HIGH TEMPERATURE SINTERING SYSTEMS AND METHODS
20220219986 · 2022-07-14
Inventors
Cpc classification
C01B32/05
CHEMISTRY; METALLURGY
C04B2235/3256
CHEMISTRY; METALLURGY
F27D2099/0011
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
C04B2235/666
CHEMISTRY; METALLURGY
C04B2235/3251
CHEMISTRY; METALLURGY
B22F2998/10
PERFORMING OPERATIONS; TRANSPORTING
Y02E60/10
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
B33Y80/00
PERFORMING OPERATIONS; TRANSPORTING
F27M2003/04
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
B22F3/105
PERFORMING OPERATIONS; TRANSPORTING
B28B3/025
PERFORMING OPERATIONS; TRANSPORTING
C04B2235/3203
CHEMISTRY; METALLURGY
C04B35/491
CHEMISTRY; METALLURGY
F27D11/02
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
B22F2998/10
PERFORMING OPERATIONS; TRANSPORTING
C04B35/495
CHEMISTRY; METALLURGY
C04B2235/3227
CHEMISTRY; METALLURGY
B22F3/105
PERFORMING OPERATIONS; TRANSPORTING
C04B2235/3224
CHEMISTRY; METALLURGY
Y02P10/25
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
International classification
C01B32/05
CHEMISTRY; METALLURGY
C04B35/622
CHEMISTRY; METALLURGY
F27D11/02
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
H05B1/02
ELECTRICITY
Abstract
Disclosed are fast high-temperature sintering systems and methods. A method of fabrication includes positioning a material at a distance of 0-1 centimeters from a first conductive carbon element and at a distance of 0-1 centimeters from a second conductive carbon element, heating the first conductive carbon element and the second conductive carbon element by electrical current to a temperature between 500° C. and 3000° C., inclusive, and fabricating a sintered material by heating the material with the heated first conductive carbon element and the heated second conductive carbon element for a time period between one second and one hour. Other variations of the fast high-temperature sintering systems and methods are also disclosed. The disclosed systems and methods can quickly fabricate unique structures not feasible with conventional sintering processes.
Claims
1-17. (canceled)
18. A method of fabrication comprising: positioning a conductive carbon element at a distance of at most 1 centimeter from a material, the material having a larger size than a size of the conductive carbon element; heating the conductive carbon element by electrical current to a temperature between 500° C. and 3000° C., inclusive; and moving the heated conductive carbon element over the material to provide a treated material.
19. The method according to claim 18, wherein moving the heated conductive carbon element over the material causes annealing of the material.
20. The method according to claim 19, wherein the annealing of the material creates a new surface layer at a surface of the material.
21. The method according to claim 19, wherein the material includes a thin film over a substrate, the method further comprising depositing the thin film onto the substrate by using one of: sputtering, chemical vapor deposition, atomic layer deposition, or physical vapor deposition.
22. The method according to claim 18, wherein moving the heated conductive carbon element over the material causes sintering of the material to provide a sintered material.
23. The method according to claim 22, further comprising: applying a layer over the sintered material; and moving the heated conductive carbon element over the layer to provide a sintered layer, wherein the sintered material and the sintered layer together form a sintered multilayer structure.
24. The method according to claim 22, wherein the material includes a coated powder over a substrate and the sintered material includes a sintered coating over the substrate.
25. The method according to claim 22, wherein the material is one of: a printed film of solid state electrolyte (SSE) precursor or a film of an SSE powder, the method further comprising dispensing one of an SSE precursor slurry or the SSE powder into a film, wherein the sintered material is a sintered SSE film.
26. The method according to claim 22, wherein the material is a thermal barrier coating coated over a metal substrate, the thermal barrier coating including a top porous layer and a bottom dense layer, wherein the top porous layer has pore sizes between 1-10,000 nm, wherein the sintered material is a sintered thermal barrier coating on the metal substrate, and wherein the top porous layer and the bottom dense layer are one of: co-sintered in a single sintering process, or sintered one layer at a time in separate sintering processes.
27. The method according to claim 22, wherein the material is an environmental barrier coating coated over a metal substrate, wherein the sintered material is a sintered environmental barrier coating on the metal substrate.
28. A furnace comprising: a material; a conductive carbon element positioned at a distance of at most 1 centimeter from the material, the material having a larger size than a size of the conductive carbon element; an electrical source configured to cause the conductive carbon element to heat by electrical current to a temperature between 500° C. and 3000° C., inclusive; a mechanical arm configured to move the heated conductive carbon element over the material to provide a treated material; and a controller configured to control the electrical source to heat the conductive carbon element and configured to control the mechanical arm to move the heated conductive carbon element.
29-45. (canceled)
46. The furnace according to claim 28, wherein moving the heated conductive carbon element over the material causes annealing of the material.
47. The furnace according to claim 46, wherein the annealing of the material creates a new surface layer at a surface of the material.
48. The furnace according to claim 46, wherein the material includes a thin film over a substrate, the method further comprising depositing the thin film onto the substrate by using one of: sputtering, chemical vapor deposition, atomic layer deposition, or physical vapor deposition.
49. The furnace according to claim 28, wherein moving the heated conductive carbon element over the material causes sintering of the material to provide a sintered material.
