CN114686866A - Non-phosphorus conversion film treatment process - Google Patents

Non-phosphorus conversion film treatment process Download PDF

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CN114686866A
CN114686866A CN202210239859.2A CN202210239859A CN114686866A CN 114686866 A CN114686866 A CN 114686866A CN 202210239859 A CN202210239859 A CN 202210239859A CN 114686866 A CN114686866 A CN 114686866A
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phosphorus
parts
treatment
steel
water
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CN114686866B (en
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李翀
俞春风
陆国建
季建华
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Zhejiang Pentatomic Sciences & Technology Inc
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Zhejiang Pentatomic Sciences & Technology Inc
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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
    • C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/50—Treatment of iron or alloys based thereon
    • 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
    • C23C22/78—Pretreatment of the material to be coated
    • 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
    • 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
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124—Water desalination
    • Y02A20/131—Reverse-osmosis

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  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

The invention discloses a non-phosphorus conversion film treatment process, which comprises the following preparation 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) non-phosphorus conversion film treatment with the addition of the composition: adding the composition into a phosphorus-free conversion treatment working solution according to the concentration of 0.5-1.5 g/L, treating for 1-5 minutes at the pH value of 3.5-5 and the temperature of 10-40 ℃, wherein the treatment mode is spraying or 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. 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 iron and steel non-phosphorus conversion treatment is obviously improved, and 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.

Description

Non-phosphorus conversion film treatment process
Technical Field
The invention relates to the technical field of surface treatment, in particular to a non-phosphorus conversion film treatment process.
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 a coating,the corrosion resistance requirement can be effectively met, and the corrosion resistance of the composite coating is generally evaluated by 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, it also has a significant disadvantage over phosphating in that the film thickness of the phosphorus-free conversion film is very thin (20 mg/m)2～200mg/m2) The corrosion resistance of the film is relatively poor, and after the film is matched with paint, powder coating, electrophoretic coating and the like to form a coating, the neutral salt spray resistance of the film is difficult to meet the requirement, so that the phosphorus-free conversion process is limited in the application and popularization process.
In the prior art, the phosphorus-free conversion coating treated by the phosphorus-free conversion coating treatment process has the following technical problems: 1. the thickness of the phosphorus-free conversion film is very thin (20 mg/m)2～200mg/m2) The corrosion resistance of the film 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 phosphorus-free conversion film treatment process, after the treatment by the phosphorus-free conversion film treatment process, the treatment by the phosphorus-free conversion film added with the composition in the step 3) finally ensures that the conversion film has good corrosion resistance, the treatment of wastewater is further reduced, and the phosphorus-free and chromium-free treatment process is environment-friendly.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a non-phosphorus conversion film treatment process comprises the following preparation 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) non-phosphorus conversion film treatment with the addition of the composition: adding the composition into a phosphorus-free conversion treatment working solution according to the concentration of 0.5-1.5 g/L, treating for 1-5 minutes at the pH value of 3.5-5 and the temperature of 10-40 ℃, wherein the treatment mode is spraying or soaking;
4) rinsing with water: cleaning the residual treating fluid on the surface of steel or in the gaps of structural members;
5) drying: drying with hot air at 80-120 deg.C.
As a further improvement of the present solution,
the composition comprises the following components in parts by mass:
20-40 parts of S1 tannin extract modified substances;
2-5 parts of polyhydroxy dispersion liquid;
3-8 parts of an alkyl silane coupling agent;
3-8 parts of an organic metal ester coupling agent;
5-15 parts of an 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 present solution,
the S1 tannin extract modifier is prepared by the following steps:
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 then supplementing water to 100 parts by mass.
As a further improvement of the present solution,
the condensed tannin extract is any one or more of quebracho tannin extract, waxberry tannin extract, emblic leafflower tannin extract and acacia tannin extract.
As a further improvement of the present solution,
the organic metal ester coupling agent is di (triethanolamine) diisopropyl titanate.
As a further improvement of the present solution,
the organic amine in the S1 is any one or more of triethanolamine, dimethylamine, hydroxyethyl ethylenediamine, acrylamide and meglumine.
As a further improvement of the present solution,
the polyhydroxy dispersion liquid is nano silicon dioxide water dispersion liquid.
As a further improvement of the present solution,
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.
As a further improvement of the present solution,
the organic metal ester coupling agent is di (triethanolamine) diisopropyl titanate.
As a further improvement of the present solution,
the alcohol ether cosolvent is 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.
After the treatment by the phosphorus-free conversion film treatment process, the treatment by the phosphorus-free conversion film added with the composition in the step 3) 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 the treatment of the composition in the 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 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;
5) unlike the hydrolyzed tannin prepared from gallnut and other extracts, the condensed tannin extract mainly comprises condensed tannin, and the complex polycondensate formed by combining compounds such as flavanol and the like with C-C bonds is difficult to decompose in aqueous solution, and the intermediate film layer between the metal and the coating can be generated by utilizing the natural macromolecules which are difficult to hydrolyze, so that the interface between the metal and the coating can be prevented or hindered from being damaged by a saline medium;
Figure BDA0003543989010000041
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 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 condensed tannin extract is modified as follows:
Figure BDA0003543989010000042
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:
Figure BDA0003543989010000051
7) the polyhydroxy inorganic dispersion can not only fill up the gaps of condensed tannin, but also provide a large amount of hydroxyl groups to be combined 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, forms silanol with the short-chain alkyl after hydrolysis, has certain hydrophobicity, and endows a composite film layer with the performance of preventing saline contact or avoiding infiltration after being combined with condensed tannin. 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:
a non-phosphorus conversion film treatment process of a preparation method of a composition for improving the salt spray resistance of a coating after steel non-phosphorus conversion treatment comprises the following preparation 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) non-phosphorus conversion film treatment with the addition of the composition: the composition is added into a phosphorus-free conversion treatment working solution according to the concentration of 0.5-1.5 g/L, the pH value is 3.5-5, and the treatment is carried out for 1-5 minutes at the temperature of 10-40 ℃, wherein the treatment mode is spraying or 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.
The composition comprises the following components in parts by mass:
20-40 parts of S1 tannin extract modified substances;
2-5 parts of polyhydroxy dispersion liquid;
3-8 parts of an alkyl silane coupling agent;
3-8 parts of an organic metal ester coupling agent;
5-15 parts of alcohol ether cosolvent;
wherein the total mass part of the composition is 100 parts, and the balance is deionized water.
Example 1
Modified product of S1
Figure BDA0003543989010000061
S2 composition
Figure BDA0003543989010000062
Example 2
S1
Figure BDA0003543989010000063
S2 composition
Figure BDA0003543989010000064
Figure BDA0003543989010000071
Example 3
S1
Figure BDA0003543989010000072
S2 composition
Figure BDA0003543989010000073
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
Figure BDA0003543989010000081
Figure BDA0003543989010000091
Table 4: the performance of the coatings after synergistic treatment in examples 2 and 3 was compared with the performance of the coatings after treatment in the manner of treatment in comparative example 2
Figure BDA0003543989010000092
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 after the salt water solution enters the metal/coating interface, the speed of permeation through the film to the metal surface is reduced;
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;
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;
Figure BDA0003543989010000101
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 bonded with the group such as the hydroxyl group in the metal oxide and the coating, can preferentially react with oxygen invading into the coating, and has good oxidation resistance and corrosion retarding effect. The composite coating after synergistic phosphorus-free conversion treatment has no bad phenomena of peeling, bubbling and the like in a 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 such as 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 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 (10)

