Three dimensional printing material system and method

Abstract

The present invention is directed to a three-dimensional printing system 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 using an ink-jet printhead to deliver an aqueous fluid to a particle material that includes a first particulate material, a second particulate material, and a third particulate material, wherein the first and second particulate materials react in the presence of the fluid in a period of time, and the third particulate material reacts in the presence of the fluid to form a solid in a longer period of time.

1 . A solid article comprising: 
 a product of a mixture of a plurality of particles of:    a first particulate material comprising a phosphate;    a second particulate material comprising an oxide; and    a third particulate material comprising an adhesive,    wherein the first particulate material and the second particulate material can react to form a solid in a period of time, and the third particulate material can solidify in a longer period of time when the mixture is contacted by a fluid during three-dimensional printing, the article having been formed by three-dimensional printing and comprising a plurality of layers of the mixture.    
     
     
         2 . The article of  claim 1 , wherein the first particulate material and the second particulate material react in the presence of a fluid.  
     
     
         3 . The article of  claim 2 , wherein at least one of the first particulate material and the second particulate material is substantially soluble in the fluid.  
     
     
         4 . (canceled)  
     
     
         5 . The article of  claim 1 , wherein the phosphate is selected from the group consisting of monoammonium phosphate; sodium aluminum phosphate, acidic; monocalcium phosphate, anhydrous; monopotassium phosphate; monosodium phosphate; and aluminum acid phosphate.  
     
     
         6 . The article of  claim 1 , wherein the phosphate is selected from the group consisting of: sodium tripolyphosphate; sodium hexametaphosphate; sodium polyphosphate, anhydrous; phosphoric acid, sodium salt; sodium trimetaphosphate; and ammonium polyphosphate.  
     
     
         7 . The article of  claim 1 , wherein the phosphate is selected from the group consisting of diammonium phosphate; dipotassium phosphate; disodium phosphate; monocalcium phosphate dihydrate; monocalcium phosphate, monohydrate; dicalcium phosphate, dihydrate; dicalcium phosphate, anhydrous; tricalcium phosphate; disodium phosphate; and tripotassium phosphate.  
     
     
         8 . The article of  claim 1 , wherein the phosphate is selected from the group consisting of sodium acid pyrophosphate; tetrasodium pyrophosphate; and tetrapotassium pyrophosphate.  
     
     
         9 . (canceled)  
     
     
         10 . The article of  claim 1 , wherein the second particulate material comprises at least one of an alkaline oxide, an alkaline hydroxide, and a combination thereof.  
     
     
         11 . The article of  claim 10 , wherein the alkaline oxide is selected from the group consisting of: zinc oxide; magnesium oxide; calcium oxide; copper oxide; bismuth oxide; cadmium oxide; tin oxide; red lead oxide; and combinations thereof.  
     
     
         12 . The article of  claim 10 , wherein the alkaline hydroxide is selected from the group consisting of: magnesium hydroxide; cobalt trihydroxide; beryllium dihydroxide and combinations thereof.  
     
     
         13 . The article of  claim 10 , wherein the alkaline oxide comprises magnesium oxide.  
     
     
         14 - 15 . (canceled)  
     
     
         16 . The article of  claim 1 , wherein the adhesive is selected from the group consisting of: copolymer of octylacrylamide/acrylates/butylaminoethyl methacrylate; polyvinyl alcohol; polyethylene oxide; sodium polystyrene sulfonate; polyacrylic acid; polyvinyl pyrrolidone; maltodextrine; hydrolyzed gelatin; sugar; hydrolyzed starch; sodium salt of polymethacrylic acid; ammonium salt of polymethacrylic acid; polyvinyl sulfonic acid; sulfonated polyester; poly(2-ethyl-2-oxazoline); polymethacrylic acid; sodium salt of polyacrylic acid; ammonium salt of polyacrylic acid; and combinations thereof.  
     
     
         17 . The article of  claim 1 , wherein the mixture of plurality of particles further comprises a filler.  
     
