CN102560216B - Preparation method of dense coated composite powder and super coarse and extra coarse grained cemented carbide - Google Patents
Preparation method of dense coated composite powder and super coarse and extra coarse grained cemented carbide Download PDFInfo
- Publication number
- CN102560216B CN102560216B CN 201210045580 CN201210045580A CN102560216B CN 102560216 B CN102560216 B CN 102560216B CN 201210045580 CN201210045580 CN 201210045580 CN 201210045580 A CN201210045580 A CN 201210045580A CN 102560216 B CN102560216 B CN 102560216B
- Authority
- CN
- China
- Prior art keywords
- composite powder
- powder
- cemented carbide
- naoh
- type composite
- 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.)
- Expired - Fee Related
Links
- 239000000843 powder Substances 0.000 title claims abstract description 118
- 239000002131 composite material Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 33
- 239000001257 hydrogen Substances 0.000 claims abstract description 33
- 238000005245 sintering Methods 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 16
- 230000000694 effects Effects 0.000 claims abstract description 10
- 238000011282 treatment Methods 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 238000009792 diffusion process Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 5
- 230000006911 nucleation Effects 0.000 claims abstract description 4
- 238000010899 nucleation Methods 0.000 claims abstract description 4
- 230000001235 sensitizing effect Effects 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 102
- 239000000956 alloy Substances 0.000 claims description 37
- 229910045601 alloy Inorganic materials 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 28
- 238000004137 mechanical activation Methods 0.000 claims description 25
- 239000002002 slurry Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 230000009467 reduction Effects 0.000 claims description 18
- 239000007795 chemical reaction product Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 238000004806 packaging method and process Methods 0.000 claims description 12
- 238000012545 processing Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 239000007791 liquid phase Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 125000000129 anionic group Chemical group 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000001994 activation Methods 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 3
- 239000012190 activator Substances 0.000 claims description 3
- 238000005844 autocatalytic reaction Methods 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 2
- -1 transition metal carbides Chemical class 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000003213 activating effect Effects 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 238000000265 homogenisation Methods 0.000 abstract 1
- 238000011946 reduction process Methods 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 46
- 238000006722 reduction reaction Methods 0.000 description 17
- 239000012071 phase Substances 0.000 description 16
- 238000005516 engineering process Methods 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 230000002950 deficient Effects 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- 238000005452 bending Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 4
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 4
- 240000007762 Ficus drupacea Species 0.000 description 3
- 101150003085 Pdcl gene Proteins 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- JPNWDVUTVSTKMV-UHFFFAOYSA-N cobalt tungsten Chemical compound [Co].[W] JPNWDVUTVSTKMV-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 3
- 238000005453 pelletization Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910000531 Co alloy Inorganic materials 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000001238 wet grinding Methods 0.000 description 2
- 230000003245 working effect Effects 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000003701 mechanical milling Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000010327 methods by industry Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
Images
Abstract
The invention discloses a preparation method of dense coated composite powder and super coarse and extra coarse grained cemented carbide, which is characterized in that: mechanical activated powder mainly comprising WC, and a Co/Ni hydroxide alkaline pulp material are used as raw materials, and by utilizing the self catalytic activity and the heterogeneous nucleation effect of the mechanical activated powder, without adding a sensitizing agent, an activating agent, a catalyst, and other foreign substances, Co/Ni coated WC composite powder with a nano-assembled structure is prepared by a hydrothermal high-pressure hydrogen reduction process; and the thermal diffusion homogenization treatment of the composite powder is carried out in a hydrogen atmosphere by utilizing a nano-diffusion sintering effect to obtain the dense Co/Ni coated WC composite powder, and the composite powder is used as a raw material to prepare the high-quality super coarse and extra coarse-grained cemented carbide.The preparation method has the characteristics of environmental protection, low cost and the like.
Description
Technical field
The present invention relates to a kind of preparation method of Wimet, particularly relate to the method for the super thick and extraordinarily thick cemented carbide of a kind of fine and close cladded type composite powder prepared.
Background technology
Wimet produces with powder metallurgy process, is made of the engineered composite material with hard phase+bonding phase constitution constitutional features transition group refractory metal compound (WC, TiC, TaC, NbC etc.) and matrix metal (Co, Ni, Fe etc.).In the sintering process, Wimet forms liquid phase by eutectic reaction, and the sintering of Wimet belongs to typical liquid phase sintering.The bonding of Wimet be mutually a kind of with the matrix metal be matrix, contain C, contain the sosoloid of magnesium-yttrium-transition metals such as W.
