CN100467649C - Production method for hard carbide with graded distributed cobalt content - Google Patents
Production method for hard carbide with graded distributed cobalt content Download PDFInfo
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- CN100467649C CN100467649C CNB2004100217857A CN200410021785A CN100467649C CN 100467649 C CN100467649 C CN 100467649C CN B2004100217857 A CNB2004100217857 A CN B2004100217857A CN 200410021785 A CN200410021785 A CN 200410021785A CN 100467649 C CN100467649 C CN 100467649C
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims description 14
- 229910017052 cobalt Inorganic materials 0.000 title claims description 13
- 239000010941 cobalt Substances 0.000 title claims description 13
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 22
- 239000000956 alloy Substances 0.000 claims abstract description 22
- 238000005245 sintering Methods 0.000 claims abstract description 17
- 238000001238 wet grinding Methods 0.000 claims abstract description 14
- 239000003292 glue Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000000465 moulding Methods 0.000 claims abstract description 8
- 239000006229 carbon black Substances 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 235000015895 biscuits Nutrition 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000000748 compression moulding Methods 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000001513 hot isostatic pressing Methods 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000005255 carburizing Methods 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 238000013329 compounding Methods 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 3
- 238000004886 process control Methods 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 208000037656 Respiratory Sounds Diseases 0.000 description 2
- 241001074085 Scophthalmus aquosus Species 0.000 description 2
- 229910009043 WC-Co Inorganic materials 0.000 description 2
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- 229910000967 As alloy Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
Images
Abstract
The hard alloy producing process includes compounding material, wet milling, adding glue, molding to form, loading the plain blank into boat, covering with pure carbon black, sintering in sintering furnace under the protection of hydrogen, and post-treatment to eliminate internal stress and to obtain the hard alloy with gradiently distributed Co content. Owing to the sintering and carburizing with pure carbon black as carburizing agent and the increased post-treatment step, the advanced technological process has high reliability, strong carburizing reaction activity, simple operation process, obvious Co content gradient in the hard alloy product, high comprehensive mechanical performance, low production cost, and other advantages.
Description
Technical field
The invention belongs to the production method of hard metal article, the production method of the hard metal article that the intravital cobalt element content of particularly a kind of Wimet from outward appearance to inner essence changes in gradient.This method especially is suitable for the manufacturing of workers such as WC-Co series hard alloy blade (tool) and drawing die, mould, to improve its comprehensive mechanical performance.
Background technology
The inside and outside metallographic structure of workers such as conventional WC-Co series hard alloy blade, brill tooth, rock cutting and wortle, mould is even, mechanical property is consistent.There is the contradiction that is difficult to be in harmonious proportion between high rigidity and wear resistance and the obdurability in the hard metal article of this uniform texture, and promptly the content of cobalt (Co) is when improving its hardness and wear resistance in reducing alloy, and the toughness of alloy body promptly descends thereupon; Otherwise then influence its hardness and wear resistance; In addition, hard metal articles such as blade, brill tooth, rock cutting tool, mould, require the surface to have very high hardness and wear resistance in use, but, require the alloy body planted agent to possess stronger toughness again in order to make it can bear bigger surging force and to stop the surperficial crackle that produces to internal diffusion; And the product of metallographic and mechanical property unanimity in use, in case when the surface cracked, its crackle was with very fast expansion and cause whole worker, mould to damage, break and scrap.In order to overcome this disadvantage, in notification number is the patent documentation " being suitable for the cemented carbide body of rock-boring and ore cutting most " of CN1016711B the Wimet that the intravital cobalt element content of a kind of alloy changes is in gradient disclosed.The production method of this cemented carbide body is that to adopt low-carbon (LC) WC and an amount of cobalt (Co) powder be raw material, after mixing and being pressed into blank, at 900 ℃ of left and right sides temperature and N
2Pre-burning is 1 hour in the atmosphere, becomes the conventional cemented carbide sintered body of metallographic and mechanical property uniformity again at 1450 ℃ sintering temperature; And then be placed in the graphite boat and adopt Al
2O
3Fine powder is filled back thermal treatment more than 2 hours in 1450 ℃ carburizing atmosphere, and make the alloy surface layer is to contain the WC+ γ phase region that the Co amount is lower than alloy mean value, the middle layer is higher than alloy mean value WC+ γ phase region for containing the Co amount, and core is still for containing the cemented carbide body of η phase.Though this invention has surface hardness and wear resistance height; The formation of the rich cobalt in alloy middle part (Co) layer, it is strong and can absorb the impact of bearing on the alloy body surface, effectively stop inwardly characteristics such as expansion of surface crack to have toughness again.But exist: the one, two-step sintering, the production cycle is long, production cost is high; The 2nd, adopt Al
2O
3Fine powder is filled, and has both hindered alloy body and has fully contacted with carburizing atmosphere, can produce decarburizing reaction with sintered compact again; By gaseous carbon sources carburizing, high to device control precision and operating process control requirement, it is slow that the carburization reaction activity is low, carburizing time long, structure gradient forms speed; The 3rd, at carbusintering---cobalt antimony degree forms the back because the quality that variation caused of weave construction and body precision, poor stability, side effect such as yielding, make it can only produce the product of geological drilling, and can not satisfy quality and the higher production requirement of accuracy requirement such as products such as alloy blade, wire-drawing dies with ball tooth, the certain height of post tooth class, wide ratio.Therefore, this background technology exist to device control precision and operating process control require high, the production cycle is long, production cost is high, carburization reaction active low, that carburizing time long, the Co gradient forms speed is slow, quality of item of being produced and body precision stability are poor, are not suitable for producing defectives such as blade, wortle class quality and accuracy requirement high product.
Summary of the invention
The objective of the invention is defective at the background technology existence, the production method of a kind of cobalt contents distribution gradient of research and design Wimet, simplify and optimization production technology to reach, improve the carburization reaction activity, shorten carburizing time, reduction improves the purposes such as comprehensive mechanical performance, body precision and stability thereof of worker, mould hard metal article to the production unit performance demands.
Solution of the present invention is that the sintering of background technology and one step of carburizing (sintering) processing merging are carried out, and adopts pure carbon black filled to improve its carburizing treatment efficient simultaneously; Again sintered compact is carried out aftertreatment eliminating stress, to improve the stability of Products Quality and body precision after the carburizing treatment, thereby realize its purpose.Thereby production method of the present invention comprises:
A, batching wet-milling: by weight percentage, the cobalt powder of low-carbon (LC) WC powder 75～98Wt% and 2～25Wt% is placed in the ball mill, with dehydrated alcohol make medium, sintered carbide ball is made grinding element, behind the mixed grinding 24～48 hours, discharging, drying, grind and make WC-2～25Wt%Co wet-milling compound powder;
B, mix glue: mix concentration and be 4～15% rubber solutions in above-mentioned wet-milling compound, the rubber mass that mixes is counted 0.5～1.5Wt% with wet-milling compound weight percent, mixes the back drying, grinds, and must mix the glue compound;
C, compression molding: the above-mentioned glue compound of mixing is sent in the mould, be pressed into corresponding hard metal article biscuit (pressed compact), biscuit density is 20～40% of sintered compact final densities;
D, sinter molding: the biscuit of above-mentioned compression moulding placed graphite boat and with pure carbon powder as stopping composition (carburizing agent), send in the sintering oven sintering under hydrogen shield after covering whole base substrates; 1300 °～1600 ℃ of sintering temperatures are incubated 0.5～2 hour;
E, aftertreatment: will be through the alloy body of D sinter molding again through sandblast or hot isostatic pressing, vacuum heat treatment, eliminating the sintered compact internal stress.
Above-mentioned low-carbon (LC) WC, its C content are 5.0～5.8Wt%.Describedly make stopping composition with pure carbon powder, in its carbon black contained ash should be less than 0.1%, volatile content less than 1.5%, water content is less than 0.5%.And described alloy body with sinter molding is again through sandblast or hot isostatic pressing, vacuum heat treatment; Its sandblast stream pressure 0.3～0.6MPa, hip treatment is carried out under argon or nitrogen protection, and its temperature is 1000 °～1400 ℃; pressure 3～100MPa is incubated 30～60 minutes, 1000 °～1500 ℃ of vacuum heat treatment temperature; vacuum tightness≤10Pa is incubated 30～90 minutes.
The present invention is owing to merge into a step with the two-step sintering method of background technology and carry out, and adopt pure carbon black as carburizing agent to replace Al2O
3And gaseous carbon sources carburizing, improved the carburization reaction activity greatly, reduced requirement to equipment and operating process control, thereby can shorten sintering and carburization processing time more than 50%, reduce production costs about 30%, after the carbusintering moulding, increase by a postprocessing working procedures, to eliminate the internal stress in the goods, improve mechanical property and the body precision and the stability thereof of goods again, enlarged the production and the range of application of goods.Therefore, the present invention has technology advanced person, reliable, and carburization reaction is active strong, low to the production unit performance requriements, be convenient to operation control, the cobalt contents structure gradient is obvious in the hard metal article, comprehensive mechanical performance and body precision height and good stability, characteristics such as low and applied range of production cost.
Accompanying drawing and description of drawings
Fig. 1, Fig. 2 and Fig. 3 are embodiment 1 alloy body internal organizational structure electronic probe (3000X) morphology analysis figure; Wherein: Fig. 1, Fig. 2, Fig. 3 are respectively top layer (poor Co layer), middle layer (rich Co layer) and the figure of core contextual analysis of organization.
Embodiment 1
Present embodiment is that the Wimet of YG6T is an example to produce the trade mark:
A, batching wet-milling: in the WC powder 940g of 5.15wt% and the Co powder 60g input 2L experiment ball grinding cylinder, adding purity is 99.0% dehydrated alcohol with total carbon containing (C) amount, and wet-milling was clarified after 36 hours; To clarify the gained wet mash then and place under 80 ℃ of temperature drying treatment 30 minutes, after wiping dry thing broken again and crossing 60 mesh sieves, the wet-milling compound;
B, mix glue: with concentration is that 10% gasoline rubber solution 110g (promptly containing rubber 11.0g) adds in the above-mentioned wet-milling compound, and it is dry under 100 ℃ of temperature to mix the back, dry thing with the wiping of 60 mesh sieves broken after, promptly get and mix the glue compound;
C, compression molding: will mix the glue compound and place A118A blade and alloy bar pressing mold respectively, and under 220KN pressure, be pressed into the YG6T Wimet bar biscuit of A118A blade biscuit and 5.25 * 6.50 * 20.00;
D, sintering: will place graphite boat and cover whole billet surface through the C pressed green body with pure carbon black fines, cover thickness is higher than more than the base substrate 10mm of the superiors, then it is sent in the two band molybdenum wire furnaces carbusintering under hydrogen atmosphere and 1400 ℃ of temperature, soaking time 50 minutes; Get the alloy product sintered compact;
E, aftertreatment; Above-mentioned sintered compact is placed under 1300 ℃ of temperature and the 40MPa pressure, and insulation, pressurize made hip treatment in 40 minutes, eliminate its internal stress after, promptly get A118A carbide chip and YG6T Wimet bar.
Resulting product is after testing: hardness HRA92.0, bending strength 2630N/mm
2, density 14.95g/cm
3
Dissect the metallographic structure of sample section through YG6T and detect, 100 times of assays are not amplified in etch: porosity category-A: A
02, category-B: B
00Graphite: center decarburization; Corner C
02
After the section polishing, macroscopical visual inspection can be seen tangible three-decker feature, the thick 0.3～1.00mm in top layer, the about 0.3～0.8mm of middle bed thickness; Make the electronic probe morphology analysis respectively: get accompanying drawing 1 top layer (poor Co layer), Fig. 2 middle layer (rich Co layer), Fig. 3 core, morphology analysis figure.
Embodiment 2
Present embodiment is that the Wimet of YG13T is an example to produce the trade mark:
With low-carbon (LC) WC powder 870g, Co powder 130g is made into total C content 4.8%, and the compound 1.0kg of Co content 13% places 2L experiment ball grinding cylinder wet-milling 40 hours; Below except that sintering temperature be 1420 ℃, all the other all with embodiment 1 with.Prepared 5.25 * 6.50 * 20.00 Wimet bars and A118A blade detect through physical and mechanical properties, and its comprehensive mechanical performance is far above the YG13 Wimet of produced in conventional processes.
Claims (3)
1, a kind of production method of cobalt contents distribution gradient Wimet; It is characterized in that this method comprises:
A, batching wet-milling: by weight percentage, with C content is that the low-carbon (LC) WC powder 75～98Wt% of 5.0～5.8wt% and the cobalt powder of 2～25wt% place in the ball mill, with dehydrated alcohol make medium, sintered carbide ball is made grinding element, behind the mixed grinding 24～48 hours, discharging, drying, grind and make WC-2～25wt%Co wet-milling compound powder;
B, mix glue: mix the rubber solutions that concentration is 4～15wt% in above-mentioned wet-milling compound, the rubber mass that mixes is counted 0.5～1.5wt% with wet-milling compound weight percent, mixes the back drying, grinds, and must mix the glue compound;
C, compression molding: the above-mentioned glue compound of mixing is sent in the mould, be pressed into corresponding hard metal article biscuit, biscuit density is 20～40% of sintered compact final densities;
D, sinter molding: the biscuit of above-mentioned compression moulding placed graphite boat and with pure carbon powder as stopping composition, send in the sintering oven sintering under hydrogen shield after covering whole base substrates; 1300 °～1600 ℃ of sintering temperatures are incubated 0.5～2 hour;
E, aftertreatment: will be through the alloy body of D sinter molding again through sandblast, hot isostatic pressing or vacuum heat treatment, eliminating the sintered compact internal stress.
2, press the production method of the described cobalt contents distribution gradient of claim 1 Wimet; It is characterized in that making stopping composition with pure carbon powder, contained ash should be less than 0.1% in its carbon black, and volatile content is less than 1.5%, and water content is less than 0.5%.
3, press the production method of the described cobalt contents distribution gradient of claim 1 Wimet; It is characterized in that described alloy body with sinter molding is again through sandblast, hot isostatic pressing or vacuum heat treatment; Its sandblast stream pressure 0.3～0.6MPa, hip treatment is carried out under argon or nitrogen protection, and its temperature is 1000 °～1400 ℃; pressure 3～100MPa is incubated 30～60 minutes, 1000 °～1500 ℃ of vacuum heat treatment temperature; vacuum tightness≤10bar is incubated 30～90 minutes.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2004100217857A CN100467649C (en) | 2004-02-09 | 2004-02-09 | Production method for hard carbide with graded distributed cobalt content |
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| CNB2004100217857A CN100467649C (en) | 2004-02-09 | 2004-02-09 | Production method for hard carbide with graded distributed cobalt content |
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| CN100467649C true CN100467649C (en) | 2009-03-11 |
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-
2004
- 2004-02-09 CN CNB2004100217857A patent/CN100467649C/en not_active Expired - Lifetime
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| CN1557983A (en) | 2004-12-29 |
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