CN101077838A - Technique for preparing liquid phase sintering silicon carbide ceramic - Google Patents
Technique for preparing liquid phase sintering silicon carbide ceramic Download PDFInfo
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- CN101077838A CN101077838A CN 200610084395 CN200610084395A CN101077838A CN 101077838 A CN101077838 A CN 101077838A CN 200610084395 CN200610084395 CN 200610084395 CN 200610084395 A CN200610084395 A CN 200610084395A CN 101077838 A CN101077838 A CN 101077838A
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Abstract
The present invention relates to ceramic technology, and is especially liquid phase sintering technology for silicon carbide ceramic. The present invention provides one new technological scheme capable of raising production efficiency and reducing power consumption. The silicon carbide ceramic product is produced with the materials including silicon carbide powder, yttria, alumina and binding agent and through the following steps: 1. mixing yttria and alumina, ball milling, and producing flux material through a mechanochemical process; and 2. mixing the flux material, silicon carbide powder, binding agent and other material, molding, curing and high temperature sintering to form silicon carbide ceramic product.
Description
The present invention relates to ceramic production technology, particularly the liquid phase sintering production technology of silicon carbide ceramics.The invention provides a kind of new technical scheme.Technical scheme provided by the invention helps to improve the related production usage ratio of equipment, improves the production efficiency of silicon carbide ceramics, reduces the energy consumption in the production process.
Good characteristics such as thyrite has that hot strength is big, high-temperature oxidation resistance is strong, abrasion resistance properties is good, thermostability is good, thermal expansivity is little, thermal conductivity is big, hardness is high, anti-thermal shock and resistance to chemical attack; in fields such as automobile, mechanical chemical industry, environment protection, space technology, information electronics, the energy increasingly extensive application is arranged, become a kind of irreplaceable structural ceramics of other materials at a lot of industrial circle excellent performances.
In automotive industry,, make full use of the energy in order to improve the thermo-efficiency of engine, reduce fuel consumption, reduce topsoil, the working temperature of wishing engine is higher than 1200 degree and (it is calculated that, the working temperature of engine brings up to 1370 when spending by 1100 degree, and thermo-efficiency can increase by 30%).The hot strength of silicon carbide ceramics because of being had, lower thermal expansivity, higher thermal conductivity and thermal-shock resistance and be considered to the most promising candidate materials that use temperature surpasses 1200 degree preferably.The country such as the U.S., Germany and the Japan that have the advanced ceramics technology have developed engine component such as motor stator, rotor, burner and the volute pipe that adopts silicon carbide ceramics and have obtained good result of use, just are being devoted to the development research of full ceramic engine at present.
Dynamic seal in the mechanical means is to be undertaken by the rotational slide of two seal face materials, as the seal face material, requires the hardness height, has wearability.Suitable height of the hardness of silicon carbide ceramics and frictional coefficient are little, so silicon carbide ceramics can obtain sliding properties that other material is beyond one's reach as the mechanical seal end surface material.On the other hand, two mechanical seal materials can produce certain heat owing to rub in rotary movement, thereby the local temperature of seal face is raise, so the end face material also must can tolerate certain temperature.In the rotational slide process, produce thermal strain and hot tearing for fear of the mechanical seal material, require thermal conductivity height, the good thermal shock of end face material.At present, silicon carbide ceramics has obtained a large amount of application in all kinds of mechanical seals, and for the laborsaving of mechanical means with energy-conservationly made very big contribution, demonstrate other materials incomparable superiority.Silicon carbide ceramics also successfully is used as various bearings, cutting tool in mechanical industry.
What need in the occasion of needs such as aerospace, nuclear industry tolerances ultra high temp such as nuclear fission and the fusion reactor bears 2000 degree left and right sides pyritous heat-stable materials; Rocket and aerospacecraft surface are used for tolerating the thermal insulation tile up to thousands of K temperature that produces with the violent friction of atmosphere; Rocket combustion chamber's larynx lining and inner lining material, gas-turbine blade; The top board of High Temperature Furnaces Heating Apparatus, support, and the high temperature members such as jig of high temperature experiment usefulness also generally adopt the silicon carbide ceramics member.Silicon carbide ceramics also is widely used as various corrosion-resistant with container and pipeline in petrochemical industry;
When the industrial production field obtained widespread use, as a kind of function ceramics, the also start to excel in fields such as power electronics, micro electronmechanical, communications was about to obtain breakthrough market to thyrite as structural ceramics.
