CN103215582B - Trivalent chromium passivating agent used for rapid film formation on steel plate surface - Google Patents
Trivalent chromium passivating agent used for rapid film formation on steel plate surface Download PDFInfo
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- CN103215582B CN103215582B CN201310094638.1A CN201310094638A CN103215582B CN 103215582 B CN103215582 B CN 103215582B CN 201310094638 A CN201310094638 A CN 201310094638A CN 103215582 B CN103215582 B CN 103215582B
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Abstract
The invention provides a passivating agent free of hexavalent chromium, is mainly used for the continuous passivation step of steel plates after degreasing, and is characterized by including the following compositions by weight: 5-40% of a trivalent chromium main salt, 5-20% of nitrate of non-main salt, 1-25% of phosphate, 1-10% of a chelating agent, 1-10% of organic acids, 1-5% of a surfactant, and 20-65% of water. The trivalent chromium passivating agent provided by the present invention can be rapidly and continuously passivated to form film, is fast in passivation reaction time, long in time of resistance to salt spray, and stable in tank liquor, is suitable for dipping and roller coating of processed sample parts, and is more preferably used for rapid roll coating passivation process of steel plates continuously.
Description
Technical field
trivalent chromium passivator used when the invention belongs to a kind of roller coat formula surface of steel plate process, particularly selected during a kind of continual sheet material passivation continuous in the steel mill's steel plate production line trivalent chromium passivator for surface of steel plate fast filming.
Background technology
along with China's economic strength increases, its automotive industry, household electric appliances and large scale industry etc. constantly increase steel plate demand; To board quality, environmental requirement is also constantly increased.This just needs should ensure that certain output meets the environmental requirement of various countries again when processing sheet material.Such as European Union is to chromic restriction effects on surface treatment industry generation far-reaching influence, and it, in the decree of in September, 2000 Brussels signature, specifies to forbid using sexavalent chrome from January, 2003 in vehicle material and parts." the End 0f life vehicle " bill that European Commission publishes, formally legal provision is become in July, 2003, wherein the heavy metals such as cadmium, mercury, lead, sexavalent chrome are effectively eliminated in a requirement, and this bill reclaims the Legislation Frame of industry by becoming following European Union automobile.And present stage process iron system exemplar time trivalent chromium passivator used be mainly immersion type process, long time treatment exemplar can make the Zn content in tank liquor increase, and causes tank liquor aging.And the production technique of some industry is not suitable for the immersion type process having the residence time yet, such as steel mill produces the surface passivation of coil of strip, just needs to generate passive film at surface of steel plate incessantly fast continuously.Just need a kind of coating effective in this case, the reaction times fast and steel plate passivation medicament meeting various countries' environmental requirement is for scene.
Summary of the invention
the object of the invention is by providing a kind of chromic salt, a kind of trivalent chromium passivation medicament that the reasonable preparation of inorganic salt and organic acid and additive obtains, sheet material can be processed incessantly fast continuously with this medicament, the film formed has excellent erosion resistance, coating is good, humidity resistance, yellowing resistance is good, there are the characteristics such as stronger solvent resistance, this trivalent chromium passivator product stability is good, does not have layering and crystalline polamer, and non-foam produces, execute-in-place is convenient, meets various countries' environmental requirement.
trivalent chromium passivation medicament provided by the invention, is made up of following substances in percentage by weight:
the main salt 5 ~ 40% of trivalent chromium,
non-master salt nitrate 5 ~ 20%,
phosphoric acid salt or phosphatase 11 ~ 25%,
organic acid 1 ~ 10%,
sequestrant 1 ~ 10%,
tensio-active agent 1 ~ 5%,
water 20 ~ 65%;
wherein, chromic salt is chromium sulphate or chromium nitrate; Non-master salt nitrate is SODIUMNITRATE, saltpetre, 1 ~ 2 kind in Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES; Phosphoric acid salt is sodium phosphate, potassiumphosphate, Sodium phosphate dibasic, 1 ~ 2 kind in dipotassium hydrogen phosphate or from price consider select phosphoric acid; Sequestrant is 1 ~ 2 kind in Neutral ammonium fluoride, hydrofluotitanic acid, fluorine zirconic acid; Organic acid is lactic acid, acetic acid, oxalic acid, one kind or two or more in citric acid; Tensio-active agent is wetting agent 104PA.
