CN114351095A - Nanocrystalline molybdenum alloy target and preparation method thereof - Google Patents
Nanocrystalline molybdenum alloy target and preparation method thereof Download PDFInfo
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- 239000013077 target material Substances 0.000 claims abstract description 29
- 238000005096 rolling process Methods 0.000 claims abstract description 26
- 238000005516 engineering process Methods 0.000 claims abstract description 21
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 19
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011733 molybdenum Substances 0.000 claims abstract description 16
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- 239000011812 mixed powder Substances 0.000 claims description 19
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 15
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- 229910002651 NO3 Inorganic materials 0.000 claims description 11
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- 239000012467 final product Substances 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 10
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- -1 polytetrafluoroethylene Polymers 0.000 claims description 10
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- 238000004381 surface treatment Methods 0.000 claims description 10
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 10
- 239000002019 doping agent Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
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- 230000008569 process Effects 0.000 claims description 8
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- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 5
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- 238000001914 filtration Methods 0.000 claims description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 3
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- 239000000463 material Substances 0.000 abstract description 9
- 238000004544 sputter deposition Methods 0.000 abstract description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 abstract description 3
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- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
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- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a nanocrystalline molybdenum alloy target and a preparation method thereof, wherein the molybdenum alloy target comprises a molybdenum base and a small amount of secondary phase adulterant, the secondary phase adulterant at least comprises one of aluminum oxide, zirconium oxide and lanthanum oxide, and the addition amount of the secondary phase adulterant is not more than 10%. According to the invention, the original nano powder is prepared by a hydrothermal method, the high-density blank with fine grains is prepared by isostatic pressing and low-temperature rapid sintering, the residual processing traces on the surface of the target material are effectively removed by an ultrasonic surface rolling technology, and the roughness of the surface of the material is reduced. The nano-crystal molybdenum alloy target prepared by the invention has the advantages of smaller matrix grain size, high interface density, ultrafine crystal structure on the surface, higher microhardness, lower surface roughness and good wear resistance, and can meet the requirement of high-requirement sputtering coating.
Description
Technical Field
The invention relates to the technical field of metal powder metallurgy, in particular to a nanocrystal molybdenum alloy target material and a preparation method thereof.
Background
In the modern industrial field, higher requirements are put on the service performance of the molybdenum alloy target material, such as the uniformity of sputtering thickness, sputtering efficiency and service life. The prior art is very difficult to prepare the high-quality molybdenum alloy target material, so that the preparation of the high-quality molybdenum alloy target material becomes an important direction for the current research.
It is well known that nanocrystalline materials exhibit unique properties over traditional macrocrystalline materials due to their small grain size, high interfacial density, and large volume fraction. The grain size of the molybdenum target directly influences the performance of the molybdenum alloy target, and the prepared nanocrystalline molybdenum alloy target has wide market prospect.
The molybdenum alloy target has strict requirements on the surface, the comprehensive mechanical property of the material needs to be further improved through optimization of the surface structure property, and the mechanical property of the material can be improved in a limited way and the surface quality is influenced adversely through surface treatment methods such as a surface mechanical grinding technology (SMAT), an ultrasonic surface shot blasting technology (USSP), a laser shock peening technology (LSP) and the like.
Disclosure of Invention
The invention aims to provide a nanocrystalline molybdenum alloy target and a preparation method thereof, the steps are simple, the raw material cost is low, the process is controllable, the prepared finished molybdenum alloy target has higher microhardness, lower surface roughness and good wear resistance, the requirement of high-requirement sputtering coating can be met, the material is fully utilized, the resource waste is reduced to the greatest extent, and the large-scale production is realized.
The invention firstly provides a nanocrystalline molybdenum alloy target material which comprises a molybdenum base and a small amount of secondary phase adulterant, wherein the secondary phase adulterant at least comprises one of aluminum oxide, zirconium oxide and lanthanum oxide, and the addition amount of the secondary phase adulterant is not more than 10%.
The density of the molybdenum alloy target is more than 99%, the grain size is less than 300nm, and secondary phase dopants are dispersedly distributed in a molybdenum matrix.
