CN102644001A - Hard alloy coating matrix added with rare earth - Google Patents
Hard alloy coating matrix added with rare earth Download PDFInfo
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- CN102644001A CN102644001A CN2012100607833A CN201210060783A CN102644001A CN 102644001 A CN102644001 A CN 102644001A CN 2012100607833 A CN2012100607833 A CN 2012100607833A CN 201210060783 A CN201210060783 A CN 201210060783A CN 102644001 A CN102644001 A CN 102644001A
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Abstract
The invention provides a hard alloy coating matrix added with rare earth and relates to the technical field of rare earth hard alloy processes. The hard alloy coating matrix is prepared through the following steps: proportioning the components of 81-86.8% of WC (Wolfram Carbide) powder, 6-8% of cobalt powder, 3-4% of TiCN, 4-6% of tantalum-niobium solid solution (TaC:NbC=6:4) and 0.2-1% of the rear earth, and then adding the components into a rolling ball mill by using a hard alloy as a grinding body; meanwhile, adding a molding regent which is 4.0-4.5% of a total mass of raw materials and a surfactant which is 0.5-1.0% of the total mass of the raw materials, wherein the accumulated ball-milling time is 72-120 hours; atomizing and drying ball-milled slurry through spray drying; and sintering atomized granules which meet requirements and are formed in a pressure sintering furnace through a precise press. The hard alloy coating matrix is added in a state of rear earth-cobalt intermediate alloy powder, so that not only can the rear earth be ensured to achieve dispersible uniformity in a hard alloy, but also the rear earth can be effectively prevented from being oxidized. The purposes of purifying an interface with the rear earth and strengthening the alloy can be achieved.
Description
Technical field:
The present invention relates to carbide alloy of rare earth Technology field, be specifically related to a kind of hard alloy coating matrix that adds rare earth.
Background technology:
The problem of oxidation of scattering problem and the carbide alloy mixture drying process middle-weight rare earths of rare earth in wimet is to be engaged in the common problem that the worker ran into of carbide alloy of rare earth research, also is the major cause that causes the carbide alloy of rare earth unstable properties.Form with oxide compound adds, and then rare earth is very stable, is difficult to take place other reaction; It is very little basically or do not exist to purify the effect at interface; There is not the rare earth solution strengthening yet, because rare earth oxide is insoluble among the Co basically, and if the larger-size words of rare earth oxide particles that add; Also can't play and hinder the effect of α-Co, because bigger particle is very little to the dislocation glide inhibition to β-Co phase transformation.When adding, in the slip drying process, add rare earth and just can all become oxide compound with forms such as pure rare earth, hydrogenate; Though with vacuum drying oven can alleviate add the degree of oxidation of rare earth, the extremely difficult control of this process.Therefore, the current key issue that will solve be exactly rare earth interpolation form and addition manner.
Summary of the invention:
The purpose of this invention is to provide a kind of hard alloy coating matrix that adds rare earth; It adds with the form of rare earth-cobalt master alloy powder, can guarantee that rare earth gets dispersing uniformity in wimet, can effectively prevent rare-earth oxidation again; Reach rare earth and purify interface, the purpose of reinforced alloys.
In order to solve the existing problem of background technology, the present invention adopts following technical scheme: (TaC: NbC=6: 4) carry out adding after the proportioning with the rare earth of 0.2-1% and make the rotary mill of grinding element with wimet, the rotating speed of ball mill is: 30-40 rev/min with the TiCN of the cobalt powder of the WC powder of 81-86.8%, 6-8%, 3-4%, the tantalum niobium sosoloid of 4-6% for it; The ball-to-powder weight ratio of ball milling is: 5-11: 1; Ball-milling medium is an absolute ethyl alcohol, and liquid-solid ratio is 280-330ml/kg, adds the forming agent of raw material total mass 4.0-4.5% and the surfactant of 0.5-1.0% simultaneously; The ball milling time of accumulative total is: 72-120 hour; Ball milling slip when time is up adopts spraying drying to carry out atomization drying, drying temperature: 80 ℃-100 ℃, and time of drying: 100-160 minute; The loose density that the spraying drying that obtains is mixed pellet is: 2.0-3.3g/cm3; Flowability is: 30-50 second/50g, and the spraying pellet that will reach this requirement is molded over through precise press and carries out sintering in the pressure sintering furnace, and its sintering process is: take off 30 ℃-500 ℃ of forming agent temperature; Time 360-480 minute, carrier gas flux 15-60 liter/minute; 1410 ℃-1460 ℃ of sintering temperatures, nebulizer gas pressure: 4.0-6.0MPa, soaking time: 40-70 minute.
