METHOD OF ADDITIVE MANUFACTURING BY FABRICATION THROUGH MULTIPLE ZONES

• US 20160303793A1
• Filed: 06/29/2016
• Published: 10/20/2016
• Est. Priority Date: 02/05/2015
• Status: Active Grant

• Current Assignee: Carbon, Inc.
• Original Assignee: Carbon3D, Inc.
• Inventors: Ermoshkin, Alexander, Shirvanyants, David, Tumbleston, John R.
• Granted Patent: US 10,155,345 B2
• Time in Patent Office: Days
• US Class Current: 1/1
• CPC Class Codes: B29C 64/106 using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
• CPC Class Codes: B29C 64/124 using layers of liquid which are selectively solidified
• CPC Class Codes: B29C 64/129 characterised by the energy source therefor, e.g. by global irradiation combined with a mask
• CPC Class Codes: B29C 64/20 Apparatus for additive manufacturing; Details thereof or accessories therefor
• CPC Class Codes: B29C 64/245 Platforms or substrates support structures intended to be sacrificed after manufacture B29C64/40
• CPC Class Codes: B29C 64/386 Data acquisition or data processing for additive manufacturing
• CPC Class Codes: B29C 64/393 for controlling or regulating additive manufacturing processes
• CPC Class Codes: B29C 64/40 Structures for supporting 3D objects during manufacture and intended to be sacrificed after completion thereof
• CPC Class Codes: B33Y 10/00 Processes of additive manufacturing
• CPC Class Codes: B33Y 50/02 for controlling or regulating additive manufacturing processes
• CPC Class Codes: B33Y 70/00 Materials specially adapted for additive manufacturing

Abstract

A method of forming a three-dimensional object is carried out by: (a) providing a carrier and an optically transparent member having a build surface, the carrier and the build surface defining a build region therebetween, with the carrier positioned adjacent and spaced apart from the build surface at a start position; then (b) forming an adhesion segment of the three-dimensional object (c) optionally but preferably forming a transition segment of the three dimensional object; and then (d) forming a body segment of the three dimensional object. In each case, the segment can be formed by: (i) filling the build region with a polymerizable liquid, (ii) continuously or intermittently irradiating the build region with light through the optically transparent, and (iii) continuously or intermittently advancing the carrier away from the build surface, to thereby form that segment from the polymerizable liquid.

Claims

1. A method of forming a three-dimensional object, comprising:

(a) providing a carrier and an optically transparent member having a build surface, said carrier and said build surface defining a build region therebetween, with said carrier positioned adjacent and spaced apart from said build surface at a start position;

then

(b) forming an adhesion segment of said three-dimensional object by;

(i) filling said build region with a polymerizable liquid,

(ii) irradiating said build region with light through said optically transparent member (e.g., by a single exposure), while

(iii) maintaining said carrier stationary or advancing said carrier away from said build surface at a first cumulative rate of advance, to thereby form from said polymerizable liquid a solid polymer adhesion segment of said object adhered to said carrier;

then

(c) optionally but preferably forming a transition segment of said three dimensional object by

(i) filling said build region with a polymerizable liquid,

(ii) continuously or intermittently irradiating said build region with light through said optically transparent member, and

(iii) continuously or intermittently advancing said carrier away from said build surface at a second cumulative rate of advance to thereby form from said polymerizable liquid a transition segment of said object between said adhesion segment and said build surface;

wherein said second cumulative rate of advance is greater than said first cumulative rate of advance; and

then

(d) forming a body segment of said three dimensional object by;

(i) filling said build region with a polymerizable liquid,

(ii) continuously or intermittently irradiating said build region with light through said optically transparent, and

(iii) continuously or intermittently advancing said carrier away from said build surface at a third cumulative rate of advance, to thereby form from said polymerizable liquid a body segment of said object between said transition segment and said build surface;

wherein said third cumulative rate of advance is greater than said first and/or said second cumulative rate of advance.

2. The method of claim 1, wherein said start position can be any position among a range of positions, and said irradiating step (b)(ii) is carried out at an intensity sufficient to adhere said solid polymer to said carrier when said carrier is at any position within said range of positions.

3. The method of claim 1, wherein said filling step (d)(i), said irradiating step (d)(ii), and/or said advancing step (d)(iii), and/or wherein said filling step (c)(i), said irradiating step (c)(ii), and/or said advancing step (d)(iii), are carried out while also concurrently:

(i) continuously maintaining a dead zone of polymerizable liquid in contact with said build surface, and

(ii) continuously maintaining a gradient of polymerization zone between said dead zone and said solid polymer and in contact with each thereof, said gradient of polymerization zone comprising said polymerizable liquid in partially cured form.

4. The method claim 1, wherein said build surface is fixed and stationary in the lateral dimensions.

5. The method of claim 1, wherein said advancing is carried out at a cumulative rate of at least 0.1 microns per second.

6. The method of claim 1, wherein said optically transparent member comprises a semipermeable member, and said continuously maintaining a dead zone is carried out by feeding an inhibitor of polymerization through said optically transparent member in an amount sufficient to maintain said dead zone and said gradient of polymerization.

7. The method of claim 1, wherein said optically transparent member is comprised of a semipermeable polymer.

8. The method of claim 1, wherein said gradient of polymerization zone and said dead zone together have a thickness of from 1 to 1000 microns.

9. The method of claim 1, wherein said gradient of polymerization zone is maintained for a time of at least 5 seconds.

10. The method of claim 1, further comprising the step of heating said polymerizable liquid to reduce the viscosity thereof in said build region.

