CN105965026B - It is a kind of that the method for preparing nanometer MeC W powder is spray-dried with colloidal sol non-homogeneous phase deposition - Google Patents
It is a kind of that the method for preparing nanometer MeC W powder is spray-dried with colloidal sol non-homogeneous phase deposition Download PDFInfo
- Publication number
- CN105965026B CN105965026B CN201610558973.6A CN201610558973A CN105965026B CN 105965026 B CN105965026 B CN 105965026B CN 201610558973 A CN201610558973 A CN 201610558973A CN 105965026 B CN105965026 B CN 105965026B
- Authority
- CN
- China
- Prior art keywords
- powder
- mec
- nanometer
- carbide
- tungsten
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
Abstract
The present invention relates to a kind of preparation method of nano-carbide/tungsten composite powder, carbide particle ball milling modification is first obtained into the nano-carbide particle of favorable dispersibility homogeneous grain diameter, nano-carbide particle is added in tungsten salt solution again, regulation pH value of solution makes part nanometer tungsten form non-homogeneous phase deposition on carbide particle surface, add dispersant and thickener, effectively prevent carbide particle from settling and reuniting, form the suspension colloid that nano-carbide disperse is uniformly distributed in liquid;Then carry out fast spraying drying and prepare compound precursor, then precursor powder is calcined in nonoxidizing atmosphere, reduced in hydrogen atmosphere.Composite powder prepared by this method, carbide can be the one or more in ZrC, TiC, HfC, and content is 0.01 ~ 10%;Nano-carbide uniform particle Dispersed precipitate is in nanometer tungsten, and the size of carbide is 10 ~ 50nm, and the size of tungsten is 30 ~ 100nm, has good sintering activity.
Description
Technical field
The present invention relates to the preparation method of powdered metallurgical material, especially with powder modification-colloidal sol-non-homogeneous phase deposition-
The method that spray drying prepares nanometer MeC-W composite powders.
Background technology
Tungsten has high-melting-point, high heat conductance, low thermal coefficient of expansion, high anti-neutron irradiation ability and low sputtering raste etc. excellent
Different in nature energy, as a kind of critically important high-temperature material, is widely used in the fields such as nuclear energy, Aero-Space.But utilize traditional micron
Pure tungsten material prepared by level powder is after 2700 DEG C are sintered, and consistency is only 93 ~ 95%, and grain structure is thick(>100
μm), performance extreme difference.To eliminate high temperature sintering tungsten residual porosity, business typically using forging, rolling and is squeezed with pure tungsten material at present
Pressure etc. large deformation strengthen means, but the pure tungsten material after large deformation still suffer from tissue it is very thick, in threadiness orientation, it is tough crisp turn
The defects of temperature is high, recrystallization temperature is low, fragility is big.
In order to improve the performance of pure tungsten, researcher is by adding a small amount of carbide particle(MeC, HfC, ZrC etc.)Carefully
Change the black brittleness that the modes such as crystal grain overcome tungsten, reduce the ductile-brittle transition temperature of tungsten, obtained preferable effect.Japanese scholars are adopted
W- (0.25 ~ 0.8%) MeC is prepared with high-energy ball milling+high temperature insostatic pressing (HIP)+high temperature forging(Mass fraction)Material, the results showed that addition
Tungsten grain significantly refines after MeC, and ductile-brittle transition temperature reduces, and room temperature and elevated temperature strength, recrystallization temperature are significantly improved,
Neutron irradiation environment is simulated simultaneously, in 4He+600 DEG C, 3MeV in irradiation reaction device, He particle fluxes are 2 × 1024n/m2Condition
Under tested, the results showed that its vacancy defect concentration only has the 1/3 ~ 1/4 of traditional pure tungsten, shows good anti-neutron spoke
According to ability.Therefore, addition carbide second phase dispersion-strengtherning fine grain tungsten material has become a weight of current high temperature tungsten material
Want direction.But mechanical alloying/high-energy ball milling method prepares composite powder and there are problems that:Mechanical alloying, high energy ball
Foreign peoples's impurity can be introduced during mill, second phase particles easily form reunion in alloy grain boundaries in composite powder, weaken material
Performance;Meanwhile the powder of mechanical alloying is in lamellar, crystallized ability is very poor, it is difficult to prepares the exemplar of large-size.