the preparation method of above-mentioned trivalent chromium passivator is:
the 80-90% amount taking pure water adds phosphoric acid salt or phosphoric acid, the organic acid of above-mentioned part by weight simultaneously at moderate-speed mixer, continue to stir 5min; Add the main salt of trivalent chromium of above-mentioned part by weight, non-master salt nitrate and sequestrant, continue to stir 20min; Add tensio-active agent and the surplus pure water of above-mentioned part by weight, stir.
advantage of the present invention is: this passivator can make metal surface passivation by continuous quick roller coat process incessantly, avoid the immersion type process (soaking about 50s) of residence time and the Zn content in tank liquor can be made for a long time to increase, causing the unfavorable factors such as tank liquor is aging to produce.Especially process as steel mill's this sheet material process linear speed passivation industry faster, by roller coat fast filming, within the shorter treatment time, by the lower good passive film of storing temperature forming property, there is very important actual application value (roller coat+toast complete at about 10s).This passive film has excellent erosion resistance, and coating is good, humidity resistance, and yellowing resistance is good, has the characteristics such as stronger solvent resistance; Passivating agent products good stability, does not have layering and crystalline polamer, and non-foam produces, and execute-in-place is convenient.
Embodiment
embodiment 1:
raw material is made up of following substances in percentage by weight:
chromium sulphate 10%,
sODIUMNITRATE 7%,
jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 5%,
sodium phosphate 8%,
lactic acid 2%,
acetic acid 2%,
neutral ammonium fluoride 3%,
104PA 1%，
water 62%;
wherein chromium sulphate concentration is 40%, and lactic acid concn is 88%, and acetate concentration is 99.8%.
preparation method is: take weight part be 50% pure water add at moderate-speed mixer the sodium phosphate that weight part is 8% simultaneously, add the lactic acid of 2% and the acetic acid of 2%, continue stir 5min; Adding weight part is the SODIUMNITRATE of 7% and the Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES of 5%; Weight part is the Neutral ammonium fluoride of 3%; Weight part is the chromium sulphate of 10%, continues to stir 20min; Add the 104PA that weight part is 1%, surplus pure water is supplied, and stirs.
the tensio-active agent wetting agent 104PA used in the embodiment of the present invention is the production and sales of Guangzhou Lian Gu fine chemistry company limited.
embodiment 2:
raw material is made up of following substances in percentage by weight:
chromium nitrate 10%,
sODIUMNITRATE 6%,
jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 5%,
sodium phosphate 7%,
lactic acid 3%,
acetic acid 5%,
neutral ammonium fluoride 5%,
104PA 2%，
water 57%;
wherein lactic acid concn is 88%, and acetate concentration is 99.8%.
preparation method is: take weight part be 50% pure water add at moderate-speed mixer the sodium phosphate that weight part is 7% simultaneously, add the lactic acid of 3% and the acetic acid of 5%, continue stir 5min; Adding weight part is the SODIUMNITRATE of 6% and the Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES of 5%; Weight part is the Neutral ammonium fluoride of 5%; Weight part is the chromium nitrate of 10%, continues to stir 20min; Add the 104PA that weight part is 2%, surplus pure water is supplied, and stirs.
embodiment 3:
raw material is made up of following substances in percentage by weight:
chromium nitrate 20%,
saltpetre 7%,
jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 3%,
potassiumphosphate 5%,
lactic acid 7%,
oxalic acid 3%,
hydrofluotitanic acid 8%,
104PA 1%，
water 46%;
wherein hydrofluotitanic acid concentration is 50%, and lactic acid concn is 88%.
preparation method is: take weight part be 40% pure water add at moderate-speed mixer the potassiumphosphate that weight part is 5% simultaneously, add the lactic acid of 7% and the oxalic acid of 3%, continue stir 5min; Adding weight part is 7% saltpetre and 3% Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES; Weight part is the hydrofluotitanic acid of 8%; Weight part is the chromium nitrate of 20%, continues to stir 20min; Add the wetting agent 104PA that weight part is 1%, surplus pure water is supplied, and stirs.
embodiment 4:
raw material is made up of following substances in percentage by weight:
chromium sulphate 25%,
saltpetre 7%,
jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 5%,
potassiumphosphate 7%,
lactic acid 5%,
citric acid 5%,
fluorine zirconic acid 10%,
104PA 2%，
water 34%;
wherein chromium sulphate concentration is 40%, and fluorine zirconic acid concentration is 45%, and lactic acid concn is 88%.
preparation method is: take weight part be 30% pure water add at moderate-speed mixer the potassiumphosphate that weight part is 7% simultaneously, add the lactic acid of 5% and the citric acid of 5%, continue stir 5min; Adding weight part is the saltpetre of 7% and the Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES of 5%; Weight part is the fluorine zirconic acid of 10%; Weight part is the chromium sulphate of 25%, continues to stir 20min; Add the wetting agent 104PA that weight part is 2%, surplus pure water is supplied, and stirs.
embodiment 5:
raw material is made up of following substances in percentage by weight:
chromium sulphate 30%,
sODIUMNITRATE 7%,
jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 5%,
phosphoric acid 2%,
lactic acid 3%,
acetic acid 2%,
neutral ammonium fluoride 10%,
104PA 2%，
water 39%;
wherein chromium sulphate concentration is 40%, and phosphoric acid concentration is 75%, and lactic acid concn is 88%, and acetate concentration is 99.8%.
preparation method is: take weight part be 30% pure water add at moderate-speed mixer the phosphoric acid that weight part is 2% simultaneously, add the lactic acid of 3% and the acetic acid of 2%, continue stir 5min; Adding weight part is the SODIUMNITRATE of 7% and the Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES of 5%; Weight part is the Neutral ammonium fluoride of 10%; Weight part is the chromium sulphate of 30%, continues to stir 20min; Add the wetting agent 104PA that weight part is 2%, surplus pure water is supplied, and stirs.
embodiment 6:
raw material is made up of following substances in percentage by weight:
chromium nitrate 25%,
saltpetre 6%,
jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 5%,
phosphoric acid 2%,
lactic acid 3%,
oxalic acid 1%,
hydrofluotitanic acid 8%,
104PA 1%，
water 49%;
wherein phosphoric acid concentration is 75%, and hydrofluotitanic acid concentration is 50%, and lactic acid concn is 88%.
preparation method is: take weight part be 40% pure water add at moderate-speed mixer the phosphoric acid that weight part is 2% simultaneously, add the lactic acid of 3% and the oxalic acid of 1%, continue stir 5min; Adding weight part is the saltpetre of 6% and the Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES of 5%; Weight part is the hydrofluotitanic acid of 8%; Weight part is the chromium nitrate of 25%, continues to stir 20min; Add the wetting agent 104PA that weight part is 1%, surplus pure water is supplied, and stirs.
embodiment 7:
raw material is made up of following substances in percentage by weight:
chromium nitrate 35%,
sODIUMNITRATE 6%,
jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 5%,
sodium phosphate dibasic 15%,
lactic acid 3%,
citric acid 1%,
neutral ammonium fluoride 8%,
104PA 2%，
water 25%;
wherein lactic acid concn is 88%.
preparation method is: take weight part be 20% pure water add at moderate-speed mixer the Sodium phosphate dibasic that weight part is 15% simultaneously, add the lactic acid of 3% and the citric acid of 1%, continue stir 5min; Adding weight part is the SODIUMNITRATE of 6% and the Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES of 5%; Weight part is the Neutral ammonium fluoride of 8%; Weight part is the chromium nitrate of 35%, continues to stir 20min; Add the wetting agent 104PA that weight part is 2%, surplus pure water is supplied, and stirs.
embodiment 8:
raw material is made up of following substances in percentage by weight:
chromium sulphate 20%,
sODIUMNITRATE 7%,
jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 5%,
dipotassium hydrogen phosphate 12%,
lactic acid 5%,
acetic acid 4%,
neutral ammonium fluoride 10%,
104PA 1%，
water 36%;
wherein chromium sulphate concentration is 40%, and lactic acid concn is 88%, and acetate concentration is 99.8%.
