CN1560301A - Method of WC hard alloy by electric discharge plasma in situ synthesis - Google Patents
Method of WC hard alloy by electric discharge plasma in situ synthesis Download PDFInfo
- Publication number
- CN1560301A CN1560301A CNA2004100034428A CN200410003442A CN1560301A CN 1560301 A CN1560301 A CN 1560301A CN A2004100034428 A CNA2004100034428 A CN A2004100034428A CN 200410003442 A CN200410003442 A CN 200410003442A CN 1560301 A CN1560301 A CN 1560301A
- Authority
- CN
- China
- Prior art keywords
- powder
- carbon black
- sintering
- hard alloy
- add
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000000956 alloy Substances 0.000 title abstract 3
- 229910045601 alloy Inorganic materials 0.000 title abstract 3
- 238000011065 in-situ storage Methods 0.000 title abstract 2
- 230000015572 biosynthetic process Effects 0.000 title 1
- 238000003786 synthesis reaction Methods 0.000 title 1
- 238000005245 sintering Methods 0.000 claims abstract description 24
- 239000006229 carbon black Substances 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000498 ball milling Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000009736 wetting Methods 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 14
- 238000010792 warming Methods 0.000 claims description 12
- 238000007599 discharging Methods 0.000 claims description 7
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- 241000872198 Serjania polyphylla Species 0.000 claims description 3
- 229960004756 ethanol Drugs 0.000 claims description 3
- 239000011812 mixed powder Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 15
- 239000013078 crystal Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 239000003112 inhibitor Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 229910019408 CoWO4 Inorganic materials 0.000 abstract 1
- 239000006227 byproduct Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 229910009043 WC-Co Inorganic materials 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000004826 seaming Methods 0.000 description 1
Images
Landscapes
- Powder Metallurgy (AREA)
- Ceramic Products (AREA)
Abstract
The inventnion is a mthod of in situ synthesizing hard alloy by spark plasma, including the following steps: mixing WO3 80wt%-88wt% with carbon black 12wt%-17wt%, or adding carbon black 10 wt%-17wt% in WO3 70wt%-85wt% and Co 1wt%-15wt%/CoO 1wt%-20wt%, or adding carbon black 10wt%-17wt% in CoWO4 83wt%-90wt% and simultaneously adding in alcohol for wetting according to routine process, ball-milling up to the size below 0.8 mum, and then drying; putting in a mould, sintering in a sintering device, vacuumzing to 3-4 Pa, rapidly raising the temperature up to 850 deg.C at a rate of 80-150 deg.C/min, then raising the temperature up to 1100 deg.C at a rate of 40-75 deg.C/min, as vacuum returns to 3-4 Pa, increasing pressure to 30-50MPa, preserving the heat at 1200-1300 deg.C for 2-5 min, cooling and obtaining WC hard alloy. It solves the problems of complex preparing process, high energy source consumption, purifying cost, controls crystal particle growth, and reduces the effect of inhibitor and by-product generation in chemical reaction to material properties.
Description
Technical field
The synthetic WC Wimet method of a kind of plasma discharging original position belongs to synthetic sintering technology field.
Background technology
The manufacturing processed of WC-Co Wimet is to produce WO earlier by adopt always
3, reduction WO
3Produce the W powder, produce the WC powder through carbonization again, be mixed and made into powder mix with the Co powder then, or adopt above-mentioned milling method directly to make the WC-Co composite powder, repressed, sintering creates.Producing of WC powder is particularly crucial, and the various Wimet of making both at home and abroad all are produced by WC powder or WC-Co powder at present, does not make Wimet by WC powder or WC-Co composite powder and does not still have report both at home and abroad.Along with reducing gradually of Wimet crystallite size, also the granularity of WC powder is had higher requirement, this just makes the complex process of the process of producing, technical difficulty strengthens, expensive problems such as a large amount of energy consumptions, purifying, control the grain growth of high temperature processes such as a series of powder process and sintering, but through repeatedly pyroprocess several times, crystal grain often will be grown up tens of times, even adopt strict control device to reach also very difficult below the 0.1 μ m, and the generation of a large amount of inhibitor and chemical reaction accessory products impacts to material property.
