Methods and systems for sterolithography three-dimensional printing

Abstract

The present disclosure provides method and systems for printing a three-dimensional (3D) object. A method for 3D printing may comprise providing a mixture comprising (i) a polymeric precursor, (ii) a photoinitiator configured to initiate formation of a polymeric material from the polymeric precursor, and (iii) a photoinhibitor configured to inhibit the formation of the polymeric precursor. The method may comprise exposing the mixture to (i) a first light to cause the photoinitiator to initiate formation of the polymeric material, thereby to print the 3D object, and (ii) a second light to cause the photoinhibitor to inhibit the formation of the polymeric material. During printing of the 3D object, a ratio of (i) an energy of the second light sufficient to initiate formation of the polymeric material relative to (ii) an energy of the first light sufficient to initiate formation of the polymeric material may be greater than 1.

What is claimed is: 
     
         1 . A mixture for printing a three-dimensional (3D) object, comprising:
 a polymeric precursor;   a photoinitiator configured to initiate formation of a polymeric material from said polymeric precursor upon exposure to a first light having a first wavelength; and   a photoinhibitor configured to inhibit formation of said polymeric material from said polymeric precursor upon exposure to a second light having a second wavelength,   wherein said mixture is configured such that a ratio of (i) an energy per unit area of said second light sufficient to initiate formation of said polymeric material relative to (ii) an energy per unit area of said first light sufficient to initiate formation of said polymeric material is greater than 1.   
     
     
         2 . The mixture of  claim 1 , wherein said ratio is greater than 10. 
     
     
         3 . The mixture of  claim 1 , wherein said composition is such that an additional ratio of (i) a rate of formation of said polymeric material upon exposure to said first light relative to (ii) a rate of formation of said polymeric material upon exposure to said second light is greater than 1. 
     
     
         4 . The mixture of  claim 1 , further comprising a stabilizer configured to inhibit formation of said polymeric material from at least a portion of said polymeric precursor. 
     
     
         5 . The mixture of  claim 4 , wherein said stabilizer is a radical inhibitor. 
     
     
         6 . The mixture of  claim 5 , wherein said radical inhibitor comprises t-butyl catechol, phenothiazine, or butylated hydroxytoluene. 
     
     
         7 . The mixture of  claim 1 , further comprising a co-initiator configured to initiate formation of said polymeric material from said polymeric precursor. 
     
     
         8 . The mixture of  claim 7 , wherein said co-initiator comprises a tertiary amine. 
     
     
         9 . The mixture of  claim 8 , wherein said co-initiator comprises an ethyl-dimethyl-amino benzoate or a functional variant thereof. 
     
     
         10 . The mixture of  claim 1 , further comprising a light absorber configured to absorb at least said first wavelength and/or said second wavelength. 
     
     
         11 . The mixture of  claim 1 , wherein said polymeric precursor comprises one or more acrylates. 
     
     
         12 . The mixture of  claim 1 , wherein said polymeric precursor comprises monomers configured to polymerize to form said polymeric material. 
     
     
         13 . The mixture of  claim 1 , wherein said polymeric precursor comprises oligomers configured to cross-link to form said polymeric material. 
     
     
         14 . The mixture of  claim 1 , further comprising one or more particles. 
     
     
         15 . The mixture of  claim 14 , wherein said one or more particles comprise (i) at least one metal particle, (ii) at least one ceramic particle, or (iii) said at least one metal particle and said at least one ceramic particle. 
     
     
         16 . The mixture of  claim 1 , wherein said first wavelength is from about 400 nanometers (nm) to about 500 nm, and said second wavelength is from about 300 nm to about 400 nm. 
     
     
         17 . The mixture of  claim 1 , wherein said photoinhibitor comprises a hexaarylbiimidazole or a functional variant thereof. 
     
     
         18 . The mixture of  claim 17 , wherein said hexaarylbiimidazole comprises a phenyl group with a halogen and/or an alkoxy substitution. 
     
     
         19 . The mixture of  claim 18 , wherein said phenyl group comprises an ortho-chloro-substitution. 
     
     
         20 . The mixture of  claim 19 , wherein said photoinhibitor comprises 2,2′-Bis(2-chlorophenyl)-4,4′, 5,5′-tetraphenyl-1,2′-biimidazole. 
     
     
         21 . The mixture of  claim 18 , wherein said phenyl group comprises an ortho-methoxy-substitution. 
     
     
         22 . The mixture of  claim 18 , wherein said phenyl group comprises an ortho-ethoxy-substitution. 
     
     
         23 . The mixture of  claim 1 , wherein said photoinitiator comprises camphorquinone or a functional variant thereof. 
     
     
         24 . The mixture of  claim 1 , wherein said mixture is configured such that when said mixture is provided adjacent to a build surface, (i) said first light having said first wavelength is sufficient to cause said photoinitiator to initiate formation of said polymeric material from said polymeric precursor at a location disposed away from said build surface, and (ii) said second light having said second wavelength sufficient to cause said photoinhibitor to inhibit formation of said polymeric material from said polymeric precursor at a location adjacent to said build surface. 
     
     
         25 . A mixture for printing a three-dimensional (3D) object, comprising:
 a polymeric precursor;   a photoinitiator configured to initiate formation of a polymeric material from said polymeric precursor upon exposure to a first light having a first wavelength; and   a photoinhibitor configured to inhibit formation of said polymeric material from said polymeric precursor upon exposure to a second light having a second wavelength, wherein said photoinhibitor is different than said photoinitiator, and wherein said photoinhibitor comprises a hexaarylbiimidazole or a functional variant thereof.   
     
     
         26 . The mixture of  claim 25 , wherein said hexaarylbiimidazole comprises a phenyl group with a halogen and/or an alkoxy substitution. 
     
     
         27 . The mixture of  claim 26 , wherein said phenyl group comprises an ortho-chloro-substitution. 
     
     
         28 . The mixture of  claim 27 , wherein said photoinhibitor comprises 2,2′-Bis(2-chlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole. 
     
     
         29 . The mixture of  claim 26 , wherein said phenyl group comprises an ortho-methoxy-substitution. 
     
     
         30 . The mixture of  claim 26 , wherein said phenyl group comprises an ortho-ethoxy-substitution.