-strand PTFE fibrils 20, short-strand PTFE fibrils 30, and a plurality of active particles 40. As described elsewhere herein, the long-strand PTFE fibrils 30 are longer and wider than the short-strand PTFE fibrils 30. When a composition according to the present disclosure is imaged at relatively low magnification (e.g., ×370; see FIG. 8), the long-strand PTFE fibrils can be observed. For example, in the SEM image of a matrix consistent with the present disclosure in FIG. 8 (Box 21), some of the long-strand PTFE fibrils are visible. The constituent fibrils that make up the long-strand PTFE fibrils are visible (Box 21). In the same figure, disordered short-strand PTFE fibrils, distinct from the long-strand PTFE fibrils, are also visible (Boxes 31a, 31b, and 31c). As described elsewhere herein, one or more short-strand PTFE fibrils may be disposed within a long-strand PTFE fibril 32 (e.g., FIG. 1). However, the short-strand PTFE fibrils and the long-strand PTFE fibrils are distinct entities. Thus, the short-strand PTFE fibrils disposed within a long-strand PTFE fibril are distinct from the plurality of constituent fibrils 22 (FIG. 2B) that make up the long-strand PTFE fibril. As described elsewhere herein, the constituent fibrils of a long-strand PTFE fibril are longer than the short-strand PTFE fibrils.

[0072] As shown in box 50 in FIG. 1, when imaged at relatively high magnifications (e.g., ×9000; ×7000; ×11000; ×20000), the multiple small-strand PTFE fibrils have a largely disordered configuration, i.e., the fibrils extend in different directions (e.g., x, y, and z directions). This phenomenon is clearly visible in the SEM image of a matrix consistent with the present disclosure in FIG. 7. A composition containing only short-strand PTFE fibrils does not contain two distinct populations of PTFE fibrils (i.e., short-strand PTFE fibrils and long-strand PTFE fibrils). As discussed, a composition having a single population of PTFE fibrils (e.g., short-strand PTFE fibrils) and a composition having two populations of PTFE fibrils (e.g., short-strand PTFE fibrils and long-strand PTFE fibrils) can be distinguished using microscopy (e.g., scanning electron microscopy).

[0073] A plurality of active particles are distributed throughout the matrix and contact and / or interact with long-strand PTFE fibrils 20, short-strand PTFE fibrils 30, or both (FIG. 1). Active particles that interact with other active particles, long-strand PTFE fibrils 20, short-strand PTFE fibrils 30, or combinations thereof are physically and / or chemically immobilized in the matrix. That is, the term "interaction" refers to physical forces (e.g., frictional forces, gravity, compression forces, tension forces, electrical forces, magnetic forces, spring forces, applied forces, and normal forces) or chemical forces (e.g., van der Waals forces, Debey forces, Keesom forces, London dispersion forces, dipole-dipole forces, hydrogen bonding) between two or more active particles, an active particle and a short-strand PTFE fibril (or multiple short-strand PTFE fibrils), an active particle and a long-strand PTFE fibril (or multiple long-strand PTFE fibrils), or combinations thereof.

[0074] The plurality of active particles may have one or more configurations in which they interact with short-strand PTFE fibrils, long-strand PTFE fibrils, or both. In some embodiments, when the composition is not stretched, at least a portion of the plurality of active particles and at least a portion of the plurality of PTFE fibrils adopt a catenated structure, an aggregated structure, or both. In some embodiments, when the composition is not stretched, at least a portion of the plurality of active particles form a catenated structure around one or more short-strand PTFE fibrils, one or more long-strand PTFE fibrils, or both, and at least a portion of the plurality of active particles form an aggregated structure with one or more short-strand PTFE fibrils, one or more long-strand PTFE fibrils, or both, or any combination thereof.

[0075] The terms "catenated structure" and "catenation structure" are used interchangeably to refer to a self-supporting network of active particles that at least partially surround one or more PTFE fibrils. FIG. 3A is a schematic diagram of a catenated structure 80. In a catenated structure, a plurality of active particles 40 form a self-supporting network that at least partially surrounds one or more PTFE fibrils (e.g., one or more long-strand PTFE fibrils, one or more short-strand PTFE fibrils, or both). While the self-supporting network may contact and / or interact with one or more PTFE fibrils that at least partially surround it, the primary interaction that holds the catenated structure together is the physical interaction between adjacent particles. Without wishing to be bound by theory, it is believed that if at least partially surrounded (or completely surrounded) PTFE fibrils can be removed, the self-supporting network of particles remains undisturbed. The individual active particles within the catenated structure may not be clearly defined, as the active particles may coalesce with one another to form a self-supporting network.

[0076] The self-supporting network of active particles can encapsulate a portion of a single PTFE fibril, a portion of multiple PTFE fibrils, an entire PTFE fibril, or an entire plurality of PTFE fibrils in the catenated structure. The self-supporting network of active particles may encapsulate at least a portion of one or more short-strand PTFE fibrils, at least a portion of one or more long-strand PTFE fibrils, or both in the catenated structure. In general, the catenated structure is considered to primarily comprise the encapsulation of at least a portion of one or more short-strand PTFE fibrils.

[0077] Figures 9 and 10 are SEM images of compositions corresponding to embodiments of the present disclosure. They clearly show catenated structures, as highlighted in boxes 71, 72, and 73. In these images, the particles form a self-supporting network or "beaded" structure surrounding one or more PTFE fibrils (e.g., one or more PTFE fibrils are strings, and the particle's self-supporting network is a bead). The extent of the catenated structure in box 71 is such that one or more PTFE fibrils are not discernible (e.g., the PTFE fibrils are completely covered by the catenated structure). Meanwhile, in the catenated structures shown in boxes 72 and 73, some of the PTFE fibrils contained in the catenated structure are encapsulated within the self-supporting network of the active particle. For example, the catenated structure has gaps where individual PTFE fibrils can be observed (indicated by * in Figure 10).

[0078] Without wishing to be bound by theory, it is believed that the catenated structure may reduce the likelihood of particle shedding from a composition (e.g., during processing and / or general handling of the matrix or matrix-containing composition). Furthermore, it is believed that particles adopting the catenated structure may have a large exposed surface area due to their spacing and number of exposed faces. This property may enhance their activity as catalysts, adsorbents, growth seeds, MOFs, or any combination thereof.

[0079] The terms "agglomerated structure" and "agglomerated structure" are used interchangeably to refer to active particles or agglomerates of active particles held together at least in part by one or more PTFE fibrils (e.g., short-strand PTFE fibrils or long-strand PTFE fibrils). In contrast to catenated structures, the particles in agglomerated structures typically do not form a self-supporting network independent of the PTFE fibrils. In agglomerated structures, the active particles or agglomerates of active particles are held in place through interactions with one or more PTFE fibrils (e.g., short-strand PTFE fibrils) that extend through (e.g., penetrate) the particles or agglomerates. Active particle agglomerates are clusters of two or more active particles, with each active particle interacting with at least one other active particle in the cluster. In agglomerated structures containing agglomerates, the agglomerates are held together both through interactions between the active particles and between the active particles and the PTFE fibrils. In contrast to catenated structures, the active particles in agglomerated structures are typically well-defined.

[0080] 3B is a schematic diagram of two agglomerated structures 70 and 71 corresponding to embodiments of the present disclosure. Agglomerated structure 70 is a PTFE fibril from a plurality of PTFE fibrils 20 / 30 (either short-strand PTFE fibrils or long-strand PTFE fibrils) extending through (i.e., interacting with) a single active particle from a plurality of active particles 40. Agglomerated structure 71 is a few PTFE fibrils from a plurality of PTFE fibrils 20 / 30 that are intertwined (i.e., interacting with) the agglomerate comprising a plurality of active particles 40.

[0081] 7 is an SEM image of a composition according to an embodiment of the present disclosure. This figure shows various agglomerated structures, as highlighted in boxes 81, 82, 83, and 84. Boxes 81, 82, and 83 show agglomerated structures with multiple short-strand PTFE fibrils extending through an agglomerate of active particles. Box 84 shows agglomerated structures with multiple short-strand PTFE fibrils extending through a single active particle.

[0082] Without wishing to be bound by theory, it is believed that the agglomerated structure may impart some mechanical stability to at least a portion of the plurality of active particles, at least a portion of the plurality of PTFE fibrils (e.g., long-strand PTFE fibrils, short-strand PTFE fibrils, or both). For example, it is believed that the agglomerated structure at least partially inhibits one or more PTFE fibrils involved in the agglomerated structure from shrinking (i.e., decreasing in length). It is also believed that the agglomerated structure reduces the likelihood of particle shedding due to the strength imparted by the PTFE fibrils with which the particles of the agglomerated structure interact.

[0083] composition The present disclosure provides a composition comprising a matrix of the present disclosure. The matrix may be any matrix and / or may have any of the properties described herein.

[0084] In some embodiments, the composition may include one or more additives. The additives may function to enhance the processability of the composition. For example, the additives may increase the mechanical hardness of the composition before and / or after processing, increase the retention of the solvent mixture during processing of the composition, improve the rheology and shape retention of the composition during processing, or any combination thereof. Examples of additives include binders such as kaolinite, bentonite, silicon carbide, fumed silica, zeolite, or any combination thereof. Other exemplary additives include polymers and biopolymers such as poly(vinyl) alcohol (PVA), gelatin, methylcellulose, ethylcellulose, pectin, polyethylene glycol, sodium alginate, agar, xanthan gum, additional PTFE already in fibrous form, or any combination thereof. The inclusion of binders may be advantageous in that they are included in compositions that can be used to form honeycomb structures. In some embodiments, the composition includes one or more additives, and the total mass of the composition comprises at least 0.1 wt. %, at least 1 wt. %, or at least 15 wt. % of the additive, based on the total weight of the composition. In some embodiments in which the composition includes one or more additives, the total mass of the composition comprises no more than 20 wt. %, no more than 15 wt. %, or no more than 1 wt. % of the additives, based on the total weight of the composition.

[0085] The composition may have localized porosity in the unstretched state. Localized porosity is the porosity between aggregated and / or catenated structures, as determined by analyzing one or more scanning electron micrographs. In some embodiments, when unstretched, the composition has a localized porosity of at least 10%, at least 20%, or at least 30%, as measured according to the Dimensional Analysis Test Method. In some embodiments, when unstretched, the composition has a localized porosity of 20% or less, 30% or less, 40% or less, or 50% or less, as measured according to the Dimensional Analysis Test Method.

[0086] In some embodiments, the composition is processable. As used herein, the term "processable" refers to a material that can be shape-engineered, i.e., formed into a desired two- or three-dimensional shape. Typically, a processable material has at least one, but not all, of the following properties: i) a well-dispersed phase and / or uniform dispersion of particles before shape processing; ii) flexible and mechanically robust; iii) not hydrophobic when subjected to pressure (e.g., extrusion); iv) shape-retaining after structuring; v) capable of retaining sufficient solvent for shaping but not enough to leach said solvent; and vi) mechanically robust after consolidation (e.g., minimal particle shedding, no visible macrocracks, minimal to no microcracks).

[0087] In some embodiments, the composition is processable without contact with processing aids, such as fluorinated processing aids (e.g., fluorinated lubricants). In some embodiments, the composition is processable without screening to form a powder prior to shape engineering. In some embodiments, the composition is processable without the addition of solvent; i.e., the composition is processable solely with solvent retained during the process of making the composition. In some embodiments, the composition is a processable putty that can be directly shaped.

[0088] In certain embodiments, in contrast to many matrices having a single type of PTFE fibrils (e.g., short-strand PTFE fibrils), the matrices of the present disclosure containing both short-strand PTFE fibrils and long-strand PTFE fibrils are significantly more processable, eliminating the need to form a powder prior to shape engineering or the use of processing aids (e.g., fluorinated lubricants and / or solvents) during shape engineering. A processing aid (e.g., extrusion aid) is a material that is contacted with the composition to facilitate shape engineering. One example of a processing aid is a lubricant. A lubricant is a substance that reduces friction between two materials that contact each other.

[0089] In some embodiments, the composition may be cast into a membrane. Such membranes may be further shape-engineered, for example, into a web structure, tape, or nanofiber network. A membrane is a flexible sheet of material suitable for shape engineering. A membrane may be produced by casting the components of the composition into a mold. In certain embodiments, the composition may be shaped into a web structure. A web structure is an expanded form of the composition having uniform pore size and porosity. Web structures are typically formed by expanding a processable composition in one or more directions, for example, by tentering. Such expansion results in the formation of nodes, i.e., locations where multiple fibrils join together at multiple locations into catenated and / or aggregated structures.

