CN105568237A - Chromium-molybdenum alloy target material preparation method - Google Patents
Chromium-molybdenum alloy target material preparation method Download PDFInfo
- Publication number
- CN105568237A CN105568237A CN201410544726.1A CN201410544726A CN105568237A CN 105568237 A CN105568237 A CN 105568237A CN 201410544726 A CN201410544726 A CN 201410544726A CN 105568237 A CN105568237 A CN 105568237A
- Authority
- CN
- China
- Prior art keywords
- pressure
- chrome molybdenum
- temperature
- preparation
- mixed powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Physical Vapour Deposition (AREA)
- Powder Metallurgy (AREA)
Abstract
The present invention provides a chromium-molybdenum alloy target material preparation method comprising the following steps: providing mixed chromium and molybdenum powder, loading the mixed chromium and molybdenum powder into a die, and placing the die into a hot pressing furnace for hot pressing sintering process; the hot pressing sintering process comprises the following steps: first heating treatment of the hot pressing furnace to first temperature is performed, the first temperature is lower than chromium-molybdenum eutectic temperature, meanwhile pressure inside the die is controlled to first pressure, first pressure and temperature maintaining treatment is performed at the first temperature under the first pressure to form a first green body, second heating treatment of the hot pressing furnace to second temperature is performed, the second temperature is greater than the chromium-molybdenum eutectic temperature, second pressure and temperature maintaining treatment is performed at the second temperature under the first pressure to form a second green body, and pressure treatment is performed to obtain a chromium-molybdenum alloy target material. According to the chromium-molybdenum alloy target material preparation method, density and organization uniformity of various parts of the prepared chromium-molybdenum alloy target material can be effectively improved, and the quality of the chromium-molybdenum alloy target material can be improved.
Description
Technical field
The present invention relates to semi-conductor magnetron sputtering field, be specifically related to a kind of preparation method of chrome molybdenum target.
Background technology
Chromium not only has that hardness is high, frictional coefficient is little, wear resistance is high and resistivity advantages of higher, and chromium also all has good erosion resistance for bronsted lowry acids and bases bronsted lowry, and passivation ability is strong in an atmosphere for chromium in addition, not easily occurs with air.
Thus, chromium coating is used widely in mechanical function thin film layer, microelectronic films, function solenoid film and Optical Coatings Surface engineering.As in piston ring surface treatment technology, chromium coating is the coating material commonly used the most.
Traditional technology adopts electrochemical plating to complete piston ring surface chrome-plated process, but the technique toxicity of electrochemical plating chromium plating is large, can cause severe environmental pollution.There is a kind of environment-friendly type piston ring chromium plating process now, this technique is included in and adopts magnetron sputtering method after piston ring surface chromium plating, adopt laser heat treatment process that the chromium coating of piston ring surface is spread in the substrate again, thus improve chromium plating layer by layer with the bonding force of piston ring, to improve the abilities such as piston ring surface wear resistance, erosion resistance, and reduce the frictional coefficient of piston ring surface.
But, along with the further raising required for piston ring surface wear resistance, erosion resistance and low-friction coefficient, new requirement is proposed for piston ring surface coating performance.Researchist finds that the chrome molybdenum plated film being added with molybdenum in chromium plated film has higher wear resistance, erosion resistance relative to simple chromium plated film, and has lower frictional coefficient.For this reason, employing magnetron sputtering method coating process obtains the research emphasis that the good chrome molybdenum coating of performance is this area.
But the density of the chrome molybdenum target obtained by prior art, the uniformity coefficient of each several part tissue are all undesirable, it directly affects in follow-up magnetron sputtering technique, the sputter rate of chrome molybdenum target, and then the performance such as uniformity coefficient, wear resistance of the plated film of impact acquisition.
Thus, how obtaining the chrome molybdenum target with good quality is the problem that those skilled in the art need solution badly.
Summary of the invention
The problem that the present invention solves is the preparation method by providing a kind of chrome molybdenum target, to obtain the chrome molybdenum target of excellent performance.
For solving the problem, the invention provides a kind of preparation method of chrome molybdenum target, comprising:
There is provided chrome molybdenum mixed powder, by die-filling for described chrome molybdenum mixed powder;
Chrome molybdenum mixed powder after die-filling is inserted in hot pressing furnace, carry out hot pressing furnace first hyperthermic treatment to the first temperature, described first temperature is less than the eutectic temperature of chrome molybdenum, and simultaneously to the chrome molybdenum mixed powder pressurization in described mould, the pressure controlled in mould is the first pressure;
At the first temperature and the first pressure, carry out the first heat-insulation pressure keeping process, form the first base substrate;
Under the condition of the first pressure, carry out hot pressing furnace second hyperthermic treatment to the second temperature, described second temperature is greater than the eutectic temperature of chrome molybdenum;
At the second temperature and the first pressure, carry out the second heat-insulation pressure keeping process, form the second base substrate;
Again carry out pressure treatment, the pressure controlled in described mould is the second pressure, and described second pressure is greater than the first pressure;
The 3rd heat-insulation pressure keeping process is carried out, obtained chrome molybdenum target at the second temperature and the second pressure.
Alternatively, described first temperature is 1000 ~ 1300 DEG C.
Alternatively, described second temperature is 1400 ~ 1700 DEG C.
Alternatively, described first pressure is 4 ~ 9MPa.
Alternatively, the step of described first heat-insulation pressure keeping process comprises:
Controlling described first pressure is 6 ~ 9MPa, but when the pressure in mould is greater than outside applying pressure, reduces outside applied pressure to the pressure in mould and external pressure balance; When the pressure in described mould reduces, continue to apply pressure in described mould, and to control described first pressure be 6 ~ 9MPa.
Alternatively, the step of described first hyperthermic treatment comprises: with the ramp of 5 ~ 10 DEG C/min.
Alternatively, the step of the first heat-insulation pressure keeping process comprises: at the first temperature and the first pressure, carries out heat-insulation pressure keeping process 30 ~ 90 minutes.
Alternatively, the step of described second hyperthermic treatment comprises: with the ramp of 3 ~ 7 DEG C/min.
Alternatively, described second pressure is 20 ~ 30MPa.
Alternatively, the step of described second heat-insulation pressure keeping process comprises: at the second temperature and the first pressure, carries out heat-insulation pressure keeping process 1 ~ 2 hour.
Alternatively, again carry out pressure treatment, the pressure controlled in described mould is that the step of the second pressure comprises: with 0.5 × 10
4~ 1.5 × 10
4the speed pressurization of N/min.
Alternatively, the step of described 3rd heat-insulation pressure keeping process comprises: at the second temperature and the second pressure, carries out heat-insulation pressure keeping process 30 ~ 60min.
Alternatively, in described 3rd heat-insulation pressure keeping treating processes, the preparation method of described chrome molybdenum target also comprises step: in described hot pressing furnace, pass into rare gas element, and extract hot pressing furnace gas out, be 0.02 ~ 0.04MPa to the air pressure in hot pressing furnace simultaneously.
Alternatively, being inserted after in hot pressing furnace by the chrome molybdenum mixed powder after die-filling, before carrying out the first hyperthermic treatment, the preparation method of described chrome molybdenum target also comprises: vacuumize process to air pressure to described hot pressing furnace and be less than or equal to 100Pa.
Alternatively, die-filling for described chrome molybdenum mixed powder adopted mould is comprised: for taking up the sleeve of chrome molybdenum mixed powder, and for seal described sleeve and in described sleeve chrome molybdenum mixed powder pressurization pressure head;
Step die-filling for described chrome molybdenum mixed powder is comprised:
Chrome molybdenum mixed powder is loaded in sleeve;
Cold pressing treatment is carried out to the chrome molybdenum mixed powder in described mould;
After cold pressing treatment, seal described sleeve with pressure head.
Alternatively, described cold pressing treatment comprises: adopt static pressure machine with 1.0 × 10
5~ 2.0 × 10
5n pressure is by described chrome molybdenum mixed powder pre-molding.
Alternatively, the step of chrome molybdenum mixed powder is provided to comprise: the mass ratio of described chromium and molybdenum is 7:2 ~ 7:4.
Alternatively, before step die-filling for described chrome molybdenum mixed powder, the preparation method of described chrome molybdenum target also comprises: carry out mixing process to described chrome molybdenum mixed powder.
Alternatively, the grain-size in described chrome molybdenum target is 20 ~ 30 microns.
Compared with prior art, technical scheme of the present invention has the following advantages:
Being placed in after in hot pressing furnace by chrome molybdenum mixed powder, the pressure controlled in mould is the first pressure, and carry out hot pressing furnace first hyperthermic treatment and hot pressing in-furnace temperature is risen to the first temperature, described first temperature is less than chrome molybdenum eutectic temperature.In the process of the hyperthermic treatment of described hot pressing furnace first and the first heat-insulation pressure keeping process afterwards, described chromium powder end and molybdenum powder there will be crystallization and soften, thermoplasticity deformation, between chromium crystal grain and chromium crystal grain and molybdenum crystal grain in the Contact of molybdenum crystal grain and diffusion bonding, and between each crystal grain, dislocation density increases considerably and occurs that key connects and resets, and makes molybdenum crystal grain and chromium crystal grain constantly grow up and is formed with the first base substrate; And constantly increase along with the time increases the first blank strength, pressure is controlled to be the first pressure, can guarantee to provide under chromium crystal grain and the enough growth conditions of molybdenum crystal grain, each crystal grain is drawn close mutually, the cumulative volume in intercrystalline space reduces rapidly, to promote that intercrystalline bonds, improve density and the intensity of the chrome molybdenum target obtained; In addition, pressurize under chromium crystal grain and molybdenum crystal grain are in hot plastic state, contribute to chromium, the diffusion of molybdenum intercrystalline, to improve the uniformity coefficient of chromium, molybdenum crystal grain substep;
After a heat-insulation pressure keeping, carry out hot pressing furnace second hyperthermic treatment, improve temperature to the second temperature in hot pressing furnace, the second temperature is greater than the eutectic temperature of chrome molybdenum.In hot pressing furnace second hyperthermic treatment and enter under the condition of the second temperature first pressure afterwards in the process of the second heat-insulation pressure keeping process, there is congruent melting in the chromium crystal grain in the first base substrate and molybdenum crystal grain, form the eutectic of chrome molybdenum, space in first base substrate reduces further, the density of further raising base substrate and intensity, thus form the second base substrate;
After the second heat-insulation pressure keeping process, pressure treatment is carried out to the second base substrate in mould, to reduce the space in the second base substrate between each crystal grain further, improve each intercrystalline cohesive force, to improve the density of follow-up obtained chrome molybdenum target;
The chrome molybdenum target obtained by above-mentioned hot-pressing sintering technique has good density and uniform crystal particles degree, thus can improve the quality of carrying out the plated film that observing and controlling sputtering technology is formed with described chrome molybdenum target.
In possibility, in chrome molybdenum mixed powder, the mass ratio of chromium and molybdenum is 7:2 ~ 7:4, above by above-mentioned mass ratio configuration in conjunction with above-mentioned processing condition, thus chromium atom and molybdenum atom composition in the chrome molybdenum target that can control follow-up formation, and the weave construction in chrome molybdenum target, to improve hardness, corrosion-resistant degree, the wear resistance of the inner plated film of chrome molybdenum target, and reduce the frictional coefficient of plated film, and then improve the quality of chrome molybdenum target, and the coating quality after follow-up magnetron sputtering.
Alternatively, chrome molybdenum mixed powder after die-filling is inserted after in hot pressing furnace, before carrying out the first hyperthermic treatment, first process is vacuumized to described hot pressing furnace, thus effectively can get rid of hot pressing furnace, and the composition such as oxygen in mould, thus avoid in follow-up hot-pressing sintering technique, cause the defects such as product oxidation, to improve the chrome molybdenum target quality of formation.
Alternatively, in described 3rd heat-insulation pressure keeping treating processes, in described hot pressing furnace, pass into rare gas element simultaneously, and (air pressure is 0.02 ~ 0.04MPa) will be vacuumized in hot pressing furnace thus the chrome molybdenum target that obtains can be prevented at high temperature oxidized, to improve chrome molybdenum target quality.
Accompanying drawing explanation
Fig. 1 is the schema of the preparation method of chrome molybdenum target of the present invention;
Fig. 2 to Fig. 5 is the schematic diagram of each step in preparation method one embodiment of chrome molybdenum target of the present invention.
Embodiment
As described in background, the density of the chrome molybdenum target obtained by prior art, the uniformity coefficient of each several part tissue are all undesirable, thus affect in follow-up magnetron sputtering technique, the parameters such as the sputter rate of chrome molybdenum target, and then the performance such as uniformity coefficient, wear resistance of the plated film of impact acquisition.
For this reason, the invention provides a kind of preparation method of chrome molybdenum target, with reference to figure 1, the preparation method of described chrome molybdenum target comprises the following steps:
Step S1, provides chrome molybdenum mixed powder, by die-filling for described chrome molybdenum mixed powder;
Step S2, insert in hot pressing furnace by the chrome molybdenum mixed powder after die-filling, carry out hot pressing furnace first hyperthermic treatment to the first temperature, described first temperature is less than the eutectic temperature of chrome molybdenum, simultaneously to the chrome molybdenum mixed powder pressurization in described mould, the pressure controlled in mould is the first pressure;
Step S3, carries out the first heat-insulation pressure keeping process, forms the first base substrate at the first temperature and the first pressure;
Step S4, under the condition of the first pressure, carry out hot pressing furnace second hyperthermic treatment to the second temperature, described second temperature is greater than the eutectic temperature of chrome molybdenum;
Step S5, carries out the second heat-insulation pressure keeping process, forms the second base substrate at the second temperature and the first pressure;
Step S6, carries out pressure treatment again, and the pressure controlled in described mould is the second pressure, and described second pressure is greater than the first pressure;
Step S7, carries out the 3rd heat-insulation pressure keeping process at the second temperature and the second pressure, obtained chrome molybdenum target.
Grain-size in the chrome molybdenum target obtained by above-mentioned hot-pressing sintering technique is between 20 ~ 30 microns, and described chrome molybdenum target has good density and uniform crystal particles degree, thus the quality of carrying out the plated film that observing and controlling sputtering technology is formed with described chrome molybdenum target can be improved.
For enabling above-mentioned purpose of the present invention, feature and advantage more become apparent, and are described in detail specific embodiments of the invention below in conjunction with accompanying drawing.
First, perform step S1, provide chrome molybdenum mixed powder, by die-filling for described chrome molybdenum mixed powder.
The ratio of described chromium and molybdenum directly affects the composition of chromium and molybdenum in the chrome molybdenum target of follow-up formation, based on chromium and molybdenum property difference separately, in chrome molybdenum target, the composition of chromium and molybdenum directly affects wear resistance, the characteristic such as erosion resistance and frictional coefficient of the chrome molybdenum target of follow-up formation, thus affect the carrying out of follow-up observing and controlling sputtering technology, and the coating quality formed;
In addition, the present invention adopts hot-pressing sintering technique to prepare chrome molybdenum target, in hot pressed sintering process, chromium powder end and molybdenum powder there will be that crystallization is softening, chromium crystallization and molybdenum crystallization occur that key connects and rearrangement, intercrystalline are mutually drawn close and bond gradually, and the series reaction such as chromium powder end and molybdenum powder congruent melting, for this reason, the ratio of described chromium and molybdenum also can affect above-mentioned series reaction and carry out, thus the characteristic such as intensity and target hardness of each several part tissue homogeneous degree, target in the chrome molybdenum target affecting follow-up formation.
In the present embodiment, in described chrome molybdenum mixed powder, the mass ratio of chromium powder end and molybdenum powder is 7:2 ~ 7:4, thus improves the chrome molybdenum target quality of follow-up formation.
Alternatively, described chromium powder end and molybdenum powder mass ratio be about 7:3.
Further alternatively, in the present embodiment, the size of chromium powder end and molybdenum powder is less than or equal to 4 microns (μm), and less powder size is convenient to grain formation in follow-up hot-pressing sintering technique and intercrystalline mass transfer, diffusion and bonding.
Further alternatively, in the present embodiment, the purity of described chromium powder end and molybdenum powder is greater than 99.9%.Thus the foreign matter content reduced in the chrome molybdenum target of follow-up formation, reduce impurity in hot pressed sintering process simultaneously, for chromium powder end with molybdenum powder is softening in crystallization, chromium crystallization and molybdenum crystallization occur that key connects and rearrangement, intercrystalline are mutually drawn close and bond gradually, and the impact of the series reaction such as chromium powder end and molybdenum powder congruent melting, thus improve the chrome molybdenum target quality of follow-up formation.
In the present embodiment, before to the die-filling process of described chrome molybdenum mixed powder, first mixing process is carried out to described chrome molybdenum mixed powder, chromium powder end and molybdenum powder are mixed, and then improves the uniformity coefficient of chrome molybdenum target each several part tissue of follow-up formation.
In conjunction with referring to figs. 2 and 3, by chromium powder end with after molybdenum powder mixes, carry out die-filling process.
Loaded by chrome molybdenum mixed powder in mould 10, described mould 10, in follow-up hot-pressing sintering technique, plays protection chrome molybdenum mixed powder, and controls the shaping effect of chrome molybdenum mixed powder.
Described mould 10 comprises sleeve 30, and pressure head 20.
Described sleeve 30 is for taking up chrome molybdenum mixed powder, described pressure head 20 is for sealing described sleeve 30, simultaneously in hot-pressing sintering technique, described pressure head 20 also for chrome molybdenum mixed powder pressurization (this technology be single shaft pressurization) in described sleeve 30, to control the pressure of chrome molybdenum mixed powder in sleeve 30 (or chrome molybdenum mixed powder formed base substrate).
After chrome molybdenum mixed powder is loaded sleeve 30, dividing plate 40 can be adopted axially chrome molybdenum mixed powder to be separated into several part 50 along sleeve 30, thus in follow-up hot-pressing sintering technique, polylith chrome molybdenum target can be prepared simultaneously.
The chrome molybdenum mixed powder amount of described each several part 50 determines according to the follow-up chrome molybdenum target size of preparation that needs, and the present invention is not construed as limiting this.
Hot-pressing sintering technique needs to carry out under elevated temperature and pressure conditions, and described mould 10 adopts graphite to make, to bear high temperature and high pressure.Described mould 10 is the mature technology of this area, does not repeat them here.
In the present embodiment, after chrome molybdenum mixed powder is loaded sleeve 30, before pressure head installed by described sleeve 30, first cold pressing treatment is carried out to the chrome molybdenum mixed powder in sleeve 30, by the chrome molybdenum mixed powder compacting in sleeve 30, and improve the surface finish of the chrome molybdenum mixed powder loaded in sleeve 30, make chrome molybdenum mixed powder pre-molding.
Described cold pressing treatment can adopt static pressure machine (not shown) to complete.
In described cold pressing treatment process, the gap in chrome molybdenum mixed powder can be compressed, discharge additional air simultaneously.If but pressure is too small, reduces the density of chrome molybdenum mixed powder, be unfavorable for that follow-up series reaction is carried out, and the chrome molybdenum target density of follow-up formation can be reduced; If pressure is excessive, excessive burden is caused to described mould 10, be also unfavorable for that follow-up hot-pressing sintering technique carries out.
In the present embodiment, adopt static pressure machine with 1.0 × 10
5~ 2.0 × 10
5n (10 ~ 20 tons) pressure carries out cold pressing treatment, by the chrome molybdenum mixed powder pre-molding in sleeve 30.
Afterwards, with reference to figure 3, in the opening of described sleeve 30, pressure head 20 is installed, completes the die-filling process of chrome molybdenum mixed powder.
Then with reference to figure 4 and Fig. 5, the chrome molybdenum mixed powder after die-filling is inserted in hot pressing furnace 60, carries out hot-pressing sintering technique, prepare chrome molybdenum target.
In the present embodiment, the chrome molybdenum mixed powder after die-filling is inserted after in hot pressing furnace 60, before described hot pressing furnace 60 is heated up, first process is vacuumized to described hot pressing furnace 60.
Discharge the air in described hot pressing furnace 60, thus avoid follow-uply heating in process to described hot pressing furnace 60, cause the oxidized defect of chrome molybdenum mixed powder.
In the present embodiment, after process is vacuumized to described hot pressing furnace 60, hot pressing furnace 60 internal gas pressure is made to be less than or equal to 100Pa (0.1MPa), oxygen volume content in described hot pressing furnace 60 is controlled in the scope being less than 1000ppm (partpermillion, 1,000,000/).
Afterwards, perform step S2, chrome molybdenum mixed powder after die-filling is inserted in hot pressing furnace 60, carry out hot pressing furnace first hyperthermic treatment to the first temperature, described first temperature is less than the eutectic temperature of chrome molybdenum, simultaneously to the chrome molybdenum mixed powder pressurization in described mould, the pressure controlled in mould is the first pressure.
When the pressure that it should be noted that in described mould is chrome molybdenum mixed powder (or base substrate) in described pressure head 20 extrusion mould, the pressure on chrome molybdenum mixed powder surface (or billet surface).
In the present embodiment, described first temperature is 1000 ~ 1300 DEG C.
The concrete numerical value of described first temperature is determined according to the processing parameter such as mass ratio of chromium powder end and molybdenum powder.Alternatively, in the present embodiment, described chromium powder end and molybdenum powder mass ratio be about 7:3, described first temperature is about 1030 DEG C.
At a first temperature, there is not congruent melting phenomenon in described chromium and molybdenum, but in hot pressing furnace first hyperthermic treatment process, described chromium powder end and molybdenum powder there will be crystallization and soften, and occur thermoplasticity deformation, between chromium crystal grain and chromium crystal grain, molybdenum crystal grain contact diffusion boning between molybdenum crystal grain, and each intercrystalline dislocation density increases considerably and occurring that key connects and resets, molybdenum crystal grain and chromium crystal grain are constantly grown up, and the cohesive strength between molybdenum crystal grain and chromium crystal grain improves constantly.
In hot pressing furnace first hyperthermic treatment process, described hot pressing furnace 60 is warming up to the first temperature gradually by room temperature.Wherein, if temperature rise rate is too fast, can cause the chromium powder in mould 10 end and molybdenum powder local heating difference excessive, cause chromium crystal grain and the molybdenum grain growing speed difference of mould 10 different sites thus, and, in temperature-rise period, chromium powder end and molybdenum powder in gas and moisture get rid of gradually, heat up too fast gas and the moisture eliminating speed that also can affect mould 10 different sites, and above-mentioned defect all can reduce the uniformity coefficient of the chrome molybdenum target each several part tissue of follow-up formation; If but temperature rise rate is excessively slow, cause the heating-up time long, and cause the chromium crystal grain that formed and molybdenum grain-size much, reduce the characteristics such as the hardness of the chrome molybdenum target of follow-up formation and wear resistance.
In the present embodiment, in hot pressing furnace first hyperthermic treatment process, the temperature rise rate controlling hot-pressed sintering furnace 60 is 5 ~ 10 DEG C/min (centigrade per minute), be chosen as 10 DEG C/about min further, thus guarantee that chromium crystal grain in hot pressing furnace 60 and molybdenum crystal grain are fully heated, fully carry out with the bonding be conducive between chromium crystal grain and between molybdenum crystal grain and the mass transfer that flows, make the gas in chromium powder end and molybdenum powder and moisture thoroughly be got rid of simultaneously, thus effectively improve the density between each crystal grain in mould 10.
In addition, in hot pressing furnace first hyperthermic treatment process, need to apply pressure with the chromium powder end in pressure head 20 pairs of sleeves 30 and molybdenum powder, the pressure controlled in mould 10 is the first pressure, thus each intercrystalline is drawn close mutually, reduce intercrystalline space, to promote that intercrystalline bonds, to improve density and the intensity of the base substrate of acquisition; Pressurize under crystal grain hot plastic state simultaneously, contribute to intercrystalline diffusion, to improve the uniformity coefficient of each crystal grain substep.
If described pressure head 20 applied pressure is inadequate, the density of the base substrate of follow-up formation can be reduced; But in hot pressing furnace first hyperthermic treatment process, chromium crystal grain and molybdenum crystal grain constantly increase, if described pressure is excessive, the pressure in base substrate can be caused excessive, intercrystalline diffusion can be suppressed, thus reduce the uniformity coefficient of the chrome molybdenum target each several part tissue of follow-up formation, but also the defects such as burn failure can be caused.
In the present embodiment, controlling described first pressure is 4 ~ 9MPa, and controlling described first pressure is alternatively 6 ~ 9MPa.The concrete operations controlling the pressure in described mould 10 comprise, and can apply 8 × 10 by described pressure head 20 to the base substrate 51 in sleeve 30
5~ 18 × 10
5the pressure of N (8 ~ 18 tons) left and right.
It should be noted that the mass ratio of described first pressure and described chromium powder end and molybdenum powder, the first temperature correlation.
In the present embodiment, the mass ratio of the first pressure and described chromium powder end and molybdenum powder is chosen as about 7:3, and the first temperature is chosen as about 103. DEG C, and described first pressure is chosen as about 7.5MPa.
The obtain manner of described first pressure realizes by arranging the modes such as pressure transmitter at sleeve 30, and described first pressure data, and pressure head applied pressure sets as the case may be, foregoing does not repeat them here.
Perform step S3, at the first temperature and the first pressure, carry out the first heat-insulation pressure keeping process, form the first base substrate.
After temperature in described hot pressing furnace 60 rises to the first temperature, the first heat-insulation pressure keeping process is carried out at the first temperature and the first pressure conditions, each crystal grain in mould 10 is fully grown, spread and intercrystalline well-bonded, to improve the tissue homogeneous degree of base substrate each several part, and improve the intensity of the first base substrate 51 formed.
If the described first heat-insulation pressure keeping treatment time is long, each crystal grain in the first base substrate 51 is excessive, is unfavorable for follow-up formation chrome molybdenum target quality; If the time is too short, be unfavorable for diffusion and the bonding of each crystal grain, reduce the uniformity coefficient of the first base substrate 51 each several part tissue.
In the present embodiment, the time remaining 30 ~ 90min (minute) of described first heat-insulation pressure keeping process is about 60min alternatively.
In described first heat-insulation pressure keeping treating processes, under the high temperature conditions, the crystal grain meeting expanded by heating in mould 10 is also grown up.In this process, the pressure in mould 10 can increase, and is even greater than outside pressure head 20 applied pressure, now, can reduce pressure head 20 applied pressure, makes the pressure in mould 10 reach balance with outside pressure; And in grain growth process, intercrystalline gap can be extruded, gas in mould 10 can be excluded, the cumulative volume of the crystal grain in mould 10 is shunk, pressure in mould 10 reduces, thus after reaching balance, when being experienced the pressure in mould 10 by devices such as the pressure transmitters in mould 10 and reducing, continue in mould, to apply pressure with pressure head 20, and to control described first pressure be 6 ~ 9MPa.
After the first heat-insulation pressure keeping process, perform step S4, under the condition of the first pressure, carry out hot pressing furnace second hyperthermic treatment to the second temperature, described second temperature is greater than the eutectic temperature of chrome molybdenum.
Described second Temperature numerical is determined according to the processing parameter such as mass ratio of the chromium powder end in chrome molybdenum mixed powder and molybdenum powder.
In the present embodiment, the mass ratio of chromium powder end and molybdenum powder is about 7:3, and adjusting the second Temperature numerical is 1400 ~ 1700 DEG C.
In above-mentioned steps S2 and S3, described chromium powder end and molybdenum powder all occur that crystallization is softened, and between chromium crystal grain chromium, and contact diffusion bonding between chromium crystal grain, and occurring that key connects and resets, form the first base substrate 51 of ad hoc structure, in step s 4 which, there is congruent melting in part chromium crystal grain and molybdenum crystal grain, spread further between chromium crystal grain and molybdenum crystal grain, and occur binding and rearrangement between chromium crystal grain and molybdenum crystal grain, form the eutectic of chrome molybdenum, reduce the space in base substrate simultaneously further, improve density and the intensity of the first base substrate 51.
In the present embodiment, in hot pressing furnace second hyperthermic treatment, improve the temperature in hot pressing furnace 60 gradually, thus hot pressing furnace 60 inside is risen to the second temperature by the first temperature.Period, if temperature rise rate is too fast, can cause the chromium crystal grain of different sites in the first base substrate 51 and molybdenum crystal grain local heating difference excessive, cause chromium crystal grain and the molybdenum crystal grain throughput rate difference of different sites in the first base substrate 51 thus, thus reduce the first base substrate 51 each several part tissue homogeneous degree; If but temperature rise rate is excessively slow, the heating-up time is long cause the chromium crystal grain of formation and molybdenum grain-size much, reduce the hardness of the chrome molybdenum target of follow-up formation, and the characteristic such as wear resistance.
In the present embodiment, the temperature rise rate controlling hot pressing furnace second hyperthermic treatment is 3 ~ 7 DEG C/min.
In addition, in hot pressing furnace 60 temperature-rise period, applying suitable pressure by pressure head 20 to the base substrate 51 in mould 10, is the first pressure (6 ~ 9MP is optionally about 7.5MPa) to keep the pressure in mould 10, thus each intercrystalline is drawn close mutually, reduce intercrystalline space, to promote that each intercrystalline bonds, improve density and the intensity of acquisition first base substrate, help intercrystalline diffusion, to improve the uniformity coefficient of each crystal grain substep simultaneously.
Afterwards, performing step S5, at the second temperature and the first pressure, carry out the second heat-insulation pressure keeping process, forming the second base substrate (for indicating in figure).
By after in described hot pressing furnace 60, temperature rises to the second temperature, the second heat-insulation pressure keeping process is carried out at the second temperature and the first pressure, the crystal grain in the first base substrate 51 is made fully to spread, bond, to improve the tissue homogeneous degree of the first base substrate 51 each several part, and first intensity of base substrate 51, form the second base substrate.
If the described second heat-insulation pressure keeping treatment time is too short, be unfavorable for diffusion and the bonding of each crystal grain in the first base substrate 51, affect the uniformity coefficient of the first base substrate 51 each several part tissue; If overlong time, in the first base substrate 51, crystal grain is excessive, is unfavorable for follow-up formation chrome molybdenum target quality.
In the present embodiment, the time remaining 1 ~ 2 hour (h) of described second heat-insulation pressure keeping process.
After forming the second base substrate, perform step S6, again carry out pressure treatment, the pressure controlled in described mould is the second pressure, and described second pressure is greater than the first pressure.
In step s 6, adopt the further pressure treatment of the second base substrate in pressure head 20 pairs of moulds 10, to reduce the space between each crystal grain, improve each intercrystalline cohesive force, improve the density of follow-up obtained chrome molybdenum target.
If described second too little pressure, can reduce the density of the second base substrate; If described pressure is excessive, burn failure can be caused.
In the present embodiment, the pressure that described second pressure measures for the second billet surface in mould 10, described second pressure is chosen as 20 ~ 30MPa/cm
2.
In the present embodiment, exerted pressure to the second base substrate in sleeve 30 by described pressure head 20, to improve the density of the second base substrate, based on hot pressed sintering be single shaft pressurization, cause each second base substrate each several part pressurized in sleeve 30 uneven if the speed of pressurization is excessive, thus reduce the uniformity coefficient of the chrome molybdenum target each several part tissue of follow-up formation, but also mould 10 can be caused impaired; If compression rate is too small, causes clamping time long, not only affect process efficiency, and make each grain growing overlong time in the second base substrate, make grain-size excessive and affect the quality of the chrome molybdenum target of follow-up formation.
In the present embodiment, again carry out pressure treatment, the pressure controlled in described mould is that the step of the second pressure comprises: with 0.5 ~ 1.5 × 10
4the speed pressurization of ox/minute (N/min), compression rate is 1.0 × 10 alternatively further
4about N/min.
Perform step S7, at the second temperature and the second pressure, carry out the 3rd heat-insulation pressure keeping process, obtained chrome molybdenum target.
The 3rd heat-insulation pressure keeping process is carried out under the second temperature second pressure, in second base substrate, each crystal grain spreads further, bonds, and removes the space in the second base substrate simultaneously, improves the density of the second base substrate, and second blank strength, thus obtained chrome molybdenum target 52.
If the 3rd heat-insulation pressure keeping treatment time is too short, be unfavorable for the diffusion between each crystal grain and bonding, reduce the uniformity coefficient of base substrate each several part tissue; If overlong time, for increasing further the uniformity coefficient of intensity and each several part tissue in the second base substrate without too large effect, and defect, the reduction chrome molybdenum target quality such as the grain-size in the second target material blank body can be caused excessive.
In the present embodiment, the time of the 3rd heat-insulation pressure keeping process is 30 ~ 60min.
Alternatively, in the preparation method of the present embodiment chrome molybdenum target, in described 3rd heat-insulation pressure keeping treating processes, in described hot pressing furnace 60, pass into rare gas element simultaneously.
In the present embodiment, described rare gas element comprises nitrogen (N
2), helium (He), argon gas (Ar) or neon (Ne) etc.
The chrome molybdenum target that rare gas element can prevent from obtaining is passed at high temperature oxidized to improve chrome molybdenum target quality in described hot pressing furnace 60.
In the present embodiment, in described hot pressing furnace 60, pass into rare gas element, constantly extract the gas in hot pressing furnace 60 out, the air pressure be evacuated to by hot pressing furnace 60 in hot pressing furnace 60 is 0.02 ~ 0.04MPa simultaneously.
In described 3rd heat-insulation pressure keeping process, after obtained chrome molybdenum target 52, close hot pressing furnace 60, and after hot pressing furnace 60 naturally cooling, take out chrome molybdenum target 52.Afterwards ground finish is carried out, the techniques such as Linear cut to described chrome molybdenum target 52.
After tested, the grain-size in the chrome molybdenum target adopting above-mentioned hot-pressing sintering technique to be formed is 20 ~ 30 microns, and density reaches 99.9%, and the tissue of chrome molybdenum target each several part has good uniformity coefficient.
In the present embodiment, choose extra fine quality ratio chromium powder end and molybdenum powder (mass ratio of chromium and molybdenum is 7:2 ~ 7:4) after, by die-filling for chrome molybdenum mixed powder and insert in hot pressing furnace and carry out hot-pressing sintering technique, first hot pressing furnace first hyperthermic treatment is carried out, make hot pressing in-furnace temperature to the first temperature (1000 ~ 1300 DEG C), described first temperature is less than the eutectic temperature of chrome molybdenum, simultaneously to the chrome molybdenum mixed powder pressurization in described mould, the pressure controlled in mould is the first pressure, chromium powder end and molybdenum powder are softened, and carry out binding and rearrangement between chromium crystal grain, binding and rearrangement is carried out between molybdenum crystal grain, carry out after the first heat-insulation pressure keeping process forms the first base substrate at the first temperature and the first pressure, carry out hot pressing furnace second hyperthermic treatment, make hot pressing in-furnace temperature to the second temperature (1400 ~ 1700 DEG C), described second temperature is greater than the eutectic temperature of chrome molybdenum, make congruent melting between chromium crystal grain and molybdenum crystal grain, binding and rearrangement is carried out between chromium crystal grain and molybdenum crystal grain, and carry out after the second heat-insulation pressure keeping process forms the second base substrate at the second temperature and the first pressure, again carry out pressure treatment, the pressure controlled in described mould is the second pressure, described second pressure is greater than the first pressure, to reduce the gap in the second base substrate further, improve density and the intensity of the second base substrate, the 3rd heat-insulation pressure keeping process is carried out afterwards at the second temperature and the second pressure, obtained chrome molybdenum target.
The grain-size of the chrome molybdenum target obtained by the preparation method of above-mentioned chrome molybdenum target is 20 ~ 30 microns, density reaches 99.9%, and the tissue homogeneous degree of each several part is good, the defects such as flawless, thus the sputtering performance that effectively can improve chrome molybdenum target.
Although the present invention discloses as above, the present invention is not defined in this.Any those skilled in the art, without departing from the spirit and scope of the present invention, all can make various changes or modifications, and therefore protection scope of the present invention should be as the criterion with claim limited range.
Claims (19)
1. a preparation method for chrome molybdenum target, is characterized in that, comprising:
There is provided chrome molybdenum mixed powder, by die-filling for described chrome molybdenum mixed powder;
Chrome molybdenum mixed powder after die-filling is inserted in hot pressing furnace, carry out hot pressing furnace first hyperthermic treatment to the first temperature, described first temperature is less than the eutectic temperature of chrome molybdenum, and simultaneously to the chrome molybdenum mixed powder pressurization in described mould, the pressure controlled in mould is the first pressure;
At the first temperature and the first pressure, carry out the first heat-insulation pressure keeping process, form the first base substrate;
Under the condition of the first pressure, carry out hot pressing furnace second hyperthermic treatment to the second temperature, described second temperature is greater than the eutectic temperature of chrome molybdenum;
At the second temperature and the first pressure, carry out the second heat-insulation pressure keeping process, form the second base substrate;
Again carry out pressure treatment, the pressure controlled in described mould is the second pressure, and described second pressure is greater than the first pressure;
The 3rd heat-insulation pressure keeping process is carried out, obtained chrome molybdenum target at the second temperature and the second pressure.
2. the preparation method of chrome molybdenum target according to claim 1, is characterized in that, described first temperature is 1000 ~ 1300 DEG C.
3. the preparation method of chrome molybdenum target according to claim 1, is characterized in that, described second temperature is 1400 ~ 1700 DEG C.
4. the preparation method of chrome molybdenum target according to claim 1, is characterized in that, described first pressure is 4 ~ 9MPa.
5. the preparation method of chrome molybdenum target according to claim 4, is characterized in that, the step of described first heat-insulation pressure keeping process comprises:
Controlling described first pressure is 6 ~ 9MPa, but when the pressure in mould is greater than outside applying pressure, reduces outside applied pressure to the pressure in mould and external pressure balance; When the pressure in described mould reduces, continue to apply pressure in described mould, and to control described first pressure be 6 ~ 9MPa.
6. the preparation method of chrome molybdenum target according to claim 1, is characterized in that, the step of described first hyperthermic treatment comprises: with the ramp of 5 ~ 10 DEG C/min.
7. the preparation method of chrome molybdenum target according to claim 1, is characterized in that, the step of the first heat-insulation pressure keeping process comprises: at the first temperature and the first pressure, carries out heat-insulation pressure keeping process 30 ~ 90 minutes.
8. the preparation method of chrome molybdenum target according to claim 1, is characterized in that, the step of described second hyperthermic treatment comprises: with the ramp of 3 ~ 7 DEG C/min.
9. the preparation method of chrome molybdenum target according to claim 1, is characterized in that, described second pressure is 20 ~ 30MPa.
10. the preparation method of chrome molybdenum target according to claim 1, is characterized in that, the step of described second heat-insulation pressure keeping process comprises: at the second temperature and the first pressure, carries out heat-insulation pressure keeping process 1 ~ 2 hour.
The preparation method of 11. chrome molybdenum targets according to claim 1, is characterized in that, again carry out pressure treatment, and the pressure controlled in described mould is that the step of the second pressure comprises: with 0.5 × 10
4~ 1.5 × 10
4the speed pressurization of N/min.
The preparation method of 12. chrome molybdenum targets according to claim 1, is characterized in that, the step of described 3rd heat-insulation pressure keeping process comprises: at the second temperature and the second pressure, carries out heat-insulation pressure keeping process 30 ~ 60min.
The preparation method of 13. chrome molybdenum targets according to claim 1, it is characterized in that, in described 3rd heat-insulation pressure keeping treating processes, the preparation method of described chrome molybdenum target also comprises step: in described hot pressing furnace, pass into rare gas element, extract hot pressing furnace gas out, be 0.02 ~ 0.04MPa to the air pressure in hot pressing furnace simultaneously.
The preparation method of 14. chrome molybdenum targets according to claim 1, it is characterized in that, the chrome molybdenum mixed powder after die-filling is inserted after in hot pressing furnace, before carrying out the first hyperthermic treatment, the preparation method of described chrome molybdenum target also comprises: vacuumize process to air pressure to described hot pressing furnace and be less than or equal to 100Pa.
The preparation method of 15. chrome molybdenum targets according to claim 1, it is characterized in that, die-filling for described chrome molybdenum mixed powder adopted mould is comprised: for taking up the sleeve of chrome molybdenum mixed powder, and for seal described sleeve and in described sleeve chrome molybdenum mixed powder pressurization pressure head;
Step die-filling for described chrome molybdenum mixed powder is comprised:
Chrome molybdenum mixed powder is loaded in sleeve;
Cold pressing treatment is carried out to the chrome molybdenum mixed powder in described mould;
After cold pressing treatment, seal described sleeve with pressure head.
The preparation method of 16. chrome molybdenum targets according to claim 15, it is characterized in that, described cold pressing treatment comprises: adopt static pressure machine with 1.0 × 10
5~ 2.0 × 10
5n pressure is by described chrome molybdenum mixed powder pre-molding.
The preparation method of 17. chrome molybdenum targets according to claim 1, is characterized in that, provides the step of chrome molybdenum mixed powder to comprise: the mass ratio of described chromium and molybdenum is 7:2 ~ 7:4.
The preparation method of 18. chrome molybdenum targets according to claim 1, is characterized in that, before step die-filling for described chrome molybdenum mixed powder, the preparation method of described chrome molybdenum target also comprises: carry out mixing process to described chrome molybdenum mixed powder.
The preparation method of 19. chrome molybdenum targets according to claim 1, is characterized in that, the grain-size in described chrome molybdenum target is 20 ~ 30 microns.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410544726.1A CN105568237A (en) | 2014-10-15 | 2014-10-15 | Chromium-molybdenum alloy target material preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410544726.1A CN105568237A (en) | 2014-10-15 | 2014-10-15 | Chromium-molybdenum alloy target material preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105568237A true CN105568237A (en) | 2016-05-11 |
Family
ID=55878848
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410544726.1A Pending CN105568237A (en) | 2014-10-15 | 2014-10-15 | Chromium-molybdenum alloy target material preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105568237A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106141190A (en) * | 2015-04-22 | 2016-11-23 | 宁波江丰电子材料股份有限公司 | The manufacture method of chrome molybdenum target |
| CN106583733A (en) * | 2016-11-10 | 2017-04-26 | 洛阳科威钨钼有限公司 | Preparing method for high-density molybdenum alloy plate |
| CN109226768A (en) * | 2018-10-09 | 2019-01-18 | 北京航空航天大学 | A kind of preparation method of transient metal doped antimony telluride alloy target material |
| CN112376022A (en) * | 2020-09-17 | 2021-02-19 | 洛阳科威钨钼有限公司 | Preparation method of rotary molybdenum tube target |
| CN112538607A (en) * | 2020-11-19 | 2021-03-23 | 宁波江丰电子材料股份有限公司 | Preparation method of vanadium-tungsten alloy target blank |
| CN113770360A (en) * | 2021-09-08 | 2021-12-10 | 宁波江丰电子材料股份有限公司 | Chromium-silicon alloy sputtering target material and preparation method thereof |
| CN115416358A (en) * | 2022-08-24 | 2022-12-02 | 山东英乐威装备科技有限公司 | Pressing process for silicon carbide reaction plate |
| CN116947491A (en) * | 2023-07-31 | 2023-10-27 | 宁波江丰电子材料股份有限公司 | Germanium antimony tellurium phase change target material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101224496A (en) * | 2007-01-18 | 2008-07-23 | 光洋应用材料科技股份有限公司 | Manufacture method of sputtering targets |
| CN102400004A (en) * | 2011-11-25 | 2012-04-04 | 宁波江丰电子材料有限公司 | Manufacturing methods of tungsten-titanium alloy target billet and target material |
| CN102756126A (en) * | 2011-04-28 | 2012-10-31 | 日立金属株式会社 | A manufacture method of MoCr target and the MoCr target |
| CN103143710A (en) * | 2013-03-27 | 2013-06-12 | 宁夏东方钽业股份有限公司 | Method of producing molybdenum alloy target |
-
2014
- 2014-10-15 CN CN201410544726.1A patent/CN105568237A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101224496A (en) * | 2007-01-18 | 2008-07-23 | 光洋应用材料科技股份有限公司 | Manufacture method of sputtering targets |
| CN102756126A (en) * | 2011-04-28 | 2012-10-31 | 日立金属株式会社 | A manufacture method of MoCr target and the MoCr target |
| CN102400004A (en) * | 2011-11-25 | 2012-04-04 | 宁波江丰电子材料有限公司 | Manufacturing methods of tungsten-titanium alloy target billet and target material |
| CN103143710A (en) * | 2013-03-27 | 2013-06-12 | 宁夏东方钽业股份有限公司 | Method of producing molybdenum alloy target |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106141190A (en) * | 2015-04-22 | 2016-11-23 | 宁波江丰电子材料股份有限公司 | The manufacture method of chrome molybdenum target |
| CN106583733A (en) * | 2016-11-10 | 2017-04-26 | 洛阳科威钨钼有限公司 | Preparing method for high-density molybdenum alloy plate |
| CN109226768A (en) * | 2018-10-09 | 2019-01-18 | 北京航空航天大学 | A kind of preparation method of transient metal doped antimony telluride alloy target material |
| CN112376022A (en) * | 2020-09-17 | 2021-02-19 | 洛阳科威钨钼有限公司 | Preparation method of rotary molybdenum tube target |
| CN112376022B (en) * | 2020-09-17 | 2022-08-26 | 洛阳科威钨钼有限公司 | Preparation method of rotary molybdenum tube target |
| CN112538607A (en) * | 2020-11-19 | 2021-03-23 | 宁波江丰电子材料股份有限公司 | Preparation method of vanadium-tungsten alloy target blank |
| CN113770360A (en) * | 2021-09-08 | 2021-12-10 | 宁波江丰电子材料股份有限公司 | Chromium-silicon alloy sputtering target material and preparation method thereof |
| CN113770360B (en) * | 2021-09-08 | 2023-09-08 | 宁波江丰电子材料股份有限公司 | Chromium silicon alloy sputtering target material and preparation method thereof |
| CN115416358A (en) * | 2022-08-24 | 2022-12-02 | 山东英乐威装备科技有限公司 | Pressing process for silicon carbide reaction plate |
| CN115416358B (en) * | 2022-08-24 | 2024-05-28 | 山东英乐威装备科技有限公司 | Lamination process for silicon carbide reaction plate |
| CN116947491A (en) * | 2023-07-31 | 2023-10-27 | 宁波江丰电子材料股份有限公司 | Germanium antimony tellurium phase change target material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105568237A (en) | Chromium-molybdenum alloy target material preparation method | |
| CN105483624B (en) | The manufacturing method of molybdenum silicon target and combinations thereof | |
| CN108070832A (en) | The manufacturing method of molybdenum niobium target blankss | |
| CN104846341A (en) | Isothermal extrusion production method of refractory metal rotating target material | |
| CN112376023A (en) | Preparation method of chromium-silicon alloy sputtering target material | |
| CN106312071A (en) | A tungsten-titanium tube target manufacture method | |
| CN113004040B (en) | Carbon silicon carbide target material and preparation method and application thereof | |
| CN111945089A (en) | Additive manufacturing titanium part and heat treatment process thereof | |
| CN115353373B (en) | Alumina target material and preparation method and application thereof | |
| CN105441881A (en) | Making method of chromium target and making method of combination of chromium target | |
| CN106380198A (en) | Cadmium zinc telluride target material as well as preparation method and application thereof | |
| CN106475566A (en) | The manufacture method of molybdenum titanium target base | |
| JP2006207007A (en) | Method for producing tungsten alloy and the tungsten alloy | |
| CN110202109B (en) | Semisolid thixotropic-plastic composite multi-section forming process | |
| CN105624622B (en) | The manufacture method of target material assembly | |
| CN104342619A (en) | Method for manufacturing molybdenum target material | |
| CN106475567A (en) | The manufacture method of chrome molybdenum target blankss | |
| CN112809002B (en) | Preparation method of aluminum-silicon alloy target blank | |
| CN116813342A (en) | Preparation method of high-density molybdenum tantalum oxide target | |
| CN105274373A (en) | Powder metallurgy preparation technology of gamma'' phase reinforced high temperature alloy | |
| CN116329549A (en) | Preparation method of TC4 titanium alloy small die forging | |
| CN108856708B (en) | TiAl-based material with gradient structure and manufacturing method thereof | |
| CN106141190A (en) | The manufacture method of chrome molybdenum target | |
| CN113444949A (en) | High-density W-Ta-Nb series refractory solid solution alloy and preparation method thereof | |
| CN115786755A (en) | Dewaxing and sintering integrated process method for tungsten-nickel hard alloy |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160511 |