CN104630532A - Preparation method of carbide/rare-earth oxide composite reinforced fine-grain tungsten material - Google Patents
Preparation method of carbide/rare-earth oxide composite reinforced fine-grain tungsten material Download PDFInfo
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Abstract
The invention relates to a preparation method of a carbide/rare-earth oxide composite reinforced fine-grain tungsten material. The carbide/rare-earth oxide composite reinforced fine-grain tungsten material is composed of 0.1-2.0% of carbide, 0.1-2.0% of rare-earth oxide and tungsten. The carbide is one or both of TiC and ZrC, and the rare-earth oxide is one or both of La2O3 and Y2O3. The preparation method comprises the following steps: designing and preparing carbide/rare-earth oxide nano composite reinforcing-phase powder; carrying out PCA high-energy ball milling or sol-spray drying-hot reduction on composite reinforced fine-grain tungsten powder; and finally, forming and sintering to obtain the tungsten material with the density of higher than 99%. The tungsten material integrates the reinforcing actions of the two reinforcing phases, the grain size is 8 mu m below, and the second-phase particle is 0.05-1.0 mu m; and the two reinforcing phases are dispersed and distributed in the tungsten grains and grain boundary. The tensile strength at room temperature exceeds 580 MPa, and the tensile strength at 1200 DEG C exceeds 450 MPa. The carbide/rare-earth oxide composite reinforced fine-grain tungsten material is suitable for the fields of nuclear energy, aerospace and the like.
Description
technical field:
The present invention relates to the preparation method of carbide and the thin brilliant tungsten material of rare earth oxide complex intensifying, relate to field of powder metallurgy.
background technology:
W has high-melting-point, high rigidity, good hot strength, excellent heat conduction and conductivity, low thermal expansivity, with sputtering low during plasma effect, there is not chemical reaction with H, H+ is detained the characteristics such as low, be considered to the most ideal chose of flux of plasma Divertor Materials, it has a wide range of applications in the field such as nuclear energy and aerospace.In the tungsten material obtaining application, pure tungsten material is the high temperatures typical material applied at present widely.Adopt the means preparation sintering pure tungsten material of powder High Purity and grain boundaries purification at present both at home and abroad, then through big distortion means strengthening tungsten material, grain fineness number at about 100 μm, ductile-brittle transition temperature (DBTT) 300 ~ 350 DEG C, recrystallization temperature 1300 ~ 1350 DEG C.But, due to the limitation of conventional powder sintering rolling method, pure tungsten material exist organize very thick, in fibrous orientation, the defect such as DBTT is high, recrystallization temperature is low, fragility is large, property anisotropy.Adding rare earth oxide or carbide can refinement tungsten grain, the anti-neutron irradiation ability improving material and anti-high heat load ability as second phase particles, becomes 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 compound strengthening tungsten, people such as state inner circumferential Zhang Jian 2010 in patent " a kind of preparation method of nano oxide dispersion reinforced superfine crystal tungsten-based matrix material " (patent No.: ZL201010250552.X), with tungsten powder, Y
2o
3or Y, sintering aid Ti are raw material, the method for mechanical alloying is adopted to make tungsten powder and Y
2o
3or Y and Ti solid solution forms superfine alloy powder, then discharge plasma method sintering is adopted to prepare rare-earth oxidation yttrium dispersion-strengthened tungsten material, its relative density is 96% ~ 99%, and tungsten grain size≤3 μm have good mechanical property and thermal shock resistance.The people such as external Kim, Mu oz adopt mechanical alloying to prepare tungsten and rare-earth oxidation composite powder equally, and adopting electrical spark plasma agglomeration (SPS) and hot isostatic pressing (HIP) method to prepare oxide dispersion intensifying tungsten material respectively, result shows to add trace rare earth oxides can refinement tungsten grain, raising intensity and anti-high heat load performance.