[0090] In some embodiments, the web structure is embodied as a tape. As used herein, the term "tape" refers to a stretched film having increased porosity compared to the composition prior to stretching. As known in the art, tapes can be formed by extrusion and / or calendaring followed by expansion in one or more directions (e.g., tentering).

[0091] In certain embodiments, the composition may be shape-engineered into a network of nanofibers. The nanofibers comprise a plurality of PTFE fibrils (e.g., short-strand PTFE fibrils, long-strand PTFE fibrils, or both) and a plurality of active particles. Such a network may be formed by electrospinning the composition. In some such embodiments, the composition may be electrospun with a stabilizer such as low-strength gelatin, collagen, polylactic acid, polyurethane, poly(vinyl) alcohol, nylon, or any combination thereof. Following electrospinning, the stabilizer is removed (e.g., by baking) to form a network of nanofibers. The shape-engineered network of nanofibers may be applied to a substrate.

[0092] In some embodiments, the composition is shaped into a composite structure, such as a honeycomb structure. A "honeycomb structure" refers to a structure with parallel channels that are isolated from one another. Honeycomb structures may be formed by hydraulic or screw extrusion techniques, as well as 3D printing. Extrusion is the compression of a material by forcing it through a constricted opening, removing at least a portion of the excess air from the material, so that the exit cross-sectional area is smaller than the entrance cross-sectional area. In extrusion techniques, the composition is forced through a pre-machined die with a set number of cells per specific cross-sectional area. Hydraulic extrusion involves applying overhead force from a piston to move the composition and force the extrudate through a die. Screw extrusion uses a similar mechanism, but the movement of the composition is driven by feeding the composition through a hopper on a rotating threaded shaft before forcing the material through the desired die. 3D printing uses a similar mechanism to extrusion in that overhead pressure is applied to the composition, forcing it through a nozzle tip of a specific diameter, but instead of pre-machining the geometric features into the extrusion die, the pattern is generated virtually using computer-aided design software.

[0093] In some embodiments, extrusion aids are used to facilitate extrusion or 3D printing of the composition. Hydrocarbon extrusion aids are materials that can facilitate the extrusion process and result in a uniform product. Examples of hydrocarbon extrusion aids include mineral spirits, naphtha, and ISOPAR-K (available from ExxonMobil, Iriving, Texas).

[0094] In some embodiments, the composition may include a binder to facilitate shape processing. In such embodiments, the composition and structures produced from shape engineering of the composition may include 0.1% by weight or more, 1% by weight or more, or 3% by weight or more of a binder. In some embodiments, the composition and structures produced from shape engineering of the composition include 15% by weight or less, 10% by weight or less, or 3% by weight or less of a binder. The binder may be any binder as described elsewhere in this application.

[0095] Substrates and Structures The present disclosure provides structures formed from the compositions of the present disclosure, and substrates having the compositions disposed thereon. Such structures or substrates may be further processed into various materials, such as filter media, membranes, or reactive surfaces, for the coordination of secondary materials. The materials may also be included in filters, used as catalytic media for various chemical syntheses in petrochemical or pharmaceutical applications, as air intake filters in engine air systems, or function as destruction catalysts for the chemical protection of membrane materials.

[0096] Structures formed from the compositions are disclosed, including web structures, tapes, honeycomb structures, cast films, putties, and nanofiber networks as described elsewhere herein.

[0097] In some embodiments where the active particles comprise a catalyst, the composition may be configured into a honeycomb structure. A honeycomb structure may be a preferred structure when the active particles comprise a catalyst because long channels create turbulence, which can enhance contact between the particles and chemicals along the channel walls, potentially enhancing catalytic activity. In certain embodiments where the composition is configured into a honeycomb structure, the composition may include a binder. In such embodiments, the composition used to fabricate the honeycomb structure, and thus the honeycomb structure itself, may include 0.1% by weight or more, 1% by weight or more, or 3% by weight or more of binder. In some embodiments, the honeycomb structure may include 15% by weight or less, 10% by weight or less, or 3% by weight or less of binder. The composition used to form the honeycomb structure, and thus the honeycomb structure itself, may include any suitable binder, as disclosed elsewhere herein.

[0098] In some embodiments where the plurality of active particles comprises an adsorbent, the composition may be formed into a nanofiber web structure or network. The web structure or nanofiber network may be further processed and / or may include other materials. For example, the nanofiber web structure or network may be contained in or formed into a filter medium.

[0099] Disclosed is a substrate having one or more compositions and / or structures formed thereon from the compositions of the present disclosure. In some embodiments, the structures formed from the compositions of the present disclosure are disposed on the substrate. For example, a nanofiber web structure or network can be disposed on the substrate.

[0100] As used herein, the terms "disposed on" and "disposed on" refer to a composition in contact with at least a portion of the outer surface of a substrate. The composition may be attached to at least a portion of the outer surface of the substrate. The "outer surface" of a substrate is the surface that directly interacts with the surrounding environment. The outer surface may be rough or smooth.

[0101] The substrate may be made of any suitable material, including non-porous materials. In the embodiment where the substrate is non-porous, the composition is disposed on at least a portion of the outer surface. Examples of suitable non-porous substrates include corrugated honeycomb, such as corrugated steel honeycomb and corrugated aluminum honeycomb; non-porous polyurethane; polyethylene honeycomb; silicon carbide honeycomb; cordierite honeycomb; or any combination thereof. method A method for making a composition comprising a matrix is ​​disclosed. Also disclosed is a method for disposing the composition on a substrate. The matrix comprises a plurality of PTFE fibrils formed from a PTFE resin and a plurality of active particles. The plurality of PTFE fibrils may comprise any PTFE composition and have any of the properties described herein. In some embodiments, the plurality of PTFE fibrils are a single type of fibrils; i.e., the plurality of PTFE fibrils are formed from a single type of PTFE resin (e.g., short-strand PTFE fibrils formed from a short-strand PTFE resin, or long-strand PTFE fibrils formed from a long-strand PTFE resin). In some embodiments, the plurality of PTFE fibrils include short-strand PTFE fibrils and long-strand PTFE fibrils (i.e., the short-strand PTFE fibrils are formed from a short-strand PTFE resin, and the long-strand PTFE fibrils are formed from a long-strand PTFE resin). The plurality of active particles may include any particle and may have any of the characteristics described herein (e.g., catalyst, adsorbent, metal-organic framework, and / or growth seed). In some embodiments, the composition may be any composition and may have any of the characteristics described herein.

[0102] Figures 4, 5, and 6 are flow diagrams illustrating exemplary method aspects disclosed herein. The steps may be performed in any order. In some embodiments, multiple steps may be performed simultaneously. Steps indicated by dashed boxes are optional. Each optional step may be performed in a manner that includes none, one, or more of the optional additional steps (if multiple optional steps are included). For example, the first optional step may be performed in conjunction with one or more additional optional steps, or may not be performed in conjunction with any additional optional steps. The flow diagrams also include boxes that relate to components that make up various compositions in the method (e.g., concentrated matrix premix, matrix premix, emulsion, aerated emulsion, matrix premix, (aerated) matrix premix, hydrated solid, etc.). Such boxes have element designations indicated by a "c." It is understood that elements included in a step are also included in any downstream steps, except for the drying step. For example, the dispersant contained in the first step may be contained in the second step, the third step, etc. (including any step) until the drying step is completed, in which case the dispersant may be at least partially removed during the drying step.

[0103] 4 is a flow diagram illustrating a first exemplary method 200 for producing a composition comprising a matrix. The matrix comprises a plurality of active particles and a plurality of PTFE fibrils formed from a PTFE resin (i.e., resin particles of the PTFE resin).

[0104] The method 200 includes, at step 210, aerating the emulsion to form an aerated emulsion. An aerated emulsion, mixture, or suspension is characterized by the presence of air bubbles and / or air pockets. For example, an aerated emulsion may be characterized by having air bubbles on the surface. Aeration may be performed using various techniques, such as mechanical vibration, gas injection, bottom-up bubbling, or any combination thereof.

[0105] The emulsion (210c) includes a PTFE resin, a dispersant, and a surfactant. The surfactant may be any surfactant described elsewhere herein. The dispersant may be any dispersant described elsewhere herein. The aerated emulsion (210c) includes a PTFE resin, a dispersant, and a surfactant.

[0106] In some embodiments, method 200 further includes forming an emulsion by diluting the concentrated mixture to form an emulsion (not shown in FIG. 4). The concentrated mixture includes a PTFE resin and a dispersant. In some embodiments, the concentrated mixture includes at least a portion of a surfactant. In some embodiments, the concentrated mixture includes 60% by weight of the PTFE resin (e.g., 60% by weight of short-strand PTFE resin), based on the total weight of the concentrated mixture. In some embodiments, the concentrated mixture is diluted with a dispersant. In some embodiments, the concentrated mixture is diluted with a solution including a dispersant and a surfactant. The surfactant may be the same surfactant as in the emulsion or may be a different surfactant.

[0107] The first exemplary method 200 includes, at step 220, adding a solid particle composition to the aerated emulsion to form a matrix premix. The matrix premix (220c) includes a PTFE resin, a surfactant, a solid particle composition, and a dispersant. The solid particle composition includes solid particles. In some embodiments, the solid particle composition includes 100% solid particles by weight (i.e., the solid particle composition includes no other components). In some embodiments, the solid particle composition includes solid particles and a liquid carrier. The liquid carrier may include methanol, ethanol, isopropanol, acetone, dimethylformamide, dichloromethane, toluene, ethyl acetate, acetonitrile, dioxane, petroleum ether, dimethyl sulfoxide, tetrahydrofuran, or any combination thereof. In some such embodiments, the solid particles in the solid particle composition are dissolved in the liquid carrier. In other embodiments, the solid particles of the solid particle composition are suspended in the liquid carrier. In still other embodiments, a first portion of the solid particles are dissolved in the liquid carrier and a second portion of the solid particles are suspended in the liquid carrier.

[0108] The plurality of active particles comprises at least a portion of the solid particles. In some embodiments, the solid particles may already be in the form of a plurality of active particles. In some embodiments, the solid particles are not in the form of a plurality of active particles. In some such embodiments, at least a portion of the solid particles become the plurality of active particles through solid particle aggregation and / or precipitation.

[0109] The amount of solid particles (in the solid particle composition) can vary depending on the type of solid particles and the desired end use of the composition. In some embodiments, the aerated matrix premix contains at least 0.5 wt.%, at least 10 wt.%, or at least 30 wt.%, of solid particles, based on the total weight of the aerated matrix premix. In some embodiments, the aerated matrix premix contains no more than 50 wt.%, no more than 30 wt.%, or no more than 10 wt.%, of solid particles, based on the total weight of the aerated matrix premix. In some embodiments, the solid particles include potassium carbonate, activated carbon, or both.

[0110] The first exemplary method 200 includes aerating the matrix premix to form an aerated matrix premix at step 230. Aeration may be achieved by any means described elsewhere herein. The aerated matrix premix (230c) includes a PTFE resin, a dispersant, a surfactant, and a solid particle composition.

[0111] The first exemplary method 200 includes, in step 240(A), mixing the aerated matrix premix to form a hydrated solid. The hydrated solid (240c) includes a plurality of PTFE fibrils, a plurality of active particles, at least a portion of the dispersing agent, and at least a portion of the surfactant. The plurality of active particles includes at least a portion of the solid particles. Mixing may be performed via various methods, including mechanical rotation (e.g., on a rotating table), mechanical stirring, immersion mixing, vibrational stirring, ultrasonic stirring, or any combination thereof. In some embodiments, it is desirable to use a shear-free mixing method. Using a shear-free mixing method can reduce fibrillation of the PTFE fibrils, thereby imparting more processable properties to the composition. Mixing allows for fibrillation (stretching) of the PTFE resin into PTFE fibrils and emulsification of the PTFE resin. The mixing also homogenizes the active particles within the aerated matrix premix, allowing for the formation of catenated and / or agglomerated structures with and / or fibrillating PTFE fibrils.

[0112] The mixing time may vary depending on the desired use of the composition and / or the identity and / or amount of each component (e.g., PTFE resin, surfactant, solid particles, and / or any additives) in the aerated matrix premix. The mixing time may be 10 minutes or more, 1 hour or more, 3 hours or more, or 24 hours or more. The mixing time may be 48 hours or less, 24 hours or less, 3 hours or less, or 1 hour or less. In some embodiments, the mixing time is 10 minutes to 3 hours, 1 hour to 3 hours, 1 hour to 24 hours, or 3 hours to 24 hours.

[0113] The first exemplary method 200 includes, in step 250, drying the hydrated solids to form a matrix. Drying the hydrated solids includes removing at least a portion of the dispersant and at least a portion of the surfactant from the hydrated solids. Drying may be accomplished to various degrees (i.e., after drying the hydrated solids, some amount of dispersant, liquid carrier, and / or surfactant may be present in the matrix) and includes various techniques as described herein (e.g., see the discussion of FIG. 6).

