CN104630532A - Preparation method of carbide/rare-earth oxide composite reinforced fine-grain tungsten material - Google Patents

Abstract

The invention relates to a preparation method of carbide and rare earth oxide compound reinforced fine-grained tungsten material, which is composed of 0.1-2.0% carbide, 0.1-2.0% rare earth oxide and tungsten, and the carbide is one or more of TiC and ZrC. Two kinds, the rare earth oxide is one or both of La ₂ O ₃ and Y ₂ O ₃ . First, design and prepare carbide and rare earth oxide nanocomposite strengthening phase powder; then, PCA high-energy ball milling or sol-spray drying-thermal reduction to obtain composite reinforced fine-grained tungsten powder; finally, forming and sintering to obtain more than 99% dense tungsten Material. The tungsten material prepared by the present invention combines the strengthening effects of two strengthening phases, and the grain size is below 8 μm, the second phase particles are 0.05-1.0 μm, and are dispersed in the tungsten grains and grain boundaries, and the tensile strength at room temperature exceeds 580 MPa. The tensile strength at 1200°C exceeds 450MPa, which is suitable for nuclear energy, aerospace and other fields.

Description

A preparation method of carbide and rare earth oxide compound reinforced fine-grained tungsten material

Technical field:

The invention relates to a preparation method of carbide and rare earth oxide compound reinforced fine-grained tungsten material, and relates to the field of powder metallurgy.

Background technology :

W has the characteristics of high melting point, high hardness, good high temperature strength, excellent thermal and electrical conductivity, low thermal expansion coefficient, low sputtering when interacting with plasma, no chemical reaction with H, and low H+ retention. The most ideal choice of plasma divertor material, which has a wide range of applications in the fields of nuclear energy and aerospace. Among the tungsten materials that have been applied, pure tungsten materials are typical high-temperature materials that are widely used at present. At present, sintered pure tungsten materials are prepared by means of high powder purification and material grain boundary purification at home and abroad, and then strengthened by large deformation processing. The grain size is about 100 μm, and the ductile-brittle transition temperature (DBTT) is 300-350 ° C. The crystallization temperature is 1300-1350°C. However, due to the limitations of traditional powder sintering and rolling methods, pure tungsten materials have defects such as very coarse structure, fibrous orientation, high DBTT, low recrystallization temperature, high brittleness, and anisotropy in properties. Adding rare earth oxides or carbides as the second phase particles can refine the tungsten grains, improve the neutron radiation resistance and high thermal load resistance of the material, and has become an important direction for the research and development of plasma-oriented materials.

At present, the strengthening of tungsten is mainly to add a single rare earth oxide or carbide. In the study of strengthening tungsten by adding a single rare earth oxide, in 2010, Zhou Zhangjian and others in China patented "a preparation method of nano-oxide dispersion-reinforced ultra-fine-grained tungsten-based composite material" (patent number: ZL201010250552.X). Tungsten powder, Y ₂ O ₃ or Y, and sintering aid Ti are used as raw materials, and the method of mechanical alloying is used to make tungsten powder and Y ₂ O ₃ or Y, and Ti form a solid solution to form ultrafine alloyed powder, and then use discharge plasma Rare earth yttrium oxide dispersion strengthened tungsten material was prepared by sintering method. Its relative density is 96%-99%, tungsten grain size is ≤3μm, and it has good mechanical properties and thermal shock resistance. Foreign Kim, Muñoz and others also used mechanical alloying to prepare composite powders of tungsten and rare earth oxides, and prepared oxide dispersion strengthened tungsten materials by spark plasma sintering (SPS) and hot isostatic pressing (HIP) respectively. The results showed that Adding traces of rare earth oxides can refine tungsten grains, improve strength and high heat load resistance.

In the study of adding carbides to strengthen tungsten, Wu Yucheng et al. prepared W-1wt% The nanocomposite material of TiC has improved mechanical properties, but the density of the material only reaches 98.4%; Japanese H.Kurishita et al. in the 2008 paper "Deformability enhancement in ultra-fine grained, Ar-contained W compacts by TiC additions up to 1.1%" using mechanical alloying method to form an alloyed composite powder of W powder and 0-1.1% TiC powder, and then prepared W-(0-1.5)wt%TiC material by hot isostatic pressing, and found that It can increase the toughness of the material, enhance the high-temperature mechanical properties of the material, and improve the neutron radiation resistance of tungsten; the applicant of this patent patented "an ultra-high temperature tungsten composite material and its preparation method" in 2011 (patent number: ZL201110013981. In X), mechanical alloying is used to mix uniform tungsten-based composite powder, and the material has excellent high-temperature mechanical properties.