50. The furnace according to claim 49, further comprising a layer over the sintered material, wherein the mechanical arm is further configured to move the heated conductive carbon element over the layer to provide a sintered layer, and wherein the sintered material and the sintered layer together form a sintered multilayer structure.
51. The furnace according to claim 49, wherein the material includes a coated powder over a substrate and the sintered material includes a sintered coating over the substrate.
52. The furnace according to claim 49, wherein the material is one of: a printed film of solid state electrolyte (SSE) precursor or a film of an SSE powder, the method further comprising dispensing one of an SSE precursor slurry or the SSE powder into a film, wherein the sintered material is a sintered SSE film.
53. The furnace according to claim 49, wherein the material is a thermal barrier coating coated over a metal substrate, the thermal barrier coating including a top porous layer and a bottom dense layer, wherein the top porous layer has pore sizes between 1-10,000 nm, wherein the sintered material is a sintered thermal barrier coating on the metal substrate, and wherein the top porous layer and the bottom dense layer are one of: co-sintered in a single sintering process, or sintered one layer at a time in separate sintering processes.
54. The furnace according to claim 49, wherein the material is an environmental barrier coating coated over a metal substrate, wherein the sintered material is a sintered environmental barrier coating on the metal substrate.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0052] The above and other aspects and features of the present disclosure will become more apparent in view of the following detailed description when taken in conjunction with the accompanying drawings wherein like reference numerals identify similar or identical elements and:
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DETAILED DESCRIPTION
[0074] The present disclosure relates to fast high-temperature sintering systems and methods. Aspects of the present disclosure provide innovative non-material-specific, ultrafast, energy-saving sintering technology that can be applied to different materials to enable high-throughput fabrication of bulk ceramics for a broad range of technological applications. As will be explained below and in connection with the figures, the present disclosure provides systems and methods for sintering many types of materials in a process that can be as fast as forty-five seconds or less, providing a significant improvement over conventional furnace sintering times of more than twenty hours.
[0075] As used herein, and unless otherwise indicated otherwise, the term “sintering” refers to a process which forms a solid mass of material by heat and/or pressure without completely liquefying the material and can include processes which partially melt a material without completely liquefying it. In certain situations, the term “sintering” may refer to a process that melts materials, as explained for various situations described below.
[0076] The sintering process disclosed herein may be referred to as ultrafast high-temperature sintering (“UHS”) or as high temperature pulse (“HTP”) sintering. The UHS process features uniform temperature distribution, fast heating rates (e.g., 2,000-100,000° C./min) and fast cooling rates (e.g., up to about 10,000° C./min), and high sintering temperatures (e.g., up to about 3,000° C.). The high heating rates and high temperature of the heating source enable ultrafast sintering times of less than ten seconds and overall processing times of approximately forty-five seconds or less. Additionally, the UHS process is scalable and has minimal sample requirements in terms of intrinsic properties and preparation, thus providing universal and rapid ceramic synthesis and sintering. UHS enables rapid experimental validation for new material predictions from computation to facilitate materials discovery. Accordingly, the systems and methods disclosed herein provide a significant advance for rapid materials screening and synthesis that could be applied in a wide range of fields, including batteries, 3D printed ceramics, and high-entropy ceramics with vast compositional space that is otherwise difficult to explore.
[0077] In accordance with aspects of the present disclosure, and as explained in more detail later herein, the UHS process directly synthesizes ceramics from oxide precursors in a single step, in which the precursor pellet is quickly and uniformly sintered between two carbon strips through radiative heating. The short sintering time prevents volatile evaporation and undesirable interdiffusion at interfaces (i.e., cross-contamination). Additionally, the UHS process is compatible with 3D printing of ceramic precursors, producing novel structures that are retained after sintering, in addition to well-defined interfaces between multilayer ceramic compounds, with applicability for thin film SSE applications.
[0078] The UHS process for synthesizing ceramics or other solid materials has the following attributes. (1) The UHS process can directly synthesize and sinter precursors into solid, dense ceramics or glass thin films, reducing sintering time from tens of hours to less than ten seconds, which allows fast converging to successful synthesis for rapid materials screening. (2) High temperature leads to melted and merged grain boundaries while avoiding/mitigating uncontrolled grain growth. Such control results in outstanding performance and superior mechanical and electrochemical properties. (3) Short sintering time avoids/mitigates Li loss problem of solid state electrolytes (SSEs) during synthesis and avoids/mitigates side reactions, and results in multilayer structures without crossover diffusion. (4) The UHS process is a universal process for a wide range of ceramics, glass, and other solid materials. These attributes demonstrate the uniqueness of the UHS process as a physicochemical process for discovering ceramics, glass, and other solid materials.
[0079] Portions of the present disclosure refer to U.S. Provisional Patent Application No. 62/849,578, filed on May 17, 2019, which has been incorporated by reference in its entirety, and which may be referred to herein as “Supplement.”
[0080] Portions of the present disclosure refer to U.S. Provisional Patent Application No. 63/022,083, filed on Apr. 30, 2020, which has been incorporated by reference in its entirety, and which may be referred to herein as “Supplement B.”