In the research adding carbide reinforced tungsten, people such as Wu Yucheng 2008 are in paper " weave construction of W-1wt%TiC nano composite material and mechanical property ", the method of high-energy ball milling and hot pressed sintering is adopted to prepare the nano composite material of W-1wt%TiC, its mechanical property is improved, but the density of material only reaches 98.4%; The people from Japan such as H.Kurishita adopted Mechanical Alloying that the TiC powder of W powder and 0 ~ 1.1% is formed the composite powder of alloying in paper " Deformability enhancement in ultra-fine grained; Ar-contained W compacts by TiC additions up to 1.1% " in 2008, then the material of W-(0-1.5) wt%TiC has been prepared through hot isostatic pressing, find that it can increase the toughness of material, the mechanical behavior under high temperature of strongthener, improves the anti-neutron irradiation ability of tungsten; Applicant is in 2011 patent " a kind of ultrahigh-temperature composite tungsten material and preparation method " (patent No.: ZL201110013981.X), and adopt mechanical alloying to mix tungsten base composite powder, this material has excellent mechanical behavior under high temperature.
Above research fully indicates to add carbide and rare earth oxide for the advantage in refinement tungsten grain, the mechanical property improving tungsten and anti-neutron irradiation ability etc. in tungsten, but single rare earth oxide or carbide are to material reinforcement limited efficiency.For this reason, the people such as Renmin University of China Y.Chen is at " Microstructure and mechanical properties of tungsten composites co-strengthened by dispersed TiC and La
2o
3particles " in have studied TiC and La
2o
3the collaborative tungsten basal body strengthened, it is improved at all more single interpolation rare earth oxide of the performance such as intensity and fracture toughness property or carbide, but, its relative density is lower, the highlyest only reach about 95%, under load effect, hole easily preferentially forms tiny crack thus becomes toughness and the intensity that formation of crack reduces tungsten.Adopt the sintering method of hot isostatic pressing or hot pressing to be not too suitable for the through engineering approaches preparation of large size or irregularly shaped sample simultaneously.
summary of the invention:
The object of this invention is to provide a kind of preparation method for facing plasma material and parts and high-temperature field tungsten material, to meet nuclear industry or high-temperature field to the demand of High Performance W.The present invention mainly adopts " colloidal sol-non-homogeneous phase deposition-calcining " prepares carbide and nanometer rare earth oxide complex intensifying phase powder, then enter PCA high-energy ball milling or aerosol spray drying obtains carbide and the equally distributed composite powder of rare earth oxide, to be conventionally shaped and sintering obtains the thin brilliant tungsten material of high more than 99.0% density.
The preparation method of a kind of carbide provided by the present invention and the thin brilliant tungsten material of rare earth oxide complex intensifying, described thin brilliant tungsten is made up of 0.1 ~ 2.0% carbide, 0.1 ~ 2.0% rare earth oxide and tungsten, carbide is one or both in TiC, ZrC, and rare earth oxide is La
2o
3, Y
2o
3in one or both.Its preparation process is as follows:
(1) carbide and nanometer rare earth oxide complex intensifying phase powder preparation
Complex intensifying phase powder preparation mainly comprises the steps: 1. to choose one or both carbide, is mixed with 10 ~ 30g/L carbide suspension liquid; Choose one or both rare-earth saltss, be mixed with 0.01 ~ 0.5mol/L rare earths salt; 2. carbide suspension liquid is mixed with rare earths salt, add reaction dispersion agent and stir; 3. under the effect of ultrasonic vibration and stirring, in rare-earth salts and carbide mixing solutions, slowly add basic solution, control the pH value 9 ~ 13 of reaction soln, make rare-earth salts form colloid and be evenly coated on carbide surface; 4. precipitate, the presoma that still aging, suction filtration obtains carbide and nanometer rare earth oxide complex intensifying phase powder; 5. calcine in a hydrogen atmosphere, prepare carbide and nanometer rare earth oxide complex intensifying phase powder;
(2) carbide and the thin brilliant tungsten powder preparation of rare earth oxide complex intensifying
Carbide and the thin brilliant tungsten powder of rare earth oxide complex intensifying prepare employing PCA high-energy ball milling or colloidal sol-spray drying process preparation: wherein the method for PCA high-energy ball milling adopts liquid process control agent medium, add protective atmosphere, by carbide and nanometer rare earth oxide complex intensifying phase powder and tungsten powder mixing and high-energy ball milling 5 ~ 30h; Colloidal sol-spray-dired method is that carbide and nanometer rare earth oxide complex intensifying phase powder and tungstate are prepared into sol, and spraying dry, thermal reduction;
(3) drying and granulating
Dry under vacuum conditions, drying temperature 50 ~ 100 DEG C, insulation 1 ~ 5h; Adopt pressing mode composite powder is made tabular or bar-shaped after carry out pulverizing, sieving;
(4) be shaped
Composite powder is loaded in die cavities, adopt mold pressing or isostatic pressed, composite powder is formed;
(5) high temperature sintering
Employing protective atmosphere sinters, and sintering temperature is 1700 ~ 2100 DEG C, and soaking time is that 1 ~ 10h obtains carbide and the thin brilliant tungsten material of rare earth oxide complex intensifying; Its uniform crystal particles, grain fineness number 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 comprises the nitrate of Y, La, oxalate, carbonate, muriate or vitriol.
