CN103276426A - Manufacturing method of corrosion-resistant and antibacterial oxide film stainless steel - Google Patents
Manufacturing method of corrosion-resistant and antibacterial oxide film stainless steel Download PDFInfo
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- CN103276426A CN103276426A CN2013101843912A CN201310184391A CN103276426A CN 103276426 A CN103276426 A CN 103276426A CN 2013101843912 A CN2013101843912 A CN 2013101843912A CN 201310184391 A CN201310184391 A CN 201310184391A CN 103276426 A CN103276426 A CN 103276426A
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- oxide film
- corrosion
- antibiotic
- stainless steel
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Abstract
The invention discloses a manufacturing method of a corrosion-resistant and antibacterial oxide film stainless steel. The manufacturing method comprises the steps of: carrying out passivation treatment on a stainless steel matrix firstly to form a layer of passive film with the thickness of 10-20nm; then treating the passive film in an acid solution to from a layer of spinel oxide film with the thickness of 200-500nm; and finally, carrying out sealing treatment and drying treatment on the spinel oxide film to prepare the stainless steel. The corrosion-resistant and antibacterial oxide film stainless steel has the advantages of antibacterium, mold prevention, resistance to pollution, corrosion, illumination, discoloration and strong wear, deodorization, innocuity and lower cost and can be used for preventing heavy metals from being precipitated, and a stainless steel in natural color or a colorful stainless steel can be manufactured.
Description
Technical field
The present invention relates to the stainless manufacture method of a kind of oxide film, specifically is the stainless manufacture method of a kind of anti-corrosion antibiotic oxide film, belongs to field of metal surface treatment technology.
Background technology
In recent years, many industrially-advanced countries competitively develop the anti-bacteria stainless steel goods, are example to produce the maximum Japan of product innovation, and coating type anti-bacteria stainless steel, alloy-type anti-bacteria stainless steel, composite bactericidal stainless steel and vacuum plating type anti-bacteria stainless steel etc. are arranged.All there are some problems in these stainless steels, as: the coating bonding force instability of coating type anti-bacteria stainless steel, can not at high temperature use, in the life-time service, cause explosion to be peeled off owing to the thermal expansivity of film and metallic matrix is different; The alloy-type anti-bacteria stainless steel, as it is not corrosion-resistant in some medium to add the copper stainless steel, especially spot corrosion is more serious, add silver-colored anti-bacteria stainless steel because the content of silver is more, increased product cost, composition is difficult for evenly, antibiotic only is that upper layer works, and the variable color of surface silver also is difficult to avoid; The composite bactericidal stainless steel is made complicated, and the antibacterial effect of antibiotic copper sheet is not good; Vacuum plating type anti-bacteria stainless steel cost is higher, and the discoloration problem of its surface silver, also is difficult to solve.
Summary of the invention
Goal of the invention: at the deficiencies in the prior art, the object of the present invention is to provide the stainless manufacture method of oxide film that a kind of antibacterial and mouldproof, corrosion-resistant, dependable performance, cost are low, can control color.
Technical scheme: in order to realize the foregoing invention purpose, the technical solution adopted in the present invention is:
The stainless manufacture method of a kind of anti-corrosion antibiotic oxide film, described method is: first Passivation Treatment forms the passive film of one deck 10～20nm on stainless steel base; In acidic solution, handle the spinel oxide film that forms one deck 200～500nm again; Namely make described stainless steel finally by crossing sealing of hole processing back drying.
Described Passivation Treatment refers to the HNO in mass concentration 3%
3The H of solution and mass concentration 2%
2O
2In the solution, act on 1～3 minute under 2～3 volts of the anode voltages.Can make the poor chromium district of stainless steel surface eliminate or dwindle by passivation, Cr content obviously increases (gets stainless steel of the same race, respectively without Passivation Treatment with through Passivation Treatment, by test stainless steel surface composition peak value, Cr content situation sees the following form 1), when changing oxidation over to, can be convenient to form at the Fu Ge place with Cr be the spinel films Me of core like this
aCr
bO
r(Me is metallic element, and a, b, r are the valence mumber sum of metal and oxygen) also just can make antibacterial inorganic metal element A g, N
i, Co, Ce etc. more chemical combination in film, improve the antibacterial and mouldproof effect.
Table 1
| Atom% | Wt% | |
| Without Passivation Treatment | 17.90% | 16.78% |
| Through Passivation Treatment | 19.83% | 18.82% |
The preparation of described spinel oxide film is in acidic solution, and with the positive and negative exchange current that replaces, the time of reversal checker is positive dirction 1～15 second, negative direction 1～15 second, and, current density 5～150mA/dm
2, 20～80 ℃ of temperature, effect 3-20 branch is planted.Current waveform can be with trilateral or square wave.Voltage is decided by the current density of determining.Oxidization time needs on thickness and color and luster is decided.
Described current density is 20～80mA/dm
2, temperature is 20～50 ℃.This current density and temperature range can form the true qualities stainless steel.
Described current density is 60～120mA/dm
2, temperature is 50～80 ℃.Under this current density and temperature range, can form Color Stainless Steel.
Described sealing of hole is handled and is referred in PH6.5～7.5, soaks in the pure water that temperature is 70～90 ℃ 5～10 minutes.
Every liter of proportioning of described acidic solution is: sulfuric acid 300-500g, chromic anhydride 120～250g, molybdenum salt 1～10g, manganous sulfate 2～10g, single nickel salt 5～20g, rose vitriol 5～20g, silver salt 0～5g, cerium salt 5～20g.
Described molybdenum salt is (NH
4)
2MoO
4Or Na
2MoO
4
Described silver salt is AgNO
3Or Ag
2SO
4
Described cerium salt is Ce (NO
3)
2Or CeSO
4Cerium salt is rare earth resources, anti-microbial effect that can catalyzing N i, Ag.
Owing to contain Ni, Mo, Mn, Ag, Co plasma in the acidic solution, it is blue that Ni, Mo show, Mn, Ag displaing yellow, it is red that Co shows, can form blueness, yellow, brown or colored stainless steel such as bronze-colored under certain condition, reddish yellow indigo plant is the element of black, can be made into the black stainless steel after the stack of three looks.
There is document to disclose antibacterial effect Ag＞Co 〉=Ni 〉=Al 〉=Zn 〉=Cu=Fe, Ni＞Cu＞Co＞Zn=Ag＞Fe 〉=Al.N
i, Co, Mo, Cr also have antibiotic, mildew-resistant preferably, deodorization, antifouling effect, considers production cost, Ag, Ce can add less also and can not add, and antibiotic anti-mildew effect is preferably arranged equally.
The principle of antibiotic, mildew-resistant, deodorization, antifouling effect is:
N
i, Co and Ag ion itself have germ resistance, thereby can directly make the variation of bacterium outer tissue make bacteria inactivation, and the silver ions of high oxidation state has high reduction potential, can make the oxygen in the sky G﹠W, activates into electronegative atomic oxygen O
-, activate water molecules H
2O becomes electronegative hydroxyl oxygen groups OH
-, O
-And OH
-Can make microbial cell coat protein variations such as bacterium, virus, and growth and breedings such as bacterium, virus are suppressed, and short its deactivation, so sterilizing function is arranged, and contain N
i, element such as Mo can promote anti-mildew, kill the function of mould.In like manner, because O
-And OH
-Effect, can make the dirt removal that is attached on the wall, make the dirt that wall of container, workpiece surface be difficult for being stained with and remove easily.Simultaneously, can make airborne sulfide and nitride at O
-And OH
-Effect under, become acidic substance and be removed, so can play the effect of deodorizing.
Beneficial effect: compared with prior art, remarkable advantage of the present invention is:
1) antibiotic, the mildew-resistant of sample of the present invention, anti-soil, deodorization, corrosion-resistant, and can prevent that heavy metal from separating out;
2) sample of the present invention is fast light according to anti-discolouring, through reaching the sun exposure in 2 years, reach 28 days ultraviolet Continuous irradiation, all nondiscolorations;
3) sample processing characteristics of the present invention is strong, the wear resistance height, can bear bending, deep-drawing and the mold pressing processing of 180 degree, wear-resisting and anti-delineation performance is all than former body stainless steel height, can rub more than 200 times through the rubber of 500 grams of must loading, and can stand the draw points portrayal that 120 grams bear a heavy burden, measure wear resistance by the sand trial method, knockout quality 1Kg is qualified, and sample of the present invention can reach 4.9Kg;
4) the male and female chmice acute per os LO50 value of chmice acute mouth toxicity test illustrates that all greater than 15000mg/Kg bwt test agent of the present invention belongs to nontoxic level;
5) sample of the present invention forms one deck passive film earlier and forms oxide film again, and strong adhesion is not subjected to the influence of high temperature and matrix alloy thermal expansivity, and is more reliable, more firm;
6) the present invention brings into play antibiotic anti-mildew effect with the lower nickel of price, relatively silver, the cerium cost is lower;
7) can to make the stainless steel of making by parameters such as control temperature, current densities be true qualities or colour in the present invention, satisfy industrial diversified demand more, the colour film that forms is as blue, black, fill up the industrial technology vacancy that is difficult to prepare, and yellow, brown, bronze-colored etc. have excellent properties such as anti-corrosion, that outward appearance is beautiful and prevent that heavy metal from separating out.
Embodiment
The present invention is further described below by specific embodiment; should be pointed out that for the person of ordinary skill of the art, under the prerequisite that does not break away from the principle of the invention; can also make some modification and improvement, these also should be considered as belonging to protection scope of the present invention.
Embodiment 1
Choose 304 material stainless steels and 201 material stainless steels, do not Passivation Treatment and Passivation Treatment respectively, use the HNO of mass concentration 3% during Passivation Treatment earlier
3The H of solution and mass concentration 2%
2O
2Solution by 2 volts anodic current, kept 1 minute under the room temperature.Stainless steel after handling is placed mass concentration 20%FeCl
330 ℃ of temperature were soaked 1 hour.Test corrosion rate after 1 hour, corrosion rate (%)=(weight before the erosion-erosion back weight)/(weight before the erosion) * 100%.
Test result sees Table 2.
Table 2
The result shows that through after the Passivation Treatment, stainless corrosion rate reduces, and is more corrosion-resistant.
Embodiment 2
Use the HNO of mass concentration 3% earlier
3The H of solution and mass concentration 2%
2O
2Solution by 3 volts anodic current, kept 3 minutes under the room temperature.Use the acidic solution of A～F again, with the positive and negative exchange current that replaces, form the spinel oxide film down certain current density, temperature, action time.At PH7, soak in the pure water that temperature is 70 ℃ and took out seasoning in 10 minutes afterwards.A～F solution composition contains measuring and sees Table 3.
Table 3
The test result of the sample of making sees Table 4.
Table 4
Test result is estimated:
1, erosion resistance
At mass concentration 20%FeCl
3Soaked 2 hours in the solution, weightlessness is no more than 5% for excellent, and weightlessness is no more than 10% for good, and the erosion resistance of said sample is all excellent.
2, preventing from heavy metal is separated out
In mass concentration 4% acetic acid water solution, boiled 1 hour, be down to behind the normal temperature bubble 24 hours, survey Cr, Ni, the content of heavy metals such as Fe.Said sample is separated out heavy metal quantity and is all 0.
3, germ resistance
Stainless steel substrates is carried out antibiotic detection, and the result shows, said sample to intestinal bacteria 8099, streptococcus aureus ATCC6538 antibiotic rate all up to more than 99%.
4, mould resistance
Stainless steel substrates is carried out anti-mildew detect, detection with bacterium is
| Bacterial classification | Bacterium number |
| Aspergillus niger | AS3.4463 is equal to ATCC6275 |
| Have a liking for loose mould | AS3.745 |
| Ball hair shell | AS3.4254 |
| Green sticking broom is mould | AS3.3987 |
| Aureobasidium pullulans | AS3.3984 |
The sample cultivation that test specimen is made is observed the mildew degree after 28 days, grade scale is
| Not long | 0 grade |
| Vestige growth (＜10%) | 1 grade |
| Slight growth (〉=10%～＜30%) | 2 grades |
| Moderate growth (〉=30%～＜60%) | 3 grades |
| Serious growth (〉=60%～cover) comprehensively | 4 grades |
Above-mentioned test specimen all reaches 1 grade or 2 grades of anti-mildews, i.e. outstanding rank.
5, color, gloss
Above-mentioned test specimen can be controlled the generation color of sample by regulating parameters such as temperature, current density, exchange current conversion time, action time, and the stainless steel glossiness height of making, and can satisfy industrial controlization, diversified demand.
Claims (10)
1. the stainless manufacture method of anti-corrosion antibiotic oxide film is characterized in that: the passive film of first Passivation Treatment formation one deck 10 ~ 20nm on stainless steel base; In acidic solution, handle the spinel oxide film that forms one deck 200 ~ 500nm again; Namely make described stainless steel finally by crossing sealing of hole processing back drying.
2. the stainless manufacture method of anti-corrosion antibiotic oxide film as claimed in claim 1, it is characterized in that: described Passivation Treatment refers to the HNO in mass concentration 3%
3The H of solution and mass concentration 2%
2O
2In the solution, act on 1 ~ 3 minute under 2 ~ 3 volts of the anode voltages.
3. the stainless manufacture method of anti-corrosion antibiotic oxide film as claimed in claim 1, it is characterized in that: the preparation of described spinel oxide film is in acidic solution, with the positive and negative exchange current that replaces, the time of reversal checker is positive dirction 1 ~ 15 second, negative direction 1 ~ 15 second, current density 5 ~ 150mA/dm
2, 20 ~ 80 ℃ of temperature, effect 3-20 branch is planted.
4. the stainless manufacture method of anti-corrosion antibiotic oxide film as claimed in claim 3, it is characterized in that: described current density is 20 ~ 80mA/dm
2, temperature is 20 ~ 50 ℃.