[0081] Referring now to
[0082] In
[0083] The temperature of the heating elements 120 is tunable to different ramp rates, including heating rates of about 100° C./min to about 20,000° C./min, and cooling rates of about 100° C./min to about 10,000° C./min. The achievable temperature of the heating elements 120 can range from about 500° C. up to about 3,500° C. At maximum sintering temperature, the UHS process enables direct sintering of ceramics, glass, or other solid materials from precursors 110 to dense pellets 130 in less than ten seconds. Due to the rapid sintering speed, evaporation of volatile materials and potential cross-contamination can be significantly minimized, which enables co-sintering of multiple materials in one step.
[0084] In contrast, the conventional ceramic synthesis process involves multiple steps and long time. The precursors are first calcinated at about 800-1000° C. for 5-10 hours to form ceramic phase. Then the materials are re-grinded to ceramic power and pressed to pellets, which are sintered at about 1000-1200° C. for another 10-30 hours to form dense pellets. If the ceramics contain volatile components, additional ceramic powder beds with excess volatile components are necessary to compensate the evaporation at high temperature during the long-time sintering. The long sintering time can lead to uncontrollable grain growth and nonuniform size distribution (Supplement, Figure B1A), while the relative low sintering temperature can result in the weak-bonded grain boundaries, which will decrease the mechanical strength and affect the uniformity of the ceramic properties.
[0085] When the space between the heating element 120 and the material 110 is small, or the material 110 directly contacts the heating element 120, the temperature ramp rate of the sample 110 can be much faster, and the temperature distribution is more uniform than conventional furnaces. The short sintering time of the UHS process enables control of the grain growth, while the high sinter temperature ensures the excellent welding of the grain boundaries, which leads to uniformly distributed and well-merged small grains for UHS sintered ceramics (Supplement, Figure B1B). Various embodiments of UHS systems and processes are described below in connection with the figures.
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[0087] In various embodiments, the heating elements 210, 220 can be made of conductive carbon materials, such as carbon papers, carbon felts, carbon clothes, graphite papers, graphite felts, graphite clothes, graphite films, or graphite plates. In various embodiments, other conductive materials or composites can be used for the heating elements. The heating elements 210, 220 can be sized based on sizes of the materials to be sintered and to meet manufacturing needs. When the heating elements 210, 220 are made of conductive materials, the heating elements 210, 220 can be heated by an electrical source (not shown) passing electrical current through the conductive materials of the heating elements 210, 220. The amount of current through the conductive material of the heating elements 210, 220 corresponds to the heating rate, such that the heating rate and electrical source can be controlled by a controller (not shown) by providing a desired amount of current through the conductive materials of the heating elements 210, 220. Heating profiles are described in more detail in Supplement with respect to particular materials. It is sufficient to note here that current should be passed through the heating elements in the same direction to cause the heating elements 210, 220 to apply heat to the material 230 in the same direction. In various embodiments, the heating elements 210, 220 can have approximately a width of 2 cm and a length of 10 cm. Other shapes and sizes for the heating elements are contemplated to be within the scope of the present disclosure.
[0088] The heating environment can be a vacuum or can include one or more of inert gas, Ar, N.sub.2, hydrogen, carbon dioxide, oxygen, air, and/or other gases. The heating environment can be varied based on the type of material and type of heating elements.
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[0091] Not every components of a conveyor system is shown or described, as persons skilled in the art will recognize and understand such components. For example, a conveyor system that moves the conveyor strip can include rollers, motors, and controllers, among other components. A controller (not shown) can control an electrical source to heat the heating elements and can control the conveyor system to advance the material. Additionally, the conveyor strip can be used for other purposes, such as post-treatment of solid materials which will be described in connection with
[0092] The embodiments of
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[0094] In various embodiments, the heating bar 530 UHS system can be applied to a coating 510 process involving steel powder. As an example, in the coating process, a steel powder (e.g., powder mixture of elemental metals, i.e. Fe, Mn, Ni, Cr, 1-5 μm powder size) with 3-5 wt % polymer binder can be dispersed in ethanol to make a slurry. The viscosity of the slurry can be controlled by tuning the concentration of the metal powders and polymer binder for different coating techniques, including spray coating and doctor blade. The powder slurry can then deposited on a steel substrate or the pipe wall with a wet thickness of ˜5 mm. After the coating layer dries in air, a carbon heating bar with a temperature of ˜1500° C. can be closely run over the coating layer to sinter the coating into a dense steel layer. After the UHS sintering process, the area of the coating layer close to the carbon heating bar was sintered into dense and shiny steel in about five seconds. Cross-sectional SEM image show that the sintered steel is about 1 mm thick, dense, and has a tight binding with the steel substrate (Supplement B).
[0095] Accordingly, various systems for performing the UHS process are described above. The following paragraphs will describe applications of the UHS process for various structures and uses.
