CN103276426B - 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 PDF

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CN103276426B
CN103276426B CN201310184391.2A CN201310184391A CN103276426B CN 103276426 B CN103276426 B CN 103276426B CN 201310184391 A CN201310184391 A CN 201310184391A CN 103276426 B CN103276426 B CN 103276426B
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oxide film
stainless steel
corrosion
manufacture method
stainless
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CN103276426A (en
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周国桢
王思勤
周红
朱文川
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Southeast University
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Southeast University
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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

The stainless manufacture method of a kind of anti-corrosion antibacterial oxide film
Technical field
The present invention relates to the stainless manufacture method of a kind of oxide film, specifically the stainless manufacture method of a kind of anti-corrosion antibacterial oxide film, belongs to field of metal surface treatment technology.
Background technology
In recent years, many industrially-advanced countries competitively develop anti-bacteria stainless steel goods, to produce the maximum Japan of product innovation, have coating type anti-bacteria stainless steel, alloy-type anti-bacteria stainless steel, composite bactericidal stainless steel and Vacuum Deposition membranous type anti-bacteria stainless steel etc.All there are some problems in these stainless steels, the coating binding force as: coating type anti-bacteria stainless steel is unstable, can not at high temperature apply, in life-time service, because film is different with the thermal expansivity of metallic matrix and cause explosion to be peeled off; Alloy-type anti-bacteria stainless steel, as not corrosion-resistant in some medium in added copper stainless steel, especially spot corrosion is more serious, add silver-colored anti-bacteria stainless steel due to the content of silver more, add product cost, composition is not easily even, antibacterial is only that upper layer works, and the variable color of surface silver is also difficult to avoid; Composite bactericidal stainless steel makes complicated, and the antibacterial effect of antibacterial copper sheet is not good; Vacuum Deposition membranous type anti-bacteria stainless steel cost is higher, and the discoloration problem of its surface silver, is also difficult to solve.
Summary of the invention
Goal of the invention: for the deficiencies in the prior art, the object of the present invention is to provide a kind of antibacterial and mouldproof, corrosion-resistant, dependable performance, cost are low, can control the stainless manufacture method of oxide film of color.
Technical scheme: in order to realize foregoing invention object, the technical solution adopted in the present invention is:
The stainless manufacture method of a kind of anti-corrosion antibacterial oxide film, described method is: on stainless steel base, first Passivation Treatment forms the passive film of one deck 10 ~ 20nm; Process forms the spinel oxide film of one deck 200 ~ 500nm in an acidic solution again; After eventually passing sealing pores, namely drying obtains described stainless steel.
Described Passivation Treatment refers to the HNO in mass concentration 3% 3the H of solution and mass concentration 2% 2o 2in solution, under anode voltage 2 ~ 3 volts, act on 1 ~ 3 minute.The Cr depletion zone of stainless steel surface can be made to eliminate or reduce 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), like this when proceeding to oxidation, the spinel films Me that formation take Cr as core can be convenient at Fu Ge place 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 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 replaced, the time of reversal checker is positive dirction 1 ~ 15 second, negative direction 1 ~ 15 second, current density 5 ~ 150mA/dm 2, temperature 20 ~ 80 DEG C, effect 3-20 divide kind.Current waveform can with trilateral or square wave.Voltage is determined by the current density determined.Oxidization time needs and color and luster depending on thickness.
Described current density is 20 ~ 80mA/dm 2, temperature is 20 ~ 50 DEG C.This current density and temperature range can form true qualities stainless steel.
Described current density is 60 ~ 120mA/dm 2, temperature is 50 ~ 80 DEG C.Color Stainless Steel can be formed under this current density and temperature range.
Described sealing pores refers in PH6.5 ~ 7.5, soaks 5 ~ 10 minutes in the pure water that temperature is 70 ~ 90 DEG C.
Often 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 4.Cerium salt is rare earth resources, can the anti-microbial effect of catalyzing N i, Ag.
Owing to containing Ni, Mo, Mn, Ag, Co plasma in acidic solution, Ni, Mo are aobvious blue, Mn, Ag displaing yellow, Co is aobvious red, blueness, yellow, brown or the colored stainless steel such as bronze-colored can be formed under certain condition, reddish yellow indigo plant is the element of black, can be made into black stainless steel after three look superpositions.
Document is had 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 antibacterial, mildew-resistant preferably, deodorization, antifouling efficacy, consider production cost, Ag, Ce can add less and also can not add, and have good antibacterial anti-mildew effect equally.
The principle of antibacterial, mildew-resistant, deodorization, antifouling efficacy is:
N i, Co and Ag ion itself has germ resistance, can directly make bacterium outer tissue make a variation thus make bacteria inactivation, and the silver ions of high oxidation state, there is high reduction potential, the oxygen in sky G&W can be made, activate into electronegative atomic oxygen O -, activate water molecules H 2o becomes electronegative hydroxyl oxygen groups OH -, O -and OH -the microbial cell such as bacterium, virus coat protein can be made to make a variation, and the growth and breeding such as bacterium, virus is suppressed, and its deactivation short, so there is sterilizing function, and containing N i, the element such as Mo can promote anti-mildew, kill the function of mould.In like manner, because O -and OH -effect, the dirt removal be attached on wall can be made, make wall of container, dirt that workpiece surface is not easily stained with and easily removing.Meanwhile, sulfide in air and nitride can be made at O -and OH -effect under, become acidic substance and be removed, therefore the effect of deodorizing can be played.
Beneficial effect: compared with prior art, remarkable advantage of the present invention is:
1) antibacterial, the mildew-resistant of sample of the present invention, anti-soil, deodorization, corrosion-resistant and can prevent heavy metal from separating out;
2) the resistance to illumination anti-discolouring of sample of the present invention, through reaching the sun exposure of 2 years, reaching the ultraviolet Continuous irradiation of 28 days, equal nondiscoloration;
3) sample processing characteristics of the present invention is strong, wear resistance is high, bending, deep-drawing and the mold pressing processing of 180 degree can be born, wear-resisting and resistance to delineation performance is all high than former body stainless steel, can through the rubber friction more than 200 times of load 500 grams, and 120 grams of draw points born a heavy burden can be stood portray, measure wear resistance by sand trial method, knockout quality 1Kg is qualified, and inventive samples can reach 4.9Kg;
4) the male and female chmice acute per os LO50 value of chmice acute mouth toxicity test is all greater than 15000mg/Kg bwt, illustrates that test agent of the present invention belongs to nontoxic level;
5) sample of the present invention first forms one deck passive film and forms oxide film again, strong adhesion, is not subject to the impact of high temperature and matrix alloy thermal expansivity, more reliably, more firmly;
6) nickel that the present invention price is lower plays antibacterial anti-mildew effect, relatively silver, cerium cost is lower;
7) the present invention makes the stainless steel made be true qualities or colour by the parameter such as control temperature, current density, more meet industrial diversified demand, the colour film formed is as blue, black, fill up the industrial technology vacancy being difficult to prepare, and yellow, brown, bronze-colored etc. have anti-corrosion, outward appearance is beautiful and prevent the excellent properties such as heavy metal precipitation.
Embodiment
Below by specific embodiment, the present invention is further described; it should be pointed out that for the person of ordinary skill of the art, under the premise without departing from the principles 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 non-Passivation Treatment and Passivation Treatment respectively, during Passivation Treatment, first use the HNO of mass concentration 3% 3the H of solution and mass concentration 2% 2o 2solution, by the anodic current of 2 volts, keeps 1 minute under room temperature.Stainless steel after process is placed in mass concentration 20%FeCl 3temperature 30 DEG C, soaks 1 hour.Corrosion rate is tested, corrosion rate (%)=(before erosion the rear weight of weight-erosion)/(before erosion weight) × 100% after 1 hour.
Test result is in table 2.
Table 2
Result shows, after Passivation Treatment, stainless corrosion rate reduces, more corrosion-resistant.
Embodiment 2
First use the HNO of mass concentration 3% 3the H of solution and mass concentration 2% 2o 2solution, by the anodic current of 3 volts, keeps 3 minutes under room temperature.Use the acidic solution of A ~ F again, with the positive and negative exchange current replaced, under certain current density, temperature, action time, form spinel oxide film.Afterwards at PH7, soak in the pure water of temperature 70 C and take out seasoning in 10 minutes.A ~ F solution composition content is specifically in table 3.
Table 3
The test result of the sample made is in table 4.
Table 4
Test result is evaluated:
1, erosion resistance
At mass concentration 20%FeCl 3soak 2 hours in 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% second aqueous acid, boil 1 hour, steep 24 hours after being down to normal temperature, survey the content of the heavy metals such as Cr, Ni, Fe.Said sample is separated out heavy metal quantity and is all 0.
3, germ resistance
Antibacterial detection is carried out to stainless steel substrates, result show, said sample to intestinal bacteria 8099, streptococcus aureus ATCC6538 antibiotic rate all up to more than 99%.
4, mould resistance
Carry out anti-mildew detection to stainless steel substrates, detection with bacterium is
Bacterial classification Bacterium number
Aspergillus niger AS3.4463 is equal to ATCC6275
Addicted to loose mould AS3.745
Ball hair shell AS3.4254
G virens AS3.3987
Aureobasidium pullulans AS3.3984
The sample cultivation made by test specimen observes mildew degree in 28 days afterwards, and grade scale is
Not long 0 grade
Vestige growth (< 10%) 1 grade
Slight growth (>=10% ~ < 30%) 2 grades
Moderate growth (>=30% ~ < 60%) 3 grades
Severe 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 the generation color of Control Assay by regulating the parameter such as temperature, current density, exchange current conversion time, action time, and the stainless steel glossiness made is high, can meet industrial controlization, diversified demand.

