CN103320779A - Passivation solution capable of inhibiting formation of hexavalent chromium in trivalent chromium passivation layer as well as preparation method and application of passivation solution - Google Patents
Passivation solution capable of inhibiting formation of hexavalent chromium in trivalent chromium passivation layer as well as preparation method and application of passivation solution Download PDFInfo
- Publication number
- CN103320779A CN103320779A CN2013102559557A CN201310255955A CN103320779A CN 103320779 A CN103320779 A CN 103320779A CN 2013102559557 A CN2013102559557 A CN 2013102559557A CN 201310255955 A CN201310255955 A CN 201310255955A CN 103320779 A CN103320779 A CN 103320779A
- Authority
- CN
- China
- Prior art keywords
- passivation layer
- trivalent chromium
- sexavalent chrome
- passivating solution
- chromium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium
Abstract
The invention discloses a passivation solution capable of inhibiting formation of hexavalent chromium in a trivalent chromium passivation layer as well as a preparation method of the passivation solution. Every liter of the passivation solution capable of inhibiting formation of hexavalent chromium in the trivalent chromium passivation layer comprises 15-25g of chromium sulphate, 1.5-3.0g of sodium nitrate, 4.0-9.0g of cobaltous sulphate heptahydrate, 2.5-5.0g of sodium hypophosphite, 0.4-1.0g of citric acid, 0.15-0.25g of ammonium hydrogen fluoride, 0.8-1.25g of D-sodium gluconate, 0.4-1.0g of acetic acid and the balance of deionized water. The preparation method of the passivation solution capable of inhibiting formation of hexavalent chromium in the trivalent chromium passivation layer comprises the following steps of: firstly sequentially adding sodium hypophosphite, citric acid, sodium nitrate and cobaltous sulphate heptahydrate into a chromium sulphate aqueous solution and dissolving, then sequentially adding ammonium hydrogen fluoride and D-sodium gluconate, and finally dropwise adding acetic acid, and adding water to maintain constant volume, thus the passivation solution capable of inhibiting formation of hexavalent chromium in the trivalent chromium passivation layer is obtained. The passivation solution can improve stability and tightness of a passivation layer and inhibit formation of hexavalent chromium.
Description
Technical field
The present invention relates to a kind of passivating solution of metal, particularly a kind of passivating solution and preparation method and application that suppress sexavalent chrome formation in the trivalent chromium passivation layer.
Background technology
Process after best sexavalence chromic salts is under an embargo as Zincing passivation, seek a kind of suitable sexavalent chrome substitute, people have carried out the research of chromium-free deactivation aspect, seek suitable novel material element, are applied in the metal passivation material; But, the molybdate of at present chromium-free deactivation employing, titanate, tungstate, rare earth, silicate etc. in outward appearance, all do not reach desirable effect as corrosion-resistant novel material on the anticorrosion effect, still have certain limitation in production application.Do not occur in the development at home and abroad of novel chrome-free tanning agent in the situation of important breakthrough progress, it only is that the centesimal trivalent chromium of sexavalent chrome toxicity is as replacing chromic best practice that each production firm generally adopts toxicity.Trivalent chromium is easy to process because of it, and dispersed and covering power advantages of higher obtains people's consistent approval.Chinese invention patent (publication number CN1584117A) " trivalent chromic rainbow color passivating agent for galvanizing and manufacture method thereof "; Chinese invention patent (publication number CN1858303A) " normal temperature passivated zinc coating trivalent chromium color passivating agent "; Chinese invention patent (publication number CN101130867) " trivalent chromium iridescent passivator and preparation method thereof "; Chinese invention patent (publication number CN101130866) " trivalent chromium iridescent passivator with high corrosion resistance and preparation method thereof "; All announce out successively the patent formulation of chromic salt as main passivator, and all obtained more excellent anticorrosion effect.Trivalent chromium is expected to replace the scale operation that sexavalent chrome guarantees plated item.