To solve problem above, we are prepared for ultra-fine/nanometer using colloidal sol-spray drying-thermal reduction and activate tungsten powder,
Compared with mechanical alloying powder, the powder purity height of this method preparation, composition is uniform and sphericity is high, good moldability, simultaneously
Due to the addition of the active elements such as micro Ni, Co, Fe in powder, there is good sintering activity.This method was applied in 2010
Patent " preparation method of a kind of ultra-fine or nanometer activation tungsten powder "(The patent No.:ZL201010049432.3).But due to active member
Plain Ni brittle can reduce material property under neutron irradiation effect, while in sintering, there is what crystal grain was grown up to ask for pure tungsten powder
Topic, its grain size are more than more than 20 μm, it is difficult to prepare the fine grain tungsten material that grain size is less than 10 μm.Carbide particle is added to
It can preferably play a part of refining tungsten grain in tungsten, while improve the anti-neutron irradiation ability of tungsten, our to tungsten salt early stages
Middle addition ZrC/TiC particles, preparing ZrC/TiC by the method for colloidal sol-spray drying-thermal reduction strengthens fine grain tungsten material, and
Publish an article " Micro/nano composited tungsten on Journal of Nuclear Materials
material and its high thermal loading behavior”.By adding ZrC/TiC particle phases, the crystalline substance of tungsten
Grain is refined to less than 10 μm, while its anti-high heat load ability increases substantially.However, common dispersants produce in salting liquid
Electric double layer compressed, do not have dispersion effect, carbide particle easily produces reunion, segregation and sinking, causes carbide to exist
Alloy grain boundaries produce segregation, make its performance unstable.
The content of the invention
To solve the above problems, the homogeneous nanoscale of carbide particle ball milling modification prepared sizes is carbonized by the present invention first
Thing particle, improve its dispersiveness in the solution;Regulation solution ph makes nanometer tungsten be precipitated in carbide surface, improves W and MeC
Interfacial combined function;Further add dispersant and add haloduric thickener simultaneously, change the surface of MeC particles using dispersant
Current potential, the salt ion in thickener chelate solution, the two synergy prevent carbide particle from settling and reuniting, form nano-sized carbon
Compound disperse is dispersed in the suspension colloid in liquid.
The present invention nanometer MeC-W composite powder compositions be by mass percentage:MeC contents are 0.01-10%, surplus
For W.MeC can be ZrC, TiC, HfC etc..
To reach above-mentioned purpose, concrete scheme of the present invention is as follows:
(1)Powder modification processing is carried out to MeC powder using ball milling method first, ball milling modification technique is that ratio of grinding media to material is 1:
1~5:1, rotating speed is 100 ~ 300rad/s, and Ball-milling Time is 1 ~ 10h.
(2)Soluble tungsten salt is added into deionized water, it is 10 ~ 80mmol/L to control its concentration, is then added thereto
Modified nanometer MeC, the PH for adjusting solution is 10 ~ 12, and the dispersant for accounting for overall solution volume 0.01 ~ 10% is added after stirring, then
The thickener of solution gross mass 0.1 ~ 2% is added, forms stable sol.
(3)Colloidal sol is spray-dried, obtained composite precursor powder.
(4)By composite precursor powder at 150 ~ 500 DEG C, hydrogen, nitrogen, the nonoxidizing atmosphere environment such as ammonia, argon gas are decomposed
Middle calcining 1-5h.
(5)Powder after calcining is placed in reduction furnace and carries out two step hydrogen reductions.First step hydrogen reduction reduction temperature is 450
~ 650 DEG C, soaking time 2h;Second step hydrogen reduction temperature is 680 ~ 900 DEG C, and soaking time is 2 ~ 6h.
The advantages and positive effects of the present invention are embodied in:
(1)The present invention adds dispersant and thickener into tungsten salt solution, changes TiC particle surfaces electricity by dispersant
Position, thickener carry out chelation to salt ion, realize that even dispersion of the TiC particles in salting liquid is disperseed.
(2)MeC-W composite powder distributed components prepared by the present invention:Nanometer MeC particle even dispersions, which are distributed in, to be received
In rice tungsten powder, wherein nano-carbide particle size is 10 ~ 50nm, and the size of nano-tungsten powder is 30 ~ 100nm.
