CN112281146A - Metal surface treatment method - Google Patents
Metal surface treatment method Download PDFInfo
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- CN112281146A CN112281146A CN202011164113.7A CN202011164113A CN112281146A CN 112281146 A CN112281146 A CN 112281146A CN 202011164113 A CN202011164113 A CN 202011164113A CN 112281146 A CN112281146 A CN 112281146A
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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
- C23C22/07—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 phosphates
- C23C22/08—Orthophosphates
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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
- C23C22/06—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
- C23C22/36—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 containing also phosphates
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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
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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
- C23C22/53—Treatment of zinc or alloys based thereon
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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
- C23C22/56—Treatment of aluminium or alloys based thereon
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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
- C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention relates to a metal surface treatment method, which utilizes the existing metal surface treatment agent and a die coating method of double-layer coating, wherein the content of trivalent chromium in each layer of the coated metal surface treatment agent is different, when a metal substrate is pressed and filmed, the bonding strength of chromium in a first metal surface treatment agent and the surface of the metal substrate is high, when the metal extends, the thickness of a film of the first metal surface treatment agent is lower than that of the film in the prior art, partial cracks occur but the reverse acting force on the bonding surface of the metal substrate is reduced, and simultaneously, a second metal surface treatment agent can be supplemented into the cracks under the action of pressure to form supplement, and the supplement is the same as that if the same metal surface treatment agent is used, even if the first metal surface treatment agent is coated to the enough thickness by two times or one time, the content of the local trivalent chromium in the contact part of the metal substrate can not be influenced, the problem that bubbles or wrinkles appear on the surface of the metal substrate due to different forces is avoided.
Description
Technical Field
The invention belongs to the technical field of metal corrosion prevention, and particularly relates to a metal surface treatment method.
Background
Lamination is a process of laminating a resin film on the surface of a metal material under heat and pressure, and one of metal material surface coating methods used for preventing corrosion of the surface of a metal material has been widely used in various fields. In comparison with a method of forming a resin protective film by coating a resin composition on the surface of a metal material and drying the resin composition, a lamination process generates less solvent during drying and generates less exhaust gas, and the use thereof has been gradually expanded from the viewpoint of environmental protection, and has been used for aluminum sheet materials, steel sheet materials, aluminum foils for packaging, stainless steel foils, and the like as raw materials, and the like.
In particular, in recent years, metal foils such as aluminum foils and stainless steel foils, which are lightweight and have high barrier properties, have been used for electronic products and exterior materials for lithium ion batteries. The laminate film used in the above lamination process has advantages that waste of raw materials can be suppressed, pinholes are less, and processability is excellent, compared to a general resin coating film formed by applying a resin composition and drying, by bonding the laminate film to a metal material and then heating and pressing the laminate film.
When a laminated film is laminated on the surface of a metal material, in order to improve the adhesion between the laminated film and the metal surface and the corrosion resistance of the metal surface, after degreasing and washing the metal surface, chemical conversion treatment such as chromate phosphate is generally required, and a treatment solution containing hexavalent chromium is present, which causes environmental damage.
For this purpose, CN 102741453 a proposes a technique of forming a metal surface treatment agent coating film for a substrate of a laminate film or a resin coating film on the surface of a base material made of stainless steel, and the metal surface treatment agent contains a trivalent chromium compound a and at least one compound selected from organic compounds and inorganic compounds having film forming properties, and the mass ratio of the metal chromium equivalent mass of the trivalent chromium compound a to the compound B is 0.005 to 1, by applying the above metal surface treatment agent on the surface of the base material made of stainless steel, and then performing heat drying at a temperature of 60 to 250 degrees to form a surface treatment coating film. According to this aspect, a surface-treated film can be formed which has high adhesion to prevent peeling or cracking from occurring in the surface-treated film, and which can maintain stable adhesion for a long period of time even when exposed to a solvent or an acid.
The metal surface treating agent of the technical scheme does improve the stripping resistance and the corrosion resistance between a stainless steel substrate and a laminated film or a resin coating, but in the using process, the technology still has some defects, the effect is better when the treating agent is used for the stainless steel substrate, but when the treating agent is used for other metal materials, such as an aluminum substrate or a zinc substrate, because the ductility is different in the laminating process, and trivalent chromium in the metal surface treating agent is combined with the metal surface, the surface treating coating has crack phenomena, usually, the crack phenomena are supplemented by the laminated film or the resin coating in the laminating process, but the combination force of the laminated film or the resin coating and the metal surface treating agent is changed, and the foaming phenomenon is caused.
Disclosure of Invention
The invention aims to provide a metal surface treatment method to solve the problem that the prior art metal surface treatment laminated film or resin coating film has foaming phenomenon.
The invention is realized by the following technical scheme:
a metal surface treatment method comprises the following steps:
s1, cleaning the surface of the metal matrix;
s2, coating the cleaned metal substrate with a first metal surface treating agent, and naturally drying for 0.5-1 hour at normal temperature;
s3, coating the second metal surface treating agent on the naturally dried first metal surface treating agent, and then heating and drying at 80-220 ℃ to form the surface treatment coating.
Preferably, the first metal surface treatment agent has the same composition as the second metal surface treatment agent except for a different trivalent chromium content.
Preferably, the first metal surface treating agent and the second metal surface treating agent are both composed of a compound A containing trivalent chromium and a compound B, wherein the compound B is one of a vinyl resin, an acrylic resin or a polyurethane resin with film-forming property;
wherein in the first metal surface treatment agent, the mass ratio of the compound B to the metallic chromium in the trivalent chromium compound is 0.05-0.1;
in the second metal surface treatment agent, the mass ratio of the compound B to metallic chromium in the trivalent chromium compound is 0.2 to 0.25.
Preferably, the compound B further includes at least one of an inorganic compound or an organic chelate compound; wherein the inorganic compound is one or more selected from silicic acid compound, zirconium compound, titanium compound and phosphate compound; the organic chelate compound has two or more functional groups selected from a hydroxyl group, a carboxyl group, a phosphonic acid group, a phosphoric acid group, an amino group and an amide group in each molecule.
Preferably, after the first metal surface treatment agent and the second metal surface treatment agent are coated on the metal substrate, the thickness of the first metal surface treatment agent is larger than that of the second metal surface treatment agent.
Preferably, the metal matrix includes, but is not limited to, aluminum, iron alloy, zinc, and zinc alloy.
The invention has the beneficial effects that:
the technical scheme is that the existing metal surface treating agent is utilized, a double-layer coating method is utilized, and the content of trivalent chromium in each layer of coated metal surface treating agent is combined to be different, wherein the content of trivalent chromium in the metal surface treating agent in contact with a metal substrate is higher than that of trivalent chromium in the metal surface treating agent in contact with a laminated film or a resin coating film, so that the structure is that when the metal substrate is subjected to film pressing, the bonding strength of chromium in a first metal surface treating agent and the metal substrate surface is high, when the metal is extended, the film thickness of the first metal surface treating agent is lower than that of the film thickness in the prior art, partial cracks occur but the reverse acting force on the bonding surface of the metal substrate is reduced, meanwhile, a second metal surface treating agent is supplemented into the cracks under the action of pressure to form supplement, and the supplement is the same as that if the same metal surface treating agent is used, namely, the first metal surface treating agent is used to be coated twice or coated once to a sufficient thickness difference, so that the content of local trivalent chromium at the contact part with the metal matrix is not influenced, and the problem of bubbles or wrinkles on the surface of the metal matrix due to the difference of force is avoided.
Drawings
FIG. 1 is a sectional view of a coating film of a metal surface treatment agent of the present invention.
Description of the reference numerals
1. A metal substrate, 2, a first metal surface treatment agent layer, 3, a second metal surface treatment agent layer, 4, a laminate film or a resin coating.
Detailed Description
The technical solutions of the present invention are described in detail below by examples, and the following examples are only exemplary and can be used only for explaining and explaining the technical solutions of the present invention, but not construed as limiting the technical solutions of the present invention.
The technical scheme of the application is an improved technology based on the prior art CN 102741453A, the composition of the metal surface treating agent is not improved, the key point of the application is to improve the technology of a heating and drying coating after one-time coating in the prior art into a heating and drying coating after two-time coating, and the composition of the metal surface treating agent used in the two-time coating is not changed, but the content of trivalent chromium is different. According to research analysis, the content of trivalent chromium in the optimal metal surface treatment agent should be gradually reduced from the metal substrate to the laminated film or the resin coating film, but such a technique is difficult to realize in actual production, so the technical proposal adopts two-layer coating and uses metal surface treatment agents with different trivalent chromium contents, of course, if the technique permits, three-layer coating or more-than-three-layer coating can be adopted, and the content of trivalent chromium in the metal surface treatment agent used in each layer of coating is different.
In the technical scheme of the application, the composition of the metal surface treating agent is the same as that of CN 102741453A, and detailed description is not provided herein, and specific reference is made to the prior technical scheme.
The application provides a metal surface treatment method, which comprises the following steps:
s1, the specific cleaning process for cleaning the surface of the metal substrate 1 is a conventional technique, and the applicant herein does not describe in detail, and all techniques applicable to cleaning a metal substrate can be applied.
S2, coating the cleaned metal substrate with a first metal surface treating agent, and naturally drying for 0.5-1 hour at normal temperature to form a first metal surface treating agent layer 2; in the technical solution of the present application, the mass ratio of the compound B to the metallic chromium in the trivalent chromium compound in the first metal surface treating agent is 0.05-0.1, and in different embodiments, the mass ratio can be changed within this range as required, such as 0.05, 0.06, 0.07, 0.08, 0.09 or 0.1 or other data therebetween are applicable to the technical solution of the present application. In the embodiments of the present application, in order to increase the drying speed of the first metal surface treating agent, the treatment may be performed by increasing the wind speed, but the temperature cannot be higher than 40 ℃, otherwise the fusion between the second metal surface treating agent and the first metal surface treating agent, and the quality of the whole coating film, may be affected.
S3, coating a second metal surface treating agent on the naturally dried first metal surface treating agent coating layer to form a second metal surface treating agent layer 3, then heating and drying at 80-220 ℃ to form a metal surface treating coating, and coating a laminated film or a resin coating film 4 on the metal surface treating coating.
In the second metal surface treatment agent, the mass ratio of the compound B to metallic chromium in the trivalent chromium compound is 0.2 to 0.25. In different embodiments, the mass ratio can be varied within this range as desired, for example, 0.2, 0.21, 0.22, 0.23, 0.24, 0.25 or other numbers therebetween can be applied to the embodiments of the present application.
The first metal surface treatment agent has the same composition as the second metal surface treatment agent except that the content of trivalent chromium is different, and the difference between the content of trivalent chromium in the first metal surface treatment agent and the content of trivalent chromium in the second metal surface treatment agent is not more than 0.15. In each of the examples of the present application, the first metal surface treatment agent forms a coating film having a thickness greater than that of the second metal surface treatment agent.
The first metal surface treating agent and the second metal surface treating agent are both composed of a compound A containing trivalent chromium and a compound B, wherein the compound B is one of vinyl resin, acrylic resin or polyurethane resin with film-forming property.
The compound B also comprises at least one of inorganic compounds or organic chelate compounds; wherein the inorganic compound is one or more selected from silicic acid compound, zirconium compound, titanium compound and phosphate compound; the organic chelate compound has two or more functional groups selected from a hydroxyl group, a carboxyl group, a phosphonic acid group, a phosphoric acid group, an amino group and an amide group in each molecule.
The metal matrix includes, but is not limited to, aluminum, iron alloy, zinc, and zinc alloy.
Comparative experiment
In the comparative experiment of the present application, 10 examples were prepared, and the preparation methods of the 10 examples are the same except for the difference of the metal surface treatment agent, specifically:
a metal surface treatment method comprises the following steps:
s1, cleaning the surface of the metal matrix;
s2, coating the cleaned metal substrate with a first metal surface treating agent, and naturally drying for 0.5 hour at normal temperature; wherein the mass ratios of the compound B in the first metal surface treatment agent and the metallic chromium in the trivalent chromium compound in examples 1 to 10 were 0.05, 0.055, 0.06, 0.065, 0.07, 0.075, 0.08, 0.085, 0.09, 0.1, respectively.
S3, coating the second metal surface treating agent on the naturally dried first metal surface treating agent, and then heating and drying at 200 ℃ to form the surface treatment coating. Wherein the mass ratios of the compound B in the second metal surface treatment agent and the metallic chromium in the trivalent chromium compound in examples 1 to 10 were 0.2, 0.205, 0.21, 0.215, 0.22, 0225, 0.23, 0.235, 0.24, and 0.25, respectively.
In each of examples 1 to 10, the coating thickness of the first metal surface treatment agent was 20nm, the coating thickness of the second metal surface treatment agent was 10nm, and the total thickness was 30 nm.
The comparative examples are 20, which are prepared by the technical scheme of the prior art CN 102741453A, wherein the thickness of the film is 30nm, and the mass ratio of the compound B to the metallic chromium in the trivalent chromium compound in the 20 comparative examples is 0.05, 0.055, 0.06, 0.065, 0.07, 0.075, 0.08, 0.085, 0.09, 0.1, 0.2, 0.205, 0.21, 0.215, 0.22, 0225, 0.23, 0.235, 0.24 and 0.25 respectively.
In the examples and comparative examples, a metal aluminum substrate having a thickness of 0.30mm was used as the metal substrate, and a polyester film was coated on the coating film of the metal surface treatment agent to give a film thickness of 16 μm, hot-pressed for 5 seconds at a plate temperature of 150 ℃ and a surface pressure of 15kg/cm2And preparing a clad metal plate.
The same drawing and ironing test was conducted for each of the 10 examples and 20 comparative examples described above, and all the test parameters were the same.
Evaluation of Performance
The initial adhesion, durable adhesion and acid-resistant adhesion after the coated metal sheet was subjected to drawing were evaluated by the following methods.
Initial adhesion
The test material after the stretching was evaluated for initial adhesion, and the case where no film peeling occurred was referred to as "good", the case where some film peeling occurred was referred to as "poor", and the case where no peeling was observed at all and the appearance was excellent was referred to as "good".
Durable adhesion
The distillation test was performed on the test material subjected to the drawing process in a gas atmosphere of heated and pressurized steam. The distillation test was carried out at 125 ℃ for 2 hours using a sterilizer, and the material after the test was referred to as "good" when no film separation occurred, as "poor" when some film separation occurred, as "excellent" when no film separation was observed at all, and as "excellent" when the appearance was excellent.
Acid-resistant adhesion
The test material after stretching was evaluated for adhesion after immersion in a 0.5% HF aqueous solution at 50 ℃ for 10 hours, and the test material was evaluated for "good" when no film peeling occurred, for "poor" when some film peeling occurred, for "good" when no peeling was observed and for "excellent" when the appearance was excellent.
It is statistically understood that the above examples and comparative examples are all "excellent" in initial adhesion, and in terms of durable adhesion, 10 examples of the present application are all excellent, comparative examples 1 to 10 are also all "excellent", and comparative examples 11 to 20 are all "good"; in terms of acid-resistant adhesion, 10 examples of the present application are "excellent", comparative examples 1 to 10 are "good", and comparative examples 11 to 20 are "poor".
From the above tests, it is found that the metal surface coating method of the present invention using the two-layer coating method and using different amounts of trivalent chromium is excellent.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (6)
1. A metal surface treatment method is characterized by comprising the following steps:
s1, cleaning the surface of the metal matrix;
s2, coating the cleaned metal substrate with a first metal surface treating agent, and naturally drying for 0.5-1 hour at normal temperature;
s3, coating the second metal surface treating agent on the naturally dried first metal surface treating agent, and then heating and drying at 80-220 ℃ to form the surface treatment coating.
2. A metal surface treatment process according to claim 1, wherein the first metal surface treatment agent and the second metal surface treatment agent are of the same composition except for a different content of trivalent chromium.
3. The metal surface treatment method according to claim 2, wherein the first metal surface treatment agent and the second metal surface treatment agent each consist of a compound a containing trivalent chromium and a compound B, wherein the compound B is one of a vinyl resin, an acrylic resin, or a urethane resin having film-forming properties;
wherein in the first metal surface treatment agent, the mass ratio of the compound B to the metallic chromium in the trivalent chromium compound is 0.05-0.1;
in the second metal surface treatment agent, the mass ratio of the compound B to metallic chromium in the trivalent chromium compound is 0.2 to 0.25.
4. The metal surface treatment method according to claim 3, wherein the compound B further comprises at least one of an inorganic compound or an organic chelate compound; wherein the inorganic compound is one or more selected from silicic acid compound, zirconium compound, titanium compound and phosphate compound; the organic chelate compound has two or more functional groups selected from a hydroxyl group, a carboxyl group, a phosphonic acid group, a phosphoric acid group, an amino group and an amide group in each molecule.
5. The metal surface treatment method according to claim 1, wherein after the first metal surface treatment agent and the second metal surface treatment agent are coated on the metal substrate, the thickness of the first metal surface treatment agent is larger than that of the second metal surface treatment agent.
6. The metal surface treatment process of claim 1, wherein the metal substrate includes, but is not limited to, aluminum-based, aluminum alloy-based, iron alloy-based, zinc-based, and zinc alloy-based.
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