(1) reaction dispersion agent 2. described in is stearic acid, polyoxyethylene glycol, urea, N, dinethylformamide, OP emulsifying agent, tween 20 or sodium laurylsulfonate, and reaction dispersion agent volume fraction is 0.2 ~ 1.5% of rare earths salt and carbide solution total amount.
(1) basic solution 3. described in is NaOH, KOH or ammoniacal liquor.
(1) in, calcining temperature is 5. 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, polyoxyethylene glycol, tetracol phenixin, and protective atmosphere is argon gas or hydrogen.
Described sintering atmosphere is protective atmosphere is H
2, Ar, Ar+H
2or vacuum.
The present invention is directed to the coarse grains of current pure tungsten, property anisotropy, need to improve density and performance by rolling and forging, design compound is added carbide and rare earth oxide further refinement tungsten grain, the recrystallization temperature improving tungsten and high temperature obdurability, is improved the object of anti-high heat load ability and anti-neutron irradiation ability, and it is complicated to overcome the technologies of preparing such as existing hot isostatic pressing, hot pressing, be difficult to realize bottleneck prepared by through engineering approaches, adopt conventionally to be shaped, sintering method prepares the thin brilliant tungsten material of high-performance.The tungsten material that the present invention is prepared relative to existing method, its advantage is as follows:
1, carbide effectively can strengthen the anti-neutron irradiation ability of tungsten material, rare earth oxide can improve tungsten material re-crystallizes temperature and high temperature obdurability, anti-high heat load ability, adopt carbide and rare earth oxide can further refinement tungsten grain, improve tungsten recrystallization temperature and high temperature obdurability, improve anti-high heat load ability and anti-neutron irradiation ability; At 1700 ~ 2100 DEG C, adopt normal sintering can reach more than 99.0% density, room temperature tensile intensity is more than 580MPa, and the tensile strength at 1200 DEG C is more than 450MPa, and grain-size is less than 8 μm, and homogeneous microstructure.
2, adopt carbide and nanometer rare earth oxide complex intensifying phase powder, can obtain carbide and the thin brilliant tungsten material of rare earth oxide Dispersed precipitate in matrix, carbide and rare earth oxide play good thin crystalline substance and dispersion-strengthened action to material.
3, the method is adopted to prepare carbide and the thin brilliant tungsten material of rare earth oxide complex intensifying, large size or irregularly shaped sample is prepared compared with high-energy ball milling+easier through engineering approaches of the method such as hot pressing or hot isostatic pressing, overcome the problem that traditional commerce pure tungsten sintering needs to improve by rolling and forging density and performance, meet high-temperature field and nuclear energy field to the demand of High Performance W.
embodiment:
The present invention is further illustrated below in conjunction with example, and unrestricted the present invention.
Embodiment 1:
Carbide and each material composition of the thin brilliant tungsten material of rare earth oxide complex intensifying are by mass percentage: ZrC content is 0.1%, Y
2o
3content is 0.3%, and surplus is W.
Preparation technology is as follows:
(1) carbide and nanometer rare earth oxide complex intensifying phase powder preparation
Complex intensifying phase powder preparation mainly comprises the steps: the ZrC suspension liquid 1. preparing 15g/L; Choose Y (NO)
3, and prepare the Y (NO) of 0.2mol/L
3salts solution; 2. carbide suspension liquid is mixed with rare earths salt, add stearic acid and stir; 3., under the effect of ultrasonic vibration and stirring, in rare-earth salts and carbide mixing solutions, slowly NH is added
4oH solution, controls the pH value 9 ~ 10 of reaction soln, makes rare-earth salts form colloid and is evenly coated on carbide surface; 4. precipitate, the presoma that still aging, suction filtration obtains carbide and 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) carbide and the thin brilliant tungsten powder preparation of rare earth oxide complex intensifying
Adopt dehydrated alcohol and stearic acid as process control agent, argon gas is milling protection atmosphere, by carbide and nanometer rare earth oxide complex intensifying phase powder and tungsten powder and carry out high-energy ball milling 10h, obtain carbide and the thin brilliant tungsten powder of rare earth oxide complex intensifying;
(3) drying and granulating
Dry under vacuum conditions, drying temperature 70 DEG C, insulation 2h; Adopt pressing mode composite powder is made tabular or bar-shaped after carry out pulverizing, sieving;
(4) be shaped
Composite powder is loaded in die cavities, adopt mold pressing or isostatic pressed, composite powder is formed;
(5) high temperature sintering
Adopt H
2atmosphere sintering, sintering temperature is 1920 DEG C, and soaking time is that 5h prepares carbide and the thin brilliant tungsten material of rare earth oxide complex intensifying; Its crystal grain is tiny and be 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 the thin brilliant tungsten material composition of rare earth oxide complex intensifying are by mass percentage: ZrC content is 1.2%, TiC content is 0.7%, Y
2o
3content is 0.5%, and surplus is W.
Preparation technology is as follows:
(1) carbide and nanometer rare earth oxide complex intensifying phase powder preparation
Complex intensifying phase powder preparation mainly comprises the steps: ZrC and the TiC suspension liquid 1. preparing 15g/L; Choose YCl
3, and prepare the YCl of 0.2mol/L
3salts solution; 2. carbide suspension liquid is mixed with rare earths salt, add PEG agent and stir; 3. under the effect of ultrasonic vibration and stirring, in rare-earth salts and carbide mixing solutions, slowly add NaOH solution, control the pH value 9 ~ 10 of reaction soln, make rare-earth salts form colloid and be evenly coated on carbide surface; 4. precipitate, the presoma that still aging, suction filtration obtains carbide and 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) carbide and the thin brilliant tungsten powder preparation of rare earth oxide complex intensifying
Adopt dehydrated alcohol and stearic acid as process control agent, argon gas 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, acquisition carbide and the thin brilliant tungsten powder of rare earth oxide complex intensifying;
(3) drying and granulating
Dry under vacuum conditions, drying temperature 90 DEG C, insulation 1h; Adopt pressing mode composite powder is made tabular or bar-shaped after carry out pulverizing, sieving;
(4) be shaped
Composite powder is loaded in die cavities, adopt mold pressing or isostatic pressed, composite powder is formed;
(5) high temperature sintering
Adopt H
2atmosphere sintering, sintering temperature is 1980 DEG C, and soaking time is that 3.5h prepares carbide and the thin brilliant tungsten material of rare earth oxide complex intensifying; Its crystal grain is tiny and be 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 the thin brilliant tungsten material composition of rare earth oxide complex intensifying are by mass percentage: TiC content is 0.7%, La
2o
3content is 1.5%, and surplus is W.
Preparation technology is as follows:
(1) carbide and nanometer rare earth oxide complex intensifying phase powder preparation
Complex intensifying phase powder preparation mainly comprises the steps: the TiC suspension liquid 1. preparing 15g/L; Choose La (NO)
3, and prepare the La (NO) of 0.3mol/L
3salts solution; 2. carbide suspension liquid is mixed with rare earths salt, add OP emulsifying agent and stir; 3., under the effect of ultrasonic vibration and stirring, in rare-earth salts and carbide mixing solutions, slowly NH is added
4oH solution, controls the pH value 10 ~ 11 of reaction soln, makes rare-earth salts form colloid and is evenly coated on carbide surface; 4. precipitate, the presoma that still aging, suction filtration obtains carbide and 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) carbide and the thin brilliant tungsten powder preparation of rare earth oxide complex intensifying
Adopt dehydrated alcohol and stearic acid as process control agent, argon gas 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, acquisition carbide and the thin brilliant tungsten powder of rare earth oxide complex intensifying;
(3) drying and granulating
Dry under vacuum conditions, drying temperature 75 DEG C, insulation 2h; Adopt pressing mode composite powder is made tabular or bar-shaped after carry out pulverizing, sieving;
(4) be shaped
Composite powder is loaded in die cavities, adopt mold pressing or isostatic pressed, composite powder is formed;
(5) high temperature sintering
Adopt H
2atmosphere sintering, sintering temperature is 1940 DEG C, and soaking time is that 5h prepares carbide and the thin brilliant tungsten material of rare earth oxide complex intensifying; Its crystal grain is tiny and be 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 the thin brilliant tungsten material composition of rare earth oxide complex intensifying are by mass percentage: ZrC content is 0.8%, TiC content is 0.6%, La
2o
3content is 0.5%, and surplus is W.
Preparation technology is as follows:
(1) carbide and nanometer rare earth oxide complex intensifying phase powder preparation
Complex intensifying phase powder preparation mainly comprises the steps: ZrC and the TiC suspension liquid 1. preparing 15g/L; Choose La
2(SO
4)
3, and prepare the La of 0.1mol/L
2(SO
4)
3salts solution; 2. carbide suspension liquid is mixed with rare earths salt, add PEG agent and stir; 3. under the effect of ultrasonic vibration and stirring, in rare-earth salts and carbide mixing solutions, slowly add KOH solution, control the pH value 10 ~ 11 of reaction soln, make rare-earth salts form colloid and be evenly coated on carbide surface; 4. precipitate, the presoma that still aging, suction filtration obtains carbide and 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) carbide and the thin brilliant tungsten powder preparation of rare earth oxide complex intensifying
Adopt dehydrated alcohol and stearic acid as process control agent, argon gas 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, acquisition carbide and the thin brilliant tungsten powder of rare earth oxide complex intensifying;
(3) drying and granulating
Dry under vacuum conditions, drying temperature 80 DEG C, insulation 2h; Adopt pressing mode composite powder is made tabular or bar-shaped after carry out pulverizing, sieving;
(4) be shaped
Composite powder is loaded in die cavities, adopt mold pressing or isostatic pressed, composite powder is formed;
(5) high temperature sintering
Adopt H
2atmosphere sintering, sintering temperature is 1890 DEG C, and soaking time is that 7.5h prepares carbide and the thin brilliant tungsten material of rare earth oxide complex intensifying; Its crystal grain is tiny and be 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 the thin brilliant tungsten material composition of rare earth oxide complex intensifying are by mass percentage: TiC content is 0.8%, La
2o
3content is 0.5%, Y
2o
3content is 1.0%, and surplus is W.
Preparation technology is as follows:
(1) carbide and nanometer rare earth oxide complex intensifying phase powder preparation
Complex intensifying phase powder preparation mainly comprises the steps: the TiC suspension liquid 1. preparing 15g/L; Choose La (NO)
3, Y (NO)
3, and prepare the La (NO) of 0.3mol/L
3, Y (NO)
3salts solution; 2. carbide suspension liquid is mixed with rare earths salt, add urea and stir; 3., under the effect of ultrasonic vibration and stirring, in rare-earth salts and carbide mixing solutions, slowly NH is added
4oH solution, controls the pH value 10 ~ 11 of reaction soln, makes rare-earth salts form colloid and is evenly coated on carbide surface; 4. precipitate, the presoma that still aging, suction filtration obtains carbide and 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) carbide and the thin brilliant tungsten powder preparation of rare earth oxide complex intensifying
According to component proportions, carbide and nanometer rare earth oxide complex intensifying phase powder and tungstate are prepared into sol, and spraying dry, thermal reduction are prepared as carbide and the thin brilliant tungsten powder of rare earth oxide complex intensifying;
(3) drying and granulating
Dry under vacuum conditions, drying temperature 75 DEG C, insulation 2h; Adopt pressing mode composite powder is made tabular or bar-shaped after carry out pulverizing, sieving;
(4) be shaped
Composite powder is loaded in die cavities, adopt mold pressing or isostatic pressed, composite powder is formed;
(5) high temperature sintering
Adopt H
2atmosphere sintering, sintering temperature is 1980 DEG C, and soaking time is that 3.5h prepares carbide and the thin brilliant tungsten material of rare earth oxide complex intensifying; Its crystal grain is tiny and be 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 the thin brilliant tungsten material of rare earth oxide complex intensifying, is made up of 0.1 ~ 2.0% carbide, 0.1 ~ 2.0% rare earth oxide and tungsten, and carbide is one or both in TiC, ZrC, and rare earth oxide is La
2o
3, Y
2o
3in one or both, it is characterized in that comprising the following steps:
(1) carbide and nanometer rare earth oxide complex intensifying phase powder preparation
Complex intensifying phase powder preparation mainly comprises the steps: 1. to choose one or both carbide, is mixed with 10 ~ 30g/L carbide suspension liquid; Choose one or both rare-earth saltss, be mixed with 0.01 ~ 0.5mol/L rare earths salt; 2. carbide suspension liquid is mixed with rare earths salt, add reaction dispersion agent and stir; 3. under the effect of ultrasonic vibration and stirring, in rare-earth salts and carbide mixing solutions, slowly add basic solution, control the pH value 9 ~ 13 of reaction soln, make rare-earth salts form colloid and be evenly coated on carbide surface; 4. precipitate, the presoma that still aging, suction filtration obtains carbide and nanometer rare earth oxide complex intensifying phase powder; 5. calcine in a hydrogen atmosphere, prepare carbide and nanometer rare earth oxide complex intensifying phase powder;
(2) carbide and the thin brilliant tungsten powder preparation of rare earth oxide complex intensifying
Carbide and the thin brilliant tungsten powder of rare earth oxide complex intensifying prepare employing PCA high-energy ball milling or colloidal sol-spray drying process preparation: wherein the method for PCA high-energy ball milling adopts liquid process control agent medium, add protective atmosphere, by carbide and nanometer rare earth oxide complex intensifying phase powder and tungsten powder mixing and high-energy ball milling 5 ~ 30h; Colloidal sol-spray-dired method is that carbide and nanometer rare earth oxide complex intensifying phase powder and tungstate are prepared into sol, and spraying dry, thermal reduction;
(3) drying and granulating
Dry under vacuum conditions, drying temperature 50 ~ 100 DEG C, insulation 1 ~ 5h; Adopt pressing mode composite powder is made tabular or bar-shaped after carry out pulverizing, sieving;
(4) be shaped
Composite powder is loaded in die cavities, adopt mold pressing or isostatic pressed, composite powder is formed;
(5) high temperature sintering
Employing protective atmosphere sinters, and sintering temperature is 1700 ~ 2100 DEG C, and soaking time is that 1 ~ 10h obtains carbide and the thin brilliant tungsten material of rare earth oxide complex intensifying; Its uniform crystal particles, grain fineness number 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 and the thin brilliant tungsten material of rare earth oxide complex intensifying as claimed in claim 1, is characterized in that: described rare-earth salts comprises the nitrate of Y, La, oxalate, carbonate, muriate or vitriol.
3. the preparation method of carbide and the thin brilliant tungsten material of rare earth oxide complex intensifying as claimed in claim 1, it is characterized in that: reaction dispersion agent 2. described in (1) is stearic acid, polyoxyethylene glycol, urea, N, dinethylformamide, OP emulsifying agent, tween 20 or sodium laurylsulfonate, reaction dispersion agent volume fraction is 0.2 ~ 1.5% of rare earths salt and carbide solution total amount.
4. the preparation method of carbide and the thin brilliant tungsten material of rare earth oxide complex intensifying as claimed in claim 1, is characterized in that: basic solution 3. described in (1) is NaOH, KOH or ammoniacal liquor.
5. the preparation method of carbide and the thin brilliant tungsten material of rare earth oxide complex intensifying as claimed in claim 1, is characterized in that: in (1), calcining temperature is 5. 450 ~ 800 DEG C, and is incubated 1 ~ 5h.
6. the preparation method of carbide and the thin brilliant tungsten material of rare earth oxide complex intensifying as claimed in claim 1; 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, polyoxyethylene glycol, tetracol phenixin, and protective atmosphere is argon gas or hydrogen.
7. the preparation method of carbide and the thin brilliant tungsten material of rare earth oxide complex intensifying as claimed in claim 1, is characterized in that: described sintering atmosphere is protective atmosphere is H
2, Ar, Ar+H
2or vacuum.
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