EP4669705A2 - Liant durcissable par rayonnement actinique ou par faisceau d'électrons pour matériaux céramiques - Google Patents

Liant durcissable par rayonnement actinique ou par faisceau d'électrons pour matériaux céramiques

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Publication number
EP4669705A2
EP4669705A2 EP24775615.8A EP24775615A EP4669705A2 EP 4669705 A2 EP4669705 A2 EP 4669705A2 EP 24775615 A EP24775615 A EP 24775615A EP 4669705 A2 EP4669705 A2 EP 4669705A2
Authority
EP
European Patent Office
Prior art keywords
binder composition
acrylate functional
curable binder
ceramic
acrylate
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.)
Pending
Application number
EP24775615.8A
Other languages
German (de)
English (en)
Inventor
Gary Sigel
Daniel Baumann
Donovan HENSLEY
Pamela ABBOTT
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.)
Miltec Uv International LLC
Original Assignee
Miltec Uv International LLC
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
Application filed by Miltec Uv International LLC filed Critical Miltec Uv International LLC
Publication of EP4669705A2 publication Critical patent/EP4669705A2/fr
Pending legal-status Critical Current

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Classifications

    • 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
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C04B26/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B26/06—Acrylates
    • 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
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B26/16—Polyurethanes
    • 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
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B26/18—Polyesters; Polycarbonates
    • 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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C04B35/486—Fine ceramics
    • 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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/63424—Polyacrylates; Polymethacrylates
    • 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
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
    • C04B2235/3203—Lithium oxide or oxide-forming salts thereof
    • 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
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3227—Lanthanum oxide or oxide-forming salts thereof
    • 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
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/602—Making the green bodies or pre-forms by moulding
    • C04B2235/6025—Tape casting, e.g. with a doctor blade

Definitions

  • Ceramic materials are used in a wide range of industrial applications ranging from electronics to structural material to ornamental applications. Because of their diversified utility, ceramic parts are prepared in a wide range of shapes and sizes which vary from tiny electronic components to large structural pieces. Ceramic parts can be prepared by a number of different processes and the choice of formation process depends to a great extent upon the size, shape, and the ultimate use of the ceramic part. However, many formation processes require the utilization of a binder for temporarily or permanently adhering ceramic materials to one another. For instance, ceramic processing often involves formation of a slurry that includes a ceramic particulate and a binder in a composite mixture or slurry that is formable by molding, coating, or the like.
  • the formed slurry is dried, such as by spray drying, thermal drying, or pan drying. In some formation techniques, the formed, dried composite forms a green article and the final product is formed by removal of the binder and sintering of the ceramic particulate at high temperatures.
  • a variety of polymeric binders have been utilized in the field of fabricating ceramic parts such as binders based upon waxes, starches, polyvinyl alcohol, gums, acrylates, celluloses, polyglycols, butyrals, epoxies and acetates. A good binder must satisfy several criteria.
  • a good binder should also be compatible with other additives and processing steps. Moreover, in those embodiments in which the binder is present only in the green article, it should impart suitable strength to the green article and be completely removable during formation of the final product.
  • binder compositions include an organic solvent such as an alcohol (e.g., methanol, ethanol or isopropanol) or an aromatic organic solvent (e.g. , benzene, toluene, etc.). Removal of the organic solvent is a necessary step during dry/cure of the binder composition, but often involves formation of dangerous volatile organic compounds (VOC) at removal and thus requires expensive and time consuming processes such as utilization of vacuum at reduced pressures, off-gas scrubbing and recovery, and the like.
  • an organic solvent such as an alcohol (e.g., methanol, ethanol or isopropanol) or an aromatic organic solvent (e.g. , benzene, toluene, etc.).
  • VOC dangerous volatile organic compounds
  • a binder composition for use with ceramics that includes little or no organic solvent.
  • a low solvent binder composition that can provide excellent binding characteristics for ceramics while exhibiting only limited adhesion to other materials could be of great benefit in the art.
  • a binder composition includes an acrylate functional component.
  • the acrylate functional component includes one or more acrylate functional monomers and/or one or more acrylate functional oligomers. Each molecule of the acrylate functional component including two or more acrylate functional groups.
  • the binder composition includes about 5 wt.% or less organic solvents.
