CN103468994B - Method for preparing molybdenum nickel chromium boron multivariant boride metal ceramic - Google Patents
Method for preparing molybdenum nickel chromium boron multivariant boride metal ceramic Download PDFInfo
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- CN103468994B CN103468994B CN201310425182.2A CN201310425182A CN103468994B CN 103468994 B CN103468994 B CN 103468994B CN 201310425182 A CN201310425182 A CN 201310425182A CN 103468994 B CN103468994 B CN 103468994B
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Abstract
The invention provides a method for preparing a metal ceramic by taking a square M3B2(M=Mo, Ni and Cr) multivariant boride as a hard phase, and belongs to the field of wear-resistant materials such as tools, molds and the like. The method comprises the main preparation processes: taking elemental molybdenum powder, carbonyl nickel powder, amorphous boron powder and elemental chrome powder as raw materials; preparing the multivariant boride metal ceramic by the steps of ball-milling, mixing, drying, forming and sintering, wherein the hard phase is the square M3B2(M=Mo, Ni and Cr); the binding phase is NiMo alloy. Compared with the traditional 'boride reaction sintering process', the method adopts the elemental powder as raw materials, so that the method is wide in raw material; the process has the characteristics of being simple, and relatively low in manufacturing cost; the Rockwell hardness of the prepared metal ceramic can be up to 80.0-85.5 HRA; the bending strength can be up to 1075.5-1310.8 MPa; the metal ceramic can be equivalent to Ti (C, N)-based metal ceramic and WC-based hard alloy at a certain extent.
Description
Technical field
The present invention relates to the preparation method of the polynary boride-base cerment of a kind of molybdenum nickel chromium triangle boron, be mainly used in the high-abrasive material such as work, mould field.
Background technology
At present, conventional cutter material is tool steel, Wimet, cutter pottery and ultrahard cutting tool material.Wherein Wimet accounts for 60% of whole cutter, and Wimet is also referred to as " tooth " of industry.Wimet mainly comprises tungsten and cobalt, and W elements content in the earth's crust is rare, therefore is referred to as strategy metal, and at present, China is just providing the tungsten demand of 80% to the world with the tungsten reserves accounting for the world 35%.A large amount of consumption of tungsten resource are unfavorable for the Sustainable development of conventional rigid alloy industry.The Wimet seeking tungsten-free cemented carbide or Some substitute tungsten is a research direction in current work, moulding stock field.
Sintering metal comprises hard phase and Binder Phase.Hard phase, because transition metal carbide, nitride, boride have higher intensity, hardness, wear resistance and thermostability and be widely used as ceramic-metallic hard phase, wherein most study is with WC, TiC, TiN, Ti (C, N), TiB
2be hard phase Deng compound, the sintering metal being Binder Phase with metal or alloy such as Co, Ni, Fe.TiC based ceramic metal, TiN based ceramic metal and Ti (C, N) based ceramic metal have lower toughness and are difficult to the WC base cemented carbide matching in excellence or beauty traditional.And for TiB
2based ceramic metal, because the lower self-diffusion coefficient of TiB2 makes its coking property poor, and is easy to react with matrix metal generate fragility third phase in sintering process, therefore, and TiB
2based ceramic metal is difficult to be prepared into dense material by prior powder metallurgy method, and performance is not good.
Ternary boride has the high rigidity of binary borides, wear resistance and chemical stability equally, the researchist of Amada Co., Ltd. utilizes binary borides to be easy to the characteristic of metal bonding phase reaction, with binary borides (MoB, FeB, WB etc.) and W metal, Fe, Co etc. for raw material, prepare Mo by " reaction sintering technology " method
2niB
2-Ni, Mo
2feB
2-Fe and WCoB-Co Ternary Boride Base Cermets, ternary boride hard phase (Mo
2niB
2, Mo
2feB
2, WCoB) formed by boronation reaction sintering by binary borides and metallic matrix in sintering process.Hard phase prepared by this method is that forming core is grown up in metallic matrix, therefore, hard phase surface no-pollution, the intermiscibility of hard phase and metallographic phase is good, interface bond strength is higher, so this type of sintering metal has excellent comprehensive mechanical property, its good erosion resistance and toughness are also particularly outstanding, though hardness is worse than TiC based ceramic metal and WC Wimet, be widely used in the field such as hot extruding die, sea-water pump bearing of injection moulding machine, copper.
