CN107400883B - Silane/zirconium composite treating agent and preparation method thereof before galvanized sheet coating - Google Patents
Silane/zirconium composite treating agent and preparation method thereof before galvanized sheet coating Download PDFInfo
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- CN107400883B CN107400883B CN201710657481.7A CN201710657481A CN107400883B CN 107400883 B CN107400883 B CN 107400883B CN 201710657481 A CN201710657481 A CN 201710657481A CN 107400883 B CN107400883 B CN 107400883B
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- silane
- treating agent
- zirconium
- galvanized sheet
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- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
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- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8
-
- 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
- C23C2222/20—Use of solutions containing silanes
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
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- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
The invention discloses silane/zirconium composite treating agents before a kind of galvanized sheet coating and preparation method thereof, the composite treating agent is mainly made of silane, zirconium fluoro complex, zirconate, rare earth cerium salt, pure and mild deionized water etc., the composite treating agent is prepared using the method for chemical compounding, and manufactured composite treating agent can be applied to the surface treatment of the chemical conversion before galvanized sheet coating.The composite treating agent has the characteristics that the environmentally friendly of without phosphorus Chrome-free, can room temperature handle galvanized sheet, be not necessarily to heating and energy saving energy consumption, the advantages that silane complex film layer of acquisition is fine and close, and anti-corrosion protective performance is good, alternative phosphorization treatment process technology excellent with organic coating binding performance.
Description
Technical field
The present invention relates to the technical field of surface before galvanized sheet coating, silane before especially a kind of galvanized sheet coating/
Zirconium composite treating agent and preparation method thereof.
Technical background
Galvanized sheet is prolonged its service life to prevent surface of steel plate from being corroded, and is coated with one layer of gold in surface of steel plate plating
Belong to zinc, the sheet metal of this plating zinc coating is known as galvanized sheet, corrosion feelings occurs in its surface in use, storage and transport process in order to prevent
Condition, zinc-plated plate surface need to be passivated processing, and traditional chromating can be freely from passivating film due to water soluble hexavalent chromium
Passivation again is played in middle dissolution, ensure that the self-reparing capability of passivating film, makes it have superior corrosion resistance, can be due to six
The extremely strong carcinogenicity of valence chromium and environmental hazard, use are more and more severely limited.Develop non-chromium inactivating technique technology
It has been to be concerned by more and more people.Although having various chromium-free deactivation technologies at present, can chromium-free deactivation technology there are still many defects,
Or (no self-repair function) corrosion resistance is poor or treatment process applicability limited (mostly spray process) or with high costs is difficult to reach
To application requirement.
Summary of the invention
Against the above technical problems, the purpose of the present invention is to provide silane/zirconium combined processings before a kind of galvanized sheet coating
Agent and preparation method thereof.Silane and inorganic zirconium, organic zirconium is set to carry out collaboration conversion in zinc-plated plate surface and form a film, formation strong cross-linking,
High performance composite membrane, and by the cerium modified composite membrane of rare earth, make film layer that there are self-healing properties, improves naked film corrosion resistance.This
Inventive technique scheme is specific as follows:
The present invention discloses silane/zirconium composite treating agent preparation method before a kind of galvanized sheet coating first, described zinc-plated
The mass percent of silane/zirconium composite treating agent constitutive material each component before plate coating are as follows:
Silane/zirconium composite treating agent preparation method includes the following steps: before the galvanized sheet coating
(1) 80-90% of water inventory needed for being added in reaction kettle opens reaction kettle and is stirred；
(2) zirconium fluoro complex is added in reaction kettle, stirring evenly is thoroughly mixed it；
(3) mixture of silane and alcohol is slowly added in reaction kettle, stirring dissolves it thoroughly；
(4) mixture of zirconate and alcohol is slowly added in reaction kettle, stirring evenly is thoroughly mixed it；
(5) stop stirring, stand 24 hours or more after the suspended matter, particulate matter in circulating filtration removing reaction kettle until molten
Liquid clear stable；
(6) cerium salt is added in reaction kettle, stirring evenly is thoroughly mixed it；
(7) excess water is finally supplied, is stirred evenly after being thoroughly mixed it up to composite treating agent.
