CN106636835B - A kind of preparation method of the hard alloy of the Binder Phase containing intermetallic compound - Google Patents

A kind of preparation method of the hard alloy of the Binder Phase containing intermetallic compound Download PDF

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CN106636835B
CN106636835B CN201610960484.3A CN201610960484A CN106636835B CN 106636835 B CN106636835 B CN 106636835B CN 201610960484 A CN201610960484 A CN 201610960484A CN 106636835 B CN106636835 B CN 106636835B
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hard alloy
phase
colloidal sol
intermetallic compound
sintering
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CN106636835A (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
    • 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
    • C22C29/06—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 carbides, but not containing other metal compounds
    • C22C29/08—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 carbides, but not containing other metal compounds based on tungsten carbide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/02—Compacting only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/1003—Use of special medium during sintering, e.g. sintering aid
    • B22F3/1007—Atmosphere
    • B22F3/101—Changing atmosphere
    • 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
    • C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
    • C22C1/053—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor with in situ formation of hard compounds
    • C22C1/055—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor with in situ formation of hard compounds using carbon
    • 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
    • C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
    • C22C1/053—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor with in situ formation of hard compounds
    • C22C1/056—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor with in situ formation of hard compounds using gas
    • 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
    • C22C29/06—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 carbides, but not containing other metal compounds
    • C22C29/067—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 carbides, but not containing other metal compounds comprising a particular metallic binder

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Powder Metallurgy (AREA)

Abstract

The invention discloses a kind of preparation method of the cemented carbide material of Binder Phase containing intermetallic compound, it is characterized in that first preparing Ni (OH)2Coat carbon containing Al (OH)3Compoiste adhering phase and Ni (OH)2The composite ganoine phase of WC particle is coated, the compression moulding after the processes such as ball milling, filtering, drying after the two mixing finally carries 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 form Ni3The hard alloy of the Binder Phase containing intermetallic compound is made in Al.The present invention overcomes the problem of Al in existing technology is oxidizable, and broken and homodisperse difficulty, volatile loss and sintering migrate easily formation hole, Ni is formed in situ in sintering process3Al phases, and realize being uniformly distributed around hard phase, the hard alloy prepared can be used for cutting tool to be manufactured with oxidation resistant parts.

Description

A kind of preparation method of the hard alloy of the Binder Phase containing intermetallic compound
Technical field
The present invention relates to the hard alloy of a kind of preparation method of hard alloy, the particularly Binder Phase containing intermetallic compound Preparation method belongs to hard material and cutting tool field.
Background technology
Hard alloy have high rigidity, high-wearing feature and high red hardness, be widely used as cutting tool, mine instrument and Wear part etc., but intensity hardness reduces the main binding phase metal Co of hard alloy at high temperature, and belong to rare war Slightly resource, finds new hard alloy Binder Phase and is beneficial to expand its application field instead of Co.Intermetallic compound Ni3Al's Cost is relatively lower, and its yield strength has positive temperature effect below peak temperature, has excellent elevated temperature strength, compacted Become drag and high specific strength, be the rationality substitute of hard alloy Co Binder Phases.ZL201110071828.2 has invented one kind Nickel-aluminum intermetallic compound Ni3Al is the hard alloy and preparation method of Binder Phase, and the hard alloy includes hard phase and glues Connect phase, also comprising the B element that mass percent is 0.0025%~0.0252%, Binder Phase percent by volume for 10%~ 40%；The preparation method includes successively：By the component ratio of Ni24Al, nickel powder, aluminium powder 5.04wt%~50.30wt% It is uniformly mixed with surplus carbide powder；It is placed in crystal vessel and paves thickness≤50mm, under non-oxidizing atmosphere, with≤5 DEG C/heating rate of min is heated to 1100 DEG C~1200 DEG C, when heat preservation 1 is small more than, then natural cooling, obtain carbide with Ni3The mixture of Al；It mills, crush, sieve, obtain less than 120 μm of carbide and Ni3The mixed-powder of Al；Deoxidation is located in advance Reason；It is added again by the B powder of 0.0025wt%~0.0252wt%, when wet-milling mixing 18~36 is small；Green compact is made in mixture；Through Ni is obtained after 1350 DEG C~1550 DEG C low pressure liquid-phase sinterings3Al is the hard alloy of Binder Phase.
