CN103409785B - A kind of titanium alloy surface reduces the nano coating preparation method of sea organism attachment - Google Patents
A kind of titanium alloy surface reduces the nano coating preparation method of sea organism attachment Download PDFInfo
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- CN103409785B CN103409785B CN201310286443.7A CN201310286443A CN103409785B CN 103409785 B CN103409785 B CN 103409785B CN 201310286443 A CN201310286443 A CN 201310286443A CN 103409785 B CN103409785 B CN 103409785B
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- titanium alloy
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Abstract
A kind of titanium alloy surface reduces the nano coating preparation method of sea organism attachment, electrolytic solution except containing except sodium phosphate, Sodium Benzoate, boric acid also containing the cupric ammine complex that copper sulfate and ammoniacal liquor are obtained, conventional processing is carried out to titanium alloy and as anode, stainless steel plate as negative electrode, pulse power working current, duty when pulse-repetition control at 10 ~ 20A, 10 ~ 20% and 500 ~ 650Hz respectively, electrolyte temperature controls at 50 DEG C, generates one deck Red copper oxide Cu after electrolysis 5 ~ 30min at titanium alloy surface
2o and the titanium dioxide TiO with nano-crystalline and amorphous structure
2insulating ceramic coating, coat-thickness 5 ~ 50 μm, surface hardness 400HV, bonding strength 30MPa, insulation resistance 1M Ω, 96h neutral salt spray corrosion test does not crack and corrosion product, in coating, copper quality is not less than 10%, seawater lacing film after three months sea organism attachment weight be not more than 20g/m
2.
Description
Technical field
The application belongs to oxide covering technical field, and especially a kind of titanium alloy surface reduces the nano coating preparation method of sea organism attachment.
Background technology
Differential arc oxidation MicroarcOxidation is called for short MAO, MAO be a kind of at non-ferrous metal substrate as Al, Ti, Mg, Zr, Nb, the new technology of Ta etc. and alloy surface growth in situ oxide ceramic coating, solidity to corrosion and the wear resistance on its surface is improved under the prerequisite not affecting substrate performance, due to oxide ceramic coating, to have bonding strength high, the features such as good insulating, at boats and ships, in marine industries, the part utilizing MAO can differ greatly at complicated shape and linear dimension is formed evenly and enough hard coating, prevent the copper be in contact with it in using, copper alloy, steel pipe, piping fitting and other part produce galvanic corrosion phenomena in the seawater.
The electrolytic solution coating formula that MAO is conventional is phosphoric acid salt, aluminate, silicate, glycerophosphate-acetate and sodium hydroxide solution system, the differential arc oxidation coating prepared does not have the ability preventing sea organism attachment, as seawater coupon test after three months its coatingsurface sea organism attachment weight can reach 65 ~ 100g/m
2, the larger latch up phenomenon to parts generations such as sea pipeline, pump, valves of sea organism attachment amount is larger, even causes and produces heavy corrosion in conjunction with gap, accelerates the corrosion failure of sill, affects the normal use on naval vessel, reduces the safe reliability on naval vessel.
Chinese patent CN101311326A discloses a kind of electrolytic solution for light metal differential arc oxidation and differential arc oxidation method, this electrolytic solution contains 5 ~ 100g/L Sodium hexametaphosphate 99, 2 ~ 100g/L water glass, 0.1 ~ 10g/L rose vitriol, 1 ~ 30g/L ammonium meta-vanadate, resistance to soiling is obtained at light metal surface after differential arc oxidation process, scratch resistance and the good differential arc oxidation coating of compactness, and there is higher hardness, wear resistance, erosion resistance and electrical insulating property, but this differential arc oxidation coating only has certain antibacterial effect to the unicellular organism such as bacterium and fungi, mariner growth prevent is attached to the poor ability of light metal surface.
Up to now, the nano coating preparation method that can reduce sea organism attachment at titanium alloy surface yet there are no relevant report.
Summary of the invention
For the weak point existing for existing differential arc oxidation coating, the invention provides the nano coating preparation method that a kind of titanium alloy surface reduces sea organism attachment, with the addition of cupric ammine complex in the electrolytic solution, cupric ammine complex under the effect of sodium phosphate, Sodium Benzoate and boric acid and setting electrolytic condition under define low toxicity Red copper oxide Cu
2o and the titanium dioxide TiO with nano-crystalline and amorphous structure
2insulating ceramic coating, this coating can reduce barnacle, mussel, the adhesive ability of oyster and bond area greatly, extends titanium alloy work-ing life in the seawater.
For achieving the above object, the present invention adopts following technical scheme:
A kind of titanium alloy surface reduces the nano coating preparation method of sea organism attachment, this nano coating preparation method comprises the pre-treatment to titanium alloy surface, titanium alloy nano coating preparation in the electrolytic solution and the aftertreatment of nano coating, wherein pre-treatment carries out degreasing to titanium alloy surface, oil removing, the process of cleaning, electrolytic solution contains sodium phosphate, Sodium Benzoate, boric acid, nano coating preparation uses electrolyzer, stainless steel plate, agitator and the pulse power, the aftertreatment of nano coating is the process of cleaning, drying, titanium alloy or TA1, or TA2, or TA3, or TA5, or TA16, or TA17, or TA22, or TA22-1, or TA23, or TA23-1, or TA24, or TA24-1, or TA31, or TC4, TC4ELI, feature of the present invention is as follows:
Also containing cupric ammine complex in above-mentioned electrolytic solution, cupric ammine complex is obtained after being reacted by copper sulfate and ammoniacal liquor, containing sodium phosphate, the Sodium Benzoate of 10 ~ 30g, the boric acid of 5 ~ 30g, the cupric ammine complex of 15 ~ 50g of 30 ~ 70g in often liter of electrolytic solution, all the other are deionized water;
Degreasing is carried out to titanium alloy surface, oil removing, cleaning becomes stand-by titanium alloy, the above-mentioned electrolytic solution configured to be poured in electrolyzer and to stir with agitator, using described stand-by titanium alloy as anode, using stainless steel plate as negative electrode, the working current of pulse mao power source controls at 10 ~ 20A, Duty ratio control is 10 ~ 20%, pulse-repetition controls at 500 ~ 650Hz, the temperature of above-mentioned electrolytic solution controls at 50 DEG C, described anode and described negative electrode to be immersed in above-mentioned electrolytic solution and under above-mentioned parameter controls, the preparation of differential arc oxidation nano coating to be carried out to described stand-by titanium alloy surface, time controling prepared by differential arc oxidation nano coating is at 5 ~ 30min, one deck Red copper oxide Cu is generated at described stand-by titanium alloy surface
2o and the titanium dioxide TiO with nano-crystalline and amorphous structure
2insulating ceramic coating, aftertreatment to be cleaned described coating with ionized water and dries, detect after oven dry, the thickness of described coating can reach 5 ~ 50 μm, and surface hardness is not less than 400HV, and bonding strength is not less than 30MPa, insulation resistance under drying conditions is not less than 1M Ω, do not crack and corrosion product after 96h neutral salt spray corrosion test, the copper quality in described coating is not less than 10%, seawater lacing film after three months sea organism attachment weight be not more than 20g/m
2.
Above-mentioned electrolytic solution is also applicable to aluminium alloy, nano coating and described coating are prepared in magnesium alloy, zirconium alloy, niobium alloy, tantalum alloy surface.
The preferred thickness of coating described above can control at 10 ~ 20 μm.
Owing to adopting technical scheme described above, the present invention produces following positively effect:
1, differential arc oxidation nano coating preparation method of the present invention, due to highly toxic substances such as electrolytic solution oxygen-freeization mercury, organotin, Organic leadP, therefore to the less pollution of operator and environment for use, electrolyte property is stablized, and quality of forming film is good, easily manipulates.
2, the nano coating that titanium alloy surface generates defines the titanium dioxide TiO of the nano-crystalline and amorphous structure containing Red copper oxide
2insulating ceramic coating, this coating can reduce barnacle, mussel, the adhesive ability of oyster and bond area greatly, extends titanium alloy work-ing life in the seawater.
3, differential arc oxidation nano coating preparation method of the present invention is not only applicable to titanium or titanium alloy, is also applicable to the alloy materials such as aluminium, magnesium, zirconium, niobium, tantalum.
4, insulating ceramic coating thickness can reach 5 ~ 50 μm, surface hardness is not less than 400HV, bonding strength is not less than 30MPa, insulation resistance under drying conditions is not less than 1M Ω, do not crack and corrosion product after 96h neutral salt spray corrosion test, copper quality in nano coating is not less than 10%, seawater lacing film after three months sea organism attachment weight be not more than 20g/m
2.
