WO2023077709A1 - 一种固相烧结碳化硅制品及其制备方法 - Google Patents

一种固相烧结碳化硅制品及其制备方法 Download PDF

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WO2023077709A1
WO2023077709A1 PCT/CN2022/081095 CN2022081095W WO2023077709A1 WO 2023077709 A1 WO2023077709 A1 WO 2023077709A1 CN 2022081095 W CN2022081095 W CN 2022081095W WO 2023077709 A1 WO2023077709 A1 WO 2023077709A1
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silicon carbide
temperature
drying
powder
solid
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French (fr)
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闫永杰
赵瑞康
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南通三责精密陶瓷有限公司
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Priority to US17/738,415 priority Critical patent/US20230134960A1/en
Publication of WO2023077709A1 publication Critical patent/WO2023077709A1/zh

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Definitions

  • the application relates to the field of engineering ceramic materials, more specifically, it relates to a solid-phase sintered silicon carbide product and a preparation method thereof.
  • Engineering ceramics refers to the general term of various ceramics used in the field of engineering technology, including structural ceramics, functional ceramics and ceramic matrix composites.
  • engineering materials have become a research hotspot in the field of materials due to their high temperature resistance, chemical corrosion resistance, wear resistance, oxidation resistance and other performance characteristics.
  • the currently widely used engineering ceramics mainly include alumina ceramics, silicon carbide ceramics, silicon nitride ceramics, and zirconia ceramics.
  • silicon carbide ceramics have excellent high-temperature strength and corrosion resistance, enabling them to work in high-temperature, high-humidity, high-oxygen, and strong acid and alkali environments for a long time, and are widely used in petrochemical, metallurgical machinery, aerospace, microelectronics , automobiles and other fields. Since silicon carbide is strongly covalently bonded, the diffusion rate is low during sintering, making it difficult to sinter densely under normal pressure. Therefore, pressureless sintering technology is currently used to produce silicon carbide ceramics. Pressureless sintering can be divided into liquid-phase sintering and solid-phase sintering.
  • solid-phase sintering uses boron (or boron carbide) and carbon as sintering aids, and achieves dense sintering through solid-phase diffusion; compared with liquid-phase sintering, due to The amount of sintering aid used in solid phase sintering is small, and no liquid phase is produced during the sintering process, so the solid phase sintered silicon carbide ceramics have better high temperature resistance strength and can be applied to heat exchange tubes.
  • the carbon source sintering aid used in the solid phase sintering process is generally phenolic resin.
  • phenolic resin can not only provide carbon source, but also play the role of binder. During the process of debonding, the presence of phenolic resin will make the tail gas contain some phenols and aldehydes, which will cause environmental pollution and increase the cost of environmental protection treatment.
  • nano-scale carbon black can also be used as a carbon source, but due to the strong aggregation between carbon black particles, it is difficult to disperse in solid powder, which increases the difficulty of processing; Moreover, the cohesiveness of carbon black is not as good as that of phenolic resin, which leads to poor formability of the green body and affects the performance of the product.
  • a method for preparing a silicon carbide heat exchange tube is disclosed, the steps of which include batching, mixing, mud refining, extrusion molding, drying, debonding and high-temperature sintering; in order to improve the uniformity inside the embryo body, reduce the pressing
  • the appearance of cracks and delamination during the process usually adds stale processes between mud refining and extrusion molding. After mud refining, put the mud stale for a period of time, and then extrude and dry the mud. In the process, the stale mud material has a better degree of wetting, which can improve its forming performance and is beneficial to subsequent extrusion molding.
  • the application provides a solid-phase sintered silicon carbide product and a preparation method thereof.
  • the present application provides a method for preparing a solid-phase sintered silicon carbide product, which adopts the following technical scheme:
  • a method for preparing a solid-phase sintered silicon carbide product comprising the steps of:
  • Raw material grinding mix micron-sized silicon carbide powder with boron-containing sintering aid and wet grind to obtain a slurry with a particle size of 0.4-0.8 ⁇ m;
  • Spray granulation add water-soluble carbon black and binder to the slurry, stir evenly, and spray granulate to obtain silicon carbide granulated powder;
  • Stale stale the wet powder to obtain stale material
  • Post-processing put the stale material through mud refining, extrusion, drying and heat treatment.
  • the micron-scale particle size is 3-10 ⁇ m.
  • Silicon carbide powder is the main raw material of silicon carbide products, and its purity and particle fineness affect the performance of silicon carbide ceramic products. Since silicon carbide has a lot of metal impurities, manufacturers who produce silicon carbide powder need to perform acid-base purification, grinding, and drying to obtain submicron silicon carbide powder products; then ceramic manufacturers directly purchase this submicron Grade silicon carbide powder is used as the main raw material of silicon carbide ceramics, which makes the cost higher.
  • the silicon carbide powder of the present application selects micron-sized silicon carbide powder with a particle size of 3-10 ⁇ m. Silicon carbide with this particle size has been widely used in the cutting of silicon wafers in the photovoltaic industry.
  • This application uses wet grinding.
  • silicon carbide is mixed with sintering aids.
  • the fineness of silicon carbide powder and sintering aids and the uniformity of the mixture can be improved.
  • wet grinding After wet grinding The obtained slurry can be directly used in the subsequent spray granulation without grinding the silicon carbide powder separately and then drying, which simplifies the process and reduces the processing cost of the powder; through the selection of raw materials and the cooperation of the process, it can be greatly Significantly reduce the cost of main raw materials.
  • the traditional sintering aid boron carbide has a large particle size and a high dosage, which will cause insufficient density of silicon carbide products.
  • silicon carbide heat exchange tubes because they are used in a high-pressure environment, in this Under the circumstances, the problem of fracture is easy to occur, which affects its performance; and the present application grinds it together with silicon carbide to reduce the fineness of the sintering aid boron carbide, improve its activity, and increase the density of silicon carbide products, thereby increase its strength.
  • the carbon source of this application uses carbon black to replace the traditional phenolic resin carbon source, and there is no problem of tail gas treatment, thus reducing the cost of environmental protection treatment.
  • the phenolic resin itself also acts as a binder. Therefore, when carbon black is used as a carbon source in this application, a binder and a plasticizer are added to improve the strength of the silicon carbide material.
  • the silicon carbide powder is directly mixed with the sintering aid, but due to the extremely strong aggregation between the carbon black particles, it is difficult to disperse in the solid powder. Therefore, the slurry in the present application after grinding Adding water-soluble carbon black can improve the dispersibility of carbon black.
  • the obtained wet powder is first stale, and then through mud refining, extrusion, drying, debonding, and sintering; it is different from the traditional mud refining first, then stale, extrusion, drying and other processes, and the staleness is adjusted.
  • the sequence of operations in a process is first stale, and then through mud refining, extrusion, drying, debonding, and sintering; it is different from the traditional mud refining first, then stale, extrusion, drying and other processes, and the staleness is adjusted.
  • the purpose of refining mud is to remove air, make the mud structure more uniform, and help improve the plasticity and compactness of the mud; and the role of stale is to make the interior of the green body uniform, so as to reduce cracks during pressing. After being aged, it can achieve a higher degree of wetting and improve the molding performance of the mud; therefore, in related technologies, the mud is usually extruded and solidified after being aged for dozens of hours.
  • the contriver finds, when the mud material is stale after mud refining, the drying speed of the mud material surface and the inside are inconsistent, and the surface of the mud material is easy to harden and hard particles appear; Better performance, the surface of the mud is not easy to harden to produce hard particles, which can improve the uniformity and plasticity of the mud, and is conducive to improving the plasticity of the mud in the mud refining process and the density during sintering.
  • this application directly decomposes the wet powder first, and then performs continuous mud refining, extrusion, and solidification, which shortens the intermittent pause in the subsequent process and realizes the continuous production of mud refining, extrusion, and drying processes, greatly improving The production efficiency is improved and the production cost is reduced.
  • the amount of the boron-containing sintering aid is 0.2-0.5 wt% of the weight of the micron-sized silicon carbide powder; the amount of the water-soluble carbon black is 0.5-3.0 wt% of the weight of the micron-sized silicon carbide powder.
  • this application uses the carbothermal reduction reaction of carbon black to react with free silicon and silicon dioxide to generate silicon carbide, so as to reduce the impurity content and improve product quality.
