CN111804931A - Antibacterial stainless steel prepared by powder metallurgy method assisted by in-situ decomposition - Google Patents
Antibacterial stainless steel prepared by powder metallurgy method assisted by in-situ decomposition Download PDFInfo
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/30—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
Abstract
The invention relates to a preparation method of a new generation silver-containing antibacterial stainless steel with high antibacterial performance by using an in-situ decomposition assisted powder metallurgy method, which comprises the step of adding nano-grade silver particles into a stainless steel matrix by using an in-situ decomposition reaction. Superfine stainless steel powder particles with the particle size distribution close to the size of bacteria are used, and the stainless steel powder can be stainless steel powder with any grade meeting the requirement of the particle size. The surface of stainless steel powder particles reacts to generate nano-grade pure silver particles to prepare a composite green body, and then the composite green body is sintered to obtain various industrial products, including tweezers, door handles, watches, knives, bowls and other integral or combined components. The whole matrix contains uniformly distributed nano-silver phase, so that after the surface of the appliance is abraded, uniformly distributed nano-silver particles still contact and sterilize in the using process, and the appliance plays an excellent antibacterial role.
Description
Field of the invention
The invention relates to stainless steel appliances for daily life, food industry and medical health, in particular to various stainless steel appliances prepared by using a powder metallurgy method assisted by in-situ decomposition and a preparation method thereof.
Technical Field
With the progress of science and technology, safety and environmental health problems are being increasingly emphasized, and the threat of harmful microorganisms existing in living environments to human health is becoming more serious. Especially, the surface contact infection caused by harmful bacteria is a great hidden trouble in the food industry, the public safety field and the medical and health industry for a long time. Statistically, millions of people die worldwide each year from bacterial infections, and in 2006 only, infections from surface contact result in 74000 deaths in hospitals all over the united states, with additional medical costs of $ 12 billion. However, stainless steel, which is the most widely used in the food safety and sanitary field, has no antibacterial property, and thus development of stainless steel containers having excellent antibacterial properties is of great significance and value.
The antibacterial material is a functional material which has the function of sterilizing or inhibiting the growth of bacteria, and different from stainless steel, the excellent antibacterial and bactericidal functions of metals such as silver, copper, zinc and the like are known for a long time, wherein the antibacterial property of silver and copper is the most prominent, and the antibacterial material has a very wide antibacterial spectrum. With the intensive research on metal ion sterilization, the concept of "contact sterilization" has been proposed to explain the antibacterial properties of inorganic metal ions. Generally, the surface of bacteria is negatively charged, and silver, copper and the like with bactericidal property release positively charged ions, so that the bacteria are adsorbed to the surface through electrostatic adsorption, under the action of the physicochemical action mechanism and osmotic pressure of bactericidal ions, the bacterial membrane is broken, and metal ions enter the interior of the bacteria to further destroy the metabolism, and finally the bacteria die. Compared with traditional medicine sterilization, metal ion sterilization has the advantages of wide antibacterial spectrum, long action time, wide applicable environment, low toxicity to human bodies, no drug resistance and the like.
Because of the extremely strong antibacterial property of silver and copper, the development of the current antibacterial stainless steel is mainly divided into two main categories, namely copper-containing antibacterial stainless steel and silver-containing antibacterial stainless steel. The process types mainly comprise ion implantation, surface coating, flame spraying, alloying, electroplating and the like, wherein the alloying introduction of the bactericidal metal element is one of hot research directions for developing the antibacterial stainless steel due to the advantages of long-term effectiveness, scratch resistance and the like. But the development of alloying copper-containing antibacterial stainless steel and silver-containing antibacterial stainless steel has great difference. Since copper has a higher solubility in austenitic steels but a lower solubility in ferritic steels. Therefore, at present, the copper is added by an integral smelting method, and the nanoscale copper-rich phase uniformly distributed in the stainless steel matrix can be easily obtained by subsequent quenching and aging treatment. The copper-containing antibacterial stainless steel prepared by the method has been successful in a plurality of brands of stainless steel, and shows a very excellent antibacterial effect. The typical examples include a high-strength martensitic stainless steel containing 3 to 4% of copper, a copper-containing austenitic stainless steel having a wide range of applications and excellent workability, and a ferritic stainless steel. Research shows that the copper-containing antibacterial stainless steel prepared by the method has the sterilization rate of over 98 percent on bacteria such as staphylococcus aureus, escherichia coli, salmonella and the like after 24 hours of culture through a contact sterilization mechanism of a copper-rich phase and the bacteria and copper ion sterilization.
However, copper-containing antibacterial stainless steel is not perfect due to the limitation of the bactericidal effect of copper itself and the large addition amount. The copper-containing antibacterial stainless steel has great influence on the mechanical property, the machining property and the corrosion resistance of the original grade stainless steel due to the large addition of copper, and the application of the copper-containing antibacterial stainless steel is limited to a certain extent. In addition, among a plurality of metal elements with antibacterial property, silver has the strongest antibacterial property, the antibacterial capability of silver is roughly estimated to be about 100 times that of copper, and the silver with 0.2 percent by weight can enable the silver-containing antibacterial stainless steel to have extremely strong antibacterial property, and the antibacterial spectrum of the silver is wider. In addition, related animal experiments also show that silver is less harmful to animal cells and less prone to cause allergic reactions than copper. However, the alloying preparation of silver-containing antibacterial stainless steel is very slow. This is because unlike copper, silver has little solubility in stainless steel substrates. Theoretical calculation and experiments show that silver and iron are difficult to be mutually dissolved and uniformly mixed even in a liquid state. Silver in the solid state has a solubility of only 0.0003% wt, both in austenitic and ferritic steels, which makes it extremely difficult to obtain a nano-scale homogeneously distributed silver-rich phase transformation in a stainless steel matrix by casting, quenching, ageing treatments. Therefore, the alloying preparation of silver-containing antibacterial stainless steel has been developed slowly and has been studied only a little. The solution alloying heat treatment proposed for the silver-containing antibacterial stainless steel at present has unsatisfactory effect of aging precipitation heat treatment. The silver particles obtained in the stainless steel matrix by the two methods are mostly micron-sized large particles, and only a small amount of the silver particles are nano-sized silver particles. In addition, the silver segregation phenomenon in the silver-containing antibacterial stainless steel prepared by the methods is very serious, and the silver phase distribution is often in a band shape, so that the silver phase is concentrated in a certain area, and no silver particles are distributed in a range of dozens of micrometers or even hundreds of micrometers.
However, according to the research of the existing sterilization model of the copper or silver-containing antibacterial stainless steel, the release sterilization of silver ions and copper ions is only a part of the sterilization, and the "contact sterilization" mechanism of bacteria and copper-rich phase or silver-rich phase in the stainless steel matrix is a quite important position. Experiments show that copper dissolved in austenite has no antibacterial effect. Similar results have been demonstrated for Ti-Ag alloys. Therefore, the distribution uniformity of the silver phase in the stainless steel matrix determines the antibacterial capacity of the silver-containing antibacterial stainless steel to some extent. Under certain conditions, the smaller the silver particles, the less silver can be used to obtain the same uniform distribution, thereby saving the consumption of noble metal and reducing the cost. However, in view of the extremely low solubility of silver in iron, the conventional alloying methods cannot satisfy the requirements of solution heat treatment, quenching and aging heat treatment.
In addition, the method for obtaining the antibacterial stainless steel by the traditional manufacturing process of the cast metal material also has the characteristics of high energy and raw material consumption, high production cost, environmental friendliness and the like. Compared with the traditional casting technology, the powder metallurgy technology has the following advantages: high shape freedom, no or little cutting, high material utilization up to 95%, and easy mass production. At present, the silver-containing antibacterial stainless steel is mainly produced by a smelting casting and rolling method, and although there are reports on preparing the silver-containing antibacterial stainless steel by using a powder metallurgy technology, the silver-containing antibacterial stainless steel prepared by the existing powder metallurgy method is inferior to the silver-containing antibacterial stainless steel prepared by a casting and rolling method in the particle size and distribution of silver phases in the silver-containing antibacterial stainless steel prepared by the existing powder metallurgy method because the added silver powder particles are larger in particle size and the particle size of stainless steel particles is larger.
Description of the invention
In order to utilize the advantages of powder metallurgy and solve the problem of uneven distribution of silver phases, the invention creatively considers the problems of the size of bacteria and the average spacing between the uniformly distributed silver phases. According to the existing sterilization model of the antibacterial stainless steel, a contact sterilization mechanism of silver-rich phases or copper-rich phases which are uniformly distributed or precipitated in a stainless steel matrix plays a significant role. Research shows that when antibacterial metal elements such as silver, copper and the like are dissolved in a matrix material in a solid mode, the material only shows very weak antibacterial performance, but when copper-rich phases and silver-rich phases which are uniformly distributed in the matrix are obtained through precipitation or other methods, the antibacterial property of the material is stable and efficient. Meanwhile, the typical size of the bacteria is 1um to 5um, and thus the average distance of the distribution of the antimicrobial precipitated phases is at least close to or less than this value in consideration of the mobility of the bacteria. However, as mentioned above, the silver-containing antibacterial stainless steel prepared by ordinary casting has not reached this level, and it is difficult to achieve the antibacterial property comparable to that of pure silver. Therefore, the present invention uses the ultra-fine stainless steel powder having an average particle size equivalent to that of bacteria as a raw material.
In addition, in order to ensure that the periphery of each superfine metal powder can have uniform nano-silver phase distribution, the method abandons the traditional method of directly adding antibacterial metal powder, creatively introduces the chemical method of in-situ decomposition into powder metallurgy, and simultaneously adopts the method of solution infiltration to ensure that the surface of each metal powder has silver particles. The obtained more uniform and fine silver phase distribution effectively reduces the dosage of noble metal elements and has more excellent antibacterial performance. In addition, the method has simple process, can be easily combined with the existing powder metallurgy industry, has a series of advantages of the powder metallurgy industry, can conveniently manufacture various products with complex shapes, and has wide application fields.
Disclosure of Invention
The invention aims to overcome the defects of silver-containing antibacterial stainless steel prepared by the existing process, and provides a preparation method of the silver-containing antibacterial stainless steel with simple process and excellent antibacterial performance.
The invention also aims to provide the silver-containing antibacterial stainless steel appliance prepared by the method.
The preparation method for preparing the silver-containing antibacterial stainless steel by the in-situ decomposition-assisted powder metallurgy method provided by the invention comprises the following characteristic steps.
(1) The present invention relates to the use of ultra-fine stainless steel metal powders of comparable or even smaller particle size and bacterial size, including any stainless steel grade metal powder that meets this dimensional characteristic. For example 0.01-5 μm, preferably 0.1-5 μm, preferably 1-5 μm. Such as austenitic stainless steel powder, martensitic stainless steel powder, ferritic stainless steel powder, duplex stainless steel powder, precipitation hardening stainless steel powder, etc., preferably ultrafine austenitic stainless steel powder, ultrafine martensitic stainless steel powder, ultrafine ferritic stainless steel powder, ultrafine duplex stainless steel powder, ultrafine precipitation hardening stainless steel powder, etc.
(2) And (3) according to the calculated mass fraction ratio of the added silver, calculating the mass of the required silver-containing solute, adding the mass into a proper solvent, and preparing the solution rich in silver ions. The silver-containing solute and the selected solvent may be any combination that dissolves the silver-containing solute and provides a solution that is well wettable to the stainless steel metal powder, including combinations that use surfactants to improve wettability.
(3) Adding the superfine stainless steel powder in the step (1) into the solution in the step (2), and completely dispersing metal powder particles in the solution by stirring, ultrasonic and other methods, wherein each metal particle can be contacted with the silver-containing solution.
(4) And (4) continuously drying the suspension obtained in the step (3) under certain conditions to obtain semi-dry metal powder.
(5) And (4) pressing and forming the semi-dried powder obtained in the step (4) according to a traditional powder metallurgy method to prepare a green body.
(6) And (5) sintering the green body obtained in the step (5).
The antibacterial stainless steel apparatus prepared by the method comprises various medical apparatuses, living appliances and the like. Including bowls, knives, tweezers, door handles, cups, and the like, in whole or in combination.
The invention also relates to semi-dried metal powder particles, characterized in that each metal powder particle is impregnated with a silver solution. The semi-dried metal powder particles are used for preparing the silver-containing antibacterial stainless steel appliance.
