CN108950529A - A kind of tungsten carbide-copper-nickle composite powder preparation method - Google Patents
A kind of tungsten carbide-copper-nickle composite powder preparation method Download PDFInfo
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- CN108950529A CN108950529A CN201810927085.6A CN201810927085A CN108950529A CN 108950529 A CN108950529 A CN 108950529A CN 201810927085 A CN201810927085 A CN 201810927085A CN 108950529 A CN108950529 A CN 108950529A
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- Prior art keywords
- copper
- tungsten carbide
- composite powder
- powder
- nickle
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- 239000000843 powder Substances 0.000 title claims abstract description 72
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 25
- 239000010937 tungsten Substances 0.000 title claims abstract description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 60
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000007747 plating Methods 0.000 claims abstract description 37
- 229910052802 copper Inorganic materials 0.000 claims abstract description 34
- 239000010949 copper Substances 0.000 claims abstract description 34
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 238000001291 vacuum drying Methods 0.000 claims abstract description 5
- 239000003002 pH adjusting agent Substances 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 30
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000008187 granular material Substances 0.000 claims description 11
- 239000008139 complexing agent Substances 0.000 claims description 10
- 239000012190 activator Substances 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000001509 sodium citrate Substances 0.000 claims description 8
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 8
- 229940038773 trisodium citrate Drugs 0.000 claims description 8
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 229910001431 copper ion Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- -1 control pH are 11~13 Substances 0.000 claims description 4
- 150000001879 copper Chemical class 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000004310 lactic acid Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- 229910001453 nickel ion Inorganic materials 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical group FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000013527 degreasing agent Substances 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 2
- 239000002552 dosage form Substances 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 14
- 238000000576 coating method Methods 0.000 abstract description 14
- 238000010288 cold spraying Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 abstract 1
- 239000011258 core-shell material Substances 0.000 abstract 1
- 238000004663 powder metallurgy Methods 0.000 abstract 1
- 238000004321 preservation Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 15
- 238000013019 agitation Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 230000004913 activation Effects 0.000 description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- 229910000570 Cupronickel Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000007751 thermal spraying Methods 0.000 description 2
- 229910002482 Cu–Ni Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical group [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005551 mechanical alloying Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002103 nanocoating Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 238000002663 nebulization Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
- C23C18/405—Formaldehyde
-
- 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
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1635—Composition of the substrate
- C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
- C23C18/1875—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment only one step pretreatment
- C23C18/1882—Use of organic or inorganic compounds other than metals, e.g. activation, sensitisation with polymers
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Chemically Coating (AREA)
- Powder Metallurgy (AREA)
Abstract
The present invention relates to a kind of tungsten carbide-copper-nickle composite powder preparation methods, including tungsten-carbide powder is placed in electrochemical deoiling agent and impregnates oil removing, and then by tungsten carbide powder after overactivation, clear water is rinsed, and it is spare to be placed in a vacuum drying oven heat preservation 8h.Processed tungsten carbide powder is put into carry out copper facing, after pH adjusting agent, reducing agent solution are added in the copper plating bath containing tungsten carbide powder, keep 50~60 DEG C of constant temperature, stir 30~40min, cleaning be centrifugated be made tungsten carbide-copper composite powders；The powder is subjected to nickel plating, under the conditions of 85~90 DEG C, constant temperature stirs 10~30min, and tungsten carbide-copper-nickle composite powder is made；Resulting tungsten carbide-copper-the nickle composite powder of the present invention is a kind of multi-functional powder body material with core-shell structure, have the characteristics that coating is smooth and uniformity is good, coating is tightly combined, purity is high, it can be carried out large-scale production, can be widely applied to the fields such as cold spraying, powder metallurgy, machinery, space flight and military project.
Description
Technical field
The present invention relates to a kind of preparation method of composite granule more particularly to a kind of tungsten carbide-copper-nickle composite powder systems
Preparation Method belongs to chemical surface treatment technical field.
Background technique
Tungsten carbide composite powder is to prepare hard alloy, the reinforcing of wear-and corrosion-resistant thermal spraying on surface, metal rapid shaping, surface patch
The key raw material of the new structural materials such as dress, has been widely used the miniature drill in difficult processing metal cutter, electronics industry
The fields such as head, precision die, medicine.
