CN102061419B - Hard alloy material taking Co-Cu as bonding phase and preparation method thereof - Google Patents

Hard alloy material taking Co-Cu as bonding phase and preparation method thereof Download PDF

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Publication number
CN102061419B
CN102061419B CN201010595790A CN201010595790A CN102061419B CN 102061419 B CN102061419 B CN 102061419B CN 201010595790 A CN201010595790 A CN 201010595790A CN 201010595790 A CN201010595790 A CN 201010595790A CN 102061419 B CN102061419 B CN 102061419B
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alloy
bonding phase
preparation
adopts
hardmetal materials
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CN102061419A (en
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吝楠
贺跃辉
江垚
张端锋
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Central South University
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Central South University
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Abstract

The invention relates to a hard alloy material taking a Co-Cu alloy as a bonding phase, which consists of the Co-Cu alloy, C and WC. The Co-Cu alloy is prepared by a co-precipitation method. A preparation method comprises the following steps of: weighing the Co-Cu alloy, the C and the WC according to the designed component proportion of the hard alloy material, mixing, performing ball milling, adding a forming agent, uniformly stirring, sieving, and performing die pressing in a die to form a compact; and putting the compact in argon atmosphere, performing pressure sintering, and cooling with a furnace to obtain the hard alloy material taking the Co-Cu alloy as the bonding phase. The hardness and bending strength of a hard alloy prepared by using the Co-Cu bonding phase are superior to those of the conventional hard alloy using a Co bonding phase; Co-Cu powder is cheaper than Co powder, and Co-Cu is taken as a main bonding phase of a material system, so that production cost is reduced; and the Co-Cu hard alloy has high high-temperature oxidation resistance and is suitable for industrial production.

Description

A kind of Co-Cu that adopts is as the Hardmetal materials of phase and preparation method thereof that bonds
Technical field
The present invention relates to a kind of wimet alloy material and preparation method thereof, be specifically related to a kind of Co-Cu of employing alloy, belong to the Hardmetal materials preparing technical field as the Hardmetal materials of phase and preparation method thereof that bonds.
Background technology
The production of Hardmetal materials is prior powder metallurgy technology; Generally be through mixing, stir and the ball milling starting material, processing mixed powder; Then with powder in die for molding; In certain atmosphere, obtaining alloy at last, like this, can obtain the metal and the alloy that are difficult to obtain with traditional fusion casting with powder metallurgy process with the preset temperature sintering.Hard mainly is WC mutually, and bonding mainly is Co mutually.Wimet has good hardness, intensity, makes it can be applied to cutting tool, boring tool, oil production and mine excavation instrument and various wear-resisting, withstand voltage part.But,, seeking suitable alternative metals both at home and abroad because the cobalt metal scarcity of resources costs an arm and a leg always.Iron, nickel or and with the alloy of cobalt be comparatively common substitute.
But the hardness and the bending strength of the wimet that a prerequisite that substitutes Co is its manufacturing must reach or near the standard of performance of the bonding wimet of Co.The research of the alternative metals of these Co comprises: adopt corrosion resistance nature preferably Ni as bonding phase alloy, but the hardness of this wimet and intensity all far below Co as the wimet that bonds mutually.In addition, Fe is adopted in research in addition, and Co-Ni, Fe-Ni, Co-Ni-Fe etc. are as the wimet of bonding phase, but the wimet of the bonding phase of employing mentioned component, its hardness and bending strength all significantly decrease.Therefore, adopt Ni, the alternative Co of Fe not to obtain ideal results up to now as the research work of the bonding phase of wimet.
Summary of the invention
The technical problem that the present invention is intended to solve is, to the alternative metals research of Co bonding phase in the wimet with the deficiency that exists in using, proposes a kind of wimet that adopts Co-Cu alloy that coprecipitation method prepares as bonding phase.Adopt the wimet of the prepared Co-Cu of this method as the bonding phase, performances such as its hardness, bending strength all are superior to the wimet of existing C o as the bonding phase, and owing to the cheap wimet cost that makes of Cu descends.
A kind of Hardmetal materials that adopts the Co-Cu alloy as the bonding phase of the present invention, form by weight percentage by following component:
Co-Cu alloy: 8～12%;
C:1～2%; Surplus is WC; Each composition weight percent and be 100%.
The present invention is a kind of to be adopted in the Hardmetal materials of Co-Cu alloy as the bonding phase, and said Co-Cu alloy adopts the coprecipitation method preparation; Its weight percentages of components is: Co:85%-95%, Cu:5%-15%.
The present invention is a kind of to be adopted in the Hardmetal materials of Co-Cu alloy as the bonding phase, and the preparation technology of said Co-Cu alloy is: by the Co-Cu alloy proportion of design, Co, the Cu metal of getting corresponding weight prepare the CoCl that concentration is 0.4～0.8mol/L 2, CuCl 2Mixing solutions is heated to after 60～80 ℃ the (NH with same molar ratio, equal volume, uniform temp with the gained mixing solutions 4) 2C 2O 4Solution adopts and the stream mode uniform mixing, stirs to produce deposition; Through after the ageing in 6～8 hours throw out being filtered, dry back is at 450～500 ℃ of calcining 1～2h, then in hydrogen with 520～600 ℃ of reduction 1.5～2h, prepare the Co-Cu powdered alloy.
The present invention is a kind of to be adopted in the Hardmetal materials of Co-Cu alloy as the bonding phase, and the mean particle size of said Co-Cu alloy is 0.5～3 μ m; The mean particle size of C is 1～2 μ m; The mean particle size of WC is 1～3 μ m.
A kind of preparation method who adopts the Co-Cu alloy as the Hardmetal materials of bonding phase of the present invention comprises the steps:
The first step: the Hardmetal materials component proportioning by design takes by weighing Co-Cu alloy, C, WC, and mixing and ball milling gets alloy powder mixture;
Second step: in the first step gained alloy powder mixture, add forming agent, pressed compact is processed in the back mold pressing in mould that stirs, sieves, and said molding pressure is 150～200MPa;
The 3rd step: place argon gas atmosphere to carry out pressure sintering the second step gained pressed compact, sintering temperature is 1380～1440 ℃, and furnace cooling obtains the Hardmetal materials of employing Co-Cu alloy of the present invention as the bonding phase.
The present invention is a kind of to be adopted among the preparation method of Co-Cu alloy as the Hardmetal materials of bonding phase, and said milling parameters is: ball-to-powder weight ratio is (6～8) in the roller milling machine: 1, and with 20～40 rev/mins speed ball millings 30～50 hours.
The present invention is a kind of to be adopted among the preparation method of Co-Cu alloy as the Hardmetal materials of bonding phase, and said sieving adopted 50～80 mesh sieves.
The present invention is a kind of to be adopted among the preparation method of Co-Cu alloy as the Hardmetal materials of bonding phase, said forming agent by rubber and paraffin in mass ratio with 1: after the ratio proportioning of (2～3) with industrial naptha by mass ratio 1: (10～14) mix.
The present invention is a kind of to be adopted among the preparation method of Co-Cu alloy as the Hardmetal materials of bonding phase, and the furnace pressure of said pressure sintering is 6～8MPa.
The present invention adopts chemical coprecipitation to prepare the bonding phase of Co-Cu owing to adopt above-mentioned component proportioning and preparation technology, and in the time of can making Cu in adding Co, Co, Cu element are mixed in atomic level fully, and particle diameter is even, the powder good dispersivity.In sintering process; The existence of Cu has hindered the diffusion of W, C atom; Effectively suppress the dissolving of W, C atom and separate out, reduced WC, reduced WC and separated out the speed and the probability of growing up again through dissolving in mutually in bonding in bonding solubleness in mutually; Make WC grain obtain refinement, improve the hardness of wimet.And Cu enters into the crystalline network of Co, has produced lattice distortion, to the bonding effect that solution strengthening is arranged mutually of Co-Cu, improves the intensity of wimet.
Compare with conventional WC wimet, the present invention has the following advantages:
1, the present invention adopts the wimet that the Co-Cu bonding is made mutually, and its hardness all is superior to existing Co bonding wimet mutually with bending strength.
2, the Co-Cu powder is cheap than the Co powder, uses the main bonding phase of Co-Cu as material system, has reduced production cost.
3, the Co-Cu wimet has excellent high temperature oxidation resistance.
Practical implementation
Embodiment 1
At first compound concentration is the CoCl of 0.4mol/L 2And CuCl 2Mixing solutions, contain Co85% in the said mixing solutions, Cu 15%; It is that 0.4mol/L, temperature are 80 ℃ (NH with concentration that said mixing solutions is heated to 80 ℃ 4) 2C 2O 4Solution adopts and the stream mode uniform mixing by equal volume, and stirs the generation deposition.Through after the ageing in 8 hours throw out being filtered, dry back is at 450 ℃ of calcining 1h, then in hydrogen with 520 ℃ of reduction 1.5h, prepare mass percent and be: Co 85%, and Cu 15%, and granularity is the Co-Cu powdered alloy of 0.5～3 μ m.
Selecting mean particle size is that the C powder of Co-Cu powdered alloy and 1～2 μ m of WC, 0.5～3 μ m of 1～3 μ m is as raw material; By component ratio is that powder ball-to-powder weight ratio in the roller milling machine of 89%WC+10% (Co-Cu)+1%C is 6: 1; With 50 hours ball millings of 40 rev/mins speed ball millings; Adding through super-dry sieves behind the forming agent that is mixed at 1: 10 by mass ratio with industrial naptha after with 1: 2 ratio proportioning by rubber and paraffin is pressed into pressed compact with 150MPa pressure in mould; In argon gas atmosphere, carry out sintering with 8MPa pressure then, sintering temperature is 1380 ℃, is prepared into Hardmetal materials; Carry out surface treatment according to request for utilization then, obtain alloy material of the present invention.The density of the alloy material of preparation is 14.53gcm -3, hardness is HRA93, bending strength is 2800MPa.
Embodiment 2
At first compound concentration is the CoCl of 0.5mol/L 2And CuCl 2Mixing solutions, contain Co90% in the said mixing solutions, Cu 10%; It is that 0.5mol/L, temperature are 70 ℃ (NH with concentration that said mixing solutions is heated to 70 ℃ 4) 2C 2O 4Solution adopts and the stream mode uniform mixing by equal volume, and stirs the generation deposition.Through after the ageing in 7 hours throw out being filtered, dry back is at 480 ℃ of calcining 1.5h, then in hydrogen with 580 ℃ of reduction 1.8h, prepare mass percent and be: Co 90%, and Cu 10%, and granularity is the Co-Cu powdered alloy of 0.5～3 μ m.
Selecting mean particle size is that the C powder of Co-Cu powdered alloy and 1～2 μ m of WC, 0.5～3 μ m of 1～3 μ m is as raw material; With component ratio is that powder ball-to-powder weight ratio in the roller milling machine of 91%WC+8% (Co-Cu)+1%C is 7: 1; With 40 hours ball millings of 30 rev/mins speed ball millings; Through super-dry add by rubber and paraffin with 1: 2 ratio proportioning after with industrial naptha by mass ratio 1: 12) sieving behind the forming agent that mixes is pressed into pressed compact with 180MPa pressure in mould; In argon gas atmosphere, carry out sintering with 7MPa pressure then, sintering temperature is 1420 ℃, is prepared into Hardmetal materials; Carry out surface treatment according to request for utilization then, obtain alloy material of the present invention.The density of the alloy material of preparation is 14.65gcm -3, hardness is HRA94, bending strength is 2500MPa.
Embodiment 3
At first compound concentration is the CoCl of 0.8mol/L 2And CuCl 2Mixing solutions, contain Co95% in the said mixing solutions, Cu 5%; It is that 0.4mol/L, temperature are 60 ℃ (NH with concentration that said mixing solutions is heated to 60 ℃ 4) 2C 2O 4Solution adopts and the stream mode uniform mixing by equal volume, and stirs the generation deposition.Through after the ageing in 6 hours throw out being filtered, dry back is at 500 ℃ of calcining 2h, then in hydrogen with 600 ℃ of reductase 12 h, prepare mass percent and be: Co 95%, and Cu 5%, and granularity is the Co-Cu powdered alloy of 0.5～3 μ m.
Selecting mean particle size is that the C powder of Co-Cu powdered alloy and 1～2 μ m of WC, 0.5～3 μ m of 1～3 μ m is as raw material; With component ratio is that powder ball-to-powder weight ratio in the roller milling machine of 87%WC+12% (Co-Cu)+1%C is 8: 1; With 50 hours ball millings of 20 rev/mins speed ball millings, adding through super-dry sieves behind the forming agent that is mixed at 1: 14 by mass ratio with industrial naptha after with 1: 3 ratio proportioning by rubber and paraffin is pressed into pressed compact with 200MPa pressure in mould, in argon gas atmosphere, carry out sintering with 6MPa pressure then; Sintering temperature is 1440 ℃; Be prepared into Hardmetal materials, carry out surface treatment according to request for utilization then, obtain alloy material of the present invention.The density of the alloy material of preparation is 14.51gcm -3, hardness is HRA90, bending strength is 2900MPa.

Claims (7)

  1. One kind adopt the Co-Cu alloy as the bonding phase Hardmetal materials, form by weight percentage by following component:
    Co-Cu alloy: 8～12%;
    C:1～2%; Surplus is WC; Each composition weight percent and be 100%;
    Said Co-Cu alloy adopts the coprecipitation method preparation; Its weight percentages of components is: Co:85%-95%, Cu:5%-15%;
    The preparation technology of said Co-Cu alloy is: by the Co-Cu alloy proportion of design, Co, the Cu metal of getting corresponding weight prepare the CoCl that concentration is 0.4～0.8mol/L 2, CuCl 2Mixing solutions is heated to after 60～80 ℃ the (NH with same molar ratio, equal volume, uniform temp with the gained mixing solutions 4) 2C 2O 4Solution adopts and the stream mode uniform mixing, stirs to produce deposition; Through after the ageing in 6～8 hours throw out being filtered, dry back is at 450～500 ℃ of calcining 1～2h, then in hydrogen with 520～600 ℃ of reduction 1.5～2h, prepare the Co-Cu powdered alloy.
  2. 2. a kind of Hardmetal materials that adopts the Co-Cu alloy as the bonding phase according to claim 1, it is characterized in that: the mean particle size of said Co-Cu alloy is 0.5～3 μ m; The mean particle size of C is 1～2 μ m; The mean particle size of WC is 1～3 μ m.
  3. 3. a kind of according to claim 1 or claim 2 method that adopts the Co-Cu alloy as the Hardmetal materials of bonding phase of preparation comprises the steps:
    The first step: the Hardmetal materials component proportioning by design takes by weighing Co-Cu alloy, C, the WC that adopts the coprecipitation method preparation, and mixing and ball milling gets alloy powder mixture;
    Second step: in the first step gained alloy powder mixture, add forming agent, pressed compact is processed in the back mold pressing in mould that stirs, sieves, and said molding pressure is 150～200MPa;
    The 3rd step: place argon gas atmosphere to carry out pressure sintering the second step gained pressed compact, sintering temperature is 1380～1440 ℃, and furnace cooling obtains adopting the Hardmetal materials of Co-Cu alloy as the bonding phase.
  4. 4. method according to claim 3 is characterized in that: said milling parameters is: ball-to-powder weight ratio is (6～8) in the roller milling machine: 1, and with 20～40 rev/mins speed ball millings 30～50 hours.
  5. 5. method according to claim 4 is characterized in that: said sieving adopted 50～80 mesh sieves.
  6. 6. method according to claim 5 is characterized in that: said forming agent by rubber and paraffin in mass ratio with 1: after the ratio proportioning of (2～3) with industrial naptha by mass ratio 1: (10～14) mix.
  7. 7. method according to claim 6 is characterized in that: the furnace pressure of said pressure sintering is 6～8MPa.
CN201010595790A 2010-12-20 2010-12-20 Hard alloy material taking Co-Cu as bonding phase and preparation method thereof Expired - Fee Related CN102061419B (en)

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Publication number Priority date Publication date Assignee Title
CN102417664A (en) * 2011-11-21 2012-04-18 株洲长江硬质合金工具有限公司 Forming agent for hard alloy production
CN102808085B (en) * 2012-05-14 2013-10-16 北京工业大学 Industrial method for recycling waste wolfram carbide-cobalt (WC-Co) hard alloy
CN111996432B (en) * 2020-09-02 2021-02-12 四川大学 Preparation method of ultra-coarse hard alloy material
CN111961941B (en) * 2020-09-02 2021-02-12 四川大学 Preparation method of superfine hard alloy cutter material

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1058234A (en) * 1990-07-18 1992-01-29 北京有色金属研究总院 The manufacture method that contains the Wimet of rare earth
CN1227612A (en) * 1996-08-06 1999-09-01 东洋钢钣株式会社 Hard sintered alloy
CN101760685A (en) * 2008-12-25 2010-06-30 北京有色金属研究总院 Superfine WC-Co cemented carbide containing rare-earth elements and preparation method thereof
CN101760686A (en) * 2010-01-25 2010-06-30 朱明生 Hard alloy product and spray powder

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1058234A (en) * 1990-07-18 1992-01-29 北京有色金属研究总院 The manufacture method that contains the Wimet of rare earth
CN1227612A (en) * 1996-08-06 1999-09-01 东洋钢钣株式会社 Hard sintered alloy
CN101760685A (en) * 2008-12-25 2010-06-30 北京有色金属研究总院 Superfine WC-Co cemented carbide containing rare-earth elements and preparation method thereof
CN101760686A (en) * 2010-01-25 2010-06-30 朱明生 Hard alloy product and spray powder

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