CN111266601A - WC-Ni composite powder, WC-Ni hard alloy and preparation method thereof - Google Patents
WC-Ni composite powder, WC-Ni hard alloy and preparation method thereof Download PDFInfo
- Publication number
- CN111266601A CN111266601A CN202010257212.3A CN202010257212A CN111266601A CN 111266601 A CN111266601 A CN 111266601A CN 202010257212 A CN202010257212 A CN 202010257212A CN 111266601 A CN111266601 A CN 111266601A
- Authority
- CN
- China
- Prior art keywords
- powder
- composite powder
- nickel
- hard alloy
- concentration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000843 powder Substances 0.000 title claims abstract description 139
- 239000002131 composite material Substances 0.000 title claims abstract description 82
- 239000000956 alloy Substances 0.000 title claims abstract description 60
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 174
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000007788 liquid Substances 0.000 claims abstract description 46
- 238000006722 reduction reaction Methods 0.000 claims abstract description 34
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 26
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 25
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 25
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 23
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 23
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 16
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 15
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 229910001453 nickel ion Inorganic materials 0.000 claims abstract description 14
- 150000002815 nickel Chemical class 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 238000005245 sintering Methods 0.000 claims description 12
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 10
- 229940078494 nickel acetate Drugs 0.000 claims description 10
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 10
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 9
- 239000011343 solid material Substances 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000000748 compression moulding Methods 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 6
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 238000009827 uniform distribution Methods 0.000 abstract description 4
- 239000012670 alkaline solution Substances 0.000 abstract description 3
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 239000008139 complexing agent Substances 0.000 abstract description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 20
- 229910009043 WC-Co Inorganic materials 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 229910052786 argon Inorganic materials 0.000 description 10
- 238000000498 ball milling Methods 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 7
- 238000000967 suction filtration Methods 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 241001343354 Halenia corniculata Species 0.000 description 1
- NBFQLHGCEMEQFN-UHFFFAOYSA-N N.[Ni] Chemical compound N.[Ni] NBFQLHGCEMEQFN-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B22F1/0003—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
- C22C1/1026—Alloys containing non-metals starting from a solution or a suspension of (a) compound(s) of at least one of the alloy constituents
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/005—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides comprising a particular metallic binder
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
- C22C29/067—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds comprising a particular metallic binder
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
- C22C29/08—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on tungsten carbide
Abstract
The invention provides WC-Ni composite powder, WC-Ni hard alloy and a preparation method thereof, belonging to the technical field of alloy materials. In the invention, ammonia water is adopted to adjust the pH value of mixed feed liquid of soluble nickel salt, hydrazine hydrate, ammonium sulfate, citric acid, ethylenediamine and water to 8-11, and nickel ions and NH in the system3Forming nickel ammine complex ions, creating an alkaline solution environment, and then reducing the nickel ions of the nickel ammine complex ions into Ni in situ by WC by using hydrazine hydrate as a reducing agent in the reduction reaction process; wherein ammonium sulfate, citric acid and ethylenediamine are used as complexing agent and stabilizerThe Ni and the WC powder in the finally obtained WC-Ni composite powder are reasonably distributed, wherein the Ni is uniformly coated on the surface of the WC powder. The WC-Ni hard alloy prepared by the WC-Ni composite powder provided by the invention has more uniform distribution of Ni elements, so that the mechanical property of the WC-Ni hard alloy is improved.
Description
Technical Field
The invention relates to the technical field of alloy materials, in particular to WC-Ni composite powder, WC-Ni hard alloy and a preparation method thereof.
Background
The carbide provides the hard alloy with load bearing capacity and wear resistance and the soft binding metal gives the hard alloy impact toughness through its capacity of plastic deformation at room temperature. The hard alloy combines the advantages of high-hardness refractory metal carbide and bonding metal with better ductility, has a series of excellent performances of high strength and hardness, good wear resistance, good red hardness, small thermal expansion coefficient, high elastic modulus, good chemical stability and the like, and is widely applied to the fields of cutting tools, mine tools, wear-resistant parts and the like. Because metal Co has good wettability and cohesiveness to WC hard phases and the solubility of WC in Co is low, the WC-Co hard alloy has a series of excellent performances such as high strength and hardness, good wear resistance and the like, and is the hard alloy with the largest output and the most extensive application at present.