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[0097] Uniform temperature distribution of the UHS systems and processes enable the structures to shrink uniformly in every direction, which maintains the form of the printed structures 612, 622, 632, 642 after UHS sintering. Thus, the UHS process maintains the composition and structure of the devices after sintering 612, 622, 632, 642 to achieve functional devices. In various embodiments, the sintered 3D-printed structures 612, 622, 632, 642 can maintain excellent mechanical, electrical, optical, thermal, acoustic, magnetic, and other physical and chemical properties, after undergoing the UHS process. In various embodiments, the 3D-printed structure can be used as support materials for other applications, such as catalysis. In various embodiments, the UHS systems and processes can be used to sinter complex porous 630 or textile-like porous structures 640. The porous structures 630 can be 3D or 2D structures, which can have various morphologies and can be random or ordered structures. The porosity and pore size of the porous structures 630 and vary. In various embodiments, 2D textile-like structures 642 that have gone through the UHS process can possess flexibility. In accordance with aspects of the present disclosure, the UHS systems and processes disclosed herein (e.g.,
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[0099] In aspects of the present disclosure, the UHS systems and processes disclosed herein (e.g.,
TABLE-US-00001 TABLE 1 Metals W, Fe, Cu, Mn, Ni, Al, Zn, Ti, Mg, Cr, Co, Ta, V, Nb, Mo, Au, Ag, Pt, Pd, Sn, Zr, and other metals. Alloys and metallic Fe-based, Cu-based, Ti-based, Ni-based, Al-based, Mg-based, glasses Zr-based, and other alloys and metallic glasses. High entropy alloys FeCoNiCrMn, TiZrVNbTa, Co.sub.1.5CrFeNi1.5Ti, Al.sub.0.2Co.sub.1.5CrFeNi.sub.1.5Ti, AlCoCrFeNi, Cu.sub.0.5NiAlCoCrFeSi, CoCrFeNiCu, CoCrFeNiMn, CoCrFeNiV, MoNbTaVW, MoNbTaW, AlB.sub.xMnNiTi, AlCo.sub.xCrCu.sub.0.5FeNi, Al.sub.xCrCuFeMnNi, CoCuFeMnNi, Al.sub.xC.sub.0.2CuFeMnNi, MoTiVFeNiZrCoCr, ZrTiCuNiBe, PdNiCuP, LaAlNiCu, and CuZrAlY, NbMoTaW, VNbMoTaW, CoCrFeNiCuAl.sub.0.5, VCuFeCoNi, Al.sub.0.5CrFeCoNi, Ti.sub.2CrCuFeCoNi, AlTiVYZr, ZrTiVCuNiBe, CrFeCoNiAlCu.sub.0.25, Al.sub.3CoCrCuFeNi, Ni.sub.xCo.sub.0.6Fe.sub.0.2—Cr.sub.ySi.sub.zAlTi.sub.0.2, BeCoMgTi, BeCoMgTiZn, CuNiCoZnAlTi, AlCoCrFeNiNb.sub.x, BiFeCoNiMn, CoCrCuFeNiTi.sub.x, AlCoCrFeNiTi.sub.x, TaNbHfZrTi, TaNbMoW, TaNbVMoW, and CrCoCuFeNiAl.sub.0.5, NbCrMo.sub.0.5Ta.sub.0.5TiZr, NbCrMo.sub.0.5Ta0.5TiZr, Ti.sub.0.8CoCrCuFeNi, NbTiAlVTaLa.sub.x, CoCrFeNiCu, and CoCrFeNiAl, TixCoCrCuFeNi, (Ti, Zr, Hf)—(Ni, Cu)—Al, (Fe, Co, Ni)—(Zr, Hf, Nb, Ta, Mo, W)—B, Cu.sub.0.5NiAlCoCrFeSi, SrCaYbMgZn, Zn.sub.20Ca.sub.20Sr.sub.20Yb.sub.20(Li.sub.0.55Mg.sub.0.45).sub.20, Fe.sub.64Mo.sub.14C.sub.15B.sub.6Er.sub.1, Zr.sub.41Ti.sub.14Cu.sub.12.5Ni.sub.10Be.sub.22.5, Mg.sub.65Cu.sub.25Y.sub.9Gd.sub.1, Pr.sub.60Al.sub.10Ni.sub.10Cu.sub.20, Ce.sub.62Al.sub.10Cu.sub.20Co.sub.3Ni.sub.5, (Ti.sub.33Zr.sub.33Hf.sub.33).sub.50(Ni.sub.50Cu.sub.50).sub.40Al.sub.10, (Ti.sub.25Zr.sub.25Hf.sub.25Nb.sub.25).sub.70(Ni.sub.50Cu.sub.50).sub.20Al.sub.10, (Ti.sub.33Zr.sub.33Hf.sub.33).sub.70(Ni.sub.33Cu.sub.33Ag.sub.33).sub.20Al.sub.10, Ni—Al—Cu—Co—Ti—V—Zn—Zr, TiZrHfTaNb, PdPtNiCuP, and other alloy compositions Ultrahigh-temperature Ni superalloy, Nb—Si Alloys, Mo—Si—B Alloys, IrRhNbNi, alloys PtAlTa, and other high-temperature alloys. Intermetallics Zr.sub.5Si.sub.3, Ti.sub.5Si.sub.3, MoSi.sub.2, TiSi.sub.2, NiAl, NiTi, Cu.sub.3Sn, MgCu.sub.2, Ag.sub.3Sn, Cu.sub.3Sn, FeCo, MgZn.sub.2, MgNi.sub.2, and other intermetallics.