But constantly occur in the electronic product of China's export in recent years being detected the poisonous chromic situation that contains in the trivalent chromium passivation layer of some metal productss after the trivalent chromium deactivating liquid passivation, thereby do not entered some cases in border, the export market of China is brought certain impact.Also explanation simultaneously, the trivalent chromium passivation layer of gained is not stable existence after the trivalent chromium deactivating liquid passivation, and trivalent chromium wherein can be converted into sexavalent chrome, and this stability requirement to trivalent chromium deactivating liquid has proposed again new challenge.
Summary of the invention
One of purpose of the present invention is unstable in order to solve after the above-mentioned trivalent chromium deactivating liquid passivation passivation layer of gained, and trivalent chromium wherein can be converted into chromic technical problem and a kind of passivating solution that sexavalent chrome forms in the trivalent chromium passivation layer that suppresses is provided.The used raw material of this passivating solution is easy to get, low price, and low toxicity, preparation technology is simple, and the passivating solution stability of configuration is high, and the passivation layer that the trivalent chromium in the passivating solution forms is stable existence for a long time, suppresses chromic conversion.
Two of purpose of the present invention provides above-mentioned a kind of preparation method who suppresses the passivating solution that sexavalent chrome forms in the trivalent chromium passivation layer.
Three of purpose of the present invention is to provide a kind of above-mentioned a kind of method that Passivation Treatment is carried out on sexavalent chrome forms in the trivalent chromium passivation layer the passivating solution effects on surface steel substrate surface after zinc-plated that suppresses of utilizing.
Technical scheme of the present invention
A kind of passivating solution that suppresses sexavalent chrome formation in the trivalent chromium passivation layer, by every liter of calculating, composition and the content of its raw material are as follows:
Chromium sulphate 15-25g
SODIUMNITRATE 1.5-3.0g
Heptahydrate 4.0-9.0g
Sodium hypophosphite 2.5-5.0g
Citric acid 0.4-1.0g
Ammonium bifluoride 0.15-0.25g
Maltonic acid sodium 0.8-1.25g
Acetic acid 0.4-1.0g
Surplus is deionized water.
Above-mentioned a kind of preparation method who suppresses the passivating solution that sexavalent chrome forms in the trivalent chromium passivation layer, concrete steps are as follows:
The control mixing speed is under the 12r/min chromium sulphate to be added fully dissolving in the deionized water;
Then control under 30 ℃ of conditions of temperature and add successively sodium hypophosphite, citric acid, SODIUMNITRATE, heptahydrate is cooled to 20 ℃ until completely dissolved;
Then add after ammonium bifluoride mixes, add again maltonic acid sodium it is dissolved fully; Each material before ammonium bifluoride adds must dissolve and could add ammonium bifluoride after thorough, avoids causing that owing to the adding of ammonium bifluoride separating out of crystal arranged in the solution;
Be that the control drop rate is 0.1ml/min under the 12r/min condition at rotating speed at last, add acetic acid, mix the rear deionized water constant volume of using, namely get a kind of passivating solution that sexavalent chrome forms in the trivalent chromium passivation layer that suppresses;
The rate of addition of above-mentioned acetic acid is unsuitable too fast, and the too fast passivation layer luminance brightness that forms of easily causing is poor.
The method of Passivation Treatment is carried out on steel substrate surface after the passivating solution effects on surface that utilizes sexavalent chrome in the above-mentioned inhibition trivalent chromium passivation layer to form is zinc-plated, and concrete steps are as follows:
Be that to regulate the pH that suppresses the passivating solution that sexavalent chrome forms in the trivalent chromium passivation layer be 1.5-2.4 for the dilute sulphuric acid of 0.03mol/L or aqueous sodium hydroxide solution that concentration is 0.2mol/L with concentration at first;
Then the steel substrate behind the surface galvanizing is put in the passivating solution that sexavalent chrome forms in the inhibition trivalent chromium passivation layer that above-mentioned pH is 1.5-2.4, the control temperature is 25-40 ℃ and carries out passivation 30-60s, after passivation is finished, use washed with de-ionized water, 30 ℃ of air-dry getting final product of constant temperature.
