Solid free-form fabrication of three-dimensional objects
View Patent ↗The present invention is drawn toward compositions, methods, and systems for solid free-form fabrication of three-dimensional objects. In one embodiment, a system for solid free-form fabrication of three-dimensional objects can comprise a particulate composition, a substrate configured for supporting at least a layer of the particulate composition in a defined region, and a liquid phase binder configured for being jetted in the defined region to polymerize at least a portion of the particulate composition to form a polymeric cement. Using this system in a layer by layer deposition process, three-dimensional objects can be formed. The particulate composition can include from 70 wt % to 99.9 wt % of polymeric particulates, and from 0.1 wt % to 10 wt % of a polymerization initiator. The liquid phase binder can include from 70 wt % to 90 wt % of polymerizable monomers and from 0.1 wt % to 10 wt % of a polymerization accelerator.
1. A method of fabricating a three-dimensional object, comprising:
a) depositing a particulate composition in a defined region, said particulate composition including:
i) from 70 wt % to 99.9 wt % of polymeric particulates, and
ii) from 0.1 wt % to 10 wt % of a polymerization initiator;
b) jetting a liquid phase binder onto a predetermined area of the particulate composition to form a layer of polymeric cement in the predetermined area, said liquid phase binder including:
i) from 70 wt % to 90 wt % of polymerizable monomers, and
ii) from 0.1 wt % to 10 wt % of a polymerization accelerator;
c) repeating steps a) and b) such that multiple layers of polymeric cement are formed that are bound to one another.
2. A method as in claim 1 , wherein the particulate composition further comprises from 0.1 wt % to 20 wt % of nanoparticle fillers.
3. A method as in claim 1 , wherein the polymeric particulates include a member selected from the group consisting of acrylate particulates, methacrylate particulates, siloxane particulates, and combinations thereof.
4. A method as in claim 3 , wherein the polymeric particulates include polymethylmethacrylate homopolymers or copolymers having a weight average molecular weight from 20,000 Mw to 1,000,000 Mw.
5. A method as in claim 1 , wherein the polymerization initiator includes a member selected from the group consisting of a free radical initiator base and an organic peroxide.
6. A method as in claim 5 , wherein the polymerization initiator includes dibenzoyl peroxide.
7. A method as in claim 1 , wherein the liquid phase binder further comprises a liquid stabilizer.
8. A method as in claim 1 , wherein the polymerizable monomers include a member selected from the group consisting of acrylate monomers, methacrylate monomers, and combinations thereof.
9. A method as in claim 8 , wherein the polymerizable monomers include methylmethacrylate monomers.
10. A method as in claim 1 , wherein the polymerization accelerator includes an amine.
11. A method as in claim 1 , wherein the polymerization accelerator includes N,N-dimethyl-p-toluidine.
12. A method as in claim 1 , wherein the polymerization accelerator includes dihydroxyethyl-p-toluidine.
13. A method as in claim 1 , wherein the liquid phase binder further includes a colorant.
14. A method as in claim 1 , further comprising the step of removing a portion of the particulate composition that does not form the polymeric cement.
15. A method as in claim 1 , wherein the particulate composition and the liquid phase binder are reacted in the presence of UV energy.
16. A method of fabricating a three-dimensional object, comprising:
a) depositing a particulate composition in a defined region, said particulate composition including:
i) polymeric particulates, wherein the polymeric particulates include a member selected from the group consisting of acrylate particulates, methacrylate particulates, siloxane particulates, and combinations thereof, and
ii) a polymerization initiator, wherein the polymerization initiator includes a member selected from the group consisting of a free radical initiator base and an organic peroxide;
b) jetting a liquid phase binder onto a predetermined area of the particulate composition to form a layer of polymeric cement in the predetermined area, said liquid phase binder including:
i) polymerizable monomers, and
ii) a polymerization accelerator, wherein the polymerization accelerator is selected from an amine, N,N-dimethyl-p-toluidine, and dihydroxyethyl-p-toluid me;
c) repeating steps a) and b) such that multiple layers of polymeric cement are formed that are bound to one another.