[0100] In various embodiments, metals and alloys can be sintered in the form of special structures, such as 3D-printed structures as described above in connection with
[0101] In aspects of the present disclosure, the USH systems and processes disclosed herein (e.g.,
TABLE-US-00002 TABLE 2 Piezoelectric and PZT, PMNT (Pb(Mg1/3Nb2/3)O3—PbTiO3), ferroelectric PZNT(Pb(Zn1/31/3Nb2/3)O3—PbTiO3)PbTiO3, ceramics KNN(K1/2Na1/2NbO3), BaTiO3(A═Ca, B═Zr, Sr), BZT-xBCT((1-x)Ba(Zr0.2Ti0.8)O3-x(Ba0.7Ca0.3)TiO3), ZnO, and other piezo/ferroelectric ceramics Ionic conductor La.sub.2Mo.sub.2O.sub.9, LaGaO.sub.3, Ba.sub.2In.sub.2O.sub.5, YSZ, LaAlO.sub.3, garnet, Al.sub.2O.sub.3, Li ion and their thin conductors, Na ion conductors, Mg ion conductors, Al ion films conductors, Ag ion conductors, H ion conductors, O ion conductors, and other ion conductors. Ultra-High HfC, TaC, ZrC, NbC, TiC, WC, VC, ThC, HfN, TaN, TiN, ThN, Temperature ZrN, TiCN, TiC, TiN, MgO—BeO—Al.sub.2O.sub.3, ZrB.sub.2, Al.sub.2O.sub.3, BN, VB.sub.2, Ceramics TiB.sub.2, HfB.sub.2, B.sub.4C, and other ultrahigh temperature ceramics.
[0102] In various embodiments, the ceramics can also be sintered in the form of special structures, such as 3D-printed structures as described above in connection with
[0103] In aspects of the present disclosure, the UHS systems and processes disclosed herein (e.g.,
TABLE-US-00003 TABLE 3 Glass silicate glass, soda-lime glass, borosilicate glass, lead glass, aluminosilicate, Al2O3—Si2O3, Al2O3—Si2O3—B2O3, P2O5, GeO2, As2O5, Li2O—Al2O3—SiO2, MgO—Al2O3—SiO2, Na2O—Al2O3—SiO2, ZnO—Al2O3—SiO2, BaO—TiO2—Al2O3—SiO2, BaO—TiO2—SrO—Al2O3—SiO2, MgO—CaO—SiO2—P2O5, Fe2O3—CaO•SiO2—B2O3—P2O5, Na2O—CaO—Al2O3—SiO2, Na2O—CaO—B2O3—SiO2, Na2O—CaO—Al2O3—B2O3—SiO2, Na2O—CaO—SiO2, and other glass materials or their composites. Glass (energy Multi-layer glass: glass-TCO-(a-Si)-TCO-glass; efficiency) glass-TCO-(a-Si)-Al-glass (Transparent conducting oxide is called as “TCO”) BaTiO3 (BT) and PbTiO3 (PT) doped glass BaTiO3—V2O5—B2O3 SiO2—ZnO SiO2—TiO2 VO2—SiO2—TiO2 Glass foam: glass-carbon composite Transparent Y.sub.2O.sub.3, Y.sub.3Al.sub.5O.sub.12, MgAl.sub.2O.sub.4, MgF.sub.2, ZnS, ZnSe, Al.sub.23O.sub.27N.sub.5, Al.sub.2O.sub.3 ceramics Tb.sub.3Al.sub.5O.sub.12, Tm.sub.3Al.sub.5O.sub.12, Lu.sub.2O.sub.3, Sc.sub.2O.sub.3, A.sub.2B.sub.2O.sub.7, CaF.sub.2, SrF.sub.2, BaF.sub.2, CsI, ZnSe, Sr.sub.5(PO.sub.4).sub.3F, Lu.sub.2O.sub.3, Lu.sub.3Al.sub.5O.sub.12, MgO, Y—ZrO.sub.2, YAG, YSZ, and other transparent ceramics or their composites.
[0104] In various embodiments, the glass or transparent ceramics can also be sintered in the form of special structures, such as 3D-printed structures as described above in connection with
[0105] In aspects of the present disclosure, the UHS systems and processes disclosed herein (e.g.,
TABLE-US-00004 TABLE 4 Ultra-High HfC, TaC, ZrC, NbC, TiC, WC, VC, ThC, HfN, TaN, TiN, ThN, Temperature ZrN, TiCN, TiC, TiN, MgO—BeO—Al.sub.2O.sub.3, ZrB.sub.2, VB.sub.2, TiB.sub.2, HfB.sub.2, Ceramics B.sub.4C, and other composties or high entropy ultrahigh temperature ceramics. Super hard Borides, carbides, nitrides, and other super hard materials. materials Examples: HfC, TaC, ZrC, NbC, TiC, WC, VC, ThC, HfN, TaN, TiN, ThN, ZrN, TiCN, TiC, TiN, VB.sub.2, TiB.sub.2, HfB.sub.2, WC-Co, β-SiC, ZrC, ZrB, ZrB.sub.2, WB.sub.4, MnB.sub.4, ReB.sub.2, B.sub.4C, (AlCrNbSiTiV)N, and other composties or high entropy super hard materials.
