# US 11,299,430 B2 · Formulations with active functional additives for 3D printing of preceramic polymers, and methods of 3D-printing the formulations

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- Number: US 11,299,430 B2
- Document ID: US11299430B2
- Status: Granted
- Kind: B2
- Application number: 15/822,203
- Filed: 2017-11-26
- Published: 2018-05-31
- Granted: 2022-04-12
- Earliest claimed: 2016-11-30
- Assignees: HRL Laboratories, LLC
- Applicants: HRL Laboratories, LLC
- Inventors: Zak C. Eckel; Tobias A. Schaedler; John H. Martin; Kenneth Cante
- Web page: https://patentgrep.com/patent/US11299430B2

## CPC

- C04B 35/5603: {with a well-defined oxygen content, e.g. oxycarbides}
- B28B 1/001: {Rapid manufacturing of 3D objects by additive depositing, agglomerating or laminating of material (selective deposition modelling of metallic powder B22F10/00; rapid manufacturing of 3D objects in general and in particular of plastics B29C64/00)}
- B29C 64/10: Processes of additive manufacturing
- B29C 64/379: Handling of additively manufactured objects, e.g. using robots
- B33Y 40/10: Pre-treatment
- B33Y 40/20: Post-treatment, e.g. curing, coating or polishing
- B33Y 70/10: Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
- B33Y 80/00: Products made by additive manufacturing
- C04B 35/117: Composites
- C04B 35/14: based on silica
- C04B 35/44: based on aluminates
- C04B 35/46: based on titanium oxides or titanates (containing also zirconium or hafnium oxides, zirconates or hafnates C04B35/49)
- C04B 35/488: Composites
- C04B 35/515: based on non-oxide ceramics
- C04B 35/532: containing a carbonisable binder
- C04B 35/5611: {based on titanium carbides}
- C04B 35/5622: {based on zirconium or hafnium carbides}
- C04B 35/563: based on boron carbide
- C04B 35/565: based on silicon carbide
- C04B 35/571: obtained from {Si-containing} polymer precursors {or organosilicon monomers}
- C04B 35/58: based on borides, nitrides, {i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides} or silicides {(containing free binder metal C22C29/00)}
- C04B 35/58014: {based on titanium nitrides, e.g. TiAlON}
- C04B 35/58028: {based on zirconium or hafnium nitrides}
- C04B 35/581: based on aluminium nitride
- C04B 35/589: obtained from {Si-containing} polymer precursors {or organosilicon monomers}
- C04B 35/597: based on silicon oxynitride, {e.g. SIALONS}
- C04B 35/62218: {obtaining ceramic films, e.g. by using temporary supports}
- C04B 35/62802: {Powder coating materials}
- C04B 35/62836: {Nitrides}
- C04B 35/62839: {Carbon}
- C04B 35/62842: {Metals}
- C04B 35/62844: {Coating fibres}
- C04B 35/62865: {Nitrides}
- C04B 35/62868: {Boron nitride}
- C04B 35/62873: {Carbon}
- C04B 35/62876: {with metals}
- C04B 35/63448: {obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds}
- C04B 35/64: Burning or sintering processes (C04B33/32 takes precedence {; powder metallurgy B22F})
- C04B 35/80: Fibres, filaments, whiskers, platelets, or the like
- C08L 83/08: containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C09D 5/004: {Reflecting paints; Signal paints}
- C09D 7/61: inorganic
- C09D 7/62: modified by treatment with other compounds
- C09D 7/67: {Particle size smaller than 100 nm}
- C09D 7/68: {Particle size between 100-1000 nm}
- C09D 7/69: {Particle size larger than 1000 nm}
- C09D 7/70: {characterised by shape, e.g. fibres, flakes or microspheres}
- C09D 11/03: characterised by features other than the chemical nature of the binder
- C09D 11/037: characterised by the pigment
- C09D 11/101: Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
- C09D 11/102: containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
- B29C 64/129: characterised by the energy source therefor, e.g. by global irradiation combined with a mask
- B29C 71/02: Thermal after-treatment {(B29C71/0063 and B29C71/0072 take precedence)}
- B29C 2035/0827: {using UV radiation}
- B29C 2035/0838: {using laser}
- B29K 2083/00: Use of polymers having silicon, with or without sulfur, nitrogen, oxygen, or carbon only, in the main chain, as moulding material
- B29K 2105/0002: {monomers or prepolymers}
- B29K 2509/04: Carbides; Nitrides
- B29K 2995/0026: Transparent
- B29K 2995/003: Reflective
- B33Y 10/00: Processes of additive manufacturing
- C04B 2235/3826: Silicon carbides
- C04B 2235/3895: Non-oxides with a defined oxygen content, e.g. SiOC, TiON
- C04B 2235/483: Si-containing organic compounds, e.g. silicone resins, (poly)silanes, (poly)siloxanes or (poly)silazanes
- C04B 2235/5216: Inorganic
- C04B 2235/5224: Alumina or aluminates
- C04B 2235/5232: Silica or silicates other than aluminosilicates, e.g. quartz
- C04B 2235/5236: Zirconia
- C04B 2235/524: Non-oxidic, e.g. borides, carbides, silicides or nitrides
- C04B 2235/526: characterised by the length of the fibers
- C04B 2235/5264: characterised by the diameter of the fibers
- C04B 2235/5276: Whiskers, spindles, needles or pins
- C04B 2235/5284: Hollow fibers, e.g. nanotubes
- C04B 2235/5292: Flakes, platelets or plates
- C04B 2235/5436: micrometer sized, i.e. from 1 to 100 micron
- C04B 2235/5454: nanometer sized, i.e. below 100 nm
- C04B 2235/6026: Computer aided shaping, e.g. rapid prototyping
- C04B 2235/6562: Heating rate
- C04B 2235/6565: Cooling rate
- C04B 2235/77: Density
- C04B 2235/96: Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C08G 77/18: to alkoxy or aryloxy groups
- C08G 77/20: containing silicon bound to unsaturated aliphatic groups
- C08G 77/28: sulfur-containing groups
- C08K 3/34: Silicon-containing compounds
- C08K 7/00: Use of ingredients characterised by shape
- C08K 7/10: Silicon-containing compounds
- C08K 9/04: Ingredients treated with organic substances {(treated with macromolecular compounds C08K9/08)}
- C08K 2201/005: Additives being defined by their particle size in general
- Y02P 10/25: Process efficiency
- C04B: LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE {(roofing granules E04D7/005)}; CERAMICS (devitrified glass-ceramics C03C10/00); REFRACTORIES; TREATMENT OF NATURAL STONE
- B28B: SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER (foundry moulding B22C; working stone or stone-like material B28D; shaping of substances in a plastic state, in general B29C; making layered products not composed wholly of these substances B32B)
- B29C: SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING (making preforms B29B11/00; making laminated products by combining previously unconnected layers which become one product whose layers will remain together B32B37/00 - B32B41/00)
- B33Y: ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- B29K: INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR {MOULDS, } REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