Summary of the invention
Problem to be solved by this invention is to overcome the problem that exists in the aforesaid method, and a kind of technology simple operations facility is provided, and reduces energy consumption and cost, has the high performance WC Hardmetal materials of close grain preparation method.
Technical scheme of the present invention is: the forerunner's powder with WC is combined into reduction, carbonization, sintering process one piece and finishes.Hardmetal materials organizes crystal grain tiny, and composition evenly is WC or WC-Co, does not have other dephasign except that a small amount of graphite.
Plasma discharging original position provided by the present invention is synthesized the Wimet method, it is characterized in that it may further comprise the steps:
(1) at WO with mass percent 83%～88%
3Join 12%～17% the carbon black or the WO of mass percent 70%～85%
3Add 10%～17% carbon black with 1%～15%Co powder or 1%～20%CoO powder or with mass percent 83%～90%CoWO
4Add 10%～17% carbon black and add dehydrated alcohol according to common process when mixing and make the powder mix complete wetting, ball milling to dry after granularity is below 0.8 micron to the ethanol volatilization fully;
(2) with the mixed powder dress mould after the above-mentioned oven dry, put into discharging plasma sintering equipment and carry out sintering, be evacuated to 3Pa～4Pa, under the speed of 80 ℃～150 ℃/min, be rapidly heated to 850 ℃, slowly be warming up to 1100 ℃ with 40 ℃～75 ℃/min then, treat that vacuum tightness returns to 3Pa～4Pa, pressurization 30MPa～50MPa obtains WC Wimet of the present invention after insulation 2～5min cooling down at 1200 ℃～1300 ℃.
The quality per distribution ratio of the powder mix in the step (1) and adding ethanol ball milling step belong to known technology, so do not itemize among the embodiment.
The heating process of step (2) described " being warming up to 850 ℃; slowly be warming up to 1100 ℃ with 40～75 ℃/min then ", be that the temperature rise rate that the process curve of drawing according to computer (as Fig. 6) calculates is to guarantee quality product according to synthetic discharge quantity control heat-up rate.These method of calculation belong to known technology,
The present invention mixes the directly synthetic WC of an amount of carbon black with forerunner's powder of WC on technology and sintering goes out Hardmetal materials, has avoided because of a series of powder process and sintering repeatedly the grain growth of pyroprocess several times.The present invention has adopted the sintering method of plasma discharging, at the discharge impact ripple and the electronics of Pulsed Discharge, under the reciprocal flow at high speed effect, powder surface to a certain extent can be breakdown in electric field for ion, makes powder be purified, activate, and makes WO
3, CoO react with fully fully, obtain reacting final product, the low temperature Fast Sintering realizes organizing crystal grain tiny, has the intensity height, the Hardmetal materials of good compactness.
Fig. 2 is the XRD figure of pure WC-Co Hardmetal materials, with synthetic before Fig. 1 different fully, WO as can be seen therefrom
3Single with carbon black original position synthetic Hardmetal materials composition, there are not other intermediate products.
Fig. 3 is the XRD figure of WC Hardmetal materials, therefrom only exists WC and Co mutually through original position synthetic Hardmetal materials as can be seen, and the Hardmetal materials phase composite made from traditional method is identical.
Fig. 5 is the example 1 SEM photo after synthetic, and wherein scale is 5.0 μ m, does not add any inhibitor during batching, and it is fairly obvious that the powder crystal grain behind the synthetic sintering of 48h ball milling that is about 500～1000 μ m by diameter is about 0.5 μ m thinning effect.