[0114] Using the first exemplary method 200, a composition may be disposed on a substrate (e.g., a non-porous substrate) including at least one exterior surface (i.e., exterior surface 260c). In such a case, method 200 further includes, in step 260, contacting at least a portion of the substrate with an aerated matrix pre-mix. The contacting step may include immersing at least a portion of the substrate in the aerated matrix pre-mix, pumping the aerated matrix pre-mix around at least a portion of the substrate, spraying aerosolized aerated matrix pre-mix onto at least a portion of the substrate, or any combination thereof. In step 240(B), during the mixing step of the aerated matrix pre-mix, at least a portion of the substrate is maintained in contact with the aerated matrix pre-mix, and at least a portion of a hydrated solid is formed (e.g., disposed) on at least a portion of the exterior surface of the substrate. The substrate may be any substrate and may have any of the properties described herein.

[0115] In some embodiments of the first exemplary method 200, the plurality of PTFE fibrils of the matrix include short-strand PTFE fibrils formed from short-strand PTFE resin and long-strand PTFE fibrils formed from long-strand PTFE resin. In such embodiments, the PTFE resin of the aerated matrix premix includes short-strand PTFE resin and long-strand PTFE resin. The PTFE resin of the aerated emulsion includes short-strand PTFE resin. The long-strand PTFE resin may be added at any step or multiple steps of method 200 such that the PTFE resin of one or more of the emulsion, aerated emulsion (210c), matrix premix (220c), or aerated matrix premix (230c) includes short-strand PTFE resin and long-strand PTFE resin. For example, in some embodiments, method 200 further comprises adding long-strand PTFE resin to the emulsion (prior to aeration), such that the PTFE resin of the emulsion, the PTFE resin of the aerated emulsion (210c), the PTFE resin of the premix (220c), and the PTFE resin of the aerated premix (230c) comprise short-strand PTFE resin and long-strand PTFE resin. In some embodiments, method 200 further comprises adding long-strand PTFE resin to the aerated emulsion, such that the PTFE resin of the aerated emulsion (210c), the PTFE resin of the premix (220c), and the PTFE resin of the aerated premix (230c) comprise short-strand PTFE resin and long-strand PTFE resin. In some embodiments, method 200 further comprises adding long-strand PTFE resin to the matrix pre-mix, such that the PTFE resin of the matrix pre-mix (220c) and the PTFE resin of the aerated pre-mix (230c) comprise short-strand PTFE resin and long-strand PTFE resin.In some embodiments, method 200 further comprises adding long-strand PTFE resin to the aerated matrix premix such that the PTFE resin of the aerated matrix premix (230c) comprises short-strand PTFE resin and long-strand PTFE resin.

[0116] In some embodiments of method 200, the aerated matrix pre-mix comprises at least 0.01%, at least 15%, at least 25%, at least 45%, at least 55%, or at least 65% by weight of PTFE resin, based on the total weight of the aerated matrix pre-mix. In some embodiments of method 200, the aerated matrix pre-mix comprises no more than 80%, no more than 65%, no more than 55%, no more than 45%, no more than 25%, or no more than 15% by weight of PTFE resin, based on the total weight of the aerated matrix pre-mix.

[0117] In some embodiments of method 200, the aerated matrix pre-mix comprises at least 0.01%, at least 1%, at least 5%, or at least 10% by weight of long-strand PTFE resin, based on the total weight of the aerated matrix pre-mix. In some embodiments of method 200, the aerated matrix pre-mix comprises no more than 15%, no more than 10%, no more than 5%, or no more than 1% by weight of long-strand PTFE resin, based on the total weight of the aerated matrix pre-mix.

[0118] In some embodiments of method 200, the aerated matrix premix comprises at least 0.1 wt %, at least 5 wt %, at least 15 wt %, at least 25 wt %, at least 45 wt %, or at least 55 wt % short-strand PTFE, based on the total weight of the aerated matrix premix. In some embodiments of method 200, the aerated matrix premix comprises at most 70 wt %, at most 55 wt %, at most 45 wt %, at most 25 wt %, at most 15 wt %, or at most 5 wt % short-strand PTFE resin, based on the total weight of the aerated matrix premix. FIG. 5 is a flow diagram that schematically illustrates a second exemplary method 300 for producing a composition comprising a matrix. The matrix comprises a plurality of active particles and a plurality of PTFE fibrils formed from a PTFE resin (i.e., resin particles of the PTFE resin). Method 300 is suitable for use in producing a composition comprising a plurality of active particles, including an absorbent capable of adsorbing basic compounds, acidic compounds, or both. In other words, the method 300 is preferably used in producing a composition that includes a plurality of particles that include adsorbents that are acidic, basic, or both.

[0119] Method 300 includes, in step 310(A), precipitating at least a portion of the PTFE resin particles from the (aerated) matrix premix by adding a solid particle composition to the aerated matrix premix to form a hydrated solid. The term "(aerated) matrix premix" includes aerated matrix premixes (i.e., aerated matrix premixes) and non-aerated matrix premixes (i.e., matrix premixes). The (aerated) matrix premix (330c) includes a PTFE resin, a surfactant, and a dispersing agent. The surfactant may be any surfactant described elsewhere herein. The dispersing agent may be any dispersing agent described elsewhere herein. The hydrated solid (310c) includes a plurality of PTFE fibrils formed from the PTFE resin, a plurality of active particles, at least a portion of the dispersing agent, and at least a portion of the surfactant. The plurality of active particles includes at least a portion of the solid particles.

[0120] The solid particle composition comprises solid particles. In some embodiments, the solid particle composition comprises 100% solid particles by weight (i.e., the solid particle composition does not include any other components). In some embodiments, the solid particle composition comprises solid particles and a liquid carrier. The liquid carrier may include methanol, ethanol, isopropanol, acetone, dimethylformamide, dichloromethane, toluene, ethyl acetate, acetonitrile, dioxane, petroleum ether, dimethyl sulfoxide, tetrahydrofuran, or any combination thereof. In some such embodiments, the solid particles in the solid particle composition are dissolved in the liquid carrier. In other embodiments, the solid particles of the solid particle composition are suspended in the liquid carrier. In still other embodiments, a first portion of the solid particles are dissolved in the liquid carrier and a second portion of the solid particles are suspended in the liquid carrier.

[0121] The plurality of active particles comprises at least a portion of the solid particles of the solid particle composition. In some embodiments, the solid particles may already be in the form of a plurality of active particles. In some embodiments, the solid particles are not in the form of a plurality of active particles. In some such embodiments, at least a portion of the solid particles become the plurality of active particles through aggregation and / or precipitation.

[0122] The amount of solid particles added to the (aerated) matrix premix (added as a solid particle composition) may vary depending on the identity of the solid particles and the desired end use of the composition. In some embodiments, the amount of solid particles added to the (aerated) matrix premix is ​​such that the (aerated) matrix premix contains 0.5 wt.% or more, 10 wt.% or more, or 30 wt.% or more solid particles, based on the total weight of the (aerated) matrix premix. In some embodiments, the amount of solid particles added to the (aerated) matrix premix is ​​such that the (aerated) matrix premix contains 50 wt.% or less, 30 wt.% or less, or 10 wt.% or less solid particles, based on the total weight of the (aerated) matrix premix. In some embodiments, the solid particles include potassium carbonate, activated carbon, or both.

[0123] Without wishing to be bound by theory, step 310 of method 300 is believed to be similar to polymer phase inversion. Polymer phase inversion (sometimes referred to as polymer phase separation) is a demixing process in which a polymer dissolved in a solution transitions from a liquid to a solid state. In the traditional sense, the dissolved polymer is partially or completely ionized in a suitable solvent. Unlike traditional polymer phase inversion, the PTFE in the (aerated) matrix premix is ​​not dissolved in the sense of being ionized; rather, the surfactant lowers the surface tension of the dispersant so that the PTFE can be suspended as a colloid. A colloid is a molecularly aggregated (non-ionized) solid that is found in a liquefied, homogeneous solution. Therefore, the mechanism by which a pH change causes PTFE to precipitate from the (aerated) matrix premix is ​​not a destabilization of the dissolved polymer, since the PTFE is not truly dissolved. Instead, a change in pH due to the addition of a solid particle composition containing acidic or basic solid particles results in PTFE precipitation from the destabilization of the surfactant / dispersant system (e.g., or the (aerated) matrix premix). Chemically distinct from traditional polymer phase inversion behavior, this behavior results in fibrillation of the PTFE resin, forming multiple PTFE fibrils.

[0124] As used herein, "precipitation," when used in reference to PTFE resin or PTFE fibrils, refers to the destabilization of the surfactant / dispersant system, causing the PTFE resin particles to fibrillate and clump together to form a hydrated composition. As used herein, the term precipitation does not imply that the PTFE resin is dissolved in solution.

[0125] The second exemplary method 300 includes, in step 320, drying the hydrated solid to form a matrix. Drying the hydrated solid includes removing at least a portion of the dispersant and at least a portion of the surfactant from the hydrated solid. The drying step may be accomplished in a variety of ranges (i.e., the amount of dispersant, liquid carrier, and / or surfactant present in the matrix after the drying step) and may include a variety of techniques as discussed herein (e.g., see the discussion of FIG. 6).

[0126] In some embodiments, the second exemplary method 300 includes aerating the matrix pre-mix at 330 to form an aerated matrix pre-mix. The aeration may be performed using techniques described elsewhere herein. The matrix pre-mix includes a PTFE resin, a surfactant, and a dispersant 330c.

[0127] In some embodiments, the second exemplary method 300 includes, at 340(A), forming a matrix premix. In some embodiments, the matrix premix is ​​formed by diluting a concentrated matrix premix with a solution including a dispersant or a dispersant and a surfactant. The concentrated matrix premix includes a PTFE resin and a dispersant. In some embodiments, the concentrated matrix premix includes at least a portion of the surfactant. In some embodiments, the concentrated matrix premix includes 60% by weight of PTFE resin (e.g., 60% by weight of short-strand PTFE resin), based on the total weight of the concentrated matrix premix. In some embodiments, the mixture is diluted with a dispersant. In some embodiments, the concentrated matrix premix is ​​diluted with a solution including a dispersant and a surfactant.

[0128] The second exemplary method 300 may be used to deposit a composition on a substrate (350c) including at least an outer surface (i.e., exterior). In such a case, method 300 further includes contacting at least a portion of the substrate with the (aerated) matrix premix in step 350. The contacting step may be performed using any suitable technique described herein. In step 310(B), during the step of precipitating at least a portion of the PTFE resin particles from the (aerated) matrix premix, at least a portion of the substrate is maintained in contact with the (aerated) matrix premix, forming (depositing) at least a portion of a hydrated solid on at least a portion of the outer surface of the substrate. The substrate may be any substrate and may have any of the characteristics described herein.

[0129] In some embodiments of the second exemplary method 300, the plurality of PTFE fibrils of the matrix include short-strand PTFE fibrils formed from short-strand PTFE resin and long-strand PTFE fibrils formed from long-strand PTFE resin. In such embodiments, the PTFE resin of the (aerated) matrix pre-mix (330c(A)) includes short-strand PTFE resin and long-strand PTFE resin. The long-strand PTFE resin may be added at any step or multiple steps of method 300, such that the PTFE resin of one or more of the concentrated matrix pre-mix (340c(B)), matrix pre-mix (340c), and (aerated) matrix pre-mix (330c) includes short-strand PTFE resin and long-strand PTFE resin. For example, in some embodiments, method 300 further comprises adding long-strand PTFE resin to the concentrated matrix pre-mix (340c(B)), such that the PTFE resin of pre-mix (340c(B)), and the PTFE resin of (aerated) pre-mix (330c) comprise short-strand PTFE resin and long-strand PTFE resin. In some embodiments, method 300 further comprises adding long-strand PTFE resin to the matrix pre-mix (340c(A)), such that the PTFE resin of matrix pre-mix (340c(A)), and the PTFE resin of (aerated) matrix pre-mix (330c) comprise short-strand PTFE resin and long-strand PTFE resin. In some embodiments, method 300 further comprises adding long-strand PTFE resin to the (aerated) matrix pre-mix (330c) such that the PTFE resin in the (aerated) matrix pre-mix comprises short-strand PTFE resin and long-strand PTFE resin.

[0130] In some embodiments of method 300, the (aerated) matrix pre-mix (330c) comprises at least 0.01%, at least 15%, at least 25%, at least 45%, at least 55%, or at least 65% by weight of PTFE resin, based on the total weight of the (aerated) matrix pre-mix. In some embodiments of method 300, the (aerated) matrix pre-mix comprises at most 80%, at most 65%, at most 55%, at most 45%, at most 25%, or at most 15% by weight of PTFE resin, based on the total weight of the (aerated) matrix pre-mix.

