CN103060593A - Preparation method of porous nickel titanium shape memory alloy - Google Patents
Preparation method of porous nickel titanium shape memory alloy Download PDFInfo
- Publication number
- CN103060593A CN103060593A CN2013100308802A CN201310030880A CN103060593A CN 103060593 A CN103060593 A CN 103060593A CN 2013100308802 A CN2013100308802 A CN 2013100308802A CN 201310030880 A CN201310030880 A CN 201310030880A CN 103060593 A CN103060593 A CN 103060593A
- Authority
- CN
- China
- Prior art keywords
- porous nickel
- pore
- preparation
- powder
- forming material
- 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
- 229910001000 nickel titanium Inorganic materials 0.000 title claims abstract description 33
- HZEWFHLRYVTOIW-UHFFFAOYSA-N [Ti].[Ni] Chemical compound [Ti].[Ni] HZEWFHLRYVTOIW-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910001285 shape-memory alloy Inorganic materials 0.000 title abstract 7
- 238000005245 sintering Methods 0.000 claims abstract description 31
- 239000000843 powder Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000010936 titanium Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000005303 weighing Methods 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 41
- 239000000203 mixture Substances 0.000 claims description 6
- 238000001149 thermolysis Methods 0.000 claims description 6
- 239000011812 mixed powder Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 abstract description 21
- 239000011148 porous material Substances 0.000 abstract description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 12
- 150000003839 salts Chemical class 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract 3
- 238000001816 cooling Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 238000002490 spark plasma sintering Methods 0.000 description 13
- 238000005516 engineering process Methods 0.000 description 9
- 229910052719 titanium Inorganic materials 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000012620 biological material Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052923 celestite Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001902 propagating effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000002076 thermal analysis method Methods 0.000 description 2
- 238000005842 biochemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- KHYBPSFKEHXSLX-UHFFFAOYSA-N iminotitanium Chemical compound [Ti]=N KHYBPSFKEHXSLX-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000003913 materials processing Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- -1 stupalith Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
Images
Abstract
The invention provides a preparation method of a porous nickel titanium shape memory alloy, which comprises the following steps: determining volume V total porosity of the obtained porous nickel titanium shape memory alloy according to demands, calculating the mass m of every raw material according to the formula, weighing Ni powder, Ti powder and a pore forming agent, and mixing for 30-150 minutes; carrying out discharge plasma sintering at 750-1100 DEG C for 8-30 minutes to obtain a sintered body; and after cooling to room temperature, infusing with water for 30-180 minutes until the pore forming agent is completely dissolved or reacted, thereby obtaining the porous nickel titanium shape memory alloy. The porosity and pore size are controlled through and volume percent, and the reinforced sintering action of SPS and the removal of the soluble salt pore forming agent are utilized to implement the preparation of the controllable-pore-structure porous nickel titanium shape memory alloy. The porosity of the porous nickel titanium shape memory alloy is 40-70%, and the pore size is 75-1000 mu m. The porous nickel titanium shape memory alloy has the characteristics of low cost, controllable pore structure, and simple, stable and efficient technique, and can implement industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of porous nickel-titanium marmem, belong to the porous biomaterial technical field.
Background technology
Porous nickel-titanium marmem (the atomic ratio alloy such as porous Ni-Ti) has good shape memory effect, pseudoelasticity, biocompatibility and mechanical property preferably, has wide application market in fields such as biomedicine, biomaterials.The preparation method of present known niti-shaped memorial alloy mainly is element powders mixed-sintering method, pre-alloyed powder sintering process and self propagating high temperature synthesis method.Powder metallurgic method exists pore structure control difficulty, the not high deficiency of goods porosity, although self propagating high temperature synthesis method technique is simple, has the deficiency of technology stability control and goods pore structure control difficulty.
Discharge plasma sintering (Spark plasma sintering, SPS) is a kind of new technology of preparation material, has the characteristics such as heat-up rate is fast, sintering time weak point, pressure sintering, can be used to prepare metallic substance, stupalith, matrix material etc.
The pore-forming material technology is a kind of method that adopts in the powder metallurgy porous material preparation, and removeability is the important character of pore-forming material, pore-forming material commonly used has two classes at present, the one, and have and remove in the sintering process, such as the volatile salt that can decompose and burn and organism etc.; The 2nd, remove behind the sintering, such as salt of water soluble or organic solvent etc.