However, Co is expensive and hardly adaptable to acidic conditions, and thus corrosion resistance is desired to be improved. The hard alloy prepared by adopting Ni to replace Co can effectively reduce the cost and improve the corrosion resistance of the hard alloy. The conventional method at present is to ball mill and mix WC powder and Ni powder to obtain WC-Ni composite powder; however, after the WC-Ni composite powder obtained by the method is prepared into WC-Ni hard alloy, the mechanical properties of the WC-Ni hard alloy are still a certain difference compared with that of WC-Co hard alloy, and the application range of the WC-Ni hard alloy is limited.
Disclosure of Invention
The invention aims to provide WC-Ni composite powder, WC-Ni hard alloy and a preparation method thereof, wherein the WC-Ni composite powder prepared by the method has reasonable distribution of Ni and WC powder, and the surface of the WC powder is uniformly coated with the Ni; the WC-Ni hard alloy prepared by the WC-Ni composite powder provided by the invention has more uniform distribution of Ni elements, so that the mechanical property of the WC-Ni hard alloy is improved.
In order to achieve the above object, the present invention provides the following technical solutions:
a preparation method of WC-Ni composite powder comprises the following steps:
mixing soluble nickel salt, hydrazine hydrate, ammonium sulfate, citric acid, ethylenediamine and water to obtain mixed feed liquid; the concentration of nickel ions in the mixed feed liquid is 0.25-0.8 mol/L, the concentration of hydrazine hydrate is 5-30 g/L, the concentration of ammonium sulfate is 2-15 g/L, the concentration of citric acid is 8-20 g/L, and the concentration of ethylenediamine is 15-50 mL/L;
adjusting the pH value of the mixed material liquid to 8-11 by using ammonia water, mixing the mixed material liquid with WC powder, and carrying out reduction reaction to obtain a reduction reaction product system, wherein the temperature of the reduction reaction is not higher than 95 ℃;
and carrying out solid-liquid separation on the reduction reaction product system, and drying the obtained solid material to obtain the WC-Ni composite powder.
Preferably, the soluble nickel salt comprises nickel acetate and/or nickel sulphate.
Preferably, the concentration of the ammonia water is 7.5-15 mol/L.
Preferably, the average particle size of the WC powder is 0.4-3 μm.
Preferably, the temperature of the reduction reaction is 70-95 ℃ and the time is 5-20 min.
Preferably, the reduction reaction is carried out under the condition of stirring, and the stirring speed is 50-150 r/min.
Preferably, the content of nickel in the WC-Ni composite powder is 8-16 wt%.
The invention provides WC-Ni composite powder prepared by the preparation method in the technical scheme, and the WC-Ni composite powder comprises WC powder and nickel coated on the surface of the WC powder.
The invention provides a WC-Ni hard alloy which is prepared by taking WC-Ni composite powder as a raw material in the technical scheme.
The invention provides a preparation method of WC-Ni hard alloy in the technical scheme, which comprises the following steps:
and sequentially carrying out compression molding and sintering on the WC-Ni composite powder to obtain the WC-Ni hard alloy.
The invention provides a preparation method of WC-Ni composite powder, which comprises the following steps: mixing soluble nickel salt, hydrazine hydrate, ammonium sulfate, citric acid, ethylenediamine and water to obtain mixed feed liquid; the concentration of nickel ions in the mixed feed liquid is 0.25-0.8 mol/L, the concentration of hydrazine hydrate is 5-30 g/L, the concentration of ammonium sulfate is 2-15 g/L, the concentration of citric acid is 8-20 g/L, and the concentration of ethylenediamine is 15-50 mL/L; adjusting the pH value of the mixed material liquid to 8-11 by using ammonia water, mixing the mixed material liquid with WC powder, and carrying out reduction reaction to obtain a reduction reaction product system, wherein the temperature of the reduction reaction is not higher than 95 ℃; and carrying out solid-liquid separation on the reduction reaction product system, and drying the obtained solid material to obtain the WC-Ni composite powder. In the invention, ammonia water is adopted to adjust the pH value of the mixed feed liquid to 8-11, and nickel ions and NH in the system3Forming nickel ammine complex ions, creating an alkaline solution environment, and then reducing the nickel ions of the nickel ammine complex ions into Ni in situ by WC by using hydrazine hydrate as a reducing agent in the reduction reaction process; the ammonium sulfate, the ethylenediamine and the citric acid are beneficial to promoting nickel ions to be reduced into Ni in situ in WC, so that the Ni and the WC powder in the finally obtained WC-Ni composite powder are reasonably distributed, and the surface of the WC powder is uniformly coated with the Ni. The WC-Ni hard alloy prepared by the WC-Ni composite powder provided by the invention has more uniform distribution of Ni elements, so that the mechanical property of the WC-Ni hard alloy is improved. The results of the examples show that the mechanical property of the WC-Ni hard alloy provided by the invention is higher than that of the common WC-Ni hard alloy (namely, the conventional WC-Ni hard alloy is utilizedWC-Ni hard alloy prepared from WC-Ni composite powder obtained by a ball milling and mixing method) is close to common WC-Co hard alloy and can replace the common WC-Co hard alloy to a certain extent.
