CN105755305A - Preparation method of high-hardness nano-hardness standard substance for calibrating nano indentation instrument - Google Patents

Preparation method of high-hardness nano-hardness standard substance for calibrating nano indentation instrument Download PDF

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CN105755305A
CN105755305A CN201510992223.5A CN201510992223A CN105755305A CN 105755305 A CN105755305 A CN 105755305A CN 201510992223 A CN201510992223 A CN 201510992223A CN 105755305 A CN105755305 A CN 105755305A
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王奇
王震
沈根利
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National Center for Nanosccience and Technology China
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Abstract

The invention provides a preparation method of a high-hardness nano-hardness standard substance for calibrating a nano indentation instrument.The preparation method particularly includes: mixing a tungsten source, a carbon source and a reductant for high-temperature liquid-phase reaction to obtain WC nanoparticles; performing in-situ coating of a rare earth oxide grain growth inhibitor through high-temperature liquid-phase reaction; subjecting the WC nanoparticles and spherical nano Co powder to wet ball milling to obtain WC-Co powder; subjecting the WC-Co powder to impurity removing, forming, pressing, degumming, calcining, cutting and polishing to obtain hard alloy standard sample blocks.For micro-nano technology metering standardization, the hard alloy standard substance can meet needs of the nano indentation instruction on instrument calibration and tracing chain building within a high-hardness interval.In addition, the nano tungsten-based hard alloy standard substance can fill a gap of rigid nano-hardness standard substances at home and abroad and meet needs for related detection technology studying, product arbitration and international comparison.

Description

A kind of preparation method of the high hardness value nano hardness standard substance for calibrating nano-hardness tester
Technical field
The present invention relates to the technical field of metrology and measurement typical magnitude transmission, more particularly, it relates to a kind of preparation method as high hardness value nano hardness standard substance WC-Co alloy.
Background technology
Nano material, since coming out, has almost penetrated into every subjects and each field of engineering technology.Due to the performance that nanoparticle is unique, such as quantum size effect, bulk effect, skin effect and quantum tunneling effect etc. so that the functional and suitability of nano material receives the extensive concern of people.It is known that the wearability of material and the hardness person's of having close relationship of material, it it is the comprehensive embodiment of material mechanical performance.The anti-wear performance of nano material is preferable, anti-abrasive wear and Wear and Sliding Wear Properties of Organic are significantly improved, the service life of instrument is reduced to below 300nm along with particle size and is significantly improved, this is all closely bound up with the hardness number of nano material, therefore the detection to hardness is particularly important, and corresponding various hardness measurement technology and instrument are also in the most progressive and development.
At present the hardness determination of material is roughly divided into three classes: macrohardness (Japan, the U.S. and the former Soviet Union etc. are set to more than 10N, EU member country and international body and are then set to more than 2N)；Microhardness (the upper limit: 10N or 2N；Lower limit: about 10mN) and nano hardness (typically at below 700mN).Macrohardness and microhardness are mainly in the sample of large-size, it is only capable of obtaining the plastic property of material, along with modern material Surface Engineering (vapour deposition, sputtering, ion implanting, high energy beam surface modification, thermal spraying etc.), microelectronics, integrated micro-opto-electro-mechanical systems, the development of biomaterials, sample itself live surface modification layer thickness more and more less, people when design not only it is to be understood that the plastic property of material, with greater need for the elastic property grasping material.Traditional hardness measurement cannot meet the needs of new material research, and nano hardness technology is arisen at the historic moment, and the thing followed is the measurement to nano hardness accuracy and evaluation, particularly interval in high hardness value.Therefore, the standard substance that need badly and develop a kind of stable performance, can be used as nano hardness detection, nano-hardness tester test system is corrected, comparison and transmission of quantity value.The operation principle of nano-hardness tester is to use small diamond probe press-in, by the change of the sensing testing different depth of power, draws nano hardness.So, the highest to the thing phase uniformity requirements of standard substance.The nano hardness standard substance of low durometer can use the resin materials such as PC, the used quartz etc. of higher hardness value, PC resin and quartz to be equal phase composition, and micro-variations does not interferes with the force value transmission of diamond probe.
Hard alloy is to be made binding metal by refractory carbide (WC, TiC, TaC etc.) and iron group metal (Fe, Co, Ni etc.), prepares through powder, material that compressing and high temperature sintering is constituted.Wherein, tungsten hard alloy is the most representative, it has acted on the high advantages more preferable with bonded metal ductility of carbide fusing point, there is high intensity and hardness, good wear-resisting and corrosion resistance, a series of premium properties such as high temperature resistant, thermal coefficient of expansion is little, elastic modelling quantity is high and chemical stability is good, simultaneously, be widely used at industrial circle, be drill, cut, the critical material in the field such as mold pressing.Substance identity principle according to standard substance application, meets scientific research and the many demands of production application using WC Hardmetal materials as high hardness value nano hardness reference material mass-energy.
The preparation technology of WC often uses W powder and the direct carbonization of charcoal or the improvement to this technique, but the method response speed is slow, is difficult to obtain the WC of theoretical carbon content, and the grain graininess of obtained WC and reunion degree are difficult to control.Additionally, hard alloy is metal carbide particles and two-phase structure's material of Binder Phase composition, in traditional handicraft, WC particle is realized by sintering after mechanical mixture with the combination of Binder Phase, but it is difficult to control dispersed in Binder Phase of granule, Binder Phase can not be made to reach well be coated with, it is impossible to make its hardness number reach the most homogeneous at the microscopic scale of nanoscale.After a large amount of test comparisons, find that current WC Hardmetal materials cannot meet the performance requirement for nanometer hard standard substance.Therefore, the present invention passes through the innovation of technology of preparing and solves WC hard alloy crystal grain problem excessive, inhomogenous when standard substance, thus provides a kind of high hardness value nano hardness standard substance for nano-hardness tester calibration.
Summary of the invention
The present invention relates to the preparation method of a kind of high hardness value nano hardness standard substance for nano-hardness tester calibration, this nano hardness standard substance is WC-Co hard alloy, and wherein WC grain average-size is 40nm；The nano hardness meansigma methods of hard alloy is 23.09GPa, and Young's modulus meansigma methods is 543.61GPa；Reference material mass size (diameter 1.5cm, highly 0.5cm)；Gauge block rms surface roughness is 1.2nm.
The high hardness value nano hardness standard substance WC-Co hard alloy that the present invention provides is to pass through the process route of two proposed step high-temperature liquid-phase reaction bonded wet ball grindings to synthesize primary powder, then prepared by specific compacting and sintering process.I.e. in first step high-temperature liquid-phase is reacted, obtain nanometer WC particle, it is subsequently adding surfactant and trivalent Ce salt carries out second step high-temperature liquid-phase reaction and WC particle is carried out in-stiu coating thus suppresses the growth of crystal grain, again the cobalt nanopowders that fine vacuum three rifle direct-current arc metal nano powder continuous production processes prepares is joined and powder body carries out mixed grinding, finally powder granule is pressed with specific instrument, calcines, cuts and polishes, thus obtain WC-Co hard alloy block.
Nanocrystalline WC hard alloys block set forth in the present invention is through the following steps that be prepared:
1) first step high-temperature liquid-phase reaction: W source, C source and reducing agent are mixed by a certain percentage, after stirring, pour in the autoclave of certain volume, adjust the rotating speed (100～800rpm) stirring slurry in autoclave, at 300～350 DEG C, stopped reaction after reaction 12～48h, the most cooled, centrifugal, washing obtains nanometer WC particle.Wherein W source is WO3, initial mass concentration is 25～40g/L；C source is the mixed liquor of methanol and ethanol, and volume ratio is 1:1～1:3；Reducing agent is Mg powder, and mass concentration is 16～25g/L.
2) obtained particulate matter is put into immersion certain time in the HCl solution of dilution, the reducing agent contained by sample dissolution, with pure water washing, filter；Soak certain time in the concentrated NaOH solution of heat, dissolve the MgWO that reaction generates4With the W salt that may generate.The dilutest HCl concentration is 1～4mol/L, and the concentration of NaOH is 6～10mol/L.
3) distilled water wash filtering product is used, and soak 12h in ethanol, clean sample is obtained after filtration, then it is dispersed in water, and add polyvinylpyrrolidone (PVP), it is stirring evenly and then adding into water-soluble trivalent Ce salt, until completely dissolved, mixed solution is poured in the autoclave of certain volume, adjust the rotating speed (100～800rpm) stirring slurry in autoclave, at 140～280 DEG C, stopped reaction after reaction 12～48h, the most cooled, centrifugal, washing obtains powder granule.Wherein trivalent Ce salt is cerous nitrate (Ce (NO3)3·6H2Or cerium chloride (CeCl O)3·7H2O), it is 34～78g/L with the initial mass of polyvinylpyrrolidone (PVP) than the initial mass concentration for 1:0.5～3, Ce salt.