By the criteria for classification of the international maximum relevant Wimet of Sandvik company of Wimet manufacturing concern, the WC grain degree is that the Wimet of 3.5 μ m～4.9 μ m, 5.0 μ m～7.9 μ m, 8.0 μ m～14 μ m is respectively coarse-grain, super coarse-grain and extraordinarily thick cemented carbide in the alloy.Under the identical condition of matrix metal content, with traditional in, the coarse-grain Wimet compares, super thick and extraordinarily thick cemented carbide has high thermal conductivity, higher fracture toughness property and red hardness, thermal fatigue resistance and thermal shock resistance preferably, the working continuously of the continuous exploitation (as coal mining, subway and tunnel construction) that is mainly used in soft rock under the extreme operating condition condition and modern highway, bridge (as road breaking, pave the way), the punching die that toughness and thermal fatigue resistance, thermal shock resistance are had relatively high expectations, cold heading die, roll etc. have boundless market outlook.
About the existing patent report of the preparation method of super coarse-grain Wimet.As: a kind of preparation method of extra-coarse grained carbide alloy (201010172891.0); The extra-coarse grained carbide alloy material and preparation method thereof (201110136199.7) that is used for pick or road breaking tooth; The preparation method (201010553047.2) of the super coarse-grain tungsten-cobalt hard alloy of high tenacity etc.Prepare super thick or extraordinarily thick cemented carbide and must adopt coarse-grain, super thick or extraordinarily thick brilliant WC starting material.Because the initial crystal grain of WC is thick, the dissolving of WC in matrix metal has strong energy selectivity usually in sintering process, and weak area very easily appears in the combination of the WC para-crystal by separating out formation and the thick initial intergranule of WC.Therefore, adopt existing super coarse-grain Wimet preparation technology, the cracked defective of WC/ bonding phase phase boundary place's WC grain as shown in Figure 1 very easily occurs.This defective is difficult to be observed after corrosion bonds mutually; Even only corrode the WC phase, not corrosion bonding phase also is difficult to be observed under metaloscope.The cracked defective of WC/ bonding phase phase boundary place's WC grain is to cause low, the not anti abrasive major reason problem of alloy strength.The existence of this defective will have a strong impact on applying of super thick and extraordinarily thick cemented carbide.
About the existing patent report of the preparation method of cladded type WC – Co composite powder.As: the preparation method of rare-earth modified Co-cladded wolfram carbide hard alloy composite powder (201010286211.8).This patented technology is to be solved to be that carbide alloy mixture prepares mechanical milling process (ball milling mixes powder) and has length consuming time, introduces the problem that impurity, Co easily gather partially easily.This patented technology adopts ethanol as solvent, prepares composite powder by organism water reduction reaction, and cost is higher.The preparation method (200910042940.6) of Tanization Wu – Co/Ni composite powder and Wimet, this patented technology is closed formulations prepared from solutions Co/Ni by hydro-thermal High Pressure Hydrogen reduction cobalt/nickel ammino and is coated WC type composite powder, to be solvedly be: the CEMENTED CARBIDE PRODUCTION of developing no dirtyization of tramp material element prepares technology with the hydrometallurgy of high purity MC – Co/Ni composite powder, replacing traditional MC – Co/Ni compound wet-grinding technology and relative device, thus the WC particle overcrushing problem of avoiding wet-grinding technology and relative device to cause; Solve the preparation problem of coarse-grain, super coarse-grain, extraordinarily thick cemented carbide on this basis.Above-mentioned patented technology is not paid attention to the coated state of the WC of Co, and the physical behavior of Co coating layer, is difficult to realize that the densification of the WC of Co coats.
Report about preparation WC – Co composite powder is more, and wherein the research of relevant cladded type composite powder also has bibliographical information.The preparation method of cladded type composite powder mainly contains electroless plating, plating, chemical vapor deposition (CVD), Sol – Gel, polyvalent alcohol liquid-phase reduction and hydro-thermal hydrogen reduction etc.There are problems such as preparation cost height in methods such as CVD, Sol – Gel, polyvalent alcohol liquid-phase reduction.There are problems such as easily introducing tramp material in electroless plating, plating, and must satisfy requirement of high purity as the CEMENTED CARBIDE PRODUCTION raw material.In addition, tungsten cobalt double salt precipitation, spraying drying produce tungsten-cobalt composite oxide, directly reduction and carbonization to produce the report of WC – Co composite powder a lot, but this composite powder only is suitable for the preparation of ultra-fine cemented carbide.
About the existing report of Co/Ni hydroxide slurry hydro-thermal High Pressure Hydrogen reduction (slurry hydrogen reduction) preparation Co/Ni powder.As: (1) analogy gram is peaceful, Mao Minghua, Liang Huanzhen, Xu Ju. and cobaltous hydroxide alkalescence slurry hydrogen reduction prepares ultra-fine Co powder. process engineering journal, 2001,1 (1): 62 – 65.(2) Xu Ju, the analogy gram is peaceful, Liang Huanzhen, etc. be equipped with the reaction mechanism of nano metal nickel powder with nickel hydroxide slurry hydrogen reduction legal system. investigation of materials journal, 2002,16 (2): 158 – 163.In existing report, catalyzer such as necessary interpolation precious metal are (as PdCl
2) just can carry out hydrogen reduction reaction.
