CN109136903A - A kind of the silane laminated film and its methods for making and using same of rare earth doped salt and zeolite - Google Patents
A kind of the silane laminated film and its methods for making and using same of rare earth doped salt and zeolite Download PDFInfo
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- CN109136903A CN109136903A CN201811041526.9A CN201811041526A CN109136903A CN 109136903 A CN109136903 A CN 109136903A CN 201811041526 A CN201811041526 A CN 201811041526A CN 109136903 A CN109136903 A CN 109136903A
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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
- C23C22/68—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 solutions with pH between 6 and 8
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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
- C23C2222/20—Use of solutions containing silanes
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Abstract
The invention discloses the silane laminated films and its methods for making and using same of a kind of rare earth doped salt and zeolite.The silane mixture liquid for preparing rare earth doped salt and zeolite granular impregnates again or is sprayed at metal material surface after ageing, cured to form one layer of fine and close anti-corrosion silane laminated film in aluminum alloy surface.The present invention has the rare-earth salts of inhibition and self-repair effect using the load of porous zeolite particle, and the crosslink density of zeolite granular enhancing silane film, it effectively enhances Silan-based Thin Films to act on the physical barriers of corrosive media, realizes the target for improving metal surface Silan-based Thin Films corrosion resistance.In the present invention, consistency made from the metal surface doped with rare-earth salts and the silane laminated film of zeolite is greatly improved, the infiltration of extraneous eater can effectively be hindered, and the bond strength of polymeric coating layer and metal can be improved, the corrosion resistance of metal effectively is enhanced, can satisfy the corrosion resistance service demand of metal material in harsh environments.
Description
Technical field
The present invention relates to a kind of silane laminated film and its preparation for the rare earth doped salt of corrosion-resistant and zeolite and applications
Method belongs to field of metal surface treatment technology.
Background technique
Metal material is extremely widespread as essential substance industrial production of living, but is made by the chemistry of surrounding medium
With or electrochemical action generate corrosion phenomenon, not only result in significant economic losses, also cause harmful substance pollution existence ring
The health of the mankind is destroyed in border.So many researchers have done a large amount of research to anticorrosive metal measure.It is generally divided into following
Several classes: develop corrosion-resistant metallic material, protected in metal surface protective mulch, metal surface modification, corrosion inhibiter inhibition and electrochemistry
Shield.Organic coating is also the most extensive as most economical most effective anticorrosive measure application.Organic coating coating uniformly and relatively causes
It is close, but the chemical property and architectural difference of organic coating and metal material under normal conditions are big, this will lead to organic coating with
Binding force between metal is undesirable, in order to make organic coating have good adhesive force and corrosion resistance, generally requires progress
Interface processing, that is, surface preparation is carried out to metal, on the one hand improve the corrosion resistance of metal, on the other hand can change
The binding force of kind organic coating and metallic matrix.
Currently, metal surface pretreatment mainly has rare-earth conversion coatings processing, phosphorating treatment, organic film painting treatment
Etc..Wherein organic film painting treatment is included in metal surface and prepares one layer of organosilan film, and silane (Silane) is hydridization
Molecule has organic and inorganic functional group, and hydrolyzable Inorganic functional groups will form covalent bond with metal base, in Metal Substrate
Si-O-Si network structure is formed on bottom, and organo-functional group is compatible with organic coating system, the combination that interface can be enhanced is strong
Degree.In addition, forming alcoholic extract hydroxyl group after silane hydrolyzate, there is Si-O-Si network structure by being crosslinked to be formed on the metallic substrate
Silane film can prevent water and electrolyte osmosis to metallic substrates, provide one of hydrophobic physical barriers.
But Silan-based Thin Films are very thin, thickness generally about 100~500nm, and the defects of there are some micro-cracks, micropore, it is rotten
Corrosion electrolyte is easy to contact with metal surface by these defects and lead to metal erosion.Cerous nitrate, cerium chloride and nitric acid
The rare-earth salts such as lanthanum, lanthanum chloride not only have rust inhibition, also have self-healing property.Cerium or lanthanum ion are by forming oxide or hydroxide
Object come protect affected area from corrosion.It can be certain by being surface-treated with the silane of cerium or La doped to metal base
Effective protection matrix does not weather in time, is significantly improved compared to silane film corrosion resistance.Si-Ce organic and inorganic is miscellaneous
Change film and has become one of most promising environment-friend substitution product of chromium conversion film.
There is researcher to be prepared for Si/Zr gel coat on 6 line aluminium alloy surfaces and carries out improvement acquirement using cerous nitrate
Good effect, but problem is this gel layer thicknesses up to 15 μm or so, it is too thick for interface processing.Also there is researcher
It attempts to prepare one layer of very thin silane film in surface of galvanized steel, and is doped using cerous nitrate solution, be equally dedicated to combining
As a result the barrier action of silane film and the effect of corrosion inhibition of cerous nitrate also indicate that the addition of cerous nitrate is reinforced to a certain extent
The barrier action of silane film.
The rare-earth salts such as rare earth cerium salt or lanthanum salt are as a kind of effective corrosion inhibitor, if there is a kind of good carrier can be with
Them are stored, and generate synergistic effect therewith just can greatly improve the corrosion resistance of silane film.
A kind of zeolite, alumino-silicate, belongs to inorganic material, has three dimensional skeletal structure, oxygen-octahedron and alumina four sides
The skeleton that body is formed by sharing oxygen atom connection, has microcellular structure abundant.Because of the property and structure of zeolite, no
Few researcher is by one-step method or two-step method in metal surface synthetic zeolite coating, and effect is also clearly.Firstly, since table
The presence of face alcoholic extract hydroxyl group, zeolite have stronger chemical activity, are based on this characteristic, and silane can interact with its surface and produce
Raw reaction.Secondly as the porosity of zeolite provides a good load for the rare-earth salts corrosion inhibitor such as cerium salt or lanthanum salt
Body, the two, which generates synergistic effect more, improves the corrosion resistance of silane film, and zeolite granular is filled into silane matrix
In can increase crosslink density to reduce the wetability of monolithic film membrane, hinder the entrance of hydrone medium, nano inorganic boiling
There are some hydroxyls for stone particle surface, can react to form outer hydrophobic organic chain with silanol key, so that the corrosivity such as water be hindered to be situated between
The entrance of matter.
There is presently no the relevant reports for the silane laminated film that rare-earth salts and zeolite granular adulterate simultaneously.
Summary of the invention
In view of the deficiencies of the prior art, the primary purpose of the present invention is that provide it is a kind of for the rare earth doped salt of corrosion-resistant and
The silane laminated film of zeolite.By the silane THIN COMPOSITE for preparing a kind of while rare earth doped salt and zeolite in metal material surface
Film, not only utilizes the corrosion inhibition property of rare-earth salts, but also makes full use of the micropore special construction of zeolite granular, provides one for rare-earth salts
A good carrier, the two, which generates synergistic effect more, improves the corrosion resistance of silane film.Zeolite granular filling simultaneously
Crosslink density can be increased into silane matrix to reduce the wetability of monolithic film membrane, and pass through surface hydroxyl and silanol key
Reaction forms outer hydrophobic organic chain, to hinder the entrance of the corrosive medias such as water, effectively enhances the barrier of Silan-based Thin Films
Effect also improves the corrosion resistance of metal, improves the interface bond strength of organic coating and matrix, meets metal material and disliking
Corrosion Protection requirement in bad Service Environment.
A kind of silane laminated film of rare earth doped salt and zeolite.
Preferably, in the reaction system of the silane laminated film for preparing rare earth doped salt and zeolite: rare-earth salts
Concentration is 1 × 10-4~1 × 10-1Mol/L, zeolite concentration are 0.05~5g/L.Rare earth salinity is too low to compound in the present invention
The improvement of film is not obvious；Excessive concentration can then generate phenomena such as reunion, accumulation to destroy the regular of laminated film
Property, and increase the probability that laminated film generates defect.Zeolite additive amount is very few also basic without improving effect in the present invention simultaneously
Fruit；And additive amount crosses conference and causes distribution of particles uneven while generating reunion, to seriously affect with self-regeneration
The substep of the cerium of ability.
As a further preference, the concentration of the rare-earth salts is 1 × 10-3~9 × 10-3The concentration of mol/L, zeolite is
0.1~2g/L.In currently preferred range, the two can be generated and more preferably be acted synergistically, to more improve multiple
Close the corrosion resistance of film.
Preferably, the sized zeolite particles are 30~900nm, preferably 50~200nm.To zeolite granular hole in the present invention
Diameter does not have particular/special requirement, as long as being greater than rare earth ion radius.
Preferably, the silane laminated film of the rare earth doped salt and zeolite is with a thickness of 100~2000nm.It is preferred that
300-1500nm。
Since the present invention is the preprocessing process done to metal material surface, also referred to as interface processing, to follow-up coating
Thickness there are certain requirements, interface processing cannot be too thick, otherwise influence Bulk coat thickness.
It is a second object of the invention to provide the preparation method of above-mentioned silane laminated film.The present invention uses old first
The silane mixture liquid of change impregnates or spray treatment metal material surface, and then solidification obtains silane laminated film, technique letter
Single easy to operate, mild condition is pollution-free, and reproducibility is high.
In order to achieve the above object, the present invention is implemented by following technical proposal:
(1) silane mixture liquid is prepared: rare-earth salts being added in the mixed liquor of silane and solvent, boiling is added after aged
Stone particle is up to silane mixture liquid；
(2) silane mixture liquid the solidification of silane laminated film: is attached to pretreated gold by impregnating or spraying
Belong to material surface, solidifies up to silane laminated film.
Rare-earth salts in the preparation, is preferably first added to silane by the silane laminated film of the rare earth doped salt of the present invention and zeolite
In the mixed liquor of solvent, after aged, the sequence operation of zeolite granular is added.If existing zeolite granular is added, zeolite
The micropore on surface can be closed by silane, and load capacity of the rare-earth salts in zeolite micropore is caused to substantially reduce, thus influence zeolite with
The synergy of rare-earth salts.
Preferably, the rare-earth salts includes: one of soluble cerium salt, lanthanum salt, such as cerous nitrate, cerium chloride, nitre
Sour lanthanum, lanthanum chloride.
Preferably, the silane is various single or double silane coupling agents.Such as double-[γ-(triethoxysilicane) propyl]
Tetrasulfide, γ-glycidylpropyl-trimethoxy silane, γ-methacryloxypropyl-trimethoxy silane.
Preferably, the volume ratio of the silane and solvent is 1~30:99~70.Further preferably 3~10:97~
90.Still more preferably, the volume ratio of the organic solvent, silane and deionized water is 98~80:1~10:1~10.
Preferably, the solvent is organic solvent and deionized water, such as methanol or ethyl alcohol or acetone in step (1)
And deionized water.Further preferably ethyl alcohol and deionized water.
Silane is soluble in ethyl alcohol, not soluble in water in the present invention, and silane laminated film passes through alcoholic extract hydroxyl group key, institute in conjunction with matrix
It is unfavorable for combining very little with alcoholic extract hydroxyl group, alcoholic extract hydroxyl group is too many, and residual hydroxyl can absorb water, so suitable hydrolysis can be conducive to silane film
Corrosion resistance and bond strength.
Preferably, zeolite granular is added after mixed liquor and obtains silane mixture liquid through ultrasonic agitation in step (1).
Preferably, curing process condition: temperature is 20~200 DEG C, preferably 80~120 DEG C in step (2)；Time
For 0.5~48h, preferably 1~10h.
Preferably, the time of the ageing is 1h~10d, preferably 1~5d in step (1).The very few silicon of digestion time
Alkane hydrolysis is insufficient；There is deposit in solution bottom too long in digestion time.
Preferably, the pretreated metal material is by boiling, polishing, ultrasound, cleans pretreatment or the differential of the arc
The material of oxidation pre-treatment.
Currently preferred preparation method, includes the following steps:
(1) sample pretreatment
Aluminum alloy plate materials are cut into 15 × 15 × 2mm sample, are boiled in boiling water, silicon carbide paper polishing, the tables such as ultrasonic cleaning
Face pretreatment；
(2) preparation of silane mixture liquid
By ethyl alcohol, silane, deionized water, 95:5:5 is uniformly mixed by volume, by 1 × 10-3~9 × 10-3Mol/L's
Cerous nitrate is added in mixed liquor, is aged 1~5d at room temperature, then the nano zeolite particle of 0.1~2g/L is added to mixed liquor
In, 1~100min of ultrasound after 1~100min is stirred, silane mixture liquid is obtained；
(3) solidification of silane laminated film
Pretreating specimen is put into the silane mixture liquid being aged, after impregnating 0.5~30min, 80~120 DEG C of items of temperature
Solidify 1~10h under part up to silane laminated film.
Third object of the present invention is to provide the application method of above-mentioned rare earth doped salt and the silane laminated film of zeolite,
Specifically the silane laminated film of the rare earth doped salt and zeolite is solidified and is used for anticorrosion in metal material surface.
Further preferably, the metal material includes fine aluminium, aluminium alloy, ferroalloy, magnesium alloy or copper alloy.
Advantages of the present invention and effect are as follows:
1. silane (BTESPT) is hybrid molecule, there is organic and inorganic functional group, hydrolyzable Inorganic functional groups will
Covalent bond is formed with metal base, formed has Si-O-Si network structure on the metallic substrate, and water and electrolyte can be prevented to seep
Metallic substrates are arrived thoroughly, provide one layer of physical barriers, and organo-functional group is compatible with organic coating system, to enhance organic painting
The combination of layer and metal material.Rare-earth salts is such as: cerous nitrate, cerium chloride not only have rust inhibition, also have self-healing property, Ke Yitong
It crosses to form oxide or hydroxide to protect affected area from corrosion.Zeolite is mainly made of three-dimensional silica alumina screen work, silicon
The mode of oxygen tetrahedron connection is different, forms many holes and duct in zeolite structured, can be used as rare earth ion
Effective carrier by its load and slow release, and there are some hydroxyls for zeolite surface, can react to form outside with silanol key
Hydrophobic organic chain stops the invasion of external water.
2. the silane laminated film of the invention by preparing a kind of while rare earth doped salt and zeolite in metal base surface,
Not only utilize rare-earth salts corrosion inhibition property, but also make full use of the micropore special construction of zeolite granular for rare-earth salts provide one it is good
Good carrier, the two, which generates synergistic effect more, improves the corrosion resistance of silane film.Zeolite granular is filled into silicon simultaneously
Crosslink density can be increased in alkyl matter to reduce the wetability of monolithic film membrane, and react with silanol key by surface hydroxyl
It forms outer hydrophobic organic chain and effectively enhances the barrier action of Silan-based Thin Films to hinder the entrance of the corrosive medias such as water,
The corrosion resistance of metallic matrix is improved, the interface bond strength of polymeric coating layer and matrix is improved, meets aluminium alloy severe
Corrosion Protection requirement in Service Environment.
3. the present invention first simply pre-processes test button surface, the silicon doped with rare-earth salts and zeolite is prepared
The aluminum alloy specimen pre-processed is mixed in liquid using dip coating in prepared silane after ageing and is impregnated by alkane mixed liquor
Certain time, or aged solution is sprayed at pretreated aluminum alloy surface, solidify after drying or drying up, in metal material
Surface forms one layer of fine and close silane laminated film, and simple process is easy to operate, and mild condition is pollution-free, and reproducibility is high.
4. the present invention is suitable for various anti-corrosion of metal, including fine aluminium, aluminium alloy, ferroalloy, magnesium alloy or copper alloy etc.
Interface modification, applicability are wide.
Detailed description of the invention
Fig. 1 is the pure silane membrane sample for preparing under different volumes score silane and different solidification temperatures in 3.5wt%NaCl
Polarization curve in solution；
Wherein: Fig. 1 a is that the pure silane membrane sample of different volumes score silane preparation characterizes corrosion potential and corrosion current is close
Degree；From Fig. 1 a it can be concluded that silane optimal volume score is 5% (v/v)；
The pure silane membrane sample that Fig. 1 b, which is silane optimal volume score, to be prepared under difference solidification temperature when being 5% (v/v), from
Fig. 1 b is it can be concluded that best curing temperature is 100 DEG C.
Fig. 2 be aluminum alloy surface silane film in individually doped with various concentration cerous nitrate sample and they in different immersions
Polarization curve under time conditions in 3.5wt%NaCl solution；
Wherein: Fig. 2 a is in aluminum alloy surface silane film individually doped with various concentration cerous nitrate sample in 3.5wt%
Polarization curve in NaCl solution；By the variation of corrosion electric current density it can be concluded that cerous nitrate optimum doping concentration be 5 ×
10-3moL；
Fig. 2 b is that the polarization of the different soaking times in 3.5wt%NaCl solution doped with optium concentration cerous nitrate sample is bent
Line chart.
Fig. 3 is that zeolite sample polarization curve in solution in 3.5wt%NaCl is individually added in aluminum alloy surface silane film
Figure；As can be seen from the figure the sample just rises 1 order of magnitude by polarized current density after a polarization test, can
See, corrosion resistance, which is compared, to be not added with zeolite and do not obtain improvement.
Fig. 4 is to adulterate the silane complex film sample of the cerous nitrate and zeolite different soaking times in 3.5wt%NaCl solution
Polarization curve；
Wherein: Fig. 4 a is zeolite concentration 0.25g/L, and Fig. 4 b is zeolite concentration 0.5g/L, Fig. 4 c zeolite concentration 2.5g/L；Than
Compared with polarization curve it can be concluded that when zeolite concentration is 0.5g/L, corrosion electric current density is minimum and maintains to stablize time longest.
Fig. 5 is aluminum alloy surface pure silane membrane sample AC impedance figure in 3.5wt%NaCl solution.
Fig. 6 is individually to adulterate cerous nitrate sample AC impedance figure in 3.5wt%NaCl solution in silane film.
Fig. 7 is individually to adulterate zeolite sample AC impedance figure in 3.5wt%NaCl solution in silane film.
Fig. 8 be silane film in doped with cerous nitrate and zeolite sample in 3.5wt%NaCl solution AC impedance figure；From figure
In it can be concluded that adding cerous nitrate simultaneously and low-frequency impedance value reaches 10 when zeolite8Ω.cm2, and decrease speed is most slow, phase
Relatively individually addition cerous nitrate (Fig. 6) or zeolite (Fig. 7) have great improvement.
Figure 5-8 is characterized with characterization impedance value and phase angle.
Fig. 9 is various samples immersion test photo in 3.5wt%NaCl solution；
It is followed successively by aluminum alloy surface pure silane membrane sample from top to bottom, individually adulterates cerous nitrate sample, silane in silane film
It individually adulterates in zeolite sample and silane film in film doped with cerous nitrate and zeolite sample；
These pictures more intuitively present corrosion-resistant situation of the various sample in same corrosive environment, it is evident that simultaneously
The sample corrosion resistance of addition cerous nitrate and zeolite is greatly improved.
Figure 10 is cerous nitrate/silane treatment sample surface scan electron microscope and energy spectrum analysis (being shown in Table 1)；
Characterize sample surface micro-topography, it can be seen that there is no the regularities for destroying silane film for the addition of cerous nitrate, divide
Analyse power spectrum it can be concluded that silane film surface cerium oxide presence.
Figure 11 is that the surface scan electron microscope of zeolite/cerous nitrate/silane treatment sample of the present invention and energy spectrum analysis (are shown in Table
1)；
Characterize sample surface micro-topography, it can be seen that there is no crack and hole between film layer and particle, analysis power spectrum can
Contain Ce elements on zeolite granular to obtain, shows that zeolite has the function of adsorbing cerium ion.
Figure 12 is the electron probe Surface scan figure of zeolite/cerous nitrate/silane treatment sample of the present invention；
There is individual cerium oxide from being can analyze out in silane film in figure, and adsorbed the zeolite of cerium ion, further
Demonstrate the function of zeolite absorption cerium ion.
Table 1
Specific embodiment
The present invention is further explained with reference to embodiments, is not intended to limit the present invention.
Embodiment 1
(1) sample pretreatment
7N01 aluminium alloy is cut into 15 × 15 × 2mm sample, is boiled, after silicon carbide paper polishing in boiling water, successively in nothing
It is cleaned by ultrasonic in water-ethanol and deionized water；
(2) preparation of silane mixture liquid
By ethyl alcohol, double-(γ-triethoxysilylpropyl) tetrasulfide silane, deionized water, 90:5:5 is mixed by volume
It uniformly, is 1 × 10 by concentration-3The cerous nitrate of mol/L is added in mixed liquor, is aged 3d at room temperature, receives zeolite by 0.1g/L
Rice grain is added in mixed liquor, is stirred ultrasound 2min after 2min, is obtained silane mixture liquid；
(3) solidification of silane laminated film
It will be put into the silane mixture liquid being aged by pretreated aluminum alloy specimen, take out, be placed in after impregnating 1min
Solidify 1h in baking oven at 80 DEG C and forms silane laminated film.
Embodiment 2
(1) sample pretreatment
7020 aluminium alloys are cut into 15 × 15 × 2mm sample, are boiled, after silicon carbide paper polishing in boiling water, successively in nothing
It is cleaned by ultrasonic in water-ethanol and deionized water；
(2) preparation of silane mixture liquid
By ethyl alcohol, double-(γ-triethoxysilylpropyl) tetrasulfide silane, deionized water, 90:5:5 is mixed by volume
It uniformly, is 5 × 10 by concentration-3The cerous nitrate of mol/L is added in mixed liquor, is aged 1d at room temperature, receives zeolite by 0.1g/L
Rice grain is added in mixed liquor, is stirred ultrasound 2min after 2min, is obtained silane mixture liquid；
(3) solidification of silane laminated film
It will be put into the silane mixture liquid being aged by pretreated aluminum alloy specimen, take out, be placed in after impregnating 1min
Solidify 1h in baking oven at 60 DEG C and forms silane laminated film.
Embodiment 3
(1) sample pretreatment
6063 aluminium alloys are cut into 15 × 15 × 2mm sample, are boiled, after silicon carbide paper polishing in boiling water, successively in nothing
It is cleaned by ultrasonic in water-ethanol and deionized water；
(2) preparation of silane mixture liquid
By ethyl alcohol, double-(γ-triethoxysilylpropyl) tetrasulfide silane, deionized water, 85:5:10 is mixed by volume
It closes uniformly, is 9 × 10 by concentration-3The cerous nitrate of mol/L is added in mixed liquor, is aged 2d at room temperature, by 0.5g/L by zeolite
Nano particle is added in mixed liquor, is stirred ultrasound 2min after 2min, is obtained silane mixture liquid；
(3) solidification of silane laminated film
It will be put into the silane mixture liquid being aged by pretreated aluminum alloy specimen, take out, be placed in after impregnating 1min
Solidify 1h in baking oven at 119 DEG C and forms silane laminated film.
Embodiment 4
(1) sample pretreatment
7005 aluminium alloys are cut into 15 × 15 × 2mm sample, are boiled, after silicon carbide paper polishing in boiling water, successively in nothing
It is cleaned by ultrasonic in water-ethanol and deionized water；
(2) preparation of silane mixture liquid
By ethyl alcohol, γ-methacryloxypropyl-trimethoxy silane, deionized water, 80:10:10 is mixed by volume
It closes uniformly, is 2 × 10 by concentration-2The lanthanum nitrate of mol/L is added in mixed liquor, is aged 3d at room temperature, by 0.2g/L by zeolite
Nano particle is added in mixed liquor, is stirred ultrasound 2min after 2min, is obtained silane mixture liquid；
(3) solidification of silane laminated film
It will be put into the silane mixture liquid being aged by pretreated aluminum alloy specimen, take out, be placed in after impregnating 1min
Solidify 1h in baking oven at 89 DEG C and forms silane laminated film.
Embodiment 5
(1) sample pretreatment
2A01 aluminium alloy is cut into 15 × 15 × 2mm sample, is boiled, after silicon carbide paper polishing in boiling water, successively in nothing
It is cleaned by ultrasonic in water-ethanol and deionized water；
(2) preparation of silane mixture liquid
By ethyl alcohol, vinyl three (beta-methoxy ethyoxyl) silane, deionized water, 90:5:5 is uniformly mixed by volume, will
Concentration is 7 × 10-2The cerous nitrate of mol/L is added in mixed liquor, is aged 3d at room temperature, by 0.09g/L by zeolite nano-particle
It is added in mixed liquor, stirs ultrasound 2min after 2min, obtain silane mixture liquid；
(3) solidification of silane laminated film
It will be put into the silane mixture liquid being aged by pretreated aluminum alloy specimen, take out, be placed in after impregnating 1min
Solidify 1h in baking oven at 95 DEG C and forms silane laminated film.
Embodiment 6
(1) sample pretreatment
2005 aluminium alloys are cut into 15 × 15 × 2mm sample, are boiled, after silicon carbide paper polishing in boiling water, successively in nothing
It is cleaned by ultrasonic in water-ethanol and deionized water；
(2) preparation of silane mixture liquid
By ethyl alcohol, N- (β-aminoethyl)-γ-aminopropyl-Methyl-trimethoxy silane, deionized water, by volume 95:
5:5 is uniformly mixed, and is 1 × 10 by concentration-2The cerous nitrate of mol/L is added in mixed liquor, is aged 3d at room temperature, will by 0.3g/L
Zeolite nano-particle is added in mixed liquor, is stirred ultrasound 2min after 2min, is obtained silane mixture liquid；
(3) solidification of silane laminated film
It will be put into the silane mixture liquid being aged by pretreated aluminum alloy specimen, take out, be placed in after impregnating 1min
Solidify 1h in baking oven at 85 DEG C and forms silane laminated film.
Embodiment 7
(1) sample pretreatment
7N01 aluminium alloy is subjected to differential arc oxidation pretreatment；
(2) preparation of silane mixture liquid
By ethyl alcohol, double-(γ-triethoxysilylpropyl) tetrasulfide silane, deionized water, 90:5:5 is mixed by volume
It uniformly, is 5 × 10 by concentration-3The cerous nitrate of mol/L is added in mixed liquor, is aged 3d at room temperature, receives zeolite by 0.1g/L
Rice grain is added in mixed liquor, is stirred ultrasound 2min after 2min, is obtained silane mixture liquid；
(3) solidification of silane laminated film
It will be put into the solution of silane being aged by pretreated aluminum alloy specimen, taken out after impregnating 1min, be placed in baking
Solidify 1h in case at 80 DEG C and forms silane laminated film.
Comparative example 1
The preparation of pure silane film:
Implement according to the method for embodiment 2, does not add rare-earth salts and zeolite only.
Comparative example 2
The preparation of the modified Silan-based Thin Films of rare-earth salts
Implement according to the method for embodiment 2, does not add zeolite only.
Comparative example 3
The preparation of the Silan-based Thin Films of Zeolite modifying
Implement according to the method for embodiment 2, does not add rare-earth salts only.
The result of embodiment 2 and comparative example 1,2,3 is shown in Fig. 5,6,7,8,9.
Claims (10)
1. the silane laminated film of a kind of rare earth doped salt and zeolite.
2. the silane laminated film of rare earth doped salt according to claim 1 and zeolite, which is characterized in that the preparation
In the reaction system of the silane laminated film of rare earth doped salt and zeolite: rare earth salinity is 1 × 10-4~1 × 10-1Mol/L,
Zeolite concentration is 0.05~5g/L.
3. the silane laminated film of rare earth doped salt according to claim 1 and zeolite, which is characterized in that the zeolite
Grain diameter is 30~900nm.
4. the silane laminated film of rare earth doped salt according to claim 1 and zeolite, which is characterized in that the doping
The silane laminated film of rare-earth salts and zeolite is with a thickness of 100~2000nm.
5. the preparation method of the silane laminated film of a kind of described in any item rare earth doped salt of claim 1-4 and zeolite,
It is characterized in that, comprising the following steps:
(1) silane mixture liquid is prepared: rare-earth salts being added in the mixed liquor of silane and solvent, is added zeolite after aged
Grain is up to silane mixture liquid；
(2) silane mixture liquid the solidification of silane laminated film: is attached to pretreated metal material by impregnating or spraying
Expect surface, solidifies the silane laminated film up to rare earth doped salt and zeolite.
6. preparation method according to claim 5, which is characterized in that the rare-earth salts is in soluble cerium salt and lanthanum salt
It is a kind of；The silane is single or double silane coupling agent.
7. preparation method according to claim 5, which is characterized in that in step (1), the volume ratio of the silane and solvent
For 1~30:99~70.
8. preparation method according to claim 5, which is characterized in that in step (1), zeolite granular passes through after mixed liquor is added
Ultrasonic agitation obtains silane mixture liquid.
9. preparation method according to claim 5, which is characterized in that in step (2), curing process condition: temperature 20
~200 DEG C, the time is 0.5~48h.
10. the silane laminated film or claim 5-9 of the described in any item rare earth doped salt of claim 1-4 and zeolite are any
The application method of the silane laminated film of rare earth doped salt made from preparation method described in and zeolite, which is characterized in that institute
The silane laminated film solidification of the rare earth doped salt and zeolite stated is used for anticorrosion in metal material surface.
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