CN111411309A - Stainless steel capable of inhibiting formation of bacterial biofilm and preparation method thereof - Google Patents
Stainless steel capable of inhibiting formation of bacterial biofilm and preparation method thereof Download PDFInfo
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- CN111411309A CN111411309A CN202010409124.0A CN202010409124A CN111411309A CN 111411309 A CN111411309 A CN 111411309A CN 202010409124 A CN202010409124 A CN 202010409124A CN 111411309 A CN111411309 A CN 111411309A
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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
- C22C38/40—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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- 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
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/005—Modifying the physical properties by deformation combined with, or followed by, heat treatment of ferrous alloys
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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
- C22C38/02—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
- 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
- C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L9/00—Rigid pipes
- F16L9/02—Rigid pipes of metal
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Abstract
The invention discloses stainless steel capable of inhibiting bacterial biofilm formation and a preparation method thereof, wherein the stainless steel comprises the following chemical components in percentage by weight: c: less than or equal to 0.08 percent, Si: less than or equal to 1.00 percent, Mn: less than or equal to 2.00 percent, S: less than or equal to 0.03%, P: less than or equal to 0.045%, Ni: 8.0-11.0%, Cr: 18.0-20.0%, Cu: 4.5-6.0%, Ca: 0.02-0.10%, the balance being Fe and inevitable impurity elements; the stainless steel for inhibiting the bacterial biofilm in the tap water pipeline provided by the invention innovatively realizes the perfect combination of Ca ions and Cu ions in the stainless steel, and the appearance of the Ca ions further improves the antibacterial effect of the Cu ions. On the premise of ensuring that the novel stainless steel has good mechanical property and corrosion resistance, the stainless steel is endowed with a strong function of inhibiting bacterial biofilm attachment, can obviously reduce the bacterial infection risk caused by the use of the existing tap water container or stainless steel for the pipeline, and can be widely applied to the pipeline and stainless steel equipment for the container related to the tap water transportation process.
Description
Technical Field
The invention belongs to the technical field of stainless steel materials, relates to stainless steel for a container or a pipeline in a tap water transportation process, and particularly relates to stainless steel capable of inhibiting bacterial biofilm formation and a preparation method thereof.
Background
The traditional stainless steel for tap water pipelines is generally ordinary 304 stainless steel due to the advantages of excellent corrosion resistance, comprehensive mechanical property and the like. As the traditional stainless steel is used as an inert metal material and does not have a self-cleaning biological function, bacteria are easy to breed in the long-term use process, particularly in a standing environment, and a bacterial biofilm is generated to threaten the cleanness of tap water, so that potential safety hazards are brought to the health of people.
The literature survey shows that a class of copper-containing stainless steel (also named as antibacterial stainless steel) has the advantage of inhibiting the generation of bacterial biofilms, but the copper-containing stainless steel has short action time for inhibiting the generation of the bacterial biofilms, and after the copper-containing stainless steel is contacted with a medium for a long time, the advantage of inhibiting the generation of the bacterial biofilms is limited when bacteria can secrete enough acidic substances to form a microenvironment beneficial to the growth of the bacteria.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide stainless steel capable of inhibiting the formation of bacterial biofilms, compared with the existing common stainless steel, the stainless steel disclosed by the invention can effectively inhibit the generation of the bacterial biofilms, improves the self-cleaning capability of the stainless steel, obviously reduces the bacterial infection risk caused by the use of a tap water pipeline and a container, has a unique function of inhibiting the adhesion of the bacterial biofilms, and can be widely applied to stainless steel equipment related to the tap water pipeline and the container; another object of the present invention is to provide a method for manufacturing the stainless steel.
The invention is realized by the following technical scheme:
the stainless steel capable of inhibiting the formation of bacterial biofilms comprises the following chemical components in percentage by weight: c: less than or equal to 0.08 percent, Si: less than or equal to 1.00 percent, Mn: less than or equal to 2.00 percent, S: less than or equal to 0.03%, P: less than or equal to 0.045%, Ni: 8.0-11.0%, Cr: 18.0-20.0%, Cu: 4.5-6.0%, Ca: 0.02-0.10%, and the balance of Fe and inevitable impurity elements.
The invention further improves the scheme as follows:
the stainless steel capable of inhibiting the formation of bacterial biofilms comprises the following chemical components in percentage by weight: c: less than or equal to 0.08 percent, Si: less than or equal to 1.00 percent, Mn: less than or equal to 1.00 percent, S: less than or equal to 0.005 percent, P: less than or equal to 0.02 percent, Ni: 8.0-9.0%, Cr: 18.0-19.0%, Cu: 5.5-6.0%, Ca: 0.05-0.08%, and the balance of Fe and inevitable impurity elements.
The invention further improves the scheme as follows:
a method for preparing stainless steel capable of inhibiting bacterial biofilm formation, wherein the stainless steel is obtained by adopting the following method: vacuum induction smelting or electric arc furnace + continuous casting smelting or electric arc furnace smelting + external refining.
The invention has the further improvement scheme that:
the stainless steel obtained by smelting adopts the following hot working and heat treatment processes, so that the Cu element can be uniformly distributed in the stainless steel matrix of the invention:
hot processing: homogenizing the steel ingot at 1050-1100 ℃ for 1-3 hours, cogging and forging, forging into a blank in multiple passes, wherein the final forging temperature is not lower than 950 ℃;
solution heat treatment: 1050 and 1100 ℃ solution treatment for 1-3 hours, and air cooling or water cooling to room temperature.
Further, the stainless steel capable of inhibiting the formation of the bacterial biofilm is applied to a tap water pipeline or a container.
In the component design of the stainless steel, calcium (Ca) is the most important alloying element in the alloy, and in the field of metal materials, the Ca has the main function of a deoxidizer in the metallurgy process of the iron alloy, namely, the Ca can obviously reduce the oxygen content in the steel and purify the molten steel. The invention discovers that if Ca exists in the form of calcium oxide in steel, the calcium oxide is easy to generate hydrolysis reaction under the environment of contacting with water to generate calcium hydroxide, which causes a certain alkaline environment, and is unfavorable for acidic substances such as bacteria. When the content of Ca is low, sufficient Ca-rich phase is not easily precipitated in the stainless steel matrix, and when the stainless steel matrix is contacted with a solution medium, a sufficient alkaline environment cannot be created to inhibit the adhesion and proliferation activities of bacteria. When the content of Ca is relatively excessively high, an excessive Ca-rich phase may cause severe deterioration in the formability and corrosion resistance of stainless steel, affecting its practical use. In addition, since Cu is a known antibacterial element, in a slightly alkaline environment, the release of Cu ions can further destroy the living space of bacteria, and inhibit the formation of bacterial biofilms.
Other elements in the stainless steel provided by the invention, such as Cr, Ni and the like, are used for ensuring the basic mechanical property and corrosion resistance of the material.
The invention has the beneficial effects that:
the stainless steel capable of inhibiting the formation of bacterial biofilms realizes the perfect combination of Ca ions and Cu ions in the stainless steel, and the appearance of the Ca ions further improves the antibacterial effect of the Cu ions. On the premise of ensuring that the stainless steel has good mechanical property and corrosion resistance, 0.02-0.10 percent (weight percentage) of Ca element is added into the existing 304 stainless steel, so that a slightly alkaline environment for inhibiting bacterial adhesion is obtained, the stainless steel is endowed with a function of inhibiting bacterial biofilm adhesion for a long time, the bacterial infection risk caused by the use of the existing stainless steel for the tap water container or the pipeline can be remarkably reduced, and the method can be widely applied to the stainless steel equipment for pipelines and containers related to the tap water transportation process.
The stainless steel capable of inhibiting the formation of the bacterial biofilm can be widely applied to canning equipment, drying equipment and stainless steel equipment related to a tap water conveying container or pipeline.
Drawings
FIG. 1 is a photograph showing the effect of stainless steel on inhibiting bacterial biofilm; (a) 304Cu stainless steel, and (b) stainless steel provided by the invention.
Detailed Description
According to the set chemical composition range of the stainless steel capable of inhibiting the formation of the bacterial biofilm, 25 kg of vacuum induction furnaces are adopted to smelt the novel stainless steel of the invention in the examples 1-3 and the Cu stainless steel of the comparative example 304, the chemical composition of the stainless steel is shown in the table 1, and the smelted stainless steel adopts the following thermal processing and heat treatment processes:
the forging process comprises the following steps: homogenizing the steel ingot at 1100 ℃ for 3 hours, cogging and forging, forging into a blank in multiple passes, and performing final forging at the temperature of 950 ℃;
solution heat treatment: solution treatment is carried out for 2 hours at 1100 ℃, and air cooling is carried out to room temperature.
