CN100529144C - Nano precipitated phase martensite antimicrobial stainless steel - Google Patents
Nano precipitated phase martensite antimicrobial stainless steel Download PDFInfo
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- CN100529144C CN100529144C CNB2007101992678A CN200710199267A CN100529144C CN 100529144 C CN100529144 C CN 100529144C CN B2007101992678 A CNB2007101992678 A CN B2007101992678A CN 200710199267 A CN200710199267 A CN 200710199267A CN 100529144 C CN100529144 C CN 100529144C
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Abstract
The invention discloses a nanometer precipitated phase martensitic antibiotic stainless steel. Granular nanometer scale precipitated phases Epsilon-Cu are dispersed and distributed evenly in a stainless steel matrix, to cause the stainless steel to have bacteria resistant performance. The weight percentage of the chemical compositions of the stainless steel is as follows: C is 0.10 to 0.40 percent, Cr is 12.00 to14.00 percent, Cu is 1.50 to 3.50 percent, RE is 0.04 to 0.10 percent, Mg is 0.05 to 0.15 percent, Ti is 0.03 to 0.10 percent, Si is lower than or equal to 0.60 percent, Mn is lower than or equal to 0.60 percent, P is lower than or equal to 0.03 percent, S is lower than or equal to 0.03 percent, and the residual is Fe. The components of the invention are simple, alloying elements are few, and bacterium such as coliform bacteria, salmonella typhiurium, staphyloccocus aureus rosenbach and white candidiasis contacted with the stainless steel can be effectively killed. The bacteria resistant performance is good and durative, and the invention can be widely applied to the fields of food processing, kitchen dining, daily electrical appliance, medical appliance, and equipment, etc.
Description
Technical field
The invention belongs to Materials Processing Engineering and medical microbiology crossing domain, relate to a kind of martensite antimicrobial stainless steel, by add some specific chemical ingredientss and antibiotic thermal treatment at stainless steel, can give common Martensite Stainless Steel good anti-microbial property, can be widely used in the fields such as food-processing, kitchen food and drink, daily-use electrical appliance, medicine equipment and equipment thereof that demand has the durable antibiotic performance.
Background technology
Environment protection is must needing of social sustainable development, and hygiene and health are eternal theme that human society is concerned about.According to " WHO ", the whole world dead 5,200 ten thousand people of nineteen ninety-five wherein because of the death toll that bacterial infection causes is 1,700 ten thousand, account for 1/3.These transmissible diseases comprise cholera, pneumonia, dysentery, tuberculosis etc.Nationwide MRS has taken place and has infected in Japan in 1996, Britain's outburst " mad cow disease " in 1997, the numerous and confused outburst of country " foot and mouth disease " such as Japan in 2000, Korea S, Mongolia and China in 2003 find the SARS virus propagation, this chain of events has all caused global fear, causes the great attention of people to environmental health, germ prevention.The flat 8-49085 of patent JPA, CN1566397A and CN1410587A propose the metal level at the rich silver of stainless steel surface magnetron sputtering or rich copper or rich zinc, but this coating comes off when rolling and scouring easily, surface working raises the cost in addition, is not suitable for the big area engineering and uses.Directly copper is added in austenitic stainless steel, Martensite Stainless Steel, the ferritic stainless steel for addressing the above problem the flat 8-104952 of JPA, the flat 8-104953 of JPA, the flat 9-170053 of JPA, JP99800249.6, CN1498981A, CN1504588A, CN1789471A and CN101029375A.This stainless-steel antibacterial is good, and effect is lasting, still has good antimicrobial property after the repeated friction.But exist the solubleness of Ag very little, and add the problem that copper causes stainless erosion resistance to descend easily, what add for practical application and globule size all is difficult to control.
Summary of the invention
In order to overcome above-mentioned anti-bacteria stainless steel corrosion resistance nature this shortcoming that descends, the object of the present invention is to provide a kind of nano precipitated phase martensite antimicrobial stainless steel, the even dispersion nano level precipitated phase ε-Cu that distributing has favorable mechanical performance and corrosion resistance and durable antibiotic performance in this stainless steel base.
In order to realize above-mentioned task, the present invention takes following technical solution:
A kind of nano precipitated phase martensite antimicrobial stainless steel, the stainless chemical component weight per-cent of this that makes is C:0.10%～0.40%, Cr:12.00%～14.00%, Cu:1.50%～3.50%, RE:0.04%～0.10%, Mg:0.05%～0.15%, Ti:0.03%～0.10%, Si≤0.60%, Mn≤0.60%, P≤0.03%, S≤0.03%, all the other are Fe.And the even dispersion nano level precipitated phase ε-Cu that distributing in matrix, the about 90～700nm of its size, the spacing between the precipitated phase about 100nm, thereby given Martensite Stainless Steel good anti-microbial property.
Nano precipitated phase martensite antimicrobial stainless steel of the present invention, not only have good mechanical property and physical and chemical performance, and has a good anti-microbial property, its composition is simple, valuable alloying element is less, can effectively kill the bacteriums such as intestinal bacteria, bacillus typhi murium, streptococcus aureus and candida albicans of contact with it.Can be widely used in engineering Application Areass such as water feeding system, food-processing, kitchen food and drink, medical facilities, daily-use electrical appliance.
Description of drawings
Fig. 1 is the martensite antimicrobial electromicroscopic photograph, and wherein, figure (a) is the stereoscan photograph of martensite antimicrobial stainless steel, and figure (b) is the back scattering electromicroscopic photograph after martensite antimicrobial stainless steel corrodes with 5% nitric acid alcohol;
Fig. 2 is the influences of the different action times of martensite antimicrobial stainless steel to four kinds of bacterium sterilizing rates.
The present invention is described in further detail below in conjunction with embodiment and antibacterial experiment.
Embodiment
Nano precipitated phase martensite antimicrobial stainless steel of the present invention, the even dispersion particulate state nano level precipitated phase ε-Cu that distributing in this stainless steel base that makes, make stainless steel have anti-microbial property, the weight percent of this stainless chemical ingredients is: C:0.10%～0.40%, Cr:12.00%～14.00%, Cu:1.50%～3.50%, RE:0.04%～0.10%, Mg:0.05%～0.15%, Ti:0.03%～0.10%, Si≤0.60%, Mn≤0.60%, P≤0.03%, S≤0.03%, all the other are Fe.
The preparation method of above-mentioned nano precipitated phase martensite antimicrobial stainless steel is, the employing Martensite Stainless Steel is a base material, in base material, add The addition of C u, adopt melting in the antivacuum induction furnace, before the casting, be crushed to the fritter of granularity less than 5mm with rare-earth and Mg-titanium (RE-Mg-Ti) compound modifier, after oven dry below 240 ℃, place the casting ladle bottom, add-on is 0.5%～1.0% of a molten steel weight, with the method that pours in the bag stainless steel water is carried out composite inoculating and handles; Help like this that degasification is removed slag, purify hot metal, thinning microstructure, the stainless corrosion resistance nature of raising and comprehensive mechanical performance thereof.Then foundry goods is carried out antibiotic thermal treatment, its technology is: the first step, foundry goods is incubated 1h～3h under 1000 ℃～1100 ℃ temperature, and air cooling or water-cooled make Cu supersaturation to dissolve in matrix in stainless steel to room temperature; Second step was incubated 3h～5h under 750 ℃～850 ℃ temperature, air cooling is to room temperature, through such insulation ageing treatment, particulate state nano level precipitated phase ε-Cu even dispersion in stainless steel base is distributed, and the size of precipitated phase ε-Cu is 90nm～700nm, and its spacing is about 100nm.But after soaking time surpasses 6h, the grain fineness number of precipitated phase will obviously increase, and then can significantly reduce stainless anti-microbial property.
Cu is most important antibiotic alloying constituent, and along with the increase of Cu content, stainless anti-microbial property significantly increases, but when Cu content surpasses 3.5%, except that production cost improves, little to improving the anti-microbial property effect, excessive Cu will reduce the corrosion resistance of material.
C at first can improve the intensity of Martensite Stainless Steel as the stainless steel composition, simultaneously, can promote the disperse uniform distribution of precipitated phase ε-Cu, will reduce its corrosion resistance but surpass 0.3%.
Si and Mn are indispensable in the stainless steel, except that as also can be used as reductor the alloying element.But when surpassing scope of the present invention, it can have a negative impact to the performance of material itself.
Cr is the principal element that makes Martensite Stainless Steel have martensitic stucture and have good corrosion resistance, must guarantee its minimum content.
Adopt rare-earth and Mg-titanium (RE-Mg-Ti) ternary compound modifier, alterant is crushed to the fritter of granularity less than 5mm～10mm, alterant granularity size depends on casting ladle volumetrical size, with the alterant of fragmentation after the oven dry of the temperature below 240 ℃, place the casting ladle bottom, its add-on is 0.5%～1.0% of a molten steel weight, with the method that pours in the bag stainless steel water is carried out composite inoculating and handles.Help like this that degasification is removed slag, purify hot metal, thinning microstructure, the stainless corrosion resistance nature of raising and comprehensive mechanical performance thereof.
