Special low-carbon fireproof quartziferous dry vibration material and preparation method thereof

Abstract

The invention discloses a special low-carbon fire-resistant quartziferous dry vibration material and a preparation method thereof, and relates to the technical field of fire-resistant materials. The special low-carbon fireproof quartzite dry vibration material comprises the following components in parts by weight: 70-80 parts of quartz aggregate, 20-30 parts of zirconia coated corundum micro powder, 3-6 parts of aluminum dihydrogen phosphate, 0.5-1 part of lithium borate and 0.5-1 part of yttrium oxide. The preparation method comprises the following steps: adding the quartz aggregate, the zirconia coated corundum micro powder, the dihydrogen phosphate, the lithium borate and the yttrium oxide into a mixer, and uniformly stirring to obtain the product. The quartziferous dry vibration material prepared by the invention has good thermal shock cycle resistance and low carbon content, and is green and environment-friendly.

Description

Technical Field

[0001] The present invention relates to the technical field of refractory materials, and particularly to a special low-carbon refractory quartz dry vibrating material and a preparation method thereof. Background Art

[0002] Refractory materials play a crucial role in high-temperature industrial fields such as metallurgy, glass, and ceramics. Among them, quartz dry vibrating materials are widely used in thermal equipment such as induction furnace linings and permanent ladle layers due to their high refractoriness, good chemical stability, and low cost. Quartz dry vibrating materials mainly use quartz raw materials as aggregates, combined with binders and additives, and are formed into a working lining body with certain strength and erosion resistance through vibration compaction.

[0003] However, quartz dry vibrating materials face serious problems of thermal shock stability during actual use. There are multiple crystal forms in quartz crystals, and a reversible phase change from β - quartz to α - quartz will occur during the heating process. This phase change process is accompanied by volume expansion and contraction. During the operation of high-temperature equipment, frequent heating and cooling cycles cause the quartz dry vibrating material to repeatedly withstand this volume change. Under the action of repeated thermal shock cycles, the volume change will cause micro stress concentration phenomena inside the quartz particles. With the increase in the number of thermal shocks, these stress concentration regions gradually develop into cracks and continue to expand. The appearance of cracks will not only cause spalling on the material surface, but in severe cases, it will even cause the overall cracking of the material, greatly reducing the service life of the quartz dry vibrating material and making the number of thermal cycles it can withstand far lower than the actual industrial requirements. In addition, with the in-depth promotion of the low-carbon environmental protection concept in industrial production, the carbon elements introduced by components such as binders and additives during the preparation of traditional quartz dry vibrating materials will react with the oxidizing atmosphere in the furnace at high temperatures, leading to the deterioration of the material structure and causing environmental pollution problems at the same time. Summary of the Invention

[0004] The purpose of the present invention is to provide a special low-carbon refractory quartz dry vibrating material and a preparation method thereof to solve the technical problems of poor thermal shock resistance and non-environmental protection of the existing quartz dry vibrating materials in the above background art. The quartz dry vibrating material prepared by the present invention has good thermal shock resistance and low carbon content, and is environmentally friendly.

[0005] To achieve the above purpose, the present invention provides the following technical solutions: A special low-carbon refractory quartz dry vibrating material, comprising the following components by weight: 70 - 80 parts of quartz aggregate, 20 - 30 parts of zirconia-coated corundum micropowder, 3 - 6 parts of aluminum dihydrogen phosphate, 0.5 - 1 part of lithium borate, and 0.5 - 1 part of yttrium oxide.

[0006] In the technical solution of the present invention, quartz aggregate is used as the matrix material to provide the main high-temperature resistant skeleton. In addition, its raw material cost has a great advantage over other raw materials and is suitable as the main component of the dry vibration material. Corundum (α-Al2O3) is used as the core reinforcing phase in the dry vibration material. Its high melting point and angular particles form a high-temperature rigid skeleton, which is embedded in the gaps of the quartz aggregate to increase its bulk density and cold crushing strength. Aluminum dihydrogen phosphate is used as the binder in the dry vibration material to improve the overall strength of the material and reduce the porosity of the material through chemical action. Lithium borate is used as a low-temperature cosolvent, which significantly reduces the sintering temperature of the material, plays a role in energy conservation and consumption reduction, and reduces the production cost of enterprises. In addition, the dry vibration material formula of the present invention has a low carbon content, is green and environmentally friendly, and will not cause pollution to the environment.

