Sintering system and sintered article

Abstract

A system is provided for sintering thin, wide and / or long strip material in, for example, a roll-to-roll process. The system is arranged to control sintering and limit strip distortion during sintering to produce a sintered material.

Description

[0001] This application is a divisional of patent application number 201780086844.4, filed December 19, 2017, entitled "Sintering System and Sintered Article."

[0002] Priority

[0003] This application claims priority to U.S. Application No. 62 / 437,157, filed December 21, 2016, U.S. Application No. 62 / 439,613, filed December 28, 2016, U.S. Application No. 62 / 470,550, filed March 13, 2017, U.S. Application No. 62 / 439,609, filed December 28, 2016, U.S. Application No. 62 / 526,806, filed June 29, 2017, U.S. Application No. 62 / 439,598, filed December 28, 2016, U.S. Application No. 62 / 483,726, filed April 10, 2017, U.S. Application No. 62 / 484,106, filed April 11, 2017, and U.S. Application No. 62 / 556,712, filed September 11, 2017, which are incorporated by reference herein in their entirety, on which this application is based and which are each incorporated herein in their entirety. BACKGROUND

[0004] The present disclosure relates generally to processes for sintering, for example, sintering green tape strips containing polycrystalline ceramic particles or other inorganic particles bound in a binder, and continuous and discrete sintered articles, for example, ceramic plates, tapes, or ceramic sheets, manufactured from such processes. The present disclosure relates to articles, for example, thin plates, strips, tapes, or sheets of ceramic or other inorganic materials having many potential uses, for example, as waveguides when the ceramic is transmissive to light, as substrates that can be coated or laminated, and integrated in batteries or other assemblies, or used as or in conjunction with substrates, for example, as dielectrics in electronic packages, for example, LED packages, or other applications. Various material properties, particularly for ceramic materials, for example, high electrical resistivity, low reactivity, low coefficient of thermal expansion, etc., make such articles particularly suitable for a wide range of various applications. SUMMARY

[0005] Some aspects of the present disclosure relate to a tape separation system for sintering preparation. The tape separation system includes a tape material source, which includes a green tape, and a carrier web supporting the green tape. The green tape includes particles of inorganic material in a binder. The tape separation system also includes a peeler for directing the carrier web in a rewind direction and directing the green tape in a downstream processing direction different from the rewind direction, and a vacuum drum positioned and configured to receive the tape material from the source and transport the tape material to the peeler. The vacuum drum includes apertures for applying a suction force to the carrier web to facilitate tensioning of the carrier web, and the tension in the carrier web (measured in force per cross-sectional area) is greater than the tension in the green tape as the tape material is transported from the vacuum drum to the peeler, thereby mitigating deformation of the green tape during separation of the green tape from the carrier web.

[0006] Other aspects of the present disclosure relate to a tape processing system for sintering preparation. The system includes a tape including a green portion of the tape having particles of inorganic material in an organic binder, and a binder burnout station including an active heater. The tape is advanced through the binder burnout station such that the binder burnout station receives the green portion of the tape, and the binder burnout station causes the organic binder to char or burn when the green portion of the tape is in contact with heat from the heater, thereby forming a second portion of the tape that is prepared for sintering of the inorganic material of the tape. In some embodiments, the tape simultaneously extends into, through, and out of the binder burnout station at an instant in time, such that the tape includes the green portion continuously connected to the second portion at the instant in time, e.g., where the binder burnout station chars or burns at least a majority of the organic binder (by weight) from the green portion of the tape without causing significant sintering of the particles of inorganic material. In some embodiments, the tape processing system for sintering preparation also includes an ultra-low tension dancer roll that includes a lightweight low inertia roll that directionally changes the tape without applying a significant tension such that the tension in the second portion of the tape is less than 500 grams of force per mm 2 cross-sectional area, thereby reducing the likelihood of breakage of the second portion of the tape and facilitating sintering of long continuous lengths of the tape. In some embodiments, the tape processing system for sintering preparation blows and / or sucks a gas on the tape as the tape is advanced through the binder burnout station, and the binder burnout station heats the tape to a temperature that is higher than a temperature at which the organic binder would ignite without the gas blown and / or sucked on the tape, thereby causing the organic binder to char or burn without the tape catching fire.

[0007] Additional aspects of the present disclosure relate to a production line including the above-described system for processing a tape, wherein the adhesive burn-out station is a first station, and the production line further includes a second station spaced apart from the first station. The second station at least partially sinter the inorganic material of the second portion of the tape to form a third portion of the tape, wherein, at an instant, the tape includes a green portion continuously connected to the third portion by way of the second portion. For example, in some such embodiments, the third portion of the tape is substantially more flexible than the second portion, such that a minimum bend radius without breakage of the third portion is less than half of a minimum bend radius of the second portion, and the green portion is substantially more flexible than the second portion, such that a minimum bend radius without breakage of the green portion is less than half of a minimum bend radius of the second portion. The production line further includes the tape separation system described above.

[0008] Some aspects of the present disclosure relate to a sintering system including a tape material comprising particles of inorganic material and a sintering station. The sintering station includes an inlet, an outlet, and a passageway extending between the inlet and the outlet. At an instant, the tape material extends into the inlet of the sintering station, extends through the passageway, and extends out of the outlet. Heat within the passageway sinters the inorganic material such that the inorganic material has a first porosity at the inlet and a second porosity at the outlet that is less than the first porosity. Further, the tape material is positively tensioned as it passes through the passageway of the sintering station, thereby mitigating warping. In some embodiments, the tape material moves through the sintering station at a speed of at least 1 inch per minute. In some embodiments, the passageway of the sintering station is heated by at least two independently controlled heating elements, wherein the heating elements produce a temperature profile in which the temperature of the passageway increases along a length of the passageway in a direction from the inlet toward the outlet of the sintering station, and wherein the sintering temperature in the passageway exceeds 800 °C. In some embodiments, the sintering system further includes a curved surface positioned along the passageway of the sintering station, wherein the tape material curves around the curved surface relative to a widthwise axis of the tape material as the tape material moves through the sintering station, thereby affecting a shape of the tape material. In some embodiments, the outlet and the inlet of the sintering station are positioned in a substantially horizontal plane such that an angle defined between the outlet and the inlet of the sintering station relative to the horizontal plane is less than 10 degrees, thereby at least partially controlling a flow of gas relative to the passageway; for example, in some such embodiments, the sintering station further includes an upwardly facing passageway surface (which defines a lower surface of the passageway) and a downwardly facing passageway surface (which defines an upper surface of the passageway), wherein the downwardly facing passageway surface is positioned proximate to an upper surface of the tape material such that a gap between the upper surface of the tape material and the downwardly facing passageway surface is less than 0.5 inches, thereby at least partially controlling a flow of gas in the passageway. The tape material can be particularly wide, long, and thin, having a width greater than 5 millimeters, a length greater than 30 centimeters, and a thickness of 3 micrometers to 1 millimeter, and the inorganic material of the tape can be at least one of a polycrystalline ceramic material and a synthetic mineral.

[0009] Other aspects of the present disclosure relate to a manufacturing process for a ceramic tape, the process comprising the step of sintering a tape comprising a polycrystalline ceramic to a porosity of the polycrystalline ceramic of less than 20 vol% by exposing the grains of the polycrystalline ceramic to a heat source to induce sintering between the grains. The tape is particularly thin such that the thickness of the tape is less than 500 pm, thereby facilitating rapid sintering via thermal penetration. Further, the tape is at least 5 mm wide and at least 300 cm long. In some embodiments, the process further comprises the step of tensioning the tape in the positive length direction during sintering. In some such embodiments, the process further comprises the step of moving the tape towards the heat source and then away from the heat source during sintering. In some embodiments, the amount of time for sintering is particularly short, totaling less than 2 hours, thereby helping to maintain small grain sizes in the ceramic tape; for example, in some such embodiments, the sintering time totals less than 1 hour, and after sintering, the density of the polycrystalline ceramic is greater than 95 vol% dense and / or the tape comprises closed pores after sintering. In some embodiments, the tape comprises a volatile component that evaporates during sintering, wherein the volatile component is inorganic, and wherein the tape contains at least 1 vol% more of the volatile component before sintering than after sintering.

[0010] Other aspects of the present disclosure relate to a tape comprising a body comprising particles of inorganic material sintered to one another. The body extends between first and second major surfaces, wherein the body has a thickness defined as the distance between the first and second major surfaces, a width defined as the first dimension of the first major surface perpendicular to the thickness, and a length defined as the second dimension of the first major surface perpendicular to both the thickness and the width. The tape is long, having a length of about 300 cm or more. The tape is thin, having a thickness of about 3 pm to about 1 mm. The tape is particularly wide, having a width of about 5 mm or more. According to exemplary embodiments, the tape is geometrically consistent in that the width of the tape varies by less than 100 pm when measured at locations spaced 1 m apart in the length direction; and the thickness of the tape varies by less than 10 pm when measured at locations spaced 1 m apart in the length direction along the center of the width of the tape. In some embodiments, the tape is flat or is flatabl e such that a 10 cm length of the tape pressed between parallel flat surfaces is flattened to within 0.05 mm of contact with the parallel flat surfaces without breaking; for example, in some such embodiments, the maximum in-plane stress exhibited by the tape when flattened to within 0.05 mm of contact with the parallel flat surfaces is no more than 1% of its Young's modulus. In some embodiments, the first and second major surfaces of the tape have a granular topography, wherein the particles are ceramic, and wherein at least some individual particles of the ceramic abutting one another have little to no intervening amorphous material such that the thickness of amorphous material between two abutting particles is less than 5 nm. In some embodiments, the body has a porosity of less than 10 vol%, and / or the body has closed pores. In some embodiments, the particles comprise lithium, and the ionic conductivity of the body is greater than 5 x 10 -5 S / cm. In some embodiments, the body has a particularly fine particle size, which is 5 pm or less. In some embodiments, the tape further comprises a conductive metal connected to the first major surface of the body, wherein in some such embodiments the body comprises a repeating pattern of pores and the conductive metal is arranged in the repeating pattern. In some embodiments, the first and second major surfaces have a granular topography, the tape further comprises a coating overlying the granular topography of the first major surface, and the outward-facing surface of the coating is not as rough as the granular topography of the first surface, wherein the manner in which the conductive metal is connected to the first major surface is by being adhered to the outward-facing surface of the coating. In some embodiments, the inorganic material has a viscosity of 12.5 poise at a temperature greater than 900 °C.

[0011] Additional aspects of the present disclosure relate to a roll of tape of any of the above-described embodiments, wherein the tape is wound and overlapped upon itself, curved to a radius of less than 30 cm.

[0012] Other aspects of the present disclosure relate to a plurality of sheets cut from the tape of any of the above-described embodiments.

[0013] Some aspects of the present disclosure relate to a tape comprising a body comprising sintered-together ceramic particles, the body extending between first and second major surfaces, wherein the body has a thickness defined as the distance between the first and second major surfaces, a width defined as the first dimension of the first major surface perpendicular to the thickness, and a length defined as the second dimension of the first major surface perpendicular to both the thickness and the width; wherein the tape is thin, having a thickness of about 3 pm to about 1 mm; and wherein the first and second major surfaces of the tape have a granular profile, and the first and second major surfaces of the tape have a granular profile, at least some individual particles of the ceramic abutting one another having little to no intervening amorphous material, such that the thickness of amorphous material between two abutting particles is less than 5 nm.

[0014] Some aspects of the present disclosure relate to a tape comprising a body comprising sintered-together ceramic particles, the body extending between first and second major surfaces, wherein the body has a thickness defined as the distance between the first and second major surfaces, a width defined as the first dimension of the first major surface perpendicular to the thickness, and a length defined as the second dimension of the first major surface perpendicular to both the thickness and the width; wherein the tape is thin, having a thickness of about 3 pm to about 1 mm; wherein the first and second major surfaces of the tape have a granular profile; and wherein the particles comprise lithium, and the body has an ionic conductivity greater than 5 x 10 - 5 S / cm.

[0015] Additional features and advantages are described in, and will be apparent from, the following DETAILED DESCRIPTION in conjunction with the drawings.

[0016] It is to be understood that both the foregoing general description and the following detailed description are merely exemplary, and are intended to provide an overview or framework for understanding the nature and character of the claims.

[0017] The accompanying drawings are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification. The drawings illustrate one or more embodiment(s) and together with the description serve to explain principles and operation of the various embodiments. BRIEF DESCRIPTION OF DRAWINGS

[0018] Figure 1 Examples of distorted sintered ceramic tape materials formed without the techniques disclosed herein (e.g., the controlled green tape tensioning and other techniques discussed herein).

[0019] Figure 2 Examples of distorted sintered ceramic tape material produced with a temperature profile and strip speed that results in non-uniform sintering.

[0020] Figure 3 is a roll-to-roll system for producing sintered articles according to an example embodiment.

[0021] Figure 4 is a roll-to-roll system for producing sintered articles according to an example embodiment, Figure 3 is a close-up view of an embodiment of a separation system.

[0022] Figure 5 is a side view of a continuous tape material according to an example embodiment.

[0023] Figure 6 is a perspective view of a vacuum drum according to an example embodiment.

[0024] Figure 7 is a perspective view of a vacuum drum according to an example embodiment, Figure 6 is a close-up view of a vacuum drum.

[0025] Figure 8 is a perspective view of a vacuum drum according to an example embodiment, Figure 4 is a close-up view of a peeler.

[0026] Figure 9 is a conceptual side view of a work station of a production line that prepares green tape for sintering according to an example embodiment.

[0027] Figure 10 is a perspective view of a work station according to an example embodiment, Figure 9 is a front perspective view of a work station.

[0028] Figure 11 is a block diagram of a method of processing green tape to prepare the green tape, at least in part, for sintering according to an example embodiment.

[0029] Figure 12 is a block diagram of a method of processing green tape to prepare the green tape, at least in part, for sintering according to an example embodiment, Figure 3 is a detail view of an adhesive removal work station and a sintering work station of a system.

[0030] Figure 13 is a detail view of a sintering furnace according to an example embodiment, Figure 12 is a detail view of a tape material within a channel of a sintering furnace.

[0031] Figure 14 shows sintered tape material exiting a sintering furnace according to an example embodiment.

[0032] Figure 15 is a perspective view of a sintered article according to an example embodiment, Figure 12A view of a sintering station showing a heating system.

[0033] Figure 16 A plot of predicted thermal distribution and modeling of sintering shrinkage versus distance for different strip transport speeds according to an exemplary embodiment.

[0034] Figure 17 A plot showing a predicted sintering temperature distribution projected along a channel of a sintering furnace according to an exemplary embodiment.

[0035] Figure 18 A plot showing an inline multi-furnace sintering station according to an exemplary embodiment.

[0036] Figure 19 A plot showing a sintering system with two parallel production systems according to an exemplary embodiment. Figure 18 A plot of predicted temperature distribution for the two sintering furnaces.

[0037] Figure 20 A plot showing a sintering system with two parallel production systems according to an exemplary embodiment.

[0038] Figure 21 A plot of sintering shrinkage of zirconia at various temperatures and temperature times, including a data fit curve for each temperature.

[0039] Figure 22 A plot of curve fitting of a mathematical function of sintering shrinkage of a zirconia strip at various temperatures and various times of temperature.

[0040] Figure 23 A plot modeling the peak stress at the centerline of a zirconia strip during sintering as a function of the number of heating zones, number of passes, strip transport speed, and as a function of strip width.

[0041] Figure 24 A plot modeling the peak stress at the edge of a zirconia strip during sintering as a function of the number of heating zones, number of passes, strip transport speed, and as a function of strip width.

[0042] Figure 25 A plot modeling shrinkage in a zirconia strip during sintering with two passes through a single hot zone furnace for two strip transport speeds.

[0043] Figure 26 A plot modeling stress in a zirconia strip during sintering with two passes through a single hot zone furnace for two strip transport speeds.

[0044] Figure 27 A plot modeling shrinkage in a zirconia strip during sintering with two passes through a 10 hot zone furnace for two strip transport speeds.

[0045] Figure 28 is a plot of modeled stresses (in MPa) in a zirconia tape during a sintering process using a two-pass 10 hot zone furnace for two tape transport speeds and various tape widths.

[0046] Figure 29 is a schematic perspective view of a portion of a sintered article according to an example embodiment.

[0047] Figure 30A is a digital image of an unpolished surface of a sintered article.

[0048] Figure 30B is a conceptual side profile of a sintered article of Figure 30A

[0049] Figure 31A is a digital image of a polished surface of a sintered article.

[0050] Figure 31B is a conceptual side profile of a sintered article of Figure 31A

[0051] is a side view along the width of a sintered article according to one or more embodiments. Figure 32

[0052] the accompanying drawings show thin flexural equilibrium. Figure 33

[0053] is a perspective side view of a roll sintered article according to an example embodiment. Figure 34A

[0054] is a cross-sectional view of a roll sintered article according to an example embodiment, Figure 34B Figure 34A

[0055] Figure 35 is a height profile of the sintered article of Example 5 prior to flattening, showing measured heights above the flattening plane.

[0056] Figure 36 is a height profile of the sintered article of Example 6 prior to flattening, showing measured heights above the flattening plane.

[0057] Figure 37 is a height profile of the sintered article of Comparative Example 7 prior to flattening, showing measured heights above the flattening plane.

[0058] Figure 38 is a height profile of the sintered article of Comparative Example 8 prior to flattening, showing measured heights above the flattening plane.

[0059] Figure 39 ​​​is a plot of the maximum height above the planarization plane for each of the sintered articles of Examples 5-6 and Comparative Examples 7-8.

[0060] Figure 40 is a plot of the force required to planarize each of the sintered articles of Examples 5-6 and Comparative Examples 7-8.

[0061] Figure 41 is a plot of the pressure required to planarize the sintered articles of Examples 5-6 and Comparative Examples 7-8.

[0062] Figure 42 is a plot of the maximum in-plane stress after planarization of the sintered articles of Examples 5-6 and Comparative Examples 7-8.

[0063] Figure 43A is a deformed plot showing the stresses measured in the bottom surface of the sintered article of Example 5 after planarization.

[0064] Figure 43B is a deformed plot showing the stresses measured in the top surface of the sintered article of Example 5 after planarization.

[0065] Figure 44A is a deformed plot showing the stresses measured in the bottom surface of the sintered article of Example 6 after planarization.

[0066] Figure 44B is a deformed plot showing the stresses measured in the top surface of the sintered article of Example 6 after planarization.

[0067] Figure 45A is a deformed plot showing the stresses measured in the bottom surface of the sintered article of Comparative Example 7 after planarization.

[0068] Figure 45B is a deformed plot showing the stresses measured in the top surface of the sintered article of Comparative Example 7 after planarization.

[0069] Figure 46A is a deformed plot showing the stresses measured in the bottom surface of the sintered article of Comparative Example 8 after planarization.

[0070] Figure 46B is a deformed plot showing the stresses measured in the top surface of the sintered article of Comparative Example 8 after planarization.

[0071] Figure 47 is a cross-sectional view of a segment of a package containing a sintered article according to an example embodiment.

[0072] Figure 48 is a cross-sectional view of a segment of a package containing a sintered article according to an example embodiment.

[0073] Figure 49is another cross-sectional view of a segment of a package containing a sintered article according to an exemplary embodiment.

[0074] Figure 50 is an exemplary method of manufacturing a package containing a sintered article according to an exemplary embodiment.

[0075] Figure 51 is another exemplary method of manufacturing a package containing a sintered article according to an exemplary embodiment.

[0076] Figure 52 is an exemplary cross-sectional view of a segment of a package containing a sintered article and a "flip-chip" configuration according to an exemplary embodiment.

[0077] Figure 53 is another exemplary cross-sectional view of a segment of a package containing a sintered article and a "flip-chip" configuration according to an exemplary embodiment.

[0078] Figure 54 is another exemplary cross-sectional view of a segment of a package containing a sintered article and a "flip-chip" configuration according to an exemplary embodiment.

[0079] Figure 55 is another cross-sectional view of a segment of a package containing a sintered article according to an exemplary embodiment.

[0080] Figure 56 shows a roll-to-roll system and related processes for producing a sintered article containing a length of thread-like material according to an exemplary embodiment.

[0081] Figure 57 is a detail view showing the bonding between a length of thread-like material and a strip material in the system of Figure 56

[0082] Figure 58 shows a roll-to-roll system according to an exemplary embodiment that includes a sintering station configured to form a curvature along the longitudinal direction of a continuous length of strip material.

[0083] Figure 59 is a detail view of a sintering station according to an exemplary embodiment that includes an insert defining a curved lower surface of a sintering channel.

[0084] Figure 60 is a side view of a channel of a sintering station according to an exemplary embodiment having opposing curved upper and lower surfaces that define a sintering channel.

[0085] Figure 61 ​is a side view schematic of a sintering station according to an exemplary embodiment, with a varying radius of curvature along a sintering tunnel.

[0086] Figure 62 shows a gas bearing according to an exemplary embodiment, with a curved upper surface defining a curved surface of a sintering tunnel.

[0087] Figure 63 shows a roller arrangement according to an exemplary embodiment for forming a longitudinal curvature in a continuous length of a strip during sintering.

[0088] Figure 64 shows an arrangement including multiple rollers according to an exemplary embodiment for forming multiple longitudinal curvatures in a continuous length of a strip during sintering.

[0089] Figure 65 shows a free loop arrangement according to an exemplary embodiment for forming a longitudinal curvature in a continuous length of a strip during sintering.

[0090] Figure 66 is a digital image of a sintered strip demonstrating flattening that occurs when a strip is curved during sintering.

[0091] Figure 67A and 67B is a digital image of a sintered ceramic strip roll according to an exemplary embodiment.

[0092] Figure 68 is a digital image of a sintered ceramic strip roll according to another embodiment.

[0093] Figure 69 is a digital image of a sintered ceramic strip roll according to another embodiment.

[0094] Figure 70 is a graph showing conventional batch firing versus sintering time graph of the technology disclosed herein according to an exemplary embodiment.

[0095] Figure 71A and 71B is a top view of a surface of a sintered article according to an exemplary embodiment.

[0096] Figure 72A and 72B is a side perspective view of a surface of a sintered article according to an exemplary embodiment.

[0097] Figure 73A , 73B and 73C is a micrograph of a grain boundary of a sintered article according to an exemplary embodiment.

[0098] Figure 74 and75 is a micrograph of a grain boundary of a sintered article according to other example embodiments.

[0099] Figure 76 and 77 is a top view of a surface of a sintered article according to example embodiments.

[0100] Figure 78 is a digital image of a band of a sintered article according to example embodiments.

[0101] Figure 79A and 79B is a side view of a sintered article according to example embodiments.

[0102] Figure 80 is a side view of a sintered article according to example embodiments.

[0103] Figure 81 is a side view of a sintered article according to another example embodiment, wherein the sintered material appears amorphous.

[0104] Figure 82 is a component representative diagram.

[0105] Figure 83 and 84 is a side perspective view of a surface of a sintered article according to example embodiments.

[0106] Figure 85A and 85B is a side perspective view of a surface of an unsintered green material according to example embodiments.

[0107] Figure 86A and 86B is a side perspective view of a surface of a sintered material according to example embodiments.

[0108] Figure 87 graphically represents viscosity versus temperature relationships for various materials.

[0109] Figure 88A graphically represents temperature distribution through a sintering furnace according to example embodiments.

[0110] Figure 88B is a schematic diagram of a sintering furnace of Figure 88A

[0111] Figure 89 is a schematic diagram of a sintering furnace according to another example embodiment.

[0112] Figure 90A graphically represents temperature distribution through a sintering furnace according to another example embodiment. ​

[0113] Figure 90B yes Figure 90A A schematic diagram of the sintering furnace.

[0114] Figure 91A and 91B This is a side perspective view of the surface of a sintered material according to an exemplary embodiment.

[0115] Figure 92 This is a side view of a sintered material according to an exemplary embodiment.

[0116] Figure 93 This is a schematic diagram of an electronic device in the form of a battery according to an exemplary embodiment.

[0117] Figure 94 and 95 The illustrations represent sintering schemes according to exemplary embodiments.

[0118] Figure 96 The illustration represents the relationship between sintering temperature and ionic conductivity of a sintered article according to an exemplary embodiment.

[0119] Figure 97 The illustration represents the relationship between the sintering temperature and the percentage of cubic garnet in a sintered article according to an exemplary embodiment.

[0120] Figure 98 and 99 This is a side perspective view of the surface of a sintered material according to an exemplary embodiment.

[0121] Figure 100A and 100B This is a top view of one side surface of the sintered material according to an exemplary embodiment, and Figure 101A and 101B This is a top view of the surface on the other side of the sintered material.

[0122] Figure 102 This is a side view of a sintered material according to an exemplary embodiment.

[0123] Figure 103 It is a digital image of a sintered material according to an exemplary embodiment, which has a layer that provides a smooth surface.

[0124] Figure 104 This is a schematic diagram of an electronic component in the form of a stack of sintered articles according to an exemplary embodiment. Detailed Implementation

[0125] Referring generally to the drawings, systems and processes for manufacturing long, thin and / or wide sintered articles are shown and described, where for the term sintering, applicants refer to the process of causing particles or grains (e.g., of a powdered or granular material) to coalesce (e.g., directly bond to one another) into a solid or porous body by heating the particles or grains without causing the particles or grains to completely dissolve, such that the crystalline structure of the particles or grains is preserved in the aggregate, although aspects of the present technology can also be used to manufacture amorphous materials, such as those that one of ordinary skill in the art of inorganic materials processing might directly recognize as being difficult or impossible to process using conventional manufacturing techniques. Moreover, applicants have discovered that using the systems / processes discussed herein, new sintered articles can be formed having various properties that were previously unattainable using prior art systems. In particular, applicants have developed material processing systems and processes that achieve a level of precision in the control of various conditions / forces to which the material is subjected during the formation of the sintered article that enables the production of long, thin and / or wide sintered strip materials that are believed to be unattainable using prior art systems. Moreover, articles manufactured using the technology disclosed herein can have other unique qualities, such as: strength, such as can be due to a low number of defects; purity, such as can be due to controlled air flow and sintering duration, and properties related to purity, such as dielectric constant and impermeability; consistency, such as along the length and / or width directions, such as in terms of flatness, thickness, roughness, grain size, etc.; and other unique attributes.

[0126] Generally, the systems described herein employ an input roll that supports a web of green strip around a spool or reel. As explained in greater detail below, the web supports the green strip, which includes green strip material that includes particles of inorganic material (e.g., particles of ceramic material, particles of polycrystalline ceramic material, metallic particles or grains of a synthetic material) bonded with organic binder material, and the green strip material is supported on a carrier web (e.g., a sheet of polymeric material). The input roll unwinds the web supporting the green strip, and the carrier web / backing layer is carefully separated from the green strip material. Applicants have discovered that by precisely controlling the separation of the carrier web from the green strip such that the green strip has little or no distortion, sintered articles can be produced that have very consistent / controlled various properties (e.g., thickness, flatness, density, shape, etc.) along their length. That is, in other contemplated embodiments, the green strip can not be web supported and / or can not be on a roll, such as if the strip is formed in-line (e.g., along a production line) prior to sintering.

[0127] After the carrier web is removed, the self-supporting green tape strip (comprising particles of inorganic material supported by organic binder material) moves through a binder removal station. Generally, the binder removal station applies heat to the self-supporting green tape strip in a manner that removes the organic binder or causes the organic binder to chemically change, such that the strip material exiting the binder removal station is a non-bonded strip material. By non-bonded, applicants mean that the binder material is removed, but the non-bonded strip can still remain together, for example, by charring of the binder or by interweaving or bonding between the inorganic particles, or by other means (e.g., electrostatic forces, atmospheric pressure). After the organic binder is removed, the non-bonded strip material moves into a sintering station that applies heat to the non-bonded strip material, which causes the inorganic particles to sinter (e.g., fully sinter or partially sinter), forming a sintered article that exits the sintering station.

[0128] Applicants have surprisingly discovered that even after the organic binder is removed, the particles of inorganic material support themselves as a non-bonded strip material and / or can support the strip in other ways, as described above. However, after the organic binder is removed, the non-bonded strip material is very delicate before sintering or can be very delicate before sintering. Accordingly, applicants have also determined a new binder removal and sintering station arrangement that allows for handling of the delicate unsupported strip material in a manner that allows for production of very high quality sintered articles. By unsupported in the above sentence, applicants mean that after the binder is removed or burned off, there is no support from the organic binder. In particular, a wide, long, and high quality sintered article is produced that is suitable for roll-to-roll processing without introducing significant distortion or breaking the article during the binder removal or sintering process.

[0129] Specifically, the applicant determined that airflow within the binder removal station and / or sintering station (e.g., turbulent airflow due to thermal gradients) could impact the strip material, causing deformation or breakage. Furthermore, the applicant found that highly horizontal processing paths within the binder removal station and / or sintering station reduced or eliminated turbulent airflow, which in turn produced or could produce sintered articles without significant deformation. Additionally, the applicant determined that eliminating airflow-based deformation is particularly important when forming wide sintered articles (e.g., articles wider than 5 mm), as the applicant believes that susceptibility to airflow-based deformation increases with the width of the strip material. Moreover, the applicant determined that eliminating or reducing airflow-based deformation is crucial for achieving roll-to-roll processing, as the applicant found that even minute levels of deformation can lead to breakage of the sintered article or, otherwise, improper winding onto the take-up reel (also known as the take-up roll).

[0130] Given the inorganic green materials and prior sintering techniques, determining the horizontal placement of the strips during binder removal and / or sintering is a surprising finding. For example, some strip sintering may use a downward angled placement of the strip material (e.g., a downward tilt of 12 to 20 degrees) as a way to utilize gravity to pull the fragile strip material through the heating steps of the system, possibly aiming to apply a uniformly distributed force on the strip material to pull the strip material through the heating steps of the process.

[0131] However, the applicant discovered that when the heating section of the sintering system is tilted, vortex airflow may form hot air that rises through the channels of the heating system containing the strip material. Therefore, this airflow impacting the strip material may cause deformation or even breakage. Furthermore, the applicant found that the potential for airflow-based deformation in sintered strips formed using a non-horizontal heating arrangement may increase with the width of the strip material. That is, the technical aspects disclosed herein can be used with systems including non-horizontal heating channels or systems, such as binder removal workstations. Moreover, non-horizontal heating channels or systems can be used to manufacture the technical aspects disclosed herein, such as unique materials and form factors (e.g., garnet or other material strips or geometries).