4) being dispersed in dehydrated alcohol by the powder granule that collection obtains, be subsequently adding nanometer spherical cobalt powder granule (particle mean size is 50nm), carry out wet-mixed grinding under the effect of vertical mixing mill, last centrifugal drying obtains powder body.Wherein abrasive media is ZrO2Microsphere, particle diameter is 0.1～0.5mm, and nanometer WC powder body granule is 9:1～2 with the mass ratio of Co powder, and rotational speed of ball-mill is 300～400r/min.
5) it is shaped powder body processing and using specific instrument to suppress, the composition of forming agent is the mixture of paraffin, microwax, stearic acid, glyceryl stearate, its ratio is 16:1:1:2, forming agent accounts for the 3～5% of total mixture quality, compressing pressure is 30MPa, takes two-way compacting.
6) compressing sample block is carried out degumming process, H in tube type resistance furnace2Carry out under atmosphere, H2Flow be 0.03m3/ h, operation temperature is 500-600 DEG C.
7) calcining the sample block after degumming process, the calcining heat of high temperature furnace is 1300～1400 DEG C, and protective atmosphere is N2(flow is 0.03m3/ h), the time of staying is 2～10h.
8) by the sample cutting after sintering and chemically mechanical polishing, WC-Co hard alloy block is finally given.Polishing fluid the most used is diamond polishing liquid (mean diameter is 80nm), and polishing time is 30min.
Chemical reaction involved in nanometer WC particle preparation process:
Mg+C2H5OH→MgO+2C+3H2 (1)
C2H5OH→2C+2H2+H2O (2)
Mg+C2H5OH+WO3→MgWO4+2C+3H2 (3)
Mg+MgWO4+C→W+MgO+MgCO3 (4)
2W+C→W2C (5)
W2C+C→2WC (6)
Overall reaction: 2Mg+WO3+C2H5OH→MgCO3+WC+MgO+3H2
According to method of the present invention, W source is WO3C source is the mixed liquor of methanol and ethanol, reducing agent is Mg powder, the compactedness of reactor is 50～80%, the most liquid reactive temperature is 300～350 DEG C, reaction temperature is 140～280 DEG C for the second time, and ball shaped nano Co powder is obtained by fine vacuum three rifle direct-current arc metal nano powder continuous producing apparatus.The nanometer WC particle prepared according to the present invention presents obvious crystal diffraction peak (as shown in Figure 1), material object after compressing WC-Co hard alloy block is polished is as in figure 2 it is shown, detect consistency and elasticity modulus homogeneous (see Fig. 3) through nanohardness tester.
Accompanying drawing explanation
Fig. 1 is the XRD diffracting spectrum of obtained nanometer WC particle；
Fig. 2 is pictorial diagram before and after obtained WC-Co hard alloy sample block polishing；
Fig. 3 is the scattergram of obtained WC-Co hard alloy sample block consistency and elasticity modulus.
Detailed description of the invention
Embodiment 1
First step high-temperature liquid-phase is reacted: 25kg WO3, 500L CH3OH, 500LC2H5OH and 16kg Mg joins in the high pressure stainless steel cauldron that capacity is 2000L, (rotating speed of stirring slurry is 100r/min) is sealed after stirring, heating schedule is set, initial temperature is 25 DEG C, 300 DEG C are risen to 50min, constant temperature 12h, question response naturally cools to room temperature after terminating, by centrifugation, washing obtain nanometer WC particle.Obtained particulate matter is put in the dilution HCl solution of 1mol/L and soak 2 hours, the reducing agent contained by sample dissolution, with pure water washing, filters；Soak 2 hours in the concentrated NaOH solution (6mol/L) of heat, dissolve the MgWO that reaction generates4With the W salt that may generate, finally use distilled water wash filtering product, and soak 12h in ethanol, after filtration, obtain sample 17.95kg.
Second step high-temperature liquid-phase is reacted: be scattered in 1000L water by 17.95kg WC nano-particle, and add polyvinylpyrrolidone (PVP) 17kg, it is stirring evenly and then adding into water-soluble cerous nitrate 34kg, until completely dissolved, mixed solution is poured in the autoclave of 2000L, adjust the rotating speed (100r/min) stirring slurry in autoclave, at 140 DEG C, stopped reaction after reaction 12h, the most cooled, centrifugal, washing obtains 28.28kg aqueous particulate.
Wet ball grinding: the aqueous particulate of 28.28kg collection obtained is dispersed in dehydrated alcohol, it is subsequently adding nanometer spherical cobalt powder granule (particle mean size is 50nm) 1.80kg, wet-mixed grinding (rotational speed of ball-mill is 300r/min) is carried out under the effect of vertical mixing mill, last centrifugal drying obtains 28.58kg WC-Co powder body, and wherein abrasive media is ZrO2Microsphere, particle diameter is 0.1mm.
The molding of hard alloy blocks: take paraffin 0.704kg, microwax 0.044kg, stearic acid 0.044kg, glyceryl stearate 0.088kg and 28.58kgWC-Co powder body mix, then suppress on specific forcing press, compressing after sample is carried out degumming process.H in tube type resistance furnace2Carry out under atmosphere, H2Flow be 0.03m3/ h, operation temperature is 500 DEG C.Sample is placed in high temperature furnace calcining again, and protection gas is N2(flow is 0.03m3/ h), temperature is 1300 DEG C, and the time of staying is 2h.Finally carrying out cutting and chemical mechanical polish process by the sample after sintering, finally give WC-Co hard alloy block, wherein polishing fluid used is diamond polishing liquid, and grain diameter is 1 μm, and polishing time is 30min.
Measuring through nano hardness detector, the nano hardness of WC-Co hard alloy block is 22.89 ± 0.5GPa, and elastic modelling quantity is 541.32 ± 2.8GPa.
Embodiment 2
First step high-temperature liquid-phase is reacted: 45kg WO3, 500L CH3OH, 1000LC2H5OH and 30kg Mg joins in the high pressure stainless steel cauldron that capacity is 2000L, (rotating speed of stirring slurry is 300rpm) is sealed after stirring, heating schedule is set, initial temperature is 25 DEG C, 320 DEG C are risen to 50min, constant temperature 24h, question response naturally cools to room temperature after terminating, by centrifugation, washing obtain nanometer WC particle.Obtained particulate matter is put in the dilution HCl solution of 1mol/L and soak 2.5 hours, the reducing agent contained by sample dissolution, with pure water washing, filters；Soak 2 hours in the concentrated NaOH solution (6mol/L) of heat, dissolve the MgWO that reaction generates4With the W salt that may generate, finally use distilled water wash filtering product, and soak 12h in ethanol, after filtration, obtain sample 32.31kg.
Second step high-temperature liquid-phase is reacted: be scattered in 1500L water by obtained 32.31kg WC nano-particle, and add polyvinylpyrrolidone (PVP) 75kg, it is stirring evenly and then adding into water-soluble cerous nitrate 75kg, until completely dissolved, mixed solution is poured in the autoclave of 2000L, adjust the rotating speed (300r/min) stirring slurry in autoclave, at 200 DEG C, stopped reaction after reaction 24h, the most cooled, centrifugal, washing obtains 55.84kg aqueous particulate.
Wet ball grinding: 55.84kg aqueous particulate collection obtained is dispersed in dehydrated alcohol, it is subsequently adding nanometer spherical cobalt powder granule (particle mean size is 50nm) 3.23kg, wet-mixed grinding (rotational speed of ball-mill is 350r/min) is carried out under the effect of vertical mixing mill, last centrifugal drying obtains 56.12kgWC-Co powder body, and wherein abrasive media is ZrO2Microsphere, particle diameter is 0.3mm.
The molding of hard alloy blocks: take paraffin 1.872kg, microwax 0.117kg, stearic acid 0.117kg, glyceryl stearate 0.234kg and 56.12kg WC-Co powder body mix, then suppress on specific forcing press, compressing after sample is carried out degumming process.H in tube type resistance furnace2Carry out under atmosphere, H2Flow be 0.03m3/ h, operation temperature is 600 DEG C.Sample is placed in high temperature furnace calcining again, and protection gas is N2(flow is 0.03m3/ h), temperature is 1350 DEG C, and the time of staying is 5h.Finally carrying out cutting and chemical mechanical polish process by the sample after sintering, finally give WC-Co hard alloy block, wherein polishing fluid used is diamond polishing liquid, and grain diameter is 1 μm, and polishing time is 30min.
Measuring through nano hardness detector, the nano hardness of WC-Co hard alloy block is 23.09 ± 0.4GPa, and elastic modelling quantity is 543.75 ± 1.5GPa.
Embodiment 3
First step high-temperature liquid-phase is reacted: 45kg WO3, 500L CH3OH, 1000LC2H5OH and 30kg Mg joins in the high pressure stainless steel cauldron that capacity is 2000L, (rotating speed of stirring slurry is 300rpm) is sealed after stirring, heating schedule is set, initial temperature is 25 DEG C, 320 DEG C are risen to 50min, constant temperature 24h, question response naturally cools to room temperature after terminating, by centrifugation, washing obtain nanometer WC particle.Obtained particulate matter is put in the dilution HCl solution of 1mol/L and soak the reducing agent contained by 3 hours sample dissolution, with pure water washing, filter；Soak 2 hours in the concentrated NaOH solution (6mol/L) of heat, dissolve the MgWO that reaction generates4With the W salt that may generate, finally use distilled water wash filtering product, and soak 12h in ethanol, after filtration, obtain sample 33.45kg.
Second step high-temperature liquid-phase is reacted: be scattered in 1500L water by obtained 33.45kg WC nano-particle, and add polyvinylpyrrolidone (PVP) 180kg, it is stirring evenly and then adding into water-soluble cerium chloride 90kg, until completely dissolved, mixed solution is poured in the autoclave of 2000L, adjust the rotating speed (300r/min) stirring slurry in autoclave, at 200 DEG C, stopped reaction after reaction 24h, the most cooled, centrifugal, washing obtains 67.52kg aqueous particulate.
Wet ball grinding: 67.52kg aqueous particulate collection obtained is dispersed in dehydrated alcohol, it is subsequently adding nanometer spherical cobalt powder granule (particle mean size is 50nm) 3.35kg, wet-mixed grinding (rotational speed of ball-mill is 350r/min) is carried out under the effect of vertical mixing mill, last centrifugal drying obtains 69.45kgWC-Co powder body, and wherein abrasive media is ZrO2Microsphere, particle diameter is 0.3mm.
The molding of hard alloy blocks: take paraffin 2.31kg, microwax 0.145kg, stearic acid 0.145kg, glyceryl stearate 0.29kg and 69.45kg WC-Co powder body mix, then suppress on specific forcing press, compressing after sample is carried out degumming process.H in tube type resistance furnace2Carry out under atmosphere, H2Flow be 0.03m3/ h, operation temperature is 500 DEG C.Sample is placed in high temperature furnace calcining again, and protection gas is N2(flow is 0.03m3/ h), temperature is 1350 DEG C, and the time of staying is 5h.Finally carrying out cutting and chemical mechanical polish process by the sample after sintering, finally give WC-Co hard alloy block, wherein polishing fluid used is diamond polishing liquid, and grain diameter is 1 μm, and polishing time is 30min.
Measuring through nano hardness detector, the nano hardness of WC-Co hard alloy block is 22.95 ± 0.6GPa, and elastic modelling quantity is 542.62 ± 1.5GPa.
Embodiment 4
First step high-temperature liquid-phase is reacted: 64kg WO3, 400L CH3OH, 1200LC2H5OH and 40kg Mg joins in the high pressure stainless steel cauldron that capacity is 2000L, (rotating speed of stirring slurry is 800r/min) is sealed after stirring, heating schedule is set, initial temperature is 25 DEG C, 350 DEG C are risen to 50min, constant temperature 48h, question response naturally cools to room temperature after terminating, by centrifugation, washing obtain nanometer WC particle.Obtained particulate matter is put in the dilution HCl solution of 1mol/L and soak 2 hours, the reducing agent contained by sample dissolution, with pure water washing, filters；Soak 3 hours in the concentrated NaOH solution (6mol/L) of heat, dissolve the MgWO that reaction generates4With the W salt that may generate, finally use distilled water wash filtering product, and soak 12h in ethanol, after filtration, obtain sample 45.96kg.
Second step high-temperature liquid-phase is reacted: be scattered in 1600L water by obtained 45.96kg WC nano-particle, and add polyvinylpyrrolidone (PVP) 375kg, it is stirring evenly and then adding into water-soluble cerium chloride 125kg, until completely dissolved, mixed solution is poured in the autoclave of 2000L, adjust the rotating speed (800r/min) stirring slurry in autoclave, at 280 DEG C, stopped reaction after reaction 48h, the most cooled, centrifugal, washing obtains 93.33kg aqueous particulate.
Wet ball grinding: 93.33kg aqueous particulate collection obtained is dispersed in dehydrated alcohol, it is subsequently adding nanometer spherical cobalt powder granule (particle mean size is 50nm) 8.36kg, wet-mixed grinding (rotational speed of ball-mill is 400r/min) is carried out under the effect of vertical mixing mill, last centrifugal drying obtains 96.61kgWC-Co powder body, and wherein abrasive media is ZrO2Microsphere, particle diameter is 0.5mm.
The molding of hard alloy blocks: take paraffin 4.064kg, microwax 0.254kg, stearic acid 0.254, glyceryl stearate 0.508kg and 96.61kg WC-Co powder body mix, then suppress on specific forcing press, compressing after sample is carried out degumming process.H in tube type resistance furnace2Carry out under atmosphere, H2Flow be 0.03m3/ h, operation temperature is 600 DEG C, then sample is placed in high temperature furnace calcining, and protection gas is N2(flow is 0.03m3/ h), temperature is 1400 DEG C, and the time of staying is 8h.Finally carrying out cutting and chemical mechanical polish process by the sample after sintering, finally give WC-Co hard alloy block, wherein polishing fluid used is diamond polishing liquid, and grain diameter is 1 μm, and polishing time is 30min.
Measuring through nano hardness detector, the nano hardness of WC-Co hard alloy block is 23.12 ± 0.6GPa, and elastic modelling quantity is 543.35 ± 2.1GPa.

Claims (24)

1. the invention provides a kind of high hardness value nano hardness standard substance for calibrating nano-hardness tester The preparation technology of WC-Co alloy.It is to make WC particle carry out nucleation and growth response by high temperature solution phase method, Thus realize the controlled of granularity and uniformity, after nanometer WC particle is formed, it is carried out successively two steps Grain growth suppression and Binder Phase Co's is coated, makes the material of two phase structure realize the homogenization of height, thus Improve intensity and toughness.
2. require described a kind of high hardness value nano hardness mark for calibrating nano-hardness tester according to right 1 Quasi-material, it is characterised in that described WC-Co alloy material is prepared by following steps:
1) W source, C source and reducing agent (Mg) are mixed by a certain percentage, after stirring, pour certain body into In long-pending autoclave, adjust the rotating speed stirring slurry in autoclave, carry out under uniform temperature and rotating speed for the first time High-temperature liquid-phase is reacted, after certain time, and stopped reaction.
2), after natural cooling, this product mixed liquor is carried out solid-liquor separation, under uniform temperature and rotating speed High speed centrifugation a period of time, particulate matter is sunken to bottom centrifuge tube, is poured slowly into by supernatant liquid at the cleanest In the centrifuge tube managed, high speed centrifugation a period of time under uniform temperature and rotating speed again to supernatant liquid, should Process is at least repeated twice or more than twice, finally collects gained particulate matter.
3) obtained particulate matter is put in dilution HCl and soak certain time, the Mg contained by sample dissolution Salt, with pure water washing, filters；Soak certain time in the concentrated NaOH solution of heat, dissolve reaction The MgWO generated4With the W salt generated.
4) use distilled water wash filtering product, and soak certain time in ethanol, obtain clean after filtering Sample.
5) obtained particulate matter is dispersed in water, and is added thereto to polyvinylpyrrolidone (PVP), stir Add water-soluble trivalent Ce salt after mixing uniformly, until completely dissolved, pour mixed solution into certain volume Autoclave in, adjust in autoclave the rotating speed stirring slurry, under uniform temperature and rotating speed, carry out second second highest Temperature liquid phase reactor, after certain time, stopped reaction.
6), after natural cooling, according to step above, this product mixed liquor is carried out solid-liquor separation again, This process is repeated twice or more than twice, finally collects gained particulate matter.
7) particulate matter that collection obtains is scattered in dehydrated alcohol, is subsequently adding receiving of specific morphology and granularity Rice Co powder, is sufficiently mixed grinding under the effect of vertical mixing mill, and last centrifugal drying obtains powder body.
8) powder body is shaped, suppresses, degumming and calcination processing, finally by the sample cutting of sintering with change Learn mechanical polishing, finally give WC-Co hard alloy block.
Preparation technology the most according to claim 2, it is characterised in that step 1) in selected W source For WO3。
Preparation technology the most according to claim 2, it is characterised in that step 1) in selected C source be Methanol and the mixed liquor of ethanol.
Preparation technology the most according to claim 2, it is characterised in that step 1) in selected reducing agent For Mg.
Preparation technology the most according to claim 2, it is characterised in that step 1) described in reactor fill out Degree of filling is 50～80%.
Preparation technology the most according to claim 2, it is characterised in that step 1) described in high-temperature liquid-phase The rotating speed stirring slurry in reaction is 100～800rpm, reaction temperature is 300～350 DEG C, the response time be 12～ 48h。
Preparation technology the most according to claim 2, it is characterised in that step 1) described in W source matter Amount concentration is 25～40g/L.
Preparation technology the most according to claim 2, it is characterised in that step 1) described in methanol with The volume ratio of ethanol is 1: 1～1: 3.
Preparation technology the most according to claim 2, it is characterised in that step 1) described in Mg matter Amount concentration is 16～25g/L.
11. preparation technologies according to claim 2, it is characterised in that step 2) described in high temperature When liquid-phase reaction product carries out solid-liquor separation, the rotating speed of high speed centrifuge is at least 10000rpm, centrifuging temperature At-4～0 DEG C, the single spin time is at least 20min.
12. preparation technologies according to claim 2, it is characterised in that step 3) in the concentration of dilute HCl Being 1～4mol/L, the concentration of NaOH is 6～10mol/L.
13. preparation technologies according to claim 2, it is characterised in that step 4) in soak with ethanol time Between be 24h.
14. preparation technologies according to claim 2, it is characterised in that step 5) described in trivalent Ce Salt is cerous nitrate (Ce (NO3)3·6H2Or cerium chloride (CeCl O)3·7H2O)。
15. preparation technologies according to claim 2, it is characterised in that step 5) in Ce salt and polyethylene The initial mass ratio of ketopyrrolidine (PVP) is 1: 0.5～3, and the initial mass concentration of Ce salt is 34～78g/L.
16. preparation technologies according to claim 2, it is characterised in that step 5) described in second time The rotating speed stirring slurry in high-temperature liquid-phase reaction is 100～800rpm, reaction temperature is 140～280 DEG C, reaction Time is 12～48h.
17. preparation technologies according to claim 2, it is characterised in that step 6) described in second time When high-temperature liquid-phase product carries out solid-liquor separation, the rotating speed of high speed centrifuge is at least 10000rpm, centrifugal Temperature is at-4～0 DEG C, and the single spin time is at least 20min.
18. preparation technologies according to claim 2, it is characterised in that step 7) described in nano Co Powder pattern is spherical, is prepared by fine vacuum three rifle direct-current arc metal nano powder continuous production processes, its The spheroidization factor is less than 1.2%, and particle mean size is 50nm.
19. preparation technologies according to claim 2, it is characterised in that step 7) in nanometer WC particle It is 9: 1～2 with the mass ratio of Co powder.
20. preparation technologies according to claim 2, it is characterised in that step 7) used in grinding Medium is ZrO2Microsphere, particle diameter is 0.1～0.5mm, and rotational speed of ball-mill is 300～400r/min.
21. preparation technologies according to claim 2, it is characterised in that step 8) in powder body is become Shape and compression process, the composition of forming agent is the mixing of paraffin, microwax, stearic acid, glyceryl stearate Thing, its ratio is 16: 1: 1: 2, and forming agent accounts for the 3～5% of total mixture quality.Pressing pressure is 30MPa, Take two-way compacting.
22. preparation technologies according to claim 2, it is characterised in that step 8) in molding powder body is entered Row degumming process, i.e. H in tube type resistance furnace2Carry out under atmosphere, H2Flow be 0.03m3/ h, operation temperature Degree is 500～600 DEG C.
23. preparation technologies according to claim 2, it is characterised in that step 8) in sample block is forged Burning, temperature is 1300～1400 DEG C, and protective atmosphere is N2(flow is 0.03m3/ h), the time of staying is 2～10h.
24. preparation technologies according to claim 2, it is characterised in that step 8) in hard alloy blocks Carrying out chemical mechanical polish process, polishing fluid is diamond polishing liquid (particle diameter is 1 μm), and polishing time is 30min。
It should be noted that and understand, without departing from the spirit of the present invention required by appended claims and model In the case of enclosing, it is possible to the present invention of foregoing detailed description is made various modifications and improvements.It is therefore desirable to The scope of the technical scheme of protection is not limited by given any specific exemplary teachings.
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