CN102212863A - Metal-alkoxide-improved cathode electrophoresis protective coating and application thereof - Google Patents
Metal-alkoxide-improved cathode electrophoresis protective coating and application thereof Download PDFInfo
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- CN102212863A CN102212863A CN 201110024331 CN201110024331A CN102212863A CN 102212863 A CN102212863 A CN 102212863A CN 201110024331 CN201110024331 CN 201110024331 CN 201110024331 A CN201110024331 A CN 201110024331A CN 102212863 A CN102212863 A CN 102212863A
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- metal alkoxide
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- 238000001962 electrophoresis Methods 0.000 title claims abstract description 30
- 239000011253 protective coating Substances 0.000 title description 3
- 239000011248 coating agent Substances 0.000 claims abstract description 115
- 238000000576 coating method Methods 0.000 claims abstract description 115
- 239000003973 paint Substances 0.000 claims abstract description 72
- 229910052751 metal Inorganic materials 0.000 claims abstract description 48
- 239000002184 metal Substances 0.000 claims abstract description 48
- 230000007797 corrosion Effects 0.000 claims abstract description 44
- 238000005260 corrosion Methods 0.000 claims abstract description 44
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000010439 graphite Substances 0.000 claims abstract description 5
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 5
- 239000010935 stainless steel Substances 0.000 claims abstract description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 4
- 238000004070 electrodeposition Methods 0.000 claims description 61
- 238000012986 modification Methods 0.000 claims description 34
- 230000004048 modification Effects 0.000 claims description 34
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 12
- 239000008397 galvanized steel Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000004593 Epoxy Substances 0.000 claims description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- 239000011135 tin Chemical group 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000004925 Acrylic resin Substances 0.000 claims description 4
- 229920000178 Acrylic resin Polymers 0.000 claims description 4
- 238000011010 flushing procedure Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229910000975 Carbon steel Inorganic materials 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000010962 carbon steel Substances 0.000 claims description 3
- 239000010960 cold rolled steel Substances 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 3
- 230000027555 hydrotropism Effects 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 229920005749 polyurethane resin Polymers 0.000 claims description 3
- 239000010936 titanium Chemical group 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 abstract description 5
- 239000000654 additive Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract 2
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 238000010422 painting Methods 0.000 abstract 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 31
- 238000012360 testing method Methods 0.000 description 26
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 229910000547 2024-T3 aluminium alloy Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 1
- 101710194948 Protein phosphatase PhpP Proteins 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004532 chromating Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
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- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
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- 238000002791 soaking Methods 0.000 description 1
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- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
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- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
The invention discloses a preparation method of a cathode electrophoresis coating which adopts metal alkoxide as an additive. 0.1-5.0wt% of metal alkoxide is added into an aqueous electrophoresis painting so as to be evenly stirred; a protected metal base material serves as a cathode, and graphite or acid-proof stainless steel serves as an anode; and the distance between the anode and the cathode is 20-50cm, th bath solution temperature is 25-30DEG C, the electrophoresis voltage is 40-200V, and the electrophoresis time is 1-3 minutes. Electrophoretic paint remained on the metal surface is washed with water; and after the electrophoretic paint is naturally dried, the electrophoretic paint is put into an air dry oven and is solidified at 120-200DEG C for 15-30 minutes, thus the metal-alkoxide-improved cathode electrophoretic paint coating is obtained, and the thickness is 23-25mu m. The metal alkoxide additive has the advantage of small use amount, low cost and environmental friendliness; and the mechanical performance and water absorption resistance of the electrophoretic paint can be improved, and the corrosion resistance of the electrophoretic paint coating can be greatly improved by improving the bonding force of the coating and the matrix.
Description
Technical field
The present invention relates to improved ability cathode electrophoresis protective coating of a kind of metal alkoxide and uses thereof.
