# US 11,027,487 B2 · Functional surface coating methods for additively manufactured products

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- Number: US 11,027,487 B2
- Document ID: US11027487B2
- Status: Granted
- Kind: B2
- Application number: 16/982,163
- Filed: 2019-03-22
- Published: 2021-01-28
- Granted: 2021-06-08
- Earliest claimed: 2018-03-27
- Assignees: Carbon, Inc.
- Applicants: Carbon, Inc.
- Inventors: R. Griffin Price; Raymond C. Pederkoff; Matthew S. Menyo
- Web page: https://patentgrep.com/patent/US11027487B2

## CPC

- 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 64/124: using layers of liquid which are selectively solidified
- B29C 64/129: characterised by the energy source therefor, e.g. by global irradiation combined with a mask
- B29C 64/135: the energy source being concentrated, e.g. scanning lasers or focused light sources
- B29C 64/188: involving additional operations performed on the added layers, e.g. smoothing, grinding or thickness control (surface shaping B29C59/00; after-treatment of articles without altering their shape B29C71/00)
- B29C 71/0009: {using liquids, e.g. solvents, swelling agents (spectacle cases, e.g. for cleaning contact lenses A45C11/04; disinfecting or sterilising contact lenses A61L12/00, using liquid substances A61L2/20; cleaning involving the use of liquid in general B08B3/00; for hydrating contact lenses B29D11/00067)}
- B33Y 10/00: Processes of additive manufacturing
- 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
- B05D 3/0218: {Pretreatment, e.g. heating the substrate}
- B05D 2201/02: Polymeric substrate
- B05D 2401/32: applied as powders
- B29C 71/00: After-treatment of articles without altering their shape; Apparatus therefor (B29C44/56, B29C73/00 take precedence; surface shaping B29C59/00 {; for joined or sealed parts B29C66/03; after-treatment specially adapted for vulcanising tyres B29D30/0633})
- B29C 2071/0018: {Absorbing ingredients, e.g. drugs, flavourings, UV screeners, embedded in the articles}
- B29C 2071/0045: {Washing using non-reactive liquids}
- B29K 2049/00: Use of polyacetylene or cyanic ester resins, i.e. polymers having one or more carbon-to-carbon triple bonds or derivatives thereof, as moulding material
- B29K 2063/00: Use of {EP, i.e.} epoxy resins {or derivatives thereof}, as moulding material
- 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
- B05D: PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL (conveying articles or workpieces through baths of liquid B65G, e.g. B65G49/02)
- 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

## Abstract

Provided is a method of making a coated object, which may include stereolithographically producing a green intermediate object from a dual cure polymerizable resin, the intermediate object containing uncured polymerizable material therein; then, optionally cleaning the green object; then, in any order: coating at least one surface portion of the object with a particulate material; and heating the object sufficiently to further cure the object; the coating and/or heating steps carried out under conditions in which uncured polymerizable material sweats (or exudes) to the surface of said object, and wherein the uncured polymerizable material contacts the particulate material, polymerizes, and bonds the particulate material to the surface of the object during the coating and/or heating steps. Also provided is a coated object produced by the method.

## Claims

### Claim 1

A method of making a coated object, comprising:
stereolithographically producing a green intermediate object from a dual cure polymerizable resin, wherein said polymerizable resin comprises: (a) a cyanate ester dual cure resin; or (b) an epoxy dual cure resin, said intermediate object containing uncured polymerizable material therein; then,
optionally cleaning said green object; then, in any order:
coating at least one surface portion of said object with a particulate material; and
heating said object sufficiently to further cure said object;
said coating and/or heating steps carried out under conditions in which uncured polymerizable material sweats or exudes to the surface of said object, and
wherein the uncured polymerizable material contacts said particulate material, polymerizes, and bonds said particulate material to the surface of said object during said coating and/or heating steps.

### Claim 2 (depends on 1)

The method of claim 1, wherein said producing step is carried out by bottom-up stereolithography.

### Claim 3 (depends on 1)

The method of claim 1, wherein said polymerizable resin comprises the epoxy dual cure resin, said epoxy dual cure resin comprising:
(i) low viscosity epoxy monomers;
(ii) a low surface energy epoxy monomer; and/or
(iii) from 20 or 30 percent by weight to 50 or 60 percent by weight of epoxy monomer.

### Claim 4 (depends on 1)

The method of claim 1, wherein
said heating step precedes said coating step, and said coating step is carried out by contacting said object to a fluidized bed of said particulate material.

### Claim 5 (depends on 1)

The method of claim 1, wherein said cleaning step is carried out by blowing, wiping, contacting said object to an absorbent material, contacting said object to a solvent, or a combination thereof.

### Claim 6 (depends on 1)

The method of claim 1, wherein said particulate material comprises an organic material.

### Claim 7 (depends on 1)

The method of claim 1, wherein said particulate material comprises an inorganic material.

### Claim 8 (depends on 1)

The method of claim 1, wherein said particulate material has an average particle diameter of from 1 micron to 200 microns.

### Claim 9 (depends on 1)

The method of claim 1, wherein said particulate material comprises metal particles.

### Claim 10 (depends on 1)

The method of claim 1, wherein said particulate material comprises ceramic particles or ceramic composite particles.

### Claim 11 (depends on 1)

The method of claim 1, wherein said particulate material comprises ferromagnetic particles.

### Claim 12 (depends on 1)

The method of claim 1, wherein said particulate material comprises dry lubricant particles.

### Claim 13 (depends on 1)

The method of claim 1, wherein said particulate material comprises carbon nanotubes.

### Claim 14 (depends on 1)

The method of claim 1, wherein said particulate material comprises microcapsules.

### Claim 15 (depends on 1)

The method of claim 1, wherein said polymerizable resin comprises the cyanate ester dual cure resin.

### Claim 16 (depends on 1)

The method of claim 1, wherein said producing step is carried out by continuous liquid interface production.

### Claim 17 (depends on 3)

The method of claim 3, wherein the epoxy dual cure resin comprises a low viscosity epoxy monomer selected from the group consisting of: bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, 1,4 butanediol diglycidyl ether, 2-ethylhexyl glycidyl ether, cyclohexanedimethanol diglycidylether, cresyl glycidyl ether, neopentyl glycol diglycidylether, p-tertiarybutylphenol glycidyl ether, 4,4′-methylenebis(N,N-diglycidylaniline), trimethylolpropane triglycidylether, and an aliphatic monofunctional glycidyl ether.

### Claim 18 (depends on 3)

The method of claim 3, wherein the epoxy dual cure resin comprises a low surface energy epoxy monomer derived from dicyclopentadiene and phenol.

### Claim 19 (depends on 1)

The method of claim 1, wherein said heating step follows said coating step, and said coating step is carried out by spraying said object with said particulate material.

### Claim 20 (depends on 1)

The method of claim 1, wherein said particulate material comprises particles of boron carbide, boron oxide, boron nitride, sialon, silicon carbide, silicon nitride, steatite, titanium carbide, zinc oxide, zirconium dioxide, barium titanate, strontium titanate, silica, porcelain, glass microspheres, or a combination of two or more thereof.