CN111996442A - Ferrite stainless steel with strong antibacterial function - Google Patents
Ferrite stainless steel with strong antibacterial function Download PDFInfo
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- CN111996442A CN111996442A CN202010693185.4A CN202010693185A CN111996442A CN 111996442 A CN111996442 A CN 111996442A CN 202010693185 A CN202010693185 A CN 202010693185A CN 111996442 A CN111996442 A CN 111996442A
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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
- C22C38/20—Ferrous alloys, e.g. steel alloys containing chromium with copper
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- 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
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- 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
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/002—Heat treatment of ferrous alloys containing Cr
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- 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
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/005—Heat treatment of ferrous alloys containing Mn
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- 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
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/008—Heat treatment of ferrous alloys containing Si
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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
- C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
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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
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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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- 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
- C21D2211/005—Ferrite
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Abstract
The invention aims to provide a novel ferritic stainless steel material with a strong antibacterial function, and compared with the traditional ferritic stainless steel, the novel ferritic stainless steel material is further improved in antibacterial function under the heat treatment states of solid solution and aging, so that the antibacterial rate can reach 99.9%, and the corrosion of bacterial microorganisms and the risk of secondary pollution of water caused by the use of the ferritic stainless steel are remarkably reduced. The stainless steel comprises the following chemical components in percentage by weight: 16.5-20.0; cu: 1.0-3.0; nd is 0.8-1.5; c is less than or equal to 0.025; si is less than or equal to 1.0; mn is less than or equal to 1.0; p is less than or equal to 0.04; s is less than or equal to 0.03; the balance being Fe. The ferritic stainless steel with the strong antibacterial function can become an excellent substitute product for the prior ferritic stainless steel.
Description
Technical Field
The invention relates to the technical field of ferritic stainless steel materials, in particular to ferritic stainless steel with a strong antibacterial function.
Background
In the application field of stainless steel, ferritic stainless steel can be used as a substitute material of austenitic stainless steel, has the characteristics of large heat conductivity coefficient, small expansion coefficient, good oxidation resistance, excellent stress corrosion resistance and the like, and is mainly used for manufacturing parts or closed containers resistant to corrosion of atmosphere, water vapor, water and oxidizing acid. Ferritic stainless steel contains no Ni, the main elements are Cr (> 12%) and Fe, Cr is the main element of stainless steel which plays a role in corrosion resistance, and it is relatively inexpensive and stable. The ferritic stainless steel is suitable for two medium environments of cold water and hot water, so that the ferritic stainless steel has good market application in the aspects of liquid storage containers and conveying pipelines. And, it has excellent formability and is suitable for bending, cutting and drilling. The above advantages replace traditional carbon steel and austenitic stainless steel to some extent.
Conventional ferritic stainless steel liquid transportation or storage facilities can form bacterial biofilms inside the cavities after long-term use, which can lead to extensive corrosion of pipelines and secondary contamination of the water in the pipes as a result of long-term accumulation of microorganisms contained in the transported water. As is well known, water is an important substance on which humans rely for survival, and there are always 4 sources of microorganisms in water, including indigenous microorganisms in water, microorganisms in soil, microorganisms in production and life, and microorganisms in the air. With the increasing living standard of people, the sanitation management of bacteria prevention, bacteria resistance and virus resistance becomes a problem which is very concerned by the current society, the traditional mode for preventing the propagation of bacterial microorganisms is to use bactericides, but the bactericides can easily cause pollution to the natural environment and poison the human body, so the development of stainless steel with certain antibacterial function has important significance.
Stainless steel materials having antibacterial functions are green antibacterial materials having both structural and functional properties, and have become a focus of attention for workers engaged in bacterial microorganism research. At present, the application of the antibacterial functional stainless steel can already achieve 99.9% of antibacterial performance on common gram-positive bacteria and gram-negative bacteria, but the antibacterial performance on part of microorganisms (such as bacillus subtilis, bacillus pumilus and the like) contained in water is still limited (see table 1). At the same time, the material also needs to meet the requirements of higher corrosion resistance required by the use situation.
Therefore, the ferritic stainless steel with the strong antibacterial function is provided, the existing problems are solved to a great extent, and the ferritic stainless steel plays a certain positive role in market application of the ferritic stainless steel.
Disclosure of Invention
The invention aims to provide a ferritic stainless steel material with a strong antibacterial function, which has a strong function of inhibiting the propagation of microorganisms by adding Nd element into stainless steel in a heat treatment state of solid solution and aging, and remarkably reduces the risks of bacterial and microbial contamination and corrosion caused by the use of the ferritic stainless steel. The strong antibacterial ferritic stainless steel can quickly inhibit bacterial reproduction in a use environment, reduces the damage risk of microbial corrosion, and can become an excellent substitute product for the existing ferritic stainless steel.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the novel antibacterial ferritic stainless steel material comprises the following components in percentage by weight: cr: 16.5-20.0; cu: 1.0-3.0; nd is 0.8-1.5; c is less than or equal to 0.025; si is less than or equal to 1.0; mn is less than or equal to 1.0; p is less than or equal to 0.04; s is less than or equal to 0.03; the balance being Fe. Preferred chemical compositions are: cr: 17.5-19.5; cu: 1.5-2.5; 1.0-1.3 of Nd; c is less than or equal to 0.025; si is less than or equal to 1.0; mn is less than or equal to 1.0; p is less than or equal to 0.04; s is less than or equal to 0.03; the balance being Fe.
The Nd element in the invention is an important alloy element in the ferritic stainless steel with strong antibacterial function, and is a necessary condition for ensuring that the stainless steel has strong antibacterial function, because the Nd element can influence microorganisms to generate differential protein, thereby controlling the growth, reproduction and metabolism of the microorganisms. The rare earth element has Homesis effect on the propagation of microbial strains in the environment, namely the low-concentration rare earth element has stimulation effect on the growth of microorganisms, but with the increase of the release concentration of the rare earth element, the permeability of cell walls of the microorganisms is improved, so that the inclusion is leaked out, the rare earth ions are promoted to enter cells, the metabolism of the cells is hindered, and the growth of the microorganisms is inhibited. Therefore, in the invention, the addition content of the rare earth element Nd needs to be strictly controlled within a certain range, and the component content is 0.8-1.5 in percentage by weight; the component is preferably 1.0-1.3, and according to the addition ratio, the ferritic stainless steel can continuously release Nd ions with higher concentration content in an application environment under the appropriate heat treatment condition.
The heat treatment mode of the ferritic stainless steel material with the strong antibacterial function is a mode combining solid solution and aging heat treatment, the structure of a supersaturated solid solution can be obtained through the solid solution treatment, then appropriate aging treatment is carried out, a sufficient amount of copper-rich precipitated phases are obtained, the common precipitation of Nd ions in the ferritic stainless steel is facilitated, and the antibacterial performance of the stainless steel material is improved.
The solid solution temperature and the solid solution time both influence the solid solution degree of the alloy elements in the stainless steel completely dissolved into the Fe matrix, so the proper heat treatment system in the invention is as follows: the temperature of the solution treatment is 1070-. Preferred solid solution temperature and solid solution time are characterized by: the temperature of the solution treatment is 1100-.
The aging temperature and the aging time can influence the size and the quantity of phases precipitated from the stainless steel by the Cu element, and the aging treatment process is characterized in that: the temperature of the aging treatment is 500-; preferred ageing temperatures and ageing times are characterized by: the temperature of the aging treatment is 550-650 ℃, the heat preservation time is 1.0-1.5h, and the air cooling is carried out to the room temperature.
Therefore, the beneficial effects of the invention are as follows:
1. according to the invention, by adding Nd, the ferrite stainless steel breaks through the antibacterial limitation of the traditional antibacterial ferrite stainless steel, has stronger and wider-spectrum antibacterial performance, and the antibacterial rate can reach 99%.
2. The heat treatment method of the ferritic stainless steel with the strong antibacterial function is an optimized heat treatment system, and the ferritic stainless steel material can effectively kill a wider spectrum of bacteria through solid solution and aging heat treatment.
Drawings
Fig. 1 is a graph showing the sterilization rate of conventional antibacterial ferritic stainless steel against various common bacteria, including gram-positive bacteria and gram-negative bacteria.
Detailed Description
According to the chemical composition range set by the novel ferritic stainless steel material with strong antibacterial function, 10 kg of each of the ferritic stainless steel is forged by adopting 15 kg of vacuum induction furnace smelting examples and comparative examples, and the chemical compositions are shown in Table 1.
Table 1 main chemical composition (wt.%) of strongly antibacterial ferritic stainless steel of examples and comparative examples
The parameter ranges of the heat treatment method set for the ferritic stainless steel with strong antibacterial function according to the present invention, and the detailed parameters of the established solid solution and aging heat treatment are shown in table 2.
TABLE 2 Heat treatment Process parameters of examples and comparative examples
1. In vitro antimicrobial Performance testing
The ferritic stainless steel with strong antibacterial function after heat treatment shown in Table 1 was quantitatively tested against common ferritic stainless steels after heat treatment according to the relevant standards of JIS Z2801 & 2000 antibacterial processed article-antibacterial test method and antibacterial effect, GB/T2591-2003 antibacterial Plastic antibacterial Performance test method and antibacterial effectThe bactericidal rate of gram-positive bacteria (staphylococcus aureus s. aureus and Bacillus subtilis) and gram-negative bacteria (escherichia coli e. coli and Bacillus pumilus) after the action. Wherein the concentration of co-cultured bacteria is set to (1-2) × 105CFU/mL, the time for co-incubation of bacteria with the control and the new ferritic stainless steel samples was 24 hours. The results of in vitro antibacterial performance testing are shown in table 3, wherein the calculation formula of the bactericidal rate is as follows: the sterilization rate (%) - (control sample viable count-novel antibacterial ferritic stainless steel viable count)/control sample viable count]X 100%, the viable count of the control sample is the viable count of the common ferritic stainless steel sample subjected to bacterial culture, and the viable count of the novel antibacterial ferritic stainless steel is the viable count of the ferrite stainless steel with strong antibacterial function subjected to bacterial culture after heat treatment.
2. Corrosion resistance
The anodic polarization curve test was performed on the novel antibacterial ferritic stainless steels of the examples and comparative examples according to the stainless steel pitting potential measuring method (national standard: GB/T17899-1999), and the test results are shown in Table 3.
TABLE 3 results of performance test on ferritic stainless steels of examples and comparative examples
As can be seen from the results of table 3, the ferritic stainless steels having strong antibacterial functions of examples 1 to 7 of the present invention all showed excellent antibacterial properties, and the antibacterial ratio was up to 99.9%. And simultaneously meets the use requirements of the ferritic stainless steel on the corrosion resistance performance in the application field. The appropriate Nd content and heat treatment process (solid solution and aging heat treatment) are the guarantee that the ferritic stainless steel with strong antibacterial function can exert high-efficiency antibacterial performance and show good corrosion resistance.
The solution treatment has important influence on the corrosion resistance of the novel antibacterial ferritic stainless steel material. Under the condition of ensuring that the aging temperature and the aging time are within the application range of the invention, the solid solution temperature is too low, harmful intermetallic phases can be generated in the novel antibacterial ferritic stainless steel, and the existence of the harmful intermetallic phases greatly reduces the pitting resistance potential of the material, thereby seriously affecting the corrosion resistance of the material (comparative example 1-1). The solution temperature is too high, which causes the overburning of the grain boundary, the coarse phenomenon of the crystal grains is obvious, the unbalanced tendency of the resistance between the crystal grains and the grain boundary is increased, the galvanic effect among metal elements in the alloy is caused, and the corrosion resistance of the material is reduced (comparative examples 1-2). The solid solution time is too short, and a supersaturated solid solution structure cannot be obtained, so that the corrosion resistance of the material is reduced (comparative examples 1-3); too long a solution time also causes galvanic effect, seriously destroying the corrosion resistance of the new antibacterial ferritic stainless steel (comparative examples 1-4).
The aging treatment has important influence on the antibacterial performance and the corrosion resistance of the novel antibacterial ferritic stainless steel material. Under the condition of ensuring that the solid solution temperature and the solid solution time are within the application range of the invention, after the aging treatment, the supersaturated Cu element is separated out from the steel to form a sufficient amount of copper-rich phase, so that the material can release sufficient amount of Cu ions and Nd ions to play an effective antibacterial role. The aging temperature is too low, a sufficient amount of copper-rich phase cannot be separated out from the novel antibacterial ferritic stainless steel, and the antibacterial performance is greatly reduced (comparative example 2-1). The aging temperature is too high, so that a large amount of copper-rich phases are precipitated in the novel antibacterial ferritic stainless steel, and the size of the phases is increased, so that the corrosion resistance of the material is reduced (comparative example 2-2). The aging time is too short, and a sufficient amount of copper-rich phase cannot be precipitated in the novel antibacterial ferritic stainless steel and is close to a supersaturated solid solution structure, so that the novel antibacterial ferritic stainless steel cannot obtain excellent antibacterial performance under the condition (comparative examples 2-3). The aging time is too long, the size of the precipitated copper-rich phase is rapidly increased, and the corrosion resistance of the novel antibacterial ferritic stainless steel is greatly reduced (comparative examples 2-4).
The addition of Nd element in the novel antibacterial ferritic stainless steel has an important balance effect on the antibacterial performance and the corrosion resistance of the material, the antibacterial performance of the novel antibacterial ferritic stainless steel is reduced due to the fact that the addition of Nd element is not added or is too low (comparative example 3 and comparative example 4), and the effective antibacterial effect cannot be achieved, although the effective antibacterial performance of the material can be guaranteed, the corrosion resistance of the material is damaged due to the fact that the Nd element exists in the form of inclusion, and the service life of the material is influenced (comparative example 5).
It can be known from the results of the above examples and comparative examples that the novel antibacterial ferritic stainless steel after heat treatment has both antibacterial function and good corrosion resistance only when the Nd content, the solid solution temperature and the solid solution time, and the aging temperature and the aging time are in a certain proper range and are mutually supplemented and matched.
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. A ferritic stainless steel with strong antibacterial function is characterized by comprising the following components in percentage by weight: cr: 16.5-20.0; cu: 1.0-3.0; nd is 0.8-1.5; c is less than or equal to 0.025; si is less than or equal to 1.0; mn is less than or equal to 1.0; p is less than or equal to 0.04; s is less than or equal to 0.03; the balance being Fe.
2. The antibacterial ferritic stainless steel having a strong antibacterial function according to claim 1, characterized by the preferable chemical composition in weight percentage: cr: 17.5-19.5; cu: 1.5-2.5; 1.0-1.3 of Nd; c is less than or equal to 0.025; si is less than or equal to 1.0; mn is less than or equal to 1.0; p is less than or equal to 0.04; s is less than or equal to 0.03; the balance being Fe.
3. The heat treatment method of an antibacterial ferritic stainless steel with a strong antibacterial function as claimed in claim 1, wherein: the temperature of the solution treatment is 1070-.
4. The heat treatment method of an antibacterial ferritic stainless steel with a strong antibacterial function according to claim 3, characterized in that: the temperature of the solution treatment is 1100-.
5. The heat treatment method of an antibacterial ferritic stainless steel with a strong antibacterial function according to claim 3 or 4, characterized in that: the temperature of the aging treatment is 500-700 ℃, the temperature is kept for 0.5-2.0h, and the air is cooled to the room temperature.
6. The heat treatment method of an antibacterial ferritic stainless steel with a strong antibacterial function according to claim 5, characterized in that: the temperature of the aging treatment is 550-650 ℃, the temperature is kept for 1.0-1.5h, and the air is cooled to the room temperature.
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| CN202010693185.4A CN111996442A (en) | 2020-07-17 | 2020-07-17 | Ferrite stainless steel with strong antibacterial function |
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| CN202010693185.4A CN111996442A (en) | 2020-07-17 | 2020-07-17 | Ferrite stainless steel with strong antibacterial function |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1498981A (en) * | 2002-11-07 | 2004-05-26 | 中国科学院金属研究所 | Antibacterial stainless steel of ferrite in nano precipitated phase |
| CN1924058A (en) * | 2005-08-30 | 2007-03-07 | 中国科学院金属研究所 | Rich rare earth stainless steel with excellent anti-bacterium capability |
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- 2020-07-17 CN CN202010693185.4A patent/CN111996442A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1498981A (en) * | 2002-11-07 | 2004-05-26 | 中国科学院金属研究所 | Antibacterial stainless steel of ferrite in nano precipitated phase |
| CN1924058A (en) * | 2005-08-30 | 2007-03-07 | 中国科学院金属研究所 | Rich rare earth stainless steel with excellent anti-bacterium capability |
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Application publication date: 20201127 |