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CN109231989A - A kind of alloy with high activity intercalation Ti3AlMC2The preparation method of ceramic material - Google Patents

A kind of alloy with high activity intercalation Ti3AlMC2The preparation method of ceramic material Download PDF

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CN109231989A
CN109231989A CN201811294438.XA CN201811294438A CN109231989A CN 109231989 A CN109231989 A CN 109231989A CN 201811294438 A CN201811294438 A CN 201811294438A CN 109231989 A CN109231989 A CN 109231989A
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alloy
ceramic material
almc
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alm
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彭秋明
刘先玉
王金铭
王洋洋
赵雪
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Yanshan University
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    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/56Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
    • C04B35/5607Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides
    • C04B35/5611Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides based on titanium carbides
    • C04B35/5618Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides based on titanium carbides based on titanium aluminium carbides
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    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38Non-oxide ceramic constituents or additives
    • C04B2235/3817Carbides
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    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/40Metallic constituents or additives not added as binding phase

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Abstract

The present invention relates to a kind of alloy with high activity intercalation Ti3AlMC2The preparation method of ceramic material, with TiH2, AlM alloy, TiC be raw material, synthesize Ti under high-temperature and high-pressure conditions3AlMC2Ceramic material, any one of the AlM alloy in AlLi alloy, AlNa alloy and AlK alloy.Alloy with high activity intercalation Ti of the invention3AlMC2The preparation method novel formula of ceramic material, simple process, time-consuming is few, obtained Ti3AlMC2Ceramic material purity is high, impurity are few, and Product Activity is high, can react with low concentration acid, also it can be reacted with alkali, this greatly reduces ceramic material subsequent processing difficulty, and greatly improve the application range of ceramic material, make it have very high application value.

