CN113265587A - Antibacterial ferrite stainless steel and preparation method thereof - Google Patents
Antibacterial ferrite stainless steel and preparation method thereof Download PDFInfo
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- C21D6/00—Heat treatment of ferrous alloys
- C21D6/008—Heat treatment of ferrous alloys containing Si
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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
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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
- C21D8/06—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires
- C21D8/065—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires of ferrous alloys
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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
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/0075—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for rods of limited length
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- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/0081—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for slabs; for billets
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/04—Making ferrous alloys by melting
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- C22C38/00—Ferrous alloys, e.g. steel alloys
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- 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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- 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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- 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
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
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Abstract
The antibacterial ferritic stainless steel and the preparation method thereof are characterized in that a plurality of alloying silver elements and rare earth elements are distributed in a ferritic structure, the silver elements can act on bacteria independently or in a combined manner by being naturally activated into silver ions with different valence states by the environment, the bacteria respiration is inhibited or virus structures are destroyed, so that the bacteria are killed, the rare earth elements can increase the corrosion resistance of steel and improve the antibacterial activity of the steel, and the requirements of kitchens and bathrooms, household appliances, household appliance parts, tableware, other public facilities and the like on the stainless steel are met.
Description
Technical Field
The invention relates to a broad-spectrum antiviral and antibacterial steel material technology, in particular to antibacterial ferrite stainless steel and a preparation method thereof.
Background
Bacteria and viruses are easily adsorbed in kitchens and bathrooms, tableware, household appliances, household appliance parts, public facilities and the like, and diseases are spread by human body contact, so that health is influenced. The conventional ferritic stainless steel has been satisfactory for use in the related art, but does not have an antibacterial function. Along with the progress of times, the life health of people is very important, and the realization of the antibacterial and antiviral effects of living goods and public facilities is an important way for preventing infection.
The stainless steel has a large and wide range of quality and is mostly served to the civilian life, so that the development of the stainless steel material with antibacterial effect is necessary. Many metal elements have antibacterial properties, such as Ag > Cd > Cu > Zn > Fe > Ni; safety for human body: ag, Co, Ni, Al, Zn, Cu, Fe, Mn, Sn, Ba, Mg and Ca. In the past, the antibacterial stainless steel mainly adds Cu element, and an epsilon-Cu phase is separated out through antibacterial treatment to have antibacterial property, but the antibacterial property is reduced along with the prolonging of time.
The Ag element has good antibacterial property and safety performance. The pure silver has the effects of disinfection and sterilization, infection prevention and treatment, water quality purification, corrosion prevention, fresh preservation and the like. After the silver-containing product is contacted with bacteria and viruses, silver can escape in the form of ions, inhibit the respiration of the bacteria or destroy the structure of the viruses, and kill the bacteria or the viruses. Ag in terms of antibacterial properties3+＞Ag2+＞＞Ag+＞Cu2+In which Ag is+The antibacterial activity of (A) is Cu2+100 times of the total weight of the powder. The Ag in ppm level is added into the stainless steel to achieve a good antibacterial effect, and the Ag enables the material to have lasting antibacterial effect in a slow release mode. Meanwhile, the addition of Ag in the stainless steel hardly damages the mechanical property and the processing property of the material, and even improves the mechanical property and the processing property.
In conclusion, silver-containing antibacterial stainless steel has great potential in the aspect of people's life health, can be used for the methods of stainless steel kitchens and bathrooms, household appliances, household appliance parts, tableware and other public facilities and the like, and can comprehensively, safely and efficiently prevent disease transmission and infection.
Disclosure of Invention
Aiming at the defects or shortcomings in the prior art, the invention provides the antibacterial ferrite stainless steel and the preparation method thereof, the silver element and the rare earth element are distributed in the ferrite tissue in a multi-shape alloying manner, the silver element can be activated into silver ions with different valence states by the environment naturally to act on bacteria independently or in a combined manner, the bacteria respiration is inhibited or the virus structure is destroyed, so that the bacteria are killed, the rare earth element can increase the corrosion resistance of the steel and simultaneously improve the antibacterial activity of the steel, and the requirements of kitchens, household appliances, household appliance parts, tableware and other public facilities on the stainless steel material are favorably met.
The technical solution of the invention is as follows:
the antibacterial ferritic stainless steel is characterized by comprising the following elements and the content of the elements in percentage by weight, wherein silver Ag is 0.01-0.06, rare earth RE is 0.010-0.045, chromium Cr is 16.0-18.0, carbon C is 0.035-0.10, silicon Si is less than or equal to 0.75, nickel Ni is less than or equal to 0.60, manganese Mn is less than or equal to 1.0, nitrogen N is less than or equal to 0.1, sulfur S is less than or equal to 0.030, phosphorus P is less than or equal to 0.040, and the balance of iron Fe and inevitable impurities.
The Ag is distributed in the iron-based structure in a silver polymorphic alloying mode.
The silver polymorphic alloying includes a solid solution form, an interface segregation form and a grain enrichment form of silver element in a ferrite structure.
The Ag acts on the bacteria poison by being naturally activated into silver ions with different valence states by the environment alone or in combination to inhibit the bacteria respiration or destroy the virus structure, thereby killing the bacteria poison, wherein the silver ions with different valence states comprise Ag3+、Ag2+Or Ag+。
Cr＝16.5～17.5，C＝0.06～0.08，Si≤0.50，S≤0.020，P≤0.030。
RE is at least one of cerium Ce and lanthanum La.
The Ag is a main antibacterial element, and the RE is an element which increases the corrosion resistance of the steel and improves the antibacterial activity of the steel.
The preparation method of the antibacterial ferritic stainless steel is characterized by comprising the following steps:
step a, preparing raw materials according to the following element components and the weight percent of the components of the antibacterial ferritic stainless steel: 0.01-0.06 Ag, 0.010-0.045 RE, 16.0-18.0 Cr, 0.035-0.10C, 0.75% or less Si, 0.60% or less Ni, 1.0% or less Mn, 0.1% or less N, 0.030% or less S, 0.040% or less P, and the balance Fe and inevitable impurities, wherein RE is at least one of Ce and La;
b, smelting the raw materials, wherein the smelting comprises the following processes which are sequentially carried out: the method comprises the steps of molten iron pretreatment process, primary smelting process in a primary smelting furnace, external refining process, continuous casting or forging process, and hot rolling or hot rolling and cold rolling process, so as to obtain the antibacterial ferrite stainless steel plate, bar or wire with the required specification.
And c, adopting an electric arc furnace or an argon oxygen decarburization AOD smelting furnace or an induction furnace as the primary smelting furnace in the step b, adopting a ladle refining LF furnace as the secondary refining furnace, and continuing annealing processes for continuous casting, forging, hot rolling and cold rolling.
The invention has the following technical effects: the antibacterial ferrite stainless steel and the preparation method thereof have the characteristics of high performance, especially broad-spectrum antibacterial property, high safety and easiness in forming. Compared with the existing ferritic stainless steel, the invention has the advantages of excellent mechanical property, equivalent corrosion resistance, excellent antibacterial toxicity and the like. Compared with the existing ferritic stainless steel, the steel of the invention adds the silver element and the rare earth element in the components, so that the material has excellent mechanical property, equivalent corrosion resistance and antibacterial property. The steel has the characteristics of low hardness (less than or equal to 200HV), high plasticity (more than or equal to 22 percent) and broad spectrum antibacterial toxicity. Can be used in stainless steel kitchen and toilet, household appliances, household appliance parts, tableware and other public facilities to prevent disease transmission and infection.
Compared with the prior art, the invention has the following obvious and prominent substantive characteristics and remarkable advantages:
1. compared with the existing 430 stainless steel, the antibacterial ferritic stainless steel has the characteristics of excellent mechanical property, antibacterial toxicity and the like, has excellent antibacterial toxicity characteristics while having mechanical property and corrosion resistance, can meet the requirements of users in the aspect of facing the life health of people, and improves the public health safety; the antibacterial ferrite stainless steel has low hardness (less than or equal to 200HV), good plasticity (A is more than or equal to 22 percent) and easy molding;
2. the antibacterial ferrite stainless steel strictly controls the content and the component accuracy of impurity elements, and is provided with annealing treatment after hot rolling or cold rolling so as to ensure subsequent processing; the corrosion resistance and the antibacterial property are further improved by adding the rare earth element, and the alloy cost is effectively controlled;
3. the antibacterial ferrite stainless steel has Ag dissolving-out less than 0.20 microgram/L, which is far less than the safety value of the WHO for human body of below 0.05ppm and the limit of silver ion in drinking water of 0.05mg/L, is very safe, can be used for stainless steel kitchens and bathrooms, household appliances, household appliance parts, tableware and other public facilities, comprehensively considers the cost of reasonable addition of Ag and rare earth elements, ensures that the alloy cost is controllable, and is easy to popularize and use.
Detailed Description
The present invention will be described with reference to examples.
The invention relates to an antibacterial ferritic stainless steel material and a preparation method thereof, wherein silver element and rare earth element are added in the composition design, the inclusion in the material is improved and the corrosion resistance is improved by adding the rare earth element, the durable antibacterial toxicity performance is endowed by adding the silver element, the mechanical property is not changed, the processing requirement of the product is ensured, and the market demand is met.
In order to achieve the purpose, the invention adopts the following inventive concept:
the invention adds Ag and rare earth elements on the basis of the traditional ferritic stainless steel, and endows the ferritic stainless steel with antibacterial and toxic properties. The rare earth elements are added to improve the impurities and improve the corrosion resistance and the antibacterial property. The Ag-containing ferrite stainless steel has excellent mechanical property while ensuring good corrosion resistance, has broad-spectrum, lasting and efficient antibacterial property, and can be used for stainless steel kitchens and bathrooms, household appliances, household appliance parts, tableware and other public facilities to prevent disease transmission and infection.
The method specifically comprises the following steps: (1) the addition of Ag element makes the ferritic stainless steel have antibacterial property; (2) the RE element is added to increase the corrosion resistance of the steel and improve the antibacterial activity.
According to the inventive concept, the invention adopts the following technical scheme:
the antibacterial ferritic stainless steel comprises the following components in percentage by mass:
less than or equal to 0.10 percent of C, less than or equal to 0.75 percent of Si, less than or equal to 1.0 percent of Mn, less than or equal to 0.030 percent of S, less than or equal to 0.040 percent of P, 16.0-18.0 percent of Cr, less than or equal to 0.60 percent of Ni, less than or equal to 0.1 percent of N, 0.01-0.06 percent of Ag, RE: 0.010-0.045, and the balance of iron and inevitable impurities; wherein RE is at least one rare earth element of La and Ce.
As the preferred technical scheme of the invention, the antibacterial ferritic stainless steel comprises the following components in percentage by mass: c: 0.06-0.08%, less than or equal to 0.50% of Si, less than or equal to 1.0% of Mn, less than or equal to 0.020% of S, less than or equal to 0.030% of P, 16.5-17.5% of Cr, less than or equal to 0.60% of Ni, less than or equal to 0.1% of N, 0.01-0.06% of Ag, RE: 0.010-0.045, and the balance of iron and inevitable impurities.
The invention relates to a preparation method of an antibacterial ferritic stainless steel, which comprises the following steps:
a. weighing the following raw materials in percentage by mass: c: 0.06-0.08%, less than or equal to 0.50% of Si, less than or equal to 1.0% of Mn, less than or equal to 0.020% of S, less than or equal to 0.030% of P, 16.5-17.5% of Cr, less than or equal to 0.60% of Ni, less than or equal to 0.1% of N, 0.01-0.06% of Ag, RE: 0.010-0.045, and the balance of iron and inevitable impurities; wherein RE is at least one rare earth element of La and Ce;
b. b, pretreating the raw materials taken in the step a by molten iron, performing a series of processes of primary smelting in an electric arc furnace, AOD smelting and an induction furnace, performing external refining, continuous casting (forging) and hot rolling (cold rolling) to obtain stainless steel plates and rod wires with required specifications; and respectively setting an annealing process after continuous casting (forging) and hot rolling (cold rolling), and annealing after cold rolling to finally obtain the finished product of the antibacterial ferritic stainless steel plate or the bar wire.
The functions and the proportion of the elements are as follows:
c: c is one of main elements in the stainless steel, but the affinity of C and Cr is very large, a series of complex carbides can be formed with Cr, the corrosion resistance of the ferritic stainless steel is reduced, and the strength and the hardness of the material can be improved by solid solution. Therefore, the content of C is determined to be 0.06-0.08% by comprehensive consideration.
Cr: cr is the most important alloy element in stainless steel, can improve corrosion potential, reduce pitting corrosion sensitivity and greatly improve the corrosion resistance of the stainless steel. In order to ensure the corrosion resistance of the antibacterial ferrite stainless steel, the Cr content is designed to be 16.5-17.5% on the premise of improving the corrosion resistance by the rare earth.
Si: the Si content is increased as a deoxidizer added to steel, and silicate inclusions are increased, so that the Si content in the present invention is controlled to not more than 0.50%.
Mn: mn is generally added as a deoxidizer in the steel, the Mn content is controlled below 1.0 percent in the invention, Mn can generate MnS with S in the steel, the hot brittleness is eliminated, the blank cracks are obviously reduced, the yield is improved, and the processing performance is improved.
P: micro-segregation is formed when molten steel is solidified, and then the micro-segregation is localized at a grain boundary when heated at a ferrite forming temperature, so that the brittleness of steel is remarkably increased. The content of P in steel should be reduced, and the content of P in the invention is controlled to be less than 0.030%.
S: the inevitable impurity elements in the steel can form FeS with Fe to generate hot brittleness, the lower the S content is, the better the S content is, and the S content is controlled to be less than 0.020%.
Ag: ag is an important antibacterial element. The Ag element performs best in terms of known metal ions having bactericidal ability and safety to the human body. The safety of the metal elements is sequentially arranged as follows: ag is more than Co, more than Ni, more than Zn, more than Cu, more than Fe, more than Mn, more than Sn, more than Ba, more than Mg, more than Ca. Ag ions can inhibit bacterial respiration or destroy virus structure, thereby killing bacteria and viruses. The Ag is added as a main antibacterial element from the two aspects of antibacterial toxicity and safety, and the content of the added Ag is 0.01-0.06%.
RE: the rare earth element added in the invention is at least one of La and Ce, and aims to improve the inclusion, improve the corrosion resistance and increase the antibacterial property. The rare earth added into the steel can purify the molten steel, and the rare earth and O, S elements generate high-melting-point compounds which are precipitated in a solid state before the molten steel is solidified, so that impurities in the steel are reduced. The content of the rare earth in the invention is controlled to be 0.01-0.045%.
The invention aims to realize the antibacterial property of the silver-containing ferritic stainless steel on the premise of ensuring the mechanical property and the corrosion resistance of the ferritic stainless steel. The invention adds Ag into the ferritic stainless steel by the silver polymorphic alloying technology, ensures the effective yield and the uniform distribution of the silver, and has durable antibacterial effect without antibacterial heat treatment. The invention also purifies the molten steel and modifies the inclusions by the rare earth polymorphic alloying technology, thereby improving the corrosion resistance and the antibacterial property.
The first embodiment is as follows: in the present example, the chemical composition of an antibacterial ferritic stainless steel is shown in table 1.
In this embodiment, the method for preparing an antibacterial ferritic stainless steel of this embodiment includes the following steps:
a. raw materials were weighed according to the mass percentage of the prepared target stainless steel components having the compositions of table 1:
0.07 percent of C, 0.27 percent of Si, 0.40 percent of Mn, 0.001 percent of S, 0.012 percent of P, 17.00 percent of Cr, 0.20 percent of Ni, 0.06 percent of N, 0.030 percent of Ag, 0.017 percent of La + Ce, and the balance of iron and inevitable impurities;
b. b, carrying out a series of processes of molten iron pretreatment, AOD refining, LF external refining, continuous casting, hot rolling and cold rolling on the raw materials taken in the step a to obtain a stainless steel plate with the required thickness; and respectively setting annealing processes after hot rolling and cold rolling, and annealing after cold rolling to finally obtain the finished product of the antibacterial ferrite stainless steel plate.
TABLE 1 comparison of chemical compositions of antibacterial stainless steels of examples (% by weight)
| C | Si | Mn | P | S | Cr | Ni | N | Ag | RE | FE | |
| Example one | 0.07 | 0.27 | 0.40 | 0.012 | 0.001 | 17.0 | 0.20 | 0.06 | 0.03 | 0.017 | Bal. |
Test analysis:
1. antibacterial property: the evaluation method of the antibacterial performance is a surface antibacterial performance test method of GB/T31402-2015, and stainless steel containing no Ag is used as a control sample for comparison.
The samples to be examined and the control were prepared into 50X 50 mm-sized specimens according to the standard.
Table 2 example one antimicrobial test results
2. Influenza a H1N1 virus and EV71 virus inactivation performance test: the sample is prepared into a sample wafer with the size of 50 multiplied by 50mm
Table 3 example one antiviral test results
The chemical compositions (weight percent) of the steel grade related to the antibacterial ferritic stainless steel of the above embodiment of the invention are as follows: less than or equal to 0.10 percent of C, less than or equal to 0.75 percent of Si, less than or equal to 1.0 percent of Mn, less than or equal to 0.030 percent of S, less than or equal to 0.040 percent of P, 16.0-18.0 percent of Cr, less than or equal to 0.60 percent of Ni, less than or equal to 0.1 percent of N, 0.01-0.06 percent of Ag, RE: 0.010-0.045, and the balance of iron and inevitable impurities; wherein RE is at least one rare earth element of La and Ce. The components of the ferritic stainless steel of the embodiment of the invention are added with the silver element and the rare earth element, so that the material has antibacterial and toxic properties, simultaneously maintains the mechanical property and the corrosion resistance of the ferritic stainless steel, can meet the market demand, and can be used for stainless steel kitchens and bathrooms, household appliances, household appliance parts, tableware and other public facilities.
Those not described in detail in this specification are within the skill of the art. It is pointed out here that the above description is helpful for the person skilled in the art to understand the invention, but does not limit the scope of protection of the invention. Any such equivalents, modifications and/or omissions as may be made without departing from the spirit and scope of the invention may be resorted to.
Claims (9)
1. The antibacterial ferritic stainless steel is characterized by comprising the following elements and the content of the elements in percentage by weight, wherein silver Ag is 0.01-0.06, rare earth RE is 0.010-0.045, chromium Cr is 16.0-18.0, carbon C is 0.035-0.10, silicon Si is less than or equal to 0.75, nickel Ni is less than or equal to 0.60, manganese Mn is less than or equal to 1.0, nitrogen N is less than or equal to 0.1, sulfur S is less than or equal to 0.030, phosphorus P is less than or equal to 0.040, and the balance of iron Fe and inevitable impurities.
2. The antibacterial ferritic stainless steel according to claim 1, characterized in that the Ag is distributed in an iron-based structure in a silver pleomorphic alloying.
3. The anti-microbial ferritic stainless steel of claim 2, characterized in that the silver pleomorphic alloying includes silver element solid solution morphology, interface segregation morphology and grain enrichment morphology in the ferritic structure.
4. The anti-microbial ferritic stainless steel of claim 1, wherein the Ag acts on the bacteria by naturally activating to different valence state silver ions by environment alone or in combination, thereby inhibiting bacterial respiration or destroying virus structure, thereby killing bacteria3+、Ag2+Or Ag+。
5. The antibacterial ferritic stainless steel according to claim 1, characterized in that Cr is 16.5 to 17.5, C is 0.06 to 0.08, Si is 0.50, S is 0.020 and P is 0.030.
6. The antibacterial ferritic stainless steel of claim 1, characterized in that RE is at least one of cerium Ce and lanthanum La.
7. The ferritic stainless steel according to claim 1, characterized in that Ag is a main antibacterial element and RE is an element which increases corrosion resistance and at the same time improves antibacterial activity of the steel.
8. The preparation method of the antibacterial ferritic stainless steel is characterized by comprising the following steps:
step a, preparing raw materials according to the following element components and the weight percent of the components of the antibacterial ferritic stainless steel: 0.01-0.06 Ag, 0.010-0.045 RE, 16.0-18.0 Cr, 0.035-0.10C, 0.75% or less Si, 0.60% or less Ni, 1.0% or less Mn, 0.1% or less N, 0.030% or less S, 0.040% or less P, and the balance Fe and inevitable impurities, wherein RE is at least one of Ce and La;
b, smelting the raw materials, wherein the smelting comprises the following processes which are sequentially carried out: the method comprises the steps of molten iron pretreatment process, primary smelting process in a primary smelting furnace, external refining process, continuous casting or forging process, and hot rolling or hot rolling and cold rolling process, so as to obtain the antibacterial ferrite stainless steel plate, bar or wire with the required specification.
9. The method for preparing antibacterial ferritic stainless steel according to claim 8, wherein the primary refining furnace in step b is an electric arc furnace or an Argon Oxygen Decarburization (AOD) smelting furnace or an induction furnace, the secondary refining furnace is a ladle refining (LF) furnace, and the continuous casting, the forging, the hot rolling and the cold rolling are all followed by an annealing process.
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| CN113930691A (en) * | 2021-09-29 | 2022-01-14 | 江阴市新万沅机件有限公司 | Efficient and low-cost refrigerator lower beam and production process thereof |
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| CN113930691A (en) * | 2021-09-29 | 2022-01-14 | 江阴市新万沅机件有限公司 | Efficient and low-cost refrigerator lower beam and production process thereof |
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Application publication date: 20210817 |