CN109136604A - A kind of preparation method of La doped hard alloy - Google Patents

A kind of preparation method of La doped hard alloy Download PDF

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Publication number
CN109136604A
CN109136604A CN201710457290.6A CN201710457290A CN109136604A CN 109136604 A CN109136604 A CN 109136604A CN 201710457290 A CN201710457290 A CN 201710457290A CN 109136604 A CN109136604 A CN 109136604A
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powder
cobalt
doped
hard alloy
preparation
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CN109136604B (en
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许开华
郭苗苗
陈元骁
吴伟
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Hubei green Tungsten Resource Recycling Co.,Ltd.
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Jingmen GEM New Material Co Ltd
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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
    • C22C1/051—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
    • 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

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  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)

Abstract

The present invention discloses a kind of preparation method of La doped hard alloy, and this method is achieved by the steps of: 1) weigh following components and matched: molybdenum powder, nickel powder, conventional silicon carbide tungsten powder, inhibitor, the cobalt powder of doped lanthanum, remaining is casting tungsten carbide powder；2) conventional silicon carbide tungsten powder and casting tungsten carbide powder are mixed and carries out ball milling；Inhibitor and the cobalt powder of doped lanthanum are mixed and carry out ball milling；3) the mixing tungsten carbide powder after ball milling and the cobalt powder of the doped lanthanum after ball milling are mixed and carries out wet-milling, obtain the first mixed slurry；4) wet-milling after mixing remaining component, obtains the second mixed slurry；5) wet-milled slurry is uniformly mixed, obtains hard alloy mixture；6) hard alloy is filtered with mixture, is dried and green compact is made in spraying granulation, the type of being then pressed into；7) green compact is sintered, kept the temperature, La doped hard alloy is made.The present invention can significantly promote the consistency and tensile strength of alloy by using the cobalt powder of doped lanthanum.

Description

A kind of preparation method of La doped hard alloy
Technical field
The present invention relates to cemented carbide material technical field more particularly to a kind of preparation methods of La doped hard alloy.
Background technique
Hard alloy has the spies such as high intensity, high rigidity, excellent abrasion resistance, heat resistance and good corrosion resistance Point, and it is widely used for production wear part, cutting element, mold, mine excavation tool, geological drilling tools, oil exploitation Tool, constitutional detail, high-temperature and high-presure resistent cylinder body and mechanical seal part etc..It is cut in petroleum, chemical industry, mine, water conservancy and metal It cuts machine components in industry to be usually operated in corrosive environment, can be accelerated to wear by the machine components corroded, and lead to part Premature failure, applied to the cemented carbide parts in this environment, all generally existing poor toughness, poor corrosion resistance, densification at present Degree, the problem of tensile strength is poor, poor plasticity.
Summary of the invention
In view of this, being solved the main purpose of the present invention is to provide a kind of preparation method of La doped hard alloy In the prior art hard alloy there is a problem of consistency and tensile strength difference.
In order to achieve the above objectives, the technical scheme of the present invention is realized as follows: a kind of preparation of La doped hard alloy Method, this method are achieved by the steps of:
Step 1: being matched by following components in percentage by weight: molybdenum powder 6~7%, nickel powder 4~6%, conventional silicon carbide Tungsten powder 45~50%, inhibitor 0.5~1.0%, the cobalt powder 6~8% of doped lanthanum, remaining is casting tungsten carbide powder；
Step 2: first carry out being milled to partial size being 0.3~0.8um by conventional silicon carbide tungsten powder and casting tungsten carbide powder mixing, Mixing tungsten carbide powder after obtaining ball milling, it is spare；Inhibitor and the cobalt powder of doped lanthanum are mixed be milled to partial size be 0.2~ 0.6um, the cobalt powder of the doped lanthanum after obtaining ball milling are spare；
It is added Step 3: again mixing the mixing tungsten carbide powder after the ball milling and the cobalt powder of the doped lanthanum after the ball milling Wet-milling is carried out in ball mill, obtains the first mixed slurry；
Step 4: it is 1~2um that wet-milling to granularity in ball mill is added after remaining component is mixed, the second mixing is obtained Slurry；
Step 5: first mixed slurry is uniformly mixed with second mixed slurry, acquisition hard alloy is used mixed Close material；
Step 6: be filtered, be dried and spraying granulation with mixture to the hard alloy, then 450~ Compression moulding under the pressure of 470MPa, is made green compact；
Step 7: the green compact is sintered under conditions of temperature is 1370~1390 DEG C, vacuum degree is 1~2Pa, keep the temperature La doped hard alloy is made in 3~4h.
Preferably, in the step 1, inhibitor Cr3C2、Cr3C2With VC or Cr3C2And TaC, and dosage is lower than doping The 3% of the cobalt powder of lanthanum.
Preferably, in the step 6, the mesh number of filtering is 40~50 mesh, and drying temperature is 75~80 DEG C.
Preferably, in the step 1, the preparation method of the cobalt powder of doped lanthanum is realized by following steps:
The concentration that step 1) prepares cobalt chloride solution and ammonia that the concentration of cobalt is 107~110g/L respectively in NaOH solution tank NaOH is The ammonium bicarbonate soln of 215~225g/L；
Lanthanum sesquioxide is added into NaOH solution tank NaOH for step 2) in cobalt chloride solution, stir evenly, and it is molten to obtain doping cobalt chloride Liquid；
Step 3) carries out oil removing to the ammonium bicarbonate soln and doping cobalt chloride solution respectively；
Step 4) pure water of 1~2L is added into reaction kettle as bottom liquid, to heating in reaction kettle；
Step 5) is fed with peristaltic pump, by after oil removing doping cobalt chloride solution and oil removing after ammonium bicarbonate soln simultaneously It is added in reaction kettle, keeps the flow of doping cobalt chloride solution constant in fill process, by the stream for adjusting ammonium bicarbonate soln Amount control pH value is 7.2~7.4, and 2~4h of reaction generates doping cobalt carbonate；
The doping cobalt carbonate is filtered by step 6), and is washed three times with 40~60 DEG C of hot water, every all over washing 20 ~40min；
Step 7) is dried 10 to the doping cobalt carbonate after washing under conditions of 80~120 DEG C, -0.1~0MPa~ It is crushed 20~40s after 20h, obtains the cobaltous carbonate powder of doped lanthanum；
Step 8) by the cobaltous carbonate powder of the doped lanthanum reduction 5 at 300~400 DEG C and under conditions of being passed through hydrogen~ 10h；
Doping cobaltous carbonate powder after reduction saves 12 by step 9) in nitrogen or carbon dioxide atmosphere~for 24 hours, then It is passivated and is crushed, the cobalt powder of object-doped lanthanum is made.
Preferably, in the step 1), the preparation method of cobalt chloride solution are as follows: take a certain amount of cobalt chloride, thereto plus Enter 50~70 DEG C of water, and stirring and dissolving, the concentration for being configured to cobalt is the cobalt chloride solution of 107~110g/L；Ammonium hydrogen carbonate Preparation method are as follows: take a certain amount of ammonium hydrogen carbonate, 50~60 DEG C of water, and stirring and dissolving is added, the concentration for preparing ammonification is 215 The ammonium bicarbonate soln of~225g/L.
Preferably, in the step 2), the concentration of lanthanum is 1.0~5.0g/L in the doping cobalt chloride solution.
Preferably, in the step 5), when being fed with peristaltic pump, the flow for adulterating cobalt chloride is 1.5~2.5L/h, carbonic acid The flow of hydrogen ammonium is 3~4L/h, and the reaction time is 2~4h.
Preferably, in the step 5), pH value is specially 7.3 ± 0.05.
Preferably, in the step 4), using pure water as bottom liquid, by after oil removing doping cobalt chloride solution and oil removing after Ammonium bicarbonate soln is reacted.
Pure water is heated, bottom liquid temperature is made to reach 40~55 DEG C, by the doping cobalt chloride solution after oil removing and is being removed Ammonium bicarbonate soln after oil is added bottom liquid and is reacted.
Compared with prior art, the present invention uses the cobalt powder of doped lanthanum, it is suppressed that conversion of the α-Co to ε-Co, significantly Promote the toughness and wearability of hard alloy；Lanthanum may act as bonding agent, and can improve the reaction speed of tungsten chromium and carbon, shorten sintering Time.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to Limit the present invention.
