阅读说明：本技术 一种玻璃浆料及其制备方法和3d打印玻璃器件的方法 (Glass paste, preparation method thereof and method for 3D printing of glass device ) 是由 王莉 戴婉菁 刘正中 谭鸿迪 卢秉恒 于 2019-04-15 设计创作，主要内容包括：本申请属于玻璃器件制备技术领域,特别是涉及一种玻璃浆料及其制备方法和3D打印玻璃器件的方法。传统方法制备宏观物体采用高温融化和铸造工艺,对于制备精细结构则采用化学法,制备过程危险、环境污染大、能源消耗高、效率低。本申请提供了一种玻璃浆料,包括：二氧化硅600～1000份、丙烯酸树脂600～800份、光吸收剂1～13份、光引发剂1～15份、阻聚剂1～15份、丙三醇1～10份、聚乙烯醇1～18份、消泡剂1～18份和烧结助剂1～15份。通过添加烧结助剂,避免了高粘度浆料影响打印精度的问题,获得了高精度微透镜玻璃器件；通过合理配置玻璃浆料以及氧抑制聚合的打印工艺,有效抑制开裂,提高成品率。(The application belongs to the technical field of glass device preparation, and particularly relates to glass paste, a preparation method of the glass paste and a method for 3D printing of a glass device. The traditional method adopts high-temperature melting and casting processes for preparing macroscopic objects, and adopts a chemical method for preparing fine structures, so that the preparation process is dangerous, the environmental pollution is large, the energy consumption is high, and the efficiency is low. The application provides a glass paste comprising: 600-1000 parts of silicon dioxide, 600-800 parts of acrylic resin, 1-13 parts of light absorbent, 1-15 parts of photoinitiator, 1-15 parts of polymerization inhibitor, 1-10 parts of glycerol, 1-18 parts of polyvinyl alcohol, 1-18 parts of defoaming agent and 1-15 parts of sintering aid. By adding the sintering aid, the problem that high-viscosity slurry affects printing precision is avoided, and a high-precision micro-lens glass device is obtained; through reasonably configuring the glass slurry and the printing process for inhibiting polymerization by oxygen, cracking is effectively inhibited, and the yield is improved.)

1. A glass paste characterized by: comprises the following components in parts by weight:

600-1000 parts of silicon dioxide, 600-800 parts of acrylic resin, 1-13 parts of light absorbent, 1-15 parts of photoinitiator, 1-15 parts of polymerization inhibitor, 1-10 parts of glycerol, 1-18 parts of polyvinyl alcohol, 1-18 parts of defoaming agent and 1-15 parts of sintering aid.

2. The glass paste according to claim 1, wherein: comprises the following components in parts by weight:

700-900 parts of silicon dioxide, 650-750 parts of acrylic resin, 2-10 parts of light absorbent, 2-13 parts of photoinitiator, 2-13 parts of polymerization inhibitor, 1-8 parts of glycerol, 1-15 parts of polyvinyl alcohol, 1-15 parts of defoaming agent and 2-13 parts of sintering aid.

3. The glass paste according to claim 2, wherein: comprises the following components in parts by weight:

800 parts of silicon dioxide, 700 parts of acrylic resin, 2-8 parts of light absorbent, 2-10 parts of photoinitiator, 2-10 parts of polymerization inhibitor, 1-5 parts of glycerol, 1-10 parts of polyvinyl alcohol, 1-10 parts of defoaming agent and 2-10 parts of sintering aid.

4. The glass paste according to claim 1, wherein: the silicon dioxide is nano silicon dioxide, and the particle size of the nano silicon dioxide is 40 nanometers; the acrylic resin comprises an acrylic monomer, wherein the acrylic monomer is a mixture of two or more of hydroxyethyl methacrylate, triethylene glycol diacrylate, tripropylene glycol diacrylate and polyethylene glycol diacrylate-200; the photoinitiator is one or more of 2, 4, 6-trimethylbenzoyl-diphenyl phosphine oxide, 1-hydroxy-cyclohexyl-benzophenone and phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide; the light absorber is a benzotriazole ultraviolet light absorber, and the polymerization inhibitor is hydroquinone; the defoaming agent is polyether modified silicon; the sintering aid is one or more of sodium oxide, zinc oxide, boron oxide and bismuth oxide.

5. A preparation method of glass slurry is characterized by comprising the following steps: the method comprises the following steps:

1) sequentially adding an acrylic monomer, a photoinitiator, a light absorbent and a polymerization inhibitor into a container, and treating the obtained mixture under an ultrasonic condition;

2) adding polyvinyl alcohol, glycerol and a defoaming agent into the mixture after ultrasonic treatment, and stirring;

3) adding silica particles and sintering aid into the stirred mixture for several times and then fully stirring;

4) and placing the mixture obtained in the step 3) under a vacuum condition for treatment to obtain the glass slurry.

6. The method for preparing glass paste according to claim 5, wherein: the step 1 is carried out for 20 minutes under ultrasonic conditions.

7. The method for preparing glass paste according to claim 5, wherein: and in the step 4, the treatment is carried out for 3-5 minutes under the vacuum condition.

8. A method of 3D printing a glass device, characterized by: the method comprises the following steps:

a. preparing glass slurry;

b. slicing the three-dimensional structure model of the glass device to obtain a series of two-dimensional section slices;

c. placing glass slurry into a resin tank of a photocuring printer, arranging a breathable oxygen-permeable cabin above the resin tank of the photocuring printer, enabling oxygen to be in gas-liquid contact with the photosensitive glass slurry, starting a curing light source, projecting a two-dimensional cross-section mask image of the glass component onto the surface of the printed glass slurry, performing single-layer curing molding on the printed glass slurry within the irradiation range of the mask image, closing the curing light source after the single-layer curing molding, and repeating the process to obtain a molded part with low polymerization degree;

d. determining a heat preservation point according to the differential thermal curve, and carrying out degreasing treatment on the formed part to obtain a degreased part;

e. and sintering the degreased part in vacuum or after cold isostatic pressing to obtain the glass device.

9. The method of 3D printing a glass device according to claim 8, wherein: and a ventilating oxygen-permeable cabin is arranged above the resin tank of the photocuring printer in the step c.

10. The method of 3D printing a glass device according to claim 8, wherein: and d, the heating rate of the degreasing treatment in the step d is 0.1-1 ℃/min.

Technical Field

The application belongs to the technical field of glass device preparation, and particularly relates to glass paste, a preparation method of the glass paste and a method for 3D printing of a glass device.

Background

Micro-stereolithography is a novel micro-fabrication technology developed on the basis of the traditional 3D printing process, namely stereo photo-curing molding (SL), and compared with the traditional SL process, the micro-stereolithography adopts smaller laser spots (a few microns), and the resin generates a photo-curing reaction in a very small area. The surface projection micro-stereolithography has the outstanding advantages of high forming efficiency and low production cost. Has been considered to be one of the currently promising microfabrication techniques. Micro-stereolithography has been used in numerous fields such as tissue engineering, biomedical, metamaterial, micro-optical devices, micro-electro-mechanical systems (MEMS), and the like.

Glass is one of the most important high performance materials in industrial and social scientific research, mainly due to its excellent optical transparency, mechanical properties, chemical and thermal resistance, and its thermal insulating properties. However, glass, especially high-purity glass such as fused silica glass, is difficult to form, the traditional method adopts high-temperature melting and casting technology for preparing a macroscopic object, and adopts a chemical method for preparing a fine structure, and the preparation process is dangerous, large in environmental pollution, high in energy consumption and low in efficiency.

Disclosure of Invention

1. Technical problem to be solved

Glass-based is one of the most important high performance materials in industrial and social scientific research, mainly due to its excellent optical transparency, mechanical properties, chemical and thermal resistance, and its thermal insulation properties. However, glass, especially high-purity glass such as fused silica glass, is difficult to form, a high-temperature melting and casting process is adopted for preparing a macroscopic object by a traditional method, a chemical method is adopted for preparing a fine structure, and the preparation process is dangerous, the environmental pollution is large, the energy consumption is high, and the efficiency is low.

2. Technical scheme

In order to achieve the above purpose, the present application provides a glass paste, which comprises the following components in parts by weight:

600-1000 parts of silicon dioxide, 600-800 parts of acrylic resin, 1-13 parts of light absorbent, 1-15 parts of photoinitiator, 1-15 parts of polymerization inhibitor, 1-10 parts of glycerol, 1-18 parts of polyvinyl alcohol, 1-18 parts of defoaming agent and 1-15 parts of sintering aid.

Optionally, the composition comprises the following components in parts by weight:

700-900 parts of silicon dioxide, 650-750 parts of acrylic resin, 2-10 parts of light absorbent, 2-13 parts of photoinitiator, 2-13 parts of polymerization inhibitor, 1-8 parts of glycerol, 1-15 parts of polyvinyl alcohol, 1-15 parts of defoaming agent and 2-13 parts of sintering aid.

Optionally, the composition comprises the following components in parts by weight:

800 parts of silicon dioxide, 700 parts of acrylic resin, 2-8 parts of light absorbent, 2-10 parts of photoinitiator, 2-10 parts of polymerization inhibitor, 1-5 parts of glycerol, 1-10 parts of polyvinyl alcohol, 1-10 parts of defoaming agent and 2-10 parts of sintering aid.

Optionally, the silica is nano silica, and the particle size of the nano silica is 40 nm; the acrylic resin comprises an acrylic monomer, wherein the acrylic monomer is a mixture of two or more of hydroxyethyl methacrylate, triethylene glycol diacrylate, tripropylene glycol diacrylate and polyethylene glycol diacrylate-200; the photoinitiator is one or more of 2, 4, 6-trimethylbenzoyl-diphenyl phosphine oxide, 1-hydroxy-cyclohexyl-benzophenone and phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide; the light absorber is a benzotriazole ultraviolet light absorber, and the polymerization inhibitor is hydroquinone; the defoaming agent is polyether modified silicon; the sintering aid is one or more of sodium oxide, zinc oxide, boron oxide and bismuth oxide.

The application also provides a glass paste preparation method, which comprises the following steps:

1) sequentially adding an acrylic monomer, a photoinitiator, a light absorbent and a polymerization inhibitor into a container, and treating the obtained mixture under an ultrasonic condition;

2) adding polyvinyl alcohol, glycerol and a defoaming agent into the mixture after ultrasonic treatment, and stirring;

3) adding silica particles and sintering aid into the stirred mixture for several times and then fully dispersing;

4) and placing the mixture obtained in the step 3) under a vacuum condition for treatment to obtain the glass slurry.

Optionally, the step 1 is carried out under ultrasonic conditions for 20 minutes.

Optionally, the step 4 is carried out for 3-5 minutes under vacuum condition.

The application also provides a method for 3D printing of a glass device, the method comprising the steps of:

a. preparing glass slurry;

b. slicing the three-dimensional structure model of the glass device to obtain a series of two-dimensional section slices;

c. placing glass slurry into a resin tank of a photocuring printer, arranging a breathable oxygen-permeable cabin above the resin tank of the photocuring printer, enabling oxygen to be in gas-liquid contact with the photosensitive glass slurry, starting a curing light source, projecting a two-dimensional cross-section mask image of the glass component onto the surface of the printed glass slurry, performing single-layer curing molding on the printed glass slurry within the irradiation range of the mask image, closing the curing light source after the single-layer curing molding, and repeating the process to obtain a molded part with low polymerization degree;

d. determining a heat preservation point according to the differential thermal curve, and carrying out degreasing treatment on the formed part to obtain a degreased part;

e. and sintering the degreased part in vacuum or after cold isostatic pressing to obtain the glass device.

Optionally, a gas-permeable oxygen-permeable chamber is arranged above the resin tank of the photocuring printer in the step c.

Optionally, the temperature rise rate of the degreasing treatment in the step d is 0.1-1 ℃/min.

3. Advantageous effects

Compared with the prior art, the glass paste, the preparation method thereof and the method for 3D printing of the glass device have the advantages that:

according to the glass paste and the preparation method thereof, the monomer, the oligomer, the silicon dioxide particles, the photoinitiator, the sintering aid and other additives are mixed, the material ratio is adjusted, the prepared photosensitive glass paste is printed and formed quickly and accurately by the adoption of a continuous quick surface projection printing technology, and then the quick and high-accuracy glass device is manufactured through a heat treatment process. The surface projection micro-stereolithography glass forming technology is adopted, and both printing precision and printing efficiency are taken into consideration; the structure is simple, and the cost is low; the stress is distributed uniformly, and the glass device with complicated and precise molding can be prepared. According to the method for 3D printing of the glass device, the sintering aid is added, the low-solid-content and low-viscosity slurry is used, the densification sintering (99.9%) is realized, the problem that the printing precision is affected by the high-viscosity slurry is solved, and the high-precision micro-lens glass device is obtained; through reasonably configuring the glass slurry and the printing process for inhibiting polymerization by oxygen, the formed part easy to degrease is quickly printed, cracking is effectively inhibited, and the yield is improved.

Drawings

FIG. 1 is a first schematic diagram of the inhibition of polymerization degree by oxygen inhibition according to the present application;

FIG. 2 is a second schematic diagram of the inhibition of polymerization degree by oxygen inhibition according to the present application;

FIG. 3 is a diagram of an example microlens of the present application;

figure 4 is a microlens XRD pattern of the present application.

Detailed Description

Hereinafter, specific embodiments of the present application will be described in detail with reference to the accompanying drawings, and it will be apparent to those skilled in the art from this detailed description that the present application can be practiced. Features from different embodiments may be combined to yield new embodiments, or certain features may be substituted for certain embodiments to yield yet further preferred embodiments, without departing from the principles of the present application.

The 3D printing technology is used for printing glass, so that a complex structure which cannot be prepared by the traditional method can be obtained, and the efficiency can be greatly improved. The research of the 3D glass printing technology can not only broaden the variety of materials used by the 3D printing technology and expand the application range of the 3D printing technology, but also break the barrier of difficult glass forming, and new sparks are generated by the collision of the new and old technologies.

Cold Isostatic Pressing (CIP) is a technique in which rubber or plastic is used as a sheathing die material at normal temperature, and liquid is used as a pressure medium mainly for forming powder materials, and providing a blank for further sintering, forging or hot Isostatic Pressing. The pressure is generally 100 to 630 MPa.

XRD (X-ray diffraction) is an abbreviation of X-ray diffraction, and Chinese translation is a research means for obtaining information such as components of materials, structures or forms of atoms or molecules in the materials and the like by carrying out X-ray diffraction on the materials and analyzing diffraction patterns of the materials. For determining the atomic and molecular structure of the crystal. Wherein the crystalline structure causes diffraction of an incident X-ray beam into a number of specific directions. By measuring the angle and intensity of these diffracted beams, a crystallogist can produce a three-dimensional image of the electron density within the crystal. From this electron density, the average position of the atoms in the crystal can be determined, as well as their chemical bonds and various other information.