Background technology
As everyone knows, except a small amount of valuable inert metal (platinum, gold etc.), most metals generally all will increase the service life through protective treatment to improve its corrosion resisting property before using owing to easily corrode under field conditions (factors).Although developed various novel guard technologies at present, organic coating (comprising cataphoretic coating) is still the main preventive means of metal current.Traditional organic coating paint-on technique comprises metallic surface pre-treatment-priming paint-finish paint supervisor, uses complexity, and can add chromic salt in these processes, phosphoric acid salt, and leadization things etc. to improve coating and basal body binding force, provide the corrosion corrosion inhibition simultaneously.But these additives have very big harm and toxicity to environment and organism.
Adopt electrophoresis application technique on through the metal after the pre-treatment, to prepare aqueous coating,, in automotive industry, household electric appliances, be widely used owing to have characteristics such as environmental friendliness, raw material availability height.In actual production process, preconditioning techniques such as phosphatization, chromating are mainly still adopted before applying the electrocoating paint coating in the metallic surface, and environment and biology are caused very big harm but at present.
Metal alkoxide (M-(OR) x) has the characteristic of easy distillation, facile hydrolysis, is widely used in the precursor that sol-gel method prepares inorganic oxide material.In sol-gel process, hydrolysis generation-OH takes place the alkoxyl group in the metal alkoxide-OR can form oxide skin by chemical bonding with metallic matrix.
(J Sol-gel Sci Techn 2004,31 (1-3) 329-334) adopt electro-deposition techniques to people such as Mandler, apply the TiO2 film that cathode potential prepares the dyestuff modification under the sol-gel system that tetrabutyl titanate forms through the hydrolytic condensation process.(Chem-eur J 2004,10 (8), 1936-1943) also by constructed, prepare ZrO by cathode electrodeposition in the tetrabutyl zirconate system for people such as Mandler
2Film.But do not see that as yet bibliographical information combines metal alkoxide with electrocoating paint coating or even common coating, be used for the corrosion of metal protection.
Therefore, if in electrocoating paint coating, add little a spot of metal alkoxide, when ability cathode electrophoresis, hydrolysis can take place and form the effect that one deck oxide membranous layer plays " pre-treatment " earlier in the metallic surface in metal alkoxide, simultaneously this oxide skin also can with the functional group reactions in the last coating, improve the electrocoating paint corrosion resistance coating can in also make the bonding force between the coating on matrix and the electrocoating paint.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, the method and the purposes of the single stage method preparation of the improved ability cathode electrophoresis lacquering of a kind of metal alkoxide component is provided.
The step of the improved ability cathode electrophoresis coating production of metal alkoxide is as follows:
1) adding mass percent in hydrotropisms's electrophoretic paint is 0.1 % ~ 5.0 % metal alkoxides, stir, with protected metal base is negative electrode, with graphite or acid-resistant stainless steel is anode, cathode and anode spacing is 20～50 cm, tank liquor temperature is 25～30 ℃, electrophoretic voltage 40～200V, electrophoresis time 1～3 min;
2) electrocoating paint attached to metallic surface remnants is removed in the water flushing, after drying naturally, puts into the air blast loft drier, and 120 ~ 200 ℃ solidify 15 ~ 30 min down, obtain the ability cathode electrophoresis lacquering through the metal alkoxide modification, and thickness is 23～25 μ m.
The general structure of selected metal alkoxide is:
Wherein, M is zirconium, titanium, tin etc., and R is-CH
2CH
3,-(CH
2)
2CH
3,-(CH
2)
3CH
3,-CH (CH
3)
2,-CH
2CH (CH
3)
2,-COCH
3Deng.
The mass percent that the metal alkoxide that is added accounts for is 0.1 % ~ 5.0 %.
Described water-based electrophoretic paint is: aqueous epoxy resins, acrylic resin, epoxy polyurethane resin.
Described described protected metal is carbon steel, galvanized steel, cold-rolled steel, aluminium, zinc, copper, magnesium or tin and alloy thereof.
