CN103100563A - Preparation method of ultrathin Mo-Re alloy foil - Google Patents
Preparation method of ultrathin Mo-Re alloy foil Download PDFInfo
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- CN103100563A CN103100563A CN2013100283398A CN201310028339A CN103100563A CN 103100563 A CN103100563 A CN 103100563A CN 2013100283398 A CN2013100283398 A CN 2013100283398A CN 201310028339 A CN201310028339 A CN 201310028339A CN 103100563 A CN103100563 A CN 103100563A
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Abstract
The invention provides a preparation method of an ultrathin Mo-Re alloy foil, and belongs to the technical field of Mo-Re alloy machining. The preparation method solves the problems that a Mo-Re alloy foil which is with the thickness smaller than 10 micrometers and good in surface quality is hard to prepare, and can be used for preparing the Mo-Re alloy foil which is with the thickness of 3-5 micrometers and good in surface quality. The preparation method comprises circulating operations of preparing an alloy billet with a powder metallurgy, cold rolling cogging, and cold rolling / vacuum annealing, and the method further comprises a step of annealing of a foil of 3-5 micrometers and other steps. The component range of a prepared alloy foil is, by weight, Re of 43.5-47.5%, and the balance is Mo. The thickness of the prepared alloy foil is 3-5 micrometers. The preparation method is simple in technology, the elastic coefficient of the prepared foil is 340-350 GPa, the tensile strength at 1200 DEG C is 220-260 Mpa, microhardness is 420-450 HV, the surface roughness (Rmax) is 0.02-0.05 micrometer, and the foil is suitable for platinotrons and travelling wave tubes and other vacuum components in aerospace equipment.
Description
Technical field
The present invention relates to a kind of preparation method of ultra-thin Mo-Re alloy foil, belong to Mo-Re Alloy Processing field.
Background technology
Molybdenum not only has the performances such as good heat conduction, conduction, anti-corrosion, low-expansion coefficient, low-steam pressure, and has high rigidity, high-intensity performance.Thereby molybdenum has boundless purposes in fields such as electronics industry, glass works.Yet the moulding of molybdenum-crisp transformation is to affect one of its application very key factor.After rhenium adds in molybdenum, also improved the intensity of molybdenum when having improved the plasticity of molybdenum, and reduced significantly and moulded crisp transition temperature, thereby made the Mo-Re alloy have good cryogenic property; Rhenium can improve the recrystallization temperature of molybdenum alloy again simultaneously, makes molybdenum alloy have excellent high-temperature behavior; Rhenium add the anisotropy that has also weakened molybdenum, improved molybdenum alloy processing characteristics, physicochemical property and pyroelecthc properties etc., this is called as " rhenium effect (rhenium effect) ".The application of molybdenum alloy on numerous high-tech areas such as Aero-Space, firing equipment, electronic technology, nuclear industry expanded in the raising of this combination property widely.Can be used as long-life screen, space based reactor reactor core heating tube, high-temperature furnace heating body, pyrometer couple of X-ray tube target, the microwave communication of High Rotation Speed etc. as: Mo-Re alloy.In addition, Mo-41%Re can make the structural material in Aero-Space, and Mo-50%Re makes high-temperature structural material.
The molybdenum rhenium alloys generally adopts the powder metallurgic method preparation.It is investigated pertinent literature, the molybdenum rhenium foil thickness that has in the market is generally 30 ~ 50 μ m.These foils are used to make the electronic components such as negative electrode, grid, shielding cylinder, are widely used in the military and civil areas such as radar facility.Along with the development in the zones such as Aero-Space, electron and electrician, military project national defence, the requirement of electron tube target emissive material is also more and more higher.In order to improve the emitting performance of negative electrode, just must be with the thickness reduction of foil.But when the thickness of foil further reduced, particularly when the thickness of foil during less than 10 μ m, then to process be very difficult, because at this moment foil is easily wrinkling, surface quality is bad.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of high strength, high accuracy, ultra-thin Mo-Re alloy foil that surface quality is good, the thickness of this ultra-thin Mo-Re alloy foil is 3 ~ 5 μ m, can be used for platinotron and travelling-wave tubes equal vacuum device in aerospace equipment.
The preparation method of a kind of ultra-thin Mo-Re alloy foil of the present invention comprises the following steps:
Step 1: the cogging processing of Mo-Re alloy pig
Be to remove surface impurity and greasy dirt after 90 ~ 95% Mo-Re alloy pig cuts into the base bar with density, then the base bar carried out vacuum annealing, cold rolling after annealing, obtain the alloy slab; The condition of described annealing is: Absolute truth reciprocal of duty cycle＜3 * 10
-3Pa, 1350 ~ 1600 ℃ of annealing temperatures, annealing time 40 ~ 80min, the type of cooling are for cooling to room temperature with the furnace; The described cold rolling cross rolling and vertically rolling that comprises, first carry out total deformation and be 80 ~ 85% laterally cold rolling, then carry out total deformation be 10 ~ 30% vertically cold rolling, every time cold rolling deflection is 8 ~ 10%; In described Mo-Re alloy, the quality percentage composition of Re is 43.5 ~ 47.5%;
Step 2: the roughing of alloy slab
Put into the molybdenum box after the alloy slab that step 1 is obtained cleans up, carry out total deformation after vacuum annealing and be 40 ~ 60% multi-pass cold rolling, cold rolling final vacuum annealing obtains the alloy sheets crude green body; The condition of described vacuum annealing is: Absolute truth reciprocal of duty cycle＜3 * 10
-3Pa, 1350 ~ 1600 ℃ of annealing temperatures, annealing time 40 ~ 80min, the type of cooling are for cooling to room temperature with the furnace; Every time cold rolling deflection is 8 ~ 10%;
Step 3: the processing of alloy slab
It is cold rolling that the alloy sheets crude green body that step 2 is obtained carries out multi-pass, until obtain the first thick alloy foil of 0.1 ~ 0.15mm, when cold rolling cumulative deformation reaches 50 ~ 70%, carry out a vacuum annealing, the condition of described vacuum annealing is: vacuum drying oven is vacuum molybdenum sheet stove, Absolute truth reciprocal of duty cycle＜3 * 10
-3Pa, 1350 ~ 1600 ℃ of annealing temperatures, annealing time 40 ~ 80min, the type of cooling are for cooling to room temperature with the furnace; Every time cold rolling deflection is 8 ~ 10%;
Step 4: the fine finishining of alloy foil
The first alloy foil of step 3 preparation is carried out multi-pass cold rolling, until obtain the second thick alloy foil of 0.02 ~ 0.025mm, when cold rolling cumulative deformation reaches 40 ~ 50%, carry out a vacuum annealing, described cold rolling be rolling with (stock) tension on 20 roller mills, every time cold rolling deflection is 5 ~ 8%; The condition of described vacuum annealing is: vacuum drying oven is vacuum molybdenum sheet stove, Absolute truth reciprocal of duty cycle＜3 * 10
-4Pa, annealing temperature are that 1350 ~ 1600 ℃, annealing time are that 40 ~ 60min, the type of cooling are for cooling to room temperature with the furnace;
Step 5: thickness is the preparation of the Alloy Foil of 3 ~ 5 μ m
The second alloy foil of step 4 preparation is carried out multi-pass cold rolling, until obtain the alloy foil that thickness is 3 ~ 5 μ m, the vacuum annealing of described alloy foil is obtained finished product; In cold-rolled process, when cold rolling cumulative deformation reaches 40 ~ 50%, carry out a vacuum annealing; Described cold rolling be rolling with (stock) tension on 30 roller mills, every time cold rolling deflection is 5 ~ 8%; The condition of described vacuum annealing is: vacuum drying oven is vacuum molybdenum sheet stove, Absolute truth reciprocal of duty cycle＜3 * 10
-4Pa, annealing temperature are that 1350 ~ 1600 ℃, annealing time are that 40 ~ 60min, the type of cooling are for cooling to room temperature with the furnace.
The preparation method of a kind of ultra-thin Mo-Re alloy foil of the present invention, in step 1, remove the impurity on base bar surface and greasy dirt and be the base bar is placed in cleaning agent and cleans 20 ~ 40s after, with clear water rinsing 3 times, oven dry, obtain the base bar of surface clean, described cleaning agent is that 25 ~ 30% nitric acid and concentration expressed in percentage by volume are that 5 ~ 10% hydrofluoric acid and water form for 3:3:5 by volume by concentration expressed in percentage by volume.
The preparation method of a kind of ultra-thin Mo-Re alloy foil of the present invention, in step 2, three, four, five, before vacuum annealing, the greasy dirt and the impurity that remain in material surface after cold rolling are removed, the method that greasy dirt and impurity are removed is to be first the carbon tetrachloride of 1:1 and lubricating oil and the impurity that gasoline cleans alloy surface with volume ratio, then cleans alloy surface residual dirty carbon tetrachloride and gasoline with the mixed solution that absolute ethyl alcohol and acetone form for 2:1 by volume.
The preparation method of a kind of ultra-thin Mo-Re alloy foil of the present invention, in step 1, described cold rollingly carry out on duo mill; In step 2, described cold rolling be to carry out on work roll diameter is the four-roll universal rolling machine of 150mm; In step 3, described cold rolling be to carry out on work roll diameter is the four-roll universal rolling machine of 75mm; In step 4, the work roll diameter of described 20 roller mills is 10mm, land length 130mm, work roll crown 0.03mm, and 20 roller mills are when rolling, and forward pull is 35 ~ 27kg/mm
2, backward pull is 30 ~ 20kg/mm
2In step 5, the work roll diameter of described 30 roller mills is 2mm, land length 130mm, work roll crown 0.02mm, and 30 roller mills are when rolling, and forward pull is 20 ~ 10kg/mm
2, backward pull is 15 ~ 9.5kg/mm
2
The preparation method of a kind of ultra-thin Mo-Re alloy foil of the present invention, in step 1, described Mo-Re alloy pig prepares by following proposal:
Press alloy composition composition Re:43.5 ~ 47.5wt%, surplus is Mo; Take respectively purity 〉=99.99%, particle mean size and be the Re powder of the Mo powder of 5～10 μ m and purity 〉=99.99%, particle mean size＜5 μ m, Mo powder, Re powder and absolute ethyl alcohol are mixed after vacuum drying compressing, at H
2Protection of the environment in sintering, sintering temperature is 1000 ~ 1200 ℃, temperature retention time 120 ~ 240min after cooling to room temperature with the furnace, carries out multiple pressure to sintered blank, presses again the final vacuum sintering, obtains the Mo-Re alloy pig, the density of alloy billet is 90 ~ 95%; The vacuum of vacuum-sintering＜1 * 10
-4Pa, the temperature of vacuum-sintering is 2000 ~ 2400 ℃, temperature retention time 600 ~ 720min.
The preparation method of a kind of ultra-thin Mo-Re alloy foil of the present invention, in Mo-Re alloy pig preparation process, Mo powder, Re powder, absolute ethyl alcohol mix by high-energy ball milling; The vacuum drying condition of mixed-powder is: Absolute truth reciprocal of duty cycle＜1 * 10
-4Pa, temperature is 700 ~ 750 ℃; Mixed-powder passes through to wait static pressure compressing, and pressing pressure is 200 ~ 240MPa, and the dwell time is 10 ~ 15min; The multiple pressure mode of sintered blank is for waiting static pressure, and multiple pressure of pressing is 600 ~ 640MPa, and pressing again the dwell time is 10 ~ 15min.
The preparation method of a kind of ultra-thin Mo-Re alloy foil of the present invention, the condition of high-energy-milling is: rotational speed of ball-mill 150 ~ 240rpm, Ball-milling Time 20 ~ 30h, milling atmosphere are argon gas; Ball material mass ratio is 6 ~ 13:1, and described material is comprised of Mo powder, Re powder and absolute ethyl alcohol, and wherein the mass ratio of the gross mass of powder and absolute ethyl alcohol is 2 ~ 3:1; The material of abrading-ball is carbide alloy, and the specification of abrading-ball is Φ 14 ~ 16mm.
In the prepared Mo-Re alloy foil of the present invention, the mass percent of Re is 43.5 ~ 47.5%, and the thickness of alloy foil is 3 ~ 5 μ m, coefficient of elasticity 340 ~ 350GPa, tensile strength 220 ~ 260MPa, microhardness 420 ~ 450HV, surface roughness (Rmax) 0.02 ~ 0.05 μ m 1200 ℃ the time.
The present invention has the following advantages:
The present invention controls tissue and the performance of foil by strict annealing and cold-rolling process, at first obtain favourable texture (alpha fibers texture) by controlling rational cold rolling reduction, when deflection is excessive, can form the shear band tissue in material, the formation of this tissue can cause the gamma fiber texture in material to strengthen, this tissue continues distortion and easily form micro-crack in material, and the tissue characteristic in the crystal grain of this texture is uniform formation, is conducive to rolling deformation; By selecting rational annealing temperature (temperature of initial recrystallization) that this favourable texture component is further strengthened, this is because the even tissue of α texture, preferentially reply in annealing process, and the metaplasia of γ texture is inhomogeneous, deformation energy is larger, the preferential recrystallization that occurs in annealing process.So just be conducive to control the surface quality of foil.Due to the thickness of foil during less than 0.1mm, very easily adsorb oxygen etc., make bonding and oxidation occur between foil, therefore, when the Absolute truth reciprocal of duty cycle be controlled at＜3 * 10
-4Pa, bonding and oxidation just can not occur in the surface of foil.
preparation technology of the present invention is simple, with low cost, the high strength of preparing, the thick Mo-Re alloy foil of 3 ~ 5 μ m of high accuracy and great surface quality is with existing molybdenum rhenium foil and pure Ta foil are compared in the market, foil thickness of the present invention is thinner, organizing in foil is more even, surface quality is better, have higher room temperature strength and elevated temperature strength, reliability and the life-span of using are higher, after being made into the cathode emission material of large power high efficiency microwave tube and travelling-wave tubes, at high temperature be difficult for embrittlement, cracking not after being vibrated and impacting, satisfy their harsh service condition.The present invention is significant aspect the serviceability that realizes high-power high performance microwave pipe production domesticization and raising microwave tube and service life.In addition, the Mo-Re alloy foil prepared of the present invention also can be applicable to the fields such as Aero-Space, electron and electrician, nuclear technology, microwave communication.
Description of drawings
Accompanying drawing 1: be process route of the present invention;
Accompanying drawing 2: be the microhardness curve of the alloy foil of the embodiment of the present invention 1 preparation;
Accompanying drawing 3: be the alloy foil pictorial diagram of the embodiment of the present invention 3 preparations;
Accompanying drawing 4: the texture ODF analysis figure of the alloy foil of the embodiment of the present invention 1 preparation.
As can be seen from Figure 2, the room temperature microhardness of this alloy has reached 425HV.
As can be seen from Figure 3, the surface-brightening of foil, quality is good.
As can be seen from Figure 4, formed stronger alpha fibers texture in foil.
The specific embodiment
The sample bomb property coefficient is tested on the U.S.'s 8820 hydraulic servo dynamic testing machines according to GB GB228-2002.Elevated temperature strength is being carried out on the CMT5000GL high-temperature tensile testing machine by GB GB/T4338-2006.Microhardness adopts indentation method to test on the little load Vickers of HVA-10A type.The foil surface quality adopts the test of sheet metal surface quality detecting system.
Embodiment 1:
A kind of electrovacuum of the present embodiment preparation Mo-Re alloy foil, alloying component is: Re:44.0wt%, surplus is Mo.
With purity 〉=99.99%, particle mean size is Mo powder and purity 〉=99.99% of 5～10 μ m, the Re powder of particle mean size＜5 μ m is raw material, wet-milling in high energy ball mill mixes with Mo powder and Re powder, medium is absolute ethyl alcohol, and rotational speed of ball-mill is that 180rpm, Ball-milling Time are that 20h, milling atmosphere are argon gas; Ball material mass ratio=8:1, the mass ratio 2:1 of powder gross mass and absolute ethyl alcohol in material; The material of abrading-ball is carbide alloy, and the specification of abrading-ball is Φ 14mm; Mixed alloyed powder is put into vacuum drying chamber carry out drying, the vacuum drying condition of mixed-powder is: Absolute truth reciprocal of duty cycle＜1 * 10
-4Pa, temperature is 700 ℃, and then with the alloy powder isostatic compaction, pressure is 200MPa, and pressurize 10min is then at H
2Protection of the environment in carry out once sinteredly, sintering temperature is at 1000 ℃, sintering time is 240min; With static pressure such as once sintered base 600MPa, after pressurize 10min in Absolute truth reciprocal of duty cycle＜1 * 10
-4Carry out double sintering in the environment of Pa, sintering temperature is 2000 ℃, and sintering time is 600min, and the density of having prepared metallurgicalization combination reaches 95% Mo-Re alloy billet.
With Mo-Re sintered blank bar after the electric comb sawing is slit into the base bar that thickness is 12mm, using by concentration expressed in percentage by volume is that 25 ~ 30% nitric acid and concentration expressed in percentage by volume are that 5 ~ 10% hydrofluoric acid and water carry out pickling 20 ~ 40s for the cleaning fluid that 3:3:5 forms to sintered blank by volume, then use the clear water rinsing, oven dry is to remove surface impurity and greasy dirt etc.Blank after pickling is annealed in vacuum drying oven, the Absolute truth reciprocal of duty cycle of vacuum drying oven＜3 * 10
-3Pa, annealing process are incubated 80min at 1350 ℃ of temperature, and be cooling with stove.Then billet is carried out cross rolling on duo mill, slab is cold-rolled to 2mm by 12mm, and then vertically rolling, be cold-rolled to 1.8mm by 2mm.In order to allow distortion evenly, pass deformation is controlled between 8 ~ 10%.
Be first the carbon tetrachloride of 1:1 and lubricating oil and the impurity that gasoline is washed the sheet alloy surface with volume ratio with the 1.8mm sheet material of cold rolling acquisition, use again the mixed solution that is formed for 2:1 by volume by absolute ethyl alcohol and acetone to clean dirty carbon tetrachloride and the gasoline of sheet alloy remained on surface, then slab is put into molybdenum box shove charge vacuum annealing, annealing temperature is 1350 ℃, annealing time is 60min, and the Absolute truth reciprocal of duty cycle of same vacuum annealing furnace needs＜3 * 10
-3Pa.After vacuum drying oven annealing, the sample sheet material of 1.8mm is carried out cold rolling (work roll diameter is 150mm) on four-roll universal rolling machine, be rolling to 0.64mm, pass deformation is controlled between 8 ~ 10% equally.
0.64mm after thick sheet material vacuum annealing, in the upper cold rolling processing of four-roll universal rolling machine (work roll diameter is 75mm), the centre is aided with vacuum annealing, until obtain the thick alloy foil of 0.1mm; Rolling condition is: between twice annealing, total deflection is controlled at 50 ~ 60% left and right, and pass deformation is controlled at 8 ~ 10%; The condition of vacuum annealing is: vacuum drying oven is the molybdenum sheet vacuum drying oven, and annealing temperature is 1350 ℃, and annealing time is 60min, Absolute truth reciprocal of duty cycle＜3 * 10
-3Pa, before vacuum annealing, the carbon tetrachloride and the gasoline that are first 1:1 with volume ratio are washed lubricating oil and the impurity on alloy foil surface, then use the mixed solution that is comprised of for 2:1 by volume absolute ethyl alcohol and acetone to clean dirty carbon tetrachloride and the gasoline of alloy foil remained on surface.
0.1mm rolling with (stock) tension on 20 roller mills after thick alloy foil vacuum annealing, the centre is aided with vacuum annealing, until obtain the thick foil of 0.02mm; Rolling condition is: work roll diameter is 10mm, land length 130mm, and work roll crown 0.03mm, during 20 roller mill rolling with (stock) tension, forward pull is 27kg/mm
2, backward pull is 20kg/mm
2, between twice annealing, the total deformation of foil is controlled between 40 ~ 50%, and pass deformation is controlled at 5 ~ 8%; The condition of vacuum annealing is: vacuum drying oven is the molybdenum sheet vacuum drying oven, the Absolute truth reciprocal of duty cycle is controlled at＜and 3 * 10
-4Pa, annealing temperature is 1350 ℃, annealing time is 40min, before vacuum annealing, be first the carbon tetrachloride of 1:1 and lubricating oil and the impurity that gasoline is washed alloy foil surface with volume ratio, then be the absolute ethyl alcohol of 2:1 and dirty carbon tetrachloride and the gasoline that acetone soln is cleaned alloy foil remained on surface with volume ratio.
0.02mm rolling with (stock) tension on 30 roller mills after thick alloy foil vacuum annealing, the centre is aided with vacuum annealing, until obtained the high accuracy Mo-Re alloy foil of 3 μ m, obtains finished product after the thick foil vacuum annealing of 3 μ m; Rolling condition is: work roll diameter is 2mm, land length 130mm, and work roll crown 0.02mm, during 30 roller mill rolling with (stock) tension, forward pull is 15kg/mm
2, backward pull is 9.5kg/mm
2, between twice annealing, the total deformation of foil is controlled between 40 ~ 50%, and pass deformation is controlled at 5 ~ 8%; The condition of vacuum annealing is: vacuum drying oven is the molybdenum sheet vacuum drying oven, the Absolute truth reciprocal of duty cycle is controlled at＜and 3 * 10
-4Pa, annealing temperature is 1350 ℃, annealing time is 40min, before vacuum annealing, the carbon tetrachloride and the gasoline that are first 1:1 with volume ratio are washed lubricating oil and the impurity on alloy foil surface, then use the mixed solution that is comprised of for 2:1 by volume absolute ethyl alcohol and acetone to clean dirty carbon tetrachloride and the gasoline of alloy foil remained on surface;
End properties is: coefficient of elasticity 350GPa, tensile strength 220MPa, microhardness 423HV, surface roughness (Rmax) 0.02 μ m 1200 ℃ the time.
Embodiment 2:
A kind of electrovacuum of the present embodiment preparation Mo-Re alloy foil, alloying component is: Re:45.0wt%, surplus is Mo.
With purity 〉=99.99%, particle mean size is Mo powder and purity 〉=99.99% of 5～10 μ m, the Re powder of particle mean size＜5 μ m is raw material, wet-milling in high energy ball mill mixes with Mo powder and Re powder, medium is absolute ethyl alcohol, and rotational speed of ball-mill is that 200rpm, Ball-milling Time are that 25h, milling atmosphere are argon gas; Ball material mass ratio=10:1, in material, the mass ratio of powder gross mass and absolute ethyl alcohol is 2.5:1; The material of abrading-ball is carbide alloy, and the specification of abrading-ball is Φ 15mm; Mixed alloyed powder is put into vacuum drying chamber carry out drying, the vacuum drying condition of mixed-powder is: Absolute truth reciprocal of duty cycle＜1 * 10
-4Pa, temperature is 725 ℃, and then with the alloy powder isostatic compaction, pressure is 220MPa, and pressurize 12min is then at H
2Protection of the environment in carry out once sinteredly, sintering temperature is at 1100 ℃, sintering time is 180min; With static pressure such as once sintered base 620MPa, pressurize 12min is then in Absolute truth reciprocal of duty cycle＜1 * 10
-4Carry out double sintering in the environment of Pa, sintering temperature is 2200 ℃, and sintering time is 680min, and the density of having prepared metallurgicalization combination is 92% Mo-Re alloy billet.With Mo-Re sintered blank bar after the electric comb sawing is slit into the base bar that thickness is 12mm, using by concentration expressed in percentage by volume is that 25 ~ 30% nitric acid and concentration expressed in percentage by volume are that 5 ~ 10% hydrofluoric acid and water carry out pickling 20 ~ 40s for the cleaning fluid that 3:3:5 forms to sintered blank by volume, then use the clear water rinsing, oven dry is to remove surface impurity and greasy dirt etc.Blank after pickling to be annealed in vacuum drying oven, the Absolute truth reciprocal of duty cycle of vacuum drying oven need to remain on＜and 3 * 10
-3Pa, annealing process are incubated 80min at 1500 ℃ of temperature, and be cooling with stove.Then billet is carried out cross rolling on duo mill, slab is cold-rolled to 2mm by 12mm, and then vertically rolling, be cold-rolled to 1.6mm by 2mm.In order to allow distortion evenly, pass deformation is controlled between 8 ~ 10%.
Be first the carbon tetrachloride of 1:1 and lubricating oil and the impurity that gasoline is washed the sheet alloy surface with volume ratio with the 1.6mm sheet material of cold rolling acquisition, use again the mixed solution that is formed for 2:1 by volume by absolute ethyl alcohol and acetone to clean dirty carbon tetrachloride and the gasoline of sheet alloy remained on surface, then slab is put into molybdenum box shove charge vacuum annealing, annealing temperature is 1500 ℃, annealing time is 60min, the Absolute truth reciprocal of duty cycle of same vacuum annealing furnace need to remain on＜and 3 * 10
-3Pa after vacuum drying oven annealing, carries out cold rolling (work roll diameter is 150mm) with the sample sheet material of 1.6mm on four-roll universal rolling machine, be rolling to 0.8mm, and pass deformation is controlled between 8 ~ 10% equally.
0.8mm cold rolling processing on four-roll universal rolling machine (work roll diameter is 75mm) after thick sheet material vacuum annealing, the centre is aided with vacuum annealing, until obtain the thick alloy foil of 0.12mm, rolling condition is: between twice annealing, total deflection is controlled at 60 ~ 70% left and right, pass deformation is controlled at 8 ~ 10%, the condition of vacuum annealing is: annealing temperature is 1500 ℃, and annealing time is 60min, Absolute truth reciprocal of duty cycle＜3 * 10 during annealing
-3Pa is first the carbon tetrachloride of 1:1 and lubricating oil and the impurity that gasoline is washed alloy foil surface with volume ratio, then is the absolute ethyl alcohol of 2:1 and dirty carbon tetrachloride and the gasoline that acetone soln is cleaned alloy foil remained on surface with volume ratio.
0.12mm rolling with (stock) tension on 20 roller mills after thick foil vacuum annealing, the centre is aided with vacuum annealing, until obtain the thick alloy foil of 20 μ m, rolling condition is: work roll diameter is 10mm, land length 130mm, work roll crown 0.03mm, during 20 roller mill rolling with (stock) tension, forward pull is 30kg/mm
2, backward pull is 25kg/mm
2Between twice annealing, the total deformation of foil is controlled between 40 ~ 50%, and pass deformation is controlled at 5 ~ 8%; The condition of vacuum annealing is: annealing is carried out in vacuum molybdenum sheet stove, Absolute truth reciprocal of duty cycle＜3 * 10
-4Pa, annealing temperature is 1500 ℃, annealing time is 50min, before vacuum annealing, be first the carbon tetrachloride of 1:1 and lubricating oil and the impurity that gasoline is washed alloy foil surface with volume ratio, then be the absolute ethyl alcohol of 2:1 and dirty carbon tetrachloride and the gasoline that acetone soln is cleaned alloy foil remained on surface with volume ratio.
Rolling with (stock) tension on 30 roller mills after the thick foil vacuum annealing of 20 μ m, the centre is aided with vacuum annealing, until obtained the high accuracy Mo-Re alloy foil of 5 μ m; Obtain finished product after the foil vacuum annealing of 5 μ m; Rolling condition is: work roll diameter is 2mm, land length 130mm, and work roll crown 0.02mm, during 30 roller mill rolling with (stock) tension, forward pull is 16kg/mm
2, backward pull is 12kg/mm
2Between twice annealing, the total deformation of foil is controlled between 40 ~ 50%, and pass deformation is controlled at 5 ~ 8%; The condition of vacuum annealing is: vacuum drying oven is the molybdenum sheet vacuum drying oven, Absolute truth reciprocal of duty cycle＜3 * 10
-4Pa, annealing temperature is 1500 ℃, annealing time is 50min, before vacuum annealing, be first the carbon tetrachloride of 1:1 and lubricating oil and the impurity that gasoline is washed alloy foil surface with volume ratio, then be the absolute ethyl alcohol of 2:1 and dirty carbon tetrachloride and the gasoline that acetone soln is cleaned alloy foil remained on surface with volume ratio;
End properties is: coefficient of elasticity 345GPa, tensile strength 240MPa, microhardness 430HV, surface roughness (Rmax) 0.03 μ m 1200 ℃ the time.
Embodiment 3:
A kind of electrovacuum of the present embodiment preparation Mo-Re alloy foil, alloying component is: Re:47.5wt%, surplus is Mo.
With purity 〉=99.99%, particle mean size is Mo powder and purity 〉=99.99% of 5～10 μ m, the Re powder of particle mean size＜5 μ m is raw material, wet-milling in high energy ball mill mixes with Mo powder and Re powder, medium is absolute ethyl alcohol, and rotational speed of ball-mill is that 240rpm, Ball-milling Time are that 30h, milling atmosphere are argon gas; Ratio of grinding media to material=13:1, the mass ratio 3:1 of powder gross mass and absolute ethyl alcohol in material; The material of abrading-ball is carbide alloy, and the specification of abrading-ball is Φ 16mm, mixed alloyed powder is put into vacuum drying chamber carry out drying, and the vacuum drying condition of mixed-powder is: Absolute truth reciprocal of duty cycle＜1 * 10
-4Pa, temperature is 750 ℃, and then with the alloy powder isostatic compaction, pressure is 240MPa, and pressurize 15min is then at H
2Protection of the environment in carry out once sinteredly, sintering temperature is at 1200 ℃, sintering time is 120min; With static pressure such as once sintered base 640MPa, pressurize 15min is then in Absolute truth reciprocal of duty cycle＜1 * 10
-4Carry out double sintering in the environment of Pa, sintering temperature is 2400 ℃, and sintering time is 720min, and the density of having prepared metallurgicalization combination is 90% Mo-Re alloy billet.
With Mo-Re sintered blank bar after the electric comb sawing is slit into the base bar that thickness is 12mm, using by concentration expressed in percentage by volume is that 25 ~ 30% nitric acid and concentration expressed in percentage by volume are that 5 ~ 10% hydrofluoric acid and water carry out pickling 20 ~ 40s for the cleaning fluid that 3:3:5 forms to sintered blank by volume, then use the clear water rinsing, oven dry is to remove surface impurity and greasy dirt etc.Blank after pickling to be annealed in vacuum drying oven, the Absolute truth reciprocal of duty cycle of vacuum drying oven remains on＜and 3 * 10
-3Pa, annealing process are incubated 80min at 1600 ℃ of temperature, and be cooling with stove.Then billet is carried out cross rolling on duo mill, slab is cold-rolled to 2mm by 12mm, and then vertically rolling, be cold-rolled to 1.4mm by 2mm.In order to allow distortion evenly, pass deformation is controlled between 8 ~ 10%.
Be first the carbon tetrachloride of 1:1 and lubricating oil and the impurity that gasoline is washed the sheet alloy surface with volume ratio with the 1.4mm sheet material of cold rolling acquisition, be the absolute ethyl alcohol of 2:1 and dirty carbon tetrachloride and the gasoline that acetone soln is cleaned the sheet alloy remained on surface with volume ratio again, then slab is put into molybdenum box shove charge vacuum annealing, annealing temperature is 1600 ℃, annealing time is 60min, the Absolute truth reciprocal of duty cycle of same vacuum annealing furnace remains on＜and 3 * 10
-3Pa.After vacuum drying oven annealing, the sample sheet material of 1.4mm is carried out cold rolling (work roll diameter is 150mm) on four-roll universal rolling machine, be rolling to 0.84mm, pass deformation is controlled between 8 ~ 10% equally.
0.84mm cold rolling processing on four-roll universal rolling machine (work roll diameter is 75mm) after thick sheet material vacuum annealing, the centre is aided with vacuum annealing, until obtain foil after 0.15mm, rolling condition is: between twice annealing, total deflection is controlled at 55 ~ 65% left and right, pass deformation is controlled at 8 ~ 10%, and the condition of vacuum annealing is: vacuum drying oven is the molybdenum sheet vacuum drying oven, and annealing temperature is 1600 ℃, annealing time is 60min, Absolute truth reciprocal of duty cycle＜3 * 10
-3Pa before vacuum annealing, is first the carbon tetrachloride of 1:1 and lubricating oil and the impurity that gasoline is washed alloy foil surface with volume ratio, then is the absolute ethyl alcohol of 2:1 and dirty carbon tetrachloride and the gasoline that acetone soln is cleaned alloy foil remained on surface with volume ratio.
0.15mm rolling with (stock) tension on 20 roller mills after thick foil vacuum annealing, the centre is aided with vacuum annealing, until obtain the thick foil of 0.025mm, rolling condition is: work roll diameter is 10mm, land length 130mm, work roll crown 0.03mm, during 20 roller mill rolling with (stock) tension, forward pull is 35kg/mm
2, backward pull is 30kg/mm
2Between twice annealing, the deflection of foil is controlled between 40 ~ 50%, and pass deformation is controlled at 5 ~ 8%; The condition of vacuum annealing is: vacuum drying oven is the molybdenum sheet vacuum drying oven, Absolute truth reciprocal of duty cycle＜3 * 10
-4Pa, annealing temperature is 1600 ℃, annealing time is 60min, before vacuum annealing, be first the carbon tetrachloride of 1:1 and lubricating oil and the impurity that gasoline is washed alloy foil surface with volume ratio, then be the absolute ethyl alcohol of 2:1 and dirty carbon tetrachloride and the gasoline that acetone soln is cleaned alloy foil remained on surface with volume ratio.
0.025mm rolling with (stock) tension on 30 roller mills after thick foil vacuum annealing, the centre is aided with vacuum annealing, until obtain the high accuracy Mo-Re alloy foil of 4 μ m, obtains finished product after the thick foil vacuum annealing of 4 μ m; Rolling condition is: work roll diameter is 2mm, land length 130mm, and work roll crown 0.02mm, during 30 roller mill rolling with (stock) tension, forward pull is 20kg/mm
2, backward pull is 15kg/mm
2Between twice annealing, the total deformation of foil is controlled between 40 ~ 50%, and pass deformation is controlled at 5 ~ 8%; The condition of vacuum annealing is: vacuum drying oven is the molybdenum sheet vacuum drying oven, Absolute truth reciprocal of duty cycle＜3 * 10
-4Pa, annealing temperature is 1600 ℃, annealing time is 60min, before vacuum annealing, be first the carbon tetrachloride of 1:1 and lubricating oil and the impurity that gasoline is washed alloy foil surface with volume ratio, then be the absolute ethyl alcohol of 2:1 and dirty carbon tetrachloride and the gasoline that acetone soln is cleaned alloy foil remained on surface with volume ratio;
End properties is: coefficient of elasticity 340GPa, tensile strength 260MPa, microhardness 450HV, surface roughness (Rmax) 0.05 μ m 1200 ℃ the time.
Claims (8)
1. the preparation method of a ultra-thin Mo-Re alloy foil is characterized in that comprising the following steps:
Step 1: the cogging processing of Mo-Re alloy pig
Be to remove surface impurity and greasy dirt after 90 ~ 95% Mo-Re alloy pig cuts into the base bar with density, then the base bar carried out vacuum annealing, cold rolling after annealing, obtain the alloy slab; The condition of described annealing is: Absolute truth reciprocal of duty cycle＜3 * 10
-3Pa, 1350 ~ 1600 ℃ of annealing temperatures, annealing time 40 ~ 80min, the type of cooling are for cooling to room temperature with the furnace; The described cold rolling cross rolling and vertically rolling that comprises, first carry out total deformation and be 80 ~ 85% laterally cold rolling, then carry out total deformation be 10 ~ 30% vertically cold rolling, every time cold rolling deflection is 8 ~ 10%; In described Mo-Re alloy, the quality percentage composition of Re is 43.5 ~ 47.5%;
Step 2: the roughing of alloy slab
Put into the molybdenum box after the alloy slab that step 1 is obtained cleans up, carry out total deformation after vacuum annealing and be 40 ~ 60% multi-pass cold rolling, cold rolling final vacuum annealing obtains the alloy sheets crude green body; The condition of described vacuum annealing is: Absolute truth reciprocal of duty cycle＜3 * 10
-3Pa, 1350 ~ 1600 ℃ of annealing temperatures, annealing time 40 ~ 80min, the type of cooling are for cooling to room temperature with the furnace; Every time cold rolling deflection is 8 ~ 10%;
Step 3: the processing of alloy slab
It is cold rolling that the alloy sheets crude green body that step 2 is obtained carries out multi-pass, until obtain the first thick alloy foil of 0.1 ~ 0.15mm, when cold rolling cumulative deformation reaches 50 ~ 70%, carry out a vacuum annealing, the condition of described vacuum annealing is: vacuum drying oven is vacuum molybdenum sheet stove, Absolute truth reciprocal of duty cycle＜3 * 10
-3Pa, 1350 ~ 1600 ℃ of annealing temperatures, annealing time 40 ~ 80min, the type of cooling are for cooling to room temperature with the furnace; Every time cold rolling deflection is 8 ~ 10%;
Step 4: the fine finishining of alloy foil
The first alloy foil of step 3 preparation is carried out multi-pass cold rolling, until obtain the second thick alloy foil of 0.02 ~ 0.025mm, when cold rolling cumulative deformation reaches 40 ~ 50%, carry out a vacuum annealing, described cold rolling be rolling with (stock) tension on 20 roller mills, every time cold rolling deflection is 5 ~ 8%; The condition of described vacuum annealing is: vacuum drying oven is vacuum molybdenum sheet stove, Absolute truth reciprocal of duty cycle＜3 * 10
-4Pa, annealing temperature are that 1350 ~ 1600 ℃, annealing time are that 40 ~ 60min, the type of cooling are for cooling to room temperature with the furnace;
Step 5: thickness is the preparation of the Alloy Foil of 3 ~ 5 μ m
The second alloy foil of step 4 preparation is carried out multi-pass cold rolling, until obtain the alloy foil that thickness is 3 ~ 5 μ m, the vacuum annealing of described alloy foil is obtained finished product; In cold-rolled process, when cold rolling cumulative deformation reaches 40 ~ 50%, carry out a vacuum annealing; Described cold rolling be rolling with (stock) tension on 30 roller mills, every time cold rolling deflection is 5 ~ 8%; The condition of described vacuum annealing is: vacuum drying oven is vacuum molybdenum sheet stove, Absolute truth reciprocal of duty cycle＜3 * 10
-4Pa, annealing temperature are that 1350 ~ 1600 ℃, annealing time are that 40 ~ 60min, the type of cooling are for cooling to room temperature with the furnace.
2. the preparation method of a kind of ultra-thin Mo-Re alloy foil according to claim 1, it is characterized in that: in step 1, remove the impurity on base bar surface and greasy dirt and be the base bar is placed in cleaning agent and cleans 20 ~ 40s after, with clear water rinsing 3 times, oven dry, obtain the base bar of surface clean, described cleaning agent is that 25 ~ 30% nitric acid and concentration expressed in percentage by volume are that 5 ~ 10% hydrofluoric acid and water form for 3:3:5 by volume by concentration expressed in percentage by volume.
3. the preparation method of a kind of ultra-thin Mo-Re alloy foil according to claim 2, it is characterized in that: in step 2, three, four, five, before vacuum annealing, the greasy dirt and the impurity that remain in material surface after cold rolling are removed, the method that greasy dirt and impurity are removed is to be first the carbon tetrachloride of 1:1 and lubricating oil and the impurity that gasoline cleans alloy surface with volume ratio, then cleans alloy surface residual dirty carbon tetrachloride and gasoline with the mixed solution that absolute ethyl alcohol and acetone form for 2:1 by volume.
4. the preparation method of a kind of ultra-thin Mo-Re alloy foil according to claim 3 is characterized in that: in step 1, and described cold rollingly carry out on duo mill; In step 2, described cold rolling be to carry out on work roll diameter is the four-roll universal rolling machine of 150mm; In step 3, described cold rolling be to carry out on work roll diameter is the four-roll universal rolling machine of 75mm; In step 4, the work roll diameter of described 20 roller mills is 10mm, land length 130mm, work roll crown 0.03mm, and 20 roller mills are when rolling, and forward pull is 35 ~ 27kg/mm
2, backward pull is 30 ~ 20kg/mm
2In step 5, the work roll diameter of described 30 roller mills is 2mm, land length 130mm, work roll crown 0.02mm, and 30 roller mills are when rolling, and forward pull is 20 ~ 10kg/mm
2, backward pull is 15 ~ 9.5kg/mm
2
5. the preparation method of a kind of ultra-thin Mo-Re alloy foil according to claim 4, it is characterized in that: in step 1, described Mo-Re alloy pig prepares by following proposal:
Press alloy composition composition Re:43.5 ~ 47.5wt%, surplus is Mo; Take respectively purity 〉=99.99%, particle mean size and be the Re powder of the Mo powder of 5～10 μ m and purity 〉=99.99%, particle mean size＜5 μ m, Mo powder, Re powder and absolute ethyl alcohol are mixed after vacuum drying compressing, at H
2Protection of the environment in sintering, sintering temperature is 1000 ~ 1200 ℃, temperature retention time is 120 ~ 240min, after cooling to room temperature with the furnace, sintered blank is carried out multiple pressure, presses again the final vacuum sintering, obtains the Mo-Re alloy pig, the density of alloy billet is 90 ~ 95%; The Absolute truth reciprocal of duty cycle of vacuum-sintering＜1 * 10
-4Pa, the temperature of vacuum-sintering is 2000 ~ 2400 ℃, temperature retention time 600 ~ 720min.
6. the preparation method of a kind of ultra-thin Mo-Re alloy foil according to claim 5, it is characterized in that: in Mo-Re alloy pig preparation process, Mo powder, Re powder, absolute ethyl alcohol mix by high-energy ball milling; The vacuum drying condition of mixed-powder is: Absolute truth reciprocal of duty cycle＜1 * 10
-4Pa, temperature is 700 ~ 750 ℃; Mixed-powder passes through to wait static pressure compressing, and pressing pressure is 200 ~ 240MPa, and the dwell time is 10 ~ 15min; The multiple pressure mode of sintered blank is for waiting static pressure, and multiple pressure of pressing is 600 ~ 640MPa, and the multiple dwell time of pressing is 10 ~ 15min.
7. the preparation method of a kind of ultra-thin Mo-Re alloy foil according to claim 6, it is characterized in that: the high-energy-milling parameter is: rotational speed of ball-mill 150 ~ 240rpm, Ball-milling Time 20 ~ 30h, milling atmosphere are argon gas; Ball material mass ratio is 6 ~ 13:1, and described material is comprised of Mo powder, Re powder and absolute ethyl alcohol, and wherein the mass ratio of the gross mass of powder and absolute ethyl alcohol is 2 ~ 3:1; The material of abrading-ball is carbide alloy, and the specification of abrading-ball is Φ 14 ~ 16mm.
8. the preparation method of a kind of ultra-thin Mo-Re alloy foil according to claim 7 is characterized in that: the thickness of the Mo-Re alloy foil of preparation is that 3 ~ 5 μ m, coefficient of elasticity are 340 ~ 350GPa, tensile strength 220 ~ 260MPa, microhardness 420 ~ 450HV, surface roughness (Rmax) 0.02 ~ 0.05 μ m 1200 ℃ the time.
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