[0132] The applicant attempted to use a tilted arrangement to sinter wider strips (e.g., strips wider than 5 mm, specifically, 25 micrometer-thick, 32 mm-wide green strips (containing zirconium oxide-3 mol% Y₂O₃ inorganic particles)). For example... Figure 1As shown, when partially sintered at 1250°C, the partially sintered article formed has a significant and periodic distortion or bubble along the length of the tape. The distortion is on the order of greater than 1 mm in height and large enough to impede the ability to wind the tape onto a core having a diameter of 3-6 inches. Applicant believes that the bubble formation is due to the upward flow of hot air from the sloped support surface below the tape during the heated stages of tape processing (e.g., during sintering and binder removal processes).

[0133] In addition to air flow control, Applicant has determined that control of the thermal profile within the binder removal station and / or the sintering station is important or can be important to forming high quality sintered articles. In particular, Applicant has found that when heating wide tape materials in a roll-to-roll process (e.g., as in one case described herein), the thermal stresses to which the tape material is exposed (particularly during sintering) should be precisely controlled to limit distortion or cracking, which can otherwise occur as the tape material shrinks / densifies during the sintering process, at least for at least some of the materials and / or forms disclosed herein (e.g., thin and wide tapes of at least some inorganic materials). As Figure 2 The example shown, shows a length of ceramic tape (in particular, an alumina tape) that includes a portion of the tape transitioning from unsintered to sintered material with a steep temperature increase within the high temperature sintering zone. As shown, this steep temperature increase results in or can result in distortion or a cross-web shape due to stresses within the tape material as the tape has a rapid rise in temperature within the sintering zone. Figure 2 As shown, when the tape has a rapid rise in temperature within the sintering zone, this steep temperature increase results in or can result in distortion or a cross-web shape due to stresses within the tape material. That is, in other embodiments, a steep temperature increase can be advantageous, e.g., by reducing exposure to oxidation or impurities, for example, for different materials (e.g., lithium garnet), and the distortion can be controlled by other factors (e.g., air flow control and narrower tape widths).

[0134] Accordingly, as shown and described below, Applicant has determined that by employing a sintering furnace having independently controlled heating zones and / or multiple independently controlled sintering furnaces, it is possible to sinter lengths of wide and long tape materials at high process yields without significant distortion and / or cracking. Similarly, the binder removal furnace and the sintering furnace are designed and placed relative to one another to limit the thermal shock (e.g., exposure to sharp temperature gradients) to which the tape is exposed as the tape transitions between different heating zones within the system described herein.

[0135] After sintering, the wide sintered strip can be wound or can be wound onto a take-up spool, forming a roll of sintered strip material. In contemplated embodiments, the roll is cylindrical or any other shape, for example, when rolled around a non-circular geometry (e.g., oval, triangle with rounded corners, etc.). Because of the high quality (e.g., low distortion) of the strip formed by the systems described herein, in at least some embodiments, the strip can be wound into a roll in a manner that facilitates and is efficient for use of the sintered strip roll in subsequent manufacturing processes (e.g., as a substrate in a downstream roll-to-roll manufacturing process). Applicants have found that the high level of consistency and / or other attributes (purity, strength, impermeability, dielectric properties) of the width, length, thickness, shape, and / or flatness of the strips or other articles generated by the systems described herein enable the winding of the strip onto a take-up spool. Conversely, strips with a high level of distortion or irregularities can tend to or can tend to break or otherwise form distorted and inconsistent strip rolls, and can not be suitable for take-up onto a spool to form a roll of sintered strip. That is, some contemplated non-horizonal sintering systems, particularly those employing the techniques disclosed herein, can enable the formation of untwisted strips (e.g., thin enough and sufficiently stretched, if air flow is controlled, sintering rate and temperature are controlled, as described herein).

[0136] Finally, in systems in which discrete unsintered sheet or green strip sheet is placed on a surface (referred to as a setter plate) and placed in a furnace in which the organic binder is burned off and the inorganic particles are sintered, Applicants have determined that roll-to-roll forming of the sintered articles can provide a number of advantages not available with discrete conventional sintered articles. For example, wide rolls of sintered articles can be formed at high throughput rates (e.g., at a rate of 6 inches per minute or more). Moreover, the systems / processes discussed herein form wide and thin sintered (e.g., thin ceramic and / or sintered articles) that enable the use of the sintered articles as substrates to form small and low cost devices (e.g., semiconductor devices, batteries, etc.). Similarly, providing a roll of sintered material enables the use of the sintered material as an input substrate roll for high throughput downstream manufacturing processes, further enabling the use of the sintered articles discussed herein to form downstream articles at high rates and / or at low cost.

[0137] System Overview

[0138] See Figure 3FIG. 1 shows a system 10 for producing a sintered tape article according to an exemplary embodiment. Generally, a green tape material is provided to the system 10 at an input side (separation system 12), and the green tape material moves generally in a machine direction 14 through the system 10. In the separation system 12, a source 16 of continuous tape material 18 (‘continuous’ refers to a long length, as disclosed herein for example 300 cm or more, which can be provided in the form of a roll or a web) is provided and fed to a downstream portion of the system 10.

[0139] Generally, the continuous tape material 18 includes a layer of green tape material 20 that includes particles of sinterable inorganic material bound together with an organic binder (e.g., polyvinyl butyral, dibutyl phthalate, polyalkylcarbonate, acrylic polymer, polyester, silicone, etc.). The green tape material 20 of the continuous tape material 18 is or can be supported on a carrier web or backing layer 22. As described in more detail below, in particular embodiments the system 10 is configured to form long, wide, and / or thin sintered articles, and in such embodiments the green tape material 20 that enters the system 10 is also relatively long, wide, and / or thin. For example, in particular embodiments the green tape material 20 has a width of greater than 5 mm, greater than 10 mm, greater than 40 mm, or greater than 125 mm. In particular embodiments, the green tape material 20 has a length of greater than 10 meters (m), specifically greater than 30 m, and more specifically greater than 60 m. In particular embodiments, the green tape material 20 has a thickness of 3 micrometers to 1 millimeter. Further, the green tape material 20 that is input has a porosity that is greater than the porosity of the sintered articles produced by the system 10. In other contemplated embodiments, the green tape material 20 can have a width of less than 5 mm, for example at least 0.5 mm, at least 1 mm, at least 2.5 mm, or in some such embodiments less than 0.5 mm. Similarly, the tape can have other thicknesses and / or lengths and / or porosities. In some embodiments, the tape material 20 can have a non-rectangular cross-section perpendicular to its length, for example circular, elliptical, parallelogram, diamond, etc., where as an intuitive matter the width of such embodiments refers to the largest cross-sectional dimension perpendicular to the length, and the thickness is the smallest cross-sectional dimension perpendicular to the length.

[0140] The separation system 12 includes a carrier mesh removal station 24. At the carrier mesh removal station 24, carrier mesh 22 is separated from the green strip material 20, and the removed carrier mesh 22 is wound onto, or can be wound onto, a take-up reel 26. Generally, the carrier mesh removal station 24 includes a tension isolator 28 (which may include a vacuum drum) and a stripper 30 that has removed the carrier mesh 22 in a manner that does not cause twisting or compression of the green strip material 20 and isolates the green strip 20 from the tension within the carrier mesh 22 generated by the take-up reel 26. After separation from the carrier mesh 22, the green strip 20 is, or may be, a self-supporting green strip containing particles of inorganic material supported by an organic binder material, but does not contain carrier mesh or other support structures to hold the strip material together during downstream processing through system 10.

[0141] The self-supporting green strip 20 moves into, or can move into, the ultra-low tension control system 32. Generally, the self-supporting green strip 20 is a relatively fragile structure that is pulled through the system 10 by the movement of various spools, rolls, rollers, etc. This pulling action applies tension to the self-supporting green strip 20. The applicant has found that a uniform, low level of tension applied to the self-supporting green strip 20 (e.g., g level, 0.1 g to less than 1 kg; at least 1 g, at least 5 g, and / or no more than 100 g, depending on the strip size and binder strength) is advantageous or potentially advantageous because it improves various properties of the final sintered product, such as shape and flatness in width. However, due to the fragile nature of the self-supporting green strip 20 (which becomes even more fragile after binder removal, as described in more detail below), precise control of the low level of tension ensures that sufficient tension is provided to the strip 20 to limit binder removal / deformation during the sintering process, while also limiting the maximum tension to ensure that the strip 20 does not break. In other intended implementations, in addition to tension due to the weight of the strip itself, greater tension or zero tension is applied, for example, to a stronger strip.

[0142] In one or more embodiments, such as Figure 3 As shown, the tension control system 32 includes an ultra-low tension floating roller 33, which is a lightweight, low-inertia carbon fiber roller. The ultra-low tension floating roller 33 may include air bearings to promote low-friction rotation of the carbon fiber roller of the tension floating roller 33. In other embodiments, a free loop of material or a vacuum box may be used to provide a consistent g-level tension to the strip 20.

[0143] After the tension control system 32, the self-supporting green tape 20 moves into a binder removal station 34. Generally, the binder removal station 34 includes one or more heating elements that impart heat to a passageway formed within the binder removal station 34. The heat within the binder removal station 34 causes the organic binder material of at least a portion of the self-supporting green tape 20 to chemically change and / or be removed, such that a non-bonded tape 36 exits the binder removal station 34. Generally, the non-bonded tape 36 includes particles of inorganic material that have little or no organic binder remaining. Applicants have discovered that even in the absence of organic binder, the non-bonded tape 36 holds itself together in a manner that allows the non-bonded tape 36 to move into a sintering station 38, such as by tension control, air flow control, the proximity of the binder removal station 34 to the sintering station 38 and temperature control therebetween, the orientation and alignment of the tape with the stations 34, 38, as shown. Figure 3

[0144] Generally, the binder removal station 34 is arranged and controlled in a manner that provides for low distortion as the tape 20 passes through the binder removal station 34. In addition, the binder removal station 34 can include heating elements that effectuate removal of volatile organic compounds without applying too much heat too quickly, which can otherwise ignite the organic binder compounds. Ignition can also be controlled by air flow.

[0145] In addition, the binder removal station 34 is positioned relative to the sintering station 38 in a manner such that the thermal shock or temperature gradient to which the non-bonded tape 36 is exposed during movement from the binder removal station 34 into the sintering station 38 is low (e.g., spaced apart, but path linearly aligned and corresponding opening aligned and / or proximate to one another, such as within 1 m, such as within 10 cm, such as within 2 cm and / or closer). Applicants have discovered that limiting the thermal shock to which the non-bonded tape 36 is subjected between the stations 34 and 38 also provides for production of a flat, uniform and / or unwarped sintered tape by limiting / eliminating distortion that would otherwise occur due to the temperature gradient experienced between the stations 34 and 38.

[0146] ​In various embodiments, the temperature within the workstation 34 is precisely controlled to achieve desired properties of the tape 36 exiting the workstation 34. In various embodiments, the temperature within the workstation 34 is between 200 degrees Celsius (°C) (or about 200 °C) and 500 °C (or about 500 °C), and the workstation 34 is heated so as to provide a temperature profile along its length such that little or no adhesive material remains in the tape material exiting the adhesive removal workstation 34. In addition, in some embodiments, some sintering (e.g., shrinkage, density increase, porosity decrease, etc.) of the inorganic material particles can occur during the traverse of the adhesive removal workstation 34.

[0147] After the adhesive is removed in the workstation 34, the non-bonded tape 36 is moved into a sintering workstation 38. Generally, the sintering workstation 38 includes one or more heating elements (see, e.g., the more detailed discussion below regarding heating elements and types thereof) that heat the sintering workstation 38 to a temperature above 500 degrees Celsius (e.g., 500 °C (or about 500 °C) to 3200 °C (or about 3200 °C, e.g., 3200 °C ± 10% of 3200 °C)) that results in sintering of the inorganic material particles of the non-bonded tape 36. Generally, during sintering, the porosity of the inorganic material decreases. This decrease in porosity can also result in shrinkage (e.g., a decrease in width, thickness, length, etc.) of the tape material as the material is sintered (e.g., in the sintering workstation 38). For some materials, during sintering, the elastic modulus increases, the strength increases, the shape of the porosity changes, and there is no significant decrease in porosity or significant shrinkage. In some embodiments, the sintering workstation 38 transforms the tape 38 into a partially but not fully sintered, light yellow material.

[0148] Applicants have discovered that the non-bonded tape 36 is susceptible to deformation or breakage as it traverses the sintering workstation 38, which can be due to various forces experienced by the non-bonded tape 36 during sintering. In particular, as described above, Applicants have discovered that forces due to turbulent air flow flowing through the sintering workstation 38 are a source of significant deformation, and Applicants have also discovered that internal stresses in the tape 36 during sintering are another potential source of significant deformation. Based on these discoveries, Applicants have arranged and configured the sintering workstation 38 in various ways to limit these forces to produce sintered articles having an acceptably low level of deformation.

[0149] In particular, as Figure 3As shown, the sintering workstation 38 is arranged in a substantially horizontal configuration, such that the unbonded strip 36 passes through the workstation 38 in a substantially horizontal orientation. The applicant has found that by maintaining the substantially horizontal arrangement of the sintering workstation 38, vortex airflow can be reduced or minimized, which in turn results in the sintered strip material formed at the output of the sintering workstation 38 having a low level of deformation, a low level of cross-tape shape, and / or flatness. In various embodiments, the applicant believes that for various wide strip materials, low turbulence and therefore low deformation can be achieved by maintaining the angle between the processing path of the strip material and the horizontal plane at less than 10 degrees, specifically less than 3 degrees, and even more specifically less than 1 degree. In some embodiments, the strip can move on a generally horizontal arched path, as described below. In other embodiments, the path through the sintering workstation 38 can be inclined at more than 10 degrees relative to the horizontal, as described above.

[0150] like Figure 3 As shown in the embodiment, the adhesive removal station 34 is also positioned substantially horizontally, so that the turbulent airflow does not cause deformation, cracking, or the like during heating of the adhesive removal station 34. Similarly, the adhesive removal station 34 is aligned vertically with the sintering station 38 (i.e., the corresponding openings are aligned and face each other), so that the unbonded strip 36 remains in a horizontal position when the strip 36 moves from the adhesive removal station 34 to the sintering station 38.

[0151] Furthermore, the applicant discovered that if the unbonded strip 36 is exposed to a temperature distribution with abrupt temperature increases / decreases along the length of the sintering station 38, high levels of stress are generated or potentially generated in the strip 36, which in turn leads to or may lead to deformation or breakage of the strip 36 during the sintering process. Additionally, the applicant found that as the width of the strip 36 increases, the sintering stress increases the risk of deformation. Therefore, based on these findings, the applicant determined that by employing a sintering station 38 with multiple independently controllable heating elements (and potentially multiple sintering furnaces), a temperature distribution along the length of the sintering station 38 can be generated that keeps the stress in the strip 36 below the threshold that the applicant found that tends to cause deformation or breakage based on specific strip configurations.

[0152] After traversing the sintering station 38, the partially or fully sintered strip material 40 exits the sintering station 38 and enters an output side take-up system 42. The sintered strip material 40 is wound onto a take-up spool 44. The interlayer support material 46 is paid off from a spool 48. The support material 46 is wound onto the take-up spool 44 such that a layer of support material 46 is located or can be located between each layer of sintered strip material 40 or between at least some of the layers of sintered strip material 40 on the take-up spool 44. This arrangement forms a roll or spool of supported sintered strip material 40. In general, the support material 46 is a flexible, higher friction material that enables the sintered strip material 40 to be secured on the take-up spool 44 with lower winding tension. The flexibility of the support material 46 can compensate for a cross-web shape that can be present in the strip 40 (sintered strip material 40). The support material 40 also increases the friction between adjacent layers of strip 40 (sintered strip material 40) on the spool 44, which limits slippage / creep of the strip 40 (sintered strip material 40) from the spool 44. Applicant believes that, in the absence of the support material 46, the sintered strip material 40 tends to at least partially slip (e.g., creep) off the spool 44 because the modulus of the sintered strip 40 (sintered strip material 40) is relatively high, limiting the ability of the strip 40 (sintered strip material 40) to stretch under winding tension, which in turn tends to result or can result in poor roll integrity.

[0153] As discussed herein, the system 10 is configured to form a sintered strip material 40 that has a low level of distortion, a low level of risk of breakage, consistent properties along its length, etc., regardless of the width and / or length of the sintered article. Applicant has found that, particularly as the width of the strip increases, the risk of distortion and breakage of the strip at various stages of the system 10 can increase. For example, in particular embodiments, the sintered strip 40 (sintered strip material 40) has a width of greater than 5 mm, greater than 10 mm, greater than 40 mm, or greater than 125 mm, and the various arrangements of the system 10 discussed herein limit the risk of distortion or breakage regardless of the width of the strip material. In other embodiments, the sintered strip has a width of less than 5 mm and / or at least 0.5 mm, such as at least 1 mm, such as at least 2 mm.

[0154] Further, the various material handling and heating mechanisms of system 10 enable the formation of sintered tape 40 (sintered tape material 40) at high rates. In particular embodiments, it is believed that the roll-to-roll processing of system 10 enables production speeds of sintered tape that are significantly faster than other sintering processes, such as at least in some cases, tunnel kiln processing, such as conventional tunnel kiln processing. In particular embodiments, system 10 is configured to produce sintered tape 40 at a rate of at least 6 inches per minute, at least 8 inches per minute, at least 19 inches per minute, at least 29 inches per minute, and at least 59 inches per minute. In other particular embodiments, system 10 is configured to produce sintered tape 40 at a rate of at least 3 inches per minute for green tape 20 having a width greater than 50 mm, at least 5 inches per minute for green tape 20 having a width of 35 mm to 50 mm, at least 9 inches per minute for green tape 20 having a width of 15 mm to 35 mm, and at least 10 inches per minute for green tape 20 having a width of 5 mm to 15 mm. In other particular embodiments, system 10 is configured to produce sintered tape 40 at a rate of at least 1 inch per minute (ipm) for green tape 20 having a width greater than 50 mm, at least 1.5 inches per minute for green tape 20 having a width of 35 mm to 50 mm, at least 2 inches per minute for green tape 20 having a width of 15 mm to 35 mm, and at least 3 inches per minute for green tape 20 having a width of 5 mm to 15 mm.

[0155] Support web removal station

[0156] Embodiments of forming sintered articles described herein include applying a uniform web tension to the green tape material both before and after sintering. The separation system according to one or more embodiments of the present disclosure is designed to apply such uniform web tension and uniform velocity to the green tape material as it is separated from the supporting carrier web. Thus, as disclosed herein, removal of the supporting web enables shape consistency of the green tape material, reduces or eliminates instances of necking or shrinking of the green tape, and reduces or eliminates instances of the equipment imprinting features on the surface of the green tape that can otherwise be present in the sintered tape. That is, the techniques disclosed herein can be used to produce the new sintered tapes as disclosed herein without a supporting web removal station, where the tapes can have characteristics attributed to not having a supporting web removal station, such as thickness variation, repeated imprinted surface features, etc.

[0157] As described above, system 10 includes a supporting web removal station located generally on the input side of system 10. One aspect of the supporting web removal station includes separation system 12. See Figure 4from the carrier web 22 such that the green strip material 20 can be processed downstream. In one or more embodiments, a source 16 of continuous strip material 18 to be separated is provided. As Figure 5 As shown more clearly, the continuous strip material 18 includes a green strip material 20 supported on a carrier web 22. In Figure 4 In one or more embodiments, the source 16 is provided in the form of a spool that unwinds the continuous strip material 18 to the carrier web removal station 24 (including a tension isolator 28 and a stripper 30). In one or more embodiments, the source 16 can include a belt or other form to feed the continuous strip material. In other contemplated embodiments, the source of green strip material can be another station on a production line that continuously produces or can continuously produce green strip material, forming a green strip and conditioned for subsequent processing in the systems disclosed herein. Other contemplated embodiments can use green strip material separated by organic material that is burned off by, for example, the binder removal station disclosed herein or any other means of removal.

[0158] According to exemplary embodiments, the green strip material 20 includes particles of inorganic material (as described herein) that are sinterable and bonded together with an organic binder. The carrier web 22 can include a polymer, paper, or a combination of polymer and paper material. In some embodiments, the green strip material contains an amount of polymer that is less than the polymer content of the carrier web 22, where the polymer content is measured as a volume percentage of the respective material. According to exemplary embodiments, the green strip material 20 and the carrier web 22 each have a respective thickness (t) defined as the distance between the first and second major surfaces, a respective width (w) defined as the first dimension of one of the first or second surfaces that is perpendicular to the thickness, and a respective length (L) defined as the second dimension of one of the first or second surfaces that is perpendicular to both the thickness and the width, for example, for green strips having a continuous cross-sectional geometry that is rectangular or elliptical (e.g., where edges can be removed after sintering to form straight sides). In other contemplated embodiments, a strip of sinterable inorganic material can be held together by an inorganic binder that becomes part of the sintered strip after processing in the system 10. For example, as disclosed herein, in other contemplated embodiments, a strip of inorganic material can be held together by having the inorganic material bond to itself, for example, a partially sintered yellowish strip rather than a green strip.

[0159] As will be described herein, according to exemplary embodiments, the carrier web 22 provides or can provide a contact surface for conveying the continuous strip material through the separation system 12, and in particular, through the carrier web removal station 24. In other words, in at least some such embodiments, it is primarily the carrier web 22 that comes into contact, such that the green strip material 20 is substantially free from contact and thus substantially free from defects or imperfections resulting from contact, e.g., repetitive surface features that can be detectable in the final sintered product resulting from the surface of a wheel or roller being imprinted onto the green material of the strip. Other embodiments can include such defects or imperfections, e.g., when the disclosed aspects herein are used without the carrier web removal station 24.

[0160] When the source 16 is a spool, the continuous strip material has a first tension (which is low, as will be further described herein), and has a tendency to unwind at a higher speed, even when the continuous material is held at a constant low tension. The separation system 12 functions as or can function as a brake to reduce or otherwise control or limit the speed at which the continuous strip material unwinds from the source 16.

[0161] According to at least some such exemplary embodiments, the carrier web removal station 24 includes a tension isolator 28 (positioned proximate to and downstream of the source 16) and a stripper 30 (positioned downstream of the tension isolator 28). The tension isolator 28 and the stripper 30 separate the carrier web 22 from the green strip material 20 without damaging the green strip material. In particular, the tension isolator 28 is designed and used to pinch the carrier web and to pace the speed of the continuous strip material through the separation system. In one or more embodiments, after the carrier web 22 is separated from the green strip material, the collection speed of the carrier web 22 after it is separated from the green strip material 20 is controlled to maintain a constant tension in the carrier web 22 and, in turn, a constant tension in the continuous green strip material 20. In one or more embodiments, the tension isolator 28 isolates the separation of the carrier web 22 from the green strip material 20 from the mass of incoming green strip material 20 from the source 16. Without the tension isolator 28, any or some inconsistency in the winding mass of the continuous strip material (i.e., loose winding, which can result in cinching during unwinding or feeding to the stripper 30) can result in variations in the tension and speed of the stripper 30.

[0162] According to example embodiments, the continuous web of material 18 is fed at a first tension to the tension isolator 28, and the tension isolator of one or more embodiments has a structure or is configured to apply a second tension to the carrier web 22 that is greater than the first tension of the continuous web of material 18 as the continuous web of material 18 is conveyed to the stripper 30. In some embodiments, the second tension (i.e., tensile force) is at least 20% greater than the first tension, and / or at least 25 milli-Newton (mN) greater than the first tension, for example, at least 100 mN greater, for example, at least 200 mN greater. According to some such embodiments, the second tension is applied to the carrier web 22 but not, or at least substantially not, applied to the green web of material. In one or more embodiments, the green web of material 20 maintains the first tension as the continuous web of material moves along the tension isolator 28. In one or more embodiments, the green web of material does not include or have a tension, or does not include or have a tension that exceeds supporting its own weight, or does not substantially include or have a tension that exceeds supporting its own weight, for example, a tension that exceeds supporting its own weight of less than 1 Newton (N), as the continuous web of material moves along the tension isolator 28. Thus, the tension isolator 28 creates a first tension zone 17 between the tension isolator 28 and the source 16, and a second tension zone 19 between the tension isolator 28 and the stripper 30. The tension applied to the carrier web 22 in the first tension zone 17 is less than the tension applied to the carrier web 22 in the second tension zone 19. In one or more embodiments, the tension (i.e., tensile stress) applied to the carrier web 22 in the second tension zone 19 is about 2.5 pounds per (linear) inch (PLI) or less. For example, in one or more embodiments, the tension applied to the carrier web 22 is about 2.4 PLI or less, about 2.3 PLI or less, about 2.2 PLI or less, about 2.1 PLI or less, about 2 PLI or less, about 1.8 PLI or less, about 1.6 PLI or less, about 1.5 PLI or less, about 1.4 PLI or less, about 1.2 PLI or less, or about 1 PLI or less. In one or more embodiments, the first tension is equal to or less than about 50% (e.g., about 45% or less, about 40% or less, about 35% or less, about 30% or less, or about 25% or less) of the second tension. In some embodiments, the tension (i.e., tensile force) applied to the carrier web 22 in the second tension zone 19 is at least 20% greater than the tension applied to the carrier web 22 in the first tension zone 17, and / or at least 25 milli-Newton (mN) greater, for example, at least 100 mN greater, for example, at least 200 mN greater. In one or more embodiments, the green web of material is applied an additional (nominal) tension in addition to the tension applied to the green web of material by the application of tension to the carrier web 28.In such embodiments, the carrier web can be caused to stretch due to such tensioning on the carrier web, which in turn creates some tension on the green tape material, e.g., where the majority of the tension is taken up by the carrier web.

[0163] In one or more embodiments, the tension applied to the carrier web 22 by the tension isolator 28 is greater than the tension applied to the green tape material 20. In some embodiments, the tension applied to the carrier web by the tension isolator is equal to or greater than about 2 times the tension applied to the green tape material as the continuous tape material moves from the source 16 to the stripper 30. In some embodiments, the tension applied to the carrier web 22 by the tension isolator 28 is at least 20% greater than the tension applied to the green tape material 20, and / or at least 25 milliNewtons (mN) greater, e.g., at least 100 mN greater, e.g., at least 200 mN greater. It can be intuitive that tension as used herein generally refers to pulling apart in the lengthwise or axial direction of the material, and when force units are given herein, tension refers to tensile force, and when stress units are given herein, tension refers to tensile stress, and / or tension herein can be given in other units and refer to other related parameters, such as pounds per linear inch or metric equivalents.

[0164] In Figure 4 In the illustrated embodiment, the tension isolator 28 can include a vacuum drum 25. As Figure 6 illustrated, in one or more embodiments, the vacuum drum 25 is rotated to move the continuous tape material by a drive motor input 27 that is connected to the vacuum drum by a bearing housing 29. As Figure 7As shown, the vacuum drum can include an outer surface that includes a plurality of vacuum holes 7 arranged in a uniform distribution. The vacuum holes 7 can be formed along a plurality of axial grooves 8 and / or radial grooves that intersect one another at the vacuum holes 7. A vacuum is applied to the vacuum drum 25 by a vacuum source (e.g., a vacuum drum blower) that grabs the carrier web 22 through the vacuum holes 7, thereby facilitating tensioning of the carrier web, as described herein. In one or more embodiments, the distribution of the vacuum holes 7 and the configuration of the vacuum drum, including the diameter employed and the vacuum force applied, exerts or helps to exert a uniform tension along the width of the carrier web. Through this action and configuration, the vacuum drum controls the speed of the carrier web (and continuous strip material) as it moves through the separation system 12. In one or more embodiments, the tension isolator pulls the continuous strip material from the source along the first tension zone 17. Any or some inconsistency in the transfer of the green strip material from the source 16 into the stripper 30 (e.g., loose winding that can result in pinching during transfer from the source to the stripper) does not affect or can not affect the separation process. In addition to the normal forces and friction that are proportional to tension, the vacuum drum 25 provides a cohesive or attractive force between the strip material (e.g., carrier web) and the vacuum drum 25, thereby increasing the cohesive or attractive force without the need to increase the tension in the strip material. Due at least to this advantage, Applicants believe that the use of a vacuum drum to control the cohesive or attractive force between the strip material and the roll (i.e., the vacuum drum) during the step of separating the green strip from the carrier web is a unique and effective process for protecting and controlling the shape of the green strip, which can be particularly fragile. That is, aspects of the technology herein can be used to produce new sintered products that, for example, do not have separation marks (e.g., repeated defects from the roll, variations in strip thickness, shorter strip lengths, etc.) without the use of the vacuum drum disclosed herein.

[0165] In one or more embodiments, the tension isolator 28 increases the tension in the continuous strip material (and more specifically, the carrier web or primarily the carrier web) along the second tension zone 19 as the continuous strip material is transferred to the stripper 30. In one or more embodiments, the tension isolator 28 increases the tension in the continuous strip material (and more specifically, the carrier web or primarily the carrier web) along the second tension zone 19 as the continuous strip material is transferred to the stripper 30. Figure 4 In the illustrated embodiment, the separation system 12 includes a load controller 21 to maintain tension on the carrier web. In one or more embodiments, the load controller 21 is also used to adjust the speed of the take-up spool 26 relative to the tension isolator 28.

[0166] In one or more embodiments, the stripper 30 is disposed downstream of the tension isolator 28 and directs the carrier web 22 in a rewind direction A and the green strip material 20 in a downstream processing direction B that is different from the rewind direction A, as shown in FIG. 1. In one or more embodiments, the stripper 30 is disposed downstream of the tension isolator 28 and directs the carrier web 22 in a rewind direction A and the green strip material 20 in a downstream processing direction B that is different from the rewind direction A, as shown in FIG. 1. Figure 8As shown. In one or more embodiments, the angle C formed by the rewinding direction A and the downstream processing direction is greater than about 90 degrees (e.g., 95 degrees or more, 100 degrees or more, 110 degrees or more, or about 120 degrees or more).

[0167] In one or more embodiments, the peeler 30 includes a sharp blade or edge to create a separation line in the green strip material, for example, located at or near the vertex of corner C, shown as tip 31. In one or more embodiments, the sharp blade or edge creates a separation line in the green strip material, but not in the carrier mesh, just in front of or near tip 31, such as... Figure 8 As shown. In one or more embodiments, the radius of the tip is about 0.05 inches or less (e.g., about 0.04 inches or less, about 0.035 inches or less, about 0.03125 inches or less, about 0.03 inches or less, or about 0.025 inches or less).

