CN103740994B - Nanostructure tungsten alloy and preparation method thereof - Google Patents
Nanostructure tungsten alloy and preparation method thereof Download PDFInfo
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- CN103740994B CN103740994B CN201410046913.7A CN201410046913A CN103740994B CN 103740994 B CN103740994 B CN 103740994B CN 201410046913 A CN201410046913 A CN 201410046913A CN 103740994 B CN103740994 B CN 103740994B
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Abstract
The invention discloses a kind of Nanostructure tungsten alloy and preparation method thereof.Alloy forms primarily of tungsten; be also wherein the zirconium of 0.05 ~ 1.0wt% and the rare-earth oxide particle of 0.2 ~ 2.0wt% containing weight percent, rare-earth oxide particle is be distributed in yttria particles in tungsten crystal or lanthanum oxide particles or cerium oxide particle.Method is that after first ammonium paratungstate, rare-earth metal nitrate, citric acid and deionized water being mixed with transparent mixed solution, stirring reaction obtains gel, the mixed powder of Tungsten oxide 99.999 and rare-earth oxide will be calcined to obtain again after gel heating, drying, then, first mixed powder is placed in the mixed powder that nitrogen atmosphere reduction reaction obtains tungsten and rare-earth oxide, again itself and metal zirconium or zircoium hydride powder are carried out being mixed to get the mixed powder containing tungsten, zirconium or zircoium hydride, rare-earth oxide, finally pressed compact and sintering are carried out to it, obtained object product.It can be used for the fields such as illumination, high-temperature component, aerospace device, high-temperature resistant container.
Description
Technical field
The present invention relates to a kind of tungstenalloy and preparation method, especially a kind of Nanostructure tungsten alloy and preparation method thereof.
Background technology
There is the tungsten of the advantage such as high-melting-point, high sputtering threshold value, low thermal coefficient of expansion, low-steam pressure, good corrosion resistance, can be widely used in the fields such as high-temperature component, electron tube, X-ray target, illumination, and become candidate's wall material of following fusion reactor.But, tungsten is except also existing the shortcoming such as low temperature brittleness, recrystallize fragility, also have and at high temperature easily grain growth occur and cause that recrystallize is brittle, hot strength is low, and make it be difficult to the defect of machine-shaping due to the high rigidity of tungsten and high ductile-brittle transition temperature.In the recent period, people are in order to improve the performance of tungsten, do some to attempt and effort, as being entitled as " Mechanical Behavior of W-Y2O3and W-Ti Alloys from25 DEG C of to1000 DEG C ", " METALLURGICAL AND MATERIALS TRANSACTIONS A ", 2009, the 40A(mechanical property of 25 DEG C to 1000 DEG C " tungsten-yttrium oxide and the tungsten-titanium alloy ", " metallurgical with material journal A " the 40th volume in 2009) article.The tungsten mentioned in this article-yttrium oxide alloy is that the grain boundaries of tungsten is distributed with yttria particles; Powder metallurgic method is adopted to obtain product to the nanometer powder of tungsten and yttrium oxide during preparation.But, no matter be product, or its preparation method, all there is weak point, first, though the yttria particles being distributed in tungsten grain boundaries serves the effect of dispersion-strengthened and refinement tungsten grain, improve the hot strength of product, but fail to make the toughness of product to increase relative to tungsten; Secondly, preparation method can not obtain the product that hot strength and toughness are all promoted.
Summary of the invention
The technical problem to be solved in the present invention, for overcoming weak point of the prior art, provides a kind of rational in infrastructure, the Nanostructure tungsten alloy that its hot strength and toughness all increase.
Another technical problem that the present invention will solve is for providing a kind of preparation method of above-mentioned Nanostructure tungsten alloy.
For solving technical problem of the present invention, the technical scheme adopted is: Nanostructure tungsten alloy forms primarily of tungsten, particularly,
Also containing weight percent in described tungstenalloy is the zirconium of 0.05 ~ 1.0wt% and the rare-earth oxide particle of 0.2 ~ 2.0wt%;
Described rare-earth oxide particle is be distributed in yttria particles in tungsten crystal or lanthanum oxide particles or cerium oxide particle, and its particle diameter is 10 ~ 200nm.