Summary of the invention
Technical problem to be solved by this invention provides the cracked phenomenon of the super thick and extraordinarily thick cemented carbide phase boundary of a kind of elimination place's WC grain, improve super thick and extraordinarily thick cemented carbide product performance, improve the method for the super thick and extraordinarily thick cemented carbide of the fine and close cladded type composite powder prepared in alloy work-ing life.
In order to solve the problems of the technologies described above, the method of the super thick and extraordinarily thick cemented carbide of fine and close cladded type composite powder prepared provided by the invention is handled and is realized the activation of WC and peeling off of WC particle frangible region by the WC raw material powder that contains C content＞6.12%, grain fineness number＞4.5 μ m being carried out mechanical activation; Composition proportion according to Wimet, utilize mechanical activation to handle the active and heterogeneous nucleation effect of autocatalysis of WC powder, under the condition of not adding sensitizing agent, activator and catalyzer foreign matter, Co/Ni coats WC type composite powder by hydro-thermal High Pressure Hydrogen reduction Co/Ni oxyhydroxide alkalescence pulp preparation nanometer packaging assembly, utilizing nanometer diffusion-sintering effect that composite powder is carried out the thermodiffusion homogenizing subsequently handles, preparing fine and close Co/Ni and coat WC type composite powder, is the super thick and extraordinarily thick cemented carbide of feedstock production high quality with this composite powder; Described Co/Ni refers to Co or Ni or Co+Ni.
The described mechanical activation that is wrapped by powder is handled: the WC raw material of selecting to contain C content＞6.12%, grain fineness number＞4.5 μ m is as the raw material of super thick or extraordinarily thick cemented carbide, by ball: the mass ratio of material is 3:1～5:1, in the mechanical activation machine, the WC raw material powder is carried out the mechanical activation processing of 8 h～14 h, the mill ball material is WC – Co Wimet, adopts the mode of adding W to regulate the total carbon content of composite powder.According to the carbon content of alloy species, purposes and WC raw material powder, WC powder is being carried out add transition metal carbides and W powder when mechanical activation is handled simultaneously.The powder of handling through mechanical activation does not need classification processings of sieving, and directly carries out follow-up coating processing.Mechanical activation is handled and can be realized the activation of WC and peeling off of WC particle frangible region, is conducive to the raising that the WC of Co/Ni coats intensity, improves the sintering activity of WC.
The preparation of described Co/Ni oxyhydroxide alkalescence slurry: be that raw material prepares by water react with the muriate of Co/Ni or vitriol and NaOH; The control temperature of reaction is 60 ℃～70 ℃, to improve reaction forming core efficient; Adopt the aqueous solution of single tube or multitube form dropping Co/Ni salt to the NaOH aqueous solution, with the crystalline growth velocity of control reaction product Co/Ni oxyhydroxide according to the size of reaction volume and the loading capacity of material; Diffusion and the dispersion of positively charged ion and reaction product in the employing alr mode realization solution; (Co/Ni)
2+Volumetric molar concentration be 0.5 mol/L～1.5 mol/L, the volumetric molar concentration of NaOH is 2 mol/L～4 mol/L; Press NaOH:(Co/Ni)
2+Mol ratio is the addition that 95%～100% addition of 2:1 stoichiometric ratio calculates NaOH, makes resultant of reaction Co/Ni hydroxide slurry be alkalescence; The add-on of Co/Ni salt is regulated than with the Co/Ni total content according to desired Co:Ni in the composite powder, and the add-on of NaOH is fixed therefrom; Do not add any other external goods and materials in the Co/Ni oxyhydroxide alkalescence pulp preparation process.
Described hydro-thermal High Pressure Hydrogen reduction: join in the autoclave with the alkaline slurry of Co/Ni oxyhydroxide with the WC powder or based on the raw material powder of WC, adopt alr mode to make WC or be suspended in the slurry based on the raw material powder of WC, reductive condition is as follows: 150 ℃～180 ℃ of temperature of reaction, soaking time 2 h～8 h, hydrogen pressure 2.5 MPa～4.5 MPa.Reaction process is not added foreign matters such as sensitizing agent, activator and catalyzer.
Described thermodiffusion homogenizing is handled: will be through washing, dehydrate processing back nanometer packaging assembly Co/Ni coating WC type composite powder and in hydrogen atmosphere, spread homogenizing in 600 ℃～700 ℃, deoxidation, take off remaining anionic treatments, make nanometer packaging assembly Co/Ni coating layer be transformed into level and smooth fine and close coating layer by nanometer diffusion-sintering effect, prevent nanometer packaging assembly Co/Ni the post forming agent mix with the pressed compact forming process in come off, reduce the foreign matter content in the composite powder, improve in the hard alloy sintering process Co/Ni matrix metal to the wettability of WC, realize WC dissolving and the regulation and control of separating out behavior in the WC – Co/Ni alloy liquid phase sintering process.