[0007] Preferably, the quartz aggregate has two particle sizes of 0.1-1.0 mm and 1.5-5.0 mm, and the mass ratio of the two is 1:2.

[0008] Preferably, the preparation method of the zirconia-coated corundum fine powder includes the following steps: S1. Dissolve zirconium oxychloride in deionized water, and then add acetic acid as a hydrolysis inhibitor to obtain a zirconium oxychloride solution; S2. Add polymethyl methacrylate microspheres to an aqueous solution of polyvinylpyrrolidone, and ultrasonically oscillate to disperse evenly to obtain a polymethyl methacrylate microsphere suspension; S3. Add the polymethyl methacrylate microsphere suspension to the zirconium oxychloride solution, stir and disperse evenly to obtain a coating solution; S4. Add corundum fine powder to the coating solution, and slowly drop ammonia water solution under heating and stirring conditions, control the pH to 4-4.5, and make Zr 4+ gradually hydrolyze into Zr(OH)4 colloid and evenly deposit on the surface of corundum particles, stand and age for 12 h, and obtain the as-formed zirconia-coated corundum fine powder through suction filtration separation, washing and drying; S5. Calcinate the as-formed zirconia-coated corundum fine powder in a muffle furnace to obtain the zirconia-coated corundum fine powder.

[0009] In the technical solution of the present invention, due to the expansion and contraction of the volume of quartz crystals during the phase change process, the thermal shock resistance cycle performance of the dry vibration material is poor. To solve this technical problem, the present invention performs a coating modification treatment on the jade. On the one hand, zirconia is coated on the surface of corundum particles, and Zr(OH)4 colloid is uniformly deposited on the surface of corundum under alkaline conditions, and a dense ZrO2 coating layer is formed after calcination. This coating layer actively absorbs thermal shock stress, while the corundum core provides high-temperature structural stability, initially improving the thermal shock resistance cycle performance of the material. On the other hand, polymethyl methacrylate microspheres are used as pore-forming templates. After co-depositing with Zr(OH)4, they decompose during the calcination stage, leaving a uniform closed-pore structure in the coating layer. This structure induces crack bifurcation and energy dissipation when cracks propagate, prolonging the crack path. At the same time, the pores can buffer the thermal expansion difference between quartz and corundum, reducing the interfacial stress concentration. Through the above effects, the thermal shock resistance cycle performance of the dry vibration material is significantly improved.

[0010] Preferably, in the step S2, the particle size of the polymethyl methacrylate microspheres is 0.1 - 0.3 μm.

[0011] Preferably, in the step S2, the dosage of the polymethyl methacrylate microspheres is 1.5 - 5 wt% of the mass of zirconium oxychloride.

[0012] Preferably, in the step S4, the mass ratio of the corundum fine powder to the zirconium oxychloride is 10:2 - 4.

[0013] In the technical solution of the present invention, as described above, by coating zirconia on the surface of corundum fine powder to improve its thermal shock resistance cycle performance, in order to achieve good thermal shock resistance cycle performance, a sufficient amount of zirconia must be coated on the surface of the corundum fine powder. Therefore, the present invention controls the mass ratio of the corundum fine powder to the zirconium oxychloride to be less than 10 / 2. Subsequently, as the dosage of zirconium oxychloride continues to increase, that is, when the mass ratio of the corundum fine powder to the zirconium oxychloride is less than 10 / 4, the research team of the present invention unexpectedly found that the thermal conductivity of the material suddenly decreased significantly. The decrease in thermal conductivity will cause slow heat transfer inside and outside the material, and the heat cannot be quickly transferred to the material, so it is necessary to extend the heating time or increase the furnace temperature, greatly increasing the energy consumption. After research, it was found that this is because the thermal conductivity of the zirconia coating layer is relatively low, forming an interfacial thermal barrier, thus causing a decrease in the overall thermal conductivity of the coated particles. Therefore, the present invention strictly controls the mass ratio of the corundum fine powder to the zirconium oxychloride to be 10:2 - 4 to balance the thermal shock resistance cycle performance and thermal conductivity of the dry vibration material.

[0014] Preferably, in the step S5, the calcination temperature is 1100 - 1150 °C, and the calcination time is 1 - 2 h.

[0015] A preparation method of a special low-carbon refractory quartz-based dry vibration material includes the following steps: Add quartz aggregate, zirconia-coated corundum micropowder, aluminum dihydrogen phosphate, lithium borate, and yttrium oxide into a mixer and stir evenly to obtain the product.

[0016] Compared with the prior art, the beneficial effects of the present invention are as follows: 1. A special low-carbon refractory quartz dry vibratory material is prepared with quartz aggregate as the matrix material. The raw material cost of quartz aggregate has obvious advantages compared with other raw materials and is suitable as the main component of the dry vibratory material, which can effectively reduce the production cost. At the same time, corundum, as the core reinforcing phase, forms a high-temperature rigid framework with high melting point and angular particles, and is embedded in the gaps of quartz aggregate, greatly improving the bulk density and normal temperature compressive strength of the dry vibratory material, achieving the dual effects of cost optimization and strength enhancement while ensuring performance.

[0017] 2. Aiming at the problem that the thermal shock resistance cyclic performance of the dry vibratory material is poor due to the phase change of quartz crystal, the present invention conducts zirconia coating modification treatment on corundum micropowder. On the one hand, the zirconia coating layer actively absorbs thermal shock stress, and the corundum core provides high-temperature structural stability; on the other hand, using polymethyl methacrylate microspheres as the pore-forming template, a uniform closed-pore structure is formed in the coating layer, inducing crack bifurcation to consume energy, extending the crack path, and buffering the thermal expansion difference between quartz and corundum, significantly improving the thermal shock resistance cyclic performance of the dry vibratory material and enabling it to better adapt to high-temperature environment changes.

[0018] 3. Control the mass ratio of corundum micropowder to zirconium oxychloride within a specified range to balance the thermal shock resistance cyclic performance and thermal conductivity of the dry vibratory material. Specific Embodiments

[0019] The technical solutions in the embodiments of the present invention are clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0020] Example 1 A special low-carbon refractory quartz dry vibratory material, comprising the following components by weight: 78 parts of quartz aggregate, 27 parts of zirconia-coated corundum micropowder, 5 parts of aluminum dihydrogen phosphate, 0.9 part of lithium borate, and 0.8 part of yttrium oxide. The quartz aggregate has two particle sizes of 0.1 - 1.0 mm and 1.5 - 5.0 mm, and the mass ratio of the two is 1:2.

[0021] The preparation method of the zirconia-coated corundum micropowder includes the following steps: Step S1: Weigh 3.5 g of zirconium oxychloride, pour it into a beaker, add 300 mL of deionized water, and stir with a glass rod until completely dissolved. Then add about 10 mL of acetic acid solution with a mass concentration of 10%, and stir evenly to obtain a zirconium oxychloride solution.

[0022] Step S2: Weigh 2 g of polyvinylpyrrolidone and put it into a beaker, add 200 mL of deionized water, and stir until completely dissolved to prepare an aqueous solution of polyvinylpyrrolidone. Then weigh 0.105 g of polymethyl methacrylate microspheres with a particle size of 0.2 μm, add them to the above aqueous solution, place the beaker in an ultrasonic oscillator, and oscillate for 15 minutes to disperse the microspheres evenly to obtain a suspension of polymethyl methacrylate microspheres.

[0023] Step S3: Slowly pour the suspension of polymethyl methacrylate microspheres into the beaker containing the zirconium oxychloride solution, and use a magnetic stirrer to stir at a speed of 300 r / min for 20 minutes to mix the solution evenly to obtain a coating solution.

[0024] Step S4: Add 10 g of corundum micropowder to the coating solution, place the beaker in a constant temperature water bath, set the temperature to 60 °C, turn on the magnetic stirrer, and stir at a speed of 400 r / min. Slowly drip the ammonia water solution with a mass concentration of 25% using a dropper, and continuously monitor the pH value of the solution with a pH meter to control the pH to 4.5. After dripping, continue to stir for 30 minutes to fully hydrolyze Zr 4+ into Zr(OH)4 colloid and evenly deposit it on the surface of corundum particles. Then stop stirring, let the beaker stand for aging for 12 hours. After the aging is completed, use a suction filtration device to filter the solution, collect the filter cake, and wash the filter cake 3 times with deionized water until the pH of the washing solution is close to 7. Finally, transfer the filter cake to an oven and dry it at 105 °C for 12 hours to obtain as-prepared zirconia-coated corundum micropowder.

