Stereolithography resin for rapid prototyping of ceramics and metals

• US 6,117,612 A
• Filed: 10/08/1997
• Issued: 09/12/2000
• Est. Priority Date: 04/24/1995
• Status: Expired due to Term

• Current Assignee: Board of Regents of the University of Michigan (University of Michigan)
• Original Assignee: Board of Regents of the University of Michigan (University of Michigan)
• Inventors: Griffith, Michelle, Chu, Tien-Min, Halloran, John W.
• Primary Examiner(s): Hamilton, Cynthia
• Application Number:
  US08/947,269
• Time in Patent Office: 1,070 Days
• Field of Search: 430/283.1, 430/269, 430/325, 430/330, 264/401, 264/430, 264/434
• US Class Current: 430/269
• CPC Class Codes: B33Y 10/00 Processes of additive manufacturing
• CPC Class Codes: B33Y 70/10 Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
• CPC Class Codes: C04B 2235/5436 micrometer sized, i.e. from 1 to 100 micron
• CPC Class Codes: C04B 2235/5445 submicron sized, i.e. from 0,1 to 1 micron
• CPC Class Codes: C04B 2235/6026 Computer aided shaping, e.g. rapid prototyping
• CPC Class Codes: C04B 35/111 Fine ceramics
• CPC Class Codes: C04B 35/14 based on silica
• CPC Class Codes: C04B 35/447 based on phosphates , e.g. hydroxyapatite
• CPC Class Codes: C04B 35/622 Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
• CPC Class Codes: C04B 35/632 Organic additives
• CPC Class Codes: C04B 35/63424 Polyacrylates; Polymethacrylates
• CPC Class Codes: C04B 35/63468 Polyamides
• CPC Class Codes: C22C 38/42 with copper
• CPC Class Codes: G03F 7/0037 Production of three-dimensional images
• CPC Class Codes: G03F 7/0047 characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing

Abstract

Photocurable ceramic resins having solids loadings in excess of 40 volume percent and a viscosity of less than 3000 mPa·s are suitable for multi-layer fabrication of green ceramic parts by stereolithography and similar techniques. The green ceramic parts, which may be of traditional ceramic materials, sinterable metals, or combinations thereof, exhibit low shrinkage upon firing or sintering, and may be used for such applications as rapid prototyping, biocompatible ceramic parts, ceramic cores for investment casting, ceramic molds for metal casting, and the like.

Claims

1. A process for the preparation of a multi-layer ceramic green body, comprising:

a) selecting an aqueous photopolymerizable ceramic resin comprising;

i) from 40 to about 80 volume percent of one or more sinterable powders;

ii) one or more photopolymerizable monomer(s);

iii) an effective amount of a photoinitiator; and

iv) a dispersant;

wherein said photopolymerizable ceramic resin has a viscosity at 25°

C. of less than 3000 mPa·

s;

b) coating a substrate with a first layer of said photopolymerizable ceramic resin;

c) irradiating at least a portion of said layer with an energy source effective to activate said photoinitiator and induce photopolymerization of said layer to form a polymerized ceramic layer;

d) coating said polymerized ceramic layer with a further layer of photopolymerizable ceramic resin;

e) irradiating said further layer with an energy source effective to activate said photoinitiator and induce photopolymerization of said further layer to form a further polymerized ceramic layer;

f) repeating steps d) and e) until a green ceramic body of a desired size and shape has been obtained.

2. The process of claim 1 wherein said irradiating comprises scanning the surface of a layer of photopolymerizable ceramic resin with a laser beam, the position of said laser beam being controlled by signals generated by a computer.

3. The process of claim 2 wherein said computer-generated signals are derived from a CAD program wherein said portion of said layer which is scanned corresponds to the dimensions of a plane section of a three-dimensional object having the dimensions of a ceramic green body whose preparation is desired.

4. The process of claim 1 wherein a stereolithography device is utilized to perform steps b) through f).

5. A ceramic green body prepared by the process of claim 4.

6. The process of claim 1 wherein said aqueous photopolymerizable resin comprises one or more water-soluble photopolymerizable monomers.

7. The process of claim 6 wherein at least one of said water-soluble photopolymerizable monomers comprise acrylamide, methacrylamide, methylene bisacrylamide, or mixtures thereof.

8. The process of claim 6 wherein said photoinitiators are phosphine oxide photoinitiators present in amounts such that said photoinitiators are soluble in said ceramic resin at room temperature.

9. A ceramic green body prepared by the process of claim 6.

10. The process of claim 1 wherein said photopolymerizable liquid comprises one or more photopolymerizable acrylate monomers.

11. The process of claim 10 wherein one of said one or more acrylate monomers are selected from the group consisting of hexanediol diacrylate, neopentyl glycol dipropoxylate diacrylate, and trimethylolpropane triacrylate.

12. A ceramic green body prepared by the process of claim 10.

13. The process of claim 1 wherein said photopolymerizable ceramic resin further comprises an index of refraction altering substance soluble in said liquid.

14. The process of claim 13 wherein said index of refraction altering substance is present in an amount of from about 5 weight percent to about 30 weight percent based on the weight of said liquid containing said index of refraction altering substance.

15. The process of claim 13 wherein said liquid comprises water and one or more water soluble monomers, and said index of refraction altering substance comprises one or more glycols, glycol ethers, polyhydric aliphatic polyols, or mixtures thereof.

16. A ceramic green body prepared by the process of claim 13.

17. A ceramic green body prepared by the process of claim 1.

18. The process of claim 1 wherein said photopolymerizable resin comprises water and one or more photopolymerizable monomers, said monomer(s) present in an amount of from about 5 weight percent to about 50 weight percent relative to the sum of the weights of water and monomer(s).

19. The process of claim 1 wherein said photopolymerizable resin comprises water and one or more photopolymerizable monomers, said monomer(s) present in an amount of from about 15 weight percent to about 40 weight percent relative to the sum of the weights of water and monomer(s).

20. The process of claim 1 wherein said monomer(s) comprise acrylamide and methylenebisacrylamide in an acrylamide/methylenebisacrylamide ratio of 20:

1 to 1;

1.

21. A process for the preparation of a multi-layer ceramic green body, comprising:

a) selecting a photopolymerizable ceramic resin comprising;

i) from 40 to about 80 volume percent of one or more sinterable powders;

ii) a photopolymerizable liquid;

iii) an effective amount of a photoinitiator; and

iv) a dispersant;

wherein said photopolymerizable ceramic resin has a viscosity of 25°

C. of less than 3000 mPa·

s;

b) coating a substrate with a first layer of said photopolymerizable ceramic resin;

c) irradiating at least a portion of said layer with an energy source effective to activate said photoinitiator and induce photopolymerization of said layer to form a polymerized ceramic layer;

d) coating said polymerized ceramic layer with a further layer of photopolymerizable ceramic resin;

e) irradiating said further layer with an energy source effective to activate said photoinitiator and induce photopolymerization of said further layer to form a further polymerized ceramic layer;

f) repeating steps d) and e) until a green ceramic body of a desired size and shape has been obtained;

wherein said photopolymerizable ceramic resin further comprises an index of refraction altering substance.

22. A process for the preparation of a multi-layer ceramic green body, comprising:

a) selecting an aqueous photopolymerizable ceramic resin having a continuous aqueous phase and a dispersed sinterable powder phase, comprising;

i) from 40 to about 80 volume percent of one or more sinterable powders;

ii) one or more photopolymerizable monomers;

iii) an effective amount of a photoinitiator; and

iv) a dispersant;

wherein said photopolymerizable ceramic resin has a viscosity at 25°

C. of less than 3000 mPa·

s;

b) coating a substrate with a first layer of said photopolymerizable ceramic resin;

c) irradiating at least a portion of said layer with an energy source effective to activate said photoinitiator and induce photopolymerization of said layer to form a polymerized ceramic layer;

d) coating said polymerized ceramic layer with a further layer of photopolymerizable ceramic resin;

e) irradiating said further layer with an energy source effective to activate said photoinitiator and induce photopolymerization of said further layer to form a further polymerized ceramic layer;

f) repeating steps d) and e) until a green ceramic body of a desired size and shape has been obtained;

wherein said photopolymerizable ceramic resin further comprises an index of refraction altering substance soluble in the continuous aqueous phase of said aqueous photopolymerizable ceramic resin, said index of refraction altering substance present in an amount of from about 5 weight percent to about 30 weight percent based on the weight of said continuous aqueous phase containing said index of refraction altering substance, wherein said index of refraction altering substance comprises ethylene glycol.

23. A process for the preparation of a multi-layer ceramic green body, comprising:

a) selecting an aqueous photopolymerizable ceramic resin comprising;

i) from 40 to about 80 volume percent of one or more sinterable powders;

ii) one or more photopolymerizable monomers;

iii) an effective amount of a photoinitiator; and

iv) a dispersant;

wherein said photopolymerizable ceramic resin has a viscosity at 25°

C. of less than 3000 mPa·

s;

b) coating a substrate with a first layer of said photopolymerizable ceramic resin;

c) irradiating at least a portion of said layer with an energy source effective to activate said photoinitiator and induce photopolymerization of said layer to form a polymerized ceramic layer;

d) coating said polymerized ceramic layer with a further layer of photopolymerizable ceramic resin;

e) irradiating said further layer with an energy source effective to activate said photoinitiator and induce photopolymerization of said further layer to form a further polymerized ceramic layer;

f) repeating steps d) and e) until a green ceramic body of a desired size and shape has been obtained; and

wherein said photopolymerizable ceramic resin further comprises an effective amount of an anti-skinning agent.

24. The process of claim 23 wherein said anti-skinning agent comprises a glycol, glycol ether, polyhydric aliphatic polyol, or mixture thereof.

25. The process of claim 24 wherein said anti-skinning agent comprises ethylene glycol.

26. A ceramic green body prepared by the process of claim 23.