CN115403388B - Wear-resistant silicon dioxide/silicon carbide composite ceramic and preparation method and application thereof - Google Patents
Wear-resistant silicon dioxide/silicon carbide composite ceramic and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of functional ceramic, and discloses wear-resistant silicon dioxide/silicon carbide composite ceramic and a preparation method thereof. The method comprises the steps of heating an alpha-SiC block-carbon powder mixture and metal silicon particles to 1420-1700 ℃ in a sintering furnace in vacuum or inert atmosphere to sinter to obtain siliconizing reaction sintering SiC blocks, crushing or/and classifying and screening the siliconizing reaction sintering SiC blocks, mixing the obtained siliconizing reaction sintering SiC particles, alpha-SiC particles, metal silicon and a bonding agent into ceramic materials, forming a ceramic blank, sintering in an oxidizing atmosphere at 1300-1420 ℃, and cooling to obtain wear-resistant SiO 2 SiC composite ceramics. The invention adopts a casting molding or pressure molding method, has small molding difficulty, lower cost and less equipment investment, and is easy to be large-sized. The wear resistance and mechanical property of the composite ceramic are obviously improved, and the capability of resisting large-particle scouring and grinding is also obviously improved.
Description
Technical Field
The invention belongs to the technical field of functional ceramic materials, and particularly relates to wear-resistant silicon dioxide/silicon carbide composite ceramic, and a preparation method and application thereof.
Technical Field
Currently, silicon carbide used for industrial production of oxide-combined silicon carbide products is obtained by smelting in a silicon carbide smelting furnace by an Acheson method. The silicon carbide obtained by smelting is in a block shape of 40-500 mm, the SiC crystal is alpha-SiC, the size of the crystal is generally not more than 5mm, and most of the crystal is below 3 mm. Between crystals, there are a large number of pores. The smelting silicon carbide blocks are crushed and graded, and SiC particles with different particle sizes can be obtained. During the crushing process, silicon carbide is easy to crack from pores among crystals, so when the silicon carbide particles are smaller than 1mm, the pores on the particles are obviously reducedAnd the pores are generally shallow, the particles are difficult to fracture along these shallow pores. When the silicon carbide particles are larger than 3mm, a large number of plate-like pores exist on the particles, and many depths (the dimension in the direction of the maximum outline of the plate-like pores) of the pores are several mm to several tens of mm and widths (the dimension in the direction of the minimum outline of the pores) are 0.1 μm to 1000 μm. This allows the apparent porosity of silicon carbide particles above 3mm to be 2% or even higher. In the production of oxide-bonded silicon carbide articles, the maximum particle size of the silicon carbide particles is typically no greater than 3mm, and the particles of different sizes are graded to obtain a higher bulk density; the proportion of the metal silicon is generally 5-15% of the weight of the product, and too much metal silicon is produced, so that the manufacturing cost is high, and the wear resistance of the product is obviously reduced; too little metal silicon will significantly decrease the mechanical strength of the article. If casting molding is adopted, the granularity of the metal silicon is strictly controlled, the granularity is too coarse, and the distribution of the bonding phase is uneven, so that the strength of the product is obviously reduced; the particles are too fine, the metallic silicon is easy to generate hydration reaction with water in the temporary bonding agent to generate hydrogen and silicon dioxide, so that the blank is loose and the strength and the wear resistance of the product are reduced. The particle size of the metal silicon in the casting process is generally selected to be several tens of μm to several hundreds of μm, which makes it difficult for the metal silicon particles to enter into the plate-like or needle-like pores in the particles at the time of molding. The dry forming can be carried out by adopting finer metal silicon particles with the granularity of several micrometers to tens micrometers, but the fluidity of the materials is poor because the materials of all the raw materials formed by the dry forming are almost free of liquid, the fine silicon powder is difficult to enter into pores of 0.1-10 micrometers, ultrafine powder smaller than 10 micrometers