[0025] Step S5: Put the as-prepared zirconia-coated corundum micropowder into a crucible, place it in a muffle furnace, set the calcination temperature to 1125 °C, and the calcination time to 1.5 hours. After the muffle furnace heats up to the set temperature, put the crucible in. After the calcination is completed, turn off the muffle furnace. After the temperature in the furnace naturally cools to room temperature, take out the crucible to obtain zirconia-coated corundum micropowder.

[0026] A preparation method of a special low-carbon refractory quartz dry vibration material, comprising the following steps: Add quartz aggregate, zirconia-coated corundum micropowder, aluminum dihydrogen phosphate, lithium borate, and yttrium oxide into a mixer together, set the mixer speed to 200 r / min, and stir for 30 minutes to mix each component evenly to obtain a sample of the special low-carbon refractory quartz dry vibration material.

[0027] Example 2 A special low-carbon refractory quartz dry vibration material, comprising the following components by weight: 72 parts of quartz aggregate, 21 parts of zirconia-coated corundum micropowder, 4 parts of aluminum dihydrogen phosphate, 0.6 part of lithium borate, and 0.6 part of yttrium oxide. The quartz aggregate has two particle sizes of 0.1 - 1.0 mm and 1.5 - 5.0 mm, and the mass ratio of the two is 1:2.

[0028] The preparation method of the zirconia-coated corundum micropowder includes the following steps: Step S1: Weigh 2.5 g of zirconium oxychloride, pour it into a beaker, add 300 mL of deionized water, and stir with a glass rod until completely dissolved. Subsequently, add about 10 mL of acetic acid solution with a mass concentration of 10%, and stir evenly to obtain a zirconium oxychloride solution.

[0029] Step S2: Weigh 2 g of polyvinylpyrrolidone and put it into a beaker, add 200 mL of deionized water, and stir until completely dissolved to prepare an aqueous solution of polyvinylpyrrolidone. Then weigh 0.075 g of polymethyl methacrylate microspheres with a particle size of 0.2 μm, add them to the above aqueous solution, place the beaker in an ultrasonic oscillator, and oscillate for 15 minutes to make the microspheres evenly dispersed, obtaining a polymethyl methacrylate microsphere suspension.

[0030] Step S3: Slowly pour the polymethyl methacrylate microsphere suspension into the beaker containing the zirconium oxychloride solution, and use a magnetic stirrer to stir at a speed of 300 r / min for 20 minutes to make the solution evenly mixed, obtaining a coating solution.

[0031] Step S4: Add 10 g of corundum micropowder to the coating solution, place the beaker in a constant temperature water bath, set the temperature to 60 °C, turn on the magnetic stirrer, and stir at a speed of 400 r / min. Slowly drip an ammonia water solution with a mass concentration of 25% using a dropper, and continuously monitor the pH value of the solution with a pH meter to control the pH to 4. After the dripping is completed, continue to stir for 30 minutes to make Zr 4+ fully hydrolyze into Zr(OH)4 colloid and evenly deposit on the surface of corundum particles. Then stop stirring, let the beaker stand for aging for 12 hours. After the aging is completed, use a suction filtration device to filter the solution, collect the filter cake, and wash the filter cake 3 times with deionized water until the pH of the washing solution is close to 7. Finally, transfer the filter cake to a drying oven and dry it at 105 °C for 12 hours to obtain nascent zirconia-coated corundum micropowder.

[0032] Step S5: Put the nascent zirconia-coated corundum micropowder into a crucible, place it in a muffle furnace, set the calcination temperature to 1125 °C, and the calcination time to 1.5 hours. After the muffle furnace heats up to the set temperature, put the crucible in. After the calcination is completed, turn off the muffle furnace. After the temperature in the furnace naturally cools to room temperature, take out the crucible to obtain zirconia-coated corundum micropowder.

[0033] A preparation method of a special low-carbon refractory quartz dry vibrating material, comprising the following steps: Add quartz aggregate, zirconia-coated corundum micropowder, aluminum dihydrogen phosphate, lithium borate and yttrium oxide into a mixer together. Set the rotation speed of the mixer to 200 r / min and stir for 30 minutes to make each component evenly mixed, thus obtaining a sample of the special low-carbon refractory quartz dry vibrating material.

