CN104630532B - A kind of preparation method of carbide and rare earth oxide complex intensifying carefully brilliant tungsten material - Google Patents
A kind of preparation method of carbide and rare earth oxide complex intensifying carefully brilliant tungsten material Download PDFInfo
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Abstract
The present invention relates to the preparation method of a kind of carbide and rare earth oxide complex intensifying carefully brilliant tungsten material, by 0.1～2.0% carbide, 0.1～2.0% rare earth oxide and tungsten form, carbide be in TiC, ZrC one or both, rare earth oxide is La2O3、Y2O3In one or both.First, design, prepare carbide and nanometer rare earth oxide complex intensifying phase powder；Then, PCA high-energy ball milling or aerosol spray are dried thermal reduction and obtain complex intensifying carefully brilliant tungsten powder；Finally, shape, sinter acquisition more than 99% consistency tungsten material.Tungsten material prepared by the present invention combines the potentiation of two kinds of hardening constituents, and below grain size 8 μm, second phase particles 0.05～1.0 μm, Dispersed precipitate is in tungsten grain and crystal boundary, room temperature tensile intensity is more than 580MPa, tensile strength at 1200 DEG C, more than 450MPa, is suitably applied the field such as nuclear energy, Aero-Space.
Description
Technical field:
The present invention relates to carbide and the preparation method of rare earth oxide complex intensifying carefully brilliant tungsten material, relate to field of powder metallurgy.
Background technology:
W has high-melting-point, high rigidity, good elevated temperature strength, excellent heat conduction and electric conductivity, low thermal coefficient of expansion, with low sputtering during plasma effect, do not occur chemical reaction, H+ to be detained the characteristic such as low with H, being considered as the ideal chose towards plasma Divertor Materials, it has a wide range of applications in the field such as nuclear energy and Aero-Space.In the tungsten material obtaining application, pure tungsten material is to apply high temperatures typical material widely at present.Use the means preparation sintering pure tungsten material that powder High Purity and grain boundaries purify the most both at home and abroad, it is then passed through big distortion means strengthening tungsten material, grain size about 100 μm, ductile-brittle transition temperature (DBTT) 300～350 DEG C, recrystallization temperature 1300～1350 DEG C.But, the defect such as due to the limitation of conventional powder sintering milling method, pure tungsten material exists that tissue is the thickest, is orientated in threadiness, DBTT is high, recrystallization temperature is low, fragility is big, property anisotropy.Add rare earth oxide or carbide and can refine tungsten grain, the anti-neutron irradiation ability improving material and anti-high heat load ability as second phase particles, become an important directions of current facing plasma material research and development.
At present, tungsten is strengthened mainly add single rare earth oxide or carbide.In the research adding single rare earth oxide strengthening tungsten, state's inner circumferential Zhang Jian et al. 2010 is in patent " preparation method of a kind of nano oxide dispersion reinforced superfine crystal tungsten-based composite " (patent No.: ZL201010250552.X), with tungsten powder, Y2O3Or Y, sintering aid Ti are raw material, the method for mechanical alloying is used to make tungsten powder and Y2O3Or Y and Ti solid solution forms superfine alloy powder, then discharge plasma method sintering is used to be prepared for rare-earth oxidation yttrium dispersion-strengtherning tungsten material, its relative density is 96%～99%, tungsten grain size≤3 μm, has good mechanical property and thermal shock resistance.External Kim, Mu oz et al. is same uses mechanical alloying to prepare tungsten and rare-earth oxidation composite powder, and it being respectively adopted electric spark plasma agglomeration (SPS) and high temperature insostatic pressing (HIP) (HIP) method prepares oxide dispersion intensifying tungsten material, result shows that adding trace rare earth oxides can refine tungsten grain, improve intensity and anti-high heat load performance.
