WO2018156218A1 - Improved performance of technical ceramics - Google Patents

Improved performance of technical ceramics Download PDF

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Publication number
WO2018156218A1
WO2018156218A1 PCT/US2017/060066 US2017060066W WO2018156218A1 WO 2018156218 A1 WO2018156218 A1 WO 2018156218A1 US 2017060066 W US2017060066 W US 2017060066W WO 2018156218 A1 WO2018156218 A1 WO 2018156218A1
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WO
WIPO (PCT)
Prior art keywords
ceramic particle
oxide
sintering aid
aid film
chosen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2017/060066
Other languages
English (en)
French (fr)
Inventor
Christopher BARTEL
Alan W. Weimer
Rebecca Jean O'TOOLE
Maila KODAS
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Colorado System
University of Colorado Colorado Springs
Original Assignee
University of Colorado System
University of Colorado Colorado Springs
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to KR1020237010883A priority Critical patent/KR102731530B1/ko
Priority to US16/347,585 priority patent/US11613502B2/en
Priority to JP2019523863A priority patent/JP2020513387A/ja
Priority to CN201780075924.XA priority patent/CN110382440A/zh
Priority to KR1020197016132A priority patent/KR102517378B1/ko
Priority to EP17897326.9A priority patent/EP3535230A4/en
Application filed by University of Colorado System, University of Colorado Colorado Springs filed Critical University of Colorado System
Publication of WO2018156218A1 publication Critical patent/WO2018156218A1/en
Anticipated expiration legal-status Critical
Priority to JP2022129781A priority patent/JP2022166197A/ja
Priority to US18/127,498 priority patent/US12215060B2/en
Priority to JP2024145029A priority patent/JP2024164202A/ja
Priority to US19/044,398 priority patent/US20250197296A1/en
Ceased legal-status Critical Current

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    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient
    • C04B2235/9615—Linear firing shrinkage
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M2008/1293—Fuel cells with solid oxide electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/0071—Oxides
    • H01M2300/0074—Ion conductive at high temperature
    • H01M2300/0077—Ion conductive at high temperature based on zirconium oxide
    • Y—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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • 8 mol %) yttria-stabilized cubic zirconia (“8YSZ”) has practical uses in Solid Oxide Fuel Cells (“SOFCs”), but suffers from some inherent shortcomings such as high operating temperature, high sintering temperature, low ionic conductivity, and poor mechanical strength.
  • SOFCs Solid Oxide Fuel Cells
  • alumina AI2O3
  • ball milling a process using high-energy collision of hard balls with a powder mixture of the AI2O3 and 8YSZ, has been shown to lower the sintering temperature and increase mechanical strength and ionic conductivity.
  • 8YSZ is most commonly used in SOFCs as the solid electrolyte because it is a chemically stable and inexpensive option.
  • the SOFC must be operated at high
  • 3D printing including Fused Deposition Modeling (FDM) lays down layers of ink material, with the intent that the layers fuse together, forming a laminated 3-dimensional part.
  • 3D printing, including FDM lays down layers of ink material, with the intent that the layers fuse together, forming a laminated 3- dimensional part.
  • FDM Fused Deposition Modeling
  • the final parts or output from 3D printing have not been consistently good.
  • the final 3D parts are often fragile, or delaminate easily.
  • the laminate 3D parts may not bond as well in the Z axis as they do in the X-Y planes, so that a force from the side may easily fracture the part.
  • the present invention relates, in part, to a discovery of a ceramic particle comprising a core substrate chosen from yttria-stabilized zirconia, partially stabilized zirconia, zirconium oxide, aluminum nitride, silicon nitride, silicon carbide, and cerium oxide; and a conformal coating of a sintering aid film having a thickness of less than three nanometers and covering the core substrate.
  • the conformal coating of the sintering aid film covering the core substrate has a thickness of from less than one (1) nanometer to one (1) nanometer.
  • the conformal coating of the sintering aid film has a thickness of about two (2) nanometers.
  • the conformal coating of the sintering aid film is a uniform, conformal coating of the core substrate.
  • the conformal coating of the core substrate includes well-distributed islands of film across the surface of the ceramic particles.
  • Disclosed herein is a ceramic particle wherein the core comprises yttria-stabilized zirconia or partially stabilized zirconia, and the sintering aid film comprises alumina.
  • a ceramic particle comprising a core substrate including a conformal coating of a sintering aid film having a thickness of less than three nanometers, wherein the sintering aid film covering the core substrate is formed by atomic layer deposition ("ALD").