Described Wimet preparation: the adding mass ratio is 2.0%～2.5% PEG or paraffinic base binder in the fine and close Co/Ni coating WC type composite powder that obtains after the thermodiffusion homogenizing is handled, the composite powder that mixes binder is carried out drying and granulating, the composite powder that mixes binder is formed, and in pressure sintering furnace, carry out liquid phase sintering in 1430 ℃～1480 ℃.
Adopt the method for the super thick and extraordinarily thick cemented carbide of the fine and close cladded type composite powder prepared of technique scheme, utilize mechanical activation to handle the active and heterogeneous nucleation effect of autocatalysis of WC powder, Co/Ni coats WC type composite powder by hydro-thermal High Pressure Hydrogen reduction Co/Ni oxyhydroxide alkalescence pulp preparation nanometer packaging assembly, utilizing nanometer diffusion-sintering effect that composite powder is carried out the thermodiffusion homogenizing subsequently handles, it is the fine and close WC of coating of a kind of preparation Co/Ni matrix metal type composite powder, realization is to WC dissolving and the regulation and control of separating out behavior in the WC – Co/Ni alloy liquid phase sintering process, eliminate the cracked phenomenon of super thick and extraordinarily thick cemented carbide phase boundary place's WC grain, improve super thick and extraordinarily thick cemented carbide product performance, improve the alloy effective ways in work-ing life.Because adopt water as medium in the hydro-thermal High Pressure Hydrogen reduction cladded type composite powder preparation process, hydrogen is reductive agent, only adds a kind of NaOH subsidiary material of cheapness, present method has the notable feature of low cost, environmental protection.
By the selection of WC raw material granularity, the adjustment of sintering temperature, this method is suitable for the preparation of other crystal grain grade high-quality Wimet equally.
Description of drawings
Fig. 1 is that the alloy grain degree that adopts traditional technology to prepare is scanning electron microscope (SEM) photo (1000 times) of the super coarse-grain WC – 12Ni alloy of 5.8 μ m;
Fig. 2 is the SEM photo (1000 times) that Co coats WC type WC – 12Co composite powder after the thermodiffusion homogenizing is handled;
Fig. 3 is that the power spectrum micro-area composition on light tone WC particle surface, arrow indication place among Fig. 2 is analyzed collection of illustrative plates
Fig. 4 is that the alloy grain degree that adopts preparation method of the present invention to prepare is the SEM photo (1000 times) of the extraordinarily thick brilliant WC – 12Co alloy of 11.8 μ m;
Fig. 5 is that the reduction of hydro-thermal High Pressure Hydrogen contains PdCl
2The SEM photo (20,000 times) of the metal Co powder of the cobaltous hydroxide alkaline slurry preparation of catalyzer
Fig. 6 is that the alloy grain degree that adopts preparation method of the present invention to prepare is the super coarse-grain WC of 7.2 μ m – 12Ni – 0.5Cr
3C
2The SEM photo of alloy (3000 times);
Fig. 7 is that the alloy grain degree that adopts preparation method of the present invention to prepare is the SEM photo (1000 times) of the super coarse-grain WC of 6.8 μ m – 6Co – 6Ni alloy.
Embodiment
The invention will be further described below in conjunction with drawings and Examples.
