CN114058976A - Preparation method of special plate for hydrogen-brittleness-resistant membrane of high-pressure hydrogen diaphragm compressor - Google Patents

Preparation method of special plate for hydrogen-brittleness-resistant membrane of high-pressure hydrogen diaphragm compressor Download PDF

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CN114058976A
CN114058976A CN202111223310.6A CN202111223310A CN114058976A CN 114058976 A CN114058976 A CN 114058976A CN 202111223310 A CN202111223310 A CN 202111223310A CN 114058976 A CN114058976 A CN 114058976A
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plate
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hydrogen
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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
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/26—Methods of annealing
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/26—Methods of annealing
    • C21D1/30—Stress-relieving
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0226—Hot rolling
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0236—Cold rolling
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
    • C21D8/0268—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment between cold rolling steps
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/04—Making ferrous alloys by melting
    • C22C33/06—Making ferrous alloys by melting using master alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • 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
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/001—Austenite

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Abstract

The invention relates to the field of key material components of hydrogen energy equipment, in particular to a preparation method of a special plate for a hydrogen embrittlement resistant membrane of a high-pressure hydrogen diaphragm compressor. The plate comprises the following chemical components in percentage by weight: 5.50-8.50, Cr: 19.00-22.00, Mn: 8.50-10.50, N: 0.22-0.36, Si is less than or equal to 0.80, Fe: and (4) the balance. The invention guarantees the strength and the hydrogen embrittlement resistance of the special plate based on nitrogen element solid solution strengthening and grain boundary regulation, the plate is prepared by a method of vacuum or non-vacuum induction melting → steel die casting → electroslag remelting → forging → hot rolling → cold rolling → solution treatment → small deformation cold rolling → annealing heat treatment, the plate has the width of no less than 800mm, the thickness of 0.4-0.6 mm, the length of no less than 1000mm, the surface roughness Ra of the plate is no more than 0.6 mu m, the unevenness is no more than 10mm/m, the thickness precision is +/-0.05 mm, the yield strength at room temperature and 200 ℃ can respectively reach more than 350MPa and 240MPa, and the invention has good plasticity, hydrogen embrittlement resistance and fatigue resistance, and can be used for preparing hydrogen side membranes of hydrogen diaphragm compressors of 45MPa and above.

Description

Preparation method of special plate for hydrogen-brittleness-resistant membrane of high-pressure hydrogen diaphragm compressor
Technical Field
The invention relates to the field of materials of key parts of hydrogen energy equipment, in particular to a preparation method of a special plate for a hydrogen embrittlement resistant membrane of a high-pressure hydrogen diaphragm compressor.
Background
The diaphragm compressor (hereinafter referred to as hydrogen compressor) is a special positive displacement compressor, has the characteristics of good sealing performance, no pollution to compressed media, large compression ratio, easy realization of high pressure and the like, and is indispensable key equipment in a hydrogenation 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 transmitted by hydraulic oil, thereby achieving the purpose of pressurization. The diaphragm of the hydrogen compressor is generally of a three-layer structure, wherein the diaphragm on the hydrogen side is made of 316L austenitic stainless steel. Engineering practice shows that in the service process of a hydrogen compressor (the design pressure is 35MPa) of a 30MPa demonstration hydrogen adding station, the service life of the 316L diaphragm is long, and the service life of the 316L diaphragm on the hydrogen side is remarkably shortened (even is less than 1/5-1/10 of the service life of the diaphragm of the 35MPa hydrogen adding machine) when the pressure of the hydrogen adding station is increased to 45MPa (the design pressure of the hydrogen compressor is 52 MPa). The reason for this is that, on one hand, under the working condition of higher hydrogen pressure and alternating temperature service, more hydrogen permeates into the interior of the 316L diaphragm alloy, so that the diaphragm is easy to generate hydrogen-induced fracture failure; on the other hand, under the higher temperature cycle and high pressure conditions than the 35MPa hydrogenation machine, the service life of the 316L alloy is limited due to the lower high-temperature strength of the alloy. It should be noted that most of the hydrogen stations built in the present stage and the future of China are at 45MPa level or higher, which puts higher requirements on key equipment and components of the hydrogen stations. It goes without saying that the development of a hydrogen embrittlement resistant austenitic alloy sheet material with a higher strength level meets the design and use requirements of a hydrogen press with a pressure level of 45MPa and higher, and the demand is very urgent.