A kind of preparation method of La doped hard alloy provided by the invention, this method are achieved by the steps of:
Step 1: being matched by following components in percentage by weight: molybdenum powder 6~7%, nickel powder 4~6%, conventional silicon carbide Tungsten powder 45~50%, inhibitor 0.5~1.0%, the cobalt powder 6~8% of doped lanthanum, remaining is casting tungsten carbide powder；
Step 2: first carry out being milled to partial size being 0.3~0.8um by conventional silicon carbide tungsten powder and casting tungsten carbide powder mixing, Mixing tungsten carbide powder after obtaining ball milling, it is spare；Inhibitor and the cobalt powder of doped lanthanum (La) are mixed carry out being milled to partial size be 0.2~0.6um, the cobalt powder of the doped lanthanum (La) after obtaining ball milling are spare；Cast tungsten carbide, phase conventional tungsten carbide have difference Eutectic structure, the intensity of three common sinter Binder Phase and improve intergranular microstructure, improve alloy toughness and Wearability more significantly improves the impact resistance of alloy, realizes the intensity of alloy and the matched well of microhardness, thus So that the comprehensive performance of alloy greatly improves；Cobalt powder ball milling a few hours together with inhibitor are adulterated, inhibitor is dispersed, it will Inhibitor is dispersed in doping cobalt powder, reduces the direct collision between ball and ball in this way, reduces the abrasion of ball and miscellaneous The content of matter can also further refine inhibitor, more match with the granularity of ultrafine WC；
It is added Step 3: again mixing the mixing tungsten carbide powder after the ball milling and the cobalt powder of the doped lanthanum after the ball milling Wet-milling is carried out in ball mill, obtains the first mixed slurry；
Step 4: it is 1~2um that wet-milling to granularity in ball mill is added after remaining component is mixed, the second mixing is obtained Slurry；By wet-grinding technology and relative device, inhibitor is evenly coated at around WC under the drive of doping cobalt powder, is reached inhibitor and is being mixed Evenly dispersed purpose in material；
Step 5: first mixed slurry is uniformly mixed with second mixed slurry, acquisition hard alloy is used mixed Close material；
Step 6: be filtered, be dried and spraying granulation with mixture to hard alloy, then 450~ Compression moulding under the pressure of 470MPa, is made green compact；Wherein, the mesh number of filtering is 40~50 mesh, and drying temperature is 75~80 DEG C.
Step 7: green compact is sintered under conditions of temperature is 1370~1390 DEG C, vacuum degree is 1~2Pa, heat preservation 3~ La doped hard alloy is made in 4h.
Further, in step 1, the preparation method of the cobalt powder of doped lanthanum is realized by following steps:
The concentration that step 1) prepares cobalt chloride solution and ammonia that the concentration of cobalt is 107~110g/L respectively in NaOH solution tank NaOH is The ammonium bicarbonate soln of 215~225g/L；
Specifically, the preparation method of cobalt chloride solution are as follows: take a certain amount of cobalt chloride to be put into NaOH solution tank NaOH, be added thereto 50~70 DEG C of water, and stirring and dissolving, the concentration for being configured to cobalt (Co) is the cobalt chloride solution of 107~110g/L；Ammonium hydrogen carbonate Preparation method are as follows: take a certain amount of ammonium hydrogen carbonate to be put into another NaOH solution tank NaOH, 50~60 DEG C of water be added thereto, and Stirring and dissolving, the concentration for preparing ammonification is the ammonium bicarbonate soln of 215~225g/L.
Lanthanum sesquioxide (La is added into NaOH solution tank NaOH for step 2) in prepared cobalt chloride solution2O3), it stirs evenly, obtains To doping cobalt chloride solution, wherein the concentration of lanthanum (La) is 1.0~5.0g/L；
Step 3) carries out oil removing to the ammonium bicarbonate soln and doping cobalt chloride solution respectively；
The pure water that 1~2L is added into reaction kettle for step 4) is heated as bottom liquid, and to pure water, reaches bottom liquid temperature To 40~55 DEG C, then bottom liquid is added in the doping cobalt chloride solution after oil removing and the ammonium bicarbonate soln after oil removing and is reacted；
Step 5) is fed with peristaltic pump, by after oil removing doping cobalt chloride solution and oil removing after ammonium bicarbonate soln simultaneously It is added in reaction kettle, it is that 1.5~2.5L/h is constant that the flow of doping cobalt chloride solution is kept in fill process, by adjusting carbon The flow of sour hydrogen ammonium salt solution is 3~4L/h to control pH value be 7.2~7.4, and 2~4h of reaction generates doping cobalt carbonate；
Step 6) is filtered cobalt carbonate is adulterated, and is washed three times with 30~60 DEG C of hot water, and every time washing 20~ 40min；
Step 7) under conditions of 80~120 DEG C, -0.1~0MPa to washing after doping cobalt carbonate carry out drying 10~ It is crushed 20~40s after 20h, obtains the cobaltous carbonate powder of doped lanthanum (La)；
Step 8) by the cobaltous carbonate powder of doped lanthanum (La) reduction 5 at 300~400 DEG C and under conditions of being passed through hydrogen~ 10h；
The cobaltous carbonate powder of doped lanthanum (La) after reduction is saved 12 in nitrogen or carbon dioxide atmosphere by step 9) ~for 24 hours, then it is passivated and is crushed 20~40s, the cobalt powder of doped lanthanum (La) is made.