[0131] In some embodiments of method 300, the (aerated) matrix pre-mix (330c) comprises at least 0.01%, at least 1%, at least 5%, or at least 10% by weight of long-strand PTFE resin, based on the total weight of the (aerated) matrix pre-mix. In some embodiments of method 300, the (aerated) matrix pre-mix comprises no more than 15%, no more than 10%, no more than 5%, or no more than 1% by weight of long-strand PTFE resin, based on the total weight of the (aerated) matrix pre-mix.

[0132] In some embodiments of method 300, the (aerated) matrix pre-mix (330c) comprises at least 0.1%, at least 5%, at least 15%, at least 25%, at least 45%, or at least 55% by weight of short-strand PTFE, based on the total weight of the (aerated) matrix pre-mix. In some embodiments of method 300, the (aerated) matrix pre-mix comprises at most 70%, at most 55%, at most 45%, at most 25%, at most 15%, or at most 5% by weight of short-strand PTFE resin, based on the total weight of the (aerated) matrix pre-mix.

[0133] In some embodiments, methods 200 and 300 further include extruding the hydrated solid through an extrusion die to form a composite structure. The composite structure includes the composition. The hydrated solid may also have isolated pockets of air. Extrusion compresses the hydrated solid through removal of at least a portion of the air within the hydrated solid. The extrusion die typically includes an inlet (where the composition enters the die) and an outlet (where the composition exits the die). The die may have multiple outlets. The cross-section of the inlet is larger than the cross-section of the outlet.

[0134] A dispersing agent may be added to a component of a concentrated matrix premix, an aerated emulsion, a matrix premix, an aerated matrix premix, or any combination thereof at any time during any of the methods disclosed herein. In some embodiments, a dispersing agent may be added before or during any one of the steps of the methods disclosed herein. For example, in embodiments in which long-strand PTFE resin is added to a concentrated matrix premix, an emulsion, an aerated emulsion, a matrix premix, or an aerated matrix premix, the long-strand PTFE resin may be added to the mixture containing the dispersing agent. A dispersing agent may be added to dilute a component, suspend a component, promote the formation of a colloid containing one or more components, promote the formation of an emulsion, promote aeration, or any combination thereof. For example, in some embodiments, a dispersing agent may be added to an aerated emulsion (e.g., 210c). In some embodiments, a dispersing agent may be added to a matrix premix (e.g., 220c, 340c). In some embodiments, a dispersing agent may be added to the aerated matrix premix (e.g., 230c, 330c). In some embodiments, a dispersing agent may be added to the mixture. In some embodiments, a dispersing agent may be added to the emulsion (e.g., 210c). In some embodiments, a dispersing agent is not added to the hydrated solids. In some embodiments, a dispersing agent is added to the hydrated solids.

[0135] The method of the present disclosure includes drying the hydrated solid to form a matrix. Drying the hydrated solid includes removing at least a portion of the dispersant and / or liquid carrier (if present) from the hydrated solid. In embodiments where the dispersant includes water, the drying step may be referred to as dehydration. Drying the hydrated solid also includes removing at least a portion of the surfactant from the hydrated solid. The composition formed after drying the hydrated solid contains 50% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, or 1% by weight or less of the dispersant and / or liquid carrier (if present), based on the total weight of the composition. The composition formed after drying the hydrated solid contains 50% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, or 1% by weight or less of the surfactant, based on the total weight of the composition. The degree of drying may vary depending on the desired use of the composition and / or subsequent processing steps. For example, certain dispersants and / or liquid carriers may be useful for shape engineering. Thus, in some embodiments, the hydrated solid is dried to the extent that the composition comprises a suitable amount of dispersant and / or liquid carrier (if present) to effect shape engineering without the need for the addition of additional dispersants, liquid carriers, or processing aids, such as extrusion aids, to the composition (e.g., 0.1% to 50% by weight of water / liquid carrier, based on the total weight of the composition).

[0136] Figure 6 is a flow diagram that generally illustrates steps in various drying techniques and / or methods. In some embodiments, the hydrated solid is formed by contacting it with a solution of excess dispersant (and, if present, sometimes liquid carrier) and surfactant. That is, the hydrated solid is ground from the (aerated) matrix pre-mix. In such embodiments, drying the hydrated solid comprises separating it from the remaining (aerated) matrix pre-mix in step 500. This may be accomplished by decanting the (aerated) matrix pre-mix or by physically removing the hydrated solid from the (aerated) matrix pre-mix.

[0137] In some embodiments, drying the hydrated solid comprises contacting at least a portion of the hydrated solid (e.g., the outer surface of the hydrated solid), preferably the entire hydrated solid (e.g., the entire outer surface of the hydrated solid), with an absorbent material. The absorbent material derives at least a portion of the dispersant, at least a portion of the surfactant, and at least a portion of the liquid carrier (if included) from the hydrated solid. Any suitable absorbent material may be used. Examples of absorbent materials include cotton; cellulose; sponges comprising polyester, polyurethane, vegetable cellulose, melamine, or any combination thereof; anhydrous calcium chloride; anhydrous magnesium sulfate; sodium polyacrylate; or any combination thereof. The hydrated solid may be contacted with the absorbent material for a period of time. In some embodiments, the contact time is 1 second or more, 1 minute or more, or 1 hour or more. In some embodiments, the contact time is 24 hours or less, 1 hour or less, or 1 minute or less. In such embodiments, the method further comprises removing at least a portion, preferably all, of the absorbent material from the hydrated solid in step 520.

[0138] In some embodiments, the hydrated solids are contacted with the absorbent material more than once. In other words, in some embodiments, the steps of contacting at least a portion of the hydrated solids with an absorbent in step 510 and removing at least a portion of the absorbent material from the hydrated solids in step 520 are repeated multiple times (e.g., 2 to 10 times, 2 to 20 times, or 2 to 50 times) consecutively, each time using an absorbent material that has not previously been contacted with the hydrated solids (i.e., fresh absorbent material).

[0139] In some embodiments, drying the hydrated solid further comprises exposing the hydrated solid to an elevated temperature for a period of time in step 540. In certain embodiments, the hydrated solid is exposed to a temperature of 100°C to 400°C, preferably 100°C to 300°C, for a period of 0.1 to 24 hours, preferably 1 to 5 hours. Preferably, the hydrated solid is not subjected to calcination conditions. PTFE fibrils may shrink under calcination conditions (e.g., temperatures above 330°C), which may manifest as broken PTFE fibrils and a reduced mechanical stability of the matrix.

[0140] In certain embodiments, drying the hydrated solid to form the matrix further comprises applying a vacuum to the hydrated solid, hi some such embodiments, the hydrated solid is simultaneously exposed to an elevated temperature (e.g., 25°C to 150°C).

[0141] The dispersing agent of any one of the exemplary methods may be water, one or more organic solvents, or both. In some embodiments, the dispersing agent comprises water. In some embodiments, the dispersing agent comprises an organic solvent or a mixture of organic solvents. Examples of organic solvents that may be included in the dispersing agent include methanol, acetone, tetrahydrofuran, dimethylformamide, acetonitrile, isopropanol, ethanol, ISOPAR-K, or any combination thereof. In some embodiments, the one or more organic solvents include a processing aid, such as an extrusion aid. In certain embodiments, the extrusion aid includes extruded mineral spirits or a hydrocarbon solvent described elsewhere herein. In embodiments where the dispersing agent includes an extrusion aid, drying the hydrated solids may include drying the hydrated solids so that the hydrated solids contain a sufficient amount of the extrusion aid for further processing by extrusion. In certain embodiments, the extrusion aid may be a lubricant (e.g., ISOPAR-K).

[0142] The surfactant of any one of the exemplary methods may be a nonionic non-fluorinated surfactant. A nonionic surfactant is a surfactant with an uncharged polar head group. Examples of nonionic non-fluorinated surfactants that may be used include ethoxylates, alkoxylates, and cocamides. In some embodiments, the surfactant is polyethylene glycol trimethylnonyl ether. In some embodiments, the (aerated) matrix premix contains 0.5 wt.% or more, 5 wt.% or more, or 20 wt.% or more of a surfactant, based on the total weight of the (aerated) matrix premix. In some embodiments, the (aerated) matrix premix contains 40 wt.% or less, 20 wt.% or less, or 5 wt.% or less of a surfactant, based on the total weight of the (aerated) matrix premix. In some embodiments, the (aerated) matrix premix of any one of the exemplary methods may contain 0.5 wt.% to 40 wt.%, preferably 5 wt.% to 20 wt.%, of a surfactant, based on the total weight of the (aerated) matrix premix.

[0143] The method of the present disclosure can result in various loading capacities of multiple active particles. The loading capacity of each solid particle (or any individual component of the solid particles) can be calculated according to a composition analysis test method (i.e., a loading capacity test method). The sum of the loading capacities of each component of the solid particles is considered to be the loading capacity of multiple active particles containing the components of the solid particles. For example, if the solid particles include activated carbon, the loading capacity of the activated carbon is the loading capacity of multiple active particles containing activated carbon. If the solid particles include manganese oxide and copper oxide, the loading capacity of multiple active particles containing manganese oxide and copper oxide is the sum of the loading capacity of the manganese oxide and the loading capacity of the copper oxide.

[0144] The total active particle loading capacity is the sum of the loading capacities of one or more components comprising the plurality of active particles. For example, in an embodiment in which the plurality of active particles includes manganese oxide and copper oxide, the total active particle loading capacity is the sum of the loading capacities of the manganese oxide and copper oxide. In some embodiments, the disclosed method results in a total active particle loading capacity of 50% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more. In some embodiments, the disclosed method results in a loading capacity of the plurality of active particles of 95% by weight or less, 90% by weight or less, 80% by weight or less, or 70% by weight or less.

[0145] Illustrative Embodiments Composition Embodiments Embodiment 1C is a composition comprising a matrix comprising a plurality of polytetrafluoroethylene (PTFE) fibrils and a plurality of active particles.

[0146] Embodiment 2C is the composition of embodiment 1C, wherein the plurality of PTFE fibrils comprises short-strand PTFE fibrils and long-strand PTFE fibrils.

[0147] Embodiment 3C is the composition of Embodiment 1C or 2C, wherein at least a portion of the plurality of active particles and at least a portion of the plurality of PTFE fibrils adopt a catenated structure, an aggregated structure, or both, when the composition is in an unexpanded state.

[0148] Embodiment 4C is the composition of any one of Embodiments 1C through 3C, wherein the short-strand PTFE fibrils, the long-strand PTFE fibrils, or both, comprise C3-PTFE, C2-PTFE, C1-PTFE, or any combination thereof.

[0149] Example 5C is the composition of any one of Examples 1C to 4C, wherein the plurality of active particles comprises a catalyst, an adsorbent, a growth seed, a metal-organic framework (MOF), an electroactive material, or any combination thereof.

[0150] Embodiment 6C is the composition of embodiment 5C, wherein the plurality of active particles comprises a catalyst, the catalyst being capable of ozone depletion.

[0151] Embodiment 7C is an embodiment of the present invention, wherein the plurality of active particles comprises a catalyst, the catalyst being capable of catalyzing nitrobenzene reduction, hydrogenation, NO x The composition of embodiment 5C or 6C, wherein the composition is soluble in water, soluble in water, or any combination thereof.

[0152] Embodiment 8C is an embodiment in which the plurality of active particles comprises a catalyst, the catalyst being selected from the group consisting of iron silicate, iron manganese silicate, zinc iron silicate, or any combination thereof; a transition metal oxide such as zinc oxide, manganese oxide, copper oxide, cerium dioxide, or a combination thereof; a metal including titanium, lead, iron, copper, zinc, chromium, cobalt, nickel, manganese, gold, silver, platinum, palladium, rhodium, tungsten, molybdenum, vanadium, zirconium, silicon, ruthenium, or any combination thereof; barium carbonate, magnesium carbonate, calcium carbonate, carbon dioxide, or a combination thereof. zeolites; reduced metals (i.e., zero-valent metals) including titanium, lead, iron, copper, zinc, chromium, cobalt, nickel, manganese, gold, silver, platinum, palladium, rhodium, tungsten, molybdenum, vanadium, zirconium, silicon, ruthenium, or any combination thereof; carbonates such as barium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, or any combination thereof; or combinations thereof.

[0153] Embodiment 9C is the composition of embodiment 5C, wherein the plurality of active particles comprises an adsorbent, and the adsorbent is a physisorbent, a chemisorbent, a physisorbent-chemisorbent hybrid, or any combination thereof.