The invention also provides a preparation method of the nanocrystalline molybdenum alloy target, which specifically comprises the following steps:
the method comprises the following steps: weighing a certain amount of nitrate and urea according to the requirements of a final product, and adding water to fully dissolve the nitrate and urea to obtain a mixed solution for later use;
step two: pouring all the mixed solution obtained in the step one into a polytetrafluoroethylene lining of a stainless steel hydrothermal kettle, locking the hydrothermal kettle, and electrifying and heating the hydrothermal kettle to perform hydrothermal reaction;
step three: weighing a certain amount of ammonium tetramolybdate according to the requirements of a final product, adding a proper amount of distilled water, adding a nitric acid solution to adjust the pH value, and fully stirring to obtain an ammonium tetramolybdate suspension for later use;
step four: pouring the mixed solution obtained after the hydrothermal reaction in the second step into the ammonium tetramolybdate suspension obtained in the third step, and fully stirring, filtering and drying to obtain a mixture; crushing the obtained mixture by using a high-speed crusher;
step five: performing three-stage hydrogen reduction on the mixed powder crushed in the step four to obtain nano composite powder;
step six: selecting a proper rubber mold according to the required size of a final product, weighing a certain amount of nano composite powder obtained after the five-step three-section hydrogen reduction, putting the nano composite powder into the mold, and pressing the nano composite powder by using a cold isostatic press;
step seven: sintering the green body pressed in the sixth step in a medium-frequency induction sintering furnace, wherein hydrogen is required to be introduced for protection in the sintering process to prevent oxidation, and obtaining a sintered green body;
step eight: machining the sintered blank obtained in the step seven, and performing fine grinding treatment to obtain a molybdenum alloy target I;
step nine: and (4) continuing to perform surface treatment on the molybdenum alloy target I obtained in the step eight by adopting an ultrasonic surface rolling technology (USRP) to obtain a molybdenum alloy target II, namely the nanocrystal molybdenum alloy target.
Further, in the foregoing production method:
the nitrate in the first step at least comprises one of aluminum nitrate, zirconium nitrate and lanthanum nitrate. Aluminum, zirconium or lanthanum is introduced through nitrate, so that the molybdenum alloy target containing alumina, zirconia and lanthanum oxide is prepared, and the compactness, hardness and wear resistance of the target are improved.
The temperature of hydrothermal reaction in the second step is 180-250 ℃, and the hydrothermal reaction time is 20-35 h; the nano-scale secondary phase with high purity, good dispersibility and good crystal form can be prepared by a hydrothermal method.
In the third step, the mass ratio of ammonium tetramolybdate to distilled water is 1: 2-3, and the pH value is 0-3.0.
Step five is three-stage hydrogen reduction, wherein the temperature of the first-stage hydrogen reduction is 300-400 ℃, and the flow rate of the hydrogen is 3-8 m3The reduction time is 5-20 h; the two-stage hydrogen reduction temperature is 500-700 ℃, and the hydrogen gas flow is 6-15 m3The reduction time is 5-20 h; the three-stage hydrogen reduction temperature is 800-1000 ℃, and the hydrogen isThe air flow is 10-20 m3The reduction time is 5-20 h. During the reduction process, nanoscale secondary phase Al2O3、ZrO2、La2O3When the particles are dispersed in the matrix, the growth of the particles is hindered by inhibiting gas phase migration, and the powder is refined.
And the pressure of the sixth cold isostatic press during blank pressing is 100-200 MPa, and the pressure maintaining time is 800-1200 s.
And seventhly, sintering at 1600-2000 ℃, heating at a rate of 300-500 ℃/h, keeping the temperature for 5-10 h, and cooling along with the furnace after the temperature is kept. The step adopts low-temperature rapid sintering, and can avoid the growth of crystal grains.
And step nine, when the molybdenum alloy target I is subjected to surface treatment by adopting an ultrasonic surface rolling technology, the ultrasonic vibration frequency is 20-40 Hz, the amplitude of a rolling tip is 2-15 mu m, the rolling speed is 25-50 r/min, the feeding speed is 3-10 mm/min, and the repeated processing times are 2-5 times.
The invention adopts a hydrothermal method to prepare the nano-scale micro secondary phase doped phase with high purity, good dispersibility and good crystal form, adopts a liquid-solid doping technology to disperse and distribute the secondary phase in a molybdenum matrix, prepares nano-scale mixed powder through three-stage hydrogen reduction, prepares the nano-scale molybdenum alloy through cold isostatic pressing compact and low-temperature rapid sintering, and can not only refine grains, but also improve the density and mechanical property of the matrix and increase the wear resistance of the matrix due to the introduction of the secondary phase. The sintered blank is mechanically and finely ground and then further processed by an ultrasonic surface rolling technology (USRP) to finally obtain the nano-crystal molybdenum alloy target material with the ultrafine-crystal structure on the surface.
