CN106521206B - A kind of preparation method of the cermet material of high temperature resistance softening - Google Patents

A kind of preparation method of the cermet material of high temperature resistance softening Download PDF

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CN106521206B
CN106521206B CN201610969130.5A CN201610969130A CN106521206B CN 106521206 B CN106521206 B CN 106521206B CN 201610969130 A CN201610969130 A CN 201610969130A CN 106521206 B CN106521206 B CN 106521206B
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cermet
phase
high temperature
colloidal sol
coat
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CN106521206A (en
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杨梅
刘福娇
龙剑平
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Chengdu Univeristy of Technology
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C22C1/058—Mixtures of metal powder with non-metallic powder by reaction sintering (i.e. gasless reaction starting from a mixture of solid metal compounds)
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/04—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbonitrides

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The invention discloses a kind of preparation method of the cermet material of high temperature resistance softening, it is characterized in that first preparing Ni (OH)2Coat carbon containing Al (OH)3Compoiste adhering phase, and Ni (OH)2Coat (Ti0.5,Mox,W0.5‑x) (C, N) particle (wherein x=0~0.5) composite ganoine phase, the two mixing after it is compressing after the processes such as ball milling, filtering, drying, finally carry out two sections of atmosphere sinterings, i.e., Ar/H at low temperature2Ni and Al is formed in atmosphere2O3, N at high temperature2Middle Al2O3With C around and N2Reaction production AlN, AlN and Ni react and are formed and contain Ni in Binder Phase3Al high temperature resistance softening cermet.Instant invention overcomes Al in existing technology is oxidizable, crushes and the problem of dispersed difficult, volatile loss and sintering migration easily form hole, Ni is formed in sintering process situ3Al phases, and being uniformly distributed around hard phase is realized, the cermet material prepared can be used for cutting tool to be manufactured with oxidation resistant parts.

Description

A kind of preparation method of the cermet material of high temperature resistance softening
Technical field
The present invention relates to the cermet material of a kind of preparation method of cermet material, more particularly to high temperature resistance softening Preparation method, belong to field of compound material.
Background technology
Ti (C, N) based ceramic metal is that Ni/Co is binding agent, and adds WC, Mo for base with Ti (C, N) etc.2C, TaC etc. Carbide uses multiphase solid material prepared by powder metallurgy process.Because Ti (C, N) based ceramic metal has low-density, low The features such as coefficient of friction, high rigidity, high-wearing feature and red hardness, it is especially suitable for making machining cutter material.Particularly Ti (C, N) based ceramic metal uses Ti, Ni of resource relative abundance to save rare W, Co strategy money as primary raw material Source, the alternative materials of conventional rigid alloy are had been considered as at present and are taken seriously.But machining cutting tool is under arms During with Work piece high-speed friction, the temperature of its contact zone can reach 1000 DEG C, therefore the mechanical behavior under high temperature pair of cermet It is most important in its cutting ability.
The binding metal content such as higher Ni of generally use in Ti (C, N) based ceramic metal, this causes its normal temperature obdurability The defects of insufficient, is improved, but softening even creep easily occurs at high temperature for metal phase, and this is that metal ceramic material as high temperature performance is weak One of the main reason for change.Ni3Al intermetallic compounds not only have high rigidity, high intensity and excellent wear-and corrosion-resistant at room temperature Performance, and there is excellent elevated temperature strength and high temperature and creep resistance ability, in its yield strength of 800~1000 DEG C of temperature ranges The trend of abnormality is showed, i.e. temperature rise is without reducing.(Chen Jin smoke trees, Zhu Dingyi, woods step on suitable .Ni3The research of Al based alloys with Using progress material Leaders, 2006,20 (1):35-38).Therefore, by Ni3Al intermetallic compounds are introduced into cermet Improving the high-temperature behavior of cermet turns into the emphasis paid close attention in material engineering.ZL201410082829.0 has invented one kind and contained Ni3Al Ti (C, N) based ceramic metal, the percentage by weight of its composition are：TiC34.2~43%, TiN8~15%, Mo10~ 15%th, WC5~10%, graphite 0.8~1.0%, Ni20~24%, the Ni containing B3Al6~10%.The invention first with purity >= 99.0% Ni, Al and B powder is raw material, by weight percentage Ni87.23~88.48%, Al11.47~12.68%, B0.5~ 1.0% is made compound, and wet ball-milling is carried out to compound, obtains the uniform compound slurry of composition, and compound slurry is dried Afterwards, the Ni containing B that vacuum heat obtains porosity and looseness is carried out3Al sinters block；By the Ni containing B3Al sintering blocks crush, and obtain B Ni must be contained3Al powder.Then TiC, TiN, Mo, WC, graphite, Ni powder and the Ni containing B are used3Al powder is that raw material prepares gold Belong to ceramic compound, then be prepared into by die forming, vacuum degreasing and vacuum-sintering step with Ni3Al and Ni is binding agent Ti (C, N) based ceramic metal.