  • a method for forming a ceramic article can include contacting a ceramic material with a binder composition as described herein and then contacting the binder composition that is in contact with the ceramic material with actinic radiation, e.g., radiation in the ultra-violet spectrum or electron beam radiation, upon which the binder composition can be cured and adhere to the ceramic material.
  • actinic radiation e.g., radiation in the ultra-violet spectrum or electron beam radiation
  • FIG. 1 illustrates a binder sample as described herein following cure.
  • FIG. 2 illustrates another binder sample as described herein following cure.
  • FIG. 3 illustrates another binder sample as described herein following cure.
  • FIG. 4 illustrates a ceramic coating sample as described herein following binder burnout.
  • the present disclosure is directed to binder compositions that include little or no organic solvents for use with ceramic materials.
  • the binder compositions can exhibit excellent ceramic adhesion characteristics upon cure, while also exhibiting lower adhesion characteristics to other types of materials, e.g., polymeric materials.
  • disclosed binders can be utilized in one embodiment in formation of ceramic materials on backing substrates that are intended for removal during use, e.g., releasable polymer backing sheets or the like.
  • Disclosed binder compositions can exhibit a low viscosity.
  • a binder composition can exhibit a viscosity as determined by use of a BrookfieldTM viscometer using a #21 spindle at 100 rpm at 22 °C of about 7000 centipoise (cps) or less, such as about 3000 cps or less, or about 2000 cps or less in some embodiments.
  • a binder composition can exhibit a viscosity of from about 20 cps to about 4000 cps, or from about 40 cps to about 1000 cps, in some embodiments.
  • a binder composition can exhibit a slip viscosity as determined by use of a BrookfieldTM Cone and Plate #4 plate, 200 sec -1 of from about 600 cps to about 6500 cps, such as from about 650 cps to about 3000 cps in some embodiments.
  • a binder composition can also exhibit low shrinkage upon cure. Shrinkage can be determined by density change from liquid to solid as measured by using an Anton ParrTM gas pycnometer Ultrapyc 5000) for cured material and density cup (BYK 2007787, 8.32 ml_, 1.0% Tolerance) for a liquid material. For instance, a binder composition can exhibit a shrinkage upon cure of about 10% or less, such as about 8% or less or about 6% or less in some embodiments. For example, a binder composition can exhibit shrinkage upon cure of from about 1 % to about 10%, from about 2% to about 8%, or from about 2.5% to about 7%, in some embodiments.
  • the low shrinkage values of the binder compositions can prevent structural changes (e.g., warping, cracking, etc.) to materials during cure, e.g., during formation of a green article.
  • the glass transition temperature of a cured binder composition as determined according to dynamic mechanical analysis can generally be about -30°C or higher, such as about -20°C or higher, such as from about -30°C to about 70°C, from about -30°C to about 50°C, from about -20°C to about 40°C, or from about - 20°C to about 40°C in some embodiments.
  • Disclosed binder compositions can also exhibit desirable mechanical properties. For instance, following cure, disclosed binder compositions can exhibit an elongation at break as determined by a film fixture using a StarrettTM Instron Model FLC-500 set at 1 inch/min with sample dimensions of 1 inch X 4 inch X 0.005 inch of from about 3% to about 65%, or from about 5% to about 60% in some embodiments.
  • a cured binder composition can exhibit a tensile strength at break as determined by using a StarrettTM Instron Model FLC-500 set at 1 inch/min with sample dimensions of 1 inch X 4 inch X 0.005 inch of from about 20 psi to about 2500 psi, such as from about 25 psi to about 2300 psi, or from about 200 psi to about 400 psi in some embodiments.
  • a cured binder composition can exhibit a maximum storage modulus as determined by using a TA InstrumentsTM DMA 850 using a film tension clamp (rectangular geometry: length ca 12-16mm, width 6-7mm, thickness 0.100 to 0.200mm, amplitude 10.0um, 1 Hz Frequency, preload force 0.01 N, temperature ranges from -60C to 150C, heating rate 3-5 deg/min), from about 100 MPa to about 4000 MPa, such as from about 150 MPa to about 3500 MPa, or from about 500 MPa to about 3000 MPa in some embodiments.
  • a cured binder composition can exhibit a loss modulus as determined by using a TA InstrumentsTM DMA 850 using a film tension clamp as a temperature sweep at constant Hz from about 40 MPa to about 500 MPa, such as from about 45 MPa to about 475 MPa, or from about 50 MPa to about 475 MPa in some embodiments.