The thyrite of using in different fields has different requirements to performance, needs with different preparation methods.The preparation technology of silicon carbide can be divided into several classes such as reaction sintering, pressureless sintering and hot pressing (or hot isostatic pressing) sintered silicon carbon at present.Reaction sintering is that technology is ripe relatively, and technical difficulty is less, but in the product of reaction sintering the free silica about 10% is arranged, and ability highly basic and hydrofluoric acid can not be applied in the Chemical Manufacture environment of strong acid and strong base; When temperature was spent above 1400, bending strength can sharply descend, and high temperature tolerance is more weaker relatively, can not be used for the occasion strict to hot strength.From comprehensive mechanical property (comprising bending strength, fracture toughness property, Young's modulus, bending strength etc.), reaction-sintered ceramic product and pressureless sintering and hot pressed sintering more still have bigger gap.Use as structural ceramics, reaction-sintered ceramic generally only is used in the not too high mechanical seal of requirement, high temperature member and chemical production field.The purity that the function ceramics product requirement is very high or control the composition of product easily, for reaction sintering technology, these requirements all are difficult to reach.
Silicon carbide is carbon and the Siliciumatom xln with the tetrahedron spatial arrangement of chemical bond combination, and its covalent linkage is very strong.Such covalent linkage pottery is hard-to-sinter very, if silicon carbide powder material self sintering even if under very high temperature, also only has the neck of trace to grow up, and the volumetric shrinkage densification does not take place between the powder (3～5 μ m).Therefore, its sintering needs carrying out under the high-temperature (2300-2400K) very much usually, and needs to add a small amount of additive or apply high mechanical pressure.With apply certain pressure be feature be exactly hot pressing or HIP sintering.On mechanical property, the silicon carbide ceramics of hot pressed sintering has very high sintered density, bending strength and fracture toughness property.Excellent mechanical behavior under high temperature (the above mechanical property of 1600 degree also slightly strengthens) is especially arranged, can be applied to each silicon carbide structure ceramic field.But owing to must seal biscuit of ceramics in the hot pressed sintering process, therefore can't produce in enormous quantities, limit its application in suitability for industrialized production.
Like this, in system, add sintering aid and under normal pressure agglomerating pressureless sintering method just become the industrial process of the most promising preparation high-performance silicon carbide pottery.According to the state of sintering aid in sintering process, pressureless sintering can also be divided into solid state sintering and liquid phase sintering.Solid state sintering normally adds an amount of norbide and carbon in system, liquid phase sintering then adds an amount of fusing assistant and present liquid state when sintering.Comparatively speaking, liquid phase pressureless sintering method has lower sintering temperature, (the solid state sintering fracture toughness property is relatively poor, fracture mode is typical transgranular fracture for the mechanical property suitable with hot pressed sintering, thick and the lack of homogeneity of crystal grain, interface, intensity and the toughness of reduction significantly improve, fracture mode ruptures along brilliant for typical and liquid phase sintering has) and hot strength and oxidation-resistance.Therefore, liquid phase pressureless sintering silicon carbide is the most promising industrial method of preparation high-performance silicon carbide pottery, and how to obtain the high as far as possible silicon carbide ceramics of mechanical property at lower sintering temperature also is to enlarge the assurance that silicon carbide ceramics is used in every field.
The Application Areas of silicon carbide ceramics is quite extensive, all check on the market of silicon carbide ceramics in each field is very difficult, but we can understand the supply and demand situation of silicon carbide ceramics by no side.
Silicon carbide ceramics is formed by the silicon carbide powder sintering, the silicon carbide powder material can only be by the minority manufacturer production at present, wherein Fa Guo company of Saint-Gobain (2003 with the 133rd of 45,000,000,000 Euros of volume of business arrangement 500 tops of the world) occupies main status in world markets, estimate that according to company of Saint-Gobain the silicon carbide total market size in the whole world in 2003 is about 800,000 tons/year.Wherein the annual production of company of Saint-Gobain is about 200,000 tons, China produces the silicon carbide powder industry and developed very fast in recent years, occurred a collection of as Tianjin Ai Sida, Mudanjiang Dan Feng a collection of bigger enterprises such as (2003 with 1.1 hundred million yuan of corporate buyouts of the French Saint-Gobain of quilt), the silicon carbide powder production capacity reaches about 400,000 tons, and the threat from Chinese silicon carbide powder production capacity has been experienced in the whole world.This wherein has 1/3 amount to be used to carry out the sintered silicon carbide ceramics product approximately, present industrial silicon carbide ceramics be prepared as reaction sintering and pressureless sintering coexistence.The reaction sintering production technique is comparative maturity, uses also quite extensively, and cost and price are also lower.But because performance issue, the product of reaction sintering is progressively moving towards superseded.