It can be seen that Ni is introduced at present3Al method is that mixing and ball milling based on Ni, Al metal dust and sintering crushing are formed Ni3Al powder adds.There is problems with for such a method：As oxidizable in Al powder mechanical milling processes, Al powder occurs plasticity and become Shape difficulties in dispersion broken in the form of sheets, prefabricated Ni3Also needed after Al by shattering process complex process, broken Ni3Change between Al metals Compound Task-size Controlling and the dispersed control of subsequent ball milling are difficult.
The content of the invention
The present invention introduces Ni for preparing the cermet material of high temperature resistance softening at present3Mixed during Al using Ni, Al powder With Ni after conjunction ball milling, sintering crushing3Oxidizable in Al mechanical milling processes existing for the method that Al powder types add, Al powder is moulded Property deformation broken difficulties in dispersion in the form of sheets, prefabricated Ni3The problem of crushing process complexity is with ball milling difficulties in dispersion again after Al, is proposed Using first preparing Ni (OH)2Coat carbon containing Al (OH)3Compoiste adhering phase, and Ni (OH)2Coat (Ti0.5,Mox,W0.5-x)(C,N) The composite ganoine phase of particle (wherein x=0~0.5), it is compressing after the processes such as ball milling, filtering, drying after the two mixing, Finally carry out two sections of atmosphere sinterings, i.e., Ar/H at low temperature2Ni and Al is formed in atmosphere2O3, N at high temperature2Middle Al2O3With surrounding C and N2Reaction production AlN, AlN and Ni react and are formed and contain Ni in Binder Phase3Al high temperature resistance softening cermet.
The preparation method of the cermet material of the high temperature resistance softening of the present invention, it is characterised in that successively comprising following step Suddenly：
(1)Ni(OH)2Coat carbon containing Al (OH)3Compoiste adhering mutually prepare：First by C34H62O11, n-butanol, hexamethylene adds Enter into deionized water, by weight percentage composition C34H62O1115%~30% is accounted for, n-butanol accounts for 6%~14%, and hexamethylene accounts for 6%~13%, remaining is deionized water, and 3~10h is stirred at 60~90 DEG C with magnetic stirring apparatus, then places 10~24h, Preparation forms microemulsion；Using the microemulsion of preparation as solvent, Ni (NO are added3)2, Ni (NO3)2Molar concentration for 0.1~ 1mol/L, add ammoniacal liquor and adjust solution ph to 8~9,3~12h is stirred at 60~90 DEG C with magnetic stirring apparatus, is then placed 10~24h forms Ni (OH)2Colloidal sol, and for coating carbon containing Al (OH)3(Ti0.5,Mox,W0.5-x) (C, N) (wherein x=0~ 0.5)；Using the microemulsion of preparation as solvent, while add Al (NO3)3With 30~50nm nano-graphite, Al (NO3)3Mole Concentration and Ni (NO3)2Identical, the molar concentration of nano-graphite is Al (NO3)31.55~1.65 times, add ammoniacal liquor regulation solution PH value stirs 2h, supersound process is stirred with magnetic force to 8~9 with magnetic stirring apparatus after ultrasonic disperse processing 0.5h at 60~90 DEG C Mix and be repeated 2~6 times, then place 10~24h and form carbon containing Al (OH)3Colloidal sol；Finally by Ni (OH)2Colloidal sol, which is added drop-wise to, to be contained Carbon Al (OH)3In colloidal sol, Al (OH)3Colloidal sol and Ni (OH)2The volume ratio of colloidal sol is 1:3~1:5, with magnetic stirring apparatus 60~ 3~12h is stirred at 90 DEG C, obtains Ni (OH)2Coat carbon containing Al (OH)3Compoiste adhering phase；
(2)Ni(OH)2Coat (Ti0.5,Mox,W0.5-x) composite ganoine of (C, N) mutually prepared：It it is 0.9~1.5 μm by granularity (Ti0.5,Mox,W0.5-x) (C, N) add ethanol in, (Ti0.5,Mox,W0.5-x) mass ratio of (C, N) and ethanol is 1:4~1: 0.5~1wt% Tween 80 is added after 3,48~72h of ball milling again and is ultrasonically treated 0.5~2h, (Ti is made0.5,Mox,W0.5-x) (C, N) slurry；Then by Ni (OH)2Colloidal sol is added drop-wise to (Ti0.5,Mox,W0.5-x) in (C, N) slurry, (Ti0.5,Mox,W0.5-x) (C, N) and Ni (OH)2The mol ratio of colloidal sol is 5:1~10:1,3~12h is stirred at 60~90 DEG C with magnetic stirring apparatus, is obtained Ni(OH)2Coat (Ti0.5,Mox,W0.5-x) (C, N) composite ganoine phase；
(3) prepared by cermet mixed-powder prepares with cermet green compact：By Ni (OH)2Coat carbon containing Al (OH)3Answer Close Binder Phase and Ni (OH)2Coat (Ti0.5,Mox,W0.5-x) composite ganoine of (C, N) mixes, and by compoiste adhering phase Ni(OH)2With (the Ti in composite ganoine phase0.5,Mox,W0.5-x) (C, N) mol ratio be 1:2~1:4 are mixed, Ran Houqiu 12~36h is ground, passes through 100 mesh mistakes in 100~150 DEG C of dry 1~3h, cermet mixed-powder after 400 mesh sieve net filtrations Sieve, buna forming agent is mixed by 5~10wt% of cermet mixed-powder weight, after the sieving of 80 mesh 200~ It is compressing under 400MPa pressure to obtain cermet green compact；
(4) two benches atmosphere sintering forms the cermet of high temperature resistance softening：Cermet green compact are first with Ar/H2For sintering Atmosphere sinters 2~4h at 550~650 DEG C, makes the Ni (OH) in clad2It is converted into Ni, Al (OH)3It is converted into Al2O3；Then In N21400~1600 DEG C of 1~3h of sintering make Al in sintering atmosphere2O3With C around and N2Reaction production AlN, AlN and Ni occur anti- Answer and formed and contain Ni in Binder Phase3The cermet of Al high temperature resistance softening.
The preparation method of the cermet material of the high temperature resistance softening of the present invention, further characterized in that：
(1)C34H62O11, n-butanol, hexamethylene, Ni (NO3)2、Al(NO3)3, Tween 80, ethanol and ammoniacal liquor be analysis It is pure；
(2) Ni (OH) is prepared2Coat carbon containing Al (OH)3Compoiste adhering phase and Ni (OH)2Coat (Ti0.5,Mox,W0.5-x) During the composite ganoine phase of (C, N), the speed of magnetic agitation is 20~60r/min；
(3) cermet mixed-powder is prepared and the WC-6wt% in the preparation of cermet green compact during ball milling using Φ 6mm Co sintered carbide balls, the weight of sintered carbide ball is (Ti0.5,Mox,W0.5-x) 3~5 times of (C, N) powder；
(4) programming rate during cermet of two benches atmosphere sintering formation high temperature resistance softening is 5~15 DEG C/min, is burnt Cooling rate after terminating is 5~15 DEG C/min, Ar/H used2Middle H2Content is 5vol%, pressure 0.5MPa, used N2Pressure is 2~3MPa.
