CN114134367B - High-strength hydrogen embrittlement-resistant membrane with MP-5 mark and preparation method thereof - Google Patents

High-strength hydrogen embrittlement-resistant membrane with MP-5 mark and preparation method thereof Download PDF

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CN114134367B
CN114134367B CN202111223294.0A CN202111223294A CN114134367B CN 114134367 B CN114134367 B CN 114134367B CN 202111223294 A CN202111223294 A CN 202111223294A CN 114134367 B CN114134367 B CN 114134367B
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CN114134367A (en
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赵明久
刘家兴
姜海昌
戎利建
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Institute of Metal Research of CAS
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/055—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 20% but less than 30%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/16—Remelting metals
    • C22B9/18—Electroslag remelting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C22C1/023—Alloys based on nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F04—POSITIVE - DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS FOR LIQUIDS OR ELASTIC FLUIDS
    • F04B—POSITIVE-DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS
    • F04B45/00—Pumps or pumping installations having flexible working members and specially adapted for elastic fluids
    • F04B45/04—Pumps or pumping installations having flexible working members and specially adapted for elastic fluids having plate-like flexible members, e.g. diaphragms
    • 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

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Abstract

The invention relates to the field of key material components of hydrogen energy equipment, in particular to a high-strength hydrogen embrittlement-resistant membrane with the trade mark of MP-5 and a preparation method thereof. The invention is based on a nickel-chromium-molybdenum alloy system, utilizes niobium element solid solution strengthening and grain boundary regulation to ensure the strength and hydrogen embrittlement resistance of a diaphragm, and prepares the diaphragm by a method of vacuum or non-vacuum induction melting → steel die casting → electroslag remelting → forging → hot rolling → cold rolling → solid solution treatment → small deformation cold rolling → cutting processing sizing → finished product heat treatment → diaphragm surface treatment, wherein the thickness of the diaphragm is 0.4-0.6 mm, the diameter is not less than 200mm, the surface roughness Ra is not more than 0.4 μm, the planeness is not more than 0.06mm, the yield strength at room temperature and 250 ℃ can respectively reach more than 400MPa and 350MPa, and the diaphragm has good plasticity, hydrogen embrittlement resistance and fatigue resistance, and can be used as a hydrogen side diaphragm in a hydrogen diaphragm compressor with the higher level of 45MPa, particularly 90MPa or higher pressure level.

Description

High-strength hydrogen embrittlement-resistant membrane with MP-5 mark and preparation method thereof
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 trade mark of MP-5 and a preparation method thereof.
Background
Hydrogen energy is one of the most economical and effective alternative energy sources which can be used for people to get rid of the dependence of three major energy sources, and is known as the most potential clean energy source in the 21 st century. Most of hydrogenation stations built in future of China are hydrogenation stations with 70MPa level or higher, which puts higher requirements on key equipment and parts of the hydrogenation stations. The high-pressure hydrogen diaphragm compressor (hereinafter referred to as a hydrogen compressor) is indispensable key equipment in the hydrogen station, and the stability, reliability and use efficiency of the high-pressure hydrogen diaphragm compressor are crucial to the whole hydrogen station. The diaphragm is a key part in the hydrogen compressor, not only plays a role in isolating lubricating oil and compressing hydrogen, but also reciprocates under the action of pressure transferred by hydraulic oil, thereby achieving the purpose of pressurization. The diaphragm of the hydrogen compressor is generally of a three-layer structure, and it is pointed out that the diaphragm on the hydrogen side is a part which is easy to wear in the service process of the hydrogen compressor, and the development of a fatigue-resistant and hydrogen-brittleness-resistant diaphragm material is a main difficulty in developing a high-performance hydrogen compressor. At present, 316L austenitic stainless steel is widely used for a diaphragm on the hydrogen facing side of a hydrogen compressor (the design pressure is 35 MPa) of a 30MPa exemplary hydrogen filling station. 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 316L membrane on the hydrogen side is remarkably reduced (even less than 1/5-1/10 of the service life of the 35MPa hydrogenation machine membrane), and when the service hydrogen pressure is further increased to 90MPa (the design pressure of the hydrogen compressor for the 70MPa hydrogenation station is 90 MPa), the service life of the 316L membrane is lower. The reason for this is that the high temperature strength and fatigue resistance of 316L alloy in high hydrogen pressure environment limit its service life.
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-5 and a preparation method thereof, so as to meet the urgent requirements of a hydrogen compressor with the pressure level of more than 45MPa, particularly 90MPa or higher 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-5 has the thickness of 0.4-0.6 mm, the diameter of not less than 200mm, the surface roughness Ra of not more than 0.4 mu m and the planeness of not more than 0.06mm; the main component range of the membrane is as follows according to the weight percentage:
cr:22.00 to 25.00, mo:5.00 to 8.00, nb:2.50 to 3.00, 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 copper content is controlled to be less than or equal to 0.030, the iron content is controlled to be less than or equal to 0.100, 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, and the silicon content is controlled to be less than or equal to 0.030.
The high-strength hydrogen embrittlement-resistant membrane with the mark of MP-5 is sigma 3 in the membrane alloy n Grain boundary ratio is not less than 55%, n =1,2 or3, the proportion of sigma is less than or equal to 29 crystal boundary is not less than 60 percent.
The high-strength hydrogen embrittlement-resistant membrane with the mark of MP-5 has room temperature mechanical properties meeting the following requirements: the yield strength (Rp0.2) is not less than 425MPa, the tensile strength (Rm) is not less than 825MPa, and the elongation (A) is not less than 40%.
The high-strength hydrogen embrittlement-resistant diaphragm with the mark of MP-5 has the mechanical properties at the high temperature of 200 ℃ 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%.
After the high-strength hydrogen embrittlement-resistant membrane with the mark of MP-5 is subjected to hydrogen charging 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 membrane meets the following requirements: yield strength (Rp0.2) is not less than 400MPa, tensile strength (Rm) is not less than 750MPa, and elongation (A) is not less than 35%.
The high-strength hydrogen embrittlement-resistant membrane with the mark of MP-5 has the fatigue limit of not less than 250MPa at the confidence coefficient of 50%.
The preparation method of the high-strength hydrogen embrittlement-resistant membrane with the mark of MP-5 comprises the following specific steps:
(1) Carrying out vacuum induction melting by using electrolytic nickel, metal chromium, metal molybdenum and metal niobium as raw materials;
(2) Electroslag remelting;
(3) Alloy forging; the cogging forging temperature is 1050-1150 ℃, and the finish forging temperature is 930-1030 ℃ to obtain a forging stock; allowing the steel to return to the furnace and heating again before forging to the final specification, and preserving the heat for 1-4 h at 1050-1150 ℃;
(4) Hot rolling the alloy; the forging stock is subjected to hot rolling after being subjected to heat preservation for 2 to 4 hours at 1050 to 1150 ℃, the cogging rolling temperature is 1050 to 1150 ℃, and the finish rolling temperature is 880 to 930 ℃, so that a hot rolled plate with the thickness of 4 to 6mm is obtained; allowing the steel to return to the furnace and heating again before the steel is rolled to the final specification, and preserving the heat for 0.5 to 3 hours at the temperature of 1050 to 1150 ℃;
(5) Cold rolling or finish rolling the alloy; cold rolling at room temperature to produce 30-70% of deformation in each annealing, and performing stress relief annealing at 1020-1060 ℃ for 15-60 min to obtain a cold-rolled sheet with the thickness of 0.4-0.6 mm, wherein the grain size of the cold-rolled sheet is not lower than 6 grade;
(6) Carrying out solution treatment on the plate; controlling the temperature of the plate solution treatment at 1020-1120 ℃, keeping the temperature for 20-60 min, and cooling in air;
(7) Cold rolling the plate with small deformation; the cold rolling deformation of the plate is 8-12%;
(8) Cutting and processing the membrane;
(9) Final heat treatment of the diaphragm;
(10) And (5) surface treatment of the membrane.
In the preparation method of the high-strength hydrogen embrittlement-resistant membrane with the mark of MP-5, in the step (6), the plate is subjected to solution treatment in a gas protection heat treatment 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-5 comprises the following steps in the step (9): and (3) carrying out annealing treatment by adopting a vacuum or gas protection gas quenching heat treatment furnace at 1020-1060 ℃ for 0.5-1 h.