Described WC powder total carbon is 6.1-6.15%, Fsss granularity " 3.0um.Tantalum carbide with or the niobium carbide powder can single adding also can add by sosoloid, but the additional proportion that amounts to is at 4-6%, and TaC: NbC is about 6: 4.
The purity of described cobalt powder raw material is all greater than 99.5%, mean particle size 1.0 μ m.
In described rare earth-Co alloy raw material, content of rare earth can not be too high, prevents component segregation; Powder can not be meticulous, prevents the resistance of oxidation variation.
The present invention adds with the form of rare earth-cobalt master alloy powder, can guarantee that rare earth gets dispersing uniformity in wimet, can effectively prevent rare-earth oxidation again.Through optimizing the Recipe of carbide alloy of rare earth coated substrate, through atmosphere sintering and pressure sintering process improving the wettability of liquid phase to Ti (CN), WC, strengthened crystal boundary, improved each form mutually bonding strength.Rare earth reaches the effect that bonding all has solution strengthening mutually mutually to hard in the wimet, has therefore improved the intensity and the toughness of alloy, and bending strength improves 15%, reaches 2300Mpa at least, and toughness reaches 9MPa*M
1/2Add rare earth and can improve alloy oxidation-resistance, high temperature splitting resistance, nerve and raising hot strength, hardness also slightly increases, and porosity obviously descends.
Embodiment:
This embodiment is to adopt following technical scheme: it is with the TiCN of the cobalt powder of the WC powder of 81-86.8%, 6-8%, 3-4%, the tantalum niobium sosoloid of 4-6% (TaC: NbC=6: 4) carry out grinding element is made in adding after the proportioning of wimet rotary mill with the rare earth of 0.2-1%; The rotating speed of ball mill is: 30-40 rev/min, the ball-to-powder weight ratio of ball milling is: 5-11: 1, and ball-milling medium is an absolute ethyl alcohol; Liquid-solid ratio is 280-330ml/kg; Add the forming agent of raw material total mass 4.0-4.5% and the surfactant of 0.5-1.0% simultaneously, the ball milling time of accumulative total is: 72-120 hour, ball milling slip when time is up adopted spraying drying to carry out atomization drying; Drying temperature: 80 ℃-100 ℃; Time of drying: 100-160 minute, the loose density that the spraying drying that obtains is mixed pellet was: 2.0-3.3g/cm3, and flowability is: 30-50 second/50g; The spraying pellet that will reach this requirement is molded over through precise press and carries out sintering in the pressure sintering furnace; Its sintering process is: take off 30 ℃-500 ℃ of forming agent temperature, and time 360-480 minute, carrier gas flux 15-60 liter/minute; 1410 ℃-1460 ℃ of sintering temperatures, nebulizer gas pressure: 4.0-6.0MPa, soaking time: 40-70 minute.
Described WC powder total carbon is 6.1-6.15%, Fsss granularity " 3.0um.Tantalum carbide with or the niobium carbide powder can single adding also can add by sosoloid, but the additional proportion that amounts to is at 4-6%, and TaC: NbC is about 6: 4.
The purity of described cobalt powder raw material is all greater than 99.5%, mean particle size 1.0 μ m.
In described rare earth-Co alloy raw material, content of rare earth can not be too high, prevents component segregation; Powder can not be meticulous, prevents the resistance of oxidation variation.
This embodiment adds with the form of rare earth-cobalt master alloy powder, can guarantee that rare earth gets dispersing uniformity in wimet, can effectively prevent rare-earth oxidation again.Through optimizing the Recipe of carbide alloy of rare earth coated substrate, through atmosphere sintering and pressure sintering process improving the wettability of liquid phase to Ti (CN), WC, strengthened crystal boundary, improved each form mutually bonding strength.Rare earth reaches the effect that bonding all has solution strengthening mutually mutually to hard in the wimet, has therefore improved the intensity and the toughness of alloy, and bending strength improves 15%, reaches 2300MPa at least, and toughness reaches 9MPa*M
1/2Add rare earth and can improve alloy oxidation-resistance, high temperature splitting resistance, nerve and raising hot strength, hardness also slightly increases, and porosity obviously descends.