Beneficial effect of the present invention
A kind of passivating solution that sexavalent chrome forms in the trivalent chromium passivation layer, the maltonic acid sodium of adding and the sequestrant citric acid in the passivating solution, sodium hypophosphite, stablizer NO of suppressing of the present invention
3 -1, F
-1In conjunction with tightr, improve the stability of passivation layer, tight type can effectively be alleviated the oxidized speed of trivalent chromium, suppresses chromic generation.
In addition, a kind of passivating solution that sexavalent chrome forms in the trivalent chromium passivation layer that suppresses of the present invention, by in passivating solution, adding first maltonic acid sodium, dropwise add subsequently the acetic acid solution that polarity is strong, dispersity is high, the adding of maltonic acid sodium can be played certain activation to final formed passivation layer, the slow adding of acetic acid, acetic acid is uniformly dispersed in solution, and in the passivation layer forming process, the pH that suppresses passivating solution raises fast, make the passivation layer forming process stable, evenly.Be the acting in conjunction of maltonic acid sodium and acetic acid, help passivation layer surface even, densification, stable.
The passivation layer surface that gets by SEM observation post, and with passivating solution passivation of the prior art after the figure of formed passivation layer compare explanation of the present invention a kind of to suppress the formed passivation layer surface of passivating solution that sexavalent chrome forms in the trivalent chromium passivation layer even, densification, stable.
Description of drawings
Fig. 1, suppress the histogram of content of 6-valence Cr ions in the passivation layer that sexavalent chrome forms in the trivalent chromium passivation layer the zinc-plated iron plate of passivating solution effects on surface carries out respectively gained after the passivation with commercially available trivalent chromium deactivating liquid and embodiment 1 gained a kind of;
Fig. 2 a, commercially available trivalent chromium deactivating liquid are the SEM figure that the zinc-plated iron plate of the trivalent chromium deactivating liquid effects on surface of Shanghai Shu Tan Environmental Protection Technology Co., Ltd carries out the passivation layer of gained after the passivation;
Fig. 2 b, embodiment 1 gained a kind of suppresses the SEM figure that sexavalent chrome forms in the trivalent chromium passivation layer the zinc-plated iron plate of passivating solution effects on surface carries out the passivation layer of gained after the passivation.
Embodiment
Also by reference to the accompanying drawings the present invention is described further below by specific embodiment, but protection scope of the present invention is not limited in this.
Corresponding sexavalent chrome detection method used in the embodiments of the invention is as follows:
1, topical application (IEC 62321) is adopted in the detection of chromic existence, and step is as follows:
The test fluid configuration:
Get 1 of 0.4g, the 5-diphenylcarbazone fully is dissolved in the ethanolic soln of the acetone of 20mL and 20mL, adds the ortho-phosphoric acid of 20mL and the distilled water of 20mL again;
Sexavalent chrome detects:
Sample thief is positioned in the small vessels, drips the test fluid that 1-5 drips at sample, when test fluid becomes purple from redness, illustrates and contains sexavalent chrome in the passive film.
2, the mensuration of content of 6-valence Cr ions:
Measure according to the colorimetric determination that US EPA 3060A and US EPA 7196A provide, determination step is as follows:
(1), the sample that passivation is good immerses in the digestion solution of 0.28M sodium carbonate solution/0.5M sodium hydroxide composition immersion area 50 ± 5cm
2, clear up 60min under 90-95 ℃;
(2), the solution in the beaker is transferred in the Glass Containers of 50mL, the concentration that adds 2mL is that 53% nitre acid for adjusting pH is to 1.0-2.0;
(3), the solution in (2) got 2mL mix with the ortho-phosphoric acid of 2mL, use spectrophotometer under the 540nm wavelength, to test; In order to improve measuring accuracy, to get the 5cm absorptive unit and be used for measuring, all samples is got 10% and is carried out replicate measurement, and each Measuring Time is followed successively by 24h, 96h, 192h, 384h, 576h, 720h;
3, the calculating of content of 6-valence Cr ions, formula is as follows:
The Cr(VI) concentration=(A*D*F)/S;
The digestion solution concentration (μ g/mL) that measures of A=wherein;
The D=dilution factor;
The volume of the digestion solution that F=is final (mL);
The initial quality (g) of S=sample;
The Cr(VI) unit of concentration (ppm).
Embodiment 1
A kind of passivating solution that suppresses sexavalent chrome formation in the trivalent chromium passivation layer, by every liter of calculating, composition and the content of its raw material are as follows:
Chromium sulphate 15g
SODIUMNITRATE 1.5g
Heptahydrate 4.0g
Sodium hypophosphite 2.5g
Citric acid 0.4g
Ammonium bifluoride 0.15g
Maltonic acid sodium 0.8g
Acetic acid 0.4g
Surplus is deionized water.
Above-mentioned a kind of preparation method who suppresses the passivating solution that sexavalent chrome forms in the trivalent chromium passivation layer, concrete steps are as follows:
The 15g chromium sulphate is poured in the beaker of 1500mL, added the 200mL deionized water, the control mixing speed is under the 12r/min, and the Water Tank with Temp.-controlled of beaker being put into 30 ℃ dissolves chromium sulphate fully;
Then add successively the 1.5g SODIUMNITRATE, the 4.0g heptahydrate, the 2.5g sodium hypophosphite, the 0.4g citric acid, it is dissolved fully after, beaker is moved in 20 ℃ of Water Tanks with Temp.-controlled;
And then add the 0.15g ammonium bifluoride, and solution is mixed, add 0.8g maltonic acid sodium it is dissolved fully;
Be that the control drop rate is that 0.1ml/min drips 0.4g acetic acid under the 12r/min condition at rotating speed at last, drip and be settled to 1000mL with deionized water afterwards, namely get a kind of passivating solution that sexavalent chrome forms in the trivalent chromium passivation layer that suppresses.
Application Example 1
That utilizes above-described embodiment 1 gained a kind ofly suppresses sexavalent chrome forms in the trivalent chromium passivation layer passivating solution carries out Passivation Treatment to the galvanized sheet iron surface method, and concrete steps are as follows:
(7 * 3cm) behind identical zinc-plated treatment process, for subsequent use to get 2 identical iron plates;
Take by weighing respectively a kind of passivating solution of sexavalent chrome formation in the trivalent chromium passivation layer and commercially available trivalent chromium deactivating liquid (being Shanghai Shu Tan Environmental Protection Technology Co., Ltd) of suppressing of embodiment 1 gained of 60mL with the small beaker of 2 100mL, put into respectively 30 ℃ Water Tank with Temp.-controlled, be that the pH that the sulfuric acid of 0.03M or aqueous sodium hydroxide solution that concentration is 0.1M are regulated two kinds of above-mentioned trivalent chromium deactivating liquids is 1.8 with concentration, the iron plate of 2 surface galvanizing is immersed in respectively in two kinds of above-mentioned trivalent chromium deactivating liquids, the iron plate that rocks gently 2 surface galvanizing carries out taking out behind the passivation 30s, rinse well with deionized water, then in 30 ℃ of air-dry getting final product of constant temperature.
The commercially available trivalent chromium deactivating liquid of above-mentioned usefulness be the trivalent chromium deactivating liquid of Shanghai Shu Tan Environmental Protection Technology Co., Ltd and embodiment 1 gained a kind of suppress in the passivation layer that sexavalent chrome forms in the trivalent chromium passivation layer the zinc-plated iron plate of passivating solution effects on surface carries out respectively gained after the passivation the time dependent histogram of content of 6-valence Cr ions as shown in Figure 1, ST-301A among Fig. 1 represents the time dependent histogram of content of 6-valence Cr ions in the passivation layer of gained after the trivalent chromium deactivating liquid passivation of Shanghai Shu Tan Environmental Protection Technology Co., Ltd, the time dependent histogram of content of 6-valence Cr ions in TEST-1 represents embodiment 1 gained a kind of passivation layer that suppresses gained after sexavalent chrome forms in the trivalent chromium passivation layer the passivating solution passivation, as can be seen from Figure 1:
The surperficial formed passivation layer of the iron plate of the surface galvanizing after commercially available trivalent chromium deactivating liquid passivation, during 96h after passivation, the topical application test result is positive, and content of 6-valence Cr ions is 0.12mg/L, during 720h after passivation, content of 6-valence Cr ions is 0.63 mg/L.
