CN115747575A - MP-4 high-strength hydrogen embrittlement-resistant membrane and preparation method thereof - Google Patents
MP-4 high-strength hydrogen embrittlement-resistant membrane and preparation method thereof Download PDFInfo
- Publication number
- CN115747575A CN115747575A CN202211321096.2A CN202211321096A CN115747575A CN 115747575 A CN115747575 A CN 115747575A CN 202211321096 A CN202211321096 A CN 202211321096A CN 115747575 A CN115747575 A CN 115747575A
- Authority
- CN
- China
- Prior art keywords
- less
- equal
- membrane
- diaphragm
- strength
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000001257 hydrogen Substances 0.000 title claims abstract description 76
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 76
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000012528 membrane Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 29
- 239000000956 alloy Substances 0.000 claims abstract description 29
- 238000005096 rolling process Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 19
- 230000003746 surface roughness Effects 0.000 claims abstract description 14
- 238000012545 processing Methods 0.000 claims abstract description 10
- 238000005520 cutting process Methods 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 238000004381 surface treatment Methods 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 238000004513 sizing Methods 0.000 claims abstract description 5
- 238000005242 forging Methods 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 23
- 238000000137 annealing Methods 0.000 claims description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 238000005097 cold rolling Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 230000001276 controlling effect Effects 0.000 claims description 6
- 230000006698 induction Effects 0.000 claims description 6
- 238000003303 reheating Methods 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 238000010791 quenching Methods 0.000 claims description 4
- 230000000171 quenching effect Effects 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 238000005098 hot rolling Methods 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 238000005554 pickling Methods 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 230000033228 biological regulation Effects 0.000 abstract description 8
- 238000005266 casting Methods 0.000 abstract description 8
- 150000002431 hydrogen Chemical class 0.000 abstract description 5
- 229910052804 chromium Inorganic materials 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 229910001182 Mo alloy Inorganic materials 0.000 abstract description 2
- 239000006104 solid solution Substances 0.000 abstract description 2
- 238000005728 strengthening Methods 0.000 abstract description 2
- OGSYQYXYGXIQFH-UHFFFAOYSA-N chromium molybdenum nickel Chemical compound [Cr].[Ni].[Mo] OGSYQYXYGXIQFH-UHFFFAOYSA-N 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 10
- 238000005984 hydrogenation reaction Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000013461 design Methods 0.000 description 7
- 238000007670 refining Methods 0.000 description 7
- 239000007769 metal material Substances 0.000 description 6
- 238000011049 filling Methods 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- 238000003723 Smelting Methods 0.000 description 4
- 238000009661 fatigue test Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000001887 electron backscatter diffraction Methods 0.000 description 3
- 238000003698 laser cutting Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000007431 microscopic evaluation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Abstract
The invention relates to the field of key material parts of hydrogen energy equipment, in particular to a high-strength hydrogen embrittlement-resistant membrane with the trade mark of MP-4 and a preparation method thereof. The invention is based on a nickel-chromium-molybdenum alloy system, the high strength and the hydrogen embrittlement resistance of a diaphragm are ensured by utilizing Cr, mo and Fe element solid solution strengthening and grain boundary regulation, the fatigue strength of the alloy is improved by adjusting the content of C and N elements of the alloy, the diaphragm is prepared by the method of ingot casting preparation → strip blank preparation → twenty-roller mill finish rolling → grain boundary regulation → leveling sizing → diaphragm cutting processing → diaphragm surface treatment, the thickness of the diaphragm is 0.45-0.55 mm, the diameter is not less than 200mm, the surface roughness Ra is not more than 0.2 mu m, the planeness is not more than 0.04mm, the yield strength at room temperature and 200 ℃ can respectively reach more than 350MPa and 300MPa, and the diaphragm has good plasticity, hydrogen embrittlement resistance and fatigue resistance, the fatigue limit at room temperature is not less than 230MPa, and can be used as a hydrogen side diaphragm in a 90MPa or higher-level hydrogen diaphragm compressor.
Description
Technical Field
The invention relates to the field of materials for key parts of hydrogen energy equipment, in particular to a high-strength hydrogen embrittlement-resistant membrane with the brand number of MP-4 and a preparation method thereof.
Background
Under the drive of double-carbon background, china has clearly proposed in various industrial policies to strongly support the development of hydrogen energy industry, and a hydrogenation station plays an indispensable role as an important link in storage and transportation in the hydrogen energy industry. It should be noted that most hydrogenation stations built in the future of China are hydrogenation stations with the grade of 70MPa or higher, which puts higher requirements on key equipment and parts of the hydrogenation stations. A high-pressure hydrogen diaphragm compressor (hereinafter, referred to as a hydrogen compressor) is indispensable key equipment in a hydrogen filling station, and adopts hydraulic drive diaphragm to reciprocate so as to realize pressurization of hydrogen. The stability, reliability and use efficiency of the hydrogen compressor are very important for the safe and stable operation of the whole hydrogen filling station. The hydrogen compressor at home and abroad adopts primary compression, the compression ratio is large, the compression temperature is high (up to 250 ℃), and particularly, a hydrogen-contacting membrane is easy to lose effect due to hydrogen under the environment of high temperature, high pressure and high purity hydrogen, so that the safe and stable operation of a hydrogenation station is influenced. In addition, the hydrogen compressor diaphragm also has design and processing difficulties, which leads to long delivery cycle of the whole equipment.
