CN111018321A - Method for preparing glass through 3D printing and photocuring molding - Google Patents
Method for preparing glass through 3D printing and photocuring molding Download PDFInfo
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- CN111018321A CN111018321A CN201911407148.6A CN201911407148A CN111018321A CN 111018321 A CN111018321 A CN 111018321A CN 201911407148 A CN201911407148 A CN 201911407148A CN 111018321 A CN111018321 A CN 111018321A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/06—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y80/00—Products made by additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/06—Glass compositions containing silica with more than 90% silica by weight, e.g. quartz
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2201/00—Type of glass produced
- C03B2201/06—Doped silica-based glasses
- C03B2201/08—Doped silica-based glasses doped with boron or fluorine or other refractive index decreasing dopant
- C03B2201/10—Doped silica-based glasses doped with boron or fluorine or other refractive index decreasing dopant doped with boron
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2201/00—Type of glass produced
- C03B2201/06—Doped silica-based glasses
- C03B2201/30—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2201/00—Type of glass produced
- C03B2201/06—Doped silica-based glasses
- C03B2201/30—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi
- C03B2201/32—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi doped with aluminium
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2201/00—Type of glass produced
- C03B2201/06—Doped silica-based glasses
- C03B2201/30—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi
- C03B2201/34—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi doped with rare earth metals, i.e. with Sc, Y or lanthanides, e.g. for laser-amplifiers
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2201/00—Glass compositions
- C03C2201/06—Doped silica-based glasses
- C03C2201/08—Doped silica-based glasses containing boron or halide
- C03C2201/10—Doped silica-based glasses containing boron or halide containing boron
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2201/00—Glass compositions
- C03C2201/06—Doped silica-based glasses
- C03C2201/30—Doped silica-based glasses containing metals
- C03C2201/34—Doped silica-based glasses containing metals containing rare earth metals
- C03C2201/3423—Cerium
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2201/00—Glass compositions
- C03C2201/06—Doped silica-based glasses
- C03C2201/30—Doped silica-based glasses containing metals
- C03C2201/34—Doped silica-based glasses containing metals containing rare earth metals
- C03C2201/3476—Erbium
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2203/00—Production processes
- C03C2203/20—Wet processes, e.g. sol-gel process
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2203/00—Production processes
- C03C2203/50—After-treatment
- C03C2203/52—Heat-treatment
Abstract
A method for preparing glass through 3D printing and photocuring molding belongs to the technical field of material manufacturing. Mixing organic molecules containing silicon elements, an organic solvent, deionized water and a salt doped with metal ions for reaction to obtain a solution of a three-dimensional network framework doped with metal ions and containing one or more of silicon, oxygen and the like; applying light or heat for further hydrolysis and condensation, and aging to obtain a precursor of the 3D printed inorganic component material; then mixing the mixture with organic resin to prepare 3D printing mixed slurry; printing, drying, degreasing at low temperature, and removing organic resin in the glass preform to form a porous glass green body with a nano pore channel; sintering at high temperature to obtain compact, transparent and homogeneous glass sample. The uniformity of the invention reaches the atomic level, and the problem of uneven doping in the prior art is solved.
Description
Technical Field
The invention belongs to the technical field of material manufacturing, and relates to a method for preparing glass with different components by 3D printing and photocuring molding.
Background
Glass is the basic and important component of the photoelectric technology industry, has wide application in the fields of optical instruments, optical communication, laser devices and the like, and mainly depends on excellent physical and chemical properties such as light transmission, mechanical property, electric insulation and the like. In the preparation of glass, impurities are easily introduced into the glass by a traditional high-temperature melting method, so that the extremely high loss of the glass is caused, the optical performance of the glass is influenced, the shape of the glass is limited by a forming method and a forming die, subsequent processing is often needed, and the preparation cost is increased; other emerging preparation methods such as PCVD (plasma vapor deposition) method have extremely high equipment and raw material cost, and the shape and structure of the glass are also greatly limited. Therefore, it is urgently needed to develop a proper glass preparation method, and to obtain glass with excellent performance at lower manufacturing cost.