The improved ability cathode electrophoresis coating of metal alkoxide is used for the corrosion of metal protection.
The invention has the beneficial effects as follows: the preparation technology of the ability cathode electrophoresis coating of metal alkoxide modification provided by the invention is simple, need not to change existing electrophoresis industrial production line and working condition, and before the preparation electrocoating paint, need not to carry out chromic salt or phosphoric acid salt Passivation Treatment, it is better a step to prepare corrosion resisting property, the electrocoating paint coating that bonding force improves.
Description of drawings
Fig. 1 is blank electrocoating paint and the electrocoating paint coating that contains 3.0% tetrabutyl titanate for galvanized steel applies, and 25 days electrochemical impedance spectroscopy of the immersion test low frequency membrane value in 3.5wt% NaCl is with the trend map of the variation of soak time;
Fig. 2 (a) is the 550h salt-fog test picture of blank electrocoating paint coating sample;
Fig. 2 (b) is for containing the 550h salt-fog test picture of 3.0% tetrabutyl titanate electrocoating paint coating sample.
Embodiment
The preparation method's of the improved ability cathode electrophoresis coating of metal alkoxide step is as follows:
1) adding mass percent in hydrotropisms's electrophoretic paint is 0.1 % ~ 5.0 % metal alkoxides, stir, with protected metal base is negative electrode, with graphite or acid-resistant stainless steel is anode, cathode and anode spacing is 20～50 cm, tank liquor temperature is 25～30 ℃, electrophoretic voltage 40～200V, electrophoresis time 1～3 min;
2) electrocoating paint attached to metallic surface remnants is removed in the water flushing, after drying naturally, puts into the air blast loft drier, and 120 ~ 200 ℃ solidify 15 ~ 30 min down, obtain the ability cathode electrophoresis lacquering through the metal alkoxide modification, and thickness is 23～25 μ m.
The general structure of selected metal alkoxide is:
Wherein, M is zirconium, titanium, tin etc., and R is-CH
2CH
3,-(CH
2)
2CH
3,-(CH
2)
3CH
3,-CH (CH
3)
2,-CH
2CH (CH
3)
2,-COCH
3Deng.
Described water-based electrophoretic paint is: aqueous epoxy resins, acrylic resin, epoxy polyurethane resin.
Described described protected metal is carbon steel, galvanized steel, cold-rolled steel, aluminium, zinc, copper, magnesium or tin and alloy thereof.
The improved ability cathode electrophoresis coating of metal alkoxide is used for the corrosion of metal protection.
Because electrophoretic technique has the requirement of degree of cleaning to specimen surface, therefore, at first requires the oil removing pre-treatment is carried out in the metallic surface.Selecting galvanized steel for use is matrix, and area is that 3 cm * 4 cm clean pretreatment technology and are: and pre-washing → alkali cleaning degreasing → tap water washes down → washed with de-ionized water → dry up → and acetone cleans → dries up.The alkali cleaning degreasing fluid is tripoly phosphate sodium STPP 8 g/L, water glass 5g/L, yellow soda ash 8 g/L, OP emulsifying agent 5 mL/L, sodium lauryl sulphate 1 g/L, defatting step are that ultrasonic 15 min carry out under 45 ℃, use a large amount of tap water and deionized water rinsing afterwards, use hot blast drying, ultrasonic 15 min take out and dry up stand-by in 45 ℃ of acetone.