Drawings
FIG. 1 is a scanning electron microscope image of WC-Ni cemented carbide prepared from the composite powder obtained in example 1;
FIG. 2 is a scanning electron microscope image of a WC-Ni hard alloy prepared from the composite powder obtained in comparative example 1.
Detailed Description
The invention provides a preparation method of WC-Ni composite powder, which comprises the following steps:
mixing soluble nickel salt, hydrazine hydrate, ammonium sulfate, citric acid, ethylenediamine and water to obtain mixed feed liquid; the concentration of nickel ions in the mixed feed liquid is 0.25-0.8 mol/L, the concentration of hydrazine hydrate is 5-30 g/L, the concentration of ammonium sulfate is 2-15 g/L, the concentration of citric acid is 8-20 g/L, and the concentration of ethylenediamine is 15-50 mL/L;
adjusting the pH value of the mixed material liquid to 8-11 by using ammonia water, mixing the mixed material liquid with WC powder, and carrying out reduction reaction to obtain a reduction reaction product system, wherein the temperature of the reduction reaction is not higher than 95 ℃;
and carrying out solid-liquid separation on the reduction reaction product system, and drying the obtained solid material to obtain the WC-Ni composite powder.
Soluble nickel salt, hydrazine hydrate, ammonium sulfate, citric acid, ethylenediamine and water are mixed to obtain mixed feed liquid. In the invention, the concentration of nickel ions in the mixed feed liquid is 0.25-0.8 mol/L, preferably 0.25-0.5 mol/L; the concentration of hydrazine hydrate is 5-30 g/L, preferably 10-20 g/L; the concentration of the ammonium sulfate is 2-15 g/L, preferably 8-12 g/L; the concentration of the citric acid is 8-20 g/L, preferably 12-16 g/L; the concentration of the ethylenediamine is 15-50 mL/L (i.e. each liter of the mixed feed liquid contains 15-50 mL of ethylenediamine), preferably 20-30 mL/L.
In the present invention, the soluble nickel salt preferably includes nickel acetate and/or nickel sulfate, specifically, it may be nickel acetate or nickel sulfate, or may be a mixture of both; when the soluble nickel salt is a mixture of the two, the proportion of the two is not particularly limited in the invention. In the present invention, the hydrazine hydrate is used as a reducing agent for reducing nickel ions to nickel; the ammonium sulfate and the ethylenediamine play a role of a complexing agent, the citric acid plays a role of a stabilizer, the ammonium sulfate, the ethylenediamine and the citric acid are beneficial to promoting nickel ions to be reduced into Ni in situ in WC, if the ammonium sulfate, the ethylenediamine and the citric acid are not added, Ni is generated too slowly (even is difficult to generate), and the surface of WC powder is coated unevenly; the components in the invention act cooperatively under the concentration condition, which is favorable for uniformly coating Ni in the finally obtained WC-Ni composite powder on the surface of the WC powder, and ensures that the WC-Ni hard alloy prepared by taking the WC-Ni composite powder as a raw material has better mechanical property.
After the mixed material liquid is obtained, ammonia water is adopted to adjust the pH value of the mixed material liquid to 8-11, and then the mixed material liquid is mixed with WC powder to carry out reduction reaction, so that a reduction reaction product system is obtained. In the invention, the concentration of the ammonia water is preferably 7.5-15 mol/L. According to the invention, ammonia water is adopted to adjust the pH value of the mixed feed liquid to 8-11, preferably 9-11. In the invention, the average particle size of the WC powder is preferably 0.4-3 μm, and more preferably 0.6-3 μm; the source of the WC powder is not particularly limited, and commercially available products well known to those skilled in the art can be adopted; in the embodiment of the present invention, the WC powder manufactured by the jiangzhou china tungsten material limited is specifically used. The dosage of the WC powder is not specially limited, and the WC-Ni composite powder is added according to actual needs, so that the components in the finally obtained WC-Ni composite powder meet the needs.
