CN107099788B - Improve the molybdate of steel surface and epoxy resin binding force and the preparation method of silane conversion film - Google Patents
Improve the molybdate of steel surface and epoxy resin binding force and the preparation method of silane conversion film Download PDFInfo
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- CN107099788B CN107099788B CN201710502438.3A CN201710502438A CN107099788B CN 107099788 B CN107099788 B CN 107099788B CN 201710502438 A CN201710502438 A CN 201710502438A CN 107099788 B CN107099788 B CN 107099788B
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- solution
- conversion
- coupling agent
- silane coupling
- molybdate
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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
Abstract
The present invention is to provide the preparation methods of the molybdate and silane conversion film of a kind of raising steel surface and epoxy resin binding force.Sodium molybdate aqueous solution is mixed with zinc sulfate solution, with acetic acid solution tune pH value, obtains a conversion fluid；Will treated silane coupling agent 1. 2. solution mixes solution with silane coupling agent, thereto addition sodium fluoride aqueous solution, solution, copper sulfate solution with sodium hydroxide tune pH value obtain b conversion fluid in zinc sulfate；Cleaned steel substrate is placed in a conversion fluid and is handled, taking-up is cleaned with deionized water and dries to be placed in b conversion fluid and handled.Black conversion film is formed by treatment fluid of the present invention treated metal surface, the binding force of steel and epoxy resin can be greatly improved.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, avoids generating a large amount of toxic wastewaters, pollute the environment.
Description
Technical field
The present invention relates to a kind of molybdate-silane conversion film preparation method, specifically a kind of raising steel
The preparation method of the molybdate and silane conversion film of surface and epoxy resin binding force.
Background technique
Epoxy resin is a kind of thermosetting polymer with the performances 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, electrical insulating material, glass
The manufacture of glass steel/composite material etc..It electronics, electrical, machine-building, chemical anticorrosion, aerospace, 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 has become
For the indispensable basic material of each industrial circle.However, epoxy resin and steel substrate surface binding force are weaker, industrially have
Various parts are manufactured using epoxy resin composite material cladding stainless steel art, encounter stainless steel and composite wood in production
Expect that interface bond strength is low, impact boundary layer unsticking is encountered during being on active service, a lot of accidents is caused to occur.Therefore, how to improve
Interface binding power becomes as urgent problem to be solved.But currently, there is not the special epoxy resin that improves in conjunction with steel substrate
The conversion membrane preparation method of power.Metal surface atom and the anion in medium can be made mutually reciprocal by chemical conversion film process
It answers, generates the separation layer that adhesive force is good in metal surface.Though traditional phosphorus system conversion film and chromium system conversion film can improve,
Since both the above reaction generates a large amount of toxic waste water, very big problem of environmental pollution will cause.
Summary of the invention
Epoxy resin and steel substrate adhesive force can be improved the purpose of the present invention is to provide a kind of, pollutes small raising steel
The preparation method of the molybdate and silane conversion film of iron surface and epoxy resin binding force.
The object of the present invention is achieved like this:
Sodium molybdate aqueous solution is mixed with zinc sulfate solution, with acetic acid solution tune pH to 3~5, obtains a conversion fluid；
Will treated silane coupling agent 1. 2. solution mixes solution with silane coupling agent, addition sodium fluoride is water-soluble thereto
Solution, copper sulfate solution in liquid, zinc sulfate obtain b conversion fluid with sodium hydroxide tune pH to 10~13；
Cleaned steel substrate is placed in a conversion fluid, 15~45min is handled under 40~70 DEG C of temperatures；
Taking-up is cleaned and is dried with deionized water and is placed in b conversion fluid, and 3~15min is handled at a temperature of 35~60 DEG C.
The present invention may also include:
1, the structural formula of the silane coupling agent 1. be A-Si-B, the structural formula C-Si-D of the silane coupling agent 2.,
Middle A is γ-diethylenetriamine base propyl, γ-propyl methacrylate base or γ-amine propyl, and B is ethyoxyl, and C is γ-methyl
Propyl acrylate base, β-(3,4- epoxy cyclohexyl) or γ-glycidol ether propyl, D are methoxyl group.
2, the concrete composition of a conversion fluid are as follows: 10~30g/L of sodium molybdate, 0.1~5g/L of zinc sulfate, glacial acetic acid, surplus are
Water.
3, the concrete composition of b conversion fluid are as follows: silane coupling agent 1. 20~100g/L silane coupling agent 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 present invention provides a kind of novel environment friendly conversion fluids, can greatly improve epoxy resin and steel substrate adhesive force,
To reduce unnecessary loss.
Black conversion film is formed by treatment fluid of the present invention treated metal surface, steel and epoxy can be greatly improved
The binding force 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 is avoided generating a large amount of toxic wastewaters, be polluted the environment.Meanwhile the present invention be suitable for aerospace and
Epoxy resin can be effectively avoided because the factors such as impact, rub are separated with matrix, so that reducing need not in the fields such as warship
The loss wanted.
Specific embodiment
Molybdate-silane the conversion fluid that can improve steel surface Yu epoxy resin binding force of the invention, using sodium molybdate,
Zinc sulfate, glacial acetic acid form a conversion fluid；Using silane coupling agent 1., silane coupling agent 2., sodium fluoride, zinc sulfate, copper sulphate,
Sodium hydroxide forms b conversion fluid.Wherein silane coupling agent 1. (structural formula A-Si-B) hydrolyzate and silane coupling agent 2. (structural formula
C-Si-D) hydrolyzate forms.
In structure above A may be γ-diethylenetriamine base propyl, γ-propyl methacrylate base, γ-amine propyl,
B is ethyoxyl.C may be γ-propyl methacrylate base, β-(3,4- epoxy cyclohexyl), γ-glycidol ether propyl, and D is
Methoxyl group.
The specific preparation method of molybdate-silane conversion fluid includes following steps in sequence:
A. load weighted sodium molybdate is added in a certain amount of deionized water, dissolves it sufficiently with glass bar stirring；
B. load weighted zinc sulfate is added in a certain amount of deionized water, dissolves it sufficiently with glass bar stirring；
C. step a, b acquired solution is mixed, and a certain amount of deionized water is added, solution is made to reach predetermined close；
D. by the solution of step c with acetic acid solution tune pH in 3~5 ranges；
E. the solution of step d is placed and is used as a conversion fluid on one side；
F. will treated silane coupling agent 1. 2. solution mix solution with silane coupling agent, stir 10min, mix
It is even；
G. load weighted sodium fluoride is added in a certain amount of deionized water, dissolves it sufficiently with glass bar stirring；
H. load weighted zinc sulfate is added in a certain amount of deionized water, dissolves it sufficiently with glass bar stirring；
I. load weighted copper sulphate is added in a certain amount of deionized water, dissolves it sufficiently with glass bar stirring；
J. step f, g, h, i acquired solution is mixed, and a certain amount of deionized water is added, solution is made to reach predetermined close；
K. with sodium hydroxide tune pH in 10~13 ranges；
L. the solution of step k is placed and is used as b conversion fluid on one side.
Gained a conversion fluid of the invention is clear liquid under room temperature.
Gained b conversion fluid of the invention is clear liquid under room temperature.
The cleaning of steel substrate and conversion film forming process specifically include:
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 ° after the polishing scratch of direction and continues to polish, until 1200 mesh；
B. the sample after polishing is placed in dehydrated alcohol and carries out ultrasonic cleaning；
C. the sample after ultrasonic cleaning is cleaned and is dried with deionized water, then carry out alkali cleaning；
D. the sample after alkali cleaning is cleaned and is dried with deionized water, then carry out pickling；
E. the sample after pickling is cleaned and is dried with deionized water, be placed in prepared conversion fluid a；
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 is dried with deionized water, be placed in prepared conversion fluid b；
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 is dried with deionized water.
It illustrates below and the present invention is described in more detail.
Embodiment 1
A. sample is polished, dehydrated alcohol ultrasonic cleaning, alkali cleaning, pickling, dehydrated alcohol ultrasonic cleaning；
B. film layer is converted in molybdate-silane of the steel after conversion fluid a, conversion fluid b processing:
(1) prepare conversion fluid a: the ingredient for including in conversion fluid a is sodium molybdate, zinc sulfate.Wherein, sodium molybdate 20g/L, sulphur
Sour zinc 0.5g/L, surplus are water；Using sodium hydroxide and glacial acetic acid by conversion fluid using when pH value be adjusted to 4；
(2) prepare conversion fluid b: the ingredient for including in molybdate-silane treatment liquid is silane coupling agent 1, silane coupling agent
2, sodium fluoride, zinc sulfate, copper sulphate.Wherein, silane coupling agent 1. 40g/L, silane coupling agent 2. 40g/L, sodium fluoride 2g/L, sulphur
Sour zinc 0.5g/L, copper sulphate 0.1g/L, surplus are water；PH value is adjusted when being used conversion fluid using sodium hydroxide and glacial acetic acid
It is 12；
(3) steel is placed in conversion fluid a, reacts 30min under 50 DEG C of waters bath with thermostatic control, form black film on steel surface layer
Layer；
(4) (3) treated steel is placed in conversion fluid b, after dehydrated alcohol ultrasonic cleaning in 45 DEG C of constant temperature
10min is reacted under water-bath, Film color is still black.
C. epoxy resin is coated using the method that is coated in steel surface after inverted liquid b processing, is then placed on vacuum drying
It is dried in case, obtains epoxy resin layer after baking and curing processing.
Embodiment 2
A. sample is polished, dehydrated alcohol ultrasonic cleaning, alkali cleaning, pickling, dehydrated alcohol ultrasonic cleaning；
B. film layer is converted in molybdate-silane of the steel after conversion fluid a, conversion fluid b processing:
(1) prepare conversion fluid a: the ingredient for including in conversion fluid a is sodium molybdate, zinc sulfate.Wherein, sodium molybdate 30g/L, sulphur
Sour zinc 0.1g/L, surplus are water；Using sodium hydroxide and glacial acetic acid by conversion fluid using when pH value be adjusted to 5；
(2) prepare conversion fluid b: the ingredient for including in molybdate-silane treatment liquid is silane coupling agent 1, silane coupling agent
2, sodium fluoride, zinc sulfate, copper sulphate.Wherein, silane coupling agent 1. 20g/L, silane coupling agent 2. 20g/L, sodium fluoride 4g/L, sulphur
Sour zinc 0.1g/L, copper sulphate 0.1g/L, surplus are water；PH value is adjusted when being used conversion fluid using sodium hydroxide and glacial acetic acid
It is 13；
(3) steel is placed in conversion fluid a, reacts 30min under 60 DEG C of waters bath with thermostatic control, form black film on steel surface layer
Layer；
(4) (3) treated steel is placed in conversion fluid b, after dehydrated alcohol ultrasonic cleaning in 55 DEG C of constant temperature
5min is reacted under water-bath, Film color is still black.
C. epoxy resin is coated using the method that is coated in steel surface after inverted liquid b processing, is then placed on vacuum drying
It is dried in case, obtains epoxy resin layer after baking and curing processing.
Adhesion of epoxy resin experiment:
It draws lattice experiment: embodiment treated steel samples being subjected to hundred lattice tests using hundred lattice devices, glue it using adhesive tape
Afterwards, expulsion rate zero.
Pull open method experiment: using method special instrument Pull-off tester tester measurement binding force is pulled open, through permolybdic acid
Steel surface after salt-silane conversion film conversion is obviously improved with epoxy resin binding force.When untreated, steel substrate and ring
Oxygen resin-bonded power is 1.44MPa, and binding force can reach 3.14MPa after treatment.
Claims (2)
1. a kind of preparation method of the molybdate for improving steel surface and epoxy resin binding force and silane conversion film, feature
It is:
Sodium molybdate aqueous solution is mixed with zinc sulfate solution, with acetic acid solution tune pH to 3~5, obtains a conversion fluid, a conversion fluid
Concrete composition are as follows: 10~30g/L of sodium molybdate, 0.1~5g/L of zinc sulfate, glacial acetic acid, surplus be water；
Will treated silane coupling agent 1. 2. solution mixes solution with silane coupling agent, thereto addition sodium fluoride aqueous solution,
Zinc sulfate solution, copper sulfate solution obtain b conversion fluid with sodium hydroxide tune pH to 10~13, and specific group of b conversion fluid
Become: silane coupling agent 1. 20~100g/L, silane coupling agent 2. 20~100g/L, 0.1~5g/L of sodium fluoride, zinc sulfate 0.1
~1g/L, 0.005~0.1g/L of copper sulphate, sodium hydroxide, surplus are water；
Cleaned steel substrate is placed in a conversion fluid, 15~45min is handled under 40~70 DEG C of temperatures；
Taking-up is cleaned and is dried with deionized water and is placed in b conversion fluid, and 3~15min is handled at a temperature of 35~60 DEG C.
2. the system of the molybdate for improving steel surface and epoxy resin binding force and silane conversion film according to claim 1
Preparation Method, it is characterized in that: the structural formula of the silane coupling agent 1. is A-Si-B, the structural formula C- of the silane coupling agent 2.
Si-D, it is ethyoxyl that wherein A, which is γ-diethylenetriamine base propyl, γ-propyl methacrylate base or γ-amine propyl, B, and C is
γ-propyl methacrylate base, β-(3,4- epoxy cyclohexyl) or γ-glycidol ether propyl, D are methoxyl group.
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| Application Number | Priority Date | Filing Date | Title |
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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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| 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 CN107099788A (en) | 2017-08-29 |
| CN107099788B true CN107099788B (en) | 2019-02-26 |
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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 |
|---|
| "镀锌钢上钼酸盐/硅烷复合膜的组成与耐蚀性";卢锦堂等;《华南理工大学学报（自然科学版）》;20091231;第37卷(第12期);第12页右栏第2段，表1 |
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