  • ALD atomic layer deposition
  • the ceramic particle with a conformal coating of a sintering aid film is prepared using one cycle of atomic layer deposition of the sintering aid film; and then sintered in air at about 1350 degrees Celsius for about two (2) hours.
  • the ceramic particle is prepared with from about one cycle to about nine cycles of atomic layer deposition of a sintering aid.
  • Another embodiment of the invention is a solid oxide fuel cell electrolyte comprising a ceramic particle as disclosed herein, including a core substrate and a conformal coating of a sintering aid film having a thickness of less than three nanometers and covering the core substrate.
  • FIG. 1 is a graphical representation of Relative Density measured volumetrically for different sample types having been sintered in air at 1350°C for 2 hours as a function of the number of ALD cycles, and wherein "BM" represents a Prior Art ball-milled sample.
  • FIG. 2 is a graphical representation of oxygen ion conductivity at different temperatures in °C, measured using electrochemical impedance spectroscopy for different sample types having been sintered in air at 1350°C for 2 hours, and wherein "BM" represents a Prior Art ball-milled sample.
  • FIG. 3 A is a graphical representation of the relative density (% theoretical) as a function of temperature during constant rate of heating at 10 °C/min heating rate, in dilatometer experiments for all samples analyzed (coated and uncoated).
  • FIG. 3 B is a graphical representation of the relative density (% theoretical) as a function of temperature during constant rate of heating at 15 °C/min heating rate, in dilatometer experiments for all samples analyzed (coated and uncoated).
  • FIG, 3 C is a graphical representation of the densification rate (1 ) as a function of temperature during constant rate of heating at 10 °C/min heating rate, in dilatometer experiments for all samples analyzed (coated and uncoated).
  • FIG. 3D is a graphical representation of the densification rate (1/K) as a function of temperature during constant rate of heating at 15 °C/min heating rate, in dilatometer experiments for all samples analyzed (coated and uncoated).
  • FIG. 4 is a graphical representation of the apparent activation energy of densification as a function of number of ALD cycles, wherein the activation energy was determined from a series of constant rate of heating dilatometer experiments.
  • FIG. 5 is a graphical representation of the decrease in ionic conductivity (S/cm) when decreasing the sintering temperature from 1450 °C to 1350 °C as a function of measurement temperature and number of ALD cycles, wherein conductivity was measured using electrochemical impedance spectroscopy.
  • FIG. 6 is a bar graph showing, for zero to 5 ALD cycles, the increase in GB/R bulk at 300 °C defined as (the ratio of grain boundary resistivity to bulk resistivity after sintering at 1450 °C for 2 h) minus (the ratio of grain boundary resistivity to bulk resistivity after sintering at 1350 °C for 2 h) as measured using electrochemical impedance spectroscopy at 300 °C in air.
  • the invention inter alia also includes the following exemplary embodiments, alone or in combination. It will be understood that the particular embodiments of the invention are shown by way of illustration and not as limitations of the invention. At the outset, the invention is described in its broadest overall aspects, with a more detailed description following.
  • a process comprising adding a thin film of ceramic sintering aid of desired thickness (wt%) to a primary ceramic powder by atomic layer deposition using, for example, an agitated powder reactor, and a product formed by the process.
  • a conformal coating of the sintering aid around each primary ceramic substrate particle improved the fabricated part properties associated with grain boundary phenomena such as impurity scavenging, grain boundary diffusion, grain growth, liquid-phase sintering, ionic conductivity, thermal conductivity, etc., and increased the homogeneity of dense parts compared with conventional techniques such as ball milling, spray drying, or sol-gel processing.
  • Sintering is the process of causing a material to become a coherent or compact, dense mass by applying heat and/or pressure without melting or liquefying the material.
  • densification and “sintering,” and grammatical variations thereof, have the same meaning.
  • a sintering aid helps impart integrity and compressive strength to the material being sintered.
  • the thin film of sintering aid enables facile rheology control by exposing only one surface (the sintering aid), as compared to conventional sintering aid incorporation methods wherein multiple surfaces, and thus multiple surface charges will be present ⁇ i.e., the sintering aid and the primary ceramic).
  • A1N aluminum nitride
  • the thin and pinhole-free conformal coating of an oxide ceramic sintering aid renders the particles resistant to degradation by water, thereby enabling aqueous processing which is critical in, for example, direct ink writing (additive manufacturing).
  • 3 wt% yttrium oxide is a good sintering agent for aluminum nitride.
  • a more detailed description follows.
  • Atomic Layer Deposition (ALD) a thin film deposition technique, is a self- limiting surface reaction that deposits uniform layers of the desired precursor onto the particle surface.
  • TMA trimethylaluminum
  • water one addition of TMA plus one addition of water comprises one cycle.
  • TMA trimethylaluminum
  • the reaction proceeds in a fluidized bed reactor to help ensure coating of all surfaces.
  • AI2O3 was deposited as a conformal coating on 8 YSZ particles at concentrations ranging from approximately ( ⁇ ) 1 to
  • the mass or weight of the alumina in the sintering aid film is from about 0.2 weight percent to about 2 weight percent of the ceramic particle.
  • the addition of AI2O3 reduced the temperature required for sintering by -100 °C and decreases the apparent activation energy of densification.
  • the optimal concentration of AI2O3 was found to be about 2.2 wt% corresponding with about 5 ALD cycles which reduced the apparent activation energy from -700 kJ/mol to -400 kJ/mol.
  • a ceramic particle prepared according to an embodiment of the invention is non-reactive with water.
  • the ink formulation was determined by preparing numerous batches of ink and varying the solids loading and relative polymer amounts in order to obtain the desired rheology for printing with maximum solids vol %.
  • the optimized ink was then used to print 3D structures that were sintered and examined under the SEM.
  • One embodiment of the invention is a material composition for 3D printing, the composition comprising dispersed solids in a colloid, the solids coated conformally with a solid sintering additive. In another embodiment, the dispersed solids are coated
  • the conformal coating is also uniform throughout.
  • the invention inter alia includes the following, alone or in combination.
  • Prior art ball milling of AI2O3 and 8YSZ yields only a reasonably uniform distribution of ceramic and sintering aid.
  • using ALD coating of particles yields precise, uniform, conformal coating of 8YSZ ceramic particles with AI2O3.
  • ALD ALD coating of particles
  • Uniform, conformal coating also allows use of a lower temperature for densification, which will also reduce the tendency for grain sizes / flaw sizes to grow. The lower temperature also appears to reduce the amount of sintering aid needed to be deposited on the substrate particles in order to achieve high density upon part fabrication.
  • the incorporation of the sintering aid as a particle additive will result in particulate inclusions at triple grain junctions in the densified matrix.
  • the sintering aid additive is deposited according to an embodiment of our invention as a conformal coating or a uniform, conformal coating by ALD, the additive will exist as an intergranular amorphous thin film, instead of as particulates.
  • the presence of an intergranular, amorphous, uniform, conformal film coating of the ceramic particles enables lower temperature densification and improved homogeneity of dense parts.
  • Stability is critical for use in 3D printing, or additive manufacturing, and a colloidal gel needs to be prepared from the core/shell substrate/sintering aid particles.
  • colloidal properties are the result of fine timing the dispersion in order to suspend particles in the ink/gel, it is critical to optimize the chemical characteristics of the suspended ceramic particles.
  • the substrate ceramic and the sintering aid there will be two surfaces (the substrate ceramic and the sintering aid) that require stabilization, and the gel formulation will be a compromise of properties for the substrate and sintering aid.
  • Particle ALD coatings there is only one surface to be optimized, that of the sintering aid which surrounds each particle. Hence, it is not only easier to prepare colloidal gels, but also easier to prepare gels that are truly optimized for the system. This improves the preparation of 3D inks / gels having improved flowability for additive manufacturing and ultimately part-to-part reliability.
  • 8YSZ has a high sintering temperature of 1450 °C.
  • AI2O3 has been demonstrated to lower this temperature, similarly reducing the costs of manufacturing SOFCs. It has also shown positive effects on improving ionic conductivity at lower temperatures which would in turn lower the operating temperature of the SOFC. It may be important that ionic conductivity of 8YSZ remain fairly stable when used in SOFCs.
  • the primary equipment used for the dilatometer studies included the dilatometer, planetary centrifugal mixer, hydraulic press, and cylindrical steel die.
  • the dilatometer requires ceramic powder compacts that are cylindrical in shape.
  • 8 YSZ powder, both with and without AI2O3 were mixed with a polymeric binder, which was a solution of 2 wt% poly(vinyl alcohol) (Acros Organics, 98.0-98.8% hydrolyzed, average molecular weight ⁇ 31 ,000-50,000 grams/mole) and 98 wt% deionized water.
  • the binder was incorporated by mixing 4 grams of binder, 20 grams of 8 YSZ powder, and 25 grams of grinding media (Tosoh Corp., 5 mm diameter, YTZ Grinding Media) in a planetary centrifugal mixer for 30 seconds at 1100 rpm.
  • the planetary centrifugal mixer provides sufficient dispersion of the binder throughout the ceramic powder by simultaneously undergoing high speed revolution and rotation, while the grinding media aids in dispersion.
  • the dilatometer comprises a sample holder, furnace, and push rod to measure displacement. A constant force of 35 centinewton (35 cN) was exerted on the push rod to maintain constant contact with the sample being tested as it shrinks during heating. [0029] Each sample was sintered in air. Before the compact was inserted into the dilatometer, the length was measured and recorded using calipers. The compact number was recorded along with the heating test that was to be run. Constant rate of heating
  • the principal equipment for ink formulation is a high precision scale accurate to 0.1 milligrams and a planetary centrifugal mixer.
  • the centrifugal planetary mixer allows thorough mixing of high viscosity inks. It works by orienting the container at 45 ° relative to the vertical axis and spinning the container counterclockwise. As the container spins counterclockwise on its own axis, the container is spun along the vertical axis in a clockwise direction which causes vertical spiral convection and exerts a force of 400 G on the ink, effectively evacuating all air as well.
  • the ink formulation begins with a small container fitted for the planetary mixer, which is where the ink will be made and stored. First, YTZ grinding media is added to aid in mixing.
  • PEI polyethylene imine
  • the final ingredient addition is polyethylene imine (PEI) which is in a 40 wt% solution with water to lower viscosity and allow handling.
  • PEI polyethylene imine
  • One drop was added, or about 0.02 grams, as a flocculant.
  • the ink was mixed one last time with a final solids volume of 43.5 %. The ink was then sealed from air until use.
  • the principal equipment for direct ink writing and sintering of parts includes a 3D printer, oil bath, and high temperature furnace. So that it may operate with very high precision, the 3D printer utilizes magnets to move.
  • the printer was connected to a computer and operated from there using a specifically designed program.
  • a syringe was filled with the prepared 3D ink, and fitted with a tip having a diameter of 330 microns.
  • the oil bath was placed underneath the 3D printer, and the printing substrate was placed in the oil bath.
  • the substrate was a ceramic, and dark in color to allow for visualization of the white ink.
  • the syringe was placed in the printer, and the printer was lowered until just touching the surface of the substrate; then it was raised 200 microns. Rasters, or series of parallel scanning lines, were initiated in order to get the ink flowing smoothly before beginning the print job.
  • the desired shape was selected and once ready, the printer automatically carried out the print job.
  • the piece was removed from the oil bath and left to dry for 48 hours in air. The pieces were sintered in a high temperature tube furnace. The sintering process began with binder burnout, then heated to 1450 °C at a rate of 1.5 °C/min; then held at the maximum temperature for 1 hour. It was then cooled at a rate of 20 °C/ min to room temperature.
  • the principal equipment for ionic conductivity measurements are a mechanical press, a sintering furnace, and an electrochemical impedance spectrometer.
  • 8YSZ powder (coated or uncoated) were mixed with 2-3 drops poly( vinyl alcohol) and pressed to a thickness of -0.5" by a mechanical press. Pressed pellets were then densified in air at either 1350 °C or 1450 °C for 2 h. The sintered pellets were then painted with a conductive platinum paste and inserted into a furnace for the electrochemical impedance spectrometry measurements. Ionic conductivity was measured in air at temperatures ranging from 300- 800 °C.
  • AI2O3 was deposited on commercial 8YSZ powder by means of ALD.
  • the ALD process exhibited a nearly linear growth rate with number of cycles enabling the deposition of AI2O3 at a controllable concentration.
  • the AI2O3 was precisely deposited as a uniform and conformal coating covering each primary 8YSZ particle as a thin amorphous film.
  • the presence of AI2O3 by ALD enables pellets to reach near theoretical density (>94%) after sintering in air for 2 h at 1350C. This same density is not reached for either the YSZ with no AI2O3 or the YSZ with AI2O3 incorporated by ball milling as seen in FIG. 1.
  • FIG. 3 A depicts the relative density (% theoretical) as a function of temperature during constant rate of heating at 10 °C/min heating rate.
  • FIG. 3B depicts the relative density (% theoretical) as a function of temperature during constant rate of heating at 15 °C/min heating rate.
  • the uncoated samples had less relative density than did the coated samples.
  • the densification rate in the initial stage of sintering (relative density ⁇ 80% theoretical) was found to be greater for all coated samples than the uncoated samples at all temperatures within this regime (FIG 3C and FIG. 3D.).
  • the temperature at which the maximum densification rate is obtained is similarly decreased by -100 °C for all coated samples when compared to the uncoated 8YSZ except the 9ALD sample for which the temperature is decreased by ⁇ 100 °C.
  • a reduction in sintering temperature is expected to have deleterious effects on the ionic conductivity of 8YSZ electrolytes due in part to the retention of pores or defects in the microstructure.
  • Ionic conductivity measurements were obtained for 8YSZ (coated and uncoated) using electrochemical impedance spectrometry following two sintering procedures - 1450 °C for 2 h and 1350 °C for 2 h. The decrease in conductivity
  • Low temperature (300 °C) electrochemical impedance spectrometry can be used to decouple the relative contributions of the grain boundaries and the grain interior to the total resistivity of the electrolyte.
  • the increase in grain boundary resistivity is significant for the uncoated sample but less so for the coated samples, particularly for the 5 ALD sample (FIG. 6). This suggests that the ALD coatings sufficiently alter the microstructure, and particularly the grain boundary microstructure, such that resistivity at the grain boundary is reduced following reduced temperature sintering compared with the uncoated sample.
  • colloidal gel ink formulations were developed for 8 YSZ with 0, 1 , and 3 AI2O3 ALD cycles.
  • the optimum solids volume percentage was found to be between 43.5 vol% to just under 44 vol%.
  • a printable 8 YSZ ink can be made with 44 vol% solids, but it is prone to thickening with time, causing the printer to clog and stall, rendering the printed part unusable.
  • inks consisting of 43.5 vol% solids could be printed reliably, and had a high viscosity to resist deformation and retain their shape after extrusion.
  • the optimized ink formulation for 8 YSZ was then extended to 8YSZ with 1 and 3 AI2O3 ALD cycles.
  • the ink formulation for 8YSZ with 1 AI2O3 AID cycle was 42.4 vol% 8YSZ AI2O3 powder, 42.0 vol% water, 11.4 vol% Darvan, 4.1 vol% hydroxypropyl methylcellulose, and 0.2 vol% PEL Additionally, the ink formulation for 8YSZ with 3
  • AI2O3 ALD cycles was 39.4 vol% 8YSZ/AI2O3 powder, 44.8 vol% water, 12.2 vol%
  • the rheology of the ink chosen is highly dependent on the surface chemistry of the ceramic particles.
  • a solution of 8 YSZ and water has a pH of approximately 7 and, with a basic isoelectric point, the 8YSZ surface becomes positively charged. Van der Waals forces cause the 8YSZ particles to agglomerate, so the a negatively changed polyelectrolyte, Darvan, was added to homogeneously disperse the 8YSZ powder through electrosteric repulsion.
  • the dispersant allows for ink homogeneity, but a flocculant must be added to ensure the ink is stronger and has desirable mechanical properties to resist deformation.
  • the flocculant added was PEI, which is a positively charged polyelectrolyte.
  • Viscosity was adjusted by adding hydroxypropyl methylcellulose, and ensured that the ink would not separate out into individual components. The final result was a homogenous, viscous ink that prints without separating and holds it shape during extrusion, drying, and densification.
  • the ink formulations for 8 YSZ with 0, 1 , and 3 AI2O3 ALD cycles required similar amount of dispersant and flocculant, only varying slightly in water and Darvan content, to control the particle surface chemistry and produce an ink with required rheology.
  • the ink formulation is dependent on the particle surface chemistry, and at 1 and 3 AI2O3 ALD cycles, only a sub-monolayer of AI2O3 is present.
  • the particle surface consists of both 8YSZ and ⁇ 2 ⁇ 3. Therefore, it can be seen that the particle surface chemistry of both 8YSZ and 8YSZ with 1 and 3 AI2O3 cycles respond similarly to the polyelectrolytes utilized in the production of the colloidal gel ink.
  • dimensions of the sintered pieces on average are 27.3 mm by 26.9 mm, which is a shrinkage of about 40 %. This is due to the elimination of water, hydroxypropyl methylcellulose, Darvan, and PEI from the part and the reduction of pores from between ceramic grains.
  • a ceramic particle has a conformal coating of the sintering aid film covering the core substrate, and is formed by atomic layer deposition using a system chosen from a fluid bed reactor, a vibrating reactor, a rotating reactor, a spatial system wherein precursor gases are separated in space, and a batch reactor, and any desired combinations thereof.