  • a binder composition as disclosed herein can include little or no organic solvents.
  • a binder composition can include about 5 wt.% or less organic solvents, such as about 4 wt.% or less, about 3 wt.% or less, or about 2 wt.% or less in some embodiments.
  • organic solvent refers to any carbon-based substance capable of dissolving or dispersing another substance.
  • organic solvents include, without limitation, acetone, ethyl acetate, hexane, heptane, dichloromethane, methanol, ethanol, tetrahydrofuran, acetonitrile, dimethylformamide, toluene, benzene, and dimethylsulfoxide.
  • a binder as disclosed herein includes an acrylate functional component.
  • the acrylate functional component can include one or more acrylate functional monomers and/or one or more acrylate functional oligomers.
  • Each molecule of the acrylate functional component of the binder incorporates two or more acrylate functional groups, i.e., difunctional, trifunctional, or higher acrylate functionality on each component of the acrylate functional component such that the acrylate functional monomer or oligomer is at least bifunctional with regard to the acrylate functionality.
  • the acrylate functional component can constitute about 75 wt.% or more of the binder composition, such as about 78 wt.% or more, about 80 wt.% or more, about 85 wt.% or more, about 90 wt.% or more, or about 95 wt.% or more in some embodiments.
  • oligomer generally refers to a polymer having relatively few repeating units and having a number average molecular weight of about 150,000 g/mol or less, such as about from about 7,000 to about 110,000, or from about 10,000 to about 100,000, or from about 10,000 to about 50,000, or from about 15,000 to about 40,000 in some embodiments.
  • an acrylate functional oligomer can include a polyester acrylate, e.g., an aliphatic polyester acrylate and/or an aromatic polyester acrylate.
  • an acrylate functional monomer or oligomer can include a urethane acrylate, which can encompass aliphatic urethane acrylates and/or aromatic urethane acrylates, e.g., a polyurethane acrylate.
  • an acrylate functional oligomer can include a polyester urethane acrylate.
  • Acrylate functional monomers and oligomers as may be included in a binder composition can include, without limitation, acrylate monomers, urethane acrylate monomers, polyurethane acrylates, polyester acrylates, polyether acrylates, isocyanate-terminated acrylate monomers or oligomers, epoxy acrylates, acrylate esters, and any combination thereof.
  • a binder composition can include one or more of, and without limitation to, tripropylene glycol diacrylate, ethylene glycol diacrylate, isobornyl acrylate, ethylhexyl acrylate (e.g., 2-ethylhexyl acrylate), propoxylated tetrahydrofurfurl acrylate, 4-tertbutylcyclohexyl acrylate, aliphatic or aromatic polyester acrylates (e.g., difunctional and/or trifunctional polyester acrylates), aliphatic or aromatic polyester urethane acrylates, aromatic urethane acrylates, difunctional and/or trifunctional urethane acrylates, and mixtures thereof.
  • tripropylene glycol diacrylate ethylene glycol diacrylate
  • isobornyl acrylate ethylhexyl acrylate
  • ethylhexyl acrylate e.g., 2-ethylhexyl acrylate
  • acrylate functional monomers and oligomers as may be incorporated in a binder composition are available in the market, such as from the Rahn Corporation under the tradename GenomerTM and from Sartomer Americas.
  • specific examples of acrylate functional monomers and oligomers encompassed herein can include, without limitation, aliphatic polyester urethane acrylate oligomer (e.g., GenomerTM 4316 available from Rahn USA Corp.), aromatic urethane acrylate (e.g., GenomerTM 4622 available from Rahn USA Corp.), trifunctional polyester acrylate (e.g., CN2264 available from Arkema Sartomer® Americas), polyester acrylate oligomers (e.g., CN2282, CN292, CN2273 available from Arkema Sartomer® Americas), difunctional hydrophobic urethane acrylates (e.g., BRC843S, available from BomarTM), isobornyl acrylate (e.g., BRC
  • a binder composition can include one or more acrylate functional monomers, e.g., a mixture of two or more acrylate functional monomers, optionally in conjunction with one or more additional multifunctional monomers including acrylate-reactive functionality such as, without limitation, amide, acrylonitrile, vinyl styrene, or butadiene functionality, or any combination thereof.