Antibiotic thermal treatment can guarantee that particulate state nano level precipitated phase ε-Cu even dispersion in stainless steel base distributes.The size of particulate state nano level precipitated phase ε-Cu is 90nm～700nm, and its spacing is about 100nm.
Below be that the contriver provides specific embodiment, need to prove that embodiment is one of preferable case, the present invention is not limited to this embodiment.
1. anti-biotic material preparation
The present invention is a base material with the 2Cr13 Martensite Stainless Steel, in Martensite Stainless Steel, add 5%Cu, melting in the antivacuum induction furnace of 10kg is before the casting, with commercially available rare-earth and Mg-titanium (RE-Mg-Ti) compound modifier, alterant is crushed to the fritter of granularity less than 5mm, after 240 ℃ of following temperature oven dry, add-on is 0.5%～1.0% of a molten steel weight, places the casting ladle bottom, with the method that pours in the bag stainless steel water is carried out composite inoculating and handle, pour into the coupon of Φ 25 * 250mm.
The stainless steel coupon is done antibiotic thermal treatment, and its technology is: 1050 ℃ ± 1 ℃ insulation 2h, and water-cooled makes Cu to be dissolved in the stainless steel base to supersaturation to room temperature, at 700 ℃ ± 1 ℃ insulation 4h, air cooling is to room temperature.Coupon is processed into the block sample (martensite antimicrobial stainless steel) of Φ 20 * 5mm.
With 2Cr13 material in contrast, the chemical composition analysis of anti-bacteria stainless steel and contrast material the results are shown in Table 1.
Specimen surface after polishing, polishing, with acetone deoil, ethanol cleans, behind the hot blast drying, put into drying chamber and preserve standby.Scanning electron microscope, the back scattering electromicroscopic photograph of the martensite antimicrobial stainless steel (ABSS-M) of present embodiment preparation are seen Fig. 1.By Fig. 1 (a) as seen, (grey) disperse ε-Cu phase (canescence) that distributing on martensitic matrix, the about 90～700nm of precipitated phase particle size, the spacing between the precipitated phase about 100nm, thereby given Martensite Stainless Steel good anti-microbial property.Fig. 1 (b) is the back scattering electromicroscopic photograph after martensite antimicrobial stainless steel corrodes with 5% nitric acid alcohol, after part ε-Cu is corroded mutually, stays many cavities.
Table 1 martensite antimicrobial stainless steel (ABSS-M) and control material chemical ingredients (Wt%)
| Stainless steel | C | Cr | Cu | Si | Mn | RE | Mg | Ti | P | S |
| The present invention's example ABSS-M | 0.21 | 13.17 | 3.30 | 0.53 | 0.48 | 0.72 | 0.88 | 0.07 | 0.030 | 0.028 |
| Reference examples 2Cr13 | 0.22 | 13.25 | - | 0.52 | 0.51 | - | - | - | 0.027 | 0.026 |
2. anti-microbial property test
Method with plastic film is adopted in the anti-microbial property test, and the experiment bacterium is adopted intestinal bacteria, bacillus typhi murium, streptococcus aureus and Candida albicans, and experimental arrangement is as follows:
(1) sterilize: experimental sample after ethanol is cleaned and control sample are at 121 ± 1 ℃ of following autoclaving 20min.
(2) application of sample: earlier used microbionation is cultivated 18～24h in the plain agar substratum, being diluted to concentration with stroke-physiological saline solution is 10
5The standard bacterium liquid of cfu/ml.And respectively 0.5ml bacterium liquid is evenly dripped to experimental sample and control sample surface.
(3) sampling: respectively 1h, 2h, 4h, 8h, 12h, 16h, 20h and 24h behind the application of sample placed stroke-physiological saline solution with sample, wash its surface repeatedly with dropper, getting its 1ml behind the mixing is added in the sterile petri dish, add to have sterilized in advance and be cooled to 45 ℃ of left and right sides nutrient agar 15ml then and shake up, cultivate the cooling back, and each sample is made 3 flat boards.
(4) cultivate: cultivate 24h for 37 ℃, count the bacterium number in each culture dish, calculate antibiotic rate.The antibacterial tests of martensite antimicrobial stainless steel the results are shown in Figure 2, and wherein the calculation formula of antibiotic rate is:
Contrast stainless steel aerobic plate count is the viable count after the contrast stainless steel carries out the microbial culture experiment in the formula, and the anti-bacteria stainless steel aerobic plate count is meant the viable count after anti-bacteria stainless steel carries out the microbial culture experiment.
