CN113058999A - Method for manufacturing ultrathin rhenium foil - Google Patents
Method for manufacturing ultrathin rhenium foil Download PDFInfo
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- CN113058999A CN113058999A CN202110365513.2A CN202110365513A CN113058999A CN 113058999 A CN113058999 A CN 113058999A CN 202110365513 A CN202110365513 A CN 202110365513A CN 113058999 A CN113058999 A CN 113058999A
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- rhenium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
- B21B1/40—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling foils which present special problems, e.g. because of thinness
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/16—Both compacting and sintering in successive or repeated steps
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/30—Acidic compositions for etching other metallic material
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Powder Metallurgy (AREA)
- Metal Rolling (AREA)
Abstract
The invention relates to a method for manufacturing an ultrathin rhenium foil. The method comprises the following steps: placing rhenium powder with the granularity of-100 to-300 meshes and the purity of more than 4N in a press machine, and preparing a pure rhenium pressed blank with the thickness of 10mm under the pressure of 100 to 200 Mpa; placing the pure rhenium compact in a vacuum furnace or a high-temperature furnace, and sintering at high temperature to prepare a pure rhenium plate blank with uniform crystallization; continuously rolling a pure rhenium plate blank by adopting a multi-roller mill and annealing linkage, and carrying out continuous rolling and annealing until a rhenium sheet is obtained; and (3) carrying out a combined rolling process of chemical etching thinning and multi-roller mill finish rolling on the rhenium thin sheet, and finally obtaining the ultrathin rhenium foil with the target product thickness of 9-11 microns. The method of the invention has the advantages of high efficiency, good surface quality, low equipment investment and the like.
Description
Technical Field
The invention belongs to the field of powder metallurgy preparation, and particularly relates to a manufacturing method of an ultrathin rhenium foil with the thickness of about 10 microns.
Background
The ultrathin metal rhenium foil is mainly used as high-temperature-resistant precise fine parts of various precise resistors, precise temperature fields, severe and lasting environments and the like, and is widely applied to the advanced fields of aviation, aerospace, atomic energy, ultra-high temperature alloys, semiconductor vacuum coating and the like.
The metal rhenium has the characteristics of high density, high melting point, excellent high-temperature strength and high-temperature plasticity, no high-temperature ductile-brittle transition and the like, and when the metal rhenium sheet is manufactured, due to the high melting point, the elasticity after effect is large, the hardening speed is high, the processing difficulty is large, the metal rhenium sheet with the thickness of 0.1mm is difficult to process, and the processing to the thickness of 0.01mm (namely 10 microns) is a great industrial problem. In the development of technology and engineering applications worldwide, the rhenium sheet thickness is required to be thinner and thinner, for example, the rhenium foil used for a mass spectrometer resistor is required to be thinner and thinner preferably less than 0.03mm, and the thickness of the rhenium foil cannot be achieved when many precise devices are designed for higher performance. And the rhenium sheet with the thickness of less than 0.01mm is restricted by the mechanical characteristics of rolling equipment, so the annealing efficiency is low, the production efficiency is too low, and the industrial mass production cannot be realized.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for manufacturing an ultrathin rhenium foil, which is characterized in that a blank easy to roll and thin is prepared by a special process, the early-stage rolling rapid thin is realized, and the rolling efficiency can be obviously improved by the later-stage chemical etching and fine rolling, so that the rhenium foil with the thickness of 10 microns can be economically obtained.
The technical scheme adopted by the invention is as follows: a method for manufacturing an extremely thin rhenium foil comprises the following steps:
1) preparation of pure rhenium compacts: placing rhenium powder with the granularity of-100 to-300 meshes and the purity of more than 4N in a press machine, and preparing a pure rhenium pressed blank with the thickness of 10mm under the pressure of 100 to 200 Mpa; the granularity of-100 to-300 meshes means that the material is sieved by a 100-mesh sieve, undersize is taken, and then sieved by a 300-mesh sieve, and oversize is taken.
2) Placing the pure rhenium compact in a vacuum furnace or a high-temperature furnace, and sintering at high temperature to prepare a pure rhenium plate blank with uniform crystallization;
3) continuous rolling and annealing: continuously rolling a pure rhenium plate blank by adopting a multi-roller mill and annealing linkage, and carrying out continuous rolling and annealing until a rhenium sheet is obtained;
4) etching, thinning and finish rolling into foil: and 3) carrying out a combined rolling process of chemical etching thinning and multi-roller mill finish rolling on the rhenium thin sheet obtained in the step 3) to finally obtain the ultrathin rhenium foil of the target product, wherein the thickness of the ultrathin rhenium foil is 9-11 microns.
Further, in the manufacturing method of the ultrathin rhenium foil, in the step 1), the high-purity rhenium powder is directly pressed into a blank without adding any additive in the blank pressing process.
Further, in the method for manufacturing the ultrathin rhenium foil, in the step 2), the high-temperature sintering is performed for 5-8 hours at the temperature of 2400 ℃.
Further, in the method for manufacturing the ultrathin rhenium foil, in the step 2), the density of the obtained pure rhenium plate blank is controlled to be 17.8-18.3 g/cm3。
Further, in the method for manufacturing the ultrathin rhenium foil, in the step 3), the thickness of the obtained rhenium sheet is 90-150 microns.
Further, in the method for manufacturing the ultrathin rhenium foil, in the step 3), the multi-roll mill is a multi-stage rolling combination with the rolling force of 100T-700T, the pass deformation is controlled to be 2-10%, the annealing temperature is 1600-1900 ℃, and the annealing time is 20-60 min.
Further, in the above manufacturing method of the ultrathin rhenium foil, in step 4), the chemical etching method includes: and (3) performing sand blasting treatment on the finished rhenium foil, and then immersing the finished rhenium foil into nitric acid or sulfuric acid for corrosion thinning.
Furthermore, in the method for manufacturing the ultrathin rhenium foil, the mass percentage concentration of the nitric acid or the sulfuric acid is 10-30%.
The invention has the following beneficial effects:
1. the invention adopts high-purity rhenium powder (the purity is more than or equal to 99.99%) with the granularity of-100 to-300 meshes as a raw material, reduces the harm of impurities to later-stage metal blank rolling by ensuring the purity of the material, can properly control the density of the blank, ensures the quality of the sheet material, is easy to roll and thin and provides the rolling efficiency.
2. According to the invention, the blank is made without additives, so that the impurity sources can be reduced as much as possible, and impurities influencing the performance of the final product are not mixed when the reasonable density interval of the blank is controlled.
3. According to the invention, the chemical etching is adopted for thinning, so that the density space of the rhenium sheet which is excessively dense can be opened again, the rhenium sheet metal particles can slide nearby when mechanically rolled conveniently, and the rolling efficiency is improved.
4. The process of the invention can finally prepare the product with the thickness of less than 0.01mm, the width of more than 50mm, the length of more than 500mm, the purity of not less than 99.99 percent and the density of more than 21g/cm3The very thin high-purity rhenium foil.
5. The invention has the advantages of short rolling process, high rolling efficiency, easy realization of the target and the like.
Detailed Description
EXAMPLE 1 method for producing an extremely thin rhenium foil
The method comprises the following steps:
1) preparing materials: firstly, the purity of the high-purity rhenium powder is more than 4N, and the granularity is-100 to-150 meshes (the removal granularity is more than 100 meshes and less than 150 meshes).
2) Preparation of pure rhenium green compacts: the high-purity rhenium powder is placed in a press machine, and pure rhenium green compacts with the thickness of about 10mm are prepared under the pressure of 100 Mpa. In the process of pressing and blank making, the high-purity rhenium powder can not be added with any additive, namely, can not be added with any carbon or non-carbon additive, and is directly pressed into a blank.
3) Placing the pure rhenium compact in a vacuum furnace, sintering at 2400 deg.C for 5h to obtain the final product with uniform crystal and density controlled at 17.8g/cm3Pure rhenium slabs.
4) Continuous rolling and annealing: and continuously rolling the pure rhenium plate blank by adopting a multi-roller mill and annealing linkage, and continuously rolling and annealing until a rhenium thin sheet is obtained. The method specifically comprises the following steps: the multi-roller rolling mill is a multi-stage rolling combination with the rolling force of 100T-700T, and the pass deformation is controlled to be 2-10%. Firstly, rolling a pure rhenium plate blank by a multi-roller mill, then annealing the rolled pure rhenium plate blank at 1700 ℃ for 40min, and repeating the rolling and annealing until a rhenium sheet with the thickness of about 100 microns is obtained.
5) Etching, thinning and finish rolling into foil: performing sand blasting treatment on the surface of a rhenium thin sheet with the thickness of about 100 micrometers, then placing the rhenium thin sheet in nitric acid with the mass percentage concentration of 10% for corrosion for 20min, then performing finish rolling by using a multi-roller mill, and repeating the sand blasting treatment, the corrosion in nitric acid and the finish rolling by using the multi-roller mill to finally obtain the rhenium thin sheet with the thickness of 10 micrometers, the width of 50 millimeters, the length of more than 600 millimeters and the density of 21.02g/cm3And the purity of the ultrathin rhenium foil is 99.99 percent.
Through the calculation, the yield weight of each working hour is as follows: the final product/material was 0.36, with a work-hour yield of 0.12 grams.
EXAMPLE 2 method for producing an extremely thin rhenium foil
The method comprises the following steps:
1) preparing materials: firstly, the purity of the high-purity rhenium powder is more than 4N, and the granularity is-100 to-300 meshes (the removal granularity is more than 100 meshes and less than 300 meshes);
2) preparation of pure rhenium green compacts: the high-purity rhenium powder is placed in a press machine and is made into pure rhenium green compacts with the thickness of about 10mm under the pressure of 200 Mpa. In the process of pressing and blank making, the high-purity rhenium powder can not be added with any additive, namely, can not be added with any carbon or non-carbon additive, and is directly pressed into a blank.
3) Placing the pure rhenium compact in a vacuum furnace, sintering at 2400 deg.C for 8h to obtain the final product with uniform crystal and density controlled at 18.3g/cm3Pure rhenium slabs.
4) Continuous rolling and annealing: and continuously rolling the pure rhenium plate blank by adopting a multi-roller mill and annealing linkage, and continuously rolling and annealing until a rhenium thin sheet is obtained. The method specifically comprises the following steps: the multi-roller rolling mill is a multi-stage rolling combination with the rolling force of 100T-700T, and the pass deformation is controlled to be 2-10%. Firstly, rolling a pure rhenium plate blank by a multi-roller mill, then annealing the rolled pure rhenium plate blank at 1700 ℃ for 40min, and repeating the rolling and annealing until a rhenium sheet with the thickness of about 100 microns is obtained.
5) Etching, thinning and finish rolling into foil: performing sand blasting treatment on the surface of a rhenium thin sheet with the thickness of about 100 micrometers, then placing the rhenium thin sheet in nitric acid with the mass percentage concentration of 30% for corrosion for 60min, then performing finish rolling by using a multi-roller mill, and repeating the sand blasting treatment, the corrosion in nitric acid and the finish rolling by using the multi-roller mill to finally obtain the rhenium thin sheet with the thickness of 10 micrometers, the width of 60 millimeters, the length of more than 1000 millimeters and the density of 21.02g/cm3And the purity of the ultrathin rhenium foil is 99.99 percent.
Through the calculation, the yield weight of each working hour is as follows: the final product/material was 0.45, with a work-hour yield of 0.16 g.
Claims (8)
1. A method for manufacturing an extremely thin rhenium foil is characterized by comprising the following steps:
1) preparation of pure rhenium compacts: placing rhenium powder with the granularity of-100 to-300 meshes and the purity of more than 4N in a press machine, and preparing a pure rhenium pressed blank with the thickness of 10mm under the pressure of 100 to 200 Mpa;
2) placing the pure rhenium compact in a vacuum furnace or a high-temperature furnace, and sintering at high temperature to prepare a pure rhenium plate blank with uniform crystallization;
3) continuous rolling and annealing: continuously rolling a pure rhenium plate blank by adopting a multi-roller mill and annealing linkage, and carrying out continuous rolling and annealing until a rhenium sheet is obtained;
4) etching, thinning and finish rolling into foil: and 3) carrying out a combined rolling process of chemical etching thinning and multi-roller mill finish rolling on the rhenium thin sheet obtained in the step 3) to finally obtain the ultrathin rhenium foil of the target product, wherein the thickness of the ultrathin rhenium foil is 9-11 microns.
2. The method for manufacturing the ultrathin rhenium foil as claimed in claim 1, wherein in the step 1), the high-purity rhenium powder is directly pressed into a blank without adding any additive in the process of pressing the blank.
3. The method for producing an ultrathin rhenium foil as claimed in claim 1, wherein in the step 2), the high-temperature sintering is performed at 2400 ℃ for 5 to 8 hours.
4. The method for manufacturing the ultrathin rhenium foil as claimed in claim 1, wherein in the step 2), the density of the obtained pure rhenium slab is controlled to be 17.8-18.3 g/cm3。
5. The method for producing an ultrathin rhenium foil as claimed in claim 1, wherein the thickness of the rhenium thin sheet obtained in the step 3) is 90 to 150 μm.
6. The method for manufacturing an ultrathin rhenium foil as claimed in claim 1, wherein the multi-roll mill in the step 3) is a multi-stage rolling combination with a rolling force of 100T-700T, the pass deformation is controlled to be 2-10%, the annealing temperature is 1600-1900 ℃, and the annealing time is 20-60 min.
7. The method for manufacturing an extra thin rhenium foil according to claim 1, wherein in the step 4), the chemical etching method is: after sand blasting treatment, the rhenium thin sheet is immersed into nitric acid or sulfuric acid for corrosion and thinning.
8. The method for producing an extra thin rhenium foil according to claim 7, wherein the concentration by mass of the nitric acid or the sulfuric acid is 10 to 30%.
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| CN202110365513.2A CN113058999B (en) | 2021-04-06 | 2021-04-06 | Method for manufacturing ultrathin rhenium foil |
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Cited By (2)
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| CN114535339A (en) * | 2022-01-31 | 2022-05-27 | 北京科技大学 | Processing method of large-size uniform high-purity rhenium plate |
| CN114619037A (en) * | 2022-01-31 | 2022-06-14 | 北京科技大学 | Preparation method of sintered rhenium plate |
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| CN114535339A (en) * | 2022-01-31 | 2022-05-27 | 北京科技大学 | Processing method of large-size uniform high-purity rhenium plate |
| CN114619037A (en) * | 2022-01-31 | 2022-06-14 | 北京科技大学 | Preparation method of sintered rhenium plate |
| CN114619037B (en) * | 2022-01-31 | 2023-09-01 | 北京科技大学 | Preparation method of sintered rhenium plate |
| CN114535339B (en) * | 2022-01-31 | 2023-10-10 | 安泰科技股份有限公司 | Processing method of large-size homogenized high-purity rhenium plate |
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