5, the present invention is compared with traditional differential arc oxidation coating, and the ability of mariner growth prevent attachment improves about 3 ~ 10 times.
Embodiment
The present invention is the nano coating preparation method that a kind of titanium alloy surface reduces sea organism attachment, with the addition of cupric ammine complex in the electrolytic solution, cupric ammine complex under the effect of sodium phosphate, Sodium Benzoate and boric acid and setting electrolytic condition under define low toxicity Red copper oxide Cu
2o and the titanium dioxide TiO with nano-crystalline and amorphous structure
2insulating ceramic coating, this coating can reduce barnacle, mussel, the adhesive ability of oyster and bond area greatly, extends titanium alloy work-ing life in the seawater.
Nano coating preparation method of the present invention comprises the nano coating preparation in the electrolytic solution of pre-treatment to titanium alloy surface, titanium alloy and the aftertreatment of nano coating, wherein pre-treatment is the process of titanium alloy surface being carried out to degreasing, oil removing, cleaning, electrolytic solution contains sodium phosphate, Sodium Benzoate, boric acid, nano coating preparation uses electrolyzer, stainless steel plate, agitator and the pulse power, and the aftertreatment of nano coating is the process of cleaning, drying.
Above-mentioned titanium alloy or TA1, or TA2, or TA3, or TA5, or TA16, or TA17, or TA22, or TA22-1, or TA23, or TA23-1, or TA24, or TA24-1, or TA31, or TC4, TC4ELI.
Also cupric ammine complex is contained except containing except sodium phosphate, Sodium Benzoate, boric acid in above-mentioned electrolytic solution, cupric ammine complex is obtained after being reacted by copper sulfate and ammoniacal liquor, containing sodium phosphate, the Sodium Benzoate of 10 ~ 30g, the boric acid of 5 ~ 30g, the cupric ammine complex of 15 ~ 50g of 30 ~ 70g in often liter of electrolytic solution, all the other are deionized water.
The mechanism that above-mentioned electrolytic solution prepares nano coating to titanium alloy surface is as follows:
Boric acid plays the effect suppressing electric arc, stablize film forming, and Sodium Benzoate is soluble in water, and stable in the air, suppresses the effect of yeast and bacterium strong.
Copper sulfate in cupric ammine complex and excessive ammonia react the cupric tetramminosulfate generated wherein,
2CuSO
4+10NH
4OH→[Cu(NH
3)
4]
2(OH)
2（SO
4）+(NH
4)
2SO
4+8H
2O
Under thermochemistry, plasma chemistry and electrochemical acting in conjunction, it is four ammino copper complex ions that the cupric tetramminosulfate of generation is ionized, with O
2-ionic reaction generates the Red copper oxide with anti-pollution function, and Red copper oxide is a kind of poison material, at utmost can kill marine animal.
In the electrolytic solution:
H
2o → H
++ OH
-, water is ionized into hydrogen ion and hydroxide ion;
Na
3pO
4→ 3Na
++ PO
4 3-, sodium phosphate is ionized into sodium ion and phosphate anion;
C
6h
5cOONa → Na
++ C
6h
5cOO
-, Sodium Benzoate is ionized into sodium ion and benzoate anion ion;
[Cu (NH
3)
4]
2(OH)
2(SO
4) → 2 [Cu (NH
3)
4]
2++ 2OH
-+ SO
4 2-, cupric tetramminosulfate ionization is four ammino copper complex ions and hydroxide ion, sulfate ion.
At described cathode terminal:
2H
++ 2e → H
2↑, hydrogen ion obtains electronics and generates hydrogen at described cathode surface and separate out.
At described positive terminal:
4OH
--4e → 2H
2o+O
2↑, hydroxide radical loses electronics and generates oxygen at described anode surface and separate out;
Ti-4e → Ti
4+, titanium atom loses electronics to be become titanium ion and dissolves at described positive terminal and enter in electrolytic solution;
Ti
4++ 4OH
-→ Ti (OH)
4, titanium ion is combined with hydroxide radical and generates titanium hydroxide;
Ti (OH)
4→ TiO
2+ 2H
2o, at high temperature titanium hydroxide dehydration becomes titanium dioxide;
Ti+2OH
-→ TiO+H
2o+2e, titanium is combined with hydroxide radical and generates titanium oxide;
2TiO+O
2→ 2TiO
2, titanium oxide and combination with oxygen generate titanium dioxide;
Ti+4OH
-→ TiO
2+ 2H
2o+4e, titanium is combined with hydroxide radical and generates titanium dioxide;
2 [Cu (NH
3)
4]
2++ O
2-→ Cu
2o+8NH
3↑, four ammino copper complex ion and O
2-ionic reaction generates Red copper oxide.
The highly toxic substances such as above-mentioned electrolytic solution oxygen-freeization mercury, organotin, Organic leadP, therefore to the less pollution of operator and environment for use, electrolyte property is stablized, and quality of forming film is good, easily manipulates.
Degreasing is carried out to titanium alloy surface, oil removing, cleaning become stand-by titanium alloy, the above-mentioned electrolytic solution configured to be poured in electrolyzer and to stir with agitator, using described stand-by titanium alloy as anode, using stainless steel plate as negative electrode, the working current of pulse mao power source controls at 10 ~ 20A, and current density reference value controls at 3 ~ 10A/dm
2operating voltage reference value controls at 250 ~ 450V, Duty ratio control is 10 ~ 20%, pulse-repetition controls at 500 ~ 650Hz, the temperature of above-mentioned electrolytic solution controls at 50 DEG C, described anode and described negative electrode being immersed in above-mentioned electrolytic solution and carry out the preparation of differential arc oxidation nano coating to described stand-by titanium alloy surface under above-mentioned parameter controls, time controling prepared by differential arc oxidation nano coating, at 5 ~ 30min, generates one deck low toxicity Red copper oxide Cu at described stand-by titanium alloy surface
2o and the titanium dioxide TiO with nano-crystalline and amorphous structure
2insulating ceramic coating, aftertreatment to be cleaned described coating with ionized water and dries.
Detect after oven dry, the thickness of described coating can reach 5 ~ 50 μm, preferred thickness can control at 10 ~ 20 μm, surface hardness is not less than 400HV, bonding strength is not less than 30MPa, and the insulation resistance under drying conditions is not less than 1M Ω, does not crack and corrosion product after 96h neutral salt spray corrosion test, copper quality in described coating is not less than 10%, seawater lacing film after three months sea organism attachment weight be not more than 20g/m
2.
The nano coating preparation process of titanium alloy in above-mentioned electrolytic solution is the process of a micro-arc discharge, and on the one hand in positive half-wave pulse micro arc discharge process, the plasma body in discharge channel is less than 10
-6in the time of s, instantaneous temperature can reach 20,000 DEG C, pressure reaches 100MPa, and the microplasma zone instantaneous high-temperature in electrolytic solution can make the vaporizing liquid of surrounding, oxidation film on titanium alloy surface undergoes phase transition, and oxidation products overflows and arrives the coatingsurface with electrolyte contacts from discharge channel; When negative half-wave pulse, discharge channel ejecta quick solidification under quick " cold quenching " effect of electrolytic solution of melting, is easy to form nano-crystalline granule under the suddenly cold and hot effect of positive and negative half-wave pulse.When adopting constant voltage control mode to prepare differential arc oxidation nano coating on the other hand, the discharging current in oxidation later stage is less, and reaction is comparatively steady, is beneficial to the nanocrystalline formation of titanium alloy surface and growth, thus forms low toxicity Red copper oxide Cu
2o also has the titanium dioxide TiO of nano-crystalline and amorphous structure
2insulating ceramic coating, the copper massfraction in this insulating coating can reach more than 30%, nano titanium oxide TiO
2insulating ceramic coating has the performance of the uniquenesses such as specific surface area is large, magnetic is strong, light absorption is good, surfactivity is large, heat conductance is good, good dispersity, there is a series of features such as purification, sterilization and self_cleaning effect, the attachment of barnacle, mussel, oyster can be prevented, greatly reduce the bond area of marine life.
Can explain the present invention in more detail by following table 6 example, the present invention is not limited to following table 6 example, discloses object of the present invention and is intended to protect all changes and improvements in the scope of the invention.
Upper table 6 example is all not more than 20g/m through the sea organism attachment weight of seawater lacing film after three months
2.
Above-mentioned electrolytic solution is also applicable to aluminium alloy, nano coating prepared by magnesium alloy, zirconium alloy, niobium alloy, tantalum alloy.
Claims (2)
1. the nano coating preparation method of a titanium alloy surface reduction sea organism attachment, this nano coating preparation method comprises the pre-treatment to titanium alloy surface, titanium alloy nano coating preparation in the electrolytic solution and the aftertreatment of nano coating, wherein pre-treatment carries out degreasing to titanium alloy surface, oil removing, the process of cleaning, electrolytic solution contains sodium phosphate, Sodium Benzoate, boric acid, nano coating preparation uses electrolyzer, stainless steel plate, agitator and the pulse power, the aftertreatment of nano coating is the process of cleaning, drying, titanium alloy or TA1, or TA2, or TA3, or TA5, or TA16, or TA17, or TA22, or TA22-1, or TA23, or TA23-1, or TA24, or TA24-1, or TA31, or TC4, TC4ELI, its feature is in this way:
Also containing cupric ammine complex in above-mentioned electrolytic solution, cupric ammine complex is obtained after being reacted by copper sulfate and ammoniacal liquor, containing sodium phosphate, the Sodium Benzoate of 10 ~ 30g, the boric acid of 5 ~ 30g, the cupric ammine complex of 15 ~ 50g of 30 ~ 70g in often liter of electrolytic solution, all the other are deionized water;
Degreasing is carried out to titanium alloy surface, oil removing, cleaning becomes stand-by titanium alloy, the above-mentioned electrolytic solution configured to be poured in electrolyzer and to stir with agitator, using described stand-by titanium alloy as anode, using stainless steel plate as negative electrode, the working current of pulse mao power source controls at 10 ~ 20A, Duty ratio control is 10 ~ 20%, pulse-repetition controls at 500 ~ 650Hz, the temperature of above-mentioned electrolytic solution controls at 50 DEG C, described anode and described negative electrode to be immersed in above-mentioned electrolytic solution and under above-mentioned parameter controls, the preparation of differential arc oxidation nano coating to be carried out to described stand-by titanium alloy surface, time controling prepared by differential arc oxidation nano coating is at 5 ~ 30min, one deck Red copper oxide Cu is generated at described stand-by titanium alloy surface
2o and the titanium dioxide TiO with nano-crystalline and amorphous structure
2insulating ceramic coating, aftertreatment to be cleaned described coating with ionized water and dries, detect after oven dry, the thickness of described coating can reach 5 ~ 50 μm, and surface hardness is not less than 400HV, and bonding strength is not less than 30MPa, insulation resistance under drying conditions is not less than 1M Ω, do not crack and corrosion product after 96h neutral salt spray corrosion test, the copper quality in described coating is not less than 10%, seawater lacing film after three months sea organism attachment weight be not more than 20g/m
2.
2. a kind of titanium alloy surface reduces the nano coating preparation method of sea organism attachment according to claim 1, it is characterized in that: the preferred thickness of described coating controls at 10 ~ 20 μm.
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| CN103233260B (en) * | 2013-05-10 | 2016-04-06 | 中国石油大学(华东) | One prepares the anti-fouling ceramic membrane electrolyte of titanium alloy surface and differential arc oxidation method |
| CN105297032A (en) * | 2015-12-01 | 2016-02-03 | 西北有色金属研究院 | Method preventing marine organisms from adhering to surface of titanium or titanium alloy |
| CN109485458A (en) * | 2019-01-23 | 2019-03-19 | 济南大学 | A kind of maritime concrete surface reinforcing agent and preparation method thereof |
| CN109769724A (en) * | 2019-03-25 | 2019-05-21 | 福建贝迪陶瓷科技有限公司 | A kind of production method of ceramics oyster Seedling culturing device |
| CN113089051A (en) * | 2021-03-29 | 2021-07-09 | 长安大学 | Titanium alloy with ceramic membrane with active adsorption and antibacterial performance and preparation method thereof |
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2013
- 2013-07-09 CN CN201310286443.7A patent/CN103409785B/en not_active Expired - Fee Related
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| JPS5431045A (en) * | 1977-08-12 | 1979-03-07 | Fuji Satsushi Kogyo Kk | Alternate current electrolytic coloring method of aluminum and aluminum alloy materials |
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