Embodiment 1
Step 1: being matched by following components in percentage by weight: molybdenum powder 6%, nickel powder 4%, conventional silicon carbide tungsten powder 45%, inhibitor 0.5%, the cobalt powder 6% of doped lanthanum, remaining is casting tungsten carbide powder；
Be milled to partial size Step 2: first mixing conventional silicon carbide tungsten powder and casting tungsten carbide powder as 0.3um, obtains ball Mixing tungsten carbide powder after mill, it is spare；It is 0.2um that inhibitor and the cobalt powder of doped lanthanum (La), which are mixed, and be milled to partial size, The cobalt powder of doping La after obtaining ball milling, it is spare；
It is added in ball mill Step 3: again mixing the mixing tungsten carbide powder after ball milling and the cobalt powder of the doped lanthanum after ball milling Wet-milling is carried out, the first mixed slurry is obtained；
Step 4: it is 1um that wet-milling to granularity in ball mill is added after remaining component is mixed, the second mixing slurry is obtained Material；
Step 5: the first mixed slurry is uniformly mixed with the second mixed slurry, hard alloy mixture is obtained；
Step 6: being filtered to hard alloy with mixture with the sieve of 40 mesh, being dried simultaneously at 75 DEG C Spraying granulation, then the compression moulding under the pressure of 450MPa, is made green compact.
Step 7: green compact is sintered under conditions of temperature is 1370 DEG C, vacuum degree is 1Pa, 3h is kept the temperature, La doped is made Hard alloy.
Wherein, in step 1, the preparation method of the cobalt powder of doped lanthanum passes through following steps such as and realizes:
Step 1) takes a certain amount of cobalt chloride to be put into NaOH solution tank NaOH, and 50 DEG C of water, and stirring and dissolving are added thereto, prepares The cobalt chloride solution that concentration at cobalt (Co) is 107g/L；A certain amount of ammonium hydrogen carbonate is taken to be put into another NaOH solution tank NaOH again, 50 DEG C of water, and stirring and dissolving are added thereto, the concentration for preparing ammonification is the ammonium bicarbonate soln of 215g/L, spare；
Step 2) takes the prepared cobalt chloride solution of 3L, and 1.75gLa is added2O3, stir evenly, obtain the dense of lanthanum (La) Degree is the doping cobalt chloride solution of 0.5g/L；
Step 3) carries out oil removing to prepared ammonium bicarbonate soln and doping cobalt chloride solution respectively；
The pure water that 1.5L is added into reaction kettle for step 4) is heated as bottom liquid, and to pure water, reaches bottom liquid temperature To 40 DEG C, then bottom liquid is added in the doping cobalt chloride solution after oil removing and the ammonium bicarbonate soln after oil removing and is reacted；
Step 5) is fed with peristaltic pump, by after oil removing doping cobalt chloride solution and oil removing after ammonium bicarbonate soln simultaneously It is added in reaction kettle, it is that 1.5/h is constant that the flow of doping cobalt chloride solution is kept in fill process, molten by adjusting ammonium hydrogen carbonate The flow of liquid is 3L/h to control pH value be 7.3 ± 0.05, and reaction 2h generates doping cobalt carbonate；
Step 6) is filtered cobalt carbonate is adulterated, and is washed three times with 40 DEG C of hot water, every all over washing 20min；
Step 7) under conditions of 80 DEG C, -0.1MPa to washing after doping cobalt carbonate carry out being crushed 20s after drying 10h, obtain The cobaltous carbonate powder of doped lanthanum (La)；
Step 8) restores 5h by the cobaltous carbonate powder of doped lanthanum (La) at 300 DEG C and under conditions of being passed through hydrogen；
Step 9) saves the cobaltous carbonate powder of the doped lanthanum (La) after reduction in nitrogen or carbon dioxide atmosphere 12h, then it is passivated and is crushed 20s, the cobalt powder of doped lanthanum (La) is made.