Only used the gross output value of thyrite to be about more than 8,000 ten thousand dollars in 2005 in the world in the mechanical seal field, wherein pressureless sintering silicon carbide is about 55,000,000 dollars, accounts for about 65% of total silicon carbide turnout.Germany is that maximum in the world nothing is pressed silicon carbide producing country, and its nothing that country produced presses silicon carbide with regard to about 40,000,000 dollars, accounts for the over half of Gross World Product.The year silicon carbide output of China is about 2,500 ten thousand yuans to 3,000 ten thousand yuans, rolls over more than 300 ten thousand dollars.In heat-resisting high temperature member field, the market share of silicon carbide ceramics is about 1-2 is hundred million dollars at present.Estimate that according to U.S. Argonne National Laboratory energy and environment research department Transportation Research Center 2000～2010 years motor car engines can account for the 66%-90% of after-market with silicon carbide ceramic components, total value is above 3,000,000,000 dollars.
Because the high-performance of silicon carbide ceramics and the widespread use in industrial circle, the sintering of SiC are the focuses of material circle research always.But because silicon carbide is the extremely strong covalent linkage compound of a kind of covalency, even under 2100 ℃ high temperature, the self-diffusion coefficient of C and Si also only is 1.5 * 10
-10With 2.5 * 10
-13Cm
2/ s.SiC is difficult to sintering, must could realize densification by sintering aid or external pressure.
As far back as mid-term the 1950's, the Alliegro of U.S. Norton company etc. adopt B, Al, Fe, Ni, Cr, Ca, Li, Al-Fe, Zr-B etc. to adopt the way of hot pressed sintering to prepare silicon carbide ceramics as auxiliary addition agent with regard to beginning.After this have again F.I.Lange with A1203 as sinter additives, J.M.Bind and J.V.Biggers etc. with B
4C makes additive, and the bright grade in the east of a river is with B
4C is that auxiliary agent is used different auxiliary agent hot pressed sintering silicon carbide ceramics respectively with other investigators with C, has all obtained success to a certain degree, has obtained the different silicon carbide ceramics of performance.But the employing hot-pressing sintering technique can only prepare the silicon carbide components of simple shape, and seldom and very is unfavorable for commercially producing through the quantity of the prepared product of once sintered process.So U.S. Carbortmdum company has taken the lead in carrying out the preparation of silicon carbide reaction-sintered since the seventies, reaction sintering mainly utilizes the silicon carbide biscuit of many voidages at high temperature to flood the liquid pasc reaction carborundum particle that condenses and makes.At present, typical reaction sintering SiC goods mainly contain the Refel-SiC of Britain UKAEA and the KT-SiC of U.S. Carbortmdum company.But the product of overall every index of silicon carbide reaction-sintered and performance and hot pressed sintering has certain distance to be objective.
Since the eighties of last century 70-80 age, people have carried out number of research projects and have wished and can obtain high performance silicon carbide ceramics product by sintering under non-pressurized condition.1974, the S.Prochazka of U.S. GE company adopted non-pressure sintering technology by add a spot of B and C simultaneously in highly purified B-SiC fine powder, has successfully obtained density in 2020 ℃ and has been higher than 98% SiC sintered compact.After this, the countries in the world researchist has carried out a large amount of research, has screened different sintering aids, tries hard to keep when reducing sintering temperature the mechanical property of higher material.On the whole, pressureless sintering can be divided into solid state sintering and liquid phase sintering according to the state of selecting for use auxiliary agent in sintering process.Employing B, C such as S.Prochazka, J.A.Coppola, Joe J.Cao fused second do not occur mutually with Al or its compound in sintering process, be known as solid state sintering.Solid-phase sintering method needs very high sintering temperature, and sintered product crystal grain is thick, and fracture toughness property is lower, and comparing with the hot pressed sintering product still has less gap.H.Tanaka, M.A.Mulls, T.Ohji etc. added Al afterwards
2O
3-Y
2O
3, AIN-R
2O
3Being called as liquid phase sintering by forming the liquid phase molten mixture Deng sintering aid in sintering process, also is the direction of following silicon carbide ceramics preparation.Liquid phase sintering can obtain the fracture toughness property suitable with the hot pressed sintering product and flexural strength at lower sintering temperature and have complicated shape and large-sized silicon carbide components, is considered to the most promising sintering method of silicon carbide ceramics.Liquid phase sintering system, particularly SiC-Al
2O
3-Y
2O
3, become the focus of the research of silicon carbide sintering in recent years.Colleges and universities such as Seoul, South Korea university, Korea S high-tech research institute, the general institute of German horse, U.S. Connecticut university, National Institute of Standard and Technology, Japanese national inorganic materials institute, Chinese Shanghai silicate institute and scientific research institution conduct a research one after another, be devoted to seek different sintering aids, the silicon carbide ceramics product that obtains lower sintering temperature and have better characteristic.Do not have the commercialization silicon carbide ceramics that presses solidly phase sintering at present Japanese special porcelain industry EC-422, EC-425 are arranged, U.S. GE company, Shanghai silicate institute, U.S. Hexolog, U.S. Carborundum company, German PLS etc., but owing to reasons such as technology and technologies, the liquid phase silicon carbide ceramics of domestic industryization prepares production line does not at present almost also have, and few abroad yet.
