CN110976888B - Complete solid solution molybdenum-niobium alloy powder and preparation method and application thereof - Google Patents
Complete solid solution molybdenum-niobium alloy powder and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a molybdenum-niobium alloy powder in a complete solid solution state, a preparation method and application thereof, wherein the molybdenum-niobium alloy powder is prepared by high-energy ball milling for 36-24 hours at 250-300 rpm so that the weight ratio is 9: the molybdenum powder and the niobium powder of 1 are obtained by completely dissolving molybdenum and niobium in a solid solution, and the internal crystal size of the particles is in a nanometer level. The molybdenum-niobium alloy target material prepared from the molybdenum-niobium alloy powder has the advantages of high densification degree, low porosity, greatly improved element distribution uniformity and structure uniformity, average size of target material crystal grains less than 10 mu m, and uniformity factor of the crystal grains of 1.777.
Description
Technical Field
The invention relates to molybdenum-niobium alloy powder, in particular to molybdenum-niobium alloy powder in a complete solid solution state, a preparation method and application.
Background
Molybdenum is a transition element, has a very high melting point, is named as a refractory metal in a natural simple substance, has the properties of high conductivity, low specific impedance, corrosion resistance, no pollution, environmental protection and the like, and is widely applied to the electronic and information industries, such as information storage, integrated circuits, flat panel displays, electronic control devices, capacitors and the like. With the vigorous development of the flat panel display and thin film solar cell industries, molybdenum has a huge application market and a wide application prospect, and is gradually one of the preferred materials of the sputtering target material of the flat panel display due to the advantages of specific impedance, film stress of only 1/2 chromium, environmental pollution and the like. The addition of 5-10 wt% of Nb into Mo target can raise its corrosion resistance, heat stability and specific resistance. The Mo-10 Nb-based sputtering target shows unique excellent performance, has great application market demand, and has wide application prospect in the research of high-end molybdenum-niobium sputtering targets.
Molybdenum and niobium are high-melting-point refractory metals (the melting points of molybdenum and niobium are 2893K and 2741K respectively), so the main preparation method of the molybdenum-niobium sputtering target material is a powder metallurgy technology. The molybdenum and niobium elements in the domestic vacuum sintered molybdenum and niobium target material are not uniformly distributed, have phase separation phenomenon and weak two-phase binding force, are easy to crack during rolling, have little difference with foreign high-end products in the aspects of density, porosity and grain size uniformity, and need to be further improved.
Disclosure of Invention
The invention aims to provide molybdenum-niobium alloy powder in a complete solid solution state, a preparation method and application thereof, the molybdenum-niobium alloy powder solves the problems of molybdenum-niobium phase separation, uneven element distribution, low density, larger grain size and the like in the existing molybdenum-niobium target material, and the prepared molybdenum-niobium target material has good density, low porosity, refined crystal grains and greatly improved element and tissue uniformity.
In order to achieve the purpose, the invention provides molybdenum-niobium alloy powder in a complete solid solution state, which is prepared by performing high-energy ball milling for 36-24 hours at 250-300 rpm to ensure that the weight ratio is 9: 1, the molybdenum powder and the niobium powder are obtained by realizing a complete solid solution state.
Preferably, the molybdenum-niobium alloy powder has a D50 of 2.586 to 2.634 μm and a D10-D90 of 1.306 to 5.852 μm.
The invention also provides a preparation method of the molybdenum-niobium alloy powder in the complete solid solution state, which comprises the following steps:
high-purity molybdenum powder and high-purity niobium powder are mixed according to the weight ratio of 9: 1, mixing, performing dry high-energy ball milling to realize complete solid solution of molybdenum niobium powder, and adopting three grinding balls with the diameter of 5-20 mm, wherein the mass ratio of the three grinding balls is 5: 3: 2, the ball material ratio is 3-10: 1, performing ball milling intermittently in an argon environment with the pressure of 1 atmosphere, wherein the ball milling speed is 250-300 rpm, and the ball milling time is 36-24 h, so as to obtain the Mo-10Nb alloy powder in a complete solid solution state.
Preferably, the ball milling is carried out intermittently, and the ball milling is stopped for 30min for 2 h.
The invention also provides a method for preparing the Mo-10Nb target material by adopting the molybdenum niobium alloy powder in the complete solid solution state, which comprises the following steps:
putting the molybdenum-niobium alloy powder in a complete solid solution state into a die, and performing pre-pressing molding, wherein the pressing pressure is 60-100 MPa, the pressing time is 10s, the time is 5s, and the total pressing time is 30 s;
vacuum packaging the pre-pressed and molded green body, wherein the vacuum degree is below-0.08 MPa, cold isostatic pressing is carried out by using a cold isostatic press, gradient boosting is adopted, each stage of parameters are set in a gradient manner until the target pressure is reached, the target pressure is 180-230 MPa, and the pressure maintaining time is 10-20 min;
after the pressing is finished, pressure is relieved, and the pressure relief is kept for 10s each time to play a role in buffering;
carrying out vacuum sintering on the green body subjected to cold isostatic pressing, wherein the vacuum degree is less than 1 multiplied by 10 -2 Pa; heating at a heating rate of less than 10 deg.C/min, and a vacuum degree of less than 1 × 10 -2 Pa, keeping the vacuum sintering heat preservation temperature at 1800-1950 ℃, and keeping the heat preservation time for 3-6 hours;
and after the heat preservation is finished, cooling to below 60 ℃ along with the furnace, and then opening the furnace to cool to room temperature to obtain the Mo-10Nb target material.
Preferably, the gradient boosting is provided with ten steps, and the pressure relief process is also provided with ten steps and corresponds to the gradient boosting.
Preferably, the gradient is boosted, and the pressure is supplemented when the pressure is less than the target pressure by 2 MPa.
Preferably, during the vacuum sintering, a layer of ZrO is laid on the bottom of the crucible 2 Powder, the cold isostatic pressed green body is placed on ZrO 2 And (4) powdering.
The fully solid-solution molybdenum-niobium alloy powder, the preparation method and the application solve the problem of phase separation of molybdenum and niobium in the existing molybdenum-niobium target material, and have the following advantages:
the complete solid solution molybdenum niobium alloy powder adopts high-energy ball milling to realize complete solid solution, so as to obtain complete solid solution composite powder with nano crystal size, the single-phase diffraction peak of niobium disappears, and the molybdenum powder and the niobium powder realize complete solid solution. The molybdenum-niobium alloy target material prepared from the molybdenum-niobium alloy powder in the complete solid solution state has greatly improved densification degree, element distribution uniformity, final grain size refinement and structure uniformity of the target material.
The method adopts high-energy ball mill ballsGrinding, no additive, completely dissolving the prepared powder, completely eliminating niobium peak, uniformly distributing molybdenum and niobium elements in the particles (solid solution on the specific surface), wherein the grain size of the powder is less than 3 μm and is finer, the average size of the target grain is less than 10 μm, the sintering heat preservation temperature is less than 1950 ℃, the time is less than 6h, and the sintering vacuum degree is less than 1 x 10 in the whole process -2 Pa, the resulting target uniformity factor is 1.78 (the closer to 1 the more uniform is).
Drawings
FIG. 1 is a microscopic scan of the starting powder.
FIG. 2 is a micro-topography of composite powders of comparative examples 1-4 and example 2 of the present invention.
FIG. 3 is a graph showing the morphology of the composite powders of example 1 of the present invention and comparative examples 5 to 8.
FIG. 4 is a graph showing the particle size distribution of the composite powders of comparative examples 1 to 4 and example 2 according to the present invention.
FIG. 5 is a particle size distribution diagram of composite powders of example 1 of the present invention and comparative examples 5 to 8.
Fig. 6 is an XRD diffraction pattern of the composite powder of comparative examples 1 to 4 and example 2 of the present invention.
Fig. 7 is an XRD diffraction pattern of the composite powder of example 1 of the present invention and comparative examples 5 to 8.
FIG. 8 is a graph showing the grain size and internal strain curves of the composite powders of comparative examples 1 to 4 and example 2 according to the present invention.
FIG. 9 is a graph showing the grain size and internal strain of the composite powders of example 1 of the present invention and comparative examples 5 to 8.
FIG. 10 is a scan of the internal morphology and surface scan of the composite powders of comparative examples 1-4 and example 2 of the present invention.
FIG. 11 is SEM-EDS analysis results of composite powders of comparative examples 1 to 4 and example 2 according to the present invention.
FIG. 12 is SEM-EDS analysis results of composite powders of example 1 of the present invention and comparative examples 5 to 8.
FIG. 13 is a scan of the internal morphology and the surface of the composite powders of example 1 of the present invention and comparative examples 5 to 8.
FIG. 14 is a transmission electron micrograph of a composite powder obtained by carrying out example 1 of the present invention.
Fig. 15 is a cross-sectional view and a cross-sectional polished view of the targets of example 3 of the present invention and comparative example 9.
Fig. 16 is a topographical view of the targets of example 3 and comparative example 9 of the present invention.