Embodiment 1:
By WC – 12%Co(mass ratio) composition prepares composite powder.It is raw material that selection contains the WC that C content is 6.13%, grain fineness number is 6.6 μ m, add the W powder WC – 12Co is compound in total carbon content be adjusted to 5.36%, by ball: the mass ratio of material is that 4:1 carries out the processing of 8 h mechanical activations with WC and W powder in the mechanical activation machine.By 1.5 mol/L Co
2+Volumetric molar concentration is dissolved in cobalt chloride in the deionized water.Press NaOH:Co
2+Mol ratio is the addition that 100% addition of 2:1 stoichiometric ratio calculates NaOH, by 2 mol/L volumetric molar concentrations NaOH is dissolved in the deionized water.NaOH solution after filtering is changed in the stirred tank, and control reactive tank temperature is 70 ℃, and the cobalt chloride solution after filtering is dropped in the NaOH solution by 3 pipelines.Reaction product cobaltous hydroxide alkaline slurry is transferred in the autoclave, adds WC and the W powder handled through mechanical activation simultaneously.Hydro-thermal High Pressure Hydrogen reductive condition is as follows: 180 ℃ of temperature of reaction, and soaking time 2 h, hydrogen pressure 3.5 MPa adopt alr mode to make the WC+W powder suspension in slurry.Wash, dehydrate the processing reaction product.Under scanning electron microscope, observe and the analytical reaction product, find that nanometer packaging assembly Co evenly is coated on the WC+W powder surface.In 650 ℃ nanometer packaging assembly Co being coated WC type composite powder in hydrogen atmosphere spreads homogenizing, deoxidation, takes off remaining anionic treatments.Chemical analysis results shows that Co content is that 11.98%, O content is 0.09% in the composite powder.Under scanning electron microscope, observe with analysis Co after the thermodiffusion homogenizing is handled and coat WC type composite powder, find that the WC+W powder surface has formed the fine and close coating layer of Co.Fig. 2 is the stereoscan photograph that Co coats WC type composite powder after the thermodiffusion homogenizing is handled, and Fig. 3 is that the power spectrum micro-area composition on light tone WC particle surface, arrow indication place among Fig. 2 is analyzed collection of illustrative plates.As seen from Figure 3, detected the existence of Co on the WC particle surface.The PEG binder of adding 2.5% in the fine and close cladded type WC – 12Co composite powder that after the thermodiffusion homogenizing is handled, obtains.The compound of drying pelletization treatment is pressed into Type B galley proof pressed compact, pressed compact is carried out sintering in 1480 ℃ in the pressure sintering furnace of 6 MPa.Bending strength test is the result show, the bending strength of alloy is 2360 MPa.Adopt Image J image processing software and line intercept method to measure the alloy grain degree, the result shows that the alloy grain degree is 11.8 μ m.Fig. 4 is the stereoscan photograph of alloy.As seen from Figure 4, there is not the cracked defective of WC grain in WC/ bonding phase phase boundary place in the alloy.Adopt same hydro-thermal High Pressure Hydrogen reducing process (180 ℃ of temperature of reaction, soaking time 2 h, hydrogen pressure 3.5 MPa), PdCl is mixed in reduction in autoclave
2The above-mentioned cobaltous hydroxide alkaline slurry of catalyzer, the specific surface area of the metal Co powder of the flake nano packaging assembly that obtains is 16.14 m
2/ g, specific surface particle diameter are 41.8nm, and the powder photo is seen Fig. 5.
Embodiment 2:
Press WC – 12%Ni – 0.5%Cr
3C
2(mass ratio) composition prepares composite powder.It is raw material that selection contains the WC that C content is 6.13%, grain fineness number is 6.6 μ m, adds the W powder with WC – 12Ni – 0.5Cr
3C
2Total carbon content is adjusted to 5.36% in the composite powder, and by ball: the mass ratio of material is that 3:1 is with WC, Cr
3C
2And the W powder carries out the processing of 11 h mechanical activations in the mechanical activation machine.By 1.0 mol/L Ni
2+Volumetric molar concentration is dissolved in single nickel salt in the deionized water.Press NaOH:Ni
2+Mol ratio is the addition that 95% addition of 2:1 stoichiometric ratio calculates NaOH, by 3 mol/L volumetric molar concentrations NaOH is dissolved in the deionized water.NaOH solution after filtering is changed in the stirred tank, and control reactive tank temperature is 60 ℃, and the nickel sulfate solution after filtering is dropped in the NaOH solution by 3 pipelines.Reaction product nickel hydroxide alkaline slurry is transferred in the autoclave, adds the WC, the Cr that handle through mechanical activation simultaneously
3C
2And W powder.Hydro-thermal High Pressure Hydrogen reductive condition is as follows: 165 ℃ of temperature of reaction, and soaking time 8 h, hydrogen pressure 4.5 MPa adopt alr mode to make WC+Cr
3C
2+ W powder suspension is in slurry.Wash, dehydrate the processing reaction product.In 600 ℃ Ni being coated WC type composite powder in hydrogen atmosphere spreads homogenizing, deoxidation, takes off remaining anionic treatments.Chemical analysis results shows that Ni content is that 11.97%, O content is 0.07% in the composite powder.The fine and close cladded type WC – 12Ni – 0.5Cr that after handling through the thermodiffusion homogenizing, obtains
3C
2The paraffin binder of adding 2.5% in the composite powder.The compound of drying pelletization treatment is pressed into Type B galley proof pressed compact, pressed compact is carried out sintering in 1440 ℃ in the pressure sintering furnace of 6 MPa.Bending strength test is the result show, the bending strength of alloy is 2680 MPa.Adopt Image J image processing software and line intercept method to measure the alloy grain degree, the result shows that the alloy grain degree is 7.2 μ m.Fig. 6 is the stereoscan photograph of alloy.As seen from Figure 6, alloy microstructure is even, and there is not the cracked defective of WC grain in WC/ bonding phase phase boundary place in the alloy.
