CN114231190A - Modification method for improving adhesion performance of zinc-aluminum-magnesium steel plate - Google Patents

Modification method for improving adhesion performance of zinc-aluminum-magnesium steel plate Download PDF

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Publication number
CN114231190A
CN114231190A CN202111681828.4A CN202111681828A CN114231190A CN 114231190 A CN114231190 A CN 114231190A CN 202111681828 A CN202111681828 A CN 202111681828A CN 114231190 A CN114231190 A CN 114231190A
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Prior art keywords
steel plate
zinc
aluminum
modification method
silane coupling
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CN202111681828.4A
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CN114231190B (en
Inventor
杨俊佼
陈君雪
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/02—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/10—Presence of inorganic materials
    • C09J2400/16—Metal
    • C09J2400/163—Metal in the substrate
    • 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 & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

The invention discloses a modification method for improving the bonding performance of a zinc-aluminum-magnesium steel plate. The modification method comprises the steps of mixing a silane coupling agent with a polymer, a complexing agent and inorganic salt, and diluting with deionized water; and (3) coating the diluent on the deoiled zinc-aluminum-magnesium steel plate, drying, and then cooling to obtain the product. According to the invention, pH value adjustment and ethanol treatment are not required, and only a small amount of additives such as organic chelate, nitrate and the like are used, so that the diluted silane agent forms a coupling structure of small molecular groups, a large agglomeration phenomenon is not easy to form, and cohesive failure reaches more than 90%. The method provided by the invention greatly improves the effect of bonding the zinc-aluminum-magnesium steel plate by adhesives such as automobile steel plate damping glue, spot welding sealant and edge folding glue, and does not influence the later-stage phosphorization of the zinc-aluminum-magnesium steel plate. The whole experimental process is simple and convenient, non-toxic, pollution-free, low in cost and easy for large-scale and continuous production.

Description

Modification method for improving adhesion performance of zinc-aluminum-magnesium steel plate
Technical Field
The invention belongs to the technical field of metal surface modification, and particularly relates to a modification method for improving the bonding performance of a zinc-aluminum-magnesium steel plate.
Background
The silane coupling agent has wide application, and can play a remarkable role in improving the bonding performance. However, it has been found in experiments that if the silane coupling agent is unstable after being diluted and left to stand for a long time or after being subjected to heat treatment, precipitation is generated, resulting in an unsatisfactory surface modification effect in an actual bonding process. The reason is that the Si-OR in the silane coupling agent is easy to agglomerate in the hydrolysis process to generate macromolecules, so that a T-type OR M-type structure with single dispersibility cannot be obtained, and a polymer is easy to precipitate, so that the storage stability is reduced; meanwhile, the macromolecular clusters are formed, so that the macromolecular clusters are not easy to react with hydroxyl groups on the surface of the zinc-aluminum-magnesium steel plate. Moreover, when the silane coupling agent is used to modify the zinc-aluminum-magnesium steel plate, the joint interface only partially achieves the effect of cohesive failure, the bonding effect between the surface of the zinc-aluminum-magnesium steel plate and glue is not very ideal,
disclosure of Invention
The invention aims to provide a modification method for improving the bonding performance of a zinc-aluminum-magnesium steel plate. Solves the problems of adhesive bonding and phosphorization of the zinc-aluminum-magnesium steel plate applied in the automobile industry, and widens the application field of the zinc-aluminum-magnesium steel plate.
The modification method for improving the bonding performance of the zinc-aluminum-magnesium steel plate comprises the following steps: mixing a silane coupling agent with a polymer, a complexing agent and an inorganic salt, and diluting with deionized water to obtain a diluent with Si content of 100-500 ppm; and (3) coating the diluent on the deoiled zinc-aluminum-magnesium steel plate, drying, and then cooling to obtain the product.
The silane coupling agent is an alkaline silane coupling agent.
The silane coupling agent is an amino-containing silane coupling agent with a carbon chain length of 1-20.
The silane coupling agent is amino siloxane and silazane.
The silane coupling agent is selected from one or more of KH792(N- (beta-aminoethyl) -gamma-aminopropyl trimethyl (ethyloxy) silane), KH590 (gamma-mercaptopropyl trimethoxy silane), KH550 (gamma-aminopropyl triethoxy silane) and KH560 (gamma-glycidoxypropyl trimethoxy silane).
The polymer is polyether.
The complexing agent is one or more of citric acid, sodium citrate and EDTA disodium salt.
The inorganic salt is nitrate.
The nitrate is one or two of sodium nitrate and manganese nitrate.
The mass concentration of the polymer in the diluent is 0.01-0.1%.
The mass concentration of the complexing agent in the diluent is 0.001-0.02%.
The mass concentration of the inorganic salt in the diluent is 0.001-0.02%.
The drying temperature is 150-300 ℃, and the drying time is 10-30 s.
According to the invention, pH value adjustment and ethanol treatment are not required, and only a small amount of additives such as organic chelate, nitrate and the like are used, so that the diluted silane agent forms a coupling structure of small molecular groups, a large agglomeration phenomenon is not easy to form, and cohesive failure reaches more than 90%. The method provided by the invention greatly improves the effect of bonding the zinc-aluminum-magnesium steel plate by adhesives such as automobile steel plate damping glue, spot welding sealant and edge folding glue, and does not influence the later-stage phosphorization of the zinc-aluminum-magnesium steel plate. The whole experimental process is simple and convenient, non-toxic, pollution-free, low in cost and easy for large-scale and continuous production.
Detailed Description
In order to make the objects, technical solutions and effects of the present invention clearer and clearer, the present invention will be further described in detail through specific embodiments.
Example 1
A, deoiling a zinc-aluminum-magnesium steel plate: the cotton is clamped by a pair of tweezers, the surface of the steel plate is wiped and coated for three times after the cotton is dipped in petroleum ether, then the surface of the steel plate is wiped and coated for three times by isoamyl acetate, and finally the surface of the steel plate is wiped and coated for three times by ethanol.
And B, transferring 0.5ml of silane coupling agent KH590 into a 10ml centrifuge tube by using a liquid transfer gun, adding 9ml of polyether 100 aqueous solution with the mass concentration of 1%, and adding 0.5ml of silane coupling agent KH792 by using the liquid transfer gun to obtain a treatment liquid stock solution.
And C, using a liquid transfer gun to transfer 0.2ml of citric acid solution with the mass concentration of 4% and 0.3ml of sodium nitrate solution with the mass concentration of 4% into a centrifugal tube, then adding 9.5ml of treating solution stock solution, and diluting by 20 times with deionized water to obtain a diluent with the Si element content of 300 ppm.
And D, dipping the diluted solution in cotton, quickly coating the diluted solution on the zinc-aluminum-magnesium steel plate subjected to the oil removal treatment, and putting the zinc-aluminum-magnesium steel plate into a 200 ℃ oven to be dried for 15 s.
E, after cooling the baked zinc-aluminum-magnesium steel plate, selecting the automotive glue for glue joint treatment, and gluing the automotive glue into a rectangle with the width of 12.5mm and the thickness of 2 mm. After the gluing was completed, the board was placed in an oven at 170 ℃ for 20 minutes.
And F, taking out the steel plate, airing the steel plate in a cool and ventilated place for one day, and then stretching the steel plate.
Example 2
A, deoiling a zinc-aluminum-magnesium steel plate: the cotton is clamped by a pair of tweezers, the surface of the steel plate is wiped and coated for three times after the cotton is dipped in petroleum ether, then the surface of the steel plate is wiped and coated for three times by isoamyl acetate, and finally the surface of the steel plate is wiped and coated for three times by ethanol.
And B, transferring 0.5ml of silane coupling agent KH590 into a 10ml centrifuge tube by using a liquid transfer gun, adding 9ml of polyether 100 aqueous solution with the mass concentration of 1%, and adding 0.5ml of silane coupling agent KH792 by using the liquid transfer gun to obtain a treatment liquid stock solution.
And C, using a liquid transfer gun to transfer 0.3ml of citric acid solution with the mass concentration of 4% and 0.2ml of sodium nitrate solution with the mass concentration of 4% into a centrifugal tube, then adding the centrifugal tube into 9.5ml of treating solution stock solution, and diluting the centrifugal tube by 20 times with deionized water to obtain a diluent with the Si element content of 300 ppm.
And D, dipping the diluted solution in cotton, quickly coating the diluted solution on the zinc-aluminum-magnesium steel plate subjected to the oil removal treatment, and putting the zinc-aluminum-magnesium steel plate into a 200 ℃ oven to be dried for 15 s.
E, after cooling the baked zinc-aluminum-magnesium steel plate, selecting the automotive glue for glue joint treatment, and gluing the automotive glue into a rectangle with the width of 12.5mm and the thickness of 2 mm. After the gluing was completed, the board was placed in an oven at 170 ℃ for 20 minutes.
And F, taking out the steel plate, airing the steel plate in a cool and ventilated place for one day, and then stretching the steel plate.
Experimental test comparison results: the zinc-aluminum-magnesium steel plate is directly adhered with the vehicle adhesive and then is stretched, the section presents interface desorption, the maximum value of the tensile force is 47.69N, and the tensile strength is 1.91 MPa. After the treatment according to the treatment liquid of example 1, the zinc-aluminum-magnesium steel plate was bonded with the car adhesive and then subjected to a stretching treatment, the cross section showed cohesive failure, the maximum tensile force was 77.88N, and the tensile strength was 3.12 MPa. After the treatment according to the treatment liquid of example 2, the zinc-aluminum-magnesium steel plate was bonded with the car adhesive and then subjected to the stretching treatment, the cross section showed cohesive failure, the maximum tensile force was 74.93N, and the tensile strength was 3.00 MPa. Therefore, the method provided by the invention has the advantage that the bonding performance of the zinc-aluminum-magnesium steel plate is well improved.
The above description is only an example of the present invention, and is not intended to limit the scope of the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof. Any modification, improvement or the like made on the premise of the concept of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A modification method for improving the bonding performance of a zinc-aluminum-magnesium steel plate is characterized by comprising the following specific operations: mixing a silane coupling agent with a polymer, a complexing agent and an inorganic salt, and diluting with deionized water to obtain a diluent with Si content of 100-500 ppm; and (3) coating the diluent on the deoiled zinc-aluminum-magnesium steel plate, drying, and then cooling to obtain the product.
2. The modification method according to claim 1, wherein the silane coupling agent is an alkaline silane coupling agent.
3. The modification method according to claim 1, wherein the silane coupling agent is an amino group-containing silane coupling agent having a carbon chain length of 1 to 20.
4. The modification method according to claim 1, wherein the silane coupling agent is aminosiloxane or silazane.
5. The modification method according to claim 1, wherein the silane coupling agent is selected from one or more of KH792, KH590, KH550 and KH 560.
6. The method of claim 1, wherein the polymer is a polyether.
7. The modification method according to claim 1, wherein the complexing agent is one or more of citric acid, sodium citrate and disodium EDTA.
8. The modification method according to claim 1, wherein the inorganic salt is a nitrate.
9. The modification method according to claim 1, wherein the mass concentration of the polymer in the diluent is 0.01 to 0.1%; the mass concentration of the complexing agent in the diluent is 0.001-0.02%; the mass concentration of the inorganic salt in the diluent is 0.001-0.02%.
10. The modification method as claimed in claim 1, wherein the drying temperature is 150 ℃ and 300 ℃ and the drying time is 10-30 s.
CN202111681828.4A 2021-12-27 2021-12-27 Modification method for improving adhesive property of zinc-aluminum-magnesium steel plate Active CN114231190B (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1775882A (en) * 2004-10-27 2006-05-24 日本油漆株式会社 Method for treating adhesive before coating and aluminium alloy part
JP2008119901A (en) * 2006-11-09 2008-05-29 Sumitomo Metal Ind Ltd Surface treated metal material excellent in adhesive properties and film adhesion properties
CN102575358A (en) * 2009-10-20 2012-07-11 新日本制铁株式会社 Chromium-free surface-treated galvanized steel sheet
CN108060382A (en) * 2017-12-12 2018-05-22 首钢集团有限公司 A kind of method for improving zinc-aluminium Mg Alloy Coating steel plate glueability
CN111534815A (en) * 2020-05-22 2020-08-14 山东大学 Pretreatment liquid capable of forming washable natural color conversion film on metal surface and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1775882A (en) * 2004-10-27 2006-05-24 日本油漆株式会社 Method for treating adhesive before coating and aluminium alloy part
JP2008119901A (en) * 2006-11-09 2008-05-29 Sumitomo Metal Ind Ltd Surface treated metal material excellent in adhesive properties and film adhesion properties
CN102575358A (en) * 2009-10-20 2012-07-11 新日本制铁株式会社 Chromium-free surface-treated galvanized steel sheet
CN108060382A (en) * 2017-12-12 2018-05-22 首钢集团有限公司 A kind of method for improving zinc-aluminium Mg Alloy Coating steel plate glueability
CN111534815A (en) * 2020-05-22 2020-08-14 山东大学 Pretreatment liquid capable of forming washable natural color conversion film on metal surface and preparation method thereof

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