Embodiment 2
Step 1: being matched by following components in percentage by weight: molybdenum powder 6.5%, nickel powder 5%, conventional silicon carbide tungsten powder 48%, inhibitor 0.7%, the cobalt powder 7% of doped lanthanum, remaining is casting tungsten carbide powder；
Step 2: first conventional silicon carbide tungsten powder and casting tungsten carbide powder are carried out being milled to partial size being 0.5um, after obtaining ball milling Mixing tungsten carbide powder, it is spare；It is 0.4um that inhibitor and the cobalt powder of doped lanthanum (La), which are mixed, and be milled to partial size, is obtained The cobalt powder of doping La after ball milling, it is spare；
It is added in ball mill Step 3: again mixing the mixing tungsten carbide powder after ball milling and the cobalt powder of the doped lanthanum after ball milling Wet-milling is carried out, the first mixed slurry is obtained；
Step 4: it is 1.5um that wet-milling to granularity in ball mill is added after remaining component is mixed, the second mixing slurry is obtained Material；
Step 5: the first mixed slurry is uniformly mixed with the second mixed slurry, hard alloy mixture is obtained；
Step 6: being filtered to hard alloy with mixture with the sieve of 45 mesh, being dried simultaneously at 80 DEG C Spraying granulation, then the compression moulding under the pressure of 460MPa, is made green compact.
Step 7: green compact is sintered under conditions of temperature is 1380 DEG C, vacuum degree is 1.5Pa, 3.5h is kept the temperature, La is made Adulterate hard alloy.
Wherein, in step 1, the preparation method of the cobalt powder of doped lanthanum passes through following steps such as and realizes:
Step 1) takes a certain amount of cobalt chloride to be put into NaOH solution tank NaOH, and 60 DEG C of water, and stirring and dissolving are added thereto, prepares The cobalt chloride solution that concentration at cobalt (Co) is 108g/L；A certain amount of ammonium hydrogen carbonate is taken to be put into another NaOH solution tank NaOH again, 55 DEG C of water, and stirring and dissolving are added thereto, the concentration for preparing ammonification is the ammonium bicarbonate soln of 220g/L, spare；
Step 2) takes the prepared resulting cobalt chloride solution of 3L, and 10.55gLa is added2O3, stir evenly, obtain lanthanum (La) concentration is the doping cobalt chloride solution of 3g/L (0.3%)；
Step 3) carries out oil removing to prepared ammonium bicarbonate soln and doping cobalt chloride solution respectively；
The pure water that 1.5L is added into reaction kettle for step 4) is heated as bottom liquid, and to pure water, reaches bottom liquid temperature To 40 DEG C, then bottom liquid is added in the doping cobalt chloride solution after oil removing and the ammonium bicarbonate soln after oil removing and is reacted；
Step 5) is fed with peristaltic pump, by after oil removing doping cobalt chloride solution and oil removing after ammonium bicarbonate soln simultaneously It is added in reaction kettle, it is that 2L/h is constant that the flow of doping cobalt chloride solution is kept in fill process, molten by adjusting ammonium hydrogen carbonate The flow of liquid is 3.5L/h to control pH value be 7.3 ± 0.05, and reaction 3h generates doping cobalt carbonate；
Step 6) is filtered cobalt carbonate is adulterated, and is washed three times with 50 DEG C of hot water, every all over washing 30min；
Step 7) under conditions of 100 DEG C, 0MPa to washing after doping cobalt carbonate carry out being crushed 40s after drying 20h and must mix The cobaltous carbonate powder-IV of miscellaneous lanthanum (La)；
Step 8) restores 10h by the cobaltous carbonate powder of doped lanthanum (La) at 400 DEG C and under conditions of being passed through hydrogen；
Step 9) saves the cobaltous carbonate powder of the doped lanthanum (La) after reduction in nitrogen or carbon dioxide atmosphere 20h, then it is passivated and is crushed 40s, the cobalt powder of doped lanthanum (La) is made.
Embodiment 3
Step 1: being matched by following components in percentage by weight: molybdenum powder 7%, nickel powder 6%, conventional silicon carbide tungsten powder 50%, inhibitor 1.0%, the cobalt powder 8% of doped lanthanum, remaining is casting tungsten carbide powder；
Step 2: first conventional silicon carbide tungsten powder and casting tungsten carbide powder are carried out being milled to partial size being 0.8m, after obtaining ball milling Mixing tungsten carbide powder, it is spare；It is 0.6m that inhibitor and the cobalt powder of doped lanthanum (La), which are mixed, and be milled to partial size, obtains ball The cobalt powder of doped lanthanum after mill, it is spare；
It is added in ball mill Step 3: again mixing the mixing tungsten carbide powder after ball milling and the cobalt powder of the doped lanthanum after ball milling Wet-milling is carried out, the first mixed slurry is obtained；
Step 4: it is 2m that wet-milling to granularity in ball mill is added after remaining component is mixed, the second mixed slurry is obtained；
Step 5: the first mixed slurry is uniformly mixed with the second mixed slurry, hard alloy mixture is obtained；
Step 6: being filtered to hard alloy with mixture with 50 sieves, being dried at 80 DEG C and is sprayed Granulation, then the compression moulding under the pressure of 480MPa, is made green compact.