Summary of the invention
The present invention combines pore-forming material technology and SPS technology, the pore-forming material of choosing high-melting-point, water-soluble (or water-disintegrable) and can stable existence when the SPS sintering, utilize the pore structure of pore-forming material control goods, it is efficiently intensified-sintered to utilize SPS to carry out, overcome the deficiencies such as existing technology of preparing pore structure regulation and control are difficult, technique is unstable, had short flow process, low cost, high efficiency characteristics.
The present invention realizes by following technical proposal: a kind of preparation method of porous nickel-titanium marmem, and following each step of process:
(1) elder generation determines the volume V of gained porous nickel-titanium marmem on demand
AlwaysAnd porosity, calculate each raw materials quality m by following formula again after, weighing Ni powder, Ti powder and pore-forming material, and mix 30~150min:
In the formula, V represents volume; ρ represents density; M represents quality; N represents amount of substance; Wherein
,
,
,
(2) mixed powder that step (1) is obtained is to carry out discharge plasma sintering 8~30min under 750~1100 ℃ the condition in temperature, obtains sintered compact;
(3) the sintered compact cool to room temperature that step (2) is obtained, according to the solubleness of solubility pore-forming material in water or the principle of hydrolyzable pore-forming material and water reaction, then water brews 30~180min, pore-forming material is dissolved fully or react, namely obtain porosity and be 40~70%, the aperture is the porous nickel-titanium marmem of 75~1000 μ m.
The porosity of the porous nickel-titanium marmem of described step (1) is 40~70%.
The Ni Powder Particle Size of described step (1) is that 21~44 μ m, purity are 98.8~99.9%.
The Ti Powder Particle Size of described step (1) is that 21~44 μ m, purity are 99.5~99.9%.
The fusing point of described step (1) pore-forming material is higher than 750 ℃, and thermolysis can not occur in the SPS sintering range, and granularity is 75~1000 μ m, purity 〉=98%.
Described pore-forming material is SrSO
4, BaC
2Or K
2CO
3
The present invention be with dystectic water-soluble (solution) property salt as pore-forming material, and carry out discharge plasma sintering after nickel, ti powder are mixed, use again the method for water-soluble (solution) to process and remove pore-forming material, realize the porous nickel-titanium marmem preparation that pore structure is controlled.The principle of its invention is:
1, discharge plasma sintering (SPS) principle: discharge plasma sintering be a kind of fast, the materials processing new preparation technology of low temperature, energy-saving and environmental protection.This technology is that the pressure-bearing conductive die is added the controllable pulse electric current, namely between the pressurization powder granule, directly pass into the DC pulse electric energy, cause particle to give birth to heat by joule heating and reach in granule interior and the surperficial temperature difference that produces, realize formation, expansion and the densification of sintering neck, intensified-sintered effect is arranged.
2, the thermostability of pore-forming material: pore-forming material should have good thermostability in sintering range, does not namely occur to decompose stably in sintering process to exist.The thermostability of pore-forming material can be analyzed by the TG-DSC method.For example, from the TG-DSC thermal analysis curve (Fig. 1) of SrSO4 as can be known, SrSO
4Heat physical properties in room temperature to 1100 ℃ scope is highly stable, can satisfy its safety in sintering process, stably exists.BaC
2Decompose when being heated to 1750 ℃, can stable existence in the temperature range of SPS sintering.
3, pore-forming material pore-creating and separation principle:
1) pore-creating principle: when carrying out the SPS sintering, pore-forming material energy stable existence, and do not react with other compositions, its location is the position in product formation hole.
2) pore-forming material separation principle:
For water-soluble pore-forming material, can remove by the method for aqueous fusion solution.For example, 1gSrSO under the room temperature
4Be dissolved in about 8800ml water, utilize water-soluble principle with mixed sintered body washing 30 ~ 180min, can reach the purpose of removing pore-forming material.