Embodiment 3:
By WC – 6%Co – 6%Ni(mass ratio) composition prepares composite powder.It is raw material that selection contains the WC that C content is 6.13%, grain fineness number is 6.6 μ m, add the W powder total carbon content in the WC – 6Co – 6Ni composite powder is adjusted to 5.35%, by ball: the mass ratio of material is that 5:1 carries out the processing of 14 h mechanical activations with WC and W powder in the mechanical activation machine.By 0.5 mol/L (Co/Ni)
2+Volumetric molar concentration is dissolved in cobalt chloride and nickelous chloride in the deionized water.Press NaOH:(Co/Ni)
2+Mol ratio is the addition that 98% addition of 2:1 stoichiometric ratio calculates NaOH, by 4 mol/L volumetric molar concentrations NaOH is dissolved in the deionized water.NaOH solution after filtering is changed in the stirred tank, and control reactive tank temperature is 65 ℃, and cobalt chloride, nickelous chloride mixing solutions after filtering are dropped in the NaOH solution by 3 pipelines.Reaction product cobalt, nickel hydroxide slurry are transferred in the autoclave, add WC and the W powder handled through mechanical activation simultaneously.Hydro-thermal High Pressure Hydrogen reductive condition is as follows: 150 ℃ of temperature of reaction, and soaking time 6 h, hydrogen pressure 2.5 MPa adopt alr mode that the WC+W raw material powder is suspended in the slurry.Wash, dehydrate the processing reaction product.In 700 ℃ Co, Ni being coated WC type composite powder in hydrogen atmosphere spreads homogenizing, deoxidation, takes off remaining anionic treatments.Show that through chemical analysis results Co content is 5.98 % in the composite powder, Ni content is that 5.96%, O content is 0.06%.The PEG binder of adding 2.0% in the fine and close cladded type WC – 6Co – 6Ni composite powder that after the thermodiffusion homogenizing is handled, obtains.The compound of drying pelletization treatment is pressed into Type B galley proof pressed compact, pressed compact is carried out sintering in 1430 ℃ in the pressure sintering furnace of 6 MPa.Bending strength test is the result show, the bending strength of alloy is 2720 MPa.Adopt Image J image processing software and line intercept method to measure the alloy grain degree, the result shows that the alloy grain degree is 6.8 μ m.Fig. 7 is the stereoscan photograph of alloy.As seen from Figure 7, alloy microstructure is even, and there is not the cracked defective of WC grain in WC/ bonding phase phase boundary place in the alloy.
Claims (8)
1. the method for the super thick and extraordinarily thick cemented carbide of a fine and close cladded type composite powder prepared is characterized in that: handle and realize the activation of WC and peeling off of WC particle frangible region by the WC raw material powder that contains C content＞6.12%, grain fineness number＞4.5 μ m being carried out mechanical activation; Composition proportion according to Wimet, utilize mechanical activation to handle the active and heterogeneous nucleation effect of autocatalysis of WC powder, under the condition of not adding sensitizing agent, activator and catalyzer foreign matter, Co/Ni coats WC type composite powder by hydro-thermal High Pressure Hydrogen reduction Co/Ni oxyhydroxide alkalescence pulp preparation nanometer packaging assembly, utilizing nanometer diffusion-sintering effect that composite powder is carried out the thermodiffusion homogenizing subsequently handles, preparing fine and close Co/Ni and coat WC type composite powder, is the super thick and extraordinarily thick cemented carbide of feedstock production high quality with this composite powder; Described Co/Ni refers to Co or Ni or Co+Ni.
2. the method for the super thick and extraordinarily thick cemented carbide of fine and close cladded type composite powder prepared according to claim 1, it is characterized in that: describedly the WC raw material powder is carried out mechanical activation handle and to refer to by ball: the mass ratio of material is 3:1～5:1, and the mechanical activation that in the mechanical activation machine WC raw material powder is carried out 8 h～14 h is handled; The mill ball material is WC – Co Wimet; Adopt the mode of adding W to regulate the total carbon content of composite powder; According to the carbon content of alloy species, purposes and WC raw material powder, WC powder is being carried out add transition metal carbides and W powder when mechanical activation is handled simultaneously; The powder of handling through mechanical activation does not need classification processings of sieving, and directly carries out follow-up coating processing.
3. the method for the super thick and extraordinarily thick cemented carbide of fine and close cladded type composite powder prepared according to claim 1 and 2, it is characterized in that: described hydro-thermal High Pressure Hydrogen reduction is in autoclave, adopt alr mode to make WC or be suspended in the slurry based on the raw material powder of WC, under 2.5 MPa～4.5 MPa hydrogen pressures, in 150 ℃～180 ℃ insulation 2 h～8 h reduction Co/Ni oxyhydroxide alkalescence slurry, form nanometer packaging assembly Co/Ni and coat WC type composite powder.
4. the method for the super thick and extraordinarily thick cemented carbide of fine and close cladded type composite powder prepared according to claim 1 and 2 is characterized in that: described Co/Ni oxyhydroxide alkalescence slurry is to be that raw material prepares by water react with the muriate of Co/Ni or vitriol and NaOH; The control temperature of reaction is 60 ℃～70 ℃, to improve reaction forming core efficient; Adopt the aqueous solution of single tube or multitube form dropping Co/Ni salt to the NaOH aqueous solution, with the crystalline growth velocity of control reaction product Co/Ni oxyhydroxide according to the size of reaction volume and the loading capacity of material; Diffusion and the dispersion of positively charged ion and reaction product in the employing alr mode realization solution; (Co/Ni)
2+Volumetric molar concentration be 0.5 mol/L～1.5 mol/L, the volumetric molar concentration of NaOH is 2 mol/L～4 mol/L; Press NaOH:(Co/Ni)
2+Mol ratio is the addition that 95%～100% addition of 2:1 stoichiometric ratio calculates NaOH, makes resultant of reaction Co/Ni hydroxide slurry be alkalescence; The add-on of Co/Ni salt is regulated than with the Co/Ni total content according to desired Co:Ni in the composite powder, and the add-on of NaOH is fixed therefrom.
5. the method for the super thick and extraordinarily thick cemented carbide of fine and close cladded type composite powder prepared according to claim 3 is characterized in that: described Co/Ni oxyhydroxide alkalescence slurry is to be that raw material prepares by water react with the muriate of Co/Ni or vitriol and NaOH; The control temperature of reaction is 60 ℃～70 ℃, to improve reaction forming core efficient; Adopt the aqueous solution of single tube or multitube form dropping Co/Ni salt to the NaOH aqueous solution, with the crystalline growth velocity of control reaction product Co/Ni oxyhydroxide according to the size of reaction volume and the loading capacity of material; Diffusion and the dispersion of positively charged ion and reaction product in the employing alr mode realization solution; (Co/Ni)
2+Volumetric molar concentration be 0.5 mol/L～1.5 mol/L, the volumetric molar concentration of NaOH is 2 mol/L～4 mol/L; Press NaOH:(Co/Ni)
2+Mol ratio is the addition that 95%～100% addition of 2:1 stoichiometric ratio calculates NaOH, makes resultant of reaction Co/Ni hydroxide slurry be alkalescence; The add-on of Co/Ni salt is regulated than with the Co/Ni total content according to desired Co:Ni in the composite powder, and the add-on of NaOH is fixed therefrom.
6. the method for the super thick and extraordinarily thick cemented carbide of fine and close cladded type composite powder prepared according to claim 1 and 2 is characterized in that: described thermodiffusion homogenizing handle refer to through washing, dehydrate and handle back nanometer packaging assembly Co/Ni coating WC type composite powder and in hydrogen atmosphere, spread homogenizing, deoxidation, take off remaining anionic treatments in 600 ℃～700 ℃.
7. the method for the super thick and extraordinarily thick cemented carbide of fine and close cladded type composite powder prepared according to claim 3 is characterized in that: described thermodiffusion homogenizing handle refer to through washing, dehydrate and handle back nanometer packaging assembly Co/Ni coating WC type composite powder and in hydrogen atmosphere, spread homogenizing, deoxidation, take off remaining anionic treatments in 600 ℃～700 ℃.
8. the method for the super thick and extraordinarily thick cemented carbide of fine and close cladded type composite powder prepared according to claim 1 and 2, it is characterized in that: the adding mass ratio is 2.0%～2.5% PEG or paraffinic base binder in the fine and close Co/Ni coating WC type composite powder that obtains after the thermodiffusion homogenizing is handled, the composite powder that mixes binder is carried out drying and granulating, the composite powder that mixes binder is formed, and in pressure sintering furnace, carry out liquid phase sintering in 1430 ℃～1480 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210045580 CN102560216B (en) | 2012-02-27 | 2012-02-27 | Preparation method of dense coated composite powder and super coarse and extra coarse grained cemented carbide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210045580 CN102560216B (en) | 2012-02-27 | 2012-02-27 | Preparation method of dense coated composite powder and super coarse and extra coarse grained cemented carbide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102560216A CN102560216A (en) | 2012-07-11 |
| CN102560216B true CN102560216B (en) | 2013-08-28 |
Family
ID=46406814
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201210045580 Expired - Fee Related CN102560216B (en) | 2012-02-27 | 2012-02-27 | Preparation method of dense coated composite powder and super coarse and extra coarse grained cemented carbide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102560216B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102732768A (en) * | 2012-07-12 | 2012-10-17 | 中南大学 | High-ductility, corrosion-resistant and ultra/extra-thick crystalline cemented carbide and preparation method thereof |