The hydrothermal method is carried out in a sealed container, the solvent expands after being heated to a certain temperature to fill the whole container, so that very high pressure is generated, substances are dissolved under high temperature and high pressure, temperature difference generates convection to form a supersaturated state to precipitate growing crystals, and finally, a controllable secondary phase with good dispersity, high purity and good crystal form is obtained.
According to the invention, through a liquid-solid doping technology, the secondary phase is dispersed and distributed in the matrix to block dislocation movement in the alloy, the finer the secondary phase particles are, the more uniform the distribution is, the higher the strength of the alloy is, and when the number of the secondary phase is too large, the molding is reduced. The effect of adding nitric acid is to adjust the pH on one hand and to promote the reduction and avoid the generation of molybdenum oxide in other phases and crystal forms on the other hand.
By low temperature rapid sintering, grain growth can be avoided. Along with the reduction of the grain size, the number of internal grains and grain boundaries is greatly increased, and the material is strengthened by utilizing the characteristics of irregular atomic arrangement and high atomic energy on the grain boundaries, so that the strength and the hardness of the material are improved, and the shaping and the toughness of the material are improved.
The ultrasonic surface rolling technology (USRP) is characterized in that the surface of a target material is subjected to severe plastic deformation in different directions, high-density dislocation is continuously generated, rearranged and annihilated near dislocation walls and dislocation tangles, and finally, an equiaxial fine crystal structure with randomly distributed orientation is formed on the surface of the target material. The nanocrystalline molybdenum alloy target prepared by the invention has the advantages of smaller grain size of the molybdenum matrix and high interface density, and the surface of the target has an ultrafine grain structure, thereby showing unique performance superior to that of the traditional coarse grain target.
The preparation process of the method adopts a hydrothermal method to prepare a secondary doping phase, and adopts a liquid-solid doping method and a cold isostatic pressing low-temperature rapid sintering method to prepare the uniformly dispersed molybdenum alloy target material. The molybdenum alloy target material sample with large length-diameter ratio can be prepared, and the product has high density and is uniform; further improving the surface performance of the molybdenum alloy target material by an ultrasonic surface rolling technology (USRP) technology to obtain the nanocrystalline molybdenum alloy target material. Compared with the existing preparation technology, the method has the advantages of simple operation, strong controllability, excellent product performance, extremely high cost performance and wide market application prospect.
Drawings
FIG. 1 is an SEM electron micrograph of a nanocomposite powder obtained by three-stage hydrogen reduction in example 3.
Fig. 2 is an SEM image and corresponding surface scan and energy spectrum of a # 5 molybdenum alloy target obtained after sintering in example 3, wherein (a) is an SEM image of the material obtained after sintering; (b) is Zr element surface scanning; (c) is an O element surface scan; (d) mo element surface scanning; (e) scanning an Al element surface; (f) is a distribution diagram of each element in the 5# molybdenum alloy target material obtained after sintering;
FIG. 3 is an enlarged view of FIG. 2 (f);
fig. 4 is an SEM image of the 6# molybdenum alloy target material obtained after ultrasonic surface rolling in example 3.
Fig. 5 is a graph showing the wear mass loss of pure molybdenum and the 5# molybdenum alloy target and the 6# molybdenum alloy target obtained in example 3.
Detailed Description
For a better understanding of the present invention, reference will now be made to the following examples taken in conjunction with the accompanying drawings. The following examples are given to illustrate the detailed embodiments and the operation steps based on the technology of the present invention, but the scope of the present invention is not limited to the following examples.
The nanocrystalline molybdenum alloy target comprises a molybdenum base and a secondary phase dopant which is dispersed in the molybdenum base, wherein the secondary phase dopant at least comprises one of aluminum oxide, zirconium oxide and lanthanum oxide, and the addition amount of the secondary phase dopant is not more than 10%. The density of the nano-crystal molybdenum alloy target is more than 99%, and the grain size is less than 300 nm.
