CN114717543A - Preparation method of composition for improving salt spray resistance of coating after iron and steel non-phosphorus conversion treatment - Google Patents
Preparation method of composition for improving salt spray resistance of coating after iron and steel non-phosphorus conversion treatment Download PDFInfo
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- CN114717543A CN114717543A CN202210239853.5A CN202210239853A CN114717543A CN 114717543 A CN114717543 A CN 114717543A CN 202210239853 A CN202210239853 A CN 202210239853A CN 114717543 A CN114717543 A CN 114717543A
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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
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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
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
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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
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The invention discloses a preparation method of a composition for improving salt spray resistance of a coating after steel phosphorus-free conversion treatment, which comprises the following steps: preparing the following components of S1 modified tannin extract according to the mass portion; s2 preparation of the composition for improving the salt spray resistance of the coating after the non-phosphorus conversion treatment of steel, the composition comprises the following components in parts by mass: 20-40 parts of tannin extract modified substances, 2-5 parts of polyhydroxy dispersion liquid, 3-8 parts of alkyl silane coupling agents, 3-8 parts of organic metal ester coupling agents and 5-15 parts of alcohol ether cosolvent in S1, wherein the total mass part of the composition is 100 parts, and the balance is deionized water. Compared with the prior art, the preparation method of the composition for improving the salt spray resistance of the coating after the phosphorus-free conversion treatment of steel has the following beneficial effects: the salt spray performance of the coating after the steel phosphorus-free conversion treatment is obviously improved, the treatment fluid can remove rust and form a film at the same time, and does not contain harmful substances such as phosphorus, chromium and the like, the chemical composition of the treatment fluid is stable, and the treatment quality is reliable.
Description
Technical Field
The invention relates to the technical field of surface treatment, in particular to a preparation method of a composition for improving salt spray resistance of a coating after steel phosphorus-free conversion treatment.
Background
For a long time, the phosphating process is the first choice pretreatment process in the field of steel coating and has wide application in the aspects of automobiles, household appliances, buildings, office appliances and the like.
After the phosphating film is matched with paints, powder coatings, electrophoretic coatings and the like to form coatings, the corrosion resistance requirement can be effectively met, and the corrosion resistance of the composite coating is generally evaluated according to the result of a neutral salt spray test. For example, the single-sided corrosion expansion of the scratched part of a composite coating formed by a phosphating film and an epoxy-polyester powder coating is less than 2mm after 500-hour neutral salt spray test after scratching. However, the phosphating process contains phosphorus and heavy metals, which are harmful to the environment and human health. Therefore, in recent years, the conventional highly contaminated pretreatment process has been increasingly restricted. At present, the most mature phosphorus-free pretreatment technology for replacing the phosphating process is a zirconium/silane process, and the coating performance of the zirconium/silane pretreatment technology is basically equivalent to that of phosphating. However, compared with the phosphorization, the phosphorus-free conversion coating has obvious defects, because the film thickness of the phosphorus-free conversion coating is very thin (20 mg/square meter to 200 mg/square meter), the corrosion resistance of the film layer is relatively poor, and the neutral salt fog resistance of the coating formed by matching with paint, powder coating, electrophoretic coating and the like is difficult to meet the requirement, the phosphorus-free conversion process is limited in the application and popularization process.
In the prior art, the following technical problems exist: 1. the film thickness of the phosphorus-free conversion film is very thin (20 mg/square meter to 200 mg/square meter), and the corrosion resistance of the film layer is relatively poor; 2. the relatively thin film layer makes the neutral salt fog resistance of the coating formed by matching with paint, powder coating, electrophoretic coating and the like difficult to meet the requirement.
Disclosure of Invention
The invention aims to provide a preparation method of a composition for improving the salt spray resistance of a coating after steel phosphorus-free conversion treatment, which not only has good corrosion resistance of a conversion film, but also further reduces the treatment of waste water, and is phosphorus-free and chromium-free and environment-friendly.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the preparation method of the composition for improving the salt spray resistance of the coating after the phosphorus-free conversion treatment of the steel comprises the following steps: the following components are all in parts by mass
Preparation of S1 modified tannin extract
Dissolving 30 parts by mass of condensed tannin extract in 50-65 parts by mass of deionized water, filtering to remove insoluble substances, heating to about 50-90 ℃, adding 2.4-5.0 parts by mass of organic amine, slowly adding 3.0-6.0 parts by mass of formaldehyde solution, keeping the temperature for reaction for 1.5-3 hours, and supplementing water to 100 parts by mass;
s2 preparation of composition for improving salt spray resistance of coating after steel phosphorus-free conversion treatment
The composition comprises the following components in parts by mass: 20-40 parts of S1 tannin extract modified substance, 2-5 parts of polyhydroxy dispersion liquid, 3-8 parts of alkyl silane coupling agent, 3-8 parts of organic metal ester coupling agent and 5-15 parts of alcohol ether cosolvent, wherein the total mass part of the composition is 100 parts, and the balance is deionized water.