  • acrylate functional monomers e.g., a mixture of two or more acrylate functional monomers, optionally in conjunction with one or more additional multifunctional monomers including acrylate-reactive functionality such as, without limitation, amide, acrylonitrile, vinyl styrene, or butadiene functionality, or any combination thereof.
  • a binder composition can include at least one acrylate functional oligomer in conjunction with one or more multifunctional monomers that includes non-acrylate functionality that is reactive with the acrylate functionality of the oligomer, e.g., as a crosslinking agent for the acrylate functional oligomer.
  • a binder composition can include one or more acrylate functional oligomers (e.g., a polyester acrylate, a polyester urethane acrylate, or a mixture thereof) in conjunction with one or more multifunctional monomers including reactive functionality including, without limitation, amide, acrylonitrile, vinyl styrene, butadiene reactive functionality, or a combination thereof.
  • one or more monomers of a binder composition can include acrylate functionality in conjunction with one or more acrylate oligomers as well as one or more multi-functional monomers or oligomers that includes functionality that is reactive with acrylate functionality.
  • a binder composition can include a polyester acrylate oligomer and/or a polyester urethane acrylate oligomer as well as one more acrylate functional monomers, optionally in conjunction with one or more multi-functional monomers that includes a different (non-acrylate) functionality.
  • a component that includes a non-acrylate functionality e.g., amide functionality
  • monomers and/or oligomers that include acrylate reactive functionality can generally constitute about 20 wt.% or less of a binder composition.
  • a binder composition can also include a dispersant.
  • a dispersant can constitute about 20 wt.% or less of the binder composition, such as from about 5 wt.% to about 20 wt.% of the binder composition, such as from about 8 wt.% to about 17 wt.%, or from about 10 wt.% to about 15 wt.% in some embodiments.
  • Dispersants suitable for a binder composition can include materials based on a polymeric polyester/polyamine condensate. Examples of such dispersants include those that are commercially available under the tradename Solsperse® 28000 Of course, dispersants of a binder composition are not limited to such, and other dispersants as are known in the art are encompassed herein, including, and without limitation to, esters of fish oils or surfactants, acrylic polymers, polyvinylpyridine or polyvinyl butadiene
  • a binder composition can include a cure system.
  • a binder composition can include one or more substances that act as a cure initiator to encourage curing (e.g., crosslinking) of components of the composition upon interaction with actinic radiation and/or electron beam radiation.
  • actinic radiation is intended to refer to electromagnetic radiation that is capable of producing photochemical effects.
  • the binder composition can be cured by actinic radiation in the ultraviolet (UV) or visible spectrum, both of which can encompass actinic radiation.
  • a cure system can include a photoinitiator.
  • a photoinitiator can constitute about 15 wt.% or less of the binder composition, such as about 12 wt.% or less, such as from about 2 wt.% to about 10 wt.% in some embodiments.
  • a photoinitiator can be configured to initiate cure upon interaction with light in the UV spectrum (about 100 nm to about 400 nm wavelength). Suitable UV light can include that emitted from a UV light source as is known in the art. UV light from any conventionally known source may be used in accordance with such an embodiment.
  • a UV light source can include a microwave energized light source, a medium pressure mercury vapor UV light source, an amalgam low pressure UV light source, or an LED UV light source that can emit at one or more useful wavelengths, e.g., 385 nm, 395 nm, 405 nm, or any band that encompasses UV wavelengths capable of initiating cure.
  • a photoinitiator can bond, e.g., polymerize with, a component of the mixture, e.g., the ceramic constituent and/or an oligomeric or monomer component.
  • a photoinitiator can bind or otherwise adhere to ceramic particles upon cure.
  • a photoinitiator may include one or more of, and without limitation to, a benzoin compound, an acetophenone compound, an acylphosphine oxide compound, a titanocene compound, a thioxanthone compound, a phenyl propanone, or a photosensitizer such as an amine, a butanone, or a quinone, or any combination thereof.
