CN110777305B - High-hardness high-strength foldable stainless steel foil - Google Patents
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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- 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
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- 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
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- C21D2211/001—Austenite
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- 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
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- C21D2211/008—Martensite
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Abstract
A high-hardness high-strength foldable stainless steel foil belongs to the technical field of stainless steel foils. The austenitic stainless steel sheet is used as a raw material, and the alloy comprises the following components in percentage by mass: c and N are more than or equal to 0.1 percent and less than or equal to 0.2 percent, Ni and Cu are more than or equal to 6 percent and less than or equal to 8 percent, Mn is more than or equal to 0.5 percent and less than or equal to 1.5 percent, Cr is more than or equal to 16 percent and less than or equal to 18 percent, Mo is more than or equal to 0.01 percent and less than or equal to 0.03 percent, Si is more than or equal to 0.3 percent and less than or equal to 1 percent, and the balance is Fe; based on MD30/50And stacking fault energy gammaSFAnd adjusting the formula within the above composition range, and obtaining a stainless steel foil product with the martensite accounting for 50% -80% by rolling and annealing for 3-7 times. The thickness of the steel foil is more than 15 mu m and less than 50 mu m, the hardness is more than or equal to 580HV, and the tensile strength is more than or equal to 1800 MPa; the bending angle can reach more than or equal to 170 degrees, the bearing bending radius R reaches 1.5mm-8mm, and the bending frequency is more than or equal to 200000 without fracture.
Description
Technical Field
The invention belongs to the technical field of stainless steel foils, and particularly provides a high-hardness high-strength foldable stainless steel foil with the thickness of more than 15 micrometers and less than 50 micrometers.
Background
Along with the high-speed development of modern high-end manufacturing, high-end products require more precision, high integration, light weight and high performance, and foil sheets in the high-end products are required to be thinner and have more excellent performance, and the high-strength foldable and reboundable stainless steel foil has wide application requirements in various fields such as spring sheets, gasket sheets, precision parts, etching pieces, photoelectric protection cables, temperature controllers, automobile expansion valve membranes, elastic springs, precision electronics, automobile parts, camera parts, air conditioner pressure switch membranes, electronic appliances, hardware stamping parts, air compressor spring sheets, injection needle piston ring expansion rings and the like. Particularly, with the arrival of the 5G era, the wearing technology leads the foldable ultrathin display panel with the large and wide screen to adopt the high-performance supporting pad membrane, so that the requirements of maintaining the overall strength, supporting the large screen and stably bearing the core component are met, and higher requirements are provided for the performance of the metal foil of the supporting pad membrane, namely the characteristics of high hardness, high wear resistance, flexibility, foldability, corrosion resistance and ultrahigh strength.
At present, only a few reports are made on the preparation of stainless steel foil:
1) CN1109121C, discloses a film having a thickness of 25 μm or lessThe ultra-thin stainless steel foil of (1). The number of inclusions having a major diameter of 5 μm or more is defined as 1mm per one row in the rolling direction2The average number of the cross sections is 3 or less, which solves the technical problem in the etching process. However, the patent does not describe the structure of the steel foil such as phase and grain, and the mechanical properties such as hardness and strength.
2) CN105829567(A, B), discloses a stainless steel foil with a thickness of 60 μm or less and a method for producing the same. The stainless steel foil is obtained by controlling the recrystallization ratio to 90% or more, the recrystallized grain size not to be too large (3 or more grains in the plate thickness direction), and the surface nitrogen concentration, and the phase distribution of the stainless steel foil is controlled by adjusting the rolling reduction of the final pass and the final annealing conditions.
3) CN107923012A, CN108713067A and CN104093872A disclose austenitic, martensitic and ferritic stainless steel foils and manufacturing methods thereof, respectively. However, the patents mentioned in this section all result in stainless steel foils with a predominantly recrystallized structure, suitable for battery case applications, and not high in hardness and strength.
In conclusion, the high-hardness high-strength foldable stainless steel foil and the preparation technology thereof are only reported in public.
Disclosure of Invention
The invention aims to provide a high-hardness high-strength foldable stainless steel foil, which is 15-50 mu m thick and meets the application requirements of high-hardness high-strength foldable long-life light metal foil gaskets, spring plates and the like.
The invention takes an austenitic stainless steel sheet as a raw material, and the main alloy components are in the following ranges (mass percent): c and N are more than or equal to 0.1 percent and less than or equal to 0.2 percent, Ni and Cu are more than or equal to 6 percent and less than or equal to 8 percent, Mn is more than or equal to 0.5 percent and less than or equal to 1.5 percent, Cr is more than or equal to 16 percent and less than or equal to 18 percent, Mo is more than or equal to 0.01 percent and less than or equal to 0.03 percent, Si is more than or equal to 0.3 percent and less than or equal to 1 percent, and the balance is Fe. M based onD30/50And stacking fault energy gammaSFAnd adjusting the formula within the above composition range, and obtaining a stainless steel foil product with the martensite accounting for 50% -80% by multi-pass rolling and annealing.
MD30/50The temperature (. degree. C.) at which 50% of martensite is formed under 30% cold deformation, γSFIs the room temperature stacking fault energy (mJ/m)2). License plateThe study of multiple scholars considers MD30/50The larger the value, the greater the tendency of cold deformation to induce martensite, and γSFA value of less than 20mJ/m2The tendency of cold deformation to induce martensite is large.
MD30/50551-cozeb 462(C + N) -29(Ni + Cu) -8.1(Mn) -13.7(Cr) -18.5(Mo) -9.2(Si) -1.42(G-8) (° C), wherein the alloy components are in mass fraction, and G is the grain size grade number (according to GB/T6394);
γSF＝γ0SF+1.59Ni-1.34Mn+0.06Mn2-1.75Cr+0.01Cr2+15.21Mo-5.59Si-60.69(C+1.2N)1/2+26.27(C+1.2N)×(Cr+Mn+Mo)1/2+0.61[Ni×(Cr+Mn)]1/2(mJ/m2) Wherein γ is0SF＝38mJ/m2。
Selecting a steel plate with the thickness of 0.2mm-2.5mm as a raw material, rolling the steel plate to a steel foil with the thickness of 15 μm-50 μm through 3-7 passes of rolling, wherein the single-pass deformation is 15% -60%, and performing softening annealing and final stress relief annealing between the rolling passes to obtain a sandwich structure with coexisting austenite and martensite in the thickness direction of the steel foil, namely the layered distribution of a surface structure which takes an austenite phase as a main phase and an internal structure which takes a martensite phase as a main phase is shown in figure 1.
The stainless steel foil provided by the invention is an austenite dual-phase structure with a Body Centered Cubic (BCC) structure martensite + Face Centered Cubic (FCC) structure, and rich substructures (entanglement dislocation configuration and small-angle grain boundaries) and a large amount of fine grains exist in martensite and austenite regions. The martensite structure is formed by rolling deformation induction, the austenite structure is formed by annealing reverse transformation and consists of retained austenite, the martensite structure accounts for 50-80% of the final structure, and the balance is the austenite structure. The martensite structure of BCC structure presents alpha line texture (near {223} - {112} <110> component) and near Taylor texture; the austenite structure is the typical FCC structural metal copper type ({112} <111>), Goss ({011} <100>) and brass type ({011} <211>) rolling texture.
Work hardening occurs in the rolling process, austenite is transformed into martensite, the deformation transformed martensite structure ensures the high hardness and the high strength of the steel foil, and the deformation residual austenite structure ensures the strength and the toughness. Abundant entanglement is generated in the deformation and phase change processes, the higher dislocation density in the dislocation configuration ensures the strength and hardness of the steel foil, and the refined grain structure promotes the improvement of the strength and toughness, especially under the condition that two phases exist in a staggered manner; meanwhile, in the rolling deformation process, martensite and austenite two-phase crushing exist in a staggered mode, and the formation of a strong texture is hindered to a certain extent due to the existence of a two-phase interface, so that strong anisotropy of performance caused by excessively strong deformation texture is avoided. In addition, the appropriate contents of C and N promote the solid solution strengthening of austenite phase and martensite phase and the work hardening rate; the 'fragmentation' of the deformed structure in the rolling process promotes the generation of fine-grained strengthening.
In conclusion, the high-hardness and high-strength stainless steel foil with the hardness of more than or equal to 580HV, the yield strength of more than or equal to 1800MPa and the tensile strength of more than or equal to 1800MPa is obtained through the coordination of martensite phase transformation strengthening and work hardening, solid solution strengthening and structure refining. The folding device can be folded, the bearing bending angle is more than or equal to 170 degrees, and when the bending radius R is 1.5mm-8mm, the folding times are more than or equal to 200000 and the folding device is not broken; the stainless steel foil is of an austenite + martensite dual-phase structure.
Drawings
FIG. 1 is a microstructure view of a steel foil according to the present invention in the full thickness direction on the side thereof (the gray regions are austenite phases; the black regions are martensite phases).
Detailed Description
Example 1
The solid solution austenite stainless steel sheet with the thickness of 1.0mm is adopted as the raw material and is rolled into the steel foil with the thickness of 0.035mm by 4 times. The stainless steel sheet has the composition shown in Table 1, the grain size grade G is 6, the alloy composition is the mass fraction, and M is calculatedD30/50About 35.6 ℃, and calculating gammaSF＝18.74mJ/m2. Testing the martensite content VM64.8%, austenite content VA35.2%. The measured Vickers hardness at 6 points is respectively as follows: HV595, HV571, HV 601, HV 587, HV 579, HV 602, average hardness HV589, reduced tensile strength 2050 MPa. Actually measuring that the bending radius R is about 4mm, the bending angle is 173 degrees, and the folding times are not less than 210000 times without fracture.
Example 2
Adopts raw materials with the thickness of 0.5mmRolling the solid solution austenite stainless steel sheet into a steel foil with the thickness of 0.025mm by 5 times, wherein the stainless steel sheet has the components shown in Table 1, the grain size grade number G is 7, the alloy components are mass fractions, and M is calculatedD30/50About 35.3 ℃, and calculating gammaSF＝19.24mJ/m2. Testing the martensite content VM62.3%, austenite content VA37.7 percent. The measured Vickers hardness at 6 points is respectively as follows: HV589, HV588, HV 585, HV 583, HV 585, HV 590, average hardness HV586, reduced tensile strength 2040 MPa. Actually measuring that the bending radius R is about 2.4mm, the bending angle is 174 degrees, and the folding times are not less than 210000 times without fracture.
Example 3
Solid solution austenite stainless steel sheet with thickness of 0.5mm is adopted as raw material and rolled into steel foil with thickness of 0.02mm by 5 times, the components of the stainless steel sheet are shown in table 1, the grain size grade number G is 6, the alloy components are mass fractions, M is calculatedD30/50Approximately equals 56.2 ℃, and gamma is calculatedSF＝19.06mJ/m2. Testing the martensite content VM72.4%, austenite content VA27.6%. The measured Vickers hardness at 6 points is respectively as follows: HV 602, HV 599, HV 601, HV 603, HV 601, HV 602, average hardness HV 601, and converted tensile strength 2100 MPa. Actually, when the bending radius R is about 2mm, the bending angle is between 172 degrees, and the folding times are not less than 210000 times without fracture.
Example 4
Solid solution austenite stainless steel sheet with the thickness of 0.3mm is adopted as raw material and is rolled into steel foil with the thickness of 0.015mm by 6 times, the components of the stainless steel sheet are shown in table 1, the grain size grade number G is 9, the alloy components are mass fractions, and M is calculatedD30/50About 30.7 ℃, and calculating gammaSF＝19.81mJ/m2. Testing the martensite content VM53.8%, austenite content VA46.2%. The measured Vickers hardness at 6 points is respectively as follows: HV 581, HV589, HV 577, HV 578, HV 583, HV 582, average hardness HV 582, reduced tensile strength 2026 MPa. Actually, when the bending radius R is about 1.7mm, the bending angle is 173 degrees, and the folding times are not broken for more than 210000 times.
Table 1 chemical composition (wt.%) of the board in each example
Claims (1)
1. The high-hardness high-strength foldable stainless steel foil is characterized in that an austenitic stainless steel sheet is used as a raw material, and the alloy components are as follows by mass percent: c + N is more than or equal to 0.1 percent and less than or equal to 0.2 percent, Ni + Cu is more than or equal to 6.56 percent and less than or equal to 8 percent, Mn is more than or equal to 0.82 percent and less than or equal to 1.5 percent, Cr is more than or equal to 16.4 percent and less than or equal to 18 percent, Mo is more than or equal to 0.01 percent and less than or equal to 0.03 percent, Si is more than or equal to 0.3 percent and less than or equal to 1 percent, and the balance is Fe; based on MD30/50And stacking fault energy gammaSFAdjusting the formula within the above component range, and obtaining a stainless steel foil product with the martensite accounting for 50% -80% by rolling and annealing for 3-7 times;
MD30/50is the temperature of 50% martensite formation under 30% cold deformation, gammaSFIs room temperature stacking fault energy mJ/m2；
MD30/50551-cozeb 462(C + N) -29(Ni + Cu) -8.1(Mn) -13.7(Cr) -18.5(Mo) -9.2(Si) -1.42(G-8) DEG C, wherein the alloy components are mass fractions, and G is the grain size grade number;
γSF＝γ0SF+1.59Ni-1.34Mn+0.06Mn2-1.75Cr+0.01Cr2+15.21Mo-5.59Si-60.69(C+1.2N)1/2+26.27(C+1.2N)×(Cr+Mn+Mo)1/2+0.61[Ni×(Cr+Mn)]1/2(mJ/m2) Wherein γ is0SF＝38mJ/m2；
Selecting a steel plate with the raw material thickness of 0.2mm-2.5mm, rolling the steel plate to a steel foil with the thickness of 15 μm-50 μm through 3-7 passes of rolling, wherein the single-pass deformation is 15% -60%, and performing softening annealing and final stress relief annealing between the rolling passes to obtain a sandwich structure with coexisting austenite and martensite in the thickness direction of the steel foil, namely a surface layer structure takes an austenite phase as a main part and an internal structure takes a martensite phase as a main part and is distributed in a layered manner;
obtaining a high-hardness and high-strength stainless steel foil with the hardness of more than or equal to 580HV, the yield strength of more than or equal to 1800MPa and the tensile strength of more than 1800MPa through the coordination of martensite phase transformation strengthening and work hardening, solid solution strengthening and structure refinement; the folding machine can be folded, the bending angle is more than or equal to 170 degrees, when the bending radius R is 1.5mm-8mm, the folding times are more than or equal to 200000, and the folding machine is not broken;
the stainless steel foil is of an austenite dual-phase structure with a body-centered cubic BCC structure martensite and a face-centered cubic FCC structure, rich substructures and a large number of fine grains exist in martensite and austenite regions, and the substructures refer to entanglement dislocation configurations and small-angle grain boundaries; martensite and austenite two-phase crushing exist in a staggered mode, the martensite structure is induced by rolling deformation, the austenite structure is formed by annealing reverse transformation and consists of retained austenite; the martensite structure of the BCC structure presents alpha line texture, namely near {223} - {112} <110> component and near Taylor texture; the austenite structure is a typical FCC structure metal copper type {112} <111>, Goss {011} <100> and brass type {011} <211> rolling texture.
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