As a further improvement of the scheme, the organic amine in S1 is any one or more of triethanolamine, dimethylamine, hydroxyethyl ethylenediamine, acrylamide and meglumine.
As a further improvement of the scheme, the condensed tannin extract is any one or more of quebracho tannin extract, bayberry tannin extract, emblic leafflower tannin extract and acacia tannin extract.
As a further improvement of the scheme, the polyhydroxy dispersion liquid is nano silicon dioxide aqueous dispersion liquid.
As a further improvement of the scheme, the alkyl silane coupling agent is alkyl alkoxy silane Rm-Si-(OR’)nWherein R is a linear saturated alkyl group having a carbon number of not more than 4, OR' is an ethoxy group OR a methoxy group, for example: dimethyldiethoxysilane, diethoxydimethylsilane, propyltrimethoxysilane and the like
As a further improvement of the scheme, the organic metal ester coupling agent is di (triethanolamine) diisopropyl titanate.
As a further improvement of the scheme, the alcohol ether cosolvent is a low-carbon alcohol ether of ethylene glycol and propylene glycol, such as dipropylene glycol butyl ether, dipropylene glycol methyl ether, ethylene glycol butyl ether and diethylene glycol methyl ether.
The preparation method of the composition for improving the salt spray resistance of the coating after the phosphorus-free conversion treatment of the steel has the following beneficial effects:
1) the salt spray resistance of the coating after the phosphorus-free conversion of the steel can be obviously enhanced by combining the composition with a treatment process, and the specific treatment mode can be that the composition is added into phosphorus-free conversion treatment liquid according to a certain proportion to assist in treating and forming a film, or the steel is treated by the water solution of the composition after the phosphorus-free conversion treatment;
2) the quality of the adhesive force has great relevance to the corrosion resistance of the coated metal, the adhesive force of a coating film in a salt spray environment is improved, or the attenuation speed of the adhesive force in the salt spray environment is reduced, and the salt spray resistance of the composite coating after the non-phosphorus conversion treatment is improved. After the composition is used for treating the synergistic phosphorus-free conversion coating, the adhesion between the iron and steel phosphorus-free conversion coating and the coating can be improved, and the salt spray resistance of the coating can also be improved;
3) during the salt spray test, salt spray can form a salt water permeable coating on the surface of a workpiece to reach a metal/coating interface, a de-bonding effect can be generated, the salt water can diffuse at the metal/coating interface, and the salt water reacts with steel to generate corrosion. After the composition acts, lipophilic alkyl in the short-chain alkyl silane is doped in the composite film layer, so that the lipophilic hydrophobicity of the metal interface phosphorus-free conversion film can be increased; moreover, the salt spray test can reduce the amount of salt water entering the metal/coating interface, and the salt water solution can reduce the speed of penetrating through the film to reach the metal surface after entering the metal/coating interface;
4) because the steel surface has metallographic structure defects, a complete phosphorus-free conversion film layer cannot be formed, a non-adhesion area exists between metal and a coating, the phosphorus-free conversion film layer is an amorphous film layer and always has defects such as cracks, and the composition can form a non-hydrolytic high molecular weight polymer film layer after being added or used, so that the defects of the phosphorus-free conversion film layer and the non-adhesion area between the metal and the coating are reduced, the further diffusion of a saline solution to a metal interface is prevented, the metal is corroded, the difficult-hydrolytic characteristic of the composition can also prevent the film layer from being hydrolyzed and damaged by the saline solution, and the saline solution resistance is improved;
5) unlike the hydrolyzed tannic acid prepared with gallnut and other extractive, the condensed tannin extract consists of mainly condensed tannin, and the complex condensate of flavanol and other compound with C-C bond is hard to decompose in water solution;
the condensed tannin and polyphenol structure can be combined with hydroxyl, carboxyl and other groups in the coating, can also be combined with metal ions, has amphiphilic coupling effect, and provides good adhesive force for a coating and a metal matrix. However, the tannin extract belongs to natural products, has relatively large molecular weight and has a small amount of water-insoluble components. It is necessary to perform amination modification to improve water solubility and also to improve the ability to bind to metals. The modified condensed tannin is firmly combined with iron, and simultaneously plays a role in preventing corrosive media from corroding steel and can also slow down the diffusion of iron ions. The active phenolic hydroxyl groups, particularly the ortho phenolic hydroxyl groups, which are not bonded to groups such as metal oxides, hydroxyl groups in the coating, and the like, can preferentially react with oxygen penetrating into the coating, and have good oxidation resistance until corrosion is retarded.
