CN112959755A - Multilayer antibacterial stainless steel material and preparation method thereof - Google Patents
Multilayer antibacterial stainless steel material and preparation method thereof Download PDFInfo
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
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- B32B15/18—Layered products comprising a layer of metal comprising iron or steel
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- B32—LAYERED PRODUCTS
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- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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- 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
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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- C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C—CHEMISTRY; METALLURGY
- 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
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
- B32B2307/7145—Rot proof, resistant to bacteria, mildew, mould, fungi
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Abstract
The invention relates to a multilayer antibacterial stainless steel material which sequentially comprises a surface layer, a middle layer, a second middle layer and a bottom layer from top to bottom, wherein the bottom layer is made of a stainless steel material, the surface layer and the second middle layer are made of a copper-containing antibacterial stainless steel material, the middle layer is made of a copper-gallium-containing antibacterial stainless steel material, and the thickness of the surface layer is 10-500 micrometers. The invention also relates to a preparation method of the multilayer antibacterial stainless steel material. The existing copper-containing antibacterial material has poor antibacterial effect, and Ga and copper can be complemented so as to obtain better antibacterial effect, but when the content of Ga is too high, the hot working performance and cold forming performance of the stainless steel can be seriously influenced, and the practical application of the stainless steel is limited. According to the invention, by designing the multilayer antibacterial stainless steel material and designing the copper-containing antibacterial material with high Ga content in the middle layer, the copper-containing antibacterial material on the surface has a better antibacterial effect.
Description
Technical Field
The invention relates to a multilayer antibacterial stainless steel material and a preparation method thereof.
Background
The antibacterial stainless steel is a new steel material developed in recent years, and shows strong, broad-spectrum and durable sterilization functions by utilizing continuously dissolved trace Cu ions, and the new material with integrated structure and function has realized industrial production and application.
The antibacterial effect of stainless steel in the air environment is unsatisfactory. Since copper is present in copper-containing stainless steel in a very small percentage by mass, and cannot be present in a much larger percentage than copper alloys, it is capable of forming sufficient osmotic pressure to destroy a sufficient number of bacterial cell walls when in contact with bacteria. In addition, in order to achieve better antibacterial performance in the industrial production process of the copper-containing antibacterial stainless steel, a series of heat treatment processes such as solid solution, aging and the like are additionally carried out to precipitate enough nano copper-rich phases in the matrix, so that the production process is increased for the industrial production of the copper-containing antibacterial stainless steel, and the cost is increased.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a multilayer antibacterial stainless steel material which is characterized by sequentially comprising a surface layer, a middle layer, a second middle layer and a bottom layer from top to bottom, wherein the bottom layer is made of a stainless steel material, the surface layer and the second middle layer are made of a copper-containing antibacterial stainless steel material, the middle layer is made of a copper-gallium-containing antibacterial stainless steel material, the thickness of the surface layer is 10-500 micrometers, and the copper-gallium-containing antibacterial stainless steel material comprises the following components in percentage by mass:
c: less than or equal to 0.010; si: less than or equal to 0.50; mn: less than or equal to 1.00; p: less than or equal to 0.03; s: less than or equal to 0.04; ni: 8.0-12.0; cr: 15.0-25.0; cu: 2.0-5.0; ga: 3.50-6.50; the balance being Fe.
The copper-containing antibacterial stainless steel material comprises the following components in percentage by mass:
c: less than or equal to 0.010; si: less than or equal to 0.50; mn: less than or equal to 1.00; p: less than or equal to 0.03; s: less than or equal to 0.04; ni: 8.0-12.0; cr: 15.0-25.0; cu: 2.0-6.0; the balance being Fe.
The thickness of the intermediate layer is 5-200 microns.
The bottom layer material is selected from one or more of martensitic steel, ferritic steel, austenitic-ferritic stainless steel and precipitation hardening stainless steel.
A preparation method of a multilayer antibacterial stainless steel material comprises the following steps:
manufacturing the copper-gallium-containing antibacterial stainless steel material in the middle layer into a rod shape;
manufacturing a copper-containing antibacterial stainless steel material into a filament shape and winding the filament shape on the surface of a rod-shaped copper-containing gallium-containing antibacterial stainless steel material;
pressing the copper-gallium-containing antibacterial stainless steel material wound with the copper-containing antibacterial stainless steel material to form a sheet-shaped antibacterial stainless steel material;
the sheet antibacterial stainless steel material and the stainless steel material on the bottom layer are subjected to soaking in a soaking furnace and then enter a hot continuous rolling unit for hot rolling to obtain a multilayer antibacterial stainless steel material with the surface layer thickness of 10-500 microns;
the copper-gallium-containing antibacterial stainless steel material comprises the following components in percentage by mass:
c: less than or equal to 0.010; si: less than or equal to 0.50; mn: less than or equal to 1.00; p: less than or equal to 0.03; s: less than or equal to 0.04; ni: 8.0-12.0; cr: 15.0-25.0; cu: 2.0-5.0; ga: 3.50-6.50; the balance being Fe.
The preparation method of the multilayer antibacterial stainless steel material also comprises the heat treatment step:
the method comprises the steps of firstly carrying out heat preservation for 20min at 1120 ℃, carrying out solid solution treatment, then carrying out heat preservation for 4-5 h at 850 ℃, then carrying out natural cooling for stabilization treatment, and then carrying out tempering at 380-400 ℃ for stress relief treatment.
The preparation method of the multilayer antibacterial stainless steel material also comprises the aging treatment step:
and preserving the heat of the multilayer antibacterial stainless steel material at 550 ℃ for 6 hours for aging treatment.
The copper-containing antibacterial stainless steel material comprises the following components in percentage by mass:
c: less than or equal to 0.010; si: less than or equal to 0.50; mn: less than or equal to 1.00; p: less than or equal to 0.03; s: less than or equal to 0.04; ni: 8.0-12.0; cr: 15.0-25.0; cu: 2.0-6.0; the balance being Fe.
The thickness of the intermediate layer is 5-200 microns.
The bottom layer material is selected from one or more of martensitic steel, ferritic steel, austenitic-ferritic stainless steel and precipitation hardening stainless steel.
The existing copper-containing antibacterial material has poor antibacterial effect, and Ga and copper can be complemented so as to obtain better antibacterial effect, but when the content of Ga is too high, the hot working performance and cold forming performance of the stainless steel can be seriously influenced, and the practical application of the stainless steel is limited. According to the invention, by designing the multilayer antibacterial stainless steel material and designing the copper-containing antibacterial material with high Ga content in the middle layer, the copper-containing antibacterial material on the surface has a better antibacterial effect.
The above-described and other features, aspects, and advantages of the present application will become more apparent with reference to the following detailed description.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention without any inventive step, are within the scope of protection of the invention.
Unless defined otherwise, technical or scientific terms used herein shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs. The use of "first," "second," and similar terms in the description and claims of the present application do not denote any order, quantity, or importance, but rather the terms are used to distinguish one element from another. Also, the use of the terms "a" or "an" and the like do not denote a limitation of quantity, but rather denote the presence of at least one.
The utility model provides an antibiotic stainless steel material of multilayer, its characterized in that, antibiotic stainless steel material of multilayer includes superficial layer, intermediate level, second intermediate level, bottom from top to bottom in proper order, the bottom is stainless steel material, and superficial layer and second intermediate level are antibiotic stainless steel material containing copper, and the intermediate level is antibiotic stainless steel material containing copper gallium, the thickness of superficial layer is 10-500 microns, antibiotic stainless steel material containing copper gallium comprises the following components by mass percent:
c: less than or equal to 0.010; si: less than or equal to 0.50; mn: less than or equal to 1.00; p: less than or equal to 0.03; s: less than or equal to 0.04; ni: 8.0-12.0; cr: 15.0-25.0; cu: 2.0-5.0; ga: 3.50-6.50; the balance being Fe.
The copper-containing antibacterial stainless steel material comprises the following components in percentage by mass:
c: less than or equal to 0.010; si: less than or equal to 0.50; mn: less than or equal to 1.00; p: less than or equal to 0.03; s: less than or equal to 0.04; ni: 8.0-12.0; cr: 15.0-25.0; cu: 2.0-6.0; the balance being Fe.
The thickness of the intermediate layer is 5-200 microns.
The bottom layer material is selected from one or more of martensitic steel, ferritic steel, austenitic-ferritic stainless steel and precipitation hardening stainless steel.
A preparation method of a multilayer antibacterial stainless steel material comprises the following steps:
manufacturing the copper-gallium-containing antibacterial stainless steel material in the middle layer into a rod shape;
manufacturing a copper-containing antibacterial stainless steel material into a filament shape and winding the filament shape on the surface of a rod-shaped copper-containing gallium-containing antibacterial stainless steel material;
pressing the copper-gallium-containing antibacterial stainless steel material wound with the copper-containing antibacterial stainless steel material to form a sheet-shaped antibacterial stainless steel material;
the sheet antibacterial stainless steel material and the stainless steel material on the bottom layer are subjected to soaking in a soaking furnace and then enter a hot continuous rolling unit for hot rolling to obtain a multilayer antibacterial stainless steel material with the surface layer thickness of 10-500 microns;
the copper-gallium-containing antibacterial stainless steel material comprises the following components in percentage by mass:
c: less than or equal to 0.010; si: less than or equal to 0.50; mn: less than or equal to 1.00; p: less than or equal to 0.03; s: less than or equal to 0.04; ni: 8.0-12.0; cr: 15.0-25.0; cu: 2.0-5.0; ga: 3.50-6.50; the balance being Fe.
The preparation method of the multilayer antibacterial stainless steel material also comprises the heat treatment step:
the method comprises the steps of firstly carrying out heat preservation for 20min at 1120 ℃, carrying out solid solution treatment, then carrying out heat preservation for 4-5 h at 850 ℃, then carrying out natural cooling for stabilization treatment, and then carrying out tempering at 380-400 ℃ for stress relief treatment.
The preparation method of the multilayer antibacterial stainless steel material also comprises the aging treatment step:
and preserving the heat of the multilayer antibacterial stainless steel material at 550 ℃ for 6 hours for aging treatment.
The copper-containing antibacterial stainless steel material comprises the following components in percentage by mass:
c: less than or equal to 0.010; si: less than or equal to 0.50; mn: less than or equal to 1.00; p: less than or equal to 0.03; s: less than or equal to 0.04; ni: 8.0-12.0; cr: 15.0-25.0; cu: 2.0-6.0; the balance being Fe.
The thickness of the intermediate layer is 5-200 microns.
The bottom layer material is selected from one or more of martensitic steel, ferritic steel, austenitic-ferritic stainless steel and precipitation hardening stainless steel.
The existing copper-containing antibacterial material has poor antibacterial effect, and Ga and copper can be complemented so as to obtain better antibacterial effect, but when the content of Ga is too high, the hot working performance and cold forming performance of the stainless steel can be seriously influenced, and the practical application of the stainless steel is limited. According to the invention, by designing the multilayer antibacterial stainless steel material and designing the copper-containing antibacterial material with high Ga content in the middle layer, the copper-containing antibacterial material on the surface has a better antibacterial effect.
Detection of antibacterial Properties
The antibacterial experiment adopts dry surface similar to air environment for co-culture, and comprises the following specific steps:
after the sample is placed in normal temperature water for 2 months, the sample is placed in a 24-well plate, and 5 mu L of 106CFU/mL bacterial-concentrated bacterial liquid is sucked by a sterile gun head and is dripped on the surface of the sample in each well. Due to the action of surface tension, the bacterial liquid is completely paved so that the thickness of a surface liquid film is almost 0, and the bacteria are ensured to be fully contacted with the surface of the sample. Ensuring that the environmental humidity of the co-culture is above 90 percent, the temperature is constant at 37 ℃, and the co-culture time is not more than 12 time points. After a certain time point, taking out the sample together with the bacterial liquid on the sample, putting the sample into a centrifuge tube, adding a proper phosphate buffer saline solution (PBS buffer solution) to dilute the bacterial suspension, and fully oscillating in a shaking table. And finally, sucking 0.1mL of bacterial suspension, uniformly coating the bacterial suspension on an agar medium plate, culturing at the constant temperature of 37 ℃ for 24h, and taking out the plate for colony counting after the time point is reached. The antibacterial ratio C is calculated by the following equation:
C(％)＝100×(A-B)/A
wherein A represents the colony number of the blank control group, and B represents the colony number of the experimental group.
Example 1
Making the copper-gallium-containing antibacterial stainless steel material (C is less than or equal to 0.010 percent, Si is less than or equal to 0.50 percent, Mn is less than or equal to 1.00 percent, P is less than or equal to 0.03 percent, S is less than or equal to 0.04 percent, Ni is 10 percent, Cr is 20 percent, Cu is 3 percent, Ga is 5 percent, and the balance is Fe) of the middle layer into a rod shape; preparing a copper-containing antibacterial stainless steel material (C is less than or equal to 0.010 percent, Si is less than or equal to 0.50 percent, Mn is less than or equal to 1.00 percent, P is less than or equal to 0.03 percent, S is less than or equal to 0.04 percent, Ni is 10 percent, Cr is 20 percent, Cu is 3 percent, and the balance is Fe) into threads and winding the threads on the surface of a rod-shaped copper-gallium-containing antibacterial stainless steel material; pressing the copper-gallium-containing antibacterial stainless steel material wound with the copper-containing antibacterial stainless steel material to form a sheet-shaped antibacterial stainless steel material; the sheet-shaped antibacterial stainless steel material and the stainless steel material of the bottom layer are subjected to soaking in a soaking furnace and then enter a hot continuous rolling mill for hot rolling to obtain a multilayer antibacterial stainless steel material with the surface layer thickness of 100 microns, the middle layer thickness of 20 microns and the second middle layer rear guard of 100 microns;
the method comprises the steps of shearing a continuous casting composite blank to obtain a plate blank with a fixed length, heating the plate blank at 1250 ℃ for 30min through a soaking pit, then entering a hot continuous rolling mill set for three-pass hot rolling, wherein the reduction deformation of each pass is 15-20%, the thickness of the plate is deformed from 20mm to about 11mm, heating the rolled plate at 1120 ℃ for 20min, then rolling the plate for four passes again, the reduction deformation of each pass is 10-15%, the thickness of the plate is deformed from about 7mm, heating the rolled plate at 950 ℃ for 10min, then rolling the plate for three passes again, the reduction deformation of each pass is 10-15%, and the thickness of the plate is deformed to about 5 mm.
Then, blanking is carried out by using a punch, rolling is carried out on the blanking, and then stamping is carried out by using the punch to obtain a semi-finished product. And then carrying out antibacterial heat treatment on the obtained semi-finished product with the antibacterial surface layer, specifically, carrying out aging treatment on the semi-finished product at 550 ℃ for 6h to precipitate a dispersed epsilon-Cu precipitated phase on the surface layer. The method comprises the steps of firstly carrying out coarse grinding on the surface of a material by using a grinding wheel, then carrying out fine grinding by using a polishing soap, cleaning the material after grinding and polishing by using trichloroethylene, heating by adopting an electric heating mode in the cleaning process at the temperature of 80 ℃, continuously introducing fluorine above a tank body in the heating process, directly drying by using equipment with drying equipment after cleaning, and finally packaging and warehousing the dried finished product. The antibacterial rate of escherichia coli of the multilayer antibacterial stainless steel material is 99.9%, and the antibacterial rate of staphylococcus aureus is 99.9%.
Example 2
The multi-layer antibacterial stainless steel material had a surface layer thickness of 50 microns, an intermediate layer thickness of 20 microns and a second intermediate layer backset of 50 microns as in example 1. The antibacterial rate of escherichia coli of the multilayer antibacterial stainless steel material is 99.9%, and the antibacterial rate of staphylococcus aureus is 99.9%.
Example 3
The multi-layer antibacterial stainless steel material had a surface layer thickness of 50 microns, an intermediate layer thickness of 100 microns and a second intermediate layer backset of 50 microns as in example 1. The antibacterial rate of escherichia coli of the multilayer antibacterial stainless steel material is 99.9%, and the antibacterial rate of staphylococcus aureus is 99.9%.
Comparative example 1
The surface layer thickness of the multi-layer antibacterial stainless steel material was 50 micrometers and the second intermediate layer back was 50 micrometers as in example 1. The antibacterial rate of escherichia coli of the multilayer antibacterial stainless steel material is 95.2%, and the antibacterial rate of staphylococcus aureus is 94.3%.
While there have been shown and described what are at present considered the fundamental principles and essential features of the invention and its advantages, it will be apparent to those skilled in the art that the invention is not limited to the details of the foregoing exemplary embodiments, but is capable of other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and the description is given here only for clarity, and those skilled in the art should integrate the description, and the embodiments may be combined appropriately to form other embodiments understood by those skilled in the art.
Claims (10)
1. The utility model provides an antibiotic stainless steel material of multilayer, its characterized in that, antibiotic stainless steel material of multilayer includes superficial layer, intermediate level, second intermediate level, bottom from top to bottom in proper order, the bottom is stainless steel material, and superficial layer and second intermediate level are antibiotic stainless steel material containing copper, and the intermediate level is antibiotic stainless steel material containing copper gallium, the thickness of superficial layer is 10-500 microns, antibiotic stainless steel material containing copper gallium comprises the following components by mass percent:
c: less than or equal to 0.010; si: less than or equal to 0.50; mn: less than or equal to 1.00; p: less than or equal to 0.03; s: less than or equal to 0.04; ni: 8.0-12.0; cr: 15.0-25.0; cu: 2.0-5.0; ga: 3.50-6.50; the balance being Fe.
2. The multilayer antibacterial stainless steel material as claimed in claim 1, characterized in that the copper-containing antibacterial stainless steel material consists of the following components in percentage by mass:
c: less than or equal to 0.010; si: less than or equal to 0.50; mn: less than or equal to 1.00; p: less than or equal to 0.03; s: less than or equal to 0.04; ni: 8.0-12.0; cr: 15.0-25.0; cu: 2.0-6.0; the balance being Fe.
3. A multi-layer antibacterial stainless steel material according to claim 1, characterized in that the thickness of the intermediate layer is 5-200 μm.
4. The multi-layer antibacterial stainless steel material as claimed in claim 1, wherein the primer layer material is selected from one or more of martensitic steel, ferritic steel, austenitic-ferritic stainless steel and precipitation hardening stainless steel.
5. A preparation method of a multilayer antibacterial stainless steel material is characterized by comprising the following steps:
manufacturing the copper-gallium-containing antibacterial stainless steel material in the middle layer into a rod shape;
manufacturing a copper-containing antibacterial stainless steel material into a filament shape and winding the filament shape on the surface of a rod-shaped copper-containing gallium-containing antibacterial stainless steel material;
pressing the copper-gallium-containing antibacterial stainless steel material wound with the copper-containing antibacterial stainless steel material to form a sheet-shaped antibacterial stainless steel material;
the sheet antibacterial stainless steel material and the stainless steel material on the bottom layer are subjected to soaking in a soaking furnace and then enter a hot continuous rolling unit for hot rolling to obtain a multilayer antibacterial stainless steel material with the surface layer thickness of 10-500 microns;
the copper-gallium-containing antibacterial stainless steel material comprises the following components in percentage by mass:
c: less than or equal to 0.010; si: less than or equal to 0.50; mn: less than or equal to 1.00; p: less than or equal to 0.03; s: less than or equal to 0.04; ni: 8.0-12.0; cr: 15.0-25.0; cu: 2.0-5.0; ga: 3.50-6.50; the balance being Fe.
6. The method for preparing a multi-layer antibacterial stainless steel material according to claim 5, characterized in that the method for preparing a multi-layer antibacterial stainless steel material further comprises the heat treatment steps of:
the method comprises the steps of firstly carrying out heat preservation for 20min at 1120 ℃, carrying out solid solution treatment, then carrying out heat preservation for 4-5 h at 850 ℃, then carrying out natural cooling for stabilization treatment, and then carrying out tempering at 380-400 ℃ for stress relief treatment.
7. The method for preparing a multilayer antibacterial stainless steel material according to claim 5, characterized by further comprising the step of aging treatment:
and preserving the heat of the multilayer antibacterial stainless steel material at 550 ℃ for 6 hours for aging treatment.
8. The preparation method of the multilayer antibacterial stainless steel material as claimed in claim 5, characterized in that the copper-containing antibacterial stainless steel material comprises the following components in percentage by mass:
c: less than or equal to 0.010; si: less than or equal to 0.50; mn: less than or equal to 1.00; p: less than or equal to 0.03; s: less than or equal to 0.04; ni: 8.0-12.0; cr: 15.0-25.0; cu: 2.0-6.0; the balance being Fe.
9. The method for preparing a multilayer antibacterial stainless steel material according to claim 5, wherein the thickness of the intermediate layer is 5-200 μm.
10. The method for preparing a multilayer antibacterial stainless steel material according to claim 5, characterized in that the bottom layer material is selected from one or more of martensitic steel, ferritic steel, austenitic-ferritic stainless steel and precipitation hardening stainless steel.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| TWI832432B (en) * | 2022-09-16 | 2024-02-11 | 東盟開發實業股份有限公司 | Method for preparing antibacterial stainless steel by surface alloying |
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| US20070202334A1 (en) * | 2005-12-29 | 2007-08-30 | Rong-Cai Xie | Nanoparticles containing titanium oxide |
| CN108728754A (en) * | 2018-04-04 | 2018-11-02 | 中国科学院金属研究所 | A kind of martensite antimicrobial stainless steel |
| CN111519112A (en) * | 2020-06-10 | 2020-08-11 | 滨州阳信华美不锈钢制品股份有限公司 | Preparation method of antibacterial stainless steel material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI832432B (en) * | 2022-09-16 | 2024-02-11 | 東盟開發實業股份有限公司 | Method for preparing antibacterial stainless steel by surface alloying |
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