For water-disintegrable pore-forming material, can remove pore-forming material by the anti-method of hydrolysis.For example, BaC
2Pore-forming material with the biochemical reaction of steeping in water for reconstitution is: BaC
2+ H
2O=Ba (OH)
2+ C
2H
2↑, reaction product Ba (OH)
2Soluble in water (20 ℃ the time, 1 gram Ba (OH)
2Be dissolved in about 14ml water), pass through BaC
2Hydrolysis and Ba (OH) thereafter
2Water-soluble removing, reach and remove pore-forming material BaC
2Purpose.
4, pore structure control principle:
1) control of porosity: because pore-forming material does not react with nickel, titanium, thermolysis can not occur in the sintering process, so only need be the sample porosity by determining the volume ratio of pore-forming material in product, just can in sintering process, realize the control to porosity.
2) control in aperture: powder is evenly to mix, and the sizableness of the size in aperture and pore-forming material granularity by the control of pore-forming material size range, is realized the control to the aperture.
Advantage of the present invention and positively effect: porosity and aperture are controlled by powder size, volume percent, utilize the intensified-sintered effect of SPS and the removal of solvable (solution) property salt pore-forming material, realize the preparation of controllable hole structure porous nickel-titanium marmem.The porosity of gained porous nickel-titanium marmem is 40~70%, the aperture is 75~1000 μ m, has low cost, controlled, the efficient characteristics of technique simple and stable of pore structure, can realize suitability for industrialized production.
Description of drawings
Fig. 1 is SrSO
4The TG-DSC thermal analysis curve;
Fig. 2 is process flow sheet of the present invention.
Embodiment
The present invention will be further described below in conjunction with embodiment.
Embodiment 1
(1) elder generation determines the volume V of gained porous nickel-titanium marmem on demand
Always(adopt the mould of internal diameter Φ 20mm * high 40mm, V
Always=12.56cm
3) and porosity be 40%, calculate each raw materials quality m by following formula again after, the weighing granularity is that 21~44 μ m purity are that 98.8~99.9% Ni powder, granularity are that 21~44 μ m purity are 99.5~99.9% Ti powder and SrSO
4(fusing point is higher than 750 ℃, and thermolysis can not occur in the SPS sintering range, and granularity is 75~150 μ m, purity 〉=98%), and mix 40min:
(1)
In the formula, V represents volume; ρ represents density; M represents quality; N represents amount of substance; Wherein
,
,
,
, ρ
SrSO4=3.96g/cm
3
Obtain SrSO
4Powder 19.895g, nickel powder 25.668g, titanium valve 20.935g;
(2) mixed powder that step (1) is obtained is packed in the graphite jig, in temperature is to carry out discharge plasma sintering 25min under 950 ℃ the condition, obtains sintered compact;
(3) the sintered compact cool to room temperature that step (2) is obtained, then water brews 150min, pore-forming material is dissolved fully or reacts, and namely obtains porosity and be 40%, the aperture is the porous nickel-titanium marmem of 75~150 μ m.
Embodiment 2
(1) elder generation determines the volume V of gained porous nickel-titanium marmem on demand
Always(adopt the mould of internal diameter Φ 10mm * high 25mm, V
Always=1.96cm
3) and porosity be 60%, calculate each raw materials quality m by following formula again after, the weighing granularity is that 21~44 μ m purity are that 98.8~99.9% Ni powder, granularity are that 21~44 μ m purity are 99.5~99.9% Ti powder and analytical pure K
2CO
3(fusing point is higher than 750 ℃, and thermolysis can not occur in the SPS sintering range, and granularity is 200~400 μ m, purity 〉=98%), and mix 150min:
(5)
In the formula, V represents volume; ρ represents density; M represents quality; N represents amount of substance; Wherein
,
,
,
, ρ
K2CO3=2.43g/cm
3
Obtain K
2CO
3Powder 2.859g, nickel powder 2.674g, titanium valve 2.181g;
(2) mixed powder that step (1) is obtained is packed in the graphite jig, in temperature is to carry out discharge plasma sintering 30min under 750 ℃ the condition, obtains sintered compact;
(3) the sintered compact cool to room temperature that step (2) is obtained, according to the solubleness of solubility pore-forming material in water or the principle of hydrolyzable pore-forming material and water reaction, then water brews 30min, pore-forming material is dissolved fully or react, namely obtain porosity and be 60%, the aperture is the porous nickel-titanium marmem of 200~400 μ m.
Embodiment 3
(1) elder generation determines the volume V of gained porous nickel-titanium marmem on demand
Always(adopt the mould of internal diameter Φ 20mm * high 40mm, V
Always=12.56cm
3) and porosity be 70%, calculate each raw materials quality m by following formula again after, the weighing granularity is that 21~44 μ m purity are that 98.8~99.9% Ni powder, granularity are that 21~44 μ m purity are 99.5~99.9% Ti powder and BaC
2(fusing point is higher than 750 ℃, and thermolysis can not occur in the SPS sintering range, and granularity is 300~1000 μ m, purity 〉=98%), and mix 30min:
(3)
In the formula, V represents volume; ρ represents density; M represents quality; N represents amount of substance; Wherein
,
,
,
, ρ
BaC2=3.74g/cm
3
Obtain BaC
2Powder 32.88g, nickel powder 12.85g, titanium valve 10.48g;
(2) mixed powder that step (1) is obtained is packed in the graphite jig, in temperature is to carry out discharge plasma sintering 8min under 1100 ℃ the condition, obtains sintered compact;
(3) the sintered compact cool to room temperature that step (2) is obtained, then water brews 180min, pore-forming material is dissolved fully or reacts, and namely obtains porosity and be 70%, the aperture is the porous nickel-titanium marmem of 300~1000 μ m.
Claims (6)
1. the preparation method of a porous nickel-titanium marmem is characterized in that through following each step:
(1) elder generation determines the volume V of gained porous nickel-titanium marmem on demand
AlwaysAnd porosity, calculate each raw materials quality m by following formula again after, weighing Ni powder, Ti powder and pore-forming material, and mix 30~150min:
In the formula, V represents volume; ρ represents density; M represents quality; N represents amount of substance; Wherein
,
,
,
(2) mixed powder that step (1) is obtained is to carry out discharge plasma sintering 8~30min under 750~1100 ℃ the condition in temperature, obtains sintered compact;
(3) the sintered compact cool to room temperature that step (2) is obtained, then water brews 30~180min, pore-forming material is dissolved fully or reacts, and namely obtains porous nickel-titanium marmem.
2. the preparation method of porous nickel-titanium marmem according to claim 1, it is characterized in that: the porosity of the porous nickel-titanium marmem of described step (1) is 40~70%.
3. the preparation method of porous nickel-titanium marmem according to claim 1, it is characterized in that: the Ni Powder Particle Size of described step (1) is that 21~44 μ m, purity are 98.8~99.9%.
4. the preparation method of porous nickel-titanium marmem according to claim 1, it is characterized in that: the Ti Powder Particle Size of described step (1) is that 21~44 μ m, purity are 99.5~99.9%.
5. the preparation method of porous nickel-titanium marmem according to claim 1, it is characterized in that: the fusing point of described step (1) pore-forming material is higher than 750 ℃, and thermolysis can not occur in the SPS sintering range, granularity is 75~1000 μ m, purity 〉=98%.
