CN107099788A - Improve steel surface and the molybdate of epoxy resin adhesion and the preparation method of silane conversion film - Google Patents
Improve steel surface and the molybdate of epoxy resin adhesion and the preparation method of silane conversion film Download PDFInfo
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- CN107099788A CN107099788A CN201710502438.3A CN201710502438A CN107099788A CN 107099788 A CN107099788 A CN 107099788A CN 201710502438 A CN201710502438 A CN 201710502438A CN 107099788 A CN107099788 A CN 107099788A
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- Prior art keywords
- conversion
- solution
- molybdate
- silane
- epoxy resin
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Classifications
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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
- C23C22/40—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 molybdates, tungstates or vanadates
-
- 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
- C23C22/60—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 alkaline aqueous solutions with pH greater than 8
- C23C22/62—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
- C23C22/73—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 characterised by the process
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- Chemical & Material Sciences (AREA)
- 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
Steel surface and the molybdate of epoxy resin adhesion and the preparation method of silane conversion film are improved the present invention is to provide a kind of.Sodium molybdate aqueous solution is mixed with zinc sulfate solution, pH value is adjusted with acetic acid solution, obtains a conversion fluids；By the silane coupler after processing 1. solution 2. solution is mixed with silane coupler, sodium fluoride aqueous solution, solution, copper sulfate solution in zinc sulfate are added thereto, pH value is adjusted with sodium hydroxide, obtains b conversion fluids；Cleaned steel substrate is placed in a conversion fluids and handled, taking-up clean with deionized water and processing in b conversion fluids is placed in after drying.Metal surface after treatment fluid of the present invention processing forms black conversion film, can greatly improve the adhesion of steel and epoxy resin.The present invention is a kind of conversion membrane preparation method of asepsis environment-protecting, may replace traditional phosphorus system conversion film and chromium system conversion film, it is to avoid produce a large amount of toxic wastewaters, environment is polluted.
Description
Technical field
It is specifically a kind of to improve steel the present invention relates to a kind of preparation method of molybdate-silane conversion film
Surface and the molybdate of epoxy resin adhesion and the preparation method of silane conversion film.
Background technology
Epoxy resin is the thermosetting polymer that a class has the performance such as good bonding, corrosion-resistant, electric insulation, high intensity
Synthetic material.It has been widely used in various metals and nonmetallic bonding, corrosion resistant coating, insulating material, glass
The manufacture of glass steel/composite etc..It electronics, electrically, machine-building, chemical anticorrosion, Aero-Space, Shipping and its
He plays an important role in industrial circle, while being also aircraft wing coating iron at the leading edge important component.Epoxy resin into
For the indispensable basic material of each industrial circle.However, epoxy resin and steel substrate surface adhesion are weaker, industrially have
Various parts are manufactured using epoxy resin composite material cladding stainless steel art, and stainless steel and composite wood are run into production
Expect that interface bond strength is low, impact boundary layer unsticking is run into during military service, causes a lot of accidents to occur.Therefore, how to improve
Interface binding power is become as urgent problem to be solved.But at present, there is not the special epoxy resin that improves to be combined with steel substrate
The conversion membrane preparation method of power.By chemical conversion film process metal surface atom and anion in medium can be made mutually reciprocal
Should, the good separation layer of adhesive force is generated in metal surface.Though traditional phosphorus system conversion film and chromium system conversion film can improve,
Reacted due to both the above and produce a large amount of poisonous waste water, very big problem of environmental pollution can be caused.
The content of the invention
Epoxy resin and steel substrate adhesive force can be improved it is an object of the invention to provide one kind, small raising steel is polluted
Iron surface and the molybdate of epoxy resin adhesion and the preparation method of silane conversion film.
The object of the present invention is achieved like this：
Sodium molybdate aqueous solution is mixed with zinc sulfate solution, adjusts pH to 3~5 with acetic acid solution, obtains a conversion fluids；
By the silane coupler after processing 1. solution 2. solution is mixed with silane coupler, thereto add sodium fluoride it is water-soluble
Solution, copper sulfate solution in liquid, zinc sulfate, adjust pH to 10~13, obtain b conversion fluids with sodium hydroxide；
Cleaned steel substrate is placed in a conversion fluids, 15~45min is handled under 40~70 DEG C of temperatures；
Taking-up is cleaned with deionized water and is placed in b conversion fluids after drying, and 3~15min is handled at a temperature of 35~60 DEG C.