The 3D printed transparent glass has wide application prospect in the field of photoelectric devices. At present, the preparation process of 3D printing transparent glass mainly includes two types: light-cured molding technology and melt extrusion molding technology. The existing photocuring forming technology is based on that a single powder raw material is directly added into photosensitive resin and is mechanically and uniformly mixed, and for 3D printing of multi-component materials or multi-system materials, the mutual mixing uniformity of each component in the system cannot be guaranteed, so that glass with uniform components is difficult to obtain.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for preparing glass by 3D printing photocuring forming, which comprises the steps of preparing a 3D printing precursor by a hydrolysis method or a sol-gel method, and preparing the glass by 3D printing photocuring forming. The glass prepared by the method has the component uniformity of atomic level, and the clarification and homogenization time at high temperature in the traditional preparation method is reduced or even eliminated, so that the glass achieves excellent optical characteristics; any three-dimensional shape can be constructed by 3D printing of layered stacking, and glass with excellent performance can be obtained by low-temperature sintering.
The invention provides the following technical scheme:
a method for preparing glass through 3D printing and photocuring forming comprises the following steps:
(1) mixing organic molecules containing silicon elements, an organic solvent, deionized water, salt doped with metal ions and the like, and carrying out hydrolytic condensation reaction to obtain a solution of a three-dimensional network framework doped with metal ions and containing one or more of silicon, oxygen and the like;
(2) applying light or heat to the solution obtained in the step (1) to further hydrolyze and condense the solution, aging the solution, and volatilizing part of the solvent to obtain sol with the normal-temperature viscosity of 10-300 cp as a precursor of the inorganic component material for 3D printing;
(3) mixing a precursor of an inorganic component material with an organic resin raw material to prepare 3D printing mixed slurry; the organic resin is added in a form of adding raw materials, and comprises an active monomer, a prepolymer, a photoinitiator and the like;
(4) designing a three-dimensional digital model of the glass sample by adopting drawing software;
(5) 3D printing photocuring forming is carried out by adopting the 3D printing mixed slurry to obtain a glass preform with a certain shape;
(6) drying and degreasing the glass preform at low temperature, and removing organic resin in the glass preform to form a porous glass blank with a nano pore channel;
(7) sintering at high temperature to obtain compact, transparent and homogeneous glass sample.
In the step (1), the organic molecule is a compound containing a silicon-lipid bond such as tetraethoxysilane, the organic molecule may further include a lipid compound containing a boron element such as tributyl borate, and the doped metal ion is any metal ion such as Al3+Etc. of common metal ions, e.g. Cr3+Isotransition metal ionSon, e.g. Er3+One or more of the rare earth ions.
Organic molecule: organic solvent: deionized water: 30-45 wt% of doped ionic salt: 30-45 wt%: 15-30 wt%: 0 to 5 wt%.
The organic solvent in the step (1) is selected from ethanol and the like, and the deionized water is used as a reactant and an inorganic solvent.
In step (1) or (2), in order to accelerate the hydrolysis and condensation reaction, acid or alkali is generally added to adjust the pH value, so that the solution is alkaline or acidic.
In the step (2), the precursor of the inorganic component material is a sol with a certain viscosity obtained after partial volatilization of a solvent, and the normal-temperature viscosity is 10-300 cp, so that the inorganic component material has good flowing property and excellent photocuring property. If the viscosity is moderate, the organic matter can be effectively removed in the subsequent low-temperature degreasing process, and cracks and other defects of the sample caused by overlarge internal stress can not be caused.
And the size of the particles in the precursor sol of the inorganic component material is generally between 3nm and 100 nm.
In the step (3), the reactive monomer is selected from one or a combination of more of 1,6 ethylene glycol diacrylate, aliphatic polyurethane hexaacrylate and propylene glycol acrylate. The prepolymer is one or two of bisphenol A epoxy acrylic polyester acrylate and hydroxyethyl methacrylate. The photoinitiator is a free radical polymerization initiator and is selected from azo initiators or organic peroxy initiators, such as azodiisopropyl imidazoline (AIP, VA-061 initiator for short) and the like. The formulated resin has low viscosity and high reactivity.
Reactive monomers in organic resins: prepolymer: 38-60 wt% of photoinitiator: 38-60 wt%: 1 to 5 wt%. The prepared organic resin is photosensitive resin and has low viscosity and high reactivity.
In the 3D printing mixed slurry, the precursor of the inorganic component material: 25-70 wt% of organic resin: 30 to 75 weight percent.
In the step (5), the printing time is inversely proportional to the size of the sample, and is generally 0.5 to 5 hours.
In the step (6), drying treatment is carried out at 30-100 ℃, and low-temperature degreasing treatment is carried out at 200-800 ℃, wherein the degreasing treatment process can be vacuum degreasing or degreasing under inert gas atmosphere; within the temperature range, the degreasing temperature can be properly increased, which is beneficial to more effectively removing the organic resin. But the degreasing temperature is not too high, and the degreasing temperature exceeds the temperature, so that the nano-pore canal of the prefabricated body is prevented from partially collapsing, and the preparation of uniform and transparent glass is not facilitated.
In the step (6), the degreasing time is generally 1 to 4 days, depending on the physicochemical properties of the organic resin.
In the step (7), the porous glass green body is subjected to high-temperature sintering treatment at 800-1600 ℃ for 2-8 h.
Preferably, the high-temperature sintering can be vacuum sintering or inert gas atmosphere sintering.
Compared with the prior art, the precursor sol of the inorganic component material provided by the invention has smaller particle size. The particle size determines its maximum loading in the resin, particle sizes greater than 10 μm result in a maximum loading below 20 wt%, a viscosity of the printing paste greater than 500cp, and a flowability too small to allow photocured 3D printing. The size of the particles in the precursor sol of the inorganic component material prepared by the method is generally between 3nm and 100nm, the size distribution is uniform, and the problems of complex processing technology, higher cost, non-uniform particle size distribution and the like of the existing mechanical ball milling method and other processing technologies are solved.
Meanwhile, compared with the existing method for preparing the glass blank by 3D printing, other components such as doped ions and the like are added into the three-dimensional network structure when the 3D printing precursor is prepared, the uniformity of the three-dimensional network structure reaches the atomic level, and the problems of uneven doping of the color glass, fluorescence quenching of the luminescent glass caused by uneven doping and the like in the prior art are solved.
Drawings
FIG. 1 is a schematic diagram of ion doping by hydrolysis or sol-gel method.
Fig. 2 is a graph showing a distribution of particle sizes of 3D printing precursors prepared by the hydrolysis method or the sol-gel method of example 1 (three tests).
Detailed Description
The scheme of the invention is further explained by combining the attached drawings and the specific embodiment. The following embodiments are described to illustrate the present invention, but the present invention is not limited to the following embodiments.
Example 1
The preparation method of the laser gain glass comprises the following specific steps:
using 34.3g of absolute ethyl alcohol as a solvent, adding 35.9g of tetraethoxysilane and 19.6g of deionized water, uniformly mixing, and adjusting the pH value of the solution by using nitric acid. Weighing 0.293g of erbium nitrate pentahydrate, adding the erbium nitrate pentahydrate into the solution, and uniformly stirring the mixture at the temperature of between 30 and 80 ℃ to obtain a clear solution;
heating the solution at 60-150 ℃, removing part of the inorganic solvent and organic solvent ethanol to obtain sol with the viscosity of more than 50cp, and using the sol as a 3D printing precursor;
the sol and organic resin (50 wt%: 50 wt%) are mixed and stirred uniformly, the organic resin adopts the form of adding raw materials, and is composed of 53.3 wt% of propylene glycol acrylate, 44.7 wt% of hydroxyethyl methacrylate and 2 wt% of photoinitiator azodiisopropyl imidazoline (AIP, VA-061 initiator). Ultrasonically stirring uniformly to obtain a suspension solution with the viscosity of 150cp and uniformly distributed components as 3D printing slurry;
pouring the printing slurry into a 3D printer, and performing 3D printing according to a three-dimensional graph drawn by SolidWorks to obtain a disc-shaped glass preform with the D being 8mm and the h being 3 mm;
putting the obtained glass preform into a muffle furnace, and carrying out low-temperature degreasing treatment for 1-3 days at 100-500 ℃, removing organic resin in the glass preform, so as to obtain a porous glass blank with a nano pore channel;
and putting the porous glass blank into a high-temperature furnace, and performing densification sintering for 3 hours at the high temperature of 1150 ℃ to finally obtain the dense and transparent erbium-doped quartz glass. The optical test shows that the fluorescence lifetime can reach 1.0ms, the central wavelength is 1550nm, the 3dB line width is 36.5nm, and the power is 6 nW.
Example 2
The preparation method of the aluminosilicate multi-component glass comprises the following steps:
firstly, preparing a glass 3D printing precursor. Taking 34.3g of absolute ethyl alcohol as a solvent, taking 35.9g of ethyl orthosilicate and 19.8g of deionized water to be uniformly mixed, and weighing 3.325g of AlCl3Adding the solution into the solution, and dropwise adding ethylenediamine to adjust the pH value of the solution to be alkaline, so as to prepare a clear solution;
heating the solution at 30-120 ℃ to remove most of the solvent to obtain sol with the viscosity of more than 50 cp;
the sol was mixed with a resin (45 wt%: 55 wt%) added as raw material, consisting of 50 wt% of 1,6 ethylene glycol diacrylate, 47 wt% of bisphenol a epoxy acrylate polyester acrylate and 3 wt% of Azobisisobutyronitrile (AIBN). Shaking and stirring to obtain multicomponent glass 3D printing slurry with the viscosity of 30-100 cp;
pouring the glass 3D printing slurry into a 3D printer, and printing according to the drawn three-dimensional graph to obtain a block-shaped glass preform with the thickness of 8mm x 3 mm;
putting the glass preform into a muffle furnace, degreasing at the low temperature of 100-700 ℃ for 1-3 days, and completely removing organic resin in the preform to obtain a porous structure glass blank;
and (3) treating the glass green body at 1350 ℃ for 4 hours to obtain compact and transparent aluminosilicate glass.
Example 3
The preparation method of the fluorescent luminescent borosilicate glass comprises the following steps:
taking 31.7g of absolute ethyl alcohol as a solvent, uniformly mixing 26.1g of ethyl orthosilicate, 11.3g of tributyl borate and 18.8g of deionized water, weighing 0.759g of cerium trichloride heptahydrate, adding the solution into the solution, dropwise adding ethylenediamine to adjust the pH value of the solution to be alkaline, and preparing a clear solution;
and heating the solution at 30-120 ℃ to remove part of the solvent to obtain the sol with the viscosity of more than 50 cp.
Uniformly mixing the sol and the resin, and printing according to a set three-dimensional graph in a 3D mode to obtain a glass preform; degreasing at the low temperature of 100-500 ℃ to remove organic resin to obtain a porous glass green body; and sintering at 1175 ℃ to obtain the transparent and compact luminescent glass. Other specific processes are the same as in example 1.
Example 4
The preparation method of the colored glass comprises the following steps:
34.3g of absolute ethyl alcohol is taken as a solvent, 35.9g of Tetraethoxysilane (TEOS), 19.3g of deionized water and 0.382g of chromium nitrate (green) are taken as reactants to be added into a 500mL beaker, and the mixed reagent is stirred for more than 30 minutes to obtain a uniform mixture. Adding nitric acid to adjust the pH value of the solution to be acidic, and accelerating the reaction process;
heating the solution to 30-120 ℃ to further carry out hydrolytic condensation on the mixture to form sol with a silica three-dimensional network, and carrying out hydrolytic condensation and aging to obtain sol with the viscosity of more than 50 cp;
mixing the sol with resin, and carrying out layered curing molding according to a set three-dimensional model to obtain a wafer with the D being 10mm and the h being 4 mm; putting the glass preform into a muffle furnace, and carrying out low-temperature degreasing treatment for 1-3 days at 100-500 ℃ to obtain a porous glass blank; and carrying out densification sintering at the high temperature of 1150 ℃ to finally obtain the green quartz glass. The transmittance of the material to the light wave band of 400 nm-500 nm is 62% and the transmittance to the light wave band of 530 nm-600 nm is 45% through detection. Other specific processes were the same as in example 2.
Claims (10)
1. The method for preparing the glass through 3D printing and photocuring molding is characterized by comprising the following steps of:
(1) mixing organic molecules containing silicon elements, an organic solvent, deionized water, salt doped with metal ions and the like, and carrying out hydrolytic condensation reaction to obtain a solution of a three-dimensional network framework doped with metal ions and containing one or more of silicon, oxygen and the like;
(2) applying light or heat to the solution obtained in the step (1) to further hydrolyze and condense the solution, aging the solution, and volatilizing part of the solvent to obtain sol with the normal-temperature viscosity of 10-300 cp as a precursor of the inorganic component material for 3D printing;
(3) mixing a precursor of an inorganic component material with an organic resin raw material to prepare 3D printing mixed slurry; the organic resin is realized by adopting a form of adding raw materials, and comprises an active monomer, a prepolymer, a photoinitiator and the like;
(4) designing a three-dimensional digital model of the glass sample by adopting drawing software;
(5) 3D printing photocuring forming is carried out by adopting the 3D printing mixed slurry to obtain a glass preform with a certain shape;
(6) drying and degreasing the glass preform at low temperature, and removing organic resin in the glass preform to form a porous glass blank with a nano pore channel;
(7) sintering at high temperature to obtain compact, transparent and homogeneous glass sample.
2. The method for preparing glass by 3D printing photocuring forming according to claim 1, wherein in the step (1), the organic molecule is a compound containing a silicon-lipid bond such as ethyl orthosilicate or a lipid compound containing a boron element in the organic molecule, such as tributyl borate, and the doped metal ion is any metal ion, such as Al3+Etc. of common metal ions, e.g. Cr3+Isotransition metal ions, e.g. Er3+One or more of the rare earth ions;
organic molecule: organic solvent: deionized water: 30-45 wt% of doped ionic salt: 30-45 wt%: 15-30 wt%: 0-5 wt%;
the organic solvent in the step (1) is selected from ethanol and the like, and the deionized water is used as a reactant and an inorganic solvent.
3. The method for preparing glass by 3D printing photocuring molding according to claim 1, wherein in the step (1) or (2), in order to accelerate the reaction progress of hydrolysis and condensation, acid or alkali is added to adjust the pH value of the solution so that the solution is alkaline or acidic.
4. The method for preparing glass by 3D printing and photocuring molding according to claim 1, wherein in the step (2), the precursor of the inorganic component material is a sol with a certain viscosity obtained after partial volatilization of a solvent, and the normal-temperature viscosity is 10-300 cp, so that the glass has good flowing property and excellent photocuring property; the size of the particles in the precursor sol of the inorganic component material is generally between 3nm and 100 nm.
5. The method for preparing glass by 3D printing photocuring molding according to claim 1, wherein in the step (3), the reactive monomer is one or more selected from 1,6 ethylene glycol diacrylate, aliphatic polyurethane hexaacrylate and propylene glycol acrylate; the prepolymer is selected from one or two of bisphenol A epoxy acrylic polyester acrylate and hydroxyethyl methacrylate; the photoinitiator is a free radical polymerization initiator and is selected from azo initiators or organic peroxy initiators.
6. The method for preparing glass by 3D printing and photocuring molding according to claim 1, wherein the ratio of the reactive monomer in the organic resin: prepolymer: 38-60 wt% of photoinitiator: 38-60 wt%: 1 to 5 wt%.
7. The method for preparing glass by 3D printing and photocuring molding according to claim 1, wherein in the 3D printing mixed slurry, the precursor of inorganic component materials is as follows: 25-70 wt% of organic resin: 30 to 75 weight percent.
8. The method for preparing glass by 3D printing and photocuring molding according to claim 1, wherein in the step (5), the printing time is inversely proportional to the size of the sample and is 0.5-5 hours.
9. The method for preparing glass by 3D printing and photocuring molding according to claim 1, wherein in the step (6), drying treatment is carried out at 30-100 ℃, and low-temperature degreasing treatment is carried out at 200-800 ℃ for 1-4 days, wherein the degreasing treatment process can be vacuum degreasing or degreasing in an inert gas atmosphere.
10. The method for preparing glass by 3D printing and photocuring molding according to claim 1, wherein in the step (7), the porous glass green body is subjected to high-temperature sintering treatment at 800-1600 ℃ for 2-8 h; the high-temperature sintering can be vacuum sintering or inert gas atmosphere sintering.
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| CN115636572A (en) * | 2021-07-20 | 2023-01-24 | 南开大学 | Micro-manufacturing forming method for vitrification of complex surface topography based on soft lithography technology |
| CN115838285A (en) * | 2022-12-09 | 2023-03-24 | 湖南旗滨医药材料科技有限公司 | 3D printing glass rotating tube, preparation method and application thereof |
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