CN1259279C - Titanium silicon carbon block material using aluminium as additive and its preparing method - Google Patents
Titanium silicon carbon block material using aluminium as additive and its preparing method Download PDFInfo
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Abstract
The present invention relates to titanium-silicon-carbon block material using aluminium as an additive and a preparation method thereof. The material contains the following components: 97 to 100 vol% of total contents of Ti3SiC2 and Ti3AlC2 and 0 to 3 vol% of total contents of TiC and other impurity phases. Four element powder, such as titanium, silicon, carbon and aluminum, are used as raw materials, and are weighted according to the proportion that the molar ratio of Ti to Si to C to Al is 3: (0.9 to 1.2): (1.8 to 2.0): (0.1 to 0.3) and milled in a ball milling mode for 4 to 12 hours. The raw materials are put into a hot-pressing furnace shielding by flowing argon after prepressed and formed under 8 to 10MPa of pressure. The furnace temperature rises to 1400 to 1500 DEG C at the temperature rise rate of 20-50 DEG C /min and is kept for 5 to 120 minutes under 10 to 30MPa of pressure. The titanium-silicon-carbon block material with large size is prepared by adopting hot pressing (HP) to sinter, and the purity is more than 97%.
Description
Technical field
The present invention relates to a kind of titanium silicon-carbon block materials and preparation method thereof, particularly is titanium silicon-carbon block materials of additive and preparation method thereof with aluminium.
Background technology
Titanium silicon-carbon block materials belongs to the double carbide pottery, has good electrical conductivity, resistivity against fire, workability and self lubricity, and has higher intensity and lower hardness, can make various tribology devices, Heating element etc. with it.
Titanium silicon-carbon (Ti
3SiC
2) compound as far back as 1967 by German scholar W.Jeitschko and H.Nowotny (Monatsh.Chem., 1967,98:329-37) pass through TiH
2, Si and graphite under 2000 ℃ chemical reaction and obtain.Japanese T.Goto in 1987 and T.Hirai (Mater.Res.Bull., 1987,22[9]: 1195-201) obtain single-phase Ti with chemical Vapor deposition process CVD
3SiC
2Film.After this, 1996 American scholar M.W.Barsoum and T.El-Raghy (J.Am.Ceram.Soc., 1996,79[7]: be raw material 1953-56), obtained Ti with reaction hot-pressing HP sintering process with Ti powder, Graphite Powder 99 and SiC powder
3SiC
2The block materials of volume fraction about 98%.J.-F.Li in 1999 etc. (J.Mater.Sci.Lett., 1999, be raw material 18:1595-97) with Ti powder, Si powder and C powder, obtained Ti with hot isostatic pressing HIP sintering process
3SiC
2The block materials of volume fraction about 97%.The preparation method of other various patents and research paper report comprises that all not synthetic purity of various composition of raw materials and synthesis technique surpasses 97% Ti
3SiC
2Block materials.Its maximum problem is to contain undesirable titanium carbide TiC in the reaction product to reach other dephasign mutually.Titanium carbide reaches the existence of other dephasign mutually, and the material behaviors such as electroconductibility, self lubricity and workability of material are had adverse influence.
Discover that the content of titanium silicon-carbon is very responsive to the stoichiometric balance of Ti, Si, C three urmaterie in the Ti-Si-C ternary reaction product.Si contains the generation that quantity not sufficient causes the titanium carbide phase usually, and Si loses because of quality takes place high temperature evaporation in the sintering process of material easily.In addition, in Ti-Si-C ternary reaction process " thermal explosion " phenomenon may take place.Its result not only causes the generation of titanium carbide phase and other dephasign, and causes the damage of mould easily.The generation of titanium carbide phase is also unbalance relevant with the coordination of titanium silicon-carbon crystallisation process.Studies show that in Ti-Si-C ternary reaction process, Ti and C at first react, and and then react with Si again.If do not have the Si ion of lucky potential balance to exist between the Ti-C primitive that generates, then will preferentially be combined into the titanium carbide crystal grain that is present in the final product between the Ti-C primitive.
Lose for remedying in the sintering process quality of Si, people have inquired into the method for adding Si in raw material, and what for example people such as R.Radhakrishnan reported on " J.Alloys and Compounds " magazine in 1999 adds the trial of 20mol%Si at raw material.But the effect of this method is limited, can not reach the purpose of synthesis of high purity titanium silicon-carbon.For preventing the generation of " thermal explosion ", people have inquired into the method that adds a small amount of low melting point in raw material.(CeramicsInternational, 2002,28:761-65) Bao Dao interpolation boron trioxide B such as K.Tang for example
2O
3Or the method for Sodium Fluoride NaF.But the generation of titanium carbide phase can not be effectively avoided in the adding of these low melting points, and the high temperature resistant and oxidation-resistance that remains in the low-melting-point material confrontation material in the material etc. has adverse influence.In order to promote the formation of titanium silicon-carbon phase, people such as Zhu Jiaoqun reported the method for adding Al in raw material in 2002 on " Wuhan University of Technology's journal (2002) Vol.24No.5 ".They use discharge plasma sintering method to pack into the plumbago crucible of 20mm of aluminiferous raw material powder, are warming up to the temperature of setting and are incubated 10min with the speed of 80 ℃/min, obtain the product that thickness is 2.5～4mm.This method shows that under the discharge plasma sintering condition of very high temperature rise rate, adding aluminium in raw material is resultful for the generation that suppresses titanium carbide.But also what kind of result nobody's proof interpolation aluminium under common hot pressing HP sintering condition can produce up to now.
Generally believe that the prescription of raw material and sintering process are indivisible two the basic fundamental links that constitute the ceramic material method.A kind of prescription cooperates a kind of sintering process and other relevant sport technique segment to constitute a kind of specific material preparation method, because identical prescription and different technology, and perhaps identical technology and different prescriptions may produce different sintered products.General hot-pressed sintering furnace can not resemble the temperature rise rate that reaches 80 ℃/min the discharge plasma sintering device, and temperature rise rate exactly Si the key factor of high temperature evaporation takes place.On sintering processing, discharge plasma sintering is also different with hot pressed sintering.Discharge plasma sintering heats whole base substrate by discharge between the particle of body of material simultaneously, and hot pressed sintering is the indirect heating from body of material, and the thermal conduction by base substrate raises the base substrate temperature inside.The difference of type of heating may exert an influence to the homogeneity of the chemical reaction of whole base substrate.So, not necessarily also be feasible under the hot pressed sintering condition at composition of raw materials feasible under the discharge plasma sintering condition.In addition, hot pressing HP sintering is to prepare the method that stupalith generally adopts, and can prepare the block materials of large-size, and the preparation method is converted into practical industrial production technology easily.But discharge plasma sintering is subjected to the restriction of appointed condition, can't prepare large-sized block materials at present, has therefore limited the conversion of its practical technology.
Summary of the invention
The technical problem to be solved in the present invention is, how to avoid during at hot pressed sintering synthesis of titanium silicon carbon material that the generation of titanium carbide and other dephasign proposes in the sintered product.
In raw material, add the Al powder three purposes are arranged: the first, the quality that remedies Si in the hot pressed sintering process is lost.The temperature rise rate of hot-pressed sintering furnace can not be too high generally speaking, needs the long time just can reach the needed furnace temperature of hot pressure reaction, and Si is evaporated easily and loses in this process.The second, utilize the fusing of Al that necessary liquid phase environment is provided.The fusing point of Al is 660-670 ℃, and needed 1400-1500 ℃ of needs the fastest are 20 minutes from this temperature to hot pressure reaction, during this just Si be evaporated easily lose during.The liquid phase that Al fusing back forms has plugging action to the body of material gap between particles, the evaporation of base substrate inside Si is escaped to form stop, thereby reduce losing of Si.Liquid Al also can be Ti, Si and the intergranular atomic diffusion of C provides liquid channel, thereby helps evenly carrying out of Ti-Si-C three elementary reactions, avoids the generation of " thermal explosion " phenomenon.The 3rd, the coordination of regulating between Si ion and the Ti-C primitive is unbalance.Thereby the Si ion that not necessarily existence can potential balance just around it in moment that the Ti-C primitive forms forms the crystallization of titanium silicon-carbon.Atomic radius and the Si of Al are close, but the out-shell electron number is different with Si, help the Al ion of potential balance is provided and form titanium aluminium carbon phase, thereby stop the formation of titanium carbide and other dephasign.
Technical scheme of the present invention:
With aluminium is the titanium silicon-carbon block materials of additive, and its composition is as follows:
The volume percent 97～100% of titanium silicon-carbon Ti3SiC2 and titanium aluminium carbon Ti3AlC2 total content;
The volume percent 0～3% of titanium carbide TiC and other dephasign total content.
Contained titanium aluminium carbon mutually mainly with the form even dispersion of titanium silicon-carbon eutectic among titanium silicon-carbon principal phase.Titanium aluminium carbon and titanium silicon-carbon belong to same carbide system, have identical crystalline structure and similar physicochemical property, so contain the titanium silicon carbon material of a little amount of titanium aluminium carbon phase, its characteristic and pure titanium silicon carbon material do not have difference substantially.But the character of titanium carbide and titanium silicon-carbon have than big-difference.The hardness of titanium carbide and resistivity are than titanium silicon-carbon height.Reduce the content of titanium carbide, help improving the workability of material.Particularly, when making the element of sliding contact conduction with the titanium silicon carbon material, reduce the content of titanium carbide, help improving the electroconductibility and the surface self-lubricating of material, reduce the hard titanium carbide granule the scuffing on friction pair pairing material surface and the bright erosion of electrical discharge arc.
Of the present invention is the preparation method of the titanium silicon carbon material of additive with aluminium, and this method comprises following each step:
(1) batching: with titanium Ti powder, silicon Si powder, graphite C powder or activity charcoal powder and aluminium Al powder, Ti: Si: C: Al=1 in molar ratio: (0.3～0.4): (0.6～0.67): the ratio of (0.03～0.1) takes by weighing and mixes.
(2) ball mill mixing:, roller ball mill 4-12 hour, in 60-70 ℃ of baking oven, dry then by adding 70 milliliters dehydrated alcohol, the mill ball of 200-250 gram in the above-mentioned mixed powder of per 100 grams.Mixed powder after the oven dry is ground, and cross the 70-100 mesh sieve.
(3) pre-molding: the mixed powder of certain mass is packed in the graphite jig, and apply the pressure of 8-10MPa, make the powder compaction moulding in the mould.
(4) hot pressed sintering: the mould after the precompressed is put into hot-pressed sintering furnace; under argon shield; temperature rise rate by 20-50 ℃/min is elevated to 1400-1500 ℃ with furnace temperature; when furnace temperature reaches this temperature; powder in the mould is applied the pressure of 10-30MPa, keep temperature and pressure 5-120min, then with the speed cooling of 10-15 ℃/min; after the cooling, promptly obtaining with aluminium is the highly purified titanium silicon-carbon block materials of additive.
Above-mentioned preparation method, its main feature are that above steps is interrelated, indivisible.Contain a spot of titanium aluminium carbon phase in the material with method preparation of the present invention.This titanium aluminium carbon is to generate in the process of reaction sintering mutually, and is evenly distributed in the titanium silicon-carbon principal phase.
The invention has the beneficial effects as follows: adopt hot pressing HP sintering, can prepare large-sized titanium silicon-carbon block materials, the titanium silicon-carbon block materials purity of preparation is high to surpass 97%.
Fig. 1. with aluminium is the x-ray diffraction pattern of the titanium silicon carbon material of additive.
Fig. 2 is that the microstructural SEM of the titanium silicon carbon material of additive observes photo with aluminium.
Embodiment
Embodiment 1:
Ti powder 35.92 grams; Si powder 7.02 grams; Al powder 1.35 grams; Graphite Powder 99 6.01 gram anhydrous ethanol medium intermediate roll ball milling 8 hours, is put into graphite jig after the oven dry; pre-molding under 8MPa pressure; mould is put into the hot pressing furnace of the argon shield of flowing, be warming up to 1450 ℃, under the pressure of 25MPa, be incubated 120min with the speed of 50 ℃/min.Ti in the block materials that obtains
3SiC
2The phase content volume percent is greater than 97.%.Its X-ray diffraction analysis result as shown in Figure 1, its microstructural scanning electronic microscope (SEM) observations is as shown in Figure 2.
Embodiment 2:
Ti powder 35.92 grams; Si powder 7.02 grams; Al powder 1.35 grams; Graphite Powder 99 6.01 gram anhydrous ethanol medium intermediate roll ball milling 12 hours, is put into graphite jig after the oven dry; pre-molding under 8MPa pressure; mould is put into the hot pressing furnace of the argon shield of flowing, be warming up to 1450 ℃, under the pressure of 25MPa, be incubated 10min with the speed of 20 ℃/min.The block materials that obtains, its composition and microstructure are substantially the same manner as Example 1.
Embodiment 3:
Ti powder 35.92 grams; Si powder 7.02 grams; Al powder 0.68 gram; Graphite Powder 99 5.71 gram anhydrous ethanol medium intermediate roll ball milling 6 hours, is put into graphite jig after the oven dry; pre-molding under 8MPa pressure; mould is put into the hot pressing furnace of the argon shield of flowing, be warming up to 1450 ℃, under the pressure of 15MPa, be incubated 60min with the speed of 50 ℃/min.The block materials that obtains, its composition and microstructure are substantially the same manner as Example 1.
Claims (2)
1. one kind is the titanium silicon carbon material of additive with aluminium, and it is characterized in that: the composition of this material is as follows:
The volume percent 97～100% of titanium silicon-carbon Ti3SiC2 and titanium aluminium carbon Ti3AlC2 total content;
The volume percent 0～3% of titanium carbide TiC and other dephasign total content; This material purity surpasses 97%.
2. one kind is the preparation method of the titanium silicon carbon material of additive with aluminium, and it is characterized in that: this method comprises following each step:
(1) batching: with titanium Ti powder, silicon Si powder, graphite C powder or activity charcoal powder and aluminium Al powder Ti: Si: C: Al=1 in molar ratio: (0.3～0.4): (0.6～0.67): the ratio of (0.03～0.1) takes by weighing and mixes;
(2) ball mill mixing: by the dehydrated alcohol of 70 milliliters of addings in the above-mentioned mixed powder of per 100 grams, the mill ball of 200-250 gram, roller ball mill 4-12 hour, in 60-70 ℃ of baking oven, dry then, the mixed powder after the oven dry is ground, and sieve;
(3) pre-molding: the mixed powder of certain mass is packed in the graphite jig, and apply the pressure of 8-10MPa, make the powder compaction moulding in the mould;
(4) hot pressed sintering: the mould after the precompressed is put into hot-pressed sintering furnace; under argon shield; temperature rise rate by 20-50 ℃/min is elevated to 1400-1500 ℃ with furnace temperature; when furnace temperature reaches this temperature; powder in the mould is applied the pressure of 10-30MPa, keep temperature and pressure 5-120min, then with the speed cooling of 10-15 ℃/min; after the cooling, promptly get claim 1 described a kind of be the titanium silicon carbon material of additive with aluminium.
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100357179C (en) * | 2005-04-29 | 2007-12-26 | 北京交通大学 | Titanium aluminium carbide powder and synthesis method using tin as reactive adjuvant therefor |
| CN100364928C (en) * | 2006-01-12 | 2008-01-30 | 上海大学 | Ceramet Ti3SiC2 powder preparation method |
| CN100415684C (en) * | 2006-03-10 | 2008-09-03 | 中国科学院金属研究所 | Aluminum oxide enhanced titanium-silicon-aluminum-carbon base ceramics composite material and preparing method thereof |
| CN100455688C (en) * | 2006-08-16 | 2009-01-28 | 中国科学院上海硅酸盐研究所 | Preparation method of titanium carbosilicide based gradient material and in situ reaction |
| CN100465134C (en) * | 2007-02-09 | 2009-03-04 | 上海大学 | Method of preparing compact Ti3AlC2 ceramic by low-temperature non-pressure sintering |
| CN105478756A (en) * | 2014-09-17 | 2016-04-13 | 宁波江丰电子材料股份有限公司 | Ti-A1 alloy forming method |
| CN107827477B (en) * | 2017-10-27 | 2020-09-08 | 兰州理工大学 | Based on Ti3SiC2Reaction diffusion bonding method for carbon-carbon composite material with-Al mixed powder as intermediate layer |
| CN110054496B (en) * | 2018-01-18 | 2020-09-18 | 北京交通大学 | Titanium-aluminum-silicon-tin-carbon three-phase interlayer solid solution powder and preparation method thereof |
| CN108341670B (en) * | 2018-02-02 | 2020-08-04 | 西南科技大学 | Single phase Ti3SiC2Method for preparing metal ceramic |
| CN113735585B (en) * | 2021-08-26 | 2022-06-10 | 济南大学 | Preparation method of alumina/titanium silicon carbon composite material |
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