The modification of the condensed tannin extract is as follows:
6) the titanium dioxide doped film formed after the organic titanium coupling agent is hydrolyzed has excellent corrosion resistance, can fill the defect of a phosphorus-free conversion film, and simultaneously participates in forming a macromolecular polymer film together with a silane coupling agent hydrolysate to optimize the corrosion resistance of the composite film; the silane coupling agent and the organic metal ester coupling agent can form cross-linking with-OH or-COOH groups in the coating and form covalent bonds with metals, and the synergistic tannin extract provides excellent binding force for the metal-coating. For example, the following is shown:
7) the polyhydroxy inorganic dispersion can not only fill the gaps of the condensed tannin, but also provide a large amount of hydroxyl groups to combine with the modified condensed tannin to form a cross-linked polymer film. The silane coupling agent provided by the invention has C1-C4 short-chain alkyl, silanol with the short-chain alkyl is formed after hydrolysis, certain hydrophobicity is realized, and after the silane coupling agent is combined with condensed tannin, the silane coupling agent has the performance of preventing saline contact or infiltration. Partial titanate forms titanium dioxide gel after hydrolysis, so that the film contains a certain amount of titanium dioxide, and the salt spray resistance of the composite film is improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more clear, the present invention is further described below with reference to examples a to f:
the preparation method of the composition for improving the salt spray resistance of the coating after the phosphorus-free conversion treatment of the steel comprises the following steps: the following components are all in parts by mass
Preparation of S1 modified tannin extract
Dissolving 30 parts by mass of condensed tannin extract in 50-65 parts by mass of deionized water, filtering to remove insoluble substances, heating to about 50-90 ℃, adding 2.4-5.0 parts by mass of organic amine, slowly adding 3.0-6.0 parts by mass of formaldehyde solution, keeping the temperature for reaction for 1.5-3 hours, and supplementing water to 100 parts by mass;
s2 preparation of composition for improving salt spray resistance of coating after steel phosphorus-free conversion treatment
The composition comprises the following components in parts by mass: 20-40 parts of S1 tannin extract modifier, 2-5 parts of polyhydroxy dispersion liquid, 3-8 parts of alkyl silane coupling agent, 3-8 parts of organic metal ester coupling agent and 5-15 parts of alcohol ether cosolvent, wherein the total mass part of the composition is 100 parts, and the balance is deionized water.
As a further improvement of the scheme, the organic amine in S1 is any one or more of triethanolamine, dimethylamine, hydroxyethyl ethylenediamine, acrylamide and meglumine.
As a further improvement of the scheme, the condensed tannin extract is any one or more of quebracho tannin extract, bayberry tannin extract, emblic leafflower tannin extract and acacia tannin extract.
As a further improvement of the scheme, the polyhydroxy dispersion liquid is nano silicon dioxide aqueous dispersion liquid.
As a further improvement of the scheme, the alkyl silane coupling agent is alkyl alkoxy silane Rm-Si-(OR’)nWherein R is a linear saturated alkyl group having a carbon number of not more than 4, OR' is an ethoxy group OR a methoxy group, for example: dimethyldiethoxysilane, diethoxydimethylsilane, propyltrimethoxysilane and the like
As a further improvement of the scheme, the organic metal ester coupling agent is di (triethanolamine) diisopropyl titanate.
As a further improvement of the scheme, the alcohol ether cosolvent is a low-carbon alcohol ether of ethylene glycol and propylene glycol, such as dipropylene glycol butyl ether, dipropylene glycol methyl ether, ethylene glycol butyl ether and diethylene glycol methyl ether.
Example 1
Modified product of S1
S2 composition
Example 2
S1
S2 composition
Example 3
S1
S2 composition
Comparative example 1
In the prior art, the non-phosphorus conversion film treatment process comprises the following steps:
1) degreasing and deoiling: thoroughly cleaning the steel with an alkaline cleaning agent;
2) rinsing with water: cleaning the residual cleaning agent on the surface of the steel, wherein the surface is completely soaked by water;
3) treating a phosphorus-free conversion film: preparing a phosphorus-free conversion aqueous solution according to the process formula in the blank treatment 1 in the table 3, wherein the pH value is 3.8-4.2, the temperature is normal temperature, and the treatment time is as follows: 1.5min, the treatment mode is spraying.
4) Rinsing with water: cleaning the treatment liquid residue on the surface of the steel or in the gaps of the structural member;
5) drying: drying with hot air at 80-120 deg.C.
Comparative example 2
In the prior art, the non-phosphorus conversion film treatment process comprises the following steps:
1) degreasing and deoiling: thoroughly cleaning the steel with an alkaline cleaning agent;
2) rinsing with water: cleaning the residual cleaning agent on the surface of the steel, wherein the surface is completely soaked by water;
3) treating a phosphorus-free conversion film: preparing a phosphorus-free conversion aqueous solution according to the process formula in the blank treatment 2 in the table 4, wherein the pH value is 3.8-4.5, the temperature is normal temperature, and the treatment time is as follows: for 2min, the treatment method is soaking.
4) Rinsing with water: cleaning the treatment liquid residue on the surface of the steel or in the gaps of the structural member;
5) drying: drying with hot air at 80-120 deg.C.
Table 3: the performance of the coating after synergistic treatment in example 1 was compared with the performance of the coating after treatment in the manner of treatment in comparative example 1
Table 4: the performance of the coatings of examples 2 and 3 after synergistic treatment is compared with that of comparative example 2 after treatment in the treatment mode
From table 3 the NASS test results of example 1 and comparative example blank treatment 1, and the NASS test results of example 2, example 3 and comparative example blank treatment 2 of table 4, it can be seen that: after the treatment of the composition, the salt spray performance of the coating after the steel phosphorus-free conversion treatment is obviously improved, and more customer requirements can be met; moreover, the treatment liquid can remove rust and form a film at the same time, has multiple functions and wide application range, and does not contain harmful substances such as phosphorus, chromium and the like; the operation and use are simple and convenient, the application range of parameter indexes is wide, the chemical composition of the treatment solution is stable, and the treatment quality is reliable;
after the composition is used for treating the synergistic phosphorus-free conversion coating, the adhesion between the iron and steel phosphorus-free conversion coating and the coating can be improved, and the salt spray resistance of the coating can also be improved; after the composition acts, lipophilic alkyl in the short-chain alkyl silane is doped in the composite film layer, so that the lipophilic hydrophobicity of the metal interface phosphorus-free conversion film can be increased; moreover, the salt spray test can reduce the amount of salt water entering the metal/coating interface, and the salt water solution can reduce the speed of penetrating through the film to reach the metal surface after entering the metal/coating interface;
because the steel surface has metallographic structure defect, a complete phosphorus-free conversion film layer can not be formed, a non-adhesion area exists between metal and a coating, the phosphorus-free conversion film layer is an amorphous film layer and often has defects such as cracks, and the composition can form a non-hydrolytic high molecular weight polymer film layer after being added or used, thereby being beneficial to reducing the defects of the phosphorus-free conversion film layer and the non-adhesion area between the metal and the coating, being beneficial to preventing a saline solution from further diffusing to a metal interface to corrode the metal, and preventing the film layer from being hydrolyzed and damaged by the saline solution due to the characteristic of difficult hydrolysis of the composition, so that the saline resistance is improved;
the condensed tannin extract is mainly composed of condensed tannin, complex polycondensates formed by combining compounds such as flavanol and the like with C-C bonds as main bonds are difficult to decompose in aqueous solution, and an intermediate film layer between metal and a coating is generated by utilizing the natural macromolecules which are difficult to hydrolyze, so that the interface between the metal and the coating can be effectively prevented or hindered from being damaged by a saline medium;
the condensed tannin and polyphenol structure can be combined with hydroxyl, carboxyl and other groups in the coating, can also be combined with metal ions, has amphiphilic coupling effect, and provides good adhesive force for the coating and a metal matrix. However, the tannin extract belongs to natural products, has relatively large molecular weight and has a small amount of water-insoluble components. It is necessary to perform amination modification to improve water solubility and also to improve the ability to bind to metals. The modified condensed tannin is firmly combined with iron, and simultaneously plays a role in preventing corrosive media from corroding steel and can also slow down the diffusion of iron ions. The active phenolic hydroxyl group, especially the ortho-phenolic hydroxyl group, which is not combined with the groups such as metal oxide, hydroxyl group in the coating and the like, can react with oxygen intruding into the coating preferentially, and has good oxidation resistance and corrosion retarding effect. The composite coating after synergistic phosphorus-free conversion treatment has no undesirable phenomena of peeling, bubbling and the like in an NASS test (the time is at least 500 hours or at least 1000 hours according to different coatings), and the unilateral corrosion expanding amount at a scratch part is 1.2-1.6 mm on average; the coating of the control group has no bad phenomena of peeling, bubbling and the like, the average unilateral corrosion expanding amount at the scratch part is 2.0-2.2 mm, and the salt spray resistance of the coating is effectively improved after the surface synergistic treatment.
The above description is only for the preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent modifications made by the present invention are within the scope of the present invention.
Claims (7)
1. The preparation method of the composition for improving the salt spray resistance of the coating after the phosphorus-free conversion treatment of steel is characterized by comprising the following steps: the following components are all in parts by mass
Preparation of S1 modified tannin extract
Dissolving 30 parts by mass of condensed tannin extract in 50-65 parts by mass of deionized water, filtering to remove insoluble substances, heating to about 50-90 ℃, adding 2.4-5.0 parts by mass of organic amine, slowly adding 3.0-6.0 parts by mass of formaldehyde solution, keeping the temperature for reaction for 1.5-3 hours, and supplementing water to 100 parts by mass;
s2 preparation of composition for improving salt spray resistance of coating after steel phosphorus-free conversion treatment
The composition comprises the following components in parts by mass: 20-40 parts of S1 tannin extract modifier, 2-5 parts of polyhydroxy dispersion liquid, 3-8 parts of alkyl silane coupling agent, 3-8 parts of organic metal ester coupling agent and 5-15 parts of alcohol ether cosolvent, wherein the total mass part of the composition is 100 parts, and the balance is deionized water.
2. The method for preparing the composition for improving the salt spray resistance of the coating after the phosphorus-free steel conversion treatment according to claim 1, wherein the organic amine in S1 is one or more of triethanolamine, dimethylamine, hydroxyethylethylenediamine, acrylamide and meglumine.
3. The method for preparing a composition for increasing the salt spray resistance of a coating after a non-phosphorus steel conversion treatment according to claim 1, wherein the condensed tannin extract is any one or more of quebracho tannin extract, myrica tannin extract, emblic leafflower tannin extract and acacia tannin extract.
4. The method for preparing the composition for improving the salt spray resistance of the coating after the phosphorus-free steel conversion treatment according to claim 1, wherein the polyhydroxy dispersion is nano-silica aqueous dispersion.
5. The method for preparing the composition for improving the salt fog resistance of the coating after the phosphorus-free conversion treatment of steel and iron as claimed in claim 1, wherein the alkyl silane coupling agent is alkyl alkoxy silane Rm-Si-(OR’)nWherein R is a linear saturated alkyl group having a carbon number of not more than 4, OR' is an ethoxy group OR a methoxy group, for example: dimethyldiethoxysilane, diethoxydimethylsilane, propyltrimethoxysilane, etc.
6. The method for preparing the composition for improving the salt spray resistance of the coating after the phosphorus-free conversion treatment of steel and iron as claimed in claim 1, wherein the organic metal ester coupling agent is diisopropyl di (triethanolamine) titanate.
7. The method for preparing the composition for improving the salt spray resistance of the coating after the phosphorus-free steel conversion treatment according to claim 1, wherein the alcohol ether cosolvent is a lower alcohol ether of ethylene glycol and propylene glycol, such as dipropylene glycol butyl ether, dipropylene glycol methyl ether, ethylene glycol butyl ether and diethylene glycol methyl ether.
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| CN106702363A (en) * | 2016-12-29 | 2017-05-24 | 芜湖市瑞杰环保材料科技有限公司 | Ceramization agent for electrophoretic coating pretreatment, preparation method and usage method for ceramization agent |
| CN106544662A (en) * | 2016-12-30 | 2017-03-29 | 宁波际超新材料科技有限公司 | A kind of without phosphorus transforming agent and its using method |
| CN107201513A (en) * | 2017-06-02 | 2017-09-26 | 山东大学 | A kind of pretreatment of metal surface liquid and its application based on tannic acid for the Phosphateless environmentally friendly of main film forming substance |
| CN107163758A (en) * | 2017-06-30 | 2017-09-15 | 湖南康瑞涂料科技有限公司 | A kind of anti-corrosion anti-mildew becomes coating |
| CN109536036A (en) * | 2018-10-16 | 2019-03-29 | 兴业皮革科技股份有限公司 | A kind of preparation method of the siliceous condensed tannin extract of polyethylene polyamine cross-linked structure |
| CN109321908A (en) * | 2018-10-26 | 2019-02-12 | 四川理工学院 | A kind of metal surface multifunction environment-protection type nanometer vitrification liquid and preparation method thereof and application method |
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