CN104387073A - Method for manufacturing ultrafine high-toughness silicon carbide ceramic material based on reaction sintering technology - Google Patents
Method for manufacturing ultrafine high-toughness silicon carbide ceramic material based on reaction sintering technology Download PDFInfo
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Abstract
The invention relates to a method for manufacturing an ultrafine high-toughness silicon carbide ceramic material based on a reaction sintering technology. The method solves the problem that sizes and toughness of a silicon carbide ceramic material prepared by the existing similar method need to be further improved. The method comprises the following steps of adding a Y2O3-Al2O3-SiO2 ingredient sintering additive assistant and powdered carbon into silicon carbide powder nano-particles, carrying out stirring mixing by a mixer, pouring the mixture into a methanol solution of liquid paraffin, carrying out mixing ball milling to obtain slurry, stirring the slurry, carrying out injection molding by an injection molding machine, then carrying out natural hardening in the shadow, carrying out biscuit sintering on the molded biscuit by a vacuum pre-sintering furnace, removing a binder to obtain a middle-strength biscuit, processing the biscuit by a mechanical method to obtain a blank, putting the blank into a vacuum sintering furnace, and carrying out sintering in an argon protective atmosphere to obtain the submicron-scale ultrafine high-toughness silicon carbide ceramic material.
Description
Technical field
The present invention relates to a kind of method manufacturing ultra-fine high tenacity thyrite based on reaction sintering.
Background technology
Thyrite is the stupalith that one is main component with silicon carbide (SiC); have that hot strength is large, high-temperature oxidation resistance is strong, abrasion resistance properties is good, thermostability is good, thermal expansivity is little, thermal conductivity is large, hardness is high, the good characteristic such as anti-thermal shock and resistance to chemical attack; have in fields such as automobile, mechanical chemical industry, environment protection, space technology, information electronic, the energy and apply increasingly extensively, become a kind of irreplaceable structural ceramics of other materials at a lot of industrial circle excellent performance.As: in the automotive industry, in order to improve the thermo-efficiency of engine, make full use of the energy, reduce fuel consumption, reduce topsoil, wish the working temperature of engine higher than 1200 DEG C (according to calculating, when the working temperature of engine brings up to 1370 DEG C by 1100 DEG C, thermo-efficiency can increase by 30%).Silicon carbide ceramics because of had hot strength, lower thermal expansivity, higher thermal conductivity and good thermal-shock resistance and be considered to use temperature more than 1200 DEG C of candidate materials the most promising.The country having advanced ceramics technology adopts the engine component of silicon carbide ceramics as motor stator, rotor, burner and scroll casing as the U.S., Germany and Japan have developed and achieves good result of use, and is just being devoted to the development research of full ceramic engine.
In a word, the range of application of thyrite widely, is applicable to multiple environment.In above hot environment, within the scope of Applicable temperature, although the mechanical property of thyrite is very important, under its shock resistance and higher temperature oxidation-resistance still need further Improvement and raising.Current silicon carbide, in actual production process, mainly adopts three kinds of processing methodes, i.e. reaction sintering, pressureless sintering method and hot pressing sintering method.Three kinds of processing methodes respectively have relative merits: the silicon carbide that reaction sintering is produced has the advantage that sintering temperature is low, energy consumption is low, but it is thick to there is structure particles, and physical strength is low, the shortcoming of poor toughness; The silicon carbide that pressureless sintering method is produced has high mechanical strength, high tenacity, advantage that structure particles is thin, but it is high to there is sintering temperature, the shortcoming that energy consumption is large; Hot pressed sintering silicon carbide, because of shortcomings such as cost are high, agglomerating plant technical requirements is high, is only present in laboratory stage at present, inreal commercial.Therefore, needing is exactly the respective advantage that association reaction sinters, cannot sinter, invent a kind of under the temperature condition of reaction sintering, utilize sintering to add the effect of auxiliary agent, produce the production method of the hyperfine structure similar with the silicon carbide manufactured by pressureless sintering method, high tenacity thyrite.
In addition, the preparation method of this type of stupalith existing, as the application number 200410073163.9 disclosed in Chinese patent literature, publication date on August 17th, 2005, denomination of invention " a kind of preparation method of silicon nitride/silicon carbide porous ceramic "; The method comprises batching, shaping, sintering typical ceramic material preparation technology, it is characterized in that: using resol as a kind of new pore-forming material and carbon source, utilize the carbothermic reduction reaction in sintering process, in-situ preparation nano SiC phase; Si
3n
4: Al
2o
3: Y
2o
3: the mass ratio of resol is 70 ~ 95%:1 ~ 5%:2 ~ 8%:5 ~ 28%; Add dehydrated alcohol 30 ~ 60%, batch mixing makes slip in 12 ~ 24 hours, dries and makes dry powder; By dried ceramic powder successively through overmolding, cracking binder removal, carbothermic reduction, sintering, high porosity, the high strength of 70 ~ 160MPa, the silicon nitride/silicon carbide porous ceramic of low cost of obtained 40 ~ 70%.But above-mentioned stupalith need further improvement in preparation method, particle could be obtained less, the better thyrite of toughness.
Summary of the invention
For overcoming above-mentioned deficiency, the object of the invention is to provide a kind of method manufacturing ultra-fine high tenacity thyrite based on reaction sintering to this area, making it solve existing similar thyrite preparation method designs not good enough, and obtained thyrite granular size and toughness need the technical problem improved further.Its objective is and to be achieved through the following technical solutions.
Manufacture a method for ultra-fine high tenacity thyrite based on reaction sintering, the typical process flow of this production method is: batching mixing → mixing and ball milling → mud stirring filtration → injection moulding → dry in the shade → biscuiting dewaxes → is machined under all kinds of shape → argon gas atmosphere and burns till → attrition process → finished product; It is characterized in that:
1), first in the carborundum powder of 0.1-1.20 micron particle, Y is added
2o
3-AL
2o
3-SiO
2component sintering adds auxiliary agent, carbon dust, is fully uniformly mixed, pours into and dissolved the methanol solution of whiteruss in advance through mixer, then through mixing and ball milling, obtained mud; In this process, the proportioning being dissolved with the methanol solution of whiteruss is 5:100 ~ 12:100; Paraffin solution, carborundum powder, carbon dust, Y
2o
3-AL
2o
3-SiO
2the proportioning of component is 30:100:1:0.3 ~ 60:100:3:1.50; Above-mentioned Y
2o
3-AL
2o
3-SiO
2the effect that component sintering adds auxiliary agent forms eutectic mixture when sintering temperature is about 1600-1820 DEG C, ultra-fine grain carborundum powder is arranged again and is sintered into stupalith that is fine and close, high tenacity, namely ensure that carborundum powder can realize burning till at firing temperature under lower than the condition of 1820 DEG C, reach stable fine and close ceramic matrix.
2), mud need to be placed in the stainless steel vessel of belt stirrer more than 12 hours, and period need ceaselessly stir;
3), mud after injection moulding, hardens in the cool place place seasoning of top temperature lower than 25 DEG C on injection moulding machine;
4), the biscuit of dry sclerosis aftershaping carries out biscuiting, and sloughs caking agent in vacuum pre-burning stove, and temperature is between 800-1200 DEG C, and vacuum tightness is below 0.4MPa, and the time is 0.5-4 hour, reach the biscuit of medium tenacity; Above-mentioned is the first sintering of biscuit, for ensureing that biscuit has certain physical strength.
5), again biscuit is mechanically processed into the blank of different shape and dimensional requirement;
6), after this blank is put into sintering oven, under 1600-1820 DEG C of temperature condition, make blank be placed in silicon steam and react 120-180 and divide; Argon gas needs stable existence in whole sintering process, and is in flow state, and its flow is 1L ~ 10L/min; Namely the thyrite of submicron-grade superfine high tenacity is made.
In above-mentioned steps (1), also or first liquid paraffin is dissolved in organic solvent, then adds carborundum powder, carbon dust, Y
2o
3-AL
2o
3-SiO
2component sintering adds auxiliary agent and makes mud; Wherein whiteruss, carborundum powder, carbon dust, Y
2o
3-AL
2o
3-SiO
2the weight ratio that component sintering adds auxiliary agent is 5:100:1:0.3 ~ 12:100:3:1.5.
In above-mentioned steps (1), Y
2o
3-AL
2o
3-SiO
2component sintering adds the Y of auxiliary agent
2o
3-AL
2o
3-SiO
2content is the 0.3%-1.5% of whole material total weight percent.Y
2o
3-AL
2o
3-SiO
2it is with Y that component sintering adds auxiliary agent
2o
3, AL
2o
3and SiO
2the eutectic compound of three kinds of compound compositions, it consists of 40:50:10% ~ 57:40:3%, need in advance in ceramic crucible, in the air of 1650-1820 DEG C, calcining forms Solid solution, and makes its granularity reach more than 300 orders by Ginding process to make.