The surperficial formed passivation layer of the galvanized sheet iron after above-mentioned gained a kind of suppresses sexavalent chrome forms in the trivalent chromium passivation layer passivating solution passivation, during 192h after passivation, the topical application test result is positive, content of 6-valence Cr ions is 0.09mg/L, during 720h after passivation, content of 6-valence Cr ions is 0.32mg/L.
Show by above-mentioned analytical results and of the present inventionly a kind ofly to suppress the passivating solution that sexavalent chrome in the trivalent chromium passivation layer forms and compare with commercially available trivalent chromium deactivating liquid, it is that sexavalent chrome plays good restraining effect for trivalent chromium conversion in the passivation layer.
The commercially available trivalent chromium deactivating liquid of above-mentioned usefulness is that the trivalent chromium deactivating liquid of Shanghai Shu Tan Environmental Protection Technology Co., Ltd and embodiment 1 gained a kind of suppresses sexavalent chrome forms in the trivalent chromium passivation layer the zinc-plated iron plate of passivating solution effects on surface and carry out respectively the passivation layer of gained after the passivation by scanning electron microscope (S-3400N, Japan) under 10,000-40,000 multiplying power, scan, the scintigram of gained is seen respectively Fig. 2 a, Fig. 2 b, can find out that from Fig. 2 a many tiny cracks appear in the formed trivalent chromium passivation layer of commercially available trivalent chromium deactivating liquid surface, and whole trivalent chromium passivation layer is inhomogeneous.From Fig. 2 b, can find out the formed trivalent chromium passivation layer of the passivating solution surface uniform that sexavalent chrome forms in the inhibition trivalent chromium passivation layer of embodiment 1 gained, there is not tiny crack, thereby the trivalent chromium that effectively suppresses in the atmospheric oxidation trivalent chromium passivation layer becomes sexavalent chrome, and chromic detection limit also reduces greatly in the trivalent chromium passivation layer simultaneously.
Comparison by Fig. 2 a and Fig. 2 b, can draw, the formed trivalent chromium passivation layer of passivating solution that sexavalent chrome forms in the inhibition trivalent chromium passivation layer of embodiment 1 gained is more even than the formed trivalent chromium passivation layer of commercially available trivalent chromium deactivating liquid surface, and chromic content also is starkly lower than chromic content in the formed trivalent chromium passivation layer of commercially available trivalent chromium deactivating liquid in the trivalent chromium passivation layer.
Embodiment 2
A kind of passivating solution that suppresses sexavalent chrome formation in the trivalent chromium passivation layer, by every liter of calculating, composition and the content of its raw material are as follows:
Chromium sulphate 25g
SODIUMNITRATE 3.0g
Heptahydrate 9.0g
Sodium hypophosphite 5.0g
Citric acid 1.0g
Ammonium bifluoride 0.25g
Maltonic acid sodium 1.25g
Acetic acid 1.0g
Surplus is deionized water.
Above-mentioned a kind of preparation method who suppresses the passivating solution that sexavalent chrome forms in the trivalent chromium passivation layer, concrete steps are as follows:
The 25g chromium sulphate is poured in the beaker of 1500mL, added the 200mL deionized water, the control mixing speed is under the 12r/min, and the Water Tank with Temp.-controlled of beaker being put into 30 ℃ dissolves chromium sulphate fully;
Then add successively the 3.0g SODIUMNITRATE, the 9.0g heptahydrate, 5.0 g sodium hypophosphites, the 1.0g citric acid, it is dissolved fully after, beaker is moved in 20 ℃ of Water Tanks with Temp.-controlled;
And then add the 0.25g ammonium bifluoride, and solution is mixed, add 1.25g maltonic acid sodium it is dissolved fully;
Be that the control drop rate is that 0.1ml/min drips 1.04g acetic acid under the 12 r/min conditions at rotating speed at last, drip and be settled to 1000mL with deionized water afterwards, namely get a kind of passivating solution that sexavalent chrome forms in the trivalent chromium passivation layer that suppresses.