But Ni is introduced at present3The method of Al is mixing based on Ni, Al metal powder and sinters Ni into3Then Al is broken again Broken formation powder adds in.There is problems with for such method：As Ni, Al powdered reaction form Ni3Al is volatile during Al, Reaction is difficult to control, prefabricated Ni3It is also needed after Al by shattering process, therefore complex process and broken Ni3Al intermetallic compounds Granularity controls and subsequent ball milling uniformly disperses control difficulty.
The content of the invention
The present invention is mixed based on Ni, Al metal powder for the hard alloy of the Binder Phase containing intermetallic compound is prepared at present Close and sinter into Ni3Then Al is crushed and is formed powder addition again, there is Ni, Al powdered reactions to form Ni3Al is easily waved during Al It sends out and reaction is difficult to control, prefabricated Ni3It also needs to cause complex process and broken Ni by shattering process after Al3Change between Al metals Conjunction object granularity controls and subsequent ball milling uniformly disperses the problems such as control is difficult, and proposition uses and first prepares Ni (OH)2Coat carbon containing Al (OH)3Compoiste adhering phase and Ni (OH)2The composite ganoine phase of WC particle is coated, by ball milling, filtering, drying after the two mixing Etc. compression moulding after processes, finally carry out two sections of atmosphere sinterings, i.e., Ar/H at low temperature2Ni and Al is formed in atmosphere2O3, in height The lower N of temperature2Middle Al2O3With C around and N2Reaction production AlN, AlN and Ni react and form Ni3Al is made containing intermetallic The hard alloy of object Binder Phase.
The present invention the Binder Phase containing intermetallic compound hard alloy preparation method, it is characterised in that successively include with Lower step：
(1)Ni(OH)2Coat carbon containing Al (OH)3Compoiste adhering mutually prepare：First by C34H62O11, isopropanol, hexamethylene adds Enter into deionized water, by weight percentage composition C34H62O1115%~30% is accounted for, isopropanol 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 place 10~for 24 hours, Preparation forms microemulsion；Using the microemulsion of preparation as solvent, NiCl is added in2, NiCl2Molar concentration for 0.1~1mol/L, add Enter ammonium hydroxide and adjust solution ph to 8~9, stir 3~12h at 60~90 DEG C with magnetic stirring apparatus, then placement 10~shape for 24 hours Into Ni (OH)2Colloidal sol, and for coating carbon containing Al (OH)3And WC；Using the microemulsion of preparation as solvent, while add in AlCl3And grain Spend the nano-graphite for 30~50nm, AlCl3Molar concentration and NiCl2Identical, the molar concentration of nano-graphite is AlCl3's 1.55~1.65 times, add in ammonium hydroxide and adjust solution ph to 8~9, after ultrasonic disperse processing 0.5h with magnetic stirring apparatus 60~ It stirs 2h at 90 DEG C, is ultrasonically treated and is repeated 2~6 times with magnetic agitation, then place 10~form carbon containing Al (OH) for 24 hours3 Colloidal 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 For 1:3~1:5,3~12h is stirred at 60~90 DEG C with magnetic stirring apparatus, obtains Ni (OH)2Coat carbon containing Al (OH)3It is compound Binder Phase；
(2)Ni(OH)2The composite ganoine of cladding WC is mutually prepared：The WC that granularity is 0.2~2.0 μm is added in ethyl alcohol, WC Mass ratio with ethyl alcohol is 1:4~1:Added again after 3,12~72h of ball milling the Tween 80 of 0.5~1wt% and be ultrasonically treated 0.5~ WC slurries are made in 2h；Then by Ni (OH)2Colloidal sol is added drop-wise in WC slurries, WC and Ni (OH)2The molar ratio of colloidal sol is 15:1~ 25:1,3~12h is stirred at 60~90 DEG C with magnetic stirring apparatus, obtains Ni (OH)2Coat the composite ganoine phase of WC；
(3) prepared by hard alloy mixed-powder prepares with hard alloy green body：By Ni (OH)2Coat carbon containing Al (OH)3Answer Close Binder Phase and Ni (OH)2The composite ganoine of cladding WC mixes, and by the Ni (OH) in compoiste adhering phase2With composite ganoine phase In WC molar ratio be 1:8~1:2 are mixed, then 12~36h of ball milling, 100~150 after 400 mesh sieve net filtrations DEG C dry 1~3h, hard alloy mixed-powder are mixed by the sieving of 100 mesh by 5~10wt% of hard alloy mixed-powder weight Enter buna forming agent, compression moulding obtains hard alloy green body under 200~400MPa pressure after the sieving of 80 mesh；
(4) two benches atmosphere sintering forms the hard alloy of the Binder Phase containing intermetallic compound：Hard alloy green body first with Ar/H22~4h is sintered at 550~650 DEG C for sintering atmosphere, 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 It reacts with Ni and forms Ni3The hard alloy of the Binder Phase containing intermetallic compound is made in Al.
