CN102899692A - Method for preparing marine antifouling zinc coating solution - Google Patents
Method for preparing marine antifouling zinc coating solution Download PDFInfo
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- CN102899692A CN102899692A CN2012104120164A CN201210412016A CN102899692A CN 102899692 A CN102899692 A CN 102899692A CN 2012104120164 A CN2012104120164 A CN 2012104120164A CN 201210412016 A CN201210412016 A CN 201210412016A CN 102899692 A CN102899692 A CN 102899692A
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Abstract
The invention relates to a marine environment antifouling technology and specifically relates to a method for preparing a marine antifouling zinc coating solution. The method comprises the step of mixing organic biocide with a sulfate plating solution system according to a molar fraction of 1-5mmol/L, wherein the organic biocide is an organic biocide matter with molecular weight less than 500. According to the method for preparing an antifouling zinc coating under a marine environment and other water environments provided by the invention, namely, the method for adding the organic biocide to the plating solution, the organic biocide is attached to and doped on the surface of the zinc coating during an electro-deposition process, so that the prepared zinc coating has an antifouling anti-corrosion effect.
Description
Technical field
The present invention relates to the anti-fouling technology of ocean environment, specifically a kind of method of preparing marine anti-pollution zinc coating liquid.
Background technology
When non-toxic material is exposed in the ocean environment, the marine organisms organism all might adhere on its surface and breed, when it occurred in Artificial facilities surface (such as ship, artificial ocean building), just can produce adverse influence to it, this phenomenon was known as " biodeterioration ".The resistance that causes in the ship navigation process of marine biofouling increases, and energy consumption increases; Artificial ocean facility generation biodeterioration can make ageing equipment, strain, causes the tremendous economic loss.Zinc coating Ying Jing is widely used in the protectiveness coating of oceanographic engineering material, has brought into play vital role as sacrificial anode and barrier coating in the protection against corrosion work of oceanographic engineering material, but does not have anti-fouling function.Existing organic biocide with sterilization, inactivation of algae has preferably anti-fouling effect, but can only be applied to the closed region of small area, can not be applied to open Marine System, can't directly apply to the anti-fouling work in the ocean environment.
Summary of the invention
For the problems referred to above, the purpose of this invention is to provide a kind of method of preparing marine anti-pollution zinc coating liquid.
For achieving the above object, the present invention takes following technical scheme:
A kind of method of preparing marine anti-pollution zinc coating liquid,, the molar fraction of organic biocide being pressed 1-5mmol/L mixes with the sulfate bath system; Described organic biocide is molecular weight less than organic biocidal substance of 500.Such as 2-octyl group-4-isothiazoline-3-ketone (OIT), 2-methyl-4,5-propylidene-4-isothiazoline-3-ketone (MIT) etc.
Described zinc bath system is vitriol zinc bath system, and wherein composition is: 250-400g/LZnSO
47H
2O, 80-250g/L Na
2SO
4, 25-30g/L H
3BO
3, 40g/L Al
2(SO
4)
318H
2O, 1g/L gelatin are dissolved in the 1L distilled water.
The marine anti-pollution zinc coating liquid of described preparation, under continuous current, pure zinc metal sheet is as anode in the bath system, and the oceanographic engineering ferrous materials is negative electrode, is immersed in the marine anti-pollution zinc coating liquid, at current density 0.5-2A/dm
2Lower, the plating bath galvanic deposit is in the steel disc surface.
Before using, described iron and steel parts to be protected uses 1.5A/dm
2Purify more than the 6h.
The galvanic deposit of described machine plating bath is more than the 30 μ m in steel plating sheet surface thickness, and can be in conjunction with the actual useful year requirement, according to depositing time control thickness.And the coating of this method preparation also can be applicable in other water surroundings and the ooze environment.
The present invention has advantages of:
1. present method has been added organic biocide on the basis of original electrochemical zinc coating, makes zinc coating not only have the solidity to corrosion of itself, possesses again anti-fouling performance simultaneously;
2. the coating surface of present method preparation is smooth, smooth finish good, deposit thickness is even;
Coating life-span of making of present method controlled, its life-span is directly proportional with the thickness of coating, can prepare according to hardware or the part design time limit coating protection system of respective thickness.
4. the coating that makes of present method can change this body structure of coating, strengthens its corrosion resistance nature.
Description of drawings
Fig. 1 is the XRD figure spectrum of adding OIT and the zinc coating that does not add in the plating bath of the embodiment of the invention
Fig. 2 adds OIT and the 0h of the zinc coating that does not add and the first flow impedance collection of illustrative plates of 72h in the plating bath of the embodiment of the invention.
Fig. 3 adds different concns MIT coating and blank coating SRB system 6d pH variation in the embodiment of the invention plating bath.
Fig. 4 adds different concns MIT coating and the variation of blank coating SRB system 6d redox potential in the embodiment of the invention plating bath.
Fig. 5 adds different concns MIT coating and blank coating SRB system 6d sulfonium ion change in concentration in the embodiment of the invention plating bath.
Fig. 6 adds different concns MIT coating and the variation of blank coating SRB system 6d coating corrosion potential in the embodiment of the invention plating bath.
Fig. 7 adds coating rate of weight loss behind different concns MIT coating and the blank coating SRB system 6d in the embodiment of the invention plating bath.
Fig. 8 (A) is that the blank coating of the embodiment of the invention corrodes stereoscan photograph behind the 6d in SRB.
Fig. 8 (B) adds 1mmol/L MIT coating to corrode stereoscan photograph behind the 6d in SRB in the embodiment of the invention plating bath.
Embodiment
1) preparation vitriol zinc bath system, filling a prescription is 250-400g/L ZnSO
47H
2O, 80-250g/L Na
2SO
4, 25-30g/L H
3BO
3, 40g/L Al
2(SO
4)
318H
2O, 1g/L gelatin, after being dissolved in distilled water fully, take pure Zn sheet as anode, iron plate is negative electrode, uses 1.5A/dm
2Purify 6h, remove the hetero-ion in the sulfate bath, for blank sulfate bath for subsequent use;
2) get respectively 80mL 1) in 3 parts of the vitriol zinc plating baths of preparation, in the 100mL beaker, pipette 16.8 μ L, 33.6 μ L, 84 μ L BIO-OIT-98 with 100 μ L liquid-transfering guns, its effective constituent is 2-octyl group-4-isothiazoline-3-ketone, volume fraction is 98%, and the electroplate liquid that contains OIT for preparing effective constituent after the dissolving and be 1mmol/L, 2mmol/L, 5mmol/L is for subsequent use;
3) with the SiC sand paper 20# steel disc working-surface to 2000 of polishing step by step
#, at ultrasonic 10min in dehydrated alcohol, with thorough cleaning steel disc surface and oil contaminant and impurity, as material matrix to be protected;
4) use DJS-292E type potentiostat, transfer under the constant current mode, take pure zinc metal sheet as anode, take the SCE electrode as reference electrode, steel disc to be protected is negative electrode, is immersed in the electroplate liquid for preparing, and forms three-electrode system, chooses current density 0.5A/dm
2, 1A/dm
2, 1.5A/dm
2, 2A/dm
2Carry out down galvanostatic deposition and obtain the thick electrodepositing zinc coating of 30 μ m, after galvanic deposit is finished, take out the good steel disc of plating, residual electroplate liquid is washed 2-3 time with redistilled water in the surface, pickling highlights in dilute nitric acid solution, passivation is complete rear with redistilled water flushing 2-3 time, after guaranteeing to rinse well fully, and drying.
5) 0.5A/dm to preparing
2Current density, OIT interpolation concentration is that zinc coating and the blank zinc coating of 1mmol/L done X-ray diffraction analysis (XRD) (such as Fig. 1), added as can be known the zinc coating crystalline structure generation considerable change of OIT: the interpolation of OIT has strengthened [0,0,0] growth of direction lattice, the lattice that has weakened [0,1,0] direction exists.
As described in example 1, at 20# carbon steel electrode surface preparation current density 0.5A/dm
2Add the zinc coating of 1mmol/L OI T, with this electrode as working electrode, the conduct of Pt sheet is to electrode, mercurous chloride electrode is as reference electrode, contact with experimental solutions by salt bridge, at sulphate reducing bacteria system (PGC substratum, four days SRB bacterium liquid is cultivated in inoculation 5%) the middle 72h of immersion, use Solotron 1287/1260 type electrochemical workstation to carry out electrochemical AC impedance spectrum (EIS) analysis, as shown in Figure 2: can find out, increase in time, the coating capacitive reactance arc radius that adds OIT in pure zinc coating and the plating bath all constantly increases, and illustrates that zinc coating itself has the effect that suppresses corrosion; And the coating capacitive reactance arc radius that adds 1mM OIT in the plating bath at 0h and 72h all greater than pure zinc coating, illustrate that the purer zinc coating corrosion resistance nature of the coating that has added 1mM OIT in the plating bath is better.
As described in example 1, change adding organic biocide is that BIO-MIT-50:(production company is hundred proud chemistry (BIO-Chemistry), and active substance (MIT) concentration is 50%), add respectively 1,2 in the preparation plating bath, 5mmo l/L, current density 1A/dm
2Zinc coating carry out sulphate reducing bacteria (SRB) corrosion coupon research, concrete steps are as described below:
Having in the presence of the iron with the Postage C substratum (KH that revises
2PO
4, 0.5g/L; NH
4Cl, 1g/L; CaCl
26H
2O, 0.06g/L; MgSO
47H
2O, 0.06g/L; Trisodium Citrate (C
6H
5Na
3O
72H
2O), 0.3g/L; Yeast extract paste, 1g/L; Sodium.alpha.-hydroxypropionate (C
3H
5O
3Na), 6.0ml/L cultivates SRB(22% inoculation volume) 48h;
Take out iron nail, the zinc coating of putting into example 1 preparation soaks 6d, uses pH(Fig. 3 in the thunder magnetic PHS-3C type pH meter continuous monitoring system), redox potential Eh(Fig. 4), use titration measuring sulfonium ion change in concentration (Fig. 5).
Having added in the coating lacing film system of MI T pH in the plating bath compares to some extent with blank coating in the lacing film process and raises redox potential E
hIn the lacing film process, shuffle than blank, show that its reductibility reduces.Sulfonium ion concentration has obvious reduction than blank in the lacing film process.Main organic meta-bolites saccharan, uronic acid, seminose and the glucose of sulphate reducing bacteria exist short chain fatty acid such as acetic acid in the final product, main inorganic meta-bolites is H
2S has reductibility, add the MIT Plating System with respect to the rising of blank coating pH, reductibility weaken and sulfonium ion concentration reduce to illustrate add MIT in the plating bath coating in the lacing film process establishment metabolic process of SRB.The zinc coating system performance of wherein adding 1mmol/L MIT is optimum, with respect to pure zinc coating, and pH rising 0.5, E when 6d
hThe 80mV that shuffled, S
2-Concentration reduces 4mM, prove MIT in immersion process along with molten zinc process is dissolved out, the growth metabolism of establishment SRB.
By add 1,2 in the example 3 described preparation plating baths, 5mmol/L MIT, current density 1A/dm
2Zinc coating and blank coating, carry out the research of sulphate reducing bacteria (SRB) corrosion coupon, use the open circuit potential (corrosion potential) of DJS-292E type potentiostat test constantly coating in the lacing film process (Fig. 6), and in the weightless situation of lacing film fore-and-aft survey, calculate rate of weight loss (Fig. 7).
Behind the zinc coating that adds MI T in the plating bath and the blank zinc coating lacing film in the SRB system lacing film 6d as shown in Figure 6, the blank coating OCP 70mV that shuffled, interpolation MIT zinc coating OCP shuffle respectively 26mV, 36mV and 40mV in the plating bath.Than blank zinc coating, add the zinc coating OCP that MIT obtains in the plating bath more stable, shown better corrosion resistance nature, this be since in the plating bath existence of MIT effectively changed coating structure, and be adsorbed in coating surface, the dissolving along with zinc in process-exposed discharges.And it is the most stable wherein to add 1mmol/L zinc coating OCP in process-exposed, and erosion resistance is best.
Add behind the zinc coating of MIT and the blank zinc coating lacing film in the SRB system behind the lacing film 6d weightlessness in the plating bath as shown in Figure 7, added zinc coating weightlessness that MIT obtains in the plating bath less than pure zinc coating, the rate of weight loss of pure zinc coating 6d is 0.117%, add 1,2 in the plating bath, 5mmol/LMIT zinc coating rate of weight loss compares with pure zinc coating respectively, rate of weight loss has reduced respectively 0.04086%, 0.0503% and 0.07317%, illustrate that MIT is adsorbed on the surface of coating, effectively kill SRB, reduced microorganism and meta-bolites thereof for the erosion rate of coating.
Press and add 1mmol/L MIT, current density 1A/dm in the example 3 described preparation plating baths
2Zinc coating and blank coating, carry out sulphate reducing bacteria (SRB) corrosion coupon research, use field emission scanning electron microscope (FE-SEM) to carry out Surface Characterization, show such as Fig. 8.Fig. 8 (A) shows the SEM photo of blank zinc coating, can find that slight crack appears in its surface, and compactness is poor, and Fig. 8 (B) is the zinc coating SEM photo of interpolation MIT, and the corrosion rear surface is still fine and close smooth, has showed good compactness and integrity.
Claims (4)
1. method of preparing marine anti-pollution zinc coating liquid, it is characterized in that: the molar fraction of organic biocide being pressed 1-5mmol/L is mixed with the sulfate bath system; Described organic biocide is molecular weight less than organic biocidal substance of 500.
2. by the method for preparation marine anti-pollution zinc coating liquid claimed in claim 1, it is characterized in that: described zinc bath system is vitriol zinc bath system, and wherein composition is: 250-400g/LZnSO
47H
2O, 80-250g/L Na
2SO
4, 25-30g/L H
3BO
3, 40g/L Al
2(SO
4)
318H
2O, 1g/L gelatin are dissolved in the 1L distilled water.
3. by the method for preparation marine anti-pollution zinc coating liquid claimed in claim 1, it is characterized in that:
The marine anti-pollution zinc coating liquid of described preparation, under continuous current, pure zinc metal sheet is as anode in the bath system, and the oceanographic engineering ferrous materials is negative electrode, is immersed in the marine anti-pollution zinc coating liquid, at current density 0.5-2A/dm
2Lower, the plating bath galvanic deposit is in the steel disc surface.
4. by the method for preparation marine anti-pollution zinc coating liquid claimed in claim 3, it is characterized in that: use 1.5A/dm before described iron and steel parts to be protected uses
2Purify more than the 6h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105369301A (en) * | 2015-12-17 | 2016-03-02 | 中国科学院海洋研究所 | Chitosan compounded zinc coating and preparation method thereof |
| CN107764727A (en) * | 2017-11-19 | 2018-03-06 | 西南石油大学 | A kind of rotatable corrosion coupon device |
| CN113737228A (en) * | 2021-09-30 | 2021-12-03 | 天长市飞龙金属制品有限公司 | Zinc plating solution and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105369301A (en) * | 2015-12-17 | 2016-03-02 | 中国科学院海洋研究所 | Chitosan compounded zinc coating and preparation method thereof |
| CN105369301B (en) * | 2015-12-17 | 2018-06-26 | 中国科学院海洋研究所 | Compound zinc coating of a kind of chitosan and preparation method thereof |
| CN107764727A (en) * | 2017-11-19 | 2018-03-06 | 西南石油大学 | A kind of rotatable corrosion coupon device |
| CN107764727B (en) * | 2017-11-19 | 2023-10-20 | 西南石油大学 | Rotatable corrosion hanging piece device |
| CN113737228A (en) * | 2021-09-30 | 2021-12-03 | 天长市飞龙金属制品有限公司 | Zinc plating solution and preparation method thereof |
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Application publication date: 20130130 |