1. A non-phosphorus conversion film treatment process is characterized by comprising the following preparation 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) non-phosphorus conversion film treatment with the addition of the composition: adding the composition into a phosphorus-free conversion treatment working solution according to the concentration of 0.5-1.5 g/L, treating for 1-5 minutes at the pH value of 3.5-5 and the temperature of 10-40 ℃, wherein the treatment mode is spraying or 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.
2. The phosphorus-free conversion coating treatment process according to claim 1,
the composition comprises the following components in parts by mass:
20-40 parts of S1 tannin extract modified substances;
2-5 parts of polyhydroxy dispersion liquid;
3-8 parts of an alkyl silane coupling agent;
3-8 parts of an organic metal ester coupling agent;
5-15 parts of an alcohol ether cosolvent;
wherein the total mass part of the composition is 100 parts, and the balance is deionized water.
3. The phosphorus-free conversion coating treatment process according to claim 2,
the S1 tannin extract modified substance is prepared by the following steps:
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 then supplementing water to 100 parts by mass.
4. The non-phosphorus conversion coating treatment process of claim 3, 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.
5. The process of claim 3, wherein the organometallic ester coupling agent is diisopropyl di (triethanolamine) titanate.
6. The phosphorus-free conversion coating treatment process according to claim 3, wherein the organic amine in S1 is one or more selected from triethanolamine, dimethylamine, hydroxyethylethylenediamine, acrylamide, and meglumine.
7. The phosphorus-free conversion coating treatment process according to claim 3, wherein the polyhydroxy dispersion is a nano silica aqueous dispersion.
8. The process of claim 3, wherein the alkylsilane coupling agent is alkylalkoxysilane 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.
9. The phosphorus-free conversion coating treatment process of claim 3, wherein the organometallic ester coupling agent is di (triethanolamine) diisopropyl titanate.
10. The phosphorus-free conversion coating treatment process of claim 3, 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, diethylene glycol methyl ether.
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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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