CN109338197A - A kind of preparation method of high-compactness WC/Co composite material hard alloy - Google Patents
A kind of preparation method of high-compactness WC/Co composite material hard alloy Download PDFInfo
- Publication number
- CN109338197A CN109338197A CN201811310911.9A CN201811310911A CN109338197A CN 109338197 A CN109338197 A CN 109338197A CN 201811310911 A CN201811310911 A CN 201811310911A CN 109338197 A CN109338197 A CN 109338197A
- Authority
- CN
- China
- Prior art keywords
- powder
- preparation
- composite material
- compactness
- hard alloy
- 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.)
- Pending
Links
- 239000000956 alloy Substances 0.000 title claims abstract description 63
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 239000000843 powder Substances 0.000 claims abstract description 96
- 238000007747 plating Methods 0.000 claims abstract description 34
- 238000005245 sintering Methods 0.000 claims abstract description 31
- 239000000126 substance Substances 0.000 claims abstract description 24
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 21
- 239000010941 cobalt Substances 0.000 claims abstract description 21
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 150000001868 cobalt Chemical class 0.000 claims abstract description 7
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 25
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 17
- 230000003213 activating effect Effects 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 229910002804 graphite Inorganic materials 0.000 claims description 13
- 239000010439 graphite Substances 0.000 claims description 13
- 230000036571 hydration Effects 0.000 claims description 13
- 238000006703 hydration reaction Methods 0.000 claims description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 12
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 claims description 12
- 238000007788 roughening Methods 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 12
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 11
- 230000004913 activation Effects 0.000 claims description 11
- 239000012530 fluid Substances 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- 238000003763 carbonization Methods 0.000 claims description 4
- XWROUVVQGRRRMF-UHFFFAOYSA-N F.O[N+]([O-])=O Chemical compound F.O[N+]([O-])=O XWROUVVQGRRRMF-UHFFFAOYSA-N 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- JPNWDVUTVSTKMV-UHFFFAOYSA-N cobalt tungsten Chemical compound [Co].[W] JPNWDVUTVSTKMV-UHFFFAOYSA-N 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 239000001509 sodium citrate Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 32
- 238000005516 engineering process Methods 0.000 abstract description 4
- 229910010293 ceramic material Inorganic materials 0.000 abstract 1
- 239000000696 magnetic material Substances 0.000 abstract 1
- 230000008569 process Effects 0.000 description 15
- 239000000463 material Substances 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000001914 filtration Methods 0.000 description 5
- 238000005498 polishing Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 239000000320 mechanical mixture Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000009768 microwave sintering Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910000967 As alloy Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910009043 WC-Co Inorganic materials 0.000 description 1
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000009770 conventional sintering Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
-
- 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
- C22C1/05—Mixtures of metal powder with non-metallic powder
- C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
-
- 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
- C23C18/1886—Multistep pretreatment
- C23C18/1893—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
-
- 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
-
- 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
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Optics & Photonics (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention belongs to ceramic materials preparation technology fields, and in particular to a kind of preparation method of WC/Co composite material hard alloy.After carbide powder is activated by cobalt salt first, carbide powder surface is made to coat one layer of uniform metallic cobalt using chemical plating method；Then, by the carbide powder discharge plasma sintering of coating surface cobalt layers, WC/Co composite material hard alloy is prepared.Preparation process of the present invention is easy to operate, short preparation period, and pollution is less and at low cost, and the composite material consistency of preparation is high, can be used as magnetic material, alloy material etc. applied to fields such as mine tool, buildings.
Description
Technical field
The present invention relates to a kind of preparation methods of high-compactness WC/Co composite material hard alloy, and in particular to Yi Zhongji
In the method for the chemical plating cobalt coated tungsten carbide of cobalt salt activation, belong to field of material preparation.
Background technique
As the material base of new era hi-tech development and modern civilization, material has become the three big pillars of 21 century
One of industry.Scientific and technological progress push material from unification to diversification change, two or more materials composition composite material at
For research hotspot, important development direction of the hard alloy as composite material is widely used in every field.Hard alloy is logical
Certain powder metallurgy process is crossed, form that the compound of refractory metal and Binder Phase metal are needed to design according to performance, ratio
Example, distributed combination and manufactured new material.Compared to the single metal compound material of tradition, hard alloy is keeping each component material
On the basis of the advantages of expecting performance, the performance complement and common gains between different composition materials can also be achieved.Its hardness is high, by force
Degree and good toughness, while having both the excellent performances such as wear-resisting, heat-resisting, corrosion-resistant.On this basis, it is used for different products
It is required that the material for having different physics and chemical speciality can be obtained by being changed to the design of hard alloy ingredient, simultaneously
Using modern powder metallurgical technique, cemented carbide powder can be produced and be processed into various shape and size, can be met well
The application requirement of the overwhelming majority.