Further improvement as Nanostructure tungsten alloy:
Preferably, rare-earth oxide particle is spherical, or elliposoidal.
For solving another technical problem of the present invention, another technical scheme adopted is: the preparation method of above-mentioned Nanostructure tungsten alloy comprises powder metallurgic method, and particularly key step is as follows:
Step 1, after first ammonium paratungstate, rare-earth metal nitrate, citric acid and deionized water being mixed with transparent mixed solution, stirring reaction at being placed in 50 ~ 95 DEG C, obtain gel, wherein, ammonium paratungstate in mixed solution and the mol ratio of citric acid are 1:3 ~ 24, then calcine at least 1h at gel heating, drying is placed on 400 ~ 800 DEG C, obtain the mixed powder of Tungsten oxide 99.999 and rare-earth oxide;
Step 2, first the mixed powder of Tungsten oxide 99.999 and rare-earth oxide is placed in hydrogen atmosphere, reduction reaction at least 1h at temperature is 500 ~ 900 DEG C, obtain the tungsten of nano-scale and the mixed powder of rare-earth oxide, again the tungsten of nano-scale and the mixed powder of rare-earth oxide are mixed with metal zirconium powder or zircoium hydride powder, obtain the mixed powder containing tungsten, zirconium or zircoium hydride, rare-earth oxide;
Step 3, carries out pressed compact and sintering to the mixed powder containing tungsten, zirconium or zircoium hydride, rare-earth oxide, obtained Nanostructure tungsten alloy.
Further improvement as the preparation method of Nanostructure tungsten alloy:
Preferably, obtained Nanostructure tungsten alloy being placed in temperature is carry out hot rolling at 1100 ~ 1700 DEG C or swage; Be beneficial to the overall quality promoting object product further.
Preferably, rare-earth metal nitrate is Yttrium trinitrate, or lanthanum nitrate, or cerous nitrate; Not only make the source comparatively horn of plenty of raw material, also make preparation technology more easily implement and flexibly.
Preferably, the temperature of gel heating, drying is 100 ~ 250 DEG C, the time is 1 ~ 20h; Be beneficial to and obtain dry gel.
Preferably, the process of pressed compact and sintering is, first the mixed powder containing tungsten, zirconium or zircoium hydride, rare-earth oxide being placed in pressure is be pressed into green compact under 200 ~ 600MPa, then green compact is placed in protective atmosphere or vacuum, sinter molding at 1500 ~ 2500 DEG C; Be easy to the object product obtaining higher quality.
Preferably, the process of pressed compact and sintering is that the mixed powder containing tungsten, zirconium or zircoium hydride, rare-earth oxide is placed in protective atmosphere, in pressure be 100 ~ 200MPa, temperature be 1500 ~ 2000 DEG C at HIP sintering shaping; Be easy to the object product obtaining higher quality.
Preferably, the process of pressed compact and sintering is that the mixed powder containing tungsten, zirconium or zircoium hydride, rare-earth oxide is placed in protective atmosphere or vacuum, in pressure be 30 ~ 70MPa, temperature be 1500 ~ 2000 DEG C at discharge plasma sintering shaping; Be easy to the object product obtaining higher quality.
Be preferably, protective atmosphere is hydrogen atmosphere, or nitrogen atmosphere, or argon gas atmosphere; Except make the alternative leeway of protective atmosphere comparatively large except, be also convenient to the enforcement of preparation technology.
Relative to the beneficial effect of prior art be:
One, transmission electron microscope and its subsidiary power spectrum tester is used to characterize respectively to obtained object product, from its result, object product be tungsten crystal grain in be distributed with on tiny, the homodisperse rare-earth oxide particle of particle, crystal boundary and be distributed with zirconia particles, and be solid-solution in the zirconium in object product; Wherein, in object product, the content of zirconium and rare-earth oxide is respectively 0.05 ~ 1.0wt% and 0.2 ~ 2.0wt%; surplus is tungsten; rare-earth oxide particle is yttria particles or lanthanum oxide particles or cerium oxide particle, and granule-morphology is spherical or elliposoidal, particle diameter are 10 ~ 200nm.This object product be made up of adulterate in matrix metal tungsten zirconium and rare-earth oxide, both because the zirconium of doping or zircoium hydride can reduce the impact of nonmetallic impurity elemental oxygen, carbon, nitrogen etc., particularly it can form zirconia particles with the impurity element oxygen in tungsten, reduce oxygen to the embrittling effect of tungsten crystal boundary, greatly increase the bonding force of crystal boundary; Hot strength and the toughness of object product is improve again because of the doping of rare-earth oxide; Hot strength and the toughness of object product is greatly improved in the crystal grain being also distributed in tungsten equably due to the rare-earth oxide of nano-scale; More because the common of metal zirconium and rare-earth oxide particle further increasing hot strength and the toughness of object product with interacting.
Its two, use material-testing machine to carry out material extending performance characterization to tungsten and object product respectively, from its result, the hot strength of object product and toughness are all higher than existing tungsten-yttrium oxide alloy and tungsten.During sign, the strain rate of Elongation test is 2 × 10
-4.
They are three years old, preparation method's science, effectively, not only to obtain rational in infrastructure, object product---the Nanostructure tungsten alloy that its hot strength and toughness all increase, also because the starting compound of tungsten and thulium carries out other mixing of molecular level in the solution, make the size of object product middle-weight rare earths metal oxide tiny, be evenly distributed, and the overwhelming majority is distributed in tungsten grain inside, such microtexture had both improve the hot strength of object product, made it have again good toughness simultaneously.And the rare-earth metal doped oxide compound of solid-solid blend method of prior art is in tungsten, make the size of rare-earth oxide large and mostly at grain boundaries, although can pinning crystal boundary, improve intensity, simultaneously also can become focal point of stress, cause toughness to reduce.Add trace zirconium in object product or zirconic existence and further increasing hot strength and the toughness of object product, making it while having good room temperature strength and toughness, under high temperature, be also provided with higher intensity and toughness; More there is the feature that preparation cost is low, be easy to large-scale industrial production.Object product is made to be expected be widely used in flux of plasma wall etc. in illumination, high-temperature component, aerospace device, high-temperature resistant container and fusion reactor.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, optimal way of the present invention is described in further detail.
Fig. 1 is to one of result that obtained object product uses transmission electron microscope (TEM) to characterize.The rare-earth oxide the particle spherical or ellipsoidal particle of white arrow indication (in the figure) that TEM image demonstrates nano-scale is distributed in the intra-die of tungsten equably.
Fig. 2 is to one of result that object product uses transmission electron microscope and subsidiary power spectrum (EDS) tester of transmission electron microscope to characterize.Wherein, the TEM image of product for the purpose of a in Fig. 2, its grain boundaries demonstrating tungsten is distributed with nano particle, and in Fig. 2, the illustration in a upper right corner is the image K-M of this nano particle, shows that this nano particle is zirconium white; In Fig. 2, b is the EDS spectrogram of the object product of position shown in a in Fig. 2, and the object product which confirms this position is made up of oxygen, tungsten, zirconium.
Fig. 3 is respectively to one of result that tungsten and object product use material-testing machine to characterize.Can be found out by it, 500 DEG C time, the intensity of object product and toughness are all higher than tungsten.
Embodiment
First buy from market or obtain by ordinary method:
Ammonium paratungstate; As the Yttrium trinitrate of rare-earth metal nitrate, lanthanum nitrate and cerous nitrate; Citric acid; Deionized water; Metal zirconium powder and zircoium hydride powder; As the hydrogen gas of protective atmosphere, nitrogen gas and argon gas.
Then,
Embodiment 1
The concrete steps of preparation are:
Step 1, after first ammonium paratungstate, rare-earth metal nitrate, citric acid and deionized water being mixed with transparent mixed solution, stirring reaction at being placed in 50 DEG C, obtains gel; Wherein, the mol ratio of the ammonium paratungstate in mixed solution, rare-earth metal nitrate and citric acid is 1:0.08:24, and rare-earth metal nitrate is Yttrium trinitrate.3h is calcined at again gel heating, drying being placed on 400 DEG C; Wherein, the temperature of gel heating, drying is 100 DEG C, the time is 20h, obtains the mixed powder of Tungsten oxide 99.999 and rare-earth oxide.
Step 2, is first placed in hydrogen atmosphere by the mixed powder of Tungsten oxide 99.999 and rare-earth oxide, reduction reaction 3h at temperature is 500 DEG C, obtains the tungsten of nano-scale and the mixed powder of rare-earth oxide.Again the tungsten of nano-scale and the mixed powder of rare-earth oxide are mixed with the metal zirconium powder (or zircoium hydride powder) of nano-scale; Wherein, in the zirconium in the metal zirconium powder (or zircoium hydride powder) of nano-scale and mixed powder, the mass ratio of tungsten is 0.05:100, obtains the mixed powder containing tungsten, zirconium (or zircoium hydride), rare-earth oxide.
Step 3, first the mixed powder containing tungsten, zirconium (or zircoium hydride), rare-earth oxide being placed in pressure is be pressed into green compact under 200MPa, then green compact is placed in hydrogen atmosphere (or vacuum tightness is the≤vacuum of 100Pa), sinter molding at 2500 DEG C;
Or, the mixed powder containing tungsten, zirconium (or zircoium hydride), rare-earth oxide is placed in hydrogen atmosphere, in pressure be 100MPa, temperature be 2000 DEG C at HIP sintering shaping;
Or, the mixed powder containing tungsten, zirconium (or zircoium hydride), rare-earth oxide is placed in hydrogen atmosphere (or vacuum tightness is the≤vacuum of 100Pa), in pressure be 30MPa, temperature be 2000 DEG C at discharge plasma sintering shaping;
Obtain and be similar in Fig. 1 and Fig. 2 shown in a, and the Nanostructure tungsten alloy as shown in the curve in b and Fig. 3 in Fig. 2.
Embodiment 2
The concrete steps of preparation are:
Step 1, after first ammonium paratungstate, rare-earth metal nitrate, citric acid and deionized water being mixed with transparent mixed solution, stirring reaction at being placed in 61 DEG C, obtains gel; Wherein, the mol ratio of the ammonium paratungstate in mixed solution, rare-earth metal nitrate and citric acid is 1:0.12:18, and rare-earth metal nitrate is Yttrium trinitrate.2.5h is calcined at again gel heating, drying being placed on 500 DEG C; Wherein, the temperature of gel heating, drying is 138 DEG C, the time is 15h, obtains the mixed powder of Tungsten oxide 99.999 and rare-earth oxide.
Step 2, is first placed in hydrogen atmosphere by the mixed powder of Tungsten oxide 99.999 and rare-earth oxide, reduction reaction 2.5h at temperature is 600 DEG C, obtains the tungsten of nano-scale and the mixed powder of rare-earth oxide.Again the tungsten of nano-scale and the mixed powder of rare-earth oxide are mixed with the metal zirconium powder (or zircoium hydride powder) of nano-scale; Wherein, in the zirconium in the metal zirconium powder (or zircoium hydride powder) of nano-scale and mixed powder, the mass ratio of tungsten is 0.1:100, obtains the mixed powder containing tungsten, zirconium (or zircoium hydride), rare-earth oxide.
Step 3, first the mixed powder containing tungsten, zirconium (or zircoium hydride), rare-earth oxide being placed in pressure is be pressed into green compact under 300MPa, then green compact is placed in hydrogen atmosphere (or vacuum tightness is the≤vacuum of 100Pa), sinter molding at 2300 DEG C;
Or, the mixed powder containing tungsten, zirconium (or zircoium hydride), rare-earth oxide is placed in hydrogen atmosphere, in pressure be 130MPa, temperature be 1875 DEG C at HIP sintering shaping;
Or, the mixed powder containing tungsten, zirconium (or zircoium hydride), rare-earth oxide is placed in hydrogen atmosphere (or vacuum tightness is the≤vacuum of 100Pa), in pressure be 40MPa, temperature be 1875 DEG C at discharge plasma sintering shaping;
Obtain and be similar in Fig. 1 and Fig. 2 shown in a, and the Nanostructure tungsten alloy as shown in the curve in b and Fig. 3 in Fig. 2.
Embodiment 3
The concrete steps of preparation are:
Step 1, after first ammonium paratungstate, rare-earth metal nitrate, citric acid and deionized water being mixed with transparent mixed solution, stirring reaction at being placed in 73 DEG C, obtains gel; Wherein, the mol ratio of the ammonium paratungstate in mixed solution, rare-earth metal nitrate and citric acid is 1:0.04:13, and rare-earth metal nitrate is Yttrium trinitrate.2h is calcined at again gel heating, drying being placed on 600 DEG C; Wherein, the temperature of gel heating, drying is 175 DEG C, the time is 10h, obtains the mixed powder of Tungsten oxide 99.999 and rare-earth oxide.
Step 2, is first placed in hydrogen atmosphere by the mixed powder of Tungsten oxide 99.999 and rare-earth oxide, reduction reaction 2h at temperature is 700 DEG C, obtains the tungsten of nano-scale and the mixed powder of rare-earth oxide.Again the tungsten of nano-scale and the mixed powder of rare-earth oxide are carried out ball milling with metal zirconium powder (or zircoium hydride powder) to mix; Wherein, in the zirconium in metal zirconium powder (or zircoium hydride powder) and mixed powder, the mass ratio of tungsten is 0.5:100, obtains the mixed powder containing tungsten, zirconium (or zircoium hydride), rare-earth oxide.
Step 3, first the mixed powder containing tungsten, zirconium (or zircoium hydride), rare-earth oxide being placed in pressure is be pressed into green compact under 400MPa, then green compact is placed in hydrogen atmosphere (or vacuum tightness is the≤vacuum of 100Pa), sinter molding at 2000 DEG C;
Or, the mixed powder containing tungsten, zirconium (or zircoium hydride), rare-earth oxide is placed in hydrogen atmosphere, in pressure be 150MPa, temperature be 1750 DEG C at HIP sintering shaping;
Or, the mixed powder containing tungsten, zirconium (or zircoium hydride), rare-earth oxide is placed in hydrogen atmosphere (or vacuum tightness is the≤vacuum of 100Pa), in pressure be 50MPa, temperature be 1750 DEG C at discharge plasma sintering shaping;
Obtained as shown in a in Fig. 1 and Fig. 2, and the Nanostructure tungsten alloy as shown in the curve in b and Fig. 3 in Fig. 2.
Embodiment 4
The concrete steps of preparation are:
Step 1, after first ammonium paratungstate, rare-earth metal nitrate, citric acid and deionized water being mixed with transparent mixed solution, stirring reaction at being placed in 84 DEG C, obtains gel; Wherein, the mol ratio of the ammonium paratungstate in mixed solution, rare-earth metal nitrate and citric acid is 1:0.20:8, and rare-earth metal nitrate is Yttrium trinitrate.1.5h is calcined at again gel heating, drying being placed on 700 DEG C; Wherein, the temperature of gel heating, drying is 213 DEG C, the time is 5h, obtains the mixed powder of Tungsten oxide 99.999 and rare-earth oxide.
Step 2, is first placed in hydrogen atmosphere by the mixed powder of Tungsten oxide 99.999 and rare-earth oxide, reduction reaction 1.5h at temperature is 800 DEG C, obtains the tungsten of nano-scale and the mixed powder of rare-earth oxide.Again the tungsten of nano-scale and the mixed powder of rare-earth oxide are mixed with the metal zirconium powder (or zircoium hydride powder) of nano-scale; Wherein, in the zirconium in the metal zirconium powder (or zircoium hydride powder) of nano-scale and mixed powder, the mass ratio of tungsten is 0.8:100, obtains the mixed powder containing tungsten, zirconium (or zircoium hydride), rare-earth oxide.
Step 3, first the mixed powder containing tungsten, zirconium (or zircoium hydride), rare-earth oxide being placed in pressure is be pressed into green compact under 500MPa, then green compact is placed in hydrogen atmosphere (or vacuum tightness is the≤vacuum of 100Pa), sinter molding at 1800 DEG C;
Or, the mixed powder containing tungsten, zirconium (or zircoium hydride), rare-earth oxide is placed in hydrogen atmosphere, in pressure be 180MPa, temperature be 1625 DEG C at HIP sintering shaping;
Or, the mixed powder containing tungsten, zirconium (or zircoium hydride), rare-earth oxide is placed in hydrogen atmosphere (or vacuum tightness is the≤vacuum of 100Pa), in pressure be 6MPa, temperature be 1625 DEG C at discharge plasma sintering shaping;
Obtain and be similar in Fig. 1 and Fig. 2 shown in a, and the Nanostructure tungsten alloy as shown in the curve in b and Fig. 3 in Fig. 2.
Embodiment 5
The concrete steps of preparation are:
Step 1, after first ammonium paratungstate, rare-earth metal nitrate, citric acid and deionized water being mixed with transparent mixed solution, stirring reaction at being placed in 95 DEG C, obtains gel; Wherein, the mol ratio of the ammonium paratungstate in mixed solution, rare-earth metal nitrate and citric acid is 1:0.08:3, and rare-earth metal nitrate is Yttrium trinitrate.1h is calcined at again gel heating, drying being placed on 800 DEG C; Wherein, the temperature of gel heating, drying is 250 DEG C, the time is 1h, obtains the mixed powder of Tungsten oxide 99.999 and rare-earth oxide.
Step 2, is first placed in hydrogen atmosphere by the mixed powder of Tungsten oxide 99.999 and rare-earth oxide, reduction reaction 1h at temperature is 900 DEG C, obtains the tungsten of nano-scale and the mixed powder of rare-earth oxide.Again the tungsten of nano-scale and the mixed powder of rare-earth oxide are mixed with the metal zirconium powder (or zircoium hydride powder) of nano-scale; Wherein, in the zirconium in the metal zirconium powder (or zircoium hydride powder) of nano-scale and mixed powder, the mass ratio of tungsten is 1:100, obtains the mixed powder containing tungsten, zirconium (or zircoium hydride), rare-earth oxide.
Step 3, first the mixed powder containing tungsten, zirconium (or zircoium hydride), rare-earth oxide being placed in pressure is be pressed into green compact under 600MPa, then green compact is placed in hydrogen atmosphere (or vacuum tightness is the≤vacuum of 100Pa), sinter molding at 1500 DEG C;
Or, the mixed powder containing tungsten, zirconium (or zircoium hydride), rare-earth oxide is placed in hydrogen atmosphere, in pressure be 200MPa, temperature be 1500 DEG C at HIP sintering shaping;
Or, the mixed powder containing tungsten, zirconium (or zircoium hydride), rare-earth oxide is placed in hydrogen atmosphere (or vacuum tightness is the≤vacuum of 100Pa), in pressure be 70MPa, temperature be 1500 DEG C at discharge plasma sintering shaping;
Obtain and be similar in Fig. 1 and Fig. 2 shown in a, and the Nanostructure tungsten alloy as shown in the curve in b and Fig. 3 in Fig. 2.
If promote the overall quality of object product further, obtained Nanostructure tungsten alloy can be placed in temperature is carry out hot rolling at 1100 ~ 1700 DEG C or swage.
Select as the Yttrium trinitrate of rare-earth metal nitrate or lanthanum nitrate or cerous nitrate more respectively; the metal zirconium powder of nano-scale or zircoium hydride powder; as the hydrogen gas of protective atmosphere or nitrogen gas or argon gas; repeat above-described embodiment 1 ~ 5; obtain equally as or be similar in Fig. 1 and Fig. 2 shown in a, and the Nanostructure tungsten alloy as shown in the curve in b and Fig. 3 in Fig. 2.
Obviously, those skilled in the art can carry out various change and modification to Nanostructure tungsten alloy of the present invention and preparation method thereof and not depart from the spirit and scope of the present invention.Like this, if belong within the scope of the claims in the present invention and equivalent technologies thereof to these amendments of the present invention and modification, then the present invention is also intended to comprise these change and modification.
Claims (8)
1. a preparation method for Nanostructure tungsten alloy, comprises powder metallurgic method, it is characterized in that key step is as follows:
Step 1, after first ammonium paratungstate, rare-earth metal nitrate, citric acid and deionized water being mixed with transparent mixed solution, stirring reaction at being placed in 50 ~ 95 DEG C, obtain gel, wherein, ammonium paratungstate in mixed solution and the mol ratio of citric acid are 1:3 ~ 24, then calcine at least 1h at gel heating, drying is placed on 400 ~ 800 DEG C, obtain the mixed powder of Tungsten oxide 99.999 and rare-earth oxide;
Step 2, first the mixed powder of Tungsten oxide 99.999 and rare-earth oxide is placed in hydrogen atmosphere, reduction reaction at least 1h at temperature is 500 ~ 900 DEG C, obtain the tungsten of nano-scale and the mixed powder of rare-earth oxide, again the tungsten of nano-scale and the mixed powder of rare-earth oxide are mixed with metal zirconium powder or zircoium hydride powder, obtain the mixed powder containing tungsten, zirconium or zircoium hydride, rare-earth oxide;
Step 3, carries out pressed compact and sintering to the mixed powder containing tungsten, zirconium or zircoium hydride, rare-earth oxide, obtained Nanostructure tungsten alloy;
Described Nanostructure tungsten alloy is the zirconium of 0.05 ~ 1.0wt% and the rare-earth oxide particle of 0.2 ~ 2.0wt% and surplus by weight percent is that tungsten forms; wherein, the yttria particles of rare-earth oxide particle to be its particle diameter be distributed in tungsten crystal be 10 ~ 200nm or lanthanum oxide particles or cerium oxide particle.
2. the preparation method of Nanostructure tungsten alloy according to claim 1, is characterized in that obtained Nanostructure tungsten alloy being placed in temperature is carry out hot rolling at 1100 ~ 1700 DEG C or swage.
3. the preparation method of Nanostructure tungsten alloy according to claim 1, is characterized in that rare-earth metal nitrate is Yttrium trinitrate, or lanthanum nitrate, or cerous nitrate.
4. the preparation method of Nanostructure tungsten alloy according to claim 1, is characterized in that the temperature of gel heating, drying is 100 ~ 250 DEG C, the time is 1 ~ 20h.
5. the preparation method of Nanostructure tungsten alloy according to claim 1; it is characterized in that the process of pressed compact and sintering is; first the mixed powder containing tungsten, zirconium or zircoium hydride, rare-earth oxide being placed in pressure is be pressed into green compact under 200 ~ 600MPa; again green compact are placed in protective atmosphere or vacuum, sinter molding at 1500 ~ 2500 DEG C.
6. the preparation method of Nanostructure tungsten alloy according to claim 1; it is characterized in that the process of pressed compact and sintering is; mixed powder containing tungsten, zirconium or zircoium hydride, rare-earth oxide is placed in protective atmosphere, in pressure be 100 ~ 200MPa, temperature be 1500 ~ 2000 DEG C at HIP sintering shaping.
7. the preparation method of Nanostructure tungsten alloy according to claim 1; it is characterized in that the process of pressed compact and sintering is; mixed powder containing tungsten, zirconium or zircoium hydride, rare-earth oxide is placed in protective atmosphere or vacuum, in pressure be 30 ~ 70MPa, temperature be 1500 ~ 2000 DEG C at discharge plasma sintering shaping.
8. the preparation method of the Nanostructure tungsten alloy according to claim 5 or 6 or 7, is characterized in that protective atmosphere is hydrogen atmosphere, or nitrogen atmosphere, or argon gas atmosphere.
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| CN113186438B (en) * | 2021-01-20 | 2022-09-13 | 厦门虹鹭钨钼工业有限公司 | Alloy wire and preparation method and application thereof |
| CN113913665A (en) * | 2021-09-30 | 2022-01-11 | 中国科学院重庆绿色智能技术研究院 | Nano lanthanum oxide reinforced tungsten-based composite material and preparation method thereof |
| CN114231775B (en) * | 2021-12-21 | 2022-06-28 | 厦门欧斯拓科技有限公司 | Preparation method of rare earth composite material |
| CN114657481B (en) * | 2022-03-08 | 2023-03-24 | 厦门欧斯拓科技有限公司 | Preparation method of rare earth composite material |
| CN116692865B (en) * | 2023-08-08 | 2023-11-03 | 赣州有色冶金研究所有限公司 | Preparation method of nano tungsten carbide |
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