preparation method is: take weight part be 30% pure water add at moderate-speed mixer the dipotassium hydrogen phosphate that weight part is 12% simultaneously, add the lactic acid of 5% and the acetic acid of 4%, continue stir 5min; Adding weight part is the SODIUMNITRATE of 7% and the Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES of 5%; Weight part is the Neutral ammonium fluoride of 10%; Weight part is the chromium sulphate of 20%, continues to stir 20min; Add the wetting agent 104PA that weight part is 1%, surplus pure water is supplied, and stirs.
obtained by the embodiment of the present invention for the quick processed continuously roller coat passivator of surface of steel plate, by zinc-plated sheet material through degreasing, washing, after drying and processing, Inactivation experiment is carried out by above eight embodiment proportioning roller coating machines by the present invention, its wet-heat resisting, color inhibition ⊿ E is all less than the 1.5(industry standard Re of Nai Shi ⊿ E≤5, the Bian of Nai Huang ⊿ E≤3); Surface resistivity electroconductibility is less than 0.09mΩ
(industry standard≤0.1 m Ω); Resistance to boiling water is good, and solvent resistance is good, and coating is excellent, and salt spray resistance reaches more than 200h.
Claims (1)
1., for a trivalent chromium passivator for surface of steel plate fast filming, it is characterized in that being made up of following substances in percentage by weight:
The main salt 5 ~ 40% of trivalent chromium,
Non-master salt nitrate 5 ~ 20%,
Phosphoric acid salt or phosphatase 11 ~ 25%,
Organic acid 1 ~ 10%,
Sequestrant 1 ~ 10%,
Tensio-active agent 1 ~ 5%,
Water 20 ~ 65%;
Wherein, chromic salt is chromium sulphate or chromium nitrate; Non-master salt nitrate is SODIUMNITRATE, saltpetre, 1 ~ 2 kind in Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES; Phosphoric acid salt is sodium phosphate, potassiumphosphate, Sodium phosphate dibasic, 1 ~ 2 kind in dipotassium hydrogen phosphate or from price consider select phosphoric acid; Sequestrant is 1 ~ 2 kind in Neutral ammonium fluoride, hydrofluotitanic acid, fluorine zirconic acid; Organic acid is lactic acid, acetic acid, oxalic acid, more than a kind or 2 kinds in citric acid; Tensio-active agent is wetting agent 104PA;
This passivator is used for the quick processed continuously roller coat of surface of steel plate.
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| CN201310094638.1A CN103215582B (en) | 2013-03-25 | 2013-03-25 | Trivalent chromium passivating agent used for rapid film formation on steel plate surface |
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| CN103695889B (en) * | 2014-01-08 | 2016-02-10 | 安徽工业大学 | A kind of chromium-free passivation liquid for galvanized sheet, aluminium and copper alloy surface process |
Citations (4)
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|---|---|---|---|---|
| US4578122A (en) * | 1984-11-14 | 1986-03-25 | Omi International Corporation | Non-peroxide trivalent chromium passivate composition and process |
| CN102041497A (en) * | 2009-10-13 | 2011-05-04 | 北京中科三环高技术股份有限公司 | Trivalent-chromium blue-white passivator for zinc-plated permanent magnetic material and passivation method 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 |
| CN102330082A (en) * | 2010-07-13 | 2012-01-25 | 伟业重工(安徽)有限公司 | Trivalent chromium passivation concentrated solution |
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2013
- 2013-03-25 CN CN201310094638.1A patent/CN103215582B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4578122A (en) * | 1984-11-14 | 1986-03-25 | Omi International Corporation | Non-peroxide trivalent chromium passivate composition and process |
| CN102041497A (en) * | 2009-10-13 | 2011-05-04 | 北京中科三环高技术股份有限公司 | Trivalent-chromium blue-white passivator for zinc-plated permanent magnetic material and passivation method thereof |
| CN102330082A (en) * | 2010-07-13 | 2012-01-25 | 伟业重工(安徽)有限公司 | Trivalent chromium passivation concentrated solution |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 无铬钝化与三价铬钝化的研究进展;于元春等;《表面技术》;20051031;第34卷(第5期);6-9 * |
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