Preparation method of quartz glass with complex structure

Abstract

The invention discloses a preparation method of quartz glass with a complex structure, and belongs to the technical field of 3D printing. According to the method, a special structure with periodicity is realized by adopting Creo software aiming at dot matrix structure design. The formula of the glass paste is optimized, and the glass paste comprises the glass powder, the methacrylate and the plasticizer, so that the excellent forming performance of the paste in the printing process is ensured. A blank formed after printing is subjected to ultrasonic cleaning and surface spraying treatment through special cleaning liquid, then is dried at the room temperature and is further subjected to heat treatment. The quartz glass lattice structure prepared by the method has excellent transparency and optical uniformity, effectively avoids the cracking problem in the traditional glass manufacturing process, remarkably improves the yield, and is suitable for the fields of high-precision optics and photoelectrons.

Description

Technical Field

[0001] The invention relates to the field of 3D printing glass, and in particular to a method for preparing quartz glass with a complex structure. Background Art

[0002] With the advancement of science and technology, glass is widely used in many fields such as construction, electronics, automobiles, and medical treatment due to its high transparency, excellent mechanical strength, chemical corrosion resistance, and good optical properties. However, the manufacturing and processing technology of traditional glass still faces many challenges. First of all, traditional glass manufacturing usually relies on complex processes such as high-temperature melting and mold forming, which not only increases production costs, but also makes the manufacturing process require high equipment and process precision. In addition, due to the hardness and brittleness of the glass material itself, it is easy to crack or break during the processing of cutting, engraving, drilling, etc., resulting in a low yield rate and seriously affecting production efficiency. Secondly, a large amount of scrap and dust are inevitably generated during the processing, which not only increases material waste, but also poses a challenge to environmental protection. Especially in the field of precision processing, in order to improve the quality of glass products, more stringent process control and refined processing technology are required to reduce the scrap rate and reduce resource consumption. Therefore, how to optimize the glass processing technology, improve the yield rate, reduce production costs, and reduce environmental pollution has become a key direction for the development of glass industry technology. In response to the above problems, an efficient, low-cost and environmentally friendly glass manufacturing and processing method is urgently needed to break through the existing technical bottleneck and promote the sustainable development of the glass industry.

[0003] In recent years, 3D printing technology has been widely used in the manufacturing industry due to its unique forming method. Compared with traditional processing methods, 3D printing can directly manufacture parts with complex structures by stacking materials layer by layer, avoiding material waste and complex processes in traditional cutting, casting or mold processing, and improving manufacturing efficiency and design freedom. A major advantage of 3D printing is its efficient use of raw materials. Due to the use of additive manufacturing technology, the material utilization rate is greatly improved, avoiding a large amount of scrap caused by traditional subtractive manufacturing. In addition, uncured slurry or powder can be recycled and reused, reducing material waste from the source, achieving green manufacturing, and effectively reducing production costs. At the same time, since the 3D printing process does not require traditional processing steps such as cutting and welding, it reduces pollutant emissions during the processing process, which plays a positive role in promoting environmental protection. In addition, 3D printing technology has the characteristics of one-piece forming, and can directly prepare parts with complex structures without additional assembly or subsequent processing. This not only reduces the damage to parts caused by mechanical processing, but also significantly improves the yield rate of products, which is particularly suitable for precision manufacturing, high-performance material processing and other fields. With the continuous advancement of 3D printing technology, its application prospects in industrial manufacturing, medical care, aerospace and other fields will be broader.

[0004] 3D printing technology has made significant progress in the fields of metals, ceramics and polymer materials due to its advantages in additive manufacturing. However, research on 3D printed glass is still in its infancy, and there is relatively little research on the preparation of photocurable slurries and complex structure glass products, and the technology is not yet mature. Summary of the invention

[0005] In order to solve the above technical problems, the present invention provides a method for preparing quartz glass with complex structure. This study establishes a coordinated control technology of slurry formula and green body cleaning process, successfully prepares quartz glass with a lattice structure, and effectively solves the problem of low yield of quartz glass with complex structure.

[0006] The specific process of the present invention is as follows:

[0007] (1) Preparation of slurry: Methacrylic acid and plasticizer are fully mixed to obtain a mixed resin-based slurry, wherein the content of methacrylic acid ester is 67-77wt% of the mixed resin-based slurry, and the content of plasticizer is 23-33wt% of the mixed resin-based slurry. Then, glass powder ( AEROSIL OX 50 ) is uniformly mixed into the mixed resin-based slurry to obtain a glass slurry, wherein the glass powder accounts for 55-60wt% of the glass slurry. 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and Sudan orange are added to the prepared glass slurry, wherein the content of the photoinitiator is 0.03-0.08wt% of the glass slurry, and the content of the light absorber is 0.005-0.009wt% of the glass slurry. A vacuum homogenizer is used for vacuum homogenization, and the homogenization time is 120 seconds and the rotation speed is 2200r / min.