Claims (9)

1. the stainless manufacture method of anti-corrosion antibacterial oxide film, is characterized in that: on stainless steel base, first Passivation Treatment forms the passive film of one deck 10 ~ 20nm; Process forms the spinel oxide film of one deck 200 ~ 500nm in an acidic solution again; After eventually passing sealing pores, namely drying obtains described stainless steel; Described Passivation Treatment refers to the HNO in mass concentration 3% 3the H of solution and mass concentration 2% 2o 2in solution, under anode voltage 2 ~ 3 volts, act on 1 ~ 3 minute.
2. the stainless manufacture method of anti-corrosion antibacterial 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 replaced, the time of reversal checker is positive dirction 1 ~ 15 second, negative direction 1 ~ 15 second, current density 5 ~ 150mA/dm 2, temperature 20 ~ 80 DEG C, effect 3-20 divide kind.
3. the stainless manufacture method of anti-corrosion antibacterial oxide film as claimed in claim 2, is characterized in that: described current density is 20 ~ 80mA/dm 2, temperature is 20 ~ 50 DEG C.
4. the stainless manufacture method of anti-corrosion antibacterial oxide film as claimed in claim 2, is characterized in that: described current density is 60 ~ 120mA/dm 2, temperature is 50 ~ 80 DEG C.
5. the stainless manufacture method of anti-corrosion antibacterial oxide film as claimed in claim 1, is characterized in that: described sealing pores refers in pH6.5 ~ 7.5, soaks 5 ~ 10 minutes in the pure water that temperature is 70 ~ 90 DEG C.
6. the stainless manufacture method of anti-corrosion antibacterial oxide film as claimed in claim 1, is characterized in that: often liter of proportioning of described acidic solution is: sulfuric acid 300-500g, chromic anhydride 120 ~ 250g, molybdate 1 ~ 10g, manganous sulfate 2 ~ 10g, single nickel salt 5 ~ 20g, rose vitriol 5 ~ 20g, silver salt 0 ~ 5g, cerium salt 5 ~ 20g.
7. the stainless manufacture method of anti-corrosion antibacterial oxide film as claimed in claim 6, is characterized in that: described molybdate is (NH 4) 2moO 4or Na 2moO 4.
8. the stainless manufacture method of anti-corrosion antibacterial oxide film as claimed in claim 6, is characterized in that: described silver salt is AgNO 3or Ag 2sO 4.
9. the stainless manufacture method of anti-corrosion antibacterial oxide film as claimed in claim 6, is characterized in that: described cerium salt is Ce (NO 3) 2or CeSO 4.
CN201310184391.2A 2013-05-17 2013-05-17 Manufacturing method of corrosion-resistant and antibacterial oxide film stainless steel Expired - Fee Related CN103276426B (en)

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CN106544710B (en) * 2016-11-25 2018-03-27 西华大学 A kind of anti-corrosion anti-bacteria stainless steel plate of anti-soil and preparation method thereof
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
CN112522773B (en) * 2020-11-04 2022-01-28 东南大学 Preparation method of stainless steel with antibacterial surface
CN113860733B (en) * 2021-09-17 2023-06-16 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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