Disclosure of Invention
Aiming at the material requirements of key parts of hydrogen energy equipment, the invention aims to provide a preparation method of a special plate for a hydrogen embrittlement resistant membrane of a high-pressure hydrogen diaphragm compressor, so as to meet the design and use requirements of a hydrogen membrane of a hydrogen compressor at a pressure level of 45MPa and higher.
The technical scheme of the invention is as follows:
a preparation method of a special plate for a hydrogen embrittlement-resistant diaphragm of a high-pressure hydrogen diaphragm compressor is characterized in that the width of the plate is not less than 800mm, the thickness of the plate is 0.4-0.6 mm, the length of the plate is not less than 1000mm, the surface roughness Ra of the plate is not more than 0.6 mu m, the unevenness of the plate is not more than 10mm/m, and the thickness precision is +/-0.05 mm; the plate comprises the following main components in percentage by weight:
ni: 5.50-8.50, Cr: 19.00-22.00, Mn: 8.50-10.50, N: 0.22 to 0.36, Fe and unavoidable residual elements: the balance; the inevitable residual elements include: carbon, sulfur, phosphorus and silicon, wherein the content of carbon is controlled to be less than or equal to 0.030, the content of sulfur is controlled to be less than or equal to 0.009, the content of phosphorus is controlled to be less than or equal to 0.015 and the content of silicon is controlled to be less than or equal to 0.80;
the preparation method of the special plate for the hydrogen embrittlement resistant diaphragm of the high-pressure hydrogen diaphragm compressor comprises the following specific steps of:
(1) non-vacuum or vacuum induction melting;
(2) electroslag remelting;
(3) alloy forging; the cogging forging temperature is 1060-1160 ℃, and the finish forging temperature is 880-1000 ℃, so that a forging blank is obtained; allowing the steel to return to the furnace and heating again before forging to the final specification, and preserving the heat for 1-4 hours at 1060-1160 ℃;
(4) hot rolling the alloy; carrying out hot rolling on the forged blank after heat preservation is carried out for 2-4 h at 1060-1160 ℃, wherein the cogging rolling temperature is 1060-1160 ℃, the finish rolling temperature is 850-950 ℃, and a hot rolled plate with the thickness of 4-6 mm 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 0.5-3 h at 1060-1160 ℃;
(5) cold rolling or finish rolling the alloy; cold rolling at room temperature to ensure that the deformation amount is 30-70% in each annealing process, 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 is not lower than 6 grade;
(6) carrying out solution treatment on the plate; controlling the temperature of the plate solution treatment to be 1000-1060 ℃, 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) annealing and heat treatment of the plate; the annealing heat treatment system comprises: keeping the temperature at 1000-1040 ℃ for 0.5-1 h.
The preparation method of the special plate for the hydrogen embrittlement resistant diaphragm of the high-pressure hydrogen diaphragm compressor comprises sigma 3 of the platenThe proportion of grain boundary is not less than 65%, n is 1,2 or 3, and the proportion of sigma is not more than 29, and is not less than 70%.
According to the preparation method of the special plate for the hydrogen embrittlement resistant diaphragm of the high-pressure hydrogen diaphragm compressor, the room-temperature mechanical property of the plate meets the following requirements: the yield strength (Rp0.2) is not less than 350MPa, the tensile strength (Rm) is not less than 650MPa, and the elongation (A) is not less than 50%.