[0154] Embodiment 10C is the composition of embodiment 9C, wherein the plurality of active particles comprises an adsorbent, the adsorbent being capable of adsorbing a basic compound, an acidic compound, an organic compound, an inorganic compound, or any combination thereof. The acidic compound, basic compound, organic compound, inorganic compound, or any combination thereof may be in a liquid state, a gaseous and / or vapor state (preferably), or both.

[0155] Embodiment 11C is the composition of embodiment 10C, wherein the sorbent is capable of adsorbing a basic compound, the basic compound comprising ammonia. The basic compound may be in a liquid state, a gas and / or vapor state (preferably), or both.

[0156] Embodiment 12C is the composition of embodiment 10C, wherein the sorbent is capable of sorbing acidic compounds, the acidic compounds comprising sulfur dioxide, nitrogen dioxide, hydrogen sulfide, sulfur trioxide, nitric oxide, or any combination thereof. The acidic compounds may be in a liquid state, a gaseous and / or vapor state (preferably), or both.

[0157] Embodiment 13C is the composition of embodiment 10C, wherein the sorbent is capable of adsorbing inorganic compounds, the inorganic compounds comprising carbon dioxide, carbon monoxide, water, nitrogen oxides, sulfur oxides, hydrogen sulfide, perfluorocarbons (e.g., tetrafluoromethane and hexafluoroethane); sulfur hexafluoride; ozone; or any combination thereof. The inorganic compounds may be in a liquid state, a gaseous and / or vapor state (preferably), or both.

[0158] Embodiment 14C is the composition of embodiment 10C, wherein the adsorbent is capable of adsorbing organic compounds, the organic compounds comprising aromatic hydrocarbons (e.g., toluene, benzene, xylene, ethylbenzene); siloxanes; polycyclic aromatic hydrocarbons (naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo(a)anthracene, chrysene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(a)fluoranthene, dibenzo(a,h)anthracene, benzo(ghi)perylene, indeno(1,2,3-cd)pyrene, etc.); n-alkanes (e.g., methane, ethane, propane, butane, pentane, hexane); n-alkenes (e.g., methylene, ethylene, and propylene); aldehydes (e.g., formaldehyde); alcohols; siloxanes; or any combination thereof. The organic compound may be in a liquid state, a gaseous and / or vapor state (preferably), or both.

[0159] Embodiment 15C is the composition of any one of Embodiments 10C to 14C, wherein the sorbent is a chemisorbent, a physisorbent, or a physisorbent-chemisorbent hybrid, and the physisorbent is activated carbon, a zeolite, a silicate, a metal-organic framework (MOF), a mesoporous transition metal oxide, or any combination thereof.

[0160] Embodiment 16C is the composition of embodiment 12C, wherein the sorbent comprises a chemisorbent or a physisorbent-chemisorbent hybrid, and the chemisorbent comprises a Group I metal carbonate; a metal oxide; a Group I metal hydroxide; a Group II metal hydroxide; an N-containing compound such as an amine, an imine, an ammonium salt, or any combination thereof, a carboxylic acid functional group, an inorganic acid, or any combination thereof.

[0161] Embodiment 17C is the composition of embodiment 16C, wherein the chemisorbent or physisorbent-chemisorbent hybrid comprises an N-containing compound, the N-containing compound comprising polyethyleneimine, tetraethylenepentamine, ethylenediamine, 3-aminopropyltriethoxysilane, or ammonium persulfate.

[0162] Embodiment 18C is the composition of embodiment 16C, wherein the chemisorbent or physisorbent-chemisorbent hybrid comprises a carboxylic acid functional group, and the organic acid compound has a carboxylic acid functional group, and the organic acid compound comprises citric acid, terephthalic acid, trimesic acid, tartaric acid, maleic acid, benzoic acid, or oxalic acid.

[0163] Embodiment 19C is the composition of embodiment 16C, wherein the chemisorbent or physisorbent-chemisorbent hybrid comprises an inorganic acid, the inorganic acid comprising boric acid, nitric acid, sulfuric acid, hydrochloric acid, hydrogen chloride, hydrogen fluoride, hydrogen bromide, phosphoric acid, perchloric acid, periodic acid, or any combination thereof.

[0164] Embodiment 20C is the composition of any one of Embodiments 16C through 19C, wherein the physisorbent-chemisorbent hybrid is according to Embodiment 15C.

[0165] Embodiment 21C is the composition of embodiment 5C, wherein the plurality of active particles comprises growth seeds, which are nucleation points for the growth of metal-organic frameworks (MOFs).

[0166] Embodiment 22C is the composition of embodiment 21C, wherein the growth seeds comprise copper nitrate, trimesic acid, or both.

[0167] Embodiment 23C is the composition of embodiment 5C, wherein the plurality of active particles comprises a MOF, and the MOF comprises copper benzene-1,3,5-tricarboxylate.

[0168] Embodiment 24C is the composition of Embodiment 5C, wherein the plurality of active particles comprises an electroactive material, the electroactive material being an anode electroactive material, a cathode electroactive material, or both.

[0169] Embodiment 25C is the composition of embodiment 5C or 24C, wherein the electroactive material comprises lithium, lithium and one or more metals.

[0170] Embodiment 26C is the composition of any one of Embodiments 1C to 25C, wherein the plurality of active particles has an average particle size, as measured according to the Dimensional Analysis Test Method, of 0.001 μm or more, 0.01 μm or more, 0.1 μm or more, 1 μm or more, 5 μm or more, 10 μm or more, or 100 μm or more. The plurality of active particles has an average particle size, as measured according to the Dimensional Analysis Test Method, of 500 μm or less, 100 μm or less, 10 μm or less, or 1 μm or less.

[0171] Embodiment 27C is the composition of Embodiment 26C, wherein the plurality of active particles comprises a catalyst, and the plurality of active particles has an average particle size of 0.001 μm to 5 μm or 0.001 μm to 0.1 μm as measured according to the Dimensional Analysis Test Method.

[0172] Embodiment 28C is the composition of Embodiment 27C, wherein the plurality of active particles comprises a catalyst, and the plurality of active particles has an average particle size of 0.001 μm to 1 μm as measured according to the Dimensional Analysis Test Method.

[0173] Embodiment 29C is the composition of embodiment 26C, wherein the plurality of active particles comprises an adsorbent, and the plurality of active particles have an average particle size of 0.001 μm to 100 μm, 1 μm to 100 μm, or 0.001 μm to 0.1 μm, as measured by a size and dimension analysis test method.

[0174] Embodiment 30C is the composition of any one of Embodiments 2C through 29C, wherein the short-strand PTFE fibrils have an average length, as measured by the Dimensional Analysis Test Method, that is 30 μm or less, 20 μm or less, 10 μm or less, or 5 μm or less. The short-strand PTFE fibrils have an average length, as measured according to the Dimensional Analysis Test Method, of 1 μm or more, 5 μm or more, 10 μm or more, or 20 μm or more.

[0175] Embodiment 31C is the composition of any one of Embodiments 2C through 30C, wherein the long-strand PTFE fibrils have an average length of 40 μm or more, 100 μm or more, 150 μm or more, 250 μm or more, 500 μm or more, or 1000 μm as measured according to the Dimensional Analysis Test Method. The long-strand PTFE fibrils have an average length of 2000 μm or less, 1000 μm or less, 700 μm or less, 500 μm or less, 250 μm or less, 150 μm or less, or 100 μm or less as measured according to the Dimensional Analysis Test Method.

[0176] Embodiment 32C is the composition of embodiment 31C, wherein the long-strand PTFE fibrils have an average length of from 40 μm to 700 μm as measured according to the Dimensional Analysis Test Method.

[0177] Embodiment 33C is the composition of any one of Embodiments 2C through 32C, wherein the short strand PTFE fibrils have an average diameter of 0.01 μm or more, 0.05 μm or more, 0.3 μm or more, or 0.5 μm or more, as measured according to the Dimensional Analysis Test Method. The short fiber PTFE fibrils have an average diameter of 1 μm or less, 0.5 μm or less, or 0.3 μm or less, as measured according to the Dimensional Analysis Test Method.

[0178] Embodiment 34C is the composition of any one of Embodiments 2C through 33C, wherein the long-strand PTFE fibrils have an average diameter of 100 μm or less, 50 μm or less, 10 μm or less, or 1 μm or less, as measured by the Dimensional Analysis Test Method. The long-strand PTFE fibrils have an average diameter of 0.5 μm or more, 1 μm or more, 10 μm or more, or 50 μm or more, as measured by the Dimensional Analysis Test Method.

[0179] Embodiment 35C is the composition of any one of Embodiments 1C to 34C. The composition has a localized porosity in the unstretched state of 10% or more, 20% or more, or 30% or more, as measured by Dimensional Analysis Testing. The composition has a localized porosity in the unstretched state of 50% or less, 30% or less, or 20% or less, as measured by Dimensional Analysis Testing.

[0180] Embodiment 36C is the composition of any one of Embodiments 1C through 35C, wherein the composition further comprises an additive.

[0181] Embodiment 37C is the composition of embodiment 36C, wherein the additive comprises a binder, and the binder comprises kaolinite, bentonite, silicon carbide, fumed silica, zeolite, or any combination thereof.

[0182] Embodiment 38C is the composition of embodiment 36C, wherein the additive comprises a polymeric additive.

[0183] Embodiment 39C is the composition of any one of Embodiments 36C through 38C, wherein the composition comprises 0.1 wt. % or more, 1 wt. % or more, or 15 wt. % or more of the additive, based on the total weight of the composition calculated according to the Compositional Analysis Test Method. The composition comprises 20 wt. % or less, 15 wt. % or less, or 1 wt. % or less of the additive, based on the total weight of the composition calculated according to the Compositional Analysis Test Method.

[0184] Embodiment 40C is the composition of Embodiment 39C, wherein the additive comprises a binder, and the composition contains at least 0.1%, at least 1%, or at least 3% by weight of binder, calculated according to the Compositional Analysis Test Method. The composition contains no more than 15%, no more than 10%, or no more than 3% by weight of binder, calculated according to the Compositional Analysis Test Method.

[0185] Embodiment 41C is the composition of any one of Embodiments 1C through 40C, wherein the composition comprises at least 5%, at least 15%, at least 25%, at least 45%, at least 55%, at least 65%, or at least 80% by weight of a plurality of PTFE fibrils, based on the total weight of the composition, as calculated according to the Compositional Analysis Test Method. The composition comprises no more than 95%, no more than 80%, no more than 65%, no more than 55%, no more than 45%, no more than 25%, or no more than 15% by weight of a plurality of PTFE fibrils, based on the total weight of the composition, as calculated according to the Compositional Analysis Test Method.

[0186] Embodiment 42C is the composition of any one of Embodiments 2C through 41C, wherein the composition contains at least 0.1%, at least 1%, at least 5%, at least 15%, at least 25%, at least 45%, at least 55%, at least 65%, or at least 80% short-strand PTFE fibrils by weight, based on the total weight of the composition calculated according to the Compositional Analysis Test Procedure. The composition contains no more than 95%, no more than 80%, no more than 65%, no more than 55%, no more than 45%, no more than 25%, no more than 15%, no more than 5%, or no more than 1% short-strand PTFE fibrils by weight, based on the total weight of the composition calculated according to the Compositional Analysis Test Procedure.

[0187] Embodiment 43C is the composition of any one of Embodiments 2C through 42C, wherein the composition contains at least 0.01%, at least 1%, at least 5%, at least 10%, at least 20%, at least 30%, or at least 40% by weight long-strand PTFE fibrils, based on the total weight of the composition calculated according to the Compositional Analysis Test Method. The composition contains no more than 50%, no more than 40%, no more than 30%, no more than 20%, no more than 15%, no more than 10%, no more than 5%, or no more than 1% by weight long-strand PTFE fibrils, based on the total weight of the composition calculated according to the Compositional Analysis Test Method.

[0188] Embodiment 44C(i) is the composition of any one of Embodiments 1C through 43C, wherein the active particles comprise a total active particle weight percent of the composition and / or matrix that is 50% or more, 70% or more, 80% or more, or 90% or more by weight of the composition and / or matrix, as determined by the Composition Analysis Test Method. The total active particle weight percent of the composition and / or matrix is ​​95% or less, 90% or less, 80% or less, or 70% or less by weight of the composition and / or matrix, as determined by the Composition Analysis Test Method.