In the research adding carbide reinforced tungsten, Wu Yucheng et al. 2008 is in paper " organizational structure of W-1wt%TiC nano composite material and mechanical property ", the method using high-energy ball milling and hot pressed sintering is prepared for the nano composite material of W-1wt%TiC, its mechanical property is improved, but the consistency of material only reaches 98.4%；Japan H.Kurishita et al. was at paper " Deformability in 2008
enhancement in ultra-fine grained, Ar-contained W compacts by TiC additions up
To 1.1% " in use Mechanical Alloying by W powder with 0～1.1% TiC powder formed alloying composite powder; be then passed through the material that high temperature insostatic pressing (HIP) has prepared W-(0-1.5) wt%TiC; find that it can increase the toughness of material; the mechanical behavior under high temperature of reinforcing material, raising tungsten anti-neutron irradiation ability；Applicant, in patent in 2011 " a kind of superhigh temperature composite tungsten material and preparation method " (patent No.: ZL201110013981.X), uses mechanical alloying mix homogeneously tungstenio composite powder, and this material has the mechanical behavior under high temperature of excellence.
Above research fully indicates the advantage adding carbide and rare earth oxide in tungsten for aspects such as refinement tungsten grain, the mechanical property of raising tungsten and anti-neutron irradiation abilities, but single rare earth oxide or carbide are limited to material reinforcement effect.To this end, Renmin University of China Y.Chen et al. is at " Microstructure and mechanical properties of tungsten
composites co-strengthened by dispersed TiC and La2O3
Particles " in have studied TiC and La2O3The collaborative tungsten basal body strengthened, it is improved at the performance such as intensity and fracture toughness the most single interpolation rare earth oxide or carbide, but, its relative density is relatively low, the highest only reaching about 95%, under load effect, hole easily preferentially forms micro-crack thus becomes formation of crack and reduce toughness and the intensity of tungsten.Prepared by the through engineering approaches simultaneously using the sintering method of high temperature insostatic pressing (HIP) or hot pressing to be poorly suited for large scale or irregularly shaped sample.
Summary of the invention:
It is an object of the invention to provide a kind of for facing plasma material and parts with the preparation method of high-temperature field tungsten material, to meet nuclear industry or the high-temperature field demand to High Performance W.The present invention mainly uses " colloidal sol-non-homogeneous phase deposition-calcining " to prepare carbide and nanometer rare earth oxide complex intensifying phase powder, then entering PCA high-energy ball milling or aerosol spray is dried acquisition carbide and the equally distributed composite powder of rare earth oxide, conventional shaping and sintering obtain high more than 99.0% consistency carefully brilliant tungsten material.
The preparation method of a kind of carbide provided by the present invention and rare earth oxide complex intensifying carefully brilliant tungsten material, described thin brilliant tungsten by 0.1～2.0% carbide, 0.1～2.0% rare earth oxide and tungsten form, carbide is one or both in TiC, ZrC, and rare earth oxide is La2O3、Y2O3In one or both.Its preparation process is as follows:
(1) prepared by carbide and nanometer rare earth oxide complex intensifying phase powder
The preparation of complex intensifying phase powder mainly comprises the steps: 1. to choose one or both carbides, is configured to 10～30g/L carbide suspensions；Choose one or both rare-earth salts, be configured to 0.01～0.5mol/L rare earths salt；2. carbide suspension is mixed with rare earths salt, add reaction dispersant and stir；3. under the ultrasonic vibration effect with stirring, in rare-earth salts with carbide mixed solution, it is slowly added to alkaline solution, controls the pH value 9～13 of reaction solution, make rare-earth salts form colloid and be evenly coated at carbide surface；4. precipitation, still aging, sucking filtration obtain carbide and the presoma of nanometer rare earth oxide complex intensifying phase powder；Calcine the most in a hydrogen atmosphere, prepare carbide and nanometer rare earth oxide complex intensifying phase powder；
(2) prepared by carbide and rare earth oxide complex intensifying carefully brilliant tungsten powder
The carefully brilliant tungsten powder preparation of carbide and rare earth oxide complex intensifying uses PCA high-energy ball milling or colloidal sol-spray drying process to prepare: wherein the method for PCA high-energy ball milling is to use liquid process control agent medium; add protective atmosphere, by carbide and nanometer rare earth oxide complex intensifying phase powder and tungsten powder mixing high-energy ball milling 5～30h；The method of colloidal sol-spray drying is that carbide and nanometer rare earth oxide complex intensifying phase powder and tungstates are prepared as sol, and be spray-dried, thermal reduction；
(3) drying and granulating
It is dried under vacuum conditions, baking temperature 50～100 DEG C, is incubated 1～5h；Use pressing mode composite powder is made tabular or bar-shaped after carry out pulverizing, sieving；
(4) shape
Composite powder is loaded in die cavities, use and mold or isostatic pressed, composite powder is formed；
(5) high temperature sintering
Employing protective atmosphere sinters, and sintering temperature is 1700～2100 DEG C, and temperature retention time is 1～10h to obtain carbide and rare earth oxide complex intensifying carefully brilliant tungsten material；Its crystal grain is uniform, and grain size is below 8 μm, and carbide particle is 0.05～1.0 μm mutually, and even dispersion is distributed in tungsten grain inside and crystal boundary.