The preparation of hard alloy be one from powder to block again to prepared due to different requirements referred to as different shape,
The complex techniques process of the alloy product of size and performance.By the development of many decades, the process for producing of hard alloy by
It is gradually mature.The links such as powder preparation, compression moulding and sintering are mainly passed through in the preparation of hard alloy, are led in preparation process to these
Want the technical controlling of link that will directly affect the various aspects of performance of final hard metal article.It is most common in industrial production at present
The method for preparing WC-Co powder is exactly that mechanical mixture mode-ball-milling method is used to mix hard phase and Binder Phase powder, pressure
Blank is made, then is heated to certain temperature (sintering temperature) into sintering furnace, and kept for the regular hour (soaking time), it is then cold
But get off, to obtain the cemented carbide material of required performance.(Bao Rui is easily good for macro Microwave Sintering Techniques in hard alloy to document
Application [J] China YouSe Acta Metallurgica Sinica in preparation, 2014,24 (06): 1544-1561.) report a kind of use microwave burning
Knot technology prepares the preparation method of hard alloy, outlines current situation and microwave burning that Microwave Sintering Techniques prepare hard alloy
The problem of bond hard alloy.But in temperature-rise period, the transmittance process of energy is restricted by the coefficient of heat conduction, and
And the phenomenon that easily causes that temperature distribution is non-uniform, it is unfavorable for the raising of hard metal article performance.And patent (Zhao Zhankui, grandson
Happy front yard, the method that a kind of discharge plasma sintering of Wang Ming handle of the Big Dipper prepares bulk amorphous alloys:, CN105039761A [P] .2015.)
A kind of method that discharge plasma sintering prepares bulk amorphous alloys is reported, this method is based on discharge plasma sintering technique,
Interface bond strength height is prepared by reducing pulse duty factor, consistency is high, and amorphous characteristic keeps good agglomerate body amorphous
Alloy；Document (the nanostructure 9Cr-ODS steel of Lu Chenyang, Lv Zheng, Yu Liang, Liu Chun bright discharge plasma sintering technique preparation and
Its Micro-Structure Analysis [J] Rare Metals Materials and engineering, 2016,45 (02): 454-458.) report using electric discharge etc. from
Son sintering (SPS) technology replaces traditional heat and other static pressuring processes, prepares the nanostructure 9Cr dispersed oxide with ultra-fine grain
Strengthen (ODS) steel.
For this purpose, the present invention is based on the electroless cobalt plating packet tungsten carbide powders of cobalt salt activation to use discharge plasma sintering technique,
Using conductive tungsten carbide, cobalt and graphite jig by pulse current with high-power output, the electric current of output on the one hand can
Transmission heat is carried out by graphite jig, ecto-entad heats the sample in mold, and another aspect electric current is to be carbonized
Tungsten is that conductor passes through sample interior and generates heat, is heated from inside to outside to sample.To compared to conventional sintering mode, put
The whole process time of electric plasma agglomeration is short and high-efficient, and sample, which is heated evenly, to be easier to densify.
Summary of the invention
Goal of the invention: for the present Research of cemented carbide material, the present invention provide a kind of high evenness, high-compactness and
Pollute the preparation method of few WC/Co composite material.
Technical solution: in order to solve the above technical problems, the present invention adopts the following technical scheme that: a kind of high-compactness WC/Co
The preparation method of composite material hard alloy, includes the following steps:
1) tungsten carbide powder surface preparation: tungsten carbide powder is added in coarsening solution, is roughened under ultrasonic disperse effect；
Powder after roughening, which is added in activating solution under ultrasonic disperse environment, carries out immersion treatment；Then the powder impregnated is put into
Heated in crucible using batch-type furnace, in tungsten carbide powder Surface Creation metallic cobalt, obtains tungsten carbide activation powder；
2) tungsten carbide powder surface coats: by the tungsten carbide activation powder after roughening, cobalt salt activating pretreatment in change
It learns and carries out plating reaction in plating solution, observation has a large amount of bubbles to generate, and when bubble no longer generates, reaction stops, and solution is carried out
Filtering, is washed with deionized powder and dries, and obtains the carbonization tungsten composite powder that coating surface has uniform cobalt layers；
3) sintering of tungsten-cobalt carbide composite material: the carbonization tungsten composite powder that step 2) obtains is fitted into graphite jig
It is compacted, and places pressure head to complete mold assembling, mold is put into discharge plasma sintering furnace and is vacuumized later
Alloy powder is obtained, alloy powder is sintered molding in discharge plasma sintering furnace, after, close power supply and cooling
To room temperature, sample is taken out up to high-compactness WC/Co composite material hard alloy.
Wherein, the granularity of tungsten carbide powder is 3~5 μm in step 1).
Wherein, in step 1), tungsten carbide powder is added by the useful load of 20~500g/L into coarsening solution and is carried out slightly
Change, the coarsening solution is hydrofluoric acid-nitric acid solution, and the volume ratio of the hydrofluoric acid and nitric acid is 3:2.
Wherein, in step 1), the ultrasonic frequency is 30~40kHz, and ultrasonic power is 100~150W.
Wherein, in step 1), the activating solution is cobaltous sulfate-sodium hypophosphite solution, and group becomes Cobalt monosulfate heptahydrate 40
~50g/L, a hydration 40~50g/L of sodium hypophosphite, soaking time is 30~120min.
Wherein, in step 1), the heating rate of the batch-type furnace is 5~10 DEG C/min, heat treatment temperature is 160~
220 DEG C, soaking time is 60~120min.
Wherein, in step 2), the group of chemical plating fluid becomes Cobalt monosulfate heptahydrate 30-50g/L, a hydration sodium hypophosphite
30-50g/L, trisodium citrate dihydrate 50-70g/L and boric acid 20-30g/L.
Wherein, in step 2), system pH control occurs for the chemical plating fluid phase reaction in 9-12, and chemical plating fluid is set
Heating and mechanical stirring in water-bath, at 70-90 DEG C, stirring rod revolving speed is 300-500r/min for bath temperature control, when plating
Between be 5-15min.
Wherein, in step 3), alloy powder heating speed in discharging plasma sintering equipment is 50 DEG C/min-
150 DEG C/min, pressure 50MPa-100MPa.
Wherein, in step 3), holding temperature is 1300 DEG C -1500 DEG C after the sintering alloy powder, and soaking time is
3min-10min。
Wherein, in step 3), the quality of acquired alloy powder is 5-10g.
It is further preferable that in step 3), alloy powder heating speed in discharging plasma sintering equipment is 100 DEG C/
Min, pressure 70MPa.
It is further preferable that holding temperature is 1400 DEG C after sintering alloy powder, soaking time 5min in step 3).
The utility model has the advantages that obtaining high-compactness, high uniform WC/Co composite material hard alloy the present invention provides a kind of
Technology of preparing.Make carbide powder surface coat one layer of uniform metallic cobalt using chemical plating method, and powder is put
Electric plasma agglomeration, is prepared WC/Co composite material hardmetal samples and is heated evenly and be easier to densify.Preparation process operation
Simply, the time is short and high-efficient, and pollution is less and at low cost, and the composite material consistency of preparation is high, can be used as alloy material, magnetism
Material etc. is applied to the fields such as mine tool, building, aviation machine.
Detailed description of the invention
Fig. 1 be cobalt content be respectively fracture apperance result after 11wt% cobalt coated tungsten carbide powder sintering ((Fig. 1 a) low power and
(Fig. 1 b) high power).
Specific embodiment
The following are the preferred embodiment of the present invention, for explaining only the invention, and is not intended to limit the present invention, and by this
Illustrate that made improvement belongs to the range that appended claims of the present invention are protected.
Tungsten carbide powder, that is, WC powder buys the WC powder produced in Hebei province Nangong City Plain alloy material Co., Ltd.
Embodiment 1
A kind of preparation method of high-compactness WC/Co composite material hard alloy is present embodiments provided, preparation step is such as
Under:
(1) taking average granularity is 5 μm of WC powder 2g, and WC powder is added in coarsening solution hydrofluoric acid-nitric acid solution, super
It is roughened under sound peptizaiton, wherein hydrofluoric acid concentration 60ml/L, concentration of nitric acid 40ml/L, ultrasonic frequency 30kHz,
Ultrasonic power is 100W, by powder filtering drying after roughening be put into activating solution cobaltous sulfate-sodium hypophosphite solution with roughening
It is impregnated under the identical ultrasonic disperse environment of process, Cobalt monosulfate heptahydrate content is 40g/L, a hydration hypophosphorous acid in activating solution
Sodium content is 40g/L, soaking time 60min；Then the powder impregnated is put into crucible and is heated using batch-type furnace
Processing, heating rate is 10 DEG C/min when heating, and heat treatment temperature is 180 DEG C, keeps the temperature 120mim, obtains activation powder；It will
Powder after activation is put into prepared chemical plating fluid, the composition of chemical plating fluid are as follows: Cobalt monosulfate heptahydrate 30g/L, a hydration
Sodium hypophosphite 40g/L, trisodium citrate dihydrate 70g/L, boric acid 25g/L, pH value are adjusted to 9, and bath temperature is controlled at 70 DEG C, is stirred
Mixing stick revolving speed is 350r/min, plating time 15min.Powder after chemical plating is filtered and dried, obtaining coating surface has
The diamondite powder of uniform cobalt metal.
2) alloy powder that weighing 10g step 1) obtains, which is fitted into graphite jig, is compacted, and places pressure head to complete
Mold, is put into discharge plasma sintering furnace later and is evacuated to 10Pa hereinafter, beginning to warm up later by mold assembling,
Heating speed in discharge plasma sintering furnace is 100 DEG C/min, and pressure 70Mpa keeps the temperature 5min after being heated to 1400 DEG C,
Then cool down with furnace.After sample is taken out, graphite paper is removed in two sides and side polishing, and is polished, and it is equal to obtain high-compactness
Even WC/Co composite material hard alloy.
Embodiment 2
A kind of preparation method of high-compactness WC/Co composite material hard alloy is present embodiments provided, preparation step is such as
Under:
1) taking average granularity is 3 μm of WC powder 2g, and tungsten carbide powder is added in coarsening solution, under ultrasonic disperse effect
Roughening, hydrofluoric acid concentration 60ml/L, concentration of nitric acid 40ml/L, ultrasonic frequency 40kHz, ultrasonic power 120W.
Powder filtering drying after roughening is put into cobaltous sulfate-sodium hypophosphite activating solution in ultrasonic disperse environment identical with coarsening process
Under impregnated, in activating solution Cobalt monosulfate heptahydrate content be 50g/L, one hydration sodium hypophosphite content be 40g/L, soaking time
For 120min.Then the powder impregnated is put into crucible and is heated using batch-type furnace, heating rate is 5 when heating
DEG C/min, heat treatment temperature is 160 DEG C, keeps the temperature 60min, obtains activation powder；Pretreated powder is put into prepared
In chemical plating fluid, Cobalt monosulfate heptahydrate 50g/L, hydration a sodium hypophosphite 45g/L, trisodium citrate dihydrate 50g/L, boric acid 25g/
L, pH value are adjusted to 11, and at 80 DEG C, stirring rod revolving speed is 300r/min, plating time 5min for bath temperature control.It will be chemical
Powder after plating is filtered and is dried, and obtains the diamondite powder that coating surface has uniform cobalt metal.
2) weighing 10g alloy powder, which is fitted into graphite jig, is compacted, and places pressure head to complete mold assembling.By mould
Tool is put into discharge plasma sintering furnace and is evacuated to 10Pa hereinafter, beginning to warm up later, discharge plasma sintering furnace
Middle heating speed is 50 DEG C/min, and pressure 100Mpa keeps the temperature 10min, then cools down with furnace after being heated to 1300 DEG C.By sample
After taking-up, graphite paper is removed in two sides and side polishing, and is polished, and it is hard to obtain the uniform WC/Co composite material of high-compactness
Matter alloy.
Embodiment 3
A kind of preparation method of high-compactness WC/Co composite material hard alloy is present embodiments provided, preparation step is such as
Under:
1) taking average granularity is 4 μm of WC powder 2g, and tungsten carbide powder is added in coarsening solution, under ultrasonic disperse effect
Roughening, hydrofluoric acid concentration 60ml/L, concentration of nitric acid 40ml/L, ultrasonic frequency 35kHz, ultrasonic power 150W.
Powder filtering drying after roughening is put into cobaltous sulfate-sodium hypophosphite activating solution in ultrasonic disperse environment identical with coarsening process
Under impregnated, in activating solution Cobalt monosulfate heptahydrate content be 50g/L, one hydration sodium hypophosphite content be 50g/L, soaking time
For 30min.Then the powder impregnated is put into crucible and is heated using batch-type furnace, heating rate is 8 when heating
DEG C/min, heat treatment temperature is 220 DEG C, keeps the temperature 100min, obtains activation powder；Powder after cobalt salt activating pretreatment is put into
In prepared chemical plating fluid, Cobalt monosulfate heptahydrate 30g/L, hydration sodium hypophosphite 30g/L, a trisodium citrate dihydrate 60g/L,
Boric acid 20g/L, pH value are adjusted to 10, and at 90 DEG C, stirring rod revolving speed is 500r/min for bath temperature control, and plating time is
15min.Powder after chemical plating is filtered and dried, the diamondite powder that coating surface has uniform cobalt metal is obtained.
2) weighing 10g alloy powder, which is fitted into graphite jig, is compacted, and places pressure head to complete mold assembling.By mould
Tool is put into discharge plasma sintering furnace and is evacuated to 10Pa hereinafter, beginning to warm up later.Discharge plasma sintering furnace
Middle heating speed is 150 DEG C/min, and pressure 50Mpa keeps the temperature 3min, then cools down with furnace after being heated to 1500 DEG C.By sample
After taking-up, graphite paper is removed in two sides and side polishing, and is polished, and it is hard to obtain the uniform WC/Co composite material of high-compactness
Matter alloy.
Embodiment 4
A kind of preparation method of high-compactness WC/Co composite material hard alloy is present embodiments provided, preparation step is such as
Under:
1) taking average granularity is 5 μm of WC powder 2g, and tungsten carbide powder is added in coarsening solution, under ultrasonic disperse effect
Roughening, hydrofluoric acid concentration 60ml/L, concentration of nitric acid 40ml/L, ultrasonic frequency 30kHz, ultrasonic power 100W.
Powder filtering drying after roughening is put into cobaltous sulfate-sodium hypophosphite activating solution in ultrasonic disperse environment identical with coarsening process
Under impregnated, in activating solution Cobalt monosulfate heptahydrate content be 45g/L, one hydration sodium hypophosphite content be 45g/L, soaking time
For 80min.Then the powder impregnated is put into crucible and is heated using batch-type furnace, heating rate is 10 when heating
DEG C/min, heat treatment temperature is 200 DEG C, keeps the temperature 80min, obtains activation powder；Powder after cobalt salt activating pretreatment is put into
In prepared chemical plating fluid, Cobalt monosulfate heptahydrate 40g/L, hydration sodium hypophosphite 50g/L, a trisodium citrate dihydrate 60g/L,
Boric acid 30g/L, pH value are adjusted to 12, and at 80 DEG C, stirring rod revolving speed is 400r/min for bath temperature control, and plating time is
10min.Powder after chemical plating is filtered and dried, the diamondite powder that coating surface has uniform cobalt metal is obtained.
2) weighing 10g alloy powder, which is fitted into graphite jig, is compacted, and places pressure head to complete mold assembling.By mould
Tool is put into discharge plasma sintering furnace and is evacuated to 10Pa hereinafter, beginning to warm up later, is sintered in discharge plasma
Stove heating speed is 100 DEG C/min, and pressure 50Mpa keeps the temperature 10min, then cools down with furnace after being heated to 1400 DEG C.By sample
After taking-up, graphite paper is removed in two sides and side polishing, and is polished, and it is hard to obtain the uniform WC/Co composite material of high-compactness
Matter alloy.
Comparative example
1) the pure WC powder that average granularity is 3 μm and the pure metal cobalt powder that average grain diameter is 500nm are taken, respectively down payment
Mass ratio 0wt%, 5wt%, 11wt% and the 17wt% for belonging to Co are put into agate mortar, while dehydrated alcohol is added, with grinding
Pestle carries out wet-milling with certain speed, then duration 8h is dried to obtain Co-cladded wolfram carbide alloy powder.
2) weighing 10g alloy powder, which is fitted into graphite jig, is compacted, and places pressure head to complete mold assembling.By mould
Tool is put into sintering cavity and is evacuated to 10Pa hereinafter, beginning to warm up later.Heating speed is 50 DEG C/min, and pressure is
100MPa.10min is kept the temperature after being heated to 800 DEG C, is then cooled down with furnace.After sample is taken out, stone is removed in two sides and side polishing
Black paper, and polished, obtain WC/Co composite material hard alloy.
Experimental example
By Examples 1 to 4, we show that embodiment 2 is most preferred embodiment, we are by the mechanical mixture mode of embodiment 5
The performance for obtaining different cobalt content alloys from the chemical plating mode of most preferred embodiment 2 compares again.
Table 1 be embodiment 5 mechanical mixture mode with according to 2 chemical plating of embodiment, two kinds of processes cobalt content difference
Under conditions of the Vickers hardness and the relative density table of comparisons of the WC/Co cemented carbide powder powder sintered compact that prepare, wherein embodiment 2
Plating process in tungsten-carbide powder quality 2g, then reach the composite powder that cobalt content is 5wt%, 11wt% and 17wt%
Cobalt sulfate additional amount is respectively 2.1ml, 4.9ml, 8.2ml.Calculation formula is as follows:
V-cobalt sulfate additional amount/ml；W-cobalt content/%；M-tungsten carbide quality/g.
It can be seen that tungsten carbide hardness and consistency when soap-free emulsion polymeization mutually adds are all lower, with the increase of cobalt content, chemistry
The hardness of the cemented carbide sintered body of depositing process preparation is up to 17.5Gpa, and hard alloy prepared by mechanical mixture mode is burnt
The hardness of knot body is about 16.4Gpa；The relative density of the cemented carbide sintered body of chemical plating process preparation is about
99%, the relative density of the cemented carbide sintered body of mechanical mix techniques preparation is about 93%.This illustrates chemical plating process
Effectively increase the hardness and consistency of cemented carbide sintered body.
The Vickers hardness and the relative density table of comparisons of 1 WC/Co composite material of table
Claims (10)
1. a kind of preparation method of high-compactness WC/Co composite material hard alloy, which comprises the steps of:
1) tungsten carbide powder surface preparation: tungsten carbide powder is added in coarsening solution, is roughened under ultrasonic disperse effect；Roughening
Powder afterwards, which is added in activating solution under ultrasonic disperse environment, carries out immersion treatment；Then the powder impregnated is put into crucible
It is middle to be heated using batch-type furnace, in tungsten carbide powder Surface Creation metallic cobalt, obtain tungsten carbide activation powder；
2) tungsten carbide powder surface coats: by the tungsten carbide activation powder after roughening, cobalt salt activating pretreatment in chemical plating
Plating reaction is carried out in liquid, observation has a large amount of bubbles to generate, and when bubble no longer generates, reaction stops, solution is filtered,
Powder is washed with deionized and dries, obtains the carbonization tungsten composite powder that coating surface there are uniform cobalt layers；
3) sintering of tungsten-cobalt carbide composite material: the carbonization tungsten composite powder that step 2 obtains is fitted into graphite jig and is carried out
Compacting, and pressure head is placed to complete mold assembling, mold is put into discharge plasma sintering furnace later and vacuumizes to obtain
Alloy powder, alloy powder are sintered molding in discharge plasma sintering furnace, after, it closes power supply and is cooled to room
Temperature takes out sample up to high-compactness WC/Co composite material hard alloy.
2. the preparation method of high-compactness WC/Co composite material hard alloy according to claim 1, which is characterized in that
The granularity of tungsten carbide powder is 3 ~ 5 μm in step 1).
3. the preparation method of high-compactness WC/Co composite material hard alloy according to claim 1, which is characterized in that
In step 1), tungsten carbide powder is added by the useful load of 20 ~ 500g/L and is roughened into coarsening solution, the coarsening solution is
The volume ratio of hydrofluoric acid-nitric acid solution, the hydrofluoric acid and nitric acid is 3:2.
4. the preparation method of high-compactness WC/Co composite material hard alloy according to claim 1, which is characterized in that
In step 1), the ultrasonic frequency is 30 ~ 40kHz, and ultrasonic power is 100 ~ 150W.