     
         18 . The article of  claim 17 , wherein the filler is selected from the group consisting of: limestone, staurolite, silica sand, zircon sand, olivine sand, chromite sand, magnesite, alumina silicate, calcium silicate, fused silica, calcium phosphate, rutile, bentonite, montmorillonite, glass, chamotte, fireclay, and mixtures thereof.  
     
     
         19 . The article of  claim 2 , wherein the fluid is aqueous.  
     
     
         20 - 27 . (canceled)  
     
     
         28 . A compound used in three dimensional printing comprising: 
 a dry particulate mixture of: 
 a first particulate material comprising a phosphate;  
 a second particulate material comprising an oxide; and  
 a third particulate material comprising an adhesive,  
 wherein the dry particulate mixture can be used in three-dimensional printing to form an article comprised of a plurality of layers, the first particulate material and the second particulate material can react to form a solid in a period of time, and the third particulate material can solidify in a longer period of time when the mixture is contacted by a fluid during three-dimensional printing.  
   
     
     
         29 . The compound of  claim 28 , wherein the first particulate material and the second particulate material react in the presence of the fluid.  
     
     
         30 . The compound of  claim 29 , wherein at least one of the first particulate material and the second particulate material is substantially soluble in the fluid.  
     
     
         31 . (canceled)  
     
     
         32 . The compound of  claim 28 , wherein the phosphate is selected from the group consisting of monoammonium phosphate; sodium aluminum phosphate, acidic; monocalcium phosphate, anhydrous; monopotassium phosphate; monosodium phosphate; and aluminum acid phosphate.  
     
     
         33 . The compound of  claim 28 , wherein the phosphate is selected from the group consisting of: sodium tripolyphosphate; sodium hexametaphosphate; sodium polyphosphate, anhydrous; phosphoric acid, sodium salt; sodium trimetaphosphate; and ammonium polyphosphate.  
     
     
         34 . The compound of  claim 28 , wherein the phosphate is selected from the group consisting of diammonium phosphate; dipotassium phosphate; disodium phosphate; monocalcium phosphate dihydrate; monocalcium phosphate, monohydrate; dicalcium phosphate, dihydrate; dicalcium phosphate, anhydrous; tricalcium phosphate; disodium phosphate; and tripotassium phosphate.  
     
     
         35 . The compound of  claim 28 , wherein the phosphate is selected from the group consisting of sodium acid pyrophosphate; tetrasodium pyrophosphate; and tetrapotassium pyrophosphate.  
     
     
         36 . (canceled)  
     
     
         37 . The compound of  claim 28 , wherein the second particulate material comprises at least one of an alkaline oxide, an alkaline hydroxide, and a combination thereof.  
     
     
         38 . The compound of  claim 37 , wherein the alkaline oxide is selected from the group consisting of: zinc oxide; magnesium oxide; calcium oxide; copper oxide; bismuth oxide; cadmium oxide; tin oxide; red lead oxide; and combinations thereof.  
     
     
         39 . The compound of  claim 37 , wherein the alkaline hydroxide is selected from the group consisting of: magnesium hydroxide; cobalt trihydroxide; beryllium dihydroxide and combinations thereof.  
     
     
         40 . The compound of  claim 37 , wherein the alkaline oxide comprises magnesium oxide.  
     
     
         41 - 42 . (canceled)  
     
     
         43 . The compound of  claim 28 , wherein the adhesive is selected from the group consisting of: copolymer of octylacrylamide/acrylates/butylaminoethyl methacrylate; polyvinyl alcohol; polyethylene oxide; sodium polystyrene sulfonate; polyacrylic acid; polyvinyl pyrrolidone; maltodextrine; hydrolyzed gelatin; sugar; hydrolyzed starch; sodium salt of polymethacrylic acid; ammonium salt of polymethacrylic acid; polyvinyl sulfonic acid; sulfonated polyester; poly(2-ethyl-2-oxazoline); polymethacrylic acid; sodium salt of polyacrylic acid; ammonium salt of polyacrylic acid; and combinations thereof.  
     