Embodiment 1, with mass percent according to the WC powder: 86.8%; Cobalt powder: 6%; TiCN:3%; Tantalum niobium sosoloid: 4%; The ratio batching back of Y-Co:0.2% adds the rotary mill (purity of raw material is all greater than 99.5%, and mean particle size is less than 3.0 μ m) of making grinding element of wimet, and the rotating speed of ball mill is: 35 rev/mins; The ball-to-powder weight ratio of ball milling is: 4: 1, ball-milling medium was an absolute ethyl alcohol, and liquid-solid ratio is 300ml/kg; Add the forming agent of raw material total mass 2.5% and 0.1% oleic acid simultaneously; The ball milling time of accumulative total is: 96 hours, ball milling slip when time is up adopted spraying drying to carry out atomization drying, dry temperature out: 90 ℃; Time of drying: 120 minutes, the loose density that the spraying drying that obtains is mixed pellet was: 3.5g/cm
3, flowability is: 34 seconds/50g, the spraying pellet that will reach this requirement was molded over through precise press and carries out sintering in the pressure sintering furnace, and its sintering process is: take off 30 ℃-500 ℃ of forming agent temperature, 380 minutes time, 40 liters/minute of carrier gas fluxes; 1420 ℃ of sintering temperatures, nebulizer gas pressure: 5.5MPa, soaking time: 60 minutes.
Physical and mechanical properties behind the sintering and metallurgical structure are: density: 14.65g/cm
3Hardness: HRA91.8; Intensity TRS:2320MPa; Metallographic: A02 B02 C00 E00.
Process the CNMG120408-MD cutter with this carbide alloy of rare earth material, cutting 40Cr steel, cutting speed: 240m/min; Cutting-in: 2.1mm; The amount of feed: 0.22mm/r, working durability 30min, wear of the tool flank " 0.2mm, crescent hollow abrasion " 0.25mm.
Embodiment 2, with mass percent according to the WC powder: 81.5%; Cobalt powder: 8%; TiCN:4%; Tantalum niobium sosoloid: 6%; The ratio batching back of Y-Co:0.5% adds the rotary mill (purity of raw material is all greater than 99.5%, and mean particle size is less than 3.0 μ m) of making grinding element of wimet, and the rotating speed of ball mill is: 35 rev/mins; The ball-to-powder weight ratio of ball milling is: 4: 1, ball-milling medium was an absolute ethyl alcohol, and liquid-solid ratio is 300ml/kg; Add the forming agent of raw material total mass 2.5% and 0.1% oleic acid simultaneously; The ball milling time of accumulative total is: 96 hours, ball milling slip when time is up adopted spraying drying to carry out atomization drying, dry temperature out: 90 ℃; Time of drying: 120 minutes, the loose density that the spraying drying that obtains is mixed pellet was: 3.4g/cm
3, flowability is: 36 seconds/50g, the spraying pellet that will reach this requirement was molded over through precise press and carries out sintering in the pressure sintering furnace, and its sintering process is: take off 30 ℃-500 ℃ of forming agent temperature, 380 minutes time, 40 liters/minute of carrier gas fluxes; 1420 ℃ of sintering temperatures, nebulizer gas pressure: 5.5MPa, soaking time: 60 minutes.
Physical and mechanical properties behind the sintering and metallurgical structure are: density: 14.42g/cm
3Hardness: HRA91.5; Intensity TRS:2380MPa; Metallographic: A02 B00 C00 E00.
Process SNMG 120404-MF cutter with this carbide alloy of rare earth material, cutting 40Cr steel, cutting speed: 260m/min; Cutting-in: 2.5mm; The amount of feed: 0.25mm/r, working durability 35min, wear of the tool flank " 0.2mm, crescent hollow abrasion " 0.23mm.
Embodiment 3, with mass percent according to the WC powder: 85.5%; Cobalt powder: 6%; TiCN:3%; Tantalum niobium sosoloid: 5%; The ratio batching back of La-Co:0.5% adds the rotary mill (purity of raw material is all greater than 99.5%, and mean particle size is less than 3.0 μ m) of making grinding element of wimet, and the rotating speed of ball mill is: 35 rev/mins; The ball-to-powder weight ratio of ball milling is: 4: 1, ball-milling medium was an absolute ethyl alcohol, and liquid-solid ratio is 300ml/kg; Add the forming agent of raw material total mass 2.5% and 0.1% oleic acid simultaneously, the ball milling time of accumulative total is: 96 hours, ball milling slip when time is up adopted spraying drying to carry out atomization drying; Dry temperature out: 90 ℃; Time of drying: 120 minutes, the loose density that the spraying drying that obtains is mixed pellet was: 3.3g/cm3, and flowability is: 36 seconds/50g; The spraying pellet that will reach this requirement is molded over through precise press and carries out sintering in the pressure sintering furnace; Its sintering process is: take off 30 ℃-500 ℃ of forming agent temperature, 380 minutes time, 40 liters/minute of carrier gas fluxes; 1420 ℃ of sintering temperatures, nebulizer gas pressure: 5.5MPa, soaking time: 60 minutes.