The present invention can also include：
1st, the structural formula of the silane coupler 1. be A-Si-B, the structural formula C-Si-D of the silane coupler 2., its
Middle A is γ-diethylenetriamine base propyl group, γ-propyl methacrylate base or γ-amine propyl group, and B is ethyoxyl, and C is γ-methyl
Propyl acrylate base, β-(3,4- epoxy cyclohexyl) or γ-glycidol ether propyl group, D is methoxyl group.
2nd, a conversion fluids are specifically comprised：10~30g/L of sodium molybdate, 0.1~5g/L of zinc sulfate, glacial acetic acid, surplus are
Water.
3rd, b conversion fluids are specifically comprised：Silane coupler 1. 20~100g/L silane couplers 2. 20~100g/L, fluorine
Change 0.1~5g/L of sodium, 0.1~1g/L of zinc sulfate, 0.005~0.1g/L of copper sulphate, sodium hydroxide, surplus is water.
The invention provides a kind of novel environment friendly conversion fluid, epoxy resin and steel substrate adhesive force can be greatly improved,
So as to reduce unnecessary loss.
Metal surface after treatment fluid of the present invention processing forms black conversion film, can greatly improve steel and epoxy
The adhesion of resin.The present invention is a kind of conversion membrane preparation method of asepsis environment-protecting, may replace traditional phosphorus system conversion film and
Chromium system conversion film, it is to avoid produce a large amount of toxic wastewaters, polluted to environment.Meanwhile, the present invention be applied to Aero-Space and
The fields such as warship, can be effectively prevented from epoxy resin because the factors such as impact, friction are separated with matrix, need not so as to reduce
The loss wanted.
Embodiment
The present invention can improve molybdate-silane conversion fluid of steel surface and epoxy resin adhesion, using sodium molybdate,
Zinc sulfate, glacial acetic acid composition a conversion fluids；Using silane coupler 1., silane coupler 2., sodium fluoride, zinc sulfate, copper sulphate,
Sodium hydroxide constitutes b conversion fluids.Wherein silane coupler 1. (structural formula A-Si-B) hydrolyzate and silane coupler 2. (structural formula
C-Si-D) hydrolyzate is constituted.
In structure above A may be γ-diethylenetriamine base propyl group, γ-propyl methacrylate base, γ-amine propyl group,
B is ethyoxyl.C may be γ-propyl methacrylate base, β-(3,4- epoxy cyclohexyl), γ-glycidol ether propyl group, and D is
Methoxyl group.
The specific preparation method of molybdate-silane conversion fluid is included following steps in sequence：
A. load weighted sodium molybdate is added in a certain amount of deionized water, it is fully dissolved with glass bar stirring；
B. load weighted zinc sulfate is added in a certain amount of deionized water, it is fully dissolved with glass bar stirring；
C. step a, b resulting solution is mixed, and adds a certain amount of deionized water, solution is reached predetermined close；
D. step c solution is adjusted into pH in the range of 3~5 with acetic acid solution；
E. step d solution is placed and is used as a conversion fluids on one side；
F. by the silane coupler after processing 1. solution 2. solution is mixed with silane coupler, stir 10min, mixing is equal
It is even；
G. load weighted sodium fluoride is added in a certain amount of deionized water, it is fully dissolved with glass bar stirring；
H. load weighted zinc sulfate is added in a certain amount of deionized water, it is fully dissolved with glass bar stirring；
I. load weighted copper sulphate is added in a certain amount of deionized water, it is fully dissolved with glass bar stirring；
J. step f, g, h, i resulting solution are mixed, and adds a certain amount of deionized water, solution is reached predetermined close；
K. pH is adjusted in the range of 10~13 with sodium hydroxide；
L. step k solution is placed and is used as b conversion fluids on one side.
It is clear liquid under gained a conversion fluids of the invention, normal temperature.
It is clear liquid under gained b conversion fluids of the invention, normal temperature.
The cleaning of steel substrate and conversion film forming process are specifically included：
A. occur single successively with 320 mesh, 400 mesh, 600 mesh, 800 mesh, 1000 mesh, 1200 mesh sand paper polishing sample respectively
It is rotated by 90 ° continuation after the polishing scratch of direction to polish, until 1200 mesh；
B. the sample after polishing is placed in progress ultrasonic wave cleaning in absolute ethyl alcohol；
C. the sample after ultrasonic wave is cleaned is cleaned and dried with deionized water, then carries out alkali cleaning；
D. the sample after alkali cleaning is cleaned and dried with deionized water, then carry out pickling；
E. the sample after pickling is cleaned and dried with deionized water, be placed in the conversion fluid a prepared；
F. the beaker for filling conversion fluid a and sample is placed in water bath with thermostatic control, 40~70 DEG C of temperature, 15~45min of time；
G. sample is taken out with tweezers, is cleaned and dried with deionized water, be placed in the conversion fluid b prepared；
H. the beaker for filling conversion fluid b and sample is placed in water bath with thermostatic control, 35~60 DEG C of temperature, 3~15min of time；
I. sample is taken out with tweezers, is cleaned and dried with deionized water.
Illustrate below and the present invention is described in more detail.
Embodiment 1
A. sample is polished, the cleaning of absolute ethyl alcohol ultrasonic wave, alkali cleaning, pickling, absolute ethyl alcohol ultrasonic wave cleaning；
B. in molybdate-silane conversion film layer of the steel after conversion fluid a, conversion fluid b processing：
(1) conversion fluid a is prepared：The composition that conversion fluid a includes is sodium molybdate, zinc sulfate.Wherein, sodium molybdate 20g/L, sulphur
Sour zinc 0.5g/L, surplus is water；PH value is adjusted to 4 when using sodium hydroxide and glacial acetic acid, conversion fluid is used；
(2) conversion fluid b is prepared：The composition that molybdate-silane treatment liquid includes is silane coupler 1, silane coupler
2nd, sodium fluoride, zinc sulfate, copper sulphate.Wherein, silane coupler 1. 40g/L, silane coupler 2. 40g/L, sodium fluoride 2g/L, sulphur
Sour zinc 0.5g/L, copper sulphate 0.1g/L, surplus is water；PH value is adjusted when using sodium hydroxide and glacial acetic acid, conversion fluid is used
For 12；
(3) steel is inserted in conversion fluid a, 30min is reacted under 50 DEG C of waters bath with thermostatic control, black film is formed on steel top layer
Layer；
(4) steel after (3) are handled is inserted in conversion fluid b, in 45 DEG C of constant temperature after the cleaning of absolute ethyl alcohol ultrasonic wave
10min is reacted under water-bath, Film color is still black.
C. epoxy resin is coated using the method that is coated with steel surface after inverted liquid b processing, is then placed on vacuum drying
Dried in case, epoxy resin layer is obtained after baking and curing processing.
Embodiment 2
A. sample is polished, the cleaning of absolute ethyl alcohol ultrasonic wave, alkali cleaning, pickling, absolute ethyl alcohol ultrasonic wave cleaning；
B. in molybdate-silane conversion film layer of the steel after conversion fluid a, conversion fluid b processing：
(1) conversion fluid a is prepared：The composition that conversion fluid a includes is sodium molybdate, zinc sulfate.Wherein, sodium molybdate 30g/L, sulphur
Sour zinc 0.1g/L, surplus is water；PH value is adjusted to 5 when using sodium hydroxide and glacial acetic acid, conversion fluid is used；
(2) conversion fluid b is prepared：The composition that molybdate-silane treatment liquid includes is silane coupler 1, silane coupler
2nd, sodium fluoride, zinc sulfate, copper sulphate.Wherein, silane coupler 1. 20g/L, silane coupler 2. 20g/L, sodium fluoride 4g/L, sulphur
Sour zinc 0.1g/L, copper sulphate 0.1g/L, surplus is water；PH value is adjusted when using sodium hydroxide and glacial acetic acid, conversion fluid is used
For 13；
(3) steel is inserted in conversion fluid a, 30min is reacted under 60 DEG C of waters bath with thermostatic control, black film is formed on steel top layer
Layer；
(4) steel after (3) are handled is inserted in conversion fluid b, in 55 DEG C of constant temperature after the cleaning of absolute ethyl alcohol ultrasonic wave
5min is reacted under water-bath, Film color is still black.
C. epoxy resin is coated using the method that is coated with steel surface after inverted liquid b processing, is then placed on vacuum drying
Dried in case, epoxy resin layer is obtained after baking and curing processing.
Adhesion of epoxy resin is tested：
Draw lattice experiment：Steel samples after embodiment is handled using hundred lattice devices carry out hundred lattice experiments, and it is glued using adhesive tape
Afterwards, its expulsion rate is zero.
Pull open method experiment：Using method instrumentation Pull-off tester testers measurement adhesion is pulled open, through permolybdic acid
Steel surface after salt-silane conversion film conversion is obviously improved with epoxy resin adhesion.When untreated, steel substrate and ring
Oxygen tree fat adhesion is 1.44MPa, and adhesion can reach 3.14MPa after treatment.
Claims (4)
1. a kind of improve steel surface and the molybdate of epoxy resin adhesion and the preparation method of silane conversion film, its feature
It is：
Sodium molybdate aqueous solution is mixed with zinc sulfate solution, adjusts pH to 3~5 with acetic acid solution, obtains a conversion fluids；
By the silane coupler after processing 1. solution 2. solution is mixed with silane coupler, thereto add sodium fluoride aqueous solution,
Solution, copper sulfate solution in zinc sulfate, adjust pH to 10~13, obtain b conversion fluids with sodium hydroxide；
Cleaned steel substrate is placed in a conversion fluids, 15~45min is handled under 40~70 DEG C of temperatures；
Taking-up is cleaned with deionized water and is placed in b conversion fluids after drying, and 3~15min is handled at a temperature of 35~60 DEG C.
2. according to claim 1 improve steel surface and the molybdate of epoxy resin adhesion and the system of silane conversion film
Preparation Method, it is characterized in that：The structural formula of the silane coupler 1. is A-Si-B, the structural formula C- of the silane coupler 2.
Si-D, wherein A are γ-diethylenetriamine base propyl group, γ-propyl methacrylate base or γ-amine propyl group, and B is ethyoxyl, and C is
γ-propyl methacrylate base, β-(3,4- epoxy cyclohexyl) or γ-glycidol ether propyl group, D is methoxyl group.
3. according to claim 2 improve steel surface and the molybdate of epoxy resin adhesion and the system of silane conversion film
Preparation Method, it is characterized in that a conversion fluids are specifically comprised：It is 10~30g/L of sodium molybdate, 0.1~5g/L of zinc sulfate, glacial acetic acid, remaining
Measure as water.
4. according to claim 3 improve steel surface and the molybdate of epoxy resin adhesion and the system of silane conversion film
Preparation Method, it is characterized in that b conversion fluids are specifically comprised：Silane coupler 1. 20~100g/L silane couplers 2. 20~
100g/L, 0.1~5g/L of sodium fluoride, 0.1~1g/L of zinc sulfate, 0.005~0.1g/L of copper sulphate, sodium hydroxide, surplus is water.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710502438.3A CN107099788B (en) | 2017-06-27 | 2017-06-27 | Improve the molybdate of steel surface and epoxy resin binding force and the preparation method of silane conversion film |
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|---|---|---|---|
| CN201710502438.3A CN107099788B (en) | 2017-06-27 | 2017-06-27 | Improve the molybdate of steel surface and epoxy resin binding force and the preparation method of silane conversion film |
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| CN107099788A true CN107099788A (en) | 2017-08-29 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09241576A (en) * | 1996-03-11 | 1997-09-16 | Nippon Parkerizing Co Ltd | Surface treatment composition for metallic material and method for treating therewith |
| CN101016627A (en) * | 2007-02-06 | 2007-08-15 | 重庆大学 | Method of treating magnesium alloy work-piece surface |
| CN102140634B (en) * | 2011-03-09 | 2012-08-01 | 东北大学 | Composite aqueous passivation solution and preparation method thereof for hot galvanizing surface treatment |
-
2017
- 2017-06-27 CN CN201710502438.3A patent/CN107099788B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09241576A (en) * | 1996-03-11 | 1997-09-16 | Nippon Parkerizing Co Ltd | Surface treatment composition for metallic material and method for treating therewith |
| CN101016627A (en) * | 2007-02-06 | 2007-08-15 | 重庆大学 | Method of treating magnesium alloy work-piece surface |
| CN102140634B (en) * | 2011-03-09 | 2012-08-01 | 东北大学 | Composite aqueous passivation solution and preparation method thereof for hot galvanizing surface treatment |
Non-Patent Citations (1)
| Title |
|---|
| 卢锦堂等: ""镀锌钢上钼酸盐/硅烷复合膜的组成与耐蚀性"", 《华南理工大学学报（自然科学版）》 * |
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| CN107099788B (en) | 2019-02-26 |
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