CN1485450A - Method for producing WC-Fe composite powder of ultra fine grain by tungsten alloy scrap - Google Patents
Method for producing WC-Fe composite powder of ultra fine grain by tungsten alloy scrap Download PDFInfo
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- CN1485450A CN1485450A CNA031176631A CN03117663A CN1485450A CN 1485450 A CN1485450 A CN 1485450A CN A031176631 A CNA031176631 A CN A031176631A CN 03117663 A CN03117663 A CN 03117663A CN 1485450 A CN1485450 A CN 1485450A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
A method of producing a superfine composite powder with tungsen carbon-element belong to iron group. It comprises: pulverizing the waste material containing tungsen, oxidizing and baking, grinding, wet grinding and mixing, reducing, adding carbon and carbonizing, then obtaining the superfine composite powder with tungsen carbon-element belong to iron group. It is characterized in, before reducing, adding carbon black powder, adjusting tungen and/or element of iron group, forming superfine WxCy compounds, adding some vanadium and chromium to prevent crystals from expanding.
Description
Technical field
The invention belongs in the field of powder metallurgy to adopt and contain wolfram alloy waste and produce that the superfine crystal particle wolfram varbide---iron is the method for composite powder.The composite powder of producing with this method can be directly used in manufacturing high-performance ultra-fine cemented carbide.
Background technology
The applicant is ZL91107165.2 in the patent No., denomination of invention is in the patent documentation of " recovery and treatment method of waste hand alloy material ", disclosed recovery and treatment method be with the tungstenic waste alloy through fragmentation, cleaning, roasting, handle in reduction under hydrogen or the carbon monoxide atmosphere, promptly get inferior carefully wolfram varbide---the cobalt composite powder that grain fineness number is 0.6～1.0 μ m through ball milling, screening again after adding carbon and carbonizing treatment.This method is because in directly reduction under hydrogen or carbon monoxide atmosphere behind oxidizing roasting, the ball milling, again through carbonizing treatment, therefore one is the production grain fineness number to be the inferior thin WC-Co composite powder of 0.5～1.0 μ m, can not produce ultra-fine composite powder; The 2nd, be used for producing its alloy ingredient of Wimet and only adjust in the wet-milling stage of CEMENTED CARBIDE PRODUCTION process, the element that added this moment both had been difficult to mix with former composite powder, grain fineness number also is difficult for being consistent, each element is to add with the form of single phase composition in addition, also reduced the homogeneity of the hart metal product metallographic of being produced, and can only the production grain fineness number be the inferior fine grain hard alloy product of 0.6～0.8 μ m.
Summary of the invention
It is a kind of with wolfram alloy waste production superfine crystal particle wolfram varbide---iron is the mode of composite powder to the objective of the invention is to improve on basis of background technology research, utilize the waste alloy that reclaims to reach, production performance good and can be directly used in produce ultrafine tungsten carbide crystal grain hart metal product the superfine crystal particle wolfram varbide---iron is composite powder, and technology advanced person, purpose such as reliable.
Solution of the present invention is that the iron that adopts hydrocarbon reducing process, promptly forms before reduction is handled is tungstate---in the tungstic oxide composite powder, be adjusted to the tungsten of component or/and add carbon black powder in the iron group in adding, make wherein Tungsten oxide 99.999 in hydrocarbon reduction process, form the chemical combination of a class superfine WxCy, in order in carbonization process after this, forming the superfine crystal particle wolfram varbide; In addition, add an amount of vanadium, chromium to suppress the crystal grain expansion.Therefore, the inventive method comprises:
A, oxidizing roasting: will contain wolfram alloy waste routinely mechanical means be crushed to 20～50mm, clean and remove inclusion and be placed in the heat-resisting alloy steel boat, sending in the oxidized still under 800～950 ℃ of temperature oxidizing roasting 4～6 hours, is tungstate to obtain iron---the tungstic oxide mixture;
B, pulverizing are ground: after said mixture was crushed to 1～5mm, place to grind to form 20～60 purpose mixed powders in the ball mill: the sintered carbide ball that ball mill added and the weight ratio of mixed powder were 3～7: 1;
C, wet-milling batching: add the tungsten of adjustment amount or/and iron group (cobalt or nickel, iron) and powdered carbon black according to the desired amount of each composition in the composition of mixed powder and the object, and in the material gross weight: sintered carbide ball: the ratio of ethanol=1: 3～15: 0.2～0.5 dropped in the ball mill wet-milling 24～96 hours, made uniform mixed powder;
D, reduction are handled: in the heat-resisting alloy steel boat of packing into after the wet-milling powder drying that makes, reduction reaction is 4～6 hours under hydrogen atmosphere and 750 °～920 ℃ temperature, and 40～120 mesh sieves are crossed in the cooling back;
E, join carbon: handle by reduction and contain 1.02～1.15 times of difference that tungsten and associated metal element in uncombined carbon amount and the compound generate the required carbon total amount of carbide fully in the gained material of back, in mixture, replenish the adding carbon black powder and placed grinding in ball grinder 4～96 hours;
F, carbonizing treatment: will place heat-resisting boat and send in the high-temperature alloy steel boiler tube through joining material after carbon is handled, carburizing reagent be 1～3 hour under nitrogen atmosphere protection and 750 °～920 ℃ temperature; Cross 40～120 mesh sieves at last, promptly get the ultrafine tungsten carbide of mean grain size≤0.5 μ m---iron system (iron, cobalt, nickel) composite powder.