According to the preparation method of the special plate for the hydrogen embrittlement resistant diaphragm of the high-pressure hydrogen diaphragm compressor, the mechanical property of the plate at the high temperature of 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%.
According to the preparation method of the special plate for the hydrogen embrittlement resistant diaphragm of the high-pressure hydrogen diaphragm compressor, after hydrogen filling treatment for 300 ℃, 10MPa, high-purity hydrogen (the volume purity is more than or equal to 99.999%) and 72 hours, the room-temperature mechanical property of the plate meets the following requirements: the yield strength (Rp0.2) is not less than 350MPa, the tensile strength (Rm) is not less than 650MPa, and the elongation (A) is not less than 50%.
According to the preparation method of the special plate for the hydrogen embrittlement resistant membrane of the high-pressure hydrogen diaphragm compressor, the fatigue limit of the plate is not lower than 240MPa at a confidence coefficient of 50%.
According to the preparation method of the special plate for the hydrogen embrittlement resistant membrane of the high-pressure hydrogen diaphragm compressor, the non-metallic inclusions in the plate after annealing heat treatment meet the following requirements: the fine 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.
According to the preparation method of the special plate for the hydrogen embrittlement resistant membrane of the high-pressure hydrogen diaphragm compressor, the plate is subjected to solution treatment in a gas protection heat treatment furnace, and a gas medium is argon or reducing gas.
According to the preparation method of the special plate for the hydrogen embrittlement resistant diaphragm of the high-pressure hydrogen diaphragm compressor, the annealing heat treatment of the plate adopts a vacuum or gas protection heat treatment furnace.
The design idea of the invention is as follows:
firstly, on the basis of ensuring single-phase austenitic alloy, adding a proper amount of nitrogen element on the basis of a Fe-Cr-Ni-Mn system to improve the alloy strength so as to obtain higher room-temperature and 200-DEG C high-temperature strength, wherein the room-temperature yield strength (Rp0.2) of the plate can reach more than 350MPa, the 200-DEG C yield strength (Rp0.2) can reach more than 240MPa, and the plate has good plasticity (the elongation at room temperature and 200 ℃ is respectively higher than 50 percent and 40 percent). Secondly, by adopting a crystal boundary regulation and control method of thermomechanical treatment, the number of free crystal boundaries in the alloy is reduced, and special crystal boundaries (low sigma 3) are improvedn(n-1, 2,3) superposed position lattice grain boundary) ratio, thereby remarkably improving the hydrogen-induced crack initiation and propagation resistance along the grain boundary of the special plate, and further obtaining excellent hydrogen embrittlement resistance. Thirdly, the amount of strong hydrogen traps (also as fatigue crack sources) in the special plate alloy is reduced by reducing the level of non-metallic inclusions and regulating and controlling the crystal boundary, and the fatigue limit and the hydrogen embrittlement resistance of the plate can be simultaneously improved.
The invention has the advantages and beneficial effects that:
1. the special plate disclosed by the invention has the advantages of low content of carbon, sulfur and phosphorus impurity elements and non-metallic inclusions, high lattice-grain boundary proportion at a low sigma coincidence position, excellent room temperature and 200 ℃ high-temperature strength (which is nearly doubled compared with that of a 316L plate), excellent hydrogen brittleness resistance and capability of being used for preparing a hydrogen membrane of a 45MPa or above-grade hydrogen compressor.
2. The width of the special plate is not less than 800mm, the thickness is 0.4-0.6 mm, the length is not less than 1000mm, the surface roughness Ra of the plate is not more than 0.6 mu m, the unevenness is not more than 10mm/m, and the thickness precision is +/-0.05 mm.
3. Special plate for the inventionSigma 3 of materialnThe proportion of the special crystal boundary is not less than 65 percent, and the proportion of the sigma is not more than 29 crystal boundary is not less than 70 percent.
4. The room temperature mechanical property of the special plate 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 650MPa, and the elongation (A) is not less than 50%.
5. The mechanical property of the special plate at the high temperature of 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. After the special plate is placed in high-purity hydrogen (the volume purity is more than or equal to 99.999%) gas at 300 ℃ and 10MPa for 72 hours, the room-temperature mechanical property meets the following requirements: the yield strength (Rp0.2) is not less than 350MPa, the tensile strength (Rm) is not less than 650MPa, and the elongation (A) is not less than 50%.
7. The special plate disclosed by the invention has good plasticity, hydrogen embrittlement resistance and fatigue resistance, the fatigue limit of the plate at a confidence coefficient of 50% is not lower than 240MPa, and the plate can be used for preparing a hydrogen diaphragm of a hydrogen diaphragm compressor of 45MPa or above.
Drawings
FIG. 1 is an EBSD diagram of the grain boundary structure of the special plate.
FIG. 2 is a statistical result chart of special grain boundaries of the special plate; in the figure, the abscissa represents the grain boundary type, and the ordinate frame represents the specific grain boundary ratio (%).
Detailed Description
In the specific implementation process, the strength and the hydrogen embrittlement resistance of the special plate are ensured based on nitrogen element solid solution strengthening and grain boundary regulation, and the plate 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 → annealing heat treatment. The width of the special plate is not less than 800mm, the thickness is 0.4-0.6 mm, the length is not less than 1000mm, the surface roughness Ra of the plate is not more than 0.6 mu m, the unevenness is not more than 10mm/m, and the thickness precision is +/-0.05 mm.
The present invention will be described in further detail below with reference to examples.
Example 1 sheet Material having a gauge of 1500 mm. times.830 mm. times.0.57 mm
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/finish rolling → plate solid solution → small deformation rolling → annealing heat treatment → fixed length is carried out to prepare the special plate with the size of 1500mm multiplied by 830mm multiplied by 0.57mm, the chemical components are shown in the table 1, and the preparation process is as follows:
1. the method comprises the steps of taking industrial pure iron (0.006 wt.% in the embodiment) with the phosphorus content of less than 0.007 wt.%, electrolytic nickel, metallic chromium, electrolytic manganese and chromium nitride as raw materials, loading the raw materials into a crucible before smelting, and loading a calcium desulfurizer into a hopper.
2. Carrying out vacuum induction melting by adopting an aluminum-magnesium spinel crucible, carrying out refining treatment at 1530-1570 ℃ for 10-15 minutes (refining is carried out at 1540 ℃ for 10 minutes in the embodiment), then adding a calcareous desulfurizer, carrying out refining for 5-15 minutes (refining is carried out for 10 minutes in the embodiment), carrying out desulfurization treatment by utilizing the better thermal stability of the crucible and the desulfurizer, and casting an ingot 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 240-380 mm (phi 350mm in the embodiment).
4. The electroslag cast ingot is subjected to alloy forging (the temperature is kept for 6h at 1150 ℃ in the embodiment) after the temperature is kept at 1060-1160 ℃, the cogging forging temperature is 1060-1160 ℃ (the temperature is 1150 ℃) and the finish forging temperature is 880-1000 ℃ (the finish forging temperature is 900 ℃) to obtain a forging blank; the forging blank is allowed to be returned to the furnace and heated again before being forged to the final specification, the temperature is kept for 1-4 h at the heating temperature of 1060-1160 ℃ (the time of returning to the furnace and heating is four times in the embodiment, and the temperature is kept for 1.5h at 1150 ℃), and the section specification of the forging blank is 850 multiplied by 60 mm.
5. The forged plate blank is rolled after being subjected to heat preservation for 2-4 h at 1060-1160 ℃ (the heat preservation time is 2h at 1150 ℃) and then is subjected to cogging rolling at 1060-1160 ℃ (1150 ℃) and at 850-950 ℃ (the finish rolling temperature is 880 ℃) and is allowed to return to the furnace for reheating before being rolled to the final specification, and is subjected to heat preservation for 0.5-3 h at 1060-1160 ℃ (the return to the furnace is heated for three times and the heat preservation time is 0.5h at 1150 ℃), and the section specification of the final hot rolled plate is 850 multiplied by 4.0 mm.
6. And (3) cold rolling the hot rolled plate at room temperature, wherein the deformation amount of the hot rolled plate is 30-70% (40-50% in the embodiment) in each annealing, and the stress relief annealing is performed by keeping the temperature for 15-60 min (30 min in the embodiment) at 1020-1060 ℃ (1050 ℃ in the embodiment) to obtain a cold rolled plate with the thickness of 0.4-0.6 mm (0.57 mm in the embodiment).
7. And (3) taking the cold-rolled sheet in the step (6), cutting out a metallographic sample in a direction 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 temperature of the solution treatment to be 1000-1060 ℃ (1030 ℃ in the embodiment), keeping the temperature for 20-60 min (40 min in the embodiment), and carrying out air cooling.
9. And (3) carrying out cold rolling on the plate subjected to the solution treatment in the step (8) with the deformation amount of 8-12% (10% in the embodiment), wherein the final plate thickness is 0.51 mm.
10. And (3) taking the plate in the step (9), and carrying out annealing heat treatment on the plate for 1000-1040 ℃ (1020 ℃ in the embodiment) for 0.5-1 h (1 h in the embodiment).
11. 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.
12. The sheet material after the annealing treatment in step 10 is subjected to dimension and surface quality detection, and the result shows that the sheet material has a width of not less than 800mm (830 mm in this embodiment), a thickness of 0.4 to 0.6mm (0.57 mm in this embodiment), a length of not less than 1000mm (1500 mm in this embodiment), a surface roughness Ra of not more than 0.6 μm (0.5 μm in this embodiment), an unevenness of not more than 10mm/m (5 mm/m in this embodiment), and a thickness precision of ± 0.05mm (0.02 to +0.04mm in this embodiment).
13. Taking step 10Processing samples with corresponding specifications on the annealed plate, performing EBSD analysis on the plate alloy crystal boundary, and displaying the result that sigma 3 is in the plate alloynThe special grain boundary proportion is 73.4 percent, the sigma is less than or equal to 29, the grain boundary proportion is 75.4 percent, the EBSD structure of the plate alloy is shown in figure 1, and the statistical result of the special grain boundary proportion is shown in figure 2.
14. And (3) processing the plate annealed in the step 10 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) processing the annealed plate in the step (10) 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.
16. And (3) taking the plate subjected to annealing treatment in the step (10) to process a tensile sample, 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 plate processed fatigue test sample subjected to annealing treatment in the step 10, and carrying out fatigue performance test by referring to GB/T3075-.
Table 1 chemical composition, mass fraction of the sheet alloy%
Element(s) C Si Mn S P Ni Cr N Fe
Content (wt.) 0.017 0.39 9.65 0.004 0.009 7.40 19.63 0.32 Balance of
TABLE 2 non-metallic inclusions of sheet alloys
Figure BDA0003313409570000061
TABLE 3 mechanical Properties at Room temperature of the sheets
Numbering Rp0.2/MPa Rm/MPa A/％
1 404 745 59.5
2 407 746 59.0
3 402 740 59.0
TABLE 4 mechanical Properties of the sheet at 200 ℃
Numbering Rp0.2/MPa Rm/MPa A/％
1 272 591 49.5
2 265 597 50.0
3 272 595 48.5
TABLE 5 Room temperature mechanical Properties of sheets after Hot Hydrogen Charge
Numbering Rp0.2/MPa Rm/MPa A/％
1 425 752 58.5
2 429 756 57.5
3 429 755 58.0
The experimental result shows that the prepared plate with the specification of 1500mm multiplied by 830mm multiplied by 0.6mm has the surface roughness Ra of less than or equal to 0.6 mu m and the unevenness of less than or equal to 6 mm/m; only 0.5-grade fine B-type and 0.5-grade D-type nonmetallic inclusions exist in the plate; sigma 3 in sheet alloynThe proportion of special crystal boundary is higher than 73%, sigma is not more than 29, and the proportion of crystal boundary is higher than 75%; the room-temperature mechanical properties of the plate are as follows: yield strength (Rp)0.2) More than 400MPa, tensile strength (Rm) more than 740MPa, and elongation more than 58%; the mechanical properties of the plate at 200 ℃ are as follows: yield strength (Rp)0.2) Higher than 260MPa, tensile strength (Rm) higher than 590MPa, and elongation higher than 48%; after being placed in a high-purity hydrogen environment at 300 ℃ and 10MPa for 72 hours, the yield strength (Rp)0.2) More than 420MPa, tensile strength (Rm) more than 750MPa, and elongation more than 57%; the fatigue limit of the plate at a confidence of 50% is higher than 252 MPa.
Example 2: plate with specification of 1200mm multiplied by 800mm multiplied by 0.57mm
The difference from example 1 is that a plate having a length of 1200mm and a width of 800mm was prepared.
The alloy is smelted on a 500Kg vacuum induction furnace by adopting a CaO crucible, and the alloy is smelted by taking industrial pure iron with the phosphorus content of less than 0.006 wt.%, electrolytic nickel, metallic chromium, electrolytic manganese and chromium nitride as raw materials. 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 240mm, and the chemical components are shown in Table 6. Keeping the temperature at 1150 ℃ for 4h, then forging the alloy, wherein the cogging forging temperature is 1150 ℃, the finish forging temperature is 900 ℃, returning to the furnace and reheating twice before forging to the final specification, the reheating temperature is 1150 ℃, the heat preservation time is 1.5h, and the section specification of the forged plate blank is 820 multiplied by 60 mm. Rolling at 1150 deg.C for 2 hr, and cogging at 1150 deg.CAnd the temperature of the final rolling is 860 ℃, the steel plate is returned to the furnace and reheated for three times before being rolled to the final specification, the reheating temperature is 1150 ℃, the heat preservation time is 0.5h, and the section specification of the final hot rolled plate is 820 multiplied by 4.0 mm. The method comprises the steps of carrying out multi-pass cold rolling annealing processing of stress relief annealing heat treatment with the deformation amount of 40-50% +1050 ℃ for 30min to prepare a cold-rolled plate with the thickness of 0.57mm, carrying out solution treatment of heat preservation for 40min at 1030 ℃ for air cooling on the cold-rolled plate, carrying out 10% cold rolling to obtain a plate with the thickness of 0.51mm, and carrying out annealing heat treatment for 1h at 1020 ℃ for the plate. The measurement results of the dimensions and the surface quality showed that the plate had a surface roughness Ra of 0.4 μm and an unevenness of 4 mm/m. Sigma 3 in sheet alloynThe special crystal boundary proportion is 75.1 percent, the Sigma is less than or equal to 29, the crystal boundary proportion is 77.0 percent, the evaluation result of nonmetallic inclusions is shown in table 7, the room-temperature mechanical property is shown in table 8, the 200-DEG C mechanical property is shown in table 9, the 300-DEG C mechanical property is 10MPa, the volume purity is more than or equal to 99.999 percent, and the 72-hour mechanical property after hydrogen filling 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 plate at the confidence of 50% is 258 MPa.
TABLE 6 chemical composition, mass fraction of the sheet alloy%
Element(s) C Si Mn S P Ni Cr N Fe
Content (wt.) 0.018 0.40 9.65 0.002 0.012 7.16 19.55 0.287 Balance of
TABLE 7 non-metallic inclusions of sheet alloys
Figure BDA0003313409570000081
TABLE 8 mechanical Properties at Room temperature of the sheets
Numbering Rp0.2/MPa Rm/MPa A/％
1 409 742 59.5
2 397 742 58.5
3 405 742 59.5
TABLE 9 mechanical Properties of sheet at 200 ℃
Numbering Rp0.2/MPa Rm/MPa A/％
1 275 595 48.5
2 271 591 50.5
3 268 590 49.0
TABLE 10 mechanical properties at room temperature of sheets after hot hydrogen charging
Numbering Rp0.2/MPa Rm/MPa A/％
1 428 752 57.5
2 432 753 57.5
3 428 751 58.0
The experimental result shows that the prepared plate with the specification of 1200mm multiplied by 800mm multiplied by 0.57mm has the surface roughness Ra of less than or equal to 0.5 mu m and the planeness of less than or equal to 5 mm/m; only 0.5-grade fine B-type and 0.5-grade D-type nonmetallic inclusions exist in the plate; sigma 3 in sheet alloynThe proportion of special crystal boundary is higher than 75%, sigma is not more than 29, and the proportion of crystal boundary is higher than 76%; the room-temperature mechanical properties of the plate are as follows: yield strength (Rp)0.2) Higher than 395MPa, tensile strength (Rm) higher than 740MPa, and elongation higher than 58%; the mechanical properties of the plate at 200 ℃ are as follows: yield strength (Rp)0.2) Is higher than 270MPa, the tensile strength (Rm) is higher than 590MPa, and the elongation is higher than 48 percent; after being placed in a high-purity hydrogen environment at 300 ℃ and 10MPa for 72 hours, the yield strength (Rp)0.2) More than 425MPa, tensile strength (Rm) more than 750MPa, and elongation more than 57%; the fatigue limit of the plate at a confidence of 50% is higher than 255 MPa.

Claims (9)

1. A preparation method of a special plate for a hydrogen embrittlement-resistant diaphragm of a high-pressure hydrogen diaphragm compressor is characterized in that the width of the plate is not less than 800mm, the thickness of the plate is 0.4-0.6 mm, the length of the plate is not less than 1000mm, the surface roughness Ra of the plate is not more than 0.6 mu m, the unevenness of the plate is not more than 10mm/m, and the thickness precision is +/-0.05 mm; the plate comprises the following main components in percentage by weight:
ni: 5.50-8.50, Cr: 19.00-22.00, Mn: 8.50-10.50, N: 0.22 to 0.36, Fe and unavoidable residual elements: the balance; the inevitable residual elements include: carbon, sulfur, phosphorus and silicon, wherein the content of carbon is controlled to be less than or equal to 0.030, the content of sulfur is controlled to be less than or equal to 0.009, the content of phosphorus is controlled to be less than or equal to 0.015 and the content of silicon is controlled to be less than or equal to 0.80;
the preparation method of the special plate for the hydrogen embrittlement resistant diaphragm of the high-pressure hydrogen diaphragm compressor comprises the following specific steps of:
(1) non-vacuum or vacuum induction melting;
(2) electroslag remelting;
(3) alloy forging; the cogging forging temperature is 1060-1160 ℃, and the finish forging temperature is 880-1000 ℃, so that a forging blank is obtained; allowing the steel to return to the furnace and heating again before forging to the final specification, and preserving the heat for 1-4 hours at 1060-1160 ℃;
(4) hot rolling the alloy; carrying out hot rolling on the forged blank after heat preservation is carried out for 2-4 h at 1060-1160 ℃, wherein the cogging rolling temperature is 1060-1160 ℃, the finish rolling temperature is 850-950 ℃, and a hot rolled plate with the thickness of 4-6 mm 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 0.5-3 h at 1060-1160 ℃;
(5) cold rolling or finish rolling the alloy; cold rolling at room temperature to ensure that the deformation amount is 30-70% in each annealing process, 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 is not lower than 6 grade;
(6) carrying out solution treatment on the plate; controlling the temperature of the plate solution treatment to be 1000-1060 ℃, 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) annealing and heat treatment of the plate; the annealing heat treatment system comprises: keeping the temperature at 1000-1040 ℃ for 0.5-1 h.
2. The method for preparing a plate material special for a hydrogen embrittlement resistant membrane of a high pressure hydrogen diaphragm compressor as claimed in claim 1, wherein ∑ 3 of the plate materialnThe proportion of grain boundary is not less than 65%, n is 1,2 or 3, and the proportion of sigma is not more than 29, and is not less than 70%.
3. The preparation method of the special plate for the hydrogen embrittlement-resistant membrane of the high-pressure hydrogen diaphragm compressor according to claim 1, wherein the room temperature mechanical properties of the plate meet: the yield strength (Rp0.2) is not less than 350MPa, the tensile strength (Rm) is not less than 650MPa, and the elongation (A) is not less than 50%.
4. The preparation method of the special plate for the hydrogen embrittlement-resistant membrane of the high-pressure hydrogen diaphragm compressor according to claim 1, wherein the 200 ℃ high-temperature mechanical property of the plate 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%.
5. The preparation method of the special plate for the hydrogen embrittlement-resistant diaphragm of the high-pressure hydrogen diaphragm compressor, as claimed in claim 1, is characterized in that after hydrogen charging treatment of 300 ℃, 10MPa, high-purity hydrogen (volume purity is more than or equal to 99.999%) and 72h, the room-temperature mechanical properties of the plate meet: the yield strength (Rp0.2) is not less than 350MPa, the tensile strength (Rm) is not less than 650MPa, and the elongation (A) is not less than 50%.
6. The preparation method of the special plate for the hydrogen embrittlement-resistant membrane of the high-pressure hydrogen diaphragm compressor as claimed in claim 1, wherein the fatigue limit of the plate at a confidence of 50% is not lower than 240 MPa.
7. The preparation method of the special plate for the hydrogen embrittlement-resistant membrane of the high-pressure hydrogen diaphragm compressor according to claim 1, wherein the non-metallic inclusions in the plate after annealing heat treatment meet the following requirements: the fine 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.
8. The method for preparing the special plate for the hydrogen embrittlement-resistant membrane of the high-pressure hydrogen diaphragm compressor according to claim 1, wherein the plate is subjected to solution treatment in a gas-shielded heat treatment furnace, and the gas medium is argon or reducing gas.
9. The preparation method of the special plate for the hydrogen embrittlement-resistant membrane of the high-pressure hydrogen diaphragm compressor as claimed in claim 1, wherein the annealing heat treatment of the plate is performed by a vacuum or gas protection heat treatment furnace.
CN202111223310.6A 2021-10-20 2021-10-20 Preparation method of special plate for hydrogen-brittleness-resistant membrane of high-pressure hydrogen diaphragm compressor Pending CN114058976A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009185313A (en) * 2008-02-04 2009-08-20 Japan Atomic Energy Agency Intergranular control type exposure-resistant sus316-equivalent steel and producing method therefor
CN107406934A (en) * 2015-03-06 2017-11-28 新日铁住金不锈钢株式会社 The excellent high intensity austenite stainless steel of hydrogen embrittlement resistance and its manufacture method
CN111235369A (en) * 2018-11-29 2020-06-05 南京理工大学 Method for improving hydrogen embrittlement resistance of 304 austenitic stainless steel

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009185313A (en) * 2008-02-04 2009-08-20 Japan Atomic Energy Agency Intergranular control type exposure-resistant sus316-equivalent steel and producing method therefor
CN107406934A (en) * 2015-03-06 2017-11-28 新日铁住金不锈钢株式会社 The excellent high intensity austenite stainless steel of hydrogen embrittlement resistance and its manufacture method
CN111235369A (en) * 2018-11-29 2020-06-05 南京理工大学 Method for improving hydrogen embrittlement resistance of 304 austenitic stainless steel

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