In above-mentioned steps (1), in the methanol solution of whiteruss, the content of whiteruss is the 0.3%-1.5% of total mix weight percent, and the purity of methyl alcohol is technical pure.Methyl alcohol as organic solvent medium, for the dissolving of paraffin.
In above-mentioned steps (3), forming pressure is 0.5-1.50Mpa, and temperature is 40-80 DEG C, and the time is 1-5min, and mold surface temperature is 20-50 DEG C, and in injection moulding process, mud need keep good mobility.
In above-mentioned steps (4), in order to make the hole of connection in biscuit, need to carry out pre-burning to biscuit.The object of biscuit pre-burning is make to form coherent hole in biscuit by pre-burning, is convenient to the injection of silicon steam when next step sinters.
In above-mentioned steps (6), the arrangement of blank burst sinters in a layer of silicon, makes it fully to soak and melts in silicon steam; Sintering adopts vacuum, atmosphere to combine, and cold zone vacuum heats up, and higher than 1300 DEG C, adopts argon gas atmosphere protection sintering, needs to maintain more than furnace pressure 0.12MPa in sintering process.Meanwhile, in above-mentioned steps (6), temperature rise rate adopts proceed step by step, and before 1600 DEG C, temperature rise rate is the temperature rise rate of 20 DEG C/min, 1600-1820 DEG C section is 10 DEG C/min; 120-180 minute is incubated when top temperature 1600-1820 DEG C.
In above-mentioned steps (6), after having sintered, lower the temperature with the speed of 50-180 DEG C/h; After temperature is lower than 1300 DEG C, rapid cooling, reaches room temperature to furnace temperature, takes out this material, namely makes the thyrite of submicron-grade superfine high tenacity.
The ultra-fine grain that the described basal body structure making the thyrite of submicron-grade superfine high tenacity is less than 1.0 microns by particle forms, dense arrangement, and institute reaches density at 3.05g/cm
3above, bending strength is at more than 590Mpa, and hardness is at more than 91HRA, and apparent porosity is below 0.5%, and fracture toughness property is at 3.50 × more than 106Pam1/2.
The present invention makes the carborundum powder of Submicro particles can sinter at the temperature of firing temperature lower than 1820 degree, obtain the microstructure and the physical strength that are similar to the pressureless sintering silicon carbide of sintering temperature more than 2100 degree, greatly reduce firing temperature, reduce production cost.Its production method is feasible, and produce obtained thyrite granular superfine, toughness is high; It is applicable to the production of ultra-fine high tenacity thyrite.
Accompanying drawing explanation
Fig. 1 is technical process block diagram of the present invention.
Embodiment
Now by reference to the accompanying drawings, structure of the present invention and use are further described.As shown in Figure 1, the typical process flow of this production method is: batching mixing → mixing and ball milling → mud stirring filtration → injection moulding → dry in the shade → biscuiting dewaxes → is machined under all kinds of shape → argon gas atmosphere and burns till → attrition process → finished product.
embodiment 1
In the carborundum powder 500g of 0.50 μm, add the Y of 9g
2o
3-AL
2o
3-SiO
2component sintering adds the carbon dust of auxiliary agent and 15g, is fully uniformly mixed, pours in the solution having dissolved 15g whiteruss and 250ml methyl alcohol proportioning in advance through mixer, then through stirring ball-milling, obtained mud; Above-mentioned mud is stirred 12 hours in the stainless steel vessel of belt stirrer, then by the mud injection moulding on injection moulding machine after stirring, seasoning sclerosis in the cool after shaping.The biscuit of dry sclerosis aftershaping carries out biscuiting in vacuum sintering furnace, and the additive sloughed in biscuit and caking agent, and the temperature in vacuum sintering furnace is 800 DEG C, and vacuum tightness is below 0.40MPa, sinters 1.0 hours, reach the biscuit of medium tenacity; Above-mentioned obtained biscuit is processed into the blank of different shape and dimensional requirement by machining process, the sintering oven of the argon atmosphere being full of circulation put into by blank after processing, under 1750 DEG C of temperature condition, blank is placed in the silicon steam reaction 120 points of fusing; Argon gas needs stable existence in whole sintering process, and is in flow state, and its flow is 10L/min; Namely the thyrite of the submicron-grade superfine high tenacity of 495g is made.
embodiment 2
In the carborundum powder 500g of 0.86 μm, add the Y of 4.8g
2o
3-AL
2o
3-SiO
2component sintering adds the carbon dust of auxiliary agent and 9g, is fully uniformly mixed through mixer, pours in the solution dissolving 12g whiteruss and 240ml methyl alcohol proportioning in advance, then through stirring ball-milling, obtained mud; Above-mentioned mud is stirred 15 hours in the stainless steel vessel of belt stirrer, then by the mud injection moulding on injection moulding machine after stirring, seasoning sclerosis in the cool after shaping.The biscuit of dry sclerosis aftershaping carries out biscuiting in vacuum sintering furnace, and the additive sloughed in biscuit and caking agent, and the temperature in vacuum sintering furnace is 1200 DEG C, and vacuum tightness is below 0.40MPa, sinters 2 hours, reach the biscuit of medium tenacity; Again above-mentioned obtained biscuit is machined into the blank of different shape and requirement, the sintering oven of the argon atmosphere being full of circulation put into by the blank after processing, under 1820 DEG C of temperature condition, blank is placed in the silicon steam reaction 180 points of fusing; Argon gas needs stable existence in whole sintering process, and is in flow state, and its flow is 10L/min; Namely the thyrite of submicron-grade superfine high tenacity is made.
embodiment 3
The solution of first proportioning 25g whiteruss and 300ml methyl alcohol, then add carborundum powder, the carbon dust of 15g, the Y of 7.5g of 0.50 μm of 500g
2o
3-AL
2o
3-SiO
2component sintering adds auxiliary agent and makes mud, Y
2o
3-AL
2o
3-SiO
2component sintering adds the Y that auxiliary agent is 1.5% content
2o
3-AL
2o
3-SiO
2; Again through stirring ball-milling, obtained mud; Biscuit after injection moulding is placed on cooling drying in the air of 20 DEG C of room temperatures, obtained biscuit, this biscuit has had definite shape and size through mould molding, direct for this biscuit part burst arrangement is sintered in a layer of silicon, makes it fully to soak and melt in silicon steam; Sintering adopts vacuum, atmosphere to combine, and cold zone vacuum heats up, and higher than 1300 DEG C, adopts argon gas atmosphere protection, maintains furnace pressure 0.12MPa; Temperature rise rate adopts proceed step by step, and before 1600 DEG C, temperature rise rate is the temperature rise rate of 20 DEG C/min, 1600-1680 DEG C section is 10 DEG C/min; 3 hours are incubated when top temperature 1780 DEG C.After having sintered, lower the temperature with the speed of 50-180 DEG C/h; After temperature is lower than 1300 DEG C, rapid cooling; Reach room temperature to furnace temperature, take out this material, namely make the thyrite of submicron-grade superfine high tenacity.
In above-described embodiment 1-3, in forming of green body process, forming pressure is 0.5-1.50Mpa, temperature 40-80 DEG C, and the time is 1-5min, and mold surface temperature is 40-50 DEG C, is the molding technological condition of the best.Meanwhile, during for making the hole making connection in biscuit, also need to carry out pre-burning to biscuit, the effect of guarantee sintering.
The present invention proposes a kind of brand-new silicon carbide production method, adopt ultra-fine grain carborundum powder, and the respective advantage that association reaction sinters, cannot sinter, under the temperature condition of reaction sintering, namely under low firing temperature condition, utilize sintering to add the effect of auxiliary agent, produce the thyrite of the ultra-fine microstructure similar with the silicon carbide manufactured by pressureless sintering method, high tenacity, high-tenacity.The present invention is one explained hereafter method easily, has the lower power intake that reaction sintering produces carbofrax material, the production turn around time of simple and fast, has again all advantages and the feature of the silicon carbide that pressureless sintering method is produced.The ultra-fine high tenacity thyrite density of being produced by the present invention reaches 3.00-3.15g/cm
3, particularly have the features such as ultra-fine microstructure, silicone content is low, physical strength is high, toughness is high, hardness is high, product is fine and close, chemical resistance dielectric behavior is good, under being widely used in the ambient condition of the bad working environments such as strong acid, highly basic.It is suitable for the workpiece for all kinds of complicated shape, is particularly suitable for use in the production of workpiece of the complicated shape such as ceramic engine, cylinder sleeve, size; Solving pressureless sintering carborundum craft cannot the difficult problem of production superelevation complicated shape, to this expansion with high rigidity, high strength ceramic material Application Areas, provides a kind of extraordinary production method.
Claims (10)
1. manufacture a method for ultra-fine high tenacity thyrite based on reaction sintering, the typical process flow of this production method is: batching mixing → mixing and ball milling → mud stirring filtration → injection moulding → dry in the shade → biscuiting dewaxes → is machined under all kinds of shape → argon gas atmosphere and burns till → attrition process → finished product; It is characterized in that:
1), first in the carborundum powder of 0.1-1.20 micron particle, Y is added
2o
3-AL
2o
3-SiO
2component sintering adds auxiliary agent, carbon dust, is fully uniformly mixed, pours in the methanol solution having dissolved whiteruss in advance through mixer, then through mixing and ball milling, obtained mud; In this process, the proportioning being dissolved with the methanol solution of whiteruss is 5:100 ~ 12:100; Paraffin solution, carborundum powder, carbon dust, Y
2o
3-AL
2o
3-SiO
2the proportioning of component is 30:100:1:0.3 ~ 60:100:3:1.50;
2), mud need to be placed in the stainless steel vessel of belt stirrer more than 12 hours,
3), mud on injection moulding machine after injection moulding, in the cool place place air-set of top temperature lower than 25 DEG C;
4), the biscuit of dry aftershaping carries out biscuiting, and sloughs caking agent in vacuum pre-burning stove, and temperature is between 800-1200 DEG C, and vacuum tightness is below 0.40MPa, and the time is 0.5-4 hour, reach the biscuit of medium tenacity;
5), again biscuit is mechanically processed into the blank of different shape and dimensional requirement;
6), after this blank is put into vacuum sintering furnace, under 1600-1820 DEG C of temperature condition, silicon steam blank being placed in fusing reacts 120-180 and divides; Argon gas needs stable existence in whole sintering process, and is in flow state, and its flow is 1L ~ 10L/min; Namely the thyrite of submicron-grade superfine high tenacity is made.
2. the method manufacturing ultra-fine high tenacity thyrite based on reaction sintering according to claim 1, is characterized in that in above-mentioned steps (1), also or first liquid paraffin is dissolved in organic solvent, then adds carborundum powder, carbon dust, Y
2o
3-AL
2o
3-SiO
2component sintering adds auxiliary agent and makes mud; Paraffin solution, carborundum powder, carbon dust, Y
2o
3-AL
2o
3-SiO
2the weight ratio that component sintering adds auxiliary agent is 5:100:1:0.3 ~ 12:100:3:1.5.
3. the method manufacturing ultra-fine high tenacity thyrite based on reaction sintering according to claim 1, is characterized in that in above-mentioned steps (1), Y
2o
3-AL
2o
3-SiO
2component sintering adds the Y of auxiliary agent
2o
3-AL
2o
3-SiO
2content is the 0.3%-1.5% of whole material total weight percent.
4. the method manufacturing ultra-fine high tenacity thyrite based on reaction sintering according to claim 1, it is characterized in that in above-mentioned steps (1), in the methanol solution of whiteruss, the content of whiteruss is the 0.3%-1.5% of total mix weight percent, and the purity of methyl alcohol is technical pure.
5. the method manufacturing ultra-fine high tenacity thyrite based on reaction sintering according to claim 1, it is characterized in that, in above-mentioned steps (3), forming pressure is 0.5-1.50Mpa, temperature is 40-80 DEG C, time is 1-5min, and mold surface temperature is 20-50 DEG C.
6. the method manufacturing ultra-fine high tenacity thyrite based on reaction sintering according to claim 1, is characterized in that in above-mentioned steps (4), in order to make the hole of connection in biscuit, needs to carry out pre-burning to biscuit.
7. the method manufacturing ultra-fine high tenacity thyrite based on reaction sintering according to claim 1, is characterized in that in above-mentioned steps (6), and the arrangement of blank burst sinters in a layer of silicon, makes it fully to soak and melts in silicon steam; Sintering adopts vacuum, atmosphere to combine, and cold zone vacuum heats up; After higher than 1300 DEG C, adopt argon gas atmosphere protection sintering, needing in sintering process to maintain furnace pressure is more than 0.12Mpa.
8. the method manufacturing ultra-fine high tenacity thyrite based on reaction sintering according to claim 7, it is characterized in that in above-mentioned steps (6), temperature rise rate adopts proceed step by step, before 1600 DEG C, temperature rise rate is the temperature rise rate of 20 DEG C/min, 1600-1820 DEG C section is 10 DEG C/min; 120-180 minute is incubated when top temperature 1600-1820 DEG C.
9. the method manufacturing ultra-fine high tenacity thyrite based on reaction sintering according to claim 8, is characterized in that in above-mentioned steps (6), after having sintered, lowers the temperature with the speed of 50-180 DEG C/h; After temperature is lower than 1300 DEG C, rapid cooling, reaches room temperature to furnace temperature, takes out this material, namely makes the thyrite of submicron-grade superfine high tenacity.
10. the method manufacturing ultra-fine high tenacity thyrite based on reaction sintering according to claim 1, the ultra-fine grain that the basal body structure making the thyrite of submicron-grade superfine high tenacity described in it is characterized in that is less than 1.0 microns by particle forms, dense arrangement, institute reaches density at 3.05g/cm
3above, bending strength is at more than 590Mpa, and hardness is at more than 91HRA, and apparent porosity is below 0.5%, and fracture toughness property is at 3.50 × more than 106Pam1/2.
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Cited By (7)
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| CN105174922A (en) * | 2015-10-20 | 2015-12-23 | 兰州理工大学 | Preparation method for high-toughness Al2O3/3Y-ZrO2 multiphase ceramic |
| CN106827255A (en) * | 2017-01-18 | 2017-06-13 | 北京钢研新冶精特科技有限公司 | A kind of carborundum side's mirror biscuit Pocket Machining method |
| CN107522510A (en) * | 2017-08-31 | 2017-12-29 | 安徽青花坊瓷业股份有限公司 | A kind of manufacturing process of low-porosity ceramics |
| CN109620442A (en) * | 2018-12-20 | 2019-04-16 | 四川华柚医疗器械有限公司 | A kind of novel artificial tooth and preparation method thereof |
| CN110436929A (en) * | 2017-06-07 | 2019-11-12 | 吴彬 | A kind of silicon carbide ceramics |
| CN115956064A (en) * | 2020-09-07 | 2023-04-11 | 日本碍子株式会社 | Refractory material |
| KR102527285B1 (en) * | 2022-09-16 | 2023-05-04 | (주)신일세라믹스 | Composite ceramic tube for transport in thermal power plants using silicon carbide ceramic for high wear resistance |
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| CN101289319A (en) * | 2008-06-03 | 2008-10-22 | 浙江东新密封有限公司 | Reaction sintering silicon carbide ceramic and production method thereof |
| CN103833366A (en) * | 2012-11-22 | 2014-06-04 | 沁阳市黄河碳素有限责任公司 | Preparation technology for silicon carbide base ceramic material |
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| CN101289319A (en) * | 2008-06-03 | 2008-10-22 | 浙江东新密封有限公司 | Reaction sintering silicon carbide ceramic and production method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105174922A (en) * | 2015-10-20 | 2015-12-23 | 兰州理工大学 | Preparation method for high-toughness Al2O3/3Y-ZrO2 multiphase ceramic |
| CN106827255A (en) * | 2017-01-18 | 2017-06-13 | 北京钢研新冶精特科技有限公司 | A kind of carborundum side's mirror biscuit Pocket Machining method |
| CN106827255B (en) * | 2017-01-18 | 2019-05-31 | 北京钢研新冶精特科技有限公司 | A kind of silicon carbide side's mirror biscuit Pocket Machining method |
| CN110436929A (en) * | 2017-06-07 | 2019-11-12 | 吴彬 | A kind of silicon carbide ceramics |
| CN107522510A (en) * | 2017-08-31 | 2017-12-29 | 安徽青花坊瓷业股份有限公司 | A kind of manufacturing process of low-porosity ceramics |
| CN109620442A (en) * | 2018-12-20 | 2019-04-16 | 四川华柚医疗器械有限公司 | A kind of novel artificial tooth and preparation method thereof |
| CN115956064A (en) * | 2020-09-07 | 2023-04-11 | 日本碍子株式会社 | Refractory material |
| KR102527285B1 (en) * | 2022-09-16 | 2023-05-04 | (주)신일세라믹스 | Composite ceramic tube for transport in thermal power plants using silicon carbide ceramic for high wear resistance |
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