Preferably, the silane monomer general formula indicates are as follows:
R(4-n)-Si-(OR’)n, wherein n=1,2,3；
The group that R is indicated is hydrogen, alkyl, amino, epoxy group, vinyl, urea groups or isocyanate group；The group that OR ' is indicated
For methoxyl group, ethyoxyl or acetoxyl group；
The silane is one of monomer or its oligomer or a variety of, and the degree of polymerization of the oligomer is 2-20.
Preferably, the zirconium fluoro complex is selected from one of fluorine zirconic acid and its salt or a variety of.
Preferably, the zirconate is selected from bis- (lemon diethyl phthalate) dipropoxy zirconium chelates, zirconates lactate
One of chelate, triethanolamine zirconium chelate, triethanolamine polyalcohol zirconium chelate, acetylacetone,2,4-pentanedione zirconium are a variety of.
Preferably, the cerium salt in ceric nitrate, cerous nitrate, ammonium ceric nitrate, ceric sulfate, cerous acetate one
Kind is a variety of.
Preferably, the alcohol is selected from one of ethyl alcohol, isopropanol, propylene glycol, glycerine or a variety of.
Preferably, the alcohol that the step (3) is added accounts for the 60-80% of alcohol total amount；What the step (4) was added
Alcohol is the alcohol of step (3) surplus afterwards.
The invention also discloses silane/zirconium composite treating agents before a kind of galvanized sheet coating that the above method is prepared.
Compared with existing galvanized sheet Coating Pretreatment technology, silane/zirconium composite treating agent and preparation side before galvanized sheet coating
Method has several advantages that (1) without phosphorus Chrome-free unharmful substance, and environmental protection is reliable；(2) normal-temperature operation saves energy without heating
Source；(3) processing mode compatibility is strong, is applicable in spray or impregnation technology；(4) before the galvanized sheet coating that preparation method of the present invention obtains
The composite film densification corrosion resistance of silane/zirconium composite treating agent superior performance, acquisition is good, is combined with organic coating, coating is resistance to
Neutral salt spray test is excellent.
Specific embodiment
The invention discloses silane/zirconium composite treating agent preparation method before a kind of galvanized sheet coating, the galvanized sheet is applied
The mass percent of the constitutive material each component of silane/zirconium composite treating agent before filling are as follows:
Silane/zirconium composite treating agent preparation method includes the following steps: before the galvanized sheet coating
(1) 80-90% of water inventory needed for being added in reaction kettle opens reaction kettle and is stirred；
(2) zirconium fluoro complex is added in reaction kettle, stirring evenly is thoroughly mixed it；
(3) mixture of silane and alcohol is slowly added in reaction kettle, stirring dissolves it thoroughly；
(4) mixture of zirconate and alcohol is slowly added in reaction kettle, stirring evenly is thoroughly mixed it；
(5) stop stirring, stand 24 hours or more after the suspended matter, particulate matter in circulating filtration removing reaction kettle until molten
Liquid clear stable；
(6) cerium salt is added in reaction kettle, stirring evenly is thoroughly mixed it；
(7) excess water is finally supplied, is stirred evenly after being thoroughly mixed it up to composite treating agent.
Preferably, the silane monomer general formula indicates are as follows:
R(4-n)-Si-(OR’)n, wherein n=1,2,3；
The group that R is indicated is hydrogen, alkyl, amino, epoxy group, vinyl, urea groups or isocyanate group；The group that OR ' is indicated
For methoxyl group, ethyoxyl or acetoxyl group；
The silane is one of monomer or its oligomer or a variety of, and the degree of polymerization of the oligomer is 2-20.
Preferably, the zirconium fluoro complex is selected from one of fluorine zirconic acid and its salt or a variety of.
Preferably, the zirconate is selected from bis- (lemon diethyl phthalate) dipropoxy zirconium chelates, zirconates lactate
One of chelate, triethanolamine zirconium chelate, triethanolamine polyalcohol zirconium chelate, acetylacetone,2,4-pentanedione zirconium are a variety of.
Preferably, the cerium salt in ceric nitrate, cerous nitrate, ammonium ceric nitrate, ceric sulfate, cerous acetate one
Kind is a variety of.
Preferably, the alcohol is selected from one of ethyl alcohol, isopropanol, propylene glycol, glycerine or a variety of.
Preferably, the alcohol that the step (3) is added accounts for the 60-80% of alcohol total amount；What the step (4) was added
Alcohol is the alcohol of step (3) surplus afterwards.