The preparation method of the hard alloy of the Binder Phase containing intermetallic compound of the present invention, further characterized in that：
(1)C34H62O11, isopropanol, hexamethylene, Tween 80, ethyl alcohol, AlCl3、NiCl2It is that analysis is pure with ammonium hydroxide；
(2) Ni (OH) is prepared2Coat carbon containing Al (OH)3Compoiste adhering phase and Ni (OH)2Coat the composite ganoine mutually mistake of WC Cheng Zhong, the speed of magnetic agitation is 20~60r/min；
(3) hard alloy mixed-powder is prepared and the WC-6wt% in hard alloy green body preparation during ball milling using Φ 6mm Co sintered carbide balls, the weight of sintered carbide ball are 3~5 times of WC powder；
(4) heating rate when two benches atmosphere sintering forms the hard alloy of the Binder Phase containing intermetallic compound for 5~ 15 DEG C/min, cooling rate after reaction is 5~15 DEG C/min, Ar/H used2Middle H2Content is 5vol%, and pressure is 0.5MPa, vacuum degree is 0.5~5Pa during vacuum-sintering.
The advantage of the invention is that：(1) Ni (OH) is formed in a manner of coating2Coat carbon containing Al (OH)3Binder Phase pioneer Body, and Ni is formed in situ in sintering process3Al phases, and realize being uniformly distributed around hard phase, therefore it is high to avoid mixing Can ball-milling method it is existing as Al in mechanical milling process is oxidizable, Al powder occurs that plastic deformation granularity controls and ball milling disperses to control The problem of system is difficult.(2) Ni sources are respectively coated by Al sources and WC, therefore, prevent Al sources from occurring with WC in sintering exposed earlier Reaction, Al sources primarily form Ni3Al, destroyed so as to avoid the generation of the intermetallic compounds such as hard phase W-Al hard phase and Deteriorate Cemented Carbide Properties.(3) Al sources are with Al (OH)3Form is coated on inside, without using simple metal Al；The volatilization loss of Al Phenomena such as forming hole with migration can be controlled.
