Curable nano-composites for additive manufacturing

Abstract

Curable liquid nano-composites for additive manufacturing of objects having precisely controlled mechanical and electronic properties are provided. Methods of making the curable nano-composites, and methods of additive manufacturing using the nano-composites are also provided. Additionally, objects made from additive manufacturing using the curable nano-composites are provided. In one or more embodiments the nano-composites can contain one or more cross-linkable monomers or oligomers; a photo-initiator; and a nanoparticle. In some embodiments the curable liquid nano-composite can have a viscosity prior to curing of about 1-150 cP at room temperature and pressure. The curable nano-composite can be used for additive manufacturing by printing the curable nano-composite. The printed objects can include various opto-electronic devices such as conductive coatings, electro-chromic devices, electronic interconnects, antennae, RFID tags, transistors, diodes, photovoltaics, light emitting diodes, and capacitors.

1 - 25 . (canceled) 
     
     
         26 . A curable liquid nano-composite for use with a jetable piezo head device for additive manufacturing of an object, the nano-composite comprising:
 one or more cross-linkable monomers or oligomers wherein the monomers are selected from the group consisting of cross-linkable monoacrylates, diacrylates or triacryclates, either substituted or unsubstituted and the oligomers are selected from the group of pre-polymers of one or more of the cross-linkable monomers, and wherein the monoacrylates are present in a combined amount less than 60 wt % based upon the total weight of the nano-composite, and wherein the diacrylates and/or triacryclates are present in an amount less than about 10-50 wt % based upon the total weight of the nano-composite;   a photo-initiator; and   an organic nanoparticle,
 wherein the curable liquid nano-composite is configured for use in said jetable piezo head device to produce said object. 
   
     
     
         27 . The curable liquid nano-composite of  claim 26 , further including one or more cross-linkable monomers or oligomers or both, wherein the diacrylates and/or triacrylates and the one or more cross-linkable monomers or oligomers or both are present in a combined amount from about 70-98 wt % based upon the total weight of the nano-composite. 
     
     
         28 . The curable liquid nano-composite of  claim 26 , wherein the mono-acrylates are selected from the group consisting of 2-[2-(Vinyloxy)ethoxy]ethyl acrylate, 2-hydroxyethyl methacrylate, isodecyl acrylate, cyanoethyl methacrylate, hydroxypropyl methacrylate, p-dimethylaminoethyl methacrylate, and cyclohexyl methacrylate. 
     
     
         29 . The curable liquid nano-composite of  claim 26 , wherein the mono-acrylates are an acrylate ester of an aliphatic alcohol that can be a cycloaliphatic alcohol or a long-chain aliphatic alcohol. 
     
     
         30 . The curable liquid nano-composite of  claim 26 , wherein the mono-acrylates are an acrylate ester of a substituted or unsubstituted alcohol having from 2-50 carbon atoms. 
     
     
         31 . The curable liquid nano-composite of  claim 26 , wherein the diacrylates or the triacrylates are selected from the group consisting of 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentylglycol diacrylate, diethyleneglycol diacrylate, tetraethylene glycol diacrylate, tripropyleneglycol diacrylate, and dianol diacrylate. 
     
     
         32 . The curable liquid nano-composite of  claim 26 , wherein the diacrylates can include the acrylic acid diester of a substituted or unsubstituted di-alcohol having from 2-50 carbon atoms. 
     
     
         33 . The curable liquid nano-composite of  claim 26 , wherein the triacrylates can include trimethylolpropane triacrylate, 3eo, 3po, and 5eo. 
     
     
         34 . The curable liquid nano-composite, wherein the oligomers can be a mono-functional or multifunctional oligomer containing from about 2 to about 100 repeat units of the cross-linkable monomer. 
     
     
         35 . The curable liquid nano-composite of  claim 26 , wherein of the oligomers include electronically conducting oligomers such as oligoacetylenes, oligophenylenes and derivatives thereof, and oligothiophenes and derivatives thereof. 
     
     
         36 . The curable liquid nano-composite of  claim 26 , wherein the photo-initiator is present in an amount from about 1-10 wt % based upon the total weight of the nano-composite. 
     
     
         37 . The curable liquid nano-composite of  claim 26 , wherein the nanoparticle is present in an amount from about 1-25 wt % based upon the total weight of the nano-composite. 
     
     
         38 . The curable liquid nano-composite of  claim 27 , wherein the cross-linkable monomers include one or more monoacrylates. 
     
     
         39 . The curable liquid nano-composite of  claim 26 , wherein the cross-linkable diacrylates and/or triacrylates are present in an amount from about 20-40 wt % based upon the total weight of the nano-composite. 
     
     
         40 . The curable liquid nano-composite of  claim 36 , wherein the photo-intiator is selected from the group consisting of: benzophenone and substituted benzophenones; 1-hydroxycyclohexyl phenyl ketone; thioxanthones such as isopropylthioxanthone; 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-benzyl-2-dimethylamino-(4-morpholinophenyl)butan-1-one, benzil dimethylketal, bis(2,6-dimethylbenzoyl)-2,4,4-trimethylpentylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one or 5,7-diiodo-3-butoxy-6-fluorone; and combinations thereof. 
     
     
         41 . The curable liquid nano-composite of  claim 26 , wherein the nanoparticle has a largest diameter of about 15-200 nm. 
     
     
         42 . The curable liquid nano-composite of  claim 26 , wherein the organic nanoparticle is selected from the group consisting of carbon nanotubes, fullerenes, graphene and polyaniline. 
     
     
         43 . The curable liquid nano-composite of  claim 26 , further comprising a polymerization inhibitor selected from the group consisting of phenolic antioxidants, alkylated diphenyl amines, phenyl-α-naphthylamines, phenyl-β-naphthylamines, and alkylated α-naphthylamines. 
     
     
         44 . The curable liquid nano-composite of  claim 43 , wherein the polymerization inhibitor is present in an amount less than about 2 wt %. 
     
     
         45 . The curable liquid nano-composite of  claim 26 , further comprising one or more additional additives selected from the group consisting of ultraviolet (UV) absorbers, photochromic compounds, viscosity modifiers, colorants, pH adjusters, or fillers. 
     
     
         46 . The curable liquid nano-composite of  claim 26 , wherein the liquid nano-composite has a viscosity of about 1 cP to about 150 cP at room temperature and pressure. 
     
     
         47 . A method of additive manufacturing an object comprising printing a curable liquid nano-composite of  claim 26  using said jetable piezo head device. 
     
     
         48 . A printed object formed by additive manufacturing with the curable liquid nano-composite of  claim 26  using said jetable piezo head device. 
     
     
         49 . The printed object of  claim 48 , wherein the object is an opto-electronic device selected from the group consisting of, devices having conductive coatings, electrochromic devices, electronic interconnects, antenna, RFID tags, transistors, diodes, photovoltaics, light emitting diodes, and capacitors. 
     
     
         50 . An antenna prepared by additive manufacturing using the curable liquid nano-composite of  claim 26  and said jetable piezo head device. 
     
     
         51 . The curable liquid nano-composite of  claim 26 , wherein the object is a semi-conductive component. 
     
     
         52 . The curable liquid nano-composite of  claim 51 , wherein the semi-conductive component is an electrochromic device, electronic interconnect, antenna, RFID tag, transistor, diode, photovoltaic, light emitting diode, capacitor, or combinations thereof.