  • Exemplary photoinitiators can include, without limitation, benzophenone, hydroxyacetophenone, methylbenzophenone, 4- phenylbenzophenone, 4,4'-bis(diethyl amino)benzophenone, 4,4'- bis(dimethylamino)benzophenone (Michler’s ketone), 4-(2-hydroxyethoxy)phenyl-(2- hydroxy-2-methylpropyl)ketone, 1 -hydroxycyclohexyl phenyl ketone, benzyldimethyl ketal, 2-benzyl-2-N,N-dimethylamino-1-(4-morpholinophenyl)-1 butanone; 2- dimethylamino-2-(4-methyl-benzyl)-1 (4-morpholin- 4-yl-phenyl)-butan-1-one, 2- mercaptobenzoxazole, camphorquinone, 2-hydroxy-2-methyl-1-(4-t- butyl)phenylpropan-1 -n
  • a mixed photoinitiator may be utilized such as a blend of about 70 wt. % oligo(2-hydroxy-2- methyl-1-[4-(1-methylvinyl)phenyl]propanone and about 30 wt. % 2-hydroxy-2- methyl-1-phenylpropan-1-one, commercially available from Lamberti USA, Inc., Conshohocken, Pa. under the trade name EsacureTM KIP 150 or KIP 100F.
  • Other photoinitiators sold by Lamberti USA, Inc. under the KIP or EsacureTM designation may also be utilized, such as EsacureTM SM 303.
  • polymeric photoinitiators include PL-816A from Palermo Lundahl Industries and those available under the tradename OmniradTM such as OmniradTM 379 available from IGM Resins.
  • OmniradTM such as OmniradTM 379 available from IGM Resins.
  • an oxide photoinitiator may be utilized.
  • suitable oxide photoinitiators can include bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide commercially available from Ciba Specialty Chemicals, Tarrytown, N.Y.
  • photoinitiators include, without limitation, 1 -hydroxycyclohexyl phenyl ketone available under the trade name IrgacureTM 184, and 2-hydroxy-methyl-1 -phenyl propanone under the trade name IrgacureTM 1173.
  • Other photoinitiators sold by Ciba Specialty Chemicals under the IrgacureTM trade name are also suitable for use.
  • the system need not include a photoinitiator.
  • a binder composition can be cured by utilizing an electron beam radiation, which can initiate polymerization as the accelerated electrons cleave bonds of one or more components of the composition, thereby creating radicals for polymerization initiation and instigating polymerization propagation and formation of a polymer backbone.
  • a binder composition can be cured by contact with electron beam radiation of about 100 kV potential or greater.
  • a cure system can include a thermal initiator.
  • a cure system can include both a thermal initiator and a photoinitiator, in which case the thermal initiator may facilitate UV curing of the binder composition.
  • a thermal initiator can include a free radical initiator that generates radicals upon exposure to suitable temperature.
  • a thermal initiator can generally constitute about 10 wt.% or less of a binder composition, such as about 8 wt.% or less, or about 5 wt.% or less in some embodiments, such as from about 1 wt.% to about 5 wt.%.
  • thermal initiators can include, without limitation, peroxide compounds (e.g., a benzoyl peroxide), azo compounds (e.g., azo compounds sold under the VazoTM tradename), or any combination thereof.
  • thermal initiators encompassed herein can include, without limitation, 2,2'-azobis(2- methylbutane nitrile (VazoTM 67), 2,2'-azobis(isobutyronitrile) (VazoTM64), (2,2 - azobis(2,4-dimethylpentanenitrile) (VazoTM 52), 1 ,1 '-azobis(cyclohexanecarbonitrile) (VazoTM 88), 4,4'-Azobis(4-cyanovaleric Acid) (VazoTM 56 WSP) 4,4-Azobis(4- cyanopentanecarboxylic Acid), and 4 , 4'-( 1 ,2-Diazenediyl)bis[14-cyanopentanoic Acid
  • a binder composition can include other components as are known in the art.
  • a binder composition can in one embodiment include a pore former, i.e., a sacrificial material that can be removed during processing or after formation of a ceramic component and, upon removal, creates voids (pores) within the ceramic material and/or the binder.
  • a pore former can decompose upon heat treatment, or through contact with water or other solvent that does not dissolve or unfavorably affect the ceramic material.
  • a pore former can be removed by any suitable process including, without limitation, evaporation, sublimation, or during firing.
  • a pore former can be removed during a heating phase of a sintering process, prior to a sintering process, or following a sintering process.