[0168] As the continuous strip material passes over the tip 31, the tip 31 separates the carrier web 22 from the green strip material 20. In one or more embodiments, the tip 31 separates the carrier web 22 from the green strip material 20, and then guides the carrier web in a rewinding direction A and the green strip material in a downstream processing direction B. In one or more embodiments, the tip 31 simultaneously separates the carrier web 22 from the green strip material 20 and guides the carrier web in a rewinding direction A and the green strip material in a downstream processing direction B.

[0169] like Figure 4 As shown, the separation system 12 includes a take-up reel 26 for collecting the separated carrier web 22. In the illustrated embodiment, an optional idler roller 23 may be used to further control and maintain the tension in the carrier web 22. In one or more embodiments, as more continuous strip material is conveyed through the separation system, a sensor 15 may also be used to control and maintain the tension in the carrier web, with the diameter of the source 16 decreasing and the diameter of the take-up reel 26 increasing.

[0170] Another aspect of the support mesh removal workstation pertains to a method for separating two materials (e.g., green strip material and carrier mesh). In one or more embodiments, the method includes: feeding a continuous strip material 18 into a tension isolator 28; applying tension to the carrier mesh 22 using the tension isolator 28, which is greater than the tension applied to the green strip material 20; and guiding the carrier mesh to move in a rewinding direction and guiding the green strip material in a downstream processing direction different from the rewinding direction, as described herein. In one or more embodiments, the method includes separating the carrier mesh from the green strip material, and then guiding the carrier mesh in a rewinding direction and guiding the green strip material in a downstream processing direction. In one or more embodiments, the method includes separating the carrier mesh from the green strip material while simultaneously guiding the carrier mesh in a rewinding direction and guiding the green strip material in a downstream processing direction. As taught above, this method is implemented such that the carrier mesh contacts the vacuum drum. In other embodiments, the strip material may have carrier mesh on both sides of the strip, as well as elements of the workstation that can be repeatedly separated and used to remove the two carrier meshes.

[0171] In one or more embodiments, the method includes applying no tension, substantially no tension, or very little tension (as disclosed above) to the green strip material. In one or more exemplary embodiments, the method includes applying no or substantially no tension, or very little tension, to the green strip material as the continuous strip material moves along a first tension zone 17 from source 16 to tension isolator 28. In one or more exemplary embodiments, the method includes applying no or substantially no tension, or very little tension, to the green strip material as the continuous strip material moves along a second tension zone 19 from tension isolator 28 to stripper 30. In one or more exemplary embodiments, the method includes applying no or substantially no tension, or very little tension, to the green strip material 20 as the continuous strip 18 moves (along the first tension zone) from source 16 to tension isolator 28 and (along the second tension zone) to stripper 30. In one or more embodiments, the method includes applying tension to the carrier mesh 22, at least twice the tension applied to the green strip material 20 (at any point along the separation system 12). Selecting a carrier mesh with low elasticity can help the carrier mesh bear most of the bulk of tension applied to the strip material.

[0172] In one or more embodiments, the method includes no additional tension being applied to the green tape material other than the tension applied to the green tape material by the tension applied to the carrier web 28. In such embodiments, the tension applied to the carrier web can cause the carrier web to stretch, which in turn creates some tension on the green tape material. In one or more exemplary embodiments, the method includes no additional tension being applied to the green tape material as the continuous tape material moves along the first tension zone 17 from the source 16 to the tension isolator 28. In one or more exemplary embodiments, the method includes no additional tension being applied to the green tape material as the continuous tape material moves along the second tension zone 19 from the tension isolator 28 to the stripper 30. In one or more exemplary embodiments, the method includes no additional tension being applied to the green tape material 20 as the continuous tape 18 moves from the source 16 to the tension isolator 28 (along the first tension zone) and to the stripper 30 (along the second tension zone).

[0173] In one or more embodiments, the method for separating two materials (i.e., the green tape material and the carrier web) includes feeding the continuous tape material to a tension isolator and applying a first tension to the carrier web; applying a second tension to the carrier web that is greater than the first tension; and directing the carrier web to move in a rewind direction and directing the green tape material downstream in a downstream processing direction that is different than the rewind direction. In one or more embodiments, applying the first tension includes no tension or little tension being applied, as disclosed herein. In one or more exemplary embodiments, applying the first tension includes no or little tension being applied to the carrier web as the continuous tape material moves along the first tension zone from the source 16 to the tension isolator 28. In one or more embodiments, the second tension is about 2.5 PLI or less. For example, in one or more embodiments, the tension applied to the carrier web 22 is about 2.4 PLI or less, about 2.3 PLI or less, about 2.2 PLI or less, about 2.1 PLI or less, about 2 PLI or less, about 1.8 PLI or less, about 1.6 PLI or less, about 1.5 PLI or less, about 1.4 PLI or less, about 1.2 PLI or less, or about 1 PLI or less. In one or more embodiments, the first tension is equal to or less than about 50% (e.g., about 45% or less, about 40% or less, about 35% or less, about 30% or less, or about 25% or less) of the second tension.

[0174] In one or more embodiments, the method includes at least partially sintering the green tape material after separating the green tape material from the carrier web 22 (as described in greater detail below in relation to the sintering station). In one or more embodiments, the method includes winding the carrier web 22 onto a take-up spool 26 after separating the carrier web 22 from the green tape material 20. In one or more embodiments, the method includes continuously maintaining tension on the carrier web 22 along the second tension zone until the carrier web is wound onto the take-up spool.

[0175] Adhesive removal station

[0176] As described above in relation to Figure 3 the system 10 includes a heating station configured to remove adhesive material from the green tape 20, which in at least some embodiments is actively and independently heated from the sintering station. In other embodiments, such as for the firing of the yellowish tapes disclosed herein, there can be no heating station. Applicant believes that actively heating a station intended for adhesive removal with its own controllable heat source, in a manner independent of the heaters within the sintering furnace, enables better control over the adhesive removal process, reducing the likelihood of combustion of volatile substances in the adhesive of the green tape, which is particularly advantageous for wide green tapes (e.g., at least 5 mm, at least 10 mm, at least 30 mm, at least 50 mm). Other embodiments include the passive heating adhesive removal stations disclosed herein, in which the station uses heat emitted from the sintering furnace and is adjacent to the sintering furnace.

[0177] According to exemplary embodiments, as Figure 3 shown, the adhesive removal station 34 receives the green tape 20 from the separation station 12, and then the green tape 20 proceeds through the adhesive removal station 34. Referring now to Figure 9 a detail view of the adhesive removal station 34 of the system 10 is shown and described in greater detail.

[0178] As described above, the green tape 20 includes particles of inorganic material bonded by a binder (e.g., an organic binder) as disclosed herein. The binder removal station 34 receives the green tape 20 and leaves the particles of inorganic material to form a self-supporting unbonded tape 36 by chemically altering the binder and / or removing the binder from the green tape 20, thereby preparing the green tape 20 for sintering, which can be moved in the machine direction 14 into a sintering station 38, as discussed in greater detail below. According to exemplary embodiments, the green tape 20 is simultaneously extended toward the station 34, extended into the station 34, extended through the station 34, extended within the station 34, extended proximate to the station 34, and / or extended away from the station 34 at an instant in time (i.e., at an instant). Thus, it will be appreciated that the tape material being processed in the system 10 simultaneously includes the green tape 20 continuously connected to the unbonded tape 36 as the tape material passes through the binder removal station 34.

[0179] According to exemplary embodiments, the binder of the green tape 20 can be a polymeric binder, and the binder is chemically altered and / or removed from the green tape 20 by combusting or charring the binder by heating the binder. According to exemplary embodiments, the binder removal station 34 chars or combusts at least a majority of the organic binder from the first portion of the green tape 20 without sintering the particles of inorganic material, which can be measured by weighing the green tape before the binder is removed by the station 34 and the inorganic material before the green tape is formed, then weighing the unbonded tape 36 after the binder removal station 34 is operated, and comparing the difference. If a residue of the binder (e.g., carbon) remains, applicants believe that subsequent sintering at higher temperatures will typically remove that residue. In other contemplated embodiments, the binder can be removed chemically, for example, by selecting the material from which it is formed to chemically react with other materials (e.g., catalysts, gases) delivered to the green tape at the binder removal station prior to sintering. In other contemplated embodiments, the binder can be evaporated or otherwise vaporized and outgassed from the green tape 20 at a station prior to sintering.

[0180] Still referring to Figure 9According to example embodiments, the binder removal station 34 includes an active heater 5120 that, when the green strip 20 is in contact with the binder removal station 34, burns off or combusts at least a substantial portion of the binder from the green strip 20 to form a non-bonded strip 36 (e.g., such that the portion of the green strip 20 that is not inorganic material to be sintered is reduced in weight by more than 50%, such as more than 80%, such as more than 90%, such that the overall weight of the green strip 20 is reduced by more than 30%, such as more than 50%). The active heater 5120 provides thermal energy to the green strip 20 to burn off the binder. In some embodiments, the heater 5120 is or includes an electrical heating element (e.g., an inductive or resistive heating element). In other embodiments, the heater 5120 is or includes a combustion heating element (e.g., a gas combustion heating element). In other embodiments, the heater 5120 is or includes a microwave and / or laser or other heating element. Such heating elements can also be used in the sintering station 38, but at different temperatures, as disclosed herein.

[0181] According to example embodiments, the active heater 5120 of the binder removal station 34 includes heating zones (e.g., zones 5120A, 5120B, 5120C, 5120D) such that the rate of thermal energy received by the green strip 20 increases as the green strip 20 progresses through the binder removal station 34. In some embodiments, the rate of thermal energy received by the green strip 20 increases in a non-linear manner, such as: initially slowly, as the binder decomposes and releases combustible gaseous byproducts, and then more rapidly, as the green strip 20 captures less of the potential for flame. Such a zoned approach, and more particularly a non-linear approach, can be particularly useful for sintering strips as disclosed herein that can be passed through a production line (e.g., system 10) at a constant rate. According to example embodiments, the temperature to which the green strip 20 is subjected in the binder removal station 34 can be at least 200°C, such as at least 250°C and / or below the sintering temperature of the inorganic particles carried by the green strip 20, such as less than 1200°C (e.g., less than 900°C). In contemplated embodiments, for at least some of the materials disclosed herein, the binder removal station 34 can sinter the inorganic material of the strip at least to a degree that, for example, can cause the individual particles to bond to one another, which can increase the tensile strength of the strip.

[0182] According to exemplary embodiments, as the green strip 20 is advanced through the binder removal station 34, the binder removal station 34 blows and / or draws gas over and / or under (e.g., over and under) the green strip 20. In some embodiments, the heater 5120 can provide a stream of hot air in communication with some or all of the thermal energy reaching the green strip 20, which can be delivered through an array of nozzles, through the walls of a plenum, or through a porous wall material. In other embodiments, the flow of gas is facilitated by a fan or pump adjacent to the binder removal station 34, e.g., Figure 9 The illustrated fan 5122. A pressurized gas tank can also be used as a source of gas to be blown over the strip. In some embodiments, the gas is air. In other embodiments, the gas is an inert gas, such as argon.

[0183] In some embodiments, gas is blown and / or drawn over both the top and bottom sides of the green strip 20, while in other embodiments, gas is directed over only the top or bottom side. In some such embodiments, the green strip 20 is directly supported by a gas bearing and / or an underlying surface, and the green strip 20 moves relative to the surface. For example, the green strip 20 can slide along and in contact with an underlying surface (e.g., a surface made of stainless steel). In some embodiments, the gas is heated to a temperature above room temperature (e.g., at least 100°C) prior to being blown or drawn over the strip, which applicants have found can help prevent thermal shock to the green strip 20, which can affect the properties of the resulting sintered material, e.g., by providing increased strength or flatness due to fewer surface irregularity sites and stress concentrations.

[0184] Blowing or suctioning gas (particularly air or an oxygen-containing gas) over the green strip 20 can be counterintuitive to one skilled in the art, as oxygen can be expected to become a fuel and promote the strip to trap a flame, which can distort the shape of the green strip 20 and / or otherwise impair the quality of the green strip 20 as it passes through the station 34. However, Applicants have discovered that blowing and / or suctioning gas (in some embodiments, including air) over the green strip 20 actually helps the strip to not trap a flame as the green strip 20 is conveyed through the adhesive removal station 34. For example, Applicants have discovered that the adhesive is removed and / or charred by the adhesive removal station 34 without catching fire, but the strip catches fire when passed through the station 34 at the same rate if air is not blown over the green strip 20. Applicants expect that the risk of the green strip 20 catching fire can also be reduced and / or eliminated by moving the green strip 20 more slowly through the adhesive removal station 34, spacing the heating zones 5120A, 5120B, 5120C, 5120D further apart, using a fire retardant in the adhesive and increasing ventilation of the adhesive removal station 34, and / or combinations of such techniques.

[0185] While gas can be blown and / or suctioned over the green strip 20 and / or over the non-bonded strip 36, Applicants have discovered that the non-bonded strip 36 can be particularly susceptible to damage from vibration and / or out-of-plane bending, depending on how the gas is flowing. Accordingly, in some embodiments, the gas flowing through the adhesive removal station 34 is and / or includes laminar flow. The air flow can be diffuse and / or can not be directed at the non-bonded strip 36. In some embodiments, a gas source or gas actuator (e.g., a fan, a pump, a pressurized supply) delivers gas through the adhesive removal station 34 at at least 1 liter per minute, such as through the channel 5128 (see FIG. 12) and / or the like. Figure 10 ).

[0186] According to some embodiments, the green strip 20 is advanced through the adhesive removal station 34 in a horizontal rather than a vertical orientation. Having the strip in a horizontal orientation can help control the air flow through the adhesive removal station by, for example, reducing a "chimney effect" in which hot gas rises and pulls too much air through the adhesive removal station 34, causing the non-bonded strip 36 to vibrate. In other contemplated embodiments, the air pump, fan, and ambient air conditions (e.g., high temperature) counteract and / or control the chimney effect without having the green strip 20 oriented horizontally through the adhesive removal station 34.

[0187] According to example embodiments, the non-bonding strip 36 is under a positive tensile force in the lengthwise direction as the green strip 20 is advanced through the station 34. The tensile force in the green strip 20 can help to secure the green strip 20 in a flat orientation, for example, if the green strip 20 is subsequently passed into another station of the manufacturing system (e.g., a sintering station 38) for further processing. Without the adhesive (e.g., after the adhesive is removed at the station 34), the non-bonding strip 36 can be weaker than the green strip material 20, for example, having a smaller ultimate tensile strength, for example, one-half or less, for example, one-quarter or less. According to example embodiments, the tensile force (i.e., tensile stress) in the lengthwise direction in the non-bonding strip 36 is less than 500 grams force per mm 2 cross-section. Applicant believes that the green strip 20 is significantly more flexible than the non-bonding strip 36, such that the green strip 20 has a minimum bend radius without breakage that is less than one-half (e.g., less than 1 / 4, less than 1 / 8) of the non-bonding strip 36, as measured by ASTM standards (see E290), where the bend radius is the smallest internal radius around which a corresponding portion of the green strip 20 can be bent without breakage.

[0188] In at least some embodiments, after processing through the adhesive removal station 34, the non-bonding strip material 36 is moved into a sintering station 38 (discussed in more detail below), which causes the inorganic material of the non-bonding strip 36 to at least partially sinter to form a sintered strip 40. Thus, for continuous processing, at an instant in time, the green strip 20 is continuously connected to the sintered strip 40 by way of the non-bonding strip 36.

[0189] In some such embodiments, the adhesive removal station 34 is proximate to the sintering station 38, such that the distance therebetween is less than 10 m (e.g., less than 10 mm, less than 2.5 cm, less than 5 cm, less than 10 cm, less than 25 cm, less than 100 cm, less than 5 m, etc., between the exit opening of the adhesive removal station 34 and the entrance opening 106 (see Figure 12 ) of the sintering station 38), such that the non-bonding strip 36 is less likely to be subjected to excess heat shock in the gap between the station 34 and the station 38, which can affect the properties of the resulting sintered material, for example, due to the smaller surface irregularities and points of stress concentration providing increased strength or flatness. In contemplated embodiments, the adhesive removal station 34 is in direct contact and abutment with the sintering station 38 and / or the adhesive removal station 34 and the sintering station 38 are under a common housing, but in at least some such embodiments, an intermediate vent draws away the fumes or other byproducts of the adhesive removal.

[0190] Referring now to Figure 10The adhesive removal station 34 includes walls 5126 defining a channel 5128 having inlet and outlet openings 5130, 5132 on opposite ends of the channel 5128. The channel has a length L between the inlet and outlet openings 5130, 5132 that is at least 5 cm, such as at least 10 cm and / or no more than 10 m in some embodiments. According to exemplary embodiments, the outlet opening 5132 and / or the inlet opening 5130 is narrow and elongated, such as having a height H and a width W perpendicular to the height H, where the height H is less than half the width W, such as less than 1 / 5 of the width W, such as less than 1 / 10 of the width W. In some such embodiments, the height H is less than 5 cm, such as less than 2 cm, such as less than 1 cm and / or at least greater than a thickness of the green tape 20 to be processed thereby, such as at least greater than a thickness of the green tapes disclosed herein, such as at least greater than 20 pm. Applicants have found that narrow openings improve the performance of the adhesive removal station 34 by limiting the circulation of gas (e.g., ambient air flow) at the inlet and outlet openings 5130, 5132. In some embodiments, the channel 5128 is straight, while in other embodiments, the channel is gently arcuate, such as having a radius of curvature greater than 1 m, where the arcuate and corresponding curvature of the tape can help the tape to shape or flatten.

[0191] Referring to Figure 11 The method of processing a tape 5210 includes a step of advancing the tape through a manufacturing system 5212 (e.g., the adhesive removal station 34 or other manufacturing system disclosed herein), such as where the tape includes a first portion having particles of inorganic material bonded by an adhesive (e.g., the green tape 20). The method further includes a step of preparing the tape for sintering 5214 by forming a second portion of the tape (e.g., the non-bonded tape 36) at a station of the manufacturing system by causing the adhesive to chemically change and / or removing the adhesive from the first portion of the tape, leaving the particles of inorganic material, thereby forming the second portion of the tape.

[0192] In some such embodiments, the step of preparing the tape for sintering 5214 further includes charring or burning at least a substantial portion of the adhesive from the first portion of the tape (e.g., as described above) with or without simultaneous sintering of the particles of inorganic material. In some embodiments, the station of the manufacturing system is a first station, and the method of processing 5210 further includes a step of receiving the second portion of the tape at a second station 5218 and at least partially sintering and / or further sintering 5220 the inorganic material of the second portion of the tape at the second station to form a third portion of the tape.

[0193] In some embodiments, the processing method 5210 further includes positively stretching the second portion of the tape as the tape is advanced 5212. In some such embodiments, the positive stretching is such that the tensile force (i.e., the tensile stress) in the lengthwise direction in the second portion of the tape is less than 500 grams force per mm 2 cross-section. In some embodiments, the processing method 5210 further includes blowing and / or suctioning gas on the tape as the tape is prepared for sintering 5214. In some embodiments, the advancing step 5212 of the tape further includes advancing the tape horizontally through the work station, and / or supporting the tape directly by a gas bearing and / or an underlying surface, and moving the tape relative to the surface and / or relative to the opening of 5128.

[0194] Examples of binder removal

[0195] Applicant uses a binder burnout furnace similar to the binder removal station 34 to remove the binder from the green tape prior to sintering. In one example, the green tape is a tape cast zirconia ceramic particles loaded with a polymeric binder, forming a strip that is about 42 mm wide and about 25 μm thick. The green tape is fed through a horizontal 6-zone binder burnout furnace at 20 inches per minute. The binder burnout furnace is set from 325°C inlet to 475°C outlet, with a 0 to 25°C incremental increase for the other four zones. An air flow of about 7.5 liters per minute at a temperature of 0 to 250°C is also provided. The air flow is split on both sides of the binder burnout furnace. The furnace is 36 inches long and has 18 inch zones.

[0196] Sintering station

[0197] Referring to Figures 12 to 20 Sintering station 38 is shown and described in greater detail. Generally, after the binder material is removed from green tape 20 in binder removal station 34, non-bonded tape 36 is moved into sintering station 38.

[0198] In at least one embodiment, the sintering station 38 includes a sintering furnace 100. The sintering furnace 100 includes an insulated housing 102. Generally, the insulated housing 102 includes a plurality of interior walls that define a passageway 104 that extends through the sintering furnace 100 between an inlet (shown as inlet opening 106) and an outlet (shown as outlet opening 108). The binder removal station 34 is positioned adjacent to the inlet opening 106 such that the green strip material 20 passes through the binder removal station 34, resulting in the unbonded strip material 36 as described above. The unbonded strip material 36 enters the inlet opening 106 and passes through the passageway 104. While within the passageway 104, heat generated by a heater (as explained in more detail below and above with respect to different types of heating elements) causes the unbonded strip 36 to sinter to form a sintered strip 40, and the sintered strip 40 exits through the outlet opening 108 for further processing or collection, as shown. Figure 3 Depending on the temperature profile to which the unbonded strip 36 is exposed during sintering, the strip 40 can be fully or partially sintered after exiting the sintering furnace 100. Whether the strip 40 is partially sintered or fully sintered, the porosity of the strip 40 is less than the porosity of the green strip 20 due to the sintering that occurs within the furnace 100. Similarly, in some embodiments, the width of the strip 40 is less than the width of the green strip 20. In some such embodiments and other embodiments, the shrinkage of the unbonded strip 36 during sintering can be controlled such that the thickness, width, and / or length of the strip 40 is less than the thickness of the green strip 20.

[0199] From Figure 12 As can be seen, and unlike typical discrete sheets based on sintering systems, the unbonded strip 36 is a continuous length of material that extends entirely through the furnace 100. In this arrangement, a single continuous length of the unbonded strip 36 extends into the inlet opening 106, through the passageway 104, and out the outlet opening 108. It will be appreciated that because the unbonded strip 36 is continuous throughout the furnace 100, its left edge, its right edge, and its centerline (e.g., a longitudinal line that is parallel to and equidistant from the left and right edges) are also or can also extend the entire distance through the furnace 100 between the inlet opening 106 and the outlet opening 108. For example, Figure 14The edges (as edges 130 and 132) mentioned above are shown after leaving the sintering furnace 100. This relationship between the continuous strip 36 and the furnace 100 is believed to be unique to the roll-to-roll sintering process described herein and differs from the physical arrangement of tunnel kiln processing for sintering, in which discrete sheets of material move through the furnace supported by positioning plates, with the positioning plates carrying the sheets to be sintered moving through the furnace. For example, in some embodiments, the strip slides along a surface (e.g., lower surface 126) and / or relative to a surface (e.g., lower surface 126) through the channel 104 of the furnace 100, and is not carried on a locator or conveyor. This can reduce adhesion to the locator and strip adhesive wear associated with the locator, as well as static and dynamic friction and adhesion.

[0200] As stated above, the applicant discovered that the high level of levelness of the unbonded strips 36 within channel 104 and / or channel 104 reduces the impact of the vortex airflow on the strips 36 during sintering. Figure 12 As shown, channel 104, inlet opening 106, and outlet opening 108 are located in a substantially horizontal plane. In a specific embodiment, the substantially horizontal plane and / or a gradually arcuate or curved shape (e.g., radius of curvature at least 1 m) is defined by the path defined by the central axis of channel 104, inlet opening 106, and outlet opening 108. Similarly, in such embodiments, the non-adhesive strip 36 may also be located in a substantially horizontal plane and / or gradually arcuate or curved within channel 104 (e.g., as shown in the diagram). Figure 13 As shown, the upper surface 124 and / or lower surface 126 of strip 36 are located in a substantially horizontal plane. The substantially horizontal plane of strip 36, as used herein and defined by channel 104, inlet opening 106, and outlet opening 108, is one in which the angle formed relative to the horizontal reference plane is 10 degrees or less. In other embodiments, channel 104, inlet opening 106, and outlet opening 108, and / or strip 36 within channel 104, are located in even more planar planes, for example, the angle formed by the planes relative to the horizontal reference plane is 3 degrees or less, and more specifically, the angle relative to the horizontal reference plane is 1 degree or less. In other embodiments, channel 104 is not so oriented, and the corresponding sintered strip may have markings associated with a “chimney effect” or irregular heating (e.g., rolled surface blocks or protrusions), for example, if the airflow through channel 104 is vortex-like.

[0201] To further control or limit the vortex airflow exposed to the strip material of system 10 during its passage across system 10, the binder removal station 34 can be positioned relative to sintering station 38 in such a way that the strip material (e.g., the green strip material 20 within the binder removal station and the unbonded strip material 36 within the sintering station) is maintained in a substantially horizontal position as the strips 20 and 36 cross the binder removal station 34 and sintering station 38. In such embodiments, similar to the horizontal arrangement of sintering channel 104, the binder removal station 34 is oriented or can be oriented in a substantially horizontal position, for example, where openings 116 and 118 are aligned such that the line formed therebetween is within 10 degrees of the horizontal.

[0202] In this embodiment, the adhesive removal workstation 34 includes an adhesive burn-off furnace 110. The adhesive burn-off furnace 110 includes an insulating housing 112. Generally, the insulating housing 112 includes a plurality of inner walls defining a channel 114 that extends through the adhesive burn-off furnace 110 between an inlet opening 116 and an outlet opening 118.

[0203] like Figure 12 As shown in the binder burnout furnace 110, channels 114, inlet 116, and outlet 118 are located in a substantially horizontal plane. In a specific embodiment, the substantially horizontal plane is defined by the path defined by the central axis of channel 114, inlet 116, and outlet 118. Similarly, in such embodiments, the green strip 20 within channel 114 may also be located in a substantially horizontal plane. As used herein, the substantially horizontal plane of the green strip 20 and channels 114, inlet opening 116, and outlet opening 118 is such that the angle it forms with respect to a horizontal reference plane is 10 degrees or less. In other specific embodiments, channels 114, inlet opening 116, and outlet opening 118, and / or the green strip 20 within channel 114, are located in even more horizontal planes, for example, the angle formed by the planes with respect to a horizontal reference plane is 3 degrees or less, and more specifically, the angle with respect to a horizontal reference plane is 1 degree or less. In other embodiments, these features may not be so horizontally aligned.

[0204] In addition to maintaining the levelness of the green strip 20 and the unbonded strip 36 in the binder removal furnace 110 and the sintering furnace 100 respectively, the binder removal furnace 110 (also referred to as the binder removal workstation) and the sintering furnace 100 are aligned relative to each other so that the unbonded strip 36 maintains a horizontal position when it transitions from the binder removal furnace 110 to the sintering furnace 100. The applicant found that at this transition point, the unbonded strip 36 is particularly prone to deformation or breakage due to various forces (e.g., forces caused by vortex airflow), since, with most of the organic binder removed, the unbonded inorganic particles of the unbonded strip 36 are held together by weaker forces (e.g., van der Waals forces, electrostatic interactions, small amounts of residual organic binder, frictional interactions / meshing between adjacent particles, binders, plasticizers, liquid carriers, low levels of inorganic matter carried in possible particle-particle bonding, etc.), and thus even smaller forces (e.g., those caused by the interaction of the vortex airflow with the unbonded strip 36) can lead to deformation or breakage.

[0205] Therefore, as Figure 12 As shown, to limit the vortex airflow, the channel 114 of the binder burn-off furnace 110 is aligned vertically with the channel 104 of the sintering furnace 100. Along the strip path passing through the sintering furnace 100 and the binder burn-off furnace 110, the green strip 20 flows horizontally from (as shown in the diagram). Figure 3 The input roller (shown) moves into the binder burn-off inlet 116, through the binder burn-off channel 114, and out of the binder burn-off outlet 118. While within channel 114, the heat generated by the heaters of furnace 110 causes at least a portion of the organic binder material of the green strip 20 to undergo a chemical change and / or be removed, termed "burn-off". Furthermore, the relative positions of the binder burn-off furnace 110 and the sintering furnace 100 ensure that the unbonded strip 36 moves from the binder burn-off furnace 110 into the sintering furnace 100 while always maintaining a horizontal or substantially horizontal position, as described above. Therefore, in at least some embodiments, the vertical alignment between channels 104 and 114 ensures that the unbonded strip 36 maintains substantially the same horizontal plane (i.e., no upward or downward offset between furnaces 110 and 100) as the strip material traverses both furnaces 100 and 110.

[0206] The applicant has determined that the benefits of horizontal binder removal and / or horizontal sintering become more significant as the width of the strip material increases, since wider strip materials are more susceptible to deformation based on airflow vortices. Therefore, the applicant believes that the horizontal arrangement of the sintering furnace 100 and / or binder removal furnace 110 enables the production of wider and / or longer sintered strip materials without significant deformation or breakage, which is believed to be impossible to achieve using existing systems.

[0207] Referring to Figure 13 and Figure 14 , in addition to the horizontal arrangement of the binder burnout furnace 110, the sintering furnace 100, and the strip material (e.g., green strip 20 and non-bonding strip 36) within the furnace, applicants have discovered that the eddy air flow can be limited by providing a sintering channel 104 having a lower height dimension, which in turn involves a lower clearance relative to the non-bonding strip 36. Applicants have discovered that the eddy air flow can be limited by reducing the volume of the area in which a thermal gradient is established and which thermal gradient causes air movement, which otherwise can be experienced due to the very hot air within the channel 104.

[0208] As shown in Figure 13 and 12 , the channel 104 is partially defined by a horizontal and generally upward facing surface 120, which defines at least a portion of the lower surface of the channel 104. Similarly, the channel 104 is also partially defined by a horizontal and generally downward facing surface 122, which defines at least a portion of the upper surface of the channel 104. A first gap, shown as Gl, is the vertical distance between the upward facing surface 120 and the downward facing surface 122, and G2 is the vertical distance or clearance between the downward facing surface 122 and the upper surface 124 of the non-bonding strip 36.