Description of the drawings
Fig. 1 the method for the present invention prepares the process schematic representation of the bonding phase cemented carbide containing intermetallic compound
Specific embodiment
Example 1：Using analytically pure C34H62O11, isopropanol, hexamethylene, Tween 80, ethyl alcohol, AlCl3、NiCl2And ammonium hydroxide Chemical reagent；(1) Ni (OH) is first carried out2Coat carbon containing Al (OH)3Compoiste adhering mutually prepare：By C34H62O11, isopropanol, hexamethylene Alkane is added in deionized water, by weight percentage composition C34H62O1117% is accounted for, isopropanol accounts for 8%, and hexamethylene accounts for 7%, remaining is Deionized water stirs 3h with magnetic stirring apparatus at 70 DEG C, and the speed of magnetic agitation is 25r/min, then places 10h, is prepared Form microemulsion；Using the microemulsion of preparation as solvent, NiCl is added in2, NiCl2Molar concentration for 0.1mol/L, add in ammonium hydroxide tune Solution ph is saved to 8,4h is stirred at 60 DEG C with magnetic stirring apparatus, the speed of magnetic agitation is 20r/min, then places 12h Form Ni (OH)2Colloidal sol, and for coating carbon containing Al (OH)3And WC；Using the microemulsion of preparation as solvent, while add in AlCl3With Granularity be 30nm nano-graphite, AlCl3Molar concentration and NiCl2Identical, the molar concentration of nano-graphite is AlCl3's It 1.55 times, adds in ammonium hydroxide and adjusts solution ph to 9,2h is stirred at 90 DEG C with magnetic stirring apparatus after ultrasonic disperse processing 0.5h, The speed of magnetic agitation is 60r/min, is ultrasonically treated and is repeated 2 times with magnetic agitation, then places and form carbon containing Al for 24 hours (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 body of colloidal sol Product is than being 1:3,12h is stirred at 80 DEG C with magnetic stirring apparatus, the speed of magnetic agitation is 40r/min, obtains Ni (OH)2Cladding Carbon containing Al (OH)3Compoiste adhering phase；(2) then carry out Ni (OH)2The composite ganoine of cladding WC is mutually prepared：It it is 0.5 μm by granularity WC add in ethyl alcohol, the mass ratio of WC and ethyl alcohol is 1:The Tween 80 and supersound process of 0.5wt% is added after 4, ball milling 12h again WC slurries are made in 1h；Then by Ni (OH)2Colloidal sol is added drop-wise in WC slurries, WC and Ni (OH)2The molar ratio of colloidal sol is 15:1, it uses Magnetic stirring apparatus stirs 8h at 70 DEG C, and the speed of magnetic agitation is 50r/min, obtains Ni (OH)2Coat the composite ganoine of WC Phase；(3) hard alloy mixed-powder is carried out again to prepare and hard alloy green body preparation：By Ni (OH)2Coat carbon containing Al (OH)3's Compoiste adhering phase and Ni (OH)2The composite ganoine of cladding WC mixes, and by the Ni (OH) in compoiste adhering phase2With composite ganoine The molar ratio of WC in phase is 1:8 are mixed, then ball milling 12h, using the WC-6wt%Co hard alloy of Φ 6mm during ball milling Ball, the weight of sintered carbide ball are 3 times of WC powder, in 100 DEG C of dry 3h, hard alloy mixing after 400 mesh sieve net filtrations Powder sieves by 100 mesh, buna forming agent is mixed by the 5wt% of hard alloy mixed-powder weight, by 80 mesh mistakes Compression moulding obtains hard alloy green body under 200MPa pressure after sieve；(4) two benches atmosphere sintering is finally carried out to be formed containing gold The hard alloy of bonding compound phase between category：Hard alloy green body is first with Ar/H23h is sintered at 550 DEG C for sintering atmosphere, makes bag Ni (OH) in coating2It is converted into Ni, Al (OH)3It is converted into Al2O3；Then in N21400 DEG C of sintering 2h make in sintering atmosphere Al2O3With C around and N2Reaction production AlN, AlN and Ni react and form Ni3Al；Heating rate in sintering process is 5 DEG C/min, cooling rate after reaction is 6 DEG C/min, Ar/H used2Middle H2Content is 5vol%, pressure 0.5MPa, Vacuum degree is 1Pa during vacuum-sintering, is finally made the hard alloy of the Binder Phase containing intermetallic compound.