[0008] (2) Structural design: The lattice structure was modeled using CREO software. The unit cell was set as a cube. The overall size was adjusted to make the array number 4. The file was exported in stl format and then imported into the slicing software for slicing. The slicing file was exported in goo format.

[0009] (3) Blank printing: Place the slicer software in a light-curing 3D printer, pour the prepared slurry into the material tank for printing. The layer thickness of the printer is set to 35-50 μm, and the exposure time is set to 18-21 seconds.

[0010] (4) Preparation of cleaning solution: Methanol, glycerol and deionized water are fully mixed, and then one or more methacrylates are added to obtain a cleaning solution. The content of methanol is 20-25wt% of the cleaning solution, the content of glycerol is 10-15wt% of the cleaning solution, the content of deionized water is 10-15wt% of the cleaning solution, and the content of methacrylate is 50-60wt% of the cleaning solution. The total amount of these four substances is 100wt%.

[0011] (5) Cleaning of the blank: Place an empty beaker in an ultrasonic cleaning device, and pour some deionized water into the ultrasonic cleaning device, and place the printed blank in the beaker. Then add a cleaning liquid that covers the blank in the beaker and perform ultrasonic vibration to fully clean the residual slurry on the surface of the blank. After the ultrasonic vibration ends, place the cleaning liquid in a high-atomization air gun, use the high-atomization air gun to spray the blank, and then dry it at room temperature.

[0012] (6) Post-treatment of the green body: The dried green body is placed in a muffle furnace for air degreasing and then placed in a tubular furnace for vacuum sintering.

[0013] The beneficial effects of the present invention are:

[0014] (1) A new glass paste formula is proposed, which uses dimethacrylate to make the green body have lower internal stress and better mechanical properties.

[0015] (2) The various components of the cleaning solution are coordinated and regulated, the configuration is simple, and the cleaning effect is excellent.

[0016] (3) Use physical means such as physical vibration and high-speed spraying to remove residual slurry on the surface of the green body to avoid its impact on the post-processing process of the green body. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 The quartz glass products prepared by the process are given.

[0018] Figure 2 This is the thermogravimetric analysis diagram of the green body. DETAILED DESCRIPTION

[0019] The present invention is described in detail below in conjunction with specific embodiments. The description in this section is only exemplary and explanatory and should not have any limiting effect on the scope of protection of the present invention.

[0020] The material used in the embodiment of the present invention is silicon dioxide.

[0021] Example 1.

[0022] (1) Preparation of slurry: 12 g of hydroxyethyl methacrylate, 6 g of diphenoxyethanol and 2 g of triethylene glycol dimethacrylate were fully mixed to prepare a premixed solution, and then 0.5 g of glass powder ( AEROSIL OX 50) Add 28 g of glass powder to the premixed liquid to obtain glass slurry, add 0.02 g of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 0.003 g of Sudan orange to the prepared glass slurry, and use a vacuum homogenizer to homogenize the glass slurry. The homogenization time is 120 seconds and the speed is 2200 r / min.

[0023] (2) Structural design: CREO software was used for modeling. The unit cell was a rectangular parallelepiped with dimensions set to 5 × 5 × 6 mm, the overall dimensions set to 10 × 10 × 6 mm, and the rod diameter set to 1.5 mm. The model was then exported in stl format and sliced ​​using the slicing software VoxeldanceTango 4.0 to export the sliced ​​files in goo format.

[0024] (3) Printing of the blank: The prepared glass slurry was poured into a material tank and printed using a Mars 4DLP light-curing printer. The printing layer thickness was set to 50 μm and the single layer exposure time was 21 seconds.

[0025] (4) Cleaning of the blank: 20g of hydroxyethyl methacrylate, 4g of deionized water, 8g of methanol and 5g of glycerol are fully mixed to obtain a cleaning solution. Place an empty beaker in an ultrasonic cleaning device, and pour deionized water into the ultrasonic cleaning device until it covers half of the beaker, and place the printed blank in the beaker. Then add the cleaning solution that covers the blank into the beaker for ultrasonic oscillation. The ultrasonic time is 2min and the ultrasonic frequency is 40kHz. After the ultrasonic treatment, pour the cleaning solution into a high atomization spray gun and spray the surface of the blank after ultrasonic treatment. The air pressure is controlled at 0.2MPa and the spraying time is 1min. Then the blank is dried at room temperature. The air pressure is controlled by an air pump equipped with an air pressure valve.

[0026] (5) Degreasing of the green body: Place the green body in a muffle furnace, raise the temperature from room temperature to 140°C at a rate of 1°C / min, and keep it at 140°C for 2 hours to ensure the initial removal of moisture and volatile organic matter. Subsequently, raise the temperature from 140°C to 243°C at a rate of 0.3°C / min, and keep it at 243°C for 4 hours. Then, continue to raise the temperature to 321°C at a rate of 0.3°C / min, and keep it at 321°C for 3 hours. Finally, raise the temperature to 600°C at a rate of 1°C / min, keep it at 600°C for 2 hours, and then cool it with the furnace.

[0027] (6) Sintering of the green body: First, the degreased green body is placed in a tubular atmosphere furnace, and the furnace tube is vacuumed using a Feiyue VRD-8 mechanical pump. Then, the heating rate is controlled to be 1.1℃ / min, from room temperature to 800℃, and kept at 800℃ for 2 hours. Subsequently, the temperature is continued to be raised from 800℃ to 1340℃ at a heating rate of 5℃ / min, and kept at 1340℃ for 2 hours. During the sintering process, the vacuum is always drawn to ensure that the air pressure in the tube is not higher than 100Pa, so as to reduce the gap between the powders, increase the density and achieve a transparent effect. Therefore, the mechanical pump is kept running during the sintering process, and the air pressure in the tube is monitored using a vacuum gauge.

[0028] Example 2.

[0029] (1) Preparation of slurry: 15 g of hydroxyethyl methacrylate, 6 g of diphenoxyethanol and 3 g of triethylene glycol dimethacrylate were fully mixed to prepare a premixed solution, and then 0.5 g of glass powder ( AEROSIL OX 50 ) 30 g of glass powder was added to the premixed solution to obtain glass slurry. 0.03 g of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 0.004 g of Sudan orange were added to the prepared glass slurry, and the glass slurry was homogenized using a vacuum homogenizer with a homogenization time of 120 s and a rotation speed of 2200 r / min.

[0030] (2) Structural design: The lattice structure was modeled using CREO software, with the unit cell size set to 5 × 5 × 6 mm, the overall size set to 10 × 10 × 6 mm, and the rod diameter set to 1.3 mm. The model was then exported in stl format and sliced ​​using the slicing software VoxeldanceTango 4.0 to export the sliced ​​files in goo format.

[0031] (3) Printing of the blank: The prepared slurry was poured into a material tank and printed using a Mars 4DLP light-curing printer. The printing layer thickness was set to 35 μm and the single layer exposure time was 18 seconds.

[0032] (4) Cleaning of the blank: 24g of hydroxyethyl methacrylate, 5g of deionized water, 10g of methanol and 6g of glycerol are fully mixed to obtain a cleaning solution. Place an empty beaker in an ultrasonic cleaning device, and pour deionized water into the ultrasonic cleaning device until it covers half of the beaker, and place the printed blank in the beaker. Then add the cleaning solution that covers the blank into the beaker for ultrasonic oscillation. The ultrasonic time is 1min and the ultrasonic frequency is 50kHz. After the ultrasonic treatment, pour the cleaning solution into a high atomization spray gun and spray the surface of the blank after ultrasonic treatment. The air pressure is controlled at 0.3MPa and the spraying time is 0.5min. Then the blank is dried at room temperature.

[0033] (5) Degreasing of the green body: Place the green body in a muffle furnace, raise the temperature from room temperature to 140°C at a rate of 1°C / min, and keep it at 140°C for 2 hours to ensure the initial removal of moisture and volatile organic matter. Subsequently, raise the temperature from 140°C to 243°C at a rate of 0.3°C / min, and keep it at 243°C for 4 hours. Then, continue to raise the temperature to 321°C at a rate of 0.3°C / min, and keep it at 321°C for 3 hours. Finally, raise the temperature to 600°C at a rate of 1°C / min, keep it at 600°C for 2 hours, and then cool it with the furnace.

[0034] (6) Sintering of the green body: First, the degreased green body is placed in a tubular atmosphere furnace, and the furnace tube is vacuumed using a Feiyue VRD-8 mechanical pump. Then, the heating rate is controlled to be 1.1°C / min, from room temperature to 800°C, and kept at 800°C for 2 hours. Subsequently, the temperature is continued to be raised from 800°C to 1340°C at a heating rate of 3°C / min, and kept at 1340°C for 2 hours. During the sintering process, the air pressure in the tube should be ensured to be no higher than 100Pa to reduce the gap between the powders, increase the density and achieve a transparent effect. Therefore, the mechanical pump is kept running during the sintering process, and a vacuum gauge is used to monitor the air pressure in the tube.

[0035] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing complex structure quartz glass, characterized in that: The following steps are involved: (1) Preparation of glass slurry and printing of blanks: First, prepare a mixed resin-based slurry, which consists of methacrylate and plasticizer; fully stir the methacrylate, then add the plasticizer and mix evenly to obtain a mixed resin-based slurry, wherein the content of methacrylate is 67-77wt% of the mixed resin-based slurry, and the content of the plasticizer is 23-33wt% of the mixed resin-based slurry; then add glass powder to the mixed resin-based slurry and mix evenly to obtain glass slurry, wherein the content of glass powder is 55-60wt% of the glass slurry; then add a photoinitiator and a light absorber to the glass slurry and use a vacuum homogenizer to homogenize, wherein the content of the photoinitiator is 0.03-0.08wt% of the glass slurry, and the content of the light absorber is 0.005-0.009wt% of the glass slurry; import the designed model into the slicing software for slicing, generate a goo format file, then import it into the light-curing 3D printer and pour the slurry into the material tank to print the blank; (2) Cleaning the blank: Clean the printed blank and dry it at room temperature; (3) Post-treatment of the green body: the cleaned green body is air degreased in a muffle furnace, and then vacuum sintered in a tube furnace; the degreasing is carried out in the muffle furnace, and the temperature is raised from room temperature to 100-140°C at a rate of 0.1-3°C / min, and kept at this temperature for 2-4 hours; then, the temperature is raised to 243-300°C at a rate of 0.3-2°C / min, and kept at this temperature for 4-6 hours; then, the temperature is further raised to 321-400°C at a rate of 0.3-0.5°C / min, and kept at this temperature for 3-5 hours; finally, the temperature is raised to 600-800°C at a rate of 1-2°C / min, and kept at this temperature for 2-3 hours, and then cooled with the furnace; Sintering is carried out in a tubular furnace. First, the degreased green body is placed in a tubular atmosphere furnace, and the furnace tube is evacuated using a mechanical pump. Then, the heating rate is controlled to be 1.1 to 3.3°C / min, from room temperature to 800 to 1000°C, and kept warm for 2 to 4 hours; then, the temperature is continued to be raised to 1300 to 1340°C at a heating rate of 3 to 5°C / min, and kept warm for 2 to 4 hours; during vacuum sintering, the air pressure in the tube shall not be higher than 100Pa.

2. The method for preparing a complex structure quartz glass according to claim 1, characterized in that: The methacrylate is one or more of triethylene glycol dimethacrylate, 2-hydroxyethyl methacrylate, polyethylene glycol diacrylate and hydroxyethyl methacrylate.

3. The method for preparing a complex structure quartz glass according to claim 1, characterized in that: The glass powder is silicon dioxide nanopowder with a particle size of 30 to 300 nm.

4. The method for preparing a complex structure quartz glass according to claim 1, characterized in that: The cleaning process includes the following steps: (1) Preparation of cleaning solution: alcohol substance and deionized water are fully stirred, and then methacrylate is added to mix them evenly to obtain a cleaning solution; wherein the content of the alcohol substance is 30-40wt% of the cleaning solution, the content of the deionized water is 10-15wt% of the cleaning solution, and the content of the methacrylate is 50-60wt% of the cleaning solution, and the total amount of these three substances is 100wt%; (2) Cleaning residual slurry on the blank: Place an empty beaker into an ultrasonic cleaning device, and pour a portion of deionized water into the ultrasonic cleaning device, then place the printed blank into the beaker; add the cleaning solution prepared in step (1) into the empty beaker so that it covers the blank, and perform ultrasonic oscillation at a frequency of 40 to 50 kHz and an ultrasonic time of 0.5 to 3 min; (3) Treatment of the surface of the green body: inject the cleaning liquid prepared in step (1) into a high atomization gas spray gun, and spray the green body after ultrasonic cleaning. The spraying pressure is 0.2-0.4 MPa and the spraying time is 0.5-1 min.

5. The method for preparing a complex structure quartz glass according to claim 4, characterized in that: The alcohol substance in the cleaning liquid is one or more of methanol, ethanol, glycerol and isopropanol.

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