[0106] In various embodiments, the borides, carbides, and nitrides can also be sintered in the form of special structures, such as 3D-printed structures as described above in connection with
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[0108] In various embodiments, the bilayer or multilayer structures can be ion conductors/solid state electrolytes (SSEs). By developing bilayer ceramics as solid state electrolytes, the advantages of different electrolytes can be combined to form multifunctional SSEs with superior performance in solid state batteries. For example, garnet can act as negative side for stable interface with Li metal, and another layer having good interface with cathode can be on the positive side. Other bilayer or multilayer thin films (e.g., three or more layers) can also be SSEs, and other bilayer and multilayer structure materials are also contemplated to be within the scope of the present disclosure.
[0109] In various embodiments, the UHS process can be used to sinter metal and alloy bilayers and multilayers. The composition of each layer 810-826 can be any metals, alloys, and the bulk metal glasses (BMG). The composition of the high temperature sintered metals, alloys, and BMG can be any metals, alloys, metallic glass, intermetallics, and other metals and alloys and their composites. The UHS process enables BMG and crystal compositions to be successfully co-sintered to form bilayer or multilayer structures, which combine both mechanical advantages of BMGs and crystals. Due to the short sintering time, the diffusion between the layers is very small/minimized (such as less than 10 μm) so that each layer can maintains the original structure. As an example, Fe-based BMG/crystal bilayer can be co-sintered using the UHS process. XRD patterns show pure crystal and glass phases of each layer (Supplement B), indicating no obvious side reactions between layers. The bilayer design can also be extended to other metal systems. To further improve the mechanical properties, some crystal phases can be added to the BMG layer to increase the ductility (Supplement B). In this case, the BMG compositions with low glass form ability can be used to in situ create some crystal phase in BMG layer. Due to the fast sintering rate, other crystal phase can also be added to the BMG layer without cross diffusion.
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[0111] As an example, composite SSEs can make use of advantages of different compositions to achieve superior SSEs. By introducing the melting glass state, composite SSEs can be sintered at lower temperature and form denser structure. As an example, a glass-ceramic composite SSE can be sintered by adding Li.sub.3PO.sub.4 in LLZTO garnet, where Li.sub.3PO.sub.4 can melt at high temperature and weld with LLZTO particles to form a dense composite pellet. EDS mapping indicates no obvious cross-doping (Supplement,
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[0118] The need for safer rechargeable batteries that avoid the use of flammable liquid organic electrolyte has motivated the development of solid-state electrolytes (SSEs), such as lithium phosphorus oxynitride (LiPON) and garnet-based ceramic compounds. SSE thin films (less than 10 μm) that feature a high ionic conductivity of >10.sup.−4 S/cm are desirable to achieve high energy and power densities. Various methods have been developed to synthesize thin-film ceramic SSEs (e.g., garnet), but they present challenges in sintering thin film electrolyte and cause severe Li and Na loss and corresponding low ionic conductivities. Other methods provide solid-state thin-film batteries with a low current density of 50-800 μA/cm.sup.2, but large-scale applications (e.g., electric vehicles) require a current density of up to 3-10 mA/cm.sup.2.
[0119] The present disclosure provides systems and processes to synthesize thin-film ceramic SSEs using the UHS process and will be referred to herein as “printing and radiative heating”, or PRH. PRH provides a solution-based and printable technique for synthesizing ceramic thin film SSEs with improved scalability. PRH operates using sintering temperatures up to 1500° C. for a short period of time (e.g., three seconds). The rapid heating enables the formation of a dense, polycrystalline thin-film structure, but with negligible volatile element loss due to the short sintering time. In the PRH process, a precursor film is printed on a substrate 1502 with a thickness that is tuned by controlling the ink concentration and wet thickness. The air-dried precursor film is then placed in close contact to a radiative heating strip (e.g., about 1500° C.) for rapid close-proximity sintering 1504 by using the UHS process, as shown at the top of
[0120] The PRH sintering process is based on radiative heating, which is not material specific and can be applied to sinter a wide range of compositions. For example, the universality of the PRH process can be used to fabricate Li.sub.0.3La.sub.0.567TiO.sub.3 (LLTO), Li.sub.1.3Al.sub.0.3Ti.sub.1.7(PO.sub.4).sub.3 (LATP), β-Al.sub.2O.sub.3, and PbZr.sub.0.52Ti.sub.0.48O.sub.3 (PZT) thin films from precursor ink solutions (Supplement B), all of which contain volatile components. LLTO, LATP, and β-Al.sub.2O.sub.3 are high performance Li-ion and Na-ion conductors whose thin films face the challenge of controlling Li/Na loss during synthesis. The PRH process can print the LLTO, LATP, and β-Al.sub.2O.sub.3 precursor inks on an Al.sub.2O.sub.3 substrate by spray coating, followed by high-temperature (1500° C.) sintering for about 3-5 seconds which provides uniform and dense thin films with thicknesses of 5-10 μm (Supplement B). The LATP and LLTO thin films can be sintered in air to prevent the potential reduction of Ti.sup.4+. Similar to the LLZTO thin film, no obvious cross-doping or side reactions between the SSE layer and substrate was observed, according to EDS mapping (Supplement B). The grain boundaries of the sintered thin films were well merged due to the melting effect at high sintering temperature. Furthermore, due to the rapid sintering process within three seconds, the Li/Na loss in the LATP, LLTO, and β-Al.sub.2O.sub.3SSEs was minimized, which is confirmed from the pure phases in the XRD patterns (Supplement, Figure S12-S14).
[0121] The capability of the PRH process to avoid/mitigate elemental loss can be applied to materials containing other volatile elements, such as Pb. The evaporation of Pb at high temperature is one of the main challenges to fabricating PZT, a high-performance piezoelectric ceramic. Conventional fabrication processes involve the low-temperature (˜500-800° C.) treatment of sol-gel deposited PZT thin films to avoid/mitigate Pb loss and cracking during sintering. However, low-temperature-treated PZT thin films generally have poor crystallinity, which can affect the piezoelectric behavior of the thin films. In contrast, the PRH process provides a much higher sintering temperature (˜1500° C.) to achieve a dense PZT thin film with excellent crystallinity, while the short sintering time greatly minimizes the Pb loss. As an example, PZT precursor ink can be directly printed on an Al.sub.2O.sub.3 substrate, followed by rapid sintering at 1500° C. for about three seconds. An insufficient sintering time or low sintering temperature results in porous or amorphous PZT thin films, while prolonged sintering or a high sintering temperature lead to severe Pb loss and corresponding phase changes (Supplement B). However, optimized PRH-sintering conditions result in a PZT thin film that demonstrates a dense structure with well-merged grains, while the EDS mapping illustrates the uniformly distributed Pb element (Supplement B). The XRD pattern shows a pure PZT phase without secondary phases caused by Pb loss (Supplement B), which further demonstrates the unique capability of the PRH process for the synthesis of ceramic thin films with volatile compositions. Accordingly, the PRH process has the ability to mitigate/prevent volatile element loss for superior compositional control (Supplement B).
[0122] Besides single-component thin films, the PRH process can be used to rapidly sinter composite thin films, as the short sintering time can effectively prevent side-reactions between materials. As an example, the PRH process can be used to sinter a LiBO.sub.2-LLZTO composite SSE thin film. The resulting material features LiBO.sub.2 uniformly distributed between the LLZTO grains with conformal interfaces and no obvious co-doping, likely due to the short sintering time of three seconds, even with a high sintering temperature of 1200° C. In contrast, sintering the same materials in a conventional furnace for one hour results in a porous structure with large reacted grains rather than a dense composite (Supplement B). Thus, prolonged sintering in a conventional furnace leads to significant cross-diffusion and side reactions between components, while the PRH process is able to avoid/mitigate such side-reactions to generate composite structures (Supplement B). The capability to fabricate a broad range of both single and multi-component compounds indicates the universality of the PRH process for manufacturing high-performance ceramic thin films.
[0123] The thin films sintered by the PRH process can have structure, composition, crystallinity, morphology, or other changes and have excellent mechanical, electrical, ionic, optical, thermal, acoustic, magnetic, and other physical and chemical properties. The thickness of the thin film can be 1 nm to millimeters. The composition of the thin film and the substrate can be any solid materials, including ceramics, glasses, metals, alloys, carbons, polymers, and other solid state materials and their composites.
[0124] With continuing reference to the bottom portion of
[0125] Due to the conformal interfaces, the interfacial resistance of this PRH-sintered battery was as low as about 100 Ω.Math.cm.sup.2 at 60° C. (Supplement B), which is considerably smaller than other co-sintered all solid-state batteries. The voltage profiles of the printed battery exhibited typical plateaus of the LiCoO.sub.2 cathode (Supplement B), further demonstrating the successful synthesis of LiCoO.sub.2 via the rapid PRH process. Additionally, the battery's rate and cycling performance show good capacity retention and excellent cycling stability over about 450 cycles (Supplement B). Specifically, the initial specific capacity was about 87 mA.Math.h/g at a current density of 30 mA/g. The capacity slightly decreases with increasing current density but has little change over the cycles at each current density (Supplement B). After about 450 cycles, the interfacial resistance slightly increased to about 170 Ω.Math.cm.sup.2 (Supplement B), which further demonstrates the excellent stability of the in situ sintered cathode and interface synthesized by the PRH process.
[0126] This PRH process 1510-1540 can be applied to other electrode materials (such as NMC, LiFePO.sub.4, Li.sub.2S, and other Li, Na, K, Mg, Zn electrode materials, etc.) and other ceramics or glass SSEs (such as LLTO, LATP, NASICON, LISICON, Thio-LISICON, Na ion conductors, and other solid state ion conductors or their composites).
[0127]
[0128] In accordance with aspects of the present disclosure, the UHS systems and processes disclosed herein (e.g.,
[0129] In accordance with aspects of the present disclosure, the UHS systems and processes disclosed herein (e.g.,
[0130] UHS can also be applied to co-sinter electrodes with single layer, bilayer, or multilayer SSEs to form fuel cells (with bilayer being a specific instance of multilayer). The anode and cathode are porous structures which allow the oxygen and fuel gas (hydrogen or carbon monoxide, or methane) to diffuse. Due to the short sintering time, the composition of multilayer or composite structures will maintain without or with minimal cross reaction or diffusion.
[0131]
[0132] A process of forming the thermoelectric device can include providing the p-type thin film 1720 on the substrate 1710, providing the n-type thin film 1730 on the substrate 1710, positioning at least one conductive carbon element at a distance of at most 1 centimeter from the p-type thin film 1730 and the n-type thin film 1720, heating the at least one conductive carbon element by electrical current to a temperature between 500° C. and 3000° C., inclusive, and sintering the p-type thin film and the n-type thin film by heat from the at least one heated conductive carbon element. In various embodiments, the at least one heated conductive carbon element can be moved/scanned over the thin films. In various embodiments, the at least one conductive carbon element can cover both of the thin films. The thin films can be sintered simultaneously or sintered sequentially. At least one electrode can be deposited or sintered on at least a portion of the sintered p-type thin film and/or the sintered n-type thin film. The illustrated and described embodiments are exemplary and variations contemplated to be within the scope of the present disclosure. For example, the thermoelectric device may have a different layout than as illustrated. The heating element may be made from another type of conductive material or composition.
[0133]
[0134]
[0135]
[0136] The ability of the UHS process to rapidly and reliably synthesize 2020 a wide range of ceramics enables quick verification of new materials predicted by computation, thus greatly accelerating the screening rate for bulk ceramic materials.
[0137] As an example, lithium garnet compounds (Li.sub.7A.sub.3B.sub.2O.sub.12, A=La Group, B=Mo, W, Sn, Zr) can be used to demonstrate this rapid screening ability enabled by computational prediction and the UHS process. As shown in Supplement,
[0138] As an example of the rapid synthesis and materials screening capability, the computationally predicted Zr- and Sn-based garnet compositions featuring small E.sub.hull values listed in Supplement,
[0139] An advantage of UHS is highly controllable temperature profile (i.e., heating/cooling rate and sintering temperature), which provides excellent tunability for synthesizing ceramics that are challenging to achieve using conventional procedures. For example, DFT computation predicts that Mo-based Li7-garnets have low E.sub.hull values (Supplement,
[0140]
[0141] In various embodiments, the sizes of the materials can be adjusted from millimeters to meters to suit the application, and the size of the UHS system 2110, 2120 can be adjusted accordingly. The sample materials can be in direct contact with the heating elements 2110, 2120 or can be spaced apart from the heating elements 2110, 2120. For each UHS sintering operation, the composition of the sample materials 2130 can be the same or can be different. The composition of the materials 2130 can include, without limitation, ceramics, glass, metal, alloy, carbon, and/or other solid materials.
[0142] Accordingly, described above is are systems and methods that can enable high-throughput fabrication of bulk ceramics for discovering new materials, the sintering of thermally fragile compounds containing volatile components, and the fabrication of 3D printed complex structures and devices that cannot be made by SPS or flash sintering. Moreover, the UHS process can be universally applied to different materials, independent of their electrical characteristics. The rapid sintering enables the potential for scalable roll-to-roll sintering of ceramics by a conveyor strip (
[0143] The UHS systems and process can be extended to a broad range of non-oxide high-temperature materials, including metals, carbides, borides, nitrides, and silicides, due to its high temperature (up to about 3000° C.). Also, UHS systems and processes may be used to fabricate functionally-graded materials (beyond simple multilayers) with minimum undesirable interdiffusion. The ultrafast, far-from-equilibrium nature of the UHS process may produce materials with non-equilibrium concentrations of point defects, dislocations, and other defects or metastable phases leading to desirable properties. In particular, the ultrafast UHS method can potentially produce non-equilibrium grain boundaries, thereby minimizing the detrimental equilibrium segregation of impurities, dopants, and defects (including non-stoichiometric grain boundaries). These are otherwise difficult to avoid in conventional high-temperature fabrication processes. Thus, UHS systems and processes open up new possibilities to mitigate high grain boundary resistance in solid electrolytes, as well as tailor various grain boundary properties for a broad range of other materials beyond solid electrolytes. The UHS method allows a highly controllable and tunable temperature profile to enable excellent control of sintering and microstructural evolution.
[0144] The embodiments disclosed herein are examples of the disclosure and may be embodied in various forms. For instance, although certain embodiments herein are described as separate embodiments, each of the embodiments herein may be combined with one or more of the other embodiments herein. Specific structural and functional details disclosed herein are not to be interpreted as limiting, but as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present disclosure in virtually any appropriately detailed structure. Like reference numerals may refer to similar or identical elements throughout the description of the figures.
[0145] The phrases “in an embodiment,” “in embodiments,” “in various embodiments,” “in some embodiments,” or “in other embodiments” may each refer to one or more of the same or different embodiments in accordance with the present disclosure. A phrase in the form “A or B” means “(A), (B), or (A and B).” A phrase in the form “at least one of A, B, or C” means “(A); (B); (C); (A and B); (A and C); (B and C); or (A, B, and C).”
[0146] It should be understood that the foregoing description is only illustrative of the present disclosure. Various alternatives and modifications can be devised by those skilled in the art without departing from the disclosure. Accordingly, the present disclosure is intended to embrace all such alternatives, modifications and variances. The embodiments described with reference to the attached drawing figures are presented only to demonstrate certain examples of the disclosure. The embodiments described and illustrated herein are exemplary, and variations are contemplated to be within the scope of the present disclosure. Various embodiments disclosed herein can be combined in ways not expressly described herein, and such combinations are contemplated to be within the scope of the present disclosure. Other elements, steps, methods, and techniques that are insubstantially different from those described above and/or in the appended claims are also intended to be within the scope of the disclosure.