Physical and mechanical properties behind the sintering and metallurgical structure are: density: 14.58g/cm
3Hardness: HRA91.7; Intensity TRS:2320MPa; Metallographic: A02 B02 C00 E00.
Process the CNMG120408-MD cutter with this carbide alloy of rare earth material, cutting 40Cr steel, cutting speed: 250m/min; Cutting-in: 2.3mm; The amount of feed: 0.24mm/r, working durability 33min, wear of the tool flank " 0.2mm, crescent hollow abrasion " 0.25mm.
Embodiment 4, with mass percent according to the WC powder: 81%; Cobalt powder: 8%; TiCN:4%; Tantalum niobium sosoloid: 6%; The ratio batching back of La-Co:1% adds the rotary mill (purity of raw material is all greater than 99.5%, and mean particle size is less than 3.0 μ m) of making grinding element of wimet, and the rotating speed of ball mill is: 35 rev/mins; The ball-to-powder weight ratio of ball milling is: 4: 1, ball-milling medium was an absolute ethyl alcohol, and liquid-solid ratio is 300ml/kg; Add the forming agent of raw material total mass 2.5% and 0.1% oleic acid simultaneously, the ball milling time of accumulative total is: 96 hours, ball milling slip when time is up adopted spraying drying to carry out atomization drying; Dry temperature out: 90 ℃; Time of drying: 120 minutes, the loose density that the spraying drying that obtains is mixed pellet was: 3.2g/cm3, and flowability is: 38 seconds/50g; The spraying pellet that will reach this requirement is molded over through precise press and carries out sintering in the pressure sintering furnace; Its sintering process is: take off 30 ℃-500 ℃ of forming agent temperature, 380 minutes time, 40 liters/minute of carrier gas fluxes; 1420 ℃ of sintering temperatures, nebulizer gas pressure: 5.5MPa, soaking time: 60 minutes.
Physical and mechanical properties behind the sintering and metallurgical structure are: density: 14.36g/cm
3Hardness: HRA91.5; Intensity TRS:2380MPa; Metallographic: A02 B00 C00 E00.
Process the SNMG120404-MF cutter with this carbide alloy of rare earth material, cutting 40Cr steel, cutting speed: 280m/min; Cutting-in: 2.7mm; The amount of feed: 0.28mm/r, working durability 32min, wear of the tool flank " 0.2mm, crescent hollow abrasion " 0.23mm.
Claims (4)
1. hard alloy coating matrix that adds rare earth, it is characterized in that it with the TiCN of the cobalt powder of the WC powder of 81-86.8%, 6-8%, 3-4%, the tantalum niobium sosoloid of 4-6% (TaC: NbC=6: 4) and the rare earth of 0.2-1% carry out adding the rotary mill of making grinding element of wimet after the proportioning, the rotating speed of ball mill is: 30-40 rev/min; The ball-to-powder weight ratio of ball milling is: 5-11: 1; Ball-milling medium is an absolute ethyl alcohol, and liquid-solid ratio is 280-330ml/kg, adds the forming agent of raw material total mass 4.0-4.5% and the surfactant of 0.5-1.0% simultaneously; The ball milling time of accumulative total is: 72-120 hour; Ball milling slip when time is up adopts spraying drying to carry out atomization drying, drying temperature: 80 ℃-100 ℃, and time of drying: 100-160 minute; The loose density that the spraying drying that obtains is mixed pellet is: 2.0-3.3g/cm3; Flowability is: 30-50 second/50g, and the spraying pellet that will reach this requirement is molded over through precise press and carries out sintering in the pressure sintering furnace, and its sintering process is: take off 30 ℃-500 ℃ of forming agent temperature; Time 360-480 minute, carrier gas flux 15-60 liter/minute; 1410 ℃-1460 ℃ of sintering temperatures, nebulizer gas pressure: 4.0-6.0MPa, soaking time: 40-70 minute.
2. a kind of hard alloy coating matrix that adds rare earth according to claim 1 is characterized in that described WC powder total carbon is 6.1-6.15%, Fsss granularity " 3.0um.Tantalum carbide with or the niobium carbide powder can single adding also can add by sosoloid, but the additional proportion that amounts to is at 4-6%, and TaC: NbC is about 6: 4.
3. a kind of hard alloy coating matrix that adds rare earth according to claim 1, the purity that it is characterized in that described cobalt powder raw material be all greater than 99.5%, mean particle size 1.0 μ m.
4. a kind of hard alloy coating matrix that adds rare earth according to claim 1 is characterized in that content of rare earth can not be too high, prevents component segregation in described rare earth-Co alloy raw material; Powder can not be meticulous, prevents the resistance of oxidation variation.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104630590A (en) * | 2015-02-12 | 2015-05-20 | 成都邦普合金材料有限公司 | Composite hard alloy material and preparation method thereof |
| CN105057718A (en) * | 2015-08-10 | 2015-11-18 | 江苏塞维斯数控科技有限公司 | Disc-shaped or strip-shaped cutter for cutting |
| CN106893915A (en) * | 2017-01-22 | 2017-06-27 | 苏州新锐合金工具股份有限公司 | The porous effective sintered-carbide die material of microchannel aluminium alloy flat of one kind extruding |
| CN109047772A (en) * | 2018-08-14 | 2018-12-21 | 安徽利成机电设备制造有限公司 | A kind of production method being cut by laser machine knife blade |
| CN109550972A (en) * | 2019-01-22 | 2019-04-02 | 宇辰新能源材料科技无锡有限公司 | A kind of preparation method of high temperature cemented carbide cobalt powder |
| CN109622988A (en) * | 2019-01-22 | 2019-04-16 | 宇辰新能源材料科技无锡有限公司 | A kind of preparation method of anticorrosive Processes of Cobalt Powders For Hard Alloys |
| CN109868404A (en) * | 2019-03-27 | 2019-06-11 | 成都川硬合金材料有限责任公司 | A kind of hard alloy axle sleeve and preparation method thereof |
| CN115415530A (en) * | 2022-10-13 | 2022-12-02 | 崇义章源钨业股份有限公司 | Hard alloy containing rare earth and preparation method thereof |
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| 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 |
| CN101967593A (en) * | 2010-11-16 | 2011-02-09 | 西华大学 | Ultrafine grain solid carbide material containing rare earth and preparation method thereof |
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| 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 |
| CN101967593A (en) * | 2010-11-16 | 2011-02-09 | 西华大学 | Ultrafine grain solid carbide material containing rare earth and preparation method thereof |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104630590A (en) * | 2015-02-12 | 2015-05-20 | 成都邦普合金材料有限公司 | Composite hard alloy material and preparation method thereof |
| CN105057718A (en) * | 2015-08-10 | 2015-11-18 | 江苏塞维斯数控科技有限公司 | Disc-shaped or strip-shaped cutter for cutting |
| CN106893915A (en) * | 2017-01-22 | 2017-06-27 | 苏州新锐合金工具股份有限公司 | The porous effective sintered-carbide die material of microchannel aluminium alloy flat of one kind extruding |
| CN106893915B (en) * | 2017-01-22 | 2018-12-04 | 苏州新锐合金工具股份有限公司 | It is a kind of to squeeze the porous effective sintered-carbide die material of microchannel aluminium alloy flat |
| CN109047772A (en) * | 2018-08-14 | 2018-12-21 | 安徽利成机电设备制造有限公司 | A kind of production method being cut by laser machine knife blade |
| CN109550972A (en) * | 2019-01-22 | 2019-04-02 | 宇辰新能源材料科技无锡有限公司 | A kind of preparation method of high temperature cemented carbide cobalt powder |
| CN109622988A (en) * | 2019-01-22 | 2019-04-16 | 宇辰新能源材料科技无锡有限公司 | A kind of preparation method of anticorrosive Processes of Cobalt Powders For Hard Alloys |
| CN109868404A (en) * | 2019-03-27 | 2019-06-11 | 成都川硬合金材料有限责任公司 | A kind of hard alloy axle sleeve and preparation method thereof |
| CN115415530A (en) * | 2022-10-13 | 2022-12-02 | 崇义章源钨业股份有限公司 | Hard alloy containing rare earth and preparation method thereof |
| CN115415530B (en) * | 2022-10-13 | 2023-10-24 | 崇义章源钨业股份有限公司 | Rare earth-containing hard alloy and preparation method thereof |
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Application publication date: 20120822 |