The above studies have fully demonstrated the advantages of adding carbides and rare earth oxides to tungsten to refine the tungsten grains, improve the mechanical properties of tungsten and the ability to resist neutron radiation, but a single rare earth oxide or carbide has no effect on tungsten. The effect of material strengthening is limited. To this end, Y.Chen et al. of Renmin University of China studied the tungsten matrix synergistically enhanced by TiC and La ₂ O ₃ in "Microstructure and mechanical properties of tungsten composites co-strengthened by dispersed TiC and La ₂ O ₃ particles", which in Compared with single addition of rare earth oxides or carbides, properties such as strength and fracture toughness are improved. However, its relative density is low, reaching only about 95%. Under load, pores tend to preferentially form microcracks and become crack sources. Reduce tungsten toughness and strength. At the same time, the sintering method using hot isostatic pressing or hot pressing is not suitable for the engineering preparation of large-sized or irregular-shaped samples.

Invention content:

The purpose of the present invention is to provide a preparation method for plasma-oriented materials and components and high-temperature field tungsten materials, so as to meet the demand for high-performance tungsten in the nuclear industry or high-temperature field. The present invention mainly uses "sol-heterogeneous precipitation-calcination" to prepare carbide and rare earth oxide nano-composite strengthening phase powder, and then enters PCA high-energy ball milling or sol spray drying to obtain a composite powder with uniform distribution of carbide and rare earth oxide. Conventional forming and sintering can obtain more than 99.0% dense fine-grained tungsten materials.

The preparation method of carbide and rare earth oxide compound reinforced fine-grained tungsten material provided by the present invention, the fine-grained tungsten is composed of 0.1-2.0% carbide, 0.1-2.0% rare-earth oxide and tungsten, and the carbide is One or both of TiC and ZrC, and one or both of La ₂ O ₃ and Y ₂ O ₃ for the rare earth oxide. Its preparation process is as follows:

(1) Preparation of carbide and rare earth oxide nanocomposite strengthening phase powder

The preparation of composite strengthening phase powder mainly includes the following steps: ① Select one or two kinds of carbides and prepare 10-30g/L carbide suspension; select one or two kinds of rare earth salts and prepare 0.01-0.5mol/L Rare earth salt solution; ② Mix carbide suspension with rare earth salt solution, add reaction dispersant and stir evenly; ③ Under the action of ultrasonic vibration and stirring, slowly add alkaline solution to the mixed solution of rare earth salt and carbide, Control the pH value of the reaction solution from 9 to 13, so that the rare earth salt forms a colloid and evenly covers the surface of the carbide; ④ Precipitation, static aging, and suction filtration to obtain the precursor of carbide and rare earth oxide nanocomposite strengthening phase powder; ⑤ Calcined under a hydrogen atmosphere to prepare carbide and rare earth oxide nanocomposite reinforcement phase powder;

(2) Preparation of carbide and rare earth oxide composite reinforced fine-grained tungsten powder

Carbide and rare earth oxide composite strengthened fine-grained tungsten powder is prepared by PCA high-energy ball milling or sol-spray drying method: the method of PCA high-energy ball milling is to use liquid process control agent medium, add protective atmosphere, and mix carbide and rare earth oxide The nanocomposite reinforcing phase powder and tungsten powder are mixed and high-energy ball milled for 5 to 30 hours; the method of sol-spray drying is to prepare carbide and rare earth oxide nanocomposite reinforcing phase powder and tungstate into a sol, which is then spray-dried and thermally reduced ;

(3) Dry granulation

Dry in a vacuum state, drying temperature is 50-100°C, and keep warm for 1-5 hours; the composite powder is made into a plate or rod by pressing, and then crushed and sieved;

(4) Forming

Put the composite powder into the cavity of the compression mold, and use molding or isostatic pressing to shape the composite powder;

(5) High temperature sintering

Sintering in a protective atmosphere, the sintering temperature is 1700-2100°C, and the holding time is 1-10h to obtain carbide and rare earth oxide composite reinforced fine-grained tungsten material; the grain size is uniform, the grain size is below 8μm, and the carbide particle phase 0.05~1.0μm, evenly dispersed in the interior of tungsten grains and grain boundaries.

The rare earth salts include nitrates, oxalates, carbonates, chlorides or sulfates of Y and La.

(1) The reactive dispersant described in ② is stearic acid, polyethylene glycol, urea, N, N-dimethylformamide, OP emulsifier, Tween-20 or sodium dodecylsulfonate, The volume fraction of the reaction dispersant is 0.2-1.5% of the total amount of the rare earth salt solution and the carbide solution.

(1) The alkaline solution described in ③ is NaOH, KOH or ammonia water.

(1) The calcination temperature in ⑤ is 450-800°C, and keep it warm for 1-5 hours.

In the PCA high-energy ball milling method described in (2), the liquid process control agent medium is one or more of paraffin, stearic acid, absolute ethanol, polyethylene glycol, and carbon tetrachloride, and the protective atmosphere is argon or hydrogen.

The sintering atmosphere is a protective atmosphere of H ₂ , Ar, Ar+H ₂ or vacuum.

In view of the coarse crystal grains and anisotropy of properties of pure tungsten at present, the density and properties need to be improved by rolling and forging, and the compound addition of carbides and rare earth oxides is designed to further refine the tungsten grains and increase the recrystallization temperature of tungsten and high temperature toughness, improving the ability to resist high heat load and neutron radiation, and to overcome the existing complex preparation technologies such as hot isostatic pressing and hot pressing, which are difficult to realize the bottleneck of engineering preparation, and adopt conventional forming and sintering methods Preparation of high-performance fine-grained tungsten materials. Compared with the tungsten material prepared by the existing method, the present invention has the following advantages:

1. Carbide can effectively enhance the neutron radiation resistance of tungsten materials. Rare earth oxides can improve the recrystallization temperature, high temperature strength and toughness, and high thermal load resistance of tungsten materials. The use of carbides and rare earth oxides can further refine tungsten crystals. Increase the recrystallization temperature and high temperature toughness of tungsten, improve the ability to resist high heat load and neutron radiation; use conventional sintering at 1700-2100 °C to achieve a density of more than 99.0%, and the tensile strength at room temperature exceeds 580 MPa , The tensile strength at 1200°C exceeds 450MPa, the grain size is below 8μm, and the structure is uniform.

2. Using carbide and rare earth oxide nanocomposite strengthening phase powder can obtain fine-grained tungsten materials in which carbides and rare earth oxides are dispersed in the matrix. Carbide and rare earth oxides have a good fine-grained and dispersed effect on the material Reinforcing effect.

3. Using this method to prepare carbide and rare earth oxide composite reinforced fine-grained tungsten materials, high-energy ball milling + hot pressing or hot isostatic pressing is easier to engineer large-size or irregular-shaped samples, which overcomes the traditional commercialization. Tungsten sintering needs to rely on rolling and forging to improve the density and performance, so as to meet the demand for high-performance tungsten in the high-temperature field and nuclear energy field.

Detailed ways:

The following examples further illustrate the present invention, rather than limit the present invention.

Example 1:

The components of carbide and rare earth oxide composite strengthened fine-grained tungsten material are calculated by mass percentage: ZrC content is 0.1%, Y ₂ O ₃ content is 0.3%, and the balance is W.

The preparation process is as follows:

(1) Preparation of carbide and rare earth oxide nanocomposite strengthening phase powder

The preparation of composite strengthening phase powder mainly includes the following steps: ① Prepare 15g/L ZrC suspension; select Y(NO) ₃ and prepare 0.2mol/L Y(NO) ₃ salt solution; Mix with rare earth salt solution, add stearic acid and stir evenly; ③Under the action of ultrasonic vibration and stirring, slowly add NH ₄ OH solution to the mixed solution of rare earth salt and carbide, control the pH value of the reaction solution to 9-10, Make the rare earth salt form a colloid and evenly cover the surface of the carbide; ④precipitate, stand for aging, and suction filter to obtain the precursor of the carbide and rare earth oxide nanocomposite strengthening phase powder; Produce carbide and rare earth oxide nanocomposite strengthening phase powder;

(2) Preparation of carbide and rare earth oxide composite reinforced fine-grained tungsten powder

Using absolute ethanol and stearic acid as the process control agent, argon as the ball milling protective atmosphere, the carbide and rare earth oxide nanocomposite strengthening phase powder and tungsten powder were subjected to high-energy ball milling for 10 hours to obtain carbide and rare earth oxide composite strengthening Fine crystalline tungsten powder;

(3) Dry granulation

Dry in a vacuum state at a drying temperature of 70°C and keep warm for 2 hours; use a pressing method to make the composite powder into a plate or rod shape, then crush and sieve;

(4) Forming

Put the composite powder into the cavity of the compression mold, and use molding or isostatic pressing to shape the composite powder;

(5) High temperature sintering

Using _H2 atmosphere sintering, the sintering temperature is 1920 ℃, and the holding time is 5h to prepare carbide and rare earth oxide composite reinforced fine-grained tungsten material; the grains are fine and evenly distributed, the tungsten grain size is below 8μm, and the carbide particles The phase is between 0.05 and 1.0 μm, uniformly dispersed in the tungsten grains and grain boundaries.

Example 2:

The composition of carbide and rare earth oxide composite strengthened fine-grained tungsten material is calculated by mass percentage: ZrC content is 1.2%, TiC content is 0.7%, Y ₂ O ₃ content is 0.5%, and the balance is W.

The preparation process is as follows:

(1) Preparation of carbide and rare earth oxide nanocomposite strengthening phase powder

The preparation of composite strengthening phase powder mainly includes the following steps: ① Prepare 15g/L ZrC and TiC suspension; select YCl ₃ and prepare 0.2mol/L YCl ₃ salt solution; ② mix carbide suspension with rare earth salt solution Mix, add PEG agent and stir evenly; ③Under the action of ultrasonic vibration and stirring, slowly add NaOH solution to the mixed solution of rare earth salt and carbide, control the pH value of the reaction solution to 9-10, so that the rare earth salt forms a colloid that is evenly coated Cover the surface of carbide; ④ Precipitate, stand for aging, and suction filter to obtain the precursor of carbide and rare earth oxide nanocomposite strengthening phase powder; Nano-composite reinforced phase powder;

(2) Preparation of carbide and rare earth oxide composite reinforced fine-grained tungsten powder

Using absolute ethanol and stearic acid as the process control agent, argon as the ball milling protective atmosphere, the carbide and rare earth oxide nano-composite strengthening phase powder and tungsten powder were subjected to high-energy ball milling for 8 hours to obtain carbide and rare earth oxide composite strengthening Fine crystalline tungsten powder;

(3) Dry granulation

Dry in a vacuum state at a drying temperature of 90°C and keep warm for 1 hour; use a pressing method to make the composite powder into a plate or rod shape, then crush and sieve;

(4) Forming

Put the composite powder into the cavity of the compression mold, and use molding or isostatic pressing to shape the composite powder;

(5) High temperature sintering

Using _H2 atmosphere sintering, the sintering temperature is 1980 ℃, and the holding time is 3.5h to prepare carbide and rare earth oxide composite strengthened fine-grained tungsten material; the grains are fine and evenly distributed, and the tungsten grain size is below 8μm The particle phase is between 0.05 and 1.0 μm, uniformly dispersed in the tungsten grains and grain boundaries.

Example 3:

The composition of carbide and rare earth oxide composite strengthened fine-grained tungsten material is calculated by mass percentage: the content of TiC is 0.7%, the content of La ₂ O ₃ is 1.5%, and the balance is W.

The preparation process is as follows:

(1) Preparation of carbide and rare earth oxide nanocomposite strengthening phase powder

The preparation of the composite strengthening phase powder mainly includes the following steps: ① prepare 15g/L TiC suspension; select La(NO) ₃ and prepare 0.3mol/L La (NO) ₃ salt solution; ② prepare carbide suspension Mix with rare earth salt solution, add OP emulsifier and stir evenly; ③Under the action of ultrasonic vibration and stirring, slowly add NH ₄ OH solution to the mixed solution of rare earth salt and carbide, control the pH value of the reaction solution to 10-11, Make the rare earth salt form a colloid and evenly cover the surface of the carbide; ④precipitate, stand for aging, and suction filter to obtain the precursor of the carbide and rare earth oxide nanocomposite strengthening phase powder; Preparation of carbide and rare earth oxide nanocomposite strengthening phase powder;

(2) Preparation of carbide and rare earth oxide composite reinforced fine-grained tungsten powder

Using absolute ethanol and stearic acid as the process control agent, argon as the ball milling protective atmosphere, the carbide and rare earth oxide nano-composite strengthening phase powder and tungsten powder were subjected to high-energy ball milling for 8 hours to obtain carbide and rare earth oxide composite strengthening Fine crystalline tungsten powder;

(3) Dry granulation

Dry in a vacuum state at a drying temperature of 75°C and keep warm for 2 hours; use a pressing method to make the composite powder into a plate or rod shape, then crush and sieve;

(4) Forming

Put the composite powder into the cavity of the compression mold, and use molding or isostatic pressing to shape the composite powder;

(5) High temperature sintering

Using H ₂ atmosphere sintering, the sintering temperature is 1940 ℃, and the holding time is 5h to prepare carbide and rare earth oxide composite strengthened fine-grained tungsten material; the grains are fine and evenly distributed, and the tungsten grain size is below 8 μm. The phase is between 0.05 and 1.0 μm, uniformly dispersed in the tungsten grains and grain boundaries.

Example 4:

The composition of carbide and rare earth oxide composite strengthened fine-grained tungsten material is calculated by mass percentage: ZrC content is 0.8%, TiC content is 0.6%, La ₂ O ₃ content is 0.5%, and the balance is W.

The preparation process is as follows:

(1) Preparation of carbide and rare earth oxide nanocomposite strengthening phase powder

The preparation of composite strengthening phase powder mainly includes the following steps: ① Prepare 15g/L ZrC and TiC suspension; select La ₂ (SO ₄ ) ₃ , and prepare 0.1mol/L La ₂ (SO ₄ ) ₃ salt solution; ② Mix the carbide suspension with the rare earth salt solution, add PEG agent and stir evenly; ③Under the action of ultrasonic vibration and stirring, slowly add KOH solution to the mixed solution of rare earth salt and carbide to control the pH value of the reaction solution to 10 ～11, so that the rare earth salt forms a colloid and evenly covers the surface of the carbide; ④ Precipitation, static aging, and suction filtration to obtain the precursor of carbide and rare earth oxide nanocomposite reinforcement phase powder; ⑤ Calcination at 700 ° C under a hydrogen atmosphere 2.5h, prepared carbide and rare earth oxide nanocomposite strengthening phase powder;

(2) Preparation of carbide and rare earth oxide composite reinforced fine-grained tungsten powder

Using absolute ethanol and stearic acid as the process control agent, argon as the ball milling protective atmosphere, the carbide and rare earth oxide nano-composite strengthening phase powder and tungsten powder were subjected to high-energy ball milling for 8 hours to obtain carbide and rare earth oxide composite strengthening Fine crystalline tungsten powder;

(3) Dry granulation

Dry in a vacuum state at a drying temperature of 80°C and keep warm for 2 hours; use a pressing method to make the composite powder into a plate or rod shape, then crush and sieve;

(4) Forming

Put the composite powder into the cavity of the compression mold, and use molding or isostatic pressing to shape the composite powder;

(5) High temperature sintering

Using _H2 atmosphere sintering, the sintering temperature is 1890 ℃, and the holding time is 7.5h to prepare carbide and rare earth oxide composite reinforced fine-grained tungsten material; the grains are fine and evenly distributed, and the tungsten grain size is below 8μm The particle phase is between 0.05 and 1.0 μm, uniformly dispersed in the tungsten grains and grain boundaries.

Example 5:

The composition of carbide and rare earth oxide composite strengthened fine-grained tungsten material is calculated by mass percentage: TiC content is 0.8%, La ₂ O ₃ content is 0.5%, Y ₂ O ₃ content is 1.0%, and the balance is W.

The preparation process is as follows:

(1) Preparation of carbide and rare earth oxide nanocomposite strengthening phase powder

The preparation of composite reinforcement phase powder mainly includes the following steps: ① Prepare 15g/L TiC suspension; select La(NO) ₃ , Y(NO) ₃ , and prepare 0.3mol/L La(NO) ₃ , Y(NO ) ₃ salt solution; ②mix carbide suspension with rare earth salt solution, add urea and stir evenly; ③under the action of ultrasonic vibration and stirring, slowly add NH ₄ OH solution to the mixed solution of rare earth salt and carbide, Control the pH value of the reaction solution to 10-11, so that the rare earth salt forms a colloid and evenly covers the surface of the carbide; ④ Precipitation, static aging, and suction filtration to obtain the precursor of carbide and rare earth oxide nanocomposite strengthening phase powder; ⑤ Calcined at 550°C for 3 hours in a hydrogen atmosphere to prepare carbide and rare earth oxide nanocomposite strengthening phase powder;

(2) Preparation of carbide and rare earth oxide composite reinforced fine-grained tungsten powder

Prepare carbide and rare earth oxide nanocomposite strengthening phase powder and tungstate into a sol according to the composition ratio, and spray dry and thermally reduce to prepare carbide and rare earth oxide composite strengthening fine-grained tungsten powder;

(3) Dry granulation

Dry in a vacuum state at a drying temperature of 75°C and keep warm for 2 hours; use a pressing method to make the composite powder into a plate or rod shape, then crush and sieve;

(4) Forming

Put the composite powder into the cavity of the compression mold, and use molding or isostatic pressing to shape the composite powder;

(5) High temperature sintering

Using _H2 atmosphere sintering, the sintering temperature is 1980 ℃, and the holding time is 3.5h to prepare carbide and rare earth oxide composite strengthened fine-grained tungsten material; the grains are fine and evenly distributed, and the tungsten grain size is below 8μm The particle phase is between 0.05 and 1.0 μm, uniformly dispersed in the tungsten grains and grain boundaries.

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.