is easy to form agglomeration phenomenon, and particularly, in order to improve the strength of a blank, the agglomeration phenomenon of the particles can be further increased after a certain temporary bonding agent is added into ingredients. Therefore, even if metal silicon particles with finer particles are selected, little metal silicon can enter the pores of the silicon carbide particles during the mixing or pressing process, and the pores cannot be filled. During sintering of oxide-bonded silicon carbide articles, the α -SiC particles undergo little physical or chemical change, while at the same time, at less than 1420 ℃, little glassy phase is formed in the bonded phase, which is typically due to capillary actionOnly between adjacent SiC particles, and cannot enter pores of the SiC particles. After a considerable temperature of 1420℃is reached, i.e. the melting point of the silicon metal, the silicon metal has almost completely oxidized to SiO 2 Only very little metallic silicon remains to melt into the liquid phase, but these very little liquid metallic silicon cannot undergo large displacement under capillary action and fill needle-like or plate-like pores on the α -SiC particles and fill the pores. Thus, the oxide-bonded silicon carbide product has a large number of open pores having a width of 1 to 10 μm on coarse particles of 3 to 5mm. The apparent porosity of the oxide-bonded silicon carbide article is typically in the range of 12 to 22%, with a major portion of the apparent porosity being in the bonding phase and a minor portion in the major phase. The pores, especially in the bonding phase, can obviously reduce the residual internal stress generated in the sintering and cooling processes of the oxide-bonded silicon carbide ceramic, thereby being beneficial to the enlargement of the workpiece. The oxide-bonded silicon carbide can be used to make wear resistant products such as wear resistant nozzles, slurry pump spare parts, cyclones, and the like. Particularly, when the device is used in the flushing working conditions of light abrasion and light impact, a better use effect can be obtained. However, because a large number of air holes and edges exist on the SiC large particles, the mobility of the ceramic mixture is deteriorated due to the increase of the SiC particles, the process difficulty of forming the oxide-bonded silicon carbide product is increased, and the forming quality of the ceramic blank is reduced. Therefore, the oxide-bonded silicon carbide product described above rarely uses SiC particles of 5mm or more. Because of the existence of a large number of pores on the silicon carbide particles, the density of the existing oxide-bonded silicon carbide product is generally only 2.5-2.65 g/cm 3 The existence of a large number of air holes makes the abrasion resistance of the existing oxide combined silicon carbide product not meet the requirements of many working conditions.
The reaction sintering silicon carbide ceramic is generally prepared by preparing alpha-SiC produced by Acheson method into 10-100 mu m micro powder, adding 10-100 mu m carbon powder and binding agent, placing the mixture and simple substance silicon particles into a reaction sintering furnace after molding, sintering the mixture and the simple substance silicon particles in vacuum or protective gas at 1500-1700 ℃, allowing the simple substance silicon to permeate into a blank in a liquid state or a vapor state above the melting point (about 1420 ℃) of the simple substance silicon to react with the carbon powder to generate beta-SiC, and simultaneously filling all pores in the blank with the simple substance silicon to obtain a ceramic part which contains 65-75% of alpha-SiC, 20-30% of beta-SiC and 10-15% of simple substance silicon and has almost no pores. Compared with oxide-bonded silicon carbide, the reaction-sintered silicon carbide has better wear resistance, but because of almost no pores (the apparent porosity is generally 0-0.3%), and a large amount of brittle simple substance silicon exists in a large residual internal stress after sintering, and the internal stress of the reaction-sintered silicon carbide is obviously increased along with the size increase of a workpiece, the large workpiece of the reaction-sintered silicon carbide ceramic has extremely poor impact resistance, even slight vibration can cause the breakage of the large workpiece in some cases, meanwhile, the reaction-sintered silicon carbide ceramic generally needs to be carried out in a vacuum furnace, and the vacuum furnace capable of sintering the large workpiece has high cost due to the structural characteristics of the carbonization-reaction sintering furnace.
In order to solve the problem of insufficient wear resistance and large particle impact resistance of silicon oxide-bonded carbon carbide ceramics, CN113404723A proposes a manufacturing method of complex phase reaction sintering silicon carbide ceramics, which has the basic idea that a sintered oxide-bonded silicon carbide ceramic product is carburized, a die is placed on the outer surface of the carburized oxide-bonded silicon carbide ceramic product, slurry containing silicon carbide micro powder and carbon micro powder is injected between the die and the oxide-bonded silicon carbide ceramic product for secondary molding, and the secondary molded product is dried and then placed into a reaction sintering furnace to enter secondary sintering, so that complex phase ceramics with the surface covered with the reaction sintering silicon carbide is obtained. The technical scheme has the advantages that the reaction sintering ceramic can be arranged on the surface with serious abrasion according to the requirement, and meanwhile, the overall porosity of the workpiece can be greatly reduced, so that the product can have higher abrasion resistance. However, the following problems exist in the technical scheme: (1) The product needs to be subjected to secondary molding and secondary sintering, the process is complex, and the cost is high; (2) Secondary sintering must be performed in a reaction sintering furnace, which is expensive if the workpiece is large, requiring a large investment of fixed assets; (3) Because of the characteristics of the process, the material composition and porosity of the composite ceramic obtained by secondary sintering are extremely nonuniform in macroscopic or overall, and the main components distributed on the surface of the composite ceramic are self-bonding silicon carbide (about 85-90% of weight) and metallic silicon (about 10-15% of weight), wherein the porosity is almost zero; at the position far away from the surface, the main component of the silicon carbide is still oxide-bonded silicon carbide, and the porosity of the silicon carbide can reach 15-18 percent because the carbon and the silicon are difficult to permeate. For large workpieces, large differences in macroscopic or overall materials can lead to large residual internal stresses generated during secondary sintering or after cooling of the ceramic parts, which can greatly reduce the yield of the workpieces and greatly reduce the impact resistance and reliability of the products.
Disclosure of Invention
In order to solve the defects and shortcomings of the prior art, the invention aims to provide a manufacturing method of wear-resistant oxide/silicon carbide ceramic.
It is another object of the present invention to provide a wear resistant oxide/silicon carbide ceramic prepared by the above method.
It is a further object of the present invention to provide the use of the above-described wear resistant oxide/silicon carbide ceramic.
The aim of the invention is achieved by the following technical scheme:
the preparation method of the wear-resistant silicon dioxide/silicon carbide composite ceramic comprises the following specific steps:
s1, crushing smelted alpha-SiC to obtain alpha-SiC blocks with the granularity of 3-50 mm and alpha-SiC particles with the granularity of 0.001-3 mm, immersing the alpha-SiC blocks in a liquid containing carbon black micro powder or organic carbon with the granularity of 0.0001-0.01 mm, enabling the carbon black micro powder or the organic carbon to permeate into pores of the alpha-SiC blocks, drying the carbon black micro powder or carbonizing the organic carbon at 300-800 ℃ to obtain an alpha-SiC block-carbon powder mixture with the surface covered and carbon powder filled in the pores;
s2, in a sintering furnace in vacuum or inert atmosphere, heating the alpha-SiC block-carbon powder mixture and silicon particles to 1420-1700 ℃ for sintering to obtain siliconizing reaction sintered SiC blocks, and crushing or/and classifying and screening the siliconizing reaction sintered SiC blocks after cooling to obtain siliconizing reaction sintered SiC particles;
s3, according to the mass percentage, 15 to 50 percent of silicon-impregnation reaction sintering SiC particles, 25 to 60 percent of alpha-SiC particles obtained in the step S1, 5 to 10 percent of metallic silicon and 3 to 20 percent of knots are mixedMixing the mixture into ceramic material, pouring into mould or pressure forming to obtain ceramic blank, sintering the ceramic blank in 1300-1420 deg.C oxidizing atmosphere, cooling to obtain wear-resisting SiO 2 SiC composite ceramics.
Preferably, the organic carbon in step S1 is an epoxy resin having a viscosity of less than 800 mPa.S at 25 ℃.
Preferably, the silicon particles in step S2 have a particle size of 0.001 to 5mm.
Preferably, in the step S3, the particle size of the siliconizing reaction sintered SiC particles is 2 to 20mm, and the particle size of the metallic silicon is 0.001 to 1mm.
Preferably, in step S2, the weight ratio of the mixture of α -SiC pieces and carbon powder to silicon metal is 10: (1-3).
Preferably, the binder in step S3 comprises aluminate cement and/or oxide.
Preferably, the oxide is calcium oxide, aluminum oxide or silicon oxide.
Preferably, the bonding agent in step S3 further comprises a temporary bonding agent, wherein the temporary bonding agent is water or an organic bonding agent, and the total weight of the temporary bonding agent is 5-12% of the total weight of the ceramic material.
A wear resistant silica/silicon carbide composite ceramic prepared by the method.
The wear-resistant silicon dioxide/silicon carbide composite ceramic is applied to the fields of slurry pumps, cyclones or flotation machines.