Cold spraying is got the attention in recent years as a kind of new coat preparing technology, since it avoids thermal spraying
Some disadvantages, the coating of preparation is fine and close, and porosity is low, and in addition coating oxidation object content is low, hardness is high, and thermal stress is small, coating
Hardly change the institutional framework of powder particle, therefore is suitble to prepare nano coating and composite coating.The preparation gold of cold spraying at present
Belong in ceramic composite coating, it is ideal with the coating abrasion resistant effect that tungsten carbide powder is added.Tungsten carbide requirement for spraying
Partial size is in a few to tens of microns, and the mobility of single superfine tungsten carbide is very poor, it is difficult to meet the needs of spraying process.
Its particle size can then be increased using wolfram carbine composite powder, substantially improve mobility, and be able to maintain tungsten carbide
Binding force between the geometry and crystal structure and coating and matrix of particle, to obtain high performance coating.Carbonization
Tungsten composite powder preparation method mainly has mechanical alloying method, sol-gel method, spray drying process, electroless plating method etc..
Machine-alloying has technique flexibly simple, is not necessarily to hot environment, low energy consumption, and yield is big, and the composite powder worn into is equal
It is even tiny, but repeatedly grinding will increase the iron content in composite powder for a long time, and this will affect the conductive hot property of composite granule.
The advantages such as sol-gel method has reaction temperature low, and reaction controllability is high, and out-phase side reaction is few, the powder prepared have pure
Degree is high, the advantages such as chemical uniformity is good, and structure is single tiny, and heat treatment temperature is low.But there are long preparation period, costs for the technique
The problems such as height, volume production is difficult.Spray drying process each process is easily controllable, and the oxide precursor after dry nebulization is generally in ball
Shape ghost shape, product impurity is low, is suitble to large-scale industrial production, but process is more, and energy consumption is high.
Summary of the invention
The present invention is for the existing machine-alloying for preparing carbonization tungsten composite powder, sol-gel method, spray drying process
Existing deficiency provides a kind of preparation method of tungsten composite powder that is carbonized.
The technical scheme to solve the above technical problems is that
A kind of preparation method for the tungsten composite powder that is carbonized, includes the following steps:
1) tungsten carbide powder is placed in degreaser and impregnates oil removing, rinsed after taking-up using deionized water；
2) the resulting tungsten carbide powder of step 1) is placed in activator and is activated, then rinsed using deionized water, vacuum is dry
Dry 8h；
3) the resulting tungsten carbide powder of step 2 is placed in copper plating solution, is stirred, while controlled at 60 DEG C, pH is added and adjusts
Agent, control pH are 11~13, and reducing agent solution is then added, continues to stir, reacts 30~40min, until copper plating bath after reaction
It is colourless, the obtained tungsten carbide-copper composite powders of centrifuge separation；
4) by the resulting composite granule of step 3), it is placed in nickel plating in nickel plating solution, is stirred, 85~90 DEG C of constant temperature, reaction 10~
Tungsten carbide-copper-nickle composite powder that nickel content is 5~20wt% is made in 30min；
5) the resulting tungsten carbide-copper of step 4)-nickle composite powder is washed, it is rear to be centrifugated；Vacuum drying to get.
Based on the above technical solution, the present invention can also be improved as follows.
Further, the sulfuric acid solution that activator described in step 2 is 10%.
Further, PH regulator described in step 3) is one of sodium hydroxide, ammonium hydroxide or mixture；Described goes back
Former agent is formalin.Centrifugal speed is 3000 ~ 5000r/min；The copper plating solution is by soluble copper salt and copper ion network
The mixed aqueous solution that mixture is formed, the mass ratio for controlling copper and tungsten carbide is 0.10~0.20.
Further, nickel plating solution described in step 4) is acidic nickel plating solution, and pH value is 4~5, and nickel plating solution is by sulfuric acid
The mixed aqueous solution that nickel and nickel ion complexing agent, reducing agent are formed, the mass ratio for controlling nickel and tungsten carbide is 0.05~0.15.
Further, copper ion complexing agent described in step 2 be EDTA, any one in trisodium citrate, it is described can
Dissolubility mantoquita refers to copper nitrate, copper sulphate, any one in copper chloride.
Further, the mass ratio of soluble copper salt described in step 2) and copper ion complexing agent is 1:1~2.5.
Further, nickel ion complexing agent is one or both of trisodium citrate, citric acid, lactic acid mixture；Reduction
Agent is sodium hypophosphite, a kind of in Boratex.
Further, the mass ratio of tungsten carbide powder and the reducing agent is 1~20:1.
Further, step 2, vacuum drying temperature is 80~100 DEG C in step 5).
The beneficial effects of the present invention are:
1) method provided by the invention uses electronation technology, and the pre-treating technology of tungsten-carbide powder impregnates skill using activator
Roughening, the sensitization, activating technology that art replaces traditional non-metal material surface metallization to use, are matched using novel complexing agent
Side directly in the success copper facing of tungsten-carbide powder surface, and forms the smooth layers of copper of continuous dense uniform, uses chemical plating later
Nickel, process costs are low, it is easy to accomplish large-scale production；
2) the resulting carbonization tungsten composite powder of the method for the present invention have plating copper and nickel it is smooth and uniformity is good, coating is tightly combined,
The features such as with high purity, and can be carried out large-scale production, can be widely applied in difficult processing metal cutter, electronics industry
The fields such as microbit, precision die, medicine.
Detailed description of the invention
Fig. 1 is activated treated the stereoscan photograph of 1 gained tungsten carbide of the embodiment of the present invention；
Fig. 2 is the stereoscan photograph after 1 gained tungsten carbide copper facing of the embodiment of the present invention；
Fig. 3 is the stereoscan photograph after 1 gained tungsten carbide copper facing of the embodiment of the present invention again nickel plating.
Specific embodiment
Principles and features of the present invention are described below in conjunction with example, the given examples are served only to explain the present invention, and
It is non-to be used to limit the scope of the invention.
Embodiment 1:
A kind of preparation method for the tungsten composite powder that is carbonized, includes the following steps:
1) take tungsten carbide powder 1kg to be added in the sulfuric acid of the activator 10% of 500ml and impregnate and stir 1h, after taking-up using go from
Sub- water rinses；
2) then the tungsten carbide powder after activation is added in the copper plating bath that volume is 10L, the content of each substance in copper plating bath are as follows:
Copper sulphate 10g/L, EDTA 14g/L, using ammonium hydroxide adjust copper plating bath pH be 11.8, then heat temperature raising and controlled at
60 DEG C, formaldehyde 20ml is added under constant agitation, continues to stir 10min, until blue solution becomes colorless solution,
Then it is rinsed using deionized water, and copper-plated tungsten carbide powder is isolated using centrifuge；
3) under agitation, by tungsten carbide copper powder be added to nickel plating solution (nickel sulfate 25g/L, trisodium citrate 15 g/L, it is secondary
25 g/L of sodium phosphite) in, 85 DEG C of temperature are controlled, 5% tungsten carbide of nickel content-copper-nickel composite powder is made in reaction time 10min
Body；
4) the resulting composite granule of step 3) is centrifugated, is placed at 80 DEG C and is dried in vacuo to get finished product.
Embodiment 2:
A kind of preparation method for the tungsten composite powder that is carbonized, includes the following steps:
1) take tungsten carbide powder 1kg to be added in the sulfuric acid of the activator 10% of 500ml and impregnate and stir 1h, after taking-up using go from
Sub- water rinses；
2) then the tungsten carbide powder after activation is added in the copper plating bath that volume is 20L, the content of each substance in copper plating bath are as follows:
Copper nitrate 15g/L, trisodium citrate 10g/L are 12.5 using the pH that sodium hydroxide adjusts copper plating bath, then heat temperature raising and control
Temperature processed is 60 DEG C, and formaldehyde 20ml is added under constant agitation, continues to stir 20min, until blue solution becomes colorless
It until solution, is then rinsed using deionized water, and copper-plated tungsten carbide powder is isolated using centrifuge；
3) tungsten carbide copper powder under agitation, is added to nickel plating solution (nickel sulfate 30g/L, 8 g/L of citric acid, secondary phosphorous
Sour 15 g/L of sodium) in, 85 DEG C of temperature are controlled, 10% tungsten carbide of nickel content-copper-nickle composite powder is made in reaction time 15min；
4) the resulting composite granule of step 3) is centrifugated, is placed at 80 DEG C and is dried in vacuo to get finished product.
Embodiment 3:
A kind of preparation method for the tungsten composite powder that is carbonized, includes the following steps:
1) take tungsten carbide powder 1kg to be added in the sulfuric acid of the activator 10% of 300ml and impregnate and stir 1h, after taking-up using go from
Sub- water rinses；
2) then the tungsten carbide powder after activation is added in the copper plating bath that volume is 15L, the content of each substance in copper plating bath are as follows:
Copper chloride 5g/L, copper sulphate 8g/L, trisodium citrate 10g/L are 13 using the pH that sodium hydroxide adjusts copper plating bath, then heat
It heats up and controlled at 60 DEG C, formaldehyde 25ml is added under constant agitation, continues to stir 10min, until blue solution
It becomes colorless until solution, is then rinsed using deionized water, and copper-plated tungsten carbide powder is isolated using centrifuge；
3) tungsten carbide copper powder under agitation, is added to nickel plating solution (nickel sulfate 25g/L, lactic acid 20ml/L, ortho phosphorous acid
Sodium 20g/L) in, 90 DEG C of temperature are controlled, 15% tungsten carbide of nickel content-copper-nickle composite powder is made in reaction time 15min；
4) the resulting composite granule of step 3) is centrifugated, is placed at 80 DEG C and is dried in vacuo to get finished product.
Embodiment 4:
A kind of preparation method for the tungsten composite powder that is carbonized, includes the following steps:
1) take tungsten carbide powder 1kg to be added in the sulfuric acid of the activator 10% of 300ml and impregnate and stir 1h, after taking-up using go from
Sub- water rinses；
2) then the tungsten carbide powder after activation is added in the copper plating bath that volume is 10L, the content of each substance in copper plating bath are as follows:
Copper nitrate 10g/L, copper sulphate 8g/L, trisodium citrate 10g/L are 11.5 using the pH that sodium hydroxide adjusts copper plating bath, then
Formaldehyde 18ml is added in heat temperature raising and controlled at 60 DEG C under constant agitation, continues to stir 15min, until blue
Solution becomes colorless until solution, is then rinsed using deionized water, and isolates copper-plated tungsten carbide powder using centrifuge；
3) tungsten carbide copper powder under agitation, is added to nickel plating solution (nickel sulfate 20g/L, lactic acid 20ml/L, ortho phosphorous acid
Sodium 15g/L) in, 85 DEG C of temperature are controlled, 20% tungsten carbide of nickel content-copper-nickle composite powder is made in reaction time 20min；
4) the resulting composite granule of step 3) is centrifugated, is placed at 80 DEG C and is dried in vacuo to get finished product.
In order to verify tungsten carbide-copper-nickle composite powder actual effect obtained by preparation method provided by the invention, we are right
Gained composite granule has carried out every test, as can be seen that the resulting tungsten carbide-copper-nickel of the method for the present invention is multiple from Fig. 1, Fig. 2
The partial size for closing powder is 20~50 μm, and gained composite granule has fine and close and uniform ground layers of copper and nickel layer.
Using cold spray technique, prepare hard alloy coating using the composite granule in the present invention, and to the hardness of coating,
Wearability, corrosion resistance are tested, as a result as follows:
WC-Cu-Ni coating performance comparison obtained by 1 embodiment 1-4 of table
| Test object | Hardness (HV) | Wearability (abrasion loss mg) | Corrosion resistance (the corrosion rate mm/a in 3.5%NaCl solution) |
| Embodiment 1 | 1420 | 10.1 | 0.0542 |
| Embodiment 2 | 1370 | 12.1 | 0.0821 |
| Embodiment 3 | 1500 | 9.8 | 0.0468 |
| Embodiment 4 | 1410 | 10.2 | 0.0751 |
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, all in the spirit and principles in the present invention
Within, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of tungsten carbide-copper-nickle composite powder preparation method, which comprises the steps of:
Tungsten carbide powder is placed in degreaser and impregnates oil removing, is rinsed after taking-up using deionized water；
The resulting tungsten carbide powder of step 1) is placed in activator and is activated, is then rinsed using deionized water, is dried in vacuo
8h；
The resulting tungsten carbide powder of step 2 is placed in copper plating solution, is stirred, while controlled at 60 DEG C, pH is added and adjusts
Agent, control pH are 11~13, and reducing agent solution is then added, continues to stir, reacts 30~40min, until copper plating bath after reaction
It is colourless, the obtained tungsten carbide-copper composite powders of centrifuge separation；
By the resulting composite granule of step 3), it is placed in nickel plating in nickel plating solution, is stirred, 85~90 DEG C of constant temperature, reaction 10~
Tungsten carbide-copper-nickle composite powder that nickel content is 5~20wt% is made in 30min；
It is rear to be centrifugated by the resulting tungsten carbide-copper of step 4)-nickle composite powder washing；Vacuum drying is to get finished product.
2. tungsten carbide according to claim 1-copper-nickle composite powder preparation method, which is characterized in that institute in step 2
The sulfuric acid solution that the activator stated is 10%.
3. tungsten carbide according to claim 1-copper-nickle composite powder preparation method, which is characterized in that institute in step 3)
The pH adjusting agent stated is one of sodium hydroxide, ammonium hydroxide or mixture；The reducing agent is formalin；Centrifugal speed is
3000~5000r/min；The copper plating solution is the mixed aqueous solution formed by soluble copper salt and copper ion complexing agent, control
The mass ratio of copper and tungsten carbide is 0.10~0.20.
4. tungsten carbide according to claim 1-copper-nickle composite powder preparation method, which is characterized in that institute in step 4)
The nickel plating solution stated is acidic nickel plating solution, and pH value is 4~5, and nickel plating solution is by nickel sulfate and nickel ion complexing agent, reduction dosage form
At mixed aqueous solution, the mass ratio for controlling nickel and tungsten carbide is 0.05~0.15.
5. tungsten carbide according to claim 3-copper-nickle composite powder preparation method, which is characterized in that institute in step 2
The copper ion complexing agent stated is EDTA, any one in trisodium citrate, and the soluble copper salt refers to copper nitrate, sulfuric acid
Any one in copper, copper chloride.
6. tungsten carbide according to claim 5-copper-nickle composite powder preparation method, which is characterized in that described is solvable
Property mantoquita and copper ion complexing agent mass ratio be 1:1~2.5.
7. tungsten carbide according to claim 4-copper-nickle composite powder preparation method, which is characterized in that nickel ion complexing
Agent is one or both of trisodium citrate, citric acid, lactic acid mixture；Reducing agent is sodium hypophosphite, one in Boratex
Kind.
8. tungsten carbide according to claim 7-copper-nickle composite powder preparation method, which is characterized in that tungsten carbide powder with
The mass ratio of the reducing agent is 1~20:1.
9. tungsten carbide according to claim 1-copper-nickle composite powder preparation method, which is characterized in that step 2, step
It is rapid 5) in vacuum drying temperature be 80~100 DEG C.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109702219A (en) * | 2019-01-02 | 2019-05-03 | 北京科技大学 | A kind of method of borax-assisted preparation of hollow structure particles |
| CN109825828A (en) * | 2019-04-04 | 2019-05-31 | 林庆仁 | A kind of vacuum pump screw rotor tungsten carbide-copper-nickel composite coat preparation method |
| CN113215566A (en) * | 2021-05-07 | 2021-08-06 | 常州市天河电器有限公司 | High-strength wear-resistant enclosed steel frame and processing technology thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101758230A (en) * | 2009-09-24 | 2010-06-30 | 温州宏丰电工合金有限公司 | Method for chemical plating of metal on particle surface |
| CN103046012A (en) * | 2012-11-16 | 2013-04-17 | 中国船舶重工集团公司第七二五研究所 | Method for preparing covering type compound powder for thermal spraying by vacuum magnetron sputtering |
| CN103920875A (en) * | 2014-04-30 | 2014-07-16 | 台州学院 | Preparation method of WC-rare earth-Co layer-by-layer coating hard alloy composite powder |
-
2018
- 2018-08-15 CN CN201810927085.6A patent/CN108950529A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101758230A (en) * | 2009-09-24 | 2010-06-30 | 温州宏丰电工合金有限公司 | Method for chemical plating of metal on particle surface |
| CN103046012A (en) * | 2012-11-16 | 2013-04-17 | 中国船舶重工集团公司第七二五研究所 | Method for preparing covering type compound powder for thermal spraying by vacuum magnetron sputtering |
| CN103920875A (en) * | 2014-04-30 | 2014-07-16 | 台州学院 | Preparation method of WC-rare earth-Co layer-by-layer coating hard alloy composite powder |
Non-Patent Citations (5)
| Title |
|---|
| 宣兆龙编著: "《装备环境工程》", 31 July 2015 * |
| 涂湘缃主编: "《实用防腐蚀工程施工手册》", 30 April 2000 * |
| 袁军平，王昶编著: "《流行饰品材料及生产工艺》", 30 June 2015 * |
| 贾静茹编著: "《应用化学基础实验》", 30 November 2014 * |
| 钱苗根主编: "《材料表面技术及其应用手册》", 30 November 1998 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109702219A (en) * | 2019-01-02 | 2019-05-03 | 北京科技大学 | A kind of method of borax-assisted preparation of hollow structure particles |
| CN109702219B (en) * | 2019-01-02 | 2020-07-10 | 北京科技大学 | A kind of method of borax-assisted preparation of hollow structure particles |
| CN109825828A (en) * | 2019-04-04 | 2019-05-31 | 林庆仁 | A kind of vacuum pump screw rotor tungsten carbide-copper-nickel composite coat preparation method |
| CN113215566A (en) * | 2021-05-07 | 2021-08-06 | 常州市天河电器有限公司 | High-strength wear-resistant enclosed steel frame and processing technology thereof |
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