Martensite antimicrobial stainless steel is to intestinal bacteria, bacillus typhi murium, streptococcus aureus and the candida albicans sterilizing rate of different action times (seeing Fig. 2 and table 2).As seen from Figure 2, in 2h, anti-bacteria stainless steel reaches 88% to the sterilizing rate of intestinal bacteria and streptococcus aureus; In when 8h, first three sterilizing rate of planting bacterium has all reached 100%.And relatively slow to the germicidal action of bacillus typhi murium with interior anti-bacteria stainless steel at preceding 2h, in the period, sterilization speed improves rapidly at 2h～8h.Sterilizing rate appears in candida albicans at the 4h place be 20.8% minimum value; Sterilizing rate has only 62.5% during 8h; Candida albicans needs its sterilizing rate of sterilization 24h just can reach 100%.
3. antibiotic persistence experiment
To go 0.5mm thick through the anti-bacteria stainless steel surface finish after the anti-microbial property test, specimen surface be placed 1 month after polishing repeatedly, polishing, and adopted method with plastic film again it to be carried out comprehensive anti-microbial property and detected, and detected result sees Table 2.Obviously, shown result with grind before basic identical, illustrate that the anti-bacteria stainless steel surface is through polishing repeatedly with than the time placement and have identical anti-microbial property before this.Show very good durable antibiotic performance.This be since the antimicrobial characteristic of anti-bacteria stainless steel from the nano-antibacterial precipitated phase that distributes in the stainless steel base, so its antibacterial can be because of the grinding and of long duration forfeiture of material surface.
4. corrosion resistance nature and mechanical property experiment
The corrosion resistance nature of steel of the present invention is measured by GB GB/T101125-1997 salt-fog test method: sample carries out continuous spray testing in 48 hours under 5%NaCI, 2 ℃ of 35 ℃ of scholars of temperature, pH6.5～7.2 conditions.Test-results shows: martensite antimicrobial stainless steel (ABSS-M) and control material (2Cr13) specimen surface are smooth, glossy, all no change, no rust spot.
(ABSS-M) is processed into tension specimen with martensite antimicrobial stainless steel in the table 1, carries out stretching experiment.Experimental result shows: the mechanical property of this martensite antimicrobial stainless steel and control material is basic identical, and slightly is better than control material.Martensite antimicrobial stainless steel (ABSS-M) has following mechanical property: σ b 〉=640MPa; σ 0.2 〉=440MPa; δ 〉=20%; Ψ 〉=50%; Ak 〉=63J.
Table 2 martensite antimicrobial stainless steel (ABSS-M) anti-microbial property synopsis (sterilizing rate/%)
Claims (2)
1, a kind of nano precipitated phase martensite antimicrobial stainless steel, the even dispersion particulate state nano level precipitated phase ε-Cu that distributing in this stainless steel base that makes, make stainless steel have anti-microbial property, the weight percent of this stainless chemical ingredients is: C:0.10%～0.40%, Cr:12.00%～14.00%, Cu:1.50%～3.50%, RE:0.04%～0.10%, Mg:0.05%～0.15%, Ti:0.03%～0.10%, Si≤0.60%, Mn≤0.60%, P≤0.03%, S≤0.03%, all the other are Fe.
2, nano precipitated phase martensite antimicrobial stainless steel as claimed in claim 1 is characterized in that, the size of described particulate state nano level precipitated phase ε-Cu is 90nm～700nm, and its spacing is 100nm.
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| CN102162066B (en) * | 2011-03-28 | 2012-07-18 | 徐英忱 | Medical martensitic stainless steel material and preparation method thereof |
| TWI750077B (en) * | 2020-04-15 | 2021-12-11 | 日商日鐵不鏽鋼股份有限公司 | Fertilizer-based stainless steel material and manufacturing method thereof |
| CN114657454B (en) * | 2020-12-23 | 2022-12-09 | 安徽工业大学科技园有限公司 | 30Cr13 martensite antibacterial stainless steel and preparation method thereof |
| CN114657440B (en) * | 2020-12-23 | 2022-12-09 | 安徽工业大学科技园有限公司 | Martensite antibacterial stainless steel and preparation method thereof |
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Non-Patent Citations (2)
| Title |
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| 3Cr13Cu3马氏体不锈钢抗菌性能. 张伟，李宁，胥永刚，曾蔚，贾文祥.特殊钢，第25卷第2期. 2004 |
| 3Cr13Cu3马氏体不锈钢抗菌性能. 张伟，李宁，胥永刚，曾蔚，贾文祥.特殊钢，第25卷第2期. 2004 * |
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