  • a pore former can include ionic salts. Ionic salts have a relatively high boiling and melting point and thus can maintain structure through processing until desired dissolution. Moreover, ionic salts can be formed to a wide range of particle size. Ionic salt pore forming agents can be removed by dissolving in water, and the dissolution process can be enhanced at elevated temperature. Other types of pore forming agents can include, without limitation, graphite, starch, foamed resins, water-absorbent resins, and silica gel.
  • a single type of pore former may be used, or a plurality of types of pore formers may be used.
  • a pore former can generally constitute from about 0.5 to about 10 parts by mass by 100 parts of the final porous material.
  • the pore former in formation of a porous ceramic material, can constitute from about 0.5 to about 10 parts by mass per 100 parts by mass of the ceramic.
  • a binder composition can exhibit excellent binding characteristics with any type of ceramic in any form.
  • the term “ceramic” is generally intended to refer to any of a variety of hard, brittle, heat- and corrosion-resistant materials that include at least one metallic element (which may include silicon) in combination with oxygen, carbon, nitrogen, or sulfur or a combination thereof.
  • a ceramic for use with disclosed binding compositions may be crystalline or polycrystalline.
  • exemplary ceramics can include aluminas (e.g., aluminum oxide (AI2O3), aluminum oxide hydroxide, etc.), aluminum nitrides, silicon oxides (e.g., silicas), silicon carbides, titanium oxides (e.g., titanium dioxides), titanium nitrides, magnesium oxides, boron nitrides, silicon nitrides, zirconium oxides, zirconium nitrides, doped ceramics, or any combination thereof.
  • aluminas e.g., aluminum oxide (AI2O3), aluminum oxide hydroxide, etc.
  • aluminum nitrides e.g., silicon oxides (e.g., silicas), silicon carbides, titanium oxides (e.g., titanium dioxides), titanium nitrides, magnesium oxides, boron nitrides, silicon nitrides, zirconium oxides, zirconium nitrides, doped ceramics, or any combination thereof.
  • Ceramic materials can include, without limitation, black silicon carbide, green silicon carbide, titanium diboride, boron carbide, tungsten carbide, titanium carbide, cubic boron nitride, garnet (e.g., lithium garnets such as lithium lanthanide zirconium oxides (LLZO) including Li?La3Zr20i2 (LLZ), Lii.3Alo3Tii.?(P04)3 (LATP), etc.), fused alumina zirconia, sol-gel derived ceramics (e.g., alumina ceramics doped with chromia, ceria, zirconia, titania, silica, and/or tin oxide), silica (e.g., quartz, glass beads, glass bubbles and glass fibers), feldspar, spinel, flint, or any combination thereof.
  • garnet e.g., lithium garnets such as lithium lanthanide zirconium oxides (LLZO) including
  • the ceramic can be in the form of a particulate.
  • a binder composition can be mixed with a ceramic particulate to provide a slurry that can be formed (e.g., cast, molded, etc.).
  • a green article can be formed.
  • a binder composition as described herein can constitute from about 10 wt.% to about 60 wt.% of a slurry, with solids (e.g., a ceramic particulate and any pore forming materials) constituting from about 40% to about 90% of a slurry.
  • solids e.g., a ceramic particulate and any pore forming materials
  • a slurry that incorporates a binder composition and a particulate that includes a ceramic can be mixed by using known methods and devices.
  • a slurry including a binder composition can be further processed prior to forming.
  • a slurry can be milled to provide the solid particulate of the slurry at a desired size with few or no agglomerates in the slurry.
  • a binder composition can exhibit stronger adherence to a ceramic than to other materials after cure, e.g., polymeric materials.
  • one or more components of the binder composition can adhere to a polymeric backing material, but with lower adhesion characteristics as compared to the adhesion to a ceramic material.
  • a photoinitiator of a composition can bond to a polymeric backing material upon exposure to UV radiation and cure of the binder, however, the overall adhesion of the binder to the backing material will be relatively weak as compared to the adhesion to the ceramic material.
  • binder compositions can be particularly beneficial for use in applications in which a ceramic material is formed on a backing substrate that is intended for removal during processing, e.g., after formation of a green article and prior to final sintering.
  • Backing materials as are known in the art can be utilized with a binder composition, e.g., cloth or paper, or a polymer, e.g., polyethylene, polytetrafluoroethylene, polyethylene terephthalate (MylarTM), a metal foil, etc.