Described rare-earth salts is to include the nitrate of Y, La, oxalates, carbonate, chloride or sulfate.
(1) reaction dispersant 2. described in is stearic acid, Polyethylene Glycol, carbamide, N, dinethylformamide, OP emulsifying agent, tween 20 or dodecyl sodium sulfate, and reaction dispersant volume fraction is rare earths salt and the 0.2～1.5% of carbide solution total amount.
(1) alkaline solution 3. described in is NaOH, KOH or ammonia.
(1) in, calcining heat 5. is 450～800 DEG C, and is incubated 1～5h.
(2) in the method for the PCA high-energy ball milling described in, liquid process control agent medium is one or more in paraffin, stearic acid, dehydrated alcohol, Polyethylene Glycol, carbon tetrachloride, and protective atmosphere is argon or hydrogen.
Described sintering atmosphere be protective atmosphere be H2、Ar、Ar+H2Or vacuum.
The present invention is directed to the coarse grains of current pure tungsten, property anisotropy, need to improve consistency and performance by rolling and forging, design compound interpolation carbide and rare earth oxide refine tungsten grain, the recrystallization temperature and the high temperature obdurability that improve tungsten further, improve anti-high heat load ability and the purpose of anti-neutron irradiation ability, and overcome the technologies of preparing such as existing high temperature insostatic pressing (HIP), hot pressing complicated, it is difficult to bottleneck prepared by through engineering approaches, uses routine shaping, sintering method to prepare high-performance carefully brilliant tungsten material.The tungsten material that the present invention is prepared relative to existing method, its advantage is as follows:
1, carbide can effectively strengthen the anti-neutron irradiation ability of tungsten material, rare earth oxide can improve tungsten material recrystallization temperature and high temperature obdurability, anti-high heat load ability, uses carbide and rare earth oxide can refine tungsten grain, the recrystallization temperature and the high temperature obdurability that improve tungsten further, improve anti-high heat load ability and anti-neutron irradiation ability；Using normal sintering i.e. up to more than 99.0% consistency at 1700～2100 DEG C, room temperature tensile intensity is more than 580MPa, and the tensile strength at 1200 DEG C is more than 450MPa, and crystallite dimension is below 8 μm, and even tissue.
2, using carbide and nanometer rare earth oxide complex intensifying phase powder, it is possible to obtain carbide and the rare earth oxide Dispersed precipitate thin brilliant tungsten material in matrix, material is played good thin brilliant and dispersion-strengthened action by carbide and rare earth oxide.
3, the method is used to prepare carbide and rare earth oxide complex intensifying carefully brilliant tungsten material, it is more easy to through engineering approaches compared with high-energy ball milling+method such as hot pressing or high temperature insostatic pressing (HIP) and prepares large scale or irregularly shaped sample, overcome traditional commerce pure tungsten sintering to need to improve consistency and the problem of performance by rolling and forging, meet high-temperature field and the nuclear energy field demand to High Performance W.
Detailed description of the invention:
The present invention is further illustrated below in conjunction with example, and the unrestricted present invention.
Embodiment 1:
Carbide and the rare earth oxide complex intensifying carefully brilliant each material composition of tungsten material is by mass percentage: ZrC content is 0.1%, Y2O3Content is 0.3%, and surplus is W.