  • the boron source sintering aid is usually boron carbide or boron powder.
  • the application directly adds the boron source sintering aid during the grinding process, which can make the particle size of the sintering aid smaller and more uniformly dispersed; taking boron carbide as an example, Boron carbide is added to the co-grinding of silicon carbide, so that the particle size of boron carbide reaches submicron level, and the activity is greatly increased, so that the amount of boron carbide is reduced from the currently commonly used 0.6-1.0% to 0.2-0.5%, which is greatly reduced. The amount of sintering aids is reduced, thereby reducing the cost of sintering aids.
  • the plasticizer is composed of a high molecular weight plasticizer with a molecular weight of 150,000-200,000 and a low molecular weight plasticizer with a molecular weight of 4,000-6,000.
  • the present application replaces the traditional phenolic resin with carbon black, which can solve the pollution problem caused by the phenolic resin.
  • the phenolic resin itself also functions as a binder, and although the present application has added a binder, compared with the phenolic resin, its bonding effect is limited, reducing the molding of the blank. properties, leading to a decrease in the strength of silicon carbide products; therefore, the application improves the plasticizer by combining high molecular weight plasticizers with low molecular weight plasticizers and cooperating with the mud refining process to improve the strength of silicon carbide products. Plasticity and compactness, thereby improving the problem of insufficient strength in the absence of phenolic resin.
  • the aging temperature is 5-10° C.
  • the humidity is 40-50%
  • the time is 12-24 hours.
  • the traditional process is usually to stale the kneading mud in an environment with a temperature of 20-40°C and a humidity of 80-90%, but this application adopts the above-mentioned technical solution to stale in a low-temperature and medium-humidity environment.
  • it can improve the mixing uniformity of the various raw materials of the mud material, and avoid affecting the subsequent mud refining and other processes due to the excessive viscosity of the system; Improve the formability of products.
  • the drying includes primary drying, the primary drying is far-infrared drying, the drying temperature is 80-100° C., and the material conveying speed is 0.5-1 m/min.
  • the traditional curing and drying process mostly uses microwave curing.
  • Microwave curing is the simultaneous curing of the inside and outside of the material, and the curing and drying speed is faster, but this will cause the ceramic products to be prone to delamination.
  • this application adopts the far-infrared curing and drying technology, which only dries the surface of the material to play the role of surface shaping, and then cooperates with subsequent slow drying, which can reduce the phenomenon of delamination of ceramic products. It is beneficial to improve the uniformity and compactness inside the product, and improve its mechanical properties.
  • the drying includes secondary drying after the primary drying, the secondary drying is hot air drying, the drying temperature is 120-150° C., and the drying time is 15-20 hours.
  • the material when the material is cured, it plays the role of surface shaping, and then dried by hot air, which can slowly dry the inside of the material, which is beneficial to reduce the delamination of ceramic products and improve the mechanical properties of the product.
  • the heat treatment includes debinding treatment, carbothermal reduction treatment and high temperature sintering;
  • the carbothermal reduction treatment temperature is 1400-1600°C, and the holding time is 0.5-2h.
  • the heat treatment comprises the steps of:
  • Debonding treatment raise the temperature of the material to 600-900°C and keep it warm for 1-3h;
  • Carbothermal reduction treatment raise the temperature of the debonded material to 1400-1450°C, then raise the temperature to 1550-1600°C at a rate of 0.5-2°C/min, and keep it at 1550-1600°C for 0.5-2h;
  • High-temperature sintering raise the temperature of the carbothermal reduction-treated material to 1950-2150°C, and keep it warm for 2-3 hours.
  • the heat treatment of materials in the related art generally includes two temperature zones, that is, debonding treatment and high-temperature sintering, while the heat treatment of this application can be divided into three temperature zones:
  • the temperature of the material is raised to 600-900°C, and the debonding treatment is carried out at this temperature to remove the polymer additive;
  • the temperature is first raised to 1400-1450°C, and then the temperature is raised to 1550-1600°C at a speed of 0.5-2°C/min.
  • the free silicon on the surface of the silicon powder reacts with silicon dioxide to form silicon carbide, which reduces the impurity content and makes the carbon reduction reaction more complete, thereby improving the sintering performance and obtaining high-density products;
  • the sintering section is sintered at a temperature of 1950-2150°C. Due to the smaller particle size and lower content of boron carbide in this application, the sintering temperature can be lowered by 30-50% compared with the traditional sintering temperature under the premise of satisfying sintering self-compacting. °C.
  • the spray granulation adopts centrifugal spray granulation
  • the inlet temperature is 220-230°C
  • the outlet temperature is 95-100°C.
  • the present application provides a silicon carbide product prepared by a method for preparing a solid-phase sintered silicon carbide product.
  • This application uses commercially stocked silicon carbide cutting powder as raw material, and the cost of its raw silicon carbide powder is low; compared with the currently commonly used submicron silicon carbide as raw material, this application does not require carbonization
  • Silicon carbide raw powder suppliers additionally carry out acid-base purification treatment, grinding, and drying treatment on silicon carbide raw powder.
  • This application directly uses micron-sized silicon carbide raw powder as raw material, and directly wet-grinds it into sub-micron-sized powder for subsequent Processing removes the acid-base purification process and drying process, which can reduce the processing cost of the powder, thereby greatly reducing the cost of the main raw material.
  • the boron source sintering aids are directly added during the grinding process, which can make the particle size of the sintering aids smaller and more uniformly dispersed, and improve the activity of the boron source sintering aids. Reduce its dosage, thereby reducing the cost of sintering aids.
  • the carbon source sintering aid of the present application is carbon black, which is less likely to produce polluting gas during debonding than the phenolic resin carbon source, which reduces the cost of environmental protection treatment.
  • High production efficiency the preparation method of the present application is first aged, then through the processes of mud refining, extruding, drying, etc., which is different from the traditional process of refining mud first, then aging, extruding, drying, etc., and the aging process has been adjusted.
  • the order in the process shortens the intermittent pause in the subsequent process, realizes the continuous production of mud refining, extrusion and drying processes, and greatly improves the production efficiency.
  • This application adds boron source sintering aids to grind together while grinding silicon carbide, which can improve the fineness and activity of boron source sintering aids, which is beneficial to promote solid-phase sintering and increase the density of silicon carbide products , to increase its strength;
  • This application uses carbon black as a sintering aid, and the plasticizer obtained by compounding high molecular weight and low molecular weight, combined with the mud refining process, can improve the plasticity and compactness of silicon carbide products, thereby improving the problem of insufficient strength when there is no phenolic resin ;
  • the wet powder is aged first. Since the wet powder has better wettability, the surface of the mud is not easy to harden to produce hard particles, which can improve the uniformity and plasticity of the mud, and is beneficial to improve the mud refining process. Plasticity of mud and density during sintering;
  • the drying technology of this application adopts the method of combining far-infrared curing drying and hot air drying. Compared with traditional microwave curing drying, this application uses far-infrared curing drying technology to only dry the surface of the material and play the role of surface shaping. , and then through the subsequent slow drying, it can reduce the delamination of ceramic products, which is beneficial to improve the mechanical properties of products;
  • a carbon reduction section is added.
  • the thermal reduction reaction of carbon can be promoted, so that carbon and silicon carbide powder
  • the free silicon and silicon dioxide on the surface react to form silicon carbide, reduce the impurity content, and make the carbon reduction reaction more complete, thereby improving the sintering performance and obtaining high-density products.
  • the products are widely used: the silicon carbide products prepared by the preparation method of the present application are widely used, and can be used to prepare heat exchange tubes, roller bars, square beams, and micro-reaction tubes.
  • the sintered density of extruded silicon carbide products prepared by the process of the present application can reach more than 3.10 g/cm 3 , and the highest can reach 3.16 g/cm 3 , which greatly improves the performance of extruded silicon carbide products sintered in solid state.
  • a method for preparing a solid-phase sintered silicon carbide product comprising the steps of:
  • micron-sized silicon carbide powder with a particle size of 3-10 ⁇ m as the main raw material boron-containing sintering aids with a particle size of 3-10 ⁇ m and water-soluble carbon black as solid-phase sintering aids; binder , plasticizer and lubricant as functional additives; wherein, the amount of boron-containing sintering aid is 0.2-0.5wt% of the weight of micron-sized silicon carbide powder, and the amount of water-soluble carbon black is 0.5% of the weight of micron-sized silicon carbide powder.