Step 7: green compact is sintered under conditions of temperature is 1390 DEG C, vacuum degree is 2Pa, 4h is kept the temperature, La doped is made Hard alloy.
Wherein, in step 1, the preparation method of the cobalt powder of doped lanthanum passes through following steps such as and realizes:
Step 1) takes a certain amount of cobalt chloride to be put into NaOH solution tank NaOH, and 60 DEG C of water, and stirring and dissolving are added thereto, prepares The cobalt chloride solution that concentration at cobalt (Co) is 108g/L；A certain amount of ammonium hydrogen carbonate is taken to be put into another NaOH solution tank NaOH again, 55 DEG C of water, and stirring and dissolving are added thereto, the concentration for preparing ammonification is the ammonium bicarbonate soln of 220g/L, spare；
The cobalt chloride solution that step 2) takes 3L prepared, and 3.52gLa is added2O3, stir evenly, obtain lanthanum (La) Concentration is the doping cobalt chloride solution of 1g/L (0.1%)；
Step 3) carries out oil removing to prepared ammonium bicarbonate soln and doping cobalt chloride solution respectively；
The pure water that 1.5L is added into reaction kettle for step 4) is heated as bottom liquid, and to pure water, reaches bottom liquid temperature To 50 DEG C, then bottom liquid is added in the doping cobalt chloride solution after oil removing and the ammonium bicarbonate soln after oil removing and is reacted；
Step 5) is fed with peristaltic pump, by after oil removing doping cobalt chloride solution and oil removing after ammonium bicarbonate soln simultaneously It is added in reaction kettle, it is that 2L/h is constant that the flow of doping cobalt chloride solution is kept in fill process, molten by adjusting ammonium hydrogen carbonate The flow of liquid is 3.5L/h to control pH value be 7.3 ± 0.05, and reaction 3h generates doping cobalt carbonate；
Step 6) is filtered cobalt carbonate is adulterated, and is washed three times with 50 DEG C of hot water, every all over washing 30min；
Step 7) is crushed under conditions of 100 DEG C, -0.05MPa to being adulterated after cobalt carbonate carries out drying 15h after washing 30s obtains the cobaltous carbonate powder of doped lanthanum；
Step 8) restores 8h by the cobaltous carbonate powder of doped lanthanum (La) at 350 DEG C and under conditions of being passed through hydrogen；
Step 9) saves the cobaltous carbonate powder of the doped lanthanum (La) after reduction in nitrogen or carbon dioxide atmosphere 15h, then it is passivated and is crushed 30s, the cobalt powder of doped lanthanum (La) is made.
Embodiment 4
Step 1: being matched by following components in percentage by weight: molybdenum powder 6.5%, nickel powder 5%, conventional silicon carbide tungsten powder 48%, inhibitor 0.7%, the cobalt powder 7% of doped lanthanum, remaining is casting tungsten carbide powder；
Step 2: first conventional silicon carbide tungsten powder and casting tungsten carbide powder are carried out being milled to partial size being 0.5um, after obtaining ball milling Mixing tungsten carbide powder, it is spare；It is 0.4um that inhibitor and the cobalt powder of doped lanthanum (La), which are mixed, and be milled to partial size, is obtained The cobalt powder of doping La after ball milling, it is spare；
It is added in ball mill Step 3: again mixing the mixing tungsten carbide powder after ball milling and the cobalt powder of the doped lanthanum after ball milling Wet-milling is carried out, the first mixed slurry is obtained；
Step 4: it is 1.5um that wet-milling to granularity in ball mill is added after remaining component is mixed, the second mixing slurry is obtained Material；
Step 5: the first mixed slurry is uniformly mixed with the second mixed slurry, hard alloy mixture is obtained；
Step 6: being filtered to hard alloy with mixture with the sieve of 45 mesh, being dried simultaneously at 80 DEG C Spraying granulation, then the compression moulding under the pressure of 460MPa, is made green compact.
Step 7: green compact is sintered under conditions of temperature is 1380 DEG C, vacuum degree is 1.5Pa, 3.5h is kept the temperature, La is made Adulterate hard alloy.
Wherein, in step 1, the preparation method of the cobalt powder of doped lanthanum passes through following steps such as and realizes:
Step 1) takes a certain amount of cobalt chloride to be put into NaOH solution tank NaOH, and 70 DEG C of water, and stirring and dissolving are added thereto, prepares The cobalt chloride solution that concentration at cobalt (Co) is 110g/L；A certain amount of ammonium hydrogen carbonate is taken to be put into another NaOH solution tank NaOH again, 60 DEG C of water, and stirring and dissolving are added thereto, the concentration for preparing ammonification is the ammonium bicarbonate soln of 225g/L, spare；
The cobalt chloride solution that step 2) takes 3L prepared, and 5.27gLa is added2O3, stir evenly, obtain lanthanum (La) Concentration is the doping cobalt chloride solution of 1.5g/L；
Step 3) carries out oil removing to prepared ammonium bicarbonate soln and doping cobalt chloride solution respectively；
The pure water that 1.5L is added into reaction kettle for step 4) is heated as bottom liquid, and to pure water, reaches bottom liquid temperature To 55 DEG C, then bottom liquid is added in the doping cobalt chloride solution after oil removing and the ammonium bicarbonate soln after oil removing and is reacted；
Step 5) is fed with peristaltic pump, by after oil removing doping cobalt chloride solution and oil removing after ammonium bicarbonate soln simultaneously It is added in reaction kettle, it is 2.5 constant that the flow of doping cobalt chloride solution is kept in fill process, by adjusting ammonium bicarbonate soln Flow be 4L/h to control pH value be 7.3 ± 0.05, reaction 4h generates doping cobalt carbonate；
Step 6) is filtered cobalt carbonate is adulterated, and is washed three times with 60 DEG C of hot water, every all over washing 40min；
Step 7) under conditions of 120 DEG C, 0MPa to washing after doping cobalt carbonate carry out being crushed 40s after drying 20h and must mix The cobaltous carbonate powder-III of miscellaneous lanthanum (La)；
Step 8) restores 10h by the cobaltous carbonate powder of doped lanthanum (La) at 400 DEG C and under conditions of being passed through hydrogen；
Step 9) saves the cobaltous carbonate powder of the doped lanthanum (La) after reduction in nitrogen or carbon dioxide atmosphere 20h, then it is passivated and is crushed 40s, the cobalt powder of doped lanthanum (La) is made.
Compared with the existing technology, when the cobalt powder of doped lanthanum of the present invention (La) is applied in hard alloy, in Co phase dissolved with W, WC, doped chemical chromium, these doped chemical chromium segregations improve the stacking fault energy of dislocation in the dislocation of Co phase, hinder dislocation into Line width is decomposed, thus reduces the width of fault, that is, reduces potential ε-Co plumule, while W, WC, doped chemical have " pinning " effect, keeps plumule not easily shifted, when the temperature increases, so that α-Co be inhibited to improve γ phase to the transformation of ε-Co The content of middle α-Co, improves the toughness of alloy；Cobalt may act as bonding agent, and can improve the reaction speed of tungsten chromium and carbon, shorten Sintering time.
The foregoing is only a preferred embodiment of the present invention, is not intended to limit the scope of the present invention.

Claims (10)

1. a kind of preparation method of La doped hard alloy, which is characterized in that this method is achieved by the steps of:
Step 1: being matched by following components in percentage by weight: molybdenum powder 6~7%, nickel powder 4~6%, conventional silicon carbide tungsten powder 45~50%, inhibitor 0.5~1.0%, the cobalt powder 6~8% of doped lanthanum, remaining is casting tungsten carbide powder；
Be milled to partial size Step 2: first mixing conventional silicon carbide tungsten powder and casting tungsten carbide powder as 0.3~0.8um, obtains Mixing tungsten carbide powder after ball milling, it is spare；Inhibitor and the cobalt powder of doped lanthanum are mixed be milled to partial size be 0.2~ 0.6um, the cobalt powder of the doped lanthanum after obtaining ball milling are spare；
Ball milling is added Step 3: again mixing the mixing tungsten carbide powder after the ball milling and the cobalt powder of the doped lanthanum after the ball milling Wet-milling is carried out in machine, obtains the first mixed slurry；
Step 4: it is 1~2um that wet-milling to granularity in ball mill is added after remaining component is mixed, the second mixed slurry is obtained；
Step 5: first mixed slurry is uniformly mixed with second mixed slurry, hard alloy mixture is obtained；
Step 6: be filtered, be dried and spraying granulation with mixture to the hard alloy, then 450~ Compression moulding under the pressure of 470MPa, is made green compact；
Step 7: the green compact is sintered under conditions of temperature is 1370~1390 DEG C, vacuum degree is 1~2Pa, heat preservation 3~ La doped hard alloy is made in 4h.
2. a kind of preparation method of La doped hard alloy according to claim 1, which is characterized in that the step 1 In, inhibitor Cr3C2、Cr3C2With VC or Cr3C2And TaC, and dosage is lower than the 3% of the cobalt powder of doped lanthanum.
3. a kind of preparation method of La doped hard alloy according to claim 1, which is characterized in that the step 6 In, the mesh number of filtering is 40~50 mesh, and drying temperature is 75~80 DEG C.
4. a kind of preparation method of La doped hard alloy according to claim 1, which is characterized in that the step 1 In, the preparation method of the cobalt powder of doped lanthanum is realized by following steps:
The concentration that step 1) prepares cobalt chloride solution and ammonia that the concentration of cobalt is 107~110g/L respectively in NaOH solution tank NaOH is 215 The ammonium bicarbonate soln of~225g/L；
Lanthanum sesquioxide is added into NaOH solution tank NaOH for step 2) in cobalt chloride solution, stir evenly, and obtains doping cobalt chloride solution；
Step 3) carries out oil removing to the ammonium bicarbonate soln and doping cobalt chloride solution respectively；
Step 4) pure water of 1~2L is added into reaction kettle as bottom liquid, to heating in reaction kettle；
Step 5) is fed with peristaltic pump, and the doping cobalt chloride solution after oil removing and the ammonium bicarbonate soln after oil removing are added simultaneously Keep the flow of doping cobalt chloride solution constant in reaction kettle, in fill process, by the flow control for adjusting ammonium bicarbonate soln PH value processed is 7.2~7.4, and 2~4h of reaction generates doping cobalt carbonate；
The doping cobalt carbonate is filtered by step 6), and is washed three times with 40~60 DEG C of hot water, and every time washing 20~ 40min；
After 10~20h is dried to the doping cobalt carbonate after washing under conditions of 80~120 DEG C, -0.1~0MPa in step 7) Broken 20~40s, obtains the cobaltous carbonate powder of doped lanthanum；
Step 8) restores 5~10h by the cobaltous carbonate powder of the doped lanthanum at 300~400 DEG C and under conditions of being passed through hydrogen；
Doping cobaltous carbonate powder after reduction saves 12 by step 9) in nitrogen or carbon dioxide atmosphere~for 24 hours, then carry out It is passivated and is crushed, the cobalt powder of object-doped lanthanum is made.
5. a kind of preparation method of La doped hard alloy according to claim 4, which is characterized in that the step 1) In, the preparation method of cobalt chloride solution are as follows: a certain amount of cobalt chloride is taken, 50~70 DEG C of water, and stirring and dissolving are added thereto, The concentration for being configured to cobalt is the cobalt chloride solution of 107~110g/L；The preparation method of ammonium hydrogen carbonate are as follows: take a certain amount of bicarbonate 50~60 DEG C of water, and stirring and dissolving is added in ammonium, and the concentration for preparing ammonification is the ammonium bicarbonate soln of 215~225g/L.
6. a kind of preparation method of La doped hard alloy according to claim 4, which is characterized in that the step 2) In, the concentration of lanthanum is 1.0~5.0g/L in the doping cobalt chloride solution.
7. a kind of preparation method of La doped hard alloy according to claim 4, which is characterized in that the step 5) In, when being fed with peristaltic pump, the flow for adulterating cobalt chloride is 1.5~2.5L/h, and the flow of ammonium hydrogen carbonate is 3~4L/h, described Reaction time is 2~4h.
8. a kind of preparation method of La doped hard alloy according to claim 4, which is characterized in that the step 5) In, pH value is specially 7.3 ± 0.05.
9. a kind of preparation method of La doped hard alloy according to claim 4, which is characterized in that the step 4) In, using pure water as bottom liquid, the doping cobalt chloride solution after oil removing and the ammonium bicarbonate soln after oil removing are reacted.
10. a kind of preparation method of La doped hard alloy according to claim 9, which is characterized in that carried out to pure water Heating, so that bottom liquid temperature is reached 40~55 DEG C, by after oil removing doping cobalt chloride solution and oil removing after ammonium bicarbonate soln Bottom liquid is added to be reacted.
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JPH07197180A (en) * 1993-12-29 1995-08-01 Kobe Steel Ltd High strength and high hardness sintered hard alloy excellent in corrosion resistance
CN102031436A (en) * 2011-01-17 2011-04-27 中南大学 Method for improving corrosion resistance of WC-Co hard alloy
CN104831098A (en) * 2014-02-11 2015-08-12 中国科学院金属研究所 Preparation method of WC-Co hard alloy with in-situ addition of rare earth oxide crystal grain refiner
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