The advantage of the invention is that：(1) Ni (OH) is formed in a manner of coating2Coat carbon containing Al (OH)3Compoiste adhering mutually first Body is driven, and Ni is formed in sintering process situ3Al phases, and being uniformly distributed around hard phase is realized, therefore avoid mixed It is existing as Al in mechanical milling process is oxidizable to close ball milling sintering crushing method, Al powder occurs plastic deformation in the form of sheets and broken scattered is stranded Difficulty, shattering process is complicated and the problem of Task-size Controlling and ball milling decentralised control difficulty.(2) Ni sources be respectively coated by Al sources and (Ti0.5,Mox,W0.5-x) (C, N), therefore, prevent Al sources from (Ti0.5,Mox,W0.5-x) (C, N) sintering exposed earlier and send out Raw reaction, Al sources primarily form Ni3Al, so as to avoid hard phase (Ti0.5,Mox,W0.5-x) metal such as (C, N) decomposition and TiAl Between compound generation and destroy hard phase and deteriorate cermet performance.(3) Al sources are with Al (OH)3Form is coated on inside, Without using simple metal Al；Phenomena such as Al volatilization loss and migration form hole can be controlled.
Brief description of the drawings
Fig. 1 the inventive method prepares the process schematic representation of high temperature resistance softening cermet
Embodiment
Example 1：Using analytically pure C34H62O11, n-butanol, hexamethylene, Ni (NO3)2、Al(NO3)3, Tween 80, ethanol With ammoniacal liquor chemical reagent；(1) Ni (OH) is first carried out2Coat carbon containing Al (OH)3Compoiste adhering mutually prepare：First by C34H62O11, just Butanol, hexamethylene are added in deionized water, by weight percentage composition C34H62O1130% is accounted for, n-butanol accounts for 9%, and hexamethylene accounts for 11%, remaining is deionized water, 4h is stirred at 70 DEG C with magnetic stirring apparatus, the speed of magnetic agitation is 20r/min, Ran Houfang 10h is put, preparation forms microemulsion；Using the microemulsion of preparation as solvent, Ni (NO are added3)2, Ni (NO3)2Molar concentration be 0.8mol/L, add ammoniacal liquor and adjust solution ph to 8,4h is stirred at 70 DEG C with magnetic stirring apparatus, the speed of magnetic agitation is 40r/min, then place 12h and form Ni (OH)2Colloidal sol, and for coating carbon containing Al (OH)3(Ti0.5,Mox,W0.5-x)(C,N) (wherein x=0.2)；Using the microemulsion of preparation as solvent, while add Al (NO3)3With 30nm nano-graphite, Al (NO3)3's Molar concentration and Ni (NO3)2Identical, the molar concentration of nano-graphite is Al (NO3)31.57 times, add ammoniacal liquor regulation pH value of solution It is worth 8,2h is stirred at 90 DEG C with magnetic stirring apparatus after ultrasonic disperse processing 0.5h, the speed of magnetic agitation be 50r/min, super Sonication is repeated 4 times with magnetic agitation, then places 10h and forms carbon containing Al (OH)3Colloidal sol；Finally by Ni (OH)2Colloidal sol drips It is added to carbon containing Al (OH)3In colloidal sol, Al (OH)3Colloidal sol and Ni (OH)2The volume ratio of colloidal sol is 1:3, with magnetic stirring apparatus at 80 DEG C Lower stirring 5h, the speed of magnetic agitation is 20r/min, obtains Ni (OH)2Coat carbon containing Al (OH)3Compoiste adhering phase；(2) so Ni (OH) is carried out afterwards2Coat (Ti0.5,Mo0.2,W0.3) composite ganoine of (C, N) mutually prepared：By (the Ti that granularity is 1.2 μm0.5, Mo0.2,W0.3) (C, N) add ethanol in, (Ti0.5,Mo0.2,W0.3) mass ratio of (C, N) and ethanol is 1:After 4, ball milling 70h again Add 0.6wt% Tween 80 and be ultrasonically treated 0.5h, (Ti is made0.5,Mo0.2,W0.3) (C, N) slurry；Then by Ni (OH)2 Colloidal sol is added drop-wise to (Ti0.5,Mo0.2,W0.3) in (C, N) slurry, (Ti0.5,Mo0.2,W0.3) (C, N) and Ni (OH)2Mole of colloidal sol Than for 5:1,6h is stirred at 70 DEG C with magnetic stirring apparatus, the speed of magnetic agitation is 20r/min, obtains Ni (OH)2Cladding (Ti0.5,Mo0.2,W0.3) (C, N) composite ganoine phase；(3) cermet mixed-powder is carried out again to prepare and cermet green compact Prepare：By Ni (OH)2Coat carbon containing Al (OH)3Compoiste adhering phase and Ni (OH)2Coat (Ti0.5,Mo0.2,W0.3) (C, N) answer Hard is closed to mix, and by the Ni (OH) in compoiste adhering phase2With (the Ti in composite ganoine phase0.5,Mo0.2,W0.3) (C, N) Mol ratio is 1:2 are mixed, then ball milling 24h, are closed using Φ 6mm WC-6wt%Co sintered carbide balls, hard during ball milling The weight of gold goal is (Ti0.5,Mo0.2,W0.3) 4 times of (C, N) powder, in 120 DEG C of dry 2h, metal after 400 mesh sieve net filtrations Ceramic mixed-powder is sieved by 100 mesh, and buna forming agent, warp are mixed by the 6wt% of cermet mixed-powder weight Compressing under 400MPa pressure cermet green compact are obtained after crossing the sieving of 80 mesh；(4) two benches atmosphere sintering is finally carried out Form high temperature resistance softening cermet：Cermet green compact are first with Ar/H24h is sintered at 550 DEG C for sintering atmosphere, makes clad In Ni (OH)2It is converted into Ni, Al (OH)3It is converted into Al2O3；Then in N21400 DEG C of sintering 2h make Al in sintering atmosphere2O3With Surrounding C and N2Reaction production AlN, AlN and Ni react and Ni are formed in Binder Phase3Al；Programming rate is in sintering process 5 DEG C/min, the cooling rate after terminating is 6 DEG C/min, Ar/H used2Middle H2Content is 5vol%, and pressure is 0.5MPa, N used2Pressure is 2MPa, finally prepares high temperature resistance softening cermet.
Example 2：Using analytically pure C34H62O11, n-butanol, hexamethylene, Ni (NO3)2、Al(NO3)3, Tween 80, ethanol With ammoniacal liquor chemical reagent；(1) Ni (OH) is first carried out2Coat carbon containing Al (OH)3Compoiste adhering mutually prepare：First by C34H62O11, just Butanol, hexamethylene are added in deionized water, by weight percentage composition C34H62O1115 are accounted for, n-butanol accounts for 7%, and hexamethylene accounts for 8%, remaining is deionized water, 3h is stirred at 80 DEG C with magnetic stirring apparatus, the speed of magnetic agitation is 27r/min, Ran Houfang 11h is put, preparation forms microemulsion；Using the microemulsion of preparation as solvent, Ni (NO are added3)2, Ni (NO3)2Molar concentration be 0.2mol/L, add ammoniacal liquor and adjust solution ph to 9,5h is stirred at 80 DEG C with magnetic stirring apparatus, the speed of magnetic agitation is 25r/min, then place 10h and form Ni (OH)2Colloidal sol, and for coating carbon containing Al (OH)3(Ti0.5,Mox,W0.5-x)(C,N) (wherein x=0.5)；Using the microemulsion of preparation as solvent, while add Al (NO3)3With 45nm nano-graphite, Al (NO3)3's Molar concentration and Ni (NO3)2Identical, the molar concentration of nano-graphite is Al (NO3)31.63 times, add ammoniacal liquor regulation pH value of solution It is worth 9,2h is stirred at 60 DEG C with magnetic stirring apparatus after ultrasonic disperse processing 0.5h, the speed of magnetic agitation be 60r/min, super Sonication is repeated 3 times with magnetic agitation, then places 10h and forms carbon containing Al (OH)3Colloidal sol；Finally by Ni (OH)2Colloidal sol drips It is added to carbon containing Al (OH)3In colloidal sol, Al (OH)3Colloidal sol and Ni (OH)2The volume ratio of colloidal sol is 1:5, with magnetic stirring apparatus at 80 DEG C Lower stirring 11h, the speed of magnetic agitation is 40r/min, obtains Ni (OH)2Coat carbon containing Al (OH)3Compoiste adhering phase；(2) so Ni (OH) is carried out afterwards2Coat (Ti0.5,Mox,W0.5-x) composite ganoine of (C, N) mutually prepared：By (the Ti that granularity is 1.4 μm0.5, Mo0.5) (C, N) add ethanol in, (Ti0.5,Mo0.5) mass ratio of (C, N) and ethanol is 1:1wt% is added again after 4, ball milling 48h Tween 80 and be ultrasonically treated 1.5h, (Ti is made0.5,Mo0.5) (C, N) slurry；Then by Ni (OH)2Colloidal sol is added drop-wise to (Ti0.5, Mo0.5) in (C, N) slurry, (Ti0.5,Mo0.5) (C, N) and Ni (OH)2The mol ratio of colloidal sol is 8:1, with magnetic stirring apparatus 70 12h is stirred at DEG C, the speed of magnetic agitation is 20r/min, obtains Ni (OH)2Coat (Ti0.5,Mox,W0.5-x) (C, N) it is compound Hard phase；(3) cermet mixed-powder is carried out again to prepare and the preparation of cermet green compact：By Ni (OH)2Coat carbon containing Al (OH)3Compoiste adhering phase and Ni (OH)2Coat (Ti0.5,Mo0.5) composite ganoine of (C, N) mixes, and presses compoiste adhering phase In Ni (OH)2With (the Ti in composite ganoine phase0.5,Mo0.5) (C, N) mol ratio be 1:3 are mixed, then ball milling 36h, Using Φ 6mm WC-6wt%Co sintered carbide balls during ball milling, the weight of sintered carbide ball is (Ti0.5,Mo0.5) (C, N) powder 5 times, in 110 DEG C of dry 3h after 400 mesh sieve net filtrations, cermet mixed-powder sieves by 100 mesh, by cermet The 9wt% incorporation buna forming agents of mixed-powder weight, it is compressing under 400MPa pressure after the sieving of 80 mesh to obtain To cermet green compact；(4) finally carry out two benches atmosphere sintering and form high temperature resistance softening cermet：Cermet green compact are first With Ar/H23h is sintered at 600 DEG C for sintering atmosphere, makes the Ni (OH) in clad2It is converted into Ni, Al (OH)3It is converted into Al2O3； Then in N21490 DEG C of sintering 2h make Al in sintering atmosphere2O3With C around and N2Reaction production AlN, AlN and Ni react and Ni is formed in Binder Phase3Al；Programming rate is 12 DEG C/min in sintering process, the cooling rate after terminating be 7 DEG C/ Min, Ar/H used2Middle H2Content is 5vol%, pressure 0.5MPa, N used2Pressure is 3MPa, finally prepares high temperature resistance Soften cermet.

Claims (2)

1. a kind of preparation method of the cermet material of high temperature resistance softening, it is characterised in that comprise the steps of successively：
（1）Ni(OH)2Coat carbon containing Al (OH)3Compoiste adhering mutually prepare：First by C34H62O11, n-butanol, hexamethylene is added to In deionized water, percentage composition C by weight34H62O1115%~30% is accounted for, n-butanol accounts for 6%~14%, and hexamethylene accounts for 6%~13%, its Remaining is deionized water, and 3~10h is stirred at 60~90 DEG C with magnetic stirring apparatus, then places 10~24h, and preparation forms micro emulsion Liquid；Using the microemulsion of preparation as solvent, Ni (NO are added3)2, Ni (NO3)2Molar concentration be 0.1 ~ 1mol/L, add ammoniacal liquor adjust Solution ph is saved to 8~9,3~12h is stirred at 60~90 DEG C with magnetic stirring apparatus, 10~24h is then placed and forms Ni (OH)2Colloidal sol, and for coating carbon containing Al (OH)3(Ti0.5,Mox,W0.5-x) (C, N), wherein x=0 ~ 0.5；With the micro emulsion of preparation Liquid is solvent, while adds Al (NO3)3With 30 ~ 50nm nano-graphite, Al (NO3)3Molar concentration and Ni (NO3)2It is