11. The method of claim 1, wherein said irradiating step is carried out by maskless photolithography.

12. The method of claim 1, wherein:

said polymerizable liquid comprises a free radical polymerizable liquid and said inhibitor comprises oxygen;

or

said polymerizable liquid comprises an acid-catalyzed or cationically polymerizable liquid, and said inhibitor comprises a base.

13. A method of claim 1, wherein:

said polymerizable liquid comprises a mixture of (1) a light polymerizable liquid first component, and (ii) a second solidifiable component that is different from said first component,

said method further comprising;

concurrently with or following the forming of said three dimensional object, solidifying and/or curing said second solidifiable component in said three-dimensional object.

14. The method of claim 13, wherein said second component comprises a polymerizable liquid solubilized in or suspended in said first component.

15. The method of claim 13, wherein said second component comprises:

(i) a polymerizable solid suspended in said first component;

(ii) a polymerizable solid solubilized in said first component;

or

(iii) a polymer solubilized in said first component.

16. The method of claim 13, wherein said three-dimensional intermediate is collapsible or compressible.

17. The method of claim 13, wherein said three-dimensional object comprises a polymer blend, interpenetrating polymer network, semi-interpenetrating polymer network, or sequential interpenetrating polymer network formed from said first component and said second component.

18. The method of claim 13, wherein said polymerizable liquid comprises:

from 1 percent by weight to or 99 percent by weight of said first component; and

from 1 percent by weight to 99 percent by weight of said second component.

19. The method of claim 13, wherein said solidifying and/or curing step (d) is carried out concurrently with said irradiating step (c) and:

(i) said solidifying and/or curing step is carried out by precipitation;

or

(ii) said irradiating step generates heat from the polymerization of said first component in an amount sufficient to thermally solidify or polymerize said second component.

20. The method of claim 13, wherein said solidifying and/or curing step (d) is carried out subsequent to said irradiating step (c) and is carried out by:

(i) heating said second solidifiable component;

(ii) irradiating said second solidifiable component with light at a wavelength different from that of the light in said irradiating step (c);

(iii) contacting said second polymerizable component to water; and

/or

(iv) contacting said second polymerizable component to a catalyst.

21. The method of claim 13, wherein:

said second component comprises the precursors to a polyurethane, polyurea, or copolymer thereof, a silicone resin, an epoxy resin, a cyanate ester resin, or a natural rubber; and

said solidifying step is carried out by heating and/or microwave irradiating.

22. The method of claim 13, wherein:

said second component comprises the precursors to a polyurethane, polyurea, or copolymer thereof, and

said solidifying and/or curing step is carried out by contacting said second component to water.

23. The method of claim 13, wherein:

said solidifying and/or curing step (d) is carried out subsequent to said irradiating step; and

said solidifying and/or curing step (d) is carried out under conditions in which said solid polymer scaffold degrades and forms a constituent necessary for the polymerization of said second component.

24. The method of claim 13, wherein:

said second component comprises precursors to a polyurethane, polyurea, or copolymer thereof, a silicone resin, a ring-opening metathesis polymerization resin, or a click chemistry resin, a cyanate ester resin, and

said solidifying and/or curing step is carried out by contacting said second component to a polymerization catalyst.

25. The method of claim 13, wherein said polymerizable liquid comprises a first component (Part A) and at least one additional component (Part B),

said first component comprising monomers and/or prepolymers that can be polymerized by exposure to actinic radiation or light;

said second component solidifiable on contacting to heat, water, water vapor, light at a different wavelength than that at which said first component is polymerized, catalysts, evaporation of a solvent from the polymerizable liquid, exposure to microwave irradiation, and combinations thereof.

26. The method of claim 25, said first component monomers and/or prepolymers comprising reactive end groups selected from the group consisting of acrylates, methacrylates, α

-olefins, N-vinyls, acrylamides, methacrylamides, styrenics, epoxides, thiols, 1,3-dienes, vinyl halides, acrylonitriles, vinyl esters, maleimides, and vinyl ethers.

27. The method of claim 25, said additional component comprising monomers and/or prepolymers comprising reactive end groups selected from the group consisting of:

epoxy/amine, epoxy/hydroxyl, oxetane/amine, oxetane/alcohol, isocyanate/hydroxyl, isocyanate/amine, isocyanate/carboxylic acid, cyanate ester, anhydride/amine, amine/carboxylic acid, amine/ester, hydroxyl/carboxylic acid, hydroxyl/acid chloride, amine/acid chloride, vinyl/Si—

H, Si—

Cl/hydroxyl, Si—

Cl/amine, hydroxyl/aldehyde, amine/aldehyde, hydroxymethyl or alkoxymethyl amide/alcohol, aminoplast, alkyne/azide, click chemistry reactive groups, alkene/sulfur, alkene/thiol, alkyne/thiol, hydroxyl/halide, isocyanate/water, Si—

OH/hydroxyl, Si—

OH/water, Si—

OH/Si—

H, Si—

OH/Si—

OH, perfluorovinyl, diene/dienophiles, olefin metathesis polymerization groups, olefin polymerization groups for Ziegler-Natta catalysis, and ring-opening polymerization groups and mixtures thereof.

28. The method of claim 13, wherein said three-dimensional object comprises an interpenetrating polymer network (IPN), said interpenetrating polymer network comprising a sol-gel composition, a hydrophobic-hydrophilic IPN, a phenolic resin, a polyimide, a conductive polymer, a natural product-based IPN, a sequential IPN, a polyolefin, or a combination thereof.