CN117758093A - Preparation method of rhenium plate - Google Patents
Preparation method of rhenium plate Download PDFInfo
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- CN117758093A CN117758093A CN202410025702.9A CN202410025702A CN117758093A CN 117758093 A CN117758093 A CN 117758093A CN 202410025702 A CN202410025702 A CN 202410025702A CN 117758093 A CN117758093 A CN 117758093A
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- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 title claims abstract description 182
- 229910052702 rhenium Inorganic materials 0.000 title claims abstract description 160
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000003723 Smelting Methods 0.000 claims abstract description 54
- 238000002844 melting Methods 0.000 claims abstract description 49
- 230000008018 melting Effects 0.000 claims abstract description 49
- 238000010894 electron beam technology Methods 0.000 claims abstract description 42
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 18
- 238000005096 rolling process Methods 0.000 claims abstract description 18
- 238000005520 cutting process Methods 0.000 claims abstract description 12
- 238000005498 polishing Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims description 54
- 238000005245 sintering Methods 0.000 claims description 46
- 238000000137 annealing Methods 0.000 claims description 27
- 230000008569 process Effects 0.000 claims description 24
- 238000009694 cold isostatic pressing Methods 0.000 claims description 14
- 238000005097 cold rolling Methods 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000000748 compression moulding Methods 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 3
- 238000009740 moulding (composite fabrication) Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 14
- 239000012535 impurity Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 230000007547 defect Effects 0.000 description 7
- 238000004663 powder metallurgy Methods 0.000 description 6
- 238000001513 hot isostatic pressing Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 238000001036 glow-discharge mass spectrometry Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 3
- 238000000280 densification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 238000009703 powder rolling Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- HRLYFPKUYKFYJE-UHFFFAOYSA-N tetraoxorhenate(2-) Chemical compound [O-][Re]([O-])(=O)=O HRLYFPKUYKFYJE-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
The invention provides a preparation method of a rhenium plate, which comprises the following steps: s1, preparing a vacuum electron beam melting electrode; s2, carrying out vacuum electron beam melting on the melting electrode obtained in the step S1 twice to obtain a pure rhenium metal ingot; s3, polishing the pure rhenium metal ingot obtained in the step S2, and then performing linear cutting to obtain rhenium pieces; and S4, rolling the rhenium sheet obtained in the step S3 to obtain the rhenium plate with the required specification. In the preparation method of the rhenium plate, the prepared pure rhenium sintered blank is used as a vacuum electron beam smelting electrode to carry out vacuum electron beam smelting twice, the purity of the finally obtained rhenium plate is more than or equal to 99.99 percent, and the density reaches 21.04g/cm of theoretical density 3 The material utilization rate (weight after smelting/feeding weight) can reach more than 98 percent.
Description
Technical Field
The invention relates to the technical field of powder metallurgy preparation, in particular to a preparation method of a rhenium plate.
Background
Rhenium is a rare, refractory metal. Rhenium is a high melting point metal, has higher hardness, mechanical strength and resistivity, and is widely applied to the industries of aerospace, semiconductors, electronics and the like.
Patent 108296487B discloses a preparation method of a pure rhenium plate, which uses pure rhenium powder with purity more than or equal to 99.99% as a raw material, adopts a hot isostatic pressing mode to realize densification of the material, and obtains the pure rhenium plate through a cold deformation rolling process, wherein the powder needs to be sheathed in the hot isostatic pressing process, more rhenium is lost in the sheath removing process, the rhenium is expensive, and the single furnace cost of hot isostatic pressing is very high. Patent 108160995B discloses a method for manufacturing a pure rhenium product, which comprises the procedures of rhenium powder pretreatment, compression molding, dewaxing, presintering, sheath, hot isostatic pressing, sheath removing, high-temperature sintering and the like, and products such as large-size pure rhenium rods, blocks and the like are prepared. Patent CN200710179262.9 discloses a method for manufacturing a difficult-to-deform pure rhenium sheet. The method prepares the rhenium sheet by pre-treated high-purity ammonium rhenate through two-stage reduction, forming, sintering, cold rolling and annealing. Patent CN201610684931.7 discloses a method for manufacturing ultra-thin high-purity rhenium foil, which comprises spheroidizing high-purity rhenium powder, rolling a pressed compact by a powder rolling mill, and preparing the rhenium foil through high-temperature sintering, continuous rolling and annealing.
Conventional metallic rhenium products are typically prepared using a powder metallurgy process, as in the several patents listed above, by using high purity raw material powders to obtain high purity rhenium products, the process has little purification effect on the material. Meanwhile, a compact rhenium blank cannot be obtained by the conventional powder metallurgy process, and a rhenium product can be compact only by means of external acting forces such as later hot isostatic pressing, deformation processing and the like, but the theoretical density of the metal rhenium cannot be achieved, and generally only about 98% of the theoretical density can be achieved.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a preparation method of a rhenium plate, the purity of the rhenium plate prepared by the preparation method is more than or equal to 99.99 percent, and the density reaches 21.04g/cm of theoretical density 3 。
In order to achieve the above purpose, the present invention provides the following technical solutions:
a method of preparing a rhenium plate, comprising the steps of:
s1, preparing a vacuum electron beam melting electrode;
s2, carrying out vacuum electron beam melting on the melting electrode obtained in the step S1 twice to obtain a pure rhenium metal ingot;
s3, polishing the pure rhenium metal ingot obtained in the step S2, and then performing linear cutting to obtain rhenium pieces;
and S4, rolling the rhenium sheet obtained in the step S3 to obtain the rhenium plate with the required specification.
Further, in the step S1, the preparation of the vacuum electron beam melting electrode specifically includes the following steps:
s1-1, loading rhenium metal powder with the powder purity of more than or equal to 99% into a die for compression molding treatment to obtain a pure rhenium blank;
s1-2, the pure rhenium blank is sintered at high temperature to obtain a preliminarily densified pure rhenium sintered blank, and the pure rhenium sintered blank is a vacuum electron beam melting electrode.
Further, in the step S1-1, the press forming treatment is cold isostatic pressing forming treatment, the forming pressure is 60-100MPa, and the forming time is 3-5min;
and/or, in the step S1-1, the rhenium metal powder is compacted by vibration before cold isostatic pressing treatment, and the vibration frequency is 40-80 times/min.
Further, in the step S1-2, the sintering temperature of high-temperature sintering is 2000-2300 ℃ and the sintering time is 4-8 hours;
and/or sintering under hydrogen atmosphere or vacuum atmosphere;
and/or, in the step S1-2, the density of the obtained pure rhenium sintered blank is 18-20 g/cm 3 ；
And/or the diameter size of the vacuum electron beam melting electrode is 20-100 mm, and the length is more than or equal to 200mm.
Further, in the step S2, the speed of the first vacuum melting is 50-70kg/h, and the speed of the second vacuum melting is 20-30 kg/h;
and/or smelting power is 160-200KW, and smelting vacuum degree is more than or equal to 5 multiplied by 10 -3 Pa；
And/or the density of the pure rhenium metal ingot obtained in the step S2 reaches 21.04g/cm of theoretical density 3 。
Further, in the step S3, the polishing mode includes grinding wheel polishing or lathe processing.
Further, in the step S4, the rolling process specifically includes performing a multi-pass cold rolling process on the rhenium sheet at normal temperature, and performing an annealing process on the rolled blank at least twice in the multi-pass cold rolling deformation process.
Further, in the step S4, the single rolling deformation is less than or equal to 20%;
and/or, in the step S4, the annealing temperature is 1300-1800 ℃ and the annealing time is 1-2h.
In addition, the invention also provides a rhenium plate, which is manufactured by the manufacturing method of the rhenium plate.
Further, the purity of the rhenium plate is more than or equal to 99.99 percent, and the density is 21.04g/cm 3 。
Compared with the prior art, the technical scheme of the invention has at least the following technical effects:
preparation method of rhenium plate of the inventionIn the method, the prepared pure rhenium sintered blank is used as a vacuum electron beam smelting electrode to carry out vacuum electron beam smelting twice, and the purity of the finally obtained rhenium plate is more than or equal to 99.99 percent, and the density reaches 21.04g/cm of theoretical density 3 The material utilization rate (weight after smelting/feeding weight) can reach more than 98 percent.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. Wherein:
FIG. 1 is a macroscopic photograph of a rhenium plate prepared according to example 2 of the present invention;
fig. 2 is a macroscopic photograph of a rhenium plate prepared according to comparative example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The process parameters for the specific conditions not noted in the examples below are generally as usual.
The endpoints of the ranges and any values disclosed in the present invention are not limited to the precise range or value, and the range or value should be understood to include values close to the range or value. For numerical ranges, one or more new numerical ranges may be obtained in combination with each other between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point values, and are to be considered as specifically disclosed in the present invention.
According to a first aspect of the present invention, there is provided a method of preparing a rhenium plate, comprising the steps of:
s1, preparing a vacuum electron beam melting electrode;
s2, carrying out vacuum electron beam melting on the melting electrode obtained in the step S1 twice to obtain a pure rhenium metal ingot;
s3, polishing the pure rhenium metal ingot obtained in the step S2, and then performing linear cutting to obtain rhenium pieces;
and S4, rolling the rhenium sheet obtained in the step S3 to obtain the rhenium plate with the required specification.
In the above-mentioned method for preparing a rhenium plate, as a preferred embodiment, in the step S1, the preparing a vacuum electron beam melting electrode specifically includes the steps of:
s1-1, loading rhenium metal powder with the powder purity of more than or equal to 99% into a die for compression molding treatment to obtain a pure rhenium blank;
s1-2, the pure rhenium blank is sintered at high temperature to obtain a preliminarily densified pure rhenium sintered blank, and the pure rhenium sintered blank is a vacuum electron beam melting electrode.
According to the invention, the density and the compactness of the sintered blank are improved through compression molding and high-temperature sintering, and then the sintered blank is subjected to vacuum electron beam melting twice, so that the purity and the density of the obtained pure rhenium metal ingot are further improved. In addition, the twice vacuum electron beam smelting is adopted, so that the purity of the obtained rhenium sheet is just more than or equal to 99.99 percent, and the density reaches 21.04g/cm of theoretical density 3 . If smelting is carried out once, the purity and density of the obtained rhenium sheet can not reach the height of the invention, if smelting is carried out more than twice, the purity can be improved due to volatilization of elements in the smelting process, but volatilization of impurities can also be caused, so that the more the smelting times are, the smaller the weight of the obtained rhenium ingot after smelting is, and the waste of raw materials is caused. The vacuum electron beam melting can improve the purity of the rhenium sheet, so the process of the invention does not have very high purity requirement on the raw material rhenium powder, and the purity of the rhenium powder can reach more than 99 percent.
In the above-mentioned method for preparing a rhenium plate, as an optional embodiment, in the step S1-1, the press forming process is a cold isostatic press forming process, the forming pressure is 60-100MPa (e.g., 60MPa, 70MPa, 80MPa, 90MPa, 100 MPa), and the forming time is 3-5min (e.g., 3min, 3.5min, 4min, 4.5min, 5 min). Because rhenium powder is not easy to form under high pressure conditions, the invention adopts cold isostatic pressing, the pressure of the cold isostatic pressing is lower than the pressure of the common powder metallurgy forming, and the forming pressure of the cold isostatic pressing is preferably controlled within the range of the invention, if the pressure is too high, the pressed compact cannot be formed, fracture can occur, and the pressed compact is difficult to form and cannot form solid blocks, and can be broken in the process of taking. Optionally, in the step S1-1, the rhenium metal powder is compacted by vibration before the cold isostatic pressing treatment, and the vibration frequency is 40-80 times/min.
In the above-mentioned method for preparing a rhenium plate, in view of cost saving, as an alternative embodiment, in the step S1-2, the sintering temperature of the high-temperature sintering is 2000 to 2300 ℃ (such as 2000 ℃, 2050 ℃, 2100 ℃, 2150 ℃, 2200 ℃, 2250 ℃, 2300 ℃ and the sintering time is 4 to 8 hours (such as 4 hours, 5 hours, 6 hours, 7 hours, 8 hours); the sintering temperature of the conventional powder metallurgy is generally above 2300 ℃ so as to obtain higher density; however, the method for improving the density of the invention mainly adopts an electron beam melting process, so that the sintering temperature set in the early stage can be lower than the conventional powder sintering temperature, for example, the sintering temperature is controlled to be more than or equal to 2000 ℃ (for example, 2010 ℃, 2050 ℃, 2100 ℃ and 2200 ℃).
Optionally, sintering is performed under a hydrogen atmosphere or a vacuum atmosphere;
optionally, in the step S1-2, the density of the obtained pure rhenium sintered blank is 18-20 g/cm 3 ；
Optionally, the diameter size of the vacuum electron beam melting electrode is 20-100 mm, and the length is more than or equal to 200mm.
In the above-mentioned rhenium plate preparation method, as an alternative embodiment, in the step S2, the first vacuum melting is performed at a speed of 50-70kg/h (such as 50kg/h, 52kg/h, 55kg/h, 58kg/h, 60kg/h, 62kg/h, 65kg/h, 68kg/h, 70 kg/h), and the second vacuum melting is performed at a speed of 20-30kg/h (such as 20kg/h, 21kg/h, 22kg/h, 23kg/h, 24kg/h, 25kg/h, 26kg/h, 27kg/h, 28kg/h, 29kg/h, 30 kg/h); the first vacuum melting is a preliminary melting, due to the powder metallurgy of the electrode blankThe gas content of the alloy is too high, the impurity content is also high, the density is also low, most of the impurity is eliminated through the first smelting, the electrode density is improved to a certain extent, and the material loss is easily increased when the first smelting speed is too low; and the second step of vacuum smelting is refining, and slow speed is adopted to further purify and densify. The speed of the twice vacuum melting furnace is preferably controlled within the range set by the invention, the purification and densification effects can be better achieved by controlling the melting speed of the twice, the purification effect can be influenced when the speed is too high, the density can be influenced when the speed is too low, the defects such as cold insulation and the like can be generated, the melting time can be prolonged when the speed is too low, the loss of materials can be increased, and the material utilization rate can be influenced. Optionally, the smelting power is 160-200KW (such as 160KW, 170KW, 180KW, 190KW, 200 KW), and the smelting vacuum degree is more than or equal to 5 multiplied by 10 -3 Pa；
The smelting power is preferably controlled within the range set by the invention, so that on one hand, rhenium can be melted, certain fluidity can be maintained, and the impurity removing effect is better; on the other hand, the volatilization of rhenium is avoided; rhenium cannot be melted when the smelting power is too low, or even if melted, a compact rhenium ingot cannot be obtained because of no fluidity, and the impurity removal effect is poor; the impurity removing effect is good when the smelting power is higher, but the volatilization of rhenium is serious correspondingly, and the loss of the obtained rhenium ingot is serious. In addition, the higher the smelting vacuum degree is, the better the impurity removing effect is.
Optionally, the density of the pure rhenium metal ingot obtained in the step S2 reaches 21.04g/cm of theoretical density 3 。
In the above-mentioned method for manufacturing a rhenium plate, as an alternative embodiment, in the step S3, the polishing mode includes grinding wheel polishing or lathe machining mode. Surface defects of the rhenium ingot were removed by grinding.
In the above method for manufacturing a rhenium plate, in step S4, the rolling treatment specifically includes performing a multi-pass cold rolling treatment on the rhenium sheet at normal temperature, and performing an annealing treatment on the rolled blank at least twice during the multi-pass cold rolling deformation; a rhenium plate of larger dimensions can be obtained by a rolling step.
Alternatively, the single rolling deformation is less than or equal to 20%; optionally, in the step S4, the annealing temperature is 1300-1800 ℃ and the annealing time is 1-2h.
According to a second aspect of the present invention, there is also provided a rhenium plate, which is made by the method of making a rhenium plate as described above.
As an alternative embodiment, the purity of the rhenium plate is more than or equal to 99.99 percent, and the density is more than 21.02g/cm 3 。
The present invention will be described in further detail with reference to specific examples and comparative examples.
Example 1
The embodiment provides a preparation method of a rhenium plate, which comprises the following specific processes:
(1) Preparing 40kg of rhenium powder, putting the rhenium powder with the purity of 99.5% into a rubber sleeve with the diameter of 120mm of a die, compacting by vibration, carrying out cold isostatic pressing at the vibration frequency of 60 times/min, and preparing a pure rhenium pressed compact with the forming pressure of 80Mpa and the forming time of 4 min;
(2) Sintering the pressed compact by using a hydrogen sintering furnace, wherein the sintering maximum temperature is 2300 ℃, and the highest temperature is kept for 5 hours to obtain a pure rhenium sintering blank, wherein the sintering blank is an electron beam smelting electrode, and the density of the sintering blank is 18.5g/cm 3 The diameter of the sintered compact is 84mm, and the length is 391mm;
(3) Carrying out secondary vacuum empty electron beam smelting on an electron beam smelting electrode, wherein the speed of the primary vacuum smelting is 50kg/h, the speed of the secondary vacuum smelting is 20kg/h, the smelting power is 180kw, and the smelting vacuum degree is 5 multiplied by 10 -3 Pa; obtaining pure rhenium metal ingot with the diameter of 90mm, wherein the weight of the pure rhenium metal ingot is 39.8kg, and the material utilization rate is 99.5%;
(4) Removing surface defects of a rhenium cast ingot by a grinding wheel polishing mode, cutting a rhenium wafer with the thickness of 15mm and the diameter of 85mm by adopting a linear cutting mode, preparing a rhenium plate by a plurality of cold rolling-annealing processes, wherein the single rolling deformation is 18%, the annealing times are 10, the rhenium plate is uniformly distributed among a plurality of cold rolling processes, the annealing temperature is 1800 ℃, the annealing time is 2 hours, the rhenium plate with the thickness of 2mm is obtained, the purity of the rhenium plate measured by a GDMS method is over 99.99%, and the density measured by a drainage method is theoreticalDensity 21.04g/cm 3 。
Example 2
(1) Preparing 30kg of rhenium powder, putting the rhenium powder with the purity of 99.2% into a rubber sleeve with the diameter of 100mm of a die, compacting by vibration, and preparing a pure rhenium pressed compact by cold isostatic pressing, wherein the vibration frequency is 40 times/min, the forming pressure is 100Mpa, and the forming time is 4 min;
(2) Sintering the pressed compact by using a hydrogen sintering furnace, wherein the sintering maximum temperature is 2200 ℃, the highest temperature is kept for 6 hours, and a pure rhenium sintering blank is obtained, the sintering blank is an electron beam smelting electrode, and the density of the sintering blank is 18.2g/cm 3 The diameter of the sintered compact is 72mm, and the length is 405mm;
(3) Carrying out secondary blank electron beam smelting on an electron beam smelting electrode, wherein the speed of the primary vacuum smelting is 60kg/h, the speed of the secondary vacuum smelting is 25kg/h, the smelting power is 170kw, and the smelting vacuum degree is 5 multiplied by 10 -3 Pa; pure rhenium metal ingots with the diameter of 90mm are obtained, the weight of 29.7kg, and the material utilization is 99%;
(4) Removing surface defects of a rhenium cast ingot by a grinding wheel polishing mode, cutting a rhenium wafer with the thickness of 18mm and the diameter of 85mm by adopting a linear cutting mode, preparing a rhenium plate by a plurality of cold rolling-annealing processes, wherein the single rolling deformation is 15%, the annealing times are 13, the rhenium plate is uniformly distributed among a plurality of cold rolling processes, the annealing temperature is 1700 ℃, the annealing time is 2 hours, and the rhenium plate with the thickness of 2mm is obtained, and as shown in fig. 1, no hole defects on the surface of the rhenium plate prepared by the embodiment can be seen from fig. 1; the purity of the rhenium plate by GDMS method had reached 99.9981% (see Table 1) and the density by drainage method reached 21.04g/cm 3 。
TABLE 1
Purity＝99.9981％
G.YANG(Analyst)
Example 3
(1) Preparing 20kg of rhenium powder, putting the rhenium powder with the purity of 99.3% into a rubber sleeve with the diameter of 80mm of a die, compacting by vibration, and carrying out cold isostatic pressing molding with the vibration frequency of 45 times/min, wherein the molding pressure is 80Mpa, and the molding time is 3.5min, so as to prepare a pure rhenium pressed compact;
(2) Sintering the pressed compact by using a hydrogen sintering furnace, wherein the sintering maximum temperature is 2150 ℃, the highest temperature is kept for 4 hours, and a pure rhenium sintering blank is obtained, the sintering blank is an electron beam melting electrode, and the density of the sintering blank is 18.3g/cm 3 The diameter of the sintered compact is 54mm, and the length is 478mm;
(3) Carrying out secondary blank electron beam smelting on an electron beam smelting electrode, wherein the speed of the primary vacuum smelting is 70kg/h, the speed of the secondary vacuum smelting is 30kg/h, the smelting power is 172kw, and the smelting vacuum degree is 5 multiplied by 10 -3 Pa; obtaining pure rhenium metal ingot with the diameter of 70mm, wherein the weight of the pure rhenium metal ingot is 19.7kg, and the material utilization rate is 98.5%;
(4) Removing surface defects of a rhenium cast ingot by a turning mode, cutting a rhenium wafer with the thickness of 20mm and the diameter of 65mm by adopting a linear cutting mode, preparing a rhenium plate by a plurality of cold rolling-annealing processes, wherein the single rolling deformation is 13%, the annealing times are 17, the rhenium plate is uniformly distributed among a plurality of cold rolling processes, the annealing temperature is 1600 ℃, the annealing time is 2 hours, the rhenium plate with the thickness of 1.8mm is obtained, the purity of the rhenium plate measured by a GDMS method is up to more than 99.99%, and the density measured by a drainage method is 21.04g/cm 3 。
Comparative example 1
(1) Preparing 25kg of rhenium powder, putting the rhenium powder with the purity of 99.5% into a rubber sleeve with the diameter of 85mm of a die, compacting by vibration, and preparing a pure rhenium pressed compact by cold isostatic pressing, wherein the vibration frequency is 65 times/min, the molding pressure is 80Mpa, and the molding time is 5min;
(2) Sintering the pressed compact by using a hydrogen sintering furnace, wherein the sintering highest temperature is 2250 ℃, and preserving heat for 4 hours to obtain a pure rhenium sintering blank, wherein the sintering blank is an electron beam melting electrode, and the density of the sintering blank is 18.4g/cm 3 The diameter of the sintered compact is 55mm and the length is 572mm;
(3) Carrying out primary vacuum electron beam smelting on an electron beam smelting electrode, wherein the vacuum smelting speed is 55kg/h, the smelting power is 172kw, and the smelting vacuum degree is 5 multiplied by 10 -3 PaThe method comprises the steps of carrying out a first treatment on the surface of the Obtaining pure rhenium metal ingots with the diameter of 70 mm;
(4) And removing the surface defects of the rhenium cast ingot by a turning mode, cutting a rhenium wafer with the thickness of 20mm and the diameter of 65mm by adopting a linear cutting mode, and enabling more holes and inclusions to exist on the surface of the wafer. The rhenium plate is prepared by a process of cold rolling and annealing for multiple times, wherein the single rolling deformation is 16 percent, the annealing times are 13 times, the rhenium plate is uniformly distributed among the cold rolling for multiple times, the annealing temperature is 1800 ℃, the annealing time is 2 hours, and the rhenium plate with the thickness of 2mm is obtained, as shown in figure 2, the surface of the rhenium plate prepared by the comparative example is provided with holes which can lead to low billet density on one hand, and on the other hand, the holes are generated internally because of incomplete volatilization of impurities and are macroscopic appearance of low purity; rhenium plate purity 99.983% by GDMS method (see Table 2), density 20.8g/cm by drainage method 3 。
TABLE 2
Purity＝99.983％
G，YANG(Analyst)
Comparative example 2
The remaining step parameters were the same as in example 2, except that: in the step (1), cold isostatic pressing is carried out, and the forming pressure is 50Mpa. After the pressing is finished, the blank has no forming strength, the blank is broken in the process of taking and carrying, and the subsequent sintering work cannot be finished.
Comparative example 3
The remaining step parameters were the same as in example 2, except that: in the step (1), cold isostatic pressing is carried out, and the forming pressure is 150Mpa. After the pressing is finished, the blank is broken into a plurality of small pieces, and the subsequent sintering work cannot be finished.
Comparative example 4
The remaining step parameters were the same as in example 2, except that: in the step (3), the electron beam melting electrode is subjected to secondary vacuum electron beam melting, wherein the speed of the primary vacuum melting is 80kg/h, and the secondary vacuum melting is carried outThe rate of empty smelting was 40kg/h. The obtained rhenium plate has the purity of 99.97%, high content of impurity elements Ti, fe and the like, and the material density of 21.0g/cm 3 The weight of the rhenium metal ingot obtained after the twice smelting is 29.8kg, and the material utilization rate is 99.3%.
Comparative example 5
The remaining step parameters were the same as in example 2, except that: in the step (3), the electron beam melting electrode is subjected to secondary blank electron beam melting, wherein the speed of the primary vacuum melting is 45kg/h, and the speed of the secondary vacuum melting is 18kg/h. The obtained rhenium plate has the purity of 99.998 percent and the material density of 20.4g/cm 3 The weight of the rhenium metal ingot obtained after the twice smelting is 24.5kg, and the material utilization rate is 81.6%.
Comparative example 6
The remaining step parameters were the same as in example 2, except that: in the step (3), the smelting power is 150kw. The obtained rhenium plate has the purity of 99.92 percent and the material density of 20.2g/cm 3 。
As can be seen from the above data, the rhenium plates prepared in examples 1-3 all have a purity of over 99.99% and a density of 21.04g/cm 3 As can be seen from comparative example 1, the purity and the material density of the obtained rhenium plate are lower than those of examples 1-3 only by adopting vacuum electron beam melting once; as can be seen from comparative examples 2 and 3, the green compacts could not be formed at too high or too low cold isostatic pressing pressure; as can be seen from comparative example 4, if the speed of the two vacuum melting is too high, the rhenium plate obtained has a purity and a density lower than those of examples 1-3; it is seen from comparative example 5 that the speed of the two vacuum melting, if too low, affects the density and material utilization of the rhenium plate; as can be seen from comparative example 6, the twice vacuum melting powers were too low, and the resulting rhenium plates were lower in both purity and density than examples 1-3.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method of preparing a rhenium plate, comprising the steps of:
s1, preparing a vacuum electron beam melting electrode;
s2, carrying out vacuum electron beam melting on the melting electrode obtained in the step S1 twice to obtain a pure rhenium metal ingot;
s3, polishing the pure rhenium metal ingot obtained in the step S2, and then performing linear cutting to obtain rhenium pieces;
and S4, rolling the rhenium sheet obtained in the step S3 to obtain the rhenium plate with the required specification.
2. The method for preparing a rhenium plate according to claim 1, wherein in the step S1, the preparation of the vacuum electron beam melting electrode specifically includes the steps of:
s1-1, loading rhenium metal powder with the powder purity of more than or equal to 99% into a die for compression molding treatment to obtain a pure rhenium blank;
s1-2, the pure rhenium blank is sintered at high temperature to obtain a preliminarily densified pure rhenium sintered blank, and the pure rhenium sintered blank is a vacuum electron beam melting electrode.
3. The method for preparing a rhenium plate according to claim 2, wherein in the step S1-1, the press forming treatment is a cold isostatic press forming treatment, the forming pressure is 60-100MPa, and the forming time is 3-5min;
and/or, in the step S1-1, the rhenium metal powder is compacted by vibration before cold isostatic pressing treatment, and the vibration frequency is 40-80 times/min.
4. The method for preparing a rhenium plate according to claim 2, wherein in the step S1-2, the sintering temperature of the high-temperature sintering is 2000-2300 ℃ and the sintering time is 4-8 hours;
and/or sintering under hydrogen atmosphere or vacuum atmosphere;
and/or, in the step S1-2, the obtained pure rhenium sintered blankThe density of the material is 18-20 g/cm 3 ；
And/or the diameter size of the vacuum electron beam melting electrode is 20-100 mm, and the length is more than or equal to 200mm.
5. The method for preparing a rhenium plate according to claim 1, wherein in the step S2, the first vacuum melting is performed at a speed of 50-70kg/h, and the second vacuum melting is performed at a speed of 20-30 kg/h;
and/or smelting power is 160-200KW, and smelting vacuum degree is more than or equal to 5 multiplied by 10 -3 Pa；
And/or the density of the pure rhenium metal ingot obtained in the step S2 reaches 21.04g/cm of theoretical density 3 。
6. The method for preparing a rhenium plate according to claim 1, wherein in the step S3, polishing means includes grinding wheel polishing or lathe processing means.
7. The method for manufacturing a rhenium plate according to claim 1, wherein in the step S4, the rolling treatment specifically includes a multi-pass cold rolling treatment of the rhenium sheet at normal temperature, and an annealing treatment of the rolled blank is performed at least twice during the multi-pass cold rolling deformation.
8. The method for producing a rhenium plate according to claim 7, wherein in the step S4, a single rolling deformation is 20% or less;
and/or, in the step S4, the annealing temperature is 1300-1800 ℃ and the annealing time is 1-2h.
9. A rhenium plate, characterized in that it is made by the process for the preparation of a rhenium plate according to any one of claims 1-8.
10. The rhenium plate of claim 9, wherein the rhenium plate has a purity greater than or equal to 99.99% and a density of 21.04g/cm 3 。
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