3d printing of metal containing structures

Abstract

In an aspect, a method for making a metal-containing material comprises steps of: forming a metal-containing hydrogel from an aqueous precursor mixture using a photopolymerization; wherein the aqueous precursor mixture comprises water, one or more aqueous photosensitive binders, and one or more aqueous metal salts; and thermally treating the metal-containing hydrogel to form the metal-containing material; wherein the metal-containing hydrogel is exposed to a thermal-treatment atmosphere during the step of thermally treating; wherein a composition of the metal-containing material is at least partially determined by a composition of the thermal-treatment atmosphere during the thermally treating step.

1 . A method for making a metal-containing material, the method comprising steps of:
 forming a metal-containing hydrogel from an aqueous precursor mixture using a photopolymerization;
 wherein the aqueous precursor mixture comprises water, one or more aqueous photosensitive binders, and one or more aqueous metal salts; and 
   thermally treating the metal-containing hydrogel to form the metal-containing material;
 wherein the metal-containing hydrogel is exposed to a thermal-treatment atmosphere during the thermally treating step; 
 wherein a composition of the metal-containing material is at least partially determined by a composition of the thermal-treatment atmosphere. 
   
     
     
         2 - 20 . (canceled) 
     
     
         21 . The method of  claim 1 , wherein the at least 0.5 mol. % of the composition of the metal-containing material is determined by a chemical interaction of the metal-containing hydrogel and the thermal-treatment atmosphere. 
     
     
         22 . The method of  claim 1 , wherein the thermal-treatment atmosphere is selected from the group consisting of a reducing atmosphere, an oxidizing atmosphere, and an inert atmosphere. 
     
     
         23 . The method of  claim 22 , wherein the thermal-treatment atmosphere is a reducing atmosphere and at least a portion of the metal-containing structure is a metal or metal alloy due to chemical interaction of the metal-containing hydrogel with the thermal-treatment atmosphere. 
     
     
         24 . The method of  claim 22 , wherein the thermal-treatment atmosphere is an oxidizing atmosphere and at least a portion of the metal-containing material is a metal oxide ceramic due to chemical interaction of the metal-containing hydrogel with the thermal-treatment atmosphere. 
     
     
         25 . The method of  claim 22 , wherein the thermal-treatment atmosphere is an inert atmosphere and at least a portion of the metal-containing material is a metal carbide due to the thermal-treatment atmosphere being an inert atmosphere. 
     
     
         26 . The method of  claim 1 , wherein the step of thermally treating comprises a plurality of thermally treating steps. 
     
     
         27 . The method  claim 26 , wherein the plurality of thermally treating steps comprises a first thermally treating step and a second thermally treating step, wherein:
 the first thermally treating step comprises using a first thermal-treatment atmosphere;   the second thermally treating step comprises using a second thermal-treatment atmosphere; and   a composition of the first thermal-treatment atmosphere is different from a composition of the second thermal-treatment atmosphere.   
     
     
         28 . The method of  claim 27 , wherein the first thermally treating step comprises thermally treating the metal-containing hydrogel to form an intermediate metal-containing material; and wherein the second thermally treating step comprises thermally treating the intermediate metal-containing material to form the metal-containing material. 
     
     
         29 . The method of  claim 27 , wherein the first thermal-treatment atmosphere comprises an oxidizing atmosphere and a composition of the intermediate metal-containing material comprises a metal oxide; and wherein the second thermal-treatment atmosphere comprises a reducing atmosphere and a composition of the metal-containing material comprises a metal. 
     
     
         30 . The method of  claim 27 , wherein a first portion of the metal-containing material has a composition corresponding to a chemical interaction with the first thermal-treatment atmosphere during the first thermally-treating step; and wherein a second portion of the metal-containing material has a composition corresponding to a chemical interaction with the second thermal-treatment atmosphere during the second thermally-treating step. 
     
     
         31 . The method of  claim 1 , wherein the aqueous precursor mixture does not comprise metal-containing particles. 
     
     
         32 - 34 . (canceled) 
     
     
         35 . The method of  claim 1 , wherein the aqueous precursor mixture further comprises one or more photoinitiators, one or more UV-blockers, or any combination of these. 
     
     
         36 - 37 . (canceled) 
     
     
         38 . The method of  claim 1 , wherein the aqueous precursor mixture comprises at least two different aqueous metal salts, each characterized by different metal ions; and wherein the metal-containing material has a composition comprising the metal ions of the at least two different aqueous metal salts. 
     
     
         39 . (canceled) 
     
     
         40 . The method of  claim 1 , wherein each of the one or more aqueous water-soluble metal salts is a nitrate salt, an acetate salt, a chloride salt, a sulfate salt, a bicarbonate salt, an oxynitrate salt, a hydroxide salt, a bromide salt, a fluoride salt, an iodide salt, a chlorate salt, a cyanide salt, a cyanate salt, a thiocyanate salt, a phosphate salt, a dichromate salt, a perchlorate salt, a benzoate salt, a chromate salt, or any combination of these. 
     
     
         41 . The method of  claim 1 , wherein each of the one or more aqueous metal salts is independently a water-soluble metal salt having one or more metals selected from the group consisting of Fe, Zn, Li, Co, Al, Ni, Mo, La, In, Sn, Ba, Y, and any combination of these. 
     
     
         42 . (canceled) 
     
     
         43 . The method of  claim 38 , wherein the metal-containing material has a composition characterized as a ternary or higher order material. 
     
     
         44 . The method of  claim 38 , wherein the metal-containing material has a composition characterized as a metal oxide, a metal alloy, or a metal carbide comprising at least two metal ions. 
     
     
         45 . The method of  claim 38 , wherein the metal-containing material has a spatially-varying metal ion composition. 
     
     
         46 . The method of  claim 1 , wherein the metal-containing material has a spatially-varying anion composition. 
     
     
         47 . The method of  claim 46 , wherein the spatially varying composition corresponds to a core-shell configuration. 
     
     
         48 . The method of  claim 1 , wherein the metal-containing material is a metal or metal alloy. 
     
     
         49 - 51 . (canceled) 
     
     
         52 . The method of  claim 1 , wherein the metal-containing material has structure characterized as architected, having a three-dimensional geometry, macroscopically monolithic, and a lattice. 
     
     
         53 . (canceled) 
     
     
         54 . The method of  claim 1 , wherein the step of forming the hydrogel comprises patterning or printing the hydrogel. 
     
     
         55 . The method of  claim 1 , wherein the photopolymerization is an additive manufacturing process. 
     
     
         56 . The method of  claim 1 , further comprising using the metal-containing structure in an electrode, as a biological scaffold, in a mechanical damping device, in a heat exchanger, as a catalyst, as a solid electrolyte, as a superconductor, as a thermal insulator, as an electrical insulator, as dielectrics, as a sensors, or any combination of these. 
     
     
         57 . The method of  claim 38  comprising a step of selecting relative concentrations of the at least two different aqueous metal salts in the aqueous precursor mixture based on a desired composition of the metal-containing material; wherein a concentrations of each of the at least two different aqueous metal salts is different from a concentration of each other aqueous metal salt. 
     
     
         58 . (canceled) 
     
     
         59 . The method of  claim 1 , wherein the aqueous precursor mixture comprises one aqueous metal salt and wherein the metal-containing material is a binary material. 
     
     
         60 . (canceled) 
     
     
         61 . (canceled) 
     
     
         62 . The method of  claim 59 , wherein the metal-containing material is a carbide material. 
     
     
         63 - 65 . (canceled) 
     
     
         66 . The method of  claim 1 , wherein the step of thermally treating comprises pyrolyzing, calcinating, sintering, high temperature annealing, or a combination of these. 
     
     
         67 - 69 . (canceled) 
     
     
         70 . The method of  claim 1 , wherein each of the one or more aqueous metal salts is independently a water-soluble salt having one or more metals selected from the group consisting of: B, Si, Ge, As, Sb, Te, Po, At, Se, and any combination of these. 
     
     
         71 . The method of  claim 1 , wherein the metal containing material is a ceramic material and each of the one or more aqueous metal salts is a water-soluble salt having one or more metals selected from the group consisting of: Ca, Bi, Sr, Cu, Ti, B, Si, U, Zr, Mg, Pb, or V, and any combination of these. 
     
     
         72 . The method of  claim 1 , wherein each of the one or more aqueous metal salts is independently a water-soluble salt having one or more metals selected from the group consisting of Na, Mg, K, Ca, Sc, V, Cr, Mn, Cu, Ga, Rb, Sr, Zr, Ag, Cd, In, Hf, W, Au, and any combination of these.