CN104233251A - Non-chromium passivation technology for zinc coating - Google Patents
Non-chromium passivation technology for zinc coating Download PDFInfo
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- CN104233251A CN104233251A CN201410473530.8A CN201410473530A CN104233251A CN 104233251 A CN104233251 A CN 104233251A CN 201410473530 A CN201410473530 A CN 201410473530A CN 104233251 A CN104233251 A CN 104233251A
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Abstract
The invention discloses a non-chromium passivation solution for a zinc coating and a non-chromium passivation technology using the non-chromium passivation solution. The passivation solution comprises ammonium molybdate, sodium phosphate and additives XZ-03B and OP-10. The composite passivation technology comprises the step that the passivation solution is subjected to passivation treatment for 1-2 min at the temperature of 20-60 DEG C, preferably 30-55 DEG C, more preferably 40-50 DEG C, and the preferable treatment time is 60-90 s. A non-chromium passive film prepared by adopting the non-chromium passivation solution for the zinc coating and the passivation technology is iridescent, the color is bright and uniform, the decorative effect is good, and the color is close to that of a chromate passivated film; and the performance of the passive film is close to that of the chromate passivated film, the corrosion resistance is excellent, the passivation solution does not contain hexavalent chromium, so that environment pollution is little, and the technology is environmental-friendly.
Description
Technical field
The present invention relates to Passivation Technology for Zinc Coating technical field, particularly relate to a kind of Chromium-Free Passivation Process for Zinc.
Background technology
Steel plate galvanized because its solidity to corrosion is good, low price and be widely used in the fields such as automobile, building materials, household electrical appliances, container.But steel plate galvanized easily corrodes in wet environment, form the corrosion product of white on its surface or become ash dead color, have impact on the visual appearance of steel plate galvanized and the corrosion stability of coating.Traditional zinc coating passivation process is treatment agent mainly with the hexavalent chromium compound such as chromic acid and chromic salt greatly, is called chromating, and its technique is simple, and binding force of membrane is good, and solidity to corrosion is high, has self-repairing capability.But because sexavalent chrome is carcinogenic, poisonous, serious to human and environment harm, government strictly limits using and discharging of chromic salt.European Union promulgates ROHS instruction: from 1 day July in 2006, the electronic electric equipment that all EU markets are sold must forbid the heavy metals such as lead, mercury, cadmium and sexavalent chrome.China is important household electrical appliances export State, for addressing this problem, will greatly develop chromium-free deactivation technology.
At present, the main non-chromium inactivating technique of research is both at home and abroad divided into: molybdate passivation film, tungstate passivation, silicate passivation, containing zirconium solution passivation, cobalt-carrying solution passivation, rare earth metal salt passivation, organic passivation etc.Molybdate has hypotoxicity, and be effective substitute of chromic salt, widespread use is inhibiter and the passivator of iron and steel and non-ferrous metal, and in the Passivation Treatment of zinc coating, people have also done useful exploration.
Summary of the invention
For the defect existing for existing Passivation Technology for Zinc Coating and deficiency, the object of the invention is to propose a kind of Chromium-Free Passivation Process for Zinc.
For reaching this object, the present invention by the following technical solutions:
First aspect, the invention provides a kind of zinc coating passivation liquid, and this passivating solution comprises ammonium molybdate, sodium phosphate, additive XZ-03B and OP-10.
As preferably, the concentration of described ammonium molybdate is 10-20g/L, is preferably 12-20g/L, is more preferably 15g/L.
In a particular embodiment, the concentration of described ammonium molybdate is 10g/L, 11g/L, 12g/L, 13g/L, 14g/L, 15g/L, 16g/L, 17g/L, 18g/L, 19g/L, 20g/L.
As preferably, the concentration of described sodium phosphate is 1-4g/L, is preferably 1-2g/L, is more preferably 2g/L.
In a particular embodiment, the concentration of described sodium phosphate is 1g/L, 2g/L, 3g/L, 4g/L.
As preferably, the concentration of described additive XZ-03B is 1-4g/L, is preferably 2-3g/L, is more preferably 2g/L.
In a particular embodiment, the concentration of described additive XZ-03B is 1g/L, 2g/L, 3g/L, 4g/L.
As preferably, the concentration of described OP-10 is 0.06-0.20g/L, is preferably 0.08-0.15g/L, is more preferably 0.1g/L.
In a particular embodiment, the concentration of described OP-10 is 0.06g/L, 0.07g/L, 0.08g/L, 0.09g/L, 0.10g/L, 0.11g/L, 0.12g/L, 0.13g/L, 0.14g/L, 0.15g/L, 0.16g/L, 0.17g/L, 0.18g/L, 0.19g/L, 0.20g/L.
As preferably, the pH value of described passivating solution is 2-6, is preferably 3-5, is more preferably 3-4.5.
In a particular embodiment, the pH value of described passivating solution is 2,3,4,5,6.
Most preferably, described passivating solution comprises the OP-10 of the ammonium molybdate of 15g/L, the sodium phosphate of 2g/L, additive XZ-03B and 0.1g/L of 2g/L, and its pH value is 3-4.5.
Second aspect, the invention provides a kind of Chromium-Free Passivation Process for Zinc, and this non-chromium inactivating technique uses the zinc coating passivation liquid described in Section 1.
In above-mentioned non-chromium inactivating technique, as preferably, described passivation reaction temperature is 20-60 DEG C, is preferably 30-55 DEG C, is more preferably 40-50 DEG C.
In a particular embodiment, described passivation reaction temperature is 20 DEG C, 25 DEG C, 30 DEG C, 35 DEG C, 40 DEG C, 45 DEG C, 50 DEG C, 55 DEG C, 60 DEG C.
As preferably, passivation time is 1-2min, is more preferably 60-90s.
Unchromium Passivation of Galvanized Zinc Layer liquid of the present invention and the chromium-free passivating film obtained by passivation technology thereof are iris, and evenly bright in colour, good decorating effect, close to chromate passivation film color and luster; Passive film performance is close to the performance of chromate passivation film, and high corrosion resistance, and passivating solution is not containing sexavalent chrome, environmental pollution is minimum, belongs to environmental protection technique.
Accompanying drawing explanation
Fig. 1 is the cathodic polarization curve of various sample.
Embodiment
Technical scheme of the present invention is further illustrated below by embodiment.
In embodiment 1 Unchromium Passivation of Galvanized Zinc Layer of the present invention liquid, each component concentration is on the impact of Chromating Film On Zn Deposits
(1) ammonium molybdate content is on the impact of Chromating Film On Zn Deposits
Ammonium molybdate is the main salt of passivating solution, provides the main component of passive film.Its consumption is very large, as shown in table 1 to molybdate technogenic influence.
Table 1, ammonium molybdate content are on the impact of Chromating Film On Zn Deposits
From table 1, ammonium molybdate content should control at 10-20g/L; Content is too low, and passive film is thin, light, film forming difficulty or not film forming; Too high levels, passive film color and luster is excessively dark, uneven, ornamental difference, and film surface exists micro-crack, and solidity to corrosion declines.
(2) sodium phosphate content is on the impact of Chromating Film On Zn Deposits
Add sodium phosphate in passivating solution, the molybdate in its phosphate radical and ammonium molybdate can form phosphato-molybdic heteropolyacid in acid condition.Phosphato-molybdic heteropolyacid is acid with strong oxidizing property, compensate for the deficiency that molybdate oxidisability under acidic conditions is weak, is conducive to forming passive film with the effect of Zn layer, accelerates film forming speed, plays phosphorization, forming section phosphate layer simultaneously, thus improves the solidity to corrosion of rete.On the other hand, phosphate solution has good shock-absorbing capacity, its content on the impact of passive film performance as table 2.
Table 2, sodium phosphate content are on the impact of Chromating Film On Zn Deposits
From table 2, sodium phosphate content should between 1.0-2.0g/L, and when content is too low, film forming speed obviously slows down, and look light decorative effect is not good enough; During too high levels, film forming speed is accelerated, but passive film color and luster is deepened, ornamental decline.
(3) additive level is on the impact of Chromating Film On Zn Deposits
In passivating solution, add the vitriol of transition metal and the mixture additive XZ-03B of sulfuric acid, the catalyzer of redox reaction in passivation can be provided, improve film forming speed.Test shows, additive level controls to be advisable at 2 ~ 2.5g/L; Content is too low, and film forming speed is slow, and the passive film look of formation is light, and decorative effect is not good enough; Too high levels, film forming speed is too fast, and the passive film color and luster formed is dark, in lead, loss of adhesion.
(4) OP-10 content is on the impact of Chromating Film On Zn Deposits
OP-10 emulsifying agent is a kind of non-ionic surface agent promoting agent, there is good wetting action, significantly can reduce passivating solution/zinc layers surface tension, be conducive to the precipitation of negative electrode H2 in molybdate passivation film reaction, thus accelerating film forming mistake film process, its content controls to be advisable at 0.08 ~ 0.15g/L.
Embodiment 2 passivating conditions is on the impact of Chromating Film On Zn Deposits
(1) passivating solution pH value is on the impact of Chromating Film On Zn Deposits
Passivating solution pH value affects comparatively large on the film forming of passive film and solidity to corrosion, in table 3.
Table 3, passivating solution pH are on the impact of Chromating Film On Zn Deposits
As shown in Table 3, this technique pH value should control 3 ~ 4.5.The forming process of passive film is attended by the dissolving of metal, and in metal ion and passivating solution, passivator reacts and forms passivation film.Therefore, the zinc in passivating solution should be in E-pH figure appropriateness and corrodes and produce in the region of zine ion.According to zinc E-pH figure in aqueous, zinc is be in this region in the passivating solution of 3 ~ 5 in pH value, so time passive film film forming easily carry out, after Passivation Treatment, erosion resistance is also better.And after passivating solution pH value is greater than 5, because zinc can react the more stable Zn of generation (OH)
2insolubles is deposited on zinc surface, hinders the dissolving of zinc, thus hinders formation and the growth of passive film, Passivation Treatment deleterious.
(2) passivation temperature is on the impact of Chromating Film On Zn Deposits
Temperature is very large on the impact of chromium-free deactivation.When temperature is low, passive film is thinner, ornamental poor; When temperature is higher, passive film is accelerate dissolution again, and passive film becomes broad, lighten.Temperature on the impact of Chromating Film On Zn Deposits as table 4.
The relation of table 4, passivation temperature and passive film color
As shown in Table 4: temperature controls at 45 ~ 55e, the iridescent passivation film of good decorative property can be obtained.
(3) passivation time is on the impact of Chromating Film On Zn Deposits
The Passivation Treatment time is larger to passivation effect of film formation.The Passivation Treatment time is short, and passive film is thinner, and color is more shallow, and decorative effect is poor; The Passivation Treatment time is long, and passive film is relatively thick, easily forms crackle, and color is dark, and decorative effect is also poor.Obtain the iris of good decorating effect, passivation time controls to be advisable at 60 ~ 90s.
The Performance Detection of passive film obtained by embodiment 3 passivating solution of the present invention and passivation technology
(1) the traditional performance detected result of passive film is in table 5.
Table 5, passive film traditional performance detected result
(2) passive film polarization curve
Galvanostatic method is adopted to measure the electrochemical cathode behavior in 5% sodium chloride solution of this technique passive film, non-passivation and chromate passivation film.Reference electrode is saturated calomel electrode, and supporting electrode is 1cm
2platinum electrode, sample is that (expose area is 1cm to Electrode
2), first measure the spontaneous potential of Electrode, after 10min, treat that spontaneous potential is stablized, start galvanostatic polarization and measure.Regulate electric current to be given current value, keep 1min under this given electric current after, record corresponding polarized potential value, its measurement result is as Fig. 1.
As seen from Figure 1, the cathodic polarization curve of three has obvious difference, this work passive film and chromic anhydride passive film make cathodic polarization curve move to low current density direction, because cathodic reaction is suppressed, whole electrochemical reaction is suppressed, the corrosion electric current density of zinc is reduced, thus the corrosion speed of zinc slow down.
Applicant states, the present invention illustrates the present invention by above-described embodiment, but the present invention is not limited to above-mentioned, does not namely mean that the present invention must rely on above-mentioned could enforcement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of raw material selected by the present invention, all drops within protection scope of the present invention and open scope.
Claims (10)
1. a zinc coating passivation liquid, is characterized in that, comprises ammonium molybdate, sodium phosphate, additive XZ-03B and OP-10.
2. zinc coating passivation liquid as claimed in claim 1, is characterized in that, the concentration of described ammonium molybdate is 10-20g/L, is preferably 12-20g/L, is more preferably 15g/L.
3. zinc coating passivation liquid as claimed in claim 1 or 2, is characterized in that, the concentration of described sodium phosphate is 1-4g/L, is preferably 1-2g/L, is more preferably 2g/L.
4. the zinc coating passivation liquid as described in any one of claim 1-3, is characterized in that, the concentration of described additive XZ-03B is 1-4g/L, is preferably 2-3g/L, is more preferably 2g/L.
5. the zinc coating passivation liquid as described in any one of claim 1-4, is characterized in that, the concentration of described OP-10 is 0.06-0.20g/L, is preferably 0.08-0.15g/L, is more preferably 0.1g/L.
6. the zinc coating passivation liquid as described in any one of claim 1-5, is characterized in that, its pH value is 2-6, is preferably 3-5, is more preferably 3-4.5.
7. the zinc coating passivation liquid as described in any one of claim 1-6, is characterized in that, comprise the OP-10 of the ammonium molybdate of 15g/L, the sodium phosphate of 2g/L, additive XZ-03B and 0.1g/L of 2g/L, its pH value is 3-4.5.
8. a Chromium-Free Passivation Process for Zinc, is characterized in that, uses the zinc coating passivation liquid described in any one of claim 1-7.
9. Chromium-Free Passivation Process for Zinc as claimed in claim 8, is characterized in that, passivation reaction temperature is 20-60 DEG C, is preferably 30-55 DEG C, is more preferably 40-50 DEG C.
10. the composite passivated technique of zinc coating as claimed in claim 8 or 9, it is characterized in that, passivation time is 1-2min, is preferably 60-90s.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105369237A (en) * | 2015-12-17 | 2016-03-02 | 山东建筑大学 | Brown passivant |
| CN105369236A (en) * | 2015-12-17 | 2016-03-02 | 山东建筑大学 | Non-chrome passivating agent for brown zinc coating |
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| US20040194859A1 (en) * | 2003-02-28 | 2004-10-07 | Yoshitaka Asou | Black hexavalent chromium-free plating treatment system |
| CN101235498A (en) * | 2008-02-28 | 2008-08-06 | 武汉钢铁(集团)公司 | Chromium-free inactivating liquid used for galvanized steel sheet surface |
| CN101358342A (en) * | 2008-08-12 | 2009-02-04 | 武汉钢铁(集团)公司 | Brilliant tin plate chromium-free passivation solution and passivation method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105369237A (en) * | 2015-12-17 | 2016-03-02 | 山东建筑大学 | Brown passivant |
| CN105369236A (en) * | 2015-12-17 | 2016-03-02 | 山东建筑大学 | Non-chrome passivating agent for brown zinc coating |
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