At present, the membranes on the hydrogen facing side of a hydrogen compressor (design pressure is 35 MPa) of an exemplary hydrogenation station at 30MPa are made of 301 or 316L austenitic stainless steel. Engineering practice shows that as the pressure of a hydrogenation station is increased to 45MPa (the design pressure of a hydrogen compressor is 52 MPa), the service life of the austenitic stainless steel diaphragm on the hydrogen side is remarkably shortened (even less than 1/5-1/10 of the service life of the diaphragm of the 35MPa hydrogenation machine), and the service life of the austenitic stainless steel diaphragm is lower after the service hydrogen pressure is further increased to 90MPa (the design pressure of the hydrogen compressor for the 70MPa hydrogenation station is 90 MPa). This is because the high temperature strength and fatigue resistance of the 316L alloy in a high temperature, high pressure hydrogen environment limit its service life. Therefore, development of a hydrogen embrittlement-resistant membrane with low cost and high performance is very important for development of the hydrogen energy industry.
Disclosure of Invention
Aiming at the requirement of materials of key parts of hydrogen energy equipment, the invention aims to provide a high-strength hydrogen embrittlement-resistant membrane with the mark of MP-4 and a preparation method thereof, so as to meet the urgent requirements of a 90MPa or above grade hydrogen press on the design and use of a high-performance hydrogen membrane.
The technical scheme of the invention is as follows:
the high-strength hydrogen embrittlement-resistant membrane with the mark of MP-4 has the thickness of 0.45-0.55 mm, the diameter of not less than 200mm, the surface roughness Ra of not more than 0.2 mu m and the planeness of not more than 0.04mm; the main component range of the membrane is as follows according to the weight percentage:
cr:21.00 to 23.00, mo: 8.00-10.00, fe:10.00 to 15.00, ni and unavoidable residual elements: the balance; the inevitable residual elements include: the aluminum content is controlled to be less than or equal to 0.050, the titanium content is controlled to be less than or equal to 0.030, the manganese content is controlled to be less than or equal to 0.030, the carbon content is controlled to be less than or equal to 0.030, the sulfur content is controlled to be less than or equal to 0.001, the phosphorus content is controlled to be less than or equal to 0.005, the silicon content is controlled to be less than or equal to 0.030, and the nitrogen content is controlled to be less than or equal to 0.010.
The high-strength hydrogen embrittlement-resistant diaphragm with the mark of MP-4, sigma 3 in the alloy of the diaphragm n The proportion of grain boundary is not less than 60%, n =1,2 or 3, and the proportion of sigma is not more than 29, and is not less than 65%.
The high-strength hydrogen embrittlement-resistant membrane with the mark of MP-4 has room temperature mechanical properties meeting the following requirements: the yield strength (Rp0.2) is not less than 350MPa, the tensile strength (Rm) is not less than 700MPa, and the elongation (A) is not less than 35%.
The high-strength hydrogen embrittlement-resistant membrane with the mark of MP-4 has the mechanical properties at the high temperature of 200 ℃ meeting the following requirements: yield strength (Rp0.2) is not less than 300MPa, tensile strength (Rm) is not less than 650MPa, and elongation (A) is not less than 35%.
After the high-strength hydrogen-embrittlement-resistant diaphragm with the mark of MP-4 is subjected to hydrogen filling treatment for 72 hours at 300 ℃ under 10MPa with high-purity hydrogen (the volume purity is more than or equal to 99.999%), the room-temperature mechanical property of the diaphragm meets the following requirements: yield strength (Rp0.2) is not less than 350MPa, tensile strength (Rm) is not less than 700MPa, and elongation (A) is not less than 25%.
The high-strength hydrogen embrittlement-resistant membrane with the mark of MP-4 has the fatigue limit of not less than 230MPa at the confidence coefficient of 50%.
The preparation method of the high-strength hydrogen embrittlement-resistant membrane with the mark of MP-4 comprises the following specific steps:
(1) Preparing a cast ingot: carrying out vacuum induction melting and electroslag remelting on electrolytic nickel, metallic chromium, metallic molybdenum and metallic iron serving as raw materials to obtain a cast ingot;
(2) Preparing a belt blank: the cogging and forging temperature of the cast ingot is 1150-1170 ℃, the ingot is allowed to return to the furnace and heated again before being forged to the final specification, the temperature is kept at 1150-1170 ℃ for 1-4 h, and the final forging temperature is not lower than 950 ℃, so that a forging stock is obtained; the forging stock is subjected to hot rolling after being kept at 1130-1150 ℃ for 2-4 h, the cogging rolling temperature is 1100-1150 ℃, the forging stock is allowed to return to a furnace for reheating before being rolled to the final specification, the forging stock is kept at 1100-1150 ℃ for 0.5-3 h, and the final rolling temperature is not lower than 900 ℃ to obtain a hot rolled coil with the thickness of 4-6 mm; uncoiling a hot-rolled coil, pickling, cold-rolling at room temperature, and performing stress relief annealing at 980-1030 ℃ for 15-60 min in the middle to obtain a strip blank with the thickness of 1-1.5 mm, wherein the deformation of the hot-rolled coil is 20-50% during each annealing;
(3) Finish rolling by a twenty-high roll mill: carrying out finish rolling on the cold-rolled strip blank by adopting a twenty-roller cold rolling unit with the roller surface roughness Ra of less than or equal to 0.2 mu m to obtain a finish-rolled plate with the thickness of 0.45-0.55 mm;
(4) Regulating and controlling a grain boundary: controlling the solution treatment temperature of the finish-rolled plate at 1050-1150 ℃, keeping the temperature for 20-60 min, and air cooling to ensure that the grain size is not lower than 7 grade; performing small-deformation cold rolling on the plate, wherein the deformation of the plate in the cold rolling process is 3-7%, and performing annealing heat treatment on the plate subjected to small deformation at the temperature of 1020-1050 ℃ for 5-10 min;
(5) Leveling and sizing: the flattening pressing rate is 0.5-1.0%;
(6) Cutting and processing the membrane;
(7) And (5) surface treatment of the membrane.
In the preparation method of the high-strength hydrogen-embrittlement-resistant membrane with the mark of MP-4, in the step (4), the solution treatment of the plate is carried out in a gas protection furnace, and the gas medium is argon or reducing gas.
The preparation method of the high-strength hydrogen-embrittlement-resistant membrane with the mark of MP-4 comprises the step (4) of annealing treatment by adopting a vacuum or gas-shielded gas quenching heat treatment furnace, wherein a gas medium is argon or reducing gas.
According to the preparation method of the high-strength hydrogen embrittlement-resistant membrane with the MP-4 mark, the nonmetallic inclusion in the membrane after the surface treatment in the step (7) meets the following requirements: the fine line (m), A is less than or equal to 0.5 grade, B is less than or equal to 0.5 grade, D is less than or equal to 1.0 grade, and the sum of the three grades is less than or equal to 1.5 grade; coarse system (m), A is less than or equal to 0.5 grade, B is less than or equal to 0.5 grade, D is less than or equal to 0.5 grade, and the sum of the three grades is less than or equal to 1.5 grade; wherein A is sulfide, B is alumina, D is spherical oxide, and the sum of the three is A + B + D.
The design idea of the invention is as follows:
firstly, based on the design of a single-phase austenitic alloy structure, the strength of the alloy is improved and the cost is controlled by adding a proper amount of Fe on the basis of a Ni-Cr-Mo alloy system, so that the high-temperature strength at room temperature and 200 ℃ is obtained. Wherein, the room temperature yield strength (Rp0.2) of the MP-4 alloy can reach more than 350MPa, the 200 ℃ yield strength (Rp0.2) can reach 300MPa, and the plasticity is good (the room temperature elongation and the 200 ℃ elongation are respectively higher than 35 percent and 35 percent). Firstly, by controlling the content of C and N nonmetallic elements, the precipitation of carbonitrides is reduced, and the fatigue life is prolonged. Secondly, by a grain boundary regulation method of deformation and heat treatment, the number of free grain boundaries in the alloy is reduced, and special grain boundaries (low sigma 3) are improved n (n =1,2, 3) the lattice grain boundary of the coincident position) ratio, thereby remarkably improving the resistance of the membrane alloy to hydrogen-induced crack initiation and propagation along the grain boundary, and further obtaining the excellent hydrogen embrittlement resistance of the membrane. Thirdly, the regulation and control method for reducing the level of non-metallic inclusions and the crystal boundary is prepared by vacuum induction and electroslag remelting, the number of strong hydrogen traps (also serving as fatigue crack sources) in the membrane alloy is reduced, and the fatigue limit and the hydrogen embrittlement resistance of the membrane can be synergistically improved. Fourthly, the membrane with high surface quality is obtained by finish rolling through a twenty-high roll mill, and the fatigue resistance of the plate is improved.
The invention has the advantages and beneficial effects that:
1. the high-strength hydrogen embrittlement-resistant membrane with the mark of MP-4 has the advantages of low content of carbon, nitrogen, sulfur, phosphorus impurity elements and non-metallic inclusions, high proportion of lattice grain boundaries at low sigma coincidence positions, excellent room temperature and 200 ℃ high-temperature strength (which is improved by nearly one time compared with 316L), excellent hydrogen embrittlement resistance, and capability of being used under complex and harsh working conditions of a 90MPa and above hydrogen press.
2. The diameter of the diaphragm is not less than 200mm, the surface roughness Ra is not more than 0.2 mu m, and the planeness is not more than 0.04mm.
3. Sigma 3 of the inventive diaphragm n The proportion of special crystal boundary is not less than 65%, and the proportion of sigma is not more than 29, and the proportion of crystal boundary is not less than 70%.
4. The room temperature mechanical property of the diaphragm of the invention meets the following requirements: the yield strength (Rp0.2) is not less than 350MPa, the tensile strength (Rm) is not less than 700MPa, and the elongation (A) is not less than 35%.
5. The high-temperature mechanical property of the membrane at 200 ℃ meets the following requirements: yield strength (Rp0.2) is not less than 300MPa, tensile strength (Rm) is not less than 650MPa, and elongation (A) is not less than 35%.
6. The mechanical property of the diaphragm at room temperature after hydrogen filling treatment at 300 ℃ and 10MPa, high-purity hydrogen (volume purity is more than or equal to 99.999%) and 72h meets the following requirements: the yield strength (Rp0.2) is not lower than 350MPa, the tensile strength (Rm) is not lower than 700MPa, the elongation (A) is not lower than 25%, and the hydrogen embrittlement resistant and fatigue resistant composite material has good plasticity, hydrogen embrittlement resistance and fatigue resistance, and can be used for preparing a hydrogen membrane in a hydrogen press of 90MPa or above.
7. The fatigue limit of the diaphragm of the invention is not lower than 230MPa under the confidence coefficient of 50 percent.
Drawings
FIG. 1 shows a Phi 375mm by 0.5mm MP-4 diaphragm.
FIG. 2a is an EBSD map of the grain boundary structure of the diaphragm.
FIG. 2b is a graph showing statistics of the specific grain boundaries of the film; in the figure, sigma-Value on the abscissa represents the type of grain boundary, and Fraction on the ordinate represents the specific grain boundary ratio (%).
Detailed Description
In the specific implementation process, the strength and the hydrogen embrittlement resistance of the diaphragm are ensured based on Cr, mo and Fe element solid solution strengthening and grain boundary regulation, the fatigue resistance of the diaphragm is ensured based on control of carbide forming elements, the fatigue strength of the alloy is improved by adjusting the content of C and N elements of the alloy, and the diaphragm is prepared by the methods of ingot preparation → strip preparation → twenty-roller rolling mill finish rolling → grain boundary regulation → leveling and sizing → diaphragm cutting processing → diaphragm surface treatment, so that the high-strength hydrogen embrittlement resistant diaphragm (MP-4) with the diameter of not less than 200mm, the surface roughness Ra of not more than 0.2 mu m and the planeness of not more than 0.04mm is obtained.
The present invention will be described in further detail below with reference to examples.
Example 1 MP-4 Membrane with a gauge of phi 411mm x 0.5mm
Smelting alloy in a 1.0-ton vacuum induction furnace by adopting an aluminum-magnesium spinel crucible, carrying out primary refining and primary refining desulfurization treatment in the smelting process, and then casting ingot; carrying out electroslag remelting on the cast ingot after surface polishing treatment to obtain a casting blank, carrying out polishing treatment on the casting blank, and then preparing the casting blank into a diaphragm with the diameter of 411mm multiplied by 0.5mm through belt blank preparation → twenty-high rolling mill finish rolling → grain boundary regulation → leveling sizing → cutting processing → surface treatment of the diaphragm, wherein the diaphragm is shown in a real object figure 1, the chemical components of the diaphragm are shown in a table 1, and the preparation process comprises the following steps:
1. electrolytic nickel, metal chromium, metal molybdenum and metal iron are used as raw materials, ni, cr, mo and Fe are put into a crucible before smelting, and a calcium desulfurizer is put into a hopper. Vacuum induction melting is carried out by adopting an aluminum-magnesium spinel crucible, refining treatment is carried out for 10-15 minutes at 1530-1570 ℃ (refining is carried out for 10 minutes at 1530 ℃ in the embodiment), then a calcareous desulfurizer is added for refining for 5-15 minutes (10 minutes in the embodiment), desulfurization treatment is carried out by utilizing better thermal stability of the crucible and the desulfurizer, and cast ingot is cast at 1480-1520 ℃ (1500 ℃ in the embodiment). And carrying out electroslag remelting on the cast ingot to obtain a casting blank with the specification of phi 220-360 mm (phi 350mm in the embodiment).
2. The casting blank is subjected to alloy forging after being subjected to heat preservation at 1150-1170 ℃ for 4-12 h (the heat preservation time at 1150 ℃ is 5h in the embodiment), the cogging forging temperature is 1150-1170 ℃ (1150 ℃) and the finish forging temperature is not lower than 950 ℃ (the finish forging temperature is 960 ℃) to obtain a forging blank; the forging process is carried out by allowing to return to the furnace and heating again before forging to the final specification, keeping the temperature for 1-4 h at the heating temperature of 1150-1170 ℃ (the returning to the furnace and heating for four times in the embodiment, and keeping the temperature for 1h at 1150 ℃), wherein the section specification of the forged plate blank is 400 multiplied by 70mm; the forged plate blank is rolled after being kept at 1130-1150 ℃ for 2-4 h (the holding time of 1130 ℃ in the embodiment is 2 h), the cogging rolling temperature is 1100-1150 ℃ (1130 ℃ in the embodiment), the finishing rolling temperature is not lower than 900 ℃ (the finishing rolling temperature of the embodiment is 920 ℃), the forged plate blank is allowed to return to a furnace and be reheated before being rolled to the final specification, the temperature is kept at 1100-1150 ℃ for 0.5-3 h (the return to the furnace and the heating are carried out for three times in the embodiment, the holding time of 1130 ℃ is 0.5 h), and the section specification of the final hot-rolled coil is 500 multiplied by 4.0mm; the hot-rolled coil is uncoiled, is subjected to acid cleaning and then is subjected to cold rolling at room temperature, the deformation amount of each annealing is 20-50% (40-50% in the embodiment), and the annealing is performed by adopting 980-1030 ℃ (1000 ℃ in the embodiment) and maintaining the temperature for 15-60 min (30 min in the embodiment) for stress relief annealing, so that the cold-rolled sheet with the thickness of 1-1.5 mm (1 mm in the embodiment) is obtained.
3. The cold-rolled sheet is cold-rolled at room temperature by a twenty-roller cold rolling mill with the roller surface roughness Ra of less than or equal to 0.2 mu m to obtain a finish-rolled sheet with the thickness of 0.45-0.55 mm (0.55 mm in the embodiment).
4. And carrying out solution treatment on the finish-rolled plate, wherein the solution treatment of the plate is carried out in a gas protection furnace, and the gas medium is argon. Controlling the solution treatment temperature to 1050-1150 ℃ (1100 ℃ in the embodiment), keeping the temperature for 20-60 min (40 min in the embodiment), and air-cooling; taking the plate subjected to the solution treatment, cutting a metallographic sample perpendicular to the rolling direction of the plate, preparing the sample according to a standard metallographic test method, and evaluating the grain size according to the regulation of GB/T9394 Metal average grain size determination method, wherein the evaluation result shows that the average grain size of the alloy plate is 8 grades; the plate subjected to the solution treatment is subjected to cold rolling with the deformation amount of 3-7% (5% in the embodiment), the thickness of the final plate is 0.50mm, then annealing heat treatment is carried out for 5-10 min (8 min in the embodiment) at 1020-1050 ℃ (1020 ℃ in the embodiment), and annealing treatment is carried out by adopting a gas protection gas quenching heat treatment furnace, wherein the gas medium is argon.
5. The finish-rolled sheet after annealing treatment is flattened by a twenty-high cold rolling mill with the roller surface roughness Ra of less than or equal to 0.2 mu m (Ra =0.1 mu m in the embodiment), and the reduction rate is 0.5-1% (0.5% in the embodiment); and then cutting to length.
6. Taking the plate cut to length in the step 5, and processing the plate into a membrane (phi 411mm in the embodiment) with the diameter not less than 200mm by methods such as laser cutting and the like; the flatness of the membrane is detected to be not more than 0.04mm (0.03 mm in the embodiment).
7. Taking the hot rolled plate in the step 2, cutting out a metallographic sample along the longitudinal section in the rolling direction, preparing the sample according to a standard metallographic test method, and evaluating inclusions according to GB/T10561 microscopic evaluation method for nonmetallic inclusions in steel, wherein the result is shown in Table 2.
8. Taking the membrane subjected to annealing treatment in the step 4, processing a sample with a corresponding specification, performing EBSD analysis on the membrane alloy crystal boundary, and displaying the result to show sigma 3 in the membrane alloy n The special grain boundary proportion is 62.3 percent, the sigma is less than or equal to 29, the grain boundary proportion is 65.5 percent, the EBSD structure of the diaphragm alloy is shown in figure 2a, and the statistical result of the special grain boundary proportion is shown in figure 2b.
9. And (4) processing the annealed membrane in the step (4) into a plate-shaped tensile sample, and detecting the mechanical property at room temperature according to GB/T228.1 part 1 room temperature test method of metal material tensile test, wherein the result is shown in Table 3.
10. And (4) processing the annealed membrane in the step (4) into a tensile sample, and detecting the mechanical property at 200 ℃ according to GB/T4338 'Metal material high temperature tensile test method', wherein the result is shown in Table 4.
11. And (4) taking the annealed membrane processed tensile sample in the step (4), then carrying out hydrogen charging treatment at 300 ℃ and 10MPa for 72h with high-purity hydrogen (the volume purity is more than or equal to 99.999%), and carrying out mechanical property detection according to GB/T228.1, wherein the results are shown in Table 5.
12. And (4) taking the diaphragm processed fatigue sample subjected to annealing treatment in the step (4), and carrying out fatigue performance test by referring to GB/T3075-2008 'metal material fatigue test axial force control method' and GB/T24176-2009 'metal material fatigue test data statistical scheme and analysis method', wherein the result shows that the fatigue limit of the diaphragm processed fatigue sample under the confidence coefficient of 50% is 245MPa.
13. Taking the diaphragm with the scratches after the laser cutting in the step 6, and carrying out surface grinding treatment on the diaphragm by adopting an abrasive belt of 800-1200 meshes; the surface roughness Ra of the membrane is less than or equal to 0.2 μm (Ra =0.16 μm in the embodiment).
Table 1 chemical composition, mass fraction of the film alloy%
| Element(s) | C | S | N | Cr | Mo | Fe | Al | Ti | Mn | P | Si | Ni |
| Content (wt.) | 0.020 | 0.001 | 0.002 | 22.5 | 9.0 | 13.5 | 0.02 | 0.01 | 0.020 | 0.003 | 0.021 | Balance of |
TABLE 2 non-metallic inclusions of the film alloys
TABLE 3 mechanical Properties at Room temperature of the membranes
| Number of | Rp 0.2 /MPa | R m /MPa | A/％ |
| 1 | 397 | 740 | 60 |
| 2 | 395 | 737 | 54.5 |
| 3 | 383 | 725 | 59.5 |
TABLE 4 high-temp. mechanical properties of membrane at 200 deg.C
| Number of | Rp 0.2 /MPa | R m /MPa | A/％ |
| 1 | 300 | 648 | 60 |
| 2 | 303 | 647 | 60 |
| 3 | 305 | 646 | 59.5 |
TABLE 5 mechanical properties at room temperature of membranes after saturated hydrogen charge
| Numbering | Rp 0.2 /MPa | R m /MPa | A/％ |
| 1 | 371 | 731 | 52.5 |
| 2 | 370 | 731 | 53.5 |
| 3 | 363 | 730 | 53.5 |
Experimental results show that the prepared MP-4 membrane with the specification of phi 411mm multiplied by 0.5mm has the surface roughness Ra of less than or equal to 0.2 mu m and the planeness of less than or equal to 0.04mm; only 0.5-grade D-type nonmetallic inclusion exists in the membrane; sigma 3 in diaphragm alloy n The proportion of special crystal boundary is higher than 62.0 percent, and the proportion of sigma is not more than 29 crystal boundary is higher than 65.0 percent; the mechanical property of the membrane at room temperature is as follows: yield strength (Rp) 0.2 ) Higher than 380MPa, tensile strength (Rm) higher than 720MPa, and elongation higher than 54%; the mechanical properties of the membrane at 200 ℃ are as follows: yield strength (Rp) 0.2 ) Higher than 300MPa and high tensile strengthThe degree (Rm) is higher than 640MPa, and the elongation is higher than 59%; the yield strength (Rp) after being placed in a high-purity hydrogen environment at 300 ℃ and 10MPa for 72 hours 0.2 ) Higher than 360MPa, tensile strength (Rm) higher than 730MPa, and elongation higher than 52%; the fatigue limit of the diaphragm at 50% confidence is higher than 245MPa.
Example 2: MP-4 diaphragm with specification of phi 375mm multiplied by 0.5mm
The difference from example 1 is that the film sheet prepared has a size of phi 375mm x 0.5mm.
The alloy is smelted on a 500Kg vacuum induction furnace by adopting a CaO crucible, and the electrolytic nickel, the metallic chromium, the metallic molybdenum and the metallic iron are used as raw materials to smelt the alloy. In the smelting process, firstly refining at 1530 ℃ for 10 minutes, then adding a calcareous desulfurizer for refining for 10 minutes, carrying out decarburization and desulfurization treatment by utilizing the thermal stability of a CaO crucible and the desulfurizer, and casting an ingot at 1500 ℃. And carrying out electroslag remelting on the cast ingot, wherein the specification of the remelted ingot is phi 290mm, and the chemical components are shown in Table 6. Keeping the temperature at 1150 ℃ for 5h, then forging the alloy, wherein the cogging forging temperature is 1150 ℃, the finish forging temperature is 960 ℃, returning to the furnace and reheating twice before forging to the final specification, the reheating temperature is 1150 ℃, the heat preservation time is 1h, and the section specification of the forged slab is 400 multiplied by 70mm. And (3) after the heat preservation time is 2 hours at 1130 ℃, rolling, wherein the cogging rolling temperature is 1130 ℃, the finishing rolling temperature is 920 ℃, returning and reheating for three times before rolling to the final specification, the reheating temperature is 1130 ℃, the heat preservation time is 0.5 hour, and the final hot rolled plate section specification is 500 multiplied by 5.0mm. The cold-rolled plate with the thickness of 1mm is prepared by multi-pass cold rolling and annealing of stress relief annealing heat treatment with the deformation of 40-50% +1000 ℃ for 30 min; then, cold rolling at room temperature by adopting a twenty-roller cold rolling mill with the roller surface roughness Ra =0.1 μm to prepare a finish rolling plate with the thickness of 0.53 mm; carrying out solution treatment of keeping the temperature of the finish-rolled plate at 1000 ℃ for 30min for air cooling (the solution treatment of the plate is carried out in a gas protection furnace, the gas medium is argon), and then carrying out cold rolling for 5% to obtain a plate with the thickness of 0.50 mm; then, carrying out annealing heat treatment on the plate at 1030 ℃ for 7min, and carrying out annealing treatment by adopting a gas protection gas quenching heat treatment furnace, wherein the gas medium is argon; the plate is processed into a diaphragm with the diameter of phi 375mm by laser cutting, and the diaphragm will have a surfaceThe scratched film was subjected to surface grinding treatment, and the film had a surface roughness Ra =0.18 μm and a flatness of 0.03mm. Sigma 3 in diaphragm alloy n The special crystal boundary proportion is 63.2 percent, the Sigma is not more than 29, the crystal boundary proportion is 66.7 percent, the evaluation result of the nonmetallic inclusion is shown in Table 7, the room-temperature mechanical property is shown in Table 8, the high-temperature mechanical property at 200 ℃ is shown in Table 9, the mechanical property at 300 ℃ and 10MPa is shown in the high-purity hydrogen (the volume purity is not less than 99.999 percent), and the mechanical property after 72-hour hydrogen charging treatment is shown in Table 10. The fatigue performance test is carried out by referring to GB/T3075-2008 'metal material fatigue test axial force control method' and GB/T24176-2009 'metal material fatigue test data statistical scheme and analysis method', and the result shows that the fatigue limit of the diaphragm at the confidence of 50% is 243MPa.
TABLE 6 chemical composition, mass fraction of the membrane alloys%
| Element(s) | C | S | N | Cr | Mo | Fe | Al | Ti | Mn | P | Si | Ni |
| Content (c) of | 0.022 | 0.001 | 0.002 | 22.4 | 8.8 | 13.7 | 0.043 | 0.01 | 0.022 | 0.004 | 0.026 | Allowance of |
TABLE 7 non-metallic inclusions of film alloys
TABLE 8 Room temperature mechanical Properties of the films
| Numbering | Rp 0.2 /MPa | R m /MPa | A/％ |
| 1 | 397 | 743 | 57.0 |
| 2 | 394 | 739 | 56.5 |
| 3 | 390 | 735 | 58.0 |
TABLE 9 high-temp. 200 deg.C mechanical properties of membrane
| Number of | Rp 0.2 /MPa | R m /MPa | A/％ |
| 1 | 320 | 670 | 58.5 |
| 2 | 317 | 664 | 59.0 |
| 3 | 313 | 660 | 59.0 |
TABLE 10 mechanical properties at room temperature of membrane after saturated hydrogen filling
| Number of | Rp 0.2 /MPa | R m /MPa | A/％ |
| 1 | 370 | 730 | 53.0 |
| 2 | 365 | 728 | 52.0 |
| 3 | 368 | 731 | 51.5 |
Experimental results show that the prepared MP-4 membrane with the specification of phi 375mm multiplied by 0.5mm has the surface roughness Ra of less than or equal to 0.2 mu m and the planeness of less than or equal to 0.06mm; only 0.5-grade D-type nonmetallic inclusion exists in the membrane; sigma 3 in diaphragm alloy n The proportion of special crystal boundary is higher than 63.0 percent, and the proportion of sigma is not more than 29 crystal boundary is higher than 66.0 percent; the mechanical property of the membrane at room temperature is as follows: yield strength (Rp) 0.2 ) More than 390MPa, tensile strength (Rm) more than 735MPa, and elongation more than 56%; the mechanical properties of the membrane at 200 ℃ are as follows: yield strength (Rp) 0.2 ) Higher than 310MPa, tensile strength (Rm) higher than 660MPa and elongation higher than 58%; the yield strength (Rp) after being placed in a high-purity hydrogen environment at 300 ℃ and 10MPa for 72 hours 0.2 ) More than 365MPa, tensile strength (Rm) more than 725MPa, and elongation more than 51%; the fatigue limit at 50% confidence for the diaphragm is above 240MPa.
Claims (10)
1. The high-strength hydrogen embrittlement-resistant diaphragm with the mark of MP-4 is characterized in that the thickness of the diaphragm is 0.45-0.55 mm, the diameter is not less than 200mm, the surface roughness Ra is not more than 0.2 mu m, and the planeness is not more than 0.04mm; the main component range of the membrane is as follows according to the weight percentage:
cr:21.00 to 23.00, mo: 8.00-10.00, fe:10.00 to 15.00, ni and unavoidable residual elements: the balance; the inevitable residual elements include: the aluminum content is controlled to be less than or equal to 0.050, the titanium content is controlled to be less than or equal to 0.030, the manganese content is controlled to be less than or equal to 0.030, the carbon content is controlled to be less than or equal to 0.030, the sulfur content is controlled to be less than or equal to 0.001, the phosphorus content is controlled to be less than or equal to 0.005, the silicon content is controlled to be less than or equal to 0.030, and the nitrogen content is controlled to be less than or equal to 0.010.
2. A high strength hydrogen embrittlement resistant membrane of grade MP-4 as claimed in claim 1, wherein ∑ 3 in the membrane alloy n The proportion of grain boundary is not less than 60%, n =1,2 or 3, and the proportion of sigma is not more than 29, and is not less than 65%.
3. The high strength hydrogen embrittlement resistant membrane of claim 1, grade MP-4, wherein the mechanical properties at room temperature of the membrane are: yield strength (Rp0.2) is not less than 350MPa, tensile strength (Rm) is not less than 700MPa, and elongation (A) is not less than 35%.
4. The high strength hydrogen embrittlement resistant membrane of claim 1, grade MP-4, wherein the mechanical properties at 200 ℃ meet: yield strength (Rp0.2) is not less than 300MPa, tensile strength (Rm) is not less than 650MPa, and elongation (A) is not less than 35%.
5. The MP-4 high-strength hydrogen embrittlement-resistant membrane as claimed in claim 1, wherein the membrane has room temperature mechanical properties satisfying the following conditions after hydrogen charging treatment at 300 ℃, 10MPa, high-purity hydrogen (volume purity is greater than or equal to 99.999%) for 72 h: yield strength (Rp0.2) is not less than 350MPa, tensile strength (Rm) is not less than 700MPa, and elongation (A) is not less than 25%.
6. A high strength hydrogen embrittlement resistant membrane of MP-4 designation as claimed in claim 1, wherein the membrane has a fatigue limit at 50% confidence of not less than 230MPa.
7. A preparation method of the high-strength hydrogen embrittlement-resistant membrane with the mark of MP-4 as claimed in any one of claims 1 to 6, is characterized in that the preparation method of the membrane comprises the following specific steps:
(1) Preparing a cast ingot: carrying out vacuum induction melting and electroslag remelting on electrolytic nickel, metallic chromium, metallic molybdenum and metallic iron serving as raw materials to obtain a cast ingot;
(2) Preparing a strip blank: the cogging and forging temperature of the cast ingot is 1150-1170 ℃, the cast ingot is allowed to return to the furnace and heated again before being forged to the final specification, the temperature is kept at 1150-1170 ℃ for 1-4 h, and the final forging temperature is not lower than 950 ℃ to obtain a forging blank; the forging stock is subjected to hot rolling after being kept at 1130-1150 ℃ for 2-4 h, the cogging rolling temperature is 1100-1150 ℃, the forging stock is allowed to return to a furnace for reheating before being rolled to the final specification, the forging stock is kept at 1100-1150 ℃ for 0.5-3 h, and the final rolling temperature is not lower than 900 ℃ to obtain a hot rolled coil with the thickness of 4-6 mm; uncoiling a hot-rolled coil, pickling, cold-rolling at room temperature, and performing stress relief annealing at 980-1030 ℃ for 15-60 min to obtain a strip blank with the thickness of 1-1.5 mm, wherein the deformation amount of the hot-rolled coil during each annealing is 20-50%;
(3) Finish rolling by a twenty-high roll mill: carrying out finish rolling on the cold-rolled strip blank by adopting a twenty-roller cold rolling unit with the roller surface roughness Ra of less than or equal to 0.2 mu m to obtain a finish-rolled plate with the thickness of 0.45-0.55 mm;
(4) Regulating and controlling a grain boundary: controlling the solution treatment temperature of the finish-rolled plate at 1050-1150 ℃, keeping the temperature for 20-60 min, and air cooling to ensure that the grain size is not lower than 7 grade; performing small-deformation cold rolling on the plate, wherein the deformation of the plate in the cold rolling process is 3-7%, and performing annealing heat treatment on the plate subjected to small deformation at the temperature of 1020-1050 ℃ for 5-10 min;
(5) Leveling and sizing: the flattening pressing rate is 0.5-1.0%;
(6) Cutting and processing the membrane;
(7) And (5) surface treatment of the membrane.
8. The method for preparing a high-strength hydrogen embrittlement-resistant membrane under the designation MP-4 as claimed in claim 7, wherein in the step (4), the solution treatment of the sheet is performed in a gas protection furnace, and the gas medium is argon gas or reducing gas.
9. The method for preparing a high-strength hydrogen-embrittlement-resistant membrane with the designation of MP-4 according to claim 7, wherein in the step (4), annealing treatment is performed by using a vacuum or gas-shielded gas quenching heat treatment furnace, and a gas medium is argon or a reducing gas.
10. The method for preparing the high-strength hydrogen embrittlement-resistant membrane with the MP-4 mark as claimed in claim 7, wherein the nonmetallic inclusion in the membrane after the surface treatment in the step (7) meets the following requirements: the thin line (m), A is less than or equal to 0.5 grade, B is less than or equal to 0.5 grade, D is less than or equal to 1.0 grade, and the sum of the three grades is less than or equal to 1.5 grade; coarse system (m), A is less than or equal to 0.5 grade, B is less than or equal to 0.5 grade, D is less than or equal to 0.5 grade, and the sum of the three grades is less than or equal to 1.5 grade; wherein A is sulfide, B is alumina, D is spherical oxide, and the sum of the three types is A + B + D.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211321096.2A CN115747575B (en) | 2022-10-26 | 2022-10-26 | High-strength hydrogen-embrittlement-resistant membrane with MP-4 brand and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211321096.2A CN115747575B (en) | 2022-10-26 | 2022-10-26 | High-strength hydrogen-embrittlement-resistant membrane with MP-4 brand and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115747575A true CN115747575A (en) | 2023-03-07 |
| CN115747575B CN115747575B (en) | 2023-11-10 |
Family
ID=85353448
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211321096.2A Active CN115747575B (en) | 2022-10-26 | 2022-10-26 | High-strength hydrogen-embrittlement-resistant membrane with MP-4 brand and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115747575B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3957534A (en) * | 1973-02-17 | 1976-05-18 | Firma Deutsche Automobilgesellschaft Mbh | Diaphragm for the separation of hydrogen from hydrogen-containing gaseous mixtures |
| US4245698A (en) * | 1978-03-01 | 1981-01-20 | Exxon Research & Engineering Co. | Superalloys having improved resistance to hydrogen embrittlement and methods of producing and using the same |
| JPH073368A (en) * | 1993-04-21 | 1995-01-06 | Sumitomo Metal Ind Ltd | High ni base alloy excellent in hydrogen embrittlement resistance and production thereof |
| US20080160354A1 (en) * | 2006-12-27 | 2008-07-03 | Weilong Zhang | Metal alloy bipolar plates for fuel cell |
| CN114086031A (en) * | 2021-10-20 | 2022-02-25 | 中国科学院金属研究所 | Preparation method of fatigue-resistant and hydrogen-brittleness-resistant plate for high-pressure hydrogen compressor diaphragm |
| CN114134367A (en) * | 2021-10-20 | 2022-03-04 | 中国科学院金属研究所 | High-strength hydrogen embrittlement-resistant membrane with MP-5 mark and preparation method thereof |
| CN114540732A (en) * | 2022-02-24 | 2022-05-27 | 上海电机学院 | Method for synergistically obtaining low sigma grain boundaries and saw-tooth grain boundaries |
-
2022
- 2022-10-26 CN CN202211321096.2A patent/CN115747575B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3957534A (en) * | 1973-02-17 | 1976-05-18 | Firma Deutsche Automobilgesellschaft Mbh | Diaphragm for the separation of hydrogen from hydrogen-containing gaseous mixtures |
| US4245698A (en) * | 1978-03-01 | 1981-01-20 | Exxon Research & Engineering Co. | Superalloys having improved resistance to hydrogen embrittlement and methods of producing and using the same |
| JPH073368A (en) * | 1993-04-21 | 1995-01-06 | Sumitomo Metal Ind Ltd | High ni base alloy excellent in hydrogen embrittlement resistance and production thereof |
| US20080160354A1 (en) * | 2006-12-27 | 2008-07-03 | Weilong Zhang | Metal alloy bipolar plates for fuel cell |
| CN114086031A (en) * | 2021-10-20 | 2022-02-25 | 中国科学院金属研究所 | Preparation method of fatigue-resistant and hydrogen-brittleness-resistant plate for high-pressure hydrogen compressor diaphragm |
| CN114134367A (en) * | 2021-10-20 | 2022-03-04 | 中国科学院金属研究所 | High-strength hydrogen embrittlement-resistant membrane with MP-5 mark and preparation method thereof |
| CN114540732A (en) * | 2022-02-24 | 2022-05-27 | 上海电机学院 | Method for synergistically obtaining low sigma grain boundaries and saw-tooth grain boundaries |
Non-Patent Citations (1)
| Title |
|---|
| AU, M (AU, M) ; WANG, QD (WANG, QD): "RARE-EARTH NICKEL-ALLOY FOR HYDROGEN COMPRESSION", JOURNAL OF ALLOYS AND COMPOUNDS, pages 115 - 119 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115747575B (en) | 2023-11-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP4089197A1 (en) | Chain steel for use in mine and manufacturing method therefor | |
| EP2554699B1 (en) | Steel sheet with high tensile strength and superior ductility and method for producing same | |
| EP3467136B1 (en) | Large-thickness q960e ultra-high strength steel production method | |
| TWI658145B (en) | Carburizing steel sheet and manufacturing method of carburizing steel sheet | |
| EP2333130A1 (en) | Heat resistant titanium alloy sheet excellent in cold workability and a method of production of the same | |
| EP2799578A1 (en) | High-strength hot-rolled steel sheet and manufacturing method therefor | |
| WO2023087833A1 (en) | High-strength steel with good weather resistance and manufacturing method therefor | |
| JP6093210B2 (en) | Heat-resistant ferritic stainless steel sheet with excellent low-temperature toughness and method for producing the same | |
| CN114086031B (en) | Preparation method of fatigue-resistant and hydrogen-brittleness-resistant plate for high-pressure hydrogen compressor diaphragm | |
| CN112375949A (en) | Heat treatment process of high-strength 7-series aluminum alloy sheet for vehicle body | |
| CN112941414A (en) | High-strength and high-toughness stainless steel for clockwork spring and preparation method thereof | |
| EP3623487A1 (en) | Titanium sheet | |
| CN110306103A (en) | A kind of 555MPa grades of anti-H2S corrodes oil pipe steel band and preparation method thereof | |
| CN114134367B (en) | High-strength hydrogen embrittlement-resistant membrane with MP-5 mark and preparation method thereof | |
| CN114040990B (en) | Austenitic stainless steel having improved strength and method for manufacturing the same | |
| JP4471688B2 (en) | High strength low specific gravity steel plate excellent in ductility and method for producing the same | |
| CN114032476B (en) | Preparation method of high-strength hydrogen embrittlement-resistant plate for 90MPa hydrogen compressor diaphragm | |
| CN112281064A (en) | Low-alloy high-strength steel plate forging for high-strength structure and forging method | |
| CN109047692B (en) | Ultrathin high-strength steel plate capable of being used at-60 ℃ and manufacturing method thereof | |
| CN116555672A (en) | High-strength and high-toughness medium manganese steel plate and preparation method thereof | |
| CN115747575B (en) | High-strength hydrogen-embrittlement-resistant membrane with MP-4 brand and preparation method thereof | |
| CN115747576B (en) | Preparation method of hydrogen embrittlement-resistant fatigue-resistant plate for hydrogen-contacting membrane of high-pressure hydrogen compressor | |
| CN112501504B (en) | BCA 2-grade container ship crack arrest steel plate and manufacturing method thereof | |
| WO2021132634A1 (en) | Alloy | |
| CN112739842B (en) | Ferrite-based stainless steel having excellent workability and high temperature strength and method for manufacturing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |