Yttrium-bismuth-antimony doped quartz sand and preparation method and application thereof

Abstract

The invention discloses yttrium-bismuth-antimony doped quartz sand and a preparation method and application thereof, the content of SiO2 in the quartz sand is larger than or equal to 99.995%, the content of impurities is smaller than or equal to 50 ppm, the impurities contain yttrium oxide, bismuth oxide and antimony oxide, and the total content of the yttrium oxide, the bismuth oxide and the antimony oxide is 25-45 ppm. By doping yttrium oxide, the melting temperature of the glass is obviously improved; the bismuth oxide and the antimony oxide can reduce the viscosity of quartz melt, are beneficial to overflow of a large amount of gas generated in the continuous melting process of quartz sand, and improve the compactness of the glass, so that the strength and the high temperature resistance of the quartz glass are improved.

Description

Technical Field

[0001] The invention belongs to the technical field of high-performance quartz materials, and particularly relates to yttrium-bismuth-antimony doped quartz sand and a preparation method and application thereof. Background Art

[0002] Quartz glass is a special industrial technical glass composed of a single component. It plays a very important role in modern industry and high technology fields because of its series of special properties that cannot be replaced by other materials. Temperature resistance, mechanical strength, thermal shock resistance, corrosion resistance, etc. are important properties of quartz glass.

[0003] At present, the main preparation method of quartz glass is the continuous melting method. This process can efficiently prepare various quartz glass materials such as quartz glass tubes, rods and plates through the continuous feeding, melting and continuous drawing of quartz sand. At the same time, different elements can also be added to the quartz sand to obtain various functional quartz glasses. Due to the presence of a large number of inclusions and hydroxyl groups in the quartz sand, a large amount of gas will be generated during the continuous melting process, resulting in a large number of bubbles, gas lines and invisible microbubbles visible to the naked eye in the quartz glass. These defects greatly reduce the temperature resistance, mechanical properties and service life of quartz glass. In the continuous melting process, the bubble defects of quartz glass can be reduced by controlling the melting time of molten quartz in the crucible to exhaust gas, etc., but due to the high viscosity of the molten quartz liquid phase, the gas overflow is difficult, so the effect is limited, and the strength of the drawn quartz glass tube / rod is relatively low and the temperature resistance is also poor. Summary of the invention

[0004] Purpose of the invention: The technical problem to be solved by the present invention is to provide a quartz sand doped with yttrium-bismuth-antimony in view of the shortcomings of the prior art, so as to solve the problem that a large number of bubble defects exist in the preparation of quartz glass by the continuous melting method, resulting in poor mechanical properties and temperature resistance, and greatly improve the strength and high temperature resistance of quartz glass.

[0005] In order to achieve the above-mentioned object of the invention, the technical solution adopted by the present invention is as follows: A quartz sand doped with yttrium, bismuth and antimony, wherein SiO 2 The content is ≥99.995 wt.%, and the impurity content is ≤50ppm. The impurities include yttrium oxide, bismuth oxide, and antimony oxide, and the total content of the three is 25-45ppm.

[0006] Preferably, among the impurities, the yttrium oxide content is 10-20 ppm, the bismuth oxide content is 10-15 ppm, and the antimony oxide content is 5-10 ppm.

[0007] Further preferably, among the impurities, the mass ratio of yttrium oxide, bismuth oxide and antimony oxide is 1:(0.5-1):(0.5-1).

[0008] Furthermore, the present invention also provides a method for preparing the above-mentioned yttrium-bismuth-antimony doped quartz sand, comprising the following steps: (1) preparing hydrochloric acid solutions of yttrium oxide, bismuth oxide, and antimony oxide respectively, and then mixing the three hydrochloric acid solutions and stirring to obtain a mixed doping solution; (2) Using high-purity quartz sand as raw material, adding it to the mixed doping solution of step (1) at a solid-liquid volume ratio of 1:1.5-3, and then stirring and leaching for 6-10 h at 100-150° C. and 1.2-1.5 MPa high pressure to obtain high-purity quartz sand with preliminary doping treatment; (3) washing the high-purity quartz sand obtained by the preliminary doping treatment in step (2) with ultrapure water, drying it and setting it aside; (4) subjecting the high-purity quartz sand that has been preliminarily doped after drying in step (3) to diffusion treatment at high temperature, and cooling to obtain a refined sample of doped high-purity quartz sand; (5) mixing the doped high-purity quartz sand sample obtained in step (4) with the high-purity quartz sand raw material to obtain doped high-purity quartz sand, and then performing magnetic separation to remove iron impurities; (6) The doped high-purity quartz sand after magnetic separation is subjected to high-temperature chlorination treatment to obtain.

[0009] Specifically, in step (1), in the mixed doping solution, the concentration of yttrium oxide is 0.05-0.10 wt.%, the concentration of bismuth oxide is 0.05-0.10 wt.%, and the concentration of antimony oxide is 0.02-0.05 wt.%.

[0010] Specifically, in step (3), the drying temperature is 200-300°C.

[0011] Specifically, in step (4), the diffusion treatment is carried out at a temperature of 1000-1200° C. and for a time of 4-8 h.

[0012] Specifically, in step (5), the doped high-purity quartz sand sample and the high-purity quartz sand raw material are stirred and mixed at a mass ratio of 1:100-150.

[0013] Specifically, in step (6), the temperature of the high temperature chlorination treatment is 1300-1500°C, using Cl 2 and HCl or a mixture of two gases, with a chlorination time of 30-120 minutes to remove alkali metal impurities introduced during the doping process.

[0014] Furthermore, the present invention also claims to protect the use of the above-mentioned yttrium-bismuth-antimony doped quartz sand in the preparation of high temperature resistant quartz glass by continuous melting method. Beneficial Effects

[0015] (1) The present invention uses yttrium oxide as an additive, which can significantly increase the melting temperature of glass, which is very important for manufacturing high-temperature glass. At the same time, yttrium oxide is added to quartz glass to increase the number of oxygen and non-bridging oxygen in each tetrahedron and reduce the number of connections, making SiO 2 The high-temperature viscosity of the melt is reduced, which is conducive to the removal of impurities and bubbles.

[0016] Bismuth ions are connected to silicon-oxygen tetrahedrons in glass through vertex angles or shared edges to form a special network. This special network makes bismuth oxide and SiO 2 The system has a wide glass-forming range, which determines the high flux of bismuth oxide in silicate melts, and can significantly reduce the viscosity of the glass and increase the density of the glass.

[0017] Antimony oxide has the function of inhibiting the formation of bubbles. Oxides or other impurities may exist in glass raw materials at high temperatures, which will form bubbles and affect the transparency of the glass. During the glass manufacturing process, antimony oxide will be reduced to antimony dioxide and oxidize some of the impurity elements in the glass, and then oxidized back to antimony trioxide, forming a cycle process that continuously oxidizes and removes impurities in the glass, preventing the formation of bubbles.

[0018] (2) The quartz glass prepared by the yttrium-bismuth-antimony doped quartz sand of the present invention is dense, has greatly reduced bubbles, and can withstand high temperatures of 1500°C and above for a long time, which is 100-200°C higher than that of ordinary quartz glass. The compressive strength of the quartz glass reaches above 1000MPa, which is more than 10% higher than that of ordinary quartz glass. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] The present invention will be further described in detail below in conjunction with the accompanying drawings and specific embodiments, and the above and / or other advantages of the present invention will become more clear.

[0020] Figure 1 The present invention is a flow chart for preparing yttrium-bismuth-antimony doped quartz sand. DETAILED DESCRIPTION

[0021] The present invention can be better understood with reference to the following examples. Example 1

[0022] Combination Figure 1 The process flow is to add yttrium oxide, bismuth oxide and antimony oxide into high-purity quartz sand at a mass ratio of 1:1:0.5, with the addition amount of yttrium oxide being 15 ppm, the addition amount of bismuth oxide being 15 ppm and the addition amount of antimony oxide being 7.5 ppm. The specific steps are as follows: Step 1: First, prepare hydrochloric acid solutions of yttrium oxide, bismuth oxide, and antimony oxide respectively; mix the three hydrochloric acid solutions of yttrium oxide, bismuth oxide, and antimony oxide, and stir them evenly to form a mixed doping solution; Step 2: Use high purity quartz sand (SiO 2 The high-purity quartz sand raw material is placed in the mixed doping solution of step 2 at a solid-liquid volume ratio of 1:2, and stirred and leached for 8 h under high pressure in a reactor at 120°C and 1.2 MPa to obtain high-purity quartz sand with preliminary doping treatment; Step 3: Wash the high-purity quartz sand treated in step 2 with ultrapure water, dry at 200°C, and cool; Step 4: subjecting the high-purity quartz sand that has undergone preliminary doping treatment after drying in step 3 to high-temperature diffusion treatment at 1200°C for 4 h, and cooling to obtain a refined sample of doped high-purity quartz sand; Step 5: The doped high-purity quartz sand sample obtained in step 4 and the high-purity quartz sand raw material are mixed at a mass ratio of 1:100 by high-speed stirring to obtain doped high-purity quartz sand; Step 6: subjecting the doped high-purity quartz sand obtained in step 5 to high-magnetic separation to remove the iron impurities introduced during the doping process; Step 7: The doped high-purity quartz sand obtained in step 6 is subjected to high-temperature chlorination treatment. The temperature of high-temperature chlorination is 1350°C and the chlorination gas is Cl 2 , the chlorination time is 60 min to remove the alkali metal impurities introduced in the doping process, and finally the doped high-purity quartz sand for preparing high-temperature resistant quartz glass by continuous melting method is obtained. Example 2

[0023] This embodiment is the same as Embodiment 1, except that yttrium oxide, bismuth oxide, and antimony oxide are added to high-purity quartz sand in a mass ratio of 1:1:0.5, the yttrium oxide addition amount is 10 ppm, the bismuth oxide addition amount is 10 ppm, and the antimony oxide addition amount is 5 ppm. Example 3

[0024] This embodiment is the same as Embodiment 1, except that yttrium oxide, bismuth oxide, and antimony oxide are added to high-purity quartz sand in a mass ratio of 1:0.75:0.5, the yttrium oxide addition amount is 20 ppm, the bismuth oxide addition amount is 15 ppm, and the antimony oxide addition amount is 10 ppm.

[0025] Comparative Example 1 The difference between this embodiment and embodiment 1 is that only 15 ppm of yttrium oxide is added to the high-purity quartz sand.

[0026] Comparative Example 2 The difference between this embodiment and embodiment 1 is that only 15 ppm of bismuth oxide is added to the high-purity quartz sand.

[0027] Comparative Example 3 The difference between this embodiment and embodiment 1 is that only 7.5 ppm of antimony oxide is added to the high-purity quartz sand.

[0028] Comparative Example 4 The difference between this embodiment and embodiment 1 is that 15 ppm of yttrium oxide and 15 ppm of bismuth oxide are added to high-purity quartz sand.

[0029] Comparative Example 5 The difference between this embodiment and embodiment 1 is that 15 ppm of yttrium oxide and 7.5 ppm of antimony oxide are added to the high-purity quartz sand.

[0030] Comparative Example 6 The difference between this embodiment and embodiment 1 is that 15 ppm of bismuth oxide and 7.5 ppm of antimony oxide are added to the high-purity quartz sand.

[0031] The quartz sand prepared in the above examples and comparative examples was used as raw material, high-purity quartz sand (SiO 2 Content ≥99.995%, without any additional impurities) as the blank group raw materials, respectively, by continuous melting method to obtain quartz glass rods with a diameter of 20mm. The compressive strength of each quartz glass rod was measured according to GB / T 9963-2016 "Architectural Glass: Tempered Glass". The softening point temperature was measured according to JC / T 751-1996 "Quartz Glass Softening Point Test Method (Wire Drawing Method)", and the results are shown in Table 1.

[0032] Table 1

[0033] As can be seen from Table 1, adding one or two of yttrium oxide, bismuth oxide, and antimony oxide to quartz sand can improve the compressive strength of quartz glass, but the improvement effect is limited. In addition, adding bismuth oxide and antimony oxide can help fluxing and increase the density of glass, thereby improving strength, but reducing the temperature resistance of quartz glass. The present invention finds that after yttrium oxide, bismuth oxide, and antimony oxide are doped simultaneously, the compressive strength and temperature resistance of quartz glass can be significantly improved, and the three can produce a certain synergistic effect.

[0034] The present invention provides a method and idea of ​​yttrium-bismuth-antimony doped quartz sand and its preparation method and application. There are many methods and ways to implement the technical solution. The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the protection scope of the present invention. All components not specified in this embodiment can be implemented by existing technologies.

Claims

1. A yttrium-bismuth-antimony doped quartz sand, characterized in that: The SiO2 content in quartz sand is ≥99.995 wt.%, and the impurity content is ≤50ppm. The impurities contain yttrium oxide, bismuth oxide and antimony oxide, and the total content of the three is 25-45ppm.

2. The yttrium-bismuth-antimony doped quartz sand according to claim 1, characterized in that: Among the impurities, the yttrium oxide content is 10-20 ppm, the bismuth oxide content is 10-15 ppm, and the antimony oxide content is 5-10 ppm.

3. The yttrium-bismuth-antimony doped quartz sand according to claim 1, characterized in that: Among the impurities, the mass ratio of yttrium oxide, bismuth oxide and antimony oxide is 1:(0.5-1):(0.5-1).

4. The method for preparing yttrium-bismuth-antimony doped quartz sand according to claim 1, characterized in that: The steps include: (1) preparing hydrochloric acid solutions of yttrium oxide, bismuth oxide, and antimony oxide respectively, and then mixing the three hydrochloric acid solutions and stirring to obtain a mixed doping solution; (2) Using high-purity quartz sand as raw material, adding it to the mixed doping solution of step (1) at a solid-liquid volume ratio of 1:1.5-3, and then stirring and leaching for 6-10 h at 100-150° C. and 1.2-1.5 MPa high pressure to obtain high-purity quartz sand with preliminary doping treatment; (3) washing the high-purity quartz sand obtained by the preliminary doping treatment in step (2) with ultrapure water, drying it and setting it aside; (4) subjecting the high-purity quartz sand that has been preliminarily doped after drying in step (3) to diffusion treatment at high temperature, and cooling to obtain a refined sample of doped high-purity quartz sand; (5) mixing the doped high-purity quartz sand sample obtained in step (4) with the high-purity quartz sand raw material to obtain doped high-purity quartz sand, and then performing magnetic separation to remove iron impurities; (6) The doped high-purity quartz sand after magnetic separation is subjected to high-temperature chlorination treatment to obtain.

5. The method for preparing yttrium-bismuth-antimony doped quartz sand according to claim 1, characterized in that: In step (1), in the mixed doping solution, the concentration of yttrium oxide is 0.05-0.10 wt.%, the concentration of bismuth oxide is 0.05-0.10 wt.%, and the concentration of antimony oxide is 0.02-0.05 wt.%.

6. The method for preparing yttrium-bismuth-antimony doped quartz sand according to claim 1, characterized in that: In step (3), the drying temperature is 200-300 °C.

7. The method for preparing yttrium-bismuth-antimony doped quartz sand according to claim 1, characterized in that: In step (4), the diffusion treatment is carried out at a temperature of 1000-1200° C. and for a time of 4-8 h.

8. The method for preparing yttrium-bismuth-antimony doped quartz sand according to claim 1, characterized in that: In step (5), the doped high-purity quartz sand sample and the high-purity quartz sand raw material are mixed by high-speed stirring at a mass ratio of 1:100-150.

9. The method for preparing yttrium-bismuth-antimony doped quartz sand according to claim 1, characterized in that: In step (6), the high temperature chlorination treatment is carried out at a temperature of 1300-1500° C., using a mixture of one or both of Cl 2 and HCl gases, and the chlorination time is 30-120 min to remove alkali metal impurities introduced during the doping process.

10. Use of the yttrium-bismuth-antimony doped quartz sand according to claim 1 in preparing high temperature resistant quartz glass by continuous melting method.

Images