CN114426392B - Microscale glass based on three-dimensional direct writing and manufacturing method thereof - Google Patents
Microscale glass based on three-dimensional direct writing and manufacturing method thereof Download PDFInfo
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- 239000011521 glass Substances 0.000 title claims abstract description 81
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 77
- 239000002243 precursor Substances 0.000 claims abstract description 75
- 238000010438 heat treatment Methods 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000011259 mixed solution Substances 0.000 claims abstract description 36
- 238000010146 3D printing Methods 0.000 claims abstract description 35
- 230000005499 meniscus Effects 0.000 claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 14
- 238000007639 printing Methods 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 238000011065 in-situ storage Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims abstract description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 30
- 239000002245 particle Substances 0.000 claims description 21
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 20
- 235000012239 silicon dioxide Nutrition 0.000 claims description 19
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 239000000654 additive Substances 0.000 claims description 11
- 230000000996 additive effect Effects 0.000 claims description 11
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 10
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 10
- 230000008021 deposition Effects 0.000 claims description 8
- -1 polydimethylsiloxane Polymers 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- 230000003068 static effect Effects 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Natural products CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 claims description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 3
- 239000001273 butane Substances 0.000 claims description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 3
- QWHNJUXXYKPLQM-UHFFFAOYSA-N dimethyl cyclopentane Natural products CC1(C)CCCC1 QWHNJUXXYKPLQM-UHFFFAOYSA-N 0.000 claims description 3
- 239000001023 inorganic pigment Substances 0.000 claims description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 3
- 238000005485 electric heating Methods 0.000 claims description 2
- 238000004093 laser heating Methods 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 12
- 238000005516 engineering process Methods 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000005498 polishing Methods 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000005530 etching Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 231100000956 nontoxicity Toxicity 0.000 abstract 1
- 238000002834 transmittance Methods 0.000 description 9
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 6
- 238000000465 moulding Methods 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000006073 displacement reaction Methods 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000005232 molecular self-assembly Methods 0.000 description 3
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 3
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000012938 design process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000005816 glass manufacturing process Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000005495 investment casting Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- 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
- C03B19/066—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 for the production of quartz or fused silica articles
-
- 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
-
- 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
-
- 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
Abstract
The invention discloses a preparation method of microscale glass based on three-dimensional direct writing, which comprises the following steps: (1) Dispersing silicon dioxide powder in an organic solution to form a precursor mixed solution; (2) Transferring the precursor mixed liquid into a micro needle tube with a nozzle in a 3D direct-writing printing device, and 3D printing the precursor mixed liquid to ensure that a precursor mixed liquid meniscus can be formed between the nozzle and a forming substrate in the 3D printing process; (3) And carrying out multi-stage heat treatment or in-situ micro-region heat treatment to obtain the three-dimensional direct writing-based microscale glass. The method utilizes the domain-limiting technology of the meniscus, does not need the auxiliary effect of a mould, gets rid of the restriction of the shape of the mould, simplifies the forming steps of glass preforms such as polishing or surface etching, has the advantages of easily available raw materials, low energy consumption, simple and efficient process, environmental protection, no toxicity, micro-nano scale of forming scale, high expansibility and capability of realizing individuation, refinement and complicated preparation of glass devices.
Description
Technical Field
The application belongs to the technical field of glass device preparation, and particularly relates to three-dimensional direct writing-based microscale glass and a manufacturing method thereof.
Background
The glass has excellent optical performance, mechanical performance, electric/thermal insulation and chemical stability, and plays an important role in the fields of chemistry, biology, optics and the like. Glass molding generally requires melting and manufacturing at 1500-2000 ℃, and has harsh conditions and huge energy consumption. There is currently no scalable glass manufacturing process in the market, and therefore, despite the superior optical properties of glass to polymeric components, many critical components of optical systems (e.g., microlenses) are still manufactured from polymers. The glass 3D printing technology combines 3D printing with the glass industry, not only can produce glass parts with complex shapes and structures, but also can manufacture articles with sub-millimeter processing precision which are difficult to realize by the traditional glass processing technology.
Conventional precision glass devices are typically fabricated by precision molding. It requires the preparation of a fine mold in advance, and then the expensive glass carbon material is poured into the mold to form a certain three-dimensional structure. The mould needs to be removed in the later stage, and the whole process is complicated. In addition, molding processes typically use hazardous hydrofluoric acid for grinding and polishing or chemical etching to produce microscale glass structures that are difficult to process for structures at sub-millimeter dimensions.
Precision powder injection molding techniques can also be used to make precision glass devices, but typically only produce opaque porous borosilicate or soda lime glass, such as: chinese patent publication No. CN104909558A discloses a method for preparing vitreous transparent quartz sand; comprising the following steps: putting the synthesized high-purity silicon dioxide powder into a vacuum furnace, heating, preserving heat in multiple stages, cooling again to obtain porous transparent quartz glass blocks, and crushing to obtain glassy transparent quartz sand; patent document publication No. CN1541194A discloses high purity synthetic quartz glass particles which are derived from alkali metal silicate and have a total metal impurity content of 1. Mu.g/g or less.
Glass 3D printing technology does not require expensive dies and cumbersome post-processing steps. The unique manufacturing process of 3D printing will greatly increase the speed and flexibility of producing glass structures without the limitations of conventional design and manufacturing processes. However, glass materials have a high melting point and cure rapidly, making it difficult to manufacture glass devices using standard 3D printing techniques. Thus 3D printed glass remains a difficulty in the current technology.
Chinese patent publication No. CN111825333a discloses a method for 3D printing of glass devices, which uses specific glass paste including silica, acrylic resin, light absorber, photoinitiator, polymerization inhibitor, glycerol, polyvinyl alcohol, defoamer and sintering aid, and uses light curing technology (SLA) to realize 3D printing of glass. The molding scale of the printed glass structure is about submillimeter, but the adopted printing material has low safety and is inflammable and explosive, so the popularization and application of the method are greatly limited.
Disclosure of Invention
The invention provides a manufacturing method of microscale glass based on three-dimensional direct writing, which utilizes the domain-limiting technology of a meniscus, does not need the auxiliary effect of a mould, gets rid of the restriction of the shape of the mould, simplifies the forming steps of glass preforms such as polishing or surface etching, and the like, and can prepare the microscale glass with high transparency and high precision by combining 3D printing and heat treatment steps.
The technical scheme adopted is as follows:
a preparation method of microscale glass based on three-dimensional direct writing comprises the following steps:
(1-1) dispersing silica powder in an organic solution to form a precursor mixed solution;
(1-2) transferring the precursor mixed solution into a micro needle tube with a nozzle in a 3D direct-writing printing device, and 3D printing the precursor mixed solution to obtain a precursor structure; in the 3D printing process, a precursor mixed solution forms a meniscus between the nozzle and the forming substrate;
(1-3) carrying out multi-stage heat treatment on the precursor structure, and cooling to obtain the three-dimensional direct writing-based microscale glass;
or comprises the following steps:
(2-1) dispersing silica powder in an organic solution to form a precursor mixed solution;
(2-2) transferring the precursor mixed solution into a micro needle tube with a nozzle in a 3D direct-writing printing device, and 3D printing the precursor mixed solution, wherein in the 3D printing process, the precursor mixed solution forms a meniscus between the nozzle and a forming substrate; and carrying out in-situ micro-region heat treatment while extruding and solidifying the precursor mixed liquid to obtain the three-dimensional direct-writing-based micro-scale glass.
According to the invention, the precursor mixed solution suitable for 3D printing is prepared by taking silicon dioxide powder as a raw material, a meniscus between a nozzle and a forming substrate is established in the 3D printing process, after solvent at the meniscus volatilizes, silicon dioxide particles are deposited on the forming substrate in a molecular self-assembly mode, an expected three-dimensional structure is deposited under the action of surface tension by means of the movement track of the meniscus, and the three-dimensional direct-writing-based microscale glass is formed after further solidification and sintering.
In the silicon dioxide powder, the average particle diameter of the silicon dioxide particles is 0.01-10 mu m, and the silicon dioxide particles with the diameter larger than 10 mu m can form larger pores after high-temperature heat treatment, so that the precision of the product glass is affected.
Preferably, the silica particles have an average particle size of 0.05 to 0.1 μm, and suitable silica particle sizes avoid clogging the nozzle and reduce shrinkage during subsequent heat treatment of the glass article.
The organic solvent comprises tetraethylene glycol dimethyl ether, polydimethylsiloxane and an additive; the additive is a high-volatility solvent, and comprises dimethyl ether, butane, pentane, cyclopentane or paraxylene; the mass ratio of the tetraethylene glycol dimethyl ether to the polydimethylsiloxane to the additive is 65-75:2:3.
Wherein, the tetraethylene glycol dimethyl ether has good dispersion performance on silicon dioxide particles; the polydimethylsiloxane can form a grid in the 3D printing process to strengthen the bonding force among the silicon dioxide particles and is used for improving the cracking resistance of the precursor structure in the heat treatment process; the additive can promote the volatilization of liquid at the meniscus, is favorable for the molecular self-assembly of the silicon dioxide particles, and ensures that the silicon dioxide particles are densely and uniformly stacked.
Further preferably, the additive is p-xylene.
The precursor mixed solution needs to have enough shear thinning property, can be extruded through a nozzle with a certain caliber in a flowing way, and has silicon dioxide concentration which is an important parameter affecting the shear thinning property, so that the mass fraction of the silicon dioxide in the precursor mixed solution is less than 50wt%.
Preferably, the viscosity of the precursor mixed solution is 100-1000 Pa.s. The raw materials must have the desired rheological behavior for printing and maintaining structural stability. Since the heat curing has a certain speed, typically 3-10s, to the extent that it does not collapse, the viscosity should not exceed 1000pa·s in order that the precursor structure does not deform after the shaping process.
When the concentration of silicon dioxide in the precursor mixed solution is low, the printed fiber filaments can be fused together to form a pore-free integral structure; when the concentration of the silicon dioxide is too high, the viscosity of the precursor solution is high, the mixed solution is not easy to extrude, and the printing difficulty is high.
Preferably, in the micropin tube with the nozzle, the caliber of the nozzle is 10nm-200 μm, and more preferably, the caliber of the nozzle is 1-10 μm.
In the steps (1-2) and (2-2), static pressure of 0.1-1000kPa is applied to the micro needle tube with the nozzle in the 3D printing process, so that the precursor mixed solution is uniformly and continuously extruded through the micro nozzle.
In the 3D printing process, along with the slow approaching of the nozzle and the forming substrate, under the action of the static pressure at the rear end, the precursor mixed liquid at the tip of the nozzle is contacted with the forming substrate, the liquid bridge is connected, and the liquid bridge is in a meniscus state under the action of surface tension; the silicon dioxide particles are deposited in a molecular self-assembly form, and the micro-nano structure glass is further prepared by controlling the deposition rate and the printing process.
Preferably, in steps (1-2) and (2-2), a meniscus of precursor mixture needs to be established between the nozzle and the forming substrate, the meniscus is exposed to the external environment, and the ambient humidity has a great influence on the solvent evaporation at the meniscus, so that the ambient humidity during 3D printing is 30-60% rh.
When the ambient humidity is too low, the solvent at the meniscus is too fast to volatilize, the precursor solution is fast to deposit, and the blockage of the micrometer-scale needle point is easy to cause the interruption of the 3D printing process; when the ambient humidity is too high, the silica particles in the liquid bridge are not easy to solidify, which can lead to slow deposition rate and prolong the manufacturing period.
Preferably, in the steps (1-2) and (2-2), the ambient temperature during 3D printing is room temperature. The ambient temperature influences the volatilization of the solvent at the meniscus, and the proper ambient temperature can lead the silicon dioxide particles to be densely and uniformly accumulated; the environmental temperature is too low, the volatilization rate of the meniscus solvent is slow, the diffusion of silicon dioxide particles in the raw materials is hindered, and the self-assembly of the silicon dioxide particles is slow; too high ambient temperature, too fast deposition rates, are prone to clogging of the showerhead and the precursor structure produced is relatively rough.
Preferably, in the steps (1-2) and (2-2), the deposition rate of the precursor mixture during 3D printing is 0.1-1 μm/s, and the proper deposition rate can enable the printed precursor structure to grow uniformly. The moving speed of the micro needle tube is too fast, and the silicon dioxide particles are not deposited so that the grown micro/nano wires are not uniform in intermittent thickness. The rate of movement of the micropin is too slow and can cause the spray head to clog.
The printed feedstock must be able to dry after the heat treatment and the printed structural precursor does not crack while maintaining an open porosity in order to completely remove the organics contained in the structural precursor and densify in the final high temperature sintering.
The multistage heat treatment process is to remove the organic solvent without degrading the precursor structure and maintain the structural integrity and transparency of the product glass, and preferably, in the step (1-3), the multistage heat treatment steps are as follows: the first stage: heating rate is 0.1-1 ℃/min, temperature is 20-110 ℃, and heat preservation is carried out for 60-120 h; and a second stage: heating at a rate of 1-15 ℃/min, maintaining the temperature at 110-650 ℃ for 0.5-1.5h; and a third stage: the temperature rising rate is 4-6 ℃/min, the temperature is 650-1600 ℃, and the temperature is kept for 0.01-0.06h.
The first stage heat treatment is a degreasing process, and when the temperature of the first stage heat treatment exceeds 120 ℃, cracks are generated in the green structure. Suitable first stage heat treatment parameters can maintain the stability of the printed precursor structure and the mass loss rate is relatively small, and can increase the green strength through condensation reactions forming a network between silica particles.
The second stage heat treatment, in which the precursor structure is further freed of organic solvents, is a parameter that avoids the precursor structure containing residual organics, resulting in poor glass quality after full densification, during which the green volume shrinks to form a precursor structure consisting only of chemically bonded silica powder.
The third stage heat treatment can densify the precursor structure, and the selection of the parameters can prevent deformation of the structure caused by uneven heating.
Preferably, in the step (2-2), the micro-area heat treatment mode is micro-area laser or electric heating. The micro-region heating energy is low, the thermal shock to the glass structure is small, and the glass structure is not cracked, which is very beneficial to in-situ printing of a micro-scale glass device, so that the precursor structure composed of weakly bonded silica particles can be sintered into completely compact transparent glass, and the micro-scale transparent structure is formed under the action of surface tension.
The invention also provides the three-dimensional direct-writing-based microscale glass prepared by the preparation method of the three-dimensional direct-writing-based microscale glass.
Compared with the prior art, the invention has the beneficial effects that:
(1) The method forms molecular-level printing path fusion by virtue of capillary force among liquid molecules, eliminates inherent gaps of 3D printing, and has the advantages of low defect density of the prepared micro-scale glass microstructure based on three-dimensional direct writing, high optical transparency and equivalent transmittance to commercial fused quartz.
(2) Compared with the traditional glass precision casting process, the method has a plurality of advantages: firstly, the use of high-cost glassy carbon is avoided, nontoxic polymer and silicon dioxide powder are adopted, the cost is low, and raw materials are easy to obtain; secondly, the structure obtained through multi-stage heat treatment is compact and not easy to deform, and in addition, the energy utilization rate of the in-situ micro-region heat treatment is high, so that the energy consumption is effectively reduced; finally, the method is not only suitable for manufacturing miniature products, but also has high expansibility, is beneficial to realizing the mass production of glass components with complex shapes in industry, and can realize individuation, refinement and complicated preparation of glass devices.
(3) The method utilizes the domain-limiting technology of the meniscus, does not need the auxiliary action of a mould, gets rid of the restriction of the shape of the mould, simplifies the forming steps of glass preforms such as polishing or surface etching, and the like, combines 3D printing and heat treatment steps to prepare the high-transparency high-precision microscale glass, and the forming scale reaches the micro-nano level, thereby breaking through the technical bottleneck of the sub-millimeter processing precision of the existing glass 3D printing technology.
Drawings
Fig. 1 is a schematic diagram of a manufacturing process of the three-dimensional direct-writing-based micro-scale glass, wherein reference numeral 1 is a pressure control system, 2 is a micro needle tube with a nozzle, and 3 is a forming substrate.
Fig. 2 is a picture of the precursor structure obtained in example 1.
FIG. 3 is an apparent picture of three-dimensional direct-write-based microscale glass obtained in example 1.
Fig. 4 is an apparent picture of three-dimensional direct-write-based microscale glass obtained in example 2.
Detailed Description
The invention is further elucidated below in connection with the drawings and the examples. It is to be understood that these examples are for illustration of the invention only and are not intended to limit the scope of the invention.
In order to obtain a transparent glass product, the purity of the silica powder is controlled to 98% or more.
Example 1
(1) In this example, a mixture containing 25wt% silica (average particle diameter of 0.05 to 0.1 μm), 70wt% tetraethyleneglycol dimethyl ether, 2wt% PDMS and 3wt% paraxylene was centrifuged to obtain a precursor mixture which was uniformly mixed, and the precursor mixture was yellowish, and exhibited a state of a stationary viscoelastic solid, i.e., gel, at a low shear rate and a fluid liquid state at a high shear rate. The viscosity of the precursor mixed solution is 750-800 Pa.s.
(2) Transferring the precursor mixed solution into a micro needle tube with a nozzle in a 3D direct-writing printing device, wherein the caliber of the nozzle is 1-10 mu m, and fixing the micro needle tube on a three-dimensional XYZ displacement platform;
and 3D printing is carried out according to a program designed by Labview software to obtain a precursor structure green body, so that a precursor mixed liquid meniscus can be formed between a nozzle and a forming substrate in the 3D printing process. The specific process is as follows: the three-dimensional direct writing system mainly comprises a three-dimensional XYZ displacement platform, a micro needle tube with a nozzle, a control system and a microscope, wherein the micro needle tube is fixed on the displacement platform, and as shown in fig. 1, the three-dimensional direct writing system adopted in the embodiment comprises: the high-precision three-dimensional XYZ displacement platform, the control system, the pressure control system 1, the micro needle tube 2 with the nozzle, the forming substrate 3 and the microscope system are formed together. The precursor mixture is poured into the micro needle tube 2 through an injector, and is extruded from the inside of the nozzle and contacted with the molding substrate 3 under the control of the pressure (static pressure of 500-1000 kPa) of the pressure control system 1, so as to form a stable-shape meniscus.
In the 3D printing process, the ambient humidity is controlled to be 30-60% RH, the ambient temperature is room temperature, and the deposition rate is 0.5-1 mu m/s, so that the precursor structural green body shown in figure 2 is obtained.
(3) And carrying out multi-stage heat treatment on the precursor structural green body according to the multi-stage heat treatment parameters in the table 1, and cooling to obtain the three-dimensional direct writing-based micro-scale glass, wherein the apparent picture is shown in fig. 3.
Table 1 multistage heat treatment parameters in example 1
| Temperature scheme | Heating rate | Heating temperature | Holding time |
| Heating up | 1℃/min | 25-100℃ | 110h |
| Heating up | 10℃/min | 100-600℃ | 1h |
| Heating up | 5℃/min | 600-1500℃ | 0.05h |
The volume shrinkage of the obtained microscale glass product is 75% of the precursor structure volume through the multi-stage heat treatment process.
The three-dimensional direct-write-based microscale glass prepared in this example has a minimum light transmittance of 72% at a wavelength of 200nm, a light transmittance of greater than 80% over a wavelength range of 200-1000nm, and temperature changes are no longer sensitive to the refractive index of the shaped glass. The glass article thus has an optical transparency similar to that of conventional quartz glass.
Example 2
The preparation process of example 2 is the same as the steps (1) - (2) in example 1, and micro-region heat treatment (laser or electrothermal heating) is performed in situ while the precursor mixed solution is extruded and solidified, so that transparent three-dimensional direct writing-based micro-scale glass is obtained, and when the temperature of an in-situ sintering region is too high or micro-region focusing is inaccurate, the micro-structure deformation is caused, as shown in fig. 4.
Example 3
In this example, a mixture containing 20wt% of silica (average particle diameter of 0.05 to 0.1 μm), 75wt% of tetraethyleneglycol dimethyl ether, 2wt% of PDMS and 3wt% of paraxylene was centrifuged to obtain a precursor mixture which was uniformly mixed. The viscosity of the precursor mixed solution is 800-850 Pa.s.
Steps (2) - (3) are the same as in example 1.
The microscale glass product obtained in this example has a volume shrinkage of 85% of the original volume. The three-dimensional direct-write-based microscale glass has a minimum light transmittance of 75% at a wavelength of 200nm and a light transmittance of greater than 80% over a wavelength range of 200-1000nm, and temperature variations are no longer sensitive to the refractive index of the formed glass.
Example 4
In this example, a mixture containing 30wt% of silica (average particle diameter 0.05 to 0.1 μm), 65wt% of tetraethyleneglycol dimethyl ether, 2wt% of PDMS and 3wt% of paraxylene was centrifuged to obtain a precursor mixture which was uniformly mixed. The viscosity of the precursor mixed solution is 700-750 Pa.s.
Steps (2) - (3) are the same as in example 1.
The microscale glass product obtained in this example has a volume shrinkage of 80% of the original volume. The three-dimensional direct-write-based microscale glass has a minimum light transmittance of 70% at a wavelength of 200nm and a light transmittance of greater than 75% over a wavelength range of 200-1000nm, which is less transparent than the glass products of examples 1-3.
Example 5
The three-dimensional direct-write-based microscale glass of example 5 was prepared in the same manner as in example 1, except that the precursor mixture was filled with an inorganic pigment and 0.1wt% Co was added to the precursor mixture 2 O 3 (blue) or 0.1wt% Cu 2 O (red) or 0.1wt% Fe 2 O 3 (yellow), stirring for 10 min and mixing well. The precursor mixed solution presents the corresponding inorganic pigment color.
This example gives a micro-transparent product glass colored with a corresponding colorant, which is not high in the degree of coloring, poor in the degree of color development, has a minimum light transmittance of 62% at a wavelength of 200nm, and has a light transmittance of about 72% in a wavelength range of 200 to 1000 nm.
While the foregoing embodiments have been described in detail in connection with the embodiments of the invention, it should be understood that the foregoing embodiments are merely illustrative of the invention and are not intended to limit the invention, and any modifications, additions, substitutions and the like made within the principles of the invention are intended to be included within the scope of the invention.
Claims (7)
1. The preparation method of the microscale glass based on three-dimensional direct writing is characterized by comprising the following steps of:
(1-1) dispersing silica powder in an organic solution to form a precursor mixed solution;
(1-2) transferring the precursor mixed solution into a micro needle tube with a nozzle in a 3D direct-writing printing device, and 3D printing the precursor mixed solution to obtain a precursor structure; in the 3D printing process, a precursor mixed solution forms a meniscus between the nozzle and the forming substrate;
(1-3) carrying out multi-stage heat treatment on the precursor structure, and cooling to obtain the three-dimensional direct writing-based microscale glass;
in the silicon dioxide powder, the average grain diameter of the silicon dioxide particles is 0.01-0.1 mu m;
the organic solvent comprises tetraethylene glycol dimethyl ether, polydimethylsiloxane and an additive; the additive comprises dimethyl ether, butane, pentane, cyclopentane or paraxylene; the mass ratio of the tetraethylene glycol dimethyl ether, the polydimethylsiloxane and the additive is 65-75:2:3;
the viscosity of the precursor mixed solution is 100-1000Pa s;
in the micro needle tube with the nozzle, the caliber of the nozzle is 10 nm-10 mu m;
in the 3D printing process, static pressure of 0.1-1000kPa is applied to the micro needle tube with the nozzle, the ambient humidity is 30-60% RH, the ambient temperature is room temperature, and the deposition rate of the precursor mixed solution is 0.1-1 mu m/s.
2. The preparation method of the microscale glass based on three-dimensional direct writing is characterized by comprising the following steps of:
(2-1) dispersing silica powder in an organic solution to form a precursor mixed solution;
(2-2) transferring the precursor mixed solution into a micro needle tube with a nozzle in a 3D direct-writing printing device, and 3D printing the precursor mixed solution, wherein in the 3D printing process, the precursor mixed solution forms a meniscus between the nozzle and a forming substrate; carrying out in-situ micro-region heat treatment while extruding and solidifying the precursor mixed solution to obtain the three-dimensional direct-writing-based micro-scale glass;
in the silicon dioxide powder, the average grain diameter of the silicon dioxide particles is 0.01-0.1 mu m;
the organic solvent comprises tetraethylene glycol dimethyl ether, polydimethylsiloxane and an additive; the additive comprises dimethyl ether, butane, pentane, cyclopentane or paraxylene; the mass ratio of the tetraethylene glycol dimethyl ether, the polydimethylsiloxane and the additive is 65-75:2:3;
the viscosity of the precursor mixed solution is 100-1000Pa s;
in the micro needle tube with the nozzle, the caliber of the nozzle is 10 nm-10 mu m;
in the 3D printing process, static pressure of 0.1-1000kPa is applied to the micro needle tube with the nozzle, the ambient humidity is 30-60% RH, the ambient temperature is room temperature, and the deposition rate of the precursor mixed solution is 0.1-1 mu m/s.
3. The method for preparing three-dimensional direct-write-based microscale glass according to claim 1 or 2, wherein the precursor mixture is further added with an inorganic pigment.
4. The method for preparing the three-dimensional direct-write-based microscale glass according to claim 1 or 2, wherein the mass fraction of silicon dioxide in the precursor mixed solution is less than 50 and wt percent.
5. The method for preparing three-dimensional direct-write-based microscale glass according to claim 1, wherein in the step (1-3), the multi-stage heat treatment step is as follows: the first stage: heating rate is 0.1-1 ℃/min, temperature is 20-100 ℃, and heat preservation is 60-120 h; and a second stage: heating rate is 1-15 ℃/min, temperature is 100-600 ℃, and temperature is kept at 0.5-1.5h; and a third stage: the temperature rising rate is 4-6 ℃/min, the temperature is 600-1500 ℃, and the temperature is kept at 0.01-0.06-h.
6. The method for preparing three-dimensional direct-writing-based micro-scale glass according to claim 2, wherein in the step (2-2), the micro-area heat treatment mode is micro-area laser or electric heating.
7. The three-dimensional direct-write-based microscale glass manufactured by the manufacturing method of the three-dimensional direct-write-based microscale glass according to claim 1 or 2.
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