Embodiment 1
1) in electrophoresis equipment, adds deionized water (320 g) epoxy negative electrode black wash (40g) and Virgin's milk lacquer (160g)
Electronic mixing, add 0.52 g, 2.6g, 5.2g, 15.6g, 26.0 g tetrabutyl titanates respectively, obtain the electrocoating paint of 0.1 %, 0.5 %, 1.0 %, 3.0 %, 5.0 % tetrabutyl titanates, adopt the rotating speed of 10000 r/min to stir 10 min tetrabutyl titanate emulsification in electrocoating paint is uniformly dispersed.With the galvanized steel is negative electrode, and graphite is anode, and cathode and anode spacing is 30 cm, and tank liquor temperature is 25 ℃, electrophoretic voltage 120 V, electrophoresis time 3 min;
2) electrocoating paint attached to surface of galvanized steel remnants is removed in the water flushing, after drying naturally, puts into the air blast loft drier, and 120 ~ 200 ℃ solidify 15 ~ 30 min down, obtain the ability cathode electrophoresis lacquering through the metal alkoxide modification, and thickness is 23～25 μ m.
The blank electrocoating paint coating without the tetrabutyl titanate modification is prepared simultaneously in test as a comparison under the same conditions, and thickness is 23～25 μ m.
The method of accelerated test is adopted in the evaluation of coating, and used experiment is the neutral salt spray test, Machu test and boiling water Soak Test.The neutral salt spray test: the sodium-chlor of 5 ± 1 mass parts is dissolved in 95 parts of 3 grades of water, and during 35 ℃ of atomizings, the pH value of collecting salts solution is in 6.5 ~ 7.2 scopes.The Machu test: the surface and the side of coating to be measured are sealed with electroplating glue, drawn two dark zinc-base body, orthogonal two cuts of reaching with blade on coating, the length of cut all is 4 cm, and corrosive medium is 5% NaCl+0.6 % H
2O
2, after soaking 24 hours under 36 ℃, etchant solution is upgraded, soaked again 24 hours.Take out sample, along the cut release coating, observe coating shedding degree and cut situation with adhesive tape.Boiling water test: coating/metal system is placed the ebullient deionized water, after 6 hours, stop to soak, take out sample, observe coating layering and foaming phenomenon.
Fig. 1 applies through the improved electrocoating paint coating of 3.0% tetrabutyl titanate for galvanized steel, 25 days electrochemical impedance spectroscopy of immersion test low frequency membrane value in 3.5 wt% NaCl illustrates that with the trend map of the variation of soak time the corrosion resisting property through electrocoating paint after the tetrabutyl titanate modification is greatly improved.
Fig. 2 is blank electrocoating paint coating and through the improved electrocoating paint coating of 3.0% tetrabutyl titanate for galvanized steel applies, at the picture of the salt-fog test condition gained after 550 hours that requires according to ASTM B117.Fig. 2 (a) is blank electrocoating paint coating sample, and Fig. 2 (b) is the salt-fog test picture of 3.0% tetrabutyl titanate electrocoating paint coating sample.Show that there are 8 bubbles at barren electrocoating paint coating sample cut place, wherein the diameter bubbling that reaches 1.5 mm has two, and white rust occurs through the improved electrocoating paint coating of 3.0% tetrabutyl titanate sample cut place, and 2 vesicles are arranged.The corrosion resisting property that shows electrocoating paint coating after tetrabutyl titanate improves obtains bigger raising.
Table 1 galvanized steel is through different concns tetrabutyl titanate modified epoxy electrocoating paint coating
The accelerated corrosion experimental result of protection
| Sample | The neutral salt spray test | The Machu test | The boiling water test |
| ? | Corrosion pit appearred in 720 hours | Coating almost integral body is peeled off, and undercut corrosion is serious | 5-6 bubbles |
| 0.1 the electrocoating paint coating of % tetrabutyl titanate modification | Corrosion pit appearred in 750 hours | Near wide the peeling off of about 1.3 cm of the coating cut, cut obviously corrodes | 3 bubbles |
| The electrocoating paint coating that contains 0.5 % tetrabutyl titanate modification | Corrosion pit appearred in 840 hours | Near wide the peeling off of about 0.3 cm of the coating cut, cut slightly corrodes | 1 bubble |
| The electrocoating paint coating that contains 1.0 % tetrabutyl titanate modifications | Corrosion pit appearred in 1000 hours | Near wide the peeling off of about 0.1 cm of the coating cut, cut slightly corrodes | No bubble, coating is complete |
| The electrocoating paint coating that contains 3.0 % tetrabutyl titanate modifications | Corrosion pit appearred in 1000 hours | Near wide the peeling off of about 0.1 cm of the coating cut, cut slightly corrodes | No bubble, coating is complete |
| The electrocoating paint coating that contains 5.0 % tetrabutyl titanate modifications | Corrosion pit appearred in 960 hours | Near wide the peeling off of about 0.1 cm of the coating cut, cut slightly corrodes | No bubble, coating is complete |
Concrete steps are seen embodiment 1, and changing the alkoxide that adds modification is tetrabutyl zirconate, obtains containing the electrocoating paint coating of 0 %, 0.1 %, 0.5 %, 1.0 %, 3.0 %, 5.0 % tetrabutyl zirconate modifications, and the electrocoating paint coat-thickness of gained is all at 23 ~ 25 μ m.And adopt embodiment 1 described mode to prepare coating and evaluation coating performance.
Table 2 galvanized steel is through different concns tetrabutyl zirconate modified epoxy electrocoating paint coating
The accelerated corrosion experimental result of protection
| Sample | The neutral salt spray test | The Machu test | The boiling water test |
| Electrocoating paint coating without the tetrabutyl zirconate modification | Corrosion pit appearred in 720 hours | Coating almost integral body is peeled off, and undercut corrosion is serious | 5-6 bubbles |
| The electrocoating paint coating that contains 0.1 % tetrabutyl zirconate modification | Corrosion pit appearred in 790 hours | Near wide the peeling off of about 1.3 cm of the coating cut, cut obviously corrodes | 2 bubbles |
| The electrocoating paint coating that contains 0.5 % tetrabutyl zirconate modification | Corrosion pit appearred in 840 hours | Near wide the peeling off of about 0.3 cm of the coating cut, cut slightly corrodes | 1 bubble |
| The electrocoating paint coating that contains 1.0 % tetrabutyl zirconate modifications | Corrosion pit appearred in 980 hours | Near wide the peeling off of about 0.1 cm of the coating cut, cut slightly corrodes | No bubble, coating is complete |
| The electrocoating paint coating that contains 3.0 % tetrabutyl zirconate modifications | Corrosion pit appearred in 1000 hours | Near wide the peeling off of about 0.1 cm of the coating cut, cut slightly corrodes | No bubble, coating is complete |
| The electrocoating paint coating that contains 5.0 % tetrabutyl zirconate modifications | Corrosion pit appearred in 980 hours | Near wide the peeling off of about 0.1 cm of the coating cut, cut slightly corrodes | No bubble, coating is complete |
Embodiment 3
Concrete steps are seen embodiment 1, change matrix into aviation AA 2024-T3 aluminium alloy, and the electrocoating paint coat-thickness of gained is all at 23 ~ 25 μ m.And adopt embodiment 1 described mode to prepare coating and evaluation coating performance.
Table 3 AA 2024-T3 aluminium alloy is through different concns tetrabutyl titanate modified epoxy electrocoating paint coating
The accelerated corrosion experimental result of protection
| Sample | The neutral salt spray test | The Machu test | The boiling water test |
| Electrocoating paint coating without the tetrabutyl titanate modification | Corrosion pit appearred in 670 hours | Coating almost integral body is peeled off, and undercut corrosion is serious | 4-5 bubbles |
| The electrocoating paint coating that contains 0.1% tetrabutyl titanate modification | Corrosion pit appearred in 740 hours | Near wide the peeling off of about 1.0 cm of the coating cut, cut obviously corrodes | 2 bubbles |
| The electrocoating paint coating that contains 0.5% tetrabutyl titanate modification | Corrosion pit appearred in 800 hours | Near wide the peeling off of about 0.3 cm of the coating cut, cut slightly corrodes | 1 bubble |
| The electrocoating paint coating that contains 1.0% tetrabutyl titanate modification | Corrosion pit appearred in 1000 hours | Near wide the peeling off of about 0.1 cm of the coating cut, cut slightly corrodes | No bubble, coating is complete |
| The electrocoating paint coating that contains 3.0% tetrabutyl titanate modification | Corrosion pit appearred in 1000 hours | Near wide the peeling off of about 0.1 cm of the coating cut, cut slightly corrodes | No bubble, coating is complete |
| The electrocoating paint coating that contains 5.0 % tetrabutyl titanate modifications | Corrosion pit appearred in 980 hours | Near wide the peeling off of about 0.1 cm of the coating cut, cut slightly corrodes | No bubble, coating is complete |
Embodiment 4
Concrete steps are seen embodiment 1, and the electrocoating paint raw material changes single-component acrylic resin cathode electrophoresis dope into, and the electrocoating paint coat-thickness of gained is all at 23 ~ 25 μ m.And adopt embodiment 1 described mode to prepare coating and evaluation coating performance.
Table 4 galvanized steel steel is through different concns tetrabutyl titanate modified epoxy electrocoating paint coating
The accelerated corrosion experimental result of protection
| Sample | The neutral salt spray test | The Machu test | The boiling water test |
| Electrocoating paint coating without the tetrabutyl titanate modification | Corrosion pit appearred in 780 hours | Coating almost integral body is peeled off, and undercut corrosion is serious | 4-5 bubbles |
| The electrocoating paint coating that contains 0.1 % tetrabutyl titanate modification | Corrosion pit appearred in 800 hours | Near wide the peeling off of about 1.0 cm of the coating cut, cut obviously corrodes | 2 bubbles |
| The electrocoating paint coating that contains 0.5 % tetrabutyl titanate modification | Corrosion pit appearred in 980 hours | Near wide the peeling off of about 0.3 cm of the coating cut, cut slightly corrodes | 1 bubble |
| The electrocoating paint coating that contains 1.0 % tetrabutyl titanate modifications | Corrosion pit appearred in 1100 hours | Near wide the peeling off of about 0.1 cm of the coating cut, cut slightly corrodes | No bubble, coating is complete |
| The electrocoating paint coating that contains 3.0 % tetrabutyl titanate modifications | Corrosion pit appearred in 1100 hours | Near wide the peeling off of about 0.1 cm of the coating cut, cut slightly corrodes | No bubble, coating is complete |
| The electrocoating paint coating that contains 5.0 % tetrabutyl titanate modifications | Corrosion pit appearred in 1050 hours | Near wide the peeling off of about 0.1 cm of the coating cut, cut slightly corrodes | No bubble, coating is complete |
The foregoing description is used for the present invention that explains, rather than limits the invention, and in the protection domain of spirit of the present invention and claim, any modification and change to the present invention makes all fall into protection scope of the present invention.
Claims (5)
1. the preparation method of the improved ability cathode electrophoresis coating of metal alkoxide is characterized in that its step is as follows:
1) adding mass percent in hydrotropisms's electrophoretic paint is 0.1 % ~ 5.0 % metal alkoxides, stir, with protected metal base is negative electrode, with graphite or acid-resistant stainless steel is anode, cathode and anode spacing is 20～50 cm, tank liquor temperature is 25～30 ℃, electrophoretic voltage 40～200V, electrophoresis time 1～3 min;
2) electrocoating paint attached to metallic surface remnants is removed in the water flushing, after drying naturally, puts into the air blast loft drier, and 120 ~ 200 ℃ solidify 15 ~ 30 min down, obtain the ability cathode electrophoresis lacquering through the metal alkoxide modification, and thickness is 23～25 μ m.
2. method according to claim 1 is characterized in that: the general structure of the metal alkoxide of selecting for use is:
Wherein, M is zirconium, titanium, tin, and R is-CH
2CH
3,-(CH2)
2CH
3,-(CH
2)
3CH
3,-CH (CH
3)
2,-CH
2CH (CH
3)
2,-COCH
3
3. the preparation method of the improved ability cathode electrophoresis coating of a kind of metal alkoxide according to claim 1 is characterized in that described water-based electrophoretic paint is: aqueous epoxy resins, acrylic resin, epoxy polyurethane resin.
4. the preparation method of the improved ability cathode electrophoresis coating of a kind of metal alkoxide according to claim 1 is characterized in that described described protected metal is carbon steel, galvanized steel, cold-rolled steel, aluminium, zinc, copper, magnesium or tin and alloy thereof.
5. the purposes of the improved ability cathode electrophoresis coating of metal alkoxide of method preparation according to claim 1 is characterized in that: be used for the corrosion of metal protection.
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| CN103911028A (en) * | 2014-02-27 | 2014-07-09 | 浙江大学 | Preparation method and application of cathode electrophoretic coating doped and modified by oxide |
| CN104136564A (en) * | 2012-02-21 | 2014-11-05 | 日东化成株式会社 | Electrodeposition coating composition, and catalyst for electrodeposition coating composition |
| WO2014191481A1 (en) * | 2013-05-28 | 2014-12-04 | Basf Coatings Gmbh | Method for immersion paint coating electrically conductive substrates while post-treating the immersion paint coating with an aqueous sol-gel composition prior to curing the coating |
| CN105239135A (en) * | 2015-10-20 | 2016-01-13 | 江门市前通粉末冶金厂有限公司 | Rust-prevention electrophoresis technology for powder metallurgy iron-based product |
| CN105492545A (en) * | 2013-08-12 | 2016-04-13 | 巴斯夫涂料有限公司 | Coating composition for the dip-paint coating of electrically conductive substrates containing a sol-gel composition |
| CN107164797A (en) * | 2017-04-11 | 2017-09-15 | 浙江洋铭工贸有限公司 | A kind of electrophoresis process of die casting aluminium heating radiating fin |
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| CN104136564A (en) * | 2012-02-21 | 2014-11-05 | 日东化成株式会社 | Electrodeposition coating composition, and catalyst for electrodeposition coating composition |
| WO2014191481A1 (en) * | 2013-05-28 | 2014-12-04 | Basf Coatings Gmbh | Method for immersion paint coating electrically conductive substrates while post-treating the immersion paint coating with an aqueous sol-gel composition prior to curing the coating |
| CN105408429A (en) * | 2013-05-28 | 2016-03-16 | 巴斯夫涂料有限公司 | Method for coating electrically conductive substrates with immersion paint while post-treating the immersion paint coating with an aqueous sol-gel composition prior to curing the coating |
| CN105492545A (en) * | 2013-08-12 | 2016-04-13 | 巴斯夫涂料有限公司 | Coating composition for the dip-paint coating of electrically conductive substrates containing a sol-gel composition |
| US10208213B2 (en) | 2013-08-12 | 2019-02-19 | Basf Coatings Gmbh | Dip-coating composition for electroconductive substrates, comprising a sol-gel composition |
| CN103911028A (en) * | 2014-02-27 | 2014-07-09 | 浙江大学 | Preparation method and application of cathode electrophoretic coating doped and modified by oxide |
| CN105239135A (en) * | 2015-10-20 | 2016-01-13 | 江门市前通粉末冶金厂有限公司 | Rust-prevention electrophoresis technology for powder metallurgy iron-based product |
| CN107164797A (en) * | 2017-04-11 | 2017-09-15 | 浙江洋铭工贸有限公司 | A kind of electrophoresis process of die casting aluminium heating radiating fin |
| CN112280422A (en) * | 2020-09-30 | 2021-01-29 | 中国石油天然气集团公司 | Zirconium-titanium binary modified epoxy anticorrosive paint and preparation method and application thereof |
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