Preparation technology is as follows:
(1) prepared by carbide and nanometer rare earth oxide complex intensifying phase powder
The preparation of complex intensifying phase powder mainly comprises the steps: 1. to prepare the ZrC suspension of 15g/L；Choose Y (NO)3, and prepare the Y (NO) of 0.2mol/L3Saline solution；2. carbide suspension is mixed with rare earths salt, add stearic acid and stir；3., under the ultrasonic vibration effect with stirring, in rare-earth salts with carbide mixed solution, it is slowly added to NH4OH solution, controls the pH value 9～10 of reaction solution, makes rare-earth salts form colloid and is evenly coated at carbide surface；4. precipitation, still aging, sucking filtration obtain carbide and the presoma of nanometer rare earth oxide complex intensifying phase powder；5. under 750 DEG C of hydrogen atmospheres, calcine 2h, prepare carbide and nanometer rare earth oxide complex intensifying phase powder；
(2) prepared by carbide and rare earth oxide complex intensifying carefully brilliant tungsten powder
Using dehydrated alcohol and stearic acid as process control agent, argon is milling protection atmosphere, by carbide and nanometer rare earth oxide complex intensifying phase powder and tungsten powder with carry out high-energy ball milling 10h, it is thus achieved that carbide and rare earth oxide complex intensifying carefully brilliant tungsten powder；
(3) drying and granulating
It is dried under vacuum conditions, baking temperature 70 DEG C, is incubated 2h；Use pressing mode composite powder is made tabular or bar-shaped after carry out pulverizing, sieving；
(4) shape
Composite powder is loaded in die cavities, use and mold or isostatic pressed, composite powder is formed；
(5) high temperature sintering
Use H2Atmosphere sintering, sintering temperature is 1920 DEG C, and temperature retention time is that 5h prepares carbide and rare earth oxide complex intensifying carefully brilliant tungsten material；Its crystal grain is tiny and is evenly distributed, and tungsten grain degree is below 8 μm, and carbide particle is between 0.05～1.0 μm, and even dispersion is distributed in tungsten grain and crystal boundary.
Embodiment 2:
Carbide and rare earth oxide complex intensifying carefully brilliant tungsten material composition is by mass percentage: ZrC content is 1.2%, TiC content is 0.7%, Y2O3Content is 0.5%, and surplus is W.
Preparation technology is as follows:
(1) prepared by carbide and nanometer rare earth oxide complex intensifying phase powder
The preparation of complex intensifying phase powder mainly comprises the steps: 1. to prepare ZrC and the TiC suspension of 15g/L；Choose YCl3, and prepare the YCl of 0.2mol/L3Saline solution；2. carbide suspension is mixed with rare earths salt, add PEG agent and stir；3. under the ultrasonic vibration effect with stirring, in rare-earth salts with carbide mixed solution, it is slowly added to NaOH solution, controls the pH value 9～10 of reaction solution, make rare-earth salts form colloid and be evenly coated at carbide surface；4. precipitation, still aging, sucking filtration obtain carbide and the presoma of nanometer rare earth oxide complex intensifying phase powder；5. under 700 DEG C of hydrogen atmospheres, calcine 2.5h, prepare carbide and nanometer rare earth oxide complex intensifying phase powder；
(2) prepared by carbide and rare earth oxide complex intensifying carefully brilliant tungsten powder
Using dehydrated alcohol and stearic acid as process control agent, argon is milling protection atmosphere, by carbide and nanometer rare earth oxide complex intensifying phase powder and tungsten powder with carry out high-energy ball milling 8h, it is thus achieved that carbide and rare earth oxide complex intensifying carefully brilliant tungsten powder；
(3) drying and granulating
It is dried under vacuum conditions, baking temperature 90 DEG C, is incubated 1h；Use pressing mode composite powder is made tabular or bar-shaped after carry out pulverizing, sieving；
(4) shape
Composite powder is loaded in die cavities, use and mold or isostatic pressed, composite powder is formed；
(5) high temperature sintering
Use H2Atmosphere sintering, sintering temperature is 1980 DEG C, and temperature retention time is that 3.5h prepares carbide and rare earth oxide complex intensifying carefully brilliant tungsten material；Its crystal grain is tiny and is evenly distributed, and tungsten grain degree is below 8 μm, and carbide particle is between 0.05～1.0 μm, and even dispersion is distributed in tungsten grain and crystal boundary.