5. the stainless manufacture method of anti-corrosion antibiotic oxide film as claimed in claim 3, it is characterized in that: described current density is 60 ~ 120mA/dm
2, temperature is 50 ~ 80 ℃.
6. the stainless manufacture method of anti-corrosion antibiotic oxide film as claimed in claim 1 is characterized in that: described sealing of hole is handled and is referred in PH6.5 ~ 7.5, soaks in the pure water that temperature is 70 ~ 90 ℃ 5 ~ 10 minutes.
7. the stainless manufacture method of anti-corrosion antibiotic oxide film as claimed in claim 1, it is characterized in that: every liter of proportioning of described acidic solution is: sulfuric acid 300-500g, chromic anhydride 120 ~ 250 g, molybdenum salt 1 ~ 10 g, manganous sulfate 2 ~ 10 g, single nickel salt 5 ~ 20g, rose vitriol 5 ~ 20g, silver salt 0 ~ 5 g, cerium salt 5 ~ 20 g.
8. the stainless manufacture method of anti-corrosion antibiotic oxide film as claimed in claim 7, it is characterized in that: described molybdenum salt is (NH
4)
2MoO
4Or Na
2MoO
4
9. the stainless manufacture method of anti-corrosion antibiotic oxide film as claimed in claim 7, it is characterized in that: described silver salt is AgNO
3Or Ag
2SO
4
10. the stainless manufacture method of anti-corrosion antibiotic oxide film as claimed in claim 7, it is characterized in that: described cerium salt is Ce (NO
3)
2Or CeSO
4
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|---|---|---|---|
| CN201310184391.2A CN103276426B (en) | 2013-05-17 | 2013-05-17 | Manufacturing method of corrosion-resistant and antibacterial oxide film stainless steel |
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|---|---|---|---|
| CN201310184391.2A CN103276426B (en) | 2013-05-17 | 2013-05-17 | Manufacturing method of corrosion-resistant and antibacterial oxide film stainless steel |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106544710A (en) * | 2016-11-25 | 2017-03-29 | 西华大学 | A kind of anti-soil is anti-corrosion anti-bacteria stainless steel plate and preparation method thereof |
| CN106835091A (en) * | 2016-12-16 | 2017-06-13 | 安徽宝恒新材料科技有限公司 | A kind of processing method for improving stainless steel corrosion resistance and antibiotic property |
| CN111534844A (en) * | 2020-05-14 | 2020-08-14 | 东南大学 | Antibacterial stainless steel surface treatment device and method |
| CN111647926A (en) * | 2020-05-14 | 2020-09-11 | 东南大学 | Preparation method of antibacterial aluminum alloy by anodic oxidation |
| CN111778538A (en) * | 2020-07-06 | 2020-10-16 | 上海脉诺金属表面处理技术有限公司 | Antibacterial electrochemical oxidation liquid and electrochemical oxidation process for stainless steel |
| CN112522773A (en) * | 2020-11-04 | 2021-03-19 | 东南大学 | Preparation method of stainless steel with antibacterial surface |
| CN113860733A (en) * | 2021-09-17 | 2021-12-31 | 佛山市三水区康立泰无机合成材料有限公司 | Electrostatic antibacterial glaze and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106544710A (en) * | 2016-11-25 | 2017-03-29 | 西华大学 | A kind of anti-soil is anti-corrosion anti-bacteria stainless steel plate and preparation method thereof |
| CN106835091A (en) * | 2016-12-16 | 2017-06-13 | 安徽宝恒新材料科技有限公司 | A kind of processing method for improving stainless steel corrosion resistance and antibiotic property |
| CN106835091B (en) * | 2016-12-16 | 2019-02-01 | 佛山市一派利昌金属制品有限公司 | A kind of processing method improving stainless steel corrosion resistance and antibiotic property |
| CN111534844A (en) * | 2020-05-14 | 2020-08-14 | 东南大学 | Antibacterial stainless steel surface treatment device and method |
| CN111647926A (en) * | 2020-05-14 | 2020-09-11 | 东南大学 | Preparation method of antibacterial aluminum alloy by anodic oxidation |
| CN111778538A (en) * | 2020-07-06 | 2020-10-16 | 上海脉诺金属表面处理技术有限公司 | Antibacterial electrochemical oxidation liquid and electrochemical oxidation process for stainless steel |
| CN112522773A (en) * | 2020-11-04 | 2021-03-19 | 东南大学 | Preparation method of stainless steel with antibacterial surface |
| CN112522773B (en) * | 2020-11-04 | 2022-01-28 | 东南大学 | Preparation method of stainless steel with antibacterial surface |
| CN113860733A (en) * | 2021-09-17 | 2021-12-31 | 佛山市三水区康立泰无机合成材料有限公司 | Electrostatic antibacterial glaze and preparation method thereof |
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