[0209] As noted above, in various embodiments, Gl and G2 are small, thereby limiting the eddy air flow, but Gl and G2 should generally be large enough so that various processing steps (e.g., passing through the channel 104) can be performed. In various embodiments, G2 is less than 0.5 inches (less than 12.7 mm), specifically less than 0.375 inches (less than 9.5 mm), and more specifically 0.25 inches (about 6.35 mm). It will be appreciated that Gl is generally equal to G2 plus the thickness Tl of the non-bonding strip 36. Thus, in various embodiments, because Tl is low (e.g., 3 microns to 1 mm), Gl is less than 1 inch (less than 25.4 mm), specifically less than 0.75 inches (less than 19 mm), and for thin strip material can be less than 0.5 inches (less than 12.7 mm), and for very thin strip material can be less than 0.375 inches (less than 9.5 mm).

[0210] Figure 14 An exit opening 108 of the sintering furnace 100 is shown, which according to exemplary embodiments, exhibits a small clearance G2 relative to the strip 40. In various embodiments, Gl and G2 can represent the maximum gap distance between the relevant surfaces, and in another embodiment, Gl and G2 can represent the average gap distance between the relevant surfaces measured along the length of the channel 104.

[0211] In specific embodiments, surfaces 120 and / or 122 are also substantially horizontal surfaces extending between the inlet opening 106 and the outlet opening 108 of the furnace 100 (as described above). Thus, in such embodiments, surfaces 120 and 122 define a substantially horizontal channel 104. In some embodiments, surfaces 120 and / or 122 may be flat, level surfaces extending between the inlet opening 106 and the outlet opening 108 of the furnace 100. In other embodiments, surfaces 120 and / or 122 may be gradually arcuate or curved as described above, or may be as in the case of an adhesive removal workstation. In specific embodiments, surfaces 120 and / or 122 are substantially horizontal such that the angle formed by the surfaces relative to a horizontal reference plane is less than 10 degrees, specifically less than 3 degrees, and even more specifically less than 1 degree.

[0212] like Figure 13 As shown, the lower surface 126 of the unbonded strip 36 contacts the upper surface 120, so that as the unbonded strip 36 moves forward through the furnace 100, the lower surface 126 of the unbonded strip 36 slides along or relative to the upper surface 120. In a specific embodiment, the sliding contact between the lower surface 126 and the upper surface 120 during sintering produces, or can produce, various longitudinal features (e.g., longitudinally extending marks, grooves, ridges, etc.) formed in the lower surface 126 rather than on the upper surface 124. Therefore, in a specific embodiment, the surface features on the lower surface 126 are different from those on the upper surface 124 that do not come into contact with the opposing surface during sintering. Specifically, this sliding contact is significantly different from the arrangement in some firing processes (e.g., tunnel kiln processes, in which ceramic material is placed on a fixed plate and both move simultaneously through the sintering furnace). In a specific embodiment, surfaces 20 and 122 are alumina or contain alumina, for example, the inner surface of an alumina tube defining channel 104.

[0213] In addition to the location and airflow control arrangements discussed above, the applicant has found that controlling the temperature distribution of the through furnace 100 exposed to the unbonded strip 36 is important for limiting strip deformation or breakage. The applicant has found that excessively rapid temperature increases (e.g., too fast a sintering rate or over too short a distance in the strip) can cause such strip deformation or breakage. See also... Figure 15The furnace 100 can include a plurality of independently controlled heating elements 140 arranged to deliver heat to the passageway 104 to cause sintering of the non- adhesive tape 36 as the tape 36 traverses the furnace 100. While the maximum and minimum sintering temperatures can vary based at least in part on the type of inorganic material carried by the tape 36, generally the heating elements 140 are configured to produce a temperature of at least 500 degrees Celsius along at least a portion of the passageway 104. In some embodiments, for example, for sintering of Th02(Thorium oxide) and / or Ti02(Titanium oxide), the passageway 104 can be heated to a maximum temperature of greater than 3100 degrees Celsius. Some materials (e.g., carbides, tungsten) have a melting point of greater than 3200 degrees, and in some such embodiments the temperature produced by the heaters 140 ranges between 500 degrees Celsius and a higher temperature (e.g., 3500 degrees Celsius or 3600 degrees Celsius). In particular embodiments, the heating elements 140 can be U-shaped molybdenum disilicide heating elements and / or other heating elements disclosed herein.

[0214] Generally, each of the heating elements 140 can be controlled by a control system 142 configured (e.g., by physical arrangement, programming, etc.) to independently control the individual heating elements 140 of the furnace 100 to produce a temperature profile along the length of the passageway 104 to provide a desired level of sintering in the sintered tape 40 while limiting distortion during the sintering process. In some embodiments, the control system 142 can be in communication with one or more temperature sensors 144 that detect the temperature within the passageway 104. In such embodiments, the control system 142 can control the heating elements 140 based on input signals received from the sensors 144 to maintain a desired temperature profile during continuous sintering of successive non-adhesive tapes 36. In some embodiments, the control system 142 can also receive input signals indicative of tape movement speed, position, shrinkage, and tension, and control the temperature and / or movement speed based on these signals or other signals that can be related to these or other tape properties.

[0215] As will be demonstrated in the examples below relating to sintering furnaces, Applicants have discovered that applying a sintering temperature profile along the length of the passageway 104 can be important or can be important to maintaining a low or controlled level of tape material distortion during the sintering process. In particular, Applicants have discovered that if the temperature to which the non-adhesive tape 36 is exposed during the sintering process is increased too rapidly (e.g., the slope of the temperature profile is too steep), then unacceptable high levels of stress can form or can form in the tape 36 as the material sintered and shrinks, which in turn can lead to out of plane deformation in the tape 36, for example as shown in FIG. 1C. Figure 2As shown. In particular, Applicants have discovered that by controlling the stresses at and / or along the centerline of the edges 130 and 132 of the strip 36 during sintering, the distortion of the strip 36 during sintering can be controlled. If the transition from the heated portion of the system 10 to the room temperature portion of the system 10 (e.g., after exiting the furnace 100) occurs too drastically, similar deleterious effects can occur on the strip 36. That is, the techniques of the present application can be used to sinter a strip without such temperature control or distribution, where the resulting new strip or other sintered article can have distortions or other defects of such characteristics.

[0216] Referring to Figure 16 and 17 , temperature profiles 160 and 170 along the length of the sintering channel 104 are shown, generated by the heating elements 140, according to exemplary embodiments. Referring to Figure 16 , the temperature profile 160 shows that the temperature within the channel 104 generally increases in the process direction 14 along the length of the channel 104. The profile 160 includes at least three segments: a first segment 162 representing the temperature within the channel 104 adjacent to the inlet opening 106; a second segment 164 representing the temperature along the bulk (e.g., at least 50%, at least 75%, etc.) of the length of the channel 104; and a third segment 166 representing the temperature within the channel 104 adjacent to the outlet opening 108.

[0217] As shown in Figure 16 , the average slope of the first segment 162 is greater than the average slope of the second segment 164, showing a relatively rapid increase in temperature within the channel 104 adjacent to the inlet opening 106. The average slope of the second segment 164 is lower (and less than the first segment 162). The low average slope of the second segment 164 represents a gradual increase in temperature experienced by the strip 36 as it moves along the majority of the length of the channel 104. As described below, this gradual increase is selected to maintain the stresses within the strip 36 below a threshold determined to maintain distortion below a desired level. The average slope of the third segment 166 is a negative slope, representing a cooling segment within the channel 104 adjacent to the outlet opening 108, which limits the thermal shock experienced by the strip 36 after exiting the furnace 100.

[0218] In various embodiments, the gradual temperature increase represented by the low slope of the segment 164 can be achieved by controlling the rate of temperature increase along the length of the channel 104. In various embodiments, as represented by the x-axis of Figure 16 , the length of the channel 104 can be large, e.g., at least 1 meter, at least 50 inches, at least 60 inches, or more. In a particular sintering furnace modeled and shown in Figure 16 , the heating channel 104 is 64 inches.

[0219] In various embodiments, the shape of the distribution 160 maintains an acceptably low level of compressive stress within the strip 36 during the sintering process, thereby avoiding undesirable distortion. Applicants have found that this is particularly problematic for wide strip materials and high throughput sintering systems if the strip distortion is not controlled as described herein. In particular, wider strips are more susceptible to this type of distortion, and in addition, distortion in the width direction makes it either difficult or impossible to wind onto a take-up spool. That is, the technical aspects disclosed herein (e.g., carrier separation, tension control, adhesive removal, etc.) can be practiced and used to produce new materials and products without the temperature distribution, e.g., where the resulting product is narrower and / or has the defect or distortion characteristics of such processing.

[0220] Thus, in various embodiments, the shape of the distribution 160 is such that the compressive stress at the left edge 130 and / or the right edge 132 of the non-bonded strip 36 during the sintering process is maintained below an edge stress threshold, and the compressive stress at the centerline of the non-bonded strip 36 during the sintering process is maintained below a centerline stress threshold. Generally, the edge stress threshold and the centerline stress threshold are defined as the compressive stress above which the non-bonded strip 36 experiences out-of-plane (length-width plane) distortion greater than 1 mm during the sintering process. Applicants have found that for at least some materials and strip widths, by maintaining the edge compressive stress and the centerline compressive stress below a threshold of 100 MPa (specifically 75 MPa, and more specifically 60 MPa), the out-of-plane distortion during the sintering process can be limited to less than 1 mm. In specific embodiments, Applicants have found that for at least some materials and strip widths, by maintaining the centerline compressive stress below a threshold of 100 MPa (specifically 75 MPa, and more specifically 60 MPa) and maintaining the edge stress below a threshold of 300 MPa (specifically 250 MPa, and more specifically 200 MPa), the out-of-plane distortion during the sintering process can be limited to less than 1 mm.

[0221] In specific embodiments, the slopes of the segments 162 and 166 can be controlled to provide particularly low strip stresses at the entrance and exit of the furnace 100. In one such embodiment, the control system 142 is configured to control the temperature distribution within the segments 162 and 166 in combination with controlling the speed of the strip through the furnace 100. In such embodiments, this combination of temperature control within the segments 162 and 166 in combination with speed control results in uniform sintering shrinkage (strain), and thus low stresses and low distortion within the strip 36 during the sintering process.

[0222] Referring to Figure 17, showing another exemplary temperature profile 170 projected along the view of the channel 104. As shown, the profile 170 shows an increase to a maximum temperature in zone 172 over approximately at least 75% of the total length of the channel 104. In particular embodiments, the sintering furnace 100 can be made of a high thermal conductivity material (e.g., steel or high thermal conductivity ceramic) to reduce the temperature gradient in the cross-web material (strip / tape) in the width direction. As shown, there is a low or no temperature variation in the width direction. As generally understood, the temperature profile of a particular sintering system will be based on several factors, including: material type, inorganic particle size, particle density, particle size distribution, porosity, pore size, pore size distribution, sintering atmosphere, stress threshold / amount of deformation allowed by the part (as described above), length of the channel 104, throughput speed, etc., and the desired output. Figure 17

[0223] Referring to Figure 18 , showing another embodiment of a sintering station 38 according to exemplary embodiments. In this embodiment, the sintering station 38 includes two furnaces 180 and 182 arranged in series with each other. In general, the furnaces 180 and 182 are substantially the same as the furnace 100 described above, except that in at least some embodiments, the temperature profile in the furnace 180 is different than the temperature profile in the furnace 182. With this arrangement, the non-bonded tape 36 enters the inlet opening 106 of the furnace 180. Within the furnace 180, the non-bonded tape 36 is partially sintered, forming a partially sintered tape 184 that exits the furnace 180 through the outlet opening 108. The partially sintered tape 184 then enters the second furnace 182 through the inlet opening 106 and undergoes additional sintering along the length of the channel 104 of the furnace 182, such that the sintered tape 40 exits the furnace 182 through the outlet opening 108 for spooling as described above.

[0224] In various embodiments, the furnaces 180 and 182 each include a plurality of independently controllable heating elements, such that different and independent temperature profiles can be formed in the furnaces 180 and 182, respectively. In some embodiments, the use of two thermally isolated furnaces (e.g., furnaces 180 and 182) can provide more precise control over the temperature profile to which the tape material is exposed during sintering, as compared to a single long furnace having a channel length equal to the total channel length of the furnaces 180 and 182. In other contemplated embodiments, the tape can be moved back through the same furnace, but along a different path and / or exposed to a different temperature profile for additional sintering.

[0225] ​Additionally, in some embodiments, it can be desirable to apply different tensions between the ovens 180 and 182. In such embodiments, a tension control system 186 is positioned along the sintering path defined by the passage 104 of the ovens 180 and 182. In particular embodiments, the tension control system 186 is positioned between the ovens 180 and 182 and applies tension to the partially sintered ribbon 184, such that the tension of the ribbon 184 within the second oven 182 is greater than the tension of the non-bonded ribbon 36 within the oven 180. In various embodiments, it can be desirable to increase the tension within the second sintering oven to provide for improved flatness or reduced distortion during the final sintering or subsequent sintering processes of the oven 182. Additionally, such increased tension can be suitable to apply to the partially sintered ribbon 184, as the partial sintering increases the tensile strength of the ribbon 184, which is lower than the tensile strength of the non-bonded ribbon 36 within the oven 180.

[0226] Referring to Figure 19 , a predicted temperature profile within the ovens 180 and 182 is shown according to an exemplary embodiment. As shown in Figure 19 , the heating elements of the oven 180 are controlled to produce a temperature profile 190, and the heating elements of the oven 182 are controlled to produce a temperature profile 192. It will be noted that both profiles 190 and 192 have the same low stress producing, gradual temperature increase, similar to the case of the temperature profile 160 described above. However, the profile 192 is positioned higher than the profile 190 (e.g., has a higher average temperature than the profile 190), which results in an additional higher level of sintering (e.g., additional shrinkage, additional reduction in porosity) occurring as the partially sintered ribbon 184 traverses the oven 182.

[0227] Referring to Figure 20 , a high yield sintering system 200 is shown according to an exemplary embodiment. In general, the system 200 includes two parallel systems 10, each sintering a ribbon material. The system 200 can be operated to increase the output of a single type of sintered ribbon material, similar to the arrangement of Figure 18 . Alternatively, each system 10 of the system 200 can output a different sintered ribbon material. In various embodiments, the system 200 can include 3, 4, 5,... parallel systems 10 to further increase the output of sintered ribbon materials.

[0228] Sintering station embodiments and models

[0229] Referring to Figures 21 to 28 , various sintering tests and sintering models are described, demonstrating the sintering relationships discussed herein, such as: the relationship between temperature profile and shrinkage, the relationship between temperature profile and stress of the ribbon material, the relationship between stress and distortion of the ribbon, and the relationship between ribbon width and risk of sintering distortion.

[0230] Physical sintering test example 1

[0231] In one example, a horizontal furnace with actively controlled multi-zone binder burnout furnace was tested. In this test, a strip cast "green" zirconia ceramic tape (ceramic loaded with polymeric binder) about 15 mm wide and 25 microns thick was fed through a horizontal apparatus with a multi-zone binder burnout furnace (similar to the furnace 38 and binder removal station 34 described above) at 8 inches per minute. The binder burnout furnace was set from 325°C at the inlet to 475°C at the outlet with a 0-25°C incremental increase for the four central hot zones. Air flow of 7.5 liters per minute at a temperature of about 0°C to about 250°C was also provided and was divided to both sides of the burnout furnace. The sintering furnace was 36 inches long and had hot zones 18 inches long. Within the sintering furnace, the tape was transported by sliding it over an alumina "D" tube with 20 grams of tension and the furnace was set at 1225°C. A 10-20 foot sintered zirconia strip was produced and wound onto a take-up spool with a diameter of 3 inches. The sintering shrinkage across the width was about 12%.

[0232] Sintering model 1

[0233] Referring to Figure 21 and Figure 22 , the sintering shrinkage of zirconia is shown as a function of time and temperature. Figure 21 A plot of the sintering shrinkage of a zirconia strip at various temperatures and times at temperature is shown. Figure 22 A plot of the sintering shrinkage of a zirconia strip at various temperatures and times at temperature is shown.

[0234] To generate Figure 21 the data points shown, a strip cast "green" zirconia ceramic tape (ceramic loaded with polymeric binder) about 15 mm wide and 25 microns thick was "bisque" fired to 1200°C at 8 inches per minute in the apparatus described in physical sintering test example 1 above. The bisque fired strip produced in this manner was inserted into a narrow hot zone furnace and "plunge fired" at 1250°C, 1300°C, 1350°C, 1400°C, 1450°C, and 1500°C for 30 seconds, 1 minute, 2 minutes, 3 minutes, and 5 minutes. The sintering shrinkage was measured and these data points are shown in Figure 21 .

[0235] Based on the sintering data, a mathematical curve describing the sintering shrinkage as a function of temperature and time was fit and extrapolated to lower and intermediate temperatures outside of those actually tested. This curve fit and extrapolation is shown in Figure 22 . Based on Figure 21 and Figure 22The tests and curve fitting shown determined the relationship between sintering shrinkage, sintering time, and temperature for zirconia. Applicant believes that this information can be used to establish a sintering temperature profile for zirconia to achieve a desired shrinkage and reduce stresses below a deformation threshold, as described above.

[0236] In one particular implementation, this data is used to develop a model for Figure 16 The 64 inch sintering furnace and temperature profile shown was modeled. As Figure 16 shown, the thermal gradient / profile 160 starts at 1250 °C and ends at 1450 °C. The modeled temperatures are as follows: from 0 to 8 inches into the furnace, increase from 1250 °C to 1300 °C; from 8 to 16 inches, increase from 1300 °C to 1312.5 °C; from 16 to 24 inches, increase from 1312.5 to 1325 °C; from 24 to 32 inches, maintain at 1325 °C; from 32 to 40 inches, increase from 1325 to 1375 °C; from 40 to 48 inches, increase from 1375 °C to 1400 °C; from 48 to 56 inches, increase from 1400 to 1450 °C; from 56 to 64 inches, maintain at 1450 °C; and then after 64 inches, cool to below 1000 °C.

[0237] The modeled shrinkage was functionally related to the strip transport speed. As Figure 16 shown, the model shows that a faster transport speed (20 inches per minute (ipm)) results in a more uniform sintering shrinkage over the length of the hot zone. Thus, this model demonstrates that uniform shrinkage over a longer length is desirable because the shorter the distance over which sintering strain / shrinkage occurs, the greater the stress in the strip and the greater the propensity for bending and out-of-plane plastic deformation.

[0238] Sintering Model 2

[0239] Referring to Figure 23 and 16 , sintering stresses were modeled by finite element analysis (FEA) and closed form (CF) solutions. As Figure 23 and 24It was demonstrated that as the sintering strip being processed becomes wider, the extreme sintering stresses calculated for a 100 mm wide static strip (single heat zone), for a 100 mm wide strip where only two heat zones, and the strip is transported at 8 and 16 inches per minute, are greater than -1000 MPa. Conversely, when using 9 heat zones and 2 sintering passes (equivalent to 18 heat zones single pass), the edge stresses modeled are less than about -200 MPa for a 150 mm wide sheet. In the single heat zone and 4 heat zone tests, each heat zone was modeled to have a 450 mm (18 inch) length, and the furnace was 900 mm (36 inches), so in these two modeled embodiments, additional heat zones are equivalent to longer heat zones. For example, a 1 zone 2 pass heat zone is roughly equivalent to a 900 mm long (36 inches) heat zone in total. However, for a 9 zone 2 pass heat zone, it is equivalent to a 3660 mm (144 inches) (length) heat zone in total. Thus, Figure 23 and 24 It was demonstrated that increasingly wider strips (e.g., greater than 50 mm, 100 mm, 150 mm, 200 mm, 250 mm, etc.) can be achieved by controlling the number of heat zones (e.g., the total length of sintering heat zones), the temperature profile to which the strip is exposed, and the rate at which the strip is moved through the heat zones, the sintering stresses can be maintained at a low enough level to avoid creating distortion, warping, or breaking.

[0240] Sintering Model 3

[0241] Figure 25 and 26 Model showing a light yellow zirconia strip (i.e., a partially sintered strip) that is passed twice through a single heat zone with a steep temperature gradient. For the first pass, the heat zone is set at 1250 °C, and then for the second pass, the heat zone is set at 1400 °C. Strip transport speeds of 8 and 16 inches per minute are input. The strip is modeled to be 20 microns thick and 15 mm and 40 mm wide. Figure 25 showing the shrinkage through the heat zone, and Figure 26 showing that significant compressive stresses are created in the strip due to the rapid sintering strains, greater than 90 MPa for the 40 mm wide strip at 8 ipm, and greater than 120 MPa for the 40 mm wide strip at 16 ipm. It is believed that this results in warping and out-of-plane distortion for strips having these widths and thicknesses.

[0242] Sintering Model 4

[0243] Figure 27 and Figure 28 Model showing when the model uses a multi-zone furnace with 10 heat zones and 2 passes, and the temperature set for the second pass is higher than the result of the first pass. For both strip transport speeds and strip widths, the stresses modeled are compared to Figure 26The stress is shown to decrease by an order of magnitude. It is believed that this lower stress results in a much flatter tape (e.g., less distortion). Furthermore, this model demonstrates the effect of a controlled sintering temperature profile or gradual ramping of temperature during sintering on stress and, in turn, distortion.

[0244] Physical Sintering Test Example 2

[0245] In another test example, about 25 micron thick and 15 cm wide tape cast "green" zirconia ceramic tape (ceramic loaded with polymeric binder) was produced at a sintering temperature of 1100°C using a vertically oriented sintering apparatus. About 50 feet was produced and wound onto a take-up spool having a diameter of 3 inches. The light yellow sintered shrinkage width was about 10%.

[0246] This 1100°C "light yellow" tape was then run through a horizontal sintering furnace (essentially the same as that shown in Figure 12 at speeds of about 3, 10, 20, 30, 60, and 75 inches per minute with the furnace set at 1550°C. A sintered tape having a length of 40 feet was produced and wound onto a take-up spool having a diameter of 3 inches. A tension of 10 grams was applied to the tape during sintering and porosities of less than 20% were achieved even at 75 inches per minute which resulted in the tape being in the hot zone for less than about 15 seconds. Slower speeds resulted in denser material. Thus, this test demonstrates that longer sintering furnaces result in higher density / lower porosity in the sintered tape and also demonstrates that higher temperatures result in higher density / lower porosity in the sintered tape.

[0247] Physical Sintering Test Example 3

[0248] In another test example, about 50 micron thick tape cast "green" alumina ceramic tape (ceramic loaded with polymeric binder) was fed through a system essentially the same as that shown in Figure 3 at a rate of 4-6 inches per minute. The binder burnout furnace was set from 325°C inlet to 475°C outlet with a delta increase of 0-25 degrees for the four center hot zones. Air flow of 0-250°C at 5-7.5 liters per minute was used. The sintering furnace was 36 inches long and had an 18 inch hot zone set at 1300°C. The green tape was passed through the 18 inch sintering hot zone at 1300°C to produce a partially sintered "light yellow" tape. The width of the partially sintered tape was 7% less than the width of the green tape.

[0249] The 1300°C "light yellow" tape was then passed through the sintering furnace a second time at 2 inches per minute with the sintering furnace set at 1550°C, resulting in a fully sintered alumina tape of approximately 20 feet. The tape was wound onto a take-up spool of 6 inches in diameter. The tension on the tape during sintering was approximately 100 grams, and the sintering shrinkage width for the second pass was approximately 15%. After sintering, the tape was translucent, nearly transparent. When placed over a written document, it could be read through. The grain size was less than approximately 2 microns, and the material had a porosity of less than approximately 1%.

[0250] Test Example 4

[0251] In another test example, a "green" zirconia ceramic tape (ceramic loaded with polymeric binder) approximately 50 microns thick was fed through a system substantially identical to that shown in Figure 3 The binder burnout furnace was set at 300-475°C with an air flow of 200-250°C at -7.5 liters per minute. The sintering furnace was 36 inches long with an 18 inch hot zone. The temperature gradient was 25°C to 1225°C in less than 9 inches, and 1000°C to 1225°C in 3-4 inches. Two D-tubes spaced approximately 3 / 8 inches apart were used to restrict air circulation and reduce the temperature gradient. The tension in the tape was 20-60 grams, and the sintering furnace was set at 1225°C. A sintered zirconia of 50 feet in length was produced and wound onto a take-up spool of 3 inches in diameter. The sintering shrinkage width was approximately 12%.

[0252] To physically model a furnace with a shallow temperature gradient, the 1225°C sintered "light yellow" tape was passed through a single zone furnace three times (with progressively higher temperatures), which reduced the sintering shrinkage and the out-of-plane distortion for each pass. Specifically, the 1225°C "light yellow" tape was then passed through the furnace a second time at 6 inches per minute with the furnace set at 1325°C. A sintered zirconia of 45 feet in length was produced and wound onto a take-up spool of 3 inches in diameter. The tension on the tape during sintering was 100-250 grams, and the sintering shrinkage width for this pass was 5-6%.

[0253] The 1325°C tape was then passed through the furnace a third time at 6 inches per minute with the furnace set at 1425°C. A sintered zirconia of approximately 40 feet in length was produced and wound onto a take-up spool of 3 inches in diameter. The tension on the tape during sintering was 100-250 grams, and the sintering shrinkage width for this pass was 5-6%. After the 1425°C pass, the tape was translucent, nearly transparent. When placed over a written document, it could be read through.

[0254] Then, the 1425°C strip was passed through the furnace a fourth time at 3-6 inches per minute, with the furnace set to 1550°C. This resulted in a number of feet of 1550°C sintered strip, which was wound onto a take-up spool having a diameter of 3 inches. The tension on the strip during sintering was 100-300 grams, and the sintering shrinkage (width) for this pass was 0-2%.

[0255] sintered article

[0256] Embodiments of sintered articles formed using the systems and processes described herein will now be described. Sintered articles can be provided in the form of sintered strips (i.e., continuous sintered articles) or discrete sintered articles. Unless otherwise specified, the term "sintered article" refers to both continuous sintered articles and discrete sintered articles. Further, "sintered" refers to both partially sintered articles and fully sintered articles. In one aspect, embodiments of sintered articles include previously unattainable dimensions. In one or more embodiments, sintered articles also exhibit uniformity in certain properties along these dimensions. According to another aspect, embodiments of sintered articles exhibit planarizability that indicates that the sintered articles can be planarized or subjected to planarization without imparting significant stresses in the sintered article, such that they can be successfully used in downstream processes. Another aspect pertains to embodiments of roll sintered articles, and another aspect pertains to embodiments of multiple discrete sintered articles. Other aspects include new material compositions or compositions with new microstructures, e.g., for unique grain boundaries.

[0257] Referring to Figure 29 A sintered article 1000 according to one or more embodiments includes a first major surface 1010, a second major surface 1020 opposite the first major surface, and a body 1030 extending between the first and second major surfaces. The body 1030 has a thickness (t) defined as the distance between the first and second major surfaces, a width (W) defined as the first dimension of one of the first or second surfaces perpendicular to the thickness, and a length (L) defined as the second dimension of one of the first or second surfaces perpendicular to both the thickness and the width. In one or more embodiments, the sintered article includes an opposing minor surface 1040 defining the width (W). In particular embodiments, the sintered article 1000 is an example of a sintered strip 40 produced using the system 10 as described herein, although some strips of the present technology can be longer than the strip shown. Figure 29

[0258] In one or more embodiments, the sintered article is a continuous sintered article having a width of about 5 mm or greater, a thickness of about 3 μιη to about 1 mm, and a length of about 300 cm or greater. In other embodiments, the width is less than 5 mm, as described above.

[0259] ​In one or more embodiments, the sintered article has a width in a range from about 5 mm to about 200 mm, from about 6 mm to about 200 mm, from about 8 mm to about 200 mm, from about 10 mm to about 200 mm, from about 12 mm to about 200 mm, from about 14 mm to about 200 mm, from about 15 mm to about 200 mm, from about 17 mm to about 200 mm, from about 18 mm to about 200 mm, from about 20 mm to about 200 mm, from about 22 mm to about 200 mm, from about 24 mm to about 200 mm, from about 25 mm to about 200 mm, from about 30 mm to about 200 mm, from about 40 mm to about 200 mm, from about 50 mm to about 200 mm, from about 60 mm to about 200 mm, from about 70 mm to about 200 mm, from about 80 mm to about 200 mm, from about 90 mm to about 200 mm, from about 100 mm to about 200 mm, from about 5 mm to about 150 mm, from about 5 mm to about 125 mm, from about 5 mm to about 100 mm, from about 5 mm to about 75 mm, from about 5 mm to about 50 mm, from about 5 mm to about 40 mm, from about 5 mm to about 30 mm, from about 5 mm to about 20 mm, or from about 5 mm to about 10 mm.

[0260] In some embodiments, the sintered article has a width W of at least 0.5 mm, for example at least 1 mm, for example at least 2 mm, for example at least 5 mm, for example at least 8 mm, for example at least 10 mm, for example at least 15 mm, for example at least 20 mm, for example at least 30 mm, for example at least 50 mm, for example at least 75 mm, for example at least 10 cm, for example at least 15 cm, for example at least 20 cm, and / or no more than 2 m, for example no more than 1 m, for example no more than 50 cm, for example no more than 30 cm. In other embodiments, the sintered article has a different width W.

[0261] In one or more embodiments, the sintered article has a thickness (t) in a range from about 3 μιη to about 1 mm, from about 4 μιη to about 1 mm, from about 5 μιη to about 1 mm, from about 6 μιη to about 1 mm, from about 7 μιη to about 1 mm, from about 8 μιη to about 1 mm, from about 9 μιη to about 1 mm, from about 10 μιη to about 1 mm, from about 11 μιη to about 1 mm, from about 12 μιη to about 1 mm, from about 13 μιη to about 1 mm, from about 14 μιη to about 1 mm, from about 15 μιη to about 1 mm, from about 20 μιη to about 1 mm, from about 25 μιη to about 1 mm, from about 30 μιη to about 1 mm, from about 35 μιη to about 1 mm, from about 40 μιη to about 1 mm, from about 45 μιη to about 1 mm, from about 50 μιη to about 1 mm, from about 100 μιη to about 1 mm, from about 200 μιη to about 1 mm, from about 300 μιη to about 1 mm, from about 400 μιη to about 1 mm, from about 500 μιη to about 1 mm, from about 3 μιη to about 900 μιη, from about 3 μιη to about 800 μιη, from about 3 μιη to about 700 μιη, from about 3 μιη to about 600 μιη, from about 3 μιη to about 500 μιη, from about 3 μιη to about 400 μιη, from about 3 μιη to about 300 μιη, from about 3 μιη to about 200 μιη, from about 3 μιη to about 100 μιη, from about 3 μιη to about 90 μιη, from about 3 μιη to about 80 μιη, from about 3 μιη to about 70 μιη, from about 3 μιη to about 60 μιη, from about 3 μιη to about 50 μιη, from about 3 μιη to about 45 μιη, from about 3 μιη to about 40 μιη, from about 3 μιη to about 35 μιη, from about 3 μιη to about 30 μιη, or from about 3 μιη to about 30 μιη.