  • a ceramic particle according to an embodiment of the invention has a core comprising cerium oxide and a sintering aid film chosen from alumina, titanium oxide, yttrium oxide, calcium oxide, iron oxide, copper oxide, chromium oxide, boron oxide, silicon dioxide, nickel oxide, and any desired combinations thereof.
  • a sintering aid film chosen from alumina, titanium oxide, yttrium oxide, calcium oxide, iron oxide, copper oxide, chromium oxide, boron oxide, silicon dioxide, nickel oxide, and any desired combinations thereof.
  • the core of the ceramic particle comprises aluminum nitride
  • the sintering aid film is chosen from yttrium oxide, magnesium oxide, calcium oxide, silicon dioxide, lanthanum oxide, and any desired combinations thereof.
  • a ceramic particle according to an embodiment of the invention has a core chosen from silicon nitride and silicon carbide, and the sintering aid film is chosen from yttrium oxide, alumina, magnesium oxide, lutetium oxide, ytterbium oxide, and any desired combinations thereof.
  • a colloidal gel ink formulation with maximum solids loading was determined to reliably produce 8YSZ ceramic parts that did not warp or deform during sintering.
  • the colloidal gel ink formulation for 8YSZ powder was then modified for 8YSZ powder with an AI2O3 coating by 1 and 3 AI2O3 ALD cycles, and the formulation was determined to reliably print ceramic parts from core/shell 8YSZ/AI2O3 powder that did not warp or deform during sintering.
  • the addition of an AI2O3 coating to 8 YSZ powder reduces the sintering temperature in comparison to uncoated 8 YSZ powder. That is, one can print and sinter/densify uncoated 8YSZ powder, but it would require higher
  • 3 YSZ represents zirconia doped with three mole percent (3 mol %) yttria. 3 YSZ is also referred to as "Y-TZP.”
  • the colloidal gel ink formulation for 3YSZ (partially stabilized zirconia or Y-TZP), conformally coated with alumina by atomic layer deposition, was adjusted and optimized.
  • ALD coating of zirconium ceramic particles with alumina should be beneficial as a sintering aid for any level of yttrium doping of zirconium oxide.
  • the amount of doping can be varied slightly from about 3 percent to about 8 percent in order to obtain different properties.
  • the dopant concentration in zirconia dictates the crystal structure of the material.
  • Zirconia doped with three mole percent, 3 YSZ is the mechanically strong tetragonal phase, and has been used in dental ceramics.
  • ALD Alumina toughened zirconia
  • the number preceding the "YSZ" indicates the molar percentage doping by yttria. 8 mol% doping optimally stabilizes the cubic crystal structure of Zr02 which is preferred for oxygen ion conduction (e.g., in a solid
  • 8YSZ is commonly referred to as “yttria-stabilized zirconia,” “yttria-stabilized cubic zirconia,” “cubic stabilized zirconia,” or “fully stabilized zirconia.”
  • 3YSZ can also be referred to as “yttria-stabilized zirconia,” but is more commonly referred to "tetragonal zirconia polycrystal,” “TZP,” “Y-TZP,” “tetragonal polycrystalline zirconia”, “yttria-stabilized tetragonal zirconia”, or “partially stabilized zirconia.”

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US16/347,585 US11613502B2 (en) 2016-11-07 2017-11-04 Core-shell ceramic particle colloidal gel and solid oxide fuel cell electrolyte
JP2019523863A JP2020513387A (ja) 2016-11-07 2017-11-04 工業用セラミックスの改良された性能
CN201780075924.XA CN110382440A (zh) 2016-11-07 2017-11-04 改进技术级陶瓷的性能
KR1020197016132A KR102517378B1 (ko) 2016-11-07 2017-11-04 테크니컬 세라믹의 개선된 성능
EP17897326.9A EP3535230A4 (en) 2016-11-07 2017-11-04 IMPROVED PERFORMANCE OF TECHNICAL CERAMICS
KR1020237010883A KR102731530B1 (ko) 2016-11-07 2017-11-04 테크니컬 세라믹의 개선된 성능
JP2022129781A JP2022166197A (ja) 2016-11-07 2022-08-16 工業用セラミックスの改良された性能
US18/127,498 US12215060B2 (en) 2016-11-07 2023-03-28 Performance of technical ceramics
JP2024145029A JP2024164202A (ja) 2016-11-07 2024-08-27 工業用セラミックスの改良された性能
US19/044,398 US20250197296A1 (en) 2016-11-07 2025-02-03 Performance of technical ceramics

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