  • a backing sheet can be easily removed from a green article, leaving the ceramic green article in the desired form and without any green-state slippage.
  • Binder composition samples were formed as described in Table 1 , below. Contents are provided as weight percentages, unless otherwise noted.
  • the UV cured binder composition samples illustrate the effect of glass transition temperatures (T g ) on flatness of green state ceramic/binder composites following cure and prior to burn out.
  • a slurry was prepared with each binder composition sample by mixing 4g of a binder composition with 16g of a ceramic particulate (LLZO). Mixing was performed using a ‘SpeedMixer’ set to 2300 rpm for 3 min. with a ceramic ball. The final mixed slurry was smooth and uniform with no sign of air entrapment. The slurry was further milled in a 3 roll mill and applied to a polyester sheet to an even thickness of 50-70 pm.
  • LLZO ceramic particulate
  • the binder composition of each coated material was UV cured by passing the coated sheet under an XtremaTM Plus UV unit available from Miltec UV at 20 feet per minute.
  • the UV data used in all examples was determined by use of a radiometer and is provided in Table 2, below.
  • Table 3 presents physical characteristics of the binder composition alone as well as characteristics of the composite including the binder composition mixed with the ceramic particulate prior to UV cure, following UV cure, and following burnout.
  • Shrinkage was determined by density change from liquid to solid as measured by using an Anton ParrTM gas pycnometer Ultrapyc 5000) for cured material and density cup (BYK 2007787, 8.32 mL, 1.0% Tolerance) for the liquid portion. Percent shrinkage was calculated using the formula:
  • Shrinkage (1- (liquid density (g/mL)/cured density (g/mL)) x 100.
  • Viscosity was determined by use of a BrookfieldTM RVT (serial # 8669793) viscometer using a #21 spindle at 10Orpm. Slip viscosity was determined by use of a BrookfieldTM Cone and Plate CAP2000-L (serial # 8702324) #4 plate, 200 sec-1 . Glass transition temperatures (T g ) were obtained by dynamic mechanical analysis (DMA) unless otherwise noted.
  • the characteristics for the binder/ceramic composite include slip viscosity as determined by use of a cone and plate and flatness determined as described above in Table 2 after UV cure and again after 180°C burnout for one hour.
  • the T g values range from -19°C to 30°C where the higher the T g the better the lay down was observed for green state UV cured slips.
  • Samples 1 and 3 showed the effect of T g on degree of flatness of the ‘green state' UV cured binder/ceramic composite.
  • the T g of Sample 1 was found to be -19°C and this sample did not lay flat after UV cure (FIG. 1) compared to Sample 4, which was found to have a T g for the UV binder of 30°C and laid flat after UV cure (FIG. 2).
  • Binder samples were formed as described in Table 4, below. The effect of urethane acrylate type on performance properties was investigated while keeping other component amounts constant in formation of Samples 5 and 6. For Sample 7, a trifunctional polyester acrylate was utilized rather than a urethane acrylate. Table 4
  • a slurry was prepared with each binder sample by mixing 4g of binder with 16g of a ceramic particulate (LLZO). The slurry was applied to a substrate and cured under UV as described above. Burnout of the cured material was carried out at 180°C for 1 hour. Physical properties of samples, including properties of UV cured binder samples alone and ceram ic/binder composites prior to UV cure, following UV cure, and following burnout were determined as described above and are provided in Table 5, below.
  • LLZO ceramic particulate
  • Binder samples were formed as described in Table 6, below. In these samples, the effect of the polyester oligomer T g on performance was investigated where the T g of the oligomers ranged from -45°C to 26°C. T g for the higher temperature T g material was obtained via either DMA or differential scanning calorimetry (DSC), as shown.
  • a slurry was prepared with each binder sample by mixing 4g of binder with 16g of a ceramic particulate (LLZO). The slurry was applied to a substrate and cured under UV as described above. Burnout of the cured binder was carried out at 180°C for 1 hour. Physical properties of the samples were determined as described above and are provided in Table 7, below.
  • LLZO ceramic particulate
  • Binder samples were formed as described in Table 8, below.
  • Table 8 also includes Sample 1 , described previously for comparison.
  • samples 11 and 12 a thermal radical initiator was utilized in conjunction with a traditional UV photoinitiator.
  • a slurry was prepared with each binder sample by mixing 4g of binder with 16g of a ceramic particulate (LLZO). The slurry was applied to a substrate and cured under UV as described above. Burnout of the cured binder was carried out at 180°C for 1 hour. Physical properties of the samples were determined as described above and are provided in Table 9, below.
  • the green strength of the UV cured binder/ceramic slurry exhibited improved excellent green strength as evidence by flatness after cure. Lower viscosities were also observed by incorporating the thermal radical initiator.
  • Binder sample no. 13 was formed as described in T able 10, below.
  • Binder samples were formed as described in Table 12, below without dispersant. In these samples, a masterbatch was combined with one of three different photoinitiators, including a phenyl propanone photoinitiator (PI-1), a phenyl ketone photoinitiator (PI-2), or a butanone photoinitiator (PI-3). Amounts are provided in grams unless otherwise specified.
  • PI-1 phenyl propanone photoinitiator
  • PI-2 phenyl ketone photoinitiator
  • PI-3 butanone photoinitiator
  • a slurry was prepared with each binder sample by mixing 3g of binder with 17 g of a ceramic particulate (LLZO). Mixing was performed using a ‘SpeedMixer’ set to 2300 rpm for 3 min. with a ceramic ball. The mixing was repeated a second time.
  • LLZO ceramic particulate
  • the warm slurry was applied with a K coater using a 70 pm wwr on the silicone face of a MylarTM substrate and immediately UV cured using a D bulb, 20 fpm, 100% power emitting UVA (2106 mJ/cm 2 ; 4647 mW/cm 2 ), UVB (555 mJ/cm 2 ; 1457 mW/cm 2 ), UVC (91 mJ/cm 2 ; 272 mW/cm 2 ), UVA (2003 mJ/cm 2 ; 4444 mW/cm 2 ).
  • a 4” X 4” template was used to razor cut sections of the cured coated substrate.
  • the release properties of the UV cured ceramic green layer were evaluated by placing a Tong Depressor with a tape with a 4 inch edge with overhang of by % inch. The tape edge was placed on one edge of the 4” X 4” cured ceramic layer and pulled slowly at a 45-degree angle to the substrate surface to release the ceramic layer from the underlying substrate.
  • the release properties were evaluated by the following criteria: 1) complete removal of 4”X 4” ceramic layer with no tears was a PASS. 2) Any tears in the ceramic layer, due to not releasing, that occurred while pulling the ceramic layer from the underlying substrate was a FAIL. This test was performed initially after formation and at 3 hrs. following formation.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Polymerisation Methods In General (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

L'invention concerne des compositions de liant pour céramiques qui comprennent peu ou pas de solvants organiques. Les compositions de liant présentent d'excellentes caractéristiques d'adhérence céramique lors du durcissement, tout en présentant également des caractéristiques d'adhérence inférieures à d'autres types de matériaux, par exemple, des matériaux de support polymères. Les compositions de liant sont basées sur une fonctionnalité acrylate, et comprennent au moins un monomère ou un oligomère fonctionnel acrylate.
EP24775615.8A 2023-03-20 2024-03-20 Liant durcissable par rayonnement actinique ou par faisceau d'électrons pour matériaux céramiques Pending EP4669705A2 (fr)

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US202363491163P 2023-03-20 2023-03-20
PCT/US2024/020672 WO2024197004A2 (fr) 2023-03-20 2024-03-20 Liant durcissable par rayonnement actinique ou par faisceau d'électrons pour matériaux céramiques

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Publication number Priority date Publication date Assignee Title
WO1995008596A1 (fr) * 1993-09-20 1995-03-30 Ppg Industries, Inc. Compositions de revetement durcissables aux rayonnements, a pigment noir et au fini mat
CN104470997B (zh) * 2012-07-20 2016-08-17 巴斯夫欧洲公司 快速干燥的可辐照固化的涂料混合物
US10818900B2 (en) * 2014-07-18 2020-10-27 Miltec UV International, LLC UV or EB cured polymer-bonded ceramic particle lithium secondary battery separators, method for the production thereof
EP3608372B1 (fr) * 2018-08-10 2023-10-11 Agfa Nv Fabrication de cuir décoré
US12024640B2 (en) * 2021-10-18 2024-07-02 Dupont Electronics Inc. UV-curing resin compositions for hard coat applications

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