[0189] Embodiment 44C(ii) is the composition of any one of Embodiments 1C through 43C, wherein the active particles comprise a total active particle weight percent of the composition and / or matrix, wherein the total active particle weight percent is 0% or more, 0.001% or more, 0.01% or more, 0.1% or more, 1% or more, 2% or more, 3% or more, 4% or more, 5% or more, 10% or more, or 15% or more by weight of the composition and / or matrix, as determined by the Composition Analysis Test Method. The total active particle weight percent of the composition and / or matrix is ​​less than 20% by weight, 15% or less, 10% or less, 5% or less, 4% or less, 3% or less, 2% or less, 1% or less, 0.1% or less, 0.01% or less, or 0.001% or less by weight of the composition and / or matrix, as determined by the Composition Analysis Test Method.

[0190] Embodiment 45C is the composition of any one of Embodiments 1C to 44C, wherein the composition is processable (eg, into a tape, honeycomb structure, web structure, or film) without contact with a processing aid.

[0191] Embodiment 46C is the composition of any one of Embodiments 1C through 44C, wherein the composition is processable (e.g., into a tape, honeycomb structure, web structure, or membrane) without contact with a fluorinated processing aid.

[0192] Embodiment 46C is the composition of any one of Embodiments 1C to 44C, wherein the composition is processable (e.g., into a tape, honeycomb structure, web structure, or film) without first screening the composition into a powder.

[0193] Substrate and Structure Embodiments Embodiment 1S is the composition of any one of Embodiments 1C through 44C, wherein the composition is a putty.

[0194] Embodiment 2S is a tape comprising the composition of any one of Embodiments 1C through 44C.

[0195] Embodiment 3S is a honeycomb structure comprising the composition of any one of Embodiments 1C through 44C.

[0196] Embodiment 4S is a web structure comprising the composition of any one of Embodiments 1C through 44C.

[0197] Embodiment 5S is a cast membrane comprising the composition of any one of Embodiments 1C through 44C.

[0198] Embodiment 6S is a substrate including an exterior surface, having disposed on at least a portion of the exterior surface the composition of any one of Embodiments 1C through 44C.

[0199] Embodiment 7S is the substrate of embodiment 6S, wherein the substrate comprises a corrugated honeycomb, such as a corrugated steel honeycomb and a corrugated aluminum honeycomb; a non-porous polyurethane; a polyethylene honeycomb; a silicon carbide honeycomb; a cordierite honeycomb; or any combination thereof.

[0200] Method Embodiments Embodiment 1M is a method of making a composition comprising a matrix comprising a plurality of PTFE fibrils formed from a PTFE resin and a plurality of active particles, the method comprising aerating an emulsion to form an aerated emulsion, the emulsion and aerated emulsion comprising a PTFE resin, a dispersing agent, and a surfactant; and adding a solid particle composition to the aerated emulsion to form a matrix premix, the solid particle composition comprising solid particles, the matrix premix comprising the PTFE resin, the dispersing agent, the solid particle composition, and the surfactant. aerating the matrix pre-mix to form an aerated matrix pre-mix, the aerated matrix pre-mix comprising the PTFE resin, the solid particle composition, the dispersing agent, and the surfactant; mixing the aerated matrix pre-mix to form a hydrated solid, the hydrated solid having the plurality of PTFE fibrils and the plurality of active particles, the plurality of active particles comprising at least a portion of the solid particles, at least a portion of the dispersing agent, and at least a portion of the surfactant; and drying the hydrated solid to form a matrix.

[0201] Embodiment 2M is a method of making a composition comprising a plurality of PTFE fibrils formed from a PTFE resin and a plurality of active particles, the method comprising: precipitating at least a portion of the PTFE resin particles from an (aerated) matrix premix by adding a solid particle composition to the (aerated) matrix premix to form a hydrated solid, the solid particle composition comprising solid particles, the (aerated) matrix premix comprising PTFE resin, a dispersant, and a surfactant, the hydrated solid comprising the plurality of active particles, the plurality of active particles comprising at least a portion of the solid particles, at least a portion of the dispersant, and at least a portion of the surfactant; and drying the hydrated solid to form the matrix.

[0202] Embodiment 3M is a method of disposing a composition on a substrate, the substrate comprising an exterior surface, the method comprising the method of Embodiment 1M or 2M, further comprising contacting at least a portion of the exterior surface of the substrate with an (aerated) matrix pre-mix, whereby at least a portion of the hydrated solids are formed on the exterior surface. In some embodiments, the method further comprises mixing the (aerated) matrix pre-mix while in contact with at least a portion of the substrate, whereby at least a portion of the hydrated solids are formed on the exterior surface (depending on Embodiment 1M). In some embodiments, the method further comprises adding the solid particle composition to the (aerated) matrix pre-mix, thereby precipitating the PFTE particles from the (aerated) matrix pre-mix, whereby at least a portion of the hydrated solids are formed on the exterior surface (depending on Embodiment 2M).

[0203] Embodiment 4M is the method of any one of Embodiments 1M to 3M, wherein the solid particle composition further comprises a liquid carrier methanol, ethanol, isopropanol, acetone, dimethylformamide, dichloromethane, toluene, ethyl acetate, acetonitrile, dioxane, petroleum ether, dimethyl sulfoxide, tetrahydrofuran, or any combination thereof.

[0204] Embodiment 5M is the method of any one of Embodiments 1M through 4M, wherein the composition comprises the composition of any one of Embodiments 1C through 44C.

[0205] Embodiment 6M is the method of any of embodiments 3M through 5M, wherein the substrate is a substrate according to embodiment 7S.

[0206] Embodiment 7M is the method of any one of Embodiments 1M through 6M, wherein the solid particles comprise potassium carbonate, activated carbon, or both.

[0207] Embodiment 8M is the method of any one of Embodiments 2M through 7M (depending on Embodiment 2M), further comprising aerating the matrix premix to form the (aerated) matrix premix (in this case, an aerated matrix premix), wherein the matrix premix comprises the PTFE resin, the dispersing agent, and the surfactant.

[0208] Embodiment 9M is the method of embodiment 8M, further comprising forming a matrix premix, the matrix premix comprising the PTFE resin, the surfactant, and the dispersant.

[0209] Embodiment 10M is the method of embodiment 9M, wherein the method further comprises diluting the concentrated matrix pre-mix with a dispersant to form the matrix pre-mix, the concentrated matrix pre-mix comprising the PTFE resin, the surfactant, and the dispersant.

[0210] Embodiment 11M is the method of any one of Embodiments 1M through 10M, wherein the plurality of PTFE fibrils of the matrix comprise short-strand PTFE fibrils formed from short-strand PTFE resin and long-strand PTFE fibrils formed from long-strand PTFE resin, and the PTFE resin of the (aerated) matrix premix comprises short-strand PTFE resin and long-strand PTFE resin.

[0211] Embodiment 12M is the method of Embodiment 11M, wherein the PTFE resin of the emulsion (depending on Embodiment 1M), the PTFE resin of the aerated emulsion (depending on Embodiment 1M), the PTFE resin of the concentrated matrix premix (depending on Embodiment 10M), and the PTFE resin of the matrix premix comprise short-strand PTFE resin.

[0212] Embodiment 13M is the method of Embodiment 12M (dependent on Embodiment 1M), further comprising adding long-strand PTFE resin to the aerated emulsion such that the PTFE resin of the aerated emulsion and the PTFE resin of the matrix premix further comprise long-strand PTFE resin.

[0213] Embodiment 14M is the method of Embodiment 12M (dependent on Embodiment 1M), further comprising adding long-strand PTFE resin to the emulsion such that the PTFE resin of the emulsion, the PTFE resin of the aerated emulsion, and the PTFE resin of the matrix premix further comprise long-strand PTFE resin.

[0214] Embodiment 15M is the method of Embodiment 12M (depending on Embodiment 1M or 2M), further comprising adding a long-strand PTFE resin to the matrix premix such that the PTFE resin of the matrix premix further comprises a long-strand PTFE resin.

[0215] Embodiment 16M is the method of Embodiment 12M (depending on Embodiment 1M or 2M), wherein the PTFE resin of the matrix premix further comprises long strand PTFE resin.

[0216] Embodiment 17M is the method of Embodiment 12M (dependent on Embodiment 10), further comprising adding long-strand PTFE resin to the concentrated matrix premix such that the PTFE resin of the concentrated matrix premix and the PTFE resin of the matrix premix both further comprise long-strand PTFE resin.

[0217] Embodiment 18M is the method of Embodiment 12M (dependent on Embodiment 1M), wherein the PTFE resin of the aerated emulsion further comprises long strand PTFE resin.

[0218] Embodiment 19M is the method of Embodiment 12M (dependent on Embodiment 1M), wherein the PTFE resin of the emulsion further comprises long strand PTFE resin.

[0219] Embodiment 20M is the method of Embodiment 12M (depending on Embodiment 1M or 2M), wherein the PTFE resin of the matrix premix further comprises long strand PTFE resin.

[0220] Embodiment 21M is the method of Embodiment 12M (dependent on Embodiment 10M), wherein the PTFE resin in the concentrated matrix premix further comprises long strand PTFE resin.

[0221] Embodiment 22M is the method of any one of Embodiments 1M to 21M, wherein after the drying step, the composition comprises no more than 50%, no more than 25%, no more than 10%, no more than 5%, or preferably no more than 1% by weight of dispersant, based on the total weight of the composition.

[0222] Embodiment 23M is the method of any one of Embodiments 1M to 22M, wherein after the drying step, the matrix comprises no more than 50% by weight, no more than 20% by weight, no more than 10% by weight, no more than 5% by weight, or no more than 1% by weight of surfactant, based on the total weight of the composition.

[0223] Embodiment 24M is the method of any one of embodiments 1M to 23M, wherein drying the hydrated solid from the matrix further comprises contacting at least a portion of the hydrated solid with an absorbent material to remove at least a portion of the dispersant, the liquid carrier, the surfactant, or any combination thereof.

[0224] Embodiment 25M is the method of embodiment 24M, wherein the hydrated solid is contacted with the absorbent material for 10 seconds or more, 1 minute or more, or 1 hour or more. The hydrated solid is contacted with the absorbent material for 24 hours or less, 1 hour or less, or 1 minute or less.

[0225] Embodiment 26M is the method of embodiment 24M or 25M, further comprising the steps of removing at least a portion of the absorbent material from contact with the hydrated solids, and repeating the steps of contacting the hydrated solids with the absorbent material and removing at least a portion of the absorbent material from contact with the hydrated solids a plurality of times, each time using absorbent material that has not previously been contacted with the hydrated solids.

[0226] Embodiment 27M is the method of any one of embodiments 24M to 26M, wherein the absorbent material comprises a sponge comprising cotton; cellulose; polyester, polyurethane, vegetable cellulose, melamine, or any combination thereof; anhydrous calcium chloride; anhydrous magnesium sulfate; sodium polyacrylate; or any combination thereof.

[0227] Embodiment 28M is the method of any one of Embodiments 1M to 27M, wherein drying the hydrated solid to form the matrix further comprises exposing the hydrated solid to an elevated temperature, applying a vacuum to the hydrated solid, or both.

[0228] Embodiment 29M is the method of embodiment 28M, wherein drying the hydrated solid to form a matrix further comprises exposing the matrix to a temperature of from 100°C to 400°C, preferably from 100°C to 300°C, for a period of from 0.1 hours to 24 hours, preferably from 1 hour to 5 hours.

[0229] Embodiment 30M is the method of any one of Embodiments 1M through 29M, wherein the (aerated) matrix premix contains 0.5% or more, 10% or more, or 30% or more by weight of solid particles, based on the total weight of the (aerated) matrix premix. The (aerated) matrix premix contains 50% or less, 30% or less, or 10% or less by weight of solid particles, based on the total weight of the (aerated) matrix premix.

[0230] Embodiment 31M is the method of any one of Embodiments 2M through 30M (dependent on Embodiment 2M), wherein after adding the solid particles to the (aerated) matrix premix, the (aerated) matrix premix contains 0.5% or more, 10% or more, or 30% or more by weight of solid particles, based on the total weight of the (aerated) matrix premix. The (aerated) matrix premix contains 50% or less, 30% or less, or 10% or less by weight of solid particles, based on the total weight of the (aerated) matrix premix.

[0231] Embodiment 32M is the method of any one of Embodiments 1M to 32M, wherein the (aerated) matrix premix comprises at least 0.01%, at least 15%, at least 25%, at least 45%, at least 55%, or at least 65% by weight of PTFE resin, based on the total weight of the (aerated) matrix premix. The (aerated) matrix premix comprises no more than 80%, no more than 65%, no more than 55%, no more than 45%, no more than 25%, or no more than 15% by weight of PTFE resin, based on the total weight of the (aerated) matrix premix.

[0232] Embodiment 33M is the method of any one of Embodiments 1M through 11M, or 13M through 32M, wherein the (aerated) matrix premix comprises at least 0.01%, at least 1%, at least 5%, or at least 10% by weight of long-strand PTFE resin, based on the total weight of the (aerated) matrix premix. The (aerated) matrix premix comprises no more than 15%, no more than 10%, no more than 5%, or no more than 1% by weight of long-strand PTFE resin, based on the total weight of the (aerated) matrix premix.