In sum, too high sintering temperature or pressure are the major causes that SiC is difficult to obtain industrial application always, so the selection of sintering agent still is a SiC agglomerating research topic, under lower temperature conditions, sintering goes out industrial suitable SiC, is the key that the SiC sintering moves towards widespread use.
At present, at SiC-Al
2O
3-Y
2O
3Liquid phase sintering system, the production technology of more employing are with sintering aid Al
2O
3And Y
2O
3Directly mix with carborundum powder and wedding agent, reach the ball milling of ten a few hours, then, the drying granulation, compression molding, solidifying and setting, thick mechanical workout, high temperature sintering, steps such as machine finshing finally form the silicon carbide ceramics product.It is reported that in above-mentioned technology, the mechanical milling process activity time that reached for ten a few hours is long, the overall utilization ratio of ball-grinding machine is low, and energy consumption is also bigger, and from enterprise's angle, the technology of this long-time ball milling is not ideal.
Purpose of the present invention, problem such as the low and energy consumption of long-time ball milling that is to avoid above-mentioned and ball-grinding machine utilization ratio is bigger.The present invention proposes a new technical scheme.
Idea of the present invention because of the investigation to relevant silicon carbide ceramics enterprise, in the survey, finds to exist described long-time ball milling and the overall utilization ratio of ball-grinding machine to hang down and problems such as energy consumption is bigger.Through furtheing investigate with Al
2O
3And Y
2O
3For the whole silicon carbide ceramic production technology process of sintering aid, after having consulted lot of documents, confirm, in the knowhow ratio mix by Al
2O
3And Y
2O
3The sintering aid that constitutes, at the high temperature sintering warm area, being actually progressively reacts to each other forms with the yttrium aluminum garnet is the fusion liquid phase of major ingredient, and the generation of this fusion liquid phase is the key that (1800 ℃～1950 ℃) realize silicon carbide ceramics liquid phase sintering under lower sintering temperature.So, previously described with sintering aid Al
2O
3And Y
2O
3Directly mix with carborundum powder and wedding agent, the ball milling that reached for ten a few hours, then, the drying granulation, compression molding, solidifying and setting, thick mechanical workout, high temperature sintering, steps such as machine finshing, in the production process of final formation silicon carbide ceramics product, for the effect of long-time this operation of ball milling, we think: the Al of the broken greater particle size of the first
2O
3And Y
2O
3Raw material, generate be easy to react, be easy to batch mixing the small particle size material; Its two, the small particle size material that has generated is reunited easily, ball milling can destroy described reunion, promotes the mixing of material; They are three years old, the ball milling that reached for ten a few hours may produce mechanochemical treatment to a certain degree, may tentatively generate a certain amount of yttrium aluminum garnet presoma phase in this course, a certain amount of yttrium aluminum garnet presoma of described preliminary generation may not fully become phase mutually, but it in time has a vital role for fusion liquid phase in high temperature sintering.Through consulting the documents and materials of relevant yttrium aluminum garnet, know that yttrium aluminum garnet has obtained more deep research as a kind of important laser crystal material, can find the synthetic work that some documents relate to powdery yttrium aluminum garnet presoma specially, wherein, Xu Fengxiu etc. are published in " Chinese pottery industry ", and (2004 produce June per year, the 11st the 3rd phase of volume) the being entitled as Study on Preparation Technology of the YAG nano-powder " progress " literary composition on has more detailed argumentation to the synthetic method of powdery yttrium aluminum garnet (YAG) presoma, according to this article introduction, the essence of mechanochemical reaction is several superfine powders that will not react at normal temperatures, by the mechanicals efforts that adds, make chemical action takes place between particle, be about to mechanical energy and change chemical energy into, thereby be referred to as mechanochemical effect.The mechanochemistry technology is typical solid phase method.Use the vibration of high frequency or little amplitude can obtain high-energy ball milling power, the vibration mill that is used for the powder of short run is a high energy, and the generation chemical reaction, in the serious plastic deformation of successive, the continuable nano-grade size that refine to of the internal structure of powder particle.Mechanochemical reaction can be used for the preparation of organic one inorganic, organic one an organic and inorganic inorganic compounding particle.This method technology is simple, efficient is high, can prepare nano-powders such as the refractory metal that is difficult to obtain with ordinary method and alloy, intermetallic compound, sintering metal.1999, the Xiaomei Guo and the KenjiSAKURAI of Japan utilized this method successfully to synthesize polycrystalline YAG (being yttrium aluminum garnet) nano-powder first.Detailed process is divided two stages: at first be at room temperature by certain stoichiometric aluminum oxide and yttrium oxide mixing and ball milling (planetary mills) 24 hours, generate non-equilibrium, unordered Y-Al-O phase; Under 1150 ℃ of thermal treatment temps, carry out crystallization then, can obtain nano level yttrium aluminum garnet polycrystal powder.In addition, Qiwu Zhang utilizes the sun and planet gear break-in to become unformed YAG powder with Fumio Saito, handles obtaining the good YAG powder of crystallinity then in lower temperature (700 ℃) calcination.In view of the above the literary composition, can advance a judgement, existing with Al
2O
3And Y
2O
3In the silicon carbide ceramic production technology for sintering aid, with sintering aid Al
2O
3And Y
2O
3Directly mix with whole materials such as carborundum powder and wedding agent, the ball milling that reached for ten a few hours, existing broken material, destroy and reunite, promote the effect of mixing of materials, mechanochemical treatment is to a certain degree arranged again, truly have the yttrium aluminum garnet presoma phase that may tentatively generate a certain amount of powdered form in this course.So, the very sintering aid Al of small proportion will be accounted for relatively
2O
3And Y
2O
3With accounting for very a high proportion of also is that the carborundum powder and the wedding agent of large volume directly mixes a large amount of the time, the ball milling that reached for ten a few hours, as can be seen, only from the mixing of materials angle, have little significance, and this technology takies and moves ball-grinding machine for a long time with the material of a large amount of large volumes, cause the ball-grinding machine utilization ratio low, the ball-grinding machine long-play also brings the increase of power consumption, because, when material was enough thin, simple mixing process did not need such time that reached for ten a few hours, just was enough to reach sufficient mixing much smaller than the ball milling of this time.
Technical scheme of the present invention, it is a kind of new liquid phase sintering silicon carbide ceramic production technique, raw materials used carborundum powder, yttrium oxide, aluminum oxide and the wedding agent of comprising of this programme, through processes such as batch mixing, mold pressing typing, curing, high temperature sinterings, form the silicon carbide ceramics product, the invention is characterized in, the production technique bag of this programme is fitted following steps: one of step, yttrium oxide and two kinds of raw materials of aluminum oxide are mixed, carry out ball milling, utilize mechanochemical reaction to generate the prefabricated material of fusing assistant; Two of step is mixed the prefabricated material of fusing assistant with carborundum powder and wedding agent etc., through processes such as mold pressing typing, curing, high temperature sinterings, form the silicon carbide ceramics product.Can also contain some other auxiliary agents in raw materials used, for example, softening agent, lubricant etc.Described wedding agent for example, PVA, PVB etc.; Can also contain some other processing step in the production process, for example, dry materials; Granulation for powders; Blank after solidifying is carried out mechanical cutting roughing; Base behind high temperature sintering pottery is carried out mechanical ground finish etc.; Ball milling of the present invention is made a general reference the grinding of any mechanize mode, and described ball milling can be the grinding of the ball mill mode on the ordinary meaning, and ball milling of the present invention can certainly be the grinding of vibration mill mode; Ball mill of the present invention is made a general reference any grinding machinery, described ball mill for example: the rotary type ball mill, planetary ball mill, high energy ball mill stirs mill, vibration mill (vibration mill), micronizer, ultra-fine mill, nano grinder.
Mechanochemical reaction requires the ball milling time longer, about this point, addresses in the preamble.The ball milling energy is high more, and the ball milling time is long more, just helps go into more yttrium aluminum garnet (YAG) powdery presoma phase more, and this in time brings into play fully when the high temperature sintering for the prefabricated material of fusing assistant and helps nodulizing significant; Adopt technical solutions according to the invention, described yttrium oxide and two kinds of raw materials of aluminum oxide are mixed, carry out ball milling, utilize mechanochemical reaction to generate in the processing step of the prefabricated material of fusing assistant, for reaching effect preferably, the ball milling time was preferably in more than 5 hours.Certainly, the ball milling time shortlyer also allows.
Can there be several different methods that the prefabricated material of described fusing assistant is mixed with carborundum powder and wedding agent etc.The carborundum powder particle diameter that is used for liquid sintering technology is less, and about about 0.1～1.0 μ m, and the prefabricated material particle diameter of the described fusing assistant that generates behind ball milling is also less.Described the prefabricated material of fusing assistant is mixed with carborundum powder and wedding agent etc., through processes such as mold pressing typing, curing, high temperature sinterings, form in the step of silicon carbide ceramics product, the hybrid mode of prefabricated material of fusing assistant and carborundum powder can adopt ball milling method.Because prefabricated material of fusing assistant and carborundum powder particle diameter are all enough little, ball milling mixing required time is shorter.Can reach thorough mixing in 1～2 hour.
Described the prefabricated material of fusing assistant is mixed with carborundum powder and wedding agent, through processes such as mold pressing typing, curing, high temperature sinterings, form in the step of silicon carbide ceramics product, the blending means of the prefabricated material of fusing assistant and carborundum powder and wedding agent is also made paste mixture, adopts churned mechanically method to mix.Make paste mixture with prefabricated material of all enough little fusing assistant of particle diameter and carborundum powder, adopt churned mechanically method also can reach thorough mixing.
Adopting described mechanical stirring method to carry out in the blended technology, also can utilize the ultrasonication effect in conjunction with large power supersonic equipment, with ultrasonic wave described paste mixture is carried out ultrasonication, destroy particle agglomeration, promote to intert mutually between each material composition and permeate, strengthen the material mixed effect.About effect of ultrasound such as ultrasonic cavitation, ultrasonication, in each ultrasonic technique monograph, detailed introduction is arranged all.The large power supersonic Equipment Market is on sale.
In existing technology, be with sintering aid Al
2O
3And Y
2O
3Directly mix with carborundum powder and wedding agent, reach the ball milling of ten a few hours, then, the drying granulation, compression molding, solidifying and setting, thick mechanical workout, high temperature sintering, steps such as machine finshing finally form the silicon carbide ceramics product.
And technical scheme of the present invention is to comprise two step: a, and yttrium oxide and two kinds of raw materials of aluminum oxide are mixed, and carries out ball milling, utilizes mechanochemical reaction to generate the prefabricated material of fusing assistant; B mixes the prefabricated material of fusing assistant with carborundum powder and wedding agent etc., through processes such as mold pressing typing, curing, high temperature sinterings, form the silicon carbide ceramics product.The characteristics of technical scheme of the present invention mainly contain two aspects:
1, utilize mechanochemical reaction to generate the prefabricated material of fusing assistant, as mentioned before, to generate a certain amount of yttrium aluminum garnet presoma phase in this process, the prefabricated material of the fusing assistant that is generated can in time and fully be fused into molten state in high-temperature sintering process, this is favourable to forming the high-quality silicon carbide product; Consult the documents and materials of relevant yttrium aluminum garnet (YAG), as can be known, the fusing point warm area of yttrium aluminum garnet (YAG) is consistent with silicon carbide ceramics liquid phase sintering warm area.
2, improved the utilization ratio of ball-grinding machine, reduce the energy consumption of concerned process steps; With a charging capacity is that 5 kilograms ball mill is an example, to prior art (with sintering aid Al
2O
3And Y
2O
3Directly mix with whole materials such as carborundum powder and wedding agent, reach the ball milling of ten a few hours), established the each ball milling of every ball grinder 16 hours, finish 50 kilograms dosage, palpus 10 jars times, clean 10*16=160 consuming time hour; But if reality is only accounted for the sintering aid Al of total mass about 6～10%
2O
3And Y
2O
3(50 kilograms 6～10%, be about 3～5 kilograms) carry out ball milling by the present invention program, prepare the prefabricated material of described fusing assistant, and then ball milling is clean only 16 hours consuming time; The prefabricated material of the fusing assistant that particle diameter is all enough little further mixes with carborundum powder and wedding agent again, preamble is addressed, this stage is consuming time less, can reach thorough mixing in about 1～2 hour, this stage can mix by ball, also can mix, can also carry out described mixing in conjunction with ultrasonic equipment with churned mechanically method.
Accompanying drawing 1 has been expressed technical essential of the present invention concisely.
Embodiment 1: get yttrium oxide and alumina raw material, with Y
2O
3: Al
2O
3=3: 5～7 ratio (mol ratio) by 5 kilograms of gross weight weighings, is that 5 kilograms of yttrium oxide and alumina raw material are sent in the ball mill with the gross weight that weighs up, and ball milling 18～24 hours is made 5 kilograms of prefabricated material of described fusing assistant;
Take by weighing the prefabricated material of described fusing assistant of 0.5 kilogram of amount at every turn, take by weighing 5～8 kilograms carborundum powder and other batching (an amount of wedding agent simultaneously, an amount of softening agent, moderate lubrication agent etc.), be made into the material of about 5.5～8.5 kilograms of amounts of dry weight, this material is sent in the ball mill, add suitable quantity of water, ball milling 1～2 hour, afterwards, the material that taking-up is handled well, drying, granulation, compression molding, suitable warm spot between 150 ℃～300 ℃ is cured 1～2 hour, carries out mechanical cutting roughing after being chilled to room temperature, and the blank after the roughing is sent in the graphite carbon pipe high-temperature electric resistance furnace, in 1800 ℃～2050 ℃ warm area sintering 0.5～1.5 hour, make silicon carbide base ceramic material, described silicon carbide base ceramic material is made silicon carbide ceramics precision work finished product after the ground finish operation.
10 batches of silicon carbide ceramics precision work finished products that gross weight is about 50～80 kilograms of the corresponding production of the prefabricated material of the described fusing assistant that ready-formed is 5 kilograms.
Embodiment 2: get yttrium oxide and alumina raw material, with Y
2O
3: Al
2O
3=3: 5～7 ratio (mol ratio) by 5 kilograms of gross weight weighings, is that 5 kilograms of yttrium oxide and alumina raw material are sent in the ball mill with the gross weight that weighs up, and ball milling 18～24 hours is made 5 kilograms of prefabricated material of described fusing assistant;
Take by weighing the prefabricated material of described fusing assistant of 0.5 kilogram of amount at every turn, take by weighing 5～8 kilograms carborundum powder and other batching (an amount of wedding agent simultaneously, an amount of softening agent, moderate lubrication agent etc.), be made into the material of about 5.5～6 kilograms of amounts of dry weight, this material is sent in the mechanical agitating tank, add suitable quantity of water, form pasty material,, stirred pasty material 1～2 hour in churned mechanically mode, afterwards, the material that taking-up is handled well, drying, granulation, compression molding, suitable warm spot between 150 ℃～300 ℃ is cured 1～2 hour, carries out mechanical cutting roughing after being chilled to room temperature, and the blank after the roughing is sent in the graphite carbon pipe high-temperature electric resistance furnace, in 1800 ℃～2050 ℃ warm area sintering 0.5～1.5 hour, make silicon carbide base ceramic material, described silicon carbide base ceramic material is made silicon carbide ceramics precision work finished product after the ground finish operation.
10 batches of silicon carbide ceramics precision work finished products that gross weight is about 50～80 kilograms of the corresponding production of the prefabricated material of the described fusing assistant that ready-formed is 5 kilograms.
Embodiment 3: get yttrium oxide and alumina raw material, with Y
2O
3: Al
2O
3=3: 5～7 ratio (mol ratio) by 5 kilograms of gross weight weighings, is that 5 kilograms of yttrium oxide and alumina raw material are sent in the ball mill with the gross weight that weighs up, and ball milling 18～24 hours is made 5 kilograms of prefabricated material of described fusing assistant;
Take by weighing the prefabricated material of described fusing assistant of 0.5 kilogram of amount at every turn, take by weighing 5～8 kilograms carborundum powder and other batching (an amount of wedding agent simultaneously, an amount of softening agent, moderate lubrication agent etc.), be made into the material of about 5.5～8.5 kilograms of amounts of dry weight, this material is sent in mechanical agitating tank or the machine mixer, add suitable quantity of water, form pasty material, in churned mechanically mode, stirred pasty material 1 hour, and afterwards, described pasty material was changed in the large power supersonic treatment trough, with high-power ultrasonics effect 1 hour, the material that taking-up is handled well, drying, granulation, compression molding, suitable warm spot between 150 ℃～300 ℃ is cured 1～2 hour, carries out mechanical cutting roughing after being chilled to room temperature, and the blank after the roughing is sent in the graphite carbon pipe high-temperature electric resistance furnace, in 1800 ℃～2050 ℃ warm area sintering 0.5～1.5 hour, make silicon carbide base ceramic material, described silicon carbide base ceramic material is made silicon carbide ceramics precision work finished product after the ground finish operation.
10 batches of silicon carbide ceramics precision work finished products that gross weight is about 50～80 kilograms of the corresponding production of the prefabricated material of the described fusing assistant that ready-formed is 5 kilograms.
Embodiment 4: get yttrium oxide and alumina raw material, with Y
2O
3: Al
2O
3=3: 5～7 ratio (mol ratio) by 5 kilograms of gross weight weighings, is that 5 kilograms of yttrium oxide and alumina raw material are sent in the vibration mill with the gross weight that weighs up, and 5 kilograms of prefabricated material of described fusing assistant are made in vibratory milling 5～20 hours;
The processing step of the remainder of present embodiment is identical with the corresponding part of embodiment 1 or embodiment 2 or embodiment 3.
Embodiment 5: get yttrium oxide and alumina raw material, with Y
2O
3: Al
2O
3=3: 5～7 ratio (mol ratio) by 5 kilograms of gross weight weighings, is that 5 kilograms of yttrium oxide and alumina raw material are sent in the stirring mill with the gross weight that weighs up, and stirring ball-milling 5～30 hours is made 5 kilograms of prefabricated material of described fusing assistant;
The processing step of the remainder of present embodiment is identical with the corresponding part of embodiment 1 or embodiment 2 or embodiment 3.
Claims (5)
1, a kind of production technique of liquid phase sintering silicon carbide ceramic, raw materials used carborundum powder, yttrium oxide, aluminum oxide and the wedding agent of comprising, through processes such as batch mixing, mold pressing typing, curing, high temperature sinterings, form the silicon carbide ceramics product, it is characterized in that this production technique bag is fitted following steps:
A mixes yttrium oxide and two kinds of raw materials of aluminum oxide, carries out ball milling, utilizes mechanochemical reaction to generate the prefabricated material of fusing assistant;
B mixes the prefabricated material of fusing assistant with carborundum powder and wedding agent etc., through processes such as mold pressing typing, curing, high temperature sinterings, form the silicon carbide ceramics product.
2, production technique according to claim 1 is characterized in that, described yttrium oxide and two kinds of raw materials of aluminum oxide is mixed, and carries out ball milling, utilizes mechanochemical reaction to generate in the step of the prefabricated material of fusing assistant, and the ball milling time is more than 5 hours.
3, production technique according to claim 1, it is characterized in that, described the prefabricated material of fusing assistant is mixed with carborundum powder and wedding agent etc., through processes such as mold pressing typing, curing, high temperature sinterings, form in the step of silicon carbide ceramics product, the hybrid mode of prefabricated material of fusing assistant and carborundum powder adopts ball milling method.
4, production technique according to claim 1, it is characterized in that, described the prefabricated material of fusing assistant is mixed with carborundum powder and wedding agent, through processes such as mold pressing typing, curing, high temperature sinterings, form in the step of silicon carbide ceramics product, the blending means of the prefabricated material of fusing assistant and carborundum powder and wedding agent is to make paste mixture, adopts churned mechanically method to mix.
5, production technique according to claim 4, it is characterized in that, described production technique bag is fitted following steps: in conjunction with large power supersonic equipment, utilize the ultrasonication effect, described paste mixture is carried out ultrasonication, destroy particle agglomeration with ultrasonic wave, promote to intert mutually between each material composition and permeate, strengthen the material mixed effect.
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| CNB2006100843953A CN100515994C (en) | 2006-05-23 | 2006-05-23 | Technique for preparing liquid phase sintering silicon carbide ceramic |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102537510A (en) * | 2010-12-31 | 2012-07-04 | 张光荣 | Pressureless sintering silicon carbide ceramic valve core and preparation process thereof |
| CN102584178A (en) * | 2011-11-29 | 2012-07-18 | 重庆四维卫浴(集团)有限公司 | Standardized production process of bathroom ceramic water tank |
| CN103085372A (en) * | 2011-10-31 | 2013-05-08 | 深圳光启高等理工研究院 | Metamaterial dielectric substrate and processing method thereof |
| CN110746193A (en) * | 2019-10-16 | 2020-02-04 | 上海德宝密封件有限公司 | Carbon fiber reinforced normal-pressure sintered silicon carbide |
| CN113295003A (en) * | 2021-05-26 | 2021-08-24 | 湖南仁龙特种陶瓷有限公司 | Ceramic kiln furniture with light weight and low cost |
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2006
- 2006-05-23 CN CNB2006100843953A patent/CN100515994C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102537510A (en) * | 2010-12-31 | 2012-07-04 | 张光荣 | Pressureless sintering silicon carbide ceramic valve core and preparation process thereof |
| CN102537510B (en) * | 2010-12-31 | 2014-03-19 | 张光荣 | Pressureless sintering silicon carbide ceramic valve core and preparation process thereof |
| CN103085372A (en) * | 2011-10-31 | 2013-05-08 | 深圳光启高等理工研究院 | Metamaterial dielectric substrate and processing method thereof |
| CN102584178A (en) * | 2011-11-29 | 2012-07-18 | 重庆四维卫浴(集团)有限公司 | Standardized production process of bathroom ceramic water tank |
| CN110746193A (en) * | 2019-10-16 | 2020-02-04 | 上海德宝密封件有限公司 | Carbon fiber reinforced normal-pressure sintered silicon carbide |
| CN113295003A (en) * | 2021-05-26 | 2021-08-24 | 湖南仁龙特种陶瓷有限公司 | Ceramic kiln furniture with light weight and low cost |
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|---|---|
| CN100515994C (en) | 2009-07-22 |
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