According to the invention, the pH value of the mixed material liquid is preferably adjusted to 8-11, then the mixed material liquid is heated to the temperature of reduction reaction, and then WC powder is added for reduction reaction. In the invention, ammonia water is adopted to adjust the pH value of the mixed feed liquid to 8-11, and nickel ions and NH in the system3Formation of nickel ammine complex ions while creating an alkaline solution environment, followed by hydrazine hydrate (N) during the reduction reaction2H4·H2O) is adopted, the nickel ions of the nickel ammonia complex ions are reduced into Ni, and the Ni is gradually attached to the surface of WC powder under the action of ammonium sulfate, citric acid and ethylenediamine, so that the finally obtained WC-Ni complex is ensuredNi in the mixed powder is uniformly coated on the surface of WC powder; the reaction equation involved in the reduction reaction process is as follows:
2Ni(NH3)6 2++N2H4·H2O+4OH-→2Ni↓+12NH3+N2↑+5H2O。
in the invention, the temperature of the reduction reaction is preferably 70-95 ℃, and more preferably 75-80 ℃; the time is preferably 5 to 20min, and more preferably 6 to 10 min. In the invention, the reduction reaction is preferably carried out under the condition of stirring, the stirring speed is preferably 50-150 r/min, and the stirring is preferably mechanical stirring. The invention preferably carries out the reduction reaction under the conditions of the temperature and the stirring, has higher reaction rate, and has poor stability of a reaction system if the temperature is too high, thus being not beneficial to the smooth running of the reduction reaction.
After the reduction reaction is finished, the solid-liquid separation is carried out on the obtained reduction reaction product system, and the obtained solid material is dried to obtain the WC-Ni composite powder. In the present invention, the solid-liquid separation is preferably performed by suction filtration, and in the embodiment of the present invention, the suction filtration is performed by using qualitative filter paper according to a conventional method in the art. In the invention, the drying is preferably vacuum drying, and the temperature of the vacuum drying is preferably 60-80 ℃, and more preferably 60-70 ℃; the vacuum drying time is not specially limited, and the materials can be fully dried.
In the invention, the content of nickel in the WC-Ni composite powder is preferably 8-16 wt%, and more preferably 12-15 wt%. In the invention, Ni in the WC-Ni composite powder is uniformly coated on the surface of the WC powder, and the average particle size of the WC-Ni composite powder is preferably increased by 5-10% compared with the average particle size of the WC powder.
The invention provides WC-Ni composite powder prepared by the preparation method in the technical scheme, and the WC-Ni composite powder comprises WC powder and nickel coated on the surface of the WC powder. In the invention, Ni and WC powder in the WC-Ni composite powder are reasonably distributed, wherein Ni is uniformly coated on the surface of the WC powder; the WC-Ni hard alloy prepared by the WC-Ni composite powder provided by the invention has more uniform distribution of Ni elements, and is beneficial to improving the mechanical property of the WC-Ni hard alloy.
The invention provides a WC-Ni hard alloy which is prepared by taking WC-Ni composite powder as a raw material in the technical scheme.
The invention provides a preparation method of WC-Ni hard alloy in the technical scheme, which comprises the following steps: and sequentially carrying out compression molding and sintering on the WC-Ni composite powder to obtain the WC-Ni hard alloy.
In the invention, the pressure of the compression molding is preferably 190-210 MPa, and more preferably 200 MPa. In the invention, the sintering temperature is preferably 1400-1450 ℃, and more preferably 1430 ℃; the sintering pressure is preferably 4.5-5.5 MPa, more preferably 5MPa, and the sintering pressure is preferably provided by argon; the heat preservation and pressure maintaining time is preferably 50-70 min, and more preferably 1 h. In the embodiment of the invention, the pressing forming is carried out by utilizing a hydraulic press, and the sintering is carried out by utilizing a low-pressure sintering furnace.
The WC-Ni hard alloy provided by the invention has the advantages that the distribution of Ni elements is more uniform, the mechanical property is better, the mechanical property is higher than that of the common WC-Ni hard alloy (namely, the WC-Ni hard alloy prepared from WC-Ni composite powder obtained by using a conventional ball-milling mixing method), the WC-Ni hard alloy is close to the common WC-Co hard alloy, and the WC-Ni hard alloy can replace the common WC-Co hard alloy to a certain extent.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following examples and comparative examples, WC powder having an average particle size of about 0.6 μm or 3 μm was purchased from Ganzhou Huamao tungsten materials, Inc.;
the average particle size of Ni powder is about 1 μm, and is purchased from Beijing Xinglong source technology Co., Ltd;
the average particle size of Co powder was about 1 μm, and was purchased from Kyoto-Yuan technologies, Inc. of Beijing.