The principle of the invention is as follows: stainless steel powder with the size close to or smaller than that of bacteria is used as a starting material, and the surface of each powder particle can be ensured to be soaked by the silver-rich solution through a solution soaking method. The obtained powder is sintered after being pressed into a green compact, and in the sintering process, the silver-containing substance remaining on the surface of each powder particle undergoes a decomposition reaction in situ to produce silver particles having a nano-scale size on the particle surface. Thus, the resulting stainless steel material has silver particles distributed throughout the matrix on the nanometer scale, and the average spacing of the nanosilver phases is comparable to or even smaller than the size of a typical bacterium to ensure that each bacterium can come into contact with a nanosilver-rich phase. Therefore, the silver-containing antibacterial stainless steel prepared by the invention not only can dissolve silver ions to play an antibacterial role, but also can ensure contact sterilization, thereby having very excellent antibacterial performance.
Compared with the prior art for preparing silver-containing antibacterial stainless steel, the invention has the following advantages and better performance:
(1) the silver-containing antibacterial stainless steel appliance prepared by the powder metallurgy method has high material utilization rate and high shape freedom degree, and is easy for industrial production.
(2) The stainless steel powder particles with the size close to or even smaller than the size of the typical bacteria are adopted, so that the average distance of the silver phase is close to or even smaller than the size of the typical bacteria, and the contact sterilization is ensured to be carried out.
(3) The nano-scale silver particles are generated on the surfaces of the powder particles by adopting an in-situ decomposition generation method, and the method has the characteristics of small generated particles and precious metal consumption saving.
Drawings
FIG. 1 is a silver phase distribution diagram of the antibacterial stainless steel obtained by the method of the present invention: the silver phase distribution of the silver-containing antimicrobial stainless steel of example 2.
Fig. 2 is an enlarged view of the silver phase distribution diagram of fig. 1: the silver phase distribution of the silver-containing antimicrobial stainless steel of example 2 (enlarged view).
FIG. 3 shows the result of the antibacterial test of the antibacterial stainless steel material of the present invention: the silver-containing antibacterial stainless steel of example 2 was subjected to 24-hour antibacterial test by culturing with Escherichia coli on the surface of the sample, and the left side was a blank control group and the right side was an experimental group.
Fig. 4 is an antibacterial test result of the conventional antibacterial stainless steel: escherichia coli was cultured on the surface of the sample for 24h as antibacterial test result, with blank control group on the left and experimental group on the right.
Fig. 5 is a silver phase distribution diagram of the silver-containing antimicrobial stainless steel of example 1.
Fig. 6 shows the result of the antibacterial test of the silver-containing antibacterial stainless steel of example 1, with a blank control group on the left and an experimental group on the right.
Detailed Description
Hereinafter, specific embodiments of the present invention will be described in further detail, but the embodiments of the present invention are not limited thereto.
Example 1
(1) Weighing 99.8 parts of 316L superfine austenitic stainless steel powder;
(2) weighing 0.0031 part of silver nitrate crystal according to the proportion that the added silver is 0.002 part by mass, and adding the weighed silver nitrate crystal into an ethanol solvent to prepare a solution;
(3) adding the weighed stainless steel powder in the step (1) into the solution in the step (2), and completely soaking the powder in the solution under the action of ultrasound and stirring;
(4) drying the suspension obtained in the step (3) under a certain condition to finally obtain semi-dry metal powder soaked with the silver nitrate concentrated solution;
(5) pressing and forming the metal powder in the step (4) to prepare a raw door handle blank;
(6) and (4) sintering the green body obtained in the step (5) at 1380 ℃ to obtain a final sample.
The prepared austenitic stainless steel door handle is cultured and observed on the surface of a sample for escherichia coli at 37 ℃ for 24 hours, then the washed bacterial liquid is placed on a counting flat plate for overnight culture, and then the antibacterial rate is counted and calculated, and the antibacterial effect of the austenitic stainless steel door handle reaches more than 99%.
Example 2
(1) Weighing 99.8 parts of 17-4ph superfine martensitic stainless steel powder;
(2) weighing 0.0031 part of silver nitrate crystal according to the proportion that the added silver is 0.002 part by mass, adding the weighed silver nitrate crystal into a pure water solvent to prepare a solution, and simultaneously adding a trace amount of surfactant PVA into the solution to improve the wettability;
(3) adding the weighed stainless steel powder in the step (1) into the solution in the step (2), and completely soaking the powder in the solution under the action of ultrasound and stirring;
(4) drying the suspension obtained in the step (3) under a certain condition to finally obtain semi-dry metal powder soaked with the silver nitrate concentrated solution;
(5) pressing and forming the metal powder in the step (4) to prepare a disc blank;
(6) and (4) sintering the green body obtained in the step (5) at 1380 ℃ to obtain a final sample.
The prepared martensitic stainless steel disc is subjected to escherichia coli culture observation at 37 ℃ for 24h on the surface of a sample, then the washed bacterial liquid is placed on a counting flat plate for overnight culture, and then the antibacterial rate is counted and calculated, and the antibacterial effect of the martensitic stainless steel disc reaches more than 99%.
Referring to the drawings in detail, wherein fig. 1 to 3 are a silver phase distribution diagram and bacteriostatic experimental results of the antibacterial stainless steel of example 2; FIGS. 5 and 6 are a silver phase distribution diagram and an antibacterial test result of the antibacterial stainless steel of example 1; accordingly, fig. 4 is a result of a bacteriostatic experiment of the conventional antibacterial stainless steel control. All the methods and details of the antibacterial test were tested with reference to JISZ 2801-. The result shows that the antibacterial effect of the antibacterial stainless steel is obviously better than that of a stainless steel reference substance and a blank reference.
According to the standard of an antibacterial test, the antibacterial rate is more than 90 percent, the antibacterial effect is achieved, the antibacterial rate is more than 99 percent, the strong antibacterial effect is achieved, and the antibacterial rate is less than 90 percent, and the antibacterial effect is not achieved. In the test, no bacterial growth is found in the examples 1 and 2, so that the antibacterial rate is more than 99 percent, and the antibacterial agent has strong antibacterial capability. The antibacterial rate of the antibacterial stainless steel prepared by traditional casting in the test is obviously lower than 90%.
Claims (11)
1. Semi-dried metal powder particles, characterized in that each metal powder particle is impregnated with a silver solution.
2. Metal powder particles according to claim 1, characterized in that the silver solution is a solution of silver solutes in a suitable solvent, wherein the silver solutes comprise silver nitrate, silver diammine hydroxide, etc.; the solvent is alcohol, water, ester, aldehyde, etc., such as ethanol, pure water, ethyl acetate.
3. Metal powder particles according to claim 1 or 2, characterised in that a surfactant, such as PVA, PVP, is also added to the silver solution.
4. Metal powder particles according to any one of claims 1-3, characterised in that the particle size of the metal powder particles corresponds to the size of the bacteria, such as 0.01-5 μm, preferably 0.1-5 μm, preferably 1-5 μm, such as 1 μm, 2 μm, 3 μm, 4 μm, 5 μm.
5. Metal powder particles according to any of claims 1-4, characterized in that the metal powder is such as austenitic stainless steel powder, martensitic stainless steel powder, ferritic stainless steel powder, duplex stainless steel powder, precipitation hardening stainless steel powder, etc.
6. Metal powder particles according to any of claims 1-5, characterised in that the weight ratio of the metal powder particles to the silver solute is any ratio, such as 95:5 to 99.999:0.001, preferably 99:1 to 99.9:0.1, 95:5, 96:4, 97:3, 98:2, 99:1, 99.1:0.9, 99.2:0.8, 99.3:0.7, 99.4:0.6, 99.5:0.5, 99.6:0.4, 99.7:0.3, 99.8:0.2, 99.9:0.1 etc.
7. The metal powder particles of any one of claims 1 to 6 for use in the preparation of antimicrobial stainless steel.
8. A method of preparing semi-dried metal powder particles comprising the steps of:
(1) weighing metal powder particles;
(2) weighing a silver solute, and dissolving the silver solute in a solvent to prepare a solution;
(3) adding the metal powder particles obtained in the step (1) into the solution obtained in the step (2), and carrying out ultrasonic treatment and stirring treatment;
(4) drying the suspension obtained in the step (3) to obtain semi-dried metal powder particles;
wherein the silver solute, solvent, metal powder particle type and size, and weight of metal powder particles to silver solute are as defined in any one of claims 1 to 6.
9. A method for manufacturing an antibacterial stainless steel, characterized in that the semi-dried metal powder particles of claim 8 are press-formed and then sintered to obtain a product.
10. An antimicrobial stainless steel made by the method of claim 9.
11. The antibacterial stainless steel of claim 10, which is prepared as an integral or combined member of various medical instruments, living goods, and the like, including bowls, knives, tweezers, door handles, cups, and the like.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114226716A (en) * | 2021-12-24 | 2022-03-25 | 阳江市天骄家庭用品制造有限公司 | Feed for preparing antibacterial stainless steel cutting tool, cutting tool and preparation method thereof |
| CN114606433A (en) * | 2020-12-08 | 2022-06-10 | 香港大学 | Method for preparing antibacterial stainless steel by utilizing rapid solidification process and application thereof |
| CN115283595A (en) * | 2022-08-10 | 2022-11-04 | 阳江职业技术学院 | Martensite antibacterial stainless steel outdoor knife and preparation method thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6312533B1 (en) * | 1999-04-30 | 2001-11-06 | Kawasaki Steel Corporation | Stainless steel material with excellent antibacterial property and process for producing the same |
| CN101007351A (en) * | 2007-01-24 | 2007-08-01 | 华南理工大学 | Powder metallurgy composite antimicrobial stainless steel instrument and its preparation method |
| CN101306469A (en) * | 2008-02-05 | 2008-11-19 | 南京大学 | Core-shell type nano iron-silver bimetal granule and preparation method thereof |
| CN103551589A (en) * | 2013-10-30 | 2014-02-05 | 江苏理工学院 | Method for synthesizing flower-shaped silver micro-particles |
| CN103614719A (en) * | 2013-10-22 | 2014-03-05 | 深圳大学 | Preparation method of anti-microbial stainless steel |
| CN104066535A (en) * | 2012-01-17 | 2014-09-24 | 同和电子科技有限公司 | Silver-coated copper alloy powder and method for manufacturing same |
| CA2943163A1 (en) * | 2015-12-23 | 2017-06-23 | Silver Future Co., Ltd. | Antibacterial product comprising sintered silver nitrate and methods of manufacturing the same |
| JP2017114840A (en) * | 2015-12-23 | 2017-06-29 | 銀未来株式会社 | Antibacterial product and method for producing the same |
| CN106942959A (en) * | 2015-12-23 | 2017-07-14 | 银未来株式会社 | Antimicrobial product and its manufacture method |
| WO2018235973A1 (en) * | 2017-06-22 | 2018-12-27 | 긴미라이 가부시키가이샤 | Antibacterial product and manufacturing method therefor |
-
2019
- 2019-04-11 CN CN201910288262.5A patent/CN111804931A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6312533B1 (en) * | 1999-04-30 | 2001-11-06 | Kawasaki Steel Corporation | Stainless steel material with excellent antibacterial property and process for producing the same |
| CN101007351A (en) * | 2007-01-24 | 2007-08-01 | 华南理工大学 | Powder metallurgy composite antimicrobial stainless steel instrument and its preparation method |
| CN101306469A (en) * | 2008-02-05 | 2008-11-19 | 南京大学 | Core-shell type nano iron-silver bimetal granule and preparation method thereof |
| CN104066535A (en) * | 2012-01-17 | 2014-09-24 | 同和电子科技有限公司 | Silver-coated copper alloy powder and method for manufacturing same |
| CN103614719A (en) * | 2013-10-22 | 2014-03-05 | 深圳大学 | Preparation method of anti-microbial stainless steel |
| CN103551589A (en) * | 2013-10-30 | 2014-02-05 | 江苏理工学院 | Method for synthesizing flower-shaped silver micro-particles |
| CA2943163A1 (en) * | 2015-12-23 | 2017-06-23 | Silver Future Co., Ltd. | Antibacterial product comprising sintered silver nitrate and methods of manufacturing the same |
| JP2017114840A (en) * | 2015-12-23 | 2017-06-29 | 銀未来株式会社 | Antibacterial product and method for producing the same |
| CN106942959A (en) * | 2015-12-23 | 2017-07-14 | 银未来株式会社 | Antimicrobial product and its manufacture method |
| WO2018235973A1 (en) * | 2017-06-22 | 2018-12-27 | 긴미라이 가부시키가이샤 | Antibacterial product and manufacturing method therefor |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114606433A (en) * | 2020-12-08 | 2022-06-10 | 香港大学 | Method for preparing antibacterial stainless steel by utilizing rapid solidification process and application thereof |
| CN114226716A (en) * | 2021-12-24 | 2022-03-25 | 阳江市天骄家庭用品制造有限公司 | Feed for preparing antibacterial stainless steel cutting tool, cutting tool and preparation method thereof |
| CN115283595A (en) * | 2022-08-10 | 2022-11-04 | 阳江职业技术学院 | Martensite antibacterial stainless steel outdoor knife and preparation method thereof |
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