Embodiment 3
A kind of passivating solution that suppresses sexavalent chrome formation in the trivalent chromium passivation layer, by every liter of calculating, composition and the content of its raw material are as follows:
Chromium sulphate 20g
SODIUMNITRATE 2.0g
Heptahydrate 6.0g
Sodium hypophosphite 3.0g
Citric acid 0.7g
Ammonium bifluoride 0.2g
Maltonic acid sodium 1.0g
Acetic acid 0.8g
Surplus is deionized water.
Above-mentioned a kind of preparation method who suppresses the passivating solution that sexavalent chrome forms in the trivalent chromium passivation layer, concrete steps are as follows:
The 20g chromium sulphate is poured in the beaker of 1500mL, added the 200mL deionized water, the control mixing speed is under the 12r/min, and the Water Tank with Temp.-controlled of beaker being put into 30 ℃ dissolves chromium sulphate fully;
Then add successively the 2.0g SODIUMNITRATE, the 6.0g heptahydrate, the 3.0g sodium hypophosphite, the 0.7g citric acid, it is dissolved fully after, beaker is moved in 20 ℃ of Water Tanks with Temp.-controlled;
And then add the 0.2g ammonium bifluoride, and solution is mixed, add 1.0g maltonic acid sodium it is dissolved fully;
Be that the control drop rate is that 0.1ml/min drips 0.8g acetic acid under the 12r/min condition at rotating speed at last, drip and be settled to 1000mL with deionized water afterwards, namely get a kind of passivating solution that sexavalent chrome forms in the trivalent chromium passivation layer that suppresses.
Foregoing only is the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (6)
1. one kind is suppressed the passivating solution that sexavalent chrome forms in the trivalent chromium passivation layer, it is characterized in that by every liter of calculating, and composition and the content of its raw material are as follows:
Chromium sulphate 15-25g
SODIUMNITRATE 1.5-3.0g
Heptahydrate 4.0-9.0g
Sodium hypophosphite 2.5-5.0g
Citric acid 0.4-1.0g
Ammonium bifluoride 0.15-0.25g
Maltonic acid sodium 0.8-1.25g
Acetic acid 0.4-1.0g
Surplus is deionized water.
2. a kind of passivating solution that sexavalent chrome forms in the trivalent chromium passivation layer that suppresses as claimed in claim 1 is characterized in that by every liter of calculating, and composition and the content of its raw material are as follows:
Chromium sulphate 15g
SODIUMNITRATE 1.5g
Heptahydrate 4.0g
Sodium hypophosphite 2.5g
Citric acid 0.4g
Ammonium bifluoride 0.15g
Maltonic acid sodium 0.8g
Acetic acid 0.4g
Surplus is deionized water.
3. a kind of passivating solution that sexavalent chrome forms in the trivalent chromium passivation layer that suppresses as claimed in claim 1 is characterized in that by every liter of calculating, and composition and the content of its raw material are as follows:
Chromium sulphate 25g
SODIUMNITRATE 3.0g
Heptahydrate 9.0g
Sodium hypophosphite 5.0g
Citric acid 1.0g
Ammonium bifluoride 0.25g
Maltonic acid sodium 1.25g
Acetic acid 1.0g
Surplus is deionized water.
4. a kind of passivating solution that sexavalent chrome forms in the trivalent chromium passivation layer that suppresses as claimed in claim 1 is characterized in that by every liter of calculating, and composition and the content of its raw material are as follows:
Chromium sulphate 20g
SODIUMNITRATE 2.0g
Heptahydrate 6.0g
Sodium hypophosphite 3.0g
Citric acid 0.7g
Ammonium bifluoride 0.2g
Maltonic acid sodium 1.0g
Acetic acid 0.8g
Surplus is deionized water.
5. such as claim 1,2,3 or 4 described a kind of preparation methods that suppress the passivating solution that sexavalent chrome forms in the trivalent chromium passivation layer, it is characterized in that concrete steps are as follows:
At first, the control mixing speed is under the 12r/min chromium sulphate to be added fully dissolving in the deionized water;
Then, add successively sodium hypophosphite under 30 ℃ of conditions of control temperature, citric acid, SODIUMNITRATE, heptahydrate is cooled to 20 ℃ until completely dissolved;
Then, after the adding ammonium bifluoride mixes, add again maltonic acid sodium it is dissolved fully;
At last, the control drop rate is 0.1ml/min under rotating speed 12r/min condition, adds acetic acid, mixes the rear deionized water constant volume of using, and namely gets a kind of passivating solution that sexavalent chrome forms in the trivalent chromium passivation layer that suppresses.
6. utilize as the method for Passivation Treatment is carried out on claim 1,2,3 or 4 described a kind of passivating solution effects on surfaces that suppress sexavalent chrome formation in the trivalent chromium passivation layer steel substrate surface after zinc-plated, it is characterized in that step is as follows:
Be that to regulate the pH that suppresses the passivating solution that sexavalent chrome forms in the trivalent chromium passivation layer be 1.5-2.4 for the dilute sulphuric acid of 0.03mol/L or aqueous sodium hydroxide solution that concentration is 0.2mol/L with concentration at first;
Then the steel substrate behind the surface galvanizing is put in the passivating solution that sexavalent chrome forms in the inhibition trivalent chromium passivation layer that above-mentioned pH is 1.5-2.4, the control temperature is 25-40 ℃ and carries out passivation 30-60s, after passivation is finished, with washed with de-ionized water, 30 ℃ of air-dry getting final product of constant temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310255955.7A CN103320779B (en) | 2013-06-25 | 2013-06-25 | Passivation solution capable of inhibiting formation of hexavalent chromium in trivalent chromium passivation layer as well as preparation method and application of passivation solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310255955.7A CN103320779B (en) | 2013-06-25 | 2013-06-25 | Passivation solution capable of inhibiting formation of hexavalent chromium in trivalent chromium passivation layer as well as preparation method and application of passivation solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103320779A true CN103320779A (en) | 2013-09-25 |
| CN103320779B CN103320779B (en) | 2015-05-20 |
Family
ID=49189809
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310255955.7A Active CN103320779B (en) | 2013-06-25 | 2013-06-25 | Passivation solution capable of inhibiting formation of hexavalent chromium in trivalent chromium passivation layer as well as preparation method and application of passivation solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103320779B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103849864A (en) * | 2014-02-24 | 2014-06-11 | 昆明理工大学 | Galvanizing chrome-free iridescent passivation liquid as well as preparation and application methods thereof |
| CN107236948A (en) * | 2017-06-07 | 2017-10-10 | 广州传福化学技术有限公司 | It is a kind of to suppress the passivator that zinc coating trivalent chromium is oxidized to Cr VI |
| RU2643759C2 (en) * | 2015-11-13 | 2018-02-05 | Закрытое акционерное общество "ФК" | Chromating composition for processing of zinc curtain and zinc wire |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009020097A1 (en) * | 2007-08-03 | 2009-02-12 | Dipsol Chemicals Co., Ltd. | Corrosion-resistant trivalent-chromium chemical conversion coating and solution for trivalent-chromium chemical treatment |
| CN102260868A (en) * | 2011-07-22 | 2011-11-30 | 上海交通大学 | High-corrosion resistant passivating liquid and production process thereof |
| CN102260867A (en) * | 2011-06-30 | 2011-11-30 | 南通飞拓界面工程科技有限公司 | Trivalent chromium five-color passivating agent |
| CN103046037A (en) * | 2012-11-19 | 2013-04-17 | 上海应用技术学院 | High corrosion resistance trivalent chromium blue and white passivating liquid as well as preparation method and application of blue and white passivating liquid |
-
2013
- 2013-06-25 CN CN201310255955.7A patent/CN103320779B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009020097A1 (en) * | 2007-08-03 | 2009-02-12 | Dipsol Chemicals Co., Ltd. | Corrosion-resistant trivalent-chromium chemical conversion coating and solution for trivalent-chromium chemical treatment |
| CN102260867A (en) * | 2011-06-30 | 2011-11-30 | 南通飞拓界面工程科技有限公司 | Trivalent chromium five-color passivating agent |
| CN102260868A (en) * | 2011-07-22 | 2011-11-30 | 上海交通大学 | High-corrosion resistant passivating liquid and production process thereof |
| CN103046037A (en) * | 2012-11-19 | 2013-04-17 | 上海应用技术学院 | High corrosion resistance trivalent chromium blue and white passivating liquid as well as preparation method and application of blue and white passivating liquid |
Non-Patent Citations (1)
| Title |
|---|
| 李金花等: "抑制钝化层六价铬形成的三价铬彩色钝化液及其工艺研究", 《2009年全国电子电镀及表面处理学术交流会论文集》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103849864A (en) * | 2014-02-24 | 2014-06-11 | 昆明理工大学 | Galvanizing chrome-free iridescent passivation liquid as well as preparation and application methods thereof |
| RU2643759C2 (en) * | 2015-11-13 | 2018-02-05 | Закрытое акционерное общество "ФК" | Chromating composition for processing of zinc curtain and zinc wire |
| CN107236948A (en) * | 2017-06-07 | 2017-10-10 | 广州传福化学技术有限公司 | It is a kind of to suppress the passivator that zinc coating trivalent chromium is oxidized to Cr VI |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103320779B (en) | 2015-05-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yasakau et al. | A novel bilayer system comprising LDH conversion layer and sol-gel coating for active corrosion protection of AA2024 | |
| CN103184446B (en) | Forming solution for environment-friendly non-phosphate ceramic film and preparation method and application thereof | |
| CN105779988B (en) | A kind of electrogalvanizing chromium-free deactivation solution and its passivation technology | |
| CN104264144A (en) | Aluminum alloy product chemical conversion treatment process and nonferrous chromium-free film-forming agent | |
| CN1986883A (en) | Environment friendly no-chromium conversion treating solution | |
| CN103695889B (en) | A kind of chromium-free passivation liquid for galvanized sheet, aluminium and copper alloy surface process | |
| CN102268667A (en) | Corrosion-resistant trivalent-chromium chemical conversion coating and solution for trivalent-chromium chemical treatment | |
| CN103173754B (en) | Treating agent for stabilizing rust layer on surface of weathering-resistant steel and method for preparing same | |
| CN103255405A (en) | Rare earth chromate-free passivation liquid for coating treatment of material and application of rare earth chromate-free passivation liquid | |
| CN101135050B (en) | Metasilicate cleaning inactivating process | |
| CN111593335A (en) | Improved zirconium-based conversion film for metal surface treatment and preparation method and application thereof | |
| CN105220138A (en) | The agent of a kind of Surface Rust of Weathering Steel stabilization treatment | |
| CN104073796A (en) | Metal plating passivation solution and preparation method thereof | |
| Ferreira Jr et al. | Electrochemical and chemical characterization of electrodeposited zinc surface exposed to new surface treatments | |
| CN103320779B (en) | Passivation solution capable of inhibiting formation of hexavalent chromium in trivalent chromium passivation layer as well as preparation method and application of passivation solution | |
| CN103243320B (en) | Zinc plating chrome-free blue-white passivator | |
| CN101565827A (en) | Passivation method of high-corrosion-resistance organic trivalent chromium applicable to surface of zinc coating | |
| CN103046037B (en) | High corrosion resistance trivalent chromium blue and white passivating liquid as well as preparation method and application of blue and white passivating liquid | |
| CN108572235B (en) | Method for detecting chromium content in chromium passivation waste liquid | |
| CN104451634A (en) | Aluminum and aluminum alloy passivation solution, preparation method and using method thereof | |
| CN101173354A (en) | Trivalent chromium colorful passivation liquid for NdFeB Zinc-plated parts in normal temperature, method for producing the same and passivation method | |
| CN107794523B (en) | Rapid corrosion method for weather-resistant steel plate | |
| CN102605364B (en) | Intermediate-temperature low-sediment and low-emission thick membrane phosphorizing liquid and phosphorizing method thereof | |
| CN105525282A (en) | Alkaline chromate-free passivation liquid and method for normal temperature passivation of chemical Ni-P plated layer through alkaline chromate-free passivation liquid | |
| CN101200799B (en) | Medium-low temperature high corrosion resistant black phosphating solution on steel surface |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |