# US 10,479,733 B2 · Powder comprising polymer-coated core particles comprising metals, metal oxides, metal nitrides or semimetal nitrides

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- Number: US 10,479,733 B2
- Document ID: US10479733B2
- Status: Granted
- Kind: B2
- Application number: 13/537,148
- Filed: 2012-06-29
- Published: 2013-01-10
- Granted: 2019-11-19
- Earliest claimed: 2011-07-06
- Assignees: Evonik Degussa GmbH
- Applicants: Wolfgang Diekmann; Franz-Erich Baumann; Maik Grebe; Kristiane Warnke; Sylvia Monsheimer
- Inventors: Wolfgang Diekmann; Franz-Erich Baumann; Maik Grebe; Kristiane Warnke; Sylvia Monsheimer
- Web page: https://patentgrep.com/patent/US10479733B2

## CPC

- C04B 35/628: Coating the powders {or the macroscopic reinforcing agents}
- B22F 1/102: Metallic powder coated with organic material
- B22F 10/28: Powder bed fusion, e.g. selective laser melting [SLM] or electron beam melting [EBM]
- B29C 64/153: using layers of powder being selectively joined, e.g. by selective laser sintering or melting
- B29C 67/04: Sintering (combined with compression B29C43/00)
- B33Y 70/10: Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
- C04B 35/6264: {Mixing media, e.g. organic solvents}
- C04B 35/62897: {Coatings characterised by their thickness}
- C04B 35/634: Polymers (C04B35/636 takes precedence)
- C04B 35/63468: {Polyamides}
- C09C 3/10: Treatment with macromolecular organic compounds {(C09C3/006 takes precedence)}
- C09D 177/02: Polyamides derived from omega-amino carboxylic acids or from lactams thereof (C09D177/10 takes precedence)
- C01P 2002/88: by thermal analysis data, e.g. TGA, DTA, DSC
- C01P 2004/62: Submicrometer sized, i.e. from 0.1-1 micrometer
- C01P 2004/84: one phase coated with the other
- C01P 2006/12: Surface area
- C04B 2235/3217: Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
- C04B 2235/3852: Nitrides, e.g. oxynitrides, carbonitrides, oxycarbonitrides, lithium nitride, magnesium nitride
- C04B 2235/5409: expressed by specific surface values
- C04B 2235/5436: micrometer sized, i.e. from 1 to 100 micron
- C04B 2235/6026: Computer aided shaping, e.g. rapid prototyping
- C04B 2235/665: Local sintering, e.g. laser sintering
- Y02P 10/25: Process efficiency
- Y10T 428/25: Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T 428/2998: including synthetic resin or polymer
- 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
- B22F: WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER (making alloys by powder metallurgy C22C); APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- 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
- C09C: TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES (treatment of materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone C04B14/00, C04B18/00, C04B20/00); PREPARATION OF CARBON BLACK {; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS}
- 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)
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

Composite particles comprising core particles completely or partially coated with a precipitated polymer, where the d50 median diameter of the core particles is 1 μm or greater and the ratio of the d50 median diameter of the composite particles to the d50 median diameter of the core particles is 1.15 or greater, are provided. A method to prepare the particles includes dissolution of a polymer in a solvent and reprecipitation of the polymer in the presence of a suspension of the core particles. Further provided is a layer by layer moulding process employing the composite particles and mouldings obtained therefrom.

## Claims

### Claim 1

A powder, comprising composite particles:
wherein the composite particles, comprise:
a core particle; and
a coating of a precipitated polymer on the core;
wherein
a thickness of the precipitated polymer coating of the composite particle is from 1.5 to 35 μm,
the core particle is at least one material selected from the group consisting of a metal, a metal nitride, a semimetal nitride and a metal oxide selected from the group consisting of Al2O3, ZrO2, ZnO, Bi2O3, CeO2, ITO (indium oxide doped with tin(IV) oxide), having a d50 median diameter of from 1 to 100 μm,
the precipitated polymer of the coating comprises at least one polymer selected from the group consisting of nylon-11, nylon-12, PA1010, PA1012, PA1212 and PA1013,
the melting point of the precipitated polymer in a first heating procedure is greater than in a second heating procedure, as measured by differential scanning calorimetry (DSC),
a ratio of a d50 median diameter of the composite particles to the d50 median diameter of the core particles is 1.15 to 30, and
the melting point of the precipitated coating polymer is obtainable when the polymer is exposed to an electromagnetic energy.

### Claim 2 (depends on 1)

The powder according to claim 1, wherein a d50 median diameter of the composite particles is from 20 to 150 μm.

### Claim 3 (depends on 1)

The powder according to claim 1, wherein a number average weight ratio of the polymer coating to the core particle, is from 0.1 to 30.

### Claim 4 (depends on 1)

The powder according to claim 1, wherein a BET specific surface area of the composite particle is from 1 to 60 m2/g.

### Claim 5 (depends on 1)

The powder according to claim 1, wherein an enthalpy of fusion of the precipitated polymer in the first heating procedure is at least 50% greater than in the second heating procedure, as measured by differential scanning calorimetry (DSC).

### Claim 6 (depends on 1)

The powder according to claim 1, which further comprises at least one selected from the group consisting of a powder-flow aid, an organic pigment, an inorganic pigment, and a sterically hindered phenol.

### Claim 7 (depends on 6)

The powder according to claim 6, wherein a content of the composite particles in the powder is at least 50% by weight.

### Claim 8 (depends on 1)

A process for producing the composite particles according to claim 1, the process comprising: at least partially dissolving a polymer for the coating in a medium comprising a solvent which at least partially dissolves the polymer; adding the core particles to the medium, before, during or after at least partially dissolving the polymer; suspending the core particles in the medium; and then precipitating the polymer from the at least partial solution onto the core particles to obtain the composite particles.

### Claim 9 (depends on 8)

The process according to claim 8, wherein a density of the core particles is not more than 20% smaller than the density of the solvent used for the precipitation of the polymer.

### Claim 10 (depends on 8)

The process according to claim 8, wherein the solvent for the polymer is ethanol and a density of the core particles is not more than 20% smaller than the density of ethanol.

### Claim 11 (depends on 1)

A process for producing a moulded article, the process comprising:
applying a layer of the composite particles according to claim 1;
selectively melting at least one region of the layer by introduction of electromagnetic energy;
allowing the melted region to solidify;
applying another layer of the composite particles and repeating the melting and solidification to perform a layer-by-layer process in which a molding having a structure according to the selective treatment is obtained;
wherein the melting selectivity is achieved by applying susceptors, inhibitors, or absorbers to each applied layer or by applying a mask to the applied layer.

### Claim 12 (depends on 11)

A moulded article obtained according to the process of claim 11.