Fig. 17 is an elemental surface scan of the targets of example 3 and comparative example 9 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A method for preparing molybdenum-niobium alloy powder in a complete solid solution state comprises the following steps: high-purity molybdenum powder (the purity of the molybdenum powder is more than 99.95 percent and the Fisher size is 3 mu m) and high-purity niobium powder (the purity of the niobium powder is more than 99.95 percent and the Fisher size is 10.17 mu m) are mixed according to the weight ratio of 9: 1, mixing, and performing dry high-energy ball milling by using a high-energy ball mill to realize a molybdenum-niobium complete solid solution state, wherein the size of a ball milling tank is 250-1000 mL, the diameter of grinding balls is 5-20 mm, and the mass ratio of the grinding balls is 5: 3: 2, fixing the ball-material ratio to be 3-10: 1, replacing a ball milling tank with 1 atmosphere argon environment, stopping for 30min every 2h to avoid overheating caused by ball milling, wherein the ball milling speed is 250rpm, the ball milling time is 36h, and obtaining the complete solid solution Mo-10Nb alloy powder which has uniform element distribution, good particle size distribution and nano-sized crystal grains, wherein the crystal grain size of the Mo-10Nb alloy powder is 13.56nm, the D50 (the corresponding particle size value when the cumulative distribution percentage reaches 50%) is 2.63 mu m, the particle size distribution is narrow, and the powder appearance is in a sphere shape.
As shown in FIG. 1, which is a microscopic scanning image of the raw material powder (a is Mo and b is Nb), it can be seen that the molybdenum powder mostly has approximately spherical particles of about 2 μm, which are agglomerated into approximately sheet-shaped aggregates of about 15 μm, Fisher particle size is 3 μm, the niobium powder has irregular block-shaped particles, which are non-uniform in particle size distribution, large in particle size distribution span, mostly 1-48 μm in particle size distribution, and Fisher particle size is 10.17 μm.
Example 2
A method for preparing molybdenum-niobium alloy powder in a complete solid solution state is basically the same as that in example 1, except that: the ball milling speed is 300rpm, and the ball milling time is 24 h.
Comparative examples 1 to 4
Substantially the same as example 1 except that the ball milling rotation speeds of comparative examples 1 to 4 were 100rpm, 150rpm, 200rpm and 250rpm, respectively, and the ball milling time was 24 hours.
Comparative examples 5 to 8
Substantially the same as in example 1 except that comparative examples 5 to 8 were carried out at a ball milling rotation speed of 250rpm for ball milling times of 1 hour, 4 hours, 8 hours and 48 hours, respectively.
Experimental example 1 microscopic morphology observation of composite powder
As shown in FIG. 2, the micro-topography of the composite powders of comparative examples 1 to 4 and example 2 according to the present invention (a is 100rmp, b is 150rmp, c is 200rmp, d is 250rmp, and e is 300rmp) was obtained as follows:
after ball milling at 100rpm, comparing the original molybdenum particle powder and niobium particle powder, the size of the large niobium powder particles is obviously reduced, the shape is changed from irregular blocks into sheets, the size and the length of the sheet niobium particles are reduced to about 30 mu m, and the agglomeration of the molybdenum powder is opened, and the appearance is changed from agglomeration into single particles.
After ball milling at 150rpm, the particle size distribution was relatively uniform compared to 100rmp and the morphology was transformed into spheroidal particles around 20 μm.
After 200rmp ball milling, the appearance is greatly changed, irregular large niobium particles disappear, powder particles are mostly spherical and the particle size distribution is uniform, the particle span is obviously reduced and is about 0.1-15 mu m.
After 250rmp ball milling, the spherical morphology of the particles was better, with little difference in particle size distribution between the 200rpm, 250rpm and 300rpm powder particles.
After 300rmp ball milling, large particles of about 10 μm are still present, but the relative proportion of large particles to medium particles can be clearly reduced and small particles can be clearly increased by comparison.
As shown in FIG. 3, which is a graph showing the morphology of the composite powder of example 1 of the present invention and comparative examples 5 to 8 (a is 1 h; b is 4 h; c is 8 h; d is 24 h; e is 36 h; f is 48h), the results are as follows:
after ball milling is carried out for 1 hour at 250rpm, the change is obvious compared with the original molybdenum niobium powder particles, the shapes of the larger particles after ball milling are mostly flaky or spherical, and the molybdenum powder agglomeration disappears.
After ball milling for 4h at 250rpm, the bulk particles tend to be more spherical, and the particle morphology is changed from irregular to regular.
After ball milling is carried out for 8 hours at 250rpm, the particle size is obviously reduced, the sphericity is better, and the ball milling is in an intermediate state.
After ball milling for 24h at 250rpm, the powder particle morphology transformation is almost completed, the particle morphology is mostly spherical, and the proportion of large particles and medium particles is obviously more than 36 h.
After ball milling is carried out for 36 hours at 250rpm, the particle morphology is more likely to obviously increase the proportion of spherical small particles, the proportion of large particles and medium particles is obviously reduced, and the proportion of small particles is increased because the breakage plays a main role in the later stage of ball milling.
After milling at 250rpm for 48h, it can be seen that the size distribution is more uniform and the morphology is more spherical, only because the relative equilibrium of the weld and fracture is reached, but the difference from 36h and 24h is small and the morphology change is substantially completed in 24 h.
Experimental example 2 particle size distribution of composite powder
The particle size distribution of the composite powder at different ball milling speeds was characterized by a laser particle sizer, as shown in fig. 4, which is a particle size distribution diagram of the composite powder of comparative examples 1-4 and example 2 according to the present invention (a mix; b is 100 rpm; c is 150 rpm; d is 200 rpm; e is 250 rpm; f is 300rpm), and the results are:
in the mixing stage, because the molybdenum powder mostly exists in an agglomerated state, the agglomeration is about 15 microns mostly 2 microns, the niobium powder has large particles and large span (1-48 microns), and the particle D50 (the particle size value corresponding to the cumulative distribution percentage of D50 reaching 50%) after mixing is 14.764 microns.
After ball milling at 100rpm, the particle D50 is obviously reduced, the particle size distribution range is obviously reduced from 14.764 mu m to 3.927 mu m, the particle size distribution range is obviously reduced from D10-D90(D10 is the particle size value corresponding to the cumulative distribution percentage reaching 10%, and D90 is the particle size value corresponding to the cumulative distribution percentage reaching 90%), and the particle size distribution range is obviously reduced from 4.098-48.971 mu m to 1.772-10.968 mu m, because the molybdenum powder is agglomerated and opened by ball milling, and the large particles of the niobium powder are refined.
After ball milling at 150rpm, D50 is 3.060m, the particle size distribution is narrower, and D10-D90 are 1.617-11.177 m.
After ball milling at 200rpm, the powder particles D50 are reduced to 2.799 μm, the particle size range D10-D90 is further reduced to 1.389-8.570 μm, and the ratio of large particles about 10 μm is still high.
After ball milling at 250rpm, D50 was 2.658m, with a drop, but the particle size distribution of D10-D90 increased slightly over 200 rpm.
After ball milling at 300rpm, D50 is 2.586 microns, and D10-D90 is 1.478-3.948 microns, because the breaking at the later stage of ball milling plays a dominant role.
As shown in FIG. 5, which is a graph showing the particle size distribution of the composite powder of example 1 of the present invention and comparative examples 5 to 8 (a is 1 h; b is 4 h; c is 8 h; d is 24 h; e is 36 h; f is 48h), the results are:
after ball milling for 1h, 4h and 8h at 250rpm, the D50 of the powder particles is reduced to 3.096 μm, 2.744 μm and 2.720 μm from 14.764 μm of the mixed material, and the D10-D90 is also reduced to 1.686-11.273 μm, 1.302-9.922 μm and 1.313-9.900 μm from 4.098-48.97 μm of the mixed material. The particle size of the particles is rapidly reduced in 1 hour of ball milling, mainly in the process of high-energy ball milling, the original molybdenum powder agglomeration is opened, and the large niobium particles are mainly broken, so that the large particles with the particle size of about 10 mu m are obviously reduced in 4 hours compared with 1 hour, and the large particle size is obviously reduced in 8 hours. Under the condition of ball milling for 24 hours, the particle D50 is 2.658, the particle size distribution is widened, the particle D10-D90 is 1.273-9.776 m, and the particle size of about 10 mu m is obviously more than 36 hours, because the plastic deformation and the welding are mainly in the early stage of solid solution. D50 dropped to 2.634 μm and 2.530 μm at 36h and 48h, and the large grain fraction at around 10 μm dropped significantly because the fracture predominated but the weld still existed, with a grain size range and grain size comparable to 24 h.
Experimental example 3 XRD diffraction Pattern of composite powder
X-ray diffraction (XRD) analysis was performed using a D8ADVANCEX X-ray diffractometer with an acceleration voltage of 40KV and an acceleration current of 40mA, using a copper target
The sample was scanned from 30 to 130 degrees and an XRD diffraction pattern was obtained. As shown in fig. 6, XRD diffraction patterns (a is a diffraction pattern, b is a partial enlarged view) of the composite powders of comparative examples 1 to 4 and example 2 of the present invention are shown, and as a result:
in the material mixing stage, the molybdenum and the niobium are all in body-centered cubic crystal structures, and the crystal structures are completely consistent.
The niobium peak was still easily detected by ball milling at 100rpm and 150rpm for 24h, indicating that the solid solution was low or even not.
Under the condition of ball milling at the rotating speed of 200rpm and 250rpm for 24 hours, the niobium peak is no longer obvious, only a weak peak is strong, and the molybdenum niobium generates solid solution, the content of simple substance niobium is already low, and most of the simple substance niobium exists in a form of molybdenum niobium solid solution intermediate state.
And the diffraction peak of the niobium completely disappears under the condition of ball milling for 24 hours at the rotating speed of 300rpm, and the molybdenum-niobium solid solution is completed.
B in fig. 6 is a partial enlarged view from 39 ° to 42 °, and it can be seen that the overall intensity of the diffraction peak gradually decreases with increasing rotation speed, and there is a certain peak broadening and slight shift, the diffraction peak at the molybdenum (110) crystal face shifts from 40.598 ° of the mixed material to 40.401 ° after ball milling for 24h at 300rpm, the intensity of the diffraction peak decreases, and the diffraction peak broadening is caused by the decrease of the grain size and the generation of considerable defect density during the ball milling process; the diffraction peak of niobium gradually disappears and the diffraction peak of molybdenum gradually shifts to a small angle because a mo (nb) solid solution is formed and lattice distortion is generated in the process, niobium atoms are dissolved in the molybdenum element structure in a ball milling process to increase the interplanar spacing d thereof and the diffraction angle of molybdenum element is shifted to a small angle, thereby forming a mo (nb) solid solution. As the rotation speed was increased, the relative intensity of each diffraction peak was significantly reduced and the width was increased due to the reduction in the size of the crystal grains during the ball milling and the generation of a considerable defect density.
As shown in fig. 7, XRD diffraction patterns of the composite powders of example 1 of the present invention and comparative examples 5 to 8 (a is a diffraction pattern, b is a partial enlarged view of the range of the main peak (110) of molybdenum) are shown, and the results are:
niobium peaks can be easily found under ball milling for 1h, 4h and 8h, niobium powder particles are in solid solution with molybdenum powder while being plastically deformed and crushed, while a main molybdenum peak shifts to 40.542 degrees from 40.598 degrees after ball milling for 8h, and only a slight shift occurs, which shows that the solid solution is in an initial stage due to short ball milling time, and only a slight peak is strong at the niobium peak under 24h, and simultaneously the main molybdenum peak shifts to 40.422 degrees, which shows that the niobium peak is in a solid solution intermediate state at the moment and is close to a complete solid solution state, the niobium peak completely disappears under ball milling for 36h and 48h, and the main molybdenum peaks shift to 40.40 degrees and 40.38 degrees respectively, and the phase difference is very small, thus proving that the solid solution is completed under ball milling for 36h and 48 h.
Experimental example 4 grain size and internal Strain of composite powder
As shown in fig. 8, which are the grain sizes and internal strain curves of the composite powders of comparative examples 1 to 4 and example 2 of the present invention, the results are:
the grain size was 27.02nm at 100rpm ball milling for 24h, 23.23nm, 17.44nm and 14.97nm at 150rpm, 200rpm and 250rpm, respectively, and 13.68nm at 300rpm from 118.12nm of the batch. In the process of increasing the rotating speed, the internal strain is gradually increased and is increased to 0.572% from 0.065% to 300rpm under the rotating speed of 100 rpm.
As shown in fig. 9, which is the grain size and internal strain curves of the composite powders of example 1 of the present invention and comparative examples 5 to 8, the results are:
diffraction broadening was evident during 4h of ball milling, and the grain size rapidly decreased from 118.12nm to 22.63nm with a rapid increase in internal strain to 0.34%, which may be due to a major cause of grain refinement and plastic deformation at the early stage of ball milling, probably due to the breaking of long-range ordered structures in the structure into short-range orders, followed by deformation. The rate of grain size reduction slows down in 4-36 h, decreases to 13.56nm and increases to 0.57% internal strain at 36h because of the introduction of high density defects (mainly at grain boundaries, stacking faults, etc.) in the powder particles during ball milling, causing grain size reduction and internal strain, while at 48h of ball milling the grain size slightly increases to 14.61nm and the internal strain slightly decreases to 0.54%, probably due to the equilibrium of fracture and coalescence during high energy ball milling and relaxation of the nanostructured phase during ball milling.
Experimental example 5 scanning analysis of the interior of particles of composite powder
The composite powders of comparative examples 1 to 4 and example 2 were subjected to insert polishing, the interior of the particles was discarded, surface scanning analysis was performed on the element distribution inside the powder using a scanning electron microscopy-EDS, and the area was subjected to point scanning according to the surface scanning result as verification of surface scanning, thereby determining the internal uniformity of the composite powder. As shown in FIG. 10, the internal morphology of the composite powder of comparative examples 1 to 4 and example 2 according to the present invention (a1 at 100 rmp; a2 at 150 rpm; a3 at 200 rpm; a4 at 250 rpm; a5 at 300 rpm; b1-b5 at the distribution corresponding to Mo element; c1-c5 at the distribution corresponding to Nb element) shows an element aggregation region with more distinct brightness. The results of point scan verification analysis of SEM-EDS for the areas of different brightness are shown in FIG. 11, which are the results of SEM-EDS analysis of the composite powders of comparative examples 1-4 and example 2 of the present invention, and are as follows:
after ball milling at 100rpm, the niobium element is in a relatively obvious aggregation state and basically corresponds to the relative position outline of the particles, and analysis combined with the scanning percentage content of points shows that the percentage content of niobium is almost 100 percent at the place where the niobium brightness is obvious, only the percentage content of niobium at the upper right corner is 96.56 percent, and the percentage content of niobium at a dark place is 0 percent, which shows that no solid solution is generated at the rotating speed of 100rpm, and the powder particles only have appearance change, mainly the effects of grinding refinement and plastic deformation.
After ball milling at 150rpm, the percent niobium was 100% in the bright areas of niobium enrichment and the bright areas of the particles had a good profile corresponding to the particles, indicating that the entire niobium particles were still present, while the percent of niobium in the dark areas was 0% and striking verification at intermediate brightness found that the percent niobium was 8.71% and 11.58%, indicating that solid solution had begun and that the large particles were almost molybdenum according to the SEM image, which is evidence of secondary granulation.
After ball milling at 200rpm, it was found that there was still an aggregated region of the niobium particles in bulk, with a percentage of 100%, in the dark region of 0%, but when analyzed at medium brightness, the percentage of niobium was found to be 63.34%, 18.95%, 10.05%, respectively, which, in comparison with 100rpm and 150rmp, was excessive from disorder to uniform distribution, with 200rpm being in the intermediate process of solid solution.
After the ball milling at 250rpm, the comparison of the element brightness profile and the particle profile shows that no single molybdenum-niobium gathering area exists, the distribution of the molybdenum-niobium element is relatively uniform, the point scanning of areas with different brightness shows that the surface scanning is good, the percentage content of niobium in a small area is 0%, the maximum content of niobium is 55.26% of the relatively bright area, the percentage content of niobium in the middle is 10.05%, 8.95% and 5.24%, respectively, and the uniformity of the molybdenum-niobium element at the rotating speed of 250rpm is greatly improved, but due to the insufficient ball milling time, individual nonuniform areas exist.
After ball milling at 300rpm, the molybdenum and niobium are found to be distributed very uniformly through SEM images, no aggregation area or blank area of the molybdenum and niobium elements is found, random point scanning is carried out on the particles, the percentage of niobium is in the range of 9.53-10.03%, the percentage is very close to 10%, and the molybdenum and niobium finish the solid solution process to form Mo-10Nb alloy particles after ball milling at 300rpm for 24 hours.
As shown in FIG. 13, which is an internal morphology pattern of the composite powders of example 1 of the present invention and comparative examples 5 to 8 (a1 is 1 h; a2 is 4 h; a3 is 8 h; a4 is 24 h; a5 is 36 h; a6 is 48 h; b1-b6 is a distribution corresponding to Mo element, c1-c6 is a distribution corresponding to Nb element), as shown in FIG. 12, it is a SEM-EDS analysis result of the composite powders of example 1 of the present invention and comparative examples 5 to 8, and it is:
after ball milling is carried out at 250rpm for 1 hour, no whole particle is molybdenum element or niobium element, the outline of a niobium element enrichment region of the particle is obviously smaller than that of a powder particle, point scanning is carried out on different regions in different niobium element aggregation states by combining an internal topography diagram for verification and analysis, the percentage content of niobium in a bright region is 100%, the percentage content of niobium in a dark region is 1.56%, the percentage content of niobium in a middle brightness is 54.31%, 8.91% and 4.62%, respectively, the molybdenum and niobium proportion is obviously changed, the content distribution span is very large, the molybdenum and niobium particle powder is indicated to be subjected to solid solution, and the molybdenum and niobium element distribution states are known by comparing ball milling at 100rpm, 150rpm and 200rpm for 24 hours, and the influence of the rotating speed is larger than that of the ball milling time.
After ball milling at 250rpm for 4 hours, the distribution of the molybdenum and niobium elements is not uniform, and the percentage of niobium in the bright area is 87.78%, the percentage of niobium in the dark area is 0%, and the percentage of niobium in the middle area is 32.68% and 19.13%, respectively.
After ball milling at 250rpm for 8h, the enriched area of niobium or molybdenum is obviously reduced compared with 4h of ball milling, the high part and the low part of niobium percentage are 46.37 percent and 0 percent respectively, the highest part of niobium content is greatly reduced compared with 4h of ball milling, the relative content difference of molybdenum and niobium is obviously reduced, and the middle niobium percentage is 35.75 percent, 26.6 percent and 0.02 percent respectively.
After ball milling at 250rpm for 24h, the distribution uniformity of the molybdenum and niobium particles is greatly improved, only a small area is a niobium gathering area, the niobium percentage height is 55.26%, a 0% area still exists, and the niobium percentage in the middle is 10.05%, 8.95% and 5.24%, respectively.
After ball milling for 36 hours at 250rpm, surface scanning particle element distribution and particle self-correspondence are good, random analysis is carried out on the particles by combining point scanning, and the relative proportion of molybdenum elements and niobium elements is very close to 9 when the percentage content of niobium is 9.62-11.17 percent: 1, the distribution of the elements is uniform, and the complete solid solution of molybdenum and niobium is completed.
After the ball milling at 250rpm for 48h, the distribution is very uniform at the moment through comprehensive analysis of surface scanning and point scanning, the percentage content of niobium is 9.30-10.58%, the niobium is not greatly different from that of the ball milling for 36h, the molybdenum and niobium are completely dissolved after the ball milling for 36h, and more impurity pollution is brought along with the prolonging of the ball milling time.
Experimental example 6 Transmission Electron microscopy of the composite powder of example 1
The particles were examined by transmission electron microscopy, and as shown in fig. 14, the transmission electron microscopy image of the composite powder of embodiment 1 of the present invention shows the following results:
in fig. 14, a is a bright field image showing TEM transmission of particles, and B is a high resolution TEM (hrtem) micrograph and SAED pattern (selected area electron diffraction) in fig. 14, wherein a and B show a typical crystalline microstructure with certain lattice spacing, indicating that the region is composed of several nano-scale crystals. And the crystal sizes of the area A and the area B are 10nm, the TEM result is consistent with the XRD result, and the molybdenum-niobium complete solid solution alloy powder obtained by high-energy ball milling with nano-grade crystal grain size is formed.
Example 3
A method for preparing Mo-10Nb target material by adopting molybdenum-niobium alloy powder in a complete solid solution state comprises the following steps: placing the molybdenum-niobium alloy powder in the embodiment 1 in a die, performing compaction and vibration until the surface of the powder has no height difference, and performing pre-pressing molding by using an oil press, wherein the pressing pressure is 60-100 MPa, the pressing time is 10s, the stopping time is 5s, and the total pressing time is 30 s; placing the pressed green body in a wrinkle-free aluminum foil bag for vacuum packaging, wherein the vacuum degree at least reaches below-0.08 MPa, then carrying out cold isostatic pressing by using a cold isostatic press, adopting gradient boosting, setting each stage of parameters in a gradient manner until the target pressure is reached, setting ten stages in the boosting process, wherein the target pressure is 180-230 MPa, the pressure maintaining time is 10-20 min, and carrying out pressure supplementing when the pressure is less than the target pressure by 2 MPa; after the pressing is finished, pressure relief is carried out, ten stages are also set in the pressure relief process, the pressure relief corresponds to pressurization, and the pressure relief and the pressure maintaining each time are carried out for 10s to play a buffering role; placing the green body pressed by cold isostatic pressing at the bottom of a crucible and paving ZrO with a certain thickness 2 The powder crucible (in order to prevent the heating element graphite from carburizing the surface of the target material in the sintering process, ZrO with a certain thickness needs to be laid at the bottom of the crucible 2 Powder), placing into a vacuum sintering furnace, tightening the furnace door, and vacuumizing to less than 1 × 10 -2 Pa; heating at a heating rate of less than 10 deg.C/min, and a vacuum degree of less than 1 × 10 -2 Pa, setting heat preservation treatment near the temperature point where vacuum degree mutation and gas emission are generated in the temperature rise process, wherein the maximum heat preservation temperature of vacuum sintering is 1800-1950 ℃, and the heat preservation time is 3-6 hours at 1800-1950 ℃ for heat preservationAnd after the temperature is over, cooling to below 60 ℃ along with the furnace, and then opening the furnace to cool to room temperature to obtain the Mo-10Nb target material.
The molybdenum-niobium solid solution powder particles with uniformly distributed elements prepared in the embodiment 1 can improve the performance index of the molybdenum-niobium sputtering target material which is a final product.
Comparative example 9
Essentially the same as example 3, except that: instead of the molybdenum niobium alloy powder of example 1, a direct mix of molybdenum and niobium powders (without high energy ball milling) was used.
1. Density and porosity
As shown in fig. 15, a cross-sectional view and a cross-sectional polished view of the targets of example 3 and comparative example 9 according to the present invention (a1 and a2 are the cross-sectional view and the cross-sectional polished view of the target prepared in comparative example 9, and b1 and b2 are the cross-sectional view and the cross-sectional polished view of the target prepared in example 3, respectively), it can be seen that the target prepared by directly mixing molybdenum powder and niobium powder (without high energy ball milling) in comparative example 9 has more large voids of 50 μm, and the large voids of the molybdenum target prepared by the molybdenum niobium alloy powder in the completely solid solution state in example 3 are significantly reduced in size, are mostly fine and dispersed, and the density is also greatly improved.
2. Grain refinement and uniformity
As shown in fig. 16, which is the texture morphology diagrams of the targets of example 3 and comparative example 9 of the present invention (a1 and a2 are the metallographic structure diagram and the back-scattered electron image of the target prepared in comparative example 9, respectively, and b1 and b2 are the targets prepared in example 3, respectively), it can be seen that the grain sizes of the targets prepared by directly mixing molybdenum powder and niobium powder (without high energy ball milling) in comparative example 9 are large and different, and the grain size distribution is 2.62 μm to 50.88 μm; the average grain size was 20.76 μm, and the grain uniformity factor (average of 5 maxima/average size of most probable grains) was 2.101; example 3 preparation of molybdenum niobium target material from molybdenum niobium alloy powder in complete solid solution state the grain size distribution was 1.71 μm to 12.6 μm, the average grain size was 6.7 μm, the grain uniformity factor was 1.777, it is known by comparison that after high energy ball milling the grain size decreased by about 3 times and the grain uniformity factor increased by 15.42%.
3. Uniformity of element distribution
As shown in fig. 17, which is the distribution diagram of the elements of the targets of example 3 and comparative example 9 of the present invention (a1 and a2 are the targets prepared in comparative example 9, respectively, and b1 and b2 are the targets prepared in example 3, respectively), it can be seen that comparative example 9 has a significant niobium accumulation region, the niobium element in example 3 is uniformly distributed, and the element uniformity is greatly improved.
The research shows that: the molybdenum-niobium alloy target material prepared from the molybdenum-niobium alloy powder has good density, low porosity, uniform element distribution, refined grain size and greatly improved structure uniformity.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. Various modifications and alterations to this invention will become apparent to those skilled in the art upon reading the foregoing description. Accordingly, the scope of the invention should be determined from the following claims.
Claims (5)
1. A method for preparing molybdenum-niobium alloy powder in a complete solid solution state is characterized by comprising the following steps:
high-purity molybdenum powder and high-purity niobium powder are mixed according to the weight ratio of 9: 1, mixing, performing dry high-energy ball milling to realize complete solid solution of molybdenum niobium powder, and adopting three grinding balls with the diameter of 5-20 mm, wherein the mass ratio of the three grinding balls is 5: 3: 2, the ball material ratio is 3-10: 1, performing intermittent ball milling in an argon atmosphere with the atmospheric pressure of 1, wherein the ball milling rotation speed is 250-300 rpm, and the ball milling time is 36-24 h, so as to obtain Mo-10Nb alloy powder in a complete solid solution state;
wherein, the batch-type ball milling is carried out, and each ball milling is stopped for 2 hours and 30 minutes;
the molybdenum-niobium alloy powder has D50 of 2.586-2.634 microns and D10-D90 of 1.306-5.852 microns.
2. A method for preparing Mo-10Nb target material by adopting molybdenum-niobium alloy powder in a complete solid solution state is characterized by comprising the following steps:
placing the molybdenum-niobium alloy powder in a complete solid solution state obtained by the preparation method according to claim 1 in a mold, and performing pre-pressing molding, wherein the pressing pressure is 60-100 MPa, the pressing time is 10s, the time is 5s, and the total pressing time is 30 s;
vacuum packaging the pre-pressed and molded green body, keeping the vacuum degree below-0.08 MPa, performing cold isostatic pressing by using a cold isostatic press, and performing gradient boosting, wherein parameters of each stage are set in a gradient manner until a target pressure is reached, the target pressure is 180-230 MPa, and the pressure maintaining time is 10-20 min;
after the pressing is finished, pressure relief is carried out, and the pressure relief is carried out for 10s each time to play a buffering role;
carrying out vacuum sintering on the green body subjected to cold isostatic pressing, wherein the vacuum degree is less than 1 multiplied by 10 -2 Pa; heating at a heating rate of less than 10 deg.C/min, and a vacuum degree of less than 1 × 10 -2 Pa, keeping the vacuum sintering heat preservation temperature at 1800-1950 ℃, and keeping the heat preservation time for 3-6 hours;
and after the heat preservation is finished, cooling to below 60 ℃ along with the furnace, and then opening the furnace to cool to room temperature to obtain the Mo-10Nb target material.
3. The method for preparing the Mo-10Nb target material by adopting the molybdenum niobium alloy powder in the complete solid solution state as claimed in claim 2, wherein the gradient pressure rise is ten-level, the pressure relief process is also ten-level, and the pressure rise corresponds to the gradient pressure rise.
4. The method for preparing the Mo-10Nb target material by adopting the molybdenum niobium alloy powder in the complete solid solution state as claimed in claim 2, wherein the gradient pressure is increased, and the pressure is supplemented when the pressure is less than the target pressure by 2 MPa.
5. The method for preparing Mo-10Nb target material by using molybdenum niobium alloy powder in complete solid solution state according to any one of claims 2 to 4, characterized in that during the vacuum sintering, a layer of ZrO is laid on the bottom of the crucible 2 Powder, the green compact after cold isostatic pressing is placed on ZrO 2 And (4) powdering.
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