Material systems and methods of three-dimensional printing

• US 20060208388A1
• Filed: 05/24/2006
• Published: 09/21/2006
• Est. Priority Date: 11/05/1999
• Status: Active Grant

• Current Assignee: 3D Systems, Inc. (3D Systems Corporation)
• Original Assignee: Z CORPORATION (A Holdings Corp.)
• Inventors: Anderson, Timothy C., DiCologero, Matthew, Bredt, James F., Russell, David B., Clark, Sarah L.
• Granted Patent: US 7,795,349 B2
• Time in Patent Office: Days
• US Class Current: 264/123
• CPC Class Codes: B29C 64/112 using individual droplets, e.g. from jetting heads
• 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: B33Y 70/00 Materials specially adapted for 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 is directed to three-dimensional printing material systems and method, and an article made therefrom. The method of the present invention includes building cross-sectional portions of a three-dimensional article, and assembling the individual cross-sectional areas in a layer-wise fashion to form a final article. The individual cross-sectional areas are built by using an ink-jet printhead to deliver a fluid to a particulate material that includes particulate material.

Claims

1-119. -119. (canceled)

120. A material system for three dimensional printing comprising:

a dry particulate material;

a fluid monomer; and

a fluid comprising an initiator, a humectant, and a flowrate enhancer,

wherein the dry particulate material is suitable for use in three dimensional printing to form an article comprised of a plurality of layers, and after application of the fluid monomer and the fluid comprising the initiator to a first region of a layer of the dry particulate material, a solidified material forms in the first region.

121. The material system of claim 120, wherein the initiator is selected from the group consisting of a cationic initiator and a free-radical initiator.

122. The material system of claim 121, wherein the cationic initiator is selected from the group consisting of sulfuric acid, perchloric acid, fluorosulfonic acid, trifluoromethyl sulfonic acid, trifluoroacetic acid, tin tetrachloride, aluminum trichloride, and boron trifluoride

123. The material system of claim 122, wherein the fluid monomer is selected from the group consisting of isobutene, alkenes, alkyl-vinyl ethers, vinylacetals, dienes, styrene, n-vinyl carbazole, beta-pinene, oxiranes, n-substituted aziridines, lactams, and oxazolines.

124. The material system of claim 121, wherein the free-radical initiator is selected from the group consisting of potassium peroxodisulfate, ammonium persulfate with n,n,n′

,n′

-tetramethylethylenediamine, ammonium persulfate with 3-dimethylaminopropionitrile, 4,4-azobis(4-cyanovaleric acid), dibenzoyl peroxide, t-butyl perbenzoate, and azobisisobutyronitrile.

125. The material system of claim 124, wherein the fluid monomer is selected from the group consisting of vinylic monomers, acrylic monomers, dienic monomers, acrylic acid, methacrylic acid, and acrylamide.

126. The material system of claim 120, wherein at least one of the dry particulate material, the fluid monomer, and the fluid comprising and initiator, a humectant, and a flowrate enhancer further comprises a dye.

127. A material system for three dimensional printing comprising:

a dry particulate material comprising a monomer; and

a fluid comprising an initiator,

wherein the dry particulate material is suitable for use in three dimensional printing to form an article comprised of a plurality of layers, and after application of the fluid comprising the initiator to a first region of a layer of the dry particulate material, a solidified material forms in the first region.

128. The material system of claim 127, wherein the monomer is selected from the group consisting of vinylic monomer, an acrylic monomer, a dienic monomer, acrylic acid, methacrylic acid, acrylamide, and styrene.

129. The material system of claim 127, wherein the initiator is selected from the group consisting of a cationic initiator and a free-radical initiator.

130. The material system of claim 129, wherein the cationic initiator is selected from the group consisting of potassium persulfate, ammonium persulfate, sulfuric acid, perchloric acid, fluorosulfonic acid, trifluoromethylsulfonic acid, trifluroacetic acid, tin tetrachloride, aluminum tricholoride, and boron trifluoride.

131. The material system of claim 129, wherein the free-radical initiator is selected from the group consisting of potassium peroxodisulfate, ammonium persulfate with n,n,n′

,n′

-tetramethylethylenediamine, ammonium persulfate with 3-dimethylaminopropionitrile, potassium persulfate with 4,4-azobis(4-cyanovaleric acid), dibenzoyl peroxide, t-butyl perbenzoate, and azobisisobutyronitrile.

132. A material system for three dimensional printing comprising:

a dry particulate material comprising a collection of particles having a reactive coating; and

a fluid comprising a reactant,

wherein the dry particulate material is suitable for use in three dimensional printing to form an article comprised of a plurality of layers, and after application of the fluid comprising the reactant to a first region of a layer of the dry particulate material, a solidified material forms in the first region.

133. The material system of claim 132, wherein the reactive coating is selected from the group consisting of phenolic precursors, vinyl groups, acids, bases, isocyanates, cyanoacrylates, epoxides, amines, carboxylic acids, hydroxyl groups, acetates, amides, and esters.

134. The material system of claim 132, wherein the reactive coating comprises a catalyst.

135. The material system of claim 134, wherein the catalyst is a metal selected from the group consisting of iron, cooper, carbon steel, stainless steel, aluminum, brass, molybdenum, tungsten, magnesium, and cobalt.

136. The material system of claim 134, wherein the reactant comprises a monomer.

137. The material system of claim 134, wherein the reactive coating comprises an initiator selected from the group consisting of a cationic initiator and a free-radical initiator.

138. The materials system of claim 137, wherein the cationic initiator selected from the group consisting of sulfuric acid, perchloric acid, fluorosulfonic acid, trifluoromethyl sulfonic acid, trifluoroacetic acid, tin tetrachloride, aluminum trichloride, and boron trifluoride

139. The material system of claim 138, wherein the reactant comprises a monomer selected from the group consisting of isobutene, alkenes, alkyl-vinyl ethers, vinylacetals, dienes, styrene, n-vinyl carbazole, beta-pinene, oxiranes, n-substituted aziridines, lactams, and oxazolines.

140. The material system of claim 137, wherein the free-radical initiator is selected from the group consisting of potassium peroxodisulfate, ammonium persulfate with n,n,n′

,n′

-tetramethylethylenediamine, ammonium persulfate with 3-dimethylaminopropionitrile, 4,4-azobis(4-cyanovaleric acid), dibenzoyl peroxide, t-butyl perbenzoate, azobisisobutyronitrile, and combinations thereof.

141. The material system of claim 140, wherein the reactant comprises a monomer selected from the group consisting of vinylic monomers, acrylic monomers, dienic monomers, acrylic acid, methacrylic acid, acrylamide, and combinations thereof.

142. A material system for three dimensional printing comprising:

a dry particulate material comprising an adhesive;

a first fluid suitable for dissolving the adhesive; and

a second fluid comprising a solidification agent,

wherein the dry particulate material is suitable for use in three dimensional printing to form an article comprised of a plurality of layers, and upon application of the first and second fluids to a first region of a layer of the dry particulate material, the first fluid dissolves the adhesive, and a reaction between the first fluid and the solidification agent causes a solidified material to form in the first region.

143. The material system of claim 142 wherein the adhesive comprises an inert polymer selected from the group consisting of poly(methyl methacrylate), polystyrene. polyamide, polyester, a latex, polyethylene, polypropylene, polyurethane, polyvinyl chloride, polyvinyl acetate, cross-linked polyvinyl pyrrolidone, hydrophilic polyurethane, poly(ethylene terephthalate), thermoplastic urethane, styrene-acrylonitrile copolymer, thermoplastic polyolefin, an epoxy-based polymer, polyether, polyamine, a polyacid, a polycarbonate, a vinyl polymer, an aromatic polyamide, a diene polymer, poly(phenylene oxide), polysiloxane, polynorbornene, polyisoprene, a polyphenylene ether, styrene-butadiene block copolymer, acrylonitrile-butadiene-styrene, high impact polystyrene, and copolymers thereof.

144. The material system of claim 142 wherein the first fluid comprises at least one of a pure fluid and a solution.

145. The material system of claim 142, wherein the solidification agent is selected from the group consisting of a cationic initiator and a free-radical initiator.

146. The material system of claim 145, wherein the cationic initiator is selected from the group consisting of sulfuric acid, perchloric acid, fluorosulfonic acid, trifluoromethyl sulfonic acid, trifluoroacetic acid, tin tetrachloride, aluminum trichloride, and boron trifluoride

147. The material system of claim 146, wherein the first fluid is selected from the group consisting of isobutene, alkenes, alkyl-vinyl ethers, vinylacetals, dienes, styrene, n-vinyl carbazole, beta-pinene, oxiranes, n-substituted aziridines, lactams, and oxazolines.

148. The material system of claim 145, wherein the free-radical initiator is selected from the group consisting of potassium peroxodisulfate, ammonium persulfate with n,n,n′

,n′

-tetramethylethylenediamine, ammonium persulfate with 3-dimethylaminopropionitrile, 4,4-azobis(4-cyanovaleric acid), dibenzoyl peroxide, t-butyl perbenzoate, and azobisisobutyronitrile.

149. The material system of claim 156, wherein the first fluid is selected from the group consisting of vinylic monomers, acrylic monomers, dienic monomers, acrylic acid, methacrylic acid, and acrylamide.