CN111116016A - Low-viscosity slurry for photocuring 3D printing glass and application thereof - Google Patents
Low-viscosity slurry for photocuring 3D printing glass and application thereof Download PDFInfo
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- CN111116016A CN111116016A CN201911294841.7A CN201911294841A CN111116016A CN 111116016 A CN111116016 A CN 111116016A CN 201911294841 A CN201911294841 A CN 201911294841A CN 111116016 A CN111116016 A CN 111116016A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B20/00—Processes specially adapted for the production of quartz or fused silica articles, not otherwise provided for
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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
- B33Y10/00—Processes of 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
- B33Y70/00—Materials specially adapted for additive manufacturing
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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
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Abstract
The invention provides low-viscosity paste for photocuring 3D printing glass and application thereof, and a preparation method of the low-viscosity paste comprises the following steps: preparing a premixed solution: mixing 50-95 wt% of monofunctional photocuring monomer and 5-50 wt% of cross-linking agent to obtain a first solution, mixing 30-100 wt% of the first solution and 0-70 wt% of non-reactive component, and uniformly mixing to obtain a premixed solution; preparing silicon dioxide slurry: uniformly mixing 20-80 wt% of premixed liquid and 20-80 wt% of silicon dioxide powder, adding 0.1-5 wt% of photoinitiator, 0-5 wt% of inhibitor and 0-3 wt% of ultraviolet absorber, continuously mixing uniformly, and removing bubbles. By utilizing the slurry and the preparation method thereof, the high-quality quartz glass device with a complex structure can be prepared through photocuring 3D printing and heat treatment, a mold is not needed, the design and production period is short, and compared with the traditional process, the preparation method has the advantages of low energy consumption and low cost.
Description
Technical Field
The invention relates to the technical field of photocuring materials, in particular to low-viscosity slurry for photocuring 3D printing glass and application thereof.
Background
The quartz glass is called as the king of glass, has the advantages of high temperature resistance, thermal shock resistance, low thermal expansion coefficient, good chemical stability and electrical insulation, large hardness, good transmission performance in the whole spectral band from ultraviolet to near infrared and the like, and is widely applied to the fields of optical fibers, lasers, electric light sources, semiconductor integrated circuits, chemical industry, metallurgy, aerospace, nuclear industry and the like. Although the silica glass has very excellent properties, it has been limited in use because it has problems of high production cost, difficulty in forming complicated devices, difficulty in processing, etc.
The traditional preparation technology of quartz glass mainly comprises a high-temperature melting method, a chemical synthesis method, a sol-gel method and the like. The high-temperature melting method is to melt natural crystal and silica as raw materials at high temperature, and the melting method comprises an electric melting method and a gas refining method. The high-temperature melting method is simple in process and the most common preparation method of quartz glass, but the prepared quartz glass has the defects of low purity, poor ultraviolet transmittance, more bubbles, miscellaneous points and the like, the optical performance of the quartz glass is seriously influenced, and the application requirements in the high-end photoelectric technical field cannot be met. In addition, the melting temperature of the quartz glass is as high as 1700 ℃ or higher, so that the energy consumption is large. The chemical synthesis methods are classified into Chemical Vapor Deposition (CVD), Plasma Chemical Vapor Deposition (PCVD), and indirect bondingBy CVD or PCVD, using a silicon-containing precursor such as SiCl4Heating by oxyhydrogen or plasma flame, hydrolyzing or oxidizing at high temperature to generate silicon dioxide particles, and depositing the silicon dioxide particles on a substrate layer by layer to form quartz glass; the indirect synthesis method is to use a silicon-containing precursor such as SiCl4Firstly, a low-density silicon dioxide loose body is formed by deposition through a low-temperature CVD process, and then vitrification is achieved by sintering. The quartz glass prepared by the chemical synthesis method has high purity and good optical uniformity, but the production equipment is complex, the cost is higher, the yield is low, and the method is only suitable for manufacturing high-quality quartz glass. The sol-gel method can prepare quartz glass at a lower temperature, but a blank is easy to crack in the preparation process, large glass is difficult to obtain, the reaction time is longer, and the method is not favorable for industrial mass production.
Since the silica glass has a high melting temperature and a high viscosity, bubbles are difficult to remove, and it is more difficult to perform hot forming than ordinary glass, and only silica products having simple structures such as rods, blocks, silica tubes, and silica crucibles can be obtained by using a mold at a high temperature. The quartz glass device with a complex shape is generally synthesized into a large quartz lump and then machined. Since quartz glass is a hard and brittle material, the processing is very difficult, and the traditional processing modes mainly comprise mechanical grinding and polishing, chemical etching, plasma etching, laser processing and the like. The mechanical grinding and polishing speed is slow, and the mechanical grinding and polishing speed is generally only used for processing the surface of glass, so that the complex shape is difficult to process. The chemical etching is mainly to etch a microstructure on the surface of the glass by means of a photoetching mask and wet etching, the quality of the chemically etched surface is higher, but the etching rate is lower, the etching isotropy is difficult to control, and hydrofluoric acid with higher risk needs to be used. The plasma etching is to form volatile substances by utilizing the reaction of plasma and a surface film in low-temperature plasma by means of a photoetching mask, or to directly bombard the surface of the film for etching. The plasma etching is anisotropic and has high etching rate, but the etching precision is not enough and the cost is higher. The laser etching is divided into a laser direct etching method, a laser-induced plasma etching method, a laser-induced back wet etching method and the like, wherein the laser direct etching method is to utilize a high-energy laser beam to directly act on the surface of quartz glass so as to melt and vaporize the glass to complete etching; the laser-induced plasma etching method and the laser-induced back wet etching method both utilize the interaction of laser penetrating through quartz glass and a target material to generate plasma so as to realize the etching of the bottom surface of the quartz glass; the laser etching has high flexibility, can conveniently process various complex structures, but has lower etching rate and higher cost.
3D printing is a rapid prototyping technique, which is a technique for building objects by layer-by-layer printing based on digital model files. Compared with the traditional forming method, the 3D printing method has the advantages of high forming precision, no need of a mold in the processing process, high material utilization rate, short research and development period, low cost and the like, can realize the rapid manufacturing of parts with complex structures such as hollow and thin walls, and has wide application prospect in the fields of microfluidic chips, micromachines, microelectronics, aerospace, automobiles, biomedicine and the like. At present, the mainstream materials for 3D printing are mainly metal, resin, ceramic and the like, and although several methods for 3D printing of glass have been reported, such as binder jet printing (3DP), glass powder laser sintering/melting (SLS/SLM), Fused Deposition Modeling (FDM), filament feeding laser sintering, Direct Ink Writing (DIW) and stereolithography, the quality of printed glass has a certain difference from that of commercially produced glass, and 3D printing of high-quality glass is still a great problem.
Compared with other 3D printing technologies, the stereolithography technology has the advantages of high forming precision, good surface quality, high forming speed and the like, and is one of the 3D printing technologies which are applied most widely at the earliest. Kotz et al first proposed that glass be prepared by using a stereolithography technique, a nano-silica resin mixture with a solid content of 37.5 vol% is prepared, and a glass device with a complex shape is obtained through 3D printing and heat treatment, but the viscosity of printing paste is too high, which limits the increase of the solid content, and simultaneously puts higher requirements on printing equipment, and the printed piece is easy to have layer cracking after sintering, which affects the use of 3D printing glass.
Disclosure of Invention
In view of the above, there is a need to provide a low viscosity paste for photocuring 3D printing glass and an application thereof. The technical scheme of the invention is as follows:
in a first aspect, the present invention provides a method for preparing a low viscosity paste for photocuring 3D printed glass, comprising the steps of:
(1) preparing a premixed solution: mixing 50-95 wt% of monofunctional photocuring monomer and 5-50 wt% of cross-linking agent to obtain a first solution, mixing 30-100 wt% of the first solution and 0-70 wt% of non-reactive component, and uniformly mixing to obtain a premixed solution;
(2) preparing silicon dioxide slurry: uniformly mixing 20-80 wt% of premixed liquid and 20-80 wt% of silicon dioxide powder, adding 0.1-5 wt% of photoinitiator, 0-5 wt% of inhibitor and 0-3 wt% of ultraviolet absorbent, continuously mixing uniformly, and removing bubbles to obtain the silicon dioxide/.
Further, the monofunctional photocurable monomer is selected from one or more of 4-hydroxybutyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, tetrahydrofuran acrylate, tetrahydrofuran methacrylate, ethoxylated tetrahydrofuran acrylate, N-vinyl pyrrolidone, 4-acryloyl morpholine, ethoxyethoxyethyl acrylate, polyethylene glycol methacrylate, polypropylene glycol methacrylate, methoxypolyethylene glycol methacrylate and cyclotrimethylolpropane formal acrylate.
Preferably, the monofunctional light-curing monomer is one or more selected from 4-hydroxybutyl acrylate, hydroxyethyl methacrylate, tetrahydrofuran methacrylate, N-vinyl pyrrolidone and 4-acryloyl morpholine.
Further, the cross-linking agent is a bifunctional or polyfunctional light-cured monomer, one or more selected from the group consisting of ethylene glycol diacrylate, ethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, 1, 4-butanediol diacrylate, 1, 4-butanediol dimethacrylate, 1, 6-hexanediol diacrylate, 1, 6-hexanediol dimethacrylate, ethoxylated 1, 6-hexanediol diacrylate, neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate and propoxylated glycerol triacrylate.
Preferably, the cross-linking agent is selected from one or more of 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate and triethylene glycol dimethacrylate.
Optionally, the non-reactive component is a chemical substance that does not participate in the photochemical reaction, and includes one or more of a plasticizer, a lubricant, and a solvent, and is used for improving the quality of the printed product, such as: can be one or more of alcohols, ethers, esters and ketones.
Further, the non-reactive component is selected from one or more of monohydric alcohol, dihydric alcohol, trihydric alcohol, glycol ethers, propylene glycol ethers, alcohol ether acetates, benzoates, phthalates, aliphatic dibasic acid esters, benzene polycarboxylic acid esters, ethylene glycol esters, propylene glycol esters, polyhydric alcohol esters, citrates, carbonates, methyl nylon acid ester, N-methylpyrrolidone, N-ethylpyrrolidone and 1,7, 7-trimethylbicyclo [2.2.1] heptane-2-one.
Preferably, the non-reactive component is selected from one or more mixtures of 1, 2-propylene glycol, tetraethylene glycol dimethyl ether, propylene glycol methyl ether acetate, diethyl phthalate, dibutyl phthalate, triacetin, triethyl citrate, dimethyl carbonate and 1,7, 7-trimethylbicyclo [2.2.1] heptan-2-one.
Preferably, in the step (2), 20-80 wt% of the premixed solution and 20-80 wt% of the silicon dioxide powder are uniformly mixed, and the mixing process is divided into multiple times: firstly, uniformly mixing 60-95% of the premixed liquid and 60-100% of the nano silicon dioxide powder, then adding the rest premixed liquid and the nano silicon dioxide powder once or for many times, and uniformly mixing.
Further, the silicon dioxide powder is nano silicon dioxide powder or submicron silicon dioxide powder or a mixture of the nano silicon dioxide powder and the submicron silicon dioxide powder with the particle size of 5-500 nm.
Optionally, the photoinitiator is one or more of benzoin and derivatives thereof, benzil and derivatives thereof, acetophenone derivatives, α -hydroxyketone derivatives, α -aminoketone derivatives, benzoyl formates, acylphosphine oxides, benzophenone and derivatives thereof, anthraquinone and derivatives thereof, camphorquinone and amine co-initiators.
Further, the photoinitiator is 2, 2-dimethoxy-2-phenylacetophenone, 2-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenylketone, 2-benzyl-2- (dimethylamino) -4' -morpholinophenylbutanone, methyl benzoylformate, 2,4, 6-trimethylbenzoylethoxyphenylphosphine oxide, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, ethyl 2,4, 6-trimethylbenzoylphenylphosphonate, phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide, benzophenone, 4-chlorobenzophenone, 4-methylbenzophenone, 4-phenylbenzophenone, methyl o-benzoylbenzoate, methyl benzoylformate, methyl benzoyl, One or more of 2-ethyl anthraquinone, camphorquinone, isooctyl p-dimethylaminobenzoate and ethyl 4-dimethylaminobenzoate.
Optionally, the inhibitor is used for preventing the photo-curing paste from polymerizing during storage, and may be one or more of hydroquinone, p-benzoquinone, methyl hydroquinone, p-hydroxyanisole, 2-tert-butyl hydroquinone, 2, 5-di-tert-butyl hydroquinone, 2, 6-di-tert-butyl-p-cresol, 4-methyl naphthol, N-nitroso-N-phenyl and nitroxyl radical piperidinol.
Optionally, the ultraviolet absorber is used for reducing the deviation of the dimension in the X-Y direction caused by over-curing in the Z-axis direction and light scattering, and improving the forming precision. Can be 2-hydroxybenzoic acid phenyl ester, 2- (2-hydroxy-5-benzyl) benzotriazole, 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 2- (5-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (2' -hydroxy-5 ' -tert-octylphenyl) benzotriazole, 2- (3, 5-di-tert-amyl-2-hydroxyphenyl) benzotriazole, 2- (2' -hydroxy-3 ',5' -di-tert-butylphenyl) benzotriazole, 2- (3, 5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 3-hydroxyphenyl benzoate, tris (1,2,2,6, 6-pentamethylpiperidinyl) phosphite, 4-benzoyloxy-2, 2,6, 6-tetramethylpiperidine, 3 oxazine-52, 4, 6-tris (2' -hydroxy-4 ' -n-butoxyphenyl), hexamethylphosphoric triamide, bis (1,2,2,6, 6-pentamethyl-4-piperidinyl) sebacate, 2,2' -methylenebis [6- (benzotriazol-2-yl) -4-tert-octylphenol ], Sudan red I to IV and Sudan orange G.
In a second aspect, the present invention provides a low viscosity paste for photocuring 3D printing glass, which is prepared by the above preparation method.
In a third aspect, the invention provides a method for photocuring 3D printing of a glass device, which adopts the low-viscosity paste and the preparation method thereof, and the method comprises the following steps:
(1) and (3) photocuring and forming: curing and molding the low-viscosity slurry by using photocuring 3D printing equipment to obtain a molded part, and cleaning the molded part;
(2) degreasing and sintering: and (3) carrying out thermal degreasing on the formed piece to fully decompose the organic matter, heating the degreased formed piece to 1050-1300 ℃ in vacuum or protective atmosphere, and keeping the temperature for 0.5-8 h to obtain the glass device.
Further, the light source wavelength of the photocuring 3D printing equipment is 250-600 nm.
Optionally, the degreasing method is a one-step thermal degreasing method, wherein the one-step thermal degreasing method is to directly heat and degrease the formed part in the air, and the temperature for degreasing and heat preservation is 500-1000 ℃.
Optionally, the degreasing method is a two-step thermal degreasing method, wherein the two-step method comprises heating and degreasing the formed part in vacuum or protective atmosphere, and then heating and degreasing in air to remove residual carbon; the degreasing and heat preservation temperature is 500-1000 ℃.
Further, the protective atmosphere adopted in the degreasing and sintering processes is nitrogen, argon or helium.
In a fourth aspect, the invention provides a glass device, which is prepared by the method for photocuring 3D printing the glass device.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) according to the invention, a 3D printing technology is adopted, so that the quartz glass device with a complex shape and a micro structure, which cannot be processed by the traditional technology, can be manufactured at one time without post-processing;
(2) the invention adopts the photocuring 3D printing technology, has high molding precision, can process the preformed piece of the required quartz glass device at room temperature without a mold, and has short design and production period;
(3) according to the invention, through optimizing the resin proportion and the mixing mode, the photocuring glass slurry with high solid content and low viscosity can be obtained, and the requirement on 3D printing equipment is low.
(4) The invention can manufacture the high-quality quartz glass device below 1300 ℃, and has the advantages of low energy consumption and low cost compared with the traditional process.
Drawings
Fig. 1 is a schematic structural view of a 3D printed molded article, a degreased molded article, and a final molded article according to example 1 of the present invention, in which 1-3D printed molded article, 2-degreased molded article, and 3-final molded article.
Fig. 2 is a schematic structural view of a complex molded part in embodiment 2 of the present invention.
FIG. 3 is a transmission spectrum of a sample of example 2 of the present invention.
FIG. 4 is a graph of viscosity versus solids content for example 3 of the present invention.
FIG. 5 is a graph of viscosity versus solids content for comparative example 3 of the present invention with direct mixing.
FIG. 6 is an XRD comparison of the sintering temperature 1300 ℃ of example 5 of the present invention and the sintering temperature 1350 ℃ of comparative example 5.
Detailed Description
In the description of the present invention, it is to be noted that those whose specific conditions are not specified in the examples are carried out according to the conventional conditions or the conditions recommended by the manufacturers. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The present invention will now be described in further detail with reference to the following figures and specific examples, which are intended to be illustrative, but not limiting, of the invention.
Example 1
The embodiment provides a method for photocuring a 3D printing glass device, which comprises the following steps:
(1) preparing a premixed solution: mixing 45 wt% of hydroxyethyl methacrylate, 10 wt% of 1, 6-hexanediol diacrylate and 45 wt% of tetraethylene glycol dimethyl ether to obtain a premixed solution;
(2) preparing silicon dioxide slurry: to obtain a light-curable paste with a lower viscosity, 47 wt% of the premix was mixed in two portions with 53 wt% of a silica powder having a particle size of 40 nm; in the mixing process, the amount of the premix added for the first time is 85%, the premix is uniformly mixed with 90% of silica powder, then 10% of the premix and the rest of silica powder are added and uniformly mixed, finally the rest of premix is added and uniformly mixed again, finally phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide accounting for 0.5 wt% of the premix, 0.5 wt% of hydroquinone and 0.05 wt% of sudan orange G are added, and bubbles are removed by ultrasound after the uniform mixing is continued, so that silica slurry is obtained;
(3) and (3) photocuring and forming: curing and molding the silicon dioxide slurry obtained in the step (2) on a platform of an LCD (liquid crystal display) photocuring 3D printer to obtain a molded part as shown in figure 1, wherein the wavelength of a light source of the photocuring 3D printer is 405 nm;
(4) degreasing and sintering: adopting a two-step thermal degreasing method, firstly heating the formed piece obtained in the step (3) to 600 ℃ in vacuum and preserving heat for 2h, then heating to 1000 ℃ in air and preserving heat for 2h, after degreasing, exhausting the air in the furnace through a vacuum pump, heating to 1275 ℃ and preserving heat for 2.5h, and then cooling to room temperature to obtain a glass device; the preform after degreasing and sintering is shown in fig. 1.
Example 2
The embodiment provides a method for photocuring a 3D printing glass device, which comprises the following steps:
(1) preparing a premixed solution: mixing 50 wt% of 4-hydroxybutyl acrylate, 5 wt% of polyethylene glycol diacrylate, 5 wt% of ethoxylated trimethylolpropane triacrylate and 40 wt% of diethyl phthalate to obtain a premixed solution;
(2) preparing silicon dioxide slurry: to obtain a light-cured slurry with a lower viscosity, 45 wt% of the premix was mixed twice with 55 wt% of silica powder having a particle size of 40 nm; in the mixing process, the amount of the premix liquid added for the first time is 90%, the premix liquid is added after being uniformly mixed with the silicon dioxide powder, the rest premix liquid is added, finally, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 0.5 wt% of p-hydroxyanisole and 0.03 wt% of Sudan orange G which account for 1 wt% of the premix liquid are added, and the silicon dioxide slurry is obtained after the uniform mixing and the ultrasonic removal of bubbles;
(3) and (3) photocuring and forming: curing and molding the silicon dioxide slurry obtained in the step (2) on a DLP photocuring 3D printer platform, wherein the light source wavelength of the photocuring 3D printer is 405 nm;
(4) degreasing and sintering: and (2) directly degreasing the formed part obtained in the step (3) in air by adopting a one-step thermal degreasing method, wherein the degreasing heat preservation temperature is 800 ℃, after degreasing, exhausting air in the furnace through a vacuum pump, heating to 1250 ℃, preserving heat for 3h, and cooling to room temperature to obtain a series of complex formed parts shown in figure 2, wherein the transmission spectrum of a sample is shown in figure 3, and the transmittance of the quartz glass device prepared in the embodiment in a region of 300nm to 1800nm exceeds 90 percent and is slightly lower than that of commercial quartz glass.
Example 3
In this example, the relation between the viscosity and the solid content of the silica paste is examined, the specific process of example 2 is adopted, the silica pastes with the solid contents of 35 wt%, 40 wt%, 45 wt%, 50 wt% and 55 wt% are respectively prepared, then the viscosity of the silica paste is measured by a digital display rotational viscometer, the relation between the viscosity and the solid content is shown in fig. 4, and as can be seen from fig. 4, the invention prepares the photocuring glass paste with high solid content and low viscosity, and the requirement of the paste on 3D printing equipment is low.
Example 4
The embodiment provides a method for photocuring a 3D printing glass device, which comprises the following steps;
(1) preparing a premixed solution: mixing 55 wt% of hydroxyethyl acrylate, 5 wt% of N-vinyl pyrrolidone, 10 wt% of dipropylene glycol diacrylate and 30 wt% of 1,7, 7-trimethylbicyclo [2.2.1] heptan-2-one to obtain a premix;
(2) preparing silicon dioxide slurry: in order to obtain the light-cured slurry with lower viscosity, mixing 40 wt% of premixed liquid with 60 wt% of silicon dioxide powder for three times, uniformly mixing 90% of premixed liquid and 80% of nano silicon dioxide powder, then adding 5% of premixed liquid and the rest of nano silicon dioxide powder, and finally adding the rest of premixed liquid; the silicon dioxide powder is a silicon dioxide powder mixture with the particle size of 40nm and 200nm, and the mixing ratio is 3: 7; finally, adding 0.5 wt% of 2, 2-dimethoxy-2-phenylacetophenone and 0.5 wt% of hydroquinone into the premixed solution, continuously mixing uniformly, and removing bubbles by ultrasonic waves to obtain silicon dioxide slurry;
(3) and (3) photocuring and forming: curing and molding the silicon dioxide slurry obtained in the step (2) on a SLA photocuring 3D printer platform, wherein the light source wavelength of the photocuring 3D printer is 355 nm;
(4) degreasing and sintering: and (3) directly degreasing the formed part obtained in the step (3) in air by adopting a one-step thermal degreasing method, wherein the degreasing heat preservation temperature is 700 ℃, after degreasing, exhausting air in the furnace through a vacuum pump, then heating to 1300 ℃, preserving heat for 2h, and cooling to room temperature to obtain the glass device.
Example 5
The embodiment provides a method for photocuring a 3D printing glass device, which comprises the following steps;
(1) preparing a premixed solution: mixing 45 wt% of 4-hydroxybutyl acrylate, 15 wt% of trimethylolpropane triacrylate, 20 wt% of propylene glycol monomethyl ether acetate and 20 wt% of dibutyl phthalate to obtain a premixed solution;
(2) preparing silicon dioxide slurry: to obtain a light-cured slurry with a lower viscosity, 45 wt% of the premix was mixed twice with 55 wt% of silica powder having a particle size of 100 nm; in the mixing process, the amount of the premix added for the first time is 80%, the premix is uniformly mixed with 85% of silicon dioxide powder, then the rest 10% of the premix and the rest silicon dioxide powder are added and uniformly mixed, finally the rest premix is added and uniformly mixed again, finally camphorquinone and 1 wt% of p-hydroxyanisole which account for 1 wt% of the premix are added, uniform mixing is continued, and then bubbles are removed by ultrasound, so that silicon dioxide slurry is obtained;
(3) and (3) photocuring and forming: curing and molding the silicon dioxide slurry obtained in the step (2) on a VLC visible light curing 3D printer platform, wherein the light source wavelength of the light curing 3D printer is 460 nm;
(4) degreasing and sintering: and (3) directly degreasing the formed piece obtained in the step (3) in air by adopting a one-step thermal degreasing method, wherein the degreasing heat preservation temperature is 800 ℃, after degreasing, exhausting air in the furnace through a vacuum pump, then heating to 1300 ℃, preserving heat for 2.5h, and cooling to room temperature to obtain the glass device.
Example 6
The embodiment provides a method for photocuring a 3D printing glass device, which comprises the following steps;
(1) preparing a premixed solution: mixing 40 wt% of hydroxyethyl methacrylate, 10 wt% of tetrahydrofuran methacrylate, 10 wt% of tripropylene glycol diacrylate, 30 wt% of glyceryl triacetate and 10 wt% of 1, 2-propanediol to obtain a premix;
the other steps and parameters were the same as in example 1.
Example 7
The embodiment provides a method for photocuring a 3D printing glass device, which comprises the following steps;
(1) preparing a premixed solution: mixing 40 wt% of 4-hydroxybutyl acrylate, 10 wt% of 4-acryloyl morpholine, 15 wt% of triethylene glycol dimethacrylate, 25 wt% of propylene glycol methyl ether and 10 wt% of triethyl citrate to obtain a premixed solution;
the other steps and parameters were the same as in example 2.
Comparative example 1
This comparative example differs from example 1 in that in step (1) the monofunctional photocurable monomer isobornyl acrylate was used instead of hydroxyethyl methacrylate.
The experimental results are as follows: and (3) failing to prepare the silicon dioxide slurry in the step (2), wherein the prepared slurry is jelly and cannot be printed.
Comparative example 2
This comparative example differs from example 2 in that the ethoxylated trimethylolpropane triacrylate is replaced in step (1) by the crosslinker ethoxylated pentaerythritol tetraacrylate.
The experimental results are as follows: and (3) failing to prepare the silicon dioxide slurry in the step (2), wherein the prepared slurry is jelly and cannot be printed.
Comparative example 3
The comparative example is different from example 3 in that the pre-mixed solution and the nano silica are directly and uniformly mixed in the step (2).
The experimental results are as follows: the viscosity of the silica slurry was measured with a digital rotary viscometer, and the relationship between the viscosity and the solid content is shown in FIG. 5. Compared to the stepwise mixing of example 3, the direct mixing of comparative example 6 has a much higher viscosity, which is approximately doubled at high solids.
Comparative example 4
This comparative example differs from example 4 in that the non-reactive component N, N-dimethylformamide is used in place of 1,7, 7-trimethylbicyclo [2.2.1] heptan-2-one in step (1).
The experimental results are as follows: and (3) failing to prepare the silicon dioxide slurry in the step (2), wherein the prepared slurry is jelly and cannot be printed.
Comparative example 5
The difference between the comparative example and the example 5 is that the sintering temperature in the step (4) is 1350 ℃, and the temperature is kept for 2 h.
As a result of the experiment, the XRD patterns of the sintered sample at 1300 ℃ in example 5 and 1350 ℃ in comparative example 5 are shown in FIG. 6, and it can be seen that the sintered sample at 1300 ℃ has no obvious diffraction peak and is amorphous, while the sintered sample at 1350 ℃ is changed from amorphous to α -cristobalite.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A preparation method of low-viscosity paste for photocuring 3D printing glass is characterized by comprising the following steps: the method comprises the following steps:
(1) preparing a premixed solution: mixing 50-95 wt% of monofunctional photocuring monomer and 5-50 wt% of cross-linking agent to obtain a first solution, mixing 30-100 wt% of the first solution and 0-70 wt% of non-reactive component, and uniformly mixing to obtain a premixed solution;
(2) preparing silicon dioxide slurry: uniformly mixing 20-80 wt% of premixed liquid and 20-80 wt% of silicon dioxide powder, adding 0.1-5 wt% of photoinitiator, 0-5 wt% of inhibitor and 0-3 wt% of ultraviolet absorbent, continuously mixing uniformly, and removing bubbles to obtain the silicon dioxide/.
2. The method for preparing the low viscosity paste for the photocuring 3D printing glass according to claim 1, wherein the method comprises the following steps: the monofunctional photocuring monomer is selected from one or more of 4-hydroxybutyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, tetrahydrofuran acrylate, tetrahydrofuran methacrylate, ethoxylated tetrahydrofuran acrylate, N-vinyl pyrrolidone, 4-acryloyl morpholine, ethoxy ethyl acrylate, polyethylene glycol methacrylate, polypropylene glycol methacrylate, methoxy polyethylene glycol methacrylate and cyclotrimethylolpropane methylal acrylate.
3. The method for preparing the low viscosity paste for the photocuring 3D printing glass according to claim 1, wherein the method comprises the following steps: the cross-linking agent is a bifunctional or polyfunctional light-cured monomer and is selected from one or a mixture of more of ethylene glycol diacrylate, ethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, 1, 4-butanediol diacrylate, 1, 4-butanediol dimethacrylate, 1, 6-hexanediol diacrylate, 1, 6-hexanediol dimethacrylate, ethoxylated 1, 6-hexanediol diacrylate, neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate and propoxylated glycerol triacrylate.
4. The method for preparing the low viscosity paste for the photocuring 3D printing glass according to claim 1, wherein the method comprises the following steps: the non-reactive component is one or more selected from monohydric alcohol, dihydric alcohol, trihydric alcohol, glycol ethers, propylene glycol ethers, alcohol ether acetates, benzoates, phthalic acid esters, aliphatic dibasic acid esters, benzene polycarboxylic acid esters, ethylene glycol esters, propylene glycol esters, polyhydric alcohol esters, citric acid esters, carbonates, nylon acid methyl ester, N-methyl pyrrolidone, N-ethyl pyrrolidone and 1,7, 7-trimethyl bicyclo [2.2.1] heptane-2-ketone.
5. The method for preparing the low viscosity paste for the photocuring 3D printing glass according to claim 1, wherein the method comprises the following steps: in the step (2), the 20-80 wt% of premixed liquid and the 20-80 wt% of silicon dioxide powder are uniformly mixed, and the mixing process is divided into multiple times: firstly, uniformly mixing 60-95% of the premixed liquid and 60-100% of the nano silicon dioxide powder, then adding the rest premixed liquid and the nano silicon dioxide powder once or for many times, and uniformly mixing.
6. A low viscosity paste for photocuring 3D printed glass, characterized by: is prepared by the preparation method of any one of claims 1 to 5.
7. A method for photocuring 3D printing of glass devices is characterized in that: the production method according to any one of claims 1 to 5 or the low viscosity slurry according to claim 6 is used, and the method comprises the steps of:
(1) and (3) photocuring and forming: curing and molding the low-viscosity slurry by using photocuring 3D printing equipment to obtain a molded part, and cleaning the molded part;
(2) degreasing and sintering: and (3) carrying out thermal degreasing on the formed piece to fully decompose the organic matter, heating the degreased formed piece to 1050-1300 ℃ in vacuum or protective atmosphere, and keeping the temperature for 0.5-8 h to obtain the glass device.
8. The method of photocuring 3D printing of glass devices of claim 7, wherein: the light source wavelength of the photocuring 3D printing equipment is 250-600 nm.
9. The method of photocuring 3D printing of glass devices of claim 7, wherein: the degreasing method is a one-step thermal degreasing method, wherein the one-step thermal degreasing method is to directly heat and degrease the formed part in the air, and the degreasing and heat preservation temperature is 500-1000 ℃;
or the degreasing method is a two-step thermal degreasing method, wherein the two-step method comprises the steps of heating and degreasing the formed part in vacuum or protective atmosphere, and then heating and degreasing in air to remove residual carbon; the degreasing and heat preservation temperature is 500-1000 ℃, and the protective atmosphere adopted in the degreasing and sintering processes is nitrogen, argon or helium.
10. A glass device, characterized in that: is prepared by the method of any one of claims 7 to 9 for photocuring 3D printing glass devices.
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