Methods for the preparation of three-dimensional bodies

• US 5,932,290 A
• Filed: 09/26/1997
• Issued: 08/03/1999
• Est. Priority Date: 08/08/1994
• Status: Expired due to Term

• Current Assignee: Advanced Ceramics Research LLC
• Original Assignee: Advanced Ceramics Research, Inc. (Rtx Corporation)
• Inventors: Calvert, Paul, Lombardi, John, Creegan, Peter, Mulligan, Anthony, Stuffle, Kevin
• Primary Examiner(s): Henderson, Christopher
• Application Number:
  US08/938,039
• Time in Patent Office: 676 Days
• Field of Search: 427/372.2, 427/226, 427/261, 427/374.1, 427/376.1, 427/379, 427/385.5, 427/393.5, 427/407.1, 427/868.26
• US Class Current: 427/385.5
• CPC Class Codes: B29C 41/22 Making multilayered or multicoloured articles
• CPC Class Codes: 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
• CPC Class Codes: B29K 2033/00 Use of polymers of unsaturated acids or derivatives thereof as moulding material B29K2035/00 takes precedence
• CPC Class Codes: B29K 2105/0002 monomers or prepolymers
• CPC Class Codes: B29K 2105/0094 having particular viscosity
• CPC Class Codes: B29K 2105/246 Uncured, e.g. green
• CPC Class Codes: B29K 2709/02 Ceramics
• 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

Abstract

The present invention generally relates compositions and methods for the preparation of three-dimensional bodies e.g., green bodies, ceramic-loaded green bodies, and polymer matrix composites by the controlled, sequential deposition of layers of material upon one another The method for preparing a green body comprises depositing a liquid composition having a viscosity of at least about 10 poise and comprising thermally-polymerizable components onto a base in a predetermined pattern to form a layer of the liquid composition on the base. Subsequently, at least one further layer of the liquid composition is deposited on a previously-formed layer in a predetermined pattern to form a multi-layered intermediate and, then, the multi-layered intermediate is heated to cause the thermally-polymerizable components to polymerize, providing the three-dimensional green body. Another method of the present invention provides a method for reinforcing a green body with fibers. More than simply reinforcing the body, however, this particular aspect of the present invention allows the alignment of reinforcing fibers in the body to be controlled. A further aspect of the present invention is the discovery of a novel composition which may be used to provide a three-dimensional polymer matrix composite using free-formation methods. This composition comprises at least one urethane acrylate oligomer, at least one vinyl monomer, and has a viscosity of at least 10 poise.

Claims

1. A method for preparing a three-dimensional green body comprising

passing a first liquid composition having a viscosity of at least about 10 poise and comprising thermally-polymerizable components through a dispensing head and onto a base in a predetermined pattern to form a layer of the first liquid composition on the base,

passing a second liquid composition through a dispensing head and onto the previously-formed layer of the first liquid composition in a predetermined pattern to provide a multi-layered intermediate,

heating the multi-layered intermediate to cause the thermally-polymerizable components in the first and second liquid compositions to polymerize,

wherein the first and second liquid compositions are the same or different.

2. The method according to claim 1, wherein during the heating step, the temperature of the multi-layered intermediate increases substantially uniformly throughout intermediate during heating until the initiation temperature is reached.

3. The method according to claim 2, wherein the multi-layered intermediate is heated by applying heat to the base.

4. The method according to claim 1, wherein at least one liquid composition is degassed prior to deposition.

5. The method according to claim 1, wherein at least one liquid composition has a viscosity of at least about 100 poise.

6. The method according to claim 1, wherein at least one liquid composition is deposited by a positive-displacement extruder.

7. The method according to claim 6, wherein at least one liquid composition is deposited by a screw-actuated, piston-type, positive-displacement extruder.

