Self-hardening material and process for layerwise formation of models

• US 9,643,360 B2
• Filed: 08/06/2007
• Issued: 05/09/2017
• Est. Priority Date: 08/20/2006
• Status: Active Grant

• Current Assignee: Voxeljet AG
• Original Assignee: Voxeljet AG
• Inventors: Kashani-Shirazi, Kaveh
• Primary Examiner(s): THROWER, LARRY W
• Application Number:
  US12/377,137
• Publication Number:
  US 20100291314A1
• Time in Patent Office: 3,564 Days
• Field of Search: 264113
• CPC Class Codes: B29C 64/153 using layers of powder being selectively joined, e.g. by selective laser sintering or melting
• 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 2033/12 Polymers of methacrylic acid esters, e.g. PMMA, i.e. polymethylmethacrylate
• CPC Class Codes: B29K 2105/16 Fillers
• 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 invention relates to a self-hardening material for layerwise construction of three-dimensional components, whereby the material comprises at least one particulate material and a separately applied bonding agent for bonding the particulate material, and has a setting time which is at least several times as long as the application time of a particulate layer.

Claims

1. A self-hardening material for layerwise construction of three-dimensional components comprising:

(i) at least one particulate material;

(ii) a bonding agent including a polymerizable monomer for bonding the particulate material; and

(iii) a delayer for delaying a polymerization reaction;

wherein the bonding agent is separate from the particulate material,

wherein the particulate material includes polymethylmethacrylate, polyethylmethacrylate acrylonitrile butadiene styrene (i.e., ABS), polycarbonate-acrylonitrile butadiene styrene (i.e., PC-ABS), polyamide (i.e., PA), polybutylene terephthalate (i.e., PBT), a metal, glass, or carbon fiber,

wherein the particulate material includes an initiator and is a loose material suitable for applying in a layerwise fashion,

wherein the bonding agent is a printable liquid suitable for applying over the particulate material and is separate from the particulate material, and

wherein a setting time of the material is greater than 20 times as long as an application time of a particulate layer.

2. The self-hardening material as per claim 1, wherein the setting time of the material is from greater than 20 times to 150 times as long as the application time of each layer.

3. The self-hardening material as per claim 1, wherein the bonding agent is based on acrylates, methacrylates, or styrols.

4. The self-hardening material as per claim 1, wherein the bonding agent contains a solvent.

5. A multi-layered structure comprising:

a first layer of a self-hardening material according to claim 1, and

a second layer of a self-hardening material according to claim 1,

wherein the first layer and the second layer each include a layer of the one particulate material to which the bonding agent is applied separately,

wherein the second layer is applied on top of the first layer while the first layer is not yet hardened, and

wherein the first layer and the second layer shrink by the same amount and at the same time.

6. The self-hardening material as per claim 1, wherein the self-hardening material includes an UV active compound.

7. The self-hardening material as per claim 1, wherein the initiator is benzoyl peroxide.

8. The self-hardening material as per claim 1, wherein the bonding agent is a polyurethane resin or epoxy resin.

9. The self-hardening material as per claim 1, wherein the bonding agent contains further ingredients that increase or decrease viscosity and/or surface tension so that printability is improved.

10. The self-hardening material as per claim 4, wherein the particulate material includes a base material that is soluble in the solvent and a filler material that is insoluble in the solvent.

11. The self-hardening material as per claim 10, wherein setting of the bonding agent takes place after formation of the three-dimensional components.

12. The self-hardening material as per claim 11, wherein the three-dimensional components demonstrate uncured setting within 72 hours, and

wherein a tension within the three-dimensional components causes curvature of the three-dimensional components.

14. The self-hardening material as per claim 1, wherein the delayer is benzochinone.

16. The self-hardening material as per claim 10, wherein the bonding agent includes a moisture-containing material, and the filler material is a metal powder, a glass, a carbon fiber, or an insoluble polymer.

18. A multi-layered structure comprising:

a first layer of a self-hardening material according to claim 1, and

a second layer of a self-hardening material according to claim 1,

wherein the first layer and the second layer each include a layer of the one particulate material to which the bonding agent is applied separately,

wherein the second layer is applied on top of the first layer when less than 5% of setting of the material and less than 5% of shrinkage of the material occur in the first layer, and

wherein the first layer and the second layer shrink by the same amount and at the same time.

19. The self-hardening material according to claim 1,

wherein the particulate material includes from 2-100 weight percent PMMA-beads, 0.1 to 5 weight percent benzoyl peroxide;

and 5 to 98 weight percent filler; and

wherein the binder includes 0 to 75 weight percent styrol monomer, 25 to 100 weight percent hydroxyethylemethacrylate monomer, 0 to 50 weight percent polyethylene glycol-dimethacrylate;

0.5 to 1.5 weight percent N,N′

dimethyl-p-toluidin, and 0.3 weight percent or less p-benzochinone.

20. The self-hardening material according to claim 1, wherein the particulate material includes polyethylmethacrylate, acrylonitrile butadiene styrene (i.e., ABS), polycarbonate-acrylonitrile butadiene styrene (i.e., PC-ABS), polyamide (i.e., PA), polybutylene terephthalate (i.e., PBT), a metal, glass, or carbon fiber.

21. The self-hardening material according to claim 1, wherein the delayer delays a polymerization reaction without dampening the polymerization reaction.

13. A self-hardening material for layerwise construction of three-dimensional components comprising:

a. at least one particulate material;

b. a printable bonding agent for bonding the particulate material;

c. an initiator; and

d. a delayer so that a setting time of the bonding agent is greater than 20 times as long as an application time of a particulate layer,

wherein the bonding agent is separate from the particulate material and the particulate material includes the initiator.

15. The self-hardening material as per claim 13, wherein the particulate material includes a filler, and the bonding agent contains a solvent and a moisture-containing material which slows down volatilisation of the solvent.

17. A self-hardening material for layerwise construction of three-dimensional components comprising:

(i) at least one particulate material;

(ii) a bonding agent, such as a polymerizable monomer, for bonding the particulate material; and

(iii) a delayer for delaying a polymerization reaction;

wherein the particulate material includes polymethylmethacrylate, polyethylmethacrylate, acrylonitrile butadiene styrene (i.e., ABS), polycarbonate-acrylonitrile butadiene styrene (i.e., PC-ABS), polyamide (i.e., PA), polybutylene terephthalate (i.e., PBT), a metal, glass, or carbon fiber,

wherein the bonding agent is based on acrylates, methacrylates, or styrols,

wherein the bonding agent contains a solvent and a material which slows down volatilisation of the solvent,

wherein the delayer is benzochinone,

wherein the initiator is benzoyl peroxide, and

wherein the particulate material is a loose material suitable for applying in a layerwise fashion, and

wherein the bonding agent is a printable liquid suitable for applying over the particulate material.

22. A self-hardening material for layerwise construction of three-dimensional components comprising:

a. at least one particulate material;

b. a printable bonding agent for bonding the particulate material; and

c. an initiator; and

wherein the initiator is dissolved in grains of the particulate material so that setting of the bonding agent is delayed;

wherein a setting time of the bonding agent is greater than 20 times as long as an application time of a particulate layer,

wherein the bonding agent is separate from the particulate material.

23. The material of claim 22, wherein the bonding agent includes a combination of different monomers for copolymerization.

24. The material of claim 23, wherein the different monomers include sterol and methylmethacrylate.

25. The material of claim 24, wherein the initiator includes benzoyl peroxide.