CN108728734B - Antibacterial stainless steel for electrical equipment - Google Patents
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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
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- 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
- C21D1/18—Hardening; Quenching with or without subsequent tempering
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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
- C22C38/002—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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- 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
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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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
- 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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- 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
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
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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
- C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
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Abstract
The invention discloses antibacterial stainless steel for electrical equipment, and belongs to the technical field of stainless steel materials. The stainless steel comprises the following chemical components (in percentage by weight): c: less than or equal to 0.08; si: less than or equal to 0.50; mn: less than or equal to 1.00; p: less than or equal to 0.05; s: less than or equal to 0.05; ni: 8.0-12.0; cr: 18.0-20.0; cu: 2.0-5.0; mo: 0.5-1.5; ga: 0.05-0.80; the balance being Fe; after the stainless steel is subjected to special heat treatment, composite antibacterial phases (copper-rich phases and gallium-rich phases) can be dispersed and precipitated in a stainless steel matrix, and because the environment of the stainless steel for electrical equipment is generally humid, gallium ions can be effectively dissolved out due to the existence of the gallium-rich phases, and the gallium ions and the copper ions together can obviously inhibit the breeding of common bacteria, particularly mold, on the surface of the stainless steel for the lining of the electrical equipment. The stainless steel solves the problem of bacterial infection caused by using a stainless steel container in the existing stainless steel lining electrical equipment, and can be widely applied to various stainless steel electrical equipment such as washing machine drums, refrigerator linings, water heaters, water purifiers, humidifiers and the like.
Description
Technical Field
The invention relates to the field of stainless steel materials, and particularly provides antibacterial stainless steel for electrical equipment.
Background
Copper-containing antibacterial stainless steel is a class of antibacterial materials that can effectively penetrate bacterial cell walls with trace amounts of copper ions released when in contact with a solution environment, causing protein efflux and bacterial death. Based on the broad-spectrum antibacterial characteristic of copper, the copper-containing antibacterial stainless steel can be applied to wide use environments. However, in practical applications, the copper-containing antibacterial stainless steel faces different use environments, and the inhibition of the copper-containing antibacterial stainless steel on some bacteria still has certain disadvantages, which are specifically expressed in the environment of electrical equipment as follows: (1) in actual environment, the bacterial environment is generally parasitized by various bacteria, particularly the occurrence of mold, so that the sterilization efficiency of the copper-containing antibacterial stainless steel is greatly reduced. The possible reason is that the concentration of copper ions dissolved out from the surface of stainless steel is distributed by a plurality of bacteria, and thus the minimum inhibitory concentration required for a single bacterium is not achieved. (2) The sterilization time of the original antibacterial stainless steel is about 6 hours generally, because the dissolution rate of copper ions is directly related to the existence form and the inherent diffusion property of copper in the stainless steel matrix, namely, the critical concentration capable of inhibiting the proliferation of enough bacteria can be achieved after six hours generally according to the calculation of the inherent diffusion coefficient of the copper ions. For the stainless steel container for the electrical equipment, the relatively humid environment of the stainless steel container is relatively favorable for the propagation of bacteria, and the relatively long antibacterial action time is obviously unfavorable for the cleaning requirement of the stainless steel container. Therefore, the prior copper-containing antibacterial stainless steel cannot meet the environmental requirements of the use of electrical equipment. More importantly, the stainless steel material is an alloy taking iron as a basic element, when the stainless steel material is in contact with a solution medium environment, a large amount of iron ions are correspondingly dissolved out, and the released iron ions promote the proliferation of bacteria to a certain extent, which is also unfavorable for the antibacterial efficiency of copper ions.
In steel materials, the melting point of gallium metal is very low, only 29.8 ℃, and the boiling point reaches 2204 ℃. This provides the possibility for its application in ferrous metallurgical processes. In the field of metallic materials, iron-gallium alloys are common magnetostrictive materials. The main effect of gallium in iron is to significantly improve the magnetostrictive property of steel, and no report about the application of gallium in stainless steel is found.
Disclosure of Invention
The invention aims to provide antibacterial stainless steel for electrical equipment, which solves the problem that the existing material has relatively low antibacterial efficiency in the use environment of the electrical equipment.
The technical scheme of the invention is as follows:
an antibacterial stainless steel for electrical equipment is characterized in that: the stainless steel comprises the following chemical components in percentage by weight: c: less than or equal to 0.08; si: less than or equal to 0.50; mn: less than or equal to 1.00; p: less than or equal to 0.05; s: less than or equal to 0.05; ni: 8.0-12.0; cr: 18.0-20.0; cu: 2.0-5.0; mo: 0.5-1.5; ga: 0.05-0.80; the balance being Fe.
In the composition design of the stainless steel of the present invention, the alloying element gallium (Ga) is the most important alloying element in the new stainless steel. Ga is a necessary condition for ensuring that the stainless steel has stronger antibacterial efficiency, and is also a main innovation point of the invention. The Ga content of the stainless steel is 0.05-0.80%, and the Ga-rich phase is uniformly dispersed and precipitated in the steel under the condition of ensuring special heat treatment. When the content of Ga is low, even though special heat treatment is carried out, a Ga-rich phase is not easy to precipitate in a stainless steel matrix, and sufficient concentration of Ga ions cannot be precipitated when the stainless steel matrix is contacted with a solution medium, so that the normal proliferation activity of bacteria is inhibited, and the synergistic antibacterial effect of the Ga ions and the Cu ions is fully exerted. When the Ga content is relatively excessively high, excessive Ga-rich phase may cause severe degradation of hot workability and cold formability of the stainless steel, affecting practical use thereof. In addition, excessive Ga-rich phase precipitation can also damage the continuity of the stainless steel passive film and reduce the corrosion resistance of the stainless steel.
The invention also provides a heat treatment process of the antibacterial stainless steel for the electrical equipment, which comprises the following steps:
hot processing: homogenizing the steel ingot at 1050 ℃ and 1120 ℃ for 1-6 hours, cogging and forging, forging into a blank in multiple passes, wherein the final forging temperature is not lower than 900 ℃;
solution heat treatment: 1050 and 1120 ℃ solution treatment for 1-3 hours, and air cooling or water cooling to room temperature.
Aging heat treatment: treating at 570-720 ℃ for 1-8 hours, and cooling in air or water to room temperature.
The invention has the beneficial effects that:
1. for the existing Cu-containing antibacterial stainless steel, the aim of inhibiting the proliferation of bacteria is achieved mainly by means of the dissolution of a trace amount of Cu ions. Due to the limit of the dissolution rate and the dissolution concentration, the Cu-containing antibacterial stainless steel has poor antibacterial effect under the condition of multi-bacterium co-parasitism environment. Therefore, the invention is based on the existing Cu-containing antibacterial stainless steel, properly increases the Ga content in the steel, and is assisted with certain heat treatment, so that a sufficient Ga-rich phase can be precipitated on a substrate in the steel. When the stainless steel is contacted with a solution environment, Ga ions are dissolved out to inhibit the normal proliferation activity of bacteria, and meanwhile, the Ga element is coupled with the original antibacterial element Cu, so that the sterilization rate of the conventional Cu-containing stainless steel on common bacteria can be greatly improved.
2. Due to the addition of Ga, the antibacterial efficiency of the Cu-containing antibacterial stainless steel can be effectively improved.
The application range is as follows:
the antibacterial stainless steel for the electrical equipment has stronger antibacterial performance and timeliness, and can be widely applied to electrical equipment such as washing machine drums, refrigerator linings, water heaters, water purifiers, humidifiers and the like as various stainless steel electrical equipment materials.
Drawings
FIG. 1 shows the antibacterial stainless steel mixed bacteria (Escherichia coli and Aspergillus, bacteria concentration is 10)
5CFU/mL). (a) Cu containing antimicrobial stainless steel (b) Ga + Cu containing antimicrobial stainless steel (example 6) (c) blank control bacterial colony plot.
FIG. 2 shows the antibacterial stainless steel mixed bacteria (Escherichia coli and Aspergillus, bacteria concentration 10)
5CFU/mL). (Cu-containing antibacterial stainless steel and Ga + Cu-containing antibacterial stainless steel, example 6).
Detailed Description
According to the chemical composition range set by the antibacterial stainless steel of the invention, 15 kg of each of the antibacterial stainless steel of the examples 1-6 and the comparative example of the furnace 1 is smelted by a 25 kg vacuum induction furnace, and the chemical composition is shown in Table 1.
The forging process comprises the following steps: the alloy cast ingot is subjected to homogenization heat treatment at 1070 +/-20 ℃ for 2.5 hours to cogging, and is forged into a bloom plate with the thickness of 40 multiplied by 90mm by three heats, and the finish forging temperature is 960 ℃.
The hot rolling process comprises the following steps: the initial rolling blank is kept at 1060 +/-5 ℃ for 2 hours and is rolled into a performance testing plate by multiple passes, and the plate thickness of the embodiment is 6 mm.
Table 1 chemical composition (wt.%) of antibacterial stainless steel of examples and comparative examples
1. Detection of antibacterial Properties
According to the relevant standards of ' JIS Z2801 & lt 2000 & gt antibacterial processed product-antibacterial property test method and antibacterial effect ', GB/T2591-2003 & lt antibacterial property test method and antibacterial effect & gt for antibacterial plastics ', the bacteria concentration is selected to be 10
5CFU/mL. The sterilization rate of the antibacterial stainless steel of the examples and the comparative examples after the antibacterial stainless steel acts on the mixed bacteria (Escherichia coli + Aspergillus) is quantitatively tested. Wherein the calculation formula of the antibacterial rate is as follows: percent antibacterial ratio [ (% viable count of blank control sample-viable count of antibacterial stainless steel sample)/viable count of blank control sample]X 100, the viable count of the blank control sample is the viable count of bacteria cultured on an inert glass flat plate, and the viable count of the antibacterial stainless steel is the viable count of bacteria cultured on the antibacterial stainless steel containing Cu or the antibacterial stainless steel containing (Cu + Ga).
2. Antimicrobial kinetic Performance testing
Selecting bacterial liquid (bacterial concentration is 10)
5CFU/mL) and the antibacterial stainless steel sample piece are acted for different times, and then calculated according to the calculation formula of the bactericidal rate and an antibacterial dynamic curve is drawn according to the operation regulations in relevant standards such as JIS Z2801 & 2000 antibacterial processing product-antibacterial property test method and antibacterial effect and GB/T2591 & 2003 antibacterial plastic antibacterial property test method and antibacterial effect.
Example 1
The heat treatment process of the antibacterial stainless steel of example 1 is as follows:
keeping the temperature at 1055 ℃ for 1h, and cooling the steel to room temperature by water to ensure that Ga in the steel is in a supersaturated state; then keeping the temperature at 590 ℃ for 5h to separate out a Ga-rich phase and a Cu-rich phase from the steel, and cooling the steel to room temperature by water.
According to the antibacterial detection method, the antibacterial performance of the mixed bacteria is detected, and the antibacterial rate result is 94.4%.
Example 2
In this embodiment, the heat treatment process of the antibacterial stainless steel is as follows:
keeping the temperature at 1060 ℃ for 2h, and cooling the steel to room temperature by water to ensure that Ga in the steel is in a supersaturated state; and then keeping the temperature at 620 ℃ for 6h to separate out enough volume fractions of Ga-rich phase and Cu-rich phase from the steel, and cooling the steel to room temperature by water. According to the antibacterial detection method, the antibacterial performance of the mixed bacteria is detected, and the antibacterial rate result is 95.0%.
Example 3
In this embodiment, the heat treatment process of the antibacterial stainless steel is as follows:
keeping the temperature at 1060 ℃ for 3h, and cooling the steel to room temperature by water to ensure that Ga in the steel is in a supersaturated state; and then keeping the temperature at 700 ℃ for 4h to separate out enough Ga-rich phase and Cu-rich phase with volume fraction in the steel, and cooling the steel to room temperature in air. According to the antibacterial detection method, the antibacterial performance of the mixed bacteria is detected, and the antibacterial rate result is 95.7%.
Example 4
In this embodiment, the heat treatment process of the antibacterial stainless steel is as follows:
keeping the temperature at 1080 ℃ for 1.5h, and cooling the steel to room temperature by water to ensure that Ga in the steel is in a supersaturated state; then keeping the temperature at 650 ℃ for 4h to separate out enough Ga-rich phase and Cu-rich phase in volume fraction from the steel, and cooling the steel to room temperature. According to the antibacterial detection method, the antibacterial performance of the mixed bacteria is detected, and the antibacterial rate result is 96.8%.
Example 5
In this embodiment, the heat treatment process of the antibacterial stainless steel is as follows:
keeping the temperature at 1100 ℃ for 3h, and cooling the steel to room temperature by water to ensure that Ga in the steel is in a supersaturated state; and then keeping the temperature at 680 ℃ for 6h to separate out enough Ga-rich phase and Cu-rich phase with volume fraction in the steel, and cooling the steel to room temperature in air. According to the antibacterial detection method, the antibacterial performance of the mixed bacteria is detected, and the antibacterial rate result is 98.9%.
Example 6
In this embodiment, the heat treatment process of the antibacterial stainless steel is as follows:
keeping the temperature at 1120 ℃ for 3h, and cooling the steel to room temperature by water to ensure that Ga in the steel is in a supersaturated state; and then keeping the temperature at 720 ℃ for 2h to separate out enough Ga-rich phase and Cu-rich phase in volume fraction from the steel, and cooling the steel to room temperature in air. According to the antibacterial detection method, the antibacterial performance of the mixed bacteria is detected, and the antibacterial rate result is 99.9%.
Comparative example
In this embodiment, the heat treatment process of the antibacterial stainless steel is as follows:
preserving heat for 4.5h at 1080 ℃, and cooling the steel to room temperature by water to ensure that Cu in the steel is in a supersaturated state; and then keeping the temperature at 600 ℃ for 6h to precipitate a Cu-rich phase with enough volume fraction in the steel, and cooling the steel to room temperature in air. According to the antibacterial detection method, the antibacterial performance of the mixed bacteria is detected, and the antibacterial rate result is 52.9%.
Generally, a material having an antibacterial rate of more than 90% may be referred to as an antibacterial material. The antibacterial result of the embodiment on the mixed bacteria shows that the antibacterial stainless steel provided by the invention has the antibacterial rate of more than 90 percent, and the antibacterial effect of the comparative example Cu-containing antibacterial stainless steel is obviously reduced. In addition, the antimicrobial kinetics curves were plotted in example 6 and comparative example, respectively, and the antimicrobial results are shown in fig. 2. Compared with the Cu-containing antibacterial stainless steel, the Cu + Ga-containing antibacterial stainless steel has better antibacterial efficiency, and the antibacterial action time is obviously shortened.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (6)
1. An antibacterial stainless steel for electrical equipment is characterized in that: the stainless steel comprises the following chemical components in percentage by weight: c: less than or equal to 0.08; si: less than or equal to 0.50; mn: less than or equal to 1.00; p: less than or equal to 0.05; s: less than or equal to 0.05; ni: 8.0-12.0; cr: 18.0-20.0; cu: 2.0-5.0; mo: 0.5-1.5; ga: 0.35-0.80; the balance being Fe; the stainless steel has a concentration of 10
5CFU/mL bacteria have effective antibacterial effect.
2. The antibacterial stainless steel for electric appliances according to claim 1, characterized in that: the stainless steel comprises the following chemical components in percentage by weight: c: less than or equal to 0.03; si: less than or equal to 0.50; mn: less than or equal to 1.00; p: less than or equal to 0.005; s: less than or equal to 0.005; ni: 8.5-9.5; cr: 18.5-19.5; cu: 3.0-4.0; mo: 0.6-1.0; ga: 0.35-0.60; the balance being Fe.
3. A method for preparing the antibacterial stainless steel for the electrical equipment as claimed in claim 1, which is characterized in that: the antibacterial stainless steel is obtained by adopting the following method: the vacuum induction smelting can also be obtained by adopting an electric arc furnace and continuous casting smelting or an electric arc furnace smelting and external refining.
4. A method for preparing the antibacterial stainless steel for electrical equipment according to claim 3, characterized in that: the stainless steel obtained by smelting adopts the following hot working and heat treatment processes:
hot processing: homogenizing the steel ingot at 1050 ℃ and 1120 ℃ for 1-6 hours, cogging and forging, forging into a blank in multiple passes, wherein the final forging temperature is not lower than 900 ℃;
solution heat treatment: 1050-1120 ℃ solution treatment for 1-3 hours, and air cooling or water cooling to room temperature;
aging heat treatment: treating at 570-720 ℃ for 1-8 hours, and cooling in air or water to room temperature.
5. Use of the antibacterial stainless steel of claim 1 as a material for manufacturing electrical equipment.
6. Use of an antimicrobial stainless steel according to claim 5, characterized in that: the electrical equipment is one or more of a washing machine roller, a refrigerator liner, a water heater, a water purifier and a humidifier.
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|---|---|---|---|---|
| CN103233174A (en) * | 2013-04-26 | 2013-08-07 | 中国科学院金属研究所 | High-nitrogen austenitic stainless steel for vascular stent and application thereof |
| JP2017014538A (en) * | 2015-06-26 | 2017-01-19 | 新日鐵住金ステンレス株式会社 | Austenitic stainless steel sheet for exhaust component excellent in heat resistance and surface smoothness and manufacturing method therefor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103233174A (en) * | 2013-04-26 | 2013-08-07 | 中国科学院金属研究所 | High-nitrogen austenitic stainless steel for vascular stent and application thereof |
| JP2017014538A (en) * | 2015-06-26 | 2017-01-19 | 新日鐵住金ステンレス株式会社 | Austenitic stainless steel sheet for exhaust component excellent in heat resistance and surface smoothness and manufacturing method therefor |
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| Title |
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| 无机镓化合物抗菌性能研究;马超;《中国优秀硕士学位论文全文数据库 医药卫生科技辑》;20160115;第E079-78页 * |
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| CN108728734A (en) | 2018-11-02 |
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