5. the preparation method of high-compactness WC/Co composite material hard alloy according to claim 1, which is characterized in that
In step 1), the activating solution is cobaltous sulfate-sodium hypophosphite solution, and group becomes 40 ~ 50g/L of Cobalt monosulfate heptahydrate, a hydration
40 ~ 50g/L of sodium hypophosphite, soaking time are 30 ~ 120min.
6. the preparation method of high-compactness WC/Co composite material hard alloy according to claim 1, which is characterized in that
In step 1), the heating rate of the batch-type furnace is 5 ~ 10oC/min, heat treatment temperature are 160 ~ 220 DEG C, soaking time
For 60 ~ 120min.
7. the preparation method of high-compactness WC/Co composite material hard alloy according to claim 1, which is characterized in that
In step 2, the group of chemical plating fluid becomes Cobalt monosulfate heptahydrate 30-50g/L, a hydration sodium hypophosphite 30-50g/L, two hydrations
Sodium citrate 50-70g/L and boric acid 20-30 g/L.
8. the preparation method of high-compactness WC/Co composite material hard alloy according to claim 1, which is characterized in that
In step 2, system pH control occurs for the chemical plating fluid phase reaction in 9-12, and chemical plating fluid is placed in water-bath and is heated
And mechanical stirring, at 70-90 DEG C, stirring rod revolving speed is 300-500 r/min, plating time 5-15min for bath temperature control.
9. the preparation method of high-compactness WC/Co composite material hard alloy according to claim 1, which is characterized in that
In step 3), alloy powder heating speed in discharging plasma sintering equipment is 50 DEG C/min-150 DEG C/min, pressure
Power is 50MPa-100MPa.
10. the preparation method of high-compactness WC/Co composite material hard alloy according to claim 1, which is characterized in that
In step 3), holding temperature is 1300 DEG C -1500 DEG C after the sintering alloy powder, soaking time 3min-10min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811310911.9A CN109338197A (en) | 2018-11-06 | 2018-11-06 | A kind of preparation method of high-compactness WC/Co composite material hard alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811310911.9A CN109338197A (en) | 2018-11-06 | 2018-11-06 | A kind of preparation method of high-compactness WC/Co composite material hard alloy |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109338197A true CN109338197A (en) | 2019-02-15 |
Family
ID=65313967
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811310911.9A Pending CN109338197A (en) | 2018-11-06 | 2018-11-06 | A kind of preparation method of high-compactness WC/Co composite material hard alloy |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109338197A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111560532A (en) * | 2020-04-10 | 2020-08-21 | 河海大学 | Preparation method and application of novel shield tunneling machine scraper |
| CN111850370A (en) * | 2020-07-31 | 2020-10-30 | 河海大学 | Preparation method of coarse-grain WC-Co hard alloy |
| CN111961941A (en) * | 2020-09-02 | 2020-11-20 | 四川大学 | Preparation method of superfine hard alloy cutter material |
| CN112063871A (en) * | 2020-09-02 | 2020-12-11 | 四川大学 | Preparation method of coarse-particle hard alloy |
| CN113174504A (en) * | 2021-04-06 | 2021-07-27 | 杭州科技职业技术学院 | High-wear-resistance Ti (C, N) -based metal ceramic cutter material and preparation method thereof |
| CN113774264A (en) * | 2021-09-16 | 2021-12-10 | 中交隧道工程局有限公司 | Preparation method of coarse-grain WC-Co-X hard alloy based on addition of ultrafine powder |
| CN115717227A (en) * | 2022-11-17 | 2023-02-28 | 湖南人文科技学院 | Metal-coated WC hard alloy coating and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104232967A (en) * | 2014-10-10 | 2014-12-24 | 台州学院 | Method for preparing low binder phase wolfram carbide hard alloy |
| CN107868948A (en) * | 2017-12-01 | 2018-04-03 | 河海大学 | A kind of method of the chemical plating cobalt coated tungsten carbide based on cobalt salt activation |
-
2018
- 2018-11-06 CN CN201811310911.9A patent/CN109338197A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104232967A (en) * | 2014-10-10 | 2014-12-24 | 台州学院 | Method for preparing low binder phase wolfram carbide hard alloy |
| CN107868948A (en) * | 2017-12-01 | 2018-04-03 | 河海大学 | A kind of method of the chemical plating cobalt coated tungsten carbide based on cobalt salt activation |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111560532A (en) * | 2020-04-10 | 2020-08-21 | 河海大学 | Preparation method and application of novel shield tunneling machine scraper |
| CN111850370A (en) * | 2020-07-31 | 2020-10-30 | 河海大学 | Preparation method of coarse-grain WC-Co hard alloy |
| CN111961941A (en) * | 2020-09-02 | 2020-11-20 | 四川大学 | Preparation method of superfine hard alloy cutter material |
| CN112063871A (en) * | 2020-09-02 | 2020-12-11 | 四川大学 | Preparation method of coarse-particle hard alloy |
| CN111961941B (en) * | 2020-09-02 | 2021-02-12 | 四川大学 | Preparation method of superfine hard alloy cutter material |
| CN113174504A (en) * | 2021-04-06 | 2021-07-27 | 杭州科技职业技术学院 | High-wear-resistance Ti (C, N) -based metal ceramic cutter material and preparation method thereof |
| CN113774264A (en) * | 2021-09-16 | 2021-12-10 | 中交隧道工程局有限公司 | Preparation method of coarse-grain WC-Co-X hard alloy based on addition of ultrafine powder |
| CN113774264B (en) * | 2021-09-16 | 2022-08-26 | 中交隧道工程局有限公司 | Preparation method of coarse-grain WC-Co-X hard alloy based on adding superfine powder |
| CN115717227A (en) * | 2022-11-17 | 2023-02-28 | 湖南人文科技学院 | Metal-coated WC hard alloy coating and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109338197A (en) | A kind of preparation method of high-compactness WC/Co composite material hard alloy | |
| CN106424713B (en) | A kind of copper carbon composite and preparation method thereof | |
| CN103572087B (en) | The preparation method of boron carbide particles reinforced aluminum matrix composites | |
| CN104313380B (en) | A kind of step sintering prepares the method for high-compactness Nanograin Cemented Carbide | |
| CN109338172A (en) | A kind of 2024 aluminum matrix composites and preparation method thereof of high-entropy alloy enhancing | |
| CN106513621A (en) | Production method of graphene-aluminum composite | |
| CN113560540A (en) | Method for preparing ZTA ceramic particle reinforced high-chromium cast iron based wear-resistant composite material | |
| CN103302294B (en) | A kind of powder metallurgic method prepares the method for nanometer Cu@SiC/Cu based composites | |
| CN104209498A (en) | Preparing method of interface modification layer of ceramic particle enhanced metal base composite material | |
| CN103924119A (en) | Ultrahigh heat conduction graphite flake/copper composite material and preparation method thereof | |
| CN106583735B (en) | A method of it prepares with high-volume fractional diamond/copper composite material parts | |
| WO2011003225A1 (en) | Preparation method for silver metal oxide made electric contact material | |
| CN105950940A (en) | Nickel-plated cubic boron nitride composite material and preparation method thereof | |
| CN103820691B (en) | A kind of normal pressure-sintered preparation method of FeAl/TiC matrix material | |
| CN106399872A (en) | Preparation method for whisker carbon nanotube/aluminum matrix composite semisolid blank coated with aluminum oxide | |
| CN109576546A (en) | A kind of preparation method of the high-strength tenacity without magnetic Ti (C, N) based ceramic metal | |
| CN112705717A (en) | Preparation method of in-situ generated nitride enhanced high-entropy alloy-based powder material | |
| CN102826856A (en) | High-purity low-density ITO target material and preparation method thereof | |
| CN115044794A (en) | Cu- (Y) with excellent performance 2 O 3 -HfO 2 ) Alloy and preparation method thereof | |
| CN103484705B (en) | Method for preparing nano SiC/Cu-based composite material employing pressureless infiltration technique | |
| CN109513905A (en) | A kind of preparation method being surface-treated the iron-based composite wear-resistant part of ZTA particle enhanced steel | |
| CN109554564A (en) | A kind of preparation method of Amorphous Alloy Grain and carbon nanotube enhanced aluminium-based composite material | |
| CN109231990A (en) | A kind of preparation method of tungsten carbide-diamond composite | |
| CN102424967B (en) | Method for preparing intermetallic-compound-based composite material reinforced by in-situ nano ceramic particles | |
| CN108441668A (en) | A kind of silver tungsten contact material and preparation method 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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190215 |
|
| RJ01 | Rejection of invention patent application after publication |