According to the preparation method of the high-strength hydrogen embrittlement-resistant membrane with the MP-5 mark, the nonmetallic inclusion in the membrane after the surface treatment in the step (10) 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 1.0 grade, D is less than or equal to 2.0 grade, and the sum of the three grades is less than or equal to 2.5 grade; coarse system (m), A is less than or equal to 0.5 grade, B is less than or equal to 1.0 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; wherein A is sulfide, B is alumina, D is spherical oxide, and the sum of the three types 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 alloy strength is improved by adding a proper amount of Nb element on the basis of a Ni-Cr-Mo alloy system so as to obtain higher room-temperature and 250-DEG C high-temperature strength, wherein the room-temperature yield strength (Rp0.2) of the MP-5 alloy can reach more than 425MPa, the 200-DEG C yield strength (Rp0.2) can reach 350MPa, and meanwhile, the alloy has good plasticity (the room-temperature and 250-DEG C elongation rates are respectively higher than 40% and 30%). 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) coincidence position lattice grain boundary) proportion, remarkably improves the resistance of the membrane alloy to hydrogen-induced crack initiation and propagation along the grain boundary, thereby obtaining the excellent hydrogen resistance of the membraneBrittleness resistance. In addition, the method for regulating and controlling the non-metallic inclusion level and the grain boundary is prepared by remelting and smelting the electric slag through vacuum induction, 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.
The invention has the advantages and beneficial effects that:
1. the high-strength hydrogen embrittlement-resistant membrane with the trademark of MP-5 has the advantages of low content of carbon, sulfur and phosphorus impurity elements and non-metallic inclusions, high proportion of lattice grain boundaries at low sigma coincidence positions, excellent room temperature (nearly one time higher than 316L) and 250 ℃ high-temperature strength (nearly 3 times higher than 316L), excellent hydrogen embrittlement resistance, and capability of being used under complex and harsh working conditions of hydrogen presses with the pressure level of more than 45MPa, particularly 90MPa or higher.
2. The diameter of the diaphragm is not less than 200mm, the surface roughness Ra is not more than 0.4 mu m, and the planeness is not more than 0.06mm.
3. Sigma 3 of the inventive diaphragm n The proportion of the special crystal boundary is not less than 55 percent, and the proportion of the sigma is not more than 29 crystal boundary is not less than 60 percent.
4. The room temperature mechanical property of the diaphragm of the invention meets the following requirements: yield strength (Rp0.2) is not less than 350MPa, tensile strength (Rm) is not less than 650MPa, and elongation (A) is not less than 50%.
5. The high-temperature mechanical property of the membrane at 200 ℃ meets the following requirements: yield strength (Rp0.2) is not less than 240MPa, tensile strength (Rm) is not less than 560MPa, and elongation (A) is not less than 40%.
6. The mechanical property of the membrane at room temperature after hydrogen charging treatment at 300 ℃, 10MPa, high-purity hydrogen (volume purity is more than or equal to 99.999%) for 72h meets the following requirements: the yield strength (Rp0.2) is not less than 350MPa, the tensile strength (Rm) is not less than 650MPa, the elongation (A) is not less than 50 percent, and the hydrogen pressure membrane has good plasticity, hydrogen embrittlement resistance and fatigue resistance and can be used as a hydrogen membrane in a 90MPa hydrogen press.
7. The fatigue limit of the diaphragm of the invention is not lower than 250MPa under the confidence coefficient of 50 percent.
Drawings
FIG. 1 shows a MP-5 membrane with a specification of phi 500mm x 0.5 mm.
FIG. 2 shows a MP-5 diaphragm of a size of phi 410mm by 0.5 mm.
FIG. 3 is an EBSD diagram of the grain boundary structure of the special plate.
FIG. 4 is a statistical result chart of special grain boundaries of the special plate; 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 Nb element solid solution strengthening and grain boundary regulation, and the diaphragm is prepared by a method of vacuum or non-vacuum induction melting → steel die casting → electroslag remelting → forging → hot rolling → cold rolling → solid solution treatment → small deformation cold rolling → cutting processing sizing → finished product heat treatment → diaphragm surface treatment, so that the high-strength hydrogen embrittlement resistant diaphragm (MP-5) with the diameter of not less than 200mm, the surface roughness Ra of not more than 0.4 mu m and the planeness of not more than 0.06mm is obtained.
The present invention will be described in further detail below with reference to examples.
Example 1 MP-5 Membrane with a specification of phi 500mm x 0.5mm
Smelting an alloy on 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 an ingot; the surface of the cast ingot is ground and then electroslag remelting is carried out, the remelted cast ingot is ground and then forged → hot rolling → cold rolling → plate solid solution → crystal boundary regulation treatment → sizing processing → heat treatment → surface treatment, and a membrane with the diameter of 500mm multiplied by 0.5mm is prepared, wherein the real object of the membrane is shown in a figure 1, the chemical components of the membrane are shown in a table 1, and the preparation process comprises the following steps:
1. the electrolytic nickel, metal chromium, metal molybdenum and metal niobium are used as raw materials, ni, cr, mo and Nb are put into a crucible before smelting, and the calcium desulfurizer is put into a hopper.
2. 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 1540 ℃ 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 ℃ (1520 ℃ in the embodiment).
3. And carrying out electroslag remelting on the cast ingot, wherein the remelting cast ingot specification is phi 220-360 mm (phi 350mm in the embodiment).
4. The electroslag cast ingot is subjected to alloy forging (the temperature is 1130 ℃ in the embodiment is 6 hours) after the temperature is kept at 1050-1150 ℃ for 4-12 hours, the cogging forging temperature is 1050-1150 ℃ (the temperature is 1130 ℃ in the embodiment), and the finish forging temperature is 850-950 ℃ (the finish forging temperature is 930 ℃ in the embodiment), so that a forging blank is obtained; and (3) returning to the furnace and reheating before forging to the final specification, keeping the temperature for 1-4 h at the heating temperature of 1050-1150 ℃ (the returning to the furnace and heating for four times in the embodiment, and keeping the temperature for 1.5h at 1130 ℃), wherein the section specification of the forged slab is 850 multiplied by 60mm.
5. The forged plate blank is rolled after being kept at 1050-1150 ℃ for 2-4 h (the keeping time is 2h at 1130 ℃ in the embodiment), the cogging rolling temperature is 1050-1150 ℃ (1130 ℃ in the embodiment), the finishing rolling temperature is 850-950 ℃ (930 ℃ in the embodiment), the forging plate blank is allowed to be returned to a furnace for reheating before being rolled to the final specification, the forging plate blank is kept at 1050-1150 ℃ for 0.5-3 h (the returning to the furnace is heated for three times in the embodiment, and the keeping time is 0.5h at 1130 ℃) so that the final hot rolled plate section specification is 850 multiplied by 4.0mm.
6. The hot rolled plate is cold rolled at room temperature, the deformation amount is 30-70% (40-50% in the embodiment) in each annealing, the stress relief annealing is carried out for 15-60 min (30 min in the embodiment) by adopting 1020-1060 ℃ (1030 ℃) in the middle, and the cold rolled plate with the thickness of 0.4-0.6 mm (0.55 mm in the embodiment) is obtained.
7. And (4) taking the cold-rolled sheet in the step (6), cutting a metallographic sample perpendicular to the rolling direction of the sheet, 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 sheet is 8.5 grades.
8. And (3) taking the cold-rolled sheet in the step (7), carrying out solution treatment, controlling the solution treatment temperature to be 1020-1120 ℃ (1030 ℃ in the embodiment), keeping the temperature for 20-60 min (40 min in the embodiment), and cooling in air.
9. Taking the plate subjected to the solution treatment in the step 8, and carrying out cold rolling with the deformation amount of 8-12% (10% in the embodiment), wherein the final thickness of the plate is 0.50mm.
10. And (4) taking the plate in the step (9), and processing the plate into a wafer (phi 500mm in the embodiment) with the diameter not less than 200mm by methods such as laser cutting and the like.
11. Taking the membrane in the step 10, and carrying out annealing treatment of 1000-1040 ℃ (1020 ℃ in the embodiment) for 0.5-1 h (1 h in the embodiment); the flatness of the diaphragm is detected to be not more than 0.06mm (0.05 mm in the embodiment).
12. And (3) taking the hot rolled plate in the step (5), 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.
13. Processing the membrane annealed in the step 11 into a sample with a corresponding specification, performing EBSD analysis on the membrane alloy crystal boundary, and displaying the result that sigma 3 in the membrane alloy n The proportion of the special grain boundary is 58.5 percent, the proportion of sigma is less than or equal to 29 grain boundary is 66.8 percent, the EBSD structure of the membrane alloy grain boundary is shown in figure 3, and the statistical result of the proportion of the special grain boundary is shown in figure 4.
14. And (3) processing the annealed membrane in the step (11) 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.
15. And (3) taking the membrane subjected to annealing treatment in the step (11), processing a tensile sample, and carrying out 250 ℃ mechanical property detection according to GB/T4338 'Metal material high temperature tensile test method', wherein the results are shown in Table 4.
16. And (3) taking the annealed membrane processed tensile sample in the step (11), 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.
17. Taking the fatigue sample processed by the diaphragm subjected to aging treatment in the step 11, and carrying out fatigue performance test by referring to GB/T3075-2008 'axial force control method for metal material fatigue test' and GB/T24176-2009 'statistical scheme and analysis method for metal material fatigue test data', wherein the result shows that the fatigue limit of the fatigue sample under 50% confidence coefficient is 266MPa.
18. And (3) performing surface grinding treatment on the membrane subjected to the aging treatment in the step (11), and detecting that the surface roughness Ra of the membrane is less than or equal to 0.4 μm (Ra =0.3 μm in the embodiment).
Table 1 chemical composition of the diaphragm alloy, mass fraction%
Element(s) C S Cr Mo Nb Fe Al Ti Ni
Content (c) of 0.025 0.001 24.3 6.7 2.3 0.05 0.04 0.03 Allowance of
TABLE 2 non-metallic inclusions of the film alloys
Figure BDA0003313410000000061
TABLE 3 mechanical Properties at Room temperature of the membranes
Number of Rp 0.2 /MPa R m /MPa A/％
1 465 928 55.5
2 461 926 56.0
3 463 921 56.0
TABLE 4 high-temp. 250 deg.C mechanical properties of membrane
Numbering Rp 0.2 /MPa R m /MPa A/％
1 429 871 51.0
2 431 873 52.0
3 433 878 51.5
TABLE 5 mechanical properties at room temperature of membranes after saturated hydrogen charge
Numbering Rp 0.2 /MPa R m /MPa A/％
1 460 924 52.0
2 455 918 51.0
3 458 925 52.0
The experimental result shows that the surface roughness Ra of the prepared MP-5 membrane with the specification of phi 500mm multiplied by 0.5mm is less than or equal to 0.4 mu m, and the planeness is not more than 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 58.0 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 ) Higher than 460MPa, tensile strength (Rm) higher than 920MPa, and elongation higher than 55%; the mechanical properties of the membrane at 250 ℃ are as follows: yield strength (Rp) 0.2 ) More than 430MPa, tensile strength (Rm) more than 870MPa, and elongation more than 50%; after being placed in a high-purity hydrogen environment at 300 ℃ and 10MPa for 72 hours, the yield strength (Rp) 0.2 ) Higher than 454MPa, tensile strength (Rm) higher than 915MPa, and elongation higher than 50%; the fatigue limit at 50% confidence of the diaphragm is higher than 265MPa.
Example 2: MP-5 diaphragm with specification of phi 410mm multiplied by 0.5mm
The difference from the example 1 is that the prepared film has the specification of phi 410mm multiplied by 0.5mm, and the physical diagram of the film is shown in figure 2.
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 niobium are used as raw materials to smelt the alloy. In the smelting process, firstly, refining is carried out for 10 minutes at 1550 ℃, then, a calcareous desulfurizer is added for refining for 10 minutes, the thermal stability of a CaO crucible and the desulfurizer are utilized for decarburization and desulfurization, and an ingot is cast at 1510 ℃. And carrying out electroslag remelting on the cast ingot, wherein the specification of the remelted ingot is phi 230mm, and the chemical components are shown in Table 6. Keeping the temperature at 1130 ℃ for 4h, then performing alloy forging, wherein the cogging forging temperature is 1130 ℃, the finish forging temperature is 930 ℃, returning and reheating twice before forging to the final specification, the reheating temperature is 1130 ℃, the keeping time is 1.5h, and the section specification of a forged plate blank is 820 multiplied by 60mm. Rolling is carried out after the heat preservation time of 1130 ℃ is 2h, the cogging rolling temperature is 1120 ℃, the finishing rolling temperature is 930 ℃, the steel is reheated for three times in a furnace before being rolled to the final specification, the reheating temperature is 1130 ℃, the heat preservation time is 0.5h, and the section specification of the final hot rolled plate is 820 multiplied by 4.0mm. The cold-rolled sheet with the thickness of 0.57mm is prepared by multi-pass cold rolling and annealing with stress relief annealing heat treatment of 40-50% of deformation and 30min of heat preservation at 1030 ℃, the cold-rolled sheet is subjected to solution treatment of heat preservation at 1020 ℃ for 40min of air cooling, and then is subjected to 10% cold rolling to obtain the sheet with the thickness of 0.53 mm. The method comprises the following steps of processing a plate into a wafer with the diameter of phi 410mm by laser cutting, and then carrying out annealing heat treatment on the plate at 980 ℃ for 1 h; and (3) performing surface grinding treatment on the annealed membrane, wherein the surface roughness Ra =0.3 μm and the flatness is 0.04mm. Sigma 3 in diaphragm alloy n The special crystal boundary proportion is 60.4 percent, the Sigma is less than or equal to 29, the crystal boundary proportion is 68.8 percent, the evaluation result of nonmetallic inclusions is shown in table 7, the room-temperature mechanical property is shown in table 8, the 250-DEG C high-temperature mechanical property is shown in table 9, the 300-DEG C high-temperature mechanical property is shown in table 10, the volume purity of high-purity hydrogen (the volume purity is more than or equal to 99.999 percent) and the mechanical property after 72-hour hydrogen charging treatment is shown in table 10. Reference GB/T3075-2008 ' metal material fatigue test axial force control method ' and GB/T24176-2009 ' metal material fatigue test data statistical scheme and analysis methodThe method carries out fatigue performance test, and the result shows that the fatigue limit of the diaphragm under 50% confidence coefficient is 262MPa.
TABLE 6 chemical composition, mass fraction of the membrane alloys%
Element(s) C S Cr Mo Nb Fe Al Ti Ni
Content (wt.) 0.026 0.001 24.2 6.9 2.4 0.05 0.04 0.03 Balance of
TABLE 7 non-metallic inclusions of the diaphragm alloys
Figure BDA0003313410000000081
TABLE 8 Room temperature mechanical Properties of the films
Number of Rp 0.2 /MPa R m /MPa A/％
1 459 916 57.0
2 463 923 56.0
3 460 920 56.5
TABLE 9 high-temp. 200 deg.C mechanical properties of the membrane
Numbering Rp 0.2 /MPa R m /MPa A/％
1 439 890 49.5
2 437 886 51.5
3 433 884 51.0
TABLE 10 mechanical properties at room temperature of membrane after saturated hydrogen filling
Number of Rp 0.2 /MPa R m /MPa A/％
1 466 925 53.0
2 463 926 52.0
3 464 922 51.5
The experimental result shows that the surface roughness Ra of the prepared MP-5 membrane with the specification of phi 410mm multiplied by 0.5mm is less than or equal to 0.4 mu m, and the planeness is not more than 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 60%, and the proportion of sigma is not more than 29, and is higher than 68%; the mechanical property of the membrane at room temperature is as follows: yield strength (Rp) 0.2 ) Higher than 458MPa, tensile strength (Rm) higher than 915MPa, and elongation higher than 55%; the mechanical properties of the membrane at 250 ℃ are as follows: yield strength (Rp) 0.2 ) Higher than 430MPa, tensile strength (Rm) higher than 883MPa, and elongation higher than 49%; after being placed in a high-purity hydrogen environment at 300 ℃ and 10MPa for 72 hours, the yield strength (Rp) 0.2 ) Higher than 462MPa, tensile strength (Rm) higher than 920MPa, and elongation higher than 51%; the fatigue limit of the diaphragm at 50% confidence is higher than 260MPa.

Claims (6)

1. A high-strength hydrogen embrittlement-resistant membrane with a trademark of MP-5 is characterized in that the thickness of the membrane is 0.4 to 0.6mm, the diameter is not less than 200mm, the surface roughness Ra is not more than 0.4 mu m, and the planeness is not more than 0.06mm; the composition range of the membrane is as follows according to weight percentage:
cr:22.00 to 25.00, mo:5.00 to 8.00, nb:2.50 to 3.00, 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 copper content is controlled to be less than or equal to 0.030, the iron content is controlled to be less than or equal to 0.100, 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, and the silicon content is controlled to be less than or equal to 0.030;
sigma 3 in diaphragm alloys n The proportion of crystal boundary is not less than 55%, n =1,2 or 3, sigma is not more than 29, and the proportion of crystal boundary is not less than 60%;
the preparation method of the high-strength hydrogen embrittlement-resistant membrane with the mark of MP-5 comprises the following specific steps:
(1) Carrying out vacuum induction melting by using electrolytic nickel, metal chromium, metal molybdenum and metal niobium as raw materials;
(2) Electroslag remelting;
(3) Alloy forging; the cogging forging temperature is 1050-1150 ℃, and the finish forging temperature is 930-1030 ℃ to obtain a forging stock; allowing the steel to return to the furnace and heating again before forging to the final specification, and preserving the heat for 1-4 h at 1050-1150 ℃;
(4) Hot rolling the alloy; the forging stock is subjected to hot rolling after being subjected to heat preservation for 2 to 4 hours at 1050 to 1150 ℃, the cogging rolling temperature is 1050 to 1150 ℃, and the finish rolling temperature is 880 to 930 ℃, so that a hot rolled plate with the thickness of 4 to 6mm is obtained; allowing the steel to return to the furnace and heating again before the steel is rolled to the final specification, and preserving the heat for 0.5 to 3 hours at the temperature of 1050 to 1150 ℃;
(5) Alloy cold rolling or finish rolling; cold rolling at room temperature to produce 30-70% of deformation in each annealing, and performing stress relief annealing at 1020-1060 ℃ for 15-60 min to obtain a cold-rolled sheet with the thickness of 0.4-0.6 mm, wherein the grain size of the cold-rolled sheet is not lower than 6 grade;
(6) Carrying out solution treatment on the plate; controlling the temperature of the plate solution treatment at 1020-1120 ℃, keeping the temperature for 20-60 min, and cooling in air;
(7) Cold rolling the plate with small deformation; the cold rolling deformation of the plate is 8-12%;
(8) Cutting and processing the membrane;
(9) Final heat treatment of the diaphragm;
(10) Surface treatment of the membrane;
in the step (6), the plate is subjected to solution treatment in a gas-shielded heat treatment furnace, and the gas medium is argon or reducing gas;
in the step (9), the heat treatment system is as follows: and (3) carrying out annealing treatment by adopting a vacuum or gas protection gas quenching heat treatment furnace at 1020-1060 ℃ for 0.5-1 h.
2. The high strength hydrogen embrittlement resistant membrane of claim 1, grade MP-5, wherein the mechanical properties at room temperature of the membrane are: the yield strength is not lower than 425MPa, the tensile strength is not lower than 825MPa, and the elongation is not lower than 40%.
3. The high-strength hydrogen embrittlement-resistant membrane with the grade of MP-5 as claimed in claim 1, wherein the mechanical properties at 200 ℃ of the membrane meet: the yield strength is not lower than 350MPa, the tensile strength is not lower than 700MPa, and the elongation is not lower than 35%.
4. The high-strength hydrogen embrittlement-resistant diaphragm with the mark of MP-5 as claimed in claim 1, wherein the room temperature mechanical properties of the diaphragm after 300 ℃, 10MPa, high-purity hydrogen with volume purity of more than or equal to 99.999% and hydrogen charging treatment for 72h meet: the yield strength is not lower than 400MPa, the tensile strength is not lower than 750MPa, and the elongation is not lower than 35%.
5. A high strength hydrogen embrittlement resistant membrane of grade MP-5 as claimed in claim 1, wherein the membrane has a fatigue limit at 50% confidence of not less than 250MPa.
6. The high strength hydrogen embrittlement resistant diaphragm of MP-5 designation as claimed in claim 1, wherein the non-metallic inclusions in the diaphragm after the surface treatment in step (10) satisfy the following requirements: the fine line, A is less than or equal to 0.5 grade, B is less than or equal to 1.0 grade, D is less than or equal to 2.0 grade, and the sum of the three grades is less than or equal to 2.5 grade; coarse, A is less than or equal to 0.5 grade, B is less than or equal to 1.0 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; wherein A is sulfide, B is alumina, D is spherical oxide, and the sum of the three types is A + B + D.
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