# US 12,110,404 B2 · Three-dimensional printing with metal oxide nanoparticle fusing agents

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- Number: US 12,110,404 B2
- Document ID: US12110404B2
- Status: Granted
- Kind: B2
- Application number: 17/312,674
- Filed: 2019-07-17
- Published: 2022-06-16
- Granted: 2024-10-08
- Earliest claimed: 2019-07-17
- Assignees: Hewlett-Packard Development Company, L.P.
- Applicants: Hewlett-Packard Development Company, L.P.
- Inventors: Krzysztof Nauka; Vladek Kasperchik
- Web page: https://patentgrep.com/patent/US12110404B2

## CPC

- C09D 11/322: Pigment inks
- B29C 64/165: using a combination of solid and fluid materials, e.g. a powder selectively bound by a liquid binder, catalyst, inhibitor or energy absorber
- B29C 64/291: for operating globally, e.g. together with selectively applied activators or inhibitors
- B33Y 10/00: Processes of additive manufacturing
- B33Y 30/00: Apparatus for additive manufacturing; Details thereof or accessories therefor
- B33Y 70/00: Materials specially adapted for additive manufacturing
- C01G 23/08: Drying; Calcining {; After treatment of titanium oxide}
- C09D 11/037: characterised by the pigment
- C09D 11/102: containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
- B29K 2077/00: Use of {PA, i.e.} polyamides, e.g. polyesteramides {or derivatives thereof}, as moulding material
- B29K 2105/0032: {Pigments, colouring agents or opacifiyng agents}
- B29K 2105/251: {Particles, powder or granules (expandable particles B29K2105/046)}
- C01P 2004/62: Submicrometer sized, i.e. from 0.1-1 micrometer
- C01P 2004/64: Nanometer sized, i.e. from 1-100 nanometer
- 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)
- 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
- C01G: COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F (metal hydrides {monoborane, diborane or addition complexes thereof} C01B6/00; salts of oxyacids of halogens C01B11/00; peroxides, salts or peroxyacids C01B15/00; thiosulfates, dithionites, polythionates C01B17/64; compounds containing selenium, or tellurium C01B19/00; binary compounds of nitrogen with metals C01B21/06; azides C01B21/08; {compounds containing nitrogen, other non-metals and metal C01B21/082}; metal amides C01B21/092; nitrites C01B21/50; {compounds of noble gases C01B23/0005}; phosphides C01B25/08; salts of oxyacids of phosphorus C01B25/16; carbides C01B32/90; compounds containing silicon C01B33/00; compounds containing boron C01B35/00; compounds having molecular sieve properties but not having base-exchange properties C01B37/00; compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites, C01B39/00; cyanides C01C3/08; salts of cyanamide C01C3/16; thiocyanates C01C3/20)
- 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
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS

## Abstract

This disclosure describes multi-fluid kits for three-dimensional printing, three-dimensional printing kits, and systems for three-dimensional printing. In one example, a multi-fluid kit for three-dimensional printing can include a fusing agent and a detailing agent. The fusing agent can include water and metal oxide nanoparticles dispersed therein. The metal oxide nanoparticles can be selected from titanium dioxide, zinc oxide, cerium oxide, indium tin oxide, or a combination thereof. The metal oxide nanoparticles can have an average particle size from about 2 nm to about 500 nm. The detailing agent can include a detailing compound.

## Claims

### Claim 1

A three-dimensional printing kit, comprising:
a fusing agent consisting of:
water;
metal oxide nanoparticles dispersed in the water, the metal oxide nanoparticles selected from the group consisting of titanium dioxide nanoparticles, zinc oxide nanoparticles, cerium oxide nanoparticles, and a combination thereof and the metal oxide nanoparticles consist of metal oxide nanoparticles having an average particle size ranging from greater than 10 nm to about 500 nm; and
optionally, at least one additive selected from the group consisting of a dispersant, a co-solvent, a surfactant, a biocide, and a sequestering agent; and
a powder bed material comprising polymer particles.

### Claim 2 (depends on 1)

The three-dimensional printing kit of claim 1, wherein the polymer particles are polyamide 12 particles.

### Claim 3 (depends on 1)

The three-dimensional printing kit of claim 1, wherein the powder bed material is devoid of a filler that absorbs electromagnetic energy within an absorption wavelength range of from about 300 nm to about 400 nm.

### Claim 4 (depends on 1)

The three-dimensional printing kit of claim 1, further comprising a detailing agent comprising a detailing compound.

### Claim 5 (depends on 1)

The three-dimensional printing kit of claim 1, further comprising multiple colored agents each separate from the fusing agent, wherein the multiple colored agents independently comprise water and colorant.

### Claim 6

A system for three-dimensional printing, comprising:
a fusing agent consisting of water, metal oxide nanoparticles dispersed in the water, and optionally at least one additive selected from the group consisting of a dispersant, a co-solvent, a surfactant, a biocide, and a sequestering agent, the metal oxide nanoparticles selected from the group consisting of titanium dioxide nanoparticles, zinc oxide nanoparticles, cerium oxide nanoparticles, and a combination thereof and the metal oxide nanoparticles consist of metal oxide nanoparticles having an average particle size ranging from greater than 10 nm to about 500 nm;
a powder bed material comprising polymer particles; and
a radiant electromagnetic energy source that emits about 80% to 100% electromagnetic energy within an absorption wavelength range of from about 300 nm to about 400 nm, the radiant electromagnetic energy source positioned to expose a layer of the powder bed material to the electromagnetic energy to selectively fuse the polymer particles in contact with the metal oxide nanoparticles.

### Claim 7 (depends on 6)

The system of claim 6, wherein the radiant electromagnetic energy source comprises a narrow band light emitting diode having a peak emission at about 365 nm, about 385 nm, or about 395 nm.

### Claim 8 (depends on 6)

The system of claim 6, further comprising a detailing agent ejectable onto a layer of the powder bed material, a colored agent ejectable onto the layer of the powder bed material, or a combination thereof, wherein the detailing agent comprises a detailing compound and the colored agent comprises water and a colorant.

### Claim 9 (depends on 1)

The three-dimensional printing kit of claim 1, wherein the metal oxide nanoparticles consist of metal oxide nanoparticles having an average particle size ranging from about 50 nm to about 60 nm.

### Claim 10 (depends on 1)

The three-dimensional printing kit of claim 1, wherein the fusing agent is free of a black pigment.