| CN103266311B (en) * | 2013-05-23 | 2015-05-13 | 成都大光热喷涂材料有限公司 | Method for preparing WC-Co powder doped with rare earth elements |
| CN105779799B (en) * | 2014-12-25 | 2017-10-10 | 北京有色金属研究总院 | A kind of method for preparing Hardmetal materials with diffusion prealloy coated composite powder |
| CN111636024B (en) * | 2020-05-26 | 2021-10-29 | 河海大学 | WC-Ni-Cr/Ta composite material hard alloy and preparation method and application thereof |
| CN111850370B (en) * | 2020-07-31 | 2021-11-26 | 河海大学 | Preparation method of coarse-grain WC-Co hard alloy |
| CN113857474A (en) * | 2021-09-01 | 2021-12-31 | 河海大学 | Preparation method of WC surface-coated Co powder added with Ce element |
| CN117385248A (en) * | 2023-10-17 | 2024-01-12 | 株洲金佰利硬质合金有限公司 | Ultra-coarse-grain WC-Co hard alloy and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2853401A (en) * | 1956-04-11 | 1958-09-23 | Sherritt Gordon Mines Ltd | Method of incorporating a metal binder or matrix phase in mixes of metals and/or metals and metal compounds |
| CN101508023A (en) * | 2009-03-24 | 2009-08-19 | 中南大学 | Preparation method of carbide-Co/Ni composite powder and hard alloy |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008525631A (en) * | 2004-12-27 | 2008-07-17 | ユミコア | Composite powder products for cemented carbide |
-
2012
- 2012-02-27 CN CN 201210045580 patent/CN102560216B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2853401A (en) * | 1956-04-11 | 1958-09-23 | Sherritt Gordon Mines Ltd | Method of incorporating a metal binder or matrix phase in mixes of metals and/or metals and metal compounds |
| CN101508023A (en) * | 2009-03-24 | 2009-08-19 | 中南大学 | Preparation method of carbide-Co/Ni composite powder and hard alloy |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102560216A (en) | 2012-07-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102560216B (en) | Preparation method of dense coated composite powder and super coarse and extra coarse grained cemented carbide | |
| Xiang et al. | Bimetallic Pd-Ni core-shell nanoparticles as effective catalysts for the Suzuki reaction | |
| JP4969008B2 (en) | Powder mixtures and composite powders, methods for their production and their use in composite materials | |
| Hu et al. | W-Y2O3 composite nanopowders prepared by freeze-drying method and its sintering characteristics | |
| US2853401A (en) | Method of incorporating a metal binder or matrix phase in mixes of metals and/or metals and metal compounds | |
| Liu et al. | Eliminating bimodal structures of W-Y2O3 composite nanopowders synthesized by wet chemical method via controlling reaction conditions | |
| Xiao et al. | A hybrid microstructure design strategy achieving W-ZrO2 (Y) alloy with high compressive strength and critical failure strain | |
| CN106732606B (en) | A kind of kerosene co grinding method ferrum-based catalyst | |
| RU2696113C1 (en) | Method of producing nanocomposite material based on copper, hardened by carbon nanofibres | |
| CN101508023A (en) | Preparation method of carbide-Co/Ni composite powder and hard alloy | |
| Ma et al. | A facile synthesis of Ag@ PdAg core-shell architecture for efficient purification of ethene feedstock | |
| CN112077331A (en) | Preparation method of carbon material-loaded nanoscale multicomponent alloy | |
| CN1130468C (en) | Micronic pre-alloyed metal powder based on three dimensional transition metal | |
| CN102839313B (en) | Nano Cr3C2-WC-Ni composite powder and preparation method thereof | |
| CN109365802B (en) | Preparation method of core-shell structure metal ceramic composite powder | |
| CN108927154A (en) | A kind of preparation method of intermetallic compound nanocatalyst | |
| Grove et al. | Effect of hydrocarbons on the morphology of synthesized niobium carbide nanoparticles | |
| Liu et al. | A new process for pre-treatment of electroless copper plating on the surface of mica powders with ultrasonic and nano-nickel | |
| CN102534341B (en) | Method for eliminating WC (Wolfram Carbide) grain fragmentation at phase boundary between ultra-coarse grain hard alloy and super-coarse grain hard alloy | |
| KR101890463B1 (en) | Method for fabricating hollow metal nano particles and hollow metal nano particles fabricated by the method | |
| CN1182026C (en) | Process for preparing Fe-series catalyst used to synthesize nano carbon tubes | |
| Pinto et al. | Synthesis and characterization of vanadium nanoparticles on activated carbon and their catalytic activity in thiophene hydrodesulphurization | |
| CN109465464B (en) | Method for preparing alumina-based metal ceramic nano composite powder | |
| CN101411980A (en) | Method for preparing silicasol-supported amorphous alloy catalyst | |
| Si et al. | Achieving highly efficient hydrogen generation and uniform Ag nanoparticle preparation via hydrolysis of Mg9Ag alloy milled under hydrogen gas |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130828 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |