CN107099247A - A kind of compound silane film and preparation method for metal surface - Google Patents
A kind of compound silane film and preparation method for metal surface Download PDFInfo
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- CN107099247A CN107099247A CN201710506147.1A CN201710506147A CN107099247A CN 107099247 A CN107099247 A CN 107099247A CN 201710506147 A CN201710506147 A CN 201710506147A CN 107099247 A CN107099247 A CN 107099247A
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- silane
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
Abstract
The invention discloses a kind of compound silane film for metal surface, the fluorine containing silane layer of the silylation layer comprising double hydrolysis head bases and single hydrolysis head base.The method of the invention can carry out anti-corrosion anti-scale, solve existing metal and the problem of local corrosion and fouling easily occurs in the bad working environments such as seawater, sewage and chemical medium, compactness is high, and antiseptic effect is superior.
Description
Technical field
The invention belongs to chemical material field, and in particular to a kind of anti-corrosion anti-scale film of metal, more particularly to for stainless
The compound silane self-assembled layer preparation method of steel surface anti-seawater corrosion.
Background technology
With the development of modern industry, people propose requirements at the higher level to the anti-corrosion of metal surface and antiscale.Wherein have
Good corrosion resistance can be widely applied with the stainless steel of plasticity, such as pipeline, sea water pump, valve, fastener, propeller, instrument
Shell etc..Why stainless steel has good corrosion resistance, is due to that Cr, Ni passivating film on its surface have self-repairability
Energy.But this material is in harsh conditions, such as seawater, long period of soaking process lower surface passivating film self-healing properties are pressed down
System, can produce local corrosion, while easily fouling.Traditional stainless steel surfaces protective treatment technology such as chromic acid salt treatment can be produced
Health problem, phosphate treated can cause the eutrophication of water body, not meet the protection marine eco-environment of country's proposition
It is required that.
Silane is a kind of environmental protection, good film-forming property, the surface conditioning agent of excellent corrosion resistance, is referred to as organic passivation
Film.The mechanism of action of silane is to form silanol after silane hydrolyzate to be self-assembly of film in metal surface, the film energy formed
Erosion of the effective barrier corrosive medium to metal.At present, silane film process for protecting is more and more valued by people, by
Gradually substitute chromate and phosphate treated technique.But there is the shortcomings of compactness is poor in single silane film, it is therefore desirable to silane film
Preparation process be designed and adjust, further improve silane film compactness and antiseptic property.[the Adhami such as Adhami
S,Atapour M,Allafchian A R.Corrosion protection of copper by silane sol–gel
coatings[J].Journal of Sol-Gel Science and Technology,2015,74(3):800-809.]
Tetraethoxysilane (TEOS), 3- trimethoxysilyl -1- propanethiols (TPS) and TEOS+ are studied in 3.5%NaCl solution
Corrosion protection of the tri- kinds of silane films of TPS to copper.Compared with Copper substrate and single TEOS and TPS coatings, mixing TEOS+TPS mixing
The thickness increase of silane film, corrosion resistance is best.Deng [ M P,Ramallo-López
J M,Benítez G,et al.Optimization of the surface properties of nanostructured
Ni-W alloys on steel by a mixed silane layer.[J].Physical Chemistry Chemical
Physics,2015,17(21):14201-14207.] by constant current pulse electrodeposition steel surface two-step method prepare four ethoxies
Base silane (TEOS) and octadecyl trichlorosilane alkane (OTS) hybrid films.The mixed silanes film improves steel surface hydrophobic performance, and
Enhance the anticorrosive behavior on surface.But existing compound film properties and preparation method also need to further improve, with
The problem of local corrosion and fouling easily occurs in the bad working environments such as seawater, sewage and chemical medium for existing metal.
The content of the invention
Present invention aims at a kind of compound silane film and preparation method for metal surface is provided, anti-corrosion can be carried out
Antiscale, solves existing metal and the problem of local corrosion and fouling easily occurs in the bad working environments such as seawater, sewage and chemical medium.
The concrete technical scheme that the present invention is taken is as follows：
The invention provides a kind of compound silane film for metal surface, the silylation layer and Dan Shui of double hydrolysis head bases are included
Solve the fluorine containing silane layer of head base.
It is further preferred that the film thickness of compound silane film of the present invention is less than 200nm；To the silicon of double hydrolysis head bases
The thickness of the fluorine containing silane layer of alkane layer and single hydrolysis head base is not specially required, the silylation layer or/and list of preferably double hydrolysis head bases
The thickness for hydrolyzing the fluorine containing silane layer of head base is 80~120nm, and the film thickness of compound silane film is less than 200nm.
The silane of double hydrolysis head base of the present invention refers to that hydrolyzable group is contained at silane molecule two ends, such as chloro,
Methoxyl group, ethyoxyl, methoxy ethoxy, acetoxyl group etc., preferably double-[γ-(triethoxysilicane) propyl group]-tetrasulfide,
One or more in 1,2- double (triethoxy silicon substrate) ethane, tetraethoxysilane, tetramethoxy-silicanes, in preferred scope
It is interior, comprehensive silicon alkane film can be made to obtain more preferably compactness.
Single hydrolysis head base silicon fluoride of the present invention refers to that hydrolyzable group, preferably 13 are contained in silane molecule one end
Fluorine octyl group trimethoxy silane, tridecafluoro-n-octyltriethoxysilane, 17 fluorine decyl trimethoxy silanes, 17 fluorine decyls three
One or more in Ethoxysilane, 1H, 1H, 2H, 2H- perfluoro decyl trichlorosilanes, in preferred scope, can make to obtain
Compound silane film obtains more preferably hydrophobicity and anti-corrosive properties.
Present invention also offers the preparation method of the compound silane film, comprise the following steps：
(1) configuration percentage by volume for 4%~12% double hydrolysis head base solution of silane, stand hydrolyze 48 hours with
On；
(2) solution of silane that step (1) is stood to double hydrolysis head base after hydrolysis is coated in metal surface 10~40 minutes,
Then the silane for removing unnecessary double hydrolysis head bases, the thermosetting under the conditions of 50~150 DEG C again after normal temperature drying are cleaned with organic solvent
Change processing 20~60 minutes, form the silylation layer of double hydrolysis head bases；
(3) configuration molar concentration is 1~15mmol/L single hydrolysis head base silicon fluoride solution, stands hydrolysis 5~30 minutes；
(4) step (3) is stood to the silane that single hydrolysis head base silicon fluoride solution after hydrolysis is coated in double hydrolysis head bases again
Layer surface, 5~30 minutes, then takes out and the unnecessary single hydrolysis head base silicon fluoride of removing is cleaned with organic solvent, at 80~150 DEG C
Under the conditions of heat cure handle 30~60 minutes, form the fluorine containing silane layer of single hydrolysis head base.
The silane and single hydrolysis head base silicon fluoride of wherein double hydrolysis head bases are as described above.
As a preferred embodiment, the percentage by volume of double hydrolysis head base silane solution described in the inventive method for 5%~
10%, pH are 5~7.
As a preferred embodiment, single hydrolysis head base silicon fluoride solution molar concentration described in the inventive method is 2~10mmol/
L。
As a preferred embodiment, present invention cleaning organic solvent used is not particularly limited, from the aspect of cost, preferably
It is one or more of in isopropanol, absolute ethyl alcohol or acetone.
As a preferred embodiment, double hydrolysis head base silane solution and single hydrolysis head base silicon fluoride solution described in the inventive method
Solvent used is from one in ethanol, methanol, isopropanol, normal propyl alcohol, fourth propyl alcohol, isooctane, toluene, n-hexane or heptane etc.
Plant or several.
Painting method used in the present invention can be method conventional in industry, including but not limited to liquid impregnation, spray gun
One or more in spraying or sterile cotton brushing.
The present invention, can be first by cleaning metal surface before the solution of silane of the double hydrolysis head bases of coating, and cleaning method can be with
Including conventional chemical cleaning method, electrochemical cleaning or ultrasonic wave cleaning.
Beneficial effects of the present invention：
(a) introducing of double end base silane of the present invention makes composite membrane compactness of the present invention high, and antiseptic effect is superior；
(b) because outer layer contains fluorine, hydrophobicity and the antiscale of coating are further increased, four ethoxies with document report
Base silane (TEOS) is compared with octadecyl trichlorosilane alkane (OTS) hybrid films, and static contact angle improves 10~30 °, anti-corrosion and
Antiscale is dramatically increased；
(c) preparation method of the present invention is simple, it is easy to large-scale production.
Brief description of the drawings
The static contact angle of the different hydride modified stainless steel surfaces of Fig. 1.
The hydride modified stainless steel ferric trichloride pitting test figures of Fig. 2.
Embodiment
The present invention is described further below in conjunction with drawings and examples, but does not limit the present invention.
Embodiment 1：
(1) 304 stainless steel surfaces Chemical Pretreatment method
304 stainless steels are cut into 1 × 2cm2Rectangle substrate, with 0.01M HCl solutions and substrate is to remove surface
Iron filings etc., make stainless steel surfaces hydroxylating within 1 hour with 1mol/L NaOH solution processing.It is standby with drying after deionized water cleaning
With.
(2) metallic surface silanization
It is 23 that double (triethoxy silicon substrate) ethane of 1,2- are added into volume ratio:In 7 ethanol-water mixture so that 1,
The percentage by volume of double (triethoxy silicon substrate) ethane of 2- is 7%.Needed before use by double (triethoxy silicon substrate) ethane of 1,2-/
Ethanol solution stands hydrolysis 48 hours.Pretreated 304 stainless steel is immersed in solution of silane 30 minutes, with different after taking-up
Propyl alcohol, absolute ethyl alcohol, acetone cleaning remove double (triethoxy silicon substrate) ethane of 1 unnecessary, 2-, again at 65 DEG C after normal temperature drying
Under the conditions of heat cure handle 30 minutes.By 1H, 1H, 2H, 2H- perfluoro decyl trichlorosilanes are added to isooctane solution, configure
Molar fraction is 2.0mmol/L.Needed 1H, 1H, 2H before use, 2H- perfluoro decyl trichlorosilanes/isooctane solution stands hydrolysis
15 minutes.It will be immersed in through 304 stainless steels after double (triethoxy silicon substrate) ethane processing of 1,2- in solution of silane 10 minutes,
Take out respectively in acetone, carbon tetrachloride, the FDTS molecules for removing excess surface, 120 DEG C of conditions are cleaned by ultrasonic in aqueous isopropanol
Lower heat cure 1 hour.
(3) coating performance is contrasted
Two kinds of method of testings that the present embodiment is used are as follows：
Static water contact angles (WCA) use DropMeter A100P model contact angle testers, and ultra-pure water is tested respectively and is existed
The static contact angle of material surface, dropwise addition droplet size is 2 μ L, is averaged after testing three times respectively.
Accelerated corrosion refers to GB/T 17897-201635, the FeCl of configuration 6%3Solution, it is 40 DEG C to control temperature, fixed
The position of sample, takes out after stainless steel is soaked 1 hour.The corrosion product on sample is removed by GB/T 16545-2015 dry
Only, the quality of sample is accurately weighed after drying with electronic balance, 0.1mg36 is accurate to.Parallel 3 groups are set, experiment every time is both needed to
The spot corrosion liquid more renewed, range estimation calculates stainless steel surfaces spot corrosion number, calculates pitting density.The corrosion mistake tested before and after spot corrosion
Rate, its calculation formula (2) again：
ω=(W1-W2)/(St) (2)
Wherein：W1 is the weight of experiment before experiment, mg；W2 is the weight of sample after removing corrosion product after experiment, mg；S
For the area of sample, cm2；T is soak time, h.
Testing result is as follows：
Fig. 1 is the contact angle of different hydride modified 304 stainless steel surfaces.Fig. 2 is hydride modified stainless steel tri-chlorination iron spot
Corrosion test figure.In Fig. 1 and Fig. 2, M is stainless steel surfaces；M-B is double (triethoxy silicon substrate) the ethane stainless steel watches of coating 1,2-
Face；M-F is coating 1H, 1H, 2H, 2H- perfluoro decyl trichlorosilane stainless steel surfaces；M-BF is that first layer is double (three second of 1,2-
Epoxide silicon substrate) ethane, the second layer is 1H, 1H, 2H, the compound membrane coat of 2H- perfluoro decyl trichlorosilanes coating, the average thickness of coating
Spend for 80nm.
Fig. 1 static contact angle test results show, M contact angle is 63 ° ± 0.3 °, M-F contact angle for 109 ° ±
4.3 °, M-B contact angle is 34 ° ± 2.6 °, and M-BF contact angle is 120 ° ± 0.9 °.Wherein double end base silane, the Si- at two ends
OCH3Si-OH is formed after hydrolysis, after film is formed in metal surface, the Si-OH of the other end has hydrophily, causes M-B's
Contact angle is reduced.M-BF contact angle is more than M-F, and compound silane film shows stronger hydrophobicity.120 ° are that fluorine element is being put down
The limiting value of whole surface contact angle, illustrates the distribution very compactness of compound silane film surface fluorine element, can effectively improve painting
The corrosion-resistant and antiscale of layer；And the performance of M-F silane films is slightly worse.
Fig. 2 is hydride modified stainless steel ferric trichloride pitting test figure.Sample surfaces after experiment occur in that varying number
Point corrosion pit (white point).The result of accelerated corrosion experiment shows M-BF corrosion resistance preferably, and M-BF's is every square centimeter
Pitting density hourly is 1 pitting density 14 for being much smaller than M, and M-F and M-B pitting density is respectively 4 and 5.Corrosion
The small order that arrives greatly of weight-loss ratio is followed successively by M>M-B>M-F>M-BF, wherein, M corrosion weight loss rate is (12.5 ± 1.5) mg
cm2H, and M-BF corrosion weight loss rate is only (3.4 ± 0.9) mgcm2H, 72.8% is reduced than M.M-F and M-B corrosion
Weight-loss ratio is respectively (8.7 ± 0.3) mgcm2·h、(9.6±2.0)mg·cm2H, 30.4% and 23.2% is reduced than M.Point
The order from high to low for losing density is consistent with corrosion weight loss rate.
Embodiment 2-7 is as shown in table 1, other be the same as Examples 1.
The embodiment 2-7 methods describeds of table 1 and result
Above said content is only the basic explanation under present inventive concept, and according to appointing that technical scheme is done
What equivalent transformation, all should belong to protection scope of the present invention.
Claims (10)
1. a kind of compound silane film for metal surface, it is characterised in that the silylation layer comprising double hydrolysis head bases and single hydrolysis head
The fluorine containing silane layer of base.
2. the compound silane film according to claim 1 for metal surface, it is characterised in that described compound silane film
Film thickness be less than 200nm, the thickness of the silylation layers of preferably double hydrolysis head bases or/and the fluorine containing silane layer of single hydrolysis head bases is 80
~120nm, and the film thickness of compound silane film is less than 200nm.
3. the compound silane film according to claim 1 for metal surface, it is characterised in that the silane of double hydrolysis head bases
Refer to that hydrolyzable group is contained at silane molecule two ends, preferably double-[γ-(triethoxysilicane) propyl group]-tetrasulfide, 1,2- are double
One or more in (triethoxy silicon substrate) ethane, tetraethoxysilane or tetramethoxy-silicane.
4. the compound silane film according to claim 1 for metal surface, it is characterised in that single hydrolysis head base silicon fluoride
Refer to that hydrolyzable group, preferably ten trifluoro octyl group trimethoxy silanes, the ethoxy of ten trifluoro octyl group three are contained in silane molecule one end
Base silane, 17 fluorine decyl trimethoxy silanes, 17 fluorine decyl triethoxysilanes or 1H, 1H, 2H, 2H- perfluoro decyl three
One or more in chlorosilane.
5. a kind of preparation method of compound silane film, it is characterised in that comprise the following steps：
(1) configuration percentage by volume is the solution of silane of 4%~12% double hydrolysis head base, stands hydrolysis more than 48 hours；
(2) solution of silane that step (1) is stood to double hydrolysis head base after hydrolysis is coated in metal surface 10~40 minutes, then
The silane for removing unnecessary double hydrolysis head bases are cleaned with organic solvent, again under the conditions of 50~150 DEG C at heat cure after normal temperature drying
Reason 20~60 minutes, forms the silylation layer of double hydrolysis head bases；
(3) configuration molar concentration is 1~15mmol/L single hydrolysis head base silicon fluoride solution, stands hydrolysis 5~30 minutes；
(4) step (3) is stood to the silylation layer table that single hydrolysis head base silicon fluoride solution after hydrolysis is coated in double hydrolysis head bases again
Face, 5~30 minutes, then takes out and the unnecessary single hydrolysis head base silicon fluoride of removing is cleaned with organic solvent, in 80~150 DEG C of conditions
Lower heat cure is handled 30~60 minutes, forms the fluorine containing silane layer of single hydrolysis head base.
6. the preparation method of compound silane film according to claim 5, it is characterised in that described double hydrolysis head base silane
The percentage by volume of solution is that 5%~10%, pH is 5~7；Described single hydrolysis head base silicon fluoride solution molar concentration is 2~
10mmol/L。
7. the preparation method of compound silane film according to claim 5, it is characterised in that described double hydrolysis head base silane
Solvent used in solution and single hydrolysis head base silicon fluoride solution is from ethanol, methanol, isopropanol, normal propyl alcohol, fourth propyl alcohol, different pungent
One or more in alkane, toluene, n-hexane or heptane etc..
8. the preparation method of compound silane film according to claim 5, it is characterised in that in the silicon of the double hydrolysis head bases of coating
Before alkane solution, first by cleaning metal surface.
9. the preparation method of compound silane film according to claim 5, it is characterised in that painting method be liquid impregnation,
One or more in spray gun spraying or sterile cotton brushing.
10. the preparation method of compound silane film according to claim 5, it is characterised in that the silane of double hydrolysis head bases is
Refer to silane molecule two ends and contain hydrolyzable group, preferably double-[γ-(triethoxysilicane) propyl group]-tetrasulfide, 1,2- are double
One or more in (triethoxy silicon substrate) ethane, tetraethoxysilane or tetramethoxy-silicane；Single hydrolysis head base silicon fluoride
Refer to that hydrolyzable group, preferably ten trifluoro octyl group trimethoxy silanes, the ethoxy of ten trifluoro octyl group three are contained in silane molecule one end
Base silane, 17 fluorine decyl trimethoxy silanes, 17 fluorine decyl triethoxysilanes or 1H, 1H, 2H, 2H- perfluoro decyl three
One or more in chlorosilane.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110054986A (en) * | 2018-01-19 | 2019-07-26 | 四川铁创科技有限公司 | A kind of high-speed rail tunnel drainage hidden pipe anti-calcium deposition coating and preparation method thereof |
| CN110548482A (en) * | 2019-09-26 | 2019-12-10 | 中国原子能科学研究院 | preparation method of stainless steel-based molecular sieve membrane material for adsorbing uranium hexafluoride |
| CN111379642A (en) * | 2018-12-29 | 2020-07-07 | 中内凯思汽车新动力系统有限公司 | Repairing process of nano coating on surface of piston and repaired piston |
| CN113584424A (en) * | 2021-07-27 | 2021-11-02 | 张艳芳 | Stainless steel surface treatment method |
| CN113584426A (en) * | 2021-07-27 | 2021-11-02 | 张艳芳 | Corrosion-resistant stainless steel material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1771096A (en) * | 2003-05-09 | 2006-05-10 | 德古萨公司 | Corrosion protection on metals |
-
2017
- 2017-06-28 CN CN201710506147.1A patent/CN107099247A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1771096A (en) * | 2003-05-09 | 2006-05-10 | 德古萨公司 | Corrosion protection on metals |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110054986A (en) * | 2018-01-19 | 2019-07-26 | 四川铁创科技有限公司 | A kind of high-speed rail tunnel drainage hidden pipe anti-calcium deposition coating and preparation method thereof |
| CN111379642A (en) * | 2018-12-29 | 2020-07-07 | 中内凯思汽车新动力系统有限公司 | Repairing process of nano coating on surface of piston and repaired piston |
| CN111379642B (en) * | 2018-12-29 | 2021-09-21 | 中内凯思汽车新动力系统有限公司 | Repairing process of nano coating on surface of piston and repaired piston |
| CN110548482A (en) * | 2019-09-26 | 2019-12-10 | 中国原子能科学研究院 | preparation method of stainless steel-based molecular sieve membrane material for adsorbing uranium hexafluoride |
| CN113584424A (en) * | 2021-07-27 | 2021-11-02 | 张艳芳 | Stainless steel surface treatment method |
| CN113584426A (en) * | 2021-07-27 | 2021-11-02 | 张艳芳 | Corrosion-resistant stainless steel material |
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Application publication date: 20170829 |