[0034] Example 3 A special low-carbon refractory quartz dry vibrating material, comprising the following components by weight: 75 parts of quartz aggregate, 25 parts of zirconia-coated corundum micropowder, 4.5 parts of aluminum dihydrogen phosphate, 0.7 part of lithium borate, and 0.8 part of yttrium oxide. The particle size of the quartz aggregate is divided into two particle sizes of 0.1 - 1.0 mm and 1.5 - 5.0 mm, and the mass ratio of the two is 1:2.

[0035] The preparation method of the zirconia-coated corundum micropowder comprises the following steps: Step S1: Weigh 3 g of zirconium oxychloride, pour it into a beaker, add 300 mL of deionized water, and stir with a glass rod until completely dissolved. Subsequently, add about 10 mL of acetic acid solution with a mass concentration of 10%, and stir evenly to obtain a zirconium oxychloride solution.

[0036] Step S2: Weigh 2 g of polyvinylpyrrolidone and put it into a beaker, add 200 mL of deionized water, and stir to completely dissolve it to prepare an aqueous solution of polyvinylpyrrolidone. Weigh 0.09 g of polymethyl methacrylate microspheres with a particle size of 0.2 μm, add them into the above aqueous solution, place the beaker in an ultrasonic oscillator, and oscillate for 15 minutes to make the microspheres evenly dispersed, thus obtaining a suspension of polymethyl methacrylate microspheres.

[0037] Step S3: Slowly pour the suspension of polymethyl methacrylate microspheres into the beaker containing the zirconium oxychloride solution, and use a magnetic stirrer to stir at a rotation speed of 300 r / min for 20 minutes to make the solution evenly mixed, thus obtaining a coating solution.

[0038] Step S4: Add 10 g of corundum micropowder into the coating solution, place the beaker in a constant temperature water bath, set the temperature to 60 °C, turn on the magnetic stirrer, and stir at a rotation speed of 400 r / min. Slowly drip an ammonia aqueous solution with a mass concentration of 25% using a dropper, and continuously monitor the pH value of the solution with a pH meter to control the pH to 4.5. After the dripping is completed, continue to stir for 30 minutes to make Zr 4+It is fully hydrolyzed into Zr(OH)4 colloid and uniformly deposited on the surface of corundum particles. Subsequently, the stirring is stopped, and the beaker is left standing for aging for 12 hours. After the aging is completed, the solution is filtered by a suction filtration device, the filter cake is collected, and the filter cake is washed 3 times with deionized water until the pH of the washing solution is close to 7. Finally, the filter cake is transferred to an oven and dried at 105 °C for 12 hours to obtain as-prepared zirconia-coated corundum fine powder.

[0039] Step S5: Put the as-prepared zirconia-coated corundum fine powder into a crucible, place it in a muffle furnace, set the calcination temperature to 1125 °C, and the calcination time to 1.5 hours. After the muffle furnace is heated to the set temperature, put the crucible in. After the calcination is completed, turn off the muffle furnace. After the temperature in the furnace naturally cools to room temperature, take out the crucible to obtain zirconia-coated corundum fine powder.

[0040] A preparation method of a special low-carbon refractory quartz dry vibrating material includes the following steps: Add quartz aggregate, zirconia-coated corundum fine powder, aluminum dihydrogen phosphate, lithium borate and yttrium oxide into a mixer together, set the rotation speed of the mixer to 200 r / min, and stir for 30 minutes to make each component mix evenly, thus obtaining a sample of the special low-carbon refractory quartz dry vibrating material.

[0041] Example 4 A special low-carbon refractory quartz dry vibrating material includes the following components by weight: 80 parts of quartz aggregate, 30 parts of zirconia-coated corundum fine powder, 6 parts of aluminum dihydrogen phosphate, 1 part of lithium borate, and 1 part of yttrium oxide. The particle size of the quartz aggregate is divided into two particle sizes of 0.1 - 1.0 mm and 1.5 - 5.0 mm, and the mass ratio of the two is 1:2.

[0042] The preparation method of the zirconia-coated corundum fine powder includes the following steps: Step S1: Weigh 4 g of zirconium oxychloride, pour it into a beaker, add 300 mL of deionized water, and stir with a glass rod until completely dissolved. Subsequently, add about 10 mL of acetic acid solution with a mass concentration of 10%, and stir evenly to obtain a zirconium oxychloride solution.

[0043] Step S2: Weigh 2 g of polyvinylpyrrolidone and put it into a beaker, add 200 mL of deionized water, and stir to completely dissolve it to prepare an aqueous solution of polyvinylpyrrolidone. Weigh 0.2 g of polymethyl methacrylate microspheres with a particle size of 0.3 μm, add them to the above aqueous solution, place the beaker in an ultrasonic oscillator, and oscillate for 15 minutes to make the microspheres disperse evenly to obtain a suspension of polymethyl methacrylate microspheres.

[0044] Step S3: Slowly pour the polymethyl methacrylate microsphere suspension into a beaker containing zirconium oxychloride solution, and use a magnetic stirrer to stir at a speed of 300 r / min for 20 minutes to make the solution evenly mixed, obtaining a coating solution.

[0045] Step S4: Add 10 g of corundum micropowder to the coating solution, place the beaker in a constant temperature water bath, set the temperature to 60 °C, turn on the magnetic stirrer, and stir at a speed of 400 r / min. Slowly drip ammonia water solution with a mass concentration of 25% using a dropper, and continuously monitor the pH value of the solution with a pH meter to control the pH to 4. After the dripping is completed, continue to stir for 30 minutes to fully hydrolyze Zr 4+ into Zr(OH)4 colloid and evenly deposit it on the surface of corundum particles. Then stop stirring, let the beaker stand for aging for 12 hours. After the aging is completed, use a suction filtration device to filter the solution, collect the filter cake, and wash the filter cake 3 times with deionized water until the pH of the washing solution is close to 7. Finally, transfer the filter cake to an oven and dry it at 105 °C for 12 hours to obtain as-prepared zirconia-coated corundum micropowder.

[0046] Step S5: Put the as-prepared zirconia-coated corundum micropowder into a crucible, place it in a muffle furnace, set the calcination temperature to 1150 °C, and the calcination time to 2 hours. After the muffle furnace is heated to the set temperature, put the crucible in. After the calcination is completed, turn off the muffle furnace. After the temperature in the furnace naturally cools to room temperature, take out the crucible to obtain zirconia-coated corundum micropowder.

[0047] A preparation method of a special low-carbon refractory quartz dry-vibrating mix includes the following steps: Add quartz aggregate, zirconia-coated corundum micropowder, aluminum dihydrogen phosphate, lithium borate, and yttrium oxide into a mixer together, set the mixer speed to 200 r / min, and stir for 30 minutes to make each component evenly mixed, thus obtaining a sample of the special low-carbon refractory quartz dry-vibrating mix.

[0048] Example 5 A special low-carbon refractory quartz dry-vibrating mix includes the following components by weight: 70 parts of quartz aggregate, 20 parts of zirconia-coated corundum micropowder, 3 parts of aluminum dihydrogen phosphate, 0.5 part of lithium borate, and 0.5 part of yttrium oxide. The particle size of the quartz aggregate is divided into two types: 0.1 - 1.0 mm and 1.5 - 5.0 mm, and the mass ratio of the two is 1:2.

[0049] The preparation method of the zirconia-coated corundum micropowder includes the following steps: Step S1: Weigh 2 g of zirconium oxychloride, pour it into a beaker, add 300 mL of deionized water, and stir with a glass rod until completely dissolved. Then add about 10 mL of acetic acid solution with a mass concentration of 10%, and stir evenly to obtain a zirconium oxychloride solution.

[0050] Step S2: Weigh 2 g of polyvinylpyrrolidone and put it into a beaker. Add 200 mL of deionized water and stir to completely dissolve it to prepare an aqueous solution of polyvinylpyrrolidone. Then weigh 0.03 g of polymethyl methacrylate microspheres with a particle size of 0.1 μm, add them to the above aqueous solution, place the beaker in an ultrasonic oscillator, and oscillate for 15 minutes to uniformly disperse the microspheres, obtaining a suspension of polymethyl methacrylate microspheres.

[0051] Step S3: Slowly pour the suspension of polymethyl methacrylate microspheres into a beaker containing zirconium oxychloride solution, and use a magnetic stirrer to stir at a speed of 300 r / min for 20 minutes to uniformly mix the solution, obtaining a coating solution.

[0052] Step S4: Add 10 g of corundum micropowder to the coating solution, place the beaker in a constant temperature water bath, set the temperature to 60 °C, turn on the magnetic stirrer, and stir at a speed of 400 r / min. Slowly drip an ammonia water solution with a mass concentration of 25% using a dropper, and continuously monitor the pH value of the solution with a pH meter to control the pH to 4.5. After the dripping is completed, continue to stir for 30 minutes to fully hydrolyze Zr 4+ into Zr(OH)4 colloid and uniformly deposit it on the surface of corundum particles. Then stop stirring, let the beaker stand for aging for 12 hours. After the aging is completed, use a suction filtration device to filter the solution, collect the filter cake, and wash the filter cake 3 times with deionized water until the pH of the washing solution is close to 7. Finally, transfer the filter cake to an oven and dry it at 105 °C for 12 hours to obtain as-prepared zirconia-coated corundum micropowder.

[0053] Step S5: Put the as-prepared zirconia-coated corundum micropowder into a crucible, place it in a muffle furnace, set the calcination temperature to 1100 °C, and the calcination time to 1 hour. After the muffle furnace heats up to the set temperature, put the crucible in. After the calcination is completed, turn off the muffle furnace. After the temperature in the furnace naturally cools to room temperature, take out the crucible to obtain zirconia-coated corundum micropowder.

[0054] A preparation method of a special low-carbon refractory quartz dry ramming mix, comprising the following steps: Add quartz aggregate, zirconia-coated corundum micropowder, aluminum dihydrogen phosphate, lithium borate, and yttrium oxide into a mixer together, set the rotation speed of the mixer to 200 r / min, and stir for 30 minutes to uniformly mix each component, thus obtaining a sample of the special low-carbon refractory quartz dry ramming mix.

[0055] Comparative Example 1 The difference between Comparative Example 1 and the example is that the zirconia-coated corundum micropowder is replaced with ordinary corundum micropowder, and the remaining steps are the same.

[0056] Comparative Example 2 The difference between Comparative Example 2 and Example 1 lies in that during the preparation process of zirconia-coated corundum micropowder, polymethyl methacrylate microspheres are not added, and the remaining steps are the same.

[0057] Comparative Example 3 The difference between Comparative Example 3 and Example 5 is that the mass ratio of corundum micropowder to zirconium oxychloride is 10:1, and the remaining steps are the same.

[0058] Comparative Example 4 The difference between Comparative Example 4 and Example 4 is that the mass ratio of corundum micropowder to zirconium oxychloride is 10:5, and the remaining steps are the same.

[0059] Comparative Example 5 The difference between Comparative Example 5 and Example 4 is that the mass ratio of corundum micropowder to zirconium oxychloride is 10:6, and the remaining steps are the same.

[0060] Performance Test: 1. Carbon content test: It is determined by high-frequency induction combustion-infrared absorption method. Grind the dry vibration material sample into fine powder, accurately weigh about 0.5 g of the sample and put it into the crucible of the high-frequency induction combustion furnace. The sample is fully burned in a pure oxygen environment by high-frequency induction heating, and the carbon element in the sample is converted into carbon dioxide gas. The generated carbon dioxide gas is purified by dust removal, water removal, etc., and then enters the infrared absorption cell. According to Lambert-Beer's law, the absorption degree of carbon dioxide to infrared light with a specific wavelength is proportional to the carbon dioxide concentration. The absorption intensity is detected by an infrared detector, and the carbon content of the sample is calculated by the data processing system. The test results are shown in Table 1.

[0061] 2. Thermal shock resistance test: According to the national standard GB / T 30873.1-2014 "Test method for thermal shock resistance of refractories", process the dry vibration material into specimens with dimensions of 50 mm×50 mm×50 mm. First, put the specimens into a high-temperature furnace and heat them to 1100°C at a heating rate of 5°C / min. After holding for 30 minutes, quickly take them out and immerse them in water at about 25°C for cooling, and the cooling time is 3 minutes. Repeat the above heating-cooling process. Take out the specimens every 5 cycles, use an ultrasonic flaw detector to detect the internal crack propagation of the specimens, and use a pressure testing machine to test their normal temperature compressive strength. Record the number of thermal shock cycles when the specimens show through cracks or the strength drops to 50% of the initial strength, so as to evaluate the thermal shock resistance of the material. The test results are shown in Table 1.

[0062] 3. Thermal Conductivity Test: The thermal conductivity of zirconia-coated corundum micropowder or corundum micropowder was measured by the Laser Flash Method. The prepared micropowder sample was pressed into a disc with a diameter of 12.7 mm and a thickness of 2 - 3 mm, and graphite coatings were sprayed on both sides to enhance infrared absorption. The thermal conductivity was tested using a thermal conductivity meter (Netzsch LFA457). Under an argon protection atmosphere, the sample was heated to 100 °C and the test was repeated 3 times. The front side of the sample was heated by a laser pulse, and the infrared detector recorded the temperature rise curve on the back side. The thermal conductivity was calculated according to the formula λ = α × C p × ρ (where α is the thermal diffusivity, C p is the specific heat capacity, and ρ is the density of the sample). The test results are shown in Table 1.

[0063] 4. Cold Crushing Strength Test: According to GB / T 5072 - 2008 "Test Method for Cold Crushing Strength of Refractory Materials", dry vibrated materials were made into cuboid specimens with dimensions of 70 mm × 30 mm × 30 mm, and 3 specimens were prepared for each group of tests. Under normal temperature conditions, the specimens were placed at the center of the bearing plate of the pressure testing machine, and pressure was uniformly applied at a rate of 1.5 MPa / s until the specimens were damaged, and the maximum pressure value F at the time of specimen failure was recorded. The cold crushing strength was calculated according to the formula σ = F / S (where S is the compression area of the specimen), and the final result was the average value of the test values of the 3 specimens. The test results are shown in Table 1.

[0064] Table 1: Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some of the technical features. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A special low-carbon refractory quartz dry vibration material, characterized in that, It comprises the following components by weight parts: 70 - 80 parts of quartz aggregate, 20 - 30 parts of zirconia-coated corundum micro-powder, 3 - 6 parts of aluminum dihydrogen phosphate, 0.5 - 1 part of lithium borate, and 0.5 - 1 part of yttrium oxide.

2. A special low-carbon refractory quartz dry vibration material according to claim 1, characterized in that, The particle size of the quartz aggregate is divided into two types: 0.1 - 1.0 mm and 1.5 - 5.0 mm, and the mass ratio of the two is 1:

2.

3. A special low-carbon refractory quartz dry vibrating material according to claim 1, characterized in that The preparation method of the zirconia-coated corundum micro-powder comprises the following steps: S1. Dissolve zirconium oxychloride in deionized water, and then add acetic acid as a hydrolysis inhibitor to obtain a zirconium oxychloride solution; S2. Add polymethyl methacrylate microspheres to an aqueous solution of polyvinylpyrrolidone, and ultrasonically oscillate to disperse evenly to obtain a polymethyl methacrylate microsphere suspension; S3. Add the polymethyl methacrylate microsphere suspension to the zirconium oxychloride solution, and stir to disperse evenly to obtain a coating solution; S4. Add corundum micropowder into the coating solution, slowly dropwise add aqueous ammonia solution under the conditions of heating and stirring, control the pH to 4 - 4.5, and make Zr 4+ gradually hydrolyze into Zr(OH)4 colloid and uniformly deposit on the surface of Al2O3 particles, stand for aging for 12 h, and obtain nascent zirconia-coated corundum micropowder through suction filtration separation, water washing and drying; S5. Place the nascent zirconia-coated corundum micro-powder in a muffle furnace for calcination to obtain the zirconia-coated corundum micro-powder.

4. A special low-carbon refractory quartz dry vibration material according to claim 3, characterized in that, In the step S2, the particle size of the polymethyl methacrylate microspheres is 0.1 - 0.3 μm.

5. A special low-carbon refractory quartz dry vibrating material according to claim 3, characterized in that, In the step S2, the dosage of the polymethyl methacrylate microspheres is 1.5 - 5 wt% of the mass of zirconium oxychloride.

6. A special low-carbon refractory quartz dry vibration material according to claim 3, characterized in that, In the step S4, the mass ratio of corundum micro-powder to zirconium oxychloride is 10:2 - 4.

7. A special low-carbon refractory quartz dry vibration material according to claim 3, characterized in that, In the step S5, the calcination temperature is 1100 - 1150 °C, and the calcination time is 1 - 2 h.

8. A preparation method of the special low-carbon refractory quartz dry vibrating material according to any one of claims 1-7, characterized in that, It comprises the following steps: Add the quartz aggregate, zirconia-coated corundum micro-powder, aluminum dihydrogen phosphate, lithium borate, and yttrium oxide into a mixer, and stir evenly to obtain the product.

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