Example 2：Using analytically pure C34H62O11, isopropanol, hexamethylene, Tween 80, ethyl alcohol, AlCl3、NiCl2And ammonium hydroxide Chemical reagent；(1) Ni (OH) is first carried out2Coat carbon containing Al (OH)3Compoiste adhering mutually prepare：By C34H62O11, isopropanol, hexamethylene Alkane is added in deionized water, by weight percentage composition C34H62O1130% is accounted for, isopropanol accounts for 10%, and hexamethylene accounts for 12%, remaining For deionized water, 10h is stirred at 90 DEG C with magnetic stirring apparatus, the speed of magnetic agitation is 60r/min, then places for 24 hours, matches somebody with somebody System forms microemulsion；Using the microemulsion of preparation as solvent, NiCl is added in2, NiCl2Molar concentration for 1mol/L, add in ammonium hydroxide tune Solution ph is saved to 9,8h is stirred at 80 DEG C with magnetic stirring apparatus, the speed of magnetic agitation is 30r/min, then places 14h Form Ni (OH)2Colloidal sol, and for coating carbon containing Al (OH)3And WC；Using the microemulsion of preparation as solvent, while add in AlCl3With Granularity be 40nm nano-graphite, AlCl3Molar concentration and NiCl2Identical, the molar concentration of nano-graphite is AlCl31.6 Times, it adds in ammonium hydroxide and adjusts solution ph to 9,2h, magnetic force are stirred at 70 DEG C with magnetic stirring apparatus after ultrasonic disperse processing 0.5h The speed of stirring is 50r/min, is ultrasonically treated and is repeated 4 times with magnetic agitation, then places 10h and forms carbon containing Al (OH)3 Colloidal 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 For 1:4,7h is stirred at 80 DEG C with magnetic stirring apparatus, the speed of magnetic agitation is 20r/min, obtains Ni (OH)2It coats carbon containing Al(OH)3Compoiste adhering phase；(2) then carry out Ni (OH)2The composite ganoine of cladding WC is mutually prepared：By the WC that granularity is 2.0 μm It adds in ethyl alcohol, the mass ratio of WC and ethyl alcohol is 1:The Tween 80 and supersound process of 0.8wt% is added after 4, ball milling 72h again WC slurries are made in 0.5h；Then by Ni (OH)2Colloidal sol is added drop-wise in WC slurries, WC and Ni (OH)2The molar ratio of colloidal sol is 25:1, 3h is stirred at 60 DEG C with magnetic stirring apparatus, the speed of magnetic agitation is 55r/min, obtains Ni (OH)2Coat the compound hard of WC Matter phase；(3) hard alloy mixed-powder is carried out again to prepare and hard alloy green body preparation：By Ni (OH)2Coat carbon containing Al (OH)3 Compoiste adhering phase and Ni (OH)2The composite ganoine of cladding WC mixes, and by the Ni (OH) in compoiste adhering phase2With it is compound hard The molar ratio of WC in matter phase is 1:4 are mixed, then ball milling 36h, are closed using the WC-6wt%Co hard of Φ 6mm during ball milling Gold goal, the weight of sintered carbide ball are 5 times of WC powder, are mixed after 400 mesh sieve net filtrations in 130 DEG C of dry 2h, hard alloy It closes powder to sieve by 100 mesh, buna forming agent is mixed by the 10wt% of hard alloy mixed-powder weight, by 80 mesh Compression moulding obtains hard alloy green body under 400MPa pressure after sieving；(4) formation of two benches atmosphere sintering is finally carried out to contain The hard alloy of intermetallic compound Binder Phase：Hard alloy green body is first with Ar/H22h is sintered at 580 DEG C for sintering atmosphere, is made Ni (OH) in clad2It is converted into Ni, Al (OH)3It is converted into Al2O3；Then in N21500 DEG C of sintering 1h make in sintering atmosphere Al2O3With C around and N2Reaction production AlN, AlN and Ni react and form Ni3Al, the heating rate in sintering process are 5 DEG C/min, cooling rate after reaction is 15 DEG C/min, Ar/H used2Middle H2Content is 5vol%, and pressure is 0.5MPa, vacuum degree is 2Pa during vacuum-sintering, is finally made the hard alloy of the Binder Phase containing intermetallic compound.

Claims (2)

1. the preparation method of the hard alloy of a kind of Binder Phase containing intermetallic compound, 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, isopropanol, hexamethylene is added to In deionized water, percentage composition C by weight34H62O1115%~30% is accounted for, isopropanol accounts for 6%~14%, and hexamethylene accounts for 6%~13%, It is remaining stir 3~10h at 60~90 DEG C with magnetic stirring apparatus for deionized water, then place 10~for 24 hours, it prepares and forms micro emulsion Liquid；Using the microemulsion of preparation as solvent, NiCl is added in2, NiCl2Molar concentration for 0.1 ~ 1mol/L, add in ammonium hydroxide and adjust solution PH value stirs 3~12h to 8~9, with magnetic stirring apparatus at 60~90 DEG C, then place 10~for 24 hours formed Ni (OH)2It is molten Glue, and for coating carbon containing Al (OH)3Colloidal sol and WC；Using the microemulsion of preparation as solvent, while add in AlCl3With granularity for 30 ~ The nano-graphite of 50nm, AlCl3Molar concentration and NiCl2Identical, the molar concentration of nano-graphite is AlCl31.55 ~ 1.65 Times, it adds in ammonium hydroxide and adjusts solution ph to 8~9, ultrasonic disperse is stirred after handling 0.5h with magnetic stirring apparatus at 60~90 DEG C 2h is ultrasonically treated and is repeated 2 ~ 6 times with magnetic agitation, then places 10~forms carbon containing Al (OH) for 24 hours3Colloidal sol；Finally will 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, obtains Ni (OH)2Coat carbon containing Al (OH)3Compoiste adhering phase；
（2）Ni(OH)2The composite ganoine of cladding WC is mutually prepared：The WC that granularity is 0.2 ~ 2.0 μm is added in ethyl alcohol, WC and ethyl alcohol Mass ratio be 1:4~1:The Tween 80 of 0.5 ~ 1wt% is added after 3,12 ~ 72h of ball milling again and is ultrasonically treated 0.5 ~ 2h, WC material are made Slurry；Then by Ni (OH)2Colloidal sol is added drop-wise in WC slurries, WC and Ni (OH)2The molar ratio of colloidal sol is 15:1~25:1, it is stirred with magnetic force It mixes device and 3~12h is stirred at 60~90 DEG C, obtain Ni (OH)2Coat the composite ganoine phase of WC；
（3）Prepared by hard alloy mixed-powder prepares with hard alloy green body：By Ni (OH)2Coat carbon containing Al (OH)3It is compound viscous Knot phase and Ni (OH)2The composite ganoine of cladding WC mixes, and by the Ni (OH) in compoiste adhering phase2With in composite ganoine phase The molar ratio of WC is 1:8~1:2 are mixed, then 12 ~ 36h of ball milling, after 400 mesh sieve net filtrations 100 ~ 150 DEG C dry 1 ~ 3h, hard alloy mixed-powder sieve by 100 mesh, and buna is mixed by 5 ~ 10wt% of hard alloy mixed-powder weight Forming agent, compression moulding obtains hard alloy green body under 200 ~ 400MPa pressure after the sieving of 80 mesh；
（4）Two benches atmosphere sintering forms the hard alloy of the Binder Phase containing intermetallic compound：Hard alloy green body is first with Ar/H2 2 ~ 4h is sintered at 550 ~ 650 DEG C for sintering atmosphere, 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 It reacts and forms Ni3The hard alloy of the Binder Phase containing intermetallic compound is made in Al.
2. the preparation method of the hard alloy of the Binder Phase according to claim 1 containing intermetallic compound, further It is characterized in that：
（1）C34H62O11, isopropanol, hexamethylene, Tween 80, ethyl alcohol, AlCl3、NiCl2It is that analysis is pure with ammonium hydroxide；
（2）Prepare Ni (OH)2Coat carbon containing Al (OH)3Compoiste adhering phase and Ni (OH)2Coat the composite ganoine phase process of WC In, the speed of magnetic agitation is 20~60r/min；
（3）Hard alloy mixed-powder is prepared and the WC-6wt%Co hard in hard alloy green body preparation during ball milling using Φ 6mm Alloying pellet, the weight of sintered carbide ball are 3 ~ 5 times of WC；
（4）Two benches atmosphere sintering formed the Binder Phase containing intermetallic compound hard alloy when heating rate for 5~15 DEG C/ Min, cooling rate after reaction is 5~15 DEG C/min, Ar/H used2Middle H2Content is 5vol%, pressure 0.5MPa, Vacuum degree is 0.5 ~ 5Pa during vacuum-sintering.
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