Table 1 chemical composition (wt,%) of stainless steels of examples 1 to 3 and comparative example
| C | Si | Mn | S | P | Ni | Cr | Cu | Ca | Fe | |
| Example 1 | 0.05 | 0.64 | 0.55 | 0.004 | 0.003 | 8.0 | 18.0 | 4.5 | 0.02 | Balance of |
| Example 2 | 0.06 | 0.81 | 0.22 | 0.004 | 0.003 | 9.0 | 19.0 | 5.5 | 0.06 | Balance of |
| Example 3 | 0.03 | 0.44 | 0.38 | 0.004 | 0.003 | 11.0 | 19.0 | 5.5 | 0.06 | Balance of |
| Comparative example | 0.02 | 0.91 | 0.39 | 0.004 | 0.003 | 9.0 | 19.0 | 5.5 | 0 | Balance of |
1. Antibacterial property and detection of biofilm inhibition
The stainless steels capable of inhibiting the formation of bacterial biofilms prepared in examples 1-3 and the stainless steel of comparative example 304Cu were subjected to the relevant standards such as "JISZ 2801-. The stainless steel capable of inhibiting the formation of bacterial biofilm prepared in examples 1-3 and the stainless steel of comparative example 304Cu were quantitatively tested for their bactericidal rate against common infectious bacteria (Escherichia coli, Staphylococcus aureus) at a bacterial concentration of 105CFU/m L, wherein the sterilization rate is calculated by the formula of sterilization rate (%) = [ (live bacteria number of blank control sample-live bacteria number of novel stainless steel)/live bacteria number of blank control sample]× 100, the viable count of the blank control sample is the viable count of bacteria cultured in a single culture medium, and the viable count of the novel stainless steel is the viable count of bacteria cultured in the stainless steel prepared in examples 1-3 and the stainless steel prepared in comparative example 304 Cu.
Meanwhile, a laser confocal live staining method is adopted, namely propidium iodide (dying bacteria in red) and SYTO-9 (dying bacteria in green) are respectively used for staining, and the thicknesses of bacterial biofilms on the surfaces of stainless steel in examples 1 to 3 and stainless steel in comparative example 304Cu after culturing for 20 days under two bacterial water environment conditions are measured, so that the effects of the two stainless steel materials on inhibiting the generation of the bacterial biofilms are reflected.
The stainless steel which can inhibit the formation of bacterial biofilms and is obtained in example 1 is tested for antibacterial performance and biofilm inhibition, and the test results are as follows:
the result of the antibacterial performance test on the typical bacteria is as follows:
for Escherichia coli (E.coli)Eschericher Coli) The antibacterial ratio of (2): more than or equal to 97.3 percent;
for Staphylococcus aureus: (Staphyococcus aureus) The antibacterial ratio of (2): more than or equal to 98.5 percent;
the thickness of the biological membrane of the two bacteria is less than or equal to 5 microns.
Generally, a material having an antibacterial rate of more than 90% may be referred to as an antibacterial material. As can be seen from the above, the novel stainless steel of example 1 has significant antibacterial and bacterial biofilm formation inhibiting effects.
The stainless steel obtained in example 2, which can inhibit the formation of bacterial biofilm, was tested for antibacterial performance and biofilm inhibition, and the test results were as follows:
the result of the antibacterial performance test on the typical bacteria is as follows:
for Escherichia coli (E.coli)Eschericher Coli) The antibacterial ratio of (2): more than or equal to 98.9 percent;
for Staphylococcus aureus: (Staphyococcus aureus) The antibacterial ratio of (2): not less than 99.3%;
the thickness of the biological membrane of the two bacteria is less than or equal to 4 microns.
As can be seen from the above, the novel stainless steel of example 2 has significant antibacterial and bacterial biofilm formation inhibiting effects.
The stainless steel which can inhibit the formation of bacterial biofilms and is obtained in example 3 is tested for antibacterial performance and biofilm inhibition, and the test results are as follows:
the result of the antibacterial performance test on the typical bacteria is as follows:
for Escherichia coli (E.coli)Eschericher Coli) The antibacterial ratio of (2): not less than 99.9%;
for Staphylococcus aureus: (Staphyococcus aureus) The antibacterial ratio of (2): not less than 99.9%;
the thickness of the biological membrane of the two bacteria is less than or equal to 3 microns.
As can be seen from the above, the novel stainless steel of example 3 has a remarkable antibacterial effect and an effect of suppressing the formation of a bacterial biofilm.
The antibacterial performance and the biological film inhibition effect of the obtained common 304Cu stainless steel in the comparative ratio are detected, and the detection results are as follows:
the result of the antibacterial performance test on the typical bacteria is as follows:
for Escherichia coli (E.coli)Eschericher Coli) The antibacterial ratio of (2): more than or equal to 97.5 percent;
for Staphylococcus aureus: (Staphyococcus aureus) The antibacterial ratio of (2): not less than 98.4 percent.
The thickness of the large intestine biofilm was 15 microns, and the thickness of the Staphylococcus aureus biofilm was 16 microns.
From the above, the antibacterial effect of the comparative example 304Cu is also significant, but after a long action time, the thicknesses of the two bacterial biofilms show a large increase.
Generally, a material having an antibacterial rate of more than 90% may be referred to as an antibacterial material. The results of the examples and the comparative examples show that the stainless steel capable of inhibiting the formation of the bacterial biofilm and the stainless steel of the comparative example 304Cu can keep the bacterial concentration at 105Compared with 304Cu stainless steel, the stainless steel capable of inhibiting the formation of the bacterial biofilm has better capability of inhibiting the formation of the bacterial biofilm, and still keeps better activity of inhibiting the bacterial biofilm within 20 days of a bacterial aqueous solution environment.
Claims (5)
1. Stainless steel capable of inhibiting bacterial biofilm formation, which is characterized by comprising the following chemical components in percentage by weight: c: less than or equal to 0.08 percent, Si: less than or equal to 1.00 percent, Mn: less than or equal to 2.00 percent, S: less than or equal to 0.03%, P: less than or equal to 0.045%, Ni: 8.0-11.0%, Cr: 18.0-20.0%, Cu: 4.5-6.0%, Ca: 0.02-0.10%, and the balance of Fe and inevitable impurity elements.
2. The stainless steel according to claim 1, wherein the stainless steel is selected from the group consisting of: the stainless steel comprises the following chemical components in percentage by weight: c: less than or equal to 0.08 percent, Si: less than or equal to 1.00 percent, Mn: less than or equal to 1.00 percent, S: less than or equal to 0.005 percent, P: less than or equal to 0.02 percent, Ni: 8.0-9.0%, Cr: 18.0-19.0%, Cu: 5.5-6.0%, Ca: 0.05-0.08%, and the balance of Fe and inevitable impurity elements.
3. A method of producing a stainless steel according to claim 1 or 2, wherein the stainless steel is obtained by: vacuum induction smelting or electric arc furnace + continuous casting smelting or electric arc furnace smelting + external refining.
4. The method for preparing stainless steel capable of inhibiting bacterial biofilm formation according to claim 3, wherein: the stainless steel obtained by smelting adopts the following hot working and heat treatment processes:
hot processing: homogenizing the steel ingot at 1050-1100 ℃ for 1-3 hours, cogging and forging, forging into a blank in multiple passes, wherein the final forging temperature is not lower than 950 ℃;
solution heat treatment: 1050 and 1100 ℃ solution treatment for 1-3 hours, and air cooling or water cooling to room temperature.
5. Use of the stainless steel according to claim 1 or 2 for inhibiting the formation of bacterial biofilm in a water supply line or vessel.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023082164A1 (en) * | 2021-11-12 | 2023-05-19 | 港大科桥有限公司 | Antibacterial and antiviral copper-containing stainless steel, and preparation method therefor and use thereof |
| CN118422072A (en) * | 2024-07-05 | 2024-08-02 | 苏州森锋医疗器械有限公司 | High-strength anti-infection traditional Chinese medicine needle capable of inhibiting formation of drug-resistant bacterial biomembrane |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10237597A (en) * | 1997-02-24 | 1998-09-08 | Nisshin Steel Co Ltd | High strength and high ductility dual-phase stainless steel excellent in antibacterial property and its production |
| CN108728767A (en) * | 2018-04-04 | 2018-11-02 | 中国科学院金属研究所 | A kind of handrail or handle anti-bacteria stainless steel |
| CN108728772A (en) * | 2018-04-04 | 2018-11-02 | 中国科学院金属研究所 | A kind of anti-bacteria stainless steel used in air environment |
| CN110064892A (en) * | 2019-04-15 | 2019-07-30 | 浙江金石家居用品有限公司 | A kind of rapidoprint and its processing method of stainless steel tableware |
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2020
- 2020-05-14 CN CN202010409124.0A patent/CN111411309A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10237597A (en) * | 1997-02-24 | 1998-09-08 | Nisshin Steel Co Ltd | High strength and high ductility dual-phase stainless steel excellent in antibacterial property and its production |
| CN108728767A (en) * | 2018-04-04 | 2018-11-02 | 中国科学院金属研究所 | A kind of handrail or handle anti-bacteria stainless steel |
| CN108728772A (en) * | 2018-04-04 | 2018-11-02 | 中国科学院金属研究所 | A kind of anti-bacteria stainless steel used in air environment |
| CN110064892A (en) * | 2019-04-15 | 2019-07-30 | 浙江金石家居用品有限公司 | A kind of rapidoprint and its processing method of stainless steel tableware |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023082164A1 (en) * | 2021-11-12 | 2023-05-19 | 港大科桥有限公司 | Antibacterial and antiviral copper-containing stainless steel, and preparation method therefor and use thereof |
| CN118422072A (en) * | 2024-07-05 | 2024-08-02 | 苏州森锋医疗器械有限公司 | High-strength anti-infection traditional Chinese medicine needle capable of inhibiting formation of drug-resistant bacterial biomembrane |
| CN118422072B (en) * | 2024-07-05 | 2024-09-27 | 苏州森锋医疗器械有限公司 | High-strength anti-infection traditional Chinese medicine needle capable of inhibiting formation of drug-resistant bacterial biomembrane |
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