(3)MeC-W composite powders prepared by the present invention have good sintering activity:The granularity of composite powder is tiny
One, regulation solution ph makes nanometer tungsten be precipitated in carbide surface, and follow-up sintering can effectively be prevented by forming special nucleocapsid structure
During carbide particle grow up.This powder is especially suitable for preparing carbide dispersion-strengthened fine grain tungsten material.
(4)MeC-W composite powders prepared by the present invention are spherical in shape, have good mouldability.
Embodiment
Example 1:
By taking preparing nano 0.01wt%TiC-W composite powders as an example.
(1)0.009g nano TiC powder is taken, is 1 by ratio of grinding media to material:1st, rotating speed 100r/min, time 3h ball-milling technology pair
TiC is modified processing.
(2)1L deionized waters are measured, add 121.9g ammonium metatungstates thereto, stirring adds to dissolving then in solution
Enter 0.009gTiC, ammoniacal liquor is added dropwise, stir.
(3)0.1g sodium carboxymethylcelluloses are added into above-mentioned suspension, 0.01ml Tween-80s, stirring, it is steady to be formed
Determine colloid.
(4)Above-mentioned colloidal sol is spray-dried at 250 DEG C, wherein rotating speed of shower nozzle is 25000 revs/min, obtains forerunner
Body powder.
(5)By precursor powder at 150 DEG C, 4h is calcined in hydrogen environment.
(6)Powder after calcining is placed in reduction furnace, carries out two step hydrogen reductions.First step hydrogen reduction reduction temperature is
550 DEG C, soaking time 2h;Second step hydrogen reduction temperature is 740 DEG C, soaking time 6h, it is compound to obtain 0.01wt%MeC-W
Powder, oxygen content in power 0.24%, powder size 55nm.
Example 2:
By taking preparing nano 0.1wt%Ti-W composite powders as an example.
(1)0.09g nano TiCs are taken, are 2 by ratio of grinding media to material:1st, rotating speed 100r/min, time 5h ball-milling technology enter to TiC
Row modification.
(2)1L deionized waters are measured, add 121.9g ammonium metatungstates, stirring to the backward above-mentioned mixed solution of dissolving thereto
Middle addition 0.09gTiC, is added dropwise ammoniacal liquor, stirs.
(3)Enter to add 5g DTABs into above-mentioned suspension(CTAB), 0.5g sodium hydroxyethlcelluloses,
Stir to form stable colloid.
(4)Above-mentioned colloidal sol is spray-dried at 250 DEG C, wherein rotating speed of shower nozzle is 25000 revs/min.
(5)By precursor powder at 250 DEG C, 4h is calcined in hydrogen environment.
(6)Powder after calcining is placed in reduction furnace, carries out two step hydrogen reductions.First step hydrogen reduction reduction temperature is
In the range of 500 DEG C, soaking time 2h;Second step hydrogen reduction temperature is 780 DEG C, soaking time 4h.Obtain 0. 1wt%TiC-
W composite powders, oxygen content in power 0.14%, powder size 80nm.
Example 3:
By taking preparing nano 0.5wt%ZrC-W composite powders as an example.
(1)0.44g nanometer ZrC are taken, are 1 by ratio of grinding media to material:1st, rotating speed 300r/min, time 10h ball-milling technology enter to ZrC
Row modification.
(2)1L deionized waters are measured, add 136.3g ammonium paratungstates, stirring to the backward above-mentioned mixed solution of dissolving thereto
Middle addition 0.44g ZrC, are added dropwise ammoniacal liquor, stir.
(3)10mlPEG400 is added dropwise into above-mentioned suspension, 1g sodium carboxymethylcelluloses, is mixing uniformly to form stable glue
Body.
(4)Above-mentioned colloidal sol is spray-dried at 250 DEG C, wherein rotating speed of shower nozzle is 25000 revs/min.
(5)By precursor powder at 300 DEG C, 4h is calcined in hydrogen environment.
(6)Powder after calcining is placed in reduction furnace, carries out two step hydrogen reductions.First step hydrogen reduction reduction temperature controls
In the range of 600 DEG C, soaking time 2h;Second step hydrogen reduction temperature control is at 780 DEG C, soaking time 2.5h.Obtain 0.
1wt% ZrC-W composite powders, oxygen content in power 0.19%, powder size 45nm.
Example 4:
By taking preparing nano 1wt% ZrC-W composite powders as an example.
(1)0.89g nanometer ZrC are taken, are 3 by ratio of grinding media to material:1st, rotating speed 200r/min, time 5h, liquid-solid ratio 2;1 ball milling work
Skill carries out high-energy ball milling de-agglomerated to ZrC, and powder is placed in vacuum drying chamber after ball milling and is dried.
(2)1L deionized waters are measured, add 136.3g ammonium paratungstates thereto, stirring is to dissolving, then to above-mentioned mixing
0.89g ZrC are added in solution, ammoniacal liquor is added dropwise, stirs.
(3)0.15g carboxymethyl celluloses are added into above-mentioned suspension, 20mlPEG400, are mixing uniformly to form stabilization
Colloid.
(4)Above-mentioned colloidal sol is spray-dried at 250 DEG C, wherein rotating speed of shower nozzle is 25000 revs/min.
(5)By precursor powder at 400 DEG C, 4h is calcined in hydrogen environment.
(5)Powder after calcining is placed in reduction furnace, carries out two step hydrogen reductions.First step hydrogen reduction reduction temperature is
In the range of 650 DEG C, soaking time 2h;Second step hydrogen reduction temperature is 820 DEG C, soaking time 2h.Obtain 1wt% ZrC-W
Composite powder, oxygen content in power 0.23%, powder size 45nm.
Example 5:
By taking preparing nano 5wt%HfC-W composite powders as an example.
(1)4.65 g nanometer HfC are taken, are 3 by ratio of grinding media to material:1st, rotating speed 300r/min, time 10h, liquid-solid ratio 3;1 ball milling
Technique carries out high-energy ball milling de-agglomerated to HfC, and powder is placed in vacuum drying chamber after ball milling and is dried.
(2)1L deionized waters are measured, add 158.33g sodium tungstates thereto, stirring is molten then to above-mentioned mixing to dissolving
4.65 HfC are added in liquid, ammoniacal liquor is added dropwise, are stirred.
(3)50ml Tween-80s are added dropwise into above-mentioned suspension, 2 carboxymethyl celluloses, are mixing uniformly to form stable glue
Body.
(4)Above-mentioned colloidal sol is spray-dried at 250 DEG C, wherein rotating speed of shower nozzle is 25000 revs/min.
(5)By precursor powder at 350 DEG C, 4h is calcined in hydrogen environment.
(6)Powder after calcining is placed in reduction furnace, carries out two step hydrogen reductions.First step hydrogen reduction reduction temperature is
In the range of 600 DEG C, soaking time 2h;Second step hydrogen reduction temperature is 860 DEG C, soaking time 2.5h.Obtain 5wt% HfC
- W composite powders, oxygen content in power 0.19%, powder size 55nm.
Example 6:
By taking preparing nano 10wt% HfC-W composite powders as an example.
(1)9.3 g nanometer HfC are taken, are 3 by ratio of grinding media to material:1st, rotating speed 200r/min, time 10h, liquid-solid ratio 4;1 ball milling
Technique carries out high-energy ball milling de-agglomerated to HfC, and powder is placed in vacuum drying chamber after ball milling and is dried.
(2)1L deionized waters are measured, add 158.33g sodium tungstates thereto, stirring is molten then to above-mentioned mixing to dissolving
9.3 HfC are added in liquid, ammoniacal liquor is added dropwise, are stirred.
(3)100ml Tween-80s are added dropwise into above-mentioned suspension, 2g carboxymethyl celluloses, are mixing uniformly to form stable glue
Body.
(4)Above-mentioned colloidal sol is spray-dried at 250 DEG C, wherein rotating speed of shower nozzle is 25000 revs/min.
(5)By precursor powder at 400 DEG C, 4h is calcined in hydrogen environment.
(6)Powder after calcining is placed in reduction furnace, carries out two step hydrogen reductions.First step hydrogen reduction reduction temperature is
In the range of 600 DEG C, soaking time 2h;Second step hydrogen reduction temperature is 900 DEG C, soaking time 2.5h.Obtain 10wt%
HfC-W composite powders, oxygen content in power 0.14%, powder size 75nm.
Claims (8)
- A kind of 1. method that nanometer MeC-W powder is prepared with colloidal sol-non-homogeneous phase deposition-spray drying, it is characterised in that:Nanometer By mass percentage, MeC contents are 0.01-10% to MeC-W composite powders composition, and surplus W, wherein MeC are ZrC, TiC or HfC;Carbide particle ball milling modification is obtained into the Nano-Scaled Carbide particle of homogeneous grain diameter first, then by modified nanometer Carbide particle is added in the tungsten salt solution that concentration is 10 ~ 80mmol/L, and regulation pH value to 10 ~ 12 makes part nanometer tungsten in carbon Compound surface non-homogeneous phase deposition, then add dispersant, the salt-resistant type thickener with ehter bond and hydroxyl enters to nano-carbide Row surface is modified, and forms the suspension colloid that nano-carbide even dispersion is distributed in liquid;Colloid progress fast spraying is done The nanometer MeC-W composite powders that nano-carbide even dispersion is distributed in nano-tungsten powder are prepared after dry-- two step hydrogen reductions of calcining The particle size at end, wherein carbide is 10 ~ 50nm, and the particle size of nanometer tungsten is 30 ~ 100nm.
- A kind of 2. side that nanometer MeC-W powder is prepared with colloidal sol-non-homogeneous phase deposition-spray drying according to claim 1 Method, it is characterised in that:Micron order or nanoscale MeC powder are subjected to ball milling, Ball-milling Time is 1 ~ 10h, ratio of grinding media to material 1:1~5: 1, rotating speed is 100 ~ 300rad/s, obtains the nanometer MeC powder of homogeneous grain diameter.
- 3. the method according to claim 1 that nanometer MeC-W powder is prepared with colloidal sol-non-homogeneous phase deposition-spray drying, its It is characterised by:Described tungsten salt is sodium tungstate, ammonium paratungstate or ammonium metatungstate.
- 4. the method according to claim 1 that nanometer MeC-W powder is prepared with colloidal sol-non-homogeneous phase deposition-spray drying, its It is characterised by:It is the one or more in hydrochloric acid, acetic acid, ammoniacal liquor, sodium hydroxide to adjust soda acid used in pH value.
- 5. the method according to claim 1 that nanometer MeC-W powder is prepared with colloidal sol-non-homogeneous phase deposition-spray drying, its It is characterised by:Dispersant is the one or more in PEG400, Tween-80, DTAB, accounts for solution totality Long-pending 0.01 ~ 10%.
- 6. the method according to claim 1 that nanometer MeC-W powder is prepared with colloidal sol-non-homogeneous phase deposition-spray drying, its It is characterised by:The described salt-resistant type thickener with ehter bond and hydroxyl is methylcellulose, sodium hydroxyethlcellulose, hydroxypropyl One or more in methylcellulose, account for the 0.1 ~ 2% of solution gross mass.
- 7. the method according to claim 1 that nanometer MeC-W powder is prepared with colloidal sol-non-homogeneous phase deposition-spray drying, its It is characterised by:Described calcining heat is 150 ~ 500 DEG C, and soaking time is 1 ~ 5h, and calcination atmosphere is nonoxidizing atmosphere, is hydrogen Gas, nitrogen, argon gas decompose ammonia atmosphere.
- 8. the method according to claim 1 that nanometer MeC-W powder is prepared with colloidal sol-non-homogeneous phase deposition-spray drying, its It is characterised by:In two step hydrogen reductions, first step hydrogen reduction reduction temperature is 450 ~ 650 DEG C, soaking time 2h;Second step hydrogen is also Former temperature is 680 ~ 900 DEG C, and soaking time is 2 ~ 6h.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610558973.6A CN105965026B (en) | 2016-07-18 | 2016-07-18 | It is a kind of that the method for preparing nanometer MeC W powder is spray-dried with colloidal sol non-homogeneous phase deposition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610558973.6A CN105965026B (en) | 2016-07-18 | 2016-07-18 | It is a kind of that the method for preparing nanometer MeC W powder is spray-dried with colloidal sol non-homogeneous phase deposition |
Publications (2)
Publication Number | Publication Date |
---|---|
CN105965026A CN105965026A (en) | 2016-09-28 |
CN105965026B true CN105965026B (en) | 2018-02-16 |
Family
ID=56952551
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610558973.6A Expired - Fee Related CN105965026B (en) | 2016-07-18 | 2016-07-18 | It is a kind of that the method for preparing nanometer MeC W powder is spray-dried with colloidal sol non-homogeneous phase deposition |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN105965026B (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112570724B (en) * | 2020-12-11 | 2022-11-25 | 江西理工大学 | Preparation method of rare earth tungsten copper composite powder |
CN112958778B (en) * | 2021-02-02 | 2021-12-03 | 长沙微纳坤宸新材料有限公司 | Superplastic nano in-situ composite W-Cu material and preparation method thereof |
CN115323213B (en) * | 2022-09-23 | 2023-02-14 | 西安稀有金属材料研究院有限公司 | Multistage nano-structured carbide dispersion-strengthened molybdenum alloy and preparation method thereof |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5341397B1 (en) * | 1970-11-17 | 1978-11-02 | ||
CN102041421B (en) * | 2011-01-13 | 2012-11-07 | 中南大学 | High-tungsten content high-compactness fine-grain tungsten-copper material and preparation method thereof |
CN102350506A (en) * | 2011-10-31 | 2012-02-15 | 西南石油大学 | Preparation method of nano-structure WC-Co composite powder |
CN104630532B (en) * | 2015-02-10 | 2016-12-07 | 中南大学 | A kind of preparation method of carbide and rare earth oxide complex intensifying carefully brilliant tungsten material |
-
2016
- 2016-07-18 CN CN201610558973.6A patent/CN105965026B/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
CN105965026A (en) | 2016-09-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN104630532B (en) | A kind of preparation method of carbide and rare earth oxide complex intensifying carefully brilliant tungsten material | |
Zhang et al. | Preparation of copper nanoparticles by chemical reduction method using potassium borohydride | |
Songping et al. | Preparation of micron size copper powder with chemical reduction method | |
CN105518169B (en) | A kind of preparation method of rare earth oxide dispersion-strengtherning fine grain tungsten material | |
CN106001545A (en) | Preparation method of nano carbide-tungsten composite powder | |
CN105965026B (en) | It is a kind of that the method for preparing nanometer MeC W powder is spray-dried with colloidal sol non-homogeneous phase deposition | |
Hu et al. | Microstructure refinement and mechanical properties improvement in the W-Y2O3 alloys via optimized freeze-drying | |
CN106216705B (en) | A kind of preparation method of 3D printing fine grained simple substance globular metallic powder | |
CN106077695B (en) | A kind of preparation method of high-copper tungsten copper nano composite powder | |
CN101428345B (en) | Method of manufacturing ultrafine molybdenum powder or ultrafine tungsten powder surface clad metal copper | |
CN105238983A (en) | Rare-earth oxide doped tungsten-copper alloy composite material and preparation method thereof | |
CN106636834B (en) | Inhibit the method and ultra-fine cemented carbide preparation process that hard alloy crystal grain is grown up | |
Lin et al. | Effect of Cu, Ni on the property and microstructure of ultrafine WC-10Co alloys by sinter–hipping | |
CN113106281B (en) | Preparation method of yttrium oxide doped tungsten-based nano composite powder and alloy thereof | |
CN101259538A (en) | Preparation of micron/nano-scale high purity tungsten powder | |
CN106011511B (en) | A kind of titanium carbide strengthens the preparation method of fine grain tungsten material | |
Li et al. | Fabrication and microstructure of W-Cu composites prepared from Ag-coated Cu powders by electroless plating | |
CN108788173B (en) | Hydrothermal preparation method of superfine yttrium oxide doped tungsten composite powder | |
CN102251130B (en) | Preparation method of superfine grain cemented carbide | |
CN107900373B (en) | Superfine W-Cu composite powder and preparation method thereof | |
CN106994517A (en) | A kind of preparation method of high-thermal-conductivity low-expansibility W Cu encapsulating materials | |
CN106799500B (en) | The preparation method of ultrafine tungsten powder | |
CN108772569B (en) | Hydrothermal preparation method of superfine nano tungsten powder | |
CN107127334B (en) | A kind of nano particle and preparation method thereof of carbide-metal nucleocapsid structure | |
Yu et al. | Synthesis of YSZ@ Ni nanoparticle by modified electroless plating process |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180216 Termination date: 20200718 |
|
CF01 | Termination of patent right due to non-payment of annual fee |