  • the plasticizer consists of a high molecular weight plasticizer with a molecular weight of 150,000-200,000 and a low molecular weight plasticizer with a molecular weight of 4000-6000 Composition, the weight ratio of high molecular weight plasticizer and low molecular weight plasticizer is 1:1-4;
  • Raw material grinding first put micron-sized silicon carbide powder and boron-containing sintering aid into a vertical or horizontal grinding machine, and use water as a solvent to grind it to obtain a particle size of 0.4-0.8 ⁇ m and a solid content of 40- 50wt% slurry;
  • Spray granulation add water-soluble carbon black and binder to the slurry, stir evenly, adopt centrifugal spray granulation, the inlet temperature is 220-230°C, and the outlet temperature is 95-100°C to obtain silicon carbide Granulated powder;
  • S5. Stale put the wet powder under the conditions of temperature 5-10°C and humidity 40-50%, seal and stale for 12-24 hours to obtain stale material;
  • Mud training put the stale material at a temperature of 20-30°C, a pressure of 1.0-1.5 MPa, and a vacuum of -0.08 to -0.1 MPa for 20-30 minutes, and repeat the mud training for 3-5 times to obtain Practicing mud;
  • Heat treatment place the dried silicon carbide blank in a high-temperature resistance furnace, and perform heat treatment under the protection of an argon atmosphere.
  • the heat treatment includes debonding treatment, carbothermal reduction treatment and sintering treatment;
  • Debonding treatment set the temperature of the high-temperature resistance furnace to raise the temperature to 300°C at a rate of 2-4°C/min, then raise the temperature to 600-650°C at a rate of 0.5-1°C/min, and then increase the temperature at a rate of 1-2°C Heat up to 850-900°C at a speed of 1/min, and keep warm at 850-900°C for 1-3h;
  • Carbothermal reduction treatment heat up to 1400-1450°C at a speed of 2-4°C/min, then heat up to 1550-1600°C at a speed of 0.5-2°C/min, and hold at a temperature of 1550-1600°C for 0.5-2h ;
  • High-temperature sintering heat up to 1950°C at a speed of 2-4°C/min, then rise to 2050-2150°C at a speed of 1-2°C/min, and hold for 2-3 hours to obtain sintered products;
  • the method of the present application can be used to prepare silicon carbide heat exchange tubes, silicon carbide rollers, silicon carbide square beams, silicon carbide micro-reaction tubes, and the like.
  • the silicon carbide heat exchange tubes with an outer diameter of 25mm and a wall thickness of 3.0mm can be resistant to temperatures above 1500°C;
  • the outer diameter that the method makes is 38mm, the silicon carbide roller bar and the square beam that wall thickness is 5.0mm, under the concentrated force test of 100MPa, pass rate can reach more than 98%;
  • Adopt the outer diameter that the method of the present application makes is The micro-reaction tube with a thickness of 6mm and a wall thickness of 0.5mm can withstand a pressure of more than 150BAR.
  • the silicon carbide powder has a particle size of 3-10 ⁇ m, a purity of >98.5%, and a content of metallic iron impurities ⁇ 0.1%;
  • boron-containing sintering aids can be selected from boron or boron carbide, and the particle size of the following examples is 3-10 ⁇ m boron carbide;
  • the water-soluble carbon black was purchased from Germany ORION Orion, the model is SPECIAL BLACK 6;
  • the binder is polyvinyl alcohol, purchased from Anhui Wanweifu New Material Co., Ltd., the model is PVA26-99;
  • the lubricant can be selected Oleic acid or glycerin, the following examples all select glycerin;
  • Plasticizer is made up of the low molecular weight plasticizer that molecular weight is 15-20 ten thousand and the low molecular weight plasticizer that molecular weight is 4000-6000, and high molecular weight plasticizer can be molecular weight Polyethylene oxide with
  • each raw material in embodiment 1-8 is shown in Table 1. As shown in Table 1, the main difference of Examples 1-8 is that the proportioning ratio of raw materials is different.
  • Embodiment 1 is taken as an example below for description.
  • the preparation method of the silicon carbide product provided in Example 1 is as follows:
  • Spray granulation add 1 kg of water-soluble carbon black and 1 kg of binder to the slurry of S1, stir evenly, adopt centrifugal spray granulation, the inlet temperature is 225°C, and the outlet temperature is 98°C to obtain silicon carbide Granulated powder;
  • Stale put the wet powder under the condition of temperature at 5°C and humidity at 40%, seal and stale for 24 hours to obtain stale material;
  • Heat treatment place the dried silicon carbide blank in a high-temperature resistance furnace, and perform heat treatment under the protection of an argon atmosphere.
  • the heat treatment includes debonding treatment, carbothermal reduction treatment and high-temperature sintering;
  • Debonding treatment set the temperature of the high-temperature resistance furnace to raise the temperature to 300°C at a rate of 3°C/min, then to 600°C at a rate of 0.6°C/min, and then to 900°C at a rate of 1.5°C/min , kept at a temperature of 900°C for 2h;
  • Carbothermal reduction treatment includes the following steps: continue to raise the temperature to 1400°C at a rate of 2°C/min, then raise the temperature to 1550°C at a rate of 0.5°C/min, and keep the temperature at 1550°C for 2 hours;
  • High-temperature sintering then raise the temperature to 1950°C at a rate of 3°C/min, then raise the temperature to 2100°C at a rate of 1.5°C/min, and keep at 2100°C for 2.5 hours to obtain a sintered product;
  • the sintered product is cut and finished with internal and external chamfering to obtain a silicon carbide heat exchange tube with an outer diameter of 14 mm and a wall thickness of 1.5 mm.
  • the consumption table of raw material in the embodiment 1-8 of table 1 (unit: kg)
  • Example 6 The difference between this example and Example 6 lies in S4.
  • the wet powder is sealed and aged for 12 hours at a temperature of 10° C. and a humidity of 50%, to obtain an aged material.
  • Example 6 The difference between this example and Example 6 lies in S4.
  • the wet powder is sealed and aged for 24 hours at a temperature of 20° C. and a humidity of 80%, to obtain an aged material.
  • the primary drying is microwave drying
  • the microwave drying frequency is 2450MHz
  • the primary drying temperature is 90°C
  • the primary drying time is 20min
  • the secondary drying is hot air drying
  • the secondary drying temperature The temperature is 120°C, and the secondary drying time is 12 hours.
  • Example 6 The difference between this example and Example 6 is that in S7, the plain blank is dried in a hot air drying oven at a drying temperature of 120° C. and a drying time of 20 hours to obtain a dried silicon carbide blank.
  • the carbothermal reduction treatment includes the following steps: continue to raise the temperature to 1500°C at a rate of 4°C/min, and then raise the temperature to 1600°C at a rate of 2°C/min. °C temperature for 0.5h.
  • the carbothermal reduction treatment includes the following steps: continue to raise the temperature to 1400°C at a rate of 2°C/min, and then raise the temperature to 1550°C at a rate of 3°C/min, and at 1550°C Incubate at a temperature of °C for 2h.
  • Debonding treatment set the temperature of the high-temperature resistance furnace to raise the temperature to 300°C at a rate of 3°C/min, then to 600°C at a rate of 0.6°C/min, and then to 900°C at a rate of 1.5°C/min , kept at a temperature of 900°C for 2h;
  • High-temperature sintering Then raise the temperature from 900°C to 1950°C at a rate of 3°C/min, then increase the temperature to 2100°C at a rate of 1.5°C/min, and keep at 2100°C for 2.5 hours to obtain a sintered product.
  • Example 1 The difference between this comparative example and Example 1 is that S4, S5, S6, S7, S8, other steps and process parameters are the same as Example 1; the order of aging and refining mud is exchanged, as follows:
  • Mud refining the wet powder obtained in S3 was conditioned for 25 minutes at a temperature of 25° C., a pressure of 1.0 MPa, and a vacuum of -0.08 MPa, and repeated 4 times of mud refining to obtain a mud for refining;
  • S5. Seal and stale the mud obtained in S4 for 24 hours at a temperature of 20°C and a humidity of 80% to obtain a stale material;
  • Extrusion Extrude the stale material under the conditions of extrusion pressure of 1.0MPa, vacuum degree of -0.08MPa, and extrusion speed of 0.5m/min. After synchronous speed measurement and synchronous fixed-length cutting, the plain material is obtained. Embryo;
  • Heat treatment place the dried silicon carbide blank in a high-temperature resistance furnace, and perform heat treatment under the protection of an argon atmosphere.