This invention provides resin formulations which may be used for 3D printing and pyrolyzing to produce a ceramic matrix composite. The resin formulations contain a solid-phase filler, to provide high thermal stability and mechanical strength (e.g., fracture toughness) in the final ceramic material. The invention provides direct, free-form 3D printing of a preceramic polymer loaded with a solid-phase filler, followed by converting the preceramic polymer to a 3D-printed ceramic matrix composite with potentially complex 3D shapes or in the form of large parts. Other variations provide active solid-phase functional additives as solid-phase fillers, to perform or enhance at least one chemical, physical, mechanical, or electrical function within the ceramic structure as it is being formed as well as in the final structure. Solid-phase functional additives actively improve the final ceramic structure through one or more changes actively induced by the additives during pyrolysis or other thermal treatment.

## Claims

### Claim 1

A 3D-printing composition comprising:
(a) from about 10 vol % to about 99 vol % of one or more preceramic, UV-curable monomers;
(b) from about 1 vol % to about 70 vol % of solid-phase functional additives, wherein said functional additives have at least one average dimension from about 5 nanometers to about 50 microns, and wherein said functional additives are characterized by the property that at a temperature of 800° C., said functional additives react with said preceramic, UV-curable monomers, or a polymer derived therefrom to cause an increase in volume of said composition;
(c) a photoinitiator or photoacid generator; and
(d) a 3D-printing resolution agent,
wherein said functional additives are selected from the group consisting of scandium, yttrium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, zinc, boron, aluminum, gallium, silicon, germanium, phosphorus, titanium silicide, chromium silicide, magnesium silicide, zirconium silicide, molybdenum silicide, and combinations thereof.

### Claim 2 (depends on 1)

The composition of claim 1, wherein said preceramic, UV-curable monomers are selected from unsaturated ethers, vinyls, acrylates, methacrylates, cyclic ethers, epoxies, oxetanes, thiols, or a combination thereof.

### Claim 3 (depends on 1)

The composition of claim 1, wherein said preceramic, UV-curable monomers are selected from silazanes, siloxanes, silanes, carbosilanes, or a combination thereof.

