CN103409785A - Preparation method of nano coating with reduced marine organism attachment on surface of titanium alloy - Google Patents
Preparation method of nano coating with reduced marine organism attachment on surface of titanium alloy Download PDFInfo
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- CN103409785A CN103409785A CN2013102864437A CN201310286443A CN103409785A CN 103409785 A CN103409785 A CN 103409785A CN 2013102864437 A CN2013102864437 A CN 2013102864437A CN 201310286443 A CN201310286443 A CN 201310286443A CN 103409785 A CN103409785 A CN 103409785A
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Abstract
The invention relates to a preparation method of a nano coating with reduced marine organism attachment on the surface of a titanium alloy, which comprises the following steps: enabling an electrolyte to contain sodium phosphate, sodium benzoate and boric acid and further contain a copper ammonia complex prepared from copper sulfate and ammonia water; performing conventional treatment on a titanium alloy, enabling the titanium alloy to serve as an anode, enabling a stainless steel plate to serve as a cathode, respectively controlling the working current, the duty ratio and the pulse frequency of a pulse power source at 10-20 A, 10-20% and 500-650 Hz, and controlling the temperature of the electrolyte at 50 DEG C; and electrolyzing for 5-30 minutes to generate a cuprous oxide Cu2O layer and a titanium dioxide TiO2 ceramic insulation coating having a nanocrystalline and non-crystalline structure on the surface of the titanium alloy, wherein the coating thickness is 5-50 mu m, the surface hardness is 400 hV, the bonding strength is 30 MPa, the insulation resistance is 1 Mohm, the 96h neutral salt spray corrosion test proves that no cracks and corrosion products are generated, the mass of the element copper in the coating is not less than 10%, and the marine organism attachment weight 3 months after hanging in marine water is not more than 20g/m<2>.
Description
Technical field
The application belongs to the oxide covering technical field, and especially a kind of titanium alloy surface reduces the nano coating preparation method that marine life adheres to.
Background technology
Differential arc oxidation Microarc Oxidation is called for short MAO, MAO is a kind of at non-ferrous metal base material such as Al, Ti, Mg, Zr, Nb, the new technology of Ta etc. and alloy surface growth in situ oxide ceramic coating, under the prerequisite that does not affect substrate performance, improve its surperficial solidity to corrosion and wear resistance, to have bonding strength high due to oxide ceramic coating, the characteristics such as good insulating, at boats and ships, in navigation industry, utilize MAO on the part that complicated shape and linear dimension differ greatly, to form evenly and enough hard coatings, the copper be in contact with it in preventing from using, copper alloy, steel pipe, piping fitting and other part produce the galvanic corrosion phenomenon in seawater.
The electrolytic solution coating formula that MAO is commonly used is phosphoric acid salt, aluminate, silicate, glycerophosphate-acetate and sodium hydroxide solution system, the differential arc oxidation coating of preparing does not have the ability that prevents that marine life from adhering to, as the seawater coupon test after three months its coatingsurface marine life adhesion weight can reach 65～100g/m
2, the larger latch up phenomenon that the parts such as sea pipeline, pump, valve are produced of marine life adhesion amount is just larger, even causes in conjunction with gap and produces heavy corrosion, 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 the 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, differential arc oxidation obtains resistance to soiling at light metal surface after processing, the good differential arc oxidation coating of scratch resistance and compactness, and has higher hardness, wear resistance, erosion resistance and electrical insulating property, but this differential arc oxidation coating only has certain antibacterial effect to unicellular organisms such as bacterium and fungies, mariner growth prevent is attached to the poor ability of light metal surface.
Up to now, at titanium alloy surface, can reduce the nano coating preparation method that marine life adheres to and yet there are no relevant report.
Summary of the invention
For the existing weak point of existing differential arc oxidation coating, the invention provides a kind of titanium alloy surface and reduce the nano coating preparation method that marine life adheres to, in electrolytic solution, added cupric ammine complex, cupric ammine complex is forming low toxicity Red copper oxide Cu under the effect of sodium phosphate, Sodium Benzoate and boric acid and under the setting electrolytic condition
2O and the titanium dioxide TiO with nano-crystalline and amorphous structure
2Insulating ceramic coating, this coating can reduce adhesive ability and the bond area of barnacle, mussel, oyster greatly, has extended the work-ing life of titanium alloy in 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 that marine life adheres to, this nano coating preparation method comprises the pre-treatment to titanium alloy surface, the nano coating preparation of titanium alloy in electrolytic solution and the aftertreatment of nano coating, wherein pre-treatment is that titanium alloy surface is carried out to degreasing, oil removing, the process of cleaning, electrolytic solution contains sodium phosphate, Sodium Benzoate, boric acid, the 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:
In above-mentioned electrolytic solution, also contain cupric ammine complex, cupric ammine complex makes after by copper sulfate and ammoniacal liquor, being reacted, in every liter of electrolytic solution, contain the sodium phosphate of 30～70g, the Sodium Benzoate of 10～30g, the boric acid of 5～30g, the cupric ammine complex of 15～50g, all the other are deionized water;
Titanium alloy surface is carried out to degreasing, oil removing, cleaning makes it become stand-by titanium alloy, the above-mentioned electrolytic solution configured is poured in electrolyzer and with agitator and stirred, using described stand-by titanium alloy as anode, using stainless steel plate as negative electrode, the working current of pulse mao power source is controlled at 10～20A, Duty ratio control is 10～20%, pulse-repetition is controlled at 500～650Hz, the temperature of above-mentioned electrolytic solution is controlled at 50 ℃, described anode and described negative electrode are immersed in above-mentioned electrolytic solution and under above-mentioned parameter is controlled described stand-by titanium alloy surface is carried out to the preparation of differential arc oxidation nano coating, time prepared by the differential arc oxidation nano coating is controlled at 5～30min, at described stand-by titanium alloy surface, generate one deck Red copper oxide Cu
2O and the titanium dioxide TiO with nano-crystalline and amorphous structure
2insulating ceramic coating, aftertreatment is with ionized water, described coating to be cleaned and dried to get final product, after oven dry, detect, the thickness of described coating can reach 5～50 μ m, 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, after the 96h neutral salt spray corrosion test, do not crack and corrosion product, the copper quality in described coating is not less than 10%, the seawater lacing film after three months the marine life adhesion weight be not more than 20g/m
2.
Above-mentioned electrolytic solution also is applicable to aluminium alloy, magnesium alloy, zirconium alloy, niobium alloy, tantalum alloy surface, and to prepare nano coating be described coating.
The preferred thickness of coating described above can be controlled at 10～20 μ m.
Owing to adopting technical scheme as mentioned 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 oxygen-freeization of electrolytic solution mercury, organotin, organic lead, therefore to the less pollution of operator and environment for use, electrolyte property is stable, and quality of forming film is good, easily controls.
2, the nano coating of titanium alloy surface generation has formed the titanium dioxide TiO of the nano-crystalline and amorphous structure that contains Red copper oxide
2Insulating ceramic coating, this coating can reduce adhesive ability and the bond area of barnacle, mussel, oyster greatly, has extended the work-ing life of titanium alloy in seawater.
3, differential arc oxidation nano coating preparation method of the present invention is not only applicable to titanium or titanium alloy, is applicable to the alloy materials such as aluminium, magnesium, zirconium, niobium, tantalum yet.
4, insulating ceramic coating thickness can reach 5～50 μ m, 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, after the 96h neutral salt spray corrosion test, do not crack and corrosion product, copper quality in nano coating is not less than 10%, the seawater lacing film after three months the marine life adhesion weight be not more than 20g/m
2.
5, the present invention compares with traditional differential arc oxidation coating, and the ability that mariner growth prevent adheres to improves approximately 3～10 times.
Embodiment
The present invention is that a kind of titanium alloy surface reduces the nano coating preparation method that marine life adheres to, in electrolytic solution, added cupric ammine complex, cupric ammine complex is forming low toxicity Red copper oxide Cu under the effect of sodium phosphate, Sodium Benzoate and boric acid and under the setting electrolytic condition
2O and the titanium dioxide TiO with nano-crystalline and amorphous structure
2Insulating ceramic coating, this coating can reduce adhesive ability and the bond area of barnacle, mussel, oyster greatly, has extended the work-ing life of titanium alloy in seawater.
Nano coating preparation method of the present invention comprises that prepared by pre-treatment, the nano coating of titanium alloy in electrolytic solution to titanium alloy surface and the aftertreatment of nano coating, wherein pre-treatment is the process of degreasing, oil removing, cleaning that titanium alloy surface is carried out, electrolytic solution contains sodium phosphate, Sodium Benzoate, boric acid, the 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.
In above-mentioned electrolytic solution, also contain cupric ammine complex except containing sodium phosphate, Sodium Benzoate, boric acid, cupric ammine complex makes after by copper sulfate and ammoniacal liquor, being reacted, in every liter of electrolytic solution, contain the sodium phosphate of 30～70g, the Sodium Benzoate of 10～30g, the boric acid of 5～30g, the cupric ammine complex of 15～50g, all the other are deionized water.
Above-mentioned electrolytic solution is as follows to the mechanism that titanium alloy surface prepares nano coating:
Boric acid plays the effect that suppresses electric arc, stablizes film forming, and Sodium Benzoate is soluble in water, and stable in the air, and the effect that suppresses yeast and bacterium is strong.
Copper sulfate in cupric ammine complex reacts the cupric tetramminosulfate generated wherein with excessive ammonia,
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, can at utmost kill marine animal.
In 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 and separate out at described cathode surface.
At described positive terminal:
4OH
--4e → 2H
2O+O
2↑, hydroxide radical loses electronics and generates oxygen and separate out at described anode surface;
Ti-4e → Ti
4+, titanium atom loses that electronics becomes titanium ion and in described positive terminal dissolves and enters electrolytic solution;
Ti
4++ 4OH
-→ Ti (OH)
4, titanium ion is combined with hydroxide radical and is generated 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 is generated 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 is generated 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 oxygen-freeization of electrolytic solution mercury, organotin, organic lead, therefore to the less pollution of operator and environment for use, electrolyte property is stable, and quality of forming film is good, easily controls.
Titanium alloy surface is carried out to degreasing, oil removing, cleaning makes it become stand-by titanium alloy, the above-mentioned electrolytic solution configured is poured in electrolyzer and with agitator and stirred, using described stand-by titanium alloy as anode, using stainless steel plate as negative electrode, the working current of pulse mao power source is controlled at 10～20A, and the current density reference value is controlled at 3～10A/dm
2The operating voltage reference value is controlled at 250～450V, Duty ratio control is 10～20%, pulse-repetition is controlled at 500～650Hz, the temperature of above-mentioned electrolytic solution is controlled at 50 ℃, described anode and described negative electrode are immersed in above-mentioned electrolytic solution and under above-mentioned parameter is controlled described stand-by titanium alloy surface is carried out to the preparation of differential arc oxidation nano coating, and the time prepared by the differential arc oxidation nano coating is controlled 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 are with ionized water, described coating to be cleaned and dried to get final product.
After oven dry, detect, the thickness of described coating can reach 5～50 μ m, preferred thickness can be controlled at 10～20 μ m, 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 the 96h neutral salt spray corrosion test, copper quality in described coating is not less than 10%, the seawater lacing film after three months the marine life adhesion 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 in positive half-wave pulse micro-arc discharge process, the plasma body in discharge channel is in less than 10 on the one hand
-6In the time of s, instantaneous temperature can reach 20,000 ℃, pressure reaches 100MPa, the vaporizing liquid around the microplasma zone moment high temperature in electrolytic solution can make, oxidation film on titanium alloy surface undergoes phase transition, and oxidation products is from the coatingsurface overflowed discharge channel and arrival contacts with electrolytic solution; When negative half-wave pulse, the discharge channel ejecta of melting solidifies rapidly under quick " cold quenching " effect of electrolytic solution, be easy to form nano-crystalline granule under the suddenly cold and hot effect of positive and negative half-wave pulse.While adopting on the other hand the constant voltage control mode to prepare the differential arc oxidation nano coating, the discharging current in oxidation later stage is less, reacts comparatively steady, is beneficial to the nanocrystalline formation of titanium alloy surface and growth, thereby forms low toxicity Red copper oxide Cu
2O the titanium dioxide TiO with 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 unique performances such as specific surface area is large, magnetic is strong, light absorption is good, surfactivity is large, heat conductance is good, good dispersity, have a series of characteristics such as purification, sterilization and self_cleaning effect, can prevent adhering to of barnacle, mussel, oyster, greatly reduce the bond area of marine life.
By following table 6 examples, can explain in more detail that the present invention, the present invention are not limited to following table 6 examples, disclose purpose of the present invention and be intended to protect all changes and improvements in the scope of the invention.
Marine life adhesion weight after three months all is not more than 20g/m to upper table 6 example through the seawater lacing film
2.
Above-mentioned electrolytic solution also is applicable to aluminium alloy, magnesium alloy, zirconium alloy, niobium alloy, tantalum alloy and prepares nano coating.
Claims (3)
1. a titanium alloy surface reduces the nano coating preparation method that marine life adheres to, this nano coating preparation method comprises the pre-treatment to titanium alloy surface, the nano coating preparation of titanium alloy in electrolytic solution and the aftertreatment of nano coating, wherein pre-treatment is that titanium alloy surface is carried out to degreasing, oil removing, the process of cleaning, electrolytic solution contains sodium phosphate, Sodium Benzoate, boric acid, the 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:
In above-mentioned electrolytic solution, also contain cupric ammine complex, cupric ammine complex makes after by copper sulfate and ammoniacal liquor, being reacted, in every liter of electrolytic solution, contain the sodium phosphate of 30～70g, the Sodium Benzoate of 10～30g, the boric acid of 5～30g, the cupric ammine complex of 15～50g, all the other are deionized water;
Titanium alloy surface is carried out to degreasing, oil removing, cleaning makes it become stand-by titanium alloy, the above-mentioned electrolytic solution configured is poured in electrolyzer and with agitator and stirred, using described stand-by titanium alloy as anode, using stainless steel plate as negative electrode, the working current of pulse mao power source is controlled at 10～20A, Duty ratio control is 10～20%, pulse-repetition is controlled at 500～650Hz, the temperature of above-mentioned electrolytic solution is controlled at 50 ℃, described anode and described negative electrode are immersed in above-mentioned electrolytic solution and under above-mentioned parameter is controlled described stand-by titanium alloy surface is carried out to the preparation of differential arc oxidation nano coating, time prepared by the differential arc oxidation nano coating is controlled at 5～30min, at described stand-by titanium alloy surface, generate one deck Red copper oxide Cu
2O and the titanium dioxide TiO with nano-crystalline and amorphous structure
2insulating ceramic coating, aftertreatment is with ionized water, described coating to be cleaned and dried to get final product, after oven dry, detect, the thickness of described coating can reach 5～50 μ m, 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, after the 96h neutral salt spray corrosion test, do not crack and corrosion product, the copper quality in described coating is not less than 10%, the seawater lacing film after three months the marine life adhesion weight be not more than 20g/m
2.
2. a kind of titanium alloy surface reduces the nano coating preparation method that marine life adheres to according to claim 1, it is characterized in that: above-mentioned electrolytic solution is applicable to aluminium alloy, magnesium alloy, zirconium alloy, niobium alloy, tantalum alloy surface and prepares nano coating.
3. a kind of titanium alloy surface reduces the nano coating preparation method that marine life adheres to according to claim 1, and it is characterized in that: the preferred thickness of coating described above is controlled at 10～20 μ m.
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Cited By (5)
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| CN103233260A (en) * | 2013-05-10 | 2013-08-07 | 中国石油大学(华东) | Preparation of antifouling ceramic membrane electrolyte for titanium alloy surface and micro-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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| 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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