3D POLYMERIZABLE CERAMIC INKS

Abstract

Provided are formulations and processes for manufacturing 3D objects, the formulations being free of particulate materials and used in low temperature 3D printing processes.

Claims

1.-57. (canceled)

58. A process for forming a 3D ceramic or glass object or pattern, the process comprising irradiating at least one polymerizable ceramic precursor of the formula A-B or a formulation comprising same, at a temperature below 90° C., wherein in the at least one polymerizable ceramic precursor of the formula A-B: A is a ceramic precursor moiety, and B is at least one photopolymerizable group; such that B is associated with or bonded to A via a chemical bond, wherein the at least one polymerizable ceramic precursor of the formula A-B or a formulation comprising same is provided onto a substrate or in a printing bath; to obtain a 3D polymerized object or pattern; and treating the 3D polymerized object or pattern by one or more of aging the 3D object or pattern at room temperature; immersing the 3D object or pattern in an acid, a base or an electrolyte solution followed by heating at a temperature above 100° C.; or supercritical drying of the 3D object or pattern, to obtain the 3D ceramic or glass object or pattern.

59. The process according to claim 58, the process comprising: a) forming a pattern of a formulation on a surface region of a substrate or on a previously formed pattern; the formulation comprising the at least one polymerizable ceramic precursor of the formula A-B; b) affecting polymerization of at least a portion of the polymerizable moieties present in the at least one polymerizable ceramic precursors at a temperature below 90° C.; c) repeating steps (a) and (b) one or more times to obtain the 3D object or pattern.

60. The process according to claim 58, wherein the treating of the 3D polymerized object or pattern comprises burning or heating the formed 3D object or pattern to a temperature above 100° C.

61. The process according to claim 58, wherein the formulation is configured as a printable material for forming a 3D object by sol-gel.

62. The process according to claim 58, wherein A is a monomer or an oligomer thereof selected from tetraethyl orthosilicate, tetramethyl orthosilicate, tetraisopropyltitanate, trimethoxysilane, triethoxysilane, trimethylethoxysilane, phenyltriethoxysilane, phenylmethyldiethoxy silane, methyldiethoxysilane, vinylmethyldiethoxysilane; polydimethoxysilane, polydiethoxysilane, polysilazanes, titanium isopropoxide, aluminum isopropoxide, zirconium propoxide, triethyl borate, trimethoxyboroxine diethoxysiloxane-ethyltitanate, titanium diisopropoxide bis(acetylacetonate), silanol poss, aluminium tri-sec-butoxide, triisobutylaluminium, aluminium acetylacetonate, 1,3,5,7,9-pentamethylcyclo pentasiloxane, poly(dibutyltitanate) oligomers of siloxane, and oligomers of Al—O—Al, oligomers of Ti—O—Ti and/or Zn—O—Zn.

63. The process according to claim 58, wherein B is at least one photopolymerizable group selected to undergo light-induced polymerization.

64. The process according to claim 63, wherein B is selected from amines, thiols, amides, phosphates, sulphates, hydroxides, alkenes and alkynes.

65. The process according to claim 63, wherein B is selected from organic moieties comprising one or more double or triple bonds.

66. The process according to claim 65, wherein the organic moiety is selected from acryloyl groups, methacryloyl groups and vinyl groups.

67. The process according to claim 58, wherein B is selected from epoxy groups and thiol group.

68. The process according to claim 58, wherein A is modified by (1) amines, thiols, amides, phosphates, sulphates, hydroxides, epoxy, alkenes or alkynes, (2) alkenyl groups, or (3) acryloyl groups, methacryloyl groups, vinyl groups, epoxy group and thiol group.

69. The process according to claim 58, wherein the polymerizable ceramic precursors of the structure A-B are selected from (acryloxypropyl)trimethoxysilan (APTMS), 3-glycidoxypropyl methyldiethoxysilane, acryloxymethyltrimethoxysilane, (acryloxymethyl)phenethyl trimethoxysilane, (3-acryloxypropyl)trichlorosilane, 3-(n-allylamino)propyltrimethoxy silane, m-allylphenylpropyltriethoxysilane, allyltrimethoxysilane, 3-glycidoxypropylmethyl diethoxysilane, 3-glycidoxypropyl methyldiethoxysilane and POSS acrylates.

70. The process according to claim 69, wherein the polymerizable ceramic precursors of the structure A-B are selected from (acryloxypropyl)trimethoxysilan (APTMS) and POSS acrylates.

71. The process according to claim 58, wherein the non-photopolymerizable ceramic precursors are selected from tetraethoxyorthosilicate, tetraisopropyltitanate, trimethoxysilane, polydiethoxysilane, polydimethoxysilane, polysilazanes triethoxy silane, trimethyethoxysilane, phenyltriethoxysilane, phenylmethyldiethoxysilane, methyl diethoxysilane, tetraethyl orthosilicate (TEOS), titanium isopropoxide, aluminum isopropoxide, zirconium propoxide, triethyl borate, trimethoxyboroxine diethoxysiloxane-ethyltitanate, titanium diisopropoxide bis(acetylacetonate), silanol POSS, aluminium tri-sec-butoxide, triisobutylaluminium, aluminium acetylacetonate, 1,3,5,7,9-pentamethylcyclopentasiloxane, poly(dibutyl titanate) oligomers of siloxane, oligomers of Al—O—Al, and oligomers of Ti—O—Ti and/or Zn—O—Zn.

72. The process according to claim 58, comprising one or more oligomers of siloxane or oligomers with Al—O—Al or Ti—O—Ti backbones.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0111] In order to better understand the subject matter that is disclosed herein and to exemplify how it may be carried out in practice, embodiments will now be described, by way of non-limiting example only, with reference to the accompanying drawings, in which:

[0112] FIG. 1 shows a printed structure according to the invention: plate (1) shows the structure before heat treatment; plate (2) shows the structure after heating at 300° C.; and plate (3) shows the structure after heating at 700° C.

[0113] FIG. 2 summarizes TGA measurements of samples composed of 87.3 wt % AcryloPOSS, 9.7 wt % APTMS and 3 wt % TPO. The measurements were carried out on a heated sample (1); under N.sub.2 (2); under air and on a sample composed of organic polymer SR9035 heated under N.sub.2 (3).

[0114] FIG. 3 shows images of 3D printed structures burnt under air at different temperatures, as indicated. The structures was printed from: line 1—ethoxy-TMPTA ink formulation, and line 2—1:1 POSS:APTMS ink formulation according to the invention. See detail description.

[0115] FIG. 4 presents images of 3D printed structures heated under nitrogen to different temperatures, as indicated. The structures were printed from: line 1—ethoxy-TMPTA ink formulation, and line 2—1:1 POSS:APTMS ink formulation according to the invention. See disclosure.

[0116] FIG. 5 presents an image of 3D printed structures composed of formulation 5.

[0117] FIG. 6 shows the results of TGA measurements of structures composed of 92.15 wt % APTMS, 4.85 wt % ethoxy(15)TMPTA and 3 wt % TPO burn under nitrogen. (1) After immersion in HCl; (2) without immersion in HCl and compared to (3) commonly used organic monomer ethoxy-TMPTA (without the hybrid monomer).

[0118] FIG. 7 demonstrates the printing ability of a formulation of the invention and the thermal stability of printed structures: (1) immediately after printing, (2) after post treatment of 48 hours in citric acid, and (3) post treatment of 48 hours in AMP solution. The photos in the lower row are of the same structures but after heating at 150° C. for 1 h and then at 190° C. for 1 h.

[0119] FIG. 8 demonstrates the printing ability and thermal stability of printed structures: (1) immediately after printing, (2) after post treatment for 48 hours in citric acid, (3) and post treatment for 48 hours in AMP solution. The photos in the lower row are of the same structures but after heating at 150° C. for 1 h and then at 190° C. for 1 h.

[0120] FIG. 9 provides images of a printed structure made of formulation 10: (1) after printing, (2) after heating at 150° C. for 1 h and then at 190° C. for 1 h.

[0121] FIG. 10 provides images of a printed structure made of formulation 11: (1) after printing, (2) after heating at 150° C. for 1 h and then at 190° C. for 1 h.

[0122] FIGS. 11A-C provide images of 3D structures made of formulation 13 with 0.5 wt % (left star in each picture), 1 wt % (middle star in each picture) and 5 wt % (right star in each picture) of titanium isopropoxide: (FIG. 11A) after curing, (FIG. 11B) 500° C. under air; (FIG. 11C) after 1,150° C. under vacuum.

[0123] FIG. 12 provides images of a printed formulation 15, after a thermal treatment at 800° C.

[0124] FIG. 13 presents a TGA measurement of a printed structure formed of formulation 15. It can be seen that the weight loss was about 30 wt % after 600° C.

[0125] FIG. 14 present transparent 3D silica glass structure from formulation 16: (left) after printing (middle) after drying at 60° C. (right) after heating to 800° C.

[0126] FIG. 15 shows the TGA measurement of formulation 19 after printing. Heating rate of 1° C./min from 25° C. to 1,000° C.

[0127] FIG. 16 shows images of printed structures made of formulation 20: (left structure) after printing, (right structure) SiOC structure after 2 h at 1,150° C. under vacuum.

[0128] FIG. 17 provides an image of a printed structure made of formulation 22 after printing.

DETAILED DESCRIPTION OF EMBODIMENTS

EXAMPLE 1

Method for Making Printable Ceramic Silica Structure

[0129] An ink formulation is prepared by mixing 87.3 wt % Acrylo POSS (Hybrid plastics, USA), 9.7 wt % APTMS (Gelest, USA) and 3 wt % 2,4,6-trimethyldiphenyl phosphineoxide, TPO (BASF, Germany) as photoinitiator. After mixing for a few minutes in a hot water bath the mixture was poured into the monomer bath of the DLP 3D printer Freeform 39 plus (Asiga, Australia). The printing was done by curing 50 μm layer-by-layer for 5 sec. The structure then was immersed in iso-propyl alcohol (IPA) in an ultrasonic bath for 1 min to remove residues of the uncured monomer.

[0130] To demonstrate the thermal durability, the structure was heated first to 300° C. at 2° C./min, than to 500° C. at 7° C./min, than to 700° C. at 1° C./min under air. As may be observed from FIG. 1, the structure retained its form after heating to 700° C., even though it lost 42 wt %, see FIG. 2.

[0131] TGA measurements were conducted under air and nitrogen on a cured droplet (FIG. 2). For comparison the mixture was also compared to common to used monomer ethoxylated (15) TMPTA (SR9035, Sartomer) mixed with 0.5 wt % TPO.

EXAMPLE 2

Method for Making Printable Ceramic—Silica Structure

[0132] An ink formulation was prepared by mixing 48.5 wt % Acrylo POSS (Hybrid plastics, USA), 48.5 wt % APTMS (Gelest, USA) and 3 wt % 2,4,6-trimethyldiphenyl phosphineoxide, TPO (BASF, Germany) as a photoinitiator. After mixing for a few minutes in a hot water bath the mixture was poured into the monomer bath of the DLP 3D printer Freeform 39 plus (Asiga, Australia). The printing was done by curing 50 μm layer-by-layer for 4 sec. The structure then was immersed in iso propyl alcohol (IPA) in an ultrasonic bath for 1 min to remove residues of the uncured monomer.

[0133] To achieve silica structure, the structure was burnt under air at 1200° C. To remove all carbon residues, the structure was heated under air, first to 300° C. at 2° C./min for 1.5 h, than to 400° C. at 2° C./min for 1.5 h, than to 550° C. at 2° C./min for 1.5 h, than to 1200° C. at 5° C./min for 1 h. As FIG. 3 shows, a comparison of the discussed printed ink formulation to a similar 3D structure made of a commonly used monomer, ethoxylated (15) trimethylolpropane triacrylate (Ethoxy-TMPTA,SR9035, Sartomer) mixed with 0.5 wt % TPO, indicates that at 550° C. the organic structure almost completely disappeared, while the hybrid structure still remained in its original form. After further burning to 1200° C., the structure became white, suggesting complete removal of the organic parts in this hybrid structure, and formation of a ceramic structure.

EXAMPLE 3

A Method for Making Printable Ceramic Silica-Oxycarbide Structure

[0134] An ink formulation is prepared by mixing 48.5 wt % Acrylo POSS (Hybrid plastics, USA), 48.5 wt % APTMS (Gelest, USA) and 3 wt % 2,4,6-trimethyldiphenyl phosphineoxide, TPO (BASF, Germany) as photo initiator. After mixing for a few minutes in a hot water bath the mixture was poured into the bath of the DLP 3D printer Freeform 39 plus (Asiga, Australia). The printing was done by curing 50 μm layer by layer for 4 sec. The structure was then immersed in iso propyl alcohol (IPA) in ultrasonic bath for 1 min to remove the uncured monomer residue.

[0135] To achieve silica-carbide structure the structure was heated under nitrogen to 1,000° C.

[0136] The heat profile was preform under nitrogen, first increasing to 467° C. at 2° C./ min for 1.5 h than to 1,000° C. at 5° C./min for 1 h. FIG. 4 shows a comparison of the discussed printed ink formulation to a similar 3D structure made of common used monomer ethoxylated (15) Trimethylolpropane triacrylate (Ethoxy-TMPTA, SR9035, Sartomer) mixed with 0.5 wt % TPO. It can be seen from FIG. 4 that the hybrid structure remained in its original form while the organic structure lost its form completely. This attests to the formation of a ceramic structure. Furthermore, the black color of the structure, after heating, indicates a trapped carbon within the silica matrix, meaning a formation of silica-carbide within structure.

EXAMPLE 4

A Method for Making a Printable Ceramic Silica-Oxycarbide Structure

[0137] An ink formulation is prepared by mixing 49.5 wt % APTMS (Gelest, USA), 24.75 wt % Ebecryl 113, 24.75 wt % Ebecryl 8411 (Allnex, Belgium) and wt % 2,4,6-trimethyldiphenyl phosphineoxide, TPO (BASF, Germany) as photo initiator. The formulation was cured in a mold for 20 sec.

[0138] To achieve silica-carbide structure the structure was heated under nitrogen to 800° C.

[0139] The heat profile was preform under nitrogen, for 800° C. at 10° C./min for 3 h. XPS measurements shows that the object contains silica and silicon carbide.

EXAMPLE 5

Method for Making a Printable Hybrid Ceramic Organic-Silica-Silazane Structure

[0140] An ink formulation was prepared by mixing 99-X wt % Acrylo POSS (Hybrid plastics, USA), X wt % silazane (KDT HTA 1500 Rapid and Slow, wherein X=80 wt % and 90 wt %) and 1 wt % 2,4,6-trimethyldiphenyl phosphineoxide, TPO (BASF, Germany) as a photoinitiator. After mixing for a few minutes in a hot water bath the mixture was poured into the bath of the DLP 3D printer Pico2 (Asiga, Australia). The printing was done by curing 25 μm layer by layer for 1.2 sec each layer. FIG. 5 shows a printed cubes structures.

[0141] For achieving better mechanical strength, the structure was kept in an open vessel in an oven at 60° C. for several days.

EXAMPLE 6

Method for Making Printable Ceramic Silicon Oxynitride Structure

[0142] An ink formulation was prepared by mixing 99-X wt % Acrylo POSS (Hybrid plastics, USA), X wt % silazane (KDT HTA 1500 Rapid and Slow, wherein X=49 wt % , 65 wt %, 85 wt %, 90 wt % and 95 wt %) and 1 wt % 2,4,6-trimethyldiphenyl phosphineoxide, TPO (BASF, Germany) as a photoinitiator. After mixing for a few minutes in a hot water bath the mixture cured in a mold.

[0143] For achieving silica-nitride, post treatment was performed by heating the printed structures to 800° C. under nitrogen atmosphere for 3 hours at heating rate of 10° C./min. XPS measurements shows that the object contains silica and silicon nitride.

EXAMPLE 7

Method for Making Printable Hybrid Ceramic Structure

[0144] An ink formulation is prepared by mixing 92.15 wt % APTMS (Gelest, USA), 4.85 wt % ethoxy(15)TMPTA (SR9035, Sartomer) and 3 wt % 2,4,6-trimethyldiphenyl phosphineoxide, TPO (BASF, Germany) as photo initiator. After mixing for a few minutes the mixture was purred into the monomer bath of the DLP 3D printer Freeform 39 plus (Asiga, Australia). The printing was done by curing 100 μm layer by layer for 5 sec. For achieving thermal durability there is a need for post process of immersing the printed structure into HCl solution with pH 2.5 for 4 days for achieving hydration and condensation for the formation of siloxane bond within the organic matrix. Another post printing process was immersing the printed structure in citric acid solution with pH 4 for 48 hours or in 0.05% AMP solution with pH 10 for 48 hours.

[0145] TGA measurement were conducted under nitrogen on cured photocured samples. The graphs shows comparison between droplet immersed in HCl solution with pH 2.5 for 4 days and droplet that have not been immersed in HCl. The mixture is also compared to common used monomer ethoxylated (15) TMPTA (SR9035, Sartomer) mixed with 0.5 wt % TPO (FIG. 6).

[0146] The image provided in FIG. 7 demonstrates the printing ability of the formulation and the thermal stability of the printed structures, (1) immediately after printing, (2) after post treatment for 48 hours in citric acid, and (3) post treatment for 48 hours in AMP solution. The images in the lower row are the same structures but after heating at 150° C. for 1 h and then at 190° C. for 1 h.

EXAMPLE 8

Method for Making Printable Ceramic Silica Structure/Object

[0147] An ink formulation was prepared by mixing 87.3 wt % APTMS (Gelest, USA), 9.7 wt % ethoxy(15)TMPTA (SR9035, Sartomer) and 3 wt % 2,4,6-trimethyldiphenyl phosphineoxide, TPO (BASF, Germany) as a photoinitiator. After mixing for a few minutes the mixture was purred into the monomer bath of the DLP 3D printer Freeform 39 plus (Asiga, Australia). The printing was done by curing 100 μm layer by layer for 10 sec. A post process was performed by immersing the printed structures into citric acid solution with pH 4 for 48 hours or in 0.05% AMP solution with pH 10 for 48 hours

[0148] FIG. 8 demonstrates the printing ability and the thermal stability of the printed structures, (1) immediately after printing, (2) after post treatment for 48 hours in citric acid, and (3) post treatment for 48 hours in AMP solution. The images in the lower row are the same structures but after heating at 150° C. for 1 h and then at 190° C. for 1 h.

EXAMPLE 9

Method for Making a Printable Object

[0149] An ink formulation is prepared by mixing 87.6 wt % APTMS (Gelest, USA), 9.9 wt % ebecryl 113, 1.485% ebecryl 8411 (Allnex, Belgium) and 1 wt % 2,4,6-trimethyldiphenylphosphineoxide, TPO (BASF, Germany) as photo initiator. After mixing for a few minutes the mixture was purred into the monomer bath of the DLP 3D printer Freeform 39 plus (Asiga, Australia). The printing was done by curing 100 μm layer by layer for 10 sec. A post process was performed by immersing the printed structure into citric acid solution with pH 4 for or with 0.05% AMP solution with pH 10.

EXAMPLE 10

Method for Making Printable Ceramic Silica 3D Object

[0150] An ink formulation was prepared by mixing 14.85 wt % Vinyl POSS (Hybrid plastics, USA), 75.735 wt % Ebecryl 113, 8.415% Ebecryl 8411 (Allnex, Belgium) and 1 wt % 2,4,6-trimethyldiphenylphosphineoxide, TPO (BASF, Germany) as a photoinitiator. After mixing for 20 minutes in a hot water bath, the mixture was poured into the monomer bath of the DLP 3D printer Freeform 39 plus (Asiga, Australia). The printing was done by curing 100 μm layer by layer for 5 sec.

[0151] Good structures were obtained (FIG. 9) both after printing and after heating at 150° C. for 1 h and then at 190° C. for 1 h.

EXAMPLE 11

Method for Making Printable Ceramic Silica Structure

[0152] An ink formulation was prepared by mixing 14.85 wt % octasilane POSS (Hybrid plastics, USA), 75.735 wt % ebecryl 113, 8.415% ebecryl 8411 (Allnex, Belgium) and 1 wt % 2,4,6-trimethyldiphenylphosphineoxide, TPO (BASF, Germany) as a photoinitiator. After mixing for 20 minutes in a hot water bath the mixture was purred into the monomer bath of the DLP 3D printer Freeform 39 plus (Asiga, Australia). The printing was done by curing 100 μm layer by layer for 5 sec.

[0153] Good structures were obtained (FIG. 10) both after printing and after heating at 150° C. for 1 h and then at 190° C. for 1 h.

EXAMPLE 12

Method for Making Printable Hybrid Ceramic Silica Structure

[0154] An ink formulation was prepared by mixing 19.8 wt % acrylo POSS (Hybrid plastics, USA), 79.2 wt % PEG600 diacrylate (SR610, Sartomer) and 1 wt % 2,4,6-trimethyldiphenylphosphineoxide, TPO (BASF, Germany) as a photoinitiator. After mixing for 20 minutes in a hot water bath the mixture was poured into the monomer bath of the DLP 3D printer Freeform 39 plus (Asiga, Australia). The printing was done by curing 100 μm layer by layer for 2 sec.

[0155] This formulation also enabled printing of structures which were stable after heating at 150° C. for 1 h and then at 190° C. for 1 h.

EXAMPLE 13

Method for Making Printable Ceramic Titania-Silica 3D Structure

[0156] An ink formulation is prepared by mixing (97-X) wt % Acrylo POSS (Hybrid plastics, USA), X wt % (X=0.5, 1 and 5) titanium isopropoxide (Sigma Aldrich) and 3 wt % 2,4,6-trimethyldiphenylphosphineoxide, TPO (BASF, Germany) as photo initiator. After mixing for a few minutes in a hot water bath the mixture was poured into a mold and was cured for a few seconds.

[0157] For achieving silica-titania structure, the cured structure was heated at low rate under air to 500° C. for 1 h and then heated to 1150° C. under vacuum. The resulting 3D ceramic objects are shown in FIG. 11. As it can be seen from FIG. 11 larger concentration of titania resolve in darker 3D structure.

EXAMPLE 14

Method for Making Printable Ceramic Titania-Silicon Oxycarbide 3D Structure

[0158] An ink formulation is prepared by mixing (97-X) wt % Acrylo POSS (Hybrid plastics, USA), X wt % (X=0.5, 1 and 5) titanium isopropoxide (Sigma Aldrich) and 3 wt % 2,4,6-trimethyldiphenylphosphineoxide, TPO (BASF, Germany) as photo initiator. After mixing for a few minutes in a hot water bath the mixture was poured into a mold and was cured for a few seconds.

[0159] For achieving silica-carbide-titania structure, the cured structure should be heated at low rate under nitrogen or vacuum to 800° C. or higher.

EXAMPLE 15

A method for Making a Printable 3D Transparent Silica Glass Structure

[0160] An ink formulation was prepared by forming a siloxane oligomer with acrylic groups by the sol gel technique. First by hydrolyzing TEOS mixed with hybrid alkoxide-acrylic monomer for 1 h, followed by condensation.

[0161] 20 grams of ink formulation is prepared by mixing 8.54 gr of tetraethyl orthosilicate (TEOS, Acros) with 3 gr of acidic 65 wt % ethanol in water solution (0.3 wt % of HNO.sub.3 in ethanol solution) for 30 min. After 30 min 2.14 gr of APTMS and 0.053 gr of TPO was added to the solution for addition of 60 min mixing. Then 6.34 gr of basic 65 wt % ethanol in water solution (1.5 wt % of ammonium acetate (sigma Aldrich) in ethanol solution) was added for condensation and mixed for addition 50 min. This formulation was printed by DLP 3D printer asiga 2 (Asiga, Australia). After printing, the 3D object was kept in a sealed vessel at 60° C. for 24 h for further gelation, then kept in an open vessel at 60° C. for 48 h for removal of solvents. The organic residue was remove by heating to 800° C. for 1 h, at a heating rate of 0.6° C./min. It may be noted from FIG. 12 that the printed structures after treatemnt at 800° C. remained transparent.

[0162] FIG. 13 presents TGA measurements of a printed structure made from formulation 15, it can be seen that the weight loss was about 30 wt % after 600° C.

EXAMPLE 16

A Method for Making a Printable 3D Transparent Silica Glass

[0163] An ink formulation was prepared by forming a siloxane oligomer with acrylic groups by the sol gel technique. First by hydrolyzing TEOS mixed with hybrid alkoxide-acrylic monomer for 1 h, followed by condensation.

[0164] 20 grams of ink formulation is prepared by mixing in iced-water bath 8.01 gr of tetraethyl orthosilicate (TEOS, Acros) with 3 gr of acidic 65 wt % ethanol in water solution (0.3 wt % of HNO.sub.3 in ethanol solution) for 30 min. After 30 min 2.67 gr of APTMS and 0.053 gr of TPO was added to the solution for addition of 60 min mixing. Then 6.34 gr of basic 65 wt % ethanol in water solution (1.5 wt % of ammonium acetate (sigma Aldrich) in ethanol solution) was added for condensation and mixed for addition 20 min. This formulation was printed by DLP 3D printer asiga 2 (Asiga, Australia) After printing, the 3D object was kept in a sealed vessel at 60° C. for 24 h for further gelation, then kept in an open vessel at 60° C. for 48 h for removal of solvents. The organic residue was remove by heating to 800° C. for 1 h, at a heating rate of 0.6° C./min.

[0165] FIG. 14 present a printed 3D structure after printing, after drying at 60° C. and after heating to 800° C.

EXAMPLE 17

A Method for Making Printable 3D Silica Aerogel Structure

[0166] 20 grams of an ink formulation was prepared by mixing 8.54 gr of tetraethyl orthosilicate (TEOS, Acros) with 3 gr of acidic 65 wt % ethanol in water solution (0.3 wt % of HNO.sub.3 in ethanol solution) for 30 min. After 30 min 2.14 gr of APTMS and 0.053 gr of TPO was added to the solution for addition of 60 min mixing. Then 6.34 gr of basic 65 wt % ethanol in water solution (1.5 wt % of ammonium acetate (sigma Aldrich) in ethanol solution) is added for condensation and mixed for addition 50 min.

[0167] The formulation was printed by DLP 3D printer asiga 2 (Asiga, Australia). After printing, the silica structure was kept in a sealed vessel at 60° C. for 24 h, than the structure was immersed in acetone for 1 week at 40° C., replacing the acetone every day. After a week, the acetone was replaced with CO.sub.2 by supercritical drying, for 4 days. The resulting structure withstood 800° C. without cracking or shrinking, and it is composed of silica aerogel. The structure did not shrink after heating to 800° C. and were semi-transparent with light bluish color, typical to aerogels.

EXAMPLE 18

A Method for Making Printable Silica Structure

[0168] 20 grams of ink formulation was prepared by mixing 4.27 gr of tetraethyl orthosilicate (TEOS, Acros) with 3 gr of acidic 65 wt % ethanol in water solution (0.3 wt % of HNO.sub.3 (Sigma Aldrich) in ethanol solution) for 30 min. After 30 min 4.27 gr of polydiethoxysilane (Gelest, USA), 2.14 gr of APTMS and 0.053 gr of TPO was added to the solution for addition of 60 min mixing. Then 6.34 gr of basic 65 wt % ethanol in water solution (1.5 wt % of ammonium acetate (sigma Aldrich) in ethanol solution) was added for condensation and mixed for addition 50 min. This formulation is 3D printed by DLP 3D printer asiga 2 (Asiga, Australia).

[0169] After printing, the 3D structure was kept in a sealed vessel at 60° C. for 24 h for further gelation, then in open vessel at 60° C. for 48 h for removal of solvents. The organic residue was removed by heating to 800° C. for 1 h in heating rate of 0.6° C./min.

EXAMPLE 19

A Method for Making Printable 3D Silica Structure

[0170] An ink formulation was prepared by forming a siloxane oligomer with acrylic groups by the sol gel technique. First by hydrolyzing TMOS, MTMS and hybrid alkoxide-acrylic monomer which were put together, for 30 min, followed by condensation via evaporation of the by-products —alcohol and water, for 200 min, promoting the formation of the siloxsanes bonds.

[0171] The formulation was preapred by mixing 12.45 wt % of tetramethyl orthosilicate (TMOS, sigma Aldrich), 62.3 wt % of MTMS (methyltrimetoxysilane, 97% , Acros), 8.3 wt % of APTMS and 1 wt % of TPO with 16 wt % of acidic water (0.5 mM of HCl (Sigma Aldrich) in water) for 30 min in 50° C. in a closed and dark vessel. After 30 min the temperature was increased to 70° C. and the vessel was opened while the formulation continued to be stirred for additional 200 min.

[0172] The formulation was poured into a 3D DLP printer monomer bath and is ready for printing in a resolution up to 500 μm at the Z-axis.

[0173] Printing of the formulation results in transparent 3D structure with high silica content the 3D object was kept in a sealed vessel at 60° C. for 24 h, then in an open vessel at 60° C. for 48 h, the organic residues are removed by heating to 800° C. for 2 h at a heating rate of 0.6° C./min (as can be seen from FIG. 15, the structure remained with 70 wt % of the starting weight). The resulting 3D structure was composed of amorfous silica (confirmed by XRD).

EXAMPLE 20

A Method for Making Printable 3D SiOC Structure

[0174] An ink formulation was prepared by forming a siloxane oligomer with acrylic groups by the sol gel process. First by hydrolyzing mixture of TMOS, MTMS and hybrid alkoxide-acrylic monomer for 30 min, followed by condensation via evaporation of the by-products—alcohol and water, for 200 min, promoting the formation of the siloxsanes bonds.

[0175] The formulation was made by mixing 12.45 wt % of Tetramethyl orthosilicate (TMOS, sigma Aldrich), 62.3 wt % of MTMS (methyltrimetoxysilane, 97% , Acros), 8.3 wt % of APTMS and 1 wt % of TPO with 16 wt % of acidic water (0.5 mM of HCl (Sigma Aldrich) in water) for 30 min in 50° C. in close and dark vessel. After 30 min the temperature was increased to 70° C. and the vessel was opened while the formulation continued to be stirred for additional 200 min.

[0176] The formulation was poured into a 3D DLP printer monomer bath and is ready for printing in a resolution up to 500 μm at the Z-axis.

[0177] Printing of the formulation resulted in a transparent 3D structure with high silica content (FIG. 16 left), the 3D object is kept in a sealed vessel at 60° C. for 24 h, then in an open vessel at 60° C. for 48 h. The organic residues were removed by heating to 1,150° C. for 2 h under a vacuum at a heating rate of 1° C./min. The resulting 3D structure shown in FIG. 16 (right picture) is composed of SiOC.

EXAMPLE 21

A Method for Making Printable 3D Hybrid Aerogel Structure

[0178] An ink formulation was prepared by forming a siloxane oligomer with acrylic groups by the sol gel technique. First by hydrolyzing a mixture of TMOS, MTMS and hybrid alkoxide-acrylic monomer for 30 min, followed by condensation via evaporation of the by-product—alcohol and water for 90 min, thus promoting the formation of the siloxsanes bonds.

[0179] The formulation was made by mixing 10.67 wt % of Tetramethyl orthosilicate (TMOS, sigma Aldrich), 53.46 wt % of MTMS (methyltrimetoxysilane, 97% , Acros), 7.17 wt % of APTMS and 0.85 wt % of TPO with 8.88 wt % of acidic water (0.5 mM of HCl (Sigma Aldrich) in water) and 4.8 wt % of Ethanol for 30 min in 50° C. in closed and dark vessel. After 30 min 4.8 wt % ethanol, 8.88 wt % water and 0.5 wt % of ammonium acetate (sigma Aldrich) was added, the vessel was opened and the temperature was increased to 70° C. The formulation continue to be stirred for additional 90 min.

[0180] The formulation was poured into a 3D DLP printer monomer bath and was ready for printing at a resolution up to 500 μm at the Z-axis.

[0181] After printing, the transparent hybrid silica 3D structure was kept in a sealed vessel at 60° C. for 24 h, then the structure is immersed in acetone for 1 week at room temperature while replacing the acetone every day. After a week the acetone was replaced with CO.sub.2 by a supercritical drying process for 4 days, resulting in a 3D hybrid aerogel object.

EXAMPLE 22

A Method for Making Printable Transparent Hybrid High Silica Content 3D Structure

[0182] An ink formulation was prepared by forming a siloxane oligomer with acrylic groups by the sol gel technique. First by hydrolyzing TMOS, MTMS and hybrid alkoxide-acrylic monomer which were put together, for 30 min, followed by condensation via evaporation of the by-products—alcohol and water, for 200 min, promoting the formation of the siloxanes bonds.

[0183] The formulation was prepared by mixing 12.45 wt % of tetramethyl orthosilicate (TMOS, sigma Aldrich), 62.3 wt % of MTMS (methyltrimetoxysilane, 97% , Acros), 8.3 wt % of APTMS and 1 wt % of TPO with 16 wt % of acidic water (0.5 mM of HCl (Sigma Aldrich) in water) for 30 min in 50° C. in a closed and dark vessel. After 30 min the temperature was increased to 70° C. and the vessel was opened while the formulation continued to be stirred for additional 200 min.

[0184] The formulation was poured into a 3D DLP printer monomer bath and is ready for printing in a resolution up to 500 μm at the Z-axis.

[0185] Printing of the formulation resulted in a transparent 3D structure with high silica content. The 3D object was kept in a sealed vessel at 60° C. for 24 h, then in an open vessel at 60° C. for a minimum of 48 h. The resulted transparent high content silica structure is shown in FIG. 17.

EXAMPLE 23

A Method for Making A Printable 3D Silica Glass Structure at a Low Temperature

[0186] An ink formulation was prepared by forming a siloxane oligomer with acrylic groups by the sol gel technique. First by hydrolyzing TEOS mixed with hybrid alkoxide-acrylic monomer for 1 h, followed by condensation.

[0187] 20 grams of ink formulation is prepared by mixing in iced-water bath 8.54 gr of tetraethyl orthosilicate (TEOS, Acros) with 3 gr of acidic 65 wt % ethanol in water solution (0.3 wt % of HNO.sub.3 in ethanol solution) for 30 min. After 30 min 2.14 gr of APTMS and 0.053 gr of TPO was added to the solution for addition of 60 min mixing. Then 6.34 gr of basic 65 wt % ethanol in water solution (1.5 wt % of ammonium acetate (sigma Aldrich) in ethanol solution) was added for condensation and mixed for addition 50 min. This formulation was printed by DLP 3D printer asiga pico 39 (Asiga, Australia) in a cooled (ice-water circulation) monomer bath, for printing the ink in a temperature of maximum 5° C. After printing, the 3D object was kept in a sealed vessel at 60° C. for 24 h for further gelation, then kept in an open vessel at 60° C. for 48 h for removal of solvents.

[0188] The organic residue was remove by heating to 800° C. for 1 h, at a heating rate of 0.6° C./min.

EXAMPLE 24

A Method for Making a Printable 3D Transparent Silica Glass

[0189] An ink formulation was prepared by forming a siloxane oligomer with acrylic groups by the sol gel technique. First by hydrolyzing TEOS mixed with hybrid alkoxide-acrylic monomer for 1 h, followed by condensation.

[0190] 20 grams of ink formulation is prepared by mixing in iced-water bath 8.01 gr of tetraethyl orthosilicate (TEOS, Acros) with 3 gr of acidic 65 wt % ethanol in water solution (0.3 wt % of HNO.sub.3 in ethanol solution) for 30 min. After 30 min 2.67 gr of APTMS and 0.053 gr of TPO was added to the solution for addition of 60 min mixing. Then 6.34 gr of basic 65 wt % ethanol in water solution (1.5 wt % of ammonium acetate (sigma Aldrich) in ethanol solution) was added for condensation and mixed for addition 20 min. This formulation was printed by DLP 3D printer asiga 2 (Asiga, Australia) After printing, the 3D object was kept in a sealed vessel at 60° C. for 24 h for further gelation, then kept in an open vessel at 60° C. for 48 h for removal of solvents. The organic residue was removed by heating to 800° C. for 1 h, at a heating rate of 0.6° C./min.

EXAMPLE 25

A Method for Making A Printable 3D Transparent Silica Glass Structure

[0191] An ink formulation was prepared by forming a siloxane oligomer with acrylic groups by the sol gel technique. First by hydrolyzing TEOS mixed with hybrid alkoxide-acrylic monomer for 1 h, followed by condensation.

[0192] 20 grams of ink formulation is prepared by mixing 9.61 gr of tetraethyl orthosilicate (TEOS, Acros) with 3 gr of acidic 65 wt % ethanol in water solution (0.3 wt % of HNO.sub.3 in ethanol solution) for 30 min. After 30 min 1.07 gr of APTMS and 0.053 gr of TPO was added to the solution for addition of 60 min mixing. Then 6.34 gr of basic 65 wt % ethanol in water solution (1.5 wt % of ammonium acetate (sigma Aldrich) in ethanol solution) was added for condensation and mixed for addition 70 min. This formulation was cured in a mold under UV LED for 20 sec. After curing, the 3D object was kept in a sealed vessel at 60° C. for 24 h for further gelation, then kept in an open vessel at 60° C. for 48 h for removal of solvents. The organic residue was remove by heating to 800° C. for 1 h, at a heating rate of 0.6° C./min. It may be noted that the cured structures after treatemnt at 800° C. remained transparent.

EXAMPLE 26

A Method for Making a Printable 3D Borosilicate Glass Structure

[0193] An ink formulation was prepared by forming a siloxane oligomer with acrylic groups by the sol gel technique with boric acid and sodium carbonate to achieve borosilicate glass. First by hydrolyzing with TEOS and boric acid mixed with hybrid alkoxide-acrylic monomer for 1 h, followed by condensation with sodium carbonate.

[0194] 20 grams of ink formulation is prepared by mixing 8.54 gr of tetraethyl orthosilicate (TEOS, Acros) with 3 gr of acidic water solution (94 of HNO.sub.3 and 1 gr of boric acid in 3 gr of water) for 30 min. After 30 min 2.14 gr of APTMS and 0.053 gr of TPO was added to the solution for addition of 60 min mixing. Then 6.34 gr of basic water solution (0.11 gr of sodium carbonate in 6.24 gr of water) was added for condensation and mixed for 10 min. This formulation was cured in a mold under UV LED for 20 sec. After curing, the 3D object was kept in a sealed vessel at 60° C. for 24 h for further gelation, then kept in an open vessel at 60° C. for 48 h for removal of solvents. The organic residue was remove by heating to 800° C. for 1 h, at a heating rate of 0.6° C./min. then continue for additional heating of 850° C. for 24 h and 950° C. for 24 h.