6. the preparation method of porous nickel-titanium marmem according to claim 1 or 5, it is characterized in that: described pore-forming material is SrSO
4, BaC
2Or K
2CO
3
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2013100308802A CN103060593A (en) | 2013-01-28 | 2013-01-28 | Preparation method of porous nickel titanium shape memory alloy |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2013100308802A CN103060593A (en) | 2013-01-28 | 2013-01-28 | Preparation method of porous nickel titanium shape memory alloy |
Publications (1)
Publication Number | Publication Date |
---|---|
CN103060593A true CN103060593A (en) | 2013-04-24 |
Family
ID=48103482
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2013100308802A Pending CN103060593A (en) | 2013-01-28 | 2013-01-28 | Preparation method of porous nickel titanium shape memory alloy |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN103060593A (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104152738A (en) * | 2014-08-14 | 2014-11-19 | 昆明理工大学 | Method for manufacturing biomedical porous nickel titanium alloy |
CN104896231A (en) * | 2015-02-11 | 2015-09-09 | 南京工业大学 | A porous TiNi shape memory alloy composite pad and a production process thereof |
CN105200258A (en) * | 2015-08-11 | 2015-12-30 | 无锡桥阳机械制造有限公司 | Method for preparing sintered nickel alloy material |
CN110760710A (en) * | 2019-09-30 | 2020-02-07 | 西安欧中材料科技有限公司 | Preparation method of nickel-based alloy porous material |
CN112264622A (en) * | 2020-11-02 | 2021-01-26 | 昆明理工大学 | Based on TiH2Method for preparing porous Ti-Ni alloy by powder |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102251138A (en) * | 2011-06-21 | 2011-11-23 | 哈尔滨工业大学 | Preparation method of nickel titanium foam alloy with double pore structure |
-
2013
- 2013-01-28 CN CN2013100308802A patent/CN103060593A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102251138A (en) * | 2011-06-21 | 2011-11-23 | 哈尔滨工业大学 | Preparation method of nickel titanium foam alloy with double pore structure |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104152738A (en) * | 2014-08-14 | 2014-11-19 | 昆明理工大学 | Method for manufacturing biomedical porous nickel titanium alloy |
CN104896231A (en) * | 2015-02-11 | 2015-09-09 | 南京工业大学 | A porous TiNi shape memory alloy composite pad and a production process thereof |
CN105200258A (en) * | 2015-08-11 | 2015-12-30 | 无锡桥阳机械制造有限公司 | Method for preparing sintered nickel alloy material |
CN110760710A (en) * | 2019-09-30 | 2020-02-07 | 西安欧中材料科技有限公司 | Preparation method of nickel-based alloy porous material |
CN112264622A (en) * | 2020-11-02 | 2021-01-26 | 昆明理工大学 | Based on TiH2Method for preparing porous Ti-Ni alloy by powder |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103056366B (en) | Preparation method for porous stainless steel | |
CN103157803B (en) | A kind of solid state reaction prepares the method for Nanoalloy | |
CN103060593A (en) | Preparation method of porous nickel titanium shape memory alloy | |
CN106077695B (en) | A kind of preparation method of high-copper tungsten copper nano composite powder | |
CN101804459B (en) | Method for preparing nanometer nickel powder by micro passage reaction vessel | |
CN104630526A (en) | Method for preparing carbon nano-tube reinforced copper base composite material by using microwave sintering | |
CN110845237A (en) | High-entropy ceramic powder, preparation method thereof and high-entropy ceramic block | |
CN106994517B (en) | A kind of preparation method of high-thermal-conductivity low-expansibility W-Cu encapsulating material | |
CN103952588A (en) | High-strength and high-conductivity graphene copper-based composite material and preparation method thereof | |
CN103170636A (en) | Method for preparing nano metal simple substance through solid-state chemical reaction | |
CN103233136B (en) | Technology for preparing silver rare earth oxide electric contact material for low voltage electric apparatus with liquid phase method | |
CN101085466A (en) | Method for preparing ultra-fine tungsten-copper composite powder | |
CN111041318A (en) | Tungsten-copper alloy and preparation method thereof | |
CN102962470B (en) | Method for preparing spherical ultrafine nickel powder at room temperature | |
CN106672988A (en) | Preparation method of high purity rare earth boride | |
CN105215347A (en) | A kind of zinc oxide and gold nano grain composite and preparation method thereof | |
CN105798319B (en) | Preparation method of silver-tungsten electrical contact material, electrical contact material and electrical contact | |
CN101733406A (en) | Method for preparing nano porous copper/ferroferric oxide composite material | |
CN103601188B (en) | The preparation method of the carbide of high-melting-point conductive hard ceramic material tantalum | |
CN102134073B (en) | Preparation method of ultrafine tantalum carbide powder | |
CN107354333A (en) | A kind of preparation method of tungsten-copper composite material | |
CN103304228A (en) | Self-propagating combustion synthesis method for palladium-copper ferrite nano-powder | |
CN105541345A (en) | Method for preparing superfine hafnium carbide ceramic powder | |
CN101774024A (en) | Preparation method of tungsten-cobalt composite oxide powder | |
CN104445241B (en) | A kind of method of low temperature synthesis magnesium-nickel ternary metal boride |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C12 | Rejection of a patent application after its publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20130424 |