Description

A kind of alloy with high activity intercalation Ti3AlMC2The preparation method of ceramic material
Technical field
The present invention relates to field of ceramic material preparation, more particularly to a kind of alloy with high activity intercalation Ti3AlMC2Ceramic material The preparation method of material.
Background technique
Ceramic material has many advantages, such as that fusing point is high, anti-oxidant, corrosion-resistant, has in fields such as the energy, metallurgy, machinery, chemical industry Wide application prospect.The disadvantages of high, fracture toughness is low, processing difficulties but ceramic material also enbrittles simultaneously.How The performance for improving ceramic material, increases operation rate, is a problem to be solved.Currently, a kind of novel three with layer structure First ceramics Mn+1AXnMaterial causes the extensive concern of people.Wherein, M is transiting group metal elements, and A is III or IV race's element, X It is C or N, n=1,2 or 3.And most representative is Ti3AlC2Ceramic material.
Ternary layered ceramic Ti3AlC2Integrate the excellent performance of metal and ceramics, high temperature resistant, elasticity modulus is high, in height Temperature is lower to have good plasticity, is the ideal candidates material of high-temperature engine, heat exchanger.Meanwhile Ti3AlC2Resistance to thermal shock has Good conductive, thermal conductivity, easy processing, and have good self-lubricating property, but also as the conductive component of high-speed slide contact, Alternating current generator brush etc..In addition, Ti3AlC2Ceramic material also has good machining property, inoxidizability and corrosion resistance, Blender bearing etc. suitable for chemical reaction kettle.
Zhu Li is intelligent et al. using traditional Ti, Al, C simple substance as raw material, is prepared for mechanical alloying plus annealing Ti3AlC2Powder body material, but the Ti of inventive method preparation3AlC2In material, TiC content is higher, and the very low (China of activity Patent CN200510110176.3), limit the application range of product.Guo Jun is bright et al. to use self-propagating high-temperature synthesis (SHS), using Ti, Al, C as raw material, Ti is synthetically prepared by 3:1:2 molar ratio3AlC2Powder body material, but this method preparation condition Harsher, product purity is not high enough, and activity is very low, is difficult to be post-processed (Chinese patent CN200910094336.8).King Sweet smell et al. prepares Ti using the method for mechanical alloying and vacuum thermal sintering3AlC2Ceramic powder, but this method preparation Ti3AlC2Middle TiC impurity phase is more, and purity is not high, and the activity (Chinese patent not shown CN201310497696.9).In short, Ti3AlC2Preparation method there are many kinds of, but most methods hardly result in purity compared with High Ti3AlC2Material, often with some impurity phases in product, such as TiC, Ti3AlC etc. affects the performance of material;This Outside, it is often more important that, the lytic activity that traditional raw material is formulated is relatively low, hardly reacted with low concentration acid or alkali, after Continuous application is undesirable, is difficult to meet application demand.
Summary of the invention
Based on this, it is necessary to be directed to current Ti3AlC2Preparation process in the impurity that occurs is more, lytic activity is more low Problem provides a kind of alloy with high activity intercalation Ti3AlMC2The preparation method of ceramic material.
A kind of alloy with high activity intercalation Ti3AlMC2The preparation method of ceramic material, with TiH2Powder, AlM alloyed powder, TiC powder For raw material, Ti is synthesized under high-temperature and high-pressure conditions3AlMC2Ceramic material, the AlM alloy be selected from AlLi alloy, AlNa alloy, With any one in AlK alloy.
Above-mentioned alloy with high activity intercalation Ti3AlMC2The preparation method of ceramic material, novel formula, simple process are time-consuming It is few.Obtained Ti3AlMC2Ceramic material purity is high, impurity are few, and Product Activity is high, has a good application prospect.
The TiH in one of the embodiments,2, AlM alloy, TiC molar ratio be 1:(1~2): (1.5~2).
In one of the embodiments, the AlM alloy the preparation method comprises the following steps: by aluminum shot and lithium grain/sodium grain/potassium grain Any one is mixed according to the molar ratio of 1:1, is then used arc-melting furnace melt back under the electric current of 100~200A, is obtained AlM alloy.
Ti is synthesized under high-temperature and high-pressure conditions in one of the embodiments,3AlMC2By the TiH before ceramic material2Powder, AlM alloyed powder, TiC powder carry out ball-milling treatment.
The ratio of grinding media to material of the ball-milling treatment is 10:1 in one of the embodiments, and rotational speed of ball-mill is 400~600r/ Min, Ball-milling Time are 4~8h.
It is described in one of the embodiments, to synthesize alloy intercalation Ti at high temperature under high pressure3AlMC2The condition of ceramic material Are as follows: 10~30min is kept the temperature at 3~4GPa of pressure, 1250~1400 DEG C of temperature to get Ti3AlMC2Ceramic material.
After the completion of keeping the temperature in one of the embodiments, cooling 10min, then slow release, obtains Ti3AlMC2Ceramics Material.
Above-mentioned alloy with high activity intercalation Ti3AlMC2Ceramic material, due in high temperature and pressure synthesis process, TiH2Deviate from hydrogen Gas generates stomata, and material is made to generate a large amount of vacancy defects.Importantly, due to the special adsorption of AlM reactive alloys, so that The Ti arrived3AlMC2With very high activity, it can react, can also be reacted with alkali, this greatly reduces after ceramic material with acid Continuous processing difficulty, and the application range of ceramic material is greatly improved, make it have very high application value.
Detailed description of the invention
Fig. 1 is the Ti that the embodiment of the present invention 1 obtains3AlLiC2The scanning electron microscope (SEM) photograph of ceramic material;
Fig. 2 is the Ti that the embodiment of the present invention 2 obtains3AlNaC2The scanning electron microscope (SEM) photograph of ceramic material;
Fig. 3 is the Ti that the embodiment of the present invention 3 obtains3AlKC2The scanning electron microscope (SEM) photograph of ceramic material;
Fig. 4 is the Ti that the embodiment of the present invention 1 obtains3AlLiC2Ceramic material passes through 5wt.% hydrofluoric acid treatment, obtains product Scanning electron microscope (SEM) photograph;
Fig. 5 is the Ti that the embodiment of the present invention 1 obtains3AlLiC2Ceramic material passes through 10wt.% naoh treatment, obtains The scanning electron microscope (SEM) photograph of product.
Specific embodiment
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, with reference to the accompanying drawing to the present invention Specific embodiment be described in detail.Many details are explained in the following description in order to fully understand this hair It is bright.But the invention can be embodied in many other ways as described herein, those skilled in the art can be not Similar improvement is done in the case where violating intension of the present invention, therefore the present invention is not limited by the specific embodiments disclosed below.
It is of the invention the preparation method is as follows:
(1) any one in high-purity aluminum shot and lithium grain/sodium grain/potassium grain is mixed according to the molar ratio of 1:1, then electricity consumption The melt back under the electric current of 100~200A of arc smelting furnace obtains AlM alloy, spare after pulverizing;
(2) by high-purity Ti H2Powder, AlM alloyed powder, TiC powder press 1:(1~2): the molar ratio weighing ingredient of (1.5~2), so Ratio of grinding media to material 10:1 4~8h of high-energy ball milling under the revolving speed of 400~600r/min is pressed afterwards;
(3) mixed material after ball milling is pressed into the cylindrical body of diameter 10mm, high 15mm in advance at 50MPa, uses cubic apparatus Press keeps the temperature 10~30min under the conditions of 3~4GPa, 1250~1400 DEG C and carries out high-pressure synthesis;
(4) after the completion of keeping the temperature, cooling 10min, then slow release obtains the alloy with high activity intercalation of high-purity Ti3AlMC2Ceramic material.
The invention has the following advantages over the prior art:
1, alloy with high activity intercalation Ti of the invention3AlMC2The preparation method simple process of ceramic material, time-consuming few, gained Product purity is high, impurity is few;
2, alloy with high activity intercalation Ti of the invention3AlMC2The preparation method of ceramic material is due to the M metal in AlM alloy Fusing point is low, volatile, plays the role of activation, intercalation, so that the material of synthesis has very high activity, keeps it anti-with acid It answers, can also be reacted with alkali;
3, alloy with high activity intercalation Ti of the invention3AlMC2The preparation method of ceramic material is due to high temperature and pressure synthesis process In, TiH2Deviate from hydrogen, generate stomata, material is made to generate a large amount of vacancy defects, performance is good.
Embodiment 1
High purity lithium grain 7g, aluminum shot 27g are weighed, then under an argon atmosphere with arc-melting furnace, with 100A electric current melting 4 It is secondary, AlLi alloy is obtained after cooling, and pulverize;By high-purity Ti H2Powder, AlLi alloyed powder, TiC powder TiH in molar ratio2: AlLi:TiC=1:1:2 is weighed, i.e. TiH2Powder 5g, AlLi powder 3.4g, TiC powder 12g, is then weighed firmly by ratio of grinding media to material 10:1 Matter alloying pellet 204g, will be filled with argon gas in ball grinder, the high-energy ball milling 4h under 400rpm revolving speed;By the good material of ball milling in 50MPa It is pressed into the cylindrical body of diameter 10mm, high 15mm in advance down, keeps the temperature 10min under the conditions of 3GPa, 1250 DEG C with cubic hinge press and carry out High-pressure synthesis;After the completion of heat preservation, cooling 10min, then slow release obtains the high activity AlLi intercalation Ti of high-purity3AlLiC2 Ceramic material.
Embodiment 2
High pure sodium grain 23g, aluminum shot 27g are weighed, then under an argon atmosphere with arc-melting furnace, with 150A electric current melting 4 It is secondary, AlNa alloy is obtained after cooling, and pulverize;By high-purity Ti H2Powder, AlNa alloyed powder, TiC powder TiH in molar ratio2: AlNa:TiC=1:1.5:2 is weighed, i.e. TiH2Then powder 5g, AlNa alloyed powder 7.5g, TiC powder 12g presses ratio of grinding media to material 10:1 Sintered carbide ball 245g is weighed, argon gas will be filled in ball grinder, the high-energy ball milling 6h under 500rpm revolving speed;The good material of ball milling is existed The cylindrical body of diameter 10mm, high 15mm are pressed under 50MPa in advance, is kept the temperature under the conditions of 3.5GPa, 1350 DEG C with cubic hinge press 20min carries out high-pressure synthesis;After the completion of heat preservation, 10min, then slow release are cooled down, the high activity AlNa for obtaining high-purity is inserted Layer Ti3AlNaC2Ceramic material.
Embodiment 3
High-purity potassium grain 39g, aluminum shot 27g are weighed, then under an argon atmosphere with arc-melting furnace, with 200A electric current melting 4 It is secondary, AlK alloy is obtained after cooling, and pulverize;By high-purity Ti H2Powder, AlK alloyed powder, TiC powder TiH in molar ratio2:AlK: TiC=1:1.5:1.5 is weighed, i.e. TiH2Powder 5g, AlK alloyed powder 9.9g, iC powder 9g, is then weighed firmly by ratio of grinding media to material 10:1 Matter alloying pellet 239g, will be filled with argon gas in ball grinder, the high-energy ball milling 8h under 600rpm revolving speed;By the good material of ball milling in 50MPa It is pressed into the cylindrical body of diameter 10mm, high 15mm in advance down, keeps the temperature 30min under the conditions of 4GPa, 1400 DEG C with cubic hinge press and carry out High-pressure synthesis;After the completion of heat preservation, cooling 10min, then slow release obtains the high activity AlK intercalation Ti of high-purity3AlKC2Pottery Ceramic material.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.

Claims (6)

1.一种高活性合金插层Ti3AlMC2陶瓷材料的制备方法,其特征在于,以TiH2粉、AlM合金粉、TiC粉为原料,在高温高压条件下合成Ti3AlMC2陶瓷材料,所述AlM合金选自AlLi合金、AlNa合金、和AlK合金中的任意一种。1. a preparation method of high-activity alloy intercalation Ti 3 AlMC 2 ceramic material, is characterized in that, with TiH 2 powder, AlM alloy powder, TiC powder as raw material, synthesizing Ti 3 AlMC 2 ceramic material under high temperature and high pressure conditions, The AlM alloy is selected from any one of AlLi alloy, AlNa alloy, and AlK alloy. 2.根据权利要求1所述的高活性合金插层Ti3AlMC2陶瓷材料的制备方法,其特征在于,所述TiH2、AlM合金、TiC的摩尔比为1:(1~2):(1.5~2)。2. The preparation method of high-activity alloy intercalated Ti 3 AlMC 2 ceramic material according to claim 1, wherein the molar ratio of the TiH 2 , AlM alloy and TiC is 1:(1~2):( 1.5 to 2). 3.根据权利要求1所述的高活性合金插层Ti3AlMC2陶瓷材料的制备方法,其特征在于,所述AlM合金的制备方法为:将铝粒和锂粒/钠粒/钾粒中的任意一种按照1:1的摩尔比混合,然后用电弧熔炼炉在100~200A的电流下反复熔炼,得到AlM合金。3. the preparation method of high-activity alloy intercalation Ti 3 AlMC 2 ceramic material according to claim 1, is characterized in that, the preparation method of described AlM alloy is: mix aluminum particle and lithium particle/sodium particle/potassium particle Any one of them is mixed at a molar ratio of 1:1, and then repeatedly smelted in an arc melting furnace at a current of 100-200 A to obtain an AlM alloy. 4.根据权利要求1所述的高活性合金插层Ti3AlMC2陶瓷材料的制备方法,其特征在于,在高温高压条件下合成Ti3AlMC2陶瓷材料前将所述TiH2粉、AlM合金粉、TiC粉进行球磨处理。4. the preparation method of high-activity alloy intercalation Ti 3 AlMC 2 ceramic material according to claim 1, is characterized in that, before synthesizing Ti 3 AlMC 2 ceramic material under high temperature and high pressure conditions, described TiH 2 powder, AlM alloy Powder and TiC powder are ball-milled. 5.根据权利要求4所述的高活性合金插层Ti3AlMC2陶瓷材料的制备方法,其特征在于,所述球磨处理的球料比为10:1,球磨转速为400~600r/min,球磨时间为4~8h。5. The method for preparing a high-activity alloy intercalated Ti 3 AlMC 2 ceramic material according to claim 4, wherein the ball-to-material ratio of the ball-milling treatment is 10:1, and the ball-milling speed is 400-600 r/min, The ball milling time is 4-8h. 6.根据权利要求1所述的高活性合金插层Ti3AlMC2陶瓷材料的制备方法,其特征在于,所述在高温高压下合成Ti3AlMC2陶瓷材料的条件为:在压力3~4GPa、温度1250~1400℃下保温10~30min,即得Ti3AlMC2陶瓷材料。6. The preparation method of high-activity alloy intercalated Ti 3 AlMC 2 ceramic material according to claim 1, wherein the condition for synthesizing the Ti 3 AlMC 2 ceramic material under high temperature and high pressure is: at a pressure of 3 to 4 GPa , at a temperature of 1250 to 1400° C. for 10 to 30 minutes, to obtain Ti 3 AlMC 2 ceramic material.
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