Description of drawings
The original WO of Fig. 1
3The XRD analysis result of powder;
XRD analysis result behind Fig. 2 WC sintering cemented carbide;
XRD analysis result behind Fig. 3 WC-Co sintering cemented carbide;
Fig. 4 agglomerating mould synoptic diagram;
Fig. 5 embodiment sintering structure SEM photo 20000 *;
Fig. 6 discharge plasma sintering SPS original position is synthesized the sintering process curve
F is an applied pressure among Fig. 4; 1, the mould seaming chuck; 2, carbon paper; 3, mixed powder; 4, die coat; 5, the mould push-down head.
Embodiment
1. with the WO of-20 order 85.5g (weight ratio 85.5%)
3Join powder with the carbon black of 14.5g (weight ratio 14.5%) and add dehydrated alcohol, put into ball mill mix powder, ball milling 48h evenly after, 120 ℃ were toasted 1 hour down in baking oven.Taking by weighing the 15g powder mix packs in the graphite jig of φ 24, compacting, put into SPS then, be evacuated to 3Pa, under 150 ℃/min, be rapidly heated to 850 ℃, slowly be warming up to 50 ℃/min under the situation that vacuum tightness reduces by 1100 ℃ treat that vacuum tightness returns to 3Pa after, be pressurized to 30Mpa, be warming up to 1300 ℃ of insulation 2min, slowly cool to room temperature and take out, obtain the WC Hardmetal materials.XRD analysis behind the sintering all is WC, density d=15.684g/cm
3
2. with the WO of-20 order 81.7g (weight ratio 81.7%)
3Join powder with the carbon black of 13.9g (weight ratio 13.9%) and 4.4g (weight ratio 4.4%) Co and add dehydrated alcohol, put into ball mill mix powder, ball milling 48h evenly after, 120 ℃ were toasted 1 hour down in baking oven.Taking by weighing the 15g powder mix packs in the graphite jig of φ 24, compacting, put into SPS then, be evacuated to 3Pa, under 130 ℃/min, be rapidly heated to 850 ℃, slowly be warming up to 50 ℃/min under the situation that vacuum tightness reduces by 1100 ℃ treat that vacuum tightness returns to 3Pa after, be pressurized to 30Mpa, be warming up to 1240 ℃ of insulation 3min, slowly cool to room temperature and take out, obtain the WC-Co Hardmetal materials.XRD analysis behind the sintering is WC and Co, density d=14.874g/cm
3
3. with the WO of-20 order 80.3g (weight ratio 80.3%)
3Join powder with the carbon black of 14.2g (weight ratio 14.2%) and 5.5g (weight ratio 5.5%) CoO and add dehydrated alcohol, put into ball mill mix powder, ball milling 48h evenly after, 120 ℃ were toasted 1 hour down in baking oven.Taking by weighing the 12g powder mix packs in the graphite jig of φ 24, compacting, put into SPS then, be evacuated to 3Pa, under 100 ℃/min, be rapidly heated to 850 ℃, slowly be warming up to 50 ℃/min under the situation that vacuum tightness reduces by 1100 ℃ treat that vacuum tightness returns to 3Pa after, be pressurized to 40Mpa, be warming up to 1220 ℃ of insulation 3min, slowly cool to room temperature and take out, obtain the WC-Co Hardmetal materials.XRD analysis behind the sintering is WC and Co, density d=14.827g/cm
3
4. use the CoWO of 85.8g (weight ratio 85.8%)
4The carbon black of powder and 14.2g (weight ratio 14.2%) is joined powder and is added dehydrated alcohol, put into ball mill mix powder, ball milling 48h evenly after, 120 ℃ were toasted 1 hour down in baking oven.Taking by weighing the 12g powder mix packs in the graphite jig of φ 24, compacting, put into SPS then, be evacuated to 3Pa, under 140 ℃/min, be rapidly heated to 850 ℃, slowly be warming up to 50 ℃/min under the situation that vacuum tightness reduces by 1100 ℃ treat that vacuum tightness returns to 3Pa after, be pressurized to 50Mpa, be warming up to 1200 ℃ of insulation 5min, slowly cool to room temperature and take out, obtain the WC-Co Hardmetal materials.XRD analysis behind the sintering is WC and Co, density d=14.782g/cm
3
Claims (1)
1, the synthetic Wimet method of a kind of plasma discharging original position is characterized in that it may further comprise the steps:
(1) at WO with mass percent 83%～88%
3Join 12%～17% the carbon black or the WO of mass percent 70%～85%
3Add 10%～17% carbon black with 1%～15%Co powder or 1%～20%CoO powder or with mass percent 83%～90%CoWO
4Add 10%～17% carbon black and add dehydrated alcohol according to common process when mixing and make the powder mix complete wetting, ball milling to dry after granularity is below 0.8 micron to the ethanol volatilization fully;
(2) with the mixed powder dress mould after the above-mentioned oven dry, put into discharging plasma sintering equipment and carry out sintering, be evacuated to 3Pa～4Pa, under the speed of 80 ℃～150 ℃/min, be rapidly heated to 850 ℃, slowly be warming up to 1100 ℃ with 40 ℃～75 ℃/min then, treat that vacuum tightness returns to 3Pa～4Pa, pressurization 30MPa～50MPa obtains WC Wimet of the present invention after insulation 2～5min cooling down at 1200 ℃～1300 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410003442 CN1232669C (en) | 2004-03-12 | 2004-03-12 | Method of WC hard alloy by electric discharge plasma in situ synthesis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410003442 CN1232669C (en) | 2004-03-12 | 2004-03-12 | Method of WC hard alloy by electric discharge plasma in situ synthesis |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1560301A true CN1560301A (en) | 2005-01-05 |
| CN1232669C CN1232669C (en) | 2005-12-21 |
Family
ID=34439532
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410003442 Expired - Fee Related CN1232669C (en) | 2004-03-12 | 2004-03-12 | Method of WC hard alloy by electric discharge plasma in situ synthesis |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1232669C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100572579C (en) * | 2008-04-21 | 2009-12-23 | 宜兴市甲有硬质合金制品厂 | The manufacture method of major diameter hard alloy metal trombone die |
| CN102517483A (en) * | 2011-12-15 | 2012-06-27 | 北京工业大学 | Industrial production method for synthesizing cemented carbide block material in situ |
| CN102628138A (en) * | 2012-03-23 | 2012-08-08 | 华南理工大学 | Trace cobalt-containing tungsten carbide without bonding phase and preparation method thereof |
| CN102814499A (en) * | 2012-07-05 | 2012-12-12 | 中国科学院宁波材料技术与工程研究所 | Method for quickly preparing precious metal parts at low temperature |
| CN104087807A (en) * | 2014-06-27 | 2014-10-08 | 宁国市正兴耐磨材料有限公司 | Wear-resistant material for sawteeth and preparation method of wear-resistant material |
| CN104313380A (en) * | 2014-10-27 | 2015-01-28 | 北京工业大学 | Method for preparing high density nanocrystalline hard alloy by step sintering |
| CN109943739A (en) * | 2019-03-15 | 2019-06-28 | 华南理工大学 | A kind of method that plasma ball mill prepares superfine WC-Co cemented carbide |
-
2004
- 2004-03-12 CN CN 200410003442 patent/CN1232669C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100572579C (en) * | 2008-04-21 | 2009-12-23 | 宜兴市甲有硬质合金制品厂 | The manufacture method of major diameter hard alloy metal trombone die |
| CN102517483A (en) * | 2011-12-15 | 2012-06-27 | 北京工业大学 | Industrial production method for synthesizing cemented carbide block material in situ |
| CN102628138A (en) * | 2012-03-23 | 2012-08-08 | 华南理工大学 | Trace cobalt-containing tungsten carbide without bonding phase and preparation method thereof |
| CN102628138B (en) * | 2012-03-23 | 2013-10-30 | 华南理工大学 | Trace cobalt-containing tungsten carbide without bonding phase and preparation method thereof |
| CN102814499A (en) * | 2012-07-05 | 2012-12-12 | 中国科学院宁波材料技术与工程研究所 | Method for quickly preparing precious metal parts at low temperature |
| CN102814499B (en) * | 2012-07-05 | 2015-04-22 | 中国科学院宁波材料技术与工程研究所 | Method for quickly preparing precious metal parts at low temperature |
| CN104087807A (en) * | 2014-06-27 | 2014-10-08 | 宁国市正兴耐磨材料有限公司 | Wear-resistant material for sawteeth and preparation method of wear-resistant material |
| CN104313380A (en) * | 2014-10-27 | 2015-01-28 | 北京工业大学 | Method for preparing high density nanocrystalline hard alloy by step sintering |
| CN104313380B (en) * | 2014-10-27 | 2016-11-30 | 北京工业大学 | A kind of step sintering prepares the method for high-compactness Nanograin Cemented Carbide |
| CN109943739A (en) * | 2019-03-15 | 2019-06-28 | 华南理工大学 | A kind of method that plasma ball mill prepares superfine WC-Co cemented carbide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1232669C (en) | 2005-12-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107935596B (en) | MAX-phase ceramic Ti prepared by low-temperature sintering by molten salt method3AlC2Method for producing powder | |
| CN103909274B (en) | A kind of method preparing cobalt cladding nanometer WC crystal composite powder and ultra-fine cemented carbide | |
| CN103130506B (en) | Method for preparing superfine titanium carbonitride | |
| CN103695685B (en) | A kind of microwave sintering reaction prepares the method for WC-Co hard alloy | |
| CN109576545B (en) | Ti (C, N) -based metal ceramic with mixed crystal structure and preparation method thereof | |
| CN106834878A (en) | A kind of method that microwave sintering prepares endogenous high-entropy alloy-base composite material | |
| CN107512912A (en) | The preparation method of high-purity MoAlB ceramic powders and compact block | |
| CN109943739B (en) | Method for preparing ultrafine-grained WC-Co hard alloy by plasma ball milling | |
| CN110407213B (en) | (Ta, nb, ti, V) C high-entropy carbide nano powder and preparation method thereof | |
| CN113620712B (en) | High-entropy carbide ceramic nano powder and preparation method and application thereof | |
| CN106882965A (en) | A kind of method that normal pressure prepares the aluminium toner body material of high purity titanium two | |
| CN105018927A (en) | Method for preparing coating containing Ti (C and N) with melamine as carbon and nitrogen precursor | |
| CN101704682A (en) | Method for preparing titanium carbide ceramic micro powder by utilizing self-propagating high temperature synthesis | |
| CN1232669C (en) | Method of WC hard alloy by electric discharge plasma in situ synthesis | |
| CN107649165A (en) | Photocatalysis film and preparation method in a kind of foam metal graphene compound substrate | |
| CN103205589B (en) | Hard alloy taking Ni-Al intermetallic compound as binding phase and preparation method thereof | |
| CN102517483B (en) | Industrial production method for synthesizing cemented carbide block material in situ | |
| CN103276266A (en) | Method for preparing TZM alloy material through spray drying | |
| CN107285329B (en) | Tungsten diboride hard material and preparation method and application thereof | |
| CN108620586A (en) | The composite material and preparation method of 3D printing high-compactness titanium-titanium boride | |
| CN105541345A (en) | Method for preparing superfine hafnium carbide ceramic powder | |
| CN116178019B (en) | Method for preparing porous MAX phase ceramic material by pressureless wrapping calcination | |
| CN111057896B (en) | Method for preparing FeCoNiCu high-entropy alloy and TiC particle composite reinforced copper-based composite material by vacuum arc melting | |
| CN108341670B (en) | Single phase Ti3SiC2Method for preparing metal ceramic | |
| CN110483057A (en) | A kind of four tungsten boride materials and the preparation method and application thereof adulterating tantalum element |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |