CN101618873A - Production method of macrocrystalline WC powder - Google Patents
Production method of macrocrystalline WC powder Download PDFInfo
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- CN101618873A CN101618873A CN200910060159A CN200910060159A CN101618873A CN 101618873 A CN101618873 A CN 101618873A CN 200910060159 A CN200910060159 A CN 200910060159A CN 200910060159 A CN200910060159 A CN 200910060159A CN 101618873 A CN101618873 A CN 101618873A
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Abstract
The invention relates to a production method of macrocrystalline WC powder, which comprises the following steps: preparing seed crystal WC powder; then adopting Wo3 or Wo2.9 and C powder as raw materials, and processing by ball mill and mixing with Fe powder, oxides of Fe, Al-Ni alloy powder and the prepared seed crystal WC powder in a proportion; loading an obtained mixture into a boat for melting and carbonizing; and processing obtained alloy by ball milling, pulverizing, iron removing, acid washing for removing impurities, water washing, drying and sieving to obtain the macrocrystalline WC powder. Based on a background technology, the prepared seed crystal WC powder is added, and through a process of dissolving and separating, the method effectively changes the principle of generating WC mainly by C diffusion of the prior conventional process; thus the method breaks through a technical bottleneck of the conventional process, and the seed crystal granularity of the obtained WC powder is increased by more than one time compared with that of the background technology. The invention has the characteristics that the process is advanced and reliable; the produced WC powder has large seed crystal granularity and can be matched with cast WC, and the crystal granularity of a hard alloy product produced by using the macrocrystalline WC powder can be increased by 60-100 percent compared with the background technology; the physical and mechanical properties of the macrocrystalline WC powder are also obviously improved, and the like.
Description
Technical field
The invention belongs to the production method of hard alloy material WC powder, the production method of the macrocrystalline WC powder of particularly a kind of production high purity, excellent performance.This raw material powder can be widely used in production mine instrument, press tool, petroleum drilling and mining instrument and be used as hard material etc.
Background technology
Countries in the world are polarization trend to the development research of WC powder at present, and the one, develop to ultrafine WC powder even nano level WC powder direction; The 2nd, develop to high-quality coarse grain and even big crystal grain WC powder direction.Result of study proves, coarse-grain WC powder have some with in, the different special performance of fine-grained wc powder and special purposes, especially under hot conditions, have series of advantages such as textural defect is few, microhardness is high, microstrain is little, have higher intensity and (resisting) fracture toughness property in order to the alloy product of producing; Thereby, the research and the application of coarse-grain WC powder is subjected to great attention.The traditional method of coarse-grain WC powder production is at first to adopt WO
3(yellow tungsten) or WO
2.9(blue tungsten) makes coarse-grain W powder through high-temperature hydrogen reduction, this W powder high temperature C (carbon) is changed to make coarse-grain WC powder again.Though it is simple that this method has processing method, so far still by characteristics such as most manufacturing enterprise adopt, but exist: one, in producing coarse-grain W powder process, need to add catalyzer, to strengthen its volatilization deposition, but the trend (reinforcement of recrystallize trend helps obtaining undistorted crystal grain) that the sintering recrystallize of the W powder that weakened is grown up promotes that defective produces in the coarse-grain W powder, the W powder easier fragmentation when joining C that causes the shelly deposition to be grown up; Its two, the density of coarse-grain W is much larger than C, density difference between the two causes in the Cization process and produces microstress, easily makes crystal grain burst, attenuate; Its three, to internal penetration, the surface at first forms W to C from the W particle surface in carbonization process
2C also develops top layer W gradually to the depths
2C becomes WC gradually, and particle is formed centrally WC, W from show extremely
2Three layers of C and W, along with C further to internal divergence, W and W
2C will fade away; Therefore, there is the gradient of C in the coarse crystal WC powder of this explained hereafter, very causes and contain W from the core to the top layer
2C, WC
(1+X)Etc. phase, more seriously influence the quality of coarse-grain WC powder.Thereby, to adopt coarse-grain WC powder that above-mentioned traditional technology produces and exist second-rately, grain fineness number is far away＜100 μ m, be used to produce corresponding Wimet, the grain fineness number of its alloy only about 3.2 μ, is difficult to obtain high tenacity, high-intensity alloy product; As hard material again because of its granularity less can not with disadvantages such as casting tungsten carbide powder share.At above-mentioned disadvantage, it is U.S 4 in the patent No. that U.S. head receives metal company (Kennametal), 834,963, name is called and discloses a kind of employing tungsten concentrate (powder) in the patent documentation of " macrocrystalline WC powder and production technique " and make raw material, ferric oxide is made oxygenant, aluminium is made reductive agent, carbide of calcium is made carburization agent, after ball milling mixes, reduction and in fusion carbonization more than 2000 ℃ is removed unnecessary carbide of calcium, is removed Fe, Mg, Al through sulfuric acid, hydrochloric acid and a spot of hydrofluoric acid again by washing then, and makes thick (grand) crystal grain WC powder.This method reaches the coarse crystal WC powder of mm (millimeter) level and has advantages such as economical and practical though can directly make granularity from tungsten concentrate, tungsten concentrate is made raw material, its impurity is more but owing to directly adopt, the C that elements such as Ti wherein, Ta, Nb form in the fusion carbonization process (impurity) such as Solid solutions then can't be removed, thereby influences the quality of WC powder and final alloy product; In addition, adopt carbide of calcium to make carburization agent, though the activity of C is stronger when decomposing, there is the difficulty that has also increased removal of impurities in calcium as impurity.Defectives such as thereby this method exists coarse crystal WC powder purity relatively poor, also is subjected to corresponding influence in order to the quality of the alloy product produced, and its comprehensive physical and mechanical properties is also relatively poor relatively.Is CN101264524A in order to overcome above-mentioned defective applicant at publication number, and name is called in the patent documentation of " a kind of production method of coarse crystal WC powder " and discloses a kind of employing WO
3(yellow tungsten) or W
2.9The oxide compound, Al-Ni alloy powder that (blue tungsten) and C make raw material and Fe (Co, Ni), iron be batch mixes in proportion, carries out the fusion carbonization then, and the gained alloy block is through broken, ball milling after the carbonization, magnetic separation removes Fe, pickling and oven dry are sieved, thereby make the method for coarse crystal WC powder.Though having the granularity of WC powder, this method can reach millimeter (mm) level, in order to the boring tool of producing, the grain fineness number of hard metal articles such as press tool can reach about 4.0 μ m, both can be mixed for the associated workpiece of crusher, gear wheel brill and unit type machine, machining center, the surperficial reinforcement of cutter with casting WC, can be directly used in stiff matter alloy product again, and advantages such as subsurface defect is few, purity is high, excellent performance; But, be far from reaching WO owing to the starting temperature of C and tungsten oxide reaction in process of production is not high
3Or WO
2.9Melting temperature the time, under lower temperature, begin carbon reduction reaction, cause WO
3Or WO
2.9Lose oxygen too early, in addition WO
3Or WO
2.9Size ratio less, nucleus of crystal disperses (many) in the CARBON REDUCTION PROCESS OF TANTALUM, thus WC grain (seed crystal) is further grown up when having influenced carbon reduction, the WC particle degree that obtains is also less.Thereby this method exists the grain fineness number (seed crystal) of producing resulting coarse-grain WC powder still less, is difficult to further reach the defectives such as requirement of the high purity macrocrystalline WC powder that the production grain fineness number is bigger, performance is more excellent.
Summary of the invention
The objective of the invention is to research and develop a kind of production method of macrocrystalline WC powder, be used for the macrocrystalline WC powder of production high purity, excellent performance.Grain fineness number with effective raising WC powder, both reached and to cooperate as hard material, to be used for surface spraying weld easy to wear (being coated with), built-up welding with casting WC powder, can directly produce hard metal article again as alloy raw material, make it have that purity height, performance are excellent, in high rigidity and the good wear resistance, also have the purposes such as plastic degeneration ability stronger than background technology.
Solution of the present invention is still to adopt WO
3(yellow tungsten) or W
2.9(blue tungsten) and C are as main raw material, and with the oxide compound of the crystal seed WC powder that adds in proportion, Fe (Co, Ni), iron and `Al-Ni alloy powder after batch mixes, carry out the fusion carbonization then, the gained alloy block is through broken, ball milling after the carbonization, magnetic separation removes Fe, pickling and oven dry, screening promptly gets macrocrystalline WC powder; The present invention adds crystal seed WC powder on basis of background technology, mainly diffusion generates the principle of wolfram varbide (WC) by carbon (C) by having dissolved-separated out, effectively changed original traditional technology, thereby realizes its goal of the invention.Therefore, the inventive method comprises:
A, produce crystal seed WC powder: with WO
3Place under hydrogen environment and 1150～1300 ℃ of temperature, reduction handled 30～60 minutes, after making coarse particles W powder, again with this W powder together with the C of its weight 6.0～6.1wt% place in the carbon tube furnace, under 1800～2000 ℃ of temperature carbonizing treatment 40～90 minutes, make crystal seed WC powder;
B, batch mixes: with raw material WO
3Or WO
2.9Consumption is a benchmark, the crystal seed WC powder that makes through the A operation that adds its weight 1.0～6.0wt%, 12.5 the graphite of～20.0wt% or carbon powder, 0.1 the Fe of～0.5wt% or Co or Ni, 0.2 the oxide compound of the iron of～0.7wt%, 0.1 the Al-Ni alloy powder of～0.6wt% places the interior ball milling of ball mill to mix in the lump 3～5 hours;
C, dress boat and fusion carbonization: will cross 30～100 mesh sieves through B operation gained ball milling compound, screen underflow is packed in the graphite boat, is sent in the carbon tube furnace after the compacting, carbonizing treatment is 90～120 minutes under 2040～2400 ℃ of temperature, and furnace cooling promptly gets macrocrystalline WC alloy block;
D, ball mill pulverizing: will be to granularity＜6.0mm by C operation gained alloy block Mechanical Crushing, send in the ball mill, ball milling 36～60 hours, coarse crystal WC powder, ratio of grinding media to material 2.5～4: 1;
E, deironing and pickling: D operation gained WC powder after the magnet deironing is handled, is sent in rare nitric acid pickling to remove residual Al, Ni element;
F, washing and oven dry: after will adopting washed with de-ionized water by E operation gained material, send into to dry in the Vacuumdrier, under 400～500 ℃ of temperature and handled 1.5～2.5 hours, promptly get macrocrystalline WC powder after the cooling;
G, screening, packing: at first will dry the gained WC powder and cross 300 mesh sieves, screen underflow is used for directly firing hard metal article; Screen overflow then sieves to the powder of variable grain degree, packs according to purposes and subsequent product production requirement.
The granularity of above-mentioned crystal seed WC powder is 10～20 μ m.The oxide compound of described iron is FeO
2Or Fe
2O
3, or Fe
3O
4In order further to improve the quality, after the gained alloy block is removed underburnt, burning and pertusate residual, substandard products after the carbonization, carry out Mechanical Crushing and ball mill pulverizing again.In order to satisfy the requirement of special producing and Application Areas to macrocrystalline WC powder, will send into again in the selection by winnowing grading machine through the WC powder after the washing oven dry, remove under 5～7Mpa blast condition be attached to the lip-deep fine ashes of WC powder after, sieve again, pack.
The present invention at first makes the WC crystal seed, in proportion this crystal seed being added the back ball milling then in batching again mixes, in the carbonizing treatment process because the existence of crystal seed WC, tungsten, carbon atom is dissolved into Fe (Co, Ni) separate out after reaching capacity in the liquid, the growth of heterogeneous body forming core takes place on crystal seed WC, solute atoms will constantly deposit to seed surface by diffusion transport in the melt, when melt contacts with crystal seed WC, dissolving and deposition also can take place in crystal seed WC, produce a kind of effect of liquid phase sintering growth, and the part newborn WC nucleus of separating out will with crystal seed nucleating surface coherence, promptly orientation is consistent, and adjacent newborn nucleus also meets growth and last the merging grows up, (Fig. 2 is the macrocrystalline WC powder that embodiment of the present invention produces and soaks copper metallographic pattern) leaves no trace.The present invention promptly dissolves in the carbonizing treatment process-separates out by wolfram varbide (WC) the fusant reaction growth mechanism that sintering is grown up takes place, and diffusion generates nucleus of crystal in the CARBON REDUCTION PROCESS OF TANTALUM that wolfram varbide (WC) exists and disperses the grain fineness number (seed crystal) of (many), WC powder less and be difficult to further improve the technical bottleneck of its grain fineness number and performance thereof by carbon (C) to have broken through traditional technology.Thereby have technology advanced person, reliable, the seed crystal granularity of the WC powder of producing increases than background technology and is twice above and the grain fineness number hard metal article that is used to produce can increase 60～100%, characteristics such as the obvious raising of its physical and mechanical properties.
Description of drawings
Fig. 1 soaks copper metallographic pattern (1000 * times metallograph) for the coarse-grain WC tungsten powder that adopts background technology (publication number is CN101264524A) and produce;
The macrocrystalline WC powder that Fig. 2 produces for embodiment of the present invention soaks copper metallographic pattern (1000 * times metallograph).
Embodiment
Embodiment 1:A. produces crystal seed WC powder: with WO
3Place under hydrogen environment and the 1270 ℃ of temperature, reduction handled H 40 minutes
2Flow 2.0m
3/ h; After making coarse particles W powder, again with this W powder together with the C of its weight 6.1wt% place in the carbon tube furnace, under 1850 ℃ of temperature carbonizing treatment 60 minutes, make crystal seed WC powder;
B. batch mixes: be 99.9% raw material WO with purity
3(yellow tungsten) 100kg, Graphite Powder 99 15kg, Fe
2O
30.35kg, Fe powder 0.25kg, Al～Ni alloy powder 0.3kg, and after making crystal seed WC powder 3kg and place in the ball mill ball milling to mix 4 hours in the lump by the A operation, discharging;
C. adorn boat and fusion carbonization: will cross 60 mesh sieves through B operation gained ball milling compound, screen underflow is packed in the graphite boat and with sending in the carbon tube furnace after the heavy binder block compacting of 30kg, carbonizing treatment is 100 minutes under 2150～2250 ℃ of temperature, and furnace cooling gets macrocrystalline WC alloy block;
D. ball mill pulverizing: will be to granularity＜6.0mm by C operation gained alloy block Mechanical Crushing, send in the ball mill, ball milling 48 hours, macrocrystalline WC powder, ratio of grinding media to material 3: 1;
E. deironing and pickling: is after 10,000 Gausses' permanent magnet deironing is handled with D operation gained macrocrystalline WC powder through magneticstrength, sends into percentage concentration and be pickling in 30% the dilute nitric acid solution, to remove residual Al, Ni element;
F. wash and dry: after will adopting washed with de-ionized water by E operation gained material, send into to dry in the Vacuumdrier, under 450 ℃ of temperature and handled 2.0 hours, promptly get macrocrystalline WC powder after the cooling;
G. sieve, pack: at first will dry the gained WC powder and cross 300 mesh sieves, screen underflow is used for directly firing hard metal article; Screen overflow then sieves to the macrocrystalline WC powder of variable grain degree, packs according to purposes and subsequent product production requirement.
Present embodiment is at seed crystal granularity 70～90 μ m of C operation gained WC alloy block, is 3.5～4 times of background technology.The hard alloy spherical-teeth hardness that is used to be fired into is RH84.0, bending strength 2200N/mm
2, impelling strength 8.0Nm/cm
2
Embodiment 2: present embodiment is 99.9% WO except that raw material employing purity
2.9(blue tungsten) powder 100kg, carbon powder 16.5kg, FeO
20.4kg and outside the Co powder 0.25kg; All the other operations and parameter are all identical with embodiment 1.
Present embodiment is at seed crystal granularity 70～85 μ m of C operation gained WC alloy block.The hard alloy spherical-teeth hardness that is used to be fired into is RH84.5, bending strength 2200N/mm
2, impelling strength 7.8Nm/cm
2
Claims (5)
1, a kind of production method of macrocrystalline WC powder comprises:
A, produce crystal seed WC powder: with WO
3Place under hydrogen environment and 1150～1300 ℃ of temperature, reduction handled 30～60 minutes, after making coarse particles W powder, again with this W powder together with the C of its weight 6.0～6.1wt% place in the carbon tube furnace, under 1800～2000 ℃ of temperature carbonizing treatment 40～90 minutes, make crystal seed WC powder;
B, batch mixes: with raw material WO
3Or WO
2.9Consumption is a benchmark, the crystal seed WC powder that makes through the A operation that adds its weight 1.0～6.0wt%, 12.5 the graphite of～20.0wt% or carbon powder, 0.1 the Fe of～0.5wt% or Co or Ni, 0.2 the oxide compound of the iron of～0.7wt%, 0.1 the Al-Ni alloy powder of～0.6wt% places the interior ball milling of ball mill to mix in the lump 3～5 hours;
C, dress boat and fusion carbonization: will cross 30～100 mesh sieves through B operation gained ball milling compound, screen underflow is packed in the graphite boat, is sent in the carbon tube furnace after the compacting, carbonizing treatment is 90～120 minutes under 2040～2400 ℃ of temperature, and furnace cooling promptly gets macrocrystalline WC alloy block;
D, ball mill pulverizing: will be to granularity＜6.0mm by C operation gained alloy block Mechanical Crushing, send in the ball mill, ball milling 36～60 hours, coarse crystal WC powder, ratio of grinding media to material 2.5～4: 1;
E, deironing and pickling: D operation gained WC powder after the magnet deironing is handled, is sent in rare nitric acid pickling to remove residual Al, Ni element;
F, washing and oven dry: after will adopting washed with de-ionized water by E operation gained material, send into to dry in the Vacuumdrier, under 400～500 ℃ of temperature and handled 1.5～2.5 hours, promptly get macrocrystalline WC powder after the cooling;
G, screening, packing: at first will dry the gained WC powder and cross 300 mesh sieves, screen underflow is used for directly firing hard metal article; Screen overflow then sieves to the powder of variable grain degree, packs according to purposes and subsequent product production requirement.
2, by the production method of the described institute of claim 1 macrocrystalline WC powder, the granularity that it is characterized in that described crystal seed WC powder is 10～20 μ m.
3, by the production method of the described institute of claim 1 macrocrystalline WC powder, the oxide compound that it is characterized in that described iron is FeO
2Or Fe
2O
3, or Fe
3O
4
4, by the production method of the described institute of claim 1. macrocrystalline WC powder, it is characterized in that after the carbonization that the gained alloy block is removed underburnt, burning and pertusate residual, substandard products after, carry out Mechanical Crushing and ball mill pulverizing again.
5, by the production method of the described macrocrystalline WC powder of claim 1, it is characterized in that the WC powder after the washing oven dry is sent in the selection by winnowing grading machine again, remove under 5～7Mpa blast condition be attached to the lip-deep fine ashes of WC powder after, sieve again, pack.
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|---|---|---|---|
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|---|---|---|---|
| CN200910060159A CN101618873A (en) | 2009-07-29 | 2009-07-29 | Production method of macrocrystalline WC powder |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102557028A (en) * | 2010-12-16 | 2012-07-11 | 江西耀升工贸发展有限公司 | Preparation method of high-stability high-purity extra-coarse tungsten carbide powder |
| CN106006743A (en) * | 2016-05-31 | 2016-10-12 | 上海应用技术学院 | Preparation method of orthorhombic black WO3 |
| CN107089662A (en) * | 2017-06-16 | 2017-08-25 | 重庆大学 | A kind of method that CH4 reduction and carbonizations WO3 prepares WC powders |
| CN108892141A (en) * | 2018-09-06 | 2018-11-27 | 北京科技大学 | A kind of high-purity, ultrafine tungsten carbide preparation method |
-
2009
- 2009-07-29 CN CN200910060159A patent/CN101618873A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102557028A (en) * | 2010-12-16 | 2012-07-11 | 江西耀升工贸发展有限公司 | Preparation method of high-stability high-purity extra-coarse tungsten carbide powder |
| CN106006743A (en) * | 2016-05-31 | 2016-10-12 | 上海应用技术学院 | Preparation method of orthorhombic black WO3 |
| CN107089662A (en) * | 2017-06-16 | 2017-08-25 | 重庆大学 | A kind of method that CH4 reduction and carbonizations WO3 prepares WC powders |
| CN107089662B (en) * | 2017-06-16 | 2019-05-31 | 重庆大学 | A kind of method that CH4 reduction and carbonization WO3 prepares WC powder |
| CN108892141A (en) * | 2018-09-06 | 2018-11-27 | 北京科技大学 | A kind of high-purity, ultrafine tungsten carbide preparation method |
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