[0233] Embodiment 34M is the method of any one of Embodiments 1M to 33M, wherein the (aerated) matrix premix comprises at least 0.1%, at least 5%, at least 15%, at least 25%, at least 45%, or at least 55% by weight of short-strand PTFE resin, based on the total weight of the (aerated) matrix premix. The (aerated) matrix premix comprises no more than 70%, no more than 55%, no more than 45%, no more than 25%, no more than 15%, or no more than 5% by weight of short-strand PTFE resin, based on the total weight of the (aerated) matrix premix.

[0234] Embodiment 35M is the method of any one of Embodiments 1M to 34M, wherein the (aerated) matrix premix comprises 0.5% or more, 5% or more, or 20% or more by weight of a surfactant, based on the total weight of the (aerated) matrix premix. The (aerated) matrix premix comprises 40% or less, 20% or less, or 5% or less by weight of a surfactant, based on the total weight of the (aerated) matrix premix.

[0235] Embodiment 36M is the method of any one of Embodiments 1M through 35M, wherein the surfactant comprises a nonionic non-fluorinated surfactant.

[0236] Embodiment 37M is the method of Embodiment 36M wherein the surfactant comprises polyethylene glycol trimethylnonyl ether.

[0237] Embodiment 38M is the method of any one of Embodiments 1M through 37M, wherein the composition is the composition of any one of Embodiments 1C through 44C.

[0238] Embodiment 39M is the method of any one of embodiments 1M to 38M, wherein the method further comprises extruding the hydrated solid to form a composite structure, the composite structure comprising the composition.

[0239] Embodiment 40M is the method of any one of Embodiments 1M to 39M, wherein the method results in a total active particle loading capacity based on a compositional analysis test method (i.e., a loading capacity test method) of 50% or more, 70% or more, 80% or more, or 90% or more by weight. The disclosed methods result in a total active particle loading capacity based on a compositional analysis test method (i.e., a loading capacity test method) of 95% or less, 90% or less, 80% or less, or 70% or less by weight.

[0240] (Example) These examples are for illustrative purposes only and are not intended to unduly limit the scope of the appended claims. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the present disclosure are approximations, the numerical values ​​set forth in the specific examples are reported as precisely as possible. However, any numerical value inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should, at the very least, be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0241] Unless otherwise specified, all parts, percentages, ratios, etc. in the examples and elsewhere in the specification are by weight, and all reagents used in the examples are obtained or available from common chemical suppliers such as, for example, Sigma-Aldrich Company, Saint Louis, MO; Carus, Peru, IL; Calgon Carbon, Moon Township, PA; Ultramet, Los Angeles, CA, or can be synthesized by conventional methods.

[0242] In the examples which follow and / or elsewhere in this disclosure, the following abbreviations may be used: Mn = number average molecular weight; ppm = parts per million; ppb = parts per billion; mL = milliliter; L = liter; LPM = liters per minute; m = meter; mm = millimeter; min = minute; s = seconds; cm = centimeter; μm = micrometer; kg = kilogram; g = gram; min = minute; s = seconds; h = hour; °C = Celsius; °F = Fahrenheit; wt% = weight %; M = mole; μM = micromolar; mM = millimolar; DI Water = deionized water.

[0243] Table 1 is a Bill of Materials that provides a list of components used in the examples, as well as their associated vendor sources, abbreviations, and Chemical Abstracts Service (CAS) numbers.

[0244] [Table 1] Test Method: (Ozone depletion test) The following test method was used to evaluate the repeatability of various materials generated for ozone destruction. Samples were subjected to a temperature ramp under conditions of 2 liters per minute (2 LPM) air flow, ozone generation = 2V (TG-10; ozone solution), and downstream temperatures of 80 to 160°F (26.6 to 76.1°C). Ozone concentrations were measured using a Model 202 2B Technologies O3 detector (available from 2B Technologies, Zurich, Switzerland). Blank experiments were performed under these conditions, and experimental O3 conversion rates were calculated from the blank O3 concentrations at each temperature point, since the thermal stability of O3 decreases at higher temperatures. The turnover ratio per unit catalyst weight was then used to evaluate changes in catalytic activity resulting from changes in sample mass used in the test. The turnover rate is calculated as follows:

[0245]

number

[0246] (Dimensional analysis) Dimensional and topographical analysis of the various compositions of the examples was performed by scanning electron microscopy (SEM) on a JSM-7100F microscope. To prevent static buildup, samples were sputter-coated with gold / palladium for 120 seconds before imaging. Measurements were then performed using ImageJ software to calculate the average length of long-strand PTFE fibrils, the average resin particle size of long-strand PTFE resin, the average length of short-strand PTFE fibrils, the average resin particle size of short-strand PTFE resin, the average diameter of short-strand PTFE fibrils, the average diameter of long-strand PTFE fibrils, the average particle size of multiple active particles, the average particle size of free active particles, and the average porosity. Ten repeat measurements of length / width / diameter / particle size were performed, and the averages of each parameter were obtained.

[0247] Composition analysis The amount of each component in the matrix / composition is calculated according to the following Compositional Analysis Test Method: The Compositional Analysis Test Method may be referred to as the Loading Capacity Test Method.

[0248] The solids loading capacity of the material after heat treatment was calculated from the initial wetness, assuming uniform mixing of the solids and complete removal of the water / surfactant mixture. As an example, a matrix was formed from 13.3 g of CARULITE, 5 g of PTFE-E, and 3 g of PTFE-12 (total weight 21.3 g). Knowing that the PTFE-E material was composed of 60 wt. % PTFE solids as detailed by the manufacturer, the resulting weight of PTFE solids was calculated as the product of the weight fraction of PTFE solids and the weight used (e.g., if 5 g of PTFE-E was used, 60% PTFE-Solids x5g emulsion =3g PTFE solids The solids content of each component was then calculated on a dry basis, i.e., without considering any contribution from the water or surfactant components, using the following formula:

[0249]

number

[0250]

number

[0251] Example 1: Compositions Comprising Short-Strand PTFE Fibrils, Long-Strand PTFE Fibrils, and Catalyst Particles PTFE / CARULITE composite catalysts for ozone depletion were obtained by combining the weight ratios shown in Table 2. Here, the referenced weight ratios represent the wet basis used during mixing. The final dehydrated weight basis is shown in Table 3. The PTFE-40g sample was excluded from Table 3 because it did not exhibit the necessary agglomeration behavior to form a putty. The materials were processed in the following manner: First, the desired amount of PTFE-E was weighed and placed in a wide-mouth Nalgene bottle. Next, a certain amount of PTFE-12 was added to the emulsion (if applicable) to serve as a secondary binder for mechanical strength. The slurry was then diluted with 20 mL (20 g) of DI water. Next, the solution was vigorously shaken by hand to induce bubbles that suspend the PTFE-12 particles. This step was used to obtain a suspension. Without vigorous mixing, the PTFE-12 remained as characteristic solid particles.

[0252] Then first contain CeO2 (if applicable) and then CARULITE The solid components were added to the foamed slurry by adding 400 mL of DI water. The addition of the solids released surface tension from the foam bubbles, shifting the phase back to that of a homogeneous liquid slurry. At this stage, an additional 30 mL (30 g) of DI water was added to completely suspend the solid particles, after which the solution was again vigorously stirred by hand until i) all particles were uniformly suspended and ii) a soapy solution was again observed. At this stage, the slurry functioned as a surface coating, albeit with a different particle additive, as will be further described in the following paragraphs.

[0253] Following particle agitation and suspension, the slurry was tumbled on a rotating table at 30 revolutions per minute (rpm) for 24 hours at ambient temperature. After a certain time, solids separated from the surfactant / water mixture, forming a cohesive gel-like material with limited shape retention (flocculation). The separated liquid mixture was then decanted, and the gel was solidified into a moldable putty by drying via contact with an absorbent surface. More specifically, the gel was contacted with a cellulose sheet (absorbent) 10 times at 60-second intervals to extract sufficient water and transform the gel into a moldable putty with a defined three-dimensional structure capable of self-supporting behavior and shape retention.

[0254] [Table 2] The putty was then mounted on an alumina substrate for secondary drying, which served as a proof-of-concept test for ozone depletion. The coated substrates were then dried in one of two ways: i) by wrapping the material in aluminum foil and pressing it in an Emerson Model 140 Speed ​​Dryer at 300°F (148.9°C) for 1 hour, or ii) by calcining the sample at 330°C for 3 hours. Figure 11 shows a comparison of the structural integrity and particle dispersion obtained by the two heat treatment methods. There was a clear difference between the two heat treatment methods: the calcined sample (Figure 11A) tended to develop macrocracks in the mounted layer, forming micron-sized agglomerates (Figure 11B), whereas the hot-pressed sample formed a cohesive layer (Figure 11C) with smaller nanoscale catalyst particles (Figure 11D) and no macrocracks. For illustrative purposes, the 10 μm particles in Figure 11D were identified as CeO dopants and not the carulite phase. The difference between the phases prepared by the two techniques occurs in that the calcined sample (Figure 11B) experienced PTFE shrinkage at high temperatures, whereas the hot-pressed sample retained the fibrillated PTFE web structure and smaller catalyst particles (Figure 11D).

[0255] [Table 3] Next, we screened the ozone depletion potential as a function of PTFE-E loading and post-treatment method using thermal sweep tests as described above. As summarized in Figure 12, the hot-pressed samples outperformed the calcined ones. This better performance in the former is attributed to the retention of nanoscale catalyst particles and a higher active site density, as opposed to the agglomerated particles produced by calcination and shrinkage of PTFE strands. Furthermore, we observed that reducing the amount of PTFE-E used in the slurry further increased performance, which was again attributed to a higher active site density in the composite as a result of reduced interference from the inert PTFE material. Finally, we observed that the PTFE-10g (pressed) sample, which did not contain PTFE-12, performed slightly worse than the CARULTIE-CeO2 / PTFE-10µm sample.

[0256] As shown in Figure 13, these differences are due to the microstructural changes between the two media. In particular, using PTFE-E alone (Figure 13A) results in less PTFE fibrillation and more aggregation within the particle phase, whereas partially supplementing short-strand emulsified PTFE-E with PTFE-12 results in more fibrillation and a more distinct nanoparticulate catalyst (Figure 13B). Thus, these results demonstrate that catalytic properties can be manipulated by modifying the structural framework of the putty from the formulation.

[0257] Based on this, additional flocculants (e.g., compositions) were produced using the proportions in Table 4 through the use of dispersants other than water. Here, a process similar to that shown for the production of water-dispersed flocculants was used. Briefly, PTFE-E (5 g) was placed in a Nalgene bottle and 3 g of PTFE-601X was added. The resin mixture was then diluted with 20 mL (13.9 g) of ISOPAR-K and stirred. It was noted that this mixture did not result in emulsification of PTFE-501X, as opposed to PTFE-12 resin particles. This is believed to be due to the larger size of the PTFE-601X resin particles. To address this issue, 4.7 g of PEG-TMNE was added to the mixture, which was then vigorously stirred. This process resulted in a uniform emulsification of PTFE-400 in the ISOPAR-K / surfactant solution, as solids were no longer visible and the colloid became a milky white fluid, indicative of emulsified PTFE solids. After observing this change, 13.3 g of Carulite was added to the emulsion, followed by 15 mL (12.3 g) of ISOPAR-K. The mixture was stirred again and observed to immediately coagulate into an extruded putty. It is noted that there is no distinction between the coagulant and solvent phases in this process, as the putty does not separate from the dispersant and acts as a solid.

[0258] After formation, the coagulant could be i) left indefinitely with the surfactant / dispersant mixture, or ii) partially or completely dried for shape engineering. This behavior differed from water-dispersed coagulants, which i) required 24 hours of rotation to achieve coagulation and ii) exhibited a characteristic biphasic distribution of water and solid putty. Without wishing to be bound by theory, we believe the instantaneous solidification and dispersant retention occurred due to the wetting of PTFE by ISOPAR-K. In particular, while PTFE is known to be hydrophobic, ISOPAR-K's low surface tension allows it to partially penetrate and wet the PTFE solid. Such behavior rapidly destabilizes the surfactant / PTFE matrix, resulting in the formation of a uniform coagulant, particularly with PTFE-601X. This behavior is believed to be important when extruding the putty into a solid shape, as PTFE does not readily move under hydraulic pressure due to its high shear and non-Newtonian flow behavior. Therefore, an extrusion aid is required. Typically, such an aid is added directly to the PTFE. Mixing without emulsification with other additives, such as adsorbents or catalysts, would result in inhomogeneity and an unextrudable material. However, wetting the PTFE and catalyst with a dispersing agent, which can function as an extrusion aid, and forming the solids into a homogeneous putty through destabilization of the surfactant / PTFE matrix, makes the putty / additive system homogeneous and therefore extrudable. In this regard, it should be clarified that the putties in Table 4 are intended to be extruded into honeycomb or pellet shapes using a compression ram extrusion. For this reason, PTFE-12 in the previous examples was replaced with PTFE-601X from Chemours, because the larger resin diameter of PTFE-601X allows for better bonding with both the PTFE-E resin solid and the carulite phase. Longer stands allow for better polymer-polymer interaction, and therefore the extruded structure is more mechanically stable.

[0259] [Table 4] Example 2: Compositions Comprising Short-Strand PTFE Fibrils, Long-Strand PTFE Fibrils, and an Adsorbent The second example demonstrates base- or acid-initiated surfactant destabilization of emulsified PTFE as a means to produce functionalized aggregates of fibrillated fluoropolymer and solidified initiator. The composite can then be used as a medium for secondary growth of functional materials, such as metal-organic frameworks, or for adsorption applications. The material was first generated by pouring 30 mL of PTFE-E and 3 g of PTFE-12 into a beaker. The mixture was sonicated for 10 minutes at ambient temperature until homogeneity was observed and no PTFE-12 particles remained. Next, the surfactant destabilization initiator (in this case, 14 g of K2CO3) was added to the suspension, which resulted in the precipitation of a white solid that absorbed all remaining liquid. The precipitation behavior observed with this method resembles that of polymeric phase inversion, but the emulsified PTFE solid did not dissolve in the solvent in the usual dissociative sense. Rather, the PTFE was emulsified in a way that retained its intact chemical structure, and therefore functioned as a more homogeneous solid within the surfactant / water mixture and did not undergo dissociative changes. Thus, phase inversion with either basic or acidic initiators, as in this example, differed from traditional polymer phase inversion because it resulted from pH-driven destabilization of the surfactant, and not from changes in the solubility of the polymer itself.

[0260] The precipitate was converted to a dry, moldable solid by thoroughly drying the material. Unlike Example 1, the precipitate here was dried by pulling a vacuum in a vacuum oven at ambient temperature for 24 hours. This method was chosen instead of contacting with an absorbent because the initiator dissolves to some extent in the remaining water, and drying by absorption extracts the K2CO3. Instead of evacuating the precipitate through a vacuum oven, the solid was driven out of solution by supersaturation-induced precipitation, which resulted in higher initiator retention. The dried solid was then characterized by SEM, as shown in Figure 14. From Figure 14A, it was observed that the bulk material was primarily nonporous but contained localized regions of macroporosity, likely caused by mechanical fibrillation of the PTFE phase during drying under vacuum and / or surfactant destabilization. From Figures 14B and 14C, two types of K2CO3 immobilization behaviors exist at the microscopic level. The first such behavior, shown as catenated structures (Figure 14B), indicates the interconnection of K2CO3 particles precipitated around PTFE fibers, resulting in the formation of long strands of particles that form catenated structures. This behavior results from the catenation of K2CO3; i.e., rapid precipitation of the solid through vacuum resulted in the formation of an entangled particle matrix, some of which interconnect with each other. The catenated structures envelop a portion of the PTFE fibrils over a certain length, resulting in a linear network of basic initiator along the PTFE strands. The second such behavior, defined as agglomerated structures (Figure 14C), shows that individual K2CO3 particles are observed at fibril nodes, where individual PTFE strands join together and connect to a web-like network. The behavior of these agglomerated structures differs from that of catenated structures. The former produces macroscopically linearized particles / PTFE strands, whereas the latter produces a disordered arrangement of particle clusters with higher macroporosity. In the latter case, some of the K2CO3 particles precipitate around the PTFE nodules, which resembles the macroscopic embedding of multiple particles by the mechanism itself, but the number and size of the agglomerates differ. In either case, these materials are intended for use in the capture of corrosive gases, particularly the specific adsorption of SO2, H2S, NO2, NO, SO3, and NH3 (in the case of acidic initiators) in air purification applications.The materials can also be used for the secondary growth of metal-organic frameworks (MOFs) using an acidic ligand initiator such as trimesic acid followed by secondary coordination of the acidic sites with copper salts (Cu(NO3)2·2.5H2O) to form Cu(BTC)2. It is also contemplated that these materials can be used for the reduction of basic gases following a similar process, except that K2CO3 is replaced by a solid-state acid such as citric acid, terephthalic acid, trimesic acid, tartaric acid, maleic acid, benzoic acid, oxalic acid, or any combination thereof.

[0261] Example 3: Electrospinning of a composition comprising short-strand PTFE fibrils, long-strand PTFE fibrils, and a plurality of active particles In this example, a particle / PTFE matrix is ​​electrospun with a stabilizer—low-strength gelatin or some other biopolymer—to form multiple fine nanofibers containing embedded, aggregated particles. The biopolymer is then extracted at 200°C for 3 hours, producing multiple PTFE / particle nanofibers. The material described here is first prepared by sonicating 15 g of PTFE-E with 5 g of PTFE-12 to produce a uniform emulsion of short and long PTFE fibers. Next, 10 g of CARULITE and 15 g of DI are added to the emulsion, after which the solution is aerated to fully suspend the particles as described above. Next, a solution of 3–10 g of gelatin in an additional 20 g of DI is prepared by sonicating the gelatin for 15 minutes to completely dissolve it. The gelatin solution is then poured into the PTFE / CARULITE solution, followed by vigorous stirring to aerate the slurry and homogenize the two components. The solution is then immediately transferred to the electrospinning apparatus to prevent the material from gelling. The fibers are then spun onto a nonporous substrate and dried under vacuum for 24 hours. The gelatin is then extracted by calcination in air at 200-230 °C, which burns off the biopolymer. Alternative biopolymers, such as collagen or polylactic acid, as well as other synthetic polymers, such as polyurethane, poly(vinyl) alcohol, or nylon, can also function as stabilizers for spinning the PTFE / particle mixture.

[0262] Example 4: Casting the composition into a film As a proof of concept, the composition was cast into a film. The material recipe was slightly modified to produce the rheology required for casting. Using the previously described aeration technique, films were produced, but the slurry consisted of 25 g of PTFE-E, 5 g of PTFE-12, 15 g of CARULITE, and 20 g of DI. The slurry was formed as described above by aerating the PTFE-E / PTFE-12 mixture, but DI was not added during the initial aeration step. Instead, CARULITE was first suspended in DI, and the two solutions were then mixed together using mechanical vibration. The final slurry was then added to a cylindrical glass mold with a 5-inch (1.27 cm) particle size and a 0.5-inch (1.27 cm) height. The film was then placed in a fume hood at ambient temperature overnight, uncovered, to allow the suspension to solidify and begin drying. Finally, the film was contacted with an absorbent surface 10 times, followed by a final drying step under vacuum at ambient temperature to extract the surfactant. Examination of the membrane before and after drying revealed small specks of PTFE-12 on the surface. However, these are believed to be a product of the small-scale emulsification of PTFE-E and PTFE-12 together after pre-emulsification of the previous components. It is generally believed that to create a homogenous colloidal suspension, all PTFE solids must be simultaneously emulsified. Therefore, this slight inhomogeneity would not be present if the process had started with a homogenized surfactant / water / PTFE emulsion containing multiple PTFE resins of different sizes. The presence of both large and small PTFE fibrils was also observed in Figure 15, which was consistent with other materials.

Claims

1. A composition having a matrix, The matrix is a plurality of polytetrafluoroethylene (PTFE) fibrils, the plurality of polytetrafluoroethylene (PTFE) fibrils having short-strand PTFE fibrils and long-strand PTFE fibrils; a plurality of active particles; A composition comprising:

2. 10. The composition of claim 1, wherein when the composition is in an unexpanded state, at least a portion of the plurality of active particles and at least a portion of the plurality of PTFE particles adopt a catenated structure, an aggregated structure, or both.

3. the plurality of active particles comprise a catalyst, an adsorbent, a growth seed, a metal-organic framework, an electroactive material, or any combination thereof; 3. The composition of claim 1, wherein the adsorbent is a physisorbent, a chemisorbent, or a physisorbent-chemisorbent hybrid.

4. 4. The composition of claim 3, wherein the catalyst is capable of ozone destruction.

5. 5. The composition of claim 4, wherein the catalyst comprises manganese oxide, copper oxide, cerium dioxide, a reduced metal, or any combination thereof.

6. 4. The composition of claim 3, wherein the adsorbent is capable of adsorbing basic compounds, acidic compounds, organic compounds, inorganic compounds, or any combination thereof.

7. 8. The composition of claim 1, wherein the composition comprises from 0.01% to 30% by weight of long-strand PTFE fibrils, based on the total weight of the composition according to the Composition Analysis Test Method.

8. 8. The composition of claim 1, wherein the composition comprises from 50% to 95% by weight of active particles, based on total composition weight as calculated by the Compositional Analysis Test Method.

9. A substrate having an outer surface, A substrate having disposed on at least a portion of its outer surface the composition of any one of claims 1 to 7.

10. the substrate is non-porous; 10. The substrate of claim 9, wherein the substrate comprises a corrugated honeycomb, a non-porous polyurethane, a polyethylene honeycomb, a silicon carbide honeycomb, a cordierite honeycomb, or any combination thereof.

11. 1. A method of making a composition, comprising: The composition includes a matrix having a plurality of PTFE fibrils formed from a PTFE resin and a plurality of active particles; The method comprises: aerating an emulsion to form an aerated emulsion, said emulsion and said aerated emulsion comprising: the PTFE resin, dispersants, and surfactants, and adding a solid particle composition to the aerated emulsion to form a matrix premix, the solid particle composition comprising solid particles, the matrix premix comprising: the PTFE resin, the dispersant, the solid particle composition, and The surfactant and aerating the matrix premix to form an aerated matrix premix, the aerated matrix premix comprising: the PTFE resin, the solid particle composition, the dispersant, and The surfactant and mixing the aerated matrix pre-mix to form a hydrated solid, the hydrated solid comprising: the plurality of PTFE fibrils, the plurality of active particles comprising at least a portion of the solid particles; at least a portion of the dispersant; and at least a portion of the surfactant; and drying the hydrated solid to form a matrix; A method comprising:

12. 1. A method of disposing a composition on a substrate, comprising: the substrate has an outer surface; The method includes the method of claim 11, further comprising: contacting at least a portion of the exterior surface of the substrate with the aerated matrix premix; mixing the aerated matrix premix in contact with at least a portion of the substrate such that at least a portion of the hydrated solids are formed on the exterior surface; A method comprising:

13. 1. A method of making a composition, comprising: The composition includes a matrix having a plurality of PTFE fibrils formed from a PTFE resin and a plurality of active particles; The method comprises: precipitating at least a portion of the particles of the PTFE resin from the (aerated) matrix premix to form a hydrated solid by adding a solid particle composition to the (aerated) matrix premix, the solid particle composition comprising solid particles, and the (aerated) matrix premix comprising: the PTFE resin, dispersants, and surfactants and the hydrated solid has the plurality of active particles comprising at least a portion of the solid particles; at least a portion of the dispersant; and At least a portion of the surfactant and drying the hydrated solid to form the matrix; A method comprising:

14. 1. A method of disposing a composition on a substrate, comprising: the substrate has an outer surface; The method comprises the method of claim 13, further comprising: contacting at least a portion of the outer surface of the substrate with the (aerated) matrix premix; adding a solid particle composition to the aerated matrix pre-mix to precipitate at least a portion of the emulsified PFTE resin from the aerated matrix pre-mix and form at least a portion of hydrated solids on the outer surface; A method comprising:

15. 15. The method of claim 11, wherein the plurality of PTFE fibrils comprises short-strand PTFE fibrils.

16. 15. The method of claim 11, wherein the plurality of PTFE fibrils comprises long-strand PTFE fibrils and short-strand PTFE fibrils.

17. 17. The method of any one of claims 11 to 16, wherein drying the hydrated solid further comprises contacting the matrix with an absorbent material to remove at least a portion of the dispersing agent, at least a portion of the liquid carrier (if present), at least a portion of the surfactant, or any combination thereof.

18. 17. The method of any one of claims 11 to 16, wherein the surfactant comprises a non-ionic non-fluorinated surfactant.

19. 19. The method of any one of claims 11 to 18, wherein the composition is a composition according to any one of claims 1 to 7.

20. The method requires a total active particle loading capacity of 50% by weight or more based on the Loading Capacity Test Method.

20. The method according to claim 11, wherein a capacitance (capacity) is obtained.

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