Example 1
Mixing nickel sulfate, hydrazine hydrate, ammonium sulfate, citric acid, ethylenediamine and water to obtain mixed feed liquid; in the mixed feed liquid, the concentration of nickel sulfate is 50g/L, the concentration of hydrazine hydrate is 10g/L, the concentration of ammonium sulfate is 10g/L, the concentration of citric acid is 12g/L, and the concentration of ethylenediamine is 20 mL/L;
adjusting the pH value of the mixed feed liquid to 10 by using ammonia water with the concentration of 12mol/L, heating to 70 ℃, adding WC powder (the average particle size is about 0.6 mu m), and mechanically stirring for 6min under the condition of 120 r/min; and after stirring, carrying out suction filtration, and carrying out vacuum drying on the obtained solid material at 75 ℃ to obtain WC-Ni composite powder, wherein the Ni content in the WC-Ni composite powder is 12 wt%, and the average particle size is about 0.63 mu m.
Example 2
Mixing nickel acetate, hydrazine hydrate, ammonium sulfate, citric acid, ethylenediamine and water to obtain mixed feed liquid; in the mixed feed liquid, the concentration of nickel acetate is 45g/L, the concentration of hydrazine hydrate is 20g/L, the concentration of ammonium sulfate is 8g/L, the concentration of citric acid is 17g/L, and the concentration of ethylenediamine is 20 mL/L;
adjusting the pH value of the mixed feed liquid to 9.5 by using ammonia water with the concentration of 10mol/L, heating to 75 ℃, adding WC powder (the average particle size is about 3 mu m), and mechanically stirring for 8min under the condition of 60 r/min; and after stirring, carrying out suction filtration, and carrying out vacuum drying on the obtained solid material at 65 ℃ to obtain WC-Ni composite powder, wherein the Ni content in the WC-Ni composite powder is 12 wt%, and the average particle size is about 3.2 mu m.
Example 3
Mixing nickel sulfate, nickel acetate, hydrazine hydrate, ammonium sulfate, citric acid, ethylenediamine and water to obtain mixed feed liquid; in the mixed feed liquid, the concentration of nickel sulfate is 30g/L, the concentration of nickel acetate is 35g/L, the concentration of hydrazine hydrate is 15g/L, the concentration of ammonium sulfate is 11g/L, the concentration of citric acid is 16g/L, and the concentration of ethylenediamine is 25 mL/L;
adjusting the pH value of the mixed feed liquid to 10 by using ammonia water with the concentration of 11mol/L, heating to 78 ℃, adding WC powder (the average particle size is about 0.6 mu m), and mechanically stirring for 9min under the condition of 130 r/min; and after stirring, carrying out suction filtration, and carrying out vacuum drying on the obtained solid material at 73 ℃ to obtain WC-Ni composite powder, wherein the Ni content in the WC-Ni composite powder is 15 wt%, and the average particle size is about 0.65 mu m.
Example 4
Mixing nickel sulfate, nickel acetate, hydrazine hydrate, ammonium sulfate, citric acid, ethylenediamine and water to obtain mixed feed liquid; in the mixed feed liquid, the concentration of nickel sulfate is 20g/L, the concentration of nickel acetate is 65g/L, the concentration of hydrazine hydrate is 18g/L, the concentration of ammonium sulfate is 12g/L, the concentration of citric acid is 15g/L, and the concentration of ethylenediamine is 30 mL/L;
adjusting the pH value of the mixed feed liquid to 11 by using ammonia water with the concentration of 11mol/L, heating to 80 ℃, adding WC powder (the average particle size is about 3 mu m), and mechanically stirring for 10min under the condition of 150 r/min; and after stirring, carrying out suction filtration, and carrying out vacuum drying on the obtained solid material at 70 ℃ to obtain WC-Ni composite powder, wherein the Ni content in the WC-Ni composite powder is 15 wt%, and the average particle size is about 3.2 mu m.
Comparative example 1
Mixing WC powder (with average particle size of about 0.6 μm) and Ni powder (with average particle size of about 1 μm), and ball-milling for 48h under the conditions of argon protection and 300r/min of rotating speed to obtain WC-Ni composite powder, wherein the Ni content in the WC-Ni composite powder is 12 wt%.
Comparative example 2
Mixing WC powder (the average particle size is about 3 mu m) and Ni powder (the average particle size is about 1 mu m), and carrying out ball milling for 48h under the conditions of argon protection and 300r/min rotating speed to obtain WC-Ni composite powder, wherein the Ni content in the WC-Ni composite powder is 12 wt%.
Comparative example 3
Mixing WC powder (with average particle size of about 0.6 μm) and Ni powder (with average particle size of about 1 μm), and ball-milling for 48h under the conditions of argon protection and 300r/min of rotating speed to obtain WC-Ni composite powder, wherein the Ni content in the WC-Ni composite powder is 15 wt%.
Comparative example 4
Mixing WC powder (the average particle size is about 3 mu m) and Ni powder (the average particle size is about 1 mu m), and carrying out ball milling for 48h under the conditions of argon protection and 300r/min rotating speed to obtain WC-Ni composite powder, wherein the Ni content in the WC-Ni composite powder is 15 wt%.
Comparative example 5
Mixing WC powder (with average particle size of about 0.6 μm) and Co powder (with average particle size of about 1 μm), and ball-milling for 48h under the conditions of argon protection and 300r/min of rotating speed to obtain WC-Co composite powder, wherein the Co content in the WC-Co composite powder is 12 wt%.
Comparative example 6
Mixing WC powder (the average particle size is about 3 mu m) and Co powder (the average particle size is about 1 mu m), and carrying out ball milling for 48 hours under the conditions of argon protection and 300r/min rotating speed to obtain WC-Co composite powder, wherein the Co content in the WC-Co composite powder is 12 wt%.
Comparative example 7
Mixing WC powder (with average particle size of about 0.6 μm) and Co powder (with average particle size of about 1 μm), and ball-milling for 48h under the conditions of argon protection and 300r/min of rotating speed to obtain WC-Co composite powder, wherein the Co content in the WC-Co composite powder is 15 wt%.
Comparative example 8
Mixing WC powder (the average particle size is about 3 mu m) and Co powder (the average particle size is about 1 mu m), and carrying out ball milling for 48 hours under the conditions of argon protection and 300r/min rotating speed to obtain WC-Co composite powder, wherein the Co content in the WC-Co composite powder is 15 wt%.
The composite powders prepared in the examples 1-4 and the comparative examples 1-8 are prepared into corresponding hard alloys according to the following methods:
the composite powder is pressed and molded under the condition of 200MPa by adopting a hydraulic press, and then the obtained molded blank is sintered by adopting a low-pressure sintering furnace, wherein the sintering temperature is 1430 ℃, the sintering pressure is 5Mpa (argon provides the sintering pressure), and the heat preservation and pressure maintaining time is 1 h.
Scanning electron microscope characterization was performed on the cemented carbide prepared from the composite powders obtained in example 1 and comparative example 1, and the results are shown in fig. 1 and 2. As can be seen from fig. 1, in the WC — Ni hard alloy prepared by using the composite powder obtained in example 1, the nickel element is uniformly distributed as a binder phase; as can be seen from fig. 2, in the general WC — Ni cemented carbide prepared by using the composite powder obtained in comparative example 1, although most of nickel was uniformly distributed, some nickel accumulation regions were present. The WC-Ni hard alloy prepared by the composite powder has better structure than common WC-Ni hard alloy and improves the performance of the WC-Ni hard alloy.
The hard alloy prepared from the composite powder obtained in examples 1 to 4 and comparative examples 1 to 8 was subjected to a performance test, wherein the hardness test standard: GB/T7997-; and (3) the bending strength detection standard is as follows: GB/T3851-. Specific results are shown in table 1.
TABLE 1 results of performance test of cemented carbide produced using the composite powders obtained in examples 1 to 4 and comparative examples 1 to 8
As can be seen from Table 1, the WC-Ni hard alloy prepared from the WC-Ni composite powder obtained by the method provided by the invention has higher mechanical properties than common WC-Ni hard alloy, is close to common WC-Co hard alloy, and can replace common WC-Co hard alloy to a certain extent.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The preparation method of the WC-Ni composite powder is characterized by comprising the following steps of:
mixing soluble nickel salt, hydrazine hydrate, ammonium sulfate, citric acid, ethylenediamine and water to obtain mixed feed liquid; the concentration of nickel ions in the mixed feed liquid is 0.25-0.8 mol/L, the concentration of hydrazine hydrate is 5-30 g/L, the concentration of ammonium sulfate is 2-15 g/L, the concentration of citric acid is 8-20 g/L, and the concentration of ethylenediamine is 15-50 mL/L;
adjusting the pH value of the mixed material liquid to 8-11 by using ammonia water, mixing the mixed material liquid with WC powder, and carrying out reduction reaction to obtain a reduction reaction product system, wherein the temperature of the reduction reaction is not higher than 95 ℃;
and carrying out solid-liquid separation on the reduction reaction product system, and drying the obtained solid material to obtain the WC-Ni composite powder.
2. The method of claim 1, wherein the soluble nickel salt comprises nickel acetate and/or nickel sulfate.
3. The method according to claim 1, wherein the concentration of the aqueous ammonia is 7.5 to 15 mol/L.
4. The method according to claim 1, wherein the WC powder has an average particle size of 0.4 to 3 μm.
5. The method according to claim 1, wherein the temperature of the reduction reaction is 70 to 95 ℃ and the time is 5 to 20 min.
6. The preparation method according to claim 5, wherein the reduction reaction is carried out under stirring at a speed of 50 to 150 r/min.
7. The method according to any one of claims 1 to 6, wherein the content of nickel in the WC-Ni composite powder is 8 to 16 wt%.
8. The WC-Ni composite powder prepared by the preparation method of any one of claims 1 to 7, wherein the WC-Ni composite powder comprises WC powder and nickel coated on the surface of the WC powder.
9. A WC-Ni hard alloy characterized by being prepared from the WC-Ni composite powder of claim 8.
10. A method for producing a WC-Ni hard alloy according to claim 9, comprising the steps of:
and sequentially carrying out compression molding and sintering on the WC-Ni composite powder to obtain the WC-Ni hard alloy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010257212.3A CN111266601B (en) | 2020-04-03 | 2020-04-03 | WC-Ni composite powder, WC-Ni hard alloy and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010257212.3A CN111266601B (en) | 2020-04-03 | 2020-04-03 | WC-Ni composite powder, WC-Ni hard alloy and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111266601A true CN111266601A (en) | 2020-06-12 |
| CN111266601B CN111266601B (en) | 2022-07-26 |
Family
ID=70992111
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010257212.3A Active CN111266601B (en) | 2020-04-03 | 2020-04-03 | WC-Ni composite powder, WC-Ni hard alloy and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111266601B (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6230885A (en) * | 1985-04-01 | 1987-02-09 | Nippon Chem Ind Co Ltd:The | Production of nickel plated material |
| CN1435509A (en) * | 2002-09-27 | 2003-08-13 | 欧昌亚 | Pre-plating nickel dipping solution for chemical plating aluminium and aluminium alloy with nickel |
| CN1820876A (en) * | 2006-03-23 | 2006-08-23 | 北京科技大学 | Method for preparing nickel and cobalt coated inorganic powder particle coated material |
| CN101152669A (en) * | 2006-09-30 | 2008-04-02 | 深圳市新宏泰粉末冶金有限公司 | Copper-radicle antifriction compound powder and method of producing the same |
| CN101302614A (en) * | 2008-01-17 | 2008-11-12 | 中山大学 | Environment-protective plating solution for preparing high-hardness chemical plating Ni-P-SiC coating |
| CN101314848A (en) * | 2008-07-16 | 2008-12-03 | 中山大学 | Non-ammonia type plating solution for chemical nickel plating |
| CN101423398A (en) * | 2008-12-02 | 2009-05-06 | 四川大学 | Ceramic cladding powder and preparation method thereof |
| CN102168258A (en) * | 2010-02-05 | 2011-08-31 | 芝普企业股份有限公司 | Electroless nickel plating solution for solar cell electrode |
| CN103556137A (en) * | 2013-11-07 | 2014-02-05 | 杭州东方表面技术有限公司 | Environment-friendly chemical nickel deposition solution for metalizing modification of plastic surface |
| CN109628913A (en) * | 2019-01-31 | 2019-04-16 | 湖南互连微电子材料有限公司 | A kind of new chemical nickel gold production technology and chemical nickel-plating liquid |
| CN109894610A (en) * | 2019-03-12 | 2019-06-18 | 广东省材料与加工研究所 | A kind of metallic cover spherical casting tungsten carbide powder and preparation method thereof |
-
2020
- 2020-04-03 CN CN202010257212.3A patent/CN111266601B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6230885A (en) * | 1985-04-01 | 1987-02-09 | Nippon Chem Ind Co Ltd:The | Production of nickel plated material |
| CN1435509A (en) * | 2002-09-27 | 2003-08-13 | 欧昌亚 | Pre-plating nickel dipping solution for chemical plating aluminium and aluminium alloy with nickel |
| CN1820876A (en) * | 2006-03-23 | 2006-08-23 | 北京科技大学 | Method for preparing nickel and cobalt coated inorganic powder particle coated material |
| CN101152669A (en) * | 2006-09-30 | 2008-04-02 | 深圳市新宏泰粉末冶金有限公司 | Copper-radicle antifriction compound powder and method of producing the same |
| CN101302614A (en) * | 2008-01-17 | 2008-11-12 | 中山大学 | Environment-protective plating solution for preparing high-hardness chemical plating Ni-P-SiC coating |
| CN101314848A (en) * | 2008-07-16 | 2008-12-03 | 中山大学 | Non-ammonia type plating solution for chemical nickel plating |
| CN101423398A (en) * | 2008-12-02 | 2009-05-06 | 四川大学 | Ceramic cladding powder and preparation method thereof |
| CN102168258A (en) * | 2010-02-05 | 2011-08-31 | 芝普企业股份有限公司 | Electroless nickel plating solution for solar cell electrode |
| CN103556137A (en) * | 2013-11-07 | 2014-02-05 | 杭州东方表面技术有限公司 | Environment-friendly chemical nickel deposition solution for metalizing modification of plastic surface |
| CN109628913A (en) * | 2019-01-31 | 2019-04-16 | 湖南互连微电子材料有限公司 | A kind of new chemical nickel gold production technology and chemical nickel-plating liquid |
| CN109894610A (en) * | 2019-03-12 | 2019-06-18 | 广东省材料与加工研究所 | A kind of metallic cover spherical casting tungsten carbide powder and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 张允诚等: "《电镀手册》", 31 December 2011 * |
| 陈勇志等: "《机械制造工程技术基础》", 28 February 2015 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111266601B (en) | 2022-07-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107345284B (en) | Make the Ti base metal-ceramic material of Binder Phase using Ni-Cu continuous solid solution | |
| CN107245628B (en) | Make the cemented carbide material and preparation method thereof of Binder Phase using Ni-Cu continuous solid solution | |
| CN109576545B (en) | Ti (C, N) -based metal ceramic with mixed crystal structure and preparation method thereof | |
| CN112680646B (en) | Preparation method of TiC-based metal ceramic with high-entropy alloy binder phase | |
| CN102383021A (en) | WC-Co hard alloy with binding phase enhanced by Ni3Al and preparation method thereof | |
| CN109881070B (en) | Metal ceramic with high hardness and high toughness and preparation method and application thereof | |
| CN111996432B (en) | Preparation method of ultra-coarse hard alloy material | |
| CN111139390A (en) | Chromium-doped modified Mo2NiB2Base cermet and method for preparing same | |
| CN112647006A (en) | Tungsten carbide-based hard alloy and preparation method thereof | |
| CN113025861A (en) | Mixed crystal Ti (C, N) -based metal ceramic material and preparation method thereof | |
| CN109053191B (en) | Titanium carbonitride based cermet without binder phase and preparation method thereof | |
| CN101082091A (en) | Ternary boride ceramet material and preparation method thereof | |
| CN112662930A (en) | High-entropy die steel material and preparation method thereof | |
| CN102796932A (en) | Powder particle for preparing metal ceramic and preparation method of metal ceramic | |
| CN111266601B (en) | WC-Ni composite powder, WC-Ni hard alloy and preparation method thereof | |
| CN108165791B (en) | Preparation method of binderless superfine tungsten carbide hard alloy | |
| CN111185591B (en) | TiC high manganese steel composite material and preparation method thereof | |
| CN111961941A (en) | Preparation method of superfine hard alloy cutter material | |
| CN103667843B (en) | A kind of preparation method of deep hole machining ultra-fine cemented carbide cutter material | |
| CN115283670A (en) | Ti (C, N) -Mo-Fe composite powder and preparation method and application thereof | |
| CN113106314B (en) | Core-shell structure TiB2Base cermet and method for preparing same | |
| CN112080661B (en) | Preparation method of superfine hard alloy | |
| CN112410645A (en) | Binding phase double-reinforced cermet material and preparation method thereof | |
| CN112609116A (en) | Novel cemented carbide of binder phase and preparation method thereof | |
| CN110370176B (en) | Composite binder and preparation method thereof, polycrystalline cubic boron nitride composite sheet and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 341000 No.62 Yingbin Avenue, Ganzhou economic and Technological Development Zone, Jiangxi Province Applicant after: Ganzhou Nonferrous Metallurgy Research Institute Co.,Ltd. Address before: 341000 No.62 Yingbin Avenue, Ganzhou economic and Technological Development Zone, Jiangxi Province Applicant before: GANZHOU NONFERROUS METALLURGICAL Research Institute |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |