CN112429946A - 3D printing-based integrated forming preparation method for small-size inner runner glass device - Google Patents
3D printing-based integrated forming preparation method for small-size inner runner glass device Download PDFInfo
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- CN112429946A CN112429946A CN202011419735.XA CN202011419735A CN112429946A CN 112429946 A CN112429946 A CN 112429946A CN 202011419735 A CN202011419735 A CN 202011419735A CN 112429946 A CN112429946 A CN 112429946A
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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
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
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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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
Abstract
The invention provides an integrated forming preparation method of a small-size inner flow channel glass device based on 3D printing. The invention adopts a mode of adding an organic coloring agent to absorb ultraviolet light, reduces the curing thickness in the photocuring printing process, avoids the over-curing phenomenon, and can avoid the problem that the inner flow channel of the seal cover is blocked due to over-curing, so that the small-size three-dimensional inner flow channel glass device is integrally formed, the bonding splicing is not needed, the process is simplified, the flow channel with a complex structure can be more conveniently formed, the width of the printable flow channel reaches 0.5mm, and the problem that the inner flow channel of the seal cover is blocked and is difficult to form due to the over-curing phenomenon is effectively solved.
Description
Technical Field
The invention relates to a glass device preparation technology, in particular to an integrated forming preparation method of a small-size inner runner glass device based on 3D printing.
Background
Glass is a high-performance material commonly used in scientific research, has excellent mechanical properties, optical transparency, chemical resistance, heat resistance and heat insulation, and becomes a common material for manufacturing glass devices such as microfluidic chips and the like. The above-described properties of high-purity silica glass are better, and thus silica glass is a popular material for microfluidic chips used for chemical synthesis and cell research. However, glass, especially high-purity quartz glass, is difficult to form, a wet etching process is often adopted for preparing small-size inner channel glass devices such as microfluidic chips by the traditional method, the preparation process is dangerous, the environmental pollution is large, the energy consumption is high, the efficiency is low, the process is complex, and the bottom of a channel is spherical when an etchant such as HF (high frequency hydrogen) is used for wet etching because the glass is isotropic, so that the channel with a high depth-to-width ratio is difficult to manufacture. In addition, the sealing and bonding of the microfluidic chip is more difficult than etching a microstructure on glass, the yield of thermal bonding is not high, and the sealing and bonding difficulty is high.
The 3D printing technology can be used for obtaining a complex structure which is difficult to prepare by the traditional method, and the efficiency can be greatly improved. Although the current 3D printing technology is limited by forming precision and is inferior to the current micro-processing technology in the processing precision of the small-size inner flow channel glass device, the manufacturing requirements of the small-size inner flow channel glass device such as a micro-fluidic chip can be met by combining proper glass device design and a reasonable 3D printing technology. Meanwhile, the small-size inner flow channel glass device can be manufactured from model simulation analysis to printing of a solid three-dimensional structure, and the design and manufacturing mode of the small-size inner flow channel glass device, particularly the micro-fluidic chip, is improved. The research of the 3D printing glass device technology can not only expand the application range of the 3D printing technology, but also verify the feasibility of the 3D printing glass device, and provide a new method and a new idea for manufacturing the glass device.
At present, the research on the photocuring 3D printing technology of the glass device is few, and the technology is in a starting stage. The research on the photocuring 3D printing technology of the microfluidic chip is mostly focused on resin printing, and glass printing is available, but the resin is far inferior to glass in terms of biocompatibility, chemical resistance and mechanical property, so that the research on the photocuring 3D printing technology of a glass device is necessary. The glass photocuring 3D printing technology reported at present is difficult to print the inner flow channel of the seal cover, can only print an open flow channel, and can carry out encapsulation bonding in the later period, and the printable flow channel width is about 1mm, and the flow channel is simple in structure. The main problem at present is that the over-curing is serious in the printing process, and the blocking is very easy to occur when the seal cover inner flow passage is printed, so that the over-curing problem needs to be solved when the seal cover inner flow passage is printed, and the aims of not needing bonding, integrally forming the seal cover flow passage, simplifying the process, forming the flow passage with a complex structure, forming the flow passage with a three-dimensional structure and reducing the size of the flow passage are achieved.
Disclosure of Invention
Aiming at the problem that the existing photocuring 3D printing technology cannot integrally form a glass device with a sealing cover complex structure and a small-size three-dimensional inner flow channel, the invention provides an integrally forming preparation method of the small-size inner flow channel glass device based on 3D printing, and the problem that the sealing cover inner flow channel is blocked and is difficult to form due to an over-curing phenomenon is effectively solved.
The invention is realized by the following technical scheme:
the preparation method comprises the steps of preparing photosensitive glass slurry containing resin coloring agents, printing by adopting a photocuring 3D printing technology to obtain a biscuit of the small-size inner-runner glass device, and obtaining the small-size inner-runner glass device by adopting a heat treatment process on the biscuit.
Preferably, the method specifically comprises the following steps:
s1: preparing photosensitive glass slurry containing a resin coloring agent;
s2: guiding the designed three-dimensional structure model of the small-size inner runner glass device into a computer, and carrying out slicing treatment;
s3: pouring the prepared photosensitive glass slurry into a resin tank of a photocuring 3D printer, starting the photocuring 3D printer to start printing according to the three-dimensional structure model of the small-size inner runner glass device, obtaining a blank after printing, and cleaning the blank by using a cleaning solution;
s4: and degreasing and vacuum sintering the obtained biscuit to obtain the small-size inner flow channel glass device.
Further, S1 specifically includes: mixing an acrylic monomer, a photoinitiator, a light absorber and a polymerization inhibitor, performing ultrasonic treatment to obtain a premixed liquid 1, adding silicon dioxide powder into the premixed liquid 1, stirring to obtain a premixed liquid 2, adding a resin coloring agent into the premixed liquid 2, performing shearing dispersion to obtain a premixed liquid 3, and performing vacuum defoaming to obtain the photosensitive glass slurry containing the resin coloring agent.
Further, the acrylic monomer is one or more of HEMA, TEGDA, TMPTA, PEGDA and TPGDA, the photoinitiator is one or more of photoinitiator TPO, photoinitiator 819 and photoinitiator 184, the light absorber is one or more of benzotriazole cresol and 2, 2-dimethylolpropionic acid, and the polymerization inhibitor is one or more of hydroquinone and p-hydroxyanisole.
Furthermore, the silicon dioxide powder is gas-phase nano amorphous silicon dioxide powder, and according to the volume percentage, the silicon dioxide powder accounts for 35-42.5% of the photosensitive glass slurry, and the acrylic resin accounts for 65-57.5% of the photosensitive glass slurry.
Further, the mass of the polymerization inhibitor accounts for 1-1.7% of the mass of the photosensitive glass slurry, and the mass of the light absorber accounts for 0.4-0.6% of the mass of the photosensitive glass slurry.
Preferably, the resin coloring agent is oily color concentrate.
Preferably, the content of the resin coloring agent is 0.3-0.6% of the mass of the photosensitive glass paste.
Preferably, the photocuring 3D printing technology is SLA or DLP.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention adopts a mode of adding an organic coloring agent to absorb ultraviolet light, reduces the curing thickness in the photocuring printing process, avoids the over-curing phenomenon, and can avoid the problem that the inner flow channel of the seal cover is blocked due to over-curing, so that the small-size (100-600 mu m) three-dimensional inner flow channel glass device is integrally formed, bonding splicing is not needed, the process is simplified, the flow channel with a complex structure can be more conveniently formed, the width of the printable flow channel reaches 0.5mm, and the problem that the flow channel in the seal cover is difficult to form due to the over-curing phenomenon is effectively solved. According to the invention, the organic coloring agent is selected, so that the curing thickness can be reduced, and the later-stage light transmittance and mechanical property are not influenced after heat treatment.
Drawings
FIG. 1 is a flow chart of a process for preparing photosensitive glass paste.
FIG. 2 is a design drawing and a physical drawing of the glass microfluidic chip of example 1.
Fig. 3 shows a small-sized glass microfluidic chip with a closed inner channel (the left figure shows the arc-shaped channel of example 2, and the right figure shows the three-dimensional inner channel of example 3).
Fig. 4 is a graph of linear transmittance of glass devices prepared with and without the addition of colorants.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
In the glass and ceramic photocuring molding technology, the over-curing phenomenon is prominent, and the flow channel in the sealing cover is easy to block, so that the printing fails, and therefore, the curing thickness needs to be reduced, and not only can the interlayer combination be ensured, but also the flow channel is not easy to block. Meanwhile, the sizing agent can be cured only when the energy above the critical curing energy is obtained, and the light intensity of a light source of the printer is generally fixed, so that the invention adopts a mode of adding a resin coloring agent to absorb ultraviolet light, reduces the curing thickness and prints out the inner flow channel of the sealing cover. The resin coloring agent is selected, on one hand, the curing thickness is considered to be reduced, and on the other hand, the transparent glass piece can be obtained after heat treatment, namely, the introduction of the coloring agent cannot influence the light transmittance in the later period, cannot influence the components of the final piece and cannot influence the mechanical performance. Later experiments prove that the introduction of the resin coloring agent causes no relevant influence and only plays a role in controlling the curing thickness and the curing speed in the printing stage.
In the invention, glass slurry containing resin coloring agent is prepared, printed and molded, and degreased and sintered to obtain a nearly fully dense (99.8%) glass device. The plasticizer is added into the slurry formula, so that the plastic deformation of the formed part is increased, the thermal stress is reduced, and the cracking is inhibited. Bubbles in the slurry are eliminated through vacuumizing, the internal pores of the formed part are reduced, and the quality of the formed part is improved. And adding a resin coloring agent to reduce the curing thickness of the single layer and inhibit over-curing.
The method comprises the steps of preparing photosensitive glass slurry, forming a printing piece by adopting a photocuring 3D printing technology (either SLA or DLP printing can be used), and obtaining a final glass device through a heat treatment process.
The method comprises the following steps:
s1: preparing photosensitive glass paste as shown in fig. 1;
s2: guiding the designed three-dimensional structure model of the glass device into a computer, and slicing the glass device according to a certain layer thickness;
s3: pouring the prepared photosensitive glass slurry into a resin tank of a photocuring 3D printer, starting the photocuring 3D printer to start printing, obtaining a printed formed part after printing, and cleaning the formed part by using cleaning liquid;
s4: and degreasing and vacuum sintering the obtained molded part to obtain the glass device.
The preparation process of the S1 slurry, as shown in fig. 1, specifically includes: mixing an acrylic monomer, a photoinitiator, a light absorber and a polymerization inhibitor, performing ultrasonic treatment to obtain a premixed liquid 1, adding silicon dioxide powder into the premixed liquid 1, stirring to obtain a premixed liquid 2, adding a coloring agent into the premixed liquid 2, performing shearing dispersion to obtain a premixed liquid 3, and performing vacuum defoaming to obtain the final photosensitive glass slurry.
The silicon dioxide powder is gas phase nano amorphous silicon dioxide powder, the silicon dioxide powder accounts for 35-42.5 vol% of the finally prepared photosensitive glass slurry, and the acrylic resin accounts for 65-57.5 vol% of the finally prepared photosensitive glass slurry.
The acrylic monomer is one or more of HEMA, TEGDA, TMPTA, PEGDA and TPGDA, the photoinitiator is one or more of TPO, 819 and 184, the light absorber is one or more of benzotriazole cresol and 2, 2-dimethylolpropionic acid, the polymerization inhibitor is one or more of hydroquinone and p-hydroxyanisole, and the coloring agent is a common resin coloring agent, such as oily color concentrate (black, purple or blue). The plasticizer is one or more of dioctyl phthalate, diisooctyl phthalate and diethyl phthalate.
The specific embodiment is as follows:
example 1
First step S1: 59g of HEMA, 32g of TEGDA and 9g of PEGDA are added into a beaker, and 100g of the mixture is added, 0.6g of photoinitiator 819, 0.5g of polymerization inhibitor hydroquinone and 0.5g of light absorber benzotriazole cresol are added, 1.5g of plasticizer diethyl phthalate is added, and the mixture is subjected to ultrasonic treatment for 20 min. Then gradually adding 135gSiO in total to the prepared resin liquid2Powder and stirring continuously to make SiO2The powder was dispersed evenly in the resin and 0.4g of black oily color concentrate was added to inhibit over-curing. After the stirring is fully carried out, vacuumizing is carried out to remove bubbles, and good fluidity (the shear rate is 30 s) is obtained-10.9 pas) in viscosity. The cured thickness of the slurry monolayer without the addition of the coloring agent was 486 μm, and the cured thickness of the monolayer after the addition of the coloring agent was 164 μm.
Second step S2: a three-dimensional model of a glass microfluidic chip is designed, the flow channel is a direct-current channel, the width of the flow channel is designed to be 0.6mm, the height of the flow channel is 1.5mm, and the diameter of an inlet and outlet circle is 3mm, and the flow channel is converted into an STL model.
Third step S3: printing and molding on the printer, wherein the thickness of the slice layer is 100 mu m, the exposure time is 15s, and the exposure intensity is 7 mJ-cm-2。
Fourth step S4: degreasing and vacuum sintering to obtain SiO2The powder was fully densified to obtain a glass microfluidic chip with a density of 99.8%, as shown in fig. 2. The width of the flow channel is 0.47mm, the flow channel is smooth, and the finished piece is transparent. The bending strength of the glass piece reaches 82.77MPa, and the linear light transmittance at the wavelength of 400-1200nm exceeds 85 percent.
The slurry in example 1 was found to have a certain polymerization phenomenon due to an increase in viscosity after being stored for one day after printing, and the polymerization degree during the storage of the slurry was reduced by increasing the content of the polymerization inhibitor in example 2. In order to further reduce the curing thickness and improve the printing success rate of the inner flow passage, the content of the coloring agent is increased in example 2.
Example 2
First step S1: 59g of HEMA, 32g of TEGDA and 9g of PEGDA are added into a beaker, the total amount is 100g, 0.6g of photoinitiator 819, 1.5g of polymerization inhibitor hydroquinone and 0.5g of light absorber benzotriazole cresol are added, 1.5g of plasticizer dioctyl phthalate is added, and the mixture is subjected to ultrasonic treatment for 20 min. Then gradually adding 135gSiO in total to the prepared resin liquid2Powder and stirring continuously to make SiO2The powder was dispersed evenly in the resin and 0.5g of black oily color concentrate was added to inhibit over-curing. After the stirring is fully carried out, vacuumizing is carried out to remove bubbles, and good fluidity (the shear rate is 30 s) is obtained-10.9 pas) in viscosity. The cured thickness of the slurry with no coloring agent added was 486 μm in a single layer, and the cured thickness of the slurry with the coloring agent added was 147 μm in a single layer.
Second step S2: a three-dimensional model of a glass microfluidic chip is designed, the flow channel is an arc-shaped flow channel, the width of the flow channel is designed to be 0.6mm, the height of the flow channel is 1.5mm, and the diameter of an inlet and outlet circle is 2mm, so that the flow channel is converted into an STL model.
Third step S3: printing and molding on the printer, wherein the thickness of the slice layer is 100 mu m, the exposure time is 15s, and the exposure intensity is 7 mJ-cm-2。
Fourth step S4: degreasing and vacuum sintering to obtain SiO2The powder was fully densified to obtain a glass microfluidic chip with a density of 99.8%, as shown in the left figure of fig. 3. The width of the flow channel is 0.51mm, the flow channel is smooth, and the product is transparent. The bending strength of the glass piece reaches 82.77MPa, and the linear light transmittance at the wavelength of 400-1200nm exceeds 85 percent.
In examples 1 and 2, the viscosity of the slurry was relatively high, which makes it difficult to clean the residual slurry in the inner flow path, and particularly, clogging was likely to occur when printing the three-dimensional flow path, so that the viscosity of the slurry was reduced by adjusting the resin liquid ratio, and the HEMA content was increased in example 3 because HEMA is a monofunctional resin and has a good dilutability. Meanwhile, exposure time is shortened when the three-dimensional flow channel is printed, and the situation that slurry in the flow channel is solidified and blocked due to excessive energy accumulation of the flow channel close to one side of the forming table is prevented.
Example 3
First step S1: adding 65g of HEMA into a beaker, adding 25g of TEGDA, adding 10g of PEGDA, adding 100g of the total, adding 0.6g of photoinitiator 819, 1.5g of polymerization inhibitor hydroquinone, 0.5g of light absorber benzotriazole cresol, adding 1.5g of plasticizer diethyl phthalate, and carrying out ultrasonic treatment for 20 min. Then gradually adding 135gSiO in total to the prepared resin liquid2Powder and stirring continuously to make SiO2The powder was dispersed evenly in the resin and 0.5g of black oily color concentrate was added to inhibit over-curing. After the stirring is fully carried out, vacuumizing is carried out to remove bubbles, and good fluidity (the shear rate is 30 s) is obtained-10.81 pas) in viscosity. The cured thickness of the slurry monolayer without the addition of the coloring agent was 471 μm, and the cured thickness of the monolayer after the addition of the coloring agent was 123 μm.
Second step S2: a three-dimensional model of a glass microfluidic chip is designed, the flow channel is a three-dimensional flow channel, the width of the flow channel is designed to be 0.8mm, the height of the flow channel is 1.5mm, and the diameter of an inlet and outlet circle is 2mm, and the flow channel is converted into an STL model.
Third step S3: printing and molding on the printer, wherein the thickness of the slice layer is 100 mu m, the exposure time is 13s, and the exposure intensity is 7 mJ-cm-2。
Fourth step S4: degreasing and vacuum sintering to obtain SiO2The powder was fully densified to obtain a glass microfluidic chip with a density of 99.8%, as shown in the right diagram of fig. 3. The width of the flow channel is 0.6mm, the flow channel is smooth, and the finished piece is transparent. The bending strength of the glass piece reaches 82.77MPa, and the linear light transmittance at the wavelength of 400-1200nm exceeds 85 percent.
The linear transmittance of the glass devices obtained in all the above examples is not affected by the colorant, and as shown in FIG. 4, the linear transmittance at 400-1200nm wavelength is more than 85%.
The results of the orthogonal tests shown in table 1 are shown in table 2, which indicates that when the slice thickness is 100 μm, the curing thickness is slightly higher than the slice thickness, the curing thickness is smaller, the over-curing is less obvious, and the printing success rate is higher, and the determined resin coloring agent mass is 0.3-0.6% of the photosensitive glass paste mass, the polymerization inhibitor mass is 1-1.7% of the photosensitive glass paste mass, and the printing effect is better when the light absorbing agent mass is 0.4-0.6% of the photosensitive glass paste mass.
TABLE 1 curing thickness factor level table
TABLE 2 test results
According to the method for manufacturing the transparent glass device with the small-size three-dimensional inner flow channel with the complex sealing cover structure, the blank is printed by adding the coloring agent and using the slurry with lower viscosity, so that the problem that the inner flow channel of the sealing cover is blocked and difficult to form due to the over-curing phenomenon is effectively solved. Through a proper heat treatment process, densification sintering (99.8%) is realized, and the glass device with the small-size three-dimensional inner flow passage of the sealing cover is obtained.
Claims (9)
1. The method is characterized by comprising the steps of preparing photosensitive glass slurry containing resin coloring agents, printing the photosensitive glass slurry by adopting a photocuring 3D printing technology to obtain a biscuit of the small-size inner-runner glass device, and obtaining the small-size inner-runner glass device by adopting a heat treatment process.
2. The method for integrally forming the small-sized inner flow channel glass device based on 3D printing according to claim 1, which specifically comprises the following steps:
s1: preparing photosensitive glass slurry containing a resin coloring agent;
s2: guiding the designed three-dimensional structure model of the small-size inner runner glass device into a computer, and carrying out slicing treatment;
s3: pouring the prepared photosensitive glass slurry into a resin tank of a photocuring 3D printer, starting the photocuring 3D printer to start printing according to the three-dimensional structure model of the small-size inner runner glass device, obtaining a blank after printing, and cleaning the blank by using a cleaning solution;
s4: and degreasing and vacuum sintering the obtained biscuit to obtain the small-size inner flow channel glass device.
3. The integrated forming preparation method of the small-size inner flow channel glass device based on 3D printing according to claim 2, wherein S1 is specifically: mixing an acrylic monomer, a photoinitiator, a light absorber and a polymerization inhibitor, performing ultrasonic treatment to obtain a premixed liquid 1, adding silicon dioxide powder into the premixed liquid 1, stirring to obtain a premixed liquid 2, adding a resin coloring agent into the premixed liquid 2, performing shearing dispersion to obtain a premixed liquid 3, and performing vacuum defoaming to obtain the photosensitive glass slurry containing the resin coloring agent.
4. The integrated forming preparation method based on 3D printing for the small-sized inner flow channel glass device according to claim 3, wherein the acrylic monomer is one or more of HEMA, TEGDA, TMPTA, PEGDA and TPGDA, the photoinitiator is one or more of photoinitiator TPO, photoinitiator 819 and 184, the light absorber is one or more of benzotriazole cresol and 2, 2-dimethylolpropionic acid, and the polymerization inhibitor is one or more of hydroquinone and p-hydroxyanisole.
5. The integrated forming preparation method of the small-size inner flow channel glass device based on 3D printing as claimed in claim 3, wherein the silica powder is gas phase nano amorphous silica powder, and according to volume percentage, the silica powder accounts for 35% -42.5% of the photosensitive glass paste, and the acrylic resin accounts for 65% -57.5% of the photosensitive glass paste.
6. The integrated forming preparation method of the small-size inner flow channel glass device based on 3D printing as claimed in claim 3, wherein the mass of the polymerization inhibitor is 1% -1.7% of the mass of the photosensitive glass paste, and the mass of the light absorber is 0.4% -0.6% of the mass of the photosensitive glass paste according to mass percentage.
7. The integrated forming preparation method of the small-size inner flow channel glass device based on 3D printing as claimed in claim 1, wherein the resin coloring agent is oil-based color paste.
8. The integrated forming preparation method of the small-size inner flow channel glass device based on 3D printing as claimed in claim 1, wherein the resin coloring agent content is 0.3% -0.6% of the mass of the photosensitive glass paste.
9. The integrated forming preparation method of the small-size inner flow channel glass device based on 3D printing according to claim 1, wherein the photocuring 3D printing technology is SLA or DLP.
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| US20120282448A1 (en) * | 2011-05-03 | 2012-11-08 | Xerox Corporation | Methods for fabricating three-dimensional objects |
| CN107973528A (en) * | 2017-11-08 | 2018-05-01 | 沙河市远维电子科技有限公司 | A kind of formula of 3D printing coloured glass product and preparation method thereof |
| CN109395787A (en) * | 2018-08-31 | 2019-03-01 | 广东工业大学 | A method of the quick Fabrication fluid channel based on 3 D-printing |
| CN110804276A (en) * | 2019-10-18 | 2020-02-18 | 南京大学 | High-resolution photocuring three-dimensional printing compound |
| CN111825333A (en) * | 2019-04-15 | 2020-10-27 | 西安交通大学 | Glass paste, preparation method thereof and method for 3D printing of glass device |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120282448A1 (en) * | 2011-05-03 | 2012-11-08 | Xerox Corporation | Methods for fabricating three-dimensional objects |
| CN107973528A (en) * | 2017-11-08 | 2018-05-01 | 沙河市远维电子科技有限公司 | A kind of formula of 3D printing coloured glass product and preparation method thereof |
| CN109395787A (en) * | 2018-08-31 | 2019-03-01 | 广东工业大学 | A method of the quick Fabrication fluid channel based on 3 D-printing |
| CN111825333A (en) * | 2019-04-15 | 2020-10-27 | 西安交通大学 | Glass paste, preparation method thereof and method for 3D printing of glass device |
| CN110804276A (en) * | 2019-10-18 | 2020-02-18 | 南京大学 | High-resolution photocuring three-dimensional printing compound |
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