In order to improve oxidation efficiency, when oxidizing roasting, can in stove, replenish the gas mixture of sending into air or air and oxygen.For crystal grain in the inhibited reaction process expands and suitably reduces production costs, when preparing burden, wet-milling also can add 0.2～1.0% vanadium or/and chromium; The vanadium that adds, chromium can they ammonium salt or the form of oxide compound, carbide, metal-powder add.And described replenishing in wet-milling batching adds tungsten or/and iron group, and the tungsten that is added can be the ammonium salt of all kinds of Tungsten oxide 99.999s or tungsten; Iron, cobalt, the nickel that adds then is their oxalate or oxide compound, also or metal-powder.
The present invention is owing to adopt hydrocarbon reducing process and tungsten, iron group and vanadium, the chromium of adding carbon black powder and adjustment amount before reduction is handled, thereby help continue after technological process in form the superfine wolfram varbide---iron is powder and main body combined oxidation tungsten---ultrafine tungsten carbide of iron group generation---, and iron be that powder mixes fully, and crystal grain and consistent appearance, the vanadium that is added, chromium also can generate vanadium carbide, chromium carbide in recombination process.Thereby the inventive method has technology advanced person, stable, reliable, and the wolfram varbide of being produced---iron is composite powder mean grain size≤0.5 μ m, and uniform crystal particles; Wolfram varbide in the various ultra-fine composite powders is a kind of platy structure, and the vanadium carbide of cobalt, nickel, iron and generation, chromium carbide distribute very even in powder, has premium propertiess such as high intensity and hardness in order to produce ultra-fine cemented carbide.
Accompanying drawing and description of drawings
Fig. 1. be embodiment 1 composite powder * 20,000 times of metallographs (SEM figure).
Embodiment 1
Present embodiment with hard alloy scraps top hammer (containing WC:92%, cobalt about 8%) is reclaimed produce contain cobalt 10% the superfine crystal particle wolfram varbide---cobalt composite powder is an example:
A, oxidizing roasting: will be crushed to＜hard alloy scraps top hammer 2000g that 50mm and clean removes behind the impurity places the heat-resisting alloy steel boat, send in the oxidized still, 900 ℃ of temperature and send constantly into oxygen and the condition of air Mixture under roasting 5 hours, cobaltous tungstate---tungstic oxide mixture 2254g (unoxidized about 90g hard alloy scraps remnant is removed); The mixed gas flow of sending into: air 500L/ hour, oxygen 150L/ hour;
B, pulverizing, grinding: gained 2254g mixture piece material is crushed to＜5mm after, place to add the 12kg sintered carbide ball in the ball mill, ground to form the powder of 40 mesh sieves.
C, wet-milling batching: together with vanadium oxide 14.3g, chromic oxide 9.0g, cobalt oxalate 130 restrains with above-mentioned powder, and carbon black powder 178g places ball mill together with 26kg sintered carbide ball and 1.0kg ethanol, and wet-milling 72 hours makes mixed powder, dried for standby;
D, reduction are handled: the mixed powder of above-mentioned dried for standby is packed in the heat-resisting alloy steel boat, and reduction reaction is 5 hours under hydrogen atmosphere and 850 ℃ of temperature, and 80 mesh sieves are crossed in the cooling back;
E, join carbon: will reduce and handle the gained mixed powder and added in the ball mills wet-milling 72 hours together with carbon black powder 60 grams, dry back is stand-by;
F, carbonizing treatment: the powder of above-mentioned dried for standby is placed graphite boat and send in the high-temperature alloy steel boiler tube, carburizing reagent is 2 hours under nitrogen atmosphere protection and 850 ℃ of temperature; Cross 80 mesh sieves at last and get 1950g superfine crystal particle wolfram varbide---cobalt composite powder.
Each component content of present embodiment is respectively .:WC89.15%, CO10.0%, VC0.4%, CrC
30.35%, uncombined carbon＜0.05%, oxygen＜0.1%; Accompanying drawing 1 is 20,000 times of SEM figure of present embodiment composite powder.The present embodiment product can be directly used in produces high-performance Y G10 class ultra-fine cemented carbide goods.
