CN118308769A - Preparation method of surface modified antibacterial stainless steel - Google Patents
Preparation method of surface modified antibacterial stainless steelInfo
- Publication number
- CN118308769A CN118308769A CN202410350185.2A CN202410350185A CN118308769A CN 118308769 A CN118308769 A CN 118308769A CN 202410350185 A CN202410350185 A CN 202410350185A CN 118308769 A CN118308769 A CN 118308769A
- Authority
- CN
- China
- Prior art keywords
- stainless steel
- antibacterial
- pulse
- preparation
- fluorine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 68
- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 62
- 239000010935 stainless steel Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000008021 deposition Effects 0.000 claims abstract description 17
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 12
- 239000011737 fluorine Substances 0.000 claims abstract description 12
- 230000000694 effects Effects 0.000 claims abstract description 6
- 238000000151 deposition Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000005238 degreasing Methods 0.000 claims description 6
- 238000005498 polishing Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical group [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 abstract 1
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 10
- 229910052709 silver Inorganic materials 0.000 description 8
- 239000004332 silver Substances 0.000 description 8
- 230000000845 anti-microbial effect Effects 0.000 description 7
- 238000005299 abrasion Methods 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000010963 304 stainless steel Substances 0.000 description 5
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 5
- 229910001961 silver nitrate Inorganic materials 0.000 description 5
- 241000588724 Escherichia coli Species 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 230000036541 health Effects 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 2
- 206010011409 Cross infection Diseases 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 206010029803 Nosocomial infection Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005289 physical deposition Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000002094 self assembled monolayer Substances 0.000 description 1
- 239000013545 self-assembled monolayer Substances 0.000 description 1
- -1 silver ions Chemical class 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Abstract
The invention discloses a preparation method of surface modified antibacterial stainless steel, which comprises the following steps: after pretreatment, high-activity deposition holes are manufactured on the surface of the stainless steel in fluorine-containing solution containing an antibacterial medium through high-frequency pulse, and nano silver particles are deposited at the same time, so that the antibacterial stainless steel with good antibacterial effect is obtained. The experimental method is simple and efficient, the nano silver is embedded in the prepared holes, the nano silver has good antibacterial effect, and meanwhile, the nano silver is not easy to rub, so that the antibacterial effect is good.
Description
Technical Field
The invention relates to a preparation method of antibacterial stainless steel, in particular to a preparation method of surface modified antibacterial stainless steel.
Background
Stainless steel is widely used in the fields of medical and health, food processing, household kitchen ware, public facilities and the like due to its excellent corrosion resistance, wear resistance and aesthetic property. In particular, in the medical and health field, stainless steel is used for manufacturing surgical instruments, surfaces of medical equipment, door handles of hospitals and the like, and the occasions have extremely high requirements on the antibacterial performance of materials. However, the conventional stainless steel material has a certain corrosion resistance, but does not have an active antibacterial function, which limits its effectiveness in a specific application scenario.
Along with the frequent occurrence of hospital infection accidents, how to effectively prevent the growth and the transmission of bacteria on the surface of stainless steel becomes a problem to be solved urgently. Researches show that the surface modification technology can effectively improve the antibacterial performance of stainless steel, and can obviously inhibit or kill bacteria by introducing an antibacterial agent on the surface of the stainless steel or changing the surface structure of the stainless steel, thereby reducing the risk of nosocomial infection.
Although various surface modification methods have been proposed, such as physical deposition, electroless plating, self-assembled monolayer techniques, etc., for imparting antimicrobial properties to stainless steel surfaces, these methods have some limitations. For example, some methods may affect the physical and chemical stability of stainless steel, or have problems of short duration of antimicrobial effect, high cost, etc. Furthermore, the use of certain antimicrobial agents may also raise environmental and health concerns. Therefore, the novel surface modified antibacterial stainless steel which can effectively improve the antibacterial performance of the stainless steel and maintain the original physical and chemical properties of the stainless steel, is environment-friendly and high in cost effectiveness is developed, and becomes an important research direction in the fields of material science and medical treatment and health. The research and development of the novel antibacterial stainless steel not only has important significance for improving public health safety, but also has positive influence on promoting the expansion of the application range of stainless steel materials.
Disclosure of Invention
The invention aims to: the invention provides a method for forming a nano antibacterial silver layer on the surface of stainless steel through pulse oxidation deposition treatment, which aims to simplify the preparation process of antibacterial stainless steel and improve the antibacterial effect. The method utilizes combined pulse equipment, and realizes the one-step method of depositing nano silver on the surface of the stainless steel by controlling the applied voltage, the deposition time and the pulse frequency, thereby endowing the stainless steel with excellent antibacterial performance.
The technical scheme is as follows: the preparation method of the surface antibacterial stainless steel comprises the following steps: after pretreatment, high-activity deposition holes are manufactured on the surface of the stainless steel in fluorine-containing solution containing an antibacterial medium through high-frequency pulse, and nano silver is deposited at the same time, so that the antibacterial stainless steel with good antibacterial effect is obtained.
The pretreatment comprises mechanical polishing and chemical degreasing in sequence, and the fluorine-containing solution containing the antibacterial medium is an ammonium fluoride solution.
The concentration of ammonium fluoride in the fluorine-containing solution is 1-500g/L, and the concentration of the antibacterial medium is 2-10g/L.
The voltage of the high-frequency pulse is 5-20V, the reaction temperature is 10-80 ℃, and the pulse frequency is 10000-0.01HZ.
The antibacterial medium is silver salt.
The beneficial effects are that:
1. The use of strong acid such as chromic acid is avoided, the emission of harmful substances is effectively reduced, and the green and environment-friendly production process is realized.
2. The simplified experimental equipment and process flow reduce the production cost, and simultaneously, the required silver amount is reduced by optimizing the deposition parameters, so that the material cost is further reduced.
3. By precisely controlling the deposition of nano silver, the antibacterial effect with higher activity is obtained, and the performance of the antibacterial stainless steel is obviously improved.
4. Because the nano silver is only deposited at the preset position, the direct contact with the outside is reduced, and the stability and durability of the antibacterial layer are improved.
5. The color and physical properties of the stainless steel are not affected in the treatment process, and the aesthetic property and the practicability of the material are ensured.
Drawings
FIG. 1 is a morphology diagram of antibacterial element Ag deposited at a site of the surface antibacterial stainless steel prepared in example 1 of the present invention; wherein fig. 1 (a) is a scan at a low magnification, and fig. 1 (b) is a scan at a high magnification;
FIG. 2 is a graph comparing the results of the antimicrobial test of the antimicrobial stainless steel product provided in example 1 of the present invention with the stainless steel product without any treatment.
Detailed Description
The invention is described in further detail below with reference to the drawings.
The preparation method of the surface modified antibacterial stainless steel comprises the following steps: firstly, the surface of stainless steel is pretreated to remove impurities and surface oxide films, the treated stainless steel is put into fluorine-containing solution containing antibacterial stainless steel to form proper deposition holes, nano silver is deposited in the holes, and the antibacterial stainless steel with excellent antibacterial effect is obtained.
Preferably, the power amplifier is adopted to amplify the pulse electric signal, so that the process cost is reduced, and the equipment is used for preparing the effective antibacterial stainless steel rapidly and efficiently.
Preferably, under the condition of high-frequency positive and negative pulses, pits or grain boundaries are formed in the fluorine-containing solution rapidly by the stainless steel, silver is deposited in the partial area, the manufacturing site and the deposition are synchronously carried out, the process is simplified, and the activity of the deposition process is improved, so that silver is deposited on the site preferentially.
Preferably, the fluorine-containing solution containing the antimicrobial medium is an ammonium fluoride solution. The ammonium fluoride has the effect of complexing metal ions, can effectively complex ions in the solution to accelerate the deposition rate, and meanwhile, the ammonium fluoride contains moderate fluorine, so that the corrosion rate can be effectively controlled.
Preferably, under the condition of high-frequency pulse, the deposited silver is not grown up, so that proper nano silver can be deposited at the created site, the nano silver has good antibacterial effect, and the antibacterial performance of the antibacterial stainless steel is improved.
Preferably, the pulse frequency is 1000HZ-0.1HZ, and the pulse frequency is controlled to control the size of deposited silver, and the total time is 20-60min. Too short a time to form a good deposition site can result in excessive corrosion. Preferably, the pulse voltage is 5V-20V and the reaction temperature is 25 ℃.
Preferably, the antimicrobial medium is a silver salt. Silver nitrate is used as the antibacterial medium as a silver source, and is stable under fluorine-containing conditions and easy to control the release of silver ions.
Example 1
A preparation method of surface antibacterial stainless steel is characterized in that 304 stainless steel is used as a matrix material, and a sample with the thickness of 20 mm-1 mm is cut. And (3) performing mechanical polishing, chemical degreasing and pulse deposition. The pulse voltage was 10V, the pulse frequency was 100HZ, and the pulse time was 30 minutes. The electrolyte contains 10g of ammonium fluoride and 2g of silver nitrate per liter. The reaction was carried out at 20 ℃.
Test results: the antibacterial rate to the escherichia coli reaches more than 99 percent.
As shown in fig. 1, which shows a scanning diagram of the surface morphology of the surface antibacterial stainless steel prepared in this embodiment, wherein fig. 1 (a) and (b) show the surface morphology of the stainless steel under 10000 times and 200000 times of scanning electron microscope, respectively, it can be seen from fig. 1 (a) that the stainless steel surface has a large number of deposition holes, and a large number of white nano silver particles are deposited at the deposition holes;
As shown in fig. 2, wherein the left graph in fig. 2 is 304 stainless steel which is not subjected to antibacterial treatment, and the right graph in fig. 2 is surface-modified antibacterial stainless steel prepared by the method of the present invention, the results shown in fig. 2 are obtained after the two stainless steels are placed at 37 ℃ for 48 hours, and as can be seen from fig. 2, the surface-modified antibacterial stainless steel prepared by the method of the present invention has strong antibacterial property.
Example 2
A preparation method of surface antibacterial stainless steel is characterized in that 304 stainless steel is used as a matrix material, and a sample with the thickness of 20 mm-1 mm is cut. And (3) performing mechanical polishing, chemical degreasing and pulse deposition. The pulse voltage was 15V, the pulse frequency was 10HZ, and the pulse time was 60 minutes. The electrolyte contains 30g of ammonium fluoride and 2g of silver nitrate per liter. The reaction was carried out at 20 ℃.
Test results: the antibacterial rate to the escherichia coli reaches more than 99 percent.
Example 3
A preparation method of surface antibacterial stainless steel is characterized in that 304 stainless steel is used as a matrix material, and a sample with the thickness of 20 mm-1 mm is cut. And (3) performing mechanical polishing, chemical degreasing and pulse deposition. The pulse voltage was 20V, the pulse frequency was 1HZ, and the pulse time was 30 minutes. The electrolyte contains 50g of ammonium fluoride and 4g of silver nitrate per liter. The reaction was carried out at 20 ℃.
Test results: the antibacterial rate to the escherichia coli reaches more than 99 percent.
Example 4
A preparation method of surface antibacterial stainless steel is characterized in that 304 stainless steel is used as a matrix material, and a sample with the thickness of 20 mm-1 mm is cut. And (3) performing mechanical polishing, chemical degreasing and pulse deposition. The pulse voltage was 5V, the pulse frequency was 100HZ, and the pulse time was 30 minutes. The electrolyte contains 100g of ammonium fluoride and 4g of silver nitrate per liter. The reaction was carried out at 20 ℃.
Test results: the antibacterial rate to the escherichia coli reaches more than 99 percent.
The antibacterial stainless steel products prepared in examples 1-4 were subjected to corrosion resistance and abrasion resistance tests, respectively: the weight loss is no more than five percent after the samples are soaked in FeCl3 solution with the mass fraction of 20 percent for 2 hours, and the corrosion resistance of the samples in the embodiment is excellent.
Table 1 abrasion resistance versus number of stainless steel surface antimicrobial treatment before and after mass weight loss
| Numbering device | Weight before abrasion | Weight after abrasion | Weight reduction |
| Example 1 | 3.7352 | 3.7349 | 0.0003 |
| Example 2 | 3.5869 | 3.5868 | 0.0001 |
| Example 3 | 3.7154 | 3.7151 | 0.0002 |
| Example 4 | 3.6873 | 3.6871 | 0.0002 |
Abrasion resistance: and detecting the wear resistance of the stainless steel surface antibacterial layer by adopting an eraser wear tester. The rotation parameter of the rubber abrasion tester is set to be 50rpm, the surface of the sample is rubbed back and forth by using an eraser with a load of 500g, one back and forth is counted once, and after 1000 times of rubbing, the surface of the antibacterial layer is observed to be rubbed. Experimental results show that the stainless steel of different embodiments has good wear resistance after being treated by the process.
Claims (5)
1. The preparation method of the surface antibacterial stainless steel is characterized by comprising the following steps of: after pretreatment, high-activity deposition holes are manufactured on the surface of the stainless steel in fluorine-containing solution containing an antibacterial medium through high-frequency pulse, and nano silver is deposited at the same time, so that the antibacterial stainless steel with good antibacterial effect is obtained.
2. The method for preparing the surface antibacterial stainless steel according to claim 1, wherein the pretreatment comprises mechanical polishing and chemical degreasing in sequence, and the fluorine-containing solution of the antibacterial medium is an ammonium fluoride solution.
3. The method for producing a surface antibacterial stainless steel according to claim 1, wherein the concentration of ammonium fluoride in the fluorine-containing solution is 1 to 500g/L and the antibacterial medium is 2 to 10g/L.
4. The method for preparing surface antibacterial stainless steel according to claim 1, wherein the voltage of the high-frequency pulse is 5-20V, the reaction temperature is 10-80 ℃, and the pulse frequency is 10000-0.01HZ.
5. The method for preparing a surface antibacterial stainless steel according to claim 1, wherein the antibacterial medium is silver salt.
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118308769A true CN118308769A (en) | 2024-07-09 |
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