### Claim 4 (depends on 1)

The composition of claim 1, wherein said preceramic, UV-curable monomers contain (i) non-carbon atoms selected from the group consisting of Si, B, Al, Ti, Zn, P, S, Ge, and combinations thereof, and (ii) two or more functional groups selected from the group consisting of aliphatic ethers, cyclic ether, vinyl ether, epoxide, cycloaliphatic epoxide, oxetane, and combinations, analogues, or derivatives thereof.

### Claim 5 (depends on 1)

The composition of claim 1, wherein said preceramic, UV-curable monomers contain (i) non-carbon atoms selected from the group consisting of Si, B, Al, Ti, Zn, P, S, Ge, N, ), and combinations thereof, and (ii) two or more C═X double bonds, two or more C≡X triple bonds, or at least one C═X double bond and at least one C≡X triple bond, wherein X is selected from C, S, N, O, or a combination thereof.

### Claim 6 (depends on 1)

The composition of claim 1, wherein said functional additives are characterized by the property that at a temperature of 800° C., said functional additives react with said preceramic, UV-curable monomers.

### Claim 7 (depends on 1)

The composition of claim 1, wherein said functional additives are characterized by the property that at a temperature of 800° C. under a heating atmosphere, said functional additives are reactive with one or more gases contained in said heating atmosphere.

### Claim 8

A 3D-printing composition comprising:
(a) from about 10 vol % to about 99 vol % of one or more preceramic, UV-curable monomers, wherein at least some of said preceramic, UV-curable monomers contain thiol groups;
(b) from about 1 vol % to about 70 vol % of solid-phase functional additives, wherein said functional additives have at least one average dimension from about 5 nanometers to about 50 microns, and wherein said functional additives are characterized by the property that at a temperature of 800° C., said functional additives reactively bind with sulfur contained in said thiol groups of said monomers;
(c) a photoinitiator or photoacid generator; and
(d) a 3D-printing resolution agent,
wherein said functional additives are selected from the group consisting of scandium, yttrium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, zinc, boron, aluminum, gallium, silicon, germanium, phosphorus, titanium silicide, chromium silicide, magnesium silicide, zirconium silicide, molybdenum silicide, and combinations thereof.

### Claim 9 (depends on 8)

The composition of claim 8, wherein said functional additives are selected from the group consisting of titanium, zirconium, hafnium, silicon, aluminum, chromium, niobium, chromium silicide, titanium silicide, magnesium silicide, zirconium silicide, molybdenum silicide, and combinations thereof.

### Claim 10 (depends on 8)

A ceramic structure comprising a pyrolyzed form of a 3D-printed, UV-cured composition according to claim 8.

### Claim 11 (depends on 10)

The ceramic structure of claim 10, wherein said ceramic structure contains sulfur in a concentration from about 0.1 wt % to about 30 wt % on an elemental sulfur basis.

### Claim 12 (depends on 1, 8)

The composition of either one of claims 1 or 8, wherein said functional additives are in the form of fibers, whiskers, nanotubes, nanorods, flat platelets, microparticles with average diameter from 1 micron to 100 microns, nanoparticles with average diameter from 1 nanometer to 1000 nanometers, or combinations thereof.

### Claim 13 (depends on 1, 8)

The composition of either one of claims 1 or 8, wherein said functional additives are coated with one or more compounds or chemical groups that polymerize or crosslink said monomer when exposed to UV radiation and/or heat, and optionally wherein said compounds or chemical groups are selected from the group consisting of unsaturated ethers, vinyls, acrylates, methacrylates, cyclic ethers, epoxies, oxetanes, and combinations thereof.

### Claim 14 (depends on 1, 8)

The composition of either one of claims 1 or 8, wherein said functional additives are covalently bonded to one or more compounds or chemical groups selected from the group consisting of unsaturated ethers, vinyls, acrylates, methacrylates, cyclic ethers, epoxies, oxetanes, amines, hydroxyls, isocyanates, hydrides, and combinations thereof.

### Claim 15 (depends on 1, 8)

The composition of either one of claims 1 or 8, wherein at least some of said functional additives contain a surface treatment that increases the compatibility, solubility, and/or bonding reactivity of said functional additives with said monomers.

### Claim 16 (depends on 1, 8)

The composition of either one of claims 1 or 8, wherein said composition further comprises a reactive or non-reactive surfactant and/or a reactive or non-reactive wetting agent.

### Claim 17 (depends on 1, 8)

The composition of either one of claims 1 or 8, wherein said functional additives are at least partially transparent to UV light.

### Claim 18 (depends on 1, 8)

The composition of either one of claims 1 or 8, wherein said functional additives are at least partially reflective of UV light.