When the particle size of the ceramic particles is selected, the invention discovers that when the erosion property of the ceramic is verified by using a scouring medium containing solid particles with the size of about 1mm, 3-5 mm coarse SiC particles with the weight percentage of more than 5% are added into the silicon dioxide-bonded silicon carbide ceramic, so that a better wear-resisting effect can be obtained, and the SiC particles with the size of less than 1mm in the silicon dioxide-bonded silicon carbide ceramic are easy to fall off due to the impact of the solid particles with the size of about 1mm in the scouring medium. When more than 5wt% of SiC particles with the particle size of 3-5 mm are added into the ceramic, the impact energy of solid particles with the particle size of about 1mm in a scouring medium is insufficient to remove the SiC particles with the particle size of 3-5 mm in the silicon dioxide-bonded silicon carbide ceramicFalls, and is not enough to break the SiC particles of 3-5 mm along the pores among SiC crystals. Therefore, these 3-5 mm SiC particles can significantly improve wear resistance under such conditions. When the solid particles in the scouring medium are further enlarged (more than 1mm and less than 5 mm), the impact energy of the solid particles in the scouring medium is increased along with the increase of the volume of the solid particles, and the solid particles are not enough to fall off the 3-5 mm particles in the silicon dioxide-bonded silicon carbide ceramic, but are enough to break along the flaky pores among the SiC crystals. Because of the occurrence of the crushing phenomenon, the abrasion resistance of the silicon dioxide combined with the silicon carbide ceramic is hardly improved by continuously enlarging SiC particles in the ceramic, and even the abrasion resistance is reduced under some working conditions. The invention selects siliconizing reaction sintering SiC particles with the granularity of 2-20 mm, alpha-SiC particles with the granularity of 0.001-3 mm and reaction sintering SiC particles with the granularity of 2-20 mm as raw materials, and the raw materials are sintered at 1420-1700 ℃ under the condition of vacuum or inert atmosphere, and most of air holes in the particles are sintered by beta-SiC, metallic silicon and SiO after the sintering is finished 2 Filled up, and metal silicon, beta-SiC, siO 2 The silicon-impregnated reaction-sintered SiC coarse particles have good binding force with alpha-SiC, so that the possibility of breakage of the particles from original air holes is greatly reduced when the silicon-impregnated reaction-sintered SiC coarse particles are worn and impacted, and the beta-SiC has good wear resistance, and after the surface of the reaction-sintered SiC particles is partially or completely covered with a beta-SiC layer, the wear resistance and mechanical properties of the composite ceramic can be obviously improved.
Compared with the prior art, the invention has the following beneficial effects:
1. the main phase in the silicon dioxide/silicon carbide composite ceramic comprises siliconizing reaction sintering SiC particles with the granularity of 2-20 mm, alpha-SiC particles with the granularity of 0.001-3 mm and reaction sintering SiC particles with the granularity of 2-20 mm, wherein most of air holes in the particles are formed by beta-SiC, metallic silicon and SiO after sintering 2 Filled up, and metal silicon, beta-SiC, siO 2 The silicon-impregnated reaction-sintered SiC coarse particles have better binding force with alpha-SiC, so that the possibility of cracking the particles from original air holes is greatly reduced when the silicon-impregnated reaction-sintered SiC coarse particles are worn and impacted, meanwhile, beta-SiC has better wear resistance, and the surface of the reaction-sintered SiC particles is partially or completely covered with beta-SAfter the iC layer, the wear resistance and mechanical property of the ceramic are obviously improved compared with those of the silicon dioxide/silicon carbide composite ceramic in the prior art, and meanwhile, the capability of the composite ceramic for resisting large-particle scouring wear is obviously improved.
2. The wear-resistant silicon dioxide/silicon carbide composite ceramic is prepared by adopting a casting molding or pressure molding method, and only needs one-step molding in the whole manufacturing process, so that the molding difficulty is low and the cost is low. After molding, only one-time sintering is needed in an oxidation sintering furnace, so that the equipment investment is less, the large-scale is easy, and the sintering cost is low.
3. The wear-resistant silicon dioxide/silicon carbide composite ceramic is relatively uniform, and does not generate large sintering residual stress. At the same time due to the SiO of the binding phase 2 The apparent porosity of the ceramic material is generally 6-12%, and the sintering residual stress can be further reduced, so that the probability of product breakage can be greatly reduced when a large or thick ceramic workpiece is manufactured.
4. In the silicon dioxide/silicon carbide composite ceramic (silicon dioxide combined with silicon carbide) in the prior art, after the particles of the main phase are set to 3-5 mm, the granularity of the particles is continuously increased, the wear resistance and impact resistance of the particles are hardly improved, and the reactive sintering SiC particles are not easy to break from the positions of the air holes during wear or impact due to the fact that most of the air holes are filled. Therefore, the granularity of the reaction sintering SiC particles can be continuously increased to improve the impact resistance of the ceramic, and meanwhile, the reaction sintering SiC particles can improve the fluidity of the ceramic material and the molding quality of a ceramic blank and the quality of a ceramic sintered part because the pores are basically filled. However, the increasing of the particle size tends to make the ceramic blank forming process difficult, and therefore, the particle size is generally 2 to 20mm, preferably not more than 15mm.
5. The invention can obtain various siliconizing reaction sintering SiC particles with proper granularity by crushing or grading. When the alpha-SiC block is siliconizing reaction sintered, the particle size of the alpha-SiC block immersed with carbon black micropowder or organic carbon is generally 3-50 mm, and preferably 5-30 mm. If the particle size of the α -SiC block is too large, it is difficult for the carbon black micropowder or the organic carbon and the metal silicon to sufficiently fill the pores inside the α -SiC block, resulting in that many pores cannot be effectively filled. When the particles are too small, the particles have almost no pores, and the siliconizing reaction sintering has no significance.
6. According to the invention, after the alpha-SiC blocks are subjected to siliconizing reaction sintering, crushing and screening, pores in 2-20 mm siliconizing reaction sintering SiC particles are greatly reduced, so that the added large-granularity siliconizing reaction sintering SiC particles have small influence on the flowability of casting materials during casting molding or pressure molding, the molding is facilitated, the molding density is improved, and the wear resistance of ceramics is improved.
7. The bonding agent of the invention is added with oxides such as alumina, which can improve the strength of ceramic blanks, improve ceramic structures and improve the strength of the ceramic blanks.
Detailed Description
The present invention is further illustrated below in conjunction with specific examples, but should not be construed as limiting the invention. The technical means used in the examples are conventional means well known to those skilled in the art unless otherwise indicated. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
Example 1
1. Crushing and screening alpha-SiC prepared by smelting to obtain alpha-SiC blocks (granularity is 3-30 mm, siC content is more than or equal to 98%) and alpha-SiC particles (granularity is 0.001-2 mm);
2. immersing alpha-SiC blocks (particle size of 3-30 mm) into water suspension containing carbon black micropowder (particle size of 0.00001-0.01 mm), wherein the weight concentration of the carbon black micropowder is 25-35%, adding a dispersing agent into water to prevent carbon black particles from agglomerating, wherein the dispersing agent can be sodium hexametaphosphate (content of 0.5-1% of water mass) or driller PC67 (content of 0.15% of water mass). And (3) enabling the carbon black micropowder to infiltrate into the air holes of the alpha-SiC blocks, and drying to obtain the alpha-SiC block-carbon powder mixture with the surface covered and carbon powder filled in the air holes.
3. Mixing an alpha-SiC block-carbon powder mixture with the weight ratio of 10:1 with metallic silicon (granularity is 2-10mm, si content is more than or equal to 98%), sintering for 120-240 min at 1700 ℃ in a vacuum furnace, and cooling to obtain a siliconizing reaction sintered SiC block; crushing and grading the silicon carbide powder to obtain silicon carbide reaction sintered SiC particles (with the granularity of 2-20 mm);
4. according to the mass percentage, 15 percent of siliconizing reaction sintering SiC particles (with the granularity of 2-20 mm), 5 percent of metallic silicon (with the granularity of 0.01-0.5 mm), 60 percent of alpha-SiC particles (with the granularity of 0.001-2 mm) obtained in the step 1, 20 percent of bonding agent (15 percent of aluminate cement and 5 percent of alumina) are mixed into ceramic materials, 8-12 percent of water with the weight of the solid is also added as a temporary bonding agent for forming, and casting forming is adopted in a die after uniform mixing to form ceramic blanks;
5. placing the ceramic blank into an oxidation furnace, heating to 1350-1420 ℃, and oxidizing the metal silicon in the ceramic blank to generate SiO 2 Cooling to obtain wear-resistant SiO 2 SiC composite ceramic with density of 2.79g/cm 3 。
In the ceramic sintering process, the residual metal silicon part in the pores of the siliconizing reaction sintered silicon carbide block reacts with oxygen to generate silicon oxide, the volume of the silicon oxide slightly expands, the filling of the pores is facilitated, but trace metal silicon is difficult to contact with oxygen due to the structure or the position of the pores and cannot be completely oxidized, and the silicon oxide is still elemental silicon after the ceramic sintering is finished.
Example 2
The difference from example 1 is that: in the step 4, the temporary bonding agent is phenolic resin accounting for 5 percent of the total weight of the solid, and other organic bonding agents (such as starch paste, polyvinyl alcohol, furan resin and the like) can be used for replacing the temporary bonding agent. And (3) adopting pressure forming, wherein the forming pressure is 10-100 MPa. SiO of the present embodiment 2 The density of the SiC composite ceramic is 2.79g/cm 3 。
Example 3
1. Crushing the smelted alpha-SiC to obtain alpha-SiC blocks (granularity is 5-50mm, and SiC content is more than or equal to 98%) and alpha-SiC particles (granularity is 0.001-3 mm);
2. immersing alpha-SiC blocks (granularity is 5-50 mm) into CY-183 epoxy resin containing a curing agent (viscosity is about 500-600 mPa.S at 25 ℃), penetrating the resin into pores of the alpha-SiC blocks under vacuum, and curing at room temperature or heating to 120 ℃ to obtain a mixture of the alpha-SiC blocks with the surfaces covered and the pores filled with the resin;
3. the weight ratio is 10:3 (granularity is between 2 and 10mm, si content is more than or equal to 98%) and metal silicon in an argon protection furnace, heating to 300 to 800 ℃ at a speed of 200 ℃/h, decomposing and carbonizing the resin, continuously heating to 1500 to 1700 ℃ and preserving heat for 2 hours, reacting metal silicon liquid with steam and carbon, obtaining siliconizing reaction sintering SiC blocks (granularity is between 5 and 50 mm), cooling, crushing and screening to obtain siliconizing reaction sintering SiC particles (granularity is between 2 and 20 mm);
4. according to the mass percentage, 50% of siliconizing reaction sintering SiC particles (comprising 25% of particles with the particle size of 2-5.9mm and 25% of particles with the particle size of 6-20 mm), 25% of alpha-SiC particles (with the particle size of 0.001-3 mm) prepared in the step 1, 15% of metallic silicon (with the particle size of 0.01-0.5 mm) and 10% of bonding agent (5% of aluminate cement and 5% of alumina) are mixed into ceramic materials, 8-12% of water with the weight of solids is added as a temporary bonding agent, and the ceramic materials are cast and molded into ceramic blanks in a mold;
5. placing the ceramic blank into an oxidation furnace, heating to 1300-1420 ℃, and oxidizing the metal silicon in the ceramic blank to generate SiO 2 Cooling to obtain wear-resistant SiO 2 SiC composite ceramic with density of 2.82g/cm 3 。
Example 4
The difference from example 1 is that: the granularity of the metal silicon in the step 4 is 0.001-0.1 mm, the metal silicon is molded by pressure, the molding pressure is 100-200 MPa, the bonding agent is 15% of aluminate cement, and no temporary bonding agent is added. SiO of the present embodiment 2 The density of the SiC composite ceramic is 2.80g/cm 3 。
Comparative example 1
The ceramic material comprises the following raw materials in parts by weight: 15% of alpha-SiC particles (particle size 3-5 mm), 15% of alpha-SiC particles (particle size 1-2.5 mm), 20% of alpha-SiC particles (particle size 0.1-0.75 mm), 30% of alpha-SiC particles (particle size 0.001-0.074 mm), 5% of metal silicon particles (particle size 0.001-0.5 mm), 20% of bonding agent (aluminate cement 15% and alumina 5%), and phenol resin added with 5% of solid weight is used as temporary bonding agent, and the ceramic material and the temporary bonding agent are combinedThe mixture is put into a mould after being evenly mixed, and is formed into a ceramic blank by a press machine under the pressure of 10-100 MPa, the sintering process is completely the same as that of the embodiment 1, and the content of the silicon carbide and the metallic silicon is more than 98 percent. SiO of this comparative example 2 The density of the SiC composite ceramic is 2.63g/cm 3 。
TABLE 1 SiO produced in examples 1-4 and comparative example 1 2 Density and scour wear test of SiC composite ceramics
Table 1 shows the SiO's obtained in examples 1 to 4 and comparative example 1 according to the invention 2 Comparison data table of density and scour and wear test of SiC composite ceramics. As can be seen from Table 1, the SiO of the examples of the present invention 2 The density of the SiC composite ceramic is 2.79g/cm 3 The above is significantly improved compared with comparative example 1. The erosive wear test method is described in GB/T18301-2012. As can be seen from Table 1, siO of example 1 2 The scouring loss of the SiC composite ceramic was only 68.5% of that of comparative example 1, siO of example 2 2 The scouring loss of the SiC composite ceramic was 67.9% of that of comparative example 1, siO of example 3 2 The scouring loss of the SiC composite ceramic was only 43.1% of that of comparative example 1, siO of example 4 2 The scouring loss of the SiC composite ceramic is only 71.2% of that of the comparative example, and the scouring loss is obviously reduced, which shows that the SiO produced in examples 1-4 2 The abrasion resistance of the SiC composite ceramics is higher than that of SiO of comparative example 1 2 The silicon carbide composite ceramic is obviously improved.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the wear-resistant silicon dioxide/silicon carbide composite ceramic is characterized by comprising the following specific steps of:
s1, crushing smelted alpha-SiC to obtain alpha-SiC blocks with the granularity of 3-50 mm and alpha-SiC particles with the granularity of 0.001-3 mm, immersing the alpha-SiC blocks in a liquid containing carbon black micro powder or organic carbon with the granularity of 0.0001-0.01 mm, enabling the carbon black micro powder or the organic carbon to permeate into pores of the alpha-SiC blocks, drying the carbon black micro powder or carbonizing the organic carbon at 300-800 ℃ to obtain an alpha-SiC block-carbon powder mixture with the surface covered and carbon powder filled in the pores;
s2, in a sintering furnace in vacuum or inert atmosphere, heating the alpha-SiC block-carbon powder mixture and silicon particles to 1420-1700 ℃ for sintering to obtain siliconizing reaction sintered SiC blocks, and crushing or/and classifying and screening the siliconizing reaction sintered SiC blocks after cooling to obtain siliconizing reaction sintered SiC particles;
s3, according to the mass percentage, 15 to 50 percent of silicon-impregnated reaction sintering SiC particles, 25 to 60 percent of alpha-SiC particles obtained in the step S1, 5 to 10 percent of metallic silicon and 3 to 20 percent of bonding agent are mixed into ceramic materials, the ceramic materials are added into a mould for casting molding or pressure molding to form ceramic blanks, the ceramic blanks are sintered in the oxidizing atmosphere at 1300 to 1420 ℃, and the wear-resistant SiO is obtained after cooling 2 SiC composite ceramics.
2. The method for producing a composite ceramic of abrasion-resistant silica/silicon carbide according to claim 1, wherein the organic carbon in step S1 is an epoxy resin having a viscosity of less than 800 mPa-S at 25 ℃.
3. The method for producing a composite ceramic of abrasion-resistant silica/silicon carbide according to claim 1, wherein the particle size of the silicon particles in step S2 is 0.001 to 5mm.
4. The method for producing a composite ceramic of abrasion-resistant silicon dioxide/silicon carbide according to claim 1, wherein the particle size of the siliconizing reaction sintered SiC particles in step S3 is 2 to 20mm, and the particle size of the metallic silicon is 0.001 to 1mm.
5. The method for preparing a wear-resistant silicon dioxide/silicon carbide composite ceramic according to claim 1, wherein the weight ratio of the mixture of the α -SiC block and carbon powder to the metal silicon in step S2 is 10: (1-3).
6. The method of producing a composite ceramic of abrasion resistant silica/silicon carbide according to claim 1, wherein the binder in step S3 comprises aluminate cement and/or oxide.
7. The method of producing a wear resistant silica/silicon carbide composite ceramic according to claim 6, wherein the oxide is calcium oxide, aluminum oxide or silicon dioxide.
8. The method for preparing a composite ceramic of abrasion-resistant silicon dioxide/silicon carbide according to claim 1, wherein the binder in step S3 further comprises a temporary binder, the temporary binder is water or an organic binder, and the temporary binder is 5-12% of the total weight of the ceramic material.
9. A wear resistant silica/silicon carbide composite ceramic prepared by the method of any one of claims 1 to 8.
10. Use of the abrasion resistant silica/silicon carbide composite ceramic of claim 9 in the field of slurry pumps, cyclones or flotation machines.
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