In China, the research of polynary boride-base cerment mainly concentrates in the preparation of hard coat in steel matrix, utilize at high temperature to react containing the powder such as Ni, Cr, Mo, C and boron or boride mixed powder and iron-based body and generate polynary boride, reaching complete densification being sintered by high-temperature liquid-phase.People's molybdenum powders such as Zhang Guojun, nickel powder and boron powder successfully prepare Mo by " boronation reaction sintering "
2niB
2ternary Boride Base Cermets, its hard phase has orthohormbic structure.In addition, M
3b
2the research of (M=Mo, Ni, Cr) polynary boride-base cerment has seldom seen bibliographical information.Because China just to begin one's study in recent years polynary boride cement, mainly at present to study in properity and preparation, need further deeply at the real application research of industrial circle.Mainly there is two problems in current application: one is that binary borides owing to preparing needed for polynary boride cement is expensive, and therefore production cost is high, and two is prepared sintering metal performance reliability and poor reproducibility.
Summary of the invention
A kind of low cost is the object of the present invention is to provide to prepare the preparation method with the polynary boride-base cerment of tetragonal,
Technical scheme of the present invention is as follows:
A preparation method for the polynary boride-base cerment of molybdenum nickel chromium triangle boron, comprises following step: with molybdenum powder, nickel powder, chromium powder and boron powder for raw material, obtains the M with tetragonal successively by ball milling mixing, press forming and sintering step
3b
2(M=Mo, Ni, Cr) polynary boride is hard phase.Take NiMo as the sintering metal of Binder Phase.
In described raw material, the massfraction of boron powder is 4.0% ~ 5.5%, and the massfraction of molybdenum powder is 40.8% ~ 52.0%, and the massfraction of nickel powder is 34.0% ~ 40.2%, and the massfraction of chromium powder is 10.0% ~ 15.0%.Adding massfraction is in addition that the graphite of 0.3% is as oxygen scavenger and sintering aid.
The purity > of described molybdenum powder 99.0%, granularity < 3 micron; The purity > 99.5% of carbonyl nickel powder, granularity≤3 micron; The purity > of boron powder 99.0%, granularity < 10 micron; The purity > 99.5% of chromium powder, granularity-325 order.
The concrete preparation method of the polynary boride-base cerment of described molybdenum nickel chromium triangle boron, is characterized in that:
(1) described ball milling mixes in powder process, adopts and is dry mixed mode, with Stainless Steel Ball or ZrO
2ball is ball-milling medium, and ratio of grinding media to material is (2 ~ 3): 1, and the mixed powder time is 16 ~ 20 hours.
(2) under the pressure of 90 ~ 120MPa, powder pressing is shaping, 30 ~ 60 seconds dwell times.
(3) will suppress green sintering in a vacuum or inert atmosphere fine and close, heat-up rate is 5 ~ 10 DEG C/min, and sintering temperature is 1200 ~ 1500 DEG C, soaking time 30 ~ 90min.
Carry out Mechanics Performance Testing to the sintering metal adopting aforesaid method to prepare, Rockwell hardness can reach 80.0 ~ 85.5HRA, and bending strength can reach 1050.4 ~ 1300.8MPa.
Carry out surface of fracture and microstructure observation to the sintering metal adopting aforesaid method to prepare, find even particle distribution, size is at 10 microns, and fracture mode is grain boundary fracture mainly.
Carry out material phase analysis to the sintering metal adopting aforesaid method to prepare, finding phase forming process is B, Mo, Ni, Cr → NiB, Ni
2b → orthogonal Mo
2niB
2→ cubic M
3b
2(M=Mo, Ni, Cr).
The present invention is the polynary boride-base cerment of molybdenum nickel chromium triangle boron having prepared tetragonal with elemental powders molybdenum powder, nickel powder, chromium powder and boron powder, and cost reduces greatly.Compared with prior art, feature of the present invention is:
1) raw material is extensive, and cheap, and relative cost is lower;
2) production unit required for is less, and preparation technology is simple, easily operates;
3) sintering metal homogeneous microstructure, performance reliability and the favorable reproducibility of producing.
Accompanying drawing explanation
Fig. 1. the ceramic-metallic XRD figure spectrum of embodiment 4 gained.The sample of test XRD all sinters obtained under Ar protective atmosphere.
Fig. 2. the ceramic-metallic Fracture scan electromicroscopic photograph of embodiment 4 gained.
Fig. 3. the microstructure under embodiment 4 gained sintering metal back-scattered electron mode (BSE), white portion is the M of tetragonal
3b
2(M=Mo, Ni, Cr) hard phase, black part is divided into Ni/Mo Binder Phase.
Embodiment
Set forth the present invention further below in conjunction with specific examples, these examples are only not used in for illustration of the present invention and limit the scope of the invention.
Embodiment 1
Take B:4.5g respectively, Mo:49.9g, Ni:35.6g, Cr:10.0g, graphite 0.3g; Stainless Steel Ball is abrading-ball (ratio of grinding media to material 3:1); batch mixing 16h; the material mixed sieves; at the pressure compacted under of 100MPa, pressurize 30s, then sinters under Ar protective atmosphere; heat-up rate is 5 DEG C/min; at 1275 DEG C of insulation 60min, stove is cold, and gained sample is primarily of the hard phase M of tetragonal
3b
2(M=Mo, Ni, Cr) and Binder Phase NiMo two kinds of thing phase composites.Rockwell hardness can reach 80.2 ~ 81.2HRA, and bending strength can reach 1122.3 ~ 1225.5MPa, embodiment 2
Mix by embodiment 1 one-tenth assignment system mixed powder, the material after mixing sieves, at the pressure compacted under of 120MPa, pressurize 30s, then sinters under Ar protective atmosphere, and heat-up rate is 5 DEG C/min, and at 1290 DEG C of insulation 60min, stove is cold.Rockwell hardness can reach 80.0 ~ 81.2HRA, and bending strength can reach 1075.5 ~ 1200.4MPa,
Embodiment 3
Mix by embodiment 1 one-tenth assignment system mixed powder, the material after mixing sieves, at the pressure compacted under of 120MPa, pressurize 30s, then sinters under vacuum atmosphere, and heat-up rate is 10 DEG C/min, and at 1200 DEG C of insulation 60min, stove is cold.Rockwell hardness can reach 81.0 ~ 85.5HRA, and bending strength can reach 1225.6 ~ 1300.2MPa,
Embodiment 4
Take B:5.0g respectively, Mo:40.8g, Ni:39.2g, Cr:15.0g, graphite 0.3g; Stainless Steel Ball is abrading-ball (ratio of grinding media to material 3:1), batch mixing 16h, and the material mixed sieves, at the pressure compacted under of 100MPa, pressurize 30s, then sinters under vacuum atmosphere, and heat-up rate is 10 DEG C/min, at 1200 DEG C of insulation 30min, stove is cold, and gained sample is primarily of hard phase M
3b
2(M=Mo, Ni, Cr) and Binder Phase Ni two kinds of thing phase composites.Rockwell hardness can reach 82.5 ~ 84.2HRA, and bending strength can reach 1285.2 ~ 1310.8MPa.
Claims (3)
1. the preparation method of the polynary boride-base cerment of molybdenum nickel chromium triangle boron, it is characterized in that comprising following processing step: with molybdenum powder, carbonyl nickel powder, amorphous boron powder and chromium powder for raw material, after ball milling mixing, drying, compression moulding and densified sintering product, obtained the M to have tetragonal
3b
2for hard phase, M=Mo, Ni, Cr, and the sintering metal taking NiMo as Binder Phase; In described raw material, the massfraction of amorphous boron powder is 4.0% ~ 5.5%, and the massfraction of molybdenum powder is 38.5% ~ 52.0%, and the massfraction of carbonyl nickel powder is 34.0% ~ 40.2%, the massfraction of chromium powder is 10.0% ~ 15.0%, and each material composition sum is 100%; Adding massfraction is in addition that the graphite of 0.3% is as oxygen scavenger and sintering aid; The condition of densified sintering product is: will suppress green sintering in a vacuum or inert atmosphere fine and close, heat-up rate is 5 ~ 10 DEG C/min, and sintering temperature is 1200 ~ 1500 DEG C, soaking time 30 ~ 90min.
2., by the preparation method of the polynary boride-base cerment of molybdenum nickel chromium triangle boron described in claim 1, it is characterized in that: the purity > of molybdenum powder 99.0%, granularity < 3 micron; The purity > 99.5% of carbonyl nickel powder, granularity≤3 micron; The purity > of amorphous boron powder 99.0%, granularity < 10 micron; The purity > 99.5% of chromium powder, granularity-325 order.
3., by the preparation method of the polynary boride-base cerment of molybdenum nickel chromium triangle boron described in claim 1, it is characterized in that:
(1) described ball milling mixing adopts to be dry mixed mode, with Stainless Steel Ball or ZrO
2ball is ball-milling medium, and ratio of grinding media to material is (2 ~ 3): 1, and the mixed powder time is 16 ~ 20 hours;
(2) under the pressure of 90 ~ 120MPa, powder pressing is shaping, 30 ~ 60 seconds dwell times.
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| EP3192887A1 (en) * | 2014-12-23 | 2017-07-19 | Bright Time (Hubei) Industrial Ltd. | Ceramic steel material and preparation method thereof |
| CN105132778A (en) * | 2015-09-21 | 2015-12-09 | 无锡清杨机械制造有限公司 | Molybdenum-tungsten-chromium-boron multi-boride-based metal ceramic and preparation method thereof |
| CN109133937B (en) * | 2018-08-08 | 2021-05-25 | 天津德天助非晶纳米科技有限公司 | Ternary boride and preparation method and application thereof |
| CN116121579A (en) * | 2022-11-25 | 2023-05-16 | 西安近代化学研究所 | Preparation method of MoCoB-WCoB based composite material |
Citations (4)
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|---|---|---|---|---|
| US4961781A (en) * | 1987-09-30 | 1990-10-09 | Kabushiki Kaisha Kobe Seiko Sho | High corrosion-and wear resistant-powder sintered alloy and composite products |
| CN1502714A (en) * | 2002-11-26 | 2004-06-09 | 山东大学 | Ternary boride base metal ceramic covering layer material and preparation technology thereof |
| CN101716656A (en) * | 2009-12-15 | 2010-06-02 | 武汉科技大学 | Metal ceramic composite roll collar and preparation method thereof |
| CN102191393A (en) * | 2010-03-18 | 2011-09-21 | 中国科学院上海硅酸盐研究所 | Preparation method of nickel molybdenum boron ternary boride base hard alloy |
-
2013
- 2013-09-17 CN CN201310425182.2A patent/CN103468994B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4961781A (en) * | 1987-09-30 | 1990-10-09 | Kabushiki Kaisha Kobe Seiko Sho | High corrosion-and wear resistant-powder sintered alloy and composite products |
| CN1502714A (en) * | 2002-11-26 | 2004-06-09 | 山东大学 | Ternary boride base metal ceramic covering layer material and preparation technology thereof |
| CN101716656A (en) * | 2009-12-15 | 2010-06-02 | 武汉科技大学 | Metal ceramic composite roll collar and preparation method thereof |
| CN102191393A (en) * | 2010-03-18 | 2011-09-21 | 中国科学院上海硅酸盐研究所 | Preparation method of nickel molybdenum boron ternary boride base hard alloy |
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