8. The method according to claim 1, at least one liquid composition further comprising ceramic particles.

9. The method according to claim 8, at least one liquid composition further comprising reinforcing fibers.

10. The method according to claim 1, at least one liquid composition further comprising reinforcing fibers.

11. The method according to claim 8, further comprising heating the multi-layered intermediate at a temperature which sinters that ceramic particles.

12. The method according to claim 8, wherein during the heating step, the temperature of the multi-layered intermediate increases substantially uniformly throughout the intermediate during heating until the initiation temperature is reached.

13. The method according to claim 1, wherein the thermally-polymerizable components comprise at least one multifunctional monomer.

14. The method according to claim 13, wherein the at least one multifunctional monomer comprises at least one acrylate monomer.

15. The method according to claim 14, at least one liquid composition further comprising at least one polymerization initiator and a solvent for the at least one acrylate monomer.

16. The method according to claim 15, wherein the viscosity of at least one liquid composition is at least 100 poise.

17. The method according to claim 16, wherein the at least one acrylate monomer is present in the liquid composition an amount ranging from about 0.1 wt. % to about 55 wt. %.

18. The method according to claim 17, wherein the at least one acrylic monomer comprises a mixture of trimethylol propane triacrylate and hexanedioldiacrylate.

19. The method according to claim 18, at least one liquid composition further comprising reinforcing fibers.

20. The method according to claim 18, wherein trimethylol propane triacrylate is present in an amount of from about 1 wt. % to about 15 wt. % and hexanedioldiacrylate is present in an amount of from about 10 wt. % to about 70 wt. %.

21. A method for preparing a fiber-reinforced three-dimensional body comprising

passing a first fiber-laden suspension having a viscosity of at least about 10 poise and comprising fibers and thermally-polymerizable components through a flow passage of a nozzle, the flow passage being configured so that the fibers are oriented substantially parallel to each other and substantially in the direction of the first fiber-laden suspension movement relative to the nozzle as the first fiber-laden suspension passes through the flow passage,

depositing the first fiber-laden suspension after it has passed through the flow passage onto a base in a predetermined pattern to provide a layer of the first fiber-laden suspension on the base,

simultaneously with the deposition of the first fiber-laden suspension onto the base, moving the nozzle and base relative to one another so that the fibers in the deposited layer of the first fiber-laden suspension are aligned substantially parallel to the direction of relative movement of the nozzle, and

heating the layer to cause the thermally-polymerizable components of the deposited layer of the first fiber-laden suspension to polymerize.

22. The method according to claim 21, further comprising

passing a second fiber-laden suspension having a viscosity of at least about 10 poise and comprising fibers and thermally-polymerizable components through a flow passage of a nozzle, the flow passage being configured so that the fibers in the second fiber-laden suspension are oriented substantially parallel to each other and substantially in the direction of the second fiber-laden suspension movement relative to the nozzle as the second fiber-laden suspension gasses through the flow passage,

depositing the second fiber-laden suspension after it has passed through the flow passage onto the previously-formed layer of the first fiber-laden suspension in a predetermined pattern to provide a multi-layered intermediate,

simultaneously with the deposition of the second fiber-laden suspension onto the previously-formed layer of the first fiber-laden suspension, moving the nozzle and base relative to one another so that the fibers in the deposited layer of the second fiber-laden composition are aligned substantially parallel to the direction of relative movement of the nozzle, and

heating the multi-layered intermediate to cause the thermally-polymerizable components to polymerize,

wherein the first and second fiber-laden compositions are the same or different.

23. The method according to claim 22, wherein during the heating step, the temperature of the multi-layered intermediate increases substantially uniformly throughout the intermediate during heating until the initiation temperature is reached.

24. The method according to claim 21, wherein at least one suspension has a viscosity of at least about 100 poise.

25. The method according to claim 21, wherein at least one suspension is deposited by a positive-displacement extruder.

26. The method according to claim 21, wherein the fibers comprise from about 1 vol. % to about 40 vol. % of at least one suspension.

27. The method according to claim 21, wherein at least one suspension is degassed prior to deposition.