Embodiment 3:
Carbide and rare earth oxide complex intensifying carefully brilliant tungsten material composition is by mass percentage: TiC content is 0.7%, La2O3Content is 1.5%, and surplus is W.
Preparation technology is as follows:
(1) prepared by carbide and nanometer rare earth oxide complex intensifying phase powder
The preparation of complex intensifying phase powder mainly comprises the steps: 1. to prepare the TiC suspension of 15g/L；Choose La (NO)3, and prepare the La (NO) of 0.3mol/L3Saline solution；2. carbide suspension is mixed with rare earths salt, add OP emulsifying agent and stir；3., under the ultrasonic vibration effect with stirring, in rare-earth salts with carbide mixed solution, it is slowly added to NH4OH solution, controls the pH value 10～11 of reaction solution, makes rare-earth salts form colloid and is evenly coated at carbide surface；4. precipitation, still aging, sucking filtration obtain carbide and the presoma of nanometer rare earth oxide complex intensifying phase powder；5. under 700 DEG C of hydrogen atmospheres, calcine 2.5h, prepare carbide and nanometer rare earth oxide complex intensifying phase powder；
(2) prepared by carbide and rare earth oxide complex intensifying carefully brilliant tungsten powder
Using dehydrated alcohol and stearic acid as process control agent, argon is milling protection atmosphere, by carbide and nanometer rare earth oxide complex intensifying phase powder and tungsten powder with carry out high-energy ball milling 8h, it is thus achieved that carbide and rare earth oxide complex intensifying carefully brilliant tungsten powder；
(3) drying and granulating
It is dried under vacuum conditions, baking temperature 75 DEG C, is incubated 2h；Use pressing mode composite powder is made tabular or bar-shaped after carry out pulverizing, sieving；
(4) shape
Composite powder is loaded in die cavities, use and mold or isostatic pressed, composite powder is formed；
(5) high temperature sintering
Use H2Atmosphere sintering, sintering temperature is 1940 DEG C, and temperature retention time is that 5h prepares carbide and rare earth oxide complex intensifying carefully brilliant tungsten material；Its crystal grain is tiny and is evenly distributed, and tungsten grain degree is below 8 μm, and carbide particle is between 0.05～1.0 μm, and even dispersion is distributed in tungsten grain and crystal boundary.
Embodiment 4:
Carbide and rare earth oxide complex intensifying carefully brilliant tungsten material composition is by mass percentage: ZrC content is 0.8%, TiC content is 0.6%, La2O3Content is 0.5%, and surplus is W.
Preparation technology is as follows:
(1) prepared by carbide and nanometer rare earth oxide complex intensifying phase powder
The preparation of complex intensifying phase powder mainly comprises the steps: 1. to prepare ZrC and the TiC suspension of 15g/L；Choose La2(SO4)3, and prepare the La of 0.1mol/L2(SO4)3Saline solution；2. carbide suspension is mixed with rare earths salt, add PEG agent and stir；3. under the ultrasonic vibration effect with stirring, in rare-earth salts with carbide mixed solution, it is slowly added to KOH solution, controls the pH value 10～11 of reaction solution, make rare-earth salts form colloid and be evenly coated at carbide surface；4. precipitation, still aging, sucking filtration obtain carbide and the presoma of nanometer rare earth oxide complex intensifying phase powder；5. under 700 DEG C of hydrogen atmospheres, calcine 2.5h, prepare carbide and nanometer rare earth oxide complex intensifying phase powder；
(2) prepared by carbide and rare earth oxide complex intensifying carefully brilliant tungsten powder
Using dehydrated alcohol and stearic acid as process control agent, argon is milling protection atmosphere, by carbide and nanometer rare earth oxide complex intensifying phase powder and tungsten powder with carry out high-energy ball milling 8h, it is thus achieved that carbide and rare earth oxide complex intensifying carefully brilliant tungsten powder；
(3) drying and granulating
It is dried under vacuum conditions, baking temperature 80 DEG C, is incubated 2h；Use pressing mode composite powder is made tabular or bar-shaped after carry out pulverizing, sieving；
(4) shape
Composite powder is loaded in die cavities, use and mold or isostatic pressed, composite powder is formed；
(5) high temperature sintering
Use H2Atmosphere sintering, sintering temperature is 1890 DEG C, and temperature retention time is that 7.5h prepares carbide and rare earth oxide complex intensifying carefully brilliant tungsten material；Its crystal grain is tiny and is evenly distributed, and tungsten grain degree is below 8 μm, and carbide particle is between 0.05～1.0 μm, and even dispersion is distributed in tungsten grain and crystal boundary.