identical, The molar concentration of nano-graphite is Al (NO3)31.55 ~ 1.65 times, add ammoniacal liquor and adjust solution ph to 8~9, ultrasonic disperse 2h is stirred at 60~90 DEG C with magnetic stirring apparatus, be ultrasonically treated and be repeated 2 ~ 6 times with magnetic agitation, so after processing 0.5h 10~24h is placed afterwards forms carbon containing Al (OH)3Colloidal sol；Finally by Ni (OH)2Colloidal sol is added drop-wise to carbon containing Al (OH)3In colloidal sol, Al (OH)3Colloidal sol and Ni (OH)2The volume ratio of colloidal sol is 1:3~1:5,3~12h is stirred at 60~90 DEG C with magnetic stirring apparatus, is obtained To Ni (OH)2Coat carbon containing Al (OH)3Compoiste adhering phase；
（2）Ni(OH)2Coat (Ti0.5,Mox,W0.5-x) composite ganoine of (C, N) mutually prepared：It it is 0.9 ~ 1.5 μm by granularity (Ti0.5,Mox,W0.5-x) (C, N) add ethanol in, (Ti0.5,Mox,W0.5-x) mass ratio of (C, N) and ethanol is 1:4~1:3, ball 0.5 ~ 1wt% Tween 80 is added after 48 ~ 72h of mill again and is ultrasonically treated 0.5 ~ 2h, (Ti is made0.5,Mox,W0.5-x) (C, N) material Slurry；Then by Ni (OH)2Colloidal sol is added drop-wise to (Ti0.5,Mox,W0.5-x) in (C, N) slurry, (Ti0.5,Mox,W0.5-x) (C, N) and Ni (OH)2The mol ratio of colloidal sol is 5:1~10:1,3~12h is stirred at 60~90 DEG C with magnetic stirring apparatus, obtains Ni (OH)2Cladding (Ti0.5,Mox,W0.5-x) (C, N) composite ganoine phase；
（3）Prepared by cermet mixed-powder prepares with cermet green compact：By Ni (OH)2Coat carbon containing Al (OH)3It is compound viscous Knot phase and Ni (OH)2Coat (Ti0.5,Mox,W0.5-x) composite ganoine of (C, N) mixes, and by the Ni in compoiste adhering phase (OH)2With (the Ti in composite ganoine phase0.5,Mox,W0.5-x) (C, N) mol ratio be 1:2~1:4 are mixed, then ball milling 12 ~ 36h, sieved after 400 mesh sieve net filtrations in 100 ~ 150 DEG C of dry 1 ~ 3h, cermet mixed-powder by 100 mesh, down payment Belong to 5 ~ 10wt% incorporation buna forming agents of ceramic mixed-powder weight, in 200 ~ 400MPa pressure after the sieving of 80 mesh Under compressing obtain cermet green compact；
（4）Two benches atmosphere sintering forms high temperature resistance softening cermet：Cermet green compact are first with Ar/H2Exist for sintering atmosphere 550 ~ 650 DEG C of 2 ~ 4h of sintering, make the Ni (OH) in clad2It is converted into Ni, Al (OH)3It is converted into Al2O3；Then in N2Sinter gas 1400 ~ 1600 DEG C of 1 ~ 3h of sintering make Al in atmosphere2O3With C around and N2Reaction production AlN, AlN and Ni react and form bonding Contain Ni in phase3Al high temperature resistance softening cermet.
2. the preparation method of the cermet material of high temperature resistance softening according to claim 1, its further feature exist In：
（1）C34H62O11, n-butanol, hexamethylene, Ni (NO3)2、Al(NO3)3, Tween 80, ethanol and ammoniacal liquor be that analysis is pure；
（2）Prepare Ni (OH)2Coat carbon containing Al (OH)3Compoiste adhering phase and Ni (OH)2Coat (Ti0.5,Mox,W0.5-x)(C,N) Composite ganoine phase during, the speed of magnetic agitation is 20~60r/min；
（3）Cermet mixed-powder is prepared and the WC-6wt%Co hard in the preparation of cermet green compact during ball milling using Φ 6mm Alloying pellet, the weight of sintered carbide ball is (Ti0.5,Mox,W0.5-x) 3 ~ 5 times of (C, N)；
（4）Programming rate during two benches atmosphere sintering formation high temperature resistance softening cermet is 5~15 DEG C/min, and sintering terminates Cooling rate afterwards is 5~15 DEG C/min, Ar/H used2Middle H2Content is 5vol%, pressure 0.5MPa, N used2Pressure is 2~3MPa。
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