Embodiment 2
Present embodiment contains W92%, nickel, iron with 1000g, and to add up to about 8.0% high density tungsten alloy waste material be raw material, produce nickeliferous, iron add up to 10.0% ultrafine tungsten carbide---nickel, iron composite powder are example:
A, oxidizing roasting and B pulverize and grind, and be all same with embodiment 1, gets 1240g wolframic acid nickel, wolframic acid iron---tungstic oxide composite powder;
C, wet-milling batching: above-mentioned composite powder together with nickelous oxalate 72g, vanadium oxide 8.0g, chromic oxide 5.0g, carbon black powder 98g, is sent in the ball mill wet-milling after 66 hours, dried for standby;
D, reduction are handled also with embodiment 1;
E, join carbon: will reduce and handle the gained powder and send in the ball mill wet-milling after 72 hours together with the 33.5g carbon black powder, dried for standby;
Carbonizing treatment is also same with embodiment 1, gets the 1080g composition at last and is: WC89.15%, Ni+Fe10.0%, Vc0.40%, Cr
2C
30.38%, superfine crystal particle wolfram varbide---nickel, the iron composite powder of the mean grain size of uncombined carbon＜0.05%, oxygen＜0.1%≤0.5 μ m.This composite powder can be directly used in the production ultrafine tungsten carbide---nickel, iron hard metal article.
Claims (4)
1, a kind of with wolfram alloy waste production superfine crystal particle wolfram varbide---iron is the method for composite powder; It is characterized in that this method comprises:
A, oxidizing roasting: will contain wolfram alloy waste routinely mechanical means be crushed to 20～50mm, clean and remove inclusion and be placed in the heat-resisting alloy steel boat, sending in the oxidized still under 800～950 ℃ of temperature oxidizing roasting 4～6 hours, is tungstate to obtain iron---the tungstic oxide mixture;
B, pulverizing, grinding: after said mixture was crushed to 1～5mm, place to grind to form 20～60 purpose mixed powders in the ball mill: the sintered carbide ball that ball mill added and the weight ratio of mixed powder were 3～7: 1;
C, wet-milling batching: add the tungsten of adjustment amount or/and iron group and powdered carbon black according to the desired amount of each composition in the composition of mixed powder and the object, and in the material gross weight: sintered carbide ball: the ratio of ethanol=1: 3～15: 0.2～0.5 drops into ball mill wet-milling 24～96 hours, makes uniform mixed powder;
D, reduction are handled: in the heat-resisting alloy steel boat of packing into after the wet-milling powder drying that makes, reduction reaction is 4～6 hours under hydrogen atmosphere and 750 °～920 ℃ temperature, and 40～120 mesh sieves are crossed in the cooling back;
E, join carbon: handle by reduction and contain 1.02～1.15 times of difference that tungsten and associated metal element in uncombined carbon amount and the compound generate the required carbon total amount of carbide fully in the gained material of back, in mixture, replenish the adding carbon black powder and placed grinding in ball grinder 4～96 hours;
F, carbonizing treatment: will place heat-resisting boat and send in the high-temperature alloy steel boiler tube through joining material after carbon is handled, carburizing reagent be 1～3 hour under nitrogen atmosphere protection and 750 °～920 ℃ temperature; Cross 40～120 mesh sieves at last, get promptly that the ultrafine tungsten carbide of mean grain size≤0.5 μ m---iron is composite powder.
2, described by claim 1 with wolfram alloy waste production superfine crystal particle wolfram varbide---iron is the method for composite powder; It is characterized in that when oxidizing roasting, can in stove, replenishing the gas mixture of sending into air or air and oxygen.
3, described by claim 1 with wolfram alloy waste production superfine crystal particle wolfram varbide---iron is the method for composite powder; It is characterized in that when wet-milling is prepared burden, also can adding 0.2～1.0% vanadium or/and chromium; The vanadium that adds, chromium can they ammonium salt or the form of oxide compound, carbide, metal-powder add.
4, described by claim 1 with wolfram alloy waste production superfine crystal particle wolfram varbide---iron is the method for composite powder; It is characterized in that described replenishing in wet-milling batching adds tungsten or/and iron group, the tungsten that is added can be the ammonium salt of all kinds of Tungsten oxide 99.999s or tungsten; The iron that is added, cobalt, nickel then are their oxalate or oxide compound, also or metal-powder.
Priority Applications (1)
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| CNA031176631A CN1485450A (en) | 2003-04-11 | 2003-04-11 | Method for producing WC-Fe composite powder of ultra fine grain by tungsten alloy scrap |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101360575B (en) * | 2006-03-14 | 2011-07-20 | 株式会社神户制钢所 | Mixed powder for powder metallurgy, green compact thereof, and sintered body |
| CN101506096B (en) * | 2006-09-15 | 2012-06-13 | 株式会社东芝 | Carbonated tungsten powder, method for production of the same, and superhard material and tool using the same |
| CN102653404A (en) * | 2011-09-14 | 2012-09-05 | 自贡硬质合金有限责任公司 | Method for producing cast tungsten carbide by utilizing tungsten-containing hard-face material soft waste |
| CN102665973A (en) * | 2009-10-26 | 2012-09-12 | 明普罗公司 | Recycling of tungsten carbides |
| CN102758089A (en) * | 2011-04-25 | 2012-10-31 | 自贡科瑞德新材料有限责任公司 | Recovering and regenerating method of cemented carbide scrap material |
| CN103114204A (en) * | 2013-02-22 | 2013-05-22 | 宜兴市炜华合金材料有限公司 | Method for recovering tungsten-base alloy waste |
| CN103290226A (en) * | 2013-06-20 | 2013-09-11 | 北京工业大学 | Method for recovering and regenerating ultrafine grained cemented carbide containing crystal grain growth inhibitor |
| CN104386697A (en) * | 2014-11-24 | 2015-03-04 | 株洲长江硬质合金工具有限公司 | Method for producing tungsten carbide from waste tungsten cutting scraps |
| WO2017164898A1 (en) * | 2016-03-23 | 2017-09-28 | Aeroalloys Llc | Method of treating unrefined tungstic acid to produce alloy grade tungsten for use in tungsten bearing steels and nickel based superalloys |
| CN107758669A (en) * | 2017-11-30 | 2018-03-06 | 重庆大学 | A kind of method that propyl alcohol reduction prepares Molybdenum carbide powders |
| CN116103555A (en) * | 2023-01-13 | 2023-05-12 | 福建中成新材料科技有限公司 | Regenerated hard alloy extruded round bar material and preparation process thereof |
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2003
- 2003-04-11 CN CNA031176631A patent/CN1485450A/en active Pending
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101360575B (en) * | 2006-03-14 | 2011-07-20 | 株式会社神户制钢所 | Mixed powder for powder metallurgy, green compact thereof, and sintered body |
| CN101506096B (en) * | 2006-09-15 | 2012-06-13 | 株式会社东芝 | Carbonated tungsten powder, method for production of the same, and superhard material and tool using the same |
| CN102665973B (en) * | 2009-10-26 | 2014-07-16 | 明普罗公司 | Recycling of tungsten carbides |
| CN102665973A (en) * | 2009-10-26 | 2012-09-12 | 明普罗公司 | Recycling of tungsten carbides |
| CN102758089A (en) * | 2011-04-25 | 2012-10-31 | 自贡科瑞德新材料有限责任公司 | Recovering and regenerating method of cemented carbide scrap material |
| CN102653404B (en) * | 2011-09-14 | 2013-11-13 | 自贡硬质合金有限责任公司 | Method for producing cast tungsten carbide by utilizing tungsten-containing hard-face material soft waste |
| CN102653404A (en) * | 2011-09-14 | 2012-09-05 | 自贡硬质合金有限责任公司 | Method for producing cast tungsten carbide by utilizing tungsten-containing hard-face material soft waste |
| CN103114204A (en) * | 2013-02-22 | 2013-05-22 | 宜兴市炜华合金材料有限公司 | Method for recovering tungsten-base alloy waste |
| CN103114204B (en) * | 2013-02-22 | 2015-05-06 | 宜兴市炜华合金材料有限公司 | Method for recovering tungsten-base alloy waste |
| CN103290226A (en) * | 2013-06-20 | 2013-09-11 | 北京工业大学 | Method for recovering and regenerating ultrafine grained cemented carbide containing crystal grain growth inhibitor |
| CN103290226B (en) * | 2013-06-20 | 2014-10-29 | 北京工业大学 | Method for recovering and regenerating ultrafine grained cemented carbide containing crystal grain growth inhibitor |
| CN104386697A (en) * | 2014-11-24 | 2015-03-04 | 株洲长江硬质合金工具有限公司 | Method for producing tungsten carbide from waste tungsten cutting scraps |
| WO2017164898A1 (en) * | 2016-03-23 | 2017-09-28 | Aeroalloys Llc | Method of treating unrefined tungstic acid to produce alloy grade tungsten for use in tungsten bearing steels and nickel based superalloys |
| CN107758669A (en) * | 2017-11-30 | 2018-03-06 | 重庆大学 | A kind of method that propyl alcohol reduction prepares Molybdenum carbide powders |
| CN107758669B (en) * | 2017-11-30 | 2019-11-08 | 重庆大学 | A kind of method that propyl alcohol reduction prepares Molybdenum carbide powders |
| CN116103555A (en) * | 2023-01-13 | 2023-05-12 | 福建中成新材料科技有限公司 | Regenerated hard alloy extruded round bar material and preparation process thereof |
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