The nanocrystalline molybdenum alloy target material is prepared by the following method:
the method comprises the following steps: weighing a certain amount of nitrate and urea according to the requirements of a final product, and adding water to fully dissolve the nitrate and urea to obtain a mixed solution for later use; the nitrate can be at least one of aluminum nitrate, zirconium nitrate and lanthanum nitrate;
step two: and (4) pouring all the mixed solution obtained in the step one into a polytetrafluoroethylene lining of a stainless steel hydrothermal kettle, locking the hydrothermal kettle, and electrifying the hydrothermal kettle to heat so as to perform hydrothermal reaction. The temperature of the hydrothermal reaction is 180-250 ℃, and the time of the hydrothermal reaction is 20-35 h.
In the hydrothermal reaction process, under the action of certain pressure and temperature, the phenomenon of hard agglomeration and the like can be overcome by dialysis reaction, physical and chemical factors and the like, so that the nano-scale micro crystal with high purity, good dispersibility and good crystal form is prepared.
Step three: according to the requirements of final products, weighing a certain amount of ammonium tetramolybdate, adding a proper amount of distilled water, adding a nitric acid solution to adjust the pH value, and fully stirring to obtain an ammonium tetramolybdate suspension for later use. The mass ratio of ammonium tetramolybdate to distilled water is 1: 2-3, the mass fraction of the nitric acid solution can be 60%, and the pH value is adjusted to 0-3.0.
Step four: pouring the mixed solution obtained after the hydrothermal reaction in the second step into the ammonium tetramolybdate suspension obtained in the third step, and fully stirring, filtering and drying to obtain a mixture; the obtained mixture was pulverized by a high-speed pulverizer. The stirring time is 5-10 h, the drying temperature is 60-100 ℃, and the drying time is 20-30 h.
Step five: and D, performing three-stage hydrogen reduction on the mixed powder obtained in the step four. The first-stage hydrogen reduction temperature is 300-400 ℃, and the hydrogen gas flow is 3-8 m3And the reduction time is 5-20 h. The two-stage hydrogen reduction temperature is 500-700 ℃, and the hydrogen gas flow is 6-15 m3And the reduction time is 5-20 h. The three-stage hydrogen reduction temperature is 800-1000 ℃, and the hydrogen gas flow is 10-20 m3And the reduction time is 5-20 h.
Finally obtaining the nano composite powder of Mo and oxide secondary phase adulterant through three-stage hydrogen reduction, wherein the secondary phase adulterant can be Al according to the difference of nitrate used in the step one2O3、ZrO2、La2O3At least one of (1).
Step six: and (3) selecting a proper rubber mold according to the required size of the final product, weighing a certain amount of nano composite powder obtained after the five-step and three-step hydrogen reduction, filling the nano composite powder into the mold, and pressing the nano composite powder by using a cold isostatic press. The cold isostatic pressing has high density and uniformity because the stress of the blank is uniform, and a sample with large length-diameter ratio can be prepared. The pressure of the cold isostatic pressing compact is 100-200 MPa, and the pressure maintaining time is 800-1200 s.
Step seven: and sintering the green body obtained by pressing in the sixth step in a medium-frequency induction sintering furnace, wherein hydrogen is required to be introduced for protection in the sintering process to prevent oxidation, and thus the sintered green body is obtained. The sintering temperature is 1600-2000 ℃, the heating rate is 300-500 ℃/h, the heat preservation time is 5-10 h, and furnace cooling is carried out after the heat preservation is finished. The low-temperature rapid sintering is selected, so that the growth of crystal grains can be avoided.
Step eight: and machining the sintered blank obtained in the step seven, and performing fine grinding treatment to obtain the molybdenum alloy target I.
Step nine: and (4) continuing to perform surface treatment on the molybdenum alloy target I obtained in the step eight by adopting an ultrasonic surface rolling technology (USRP) to obtain a molybdenum alloy target II, namely the nanocrystal molybdenum alloy target. In the step, the ultrasonic vibration frequency is 20-40 Hz, the amplitude of the rolling tip is 2-15 μm, the rolling speed is 25-50 r/min, the feeding speed is 3-10 mm/min, and the repeated processing times are 2-5 times.
Specific embodiments of the invention are described below:
example 1
(1): 432g of aluminum nitrate and 105g of urea were weighed, and dissolved in 4.5L of distilled water with sufficient stirring to obtain a mixed solution for use.
(2): and (3) pouring all the mixed solution obtained in the step (1) into a polytetrafluoroethylene lining of a stainless steel hydrothermal kettle, locking the hydrothermal kettle, and electrifying and heating the hydrothermal kettle to perform hydrothermal reaction. The temperature of the hydrothermal reaction is 180 ℃, and the reaction time is 30 h.
(3): weighing 10kg of ammonium tetramolybdate, adding 20L of distilled water, adding a nitric acid solution to adjust the pH value of the mixed system to 1.0, and fully stirring to obtain a tetramolybdic acid suspension for later use.
(4): pouring a mixed solution obtained after hydrothermal reaction in the polytetrafluoroethylene lining in the step (2) into the tetramolybdic acid suspension obtained in the step (3), stirring for 8 hours, then performing suction filtration by using a Buchner funnel, and drying after the suction filtration is finished, wherein the drying temperature is 90 ℃ and the drying time is 20 hours; after drying, the resulting mixture was broken up with a high-speed pulverizer.
(5): performing three-stage hydrogen reduction on the powder obtained after the crushing in the step (4) in a hydrogen atmosphere, wherein in the one-stage hydrogen reduction, the reduction temperature is 350 ℃, and the hydrogen flow is 7m3The reduction time is 10 h;
reducing the first stage hydrogenThe mixed powder is sieved by a 40-mesh sieve and then subjected to secondary hydrogen reduction in a hydrogen atmosphere, wherein the reduction temperature is 600 ℃, and the hydrogen flow is 13m3The reduction time is 12 hours;
the mixed powder obtained by the two-stage hydrogen reduction is sieved by a 40-mesh sieve and then is subjected to three-stage hydrogen reduction, the reduction temperature is 1000 ℃, and the hydrogen flow is 18m3The reduction time is 10h, and Mo and Al are obtained after reduction2O3The mixed powder of (1).
(6): and (3) selecting a proper rubber mold according to the required size of the final product, filling the mixed powder obtained after the three-stage hydrogen reduction in the step (5) into the rubber mold, and pressing the mixed powder by using a cold isostatic press. The pressure is 200MPa, and the dwell time is 1200 s.
(7): and (3) sintering the green body obtained by pressing in the step (6) in a medium-frequency induction sintering furnace, introducing hydrogen for protection and preventing oxidation in the sintering process, wherein the sintering temperature in the step is 1900 ℃, the heating rate is 500 ℃/h, the temperature is kept at 1900 ℃ for 5h, and the green body is cooled along with the furnace after the temperature is kept, so that the sintered green body is obtained.
(8) And (4) machining the sintered blank obtained in the step (7), and performing fine grinding treatment to obtain the No. 1 molybdenum alloy target.
(9) And (3) continuing to perform surface treatment on the No. 1 molybdenum alloy target material obtained in the step (8) by adopting an ultrasonic surface rolling technology (USRP), wherein the ultrasonic vibration frequency is 40Hz, the amplitude of a rolling tip is 3 mu m, the rolling speed is 30r/min, the feeding speed is 5mm/min, and the repeated processing times are 2 times. And finally forming equiaxed fine crystal structures with randomly distributed orientations on the surface of the target, wherein the molybdenum alloy target treated in the step is marked as a No. 2 molybdenum alloy target, namely the final nanocrystalline molybdenum alloy target.
Example 2
(1): 305g of zirconium nitrate and 60g of urea were weighed, and dissolved in 4.5L of distilled water with sufficient stirring to obtain a mixed solution for later use.
(2): and (3) pouring all the mixed solution obtained in the step (1) into a polytetrafluoroethylene lining of a stainless steel hydrothermal kettle, locking the hydrothermal kettle, and electrifying and heating the hydrothermal kettle to perform hydrothermal reaction. The temperature of the hydrothermal reaction is 200 ℃, and the reaction time is 24 h.
(3): weighing 10kg of ammonium tetramolybdate, adding 25L of distilled water, adding a nitric acid solution to adjust the pH value of the mixed system to 1.0, and fully stirring to obtain a tetramolybdic acid suspension for later use.
(4): pouring a mixed solution obtained after hydrothermal reaction in the polytetrafluoroethylene lining in the step (2) into the tetramolybdic acid suspension obtained in the step (3), stirring for 5 hours, then performing suction filtration by using a Buchner funnel, and drying after the suction filtration is finished, wherein the drying temperature is 80 ℃, and the drying time is 30 hours; after drying, the resulting mixture was broken up with a high-speed pulverizer.
(5): performing three-stage hydrogen reduction on the powder obtained after the crushing in the step (4) in a hydrogen atmosphere, wherein in the one-stage hydrogen reduction, the reduction temperature is 300 ℃, and the hydrogen flow is 8m3The reduction time is 15 h;
sieving the mixed powder after the first-stage hydrogen reduction by a 40-mesh sieve, and then carrying out second-stage hydrogen reduction in a hydrogen atmosphere at the reduction temperature of 500 ℃ and the hydrogen flow of 15m3The reduction time is 15 h;
the mixed powder obtained by the two-stage hydrogen reduction is sieved by a 40-mesh sieve and then is subjected to three-stage hydrogen reduction at the reduction temperature of 900 ℃ and the hydrogen flow rate of 18m3The reduction time is 15h, Mo and ZrO are obtained after reduction2The mixed powder of (1).
(6): and (3) selecting a proper rubber mold according to the required size of the final product, filling the mixed powder obtained after the three-stage hydrogen reduction in the step (5) into the rubber mold, and pressing the mixed powder by using a cold isostatic press. The pressure is 100MPa, and the dwell time is 1000 s.
(7): and (3) sintering the green body obtained by pressing in the step (6) in a medium-frequency induction sintering furnace, introducing hydrogen for protection and preventing oxidation in the sintering process, wherein the sintering temperature in the step is 1800 ℃, the heating rate is 400 ℃/h, the temperature is kept at 1800 ℃ for 7h, and the green body is cooled along with the furnace after the temperature is kept, so that the sintered green body is obtained.
(8) And (4) machining the sintered blank obtained in the step (7), and performing fine grinding treatment to obtain the 3# molybdenum alloy target.
(9) And (3) continuing to perform surface treatment on the 3# molybdenum alloy target obtained in the step (8) by adopting an ultrasonic surface rolling technology (USRP), wherein the ultrasonic vibration frequency is 30Hz, the amplitude of a rolling tip is 7 mu m, the rolling speed is 25r/min, the feeding speed is 3mm/min, and the repeated processing times are 5 times. And finally forming equiaxed fine crystal structures with randomly distributed orientations on the surface of the target, wherein the molybdenum alloy target treated in the step is marked as a No. 4 molybdenum alloy target, namely the final nanocrystalline molybdenum alloy target.
Example 3
(1): 432g of aluminum nitrate and 105g of urea were weighed, and dissolved in 4.5L of distilled water with sufficient stirring to obtain a mixed solution I for use. Meanwhile, 305g of zirconium nitrate and 60g of urea are weighed and fully stirred to be dissolved in 4.5L of distilled water, so as to obtain a mixed solution II for later use.
(2): and (2) pouring all the mixed solution I obtained in the step (1) into a polytetrafluoroethylene lining of a stainless steel hydrothermal kettle, locking the hydrothermal kettle, and electrifying and heating the hydrothermal kettle to perform hydrothermal reaction. The temperature of the hydrothermal reaction is 170 ℃, and the reaction time is 28 h.
(3): and (2) pouring all the mixed solution II obtained in the step (1) into a polytetrafluoroethylene lining of a stainless steel hydrothermal kettle, locking the hydrothermal kettle, and electrifying and heating the hydrothermal kettle to perform hydrothermal reaction. The temperature of the hydrothermal reaction is 170 ℃, and the reaction time is 28 h.
(4): weighing 10kg of ammonium tetramolybdate, adding 20L of distilled water, adding a nitric acid solution to adjust the pH value of the mixed system to 1.0, and fully stirring to obtain a tetramolybdic acid suspension for later use.
(5): pouring all mixed liquor obtained after hydrothermal reaction in the polytetrafluoroethylene lining in the steps (2) and (3) into the tetramolybdic acid suspension obtained in the step (4), stirring for 10 hours, then performing suction filtration by using a Buchner funnel, and drying after the suction filtration is finished, wherein the drying temperature is 100 ℃, and the drying time is 18 hours; after drying, the resulting mixture was broken up with a high-speed pulverizer.
(6): carrying out three-stage hydrogen reduction on the powder obtained after the crushing in the step (5) in a hydrogen atmosphere, wherein in the one-stage hydrogen reduction, the reduction temperature is 400 ℃, and the hydrogen flow is 5m3The reduction time is 12 hours;
sieving the mixed powder after the first-stage hydrogen reduction by a 40-mesh sieve, and then introducing the powder into hydrogenPerforming two-stage hydrogen reduction at 700 deg.C and hydrogen flow rate of 15m3The reduction time is 12 hours;
the mixed powder obtained by the two-stage hydrogen reduction is sieved by a 40-mesh sieve and then is subjected to three-stage hydrogen reduction at the reduction temperature of 800 ℃ and the hydrogen flow rate of 20m3The reduction time is 12h, and Mo and Al are obtained after reduction2O3、ZrO2The mixed powder of (1).
(7): and (4) selecting a proper rubber mold according to the required size of the final product, filling the mixed powder obtained after the three-stage hydrogen reduction in the step (6) into the rubber mold, and pressing the mixed powder by using a cold isostatic press. The pressure is 120MPa, and the dwell time is 900 s.
(8): and (3) sintering the green body obtained by pressing in the step (7) in a medium-frequency induction sintering furnace, introducing hydrogen for protection and preventing oxidation in the sintering process, wherein the sintering temperature in the step is 1850 ℃, the heating rate is 600 ℃/h, preserving heat for 6h at 1850 ℃, and cooling along with the furnace after the heat preservation is finished to obtain the sintered green body.
(9) And (4) machining the sintered blank obtained in the step (8), and performing fine grinding treatment to obtain the 5# molybdenum alloy target.
(10) And (4) continuing to perform surface treatment on the 5# molybdenum alloy target obtained in the step (9) by adopting an ultrasonic surface rolling technology (USRP), wherein the ultrasonic vibration frequency is 35Hz, the amplitude of a rolling tip is 6 mu m, the rolling speed is 30r/min, the feeding speed is 5mm/min, and the repeated processing is performed for 4 times. And finally forming equiaxed fine crystal structures with randomly distributed orientations on the surface of the target, wherein the molybdenum alloy target treated in the step is marked as a No. 6 molybdenum alloy target, namely the final nanocrystalline molybdenum alloy target.
Mo and Al obtained after three-stage hydrogen reduction in example 32O3、ZrO2The SEM image of the nanocomposite powder of (1) is shown in FIG. 1, and it is understood from FIG. 1 that the size of crystal grains of the nanocomposite powder is about 200nm and the particles are nearly spherical.
The 5# molybdenum alloy target material prepared in example 3 was tested, the compactness thereof reached more than 99.9%, and the SEM image and the corresponding surface scan thereof are shown in fig. 2, and it can be seen from fig. 2 that the 5# molybdenum alloy target material has a grain size of about 500nm, is fine and uniform equiaxial, and the secondary phase dopant is dispersed and distributed in the matrix.
The 6# molybdenum alloy target prepared in example 3 was tested, and the SEM image thereof is shown in fig. 3, and it can be seen from fig. 3 that the grain size of the 6# molybdenum alloy target is about 200 nm. The secondary phase large particles are located at the grain boundary, and the small particles are located in the grains.
The mechanical properties obtained by testing the 5# and 6# molybdenum alloy targets and the pure molybdenum target prepared in example 3 are shown in table 1:
TABLE 1 summary of mechanical Properties of differently treated molybdenum target products
From the above table, it can be seen that: compared with a pure molybdenum target material, the yield strength of the 5# molybdenum alloy target material is improved by 59.6%, the tensile strength is improved by 78.1%, the elongation is improved by 100%, and the microhardness is improved by 54.5%; compared with a 5# molybdenum alloy target, the yield strength of the 6# molybdenum alloy target is improved by 22.3%, the tensile strength is improved by 20.1%, the elongation is improved by 12.5%, and the microhardness is improved by 18.3%.
The wear quality of the pure molybdenum target, the 5# molybdenum alloy target and the 6# molybdenum alloy target was compared, and the results are shown in fig. 4, and show that: compared with a pure molybdenum target material, the wear quality of the 5# molybdenum alloy target material is reduced by 69.3%; compared with the 5# molybdenum alloy target material, the wear quality of the 6# molybdenum alloy target material is reduced by 11.7%, which shows that the introduction of the secondary phase obviously increases the wear resistance of the molybdenum alloy target material, and the wear resistance of the target material can be further increased by carrying out surface treatment on the molybdenum alloy target material by adopting an ultrasonic surface rolling technology.
The above description is only an embodiment of the present invention, and is not intended to limit the present invention in any way, and the present invention may also have other embodiments according to the above structures and functions, and is not listed again. Therefore, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention by those skilled in the art can be made within the technical scope of the present invention.
Claims (10)
1. A nanocrystalline molybdenum alloy target material is characterized in that: comprises molybdenum base and a small amount of secondary phase dopant, the secondary phase dopant at least comprises one of alumina, zirconia and lanthana, and the addition amount of the secondary phase dopant is not more than 10 percent.
2. The nanocrystalline molybdenum alloy target according to claim 1, wherein: the density of the nanocrystalline molybdenum alloy target is more than 99%, the grain size is less than 300nm, and secondary phase dopants are dispersed and distributed in a molybdenum matrix.
3. A preparation method of a nanocrystalline molybdenum alloy target is characterized by specifically comprising the following steps:
the method comprises the following steps: weighing a certain amount of nitrate and urea according to the requirements of a final product, and adding water to fully dissolve the nitrate and urea to obtain a mixed solution for later use;
step two: pouring all the mixed solution obtained in the step one into a polytetrafluoroethylene lining of a stainless steel hydrothermal kettle, locking the hydrothermal kettle, and electrifying and heating the hydrothermal kettle to perform hydrothermal reaction;
step three: weighing a certain amount of ammonium tetramolybdate according to the requirements of a final product, adding a proper amount of distilled water, adding a nitric acid solution to adjust the pH value, and fully stirring to obtain an ammonium tetramolybdate suspension for later use;
step four: pouring the mixed solution obtained after the hydrothermal reaction in the second step into the ammonium tetramolybdate suspension obtained in the third step, and fully stirring, filtering and drying to obtain a mixture; crushing the obtained mixture by using a high-speed crusher;
step five: performing three-stage hydrogen reduction on the mixed powder crushed in the step four to obtain nano composite powder;
step six: selecting a proper rubber mold according to the required size of a final product, weighing a certain amount of nano composite powder obtained after the five-step three-section hydrogen reduction, putting the nano composite powder into the mold, and pressing the nano composite powder by using a cold isostatic press;
step seven: sintering the green body pressed in the sixth step in a medium-frequency induction sintering furnace, and introducing hydrogen for protection in the sintering process to prevent oxidation to obtain a sintered green body;
step eight: machining the sintered blank obtained in the step seven, and performing fine grinding treatment to obtain a molybdenum alloy target I;
step nine: and (4) continuing to perform surface treatment on the molybdenum alloy target I obtained in the step eight by adopting an ultrasonic surface rolling technology to obtain a molybdenum alloy target II, namely the nanocrystal molybdenum alloy target.
4. The method for preparing a nanocrystalline molybdenum alloy target according to claim 3, wherein the nitrate in the first step is at least one of aluminum nitrate, zirconium nitrate and lanthanum nitrate.
5. The method for preparing the nanocrystalline molybdenum alloy target according to claim 3, wherein the hydrothermal reaction temperature in the second step is 180-250 ℃ and the hydrothermal reaction time is 20-35 h.
6. The method for preparing the nanocrystalline molybdenum alloy target according to claim 3, wherein the mass ratio of ammonium tetramolybdate to distilled water in the step III is 1: 2-3, and the pH value is adjusted to 0-3.0.
7. The method of preparing a nanocrystalline molybdenum alloy target as claimed in claim 3, wherein: in the three-stage hydrogen reduction in the fifth step, the temperature of the first stage hydrogen reduction is 300-400 ℃, and the flow rate of the hydrogen is 3-8 m3The reduction time is 5-20 h; the two-stage hydrogen reduction temperature is 500-700 ℃, and the hydrogen gas flow is 6-15 m3The reduction time is 5-20 h; the three-stage hydrogen reduction temperature is 800-1000 ℃, and the hydrogen gas flow is 10-20 m3The reduction time is 5-20 h.
8. The method of preparing a nanocrystalline molybdenum alloy target as claimed in claim 3, wherein: and the pressure of the sixth cold isostatic press during blank pressing is 100-200 MPa, and the pressure maintaining time is 800-1200 s.
9. The method of preparing a nanocrystalline molybdenum alloy target as claimed in claim 3, wherein: and seventhly, sintering at 1600-2000 ℃, heating at a rate of 300-500 ℃/h, keeping the temperature for 5-10 h, and cooling along with the furnace after the temperature is kept.
10. The method of preparing a nanocrystalline molybdenum alloy target as claimed in claim 3, wherein: and step nine, when the molybdenum alloy target I is subjected to surface treatment by adopting an ultrasonic surface rolling technology, the ultrasonic vibration frequency is 20-40 Hz, the amplitude of a rolling tip is 2-15 mu m, the rolling speed is 25-50 r/min, the feeding speed is 3-10 mm/min, and the repeated processing times are 2-5 times.
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