  • the heat treatment includes debonding treatment and high-temperature sintering;
  • Debonding treatment heat up to 300°C at a rate of 3°C/min, then to 600°C at a rate of 0.6°C/min, and then to 900°C at a rate of 1.5°C/min, at a temperature of 900°C Keep warm for 2 hours;
  • High-temperature sintering Then raise the temperature from 900°C to 1950°C at a rate of 3°C/min, then increase the temperature to 2100°C at a rate of 1.5°C/min, and keep at 2100°C for 2.5 hours to obtain a sintered product.
  • Mud refining the wet powder obtained in S3 was conditioned for 25 minutes at a temperature of 25° C., a pressure of 1.0 MPa, and a vacuum of -0.08 MPa, and repeated 4 times of mud refining to obtain a mud for refining;
  • S5 stale: under the condition that temperature is 5 DEG C, humidity is 40% with the kneading mud obtained in S4, seal and stale for 24 hours, obtain stale material; Extrude, dry, heat treatment and process identical with embodiment 6 through stale material Finishing is enough.
  • Table 2 The performance test table of the silicon carbide heat exchange tubes of Examples 1-16 and Comparative Examples 1-2
  • Example 1 in combination with Example 1 and Comparative Example 1, it can be seen that compared with the traditional method for preparing solid-phase sintered silicon carbide products, the volume density, hardness, Fracture toughness, bending strength and compressive strength are significantly improved, indicating that the preparation method of the present application can significantly improve the sintering performance of silicon carbide products, thereby significantly improving the mechanical properties of the products.
  • the addition of carbon can react with free silicon and silicon dioxide on the surface of silicon carbide powder, reduce the impurity content, improve the surface energy and activity of the powder, promote the diffusion of boron carbide, and promote the sintering of silicon carbide. Thereby improving the compactness of sintered products.
  • carbon content continues to increase, excessive carbon will inhibit the sintering of silicon carbide, resulting in a decrease in the compactness and mechanical properties of the sintered product.
  • Example 5 In combination with Example 4, Example 5, Example 6 and Example 1, it can be seen that the amount and type of plasticizer have a great influence on the mechanical properties of the product.
  • the addition of plasticizer can improve the plasticity of the mud, which is beneficial to improve its formability and sintering performance, thereby improving the compactness and mechanical properties of sintered products.
  • the plasticity of the system can be improved, and in conjunction with the mud refining process, the uniformity of mud mixing can be improved, and the required bonding strength can be provided, thereby Improve the sintering compactness of the product and improve the mechanical properties of the product.
  • the dosage ratio of high molecular weight plasticizer and low molecular weight plasticizer is 1:1-4, the obtained sintered product has better mechanical properties.
  • Example 6 Example 9, Example 10 and Comparative Example 2
  • staleness is to improve the wettability of wet powder, improve the uniformity of mud mixing with binders, plasticizers and other raw materials, reduce the hardened particles on the surface of mud, improve the plasticity in the mud refining process and The density during sintering can significantly improve the mechanical properties of the product.
  • Example 6 From Example 6, Example 12 and Example 13, it can be seen that the drying process has a great influence on the mechanical properties of the product. Improper drying will cause quality problems such as delamination and cracking of the product during sintering, which will affect the mechanical properties of the product.
  • the drying treatment adopts a combination of far-infrared drying and hot air drying, which can improve the uniformity of the inner and outer drying of the blank, avoid the occurrence of delamination and cracks, reduce the internal defects of the product, and help improve the mechanical properties of the product .
  • Example 6 Example 14, Example 15 and Example 16 it can be seen that the heat treatment process has a great influence on the mechanical properties of the product.
  • the three-stage heat treatment process is adopted, and in the carbothermal reduction section, the heating rate is reduced, which can prolong the carbon reduction reaction time and make the carbon thermal reduction reaction more complete, which is conducive to improving the powder activity and promoting The progress of sintering improves the density and mechanical properties of sintered products.

Abstract

本申请涉及工程陶瓷材料领域，具体公开了一种固相烧结碳化硅制品及其制备方法。一种固相烧结碳化硅制品的制备方法，包括如下步骤：原料研磨：将微米级碳化硅粉末与含硼烧结助剂混合并湿法研磨，得到浆料；喷雾造粒：向浆料中加入水溶性炭黑和粘结剂，搅拌均匀，经过喷雾造粒，得到碳化硅造粒粉体；混料；陈腐：将混料得到的湿粉经过陈腐，得到陈腐料；后处理：将陈腐料经过练泥、挤出、干燥、热处理即可。本申请的制备方法制备的碳化硅制品可用作换热管、辊棒、方梁、微反应管等，其具有制品烧结密度高、抗压强度大、韧性高的优点；另外，本申请的制备方法具有生产成本低、生产效率高的优点。

Description

一种固相烧结碳化硅制品及其制备方法 技术领域
本申请涉及工程陶瓷材料领域，更具体地说，它涉及一种固相烧结碳化硅制品及其制备方法。
背景技术
工程陶瓷是指应用于工程技术领域的各种陶瓷的总称，包括结构陶瓷、功能陶瓷和陶瓷基复合材料。近年来，随着科技的进步以及工业的发展，工程材料以其耐高温性、耐化学腐蚀性、耐磨性、抗氧化性等性能特点，成为材料领域研究的热点。目前应用的比较广泛的工程陶瓷主要有氧化铝陶瓷、碳化硅陶瓷、氮化硅陶瓷以及氧化锆陶瓷等。
其中，碳化硅陶瓷具有优异的高温强度以及耐腐蚀性，使其能够长期处于高温、高湿、高氧以及强酸强碱的环境下工作，广泛应用于石油化工、冶金机械、航空航天、微电子、汽车等领域。由于碳化硅为强共价键结合，烧结时扩散速率低，使其很难在常压下烧结致密，因此目前多采用无压烧结技术来生产碳化硅陶瓷。无压烧结可以分为液相烧结和固相烧结，其中，固相烧结是以硼(或碳化硼)和碳为烧结助剂，通过固相扩散实现致密烧结；相较于液相烧结，由于固相烧结的烧结助剂用量少，且烧结过程中不产生液相，因此固相烧结的碳化硅陶瓷具有更好的耐高温强度，可在换热管上应用。
在固相烧结工艺中使用的碳源烧结助剂一般为酚醛树脂，酚醛树脂作为一种高分子材料，既能提供碳源，又能起到粘结剂的作用，但是在碳化硅制品的制备中需要进行脱粘处理，在脱粘处理的过程中，因酚醛树脂的 存在会使尾气中含有部分酚类和醛类物质，产生环境污染问题，增加环保处理的成本。为了解决酚醛树脂的污染问题，也可以采用纳米级炭黑作为碳源，但是由于炭黑颗粒之间具有极强的聚集性，使其在固体粉末中难以分散，这又增加了加工的困难；并且炭黑的粘结性又不如酚醛树脂，导致胚体的成型性变差，制品的性能受到影响。
相关技术中，公开了一种碳化硅换热管的制备方法，其步骤包括配料、混合、练泥、挤出成型、干燥、脱粘和高温烧结；为了提高胚体内部的均匀性，减少压制过程中的裂纹、分层现象的出现，通常会在练泥和挤出成型之间增加陈腐工序，在练泥后，将泥料陈腐放置一段时间后，再对泥料进行挤出、干燥等工序，陈腐后的泥料具有更好的润湿程度，可以提高其成型性能，有利于后续的挤出成型。但是陈腐通常需要经过几十个小时甚至几天，这不仅使得生产周期延长，而且使得练泥、挤出成型、干燥等工序之间有较长的间隔，无法连续进行，不利于连续化生产的进行，影响生产效率。
此外，在碳化硅制品应用于换热管时，由于换热管长期在高温、高压的环境下使用，这就对其密度以及强度有更高的要求。为了获得高性能的碳化硅制品，另一相关技术将经过混料、陈腐、挤出成型、干燥后的坯体经过等静压成型处理后，再进行高温烧结，然而等静压成型设备成本高，不易自动化生产，且生产效率较低，增加等静压成型后会导致生产成本的进一步提高。
发明内容
为了解决上述问题，本申请提供一种固相烧结碳化硅制品及其制备方 法。
第一方面，本申请提供一种固相烧结碳化硅制品的制备方法，采用如下的技术方案：
一种固相烧结碳化硅制品的制备方法，包括如下步骤：
S1、原料研磨：将微米级碳化硅粉末与含硼烧结助剂混合并湿法研磨，得到粒径为0.4-0.8μm的浆料；
S2、喷雾造粒：向浆料中加入水溶性炭黑和粘结剂，搅拌均匀，经过喷雾造粒，得到碳化硅造粒粉体；
S3、混料：将碳化硅造粒粉体与塑化剂混合均匀后，加入润滑剂以及水，搅拌均匀后，得到湿粉；
S4、陈腐：将湿粉经过陈腐，得到陈腐料；
S5、后处理：将陈腐料经过练泥、挤出、干燥、热处理即可。
优选的，微米级的粒径为3-10μm。
碳化硅粉体作为碳化硅制品的主原料，其纯度、颗粒细度影响着碳化硅陶瓷制品的性能。由于碳化硅的的金属杂质比较多，生产碳化硅粉末的厂家需要对其进行酸碱纯化处理、研磨、干燥，以得到亚微米级的碳化硅粉末成品；然后陶瓷制造商直接采购这种亚微米级的碳化硅粉末作为碳化硅陶瓷的主原料，使得成本较高。通过采用上述技术方案，本申请的碳化硅粉末选择粒径为3-10μm的微米级碳化硅粉末，这种粒径的碳化硅曾大量应用于光伏行业硅片的切割，由于近年来光伏切割逐渐被金刚线切割取代，导致市场上存在大量过剩的粒径为3-10μm的碳化硅粉末，因此相较于亚微米级的碳化硅，粒径为3-10μm的碳化硅粉末的成本较低，可以降 低主原料的成本。
本申请采用湿法研磨，在研磨的过程，将碳化硅与烧结助剂混合，一方面可以提高碳化硅粉末与烧结助剂的细度以及二者混合的均匀性，另一方面经过湿法研磨后得到的浆料可以直接用于后续的喷雾造粒，不需要单独将碳化硅粉末研磨后再干燥处理，简化了工序，降低粉体的处理成本；通过原料的选择以及工艺的配合，能够大幅度降低主原料的成本。
此外，传统的烧结助剂碳化硼的粒径较大、用量较高，会造成碳化硅制品的密度不足，对于碳化硅换热管来说，由于是在高压力的环境下使用，在这种情况下很容易出现断裂的问题，影响其使用性能；而本申请通过将其与碳化硅共同研磨，以降低烧结助剂碳化硼的细度，提高其活性，可以提高碳化硅制品的密度，从而提高其强度。
本申请的碳源选用炭黑代替传统的酚醛树脂碳源，不存在尾气处理问题，因此降低了环保处理的成本。由于酚醛树脂除了作为碳源外，其自身还会起到粘结剂的作用，因此本申请以炭黑为碳源时，通过添加粘结剂和塑化剂，以提高碳化硅材料的强度。相关技术中，是将碳化硅粉体与烧结助剂直接混合，但是由于炭黑颗粒之间具有极强的聚集性，使其在固体粉末中难以分散，因此，本申请在研磨后的浆料中加入水溶性炭黑，可以提高炭黑的分散性。
本申请的工序将得到的湿粉先经过陈腐后，再经过练泥、挤出、干燥、脱粘、烧结；区别于传统的先练泥，再陈腐、挤出、干燥等工序，调整了陈腐工序在工艺中的顺序。
在陶瓷生产中，练泥是为了排除空气，使得泥料组织更加均匀，有利 于提高泥料的可塑性和致密性；而陈腐的作用是为了使得坯体的内部均匀，以减少压制时的裂纹，经过陈腐后可以达到较高的润湿程度，提高泥料的成型性能；因此，相关技术一般在练泥后，再陈腐放置几十个小时后，再对泥料进行挤出、固化等工序。但是，发明人发现，泥料在练泥后进行陈腐时，泥料表面和内部干燥速度不一致，泥料表面容易硬化而出现硬颗粒；而本申请先对湿粉进行陈腐，湿粉的润湿性更好，泥料的表面不易硬化产生硬颗粒，可以提高泥料的均匀性以及塑性，有利于提高练泥工序中泥料的可塑性以及烧结时的致密度。此外，本申请直接先对湿粉进行陈腐后，再进行连续化的练泥、挤出、固化，缩短了后续工序中的间歇停顿，实现练泥、挤出、干燥工序的连续化生产，大大提高了生产效率，降低了生产成本。
优选的，所述含硼烧结助剂的用量为微米级碳化硅粉末重量的0.2-0.5wt％；所述水溶性炭黑的用量为微米级碳化硅粉末重量的0.5-3.0wt％。
通过采用上述技术方案，由于本申请的碳化硅的原料未经过额外的酸碱洗工序的处理，其原料中的游离硅、二氧化硅的含量会增加，会影响制品的性能，为了解决这一问题，本申请通过炭黑的碳热还原性反应，使其与游离硅、二氧化硅反应，生成碳化硅，以降低杂质含量，提高产品质量。
硼源烧结助剂通常为碳化硼或硼粉，本申请在研磨的过程中直接加入硼源烧结助剂，可以使得烧结助剂的粒径更小、分散的更加均匀；以碳化硼为例，在碳化硅研磨时加入碳化硼共同研磨，使得碳化硼的粒径达到亚微米级，活性大幅度增加，使得碳化硼的用量从目前常用的0.6-1.0％降低 至0.2-0.5％，大大降低了烧结助剂的用量，从而降低了烧结助剂的成本。
优选的，所述塑化剂由分子量为15-20万的高分子量塑化剂和分子量为4000-6000的低分子量塑化剂组成。
通过采用上述技术方案，本申请以炭黑代替传统的酚醛树脂，可以解决酚醛树脂带来的污染问题。但是由于酚醛树脂除了作为碳源外，其自身还会起到粘结剂的作用，而本申请虽然加入了粘结剂，但是其相较于酚醛树脂，粘结作用有限，降低素胚的成型性，导致碳化硅制品的强度下降；因此，本申请通过对塑化剂进行改进，通过高分子量的塑化剂与低分子量的塑化剂相配合，配合练泥工序，以提高碳化硅制品的可塑性和致密性，从而改善缺少酚醛树脂时强度不足的问题。
优选的，所述陈腐的温度为5-10℃、湿度为40-50％、时间为12-24h。
传统的工艺通常是将练泥料在温度为20-40℃、湿度为80-90％的环境中进行陈腐，而本申请通过采用上述技术方案，在低温、中湿的环境中进行陈腐，一方面可以提高泥料各原料混合的均匀性，避免因体系粘度过大而影响后续的练泥等工序，另一方面低温、中湿环境也有利于本申请的塑化剂的粘结作用，可以提高制品的成型性。
优选的，所述干燥包括一次干燥，所述一次干燥为远红外干燥，干燥温度为80-100℃，物料传送速度为0.5-1m/min。
传统的固化干燥工序多采用微波固化，微波固化是物料的内部和外部同时固化，其固化干燥速度较快，但是这会导致陶瓷制品易出现分层的现象。通过采用上述技术方案，本申请采用远红外固化干燥技术，只对物料的表面进行干燥，起到表面定型的作用，然后再经过后续的缓慢 干燥的配合，可以降低陶瓷制品分层的现象，有利于提高制品内部的均匀性以及致密性，提高其力学性能。
优选的，所述干燥包括一次干燥之后的二次干燥，所述二次干燥为热风干燥，干燥温度为120-150℃，干燥时间为15-20h。
通过采用上述技术方案，物料经过固化处理时，起到了表面定型的作用，而后经过热风干燥，可以缓慢干燥物料的内部，有利于降低陶瓷制品分层的现象，有利于提高制品力学性能。
优选的，所述热处理包括脱粘处理、碳热还原处理以及高温烧结；
所述碳热还原处理温度为1400-1600℃，保温时间为0.5-2h。
优选的，所述热处理包括如下步骤：
脱粘处理：将物料升温至600-900℃，保温1-3h；
碳热还原处理：将经过脱粘处理的物料升温至1400-1450℃，然后以0.5-2℃/min的速度升温至1550-1600℃，在1550-1600℃的温度下保温0.5-2h；
高温烧结：将经过碳热还原处理的物料升温至1950-2150℃，保温2-3h。
通过采用上述技术方案，相关技术中物料的热处理一般包括两段温区，即脱粘处理和高温烧结，而本申请的热处理可以分为三段温区：
脱粘段，物料升温至600-900℃，在此温度下保温脱粘处理，以去除高分子助剂；
碳还原段，脱粘处理后，先升温至1400-1450℃，然后以0.5-2℃/min的速度升温至1550-1600℃，在此温度下保温促进碳的还原的反应， 使碳与碳化硅粉体表面的游离硅和二氧化硅发生反应，以生成碳化硅，降低杂质含量，让碳的还原反应更加完全，从而改善了烧结性能，得到高密度的产品；
烧结段，在1950-2150℃的温度下烧结，由于本申请的碳化硼的粒径更小、含量更低，在满足烧结自密化的前提下，烧结温度可较传统烧结温度降低30-50℃。
优选的，所述喷雾造粒采用离心式喷雾造粒，进口温度为220-230℃，出口温度为95-100℃。
第二方面，本申请提供一种固相烧结碳化硅制品的制备方法制得的碳化硅制品。
综上所述，本申请具有以下有益效果：
1.主原料成本低：本申请以商业化库存的碳化硅切割用微粉为原料，其碳化硅原粉成本低；相较于目前常用的以亚微米级碳化硅为原料，本申请不需要碳化硅原粉供应商额外对碳化硅原粉进行酸碱纯化处理、研磨、干燥处理，本申请直接以微米级的碳化硅原粉为原料，直接湿法研磨成亚微米级粉体用于后续的加工，去除了酸碱纯化工序以及干燥的工序，可以降低粉体的处理成本，从而大幅度降低了主原料的成本。
2.烧结助剂成本低：本申请在研磨的过程中直接加入硼源烧结助剂，可以使得烧结助剂的粒径更小、分散的更加均匀，提高了硼源烧结助剂的活性，可以降低其用量，从而降低烧结助剂的成本。本申请的碳源烧结助剂选用炭黑，相较于酚醛树脂碳源，其脱粘时不易产生污染性气体，降低了环保处理的成本。
3.生产效率高：本申请的制备方法先经过陈腐，再经过练泥、挤出、干燥等工序，区别于传统的先练泥，再陈腐、挤出、干燥等工序，调整了陈腐工序在工艺中的顺序，缩短了后续工序中的间歇停顿，实现练泥、挤出、干燥工序的连续化生产，大大提高了生产效率。
4.制品性能高：本申请在研磨碳化硅的同时，加入硼源烧结助剂共同研磨，可以提高硼源烧结助剂的细度以及活性，有利于促进固相烧结，提高碳化硅制品的密度，提高其强度；
本申请以炭黑为烧结助剂，通过高分子量和低分子量复配得到的塑化剂，结合练泥工序，可以提高碳化硅制品的可塑性和致密性，从而改善缺少酚醛树脂时强度不足的问题；
本申请的制备方法采用先对湿粉进行陈腐，由于湿粉的润湿性更好，泥料的表面不易硬化产生硬颗粒，可以提高泥料的均匀性以及塑性，有利于提高练泥工序中泥料的可塑性以及烧结时的致密度；
本申请的干燥技术采用远红外固化干燥和热风干燥相结合的方式，相较于传统的微波固化干燥，本申请利用远红外固化干燥技术，只对物料的表面进行干燥，起到表面定型的作用，然后再经过后续的缓慢干燥的配合，可以降低陶瓷制品分层的现象，有利于提高制品的力学性能；
本申请在热处理工序相较于传统的脱粘段和烧结段，还增加了碳还原段，通过在1400-1600℃的温度下保温，可以促进碳的热还原反应，使碳与碳化硅粉体表面的游离硅和二氧化硅发生反应，以生成碳化硅，降低杂质含量，让碳的还原反应更加完全，从而改善了烧结性能，得到高密度的产品。
5.制品应用广泛：由本申请的制备方法制备的碳化硅制品的应用广泛，可以用于制备换热管、辊棒和方梁以及微反应管等。通过本申请的工艺制备的碳化硅挤出制品烧结密度可达3.10g/cm 3以上，最高可达3.16g/cm 3，大大提高了固相烧结挤出碳化硅制品的性能。
具体实施方式
一种固相烧结碳化硅制品的制备方法，包括如下步骤：
S1、配料：以粒径为3-10μm的微米级碳化硅粉末为主要原料，以粒径为3-10μm的含硼烧结助剂和水溶性炭黑作为固相烧结助剂；以粘结剂、塑化剂以及润滑剂作为功能助剂；其中，含硼烧结助剂的用量为微米级碳化硅粉末重量的0.2-0.5wt％，水溶性炭黑的用量为微米级碳化硅粉末重量的0.5-3wt％；粘结剂的用量为微米级碳化硅粉末重量的0.5-2wt％；塑化剂由分子量为15-20万的高分子量塑化剂和分子量为4000-6000的低分子量塑化剂组成，高分子量塑化剂和低分子量塑化剂的重量比为1:1-4；
S2、原料研磨：先将微米级碳化硅粉末、含硼烧结助剂投入立式或卧式研磨机中，以水为溶剂，将其研磨得到粒径为0.4-0.8μm、固含量为40-50wt％的浆料；
S3、喷雾造粒：向浆料中加入水溶性炭黑以及粘结剂，搅拌均匀后，采用离心式喷雾造粒，进口温度为220-230℃，出口温度为95-100℃，得到碳化硅造粒粉体；
S4、混料：将碳化硅造粒粉体与塑化剂在混合机中搅拌均匀，然后加入去离子水以及润滑剂，搅拌均匀，得到湿粉；其中，塑化剂的用量为碳化硅造粒粉体重量的4-10wt％；去离子水的用量为碳化硅造粒粉体重量的 15-25wt％；润滑剂的用量为碳化硅造粒粉体重量的1-2wt％；
S5、陈腐：将湿粉在温度为5-10℃、湿度为40-50％的条件下，密封陈腐12-24h后，得到陈腐料；
S6、练泥：将陈腐料在温度为20-30℃、压力为1.0-1.5MPa、真空度为-0.08～-0.1MPa的条件下练泥20-30min，反复练泥3-5次，得到练泥料；
S7、挤出：使练泥料直接进入挤出成型机中，在挤出压力为1.0-1.5MPa、真空度为-0.08～-0.1MPa、挤出速率为0.5-1m/min的条件下挤出成型，通过同步测速，同步定长切割后，得到素胚；
S8、干燥：使素胚直接进入带有气体悬浮的远红外干燥机中进行一次干燥，干燥工作区长度为2-4m，干燥温度为80-100℃，物料传送速度为0.5-1m/min；然后在带有气体悬浮的管式干燥炉或热风干燥箱中进行二次干燥，干燥温度为120-150℃，干燥时间为15-20h，得到干燥后的碳化硅素胚；
S9、热处理：将干燥后的碳化硅素胚置于高温电阻炉中，在氩气气氛保护下进行热处理，热处理包括脱粘处理、碳热还原处理以及烧结处理；
脱粘处理：设置高温电阻炉的温度，使其以2-4℃/min的速度升温至300℃，再以0.5-1℃/min的速度升温至600-650℃，而后以1-2℃/min的速度升温至850-900℃，在850-900℃的温度下保温1-3h；
碳热还原处理：以2-4℃/min的速度升温至1400-1450℃，然后以0.5-2℃/min的速度升温至1550-1600℃，在1550-1600℃的温度下保温0.5-2h；
高温烧结：以2-4℃/min的速度升温至1950℃，然后以1-2℃/min 的速度升温至2050-2150℃，保温2-3h，得到烧结制品；
S10、精加工：将烧结制品经过切割、内外圆倒角等精加工后，得到碳化硅制品。
采用本申请的方法可以用于制备碳化硅换热管、碳化硅辊棒、碳化硅方梁以及碳化硅微反应管等。
采用本申请的方法制得的外径为14mm、壁厚为1.5mm的碳化硅换热管，在200BAR的耐水压测试条件下，合格率(指未出现裂纹、未发生变形等缺陷的样品量占总测试样品量的比例)能达到98％以上；采用本申请的方法制得的外径为25mm、壁厚为3.0mm的碳化硅换热管能够耐温达1500℃以上；采用本申请的方法制得的外径为38mm、壁厚为5.0mm的碳化硅辊棒和方梁，在100MPa的集中力测试下，合格率能达到98％以上；采用本申请的方法制得的外径为6mm、壁厚为0.5mm的微反应管能耐压达150BAR以上。
以下结合实施例对本申请作进一步详细说明。
实施例中的原料均可通过市售获得。其中，碳化硅粉末的粒径为3-10μm，纯度＞98.5％，金属铁杂质的含量＜0.1％；含硼烧结助剂可以选硼或碳化硼，以下实施例均选择粒径为3-10μm的碳化硼；水溶性炭黑购自德国ORION欧励隆，型号为SPECIAL BLACK 6；粘结剂选用聚乙烯醇，购自安徽皖维富新材料股份有限公司，型号为PVA26-99；润滑剂可以选择油酸或甘油，以下实施例均选择甘油；塑化剂由分子量为15-20万的高分子量塑化剂和分子量为4000-6000的低分子量塑化剂组成，高分子量塑化剂可以为分子量为20万的聚氧化乙烯、分子量为15万或20万的羟丙基甲基纤维，低分子量塑化剂可以为分子量为4000或6000的聚乙二醇、分子量为 5000的羟丙基甲基纤维素，以下实施例的塑化剂均选择分子量为20万的聚氧化乙烯以及分子量为5000的羟丙基甲基纤维素。
实施例
实施例1-8
实施例1-8中的各原料的用量见表1。如表1所示，实施例1-8的主要区别在于原料的配比不同。
以下以实施例1为例进行说明。
实施例1提供的碳化硅制品的制备方法如下：
S1、原料研磨：将100kg微米级碳化硅粉末、0.3kg碳化硼粉末投入立式研磨机中，以水为溶剂，将其研磨，得到粒径为0.4-0.8μm、固含量为45wt％的浆料；
S2、喷雾造粒：向S1的浆料中加入1kg水溶性炭黑以及1kg粘结剂，搅拌均匀后，采用离心式喷雾造粒，进口温度为225℃，出口温度为98℃，得到碳化硅造粒粉体；
S3、混料：取100kg经S2制得的碳化硅造粒粉体，将其加入混合机中，然后加入4kg塑化剂，启动搅拌机，使二者混合均匀，然后加入20kg去离子水以及1.5kg润滑剂，搅拌均匀，得到湿粉；
S4、陈腐：将湿粉在温度为5℃、湿度为40％的条件下，密封陈腐24h后，得到陈腐料；
S5、练泥：将陈腐料在温度为25℃、压力为1.0MPa、真空度为-0.08MPa的条件下练泥25min，反复练泥4次，得到练泥料；
S6、挤出：将练泥料在挤出压力为1.0MPa、真空度为-0.08MPa、挤出 速率为0.5m/min的条件下挤出成型，通过同步测速，同步定长切割后，得到素胚；
S7、干燥：使素胚直接进入带有气体悬浮的远红外干燥机中进行一次干燥，干燥工作区长度为4m，一次干燥温度为80℃，物料传送速度为1m/min；然后在热风干燥箱中进行二次干燥，二次干燥温度为120℃，二次干燥时间为20h，得到干燥后的碳化硅素胚；
S8、热处理：将干燥后的碳化硅素胚置于高温电阻炉中，在氩气气氛保护下进行热处理，热处理包括脱粘处理、碳热还原处理以及高温烧结；
脱粘处理：设置高温电阻炉的温度，使其以3℃/min的速度升温至300℃，再以0.6℃/min的速度升温至600℃，而后以1.5℃/min的速度升温至900℃，在900℃的温度下保温2h；
碳热还原处理：碳热还原处理包括如下步骤：继续以2℃/min的速度升温至1400℃，然后以0.5℃/min的速度升温至1550℃，在1550℃的温度下保温2h；
高温烧结：然后以3℃/min的速度升温至1950℃，然后以1.5℃/min的速度升温至2100℃，在2100℃的温度下保温2.5h，得到烧结制品；
S9、精加工：将烧结制品经过切割、内外圆倒角精加工后，得到外径为14mm、壁厚为1.5mm的碳化硅热交换管。
表1实施例1-8中原料的用量表 (单位：kg)
Figure PCTCN2022081095-appb-000001
Figure PCTCN2022081095-appb-000002
实施例9-16
实施例9-16所用的原料以及用量与实施例6相同，不同之处在于工艺步骤以及工艺参数的不同。
实施例9
本实施例与实施例6的不同之处在于S4，将湿粉在温度为10℃、湿度为50％的条件下，密封陈腐12h后，得到陈腐料。
实施例10
本实施例与实施例6的不同之处在于S4，将湿粉在温度为20℃、湿度为80％的条件下，密封陈腐24h后，得到陈腐料。
实施例11
本实施例与实施例6的不同之处在于S7，使素胚直接进入带有气体悬浮的远红外干燥机中进行一次干燥，干燥温度为100℃，物料传送速度为0.5m/min；然后在热风干燥箱中进行二次干燥，干燥温度为150℃，干燥时间为15h，得到干燥后的碳化硅素胚。
实施例12
本实施例与实施例6的不同之处在于S7，一次干燥为微波干燥，微波 干燥频率为2450MHz，一次干燥温度为90℃，一次干燥时间为20min；二次干燥为热风干燥，二次干燥温度为120℃，二次干燥时间为12h。
实施例13
本实施例与实施例6的不同之处在于S7，使素胚在热风干燥箱中进行干燥，干燥温度为120℃，干燥时间为20h，得到干燥后的碳化硅素胚。
实施例14
本实施例与实施例6的不同之处在于S8，碳热还原处理包括如下步骤：继续以4℃/min的速度升温至1500℃，然后以2℃/min的速度升温至1600℃，在1600℃的温度下保温0.5h。
实施例15
本实施例与实施例6的不同之处在于S8，碳热还原处理包括如下步骤：继续以2℃/min的速度升温至1400℃，然后以3℃/min的速度升温至1550℃，在1550℃的温度下保温2h。
实施例16
本实施例与实施例6的不同之处在于S8，热处理只包括脱粘处理以及高温烧结，具体步骤如下：
脱粘处理：设置高温电阻炉的温度，使其以3℃/min的速度升温至300℃，再以0.6℃/min的速度升温至600℃，而后以1.5℃/min的速度升温至900℃，在900℃的温度下保温2h；
高温烧结：然后以3℃/min的速度，从900℃升温至1950℃，然后以1.5℃/min的速度升温至2100℃，在2100℃的温度下保温2.5h，得到烧结制品。
对比例
对比例1
本对比例与实施例1的不同之处在于S4、S5、S6、S7、S8，其他步骤以及工艺参数与实施例1相同；将陈腐与练泥的顺序调换，具体如下：
S4、练泥：将S3得到的湿粉在温度为25℃、压力为1.0MPa、真空度为-0.08MPa的条件下练泥25min，反复练泥4次，得到练泥料；
S5、陈腐：将S4得到的练泥料在温度为20℃、湿度为80％的条件下，密封陈腐24h，得到陈腐料；
S6、挤出：将陈腐料在挤出压力为1.0MPa、真空度为-0.08MPa、挤出速率为0.5m/min的条件下挤出成型，通过同步测速，同步定长切割后，得到素胚；
S7、干燥：使素胚进入微波干燥机中进行一次干燥，微波干燥频率为2450MHz、一次干燥温度为90℃，一次干燥时间为20min；二次干燥为热风干燥，二次干燥温度为120℃，二次干燥时间为12h；
S8、热处理：将干燥后的碳化硅素胚置于高温电阻炉中，在氩气气氛保护下进行热处理，热处理包括脱粘处理以及高温烧结；
脱粘处理：使其以3℃/min的速度升温至300℃，再以0.6℃/min的速度升温至600℃，而后以1.5℃/min的速度升温至900℃，在900℃的温度下保温2h；
高温烧结：然后以3℃/min的速度，从900℃升温至1950℃，然后以1.5℃/min的速度升温至2100℃，在2100℃的温度下保温2.5h，得到烧结制品。
对比例2
本对比例与实施例6的不同之处在于S4、S5，其他步骤以及工艺参数与实施例6相同；将陈腐与练泥的顺序调换，具体如下：
S4、练泥：将S3得到的湿粉在温度为25℃、压力为1.0MPa、真空度为-0.08MPa的条件下练泥25min，反复练泥4次，得到练泥料；
S5、陈腐：将S4得到的练泥料在温度为5℃、湿度为40％的条件下，密封陈腐24h，得到陈腐料；将陈腐料经过与实施例6相同的挤出、干燥、热处理以及精加工即可。
性能检测试验
按照行业标准JCT2212-2014《常压固相烧结碳化硅陶瓷热交换管》中的方法，对实施例1-16以及对比例1-2制得的碳化硅热交换管的性能进行检测，将检测结果示于表2。
表2实施例1-16以及对比例1-2的碳化硅热交换管的性能测试表
Figure PCTCN2022081095-appb-000003
Figure PCTCN2022081095-appb-000004
根据表2数据，结合实施例1和对比例1可以看出，相较于传统的固相烧结碳化硅制品的制备方法，采用本申请的方法制备的碳化硅换热管的体积密度、硬度、断裂韧性、弯曲强度以及抗压强度明显提升，说明采用本申请的制备方法可以明显提高碳化硅制品的烧结性能，从而显著改善制品的力学性能。
结合实施例1-3可以看出，当烧结助剂的用量发生变化时，可以影响碳化硅的烧结性能，从而影响到制品的力学性能。由于本申请的碳化硼的用量较小，因此实施例1-3中对碳化硅制品的力学性能产生主要影响的是炭黑的用量。通过实施例1-3的实验数据可以看出，在炭黑用量在0.5-2wt％的范围内变化时，制品的体积密度、硬度、断裂韧性、弯曲强度以及抗压强度呈上升的趋势，而当炭黑的用量超过2wt％时，制品的力学性能上升缓慢，当炭黑的用量为3wt％时，制品的部分力学性能有下降的趋势。这是因为在一定范围内，碳的加入可以与碳化硅粉末表面的游离硅和二氧化硅反应，降低杂质含量，提高粉体表面能以及活性，促进碳化硼的扩散，促进碳化硅的烧结，从而提高烧结制品的致密性。但是当碳含量继续增加时，过量的碳则会抑制碳化硅的烧结，从而导致烧结制品的致密性以及力学性 能开始下降。
结合实施例4、实施例5、实施例6以及实施例1可以看出，塑化剂的用量以及种类对制品的力学性能有较大的影响。塑化剂的加入可以改善泥料的塑性，有利于提高其成型性以及烧结性能，从而提高烧结制品的致密性以及力学性能。当采用单一的低分子量的塑化剂时，虽然可以改善体系的塑性，但是粘结强度不足，导致制品的烧结强度下降，力学性能变差；当采用单一的高分子量的塑化剂时，虽然可以提供较强的粘结力，但是其造成体系混合不均匀，内部极易产生裂纹等缺陷，导致制品烧结的致密度不足，也会导致制品的力学性能下降。因此，当采用高分子量塑化剂和低分子量塑化剂复配时，可以改善体系的塑性，配合练泥工序，可以提高泥料混合的均匀性，又能提供所需的粘结强度，从而提高制品的烧结致密性，提高制品的力学性能。特别是结合实施例6、7、8可以看出，当高分子塑化剂和低分子量塑化剂的用量比为1:1-4时，制得的烧结制品具有较优的力学性能。
结合实施例6、实施例9、实施例10以及对比例2可以看出，陈腐的工艺参数以及工序顺序对制品的力学性能也有较大的影响。在本申请中，陈腐是为了提高湿粉的润湿性，提高泥料与粘结剂、塑化剂等原料混合的均匀性，降低泥料表面的硬化颗粒，提高练泥工序中的可塑性以及烧结时的致密度，从而显著提高制品的力学性能。
结合实施例6、实施例12以及实施例13可以看出，干燥工序对制品的力学性能具有较大的影响。干燥不当时，会引起制品在烧结时出现分层、开裂等质量问题，从而影响到制品的力学性能。干燥处理采用远红外干燥 和热风干燥相结合的干燥方式，可以提高素胚内部、外部干燥的均匀性，避免分层、裂纹现象的产生，可以降低制品内部的缺陷，有利于提高制品的力学性能。
结合实施例6、实施例14、实施例15以及实施例16可以看出，热处理工序对制品的力学性能具有较大的影响。相较于二段热处理工艺，采用三段热处理工艺，并且在碳热还原段，降低升温速率，可以使得延长碳还原反应时间，让碳的热还原反应更加完全，有利于提高粉体活性，促进烧结的进行，提高烧结制品的致密度以及力学性能。
本具体实施例仅仅是对本申请的解释，其并不是对本申请的限制，本领域技术人员在阅读完本说明书后可以根据需要对本实施例做出没有创造性贡献的修改，但只要在本申请的权利要求范围内都受到专利法的保护。

Claims (10)

  1. 一种固相烧结碳化硅制品的制备方法，其特征在于，包括如下步骤：
    S1、原料研磨：将微米级碳化硅粉末与含硼烧结助剂混合并湿法研磨，得到粒径为0.4-0.8μm的浆料；
    S2、喷雾造粒：向浆料中加入水溶性炭黑和粘结剂，搅拌均匀，经过喷雾造粒，得到碳化硅造粒粉体；
    S3、混料：将碳化硅造粒粉体与塑化剂混合均匀后，加入润滑剂以及水，搅拌均匀后，得到湿粉；
    S4、陈腐：将湿粉经过陈腐，得到陈腐料；
    S5、后处理：将陈腐料经过练泥、挤出、干燥、热处理即可。
  2. 根据权利要求1所述的一种固相烧结碳化硅制品的制备方法，其特征在于，所述含硼烧结助剂的用量为微米级碳化硅粉末重量的0.2-0.5wt％；所述水溶性炭黑的用量为微米级碳化硅粉末重量的0.5-3.0wt％。
  3. 根据权利要求1所述的一种固相烧结碳化硅制品的制备方法，其特征在于，所述塑化剂由分子量为15-20万的高分子量塑化剂和分子量为4000-6000的低分子量塑化剂组成。
  4. 根据权利要求1所述的一种固相烧结碳化硅制品的制备方法，其特征在于，所述陈腐的温度为5-10℃、湿度为40-50％、时间为12-24h。
  5. 根据权利要求1所述的一种固相烧结碳化硅制品的制备方法，其特征在于，所述干燥包括一次干燥，所述一次干燥为远红外干燥，干燥温度为80-100℃，物料传送速度为0.5-1m/min。
  6. 根据权利要求5所述的一种固相烧结碳化硅制品的制备方法，其特征在于，所述干燥包括所述一次干燥之后的二次干燥，所述二次干燥为 热风干燥，干燥温度为120-150℃，干燥时间为15-20h。
  7. 根据权利要求1所述的一种固相烧结碳化硅制品的制备方法，其特征在于，所述热处理包括脱粘处理、碳热还原处理以及高温烧结；
    所述碳热还原处理温度为1400-1600℃，保温时间为0.5-2h。
  8. 根据权利要求1所述的一种固相烧结碳化硅制品的制备方法，其特征在于，所述热处理包括如下步骤：
    脱粘处理：将物料升温至600-900℃，保温1-3h；
    碳热还原处理：将经过脱粘处理的物料升温至1400-1450℃，然后以0.5-2℃/min的速度升温至1550-1600℃，在1550-1600℃的温度下保温0.5-2h；
    高温烧结：将经过碳热还原处理的物料升温至1950-2150℃，保温2-3h。
  9. 根据权利要求1所述的一种固相烧结碳化硅制品的制备方法，其特征在于，所述喷雾造粒采用离心式喷雾造粒，进口温度为220-230℃，出口温度为95-100℃。
  10. 一种由权利要求1所述的固相烧结碳化硅制品的制备方法制备的碳化硅制品。
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