     
         44 . The compound of  claim 28 , wherein the mixture of plurality of particles further comprises a filler.  
     
     
         45 . The compound of  claim 44 , wherein the filler is selected from the group consisting of: limestone, staurolite, silica sand, zircon sand, olivine sand, chromite sand, magnesite, alumina silicate, calcium silicate, fused silica, calcium phosphate, rutile, bentonite, montmorillonite, glass, chamotte, fireclay, and mixtures thereof.  
     
     
         46 . The compound of  claim 29 , wherein the fluid is aqueous.  
     
     
         47 - 83 . (canceled)  
     
     
         84 . A dry particulate mixture of solids used for three dimensional printing that, when contacted by a fluid during three-dimensional printing to form an article composed of a plurality of layers, undergoes a first solidification reaction beginning with the fluid contact and occurring at a first rate, and also undergoes a second solidification reaction beginning with the fluid contact and occurring at a second rate slower than the first rate, wherein the dry particulate mixture comprises: 
 a first particulate material comprising a phosphate;    a second particulate material comprising an oxide; and    a third particulate material comprising an adhesive.    
     
     
         85 . The compound of  claim 84 , wherein the phosphate is selected from the group consisting of monoammonium phosphate; sodium aluminum phosphate, acidic; monocalcium phosphate, anhydrous; monopotassium phosphate; monosodium phosphate; and aluminum acid phosphate.  
     
     
         86 . The compound of  claim 84 , wherein the phosphate is selected from the group consisting of: sodium tripolyphosphate; sodium hexametaphosphate; sodium polyphosphate, anhydrous; phosphoric acid, sodium salt; sodium trimetaphosphate; and ammonium polyphosphate.  
     
     
         87 . The compound of  claim 84 , wherein the phosphate is selected from the group consisting of diammonium phosphate; dipotassium phosphate; disodium phosphate; monocalcium phosphate dihydrate; monocalcium phosphate, monohydrate; dicalcium phosphate, dihydrate; dicalcium phosphate, anhydrous; tricalcium phosphate; disodium phosphate; and tripotassium phosphate.  
     
     
         88 . The compound of  claim 84 , wherein the phosphate is selected from the group consisting of sodium acid pyrophosphate; tetrasodium pyrophosphate; and tetrapotassium pyrophosphate.  
     
     
         89 . The compound of  claim 84 , wherein the second particulate material comprises at least one of an alkaline oxide, an alkaline hydroxide, and a combination thereof.  
     
     
         90 . The compound of  claim 89 , wherein the alkaline oxide is selected from the group consisting of: zinc oxide; magnesium oxide; calcium oxide; copper oxide; bismuth oxide; cadmium oxide; tin oxide; red lead oxide; and combinations thereof.  
     
     
         91 . The compound of  claim 89 , wherein the alkaline hydroxide is selected from the group consisting of: magnesium hydroxide; cobalt trihydroxide; beryllium dihydroxide and combinations thereof.  
     
     
         92 . The compound of  claim 89 , wherein the alkaline oxide comprises magnesium oxide.  
     
     
         93 . The compound of  claim 84 , wherein the adhesive is selected from the group consisting of: copolymer of octylacrylamide/acrylates/butylaminoethyl methacrylate; polyvinyl alcohol; polyethylene oxide; sodium polystyrene sulfonate; polyacrylic acid; polyvinyl pyrrolidone; maltodextrine; hydrolyzed gelatin; sugar; hydrolyzed starch; sodium salt of polymethacrylic acid; ammonium salt of polymethacrylic acid; polyvinyl sulfonic acid; sulfonated polyester; poly(2-ethyl-2-oxazoline); polymethacrylic acid; sodium salt of polyacrylic acid; ammonium salt of polyacrylic acid; and combinations thereof.