[0262] In some embodiments, the sintered article has a thickness t of at least 3 μιη, for example at least 5 μιη, for example at least 10 μιη, for example at least 15 μιη, for example at least 20 μιη, for example at least 25 μιη, for example at least 0.5 mm, for example at least 1 mm, and / or not more than 5 mm, for example not more than 3 mm, for example not more than 1 mm, for example not more than 500 μιη, for example not more than 300 μιη, for example not more than 100 μιη. In other embodiments, the sintered article has a different thickness t.

[0263] In one or more embodiments, the sintered article is continuous and has a length L in a range from about 300 cm to about 500 m, from about 300 cm to about 400 m, from about 300 cm to about 200 m, from about 300 cm to about 100 m, from about 300 cm to about 50 m, from about 300 cm to about 25 m, from about 300 cm to about 20 m, from about 350 cm to about 500 m, from about 400 cm to about 500 m, from about 450 cm to about 500 m, from about 500 cm to about 500 m, from about 550 cm to about 500 m, from about 600 cm to about 500 m, from about 700 cm to about 500 m, from about 800 cm to about 500 m, from about 900 cm to about 500 m, from about 1 m to about 500 m, from about 5 m to about 500 m, from about 10 m to about 500 m, from about 20 m to about 500 m, from about 30 m to about 500 m, from about 40 m to about 500 m, from about 50 m to about 500 m, from about 75 m to about 500 m, from about 100 m to about 500 m, from about 200 m to about 500 m, or from about 250 m to about 500 m.

[0264] In some embodiments, the sintered article has a continuous unbroken length L of at least 5 mm: for example, at least 25 mm, for example, at least 1 cm, for example, at least 15 cm, for example, at least 50 cm, for example, at least 1 m, for example, at least 5 m, for example, at least 10 m, and / or no more than 5 km, for example, no more than 3 km, for example, no more than 1 km, for example, no more than 500 m, for example, no more than 300 m, for example, no more than 100 m. In other embodiments, the sintered article has a different length L. Such continuous long lengths, particularly for the materials and qualities disclosed herein, can be surprising to one of skill in the art without the techniques disclosed herein (e.g., controlled separation, tension control, sintering zone, adhesive removal techniques, etc.).

[0265] In one or more embodiments, the body of the sintered article comprises a sintered inorganic material. In one or more embodiments, the inorganic material comprises interfaces having a primary interface dimension of less than about 1 mm. As used herein, the term "interface" when used in reference to an inorganic material is defined to include either chemical heterogeneity or crystallographic structural heterogeneity or both chemical heterogeneity and crystallographic structural heterogeneity.

[0266] Exemplary inorganic materials include ceramic materials, and glass-ceramic materials, among others. In some embodiments, the inorganic material can include any one or more of a piezoelectric material, a thermoelectric material, a pyroelectric material, a variable resistance material, or a photoelectric material. Specific examples of inorganic materials include: zirconia (e.g., yttria-stabilized zirconia), alumina, spinel, garnet, lithium lanthanum zirconium oxide (LLZO), cordierite, mullite, perovskite, pyrochlore, silicon carbide, silicon nitride, boron carbide, sodium bismuth titanate, barium titanate, titanium diboride, silicon aluminum oxynitride, aluminum oxynitride, or a reactive cerammed glass-ceramic (a glass-ceramic formed by a combination of chemical reaction and devitrification, which includes an in-situ reaction between a glass frit and a reactant powder).

[0267] In one or more embodiments, the sintered article exhibits compositional uniformity over a particular area. In one or more particular embodiments, the sintered article includes an area of at least 10 square centimeters along a length having a composition (i.e., relative amounts of chemical species, in weight percent (%)) in which at least one component of the composition varies by less than about 3 weight percent (e.g., about 2.5 weight percent or less, about 2 weight percent or less, about 1.5 weight percent or less, about 1 weight percent or less, or about 0.5 weight percent or less) across the area. For example, when the inorganic material includes alumina, the amount of aluminum can vary by less than about 3 weight percent (e.g., about 2.5 weight percent or less, about 2 weight percent or less, about 1.5 weight percent or less, about 1 weight percent or less, or about 0.5 weight percent or less) across the area of at least 10 square centimeters. Such compositional uniformity can be attributed, at least in part, to the new and unique processes disclosed herein, such as: furnace thermal zones with individual control of elements, careful and gentle handling of green tape, steady state of continuous tape processing, and the like. In other embodiments, the new and inventive tapes or other products of at least some of the techniques disclosed herein can not have such compositional uniformity.

[0268] In one or more embodiments, the sintered article exhibits crystal structure uniformity over a particular area. In one or more embodiments, the sintered article includes an area of at least 10 square centimeters along a length that has a crystal structure in which the weight percent of at least one phase varies by less than about 5 percentage points over the area. For the sake of illustration only, the sintered article can include at least one phase that constitutes 20 weight percent of the sintered article, and over the area of at least 10 square centimeters, the amount of this phase is about 15 weight percent to about 25 weight percent. In one or more embodiments, the sintered article includes an area of at least 10 square centimeters along a length that has a crystal structure in which the weight percent of at least one phase varies by less than about 4.5 percentage points, less than about 4 percentage points, less than about 3.5 percentage points, less than about 3 percentage points, less than about 2.5 percentage points, less than about 2 percentage points, less than about 1.5 percentage points, less than about 1 percentage point, or less than about 0.5 percentage points over the area. Such crystal structure uniformity can be attributed, at least in part, to the new and unique processes disclosed herein, e.g., furnace thermal zones with individual control elements, careful and gentle handling of green strip, steady state of continuous strip processing, etc. In other embodiments, the new and inventive strips or other products of at least some of the technology disclosed herein can not have such crystal structure uniformity.

[0269] In one or more embodiments, the sintered article exhibits porosity uniformity over a particular area. In one or more particular embodiments, the sintered article includes an area of at least 10 square centimeters along a length that has a porosity variation of less than about 20%. As used herein, the term "porosity" describes a volume percentage (e.g., at least 10 volume percent or at least 30 volume percent), where "porosity" refers to the portion of the volume of the sintered article that is not occupied by inorganic material. Thus, in one example, the sintered article has a porosity of 10 volume percent, and over the area of at least 10 square centimeters, this porosity is greater than about 8 volume percent to less than about 12 volume percent. In one or more particular embodiments, the sintered article includes an area of at least 10 square centimeters along a length that has a porosity variation of 18% or less, 16% or less, 15% or less, 14% or less, 12% or less, 10% or less, 8% or less, 6% or less, 5% or less, 4% or less, or about 2% or less over the area. Such porosity uniformity can be attributed, at least in part, to the new and unique processes disclosed herein, e.g., furnace thermal zones with individual control elements, careful and gentle handling of green strip, steady state of continuous strip processing, etc. In other embodiments, the new and inventive strips or other products of at least some of the technology disclosed herein can not have such porosity uniformity.

[0270] In one or more embodiments, the sintered article exhibits a granular distribution, for example, when observed under a microscope (e.g. Figure 30A The digital images shown are examples of this type of granular distribution structure, and such as Figure 30B (Conceptual side view shown) It includes particles 1034 that protrude generally outward from the body 1030 and have a height H (e.g., average height) of at least 25 nanometers (nm) and / or no more than 150 micrometers (μm) relative to a recessed portion of the surface at the boundary 1032 between the particles 1034. In one or more embodiments, the height H ranges from about 25 nm to about 125 μm, about 25 nm to about 100 μm, about 25 nm to about 75 μm, about 25 nm to about 50 μm, about 50 nm to about 150 μm, about 75 nm to about 150 μm, about 100 nm to about 150 μm, or about 125 nm to about 150 μm. In one or more embodiments, the height H ranges from about 25 nm to about 125 nm, about 25 nm to about 100 nm, about 25 nm to about 75 nm, about 25 nm to about 50 nm, about 50 nm to about 150 nm, about 75 nm to about 150 nm, about 100 nm to about 150 nm, or about 125 nm to about 150 nm. In other embodiments, the height H can be any other size. In other embodiments, processing conditions (e.g., time, temperature) can cause the sintered material to have a height H that is substantially zero. In some embodiments, for the materials and manufacturing disclosed herein, the product (e.g., strip) includes a particle height H of at least 25 nm, such as at least 50 nm, such as at least 75 nm, such as at least 100 nm, such as at least 125 nm, such as at least 150 nm, and / or no more than 200 μm, such as no more than 150 μm, such as no more than 100 μm, such as no more than 75 μm, such as no more than 50 μm. The techniques disclosed herein can be used to control the size and shape of such microstructures, for example, the rate at which the material passes through the furnace, the furnace temperature and temperature distribution, the composition, particle / particle size and density of the inorganic material in the green strip, and other factors disclosed herein.

[0271] The granular profile is or can be an indicator of the manufacturing process used to form the sintered article 1000. In particular, the granular profile is or can be an indicator that the article 1000 was sintered into a thin, continuous article (i.e., as a sheet or ribbon) rather than being cut from a boule, and that the respective surfaces 1010, 1020 were not significantly polished. Further, the granular profile can provide benefits for the sintered article 1000 in some applications, such as light scattering for a backlight unit of a display, increased surface area for better coating adhesion, or for media growth, as compared to a polished surface. In contemplated embodiments, the roughness of the surfaces 1010, 1020 is about 10 nm to about 1000 nm, such as about 15 nm to about 800 nm, over a distance of 10 mm along one dimension of the length of the sintered article. In contemplated embodiments, either or both of the surfaces 1010, 1020 have a roughness of about 1 nm to about 10 μιη over a 1 cm distance along a single axis.

[0272] In one or more embodiments, one or both of the surfaces 1010, 1020 can be polished, with the polishing resulting in the substantial removal of the grain boundary grooves and the grain asperities (or bumps). In contemplated embodiments, the sintered article 1000 manufactured according to the processes disclosed herein can be polished, with the surface resembling that shown, for example, in Figures 31A-31B depending on the particular target use of the article. For example, using the sintered article 1000 as a substrate can not require a very smooth surface, and Figures 30A-30B the unpolished surface of Figures 31A-31B may be sufficient; whereas, using the article as a mirror or lens can require polishing, as shown in Figures 31A-31B However, as described herein, polishing can be difficult for particularly thin articles or for those that are thin and have a large surface area. As shown, the substrates disclosed herein can also receive a coating, which can change the surface quality (e.g., smoothness).

[0273] Without being bound by theory, it is believed that sintered ceramic sheets or other materials cut from a boule can not have readily discernible grain boundaries on their surfaces, unlike Figures 30A-30Bpear-shaped cut articles can often be polished to correct for rough surfaces resulting from the cutting, such as grooves from the abrasion; however, surface polishing can be particularly difficult or cumbersome for very thin articles of sintered ceramic or other materials, with the difficulty increasing as such articles become thinner and as the surface area of such articles becomes larger. However, sintered articles manufactured according to the technology disclosed herein can be less constrained by such limitations, as articles manufactured according to the technology herein can be continuously manufactured in long strip lengths. Further, the size of the furnace system as concluded herein can be scaled to accommodate and sinter wider articles, as described herein.

[0274] In some embodiments (e.g., where the sintered article 1000 is in the form of a sheet or a strip), the surface uniformity is such that either or both of the first and second surfaces 1010, 1020 have fewer surface defects. Here, a surface defect is an abrasive and / or adhesive along a dimension of at least 15 pm, 10 pm, and / or 5 pm along the respective surface. In one or more embodiments, one or both of the first major surface 1010 and the second major surface 1020 have fewer than 15, fewer than 10, and / or fewer than 5 surface defects per square centimeter having a dimension greater than 15 pm, 10 pm, and / or 5 pm. In one example, on average, one or both of the first major surface 1010 and the second major surface 1020 have fewer than 3 or fewer than 1 such surface defects per square centimeter. In one or more embodiments, one or both of the first major surface and the second major surface have an area of at least 10 square centimeters having fewer than 100 surface defects from adhesion or abrasion having a dimension greater than 5 pm. Additionally or alternatively, one of the first and second major surfaces has an area of at least 10 square centimeters having fewer than 100 surface defects from adhesion or abrasion having a dimension greater than 5 pm, while the other of the first and second major surfaces includes surface defects from adhesive or abrasion having a dimension greater than 5 pm. Thus, sintered articles manufactured according to the inventive technology disclosed herein can have a high and uniform surface quality. Applicant believes that the high and uniform surface quality of the sintered article 1000 contributes to increased strength of the article 1000 by reducing stress concentrations and / or crack initiation sites.

[0275] The sintered article can be described as having a flatness of about 0.1 pm (100 nm) to about 50 pm over a 1 cm distance along a single axis (e.g., along the length or width of the sintered article). In some embodiments, the flatness can be in a range from about 0.2 pm to about 50 pm, from about 0.4 pm to about 50 pm, from about 0.5 pm to about 50 pm, from about 0.6 pm to about 50 pm, from about 0.8 pm to about 50 pm, from about 1 pm to about 50 pm, from about 2 pm to about 50 pm, from about 5 pm to about 50 pm, from about 10 pm to about 50 pm, from about 20 pm to about 50 pm, from about 25 pm to about 50 pm, from about 30 pm to about 50 pm, from about 0.1 pm to about 45 pm, from about 0.1 pm to about 40 pm, from about 0.1 pm to about 35 pm, from about 0.1 pm to about 30 pm, from about 0.1 pm to about 25 pm, from about 0.1 pm to about 20 pm, from about 0.1 pm to about 15 pm, from about 0.1 pm to about 10 pm, from about 0.1 pm to about 5 pm, or from about 0.1 pm to about 1 pm. Such flatness, in combination with the surface quality, surface uniformity, large area, thin thickness, and / or material properties of the materials disclosed herein, can enable sheets, substrates, sintered strips, articles, and the like to be particularly useful for various applications, such as, for example, rugged cover sheets for displays, high temperature substrates, flexible separators, and other applications. That is, embodiments can be free of such flatness. Flatness can be measured with a corresponding national standard (e.g., ASTM A1030).

[0276] In one or more embodiments, the sintered article exhibits a striped profile along the width dimension, as shown in Figure 32 In one or more embodiments, the body 1030 has a striped profile with a thickness along the width that is substantially constant. For example, the thickness along the entire width is about 0.9t to about 1.1t (e.g., about 0.95t to about 1.1t, about 0.1t to about 1.1t, about 0.105t to about 1.1t, about 0.9t to about 1.05t, about 0.9t to about t, or about 0.9t to about 0.95t), where t is a thickness value disclosed herein. As shown in Figure 32As shown, the striated profile includes two or more undulations along the width. As used herein, an undulation represents one complete cycle. In some embodiments, the striated profile includes 3 or more undulations, 4 or more undulations, 5 or more undulations, or 10 or more undulations along the entire width, with an upper limit of about less than about 20 undulations along the entire width. In one or more embodiments, the striations can be measured as optical distortion. In one or more embodiments, the sintered article can be placed in proximity to a zebra board, which consists of a white board with straight black stripes arranged diagonally across the board. When the zebra board is viewed through the sintered article, distortion of the black stripes can be visually detected and measured using methods and tools known in the art. In one example, the distortion can be measured according to ASTM C1048. In other embodiments, such as for articles disclosed herein that are polished or otherwise formed, there can be less distortion or no distortion. In other embodiments, the amount and / or magnitude of distortion can be greater.

[0277] In one or more embodiments, the sintered article can be planar. In one or more embodiments, a portion of the sintered article or a discrete sintered article (as will be described herein) can have a three-dimensional shape. For example, in one or more embodiments, a portion of the sintered article or a discrete sintered article can have a saddle shape (which has a convex shape along the width and a concave shape along the length, or a concave shape along the width and a convex shape along the length). In one or more embodiments, a portion of the sintered article or a discrete sintered article can have a c-shape (which has a single concave shape along the length). In one or more embodiments, the magnitude of the shape (which represents the maximum height of the portion of the sintered article or the discrete sintered article measured from the plane of placement) is less than about 0.75 mm (e.g., about 0.7 mm or less, 0.65 mm or less, 0.6 mm or less, 0.55 mm or less, 0.5 mm or less, 0.45 mm or less, 0.4 mm or less, 0.35 mm or less, 0.3 mm or less, 0.25 mm or less, 0.2 mm or less, 0.15 mm or less, or 0.1 mm or less).

[0278] According to another aspect, embodiments of the sintered article can be described as being planarizable or capable of being planarized without heating the sintered article to near the melting temperature or sintering temperature to soften the article to planarize it under standard room temperature (23 °C) conditions. In some embodiments, a portion of the sintered article is planarizable. The planarizable portion of the sintered article can have a length of about 10 cm or less. In some embodiments, the sintered article can have dimensions (e.g., a width of about 5 mm or more, a thickness of about 3 μιη to about 1 mm, and a length of about 300 cm or more) described anywhere else herein, and the planarizable portion of the sintered article has a length of 10 cm or less. In some embodiments, for example when the sintered article is a discrete sintered article, the entire sintered article is planarizable.

[0279] As used herein, planarizability is determined by planarizing the sintered article (or portion of the sintered article) by clamping the sintered article (or portion of the sintered article) between two rigid parallel surfaces, or by applying a surface pressure to a first major surface 1010 of the sintered article (or portion of the sintered article) against a rigid surface, such that the sintered article (or portion of the sintered article) is planarized along a planar plane. The measure of planarizability can be expressed as the force required to clamp the sintered article (or portion of the sintered article) to within 0.05 mm, 0.01 mm, or 0.001 mm of the planarization plane when the sintered article (or portion of the sintered article) is clamped between two rigid parallel surfaces. Alternatively, the measure of planarizability can be expressed as the surface pressure applied to the first major surface 1010 to push the sintered article (or portion of the sintered article) to within 0.001 mm of the planarization plane when the sintered article (or portion of the sintered article) is pushed against a rigid surface. The measure of planarizability can be expressed as the maximum absolute value of in-plane surface stress (compressive or tensile) on the sintered article (or portion of the sintered article) when the sintered article (or portion of the sintered article) is planarized to within 0.05 mm, 0.01 mm, or 0.001 mm of the planarization plane using either planarization method (i.e., clamped between two rigid parallel surfaces or against a rigid surface). This stress can be determined using the bending equation for thin plate bending, σ x = Et / 2R(1 - v 2 ), where E is the modulus of elasticity, v is the Poisson's ratio, and t is the thickness of the sintered article.

[0280] The thin plate bending stress equation is derived from the equation, σ x = [E / (1 - v 2 )] · (ε x + vε y ), where E is the modulus of elasticity, v is the Poisson's ratio, and ε x and ε yThis represents the strain in the corresponding direction. For a thick beam (where the deflection is much smaller than the beam thickness), ε x It is proportional to the square of the thickness. However, when the beam thickness is significantly smaller than the bending radius (e.g., when a sintered product can have a thickness t of about 20 μm and bend to a bending radius on the order of millimeters), ε y Setting it to 0 is possible. For example... Figure 33 As shown, assume a thin sheet (or sintered product) is bent into a circular ring, where the length L0 of the neutral axis is θxR, where θ is the radius in radians and R is the bending radius, and the length L1 of the outer fiber is θx(R+t / 2), where θ is the radius in radians and R is the bending radius and t is the thickness, and ε on the outer fiber... x It is (L1-L0) / L0, therefore ε x =[θx(R+t / 2)–(θx R)]x 1 / (θx R)=t / 2R. Equation σ x =[E / (1-ν 2 )]·t / 2R becomes the thin plate bending equation above (σ x =Et / 2R(1-ν 2 )).

[0281] In one or more embodiments, when planarized to at least the size described above, the sintered article or a portion thereof exhibits a maximum in-plane stress less than or equal to 25% of the flexural strength of the sintered article (as measured by two-point flexural strength). This stress is defined as the maximum absolute value of the stress determined by the flexural equation of sheet bending, regardless of whether it is compressive or tensile stress. For example, the maximum in-plane stress of the sintered article or a portion thereof may be less than or equal to 24%, 22%, 20%, 18%, 16%, 15%, 14%, 12%, 10%, 5%, or 4% of the flexural strength of the sintered article.

[0282] In one or more embodiments, the sintered article or a portion thereof is planarizable, such that when planarized as described herein, the sintered article or a portion thereof exhibits a maximum in-plane stress less than or equal to 1% of Young's modulus of the sintered article. In one or more embodiments, the maximum in-plane stress of the sintered article may be less than or equal to 0.9%, 0.8%, 0.7%, 0.6%, 0.5%, 0.4%, 0.3%, 0.2%, 0.1%, or 0.05% of Young's modulus of the sintered article.

[0283] In one or more embodiments, the sintered article or a portion of the sintered article is planarizable such that when the sintered article or a portion of the sintered article has a thickness of about 40 pm to about 80 pm (or other thicknesses disclosed herein) and is bent to a bend radius of greater than 0.03 m, the sintered article or the portion thereof exhibits a maximum in-plane stress that is less than or equal to 25% of the bend strength of the article. In one or more embodiments, the sintered article or a portion of the sintered article is planarizable such that when the sintered article or a portion of the sintered article has a thickness of about 20 pm to about 40 pm (or other thicknesses disclosed herein) and is bent to a bend radius of greater than 0.015 m, the sintered article or the portion thereof exhibits a maximum in-plane stress that is less than or equal to 25% of the bend strength of the article (as measured by 2-point bend strength). In one or more embodiments, the sintered article or a portion of the sintered article exhibits a maximum in-plane stress (as measured by 2-point bend strength) that is less than or equal to 25% of the bend strength of the article when the sintered article has a thickness of about 3 pm to about 20 pm (or other thicknesses disclosed herein) and is bent to a bend radius of greater than 0.0075 m.

[0284] In one or more embodiments, the sintered article or a portion of the sintered article is planarizable such that when the sintered article or a portion of the sintered article has a thickness of about 40 pm to about 80 pm (or other thicknesses disclosed herein) and is bent to a bend radius of greater than 0.03 m, the sintered article or the portion thereof exhibits a maximum in-plane stress that is less than or equal to 25% of the bend strength of the article. In one or more embodiments, the sintered article or a portion of the sintered article is planarizable such that when the sintered article or a portion of the sintered article has a thickness of about 20 pm to about 40 pm (or other thicknesses disclosed herein) and is bent to a bend radius of greater than 0.015 m, the sintered article or the portion thereof exhibits a maximum in-plane stress that is less than or equal to 25% of the bend strength of the article (as measured by 2-point bend strength). In one or more embodiments, the sintered article or a portion of the sintered article exhibits a maximum in-plane stress (as measured by 2-point bend strength) that is less than or equal to 25% of the bend strength of the article when the sintered article has a thickness of about 3 pm to about 20 pm (or other thicknesses disclosed herein) and is bent to a bend radius of greater than 0.0075 m.

[0285] In one or more embodiments, the sintered article or portion thereof is planarizable such that when subjected to any planarization method (i.e., clamped between two rigid parallel surfaces or against a rigid surface) the sintered article or portion thereof exhibits a maximum in-plane stress of less than 250 MPa when planarized to within 0.05 mm, 0.010 mm, or 0.001 mm of the planarization plane. In one or more embodiments, the maximum in-plane stress can be about 225 MPa or less, 200 MPa or less, 175 MPa or less, 150 MPa or less, 125 MPa or less, 100 MPa or less, 75 MPa or less, 50 MPa or less, 25 MPa or less, 15 MPa, 14 MPa or less, 13 MPa or less, 12 MPa or less, 11 MPa or less, 10 MPa or less, 9 MPa or less, 8 MPa or less, 7 MPa or less, 6 MPa or less, 5 MPa or less, or 4 MPa or less.

[0286] In one or more embodiments, the sintered article or portion thereof is planarizable such that by clamping between two rigid parallel surfaces, a force of less than 8 N (or 7 N or less, 6 N or less, 5 N or less, 4 N or less, 3 N or less, 2 N or less, 1 N or less, 0.5 N or less, 0.25 N or less, 0.1 N or less, or 0.05 N or less) is required to planarize the sintered article or portion thereof to within 0.05 mm, 0.010 mm, or 0.001 mm of the planarization plane.

[0287] In one or more embodiments, the sintered article or portion thereof is planarizable such that when the sintered article (or portion thereof) is against a rigid surface, a pressure of 0.1 MPa or less is required to push the sintered article (or portion thereof) to be planarized to within 0.05 mm, 0.010 mm, or 0.001 mm of the planarization plane. In some embodiments, the pressure can be about 0.08 MPa or less, about 0.06 MPa or less, about 0.05 MPa or less, about 0.04 MPa or less, about 0.02 MPa or less, about 0.01 MPa or less, about 0.008 MPa or less, about 0.006 MPa or less, about 0.005 MPa or less, about 0.004 MPa or less, about 0.002 MPa or less, about 0.001 MPa or less, or 0.0005 MPa or less.

[0288] According to another aspect, the sintered article can be a sintered tape material rolled into a roll-shaped sintered article, such as Figure 34AIn such embodiments, the coiled sintered article includes a core 1100 and a sintered article 1200 (according to one or more embodiments described herein) coiled onto the core. In one or more embodiments, the core is cylindrical and has a diameter 1240 of less than 60 cm (or about 20 inches). For example, the core can have a diameter of about 55 cm or less, 50 cm or less, about 48 cm or less, about 46 cm or less, about 45 cm or less, about 44 cm or less, about 42 cm or less, about 40 cm or less, about 38 cm or less, about 36 cm or less, about 35 cm or less, about 34 cm or less, about 32 cm or less, about 30 cm or less, about 28 cm or less, about 26 cm or less, about 25 cm or less, about 24 cm or less, about 22 cm or less, about 20 cm or less, about 18 cm or less, about 16 cm or less, about 15 cm or less, about 14 cm or less, about 12 cm or less, about 10 cm or less, about 8 cm or less, about 6 cm or less, about 5 cm or less, about 4 cm or less, or about 2 cm or less. In other embodiments, the core is any other shape and the radius of the curvature of the coiled core corresponds to the diameter dimensions described above.

[0289] In one or more embodiments, the sintered article coiled around the core is continuous and has the dimensions described elsewhere herein (e.g., a width of about 5 mm or more, a thickness of about 3 μιη to about 1 mm, and a length of about 30 cm or more).

[0290] Coiling a continuous sintered article (particularly a continuous sintered inorganic material such as a ceramic) onto a core presents several difficulties because the sintered article has a cross web shape and the web tension that the sintered article can tolerate (particularly in the binder burnout and green state) is extremely low (e.g., tension magnitudes of gram level). In addition, the modulus of the sintered material can be very high (e.g., up to and including about 210 GPa) so that the sintered article does not stretch under tension and the resulting coiled roll integrity can be poor when coiled around the core. During the handling of the continuous coiling process, the continuous sintered article can easily jam (i.e., the continuous winding can shift out of alignment).

[0291] Applicants have discovered that the coiled sintered article of one or more embodiments has superior integrity when coiling a continuous sintered article onto a core by using a flexible intermediate layer support material. In one or more embodiments, the continuous sintered article is disposed on the intermediate layer support material and the continuous sintered article and the intermediate layer support material are coiled around the core such that each continuous coiled of the continuous sintered article is separated from one another by the intermediate layer support material. As described above with reference to FIG. 1, the coiled sintered article can be coiled around the core in a continuous manner (e.g., without the need for a separate support material to maintain the coiled sintered article in a coiled configuration). Figure 3The sintered product (or sintered strip material) 40 is wound onto a take-up reel 44. An intermediate layer support material 46 is unwound from or can be unwound from the reel 48, and the intermediate layer support material 46 is wound onto or can be wound onto the take-up reel 44, thereby providing an intermediate layer support material 46 between each layer, between most layers, or between at least some layers of the continuous sintered product 1000 (e.g., sintered product 1200 or sintered strip material 40) on the take-up reel 44. This arrangement forms a roll of sintered material 50.

[0292] See Figure 34B Showing according to an exemplary implementation Figure 34A A specific cross-sectional view of the rolled sintered product 1200 is shown, wherein the sintered product 1200 is rolled twice on the core 1100, and an intermediate layer support material 46 is provided between the sintered product 1200 and the core 1100, and then an intermediate layer support material 46 is provided between the continuous rolls of the sintered product 1200. From Figure 34B Intuitively, when viewed from one end, the sintered article 1200 (in this case, a strip) and the intermediate layer support material 46 form a spiral wound around the core 1100. In other contemplated embodiments, the sintered article may be cut into discrete sheets and still wound around the core, separated from the adjacent winding by the continuous intermediate layer support material 46, for example, when combined, the net length of the sheet is the length L described herein. Figure 34B As shown, in various embodiments, the rolled sintered article according to exemplary embodiments includes an intermediate layer support material 46 between each layer of rolled sintered article (e.g., sintered article 1000, sintered article 1200, or sintered strip material 40). In various embodiments, the intermediate layer support material includes: a first main surface and a second main surface opposite to the first main surface; an intermediate layer thickness (t) defined as the distance between the first and second main surfaces; an intermediate layer width defined as a first dimension perpendicular to the intermediate layer thickness in one of the first or second surfaces; and an intermediate layer length defined as a second dimension perpendicular to both the intermediate layer thickness and the intermediate layer width in one of the first or second main surfaces. In one or more embodiments, the intermediate layer thickness is greater than the thickness of the sintered article. In one or more embodiments, the intermediate layer width may be greater than the width of the rolled sintered article.

[0293] In one or more embodiments, the intermediate layer support material 46 includes (or is under) tension that is greater than the tension on the continuous sintered article as measured by the load cell. In one or more embodiments, the intermediate layer support material has a lower modulus (as compared to the sintered article) and thus stretches under low tension. It is believed that this results in a higher intermediate layer roll pressure that improves the integrity of the wound roll. In addition, in some embodiments, the tension in the wound roll is controlled by controlling the tension applied to the intermediate layer support material, and the tension can be gradually decreased as a function of the diameter of the wound roll. In some such embodiments, the intermediate layer support material 46 is under tension while the sintered article (e.g., the ribbon) is under compression.

[0294] In one or more embodiments, the intermediate layer support material is thickness compliant (i.e., the thickness can be reduced by applying pressure to the major surface and thus can compensate for changes in the cross-web shape or thickness of the sintered article resulting from the sintering process). In some such embodiments, the sintered article can be hidden within the roll by the intermediate layer support material when viewed from the side, where the intermediate layer support material contacts the adjacent roll of intermediate layer support material and at least to some extent shields and isolates the sintered article, e.g., as shown in FIG. 6, where the intermediate layer support material is wider than the sintered article and extends beyond both edges of the sintered article (e.g., ribbon) in the width direction. Figure 34B In one or more embodiments, the intermediate layer support material is thickness compliant (i.e., the thickness can be reduced by applying pressure to the major surface and thus can compensate for changes in the cross-web shape or thickness of the sintered article resulting from the sintering process). In some such embodiments, the sintered article can be hidden within the roll by the intermediate layer support material when viewed from the side, where the intermediate layer support material contacts the adjacent roll of intermediate layer support material and at least to some extent shields and isolates the sintered article, e.g., as shown in FIG. 6, where the intermediate layer support material is wider than the sintered article and extends beyond both edges of the sintered article (e.g., ribbon) in the width direction.

[0295] Referring to Figure 34A In one or more embodiments, the roll-shaped article is located on a cylindrical core and has a substantially constant diameter 1220 and sidewall width 1230. The intermediate layer support material enables the continuous or discontinuous sintered article to be wound around the core without causing jamming that would increase the sidewall width of the roll-shaped article. In some embodiments, the core includes a circumference and a core centerline along the circumference, the continuous sintered article includes an article centerline along the length, and the distance between the core centerline and the article centerline is 2.5 mm or less along at least 90% or the entire length of the continuous or discontinuous sintered article.

[0296] In one or more embodiments, the roll-shaped article includes a frictional force between the intermediate layer support material and the continuous or discontinuous sintered article sufficient to resist lateral extrusion of the continuously wound roll in the wound roll, even when very low tension is applied to the intermediate layer support material. A constant tension can be applied to the intermediate layer support material; however, the tension applied to the inner portions of the roll-shaped article toward the core can be greater than the tension applied to the outer portions of the roll-shaped article away from the core, as the diameter of the roll-shaped article increases from the core to the outer portions as more of the intermediate layer support material and the continuous sintered article are wound around the core. This compresses or can compress the roll-shaped article, which, in combination with the friction between the intermediate layer support material and the continuous sintered article, prevents or limits extrusion and relative movement between the surfaces of the sintered article, thereby at least partially helping to prevent defects.

[0297] In one or more embodiments, the intermediate layer support material includes any one or both of a polymer and paper. In some embodiments, the intermediate layer support material is a combination of a polymer and paper. In one or more embodiments, the intermediate layer support material can include a foamed polymer. In some embodiments, the foamed polymer is closed cell.

[0298] According to another aspect, the sintered articles described herein can be provided as a plurality of discrete sintered articles, as disclosed above, as Figure 35 and 36In one or more embodiments, a plurality of discrete sintered articles can be formed from a roll-shaped sintered article or a continuous sintered article, as described herein. For example, the discrete sintered articles can be laser cut or otherwise separated from a larger sintered article, which can be a sheet or a tape material. In one or more embodiments, each of the plurality of discrete sintered articles has uniformity or consistency relative to some or all of the other ones of the plurality of discrete sintered articles, which can be due to the improved processes and material properties described herein. In one or more embodiments, each of the plurality of sintered articles comprises: a first major surface, a second major surface opposite the first major surface, and a body extending between the first and second surfaces. The body comprises a sintered inorganic material, and: a thickness (t) defined as a distance between the first major surface and the second major surface, a width defined as a first dimension of one of the first or second surfaces perpendicular to the thickness, and a length defined as a second dimension of one of the first or second surfaces simultaneously perpendicular to the thickness and the width. It can be intuitive that discrete sheets or other sintered articles cut or formed from a longer tape will have uniform and consistent composition, uniform and consistent crystal structure, uniform and consistent thickness, defect levels, and other properties described herein, as disclosed above, which are present or can be present in the tape or other elongated articles manufactured with the apparatus and processes of the present invention as disclosed herein.

[0299] In one or more embodiments, some, a majority, or each of the plurality of sintered articles is planarizable, as described herein. In one or more embodiments, when planarized, some, a majority, or each of the plurality of sintered articles exhibits a maximum in-plane stress (defined as the maximum absolute value of stress determined by the bending equation for thin plates bending, without regard to whether it is compressive or tensile stress) that is less than or equal to 25% of the bending strength (measured by the 2-point bending method) of the sintered article. For example, some, a majority, or each of the plurality of sintered articles can have a maximum in-plane stress that is less than or equal to 24%, less than or equal to 22%, less than or equal to 20%, less than or equal to 18%, less than or equal to 16%, less than or equal to 15%, less than or equal to 14%, less than or equal to 12%, less than or equal to 10%, less than or equal to 5%, or less than or equal to 4% of the bending strength of the sintered article.

[0300] In one or more embodiments, some, a majority, or each of the plurality of sintered articles is planarizable such that, when planarized as described herein, some, a majority, or each of the plurality of sintered articles exhibits a maximum in-plane stress that is less than or equal to 1% of the Young's modulus of the sintered article. In one or more embodiments, some, a majority, or each of the plurality of sintered articles can have a maximum in-plane stress that is less than or equal to 0.9%, 0.8%, 0.7%, 0.6%, 0.5%, 0.4%, 0.3%, 0.2%, 0.1%, or 0.05% of the Young's modulus of the respective sintered article.

[0301] In one or more embodiments, some, a majority, or each of the plurality of sintered articles is planarizable such that, when the sintered article has a thickness of about 40 μιη to about 80 μιη (or other thicknesses disclosed herein) and is bent to a bend radius greater than 0.03 m, the sintered article exhibits a maximum in-plane stress that is less than or equal to 25% of the bend strength of the article. In one or more embodiments, some, a majority, or each of the plurality of sintered articles is planarizable such that, when the sintered article has a thickness of about 20 μιη to about 40 μιη (or other thicknesses disclosed herein) and is bent to a bend radius greater than 0.015 m, the sintered article or a portion thereof exhibits a maximum in-plane stress that is less than or equal to 25% of the bend strength (as measured by 2-point bend strength) of the article. In one or more embodiments, some, a majority, or each of the plurality of sintered articles is planarizable such that, when the sintered article has a thickness of about 3 μιη to about 20 μιη (or other thicknesses disclosed herein) and is bent to a bend radius greater than 0.0075 m, the sintered article or a portion thereof exhibits a maximum in-plane stress that is less than or equal to 25% of the bend strength (as measured by 2-point bend strength) of the article.

[0302] In one or more embodiments, some, most, or each of the plurality of sintered articles is planarizable such that when the sintered article has a thickness of about 80 μιη (or other thickness disclosed herein) and is bent to a bend radius greater than 0.03 m, the sintered article exhibits a maximum in-plane stress that is less than or equal to 25% of the bend strength of the article. In one or more embodiments, some, most, or each of the plurality of sintered articles is planarizable such that when the sintered article has a thickness of about 40 μιη (or other thickness disclosed herein) and is bent to a bend radius greater than 0.015 m, the sintered article exhibits a maximum in-plane stress that is less than or equal to 25% of the bend strength of the article (as measured by 2-point bend strength). In one or more embodiments, some, most, or each of the plurality of sintered articles is planarizable such that when the sintered article has a thickness of about 20 μιη (or other thickness disclosed herein) and is bent to a bend radius greater than 0.0075 m, the sintered article exhibits a maximum in-plane stress that is less than or equal to 25% of the bend strength of the article (as measured by 2-point bend strength).

[0303] In one or more embodiments, some, most, or each of the plurality of sintered articles is planarizable such that when planarized to within 0.05 mm, 0.01 mm, or 0.001 mm of the planarization plane using any planarization method (i.e., clamped between two rigid parallel surfaces or against a rigid surface), the sintered article exhibits a maximum in-plane stress that is less than 250 MPa. In one or more embodiments, the maximum in-plane stress can be about 225 MPa or less, 200 MPa or less, 175 MPa or less, 150 MPa or less, 125 MPa or less, 100 MPa or less, 75 MPa or less, 50 MPa or less, 25 MPa or less, 15 MPa, 14 MPa or less, 13 MPa or less, 12 MPa or less, 11 MPa or less, 10 MPa or less, 9 MPa or less, 8 MPa or less, 7 MPa or less, 6 MPa or less, 5 MPa or less, or 4 MPa or less.

[0304] In one or more embodiments, some, most, or each of the plurality of sintered articles is planarizable such that when the sintered article or portion thereof is planarized to a planarization distance of 0.05 mm, 0.01 mm, or 0.001 mm by clamping between two rigid parallel surfaces such that the sintered article is planarized, a force of less than 8 N (or 7 N or less, 6 N or less, 5 N or less, 4 N or less, 3 N or less, 2 N or less, 1 N or less, 0.5 N or less, 0.25 N or less, 0.1 N or less, or 0.05 N or less) is required to planarize the sintered article or portion thereof.

[0305] In one or more embodiments, some, most, or each of the plurality of sintered articles is planarizable such that when pushed against a rigid surface, a pressure of 0.1 MPa or less is required to push the sintered article to be planarized to a distance of 0.05 mm, 0.01 mm, or 0.001 mm from the planarization plane. In some embodiments, the pressure can be about 0.08 MPa or less, about 0.06 MPa or less, about 0.05 MPa or less, about 0.04 MPa or less, about 0.02 MPa or less, about 0.01 MPa or less, about 0.008 MPa or less, about 0.006 MPa or less, about 0.005 MPa or less, about 0.004 MPa or less, about 0.002 MPa or less, about 0.001 MPa or less, or 0.0005 MPa or less.

[0306] In one or more embodiments, some, most, or each of the plurality of sintered articles has a thickness of about 0.7t to about 1.3t (e.g., about 0.8t to about 1.3t, about 0.9t to about 1.3t, about t to about 1.3t, about 1.1t to about 1.3t, about 0.7t to about 1.2t, about 0.7t to about 1.1t, about 0.7t to about 1t, or about 0.9t to about 1.1t), where t is a thickness value disclosed herein.

[0307] In one or more embodiments, some, a majority, or each of the plurality of sintered articles exhibit compositional uniformity. In one or more embodiments, at least 50% (e.g., about 55% or more, about 60% or more, or about 75% or more) of the plurality of sintered articles include a region and a composition, wherein, over the region, at least one component of the composition varies by less than about 3 wt% (as described herein). In some embodiments, over the region, at least one component of the composition varies by about 2.5 wt% or less, about 2 wt% or less, about 1.5 wt% or less, about 1 wt% or less, or about 0.5 wt% or less. In one or more embodiments, the region is about 1 square centimeter of the sintered article, or the region is the entire surface area of the sintered article.

[0308] In one or more embodiments, some, a majority, or each of the plurality of sintered articles exhibit crystallographic structure uniformity. In one or more embodiments, at least 50% (e.g., about 55% or more, about 60% or more, or about 75% or more) of the plurality of sintered articles include a region and a crystallographic structure, wherein, over the region, the weight percent of at least one phase varies by less than about 5 percentage points (as described herein). For illustrative purposes only, some, a majority, or each of the plurality of sintered articles can include at least one phase that constitutes 20 wt% of the sintered article, and in at least 50% (e.g., about 55% or more, about 60% or more, or about 75% or more) of the plurality of sintered articles, this phase is present in an amount of about 15 wt% to about 25 wt% over the region. In one or more embodiments, at least 50% (e.g., about 55% or more, about 60% or more, or about 75% or more) of some, a majority, or each of the plurality of sintered articles include a region and a crystallographic structure, over the region, the wt% of at least one phase varies by less than about 4.5 percentage points, less than about 4 percentage points, less than about 3.5 percentage points, less than about 3 percentage points, less than about 2.5 percentage points, less than about 2 percentage points, less than about 1.5 percentage points, less than about 1 percentage point, or less than about 0.5 percentage points. In one or more embodiments, the region is about 1 square centimeter of the sintered article, or the region is the entire surface area of the sintered article.

[0309] In one or more embodiments, at least 50% (e.g., about 55% or more, about 60% or more, or about 75% or more) of the plurality of sintered articles comprise regions and (as described herein) porosity, the porosity varying by less than about 20%. Thus, in one example, some, most, or each of the plurality of sintered articles has a porosity of 10% by volume, and in at least 50% of the plurality of sintered articles, in the region, this porosity is greater than about 8% by volume and less than about 12% by volume. In one or more specific embodiments, at least 50% of the plurality of sintered articles comprises regions and porosity, in which the porosity varies by 18% or less, 16% or less, 15% or less, 14% or less, 12% or less, 10% or less, 8% or less, 6% or less, 5% or less, 4% or less, or about 2% or less. In one or more embodiments, the region is a sintered article of about 1 square centimeter, or the region is the entire surface area of ​​the sintered article.

[0310] Examples 5-6 and Comparative Examples 7-8

[0311] Examples 5-6 and Comparative Examples 7-8 are discrete sintered products formed from continuous sintered products of quadrilateral or zirconium tetroxide polycrystalline materials. Examples 5-6 were formed according to the processes and systems described herein, while Comparative Examples 7-8 were formed using other processes and systems that do not include at least some of the techniques disclosed herein (e.g., tension control, zoned sintering furnace, airflow control). Examples 5-6 and Comparative Examples 7-8 each have a length of 55.88 mm, a width of 25.4 mm, a thickness of 0.04 mm, and a corner radius of 2 mm. Examples 5-6 and Comparative Examples 7-8 each have a Young's modulus of 210 GPa, a Poisson's ratio (ν) of 0.32, and a g / cm³ of 6 g / cm³. 3 The density (ρ).

[0312] like Figure 35 The illustrated embodiment 5 has a c-shape and a shape size of 0.350 mm. As... Figure 36 The illustrated embodiment 6 has a saddle shape and a size of 0.350 mm. (As shown...) Figure 37 As shown, Comparative Example 7 has a gull-wing shape and a size of 0.350 mm. Figure 38 As shown, Comparative Example 8 has a gull-wing shape and a size of 0.750 mm. Figure 39 The image shows a comparison of the shape and size of each sintered product relative to the plane before planarization.

[0313] The planarizability of the examples was evaluated using two loading methods described elsewhere herein (i.e., clamping the sintered articles between two rigid parallel surfaces or applying a surface pressure to one major surface of the sintered article to push the sintered article against a rigid surface, thereby planarizing the sintered article along the planarization plane).

[0314] Figure 40 The force (in N) required to planarize each of the sintered articles of Examples 5-6 and Comparative Examples 7-8 by clamping between two rigid parallel surfaces is shown. As shown in Figure 40 , Examples 5-6 required significantly less force to planarize the sintered articles, indicating greater planarizability. Moreover, the ability to planarize the sintered articles at such low forces indicates that such articles can be handled or subjected to downstream processing without fracturing, cracking, or any other manner of defect formation. Downstream processing can include, for example, the application of a coating, which can include a conductive or non-conductive coating. This same planarizability was also demonstrated when measuring the pressure required to push each of the sintered articles of Examples 5-6 and Comparative Examples 7-8 to planarize to within 0.001 mm of the planarization plane by pushing the sintered article against a rigid surface. The results are shown in Figure 41 , which demonstrate that Examples 5-6 required significantly less pressure to planarize than Comparative Examples 7-8. Figure 42 The maximum in-plane surface stresses in the planarized sintered articles of Examples 5-6 and Comparative Examples 7-8 are shown. Examples 5-6 exhibited stresses of less than 11 MPa, while Comparative Examples 7-8 exhibited more than 20 times that stress, indicating that the sintered articles of Comparative Examples 7-8 were more likely to fracture, crack, or have defects in downstream processing. The stress locations in Example 5 are shown in Figure 43A , (bottom surface stresses when planarized) and in Figure 43B , (top surface stresses when planarized). The stress locations in Example 6 are shown in Figure 44A , (bottom surface stresses when planarized) and in Figure 44B , (top surface stresses when planarized). The stress locations in Comparative Example 7 are shown in Figure 45A , (bottom surface stresses when planarized) and in Figure 45B , (top surface stresses when planarized). In Comparative Example 7, on the bottom surface, the center exhibited a tensile stress of 208.6 MPa, which was flanked on both sides by compressive stresses of -254.6 MPa. Correspondingly, on the front surface, the center was under a compressive stress of about -208.6 MPa, and on both sides flanking the center were tensile stresses of 254.6 MPa. The stress locations in Comparative Example 8 are shown in Figure 46Ashown (bottom surface stress when planarized) and as Figure 46B shown (top surface stress when planarized). In Comparative Example 8, on the bottom surface, the center portion exhibited a tensile stress of 399.01 MPa, which was flanked on both sides by compressive stresses of -473.63 MPa. Correspondingly, on the front surface, the center portion was under a compressive stress of about -399.08 MPa, and on both sides flanking the center portion were tensile stresses of 473.60 MPa. The high stresses at point X in Comparative Examples 7-8 indicate that these sintered articles can be prone to chipping along the high stress locations.

[0315] In some semiconductor packages, and similar light emitting diode (LED) containing packages, a substantial portion of the electrical energy provided to or through the package can be lost or dissipated as heat energy. The thermal dissipation capabilities of these semiconductor packages, and similar semiconductor packages, can be a limiting factor when attempting to provide additional electrical energy (or current) through the package. Further, in at least some LED containing packages, the brightness of the LED can be limited by the thermal dissipation capabilities of the LED containing package. It can be desirable to reduce or maintain the temperature of components in a semiconductor package, for example, from about 75 °C to about 85 °C.

[0316] In one or more embodiments and with reference to Figure 47 the sintered articles described herein (e.g., sintered article 1000, sintered article 1200, or sintered tape material 40) are directly or indirectly joined, bonded, connected, or otherwise attached to a substrate 1500 to form a package 2000. The sintered article 1000 can act as a dielectric in the package 2000. In some embodiments, the package 2000 is a semiconductor package, an electronic package, an energy transfer package, a light emitting diode (LED) package, or the like. The package 2000 of the present disclosure provides improved performance (e.g., thermal dissipation capabilities, lower thermal resistance, etc.) as compared to conventional packages. In other such embodiments, the sintered articles described herein (e.g., sintered article 1000, sintered article 1200, or sintered tape material 40) are or are the substrate 1500.

[0317] In some embodiments, the package 2000 includes an intermediate layer 1300 between the substrate 1500 and the sintered article 1000. The intermediate layer 1300 can include a material that bonds, adheres, connects, or otherwise attaches or facilitates the attachment of the substrate 1500 and the sintered article 1000. The intermediate layer 1300 can include multiple discrete layers that are bonded or bonded together to form the intermediate layer 1300. In some embodiments, the intermediate layer 1300 is a material having a high thermal conductivity, such that heat generated by an electronic component (e.g., a semiconductor device or chip) or a metal-based layer is conducted through the intermediate layer 1300 to the substrate 1500. In some embodiments, the intermediate layer 1300 includes a thermal conductivity that is greater than the sintered article 1000. In some embodiments, the intermediate layer 1300 includes a thermal conductivity that is less than the substrate 1500. The intermediate layer 1300 can have a thermal conductivity of greater than about 8 W / m-K to about 20 W / m-K, greater than about 8 W / m-K to about 16 W / m-K, or greater than about 8 W / m-K to about 13 W / m-K, or greater than about 9 W / m-K to about 12 W / m-K, such as 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 W / m-K, including all ranges and subranges therebetween. In some embodiments, the intermediate layer 1300 is an adhesive-like material. In some embodiments, the intermediate layer 1300 is a compliant material configured to deform and / or withstand shear forces resulting from differences in coefficient of thermal expansion (CTE) between the substrate 1500 and the sintered article 1000 as a result of heating and cooling of the package 2000.

[0318] In some embodiments, the intermediate layer 1300 includes a matrix of polyimide, epoxy, or a combination thereof. In some embodiments, the matrix of the intermediate layer can include non-conductive particles (e.g., boron nitride), conductive particles (e.g., silver, copper, etc.), or a combination thereof. The conductive and / or non-conductive particles can be distributed uniformly or non-uniformly throughout the matrix of the intermediate layer. In some embodiments, the intermediate layer 1300 conducts heat from the metal-based layer 1350 and the component 1401 (e.g., a semiconductor device or chip) and transfers the conducted heat to the substrate 1500. In some embodiments, the intermediate layer 1300 can have a length (L) and a width (W) that can be substantially similar to one or both of the substrate 1500 and / or the sintered article 1000. In some embodiments, the intermediate layer can have a thickness (t2) of about 0.1 pm to about 100 pm, or about 10 pm to about 75 pm, or about 15 pm to about 35 pm, or even about 20 pm to about 40 pm, such as 5, 10, 15, 20, 25, 30, 35, or 40 pm, including all ranges and subranges therebetween. Figure 50 (e)) and transfers the conducted heat to the substrate 1500. In some embodiments, the intermediate layer 1300 can have a length (L) and a width (W) that can be substantially similar to one or both of the substrate 1500 and / or the sintered article 1000. In some embodiments, the intermediate layer can have a thickness (t2) of about 0.1 pm to about 100 pm, or about 10 pm to about 75 pm, or about 15 pm to about 35 pm, or even about 20 pm to about 40 pm, such as 5, 10, 15, 20, 25, 30, 35, or 40 pm, including all ranges and subranges therebetween.

[0319] In one or more embodiments, the substrate 1500 includes a first major surface 1510, a second major surface 1520 opposite the first major surface, and a body 1530 extending between the first and second surfaces 1510, 1520. The sintered article 1000 can be directly or indirectly joined, bonded, connected, or otherwise attached to the first major surface 1510 or the second major surface 1520 of the substrate 1500. The body 1530 has a thickness (tl) defined as the distance between the first major surface 1510 and the second major surface 1520, a width (Wl) defined as the first dimension of one of the first or second surfaces perpendicular to the thickness, and a length defined as the second dimension of one of the first or second surfaces perpendicular to both the thickness and the width. In one or more embodiments, the substrate 1500 includes an opposing minor surface 1540 defining the width (Wl). In some embodiments, the length and width of the sintered article 1000 and the substrate 1500 are substantially equal (e.g., the transverse dimensions are within 5% of each other). In some embodiments, the thickness (tl) of the substrate 1500 is greater than the thickness (t) of the sintered article 1000 (e.g., the thickness (t) of the sintered article 1000 disclosed herein). In some embodiments, the thickness (tl) of the substrate 1500 is greater than the thickness (t) of the sintered article 1000 by about 25%, by about 50%, by about 75%, by about 100%, by about 200%, by about 500% or more. In some embodiments, the thickness (tl) of the substrate 1500 is about 0.5 mm to about 5.0 mm, or about 1.0 mm to about 2.0 mm, or about 1.0 mm to about 1.6 mm, or even about 1.2 mm to about 1.5 mm. In some embodiments, the substrate 1500 acts as a heat sink for the package 2000. In some embodiments, the substrate 1500 includes an electrically conductive metal, such as aluminum, copper, or a combination thereof.

[0320] Figure 47 and 48 A cross-sectional view of an exemplary package 2000 in which the intermediate layer 1300 joins the substrate 1500 and the sintered article 1000 is provided. A metal-based layer 1350 can be provided on the sintered article 1000 and the major surface of the intermediate layer 1300 opposite the major surface to which it is bonded. That is, the sintered article 1000 can include the intermediate layer 1300 on one major surface and the metal-based layer 1350 on the opposite major surface. The intermediate layer 1300 can be applied to one or both of the substrate 1500 and the sintered article 1000. Thereafter, the substrate 1500 and the sintered article 1000 can be assembled or joined together with the intermediate layer 1300 between the major surfaces of each. The intermediate layer 1300 can be activated by thermal energy, actinic wavelengths, pressure, or other similar methods to join, bond, connect, or otherwise attach the substrate 1500 to the sintered article 1000 via the intermediate layer 1300.

[0321] like Figure 47 As shown, one or both of the main surfaces 1510 and 1520 of the substrate 1500 may be patterned to include a groove 1325. The groove 1325 helps to bond the intermediate layer 1300 to the substrate 1500. The groove 1325 also helps to minimize the shear stress experienced by the intermediate layer 1300 due to CTE results between the substrate 1500 and the sintered article 1000. In some embodiments, the groove 1325 covers at least a portion of the main surface of the substrate 1500. The groove 1325 may have a depth of about 0.1 μm to about 1 mm or about 10 μm to about 50 μm in the main surface of the substrate 1500. The intermediate layer 1300 may extend at least partially within the groove 1325 of the substrate 1500. The cross-section of the groove 1325 may be rectangular, square, circular, triangular, or other similar shapes or combinations thereof, and may extend continuously, linearly, or in any other manner on the main surface of the sintered article 1000.

[0322] The metal-based layer 1350 can be directly or indirectly bonded to the sintered article 1000 by electroplating, printing, physical vapor deposition, chemical vapor deposition, sputtering, or other suitable techniques. The metal-based layer 1350 is a conductive material capable of conducting or providing electrical energy (or current) through or through the package 2000. In some embodiments, the metal-based layer is configured to minimize resistance and heat generated along its length. In some embodiments, the metal-based layer 1350 includes copper, nickel, gold, silver, brass, lead, tin, and combinations thereof. The metal-based layer 1350 can be indirectly bonded to the sintered article 1000 via a seed layer 1375. That is, the seed layer 1375 can provide a basis for bonding the metal-based layer 1350 to the sintered article 1000. In some embodiments, bonding the metal-based layer 1350 to the seed layer 1375 of the sintered article 1000 is performed by "reflow" in a reflow oven, thereby electrically connecting the metal-based layer 1350 to other electronic components in the package 2000. In some embodiments, the seed layer 1375 comprises tin, titanium, tungsten, lead, or a combination thereof. The seed layer 1375 can be applied to the main surface of the sintered article 1000 by electroplating, printing, physical vapor deposition, chemical vapor deposition, sputtering, or other suitable techniques.

[0323] In some embodiments, the metal-based layer 1350 can be directly or indirectly bonded to the sintered article 1000 before, during, or after the sintered article 1000 is bonded to the substrate 1500. In some embodiments, the metal-based layer 1350 is a continuous, semi-continuous, or discontinuous array or "ring" on a major surface of the sintered article 1000. In some embodiments, portions of one or both major surfaces of the sintered article 1000 can be masked or covered to prevent the application of the metal-based layer 1350 and / or the seed layer 1375 on the masked portions of the sintered article 1000 prior to the application of the metal-based layer 1350 and / or the seed layer 1375 to the sintered article 1000. That is, the masked portions of one or both major surfaces of the sintered article 1000 can be used to form a continuous, semi-continuous, or discontinuous array or "ring" of the metal-based layer 1350 and / or the seed layer 1375 on a major surface of the sintered article 1000. After the metal-based layer 1350 is applied to the unmasked portions of the major surface of the sintered article 1000, the masking can be removed to expose the portions of the major surface (on which there is no metal-based layer and / or seed layer) where the masking was previously present. Figure 47 and 49 Examples of the metal-based layer 1350 as an array on a major surface of a sintered article are provided. The metal-based layer 1350 includes a thickness (t3) of about 0.1 μιη to about 1 mm or about 2 μιη to about 100 μιη, about 5 μιη to about 70 μιη, or even about 5 μιη to about 50 μιη.

[0324] In one or more embodiments, the package 2000 includes a semiconductor device or chip 1400. In some embodiments, the semiconductor device 1400 is directly or indirectly bonded, adhered, connected, or otherwise attached to the first major surface 1010 or the second major surface 1020 of the substrate 1000. The semiconductor device 1400 can be indirectly bonded to the sintered article 1000 through a seed layer 1375, as shown in Figure 49 The semiconductor device 1400 can include one or more light emitting diodes (LEDs). In some embodiments, the semiconductor device 1400 is connected to the metal-based layer 1350 by one or more wires 1450. The wires 1450 can be rigid or flexible wires or electrical connections (e.g., similar to the metal-based layer 1350) that electrically connect the semiconductor device 1400 and the metal-based layer 1350. Figure 47 and 49The display lead 1450 bridges the distance between the semiconductor device 1400 and the metal-based layer 1350. Of course, in one or more embodiments, the lead 1450 can travel along or contact the surface of the sintered article 1300. The lead 1450 can provide electrical energy between the metal-based layer 1350 and the semiconductor device 1400. In some embodiments, electrical energy running through the metal-based layer 1350 is transmitted to the semiconductor device 1400 through the lead 1450. In some embodiments, the electrical energy provided to the semiconductor device 1400 powers the LEDs thereon, which emit one or more wavelengths (λ) of light. The semiconductor device 1400 can include one or more lenses 1405 to collimate or direct the light from the LEDs thereon. The semiconductor device 1400 can also include a phosphor material 1475 to filter the wavelengths (λ) of light emitted from the LEDs thereon and transmit certain wavelengths (λ).

[0325] In one or more embodiments, the method of making the package 2000 includes providing the sintered article 1000. The sintered article 1000 can be in a roll including a circular or cylindrical core having a diameter of less than 60 cm, with the continuous sintered article wound around the core. The sintered article 1000 can also be provided as discrete flat lengths. In one or more embodiments, the method of making the package 2000 includes providing a carrier or temporary substrate 1499 (see Figure 50 ), which can be on a roll or as a large flat sheet. In some embodiments, lengths of the sintered article 1000 are joined, bonded, connected, or otherwise attached to lengths of the carrier or temporary substrate 1499 to form a precursor package 1999. The carrier or temporary substrate 1499 can support the sintered article 1000 for subsequent winding onto a core. In some embodiments, the carrier or temporary substrate 1499 supports the sintered article 1000 during subsequent processes that can damage, degrade, or otherwise compromise the substrate 1500. In some embodiments, the carrier or temporary substrate 1499 includes glass, polymer, or a combination thereof. In some embodiments, the carrier or temporary substrate 1499 is a polymer tape or a polyamide tape.

[0326] In some embodiments, the precursor package 1999 includes a precursor interlayer 1299 Figure 50). The precursor interlayer 1299 can include a material that bonds, adheres, connects, or otherwise attaches the temporary substrate 1499 and the sintered article 1000. In some embodiments, the precursor interlayer 1299 is a high temperature resistant adhesive. The precursor interlayer 1299 can be activated by thermal energy, photochemical wavelengths, pressure, or other similar methods to bond, adhere, connect, or otherwise attach the temporary substrate 1499 to the sintered article 1000. In some embodiments, the precursor interlayer 1299 can be deactivated by similar or different methods than the activation, such that the sintered article 1000 can be separated or disconnected from the temporary substrate 1499. In some embodiments, the precursor interlayer 1299 and the temporary substrate 1499 are configured to withstand subsequent processing (without degrading) of the precursor package 1999, including the application of the metal-based layer 1350, the seed layer 1375, the semiconductor device 1400, the lead 1450, and / or other similar components.

[0327] Figure 50 The method of forming the package 2000 from the precursor package 1999 is shown. Figure 50 Step (a) of the method of shows the precursor package 1999 after the metal-based layer 1350 is applied to the surface of the sintered article 1000 opposite the surface bonded to the precursor interlayer 1299. Figure 50 Step (a) of the method of also shows the precursor package 1999 after the masking (e.g., between the metal-based layers 1350) is removed from the sintered article 1000. Prior to or after step (a), the seed layer 1375 can be applied to the sintered article 1000. Figure 50 Step (b) of the method of shows the application of components of the assembly 1401 (i.e., the semiconductor device 1400 and the lead 1450) to the sintered article 1000, such that the semiconductor device 1400 is electrically connected to the metal-based layer 1350. In some embodiments, the carrier or temporary substrate 1499 and the precursor interlayer 1299 are configured to support the sintered article 1000 and to withstand the processing that can be done at high temperatures (e.g., up to or greater than 320 °C) to form the semiconductor device 1400 and the lead 1450. Figure 50 No degradation or distortion occurs during the processes shown in steps (a) and (b). Figure 50Step (c) of FIG. 1 1 1 1 shows separating the sintered article 1000 (including the metal-based layer 1350, the semiconductor device 1400, and the wire 1450 thereon) from the temporary substrate 1499. In some embodiments, step (c) can be accomplished by deactivating the precursor interlayer 1299 with heat energy, photochemical wavelengths, tugging, or other similar methods. In some embodiments, the sintered article 1000 (including the metal-based layer 1350, the semiconductor device 1400, and the wire 1450 thereon) is pulled away from the temporary substrate 1499 by machine or by hand. In some embodiments, step (c) is performed in a reflow oven when the seed layer 1375 or solder electrically connects components of the assembly 1401. The precursor interlayer 1299 can be transported with the sintered article 1000, with the temporary substrate 1499, or both (a portion of each). Figure 50 Step (c) of FIG. 1 1 1 1 shows an embodiment in which the precursor interlayer 1299 is transported with the temporary substrate 1499. In some embodiments, the precursor interlayer 1299 can become the interlayer 1300 upon subsequent processing (e.g., heating) or by bonding or contacting with the substrate 1500. Figure 50 Step (d) of FIG. 1 1 1 1 shows joining the sintered article 1000 and the substrate 1500 with the interlayer 1300 therebetween. In some embodiments, the precursor interlayer 1299 can be the same as the interlayer 1300. Figure 50 Step (e) of FIG. 1 1 1 1 shows applying other components of the assembly 1401 (e.g., the lens 1405 and the phosphor 1475) to the sintered article 1000. In some embodiments, the components of the assembly 1401 can be applied at a lower temperature (e.g., < 150 °C) so that the interlayer 1300 and the substrate 1500 do not degrade or deform during the process of completing the assembly 1401. As Figure 50 The package 2000 shown in step (e) of FIG. 1 1 1 1 can include one or more of the assembly 1401.

[0328] Figure 51 Another illustrative method of forming a package 2000 from a precursor package 1999 is provided. Figure 51 Step (a) of FIG. 1 1 1 1 shows providing the sintered article 1000 as a planarized sheet or in any other manner from a roll of core. Figure 51 Step (b) of FIG. 1 1 1 1 shows joining the planarized sintered article 1000 and a carrier or temporary substrate 1499 to form the precursor package 1999. A precursor interlayer 1299 or such similar layer can be between the sintered article 1000 and the carrier or temporary substrate 1499. The precursor package 1999 can be rolled onto a core, stored, shipped, or sold for subsequent processing. Figure 51Step (c) of FIG. 1 1 shows applying components of the light emitting assembly 1401 (e.g., semiconductor device 1400, wire 1450, lens 1405, phosphor 1475, etc.) and the metal-based layer 1350 to the sintered article 1000. Step (c) can include several stages of electrically connecting the metal-based layer 1350 to the semiconductor device 1400 on the sintered article 1000 and any LEDs thereon. Step (c) also includes a solder reflow operation in a solder oven, which electrically connects all components of the assembly 1401. Figure 51 Step (d) of FIG. 1 1 shows separation or detachment of the sintered article 1000 (including assembly 1401) from the temporary substrate 1499. Step (d) can be accomplished by pulling the sintered article 1000 (including assembly 1401) away from the temporary substrate 1499 by machine or by hand. Step (d) can be catalyzed by heat, exposure to actinic wavelengths, cooling, exposure to solvent, or other similar methods. Of course, the precursor interlayer 1299, if present, can be transported with the sintered article 1000, with the temporary substrate 1499, or both (a portion of each). Figure 51 Step (e) of FIG. 1 1 shows the sintered article 1000 (including assembly 1401) joined to the substrate 1500 to form the package 2000. In some embodiments, the sintered article 1000 (including assembly 1401) can be joined to the substrate 1500 through the interlayer 1300 or similar layers therebetween to form the package 2000. Figure 51 Step (f) of FIG. 1 1 shows the package 2000 cut at various points along its length L4 into a plurality of segments 2001. The package 2000 can be cut into segments 2001 along its length L4 with localized cutting pressure, laser energy (e.g., UV ablation laser), or similar techniques. In some embodiments, each segment 2001 includes at least one or more assemblies 1401. The segments 2001 of the package 2000 can be used for a variety of applications, including filaments for light bulbs, electronic devices, hand-held devices, head-mounted displays, vehicle dashboards, etc.

[0329] Figures 52-54 A cross-sectional view of a package 2000 is shown, which includes a sintered article 1000 and a "flip-chip" configuration of semiconductor devices 1400. In these embodiments, a length of the package 2000 can include a void 1501 in the substrate 1500. The void 1501 can be formed by drilling, cutting, or partially removing the substrate 1500. The void 1501 can also be formed by spacing two pieces of the substrate 1500 apart on one major surface of the sintered article 1000. In some embodiments, the metal-based layer 1350 can be joined, bonded, connected, or otherwise attached to the major surface of the sintered article 1000 that is the same as the substrate 1500.

[0330] Figure 52 Showing an exemplary cross-sectional view of package 2000, which includes a sintered article 1000 bonded to a substrate 1500. In some embodiments, a metal-based layer 1350 is provided in apertures 1501. That is, the metal-based layer 1350 is bonded to the main surface of the sintered article 1000, which is the same as the substrate 1500. In some embodiments, a seed layer 1375 is applied to the metal-based layer 1350 and bonding occurs. The seed layer 1375 helps bond the metal-based layer 1350 and the semiconductor device 1400 in a "flip-chip" configuration. In one or more embodiments, the seed layer 1375 comprises tin, titanium, tungsten, lead, or alloys thereof. In some embodiments, the seed layer 1375 is conductive and eliminates the need for wires to electrically connect the metal-based layer to the semiconductor device 1400. In some embodiments, a volume 1485 may be formed between the sintered article 1000 and the semiconductor device 1400. Together with the metal-based layer 1350 and / or seed layer 1375, volume 1485 can be sealed between the sintered article 1000 and the semiconductor device 1400. In some embodiments, the LED on the semiconductor device 1400 is the opposite volume 1485 and is located within the aperture 1501. In some embodiments, the LED on the semiconductor device 1400 is within volume 1485. Phosphor material 1475 may be provided within volume 1485. Figure 52 and 53 In this embodiment, the sintered article 1000 may be translucent or substantially transparent, allowing light wavelengths (λ) emitted from the LED on the semiconductor device 1400 to propagate through the sintered article 1000. In some embodiments, the sintered article 1000 may transmit some, most, or all of about 35% to about 95%, or about 45% to about 85%, or about 55% to about 75% of the visible light wavelengths (λ) emitted from the LED or transmitted through the phosphor 1475, for example, 35%, 40%, 50%, 60%, 65%, 75%, 85%, 90%, 95%, or more up to 99%, including all ranges and subranges therein.

[0331] The total light transmittance (T) through 1000 of the sintered product can be defined by the following Equation 1:

[0332] T = Φ e t / Φ e i

[0333] In the formula,

[0334] Φ e t It is the radiative flux transmitted through the surface; and

[0335] Φ e i It is the radiant flux received by the surface.

[0336] The measurements of these parameters are described in ASTM standard test method D1003-13.

[0337] Although similar to Figure 52 ,but Figure 53 The intermediate layer 1300 shown is located between the sintered product 1000 and the substrate 1500. Figure 53 It also shows such an implementation, wherein, (e.g.) Figure 52 At least a portion of the pore 1501 (as shown) is blocked by the substrate 1500, which may be isolated from or connected to adjacent portions of the substrate 1500. In other embodiments, at least a portion of the pore 1501 is blocked by a filler (e.g., epoxide, plastic, polymer material, etc.) to seal the chip 1400 and the metal-based layer 1350 within the package 2000. Figure 53 In this embodiment, the substrate 1500 contacts the semiconductor device 1500, thereby conducting heat generated when electrical power is supplied to the package 2000 from the semiconductor device 1400. In some embodiments, the sintered article 1000 includes holes 1490 extending through its thickness. For example... Figure 53 and 55 As shown, the hole 1490 in the sintered product 1000 intersects with the volume 1485. The hole 1490 allows cooling of the phosphor material 1475 within the volume 1485 via ambient convection. The hole 1490 also allows light of the wavelength (λ) from the LED within the volume 1485 to be emitted from the package 2000. Figure 54 As shown, a reflector 1480 may be included in volume 1485 and / or aperture 1490 to amplify or reflect the light wavelength (λ) emitted from the LED on semiconductor device 1400. The reflector 1480 may have a conical, hemispherical, tapered, or curved shape. In some embodiments, the reflector 1480 may be coated with a coating to amplify the light wavelength (λ) emitted from the LED on semiconductor device 1400. Figure 55 This shows another possible construction.

[0338] In one or more embodiments, the sintered articles described herein can be used in microelectronic applications or articles. For example, such microelectronic articles can include a sintered article (according to one or more embodiments described herein) including a first major surface, a second major surface opposite the first major surface. In one or more embodiments, the microelectronic article can include a continuous sintered article (e.g., a long strip as described herein) or a discrete sintered article (e.g., a piece cut or diced from a strip). In one or more embodiments, the microelectronic article includes a continuous or discrete sintered article having a width of about 1 mm or greater, about 1 cm or greater, about 5 cm or greater, or about 10 cm or greater. In one or more embodiments, the microelectronic article includes a sintered article having a length of about 1 m or greater, about 5 m or greater, or about 10 m or greater. In one or more embodiments, the microelectronic article includes a continuous or discrete sintered article having a thickness of less than 1 mm, about 0.5 mm or less, or 300 microns or less, about 150 microns or less, or about 100 microns or less. In one or more embodiments, the microelectronic article includes a sintered article having a crystalline ceramic content of about 10 vol% or greater, about 25 vol% or greater, about 50 vol% or greater, about 75 vol% or greater, or about 90 vol% or greater.

[0339] In one or more embodiments, the sintered article includes one or more channels (e.g., holes, pores, wells, tubes, passages, interconnections; see FIG. 1) disposed along a given region of the first major surface of the sintered article. In one or more embodiments, the sintered article includes one or more channels disposed along a given region of the second major surface of the sintered article. In one or more embodiments, the sintered article includes one or more channels disposed along a given region of both the first and second major surfaces of the sintered article. Figure 53holes 1490). In one or more embodiments, the vias extend partially or entirely through the thickness of the sintered article. In one or more embodiments, the vias can be arranged in a pattern that can be repetitive or periodic, for example, where the vias are formed in a continuous roll-to-roll process along a strip, where the strip can later be segmented to form individual components, for example, for semiconductor or other electronic devices. In one or more embodiments, the vias are spaced apart from one another such that there is a distance of about 0.5 m or less, 10 cm or less, or 5 cm or less between vias (e.g., between at least some, a majority, or each of the vias and the closest via). In some embodiments, such a via spacing can be present in a sintered article having a thickness of less than 1 mm, about 0.5 mm or less, or 300 microns or less, about 150 microns or less, or about 100 microns or less. In one or more specific embodiments, such a via spacing can be present in a sintered article having a thickness of about 50 microns or less. The vias can be cut by laser, masking and etchant, punching, or other methods; for example, prior to sintering, during sintering (e.g., at partial sintering), or after sintering. Forming the vias after sintering can facilitate precise placement and sizing of the vias; however, due to the consistency of the processes and materials described herein, the vias can be formed in, for example, a green strip or a partially sintered strip, and the accuracy of placement, size, wall geometry, etc., can be within tolerances required for some applications.

[0340] In one or more embodiments, the sintered article includes a conductive layer (e.g., copper, aluminum, or other conductive layer; see generally Figure 47layer 1350). In one or more embodiments, the conductive layer partially or completely covers the major surface on which it is disposed, e.g., overlaps at least 20% of the respective surface, e.g., 40%, at least 60%, at least 80%. In other words, the conductive layer can form a continuous layer over the entire area of the surface on which it is disposed, or can form a discontinuous layer on the surface on which it is disposed. The conductive layer can form a repeating or periodic pattern, e.g., forming a semiconductor component that has not been segmented on a strip. In one or more embodiments, the sintered article can include one or more additional layers disposed on top of the conductive layer or between the conductive layer and the sintered article and / or intermediate the conductive layer and the strip (or other sintered article disclosed herein). Such one or more additional layers can partially or completely cover the surface on which it is disposed (i.e., a major surface of the sintered article or the conductive layer), e.g., according to the percentages described above with respect to the conductive layer. In other words, the one or more additional layers can form a continuous layer over the entire area of the surface on which it is disposed, or can form a discontinuous layer on the surface on which it is disposed. The one or more additional layers can form a pattern that can be repeating or periodic. In some embodiments, the one or more additional layers can also be a conductive layer, a dielectric layer, a sealing layer, an adhesive layer, a smooth surface layer, or other functional layer. In some embodiments, the conductive layer and optional one or more additional layers can be present in a sintered article having a thickness of less than 1 mm, about 0.5 mm or less, or 300 microns or less, about 150 microns or less, about 100 microns or less, or about 50 microns or less. Thus, the layers and sintered articles can be flexible and / or can be wound onto a roll or spool, as described herein.

[0341] In some embodiments, the sintered article can include two or more of the plurality of pores, the conductive layer, and the one or more additional layers.

[0342] In one or more embodiments, the system 10 for producing a sintered tape article can include a manufacturing system for further processing the green tape, partially sintered article, and / or sintered article described herein for a microelectronic article. In one or more embodiments, the manufacturing system can be disposed downstream of the adhesive burn-out oven 110 but upstream of the sintering station 38 to process the tape without adhesive, or after the sintering station 38 to process the partially sintered article, or before the oven 110 to process the green tape, which would then be sintered as described elsewhere herein. In one or more embodiments, the manufacturing system can be disposed downstream of the sintering station 38 but upstream of the take-up system 42 to process the sintered article. In one or more embodiments, the manufacturing system can be disposed downstream of the take-up spool 44 but upstream of the spool 48 to process the sintered article. In one or more embodiments, the manufacturing system can be disposed downstream of the spool 48 to process the sintered article. In such embodiments, the manufacturing system can process the green tape material, partially sintered article, or sintered article while it is continuous (not discrete). Other configurations can process the sintered article as a discrete article.

[0343] In one or more embodiments, the manufacturing system can expose at least a portion of the green tape material, partially sintered article, or sintered article to a mechanism for forming a via, such as a laser energy or a drill. A manufacturing system of one or more embodiments that uses laser energy to create a via can include a hug drum (see generally FIG. 2) having a surface curvature, such as the vacuum drum 25 of Figure 6 In one or more embodiments, the hug drum can facilitate focusing a laser beam onto a major surface of the green tape material, partially sintered article, or sintered article.

[0344] In one or more embodiments, a via can be created by a mechanical device. For example, the manufacturing system can include a flat plate onto which a portion of the green tape material, partially sintered article, or sintered article is temporarily secured. In this manner, one major surface of the green tape material, partially sintered article, or sintered article is in contact with the flat plate. The green tape material, partially sintered article, or sintered article can be delivered to the manufacturing system using a step and repeat movement, an accelerated or decelerated or continuous speed to achieve a portion of the sintered article being temporarily secured to the flat plate. In one or more embodiments, a portion of the green tape material, partially sintered article, or sintered article can be temporarily secured to the flat plate using a vacuum.

[0345] In one or more embodiments, the manufacturing system can form the vias by mechanically separating a portion of the green tape material, the partially sintered article, or the fired article. In one or more embodiments, the manufacturing system can include the use of a photoresist or acid to remove a portion of the green tape material, the partially sintered article, or the fired article. In such embodiments, when the manufacturing system is applied to the green tape material or the partially sintered article, the manufacturing system can include a control mechanism to control the size of the vias and the size of the pattern due to the shrinkage of the green tape material or the partially sintered article when fully sintered. For example, the control mechanism can include a sensor at the exit of the sintering station 38 that measures the distance between the vias and the pitch of the vias and feeds this information back to the manufacturing system for adjustment. For example, if the manufacturing system forms vias that are about 75 microns in diameter and the distance or pitch between the vias is 500 microns, and assuming the total sintering shrinkage from the green tape material to the sintered article is 25%, the manufacturing system can be adjusted or can adjust to form vias in the green tape material that are 667 microns in pitch and about 100 microns in diameter. After processing, the total sintering shrinkage is measured to be 23%, and the manufacturing system can then be further adjusted to the correct via pitch in the green tape material of 649 microns to accommodate the 23% total sintering shrinkage. In some embodiments, the widest cross-sectional dimension (coplanar with the surface of the sheet or tape) of the vias is at least 250 nm, for example at least 1 μιη, for example at least 10 μιη, for example at least 30 μιη, for example at least 50 μιη, and / or no more than 1 mm, for example no more than 500 μιη, for example no more than 100 μιη. In some embodiments, the vias are filled with an electrically conductive material, for example, copper, gold, aluminum, silver, alloys thereof, or other materials. The vias can be formed by laser cutting, laser and etchant, mechanical drilling, or any other manner. The vias can be arranged in a repeating pattern along the sheet or tape, which can then be singulated into individual electronic components.

[0346] Figure 104 An example of a cross-section of a stack arrangement 810 of ceramic sheets 812 with vias 814 extending into a metal layer 816. A fiducial 818 can help align the sheets 812.

[0347] The system 10 described herein provides other ways to control the via pitch during the sintering process. For example, during the sintering process, a tension in the processing direction 14 can stretch the sintered article and bias the sintering shrinkage. This tension can increase the pitch of the vias in the processing direction 14, effectively reducing the sintering shrinkage in the processing direction 14. When the tension is applied, a different sintering in the processing direction 14 as opposed to a direction perpendicular to the processing direction 14 is observed, and ranges from about 2% to about 3%. Thus, some of the otherwise circular vias can be oval or elliptical.

[0348] The size and shape of the channels can be controlled and adjusted by a combination of sinter shrinkage in a direction parallel to the processing direction 14, sinter shrinkage in a direction perpendicular to the processing direction 14, tension in both of these directions, and the shape of the sintering station 38, and / or the use of air bearings to transport the green strip material, the partially sintered article, or the sintered article while sintering or while hot.

[0349] In one or more embodiments, ceramic material can be added at any step within the system 10 to reduce sinter shrinkage. The ceramic material can be added by an inkjet print head, which can apply such ceramic material uniformly to the porous partially sintered article or sintered article when such article has open porosity. In one or more embodiments, a small amount of ceramic material can be added to the porous partially sintered article or sintered article by printing. Laser, lithography, inkjet, atomic layer deposition, and some printing and other processing means can be done from the inner radius of a curved air bearing or with segmented puck having open areas to expose the partially sintered article or sintered article to the processing equipment. Thus, a portion of the strip or other article disclosed herein can be or can include two or more co-sinterable inorganic materials (e.g., ceramics or phases), for example, where one material penetrates and fills the pores of the other. In contemplated embodiments, the fill / penetration material can be chemically the same as the porous material, but can be distinguished by crystalline content (e.g., grain size, phase).

[0350] In one or more embodiments, channels can be formed on sintered articles having a pattern of conductive layers on one or both sides. The conductive layers can be printed or patterned (screen printing, electroless deposition, etc.) after the channels are formed and the final sintering. In one or more embodiments, the conductive layers can also be printed or deposited prior to the final sintering of the sintered article. In some sintering processes where only discrete pieces (not continuous strips) of small size (e.g., about 20 cm by 20 cm in length and width dimensions) are sintered, the conductive layers are printed after the channels are formed and / or are only on the green strip material. For multi-layer substrates, up to 30-40 green strip layers are used, such that or can be such that individual green strip layers are aligned and stacked with some multi-layer substrates. With copper-based conductors, alumina and tungsten, molybdenum, or platinum conductors can be co-sintered and form cordierite (glass-ceramic) based low-fired ceramic packages. In some embodiments described herein, the conductive layers can be formed (i.e., by printing or deposition) prior to the final sintering step, and the techniques disclosed herein can help control the size of the channels and the conductor pattern during the sintering step.

[0351] Additionally, the continuous sintering process and system 10 provide a way to control the pitch and pattern of the pores during sintering and the pattern of the conductive layers in terms of pitch. During sintering, a tensile force in the machine direction can stretch the green tape material, the partially sintered article, or the sintered article and / or bias the sintering shrinkage, as disclosed above. This tensile force can increase the pitch and pattern of the pores in the machine direction and the pattern of the conductive layers, effectively reducing the sintering shrinkage in the machine direction. The different sintered ranges in the machine direction and in the direction perpendicular to the machine direction can be about 2% to about 3%, for example, when the tape is stretched in the machine direction or lengthwise.

[0352] The sintering station 38 of controlled curvature or a curved air bearing can be used to transport the green tape material, the partially sintered article, or the sintered article in the machine direction 14 and can prevent the green tape material, the partially sintered article, or the sintered article from having excessive curvature in the width of the green tape material, the partially sintered article, or the sintered article. If there is a modest on-tape or on-sheet curvature, a tensile force in the direction parallel to the machine direction can provide some tension perpendicular to the machine direction, controlling or limiting the distortion.

[0353] It can be difficult to provide a tensile force in the direction perpendicular to the machine direction 14, especially for temperatures at which the sintered article is plastically deformable and / or the sintered article is being sintered and is plastically deformable. In such regions of the system 10 (or, in particular, the sintering station 38), a roller angled relative to the direction parallel to the machine direction 14 (see, e.g., FIG. 6) can exert some tension perpendicular to the machine direction 14 (e.g., the width direction of the tape). This tensile force can increase the pitch of the pores perpendicular to the machine direction 14, effectively reducing the sintering shrinkage in the direction perpendicular to the machine direction 14. Figure 88B

[0354] The fiducial marks for alignment can be made by laser, mechanically, chemically (e.g., with a slight compositional change with visible results). These marks help align further processing steps, such as conductor printing, patterning, and / or lamination.

[0355] ​Another aspect of the present disclosure pertains to a multilayer sintered article having a width of about 1 mm or greater, about 1 cm or greater, 5 cm or greater, 10 cm or greater, or 20 cm or greater, a length of 1 m or greater, 3 m or greater, 5 m or greater, 10 m or greater, or 30 m or greater, wherein the sintered article has a thickness of less than 1 mm, less than about 0.5 mm, less than about 300 microns, less than about 150 microns, less than about 100 microns. In one or more embodiments, the sintered article has a crystalline ceramic content of more than 10 volume percent, more than 25 volume percent, more than 50 volume percent, more than 75 volume percent, or more than 90 volume percent. The article has at least two layers of sintered article and can have more than 40 such layers. The thickness of the layers of sintered article is 150 microns or less, 100 or less, 75 or less, 50 or less, 25 or less, 20 or less, 15 or less, 10 or less, 5 or less, and / or for example at least 3 microns (i.e., at least 3 microns). In one or more embodiments, the layers of sintered article need not be of the same composition and some such layers include glass. In some embodiments, such glass layers can include 100% glass, for example at least 100% amorphous silicate glass.

[0356] In one or more embodiments, the multilayer sintered article includes a plurality of vias, conductive layers, and / or optional additional layers as described herein with respect to microelectronic articles.

[0357] In one or more embodiments, system 10 can include processes and equipment to manufacture such multilayer sintered articles. The multilayers can be manufactured by casting or web coating multiple layers of green tape material (i.e., ceramic particles with a polymeric binder) on top of each other. The multilayer green tape material structure can then be processed through system 10 as described herein. In one or more embodiments, the multilayer green tape material structure can also be formed by layering multiple green tapes with ceramic particles in a continuous manner near room temperature and then feeding the layered tapes into system 10. The partially sintered articles can also be layered together in sintering station 38 with a small pressure. The pressure can be induced by having a moderate curvature in sintering station 38 through which the partially sintered articles are drawn. Each partially sintered article can have its own tension and output speed control mechanism. Each partially sintered article can have fiducial markers to help article alignment. The tension and output speed can be used to match the sintering shrinkage between articles to article so that the vias and conductors between articles are aligned. If the fiducial markers are not aligned when the multilayer article exits the furnace, the layer output speed and / or tension can be adjusted so that the layers come back into alignment. Additional pressure perpendicular to the length and width of the multilayer article can be provided by rollers at high temperature as described above.

[0358] Because the conductive bodies and ceramic materials in a multi-layer electronic substrate can not have the same coefficient of thermal expansion, some design for overall stress reduction (balancing) from the "top" side to the "bottom" side of a multi-layer sintered article can be provided. Generally, such designs have similar amounts of metal or ceramic on the top and bottom of the multi-layer, for example, such that the layers are mirror images relative to a central plane in the respective stack. For thin ceramic layers, stress / CTE unbalanced structures can experience distortion of the ceramic and / or curling of the overall stack structure.

[0359] In one or more embodiments, an electronic circuit board includes a sintered article as described herein, on which a conductive body is patterned. The conductive body for the circuit board can be printed directly onto the green tape material, the partially sintered article, or the sintered article, and / or can be printed onto a coating or layer adhered to the green tape material, the partially sintered article, or the sintered article, for example, an adhesion promoting layer, a surface smoothing layer, and / or other functional layer. The printing can be from direct screen printing, electroless deposition and patterning, photolithography, with a silicone carrier between the pattern formation and the application of the pattern on the sintered article via a gravure pattern roll and / or other process.

[0360] The conductive body for the circuit board can be printed directly onto the partially sintered article after an intermediate firing step but before the final sintering step, and / or onto a coating thereon. The porosity in the partially sintered article or the sintered article can improve adhesion of the conductive body print or pattern. The printing can be from direct screen printing, photolithography, with a silicone carrier between the pattern formation and the application of the pattern on the ceramic via a gravure pattern roll or other process.

[0361] One aspect of the process and apparatus can use drumming while patterning long continuous porous ceramic tapes or sheets. Drumming pulls the ceramic tape or sheet to match the curvature on the drum surface, making printing of the conductor pattern less difficult. Photolithography can also etch or wash away some of the conductor pattern on the green tape or sheet using solvents or acids prior to final sintering, which can be done on the drum. When patterning the conductor prior to final sintering, it is recommended to use a way to control the pattern, size, gauge, or pitch of the sintering shrinkage. Unfortunately, the sintering shrinkage of the ceramic tape or sheet can vary by one percent or more from one continuous green tape (or sheet) to another, sometimes even within a single green tape or sheet. One way to ensure accurate spacing of the conductor pattern is to have a sensor at the exit of the final sintering step and measure the spacing distance of the conductor pattern. This information can be fed into the way the pattern is printed (e.g., laser, drilling, punching, etching system), the way the photolithography is exposed (e.g., radiation or light source, masking), thereby adjusting the conductor pattern in the tape or sheet prior to final sintering to match the existing sintering shrinkage. (The length of the tape or sheet between the measuring device and the "patterning" device can not be perfectly accurate; however, it can be more accurate than if using batch sintering with a periodic kiln or using a tunnel kiln, which can result in a large amount of final product loss due to inaccuracy).

[0362] Continuous sintering (e.g., continuous firing of ceramic with roll-to-roll sintering) provides another way to control the interstitial spacing during the sintering process. The tension provided in the direction of web transport (i.e., the length of the strip) during sintering can stretch the sintered article (e.g., tape or sheet) and / or bias the sintering shrinkage. This tension can increase the spacing of the conductor pattern in the direction of tape transport, effectively reducing the sintering shrinkage in the direction of tape transport. When tension is applied, different sintering in the direction of tape transport and perpendicular to the direction of tape transport is observed, up to 2-3%.

[0363] Photolithography, inkjet, atomic layer deposition, some printing, and other processing means can be done from the inner radius of a curved air bearing or with a segmented drum with open areas (for exposing the ceramic tape or strip to the conductor patterning processing equipment).

[0364] With copper-based conductors, alumina and tungsten, molybdenum, or platinum conductors can be co-sintered with other inorganic materials disclosed herein and form cordierite (glass-ceramic) based low-fired ceramic packages.

[0365] In some such embodiments, a controlled curvature kiln apparatus or curved air bearing that the ceramic tape or web with conductor pattern is pulled through or over can keep the ceramic tape or sheet with conductor pattern from excessive curvature over the short length of the tape perpendicular to the direction of web transport.

[0366] It can be difficult to provide tension in a direction perpendicular to the direction of tape transport (the cross direction of the web), especially for ceramic tapes that are plastically deformable or for the temperature at which the ceramic tape with conductor pattern is sintered and plastically deformable. In the hot zone of the furnace, rollers that are angled relative to parallel to the direction of tape transport can apply some tension perpendicular to the direction of tape transport. This tension can increase the pitch of the channels perpendicular to the direction of tape transport, effectively reducing the sintering shrinkage perpendicular to the direction of tape transport. The dimensions and pitch of the conductor pattern can be controlled and adjusted by a combination of the sintering shrinkage along the direction parallel to the direction of tape transport (the long length of the ceramic tape), the sintering shrinkage in the direction perpendicular to the direction of tape transport, the tension in both directions and the shape of the kiln, and / or the air bearing on which the ceramic tape or sheet has on it when sintering or when hot.

[0367] The fiducial marks for alignment can be made by laser, mechanically, chemically (e.g., slight compositional changes with visible results). These marks help align further processing steps, such as conductor printing / patterning and lamination.

[0368] A multi-layer structure with ceramic and conductor can be bonded from a final sintered conductor plus a ceramic sheet or tape with fewer layers, even from a sheet with only a single ceramic plus a conductor layer at high temperature.

[0369] A stress balance from top to bottom is advantageous for thin circuit boards with ceramic insulating layers. This can be done by printing a patch or pattern of opposite material to the desired conductor pattern on the side, which can relieve the thermal expansion coefficient CTE or thermal expansion related stress between the conductor and ceramic (and sometimes can relieve the sintering differential stress between the conductor and ceramic). This can take the form of a second conductor layer on the bottom of the board with similar material thickness and mass, which balances the CTE stress (and sintering differential stress) from top to bottom, resulting in a circuit board that is almost flat instead of curled.

[0370] As the multi-layer structure and / or circuit board becomes thicker, it becomes more rigid after full sintering. Specifically, for ceramic and conductor structures of 1 mm, 0.5 mm, and 250 microns thickness, it can be problematic to wind the article onto a small roller of 30 to 7.5 cm diameter. The way that a continuous sintered article can be cut by laser, diamond saw, abrasive blasting, water jet, and other techniques can be used for a continuous sintering apparatus, for example, where individual structures or groups of structures can be cut into sheets. A cutting apparatus can be added to the exit of the final sintering furnace, and the cutting device moves or comes into contact with the long article as it exits the furnace, for example.

[0371] See Figure 56 and 57FIG. 15 shows a process to initiate sintering and threading of a green tape 20A through the adhesive removal station 34A and sintering station 38A of a system 1500A for producing sintered tape articles according to an exemplary embodiment. Overall, the system 1500A is substantially the same as the system 10 described above and functions substantially the same, except for the slightly different alternating spool arrangement / locations in the separation system 12A, tension control system 32A, and take-up system 42A.

[0372] To initiate the roll-to-roll transfer of tape material from the source spool 16A to the take-up spool 44A, the green tape 20A needs to thread through the passageway of the adhesive removal station 34A and through the sintering station 38A such that the green tape 20A is connected to the take-up spool 44A which applies tension to pull the green tape through the adhesive removal station 34A and through the sintering station 38A. Similarly, if the tape material breaks during operation of the adhesive removal station 34A and sintering station 38A (which can occur after adhesive removal), the tape material needs to thread through the adhesive removal station 34A and then through the sintering station 38A, which is done while these stations are at full operating temperature. Applicants have determined that threading would be particularly difficult (especially when the adhesive removal station 34A and sintering station 38A are at temperature) because it is difficult to pass the non-bonded tape 36 (i.e., the self-supporting tape material after the organic adhesive is removed) through the sintering station 38A after the adhesive is removed (as shown). Thus, it should be understood that while the threading process and system discussed herein primarily involves threading of the green tape 20A, the threading process can be used to pass various tape materials (including the non-bonded tape 36 (as shown) and / or partially sintered tape material) through a sintering system (e.g., system 10 or system 1500A). Figure 3 Figure 3 Thus, it should be understood that while the threading process and system discussed herein primarily involves threading of the green tape 20A, the threading process can be used to pass various tape materials (including the non-bonded tape 36 (as shown) and / or partially sintered tape material) through a sintering system (e.g., system 10 or system 1500A).

[0373] As discussed in more detail below, Applicants have developed a process that employs a threading material or leader to pull the green tape 20A through the adhesive removal station 34A and sintering station 38A to initiate the roll-to-roll processing described above. In such embodiments, the threading material passes through the sintering station 38A and adhesive removal station 34A, and the leader is connected to the green tape 20A upstream or inlet side of the adhesive removal station 34A.

[0374] ​Tension is then applied to the green strip 20A from the take-up spool 44A via the lead wire to begin the process of the green strip 20A moving through the adhesive removal station 34A and through the sintering station 38A. While various schemes of the green strip passing through the adhesive removal station 34A and through the sintering station 38A can allow for sintering of the green strip to be achieved (e.g., manually passing through), Applicant has determined that the lead wire based passing process discussed herein provides for high quality / low warping in the sintered strip material, even at the leading edge of the sintered material. This improved product quality reduces product waste, improves process efficiency by eliminating the need to dispose of warped sections on the green strip, and improves the winding integrity of the sintered material on the take-up spool 44A due to the improved shape consistency along the length of the sintered strip material. Further, in the case of hot passing (e.g., when the adhesive removal station 34A and the sintering station 38A are at temperature), Applicant has found that using the lead wire based process described herein provides for an efficient way to support and pull the fragile unsintered portion of the leading edge of the strip material (e.g., the unsintered strip 36 as shown in Figure 3 and as described above) after exiting the adhesive removal station 34A until sintering occurs during passing through the sintering station 38A.

[0375] In the embodiment shown in Figure 56 and 57 the lead-in material (shown as lead wire 1502A) passes from the take-up spool 44A through the passageway of both the sintering station 38A and the adhesive removal station 34A in the opposite direction, such that a first section (shown as end section 1504A) of the lead wire 1502A is located outside of the inlet opening 116A of the adhesive removal station 34A. As shown in Figure 56 in this arrangement, the lead wire 1502A is a single contiguous piece of material that is placed such that the lead wire 1502A extends all the way from the take-up spool 44A through the sintering station 38A and the adhesive removal station 34A.

[0376] The green strip 20A is moved from the source spool 16A (e.g., by unwinding the green strip 20A from the spool described above) toward the inlet opening 116A of the adhesive removal station 34A such that a leading section 1506A of the green strip 20A is positioned adjacent to and overlapping the end section 1504A of the lead wire 1502A. As shown in Figure 57As shown, after the leading section 1506A of the green strip 20A is placed adjacent to the end section 1504A of the lead 1502A, the leading section 1506A of the green strip 20A is connected or bonded to the end section 1504A upstream of the adhesive removal station (e.g., in the processing direction 14A between the inlet opening 116A of the adhesive removal station and the source spool 16A). This forms a joint or bond between the lead 1502A and the green strip 20A at the overlap section.

[0377] Once the lead 1502A is connected to the green strip 20A, a force is applied to the portion of the lead 1502A that is outside (e.g., downstream) of the adhesive removal station 34A and the sintering station 38A to thereby pull the lead 1502A and the green strip 20A in the processing direction 14A through the adhesive removal station 34A and the sintering furnace 38A. As shown in the particular embodiment, the second or downstream end 1508A of the lead 1502A is connected to the take-up spool 44A, and the force resulting from the rotation of the take-up spool 44A provides the force for moving / pulling the lead 1502A and the green strip 20A through the adhesive removal station 34A and the sintering furnace 38A. In some embodiments, applicants have found that a processing speed of about 3 inches / minute (e.g., the speed at which the strip material moves through the system 1500A) is used during the threading up process, and in particular embodiments, this speed can be increased to about 6 inches / minute for the sintering process once the joint between the lead 1502A and the green strip 20A passes through the adhesive removal station 34A and the sintering furnace 38A. Figure 56

[0378] Thus, by using the lead 1502A, the downstream or rewound side of the system 1500A is initially connected to the upstream or unwound side of the system 1500A to enable roll-to-roll sintering of the material of the green strip 20A. Moreover, by providing this initial threading of the adhesive removal station 34A and the sintering station 38A through the same connection between the unwound and take-up systems, which enables the green strip 20A to be advanced during the sintering process, the lead-based threading process described herein enables a suitable tension and speed to be established for the entire length of the green strip 20A that threads through the adhesive removal station 34A and the sintering station 38A, including the leading end 1506A of the green strip 20A at the overlap location. Moreover, by providing a horizontal pulling force through the lead 1502A, the lead-based process described herein enables threading through the horizontally oriented passageway of the adhesive removal station 34A and the sintering station 38A, which can otherwise be difficult (particularly given the fragile nature of the strip material after the adhesive is removed).

[0379] ​As specifically described above regarding System 10, the binder removal station 34A is heated to remove or burn off the binder from the green strip 20A, and the sintering station 38A is heated to induce sintering of the inorganic material of the green strip 20A. In one potential use of the passing process described herein, the binder removal station 34A and / or the sintering station 38A are already at their respective operating temperatures when the lead wire 1502A passes through. This is the case when the lead wire 1502A is used to pass through the green strip 20A after material breakage during reel-to-reel sintering. In another potential use of the passing process described herein, the binder removal station 34A and / or the sintering station 38A are at low temperatures (e.g., below their respective operating temperatures, at room temperature, etc.) when the lead wire 1502A passes through. This is the case when the lead wire 1502A is used to pass through the green strip 20A during the initial startup process of System 1500A.

[0380] As discussed in more detail above, after the initial movement of the junction or overlap between the lead wire 1502A and the front end 1506A of the green strip 20A through the adhesive removal workstation 34A and sintering furnace 38A, the green strip 20A is continuously unwound from the source reel 16A and moved through workstations 34A and 38A to form the length of the sintered material as described above. After sintering, the sintered material is wound onto the take-up reel 44A. In one embodiment, the lead wire 1502A is detached from the sintered strip material once the front end 1506A of the green strip 20A leaves the sintering workstation 38A and before the sintered strip material is wound onto the take-up reel 44A. In another embodiment, the lead wire 1502A is wound onto the take-up reel 44A together with the sintered strip material to form the innermost layer of the reel including the sintered material.

[0381] In various embodiments, lead 1502A is an elongated and flexible sheet of material capable of withstanding the high temperatures of the adhesive removal station 34A and the sintering station 38A. In such... Figure 57 In the connection process shown, the front section 1506A of the green strip 20A overlaps with the end section 1504A of the lead wire 1502A, forming an overlapping section 1512A. In this arrangement, the lower surface of the green strip 20A faces and contacts the upper surface of the lead wire 1502A. In this arrangement, by placing the green strip 20A on top of the lead wire 1502A, the lead wire 1502A serves to support the front section 1506A of the green strip 20A through the adhesive removal workstation 34A and the sintering furnace 38A.

[0382] In some embodiments, an adhesive material 1510A is used to form an adhesive bond between the lead 1502A and the green strip 20A. For example... Figure 57As shown, in some such embodiments, the adhesive material 1510A is located on the upper surface of the lead 1502A and forms a bond with the lower surface of the green tape 20A. As discussed in greater detail below, in various embodiments, Applicants have determined that matching of various properties (e.g., the coefficient of thermal expansion (CTE) of the materials forming the adhesive 1510A, the lead 1502A, and the green tape 20A) helps maintain the bond between the lead 1502A and the tape material, particularly during the high temperatures traversed through the sintering station 38A. In addition, a strong bond between the lead 1502A and the green tape 20A allows a desired level of tension to be applied to the lead 1502A and transmitted to the green tape 20A through the bond provided by the adhesive 1510A. As described herein, Applicants have found that a low (e.g., gram level) but consistent tension applied to the tape material during sintering reduces warping that can otherwise form across the width of the tape during sintering.

[0383] In various embodiments, Applicants have determined that the volume of adhesive material 1510A used and the shape of the adhesive material 1510A applied to the lead 1502A affects the properties of the bond formed between the lead 1502A and the green tape 20A. In particular embodiments, the adhesive material 1510A is a small volume (e.g., about 0.1 mL of an alumina-based adhesive material). In one embodiment, the adhesive 1510A is used to bond the lead 1502A to the unsintered green tape material 20A, and in such embodiments, Applicants have found that a dot of adhesive 1510A works well. Applicants theorize that the circular geometry helps to distribute thermal and mechanical stresses induced by the adhesive and tape shrinkage and CTE mismatch between the lead 1502A, the adhesive 1510A, and the materials of the green tape 20A, if present. In another embodiment, the adhesive 1510A is used to bond the lead 1502A to the tape of partially sintered material, and in such embodiments, Applicants believe that a line of adhesive 1510A extending across the width of the lead 1502A works well. Applicants theorize that the line geometry acts to apply a uniform restraint on the web as it moves through the sintering station.

[0384] In particular embodiments, the adhesive removal station 34A is operated to remove liquid and / or organic components from the adhesive 1510A (and from the green tape 20A) as the overlap section 1512A between the lead 1502A and the green tape 20A traverses the adhesive removal station 34A. Applicant believes that various properties of the adhesive material 1510A and the green tape 20A are related to the likelihood that the bond formed through the adhesive material 1510A will fracture during traversal through the adhesive removal station 34A and the sintering station 38A. Applicant theorizes that the temperature profile through the adhesive removal station 34A causes the organic material in the green tape 20A to soften and even melt before the tape has evolved into a strip, which can help limit the stress intensity around the adhesive joint as the individual components begin to change shape / size due to shrinkage and thermal expansion. Applicant theorizes that allowing the green tape to "deform" or "reform" around the location of the adhesive 1510A before losing its elastic / plastic properties helps reduce defects and improves the quality of the bond formed through the adhesive 1510A. Similarly, this elastic / plastic property can also enable the expulsion of liquid and organic material from the adhesive, which might otherwise cause an increase in pressure between the lead 1502A and the green tape 20A. This increase in pressure can cause the bond to fail, or the accumulated gas can cause the green tape 20A to burst.

[0385] In particular embodiments, the tension applied during the process of pulling the overlap section or joint between the lead 1502A and the green tape 20A can vary or increase as the overlap section 1512A traverses the adhesive removal station 34A and / or the sintering station 38A. In particular embodiments, a low level of tension (e.g., less than 25 grams) is provided initially as the overlap section 1512A traverses the adhesive removal station 34A, and then the tension is increased as the overlap section 1512A traverses the sintering station 38A. In particular embodiments, a tension of about 25 grams or more is applied once the overlap section 1512A and the adhesive material 1510A reach the center of the sintering station 38A. Applicant believes that at this point, the tension can be increased without causing the bond between the lead 1502A and the green tape 20A to separate, as sintering of the material of the green tape 20A has already occurred at this point. Applicant believes that applying a high level of tension too early typically causes the bond formed by the adhesive 1510A to fail before there is an opportunity to build up strength.

[0386] In various embodiments, the connection and / or support between the lead 1502A and the green tape 20A is enhanced through various levels of overlap between the lead 1502A and the green tape 20A. From left to right in FIG. 16, the lead 1502A is shown overlapping the green tape 20A by a first amount 1602A, a second amount 1604A, and a third amount 1606A. In particular embodiments, the first amount 1602A of overlap is less than the second amount 1604A of overlap, which is less than the third amount 1606A of overlap. In particular embodiments, the first amount 1602A of overlap is less than 10%, less than 20%, less than 30%, less than 40%, less than 50%, less than 60%, less than 70%, less than 80%, less than 90%, or less than 95% of the second amount 1604A of overlap. In particular embodiments, the second amount 1604A of overlap is less than 10%, less than 20%, less than 30%, less than 40%, less than 50%, less than 60%, less than 70%, less than 80%, less than 90%, or less than 95% of the third amount 1606A of overlap. Figure 57As can be seen, the more overlap between the lead 1502A and the green strip 20A, the greater the amount of support provided by the lead 1502A to the green strip 20A. Similarly, the level of overlap between the lead 1502A and the green strip 20A is related to the amount of friction-based connection between the lead 1502A and the green strip 20A, which can supplement the bonding provided by the adhesive 1510A. In embodiments employing the adhesive 1510A, Applicants have found that overlap segments 1512A having a length of 1 to 5 inches, measured in the machine direction 14A, perform well. In some embodiments, the connection between the lead 1502A and the green strip 20A can be provided solely by friction (e.g., without the adhesive 1510A), and in such cases, the length of the overlap segment 1512A in the machine direction 14A can be greater than 5 inches, such as greater than 10 inches, 10 inches to 30 inches, about 24 inches, etc.

[0387] In various embodiments, Applicants provide a variety of material combinations for the lead 1502A, the green strip 20A, and the adhesive 1510A described herein that cross properties / functions. In general, the lead 1502A is formed from a material that is different from the green strip 20A in at least one respect. In some such embodiments, the lead 1502A is formed from the same material type as the inorganic particles of the green strip 20A, but has a different (e.g., higher) degree of sintering than the inorganic material of the green strip 20A. In some such embodiments, the lead 1502A is a strip of elongated sintered ceramic material, and the green strip 20A carries unsintered or less sintered particles of the same type of ceramic material.

[0388] In some other embodiments, the lead 1502A is formed from an inorganic material of a different material type than the inorganic particles of the green strip 20A. In particular embodiments, the lead 1502A is formed from a ceramic material type that is different from the ceramic material type of the inorganic particles of the green strip 20A. In some other embodiments, the lead 1502A is formed from a metallic material, while the inorganic particles of the green strip 20A are a ceramic inorganic material.

[0389] Applicants have found that, Figure 57The level of connection between the lead 1502A and the green tape 20A provided by the connection arrangements shown and described herein allows the force / tension to be well transmitted from the lead to the green tape 20A without a significant risk of detachment. In addition, Applicants have found that by selecting materials for the lead 1502A, the adhesive 1510A, and the inorganic particulate material of the green tape 20A that have relatively similar coefficients of thermal expansion (CTEs) with respect to one another, the risk of detachment and warping due to sintering can be reduced. In various embodiments, the CTE of the material of the lead 1502A is within plus or minus 50% of the CTE of the inorganic material of the green tape 20A, specifically within plus or minus 40% of the CTE of the inorganic material of the green tape 20A, and more specifically within plus or minus 35% of the CTE of the inorganic material of the green tape 20A. Similarly, in various embodiments, the CTE of the material of the lead 1502A is within plus or minus 50% of the CTE of the adhesive material 1510A, specifically within plus or minus 40% of the CTE of the adhesive material 1510A, and more specifically within plus or minus 35% of the CTE of the adhesive material 1510A.

[0390] The lead 1502A can be formed from a variety of suitable materials. In some embodiments, the lead 1502A is formed from a sintered ceramic material, and in other embodiments, the lead 1502A is formed from a metallic material. In some embodiments, Applicants have found that the use of a porous ceramic material for the lead 1502A increases the ability of the adhesive material 1510A to bond to the lead 1502A. Applicants believe that the porosity of the lead 1502A enables the adhesive material 1510A to bond more readily than if the lead had fewer pores or had a polished surface. In particular embodiments, the lead 1502A can be a platinum tape or a fully sintered ceramic material (e.g., alumina or yttria-stabilized zirconia (YSZ)).

[0391] In particular embodiments, the dimensions of the lead 1502A enable handling and connection to the green tape 20A. In particular embodiments, the width of the lead 1502A substantially matches the width of the green tape 20A (e.g., within plus or minus 10%). In particular embodiments, the thickness of the lead 1502A is 5 pm to 500 pm, and more specifically, the thickness is 20 to 40 pm. In addition, the length of the lead 1502A is sufficient to extend from the take-up spool 44A through both the sintering station 38A and the adhesive removal station 34A, and thus the length of the lead 1502A varies with the size of the system 1500A.

[0392] While Figure 56 and 57Lead 1502A is shown generally as a long, thin, flat section of sintered ceramic material, but lead 1502A can have other forms. For example, in one embodiment, lead 1502A can be a length of ceramic board with a long length of platinum wire glued to a green tape. In another embodiment, lead 1502A can be a length of ceramic fiber rope or twisted fiber.

[0393] Binder material 1510A can be formed from a variety of suitable materials. In some embodiments, binder material 1510A is a ceramic binder material. In particular embodiments, binder material 1510A is an alumina-based binder material, such as alumina-based binder #C4002 available from Zircar ceramics.

[0394] Referring to Figures 58-65 , various systems and processes for bending non-bonded tape 36B in a longitudinal direction or lengthwise direction during sintering are shown and described. In general, applicants have determined that when sintering a wide, thin, and continuous length of non-bonded tape 36B, an unexpected challenge is ensuring that the final sintered tape 40B has a high level of flatness in the width direction. A high level of flatness in the width direction is desirable when using the sintered tape materials described herein in a number of applications, such as substrates for thin film circuits, thick film circuits, and solid state lithium ion batteries, among others.

[0395] Some continuous tape sintering processes can be susceptible to certain flatness distortions (e.g., bowing in the width direction, edge wrinkling, bubble formation, etc.) that are believed to be formed due to in-plane stresses that develop within the tape material during sintering. For example, applicants have found that due to various factors (e.g., ceramic grain density in non-bonded tape 36B, large temperature differentials along the length of the tape material (e.g., which can exceed 1000 degrees Celsius due to the continuous nature of the systems and processes described herein), processing speed, etc.), in-plane stresses develop during sintering that can in turn induce bending in a manner that does not have counteracting forces applied to release these in-plane stresses.

[0396] For example, an alumina tape that is being continuously sintered via the systems described herein can have regions at room temperature and at maximum sintering temperature at the same time. The tape can also have regions at the beginning of the sintering process that have minimal shrinkage, and regions of the tape near the end of sintering that have shrunk more than 8% or even 10% on a linear basis. The shrinkage and temperature gradients can be a source of complex biaxial stresses that can induce distortions, such as curling and wrinkling, even for a tape that enters the sintering station with some flatness. Such distortions can then become frozen into the sintered tape after cooling, thereby degrading its potential usefulness.

[0397] As discussed in detail below, Applicants have determined that stresses that can cause flatness distortion can be at least partially offset by inducing lengthwise or longitudinal bending in the ribbon during the sintering process. During sintering, the ribbon material plastically relaxes and deforms into the shape of the induced lengthwise bend, which creates forces in the ribbon material that tend to reduce otherwise potentially existing in-plane stresses, and as a result, can yield a sintered ribbon having a high level of flatness in the width direction. Applicants believe that by employing lengthwise bending during sintering, a relatively flat ribbon can be produced despite variations in green ribbon particle density and high production speeds.

[0398] Furthermore, in at least some embodiments, the planarization processes described herein yield a planar and thin sintered article while avoiding / limiting surface contact and the resulting surface defects and scratches that are common with contact / pressure-based planarization devices, such as can be experienced when pressing material between cover plates during sintering. As shown below, Applicants have developed several systems and processes for inducing longitudinal bending that result in at least one major surface of the ribbon that does not experience contact during sintering, and some processes that result in both the top and bottom (major) surfaces of the ribbon that do not experience contact during sintering. Applicants believe that other ceramic sintering processes are not capable of achieving high levels of flatness in the width direction during continuous sintering, or with the limited degree of surface contact provided by the systems and processes described herein.

[0399] Referring to Figure 58 , a process and system for producing a sintered continuous ribbon having a high level of flatness is shown. In particular, Figure 58 A system 1600B for producing a sintered ribbon article according to an exemplary embodiment is shown. Generally, the system 1600B is the same as and functions in the same manner as the system 10 described above, except that the system 1600B includes a sintering station 38B that includes a bending system 1602B located within the sintering station 38B. Generally, the bending system 1602B is configured or arranged to induce a radius of curvature along the lengthwise or longitudinal axis of the non-bonded ribbon 36B when the ribbon 36B is sintered at an elevated temperature (e.g., greater than 500 degrees Celsius) within the sintering station 38B. Applicants have determined that by inducing longitudinal bending in the ribbon material during sintering via bending, the shape in the width of the final sintered ribbon 40B can be improved via the mechanisms described herein.

[0400] In Figure 58In the specific embodiment shown, the bending system 1062B includes an upwardly convex bending surface 1604B that defines at least a portion of the lower channel surface passing through the sintering workstation 38B. The upwardly convex bending surface 1604B defines at least one radius of curvature (shown as R1B), which in this specific embodiment is a radius of curvature ranging from 0.01 m to 13000 m or includes a radius of curvature ranging from 0.01 m to 13000 m. Generally, the unbonded strip 36B moves through the sintering workstation 38B (as described above), and the gravity and / or tensile tension in the strip cause the strip to bend to at least partially conform to the bending surface 1604B, inducing longitudinal bending in the strip during sintering at elevated temperatures. In this specific embodiment, the tension applied to the unbonded strip 36B is at least 0.1 grams of force per linear inch of the width of the unbonded strip 36B, and the movement speed through the sintering workstation 38B is 1 to 100 inches of strip length per minute.

[0401] like Figure 58 As shown, the curved surface 1604B is about an axis parallel to the width of the unbonded strip 36B (and perpendicular to the width axis). Figure 58 The axis of the unbonded strip 36B is bent (as shown in the attached drawing plane). Therefore, in this embodiment, the path of the unbonded strip 36B through the sintering station 38B is generally defined by the channel 104B, and the convex curved surface 1604B defines the curved section of the path through the sintering station 38B. During sintering, when the unbonded strip 36B passes through the curved section of the path defined by the convex curved surface 1604B, bending is induced in the unbonded strip 36B because its shape conforms to the curved surface 1604B.

[0402] exist Figure 58 In the specific embodiment shown, the curved surface 1604B forms a continuous curved surface with a single radius of curvature that extends the entire length of the channel 104B between the inlet and outlet of the sintering workstation 38B. In this type of embodiment, the radius of curvature of the surface 1604B, which needs to simultaneously achieve a sufficient level of curvature and extend the entire length of the sintering workstation 38B, can vary based on the length of the sintering workstation. Thus, for a given maximum rise H1B of the curved surface 1604B (e.g., ...), the radius of curvature can vary. Figure 60As a specific example, a sintering station 38B that is (at least) 1 m long can have a curved surface 1604B with R1B of 1 m to 130 m. As a specific example, a sintering station 38B that is (at least) 3 m lo...

Claims

1. A sheet configured for a solid state battery, comprising: a body comprising ceramic particles sintered to one another, wherein the particles comprise lithium, wherein a body thickness between first and second major surfaces of the body is in a range of 3 pm to 1 mm; wherein the first and second major surfaces of the body have an unpolished granular profile such that the profile comprises particles projecting outward from the respective major surface, the particles having a height relative to a recessed portion of the respective major surface at a boundary between respective particles of at least 25 nm and no more than 150 pm; wherein the particles sintered to one another have an average particle size of 5 pm or less; and wherein the granular profile comprises particles having a height relative to a recessed portion of the respective major surface at a boundary between respective particles of at least 150 nm.

2. The sheet of claim 1, wherein the height of the particles is no more than 80 pm relative to a recessed portion of the respective major surface at a boundary between respective particles.

3. A sheet configured for a solid state battery, comprising: a body comprising ceramic particles sintered to one another, wherein the particles comprise lithium, wherein a body thickness between first and second major surfaces of the body is in a range of 3 pm to 1 mm; wherein the first and second major surfaces of the body have an unpolished granular profile such that the profile comprises particles projecting outward from the respective major surface, the particles having a height relative to a recessed portion of the respective major surface at a boundary between respective particles of at least 25 nm and no more than 150 pm; wherein the particles sintered to one another have an average particle size of 5 pm or less; and wherein the body has a length of 5 m or more.

4. A sheet configured for a solid state battery, comprising: a body comprising ceramic particles sintered to one another, wherein the particles comprise lithium, wherein a body thickness between first and second major surfaces of the body is in a range of 3 pm to 1 mm; wherein the first and second major surfaces of the body have an unpolished granular profile such that the profile comprises particles projecting outward from the respective major surface, the particles having a height relative to a recessed portion of the respective major surface at a boundary between respective particles of at least 25 nm and no more than 150 pm; wherein the particles sintered to one another have an average particle size of 5 pm or less; and wherein the body is flatablable without fracture as determined by pressing the body between rigid parallel surfaces at 23 °C such that the body covers or is within 0.05 mm of a flat plane.

5. A sheet configured for a solid state battery, comprising: a body comprising ceramic particles sintered to one another, wherein the particles comprise lithium, wherein a body thickness between first and second major surfaces of the body is in a range of 3 pm to 1 mm; wherein the first and second major surfaces of the body have an unpolished granular profile such that the profile includes particles protruding outward from the respective major surface having a height of at least 25 nm and no more than 150 pm relative to a recessed portion of the respective major surface at a boundary between respective particles; and wherein the body includes a closed porosity, and the porosity is less than 15 vol. %.

6. The sheet of claim 5, wherein an average of less than 10 pinholes per mm2 of surface have a cross-sectional area of at least 1 pm2 that pass through the body.

7. The sheet of claim 5, wherein the granular profile includes particles having a height of at least 150 nm relative to a recessed portion of the respective major surface at a boundary between respective particles.

8. The sheet of claim 7, wherein the height of the particles is no more than 80 pm relative to a recessed portion of the respective major surface at a boundary between respective particles.

9. The sheet of claim 5, wherein the body has a length of 5 m or more.

10. The sheet of claim 5, wherein the body is flatablable without fracture as determined by pressing the body between rigid parallel surfaces at 23 °C such that the body covers or is within 0.05 mm of a flat plane.

11. A sheet configured for a solid state battery, comprising: a body comprising ceramic particles sintered to one another, wherein the particles include lithium, lanthanum, zirconium, and oxygen, and wherein greater than 95 wt. % of the body consists of cubic lithium garnet crystals; wherein a body thickness between first and second major surfaces of the body is in a range of 3 pm to 50 pm, and wherein the body has a width of 5 mm or more; wherein the first and second major surfaces of the body have an unpolished granular profile such that the profile includes particles protruding outward from the respective major surface having a height of at least 25 nm and no more than 150 pm relative to a recessed portion of the respective major surface at a boundary between respective particles; and wherein the mutually sintered particles have an average particle size of 3 pm or less, and wherein the body has an ionic conductivity of greater than 1 x 10 -4 S / cm. wherein the mutually sintered particles have an average particle size of 3 pm or less, and wherein the body has an ionic conductivity of greater than 1 x 10 -4 S / cm. wherein the mutually sintered particles have an average particle size of 3 12. The sheet of claim 11, wherein the body has a closed porosity.

13. The sheet of claim 11, wherein the body has a porosity of less than 10 vol. %.

14. The sheet of claim 11, wherein the body is flatablable without fracture as determined by pressing the body between rigid parallel surfaces at 23 °C such that the body covers or is within 0.05 mm of a flat plane.

15. The sheet of claim 11, wherein the particles further comprise tantalum, and wherein the bulk has an ionic conductivity greater than 2 x 10 -4 S / cm.

16. The sheet of claim 11, wherein the particles further include aluminum.

17. The sheet of claim 11, wherein the body has a length of at least 10 m.

18. A roll of the sheet of claim 17 wound on a spool.

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