Embodiment 5:
Carbide and rare earth oxide complex intensifying carefully brilliant tungsten material composition is by mass percentage: TiC content is 0.8%, La2O3Content is 0.5%, Y2O3Content is 1.0%, and surplus is W.
Preparation technology is as follows:
(1) prepared by carbide and nanometer rare earth oxide complex intensifying phase powder
The preparation of complex intensifying phase powder mainly comprises the steps: 1. to prepare the TiC suspension of 15g/L；Choose La (NO)3、Y(NO)3, and prepare the La (NO) of 0.3mol/L3、Y(NO)3Saline solution；2. carbide suspension is mixed with rare earths salt, add carbamide and stir；3., under the ultrasonic vibration effect with stirring, in rare-earth salts with carbide mixed solution, it is slowly added to NH4OH solution, controls the pH value 10～11 of reaction solution, makes rare-earth salts form colloid and is evenly coated at carbide surface；4. precipitation, still aging, sucking filtration obtain carbide and the presoma of nanometer rare earth oxide complex intensifying phase powder；5. under 550 DEG C of hydrogen atmospheres, calcine 3h, prepare carbide and nanometer rare earth oxide complex intensifying phase powder；
(2) prepared by carbide and rare earth oxide complex intensifying carefully brilliant tungsten powder
According to component ratio, carbide and nanometer rare earth oxide complex intensifying phase powder and tungstates are prepared as sol, and be spray-dried, thermal reduction is prepared as carbide and rare earth oxide complex intensifying carefully brilliant tungsten powder；
(3) drying and granulating
It is dried under vacuum conditions, baking temperature 75 DEG C, is incubated 2h；Use pressing mode composite powder is made tabular or bar-shaped after carry out pulverizing, sieving；
(4) shape
Composite powder is loaded in die cavities, use and mold or isostatic pressed, composite powder is formed；
(5) high temperature sintering
Use H2Atmosphere sintering, sintering temperature is 1980 DEG C, and temperature retention time is that 3.5h prepares carbide and rare earth oxide complex intensifying carefully brilliant tungsten material；Its crystal grain is tiny and is evenly distributed, and tungsten grain degree is below 8 μm, and carbide particle is between 0.05～1.0 μm, and even dispersion is distributed in tungsten grain and crystal boundary.
Claims (7)
1. a preparation method for carbide and rare earth oxide complex intensifying carefully brilliant tungsten material, by 0.1～2.0% carbide, 0.1～2.0% rare earth oxide and tungsten form, carbide is one or both in TiC, ZrC, and rare earth oxide is La2O3、Y2O3In one or both, it is characterised in that comprise the following steps:
(1) prepared by carbide and nanometer rare earth oxide complex intensifying phase powder
The preparation of complex intensifying phase powder mainly comprises the steps: 1. to choose one or both carbides, is configured to 10～30g/L carbide suspensions；Choose one or both rare-earth salts, be configured to 0.01～0.5mol/L rare earths salt；2. carbide suspension is mixed with rare earths salt, add reaction dispersant and stir；3. under the ultrasonic vibration effect with stirring, in rare-earth salts with carbide mixed solution, it is slowly added to alkaline solution, controls the pH value 9～13 of reaction solution, make rare-earth salts form colloid and be evenly coated at carbide surface；4. precipitation, still aging, sucking filtration obtain carbide and the presoma of nanometer rare earth oxide complex intensifying phase powder；Calcine the most in a hydrogen atmosphere, prepare carbide and nanometer rare earth oxide complex intensifying phase powder；
(2) prepared by carbide and rare earth oxide complex intensifying carefully brilliant tungsten powder
The carefully brilliant tungsten powder preparation of carbide and rare earth oxide complex intensifying uses PCA high-energy ball milling or colloidal sol-spray drying process to prepare: wherein the method for PCA high-energy ball milling is to use liquid process control agent medium; add protective atmosphere, by carbide and nanometer rare earth oxide complex intensifying phase powder and tungsten powder mixing high-energy ball milling 5～30h；The method of colloidal sol-spray drying is that carbide and nanometer rare earth oxide complex intensifying phase powder and tungstates are prepared as sol, and be spray-dried, thermal reduction；
(3) drying and granulating
It is dried under vacuum conditions, baking temperature 50～100 DEG C, is incubated 1～5h；Use pressing mode composite powder is made tabular or bar-shaped after carry out pulverizing, sieving；
(4) shape
Composite powder is loaded in die cavities, use and mold or isostatic pressed, composite powder is formed；
(5) high temperature sintering
Employing protective atmosphere sinters, and sintering temperature is 1700～2100 DEG C, and temperature retention time is 1～10h to obtain carbide and rare earth oxide complex intensifying carefully brilliant tungsten material；Its crystal grain is uniform, and grain size is below 8 μm, and carbide particle is 0.05～1.0 μm mutually, and even dispersion is distributed in tungsten grain inside and crystal boundary.
2. the preparation method of carbide as claimed in claim 1 and rare earth oxide complex intensifying carefully brilliant tungsten material, it is characterised in that: described rare-earth salts is to include the nitrate of Y, La, oxalates, carbonate, chloride or sulfate.
3. the preparation method of carbide as claimed in claim 1 and rare earth oxide complex intensifying carefully brilliant tungsten material, it is characterized in that: reaction dispersant 2. described in (1) is stearic acid, Polyethylene Glycol, carbamide, N, dinethylformamide, OP emulsifying agent, tween 20 or dodecyl sodium sulfate, reaction dispersant volume fraction is rare earths salt and the 0.2 ~ 1.5% of carbide solution total amount.
4. the preparation method of carbide as claimed in claim 1 and rare earth oxide complex intensifying carefully brilliant tungsten material, it is characterised in that: alkaline solution 3. described in (1) is NaOH, KOH or ammonia.
5. the preparation method of as claimed in claim 1 carbide and rare earth oxide complex intensifying carefully brilliant tungsten material, it is characterised in that: in (1), calcining heat 5. is 450～800 DEG C, and is incubated 1～5h.
6. the preparation method of carbide as claimed in claim 1 and rare earth oxide complex intensifying carefully brilliant tungsten material; it is characterized in that: in the method for the PCA high-energy ball milling described in (2); liquid process control agent medium is one or more in paraffin, stearic acid, dehydrated alcohol, Polyethylene Glycol, carbon tetrachloride, and protective atmosphere is argon or hydrogen.
7. the preparation method of as claimed in claim 1 carbide and rare earth oxide complex intensifying carefully brilliant tungsten material, it is characterised in that: described sintering atmosphere be protective atmosphere be H2、Ar、Ar+H2Or vacuum.
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| CN115305399A (en) * | 2022-08-23 | 2022-11-08 | 自贡硬质合金有限责任公司 | Rare earth tungsten electrode material and preparation method thereof |
| CN115679174B (en) * | 2022-11-04 | 2024-02-06 | 中南大学 | Super-strong tungsten filament and preparation method thereof |
| CN116275048A (en) * | 2023-03-22 | 2023-06-23 | 中钨稀有金属新材料(湖南)有限公司 | Lanthanum-containing tungsten rod blank and preparation method and application thereof |
| CN117626084B (en) * | 2023-12-18 | 2024-06-18 | 北京北钨科技有限公司 | Composite tungsten electrode material and preparation method thereof |
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| CN1257785C (en) * | 2003-06-12 | 2006-05-31 | 中南大学 | Method for preparing nano-grade tungsten-based composite powder by sol-spray drying-thermal reduction |
| CN100582267C (en) * | 2008-02-22 | 2010-01-20 | 中南大学 | Method for preparing grain-refining W-Ni-Fe alloy containing rare earth |
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