Below with reference to embodiment, the present invention will be further described.
Embodiment 1:
Silane/zirconium composite treating agent constitutive material each component mass percent before the galvanized sheet coating of the present embodiment are as follows:
Preparation method includes the following steps:
(1) 80% of water inventory needed for being added in reaction kettle is opened reaction kettle and is stirred；
(2) fluorine zirconic acid is added in reaction kettle, stirring evenly is thoroughly mixed it；
(3) it is slowly added to propyl trimethoxy silicane and isopropanol mixture (70% isopropanol) in reaction kettle, stirs
Dissolve it thoroughly；
(4) bis- (lemon diethyl phthalate) dipropoxy zirconium chelates and isopropanol mixture are slowly added in reaction kettle
(30% isopropanol), stirring dissolve it thoroughly；
(5) stop stirring, stand 24 hours or more after the suspended matter, particulate matter in circulating filtration removing reaction kettle until molten
Liquid clear stable；
(6) cerous nitrate is added in reaction kettle, stirring evenly is thoroughly mixed it；
(7) excess water is finally supplied, is stirred evenly after being thoroughly mixed it up to composite treating agent.
The composite treating agent carries out galvanized sheet impregnation 5 minutes, epoxy powder spraying is carried out after drying, and
It is tested for the property.
Embodiment 2:
Silane/zirconium composite treating agent constitutive material each component mass percent before the galvanized sheet coating of the present embodiment are as follows:
The preparation method is the same as that of Example 1 for the galvanized sheet composite treating agent.
The composite treating agent carries out galvanized sheet spray process 2 minutes, water-based acrylic resin is sprayed after drying,
And it is tested for the property.
Embodiment 3:
Silane/zirconium composite treating agent constitutive material each component mass percent before the galvanized sheet coating of the present embodiment are as follows:
The preparation method is the same as that of Example 1 for the galvanized sheet silane composite treating agent.
The composite treating agent carries out galvanized sheet spray process 1.5 minutes, cathode electro-coating is carried out after drying,
And it is tested for the property.
Comparative example 1:
Cerous nitrate and the polynary alcohol zirconium chelating of triethanolamine will be removed in composite treating agent constitutive material described in embodiment 3
After object, galvanized sheet is carried out spray process 1.5 minutes, cathode electro-coating is carried out after drying, and be tested for the property.
Comparative example 2:
Certain ternary zinc series phosphating agent carries out galvanized sheet spray process 1.5 minutes, paint spraying is carried out after drying,
And it is tested for the property.
Composite membrane and its coating performance test result to zinc-plated plate surface show every physics and chemistry of the composite membrane
It can all be significantly improved, each Testing index is equivalent to even better than ternary Zinc phosphating processing.
Composite membrane and its coating performance test result to zinc-plated plate surface are shown in Table 1.
Table 1: the composite membrane and its coating performance test result of zinc-plated plate surface prepared by the present invention
* after soak test in coat side without peeling be bubbled and corrode phenomena such as；Without peeling drum in coat side after salt spray test
Phenomena such as bubble and draw unilateral corrosion diffusion breadth≤2mm along fork be by maximum test hourage.
Composite treating agent and its formed in zinc-plated plate surface prepared by embodiment and comparative example synthetic proof the technology of the present invention
Compound conversion film have good compactness corrosion resistance, in conjunction with organic coating number, properties are excellent, alternative phosphatization
Treatment process technology, the large-scale production applied to galvanized sheet Coating Pretreatment.
Claims (6)
1. silane/zirconium composite treating agent preparation method before a kind of galvanized sheet coating, it is characterised in that: before the galvanized sheet coating
The mass percent of silane/zirconium composite treating agent constitutive material each component are as follows:
The zirconate is selected from bis- (lemon diethyl phthalate) dipropoxy zirconium chelates, zirconates lactate chelate, three second
One of hydramine zirconium chelate, triethanolamine polyalcohol zirconium chelate, acetylacetone,2,4-pentanedione zirconium are a variety of；
The cerium salt is selected from one of ceric nitrate, cerous nitrate, ammonium ceric nitrate, ceric sulfate, cerous acetate or a variety of；
Silane/zirconium composite treating agent preparation method includes the following steps: before the galvanized sheet coating
(1) 80-90% of water inventory needed for being added in reaction kettle opens reaction kettle and is stirred；
(2) zirconium fluoro complex is added in reaction kettle, stirring evenly is thoroughly mixed it；
(3) mixture of silane and alcohol is slowly added in reaction kettle, stirring dissolves it thoroughly；
(4) mixture of zirconate and alcohol is slowly added in reaction kettle, stirring evenly is thoroughly mixed it；
(5) stop stirring, stand 24 hours or more after the suspended matter, particulate matter in circulating filtration removing reaction kettle until solution is clear
It is clear to stablize；
(6) cerium salt is added in reaction kettle, stirring evenly is thoroughly mixed it；
(7) excess water is finally supplied, is stirred evenly after being thoroughly mixed it up to composite treating agent.
2. silane/zirconium composite treating agent preparation method before galvanized sheet coating as described in claim 1, it is characterised in that described
Silane monomer general formula indicate are as follows:
R(4-n)-Si-(OR’)n, wherein n=1,2,3；
The group that R is indicated is hydrogen, alkyl, amino, epoxy group, vinyl, urea groups or isocyanate group；The group that OR ' is indicated is first
Oxygroup, ethyoxyl or acetoxyl group；
The silane is one of monomer or its oligomer or a variety of, and the degree of polymerization of the oligomer is 2-20.
3. silane/zirconium composite treating agent preparation method before galvanized sheet coating as described in claim 1, it is characterised in that described
Zirconium fluoro complex be selected from one of fluorine zirconic acid and its salt or a variety of.
4. silane/zirconium composite treating agent preparation method before galvanized sheet coating as described in claim 1, it is characterised in that described
Alcohol be selected from one of ethyl alcohol, isopropanol, propylene glycol, glycerine or a variety of.
5. silane/zirconium composite treating agent preparation method before galvanized sheet coating as described in claim 1, it is characterised in that described
The step of (3) alcohol for being added account for the 60-80% of alcohol total amount；The alcohol that the step (4) is added is step (3) surplus afterwards
Alcohol.
6. silane/zirconium composite treating agent before a kind of galvanized sheet coating that method as described in claim 1 is prepared.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710657481.7A CN107400883B (en) | 2017-08-03 | 2017-08-03 | Silane/zirconium composite treating agent and preparation method thereof before galvanized sheet coating |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710657481.7A CN107400883B (en) | 2017-08-03 | 2017-08-03 | Silane/zirconium composite treating agent and preparation method thereof before galvanized sheet coating |
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| CN107400883B true CN107400883B (en) | 2019-08-27 |
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| CN109680271A (en) * | 2018-12-29 | 2019-04-26 | 三一重机有限公司 | The method and hydraulic steel pipe of hydraulic steel pipe anti-corrosion treatment |
| CN111304641A (en) * | 2020-02-21 | 2020-06-19 | 攀钢集团攀枝花钢铁研究院有限公司 | Hot-dip aluminum-zinc plate chromium-free passivation solution and preparation method of hot-dip aluminum-zinc fingerprint-resistant plate |
Citations (4)
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|---|---|---|---|---|
| CN1918248A (en) * | 2004-02-11 | 2007-02-21 | 达克莱公司 | Anticorrosion coating composition in aqueous dispersion comprising an organic titanate and/or zirconate |
| EP1887105A1 (en) * | 2006-08-08 | 2008-02-13 | The Boeing Company | Chromium-free conversion coating |
| CN103074621A (en) * | 2012-08-29 | 2013-05-01 | 华南理工大学 | Environmental-protection cold-rolled steel surface coating pretreatment agent and preparation method thereof |
| CN105149192A (en) * | 2015-09-12 | 2015-12-16 | 杭州萧山金润表面活性材料厂 | Metal surface coating process |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1918248A (en) * | 2004-02-11 | 2007-02-21 | 达克莱公司 | Anticorrosion coating composition in aqueous dispersion comprising an organic titanate and/or zirconate |
| EP1887105A1 (en) * | 2006-08-08 | 2008-02-13 | The Boeing Company | Chromium-free conversion coating |
| CN103074621A (en) * | 2012-08-29 | 2013-05-01 | 华南理工大学 | Environmental-protection cold-rolled steel surface coating pretreatment agent and preparation method thereof |
| CN105149192A (en) * | 2015-09-12 | 2015-12-16 | 杭州萧山金润表面活性材料厂 | Metal surface coating process |
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