CN106756968A - Protective treatment method of aluminum alloy surface is carried out with nano modification silicon systems composite passivation film - Google Patents
Protective treatment method of aluminum alloy surface is carried out with nano modification silicon systems composite passivation film Download PDFInfo
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- CN106756968A CN106756968A CN201611196910.7A CN201611196910A CN106756968A CN 106756968 A CN106756968 A CN 106756968A CN 201611196910 A CN201611196910 A CN 201611196910A CN 106756968 A CN106756968 A CN 106756968A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/56—Treatment of aluminium or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
- C23C22/78—Pretreatment of the material to be coated
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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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/32—Alkaline compositions
- C23F1/36—Alkaline compositions for etching aluminium or alloys thereof
-
- 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
Abstract
The invention provides one kind Protective treatment method of aluminum alloy surface is carried out with nano modification silicon systems composite passivation film, belong to technical field of metal surface protection, its technological process is that alloy matrix aluminum is carried out into degreasing alkaline etching pretreatment, certain hour in the silicon systems composite passivation solution of the nano modification that then impregnated in preparation, after taking-up through high-temperature process aluminium alloy matrix surface formed one layer of even compact corrosion resistance it is high without chromium-silicon system comprehensive silicon alkane film.Beneficial effects of the present invention are：Preparation process is simple, low cost, treatment temperature is low, film formation time is short, silane film is combined using the Chrome-free with different functional groups, there can be long-acting decay resistance, also possesses the good combination power with organic coating simultaneously, the pollution-free material discharge of processing procedure, belongs to environmentally friendly technology in addition.
Description
Technical field
The present invention relates to technical field of metal surface protection, more particularly to aluminium is carried out with nano modification silicon systems composite passivation film
Alloy surface protection processing method.
Background technology
Under field conditions (factors), surface can form one layer of very thin oxide-film to aluminium alloy, but this layer of oxide-film is loose porous, no
Uniform and discontinuous, corrosion resistance is poor under the conditions of atmospheric environment or various corrosive mediums, it is impossible to enough tables as aluminum alloy materials
Face overcoat, therefore aluminum alloy materials must carry out preservative treatment before to its surface.Aluminium alloy surface anti-corrosion processes skill
Art mainly has chromating treatment, anodized, phosphate treated, silicic acid salt treatment, silanization treatment etc..Wherein chromium
Hydrochlorate passivation treatment technology is that metallic substrates are aoxidized using the strong oxidizing property of chromate, so as to form one layer of cause in metal surface
Close passivating film, but Cr present in Passivation Treatment process (VI) is carcinogen, and the mankind and environment can be caused with serious danger
Evil；The composition for the treatment of fluid can have a huge impact to the structure and composition of oxide-film in anodized technology, therefore the party
The research of method is still concentrated mainly in the improvement for the treatment of fluid at present；Phosphate transfection treatment be by chemistry or electrochemical reaction,
Aluminium alloy matrix surface forms one layer of conversion film, but it has high energy consumption in processing procedure, produces a large amount of salkali waste spent acid etc.
Problem.
Chinese publication, publication number：CN105088211A, once disclosed at a kind of compound chromium-free deactivation of aluminium section bar environmental protection
Reason liquid, it is characterised in that be made from the following raw materials in parts by weight：Cerous nitrate 9.6-10, potassium permanganate 2-2.2, glycerine 0.2-
0.3rd, BIT 0.1-0.2, K2ZrF61.2-1.3, styrene 0.6-0.8, acrylamide 0.2-0.3, acrylic acid
0.4-0.5, azodiisobutyronitrile 0.05-0.1, sodium allylsulfonate 0.5-0.6, lauryl sodium sulfate 0.02-0.03, hexadecane
0.9-1, nano silicon 0.3-0.4, nano titanium oxide 0.3-0.4, appropriate deionized water.But, the chromium-free passivation liquid
Complicated component, preparation process is cumbersome.
The content of the invention
The invention provides Protective treatment method of aluminum alloy surface is carried out with nano modification silicon systems composite passivation film, work is prepared
Skill is simple, low cost, and treatment temperature is low, film formation time is short, and silane film is combined using the Chrome-free with different functional groups, can
With long-acting decay resistance, while also possess the good combination power with organic coating, the pollution-free material of processing procedure in addition
Discharge, belongs to environmentally friendly technology.
In order to solve the above technical problems, the embodiment of the present application is provided carries out aluminium conjunction with nano modification silicon systems composite passivation film
Gold surface protection processing method, preparation flow is comprised the following steps：
a）, be cleaned by ultrasonic：Aluminium alloy is placed in acetone soln, insertion ultrasonic vibration installation is cleaned, after then taking out
It is no less than 3 times with deionized water rinsing；
b）, alkaline etching：15g NaOH, 2g sodium carbonate, 0.5g sodium phosphates are added in 100mL water, is stirred at room temperature, made
Obtain alkaline etching and match somebody with somebody liquid, above-mentioned gained aluminium alloy is entered into alkaline etching with treatment 3 minutes in liquid；
c）, cleaning one：The aluminium alloy of gained after alkaline etching is cleaned no less than 3 times with deionized water, is dried up stand-by；
d）, plated film：10mL MTMS are added to the aqueous solution of 100mL methyl alcohol（8mL containing methyl alcohol）In, add 15mg/L vapor phase methods
White carbon, the pH value for adjusting hydrolyzate with the acetic acid of 45wt% is 4, in constant temperature hydrolysis 24h at 25 DEG C, treats Nano-meter SiO_22Particle is complete
It is distributed in silane coupler entirely, continues, to 10mL γ-APS are added in passivating solution, in constant temperature hydrolysis 24h is continued at 25 DEG C, to obtain
To the compound silicon systems passivating solution of nano modification, then by step c）1-5 minutes in the aluminium alloy immersion passivating solution of middle gained；
e）, cleaning two：By step d）The aluminium alloy of middle gained is cleaned no less than 3 times with deionized water；
f）, drying：By step e）The aluminium alloy of gained is put into dry solidification 0.5-4h in 80-150 DEG C of baking oven, you can in aluminium alloy
The compound silane film of Chrome-free that surface is prepared for；
g）, inspection：By step f）The aluminum alloy specimen of middle gained is placed in 3.5wt% sodium chloride solutions, uses electrochemical workstation
Detect its corrosion potential, corrosion current and adhesive force.
As the preferred embodiment of this programme, according to aluminium alloy treating capacity in described plated film, by being continuously replenished concentration
Composite passivation solution keeps concentration.
Used as the preferred embodiment of this programme, described hydrophobic silane coupling agent is MTMS（Methyl trimethoxy epoxide silicon
Alkane）、PTMS（Phenyltrimethoxysila,e）、WD-10（Propyl trimethoxy silicane）Or BTESPT（Double-[3- (triethoxy) silicon
Propyl group] tetrasulfide）One kind in silane coupler with hydrophobic functional groups or without functional group.
Used as the preferred embodiment of this programme, described hydrophilic silane coupling agent is γ-APS（Gamma-aminopropyl-triethoxy
Silane）、KH792（Aminoethyl -3- aminopropyl trimethoxysilanes）、KH540（γ-aminopropyltrimethoxysilane）Or KH570
（γ-（Methacryloxypropyl）Propyl trimethoxy silicane）One kind in silane coupler with hydrophilic functional group.
Used as the preferred embodiment of this programme, described hydrophobic silane coupling agent and the volume ratio of hydrophilic silane coupling agent are
1/0-1/4。
Used as the preferred embodiment of this programme, described inertia nano particle is fume colloidal silica, preferably specific surface area
For：150~250m2/ g, addition is 5mg/L-25mg/L, and acetic acid adjusts the pH value 3-6 of hydrolyzate, and hydrolysis temperature is 25-45
℃。
Used as the preferred embodiment of this programme, described solvent solution is alcohol/aqueous solution, the wherein volume of alcohol/aqueous solution
Than for（5-15)：(45-35).
One or more technical schemes provided in the embodiment of the present application, at least have the following technical effect that or advantage：
Preparation process is simple, low cost, treatment temperature is low, film formation time is short, and silane is combined using the Chrome-free with different functional groups
Film, can have long-acting decay resistance, while also possess the good combination power with organic coating, processing procedure in addition
Pollution-free material discharge, belongs to environmentally friendly technology.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
The accompanying drawing to be used needed for having technology description is briefly described, it should be apparent that, drawings in the following description are only this hairs
Some bright embodiments, for those of ordinary skill in the art, without having to pay creative labor, can be with
Other accompanying drawings are obtained according to these accompanying drawings.
Fig. 1 is the structural representation of the embodiment of the present application；
Fig. 2 is the dynamic potential polarization curve of naked aluminium used by the embodiment of the present invention 1.
Fig. 3 is that the potentiodynamic polarization of aluminium alloy after the embodiment of the present invention 1 is processed through nano modification silicon systems composite passivation solution is bent
Line.
Fig. 4 is the SEM figures of naked aluminium surface in the embodiment of the present invention 1.
Fig. 5 is gained aluminum alloy surface composite membrane after the embodiment of the present invention 1 is processed through nano modification silicon systems composite passivation solution
SEM figure.
In Fig. 1-5：1st, be cleaned by ultrasonic, 2, alkaline etching, 3, cleaning one, 4, plated film, 5, cleaning two, 6, drying, 7, inspection.
Specific embodiment
The invention provides Protective treatment method of aluminum alloy surface is carried out with nano modification silicon systems composite passivation film, work is prepared
Skill is simple, low cost, and treatment temperature is low, film formation time is short, and silane film is combined using the Chrome-free with different functional groups, can
With long-acting decay resistance, while also possess the good combination power with organic coating, the pollution-free material of processing procedure in addition
Discharge, belongs to environmentally friendly technology.
In order to be better understood from above-mentioned technical proposal, below in conjunction with Figure of description and specific embodiment to upper
Technical scheme is stated to be described in detail.
As Figure 1-5, Protective treatment method of aluminum alloy surface is carried out with nano modification silicon systems composite passivation film, stream is prepared
Journey is comprised the following steps：
a）, be cleaned by ultrasonic 1：Aluminium alloy is placed in acetone soln, insertion ultrasonic vibration installation is cleaned, after then taking out
It is no less than 3 times with deionized water rinsing；
b）, alkaline etching 2：15g NaOH, 2g sodium carbonate, 0.5g sodium phosphates are added in 50-150mL water, stirs equal at room temperature
It is even, alkaline etching is obtained and matches somebody with somebody liquid, above-mentioned gained aluminium alloy is entered into alkaline etching with treatment 2-5 minutes in liquid；
c）, cleaning 1：The aluminium alloy of gained after alkaline etching is cleaned no less than 3 times with deionized water, is dried up stand-by；
d）, plated film 4：5-20mL MTMS are added to the aqueous solution of 50-150mL methyl alcohol（8mL containing methyl alcohol）In, add 15mg/L
Fume colloidal silica, the pH value for adjusting hydrolyzate with the acetic acid of 45wt% is 4, in constant temperature hydrolysis 24h at 25 DEG C, treats Nano-meter SiO_22
Particle is completely dispersed in silane coupler, continues, to 10mL γ-APS are added in passivating solution, to be hydrolyzed in constant temperature is continued at 25 DEG C
24h, obtains the compound silicon systems passivating solution of nano modification, then by step c）1-5 points in the aluminium alloy immersion passivating solution of middle gained
Clock；
e）, cleaning 25：By step d）The aluminium alloy of middle gained is cleaned no less than 3 times with deionized water；
f）, drying 6：By step e）The aluminium alloy of gained is put into dry solidification 0.5-4h in 80-150 DEG C of baking oven, you can closed in aluminium
The compound silane film of Chrome-free that gold surface is prepared for；
g）, inspection 7：By step f）The aluminum alloy specimen of middle gained is placed in 3.5wt% sodium chloride solutions, uses electrochemical operation
Stand and detect its corrosion potential, corrosion current and adhesive force.
Wherein, in actual applications, it is compound by being continuously replenished concentration according to aluminium alloy treating capacity in described plated film 4
Passivating solution keeps concentration.
Wherein, in actual applications, described hydrophobic silane coupling agent is MTMS（MTMS）、
PTMS（Phenyltrimethoxysila,e）、WD-10（Propyl trimethoxy silicane）Or BTESPT（Double-[3- (triethoxy) silicon third
Base] tetrasulfide）One kind in silane coupler with hydrophobic functional groups or without functional group.
Wherein, in actual applications, described hydrophilic silane coupling agent is γ-APS（Gamma-aminopropyl-triethoxy silicon
Alkane）、KH792（Aminoethyl -3- aminopropyl trimethoxysilanes）、KH540（γ-aminopropyltrimethoxysilane）Or KH570
（γ-（Methacryloxypropyl）Propyl trimethoxy silicane）One kind in silane coupler with hydrophilic functional group.
Wherein, in actual applications, the volume ratio of described hydrophobic silane coupling agent and hydrophilic silane coupling agent is 1/0-
1/4。
Wherein, in actual applications, described inertia nano particle is fume colloidal silica, and preferably specific surface area is：
150~250m2/ g, addition is 5mg/L-25mg/L, and acetic acid adjusts the pH value 3-6 of hydrolyzate, and hydrolysis temperature is 25-45 DEG C.
Wherein, in actual applications, described solvent solution is alcohol/aqueous solution, and the volume ratio of wherein alcohol/aqueous solution is
（5-15)：(45-35)
Embodiment 1
10mL MTMS are added to the aqueous solution of 100mL methyl alcohol（8mL containing methyl alcohol）In, 15mg/L fume colloidal silicas are added, use
The pH value of the acetic acid regulation hydrolyzate of 45wt% is 4, in constant temperature hydrolysis 24h at 25 DEG C, treats that nano silica particle is completely dispersed silicon
In alkane coupling agent, continue, to 10mL γ-APS are added in passivating solution, in constant temperature hydrolysis 24h is continued at 25 DEG C, to obtain nano modification
Compound silicon systems passivating solution.
15g NaOH, 2g sodium carbonate, 0.5g sodium phosphates are added in 100mL water, is stirred at room temperature, alkali is obtained
Liquid is matched somebody with somebody in erosion, and deionized water is cleaned 3 times after aluminum alloy sample is cleaned by ultrasonic into removal surface grease through acetone, is then immersed in above-mentioned
Alkaline etching is washed with deionized 3 times with 3min is soaked in liquid after taking-up, dries up stand-by.By the aluminium alloy dipping after treatment in system
3min in standby composite passivation solution, is washed with deionized 3 times, the dry solidification 1.5h in 100oC baking ovens, i.e., in aluminium alloy table
The compound silane film of Chrome-free that face is prepared for.
Detect that surface does not prepare the alloy matrix aluminum of compound silane film in 3.5wt% sodium chloride solutions with electrochemical workstation
In corrosion potential be -1.2735V, corrosion current is 4.8267 × 10-6A；Aluminum alloy specimen is in 3.5wt% sodium chloride solutions
Corrosion potential be -0.3454V, corrosion current is 2.7538 × 10·A.It is further characterization aluminum alloy surface chromium-free deactivation
The performance of compound silane film, it is organic that the present invention has brushed epoxy resin in the naked aluminum alloy surface of coating and aluminum alloy specimen respectively
Coating, with reference to GB/T5210-85《The determination method of coating adhesion-pull open method》Method determine naked aluminium surface coating epoxy coating
Adhesive force F=8.76Ncm-2；The adhesive force F=47.67 Ncm of coating on aluminum alloy specimen-2.(F=G/S, wherein to apply
Layer adhesive force（N cm-2）；G is opened load value during destruction for sample（N）；S is the cross-sectional area cm of sample2)
Embodiment 2
It is used for the preparation method without chromium-silicon system composite passivation solution of aluminum alloy surface protective treatment as described in Example 1, institute is not
Be：
15mL MTMS are added to the aqueous solution of 100mL methyl alcohol（8mL containing methyl alcohol）In, 15mg/L fume colloidal silicas are added, use
The pH value of the acetic acid regulation hydrolyzate of 45wt% is 4, in constant temperature hydrolysis 24h at 25 DEG C, treats Nano-meter SiO_22Particle is completely dispersed silicon
In alkane coupling agent, continue, to 5mL γ-APS are added in passivating solution, in constant temperature hydrolysis 24h is continued at 25 DEG C, to obtain nano modification
Compound silicon systems passivating solution.
Detect that corrosion potential of the aluminum alloy specimen in 3.5wt% sodium chloride solutions is -0.683V with electrochemical workstation,
Corrosion current is 1.6472 × 10-8A.With reference to GB/T5210-85《The determination method of coating adhesion-pull open method》Method determine aluminium
The adhesive force F=42.83Ncm- of coating on alloy sample2。
Embodiment 3
It is used for the preparation method without chromium-silicon system composite passivation solution of aluminum alloy surface protective treatment as described in Example 1, institute is not
Be：
5mL PTMS are added to the aqueous solution of 100mL methyl alcohol（8mL containing methyl alcohol）, 20mg/L fume colloidal silicas are added, use
The pH value of the acetic acid regulation hydrolyzate of 45wt% is 4, in constant temperature hydrolysis 24h at 25 DEG C, to addition 15mL KH540 in hydrolyzate,
Continue to hydrolyze 24h, obtain composite passivation solution.
Detect that corrosion potential of the aluminum alloy specimen in 3.5wt% sodium chloride solutions is -0.537V with electrochemical workstation,
Corrosion current is 1.7438 × 10-8A.With reference to GB/T5210-85《The determination method of coating adhesion-pull open method》Method determine
The adhesive force F=42.34Ncm of coating on aluminum alloy specimen-2。
Embodiment 4
It is used for the preparation method of the compound silane film of aluminum alloy surface chromium-free deactivation as described in Example 1, except that
150oDry solidification in C baking ovens.
Being detected with electrochemical workstation, corrosion potential of the aluminum alloy specimen in 3.5wt% sodium chloride solutions be-
0.7114V, corrosion current is 3.2084 × 10-7A.With reference to GB/T5210-85《The determination method of coating adhesion-pull open method》Side
Method determines the adhesive force F=40.55Ncm of coating on aluminum alloy specimen-2。
Embodiment 5
It is used for the preparation method of the compound silane film of aluminum alloy surface chromium-free deactivation as described in Example 1, except that：Step
Suddenly（2）In, the drying time of film-forming is 2.5h.
Being detected with electrochemical workstation, corrosion potential of the aluminum alloy specimen in 3.5wt% sodium chloride solutions be-
0.7473V, corrosion current is 3.5809 × 10-7A.With reference to GB/T5210-85《The determination method of coating adhesion-pull open method》Side
Method determines the adhesive force F=38.67Ncm of coating on aluminum alloy specimen-2。
Comparative example 1
As described in Example 1, the preparation process of composite passivation solution is unlike：By 10mL MTMS and 10mL γ-APS successively
It is added to the aqueous solution of 100mL methyl alcohol（8mL containing methyl alcohol）In, 15mg/L fume colloidal silicas are added, adjusted with the acetic acid of 45wt%
The pH value for saving hydrolyzate is 4, in constant temperature hydrolysis 48h at 25 DEG C.
Being detected with electrochemical workstation, corrosion potential of the aluminum alloy specimen in 3.5wt% sodium chloride solutions be-
0.8792V, corrosion current is 6.2754 × 10-8A.With reference to GB/T5210-85《The determination method of coating adhesion-pull open method》Side
Method determines the adhesive force F=11.54Ncm of coating on aluminum alloy specimen-2。
Comparative example 2
As described in Example 1, using only 20mL MTMS in passivating solution used unlike.
Being detected with electrochemical workstation, corrosion potential of the aluminum alloy specimen in 3.5wt% sodium chloride solutions be-
0.7543V, corrosion current is 5.6862 × 10-7A.With reference to GB/T5210-85《The determination method of coating adhesion-pull open method》Side
Method determines the adhesive force F=11.54Ncm of coating on aluminum alloy specimen-2。
Comparative example 3
As described in Example 1, using only 20mL γ-APS in passivating solution used unlike, 10mL MTMS are added without.
Being detected with electrochemical workstation, corrosion potential of the aluminum alloy specimen in 3.5wt% sodium chloride solutions be-
0.8425V, corrosion current is 9.6736 × 10-8A.With reference to GB/T5210-85《The determination method of coating adhesion-pull open method》Side
Method determines the adhesive force F=24.67Ncm of coating on aluminum alloy specimen-2。
The above, is only presently preferred embodiments of the present invention, and any formal limitation is not made to the present invention, though
So the present invention is disclosed above with preferred embodiment, but is not limited to the present invention, any to be familiar with this professional technology people
Member, without departing from the scope of the present invention, when making a little change or modification using the technology contents of the disclosure above
It is the Equivalent embodiments of equivalent variations, as long as being the content without departing from technical solution of the present invention, according to technical spirit of the invention
Any simple modification, equivalent variations and the modification made to above example, still fall within the range of technical solution of the present invention.
Claims (7)
1. Protective treatment method of aluminum alloy surface is carried out with nano modification silicon systems composite passivation film, it is characterised in that preparation flow
Comprise the following steps：
a）, be cleaned by ultrasonic：Aluminium alloy is placed in acetone soln, insertion ultrasonic vibration installation is cleaned, after then taking out
It is no less than 3 times with deionized water rinsing；
b）, alkaline etching：15g NaOH, 2g sodium carbonate, 0.5g sodium phosphates are added in 50-100mL water, are stirred at room temperature,
Alkaline etching is obtained and matches somebody with somebody liquid, above-mentioned gained aluminium alloy is entered into alkaline etching with treatment 3 minutes in liquid；
c）, cleaning one：The aluminium alloy of gained after alkaline etching is cleaned no less than 3 times with deionized water, is dried up stand-by；
d）, plated film：5-15mL MTMS are added to the aqueous solution of 50-150mL methyl alcohol（8mL containing methyl alcohol）In, add 15mg/L gas
Phase method white carbon, the pH value for adjusting hydrolyzate with the acetic acid of 45wt% is 4, in constant temperature hydrolysis 24h at 25 DEG C, treats Nano-meter SiO_22
Grain is completely dispersed in silane coupler, continues, to 10mL γ-APS are added in passivating solution, to be hydrolyzed in constant temperature is continued at 25 DEG C
24h, obtains the compound silicon systems passivating solution of nano modification, then by step c）1-5 points in the aluminium alloy immersion passivating solution of middle gained
Clock；
e）, cleaning two：By step d）The aluminium alloy of middle gained is cleaned no less than 3 times with deionized water；
f）, drying：By step e）The aluminium alloy of gained is put into dry solidification 0.5-4h in 80-150 DEG C of baking oven, you can in aluminium alloy
The compound silane film of Chrome-free that surface is prepared for；
g）, inspection：By step f）The aluminum alloy specimen of middle gained is placed in 3.5wt% sodium chloride solutions, uses electrochemical workstation
Detect its corrosion potential, corrosion current and adhesive force.
It is 2. according to claim 1 to carry out Protective treatment method of aluminum alloy surface with nano modification silicon systems composite passivation film,
Characterized in that, keeping concentration by being continuously replenished concentration composite passivation solution according to aluminium alloy treating capacity in described plated film.
It is 3. according to claim 1 to carry out Protective treatment method of aluminum alloy surface with nano modification silicon systems composite passivation film,
Characterized in that, described hydrophobic silane coupling agent is MTMS（MTMS）、PTMS（Phenyl trimethoxy
Silane）、WD-10（Propyl trimethoxy silicane）Or BTESPT（Double-[3- (triethoxy) silicon propyl group] tetrasulfide）With hydrophobic
One kind in property functional group or the silane coupler without functional group.
It is 4. according to claim 1 to carry out Protective treatment method of aluminum alloy surface with nano modification silicon systems composite passivation film,
Characterized in that, described hydrophilic silane coupling agent is γ-APS（Gamma-aminopropyl-triethoxy-silane）、KH792（Aminoethyl-
3- aminopropyl trimethoxysilanes）、KH540（γ-aminopropyltrimethoxysilane）Or KH570（γ-（Methacryloxypropyl）Third
Base trimethoxy silane）One kind in silane coupler with hydrophilic functional group.
It is 5. according to claim 1 to carry out Protective treatment method of aluminum alloy surface with nano modification silicon systems composite passivation film,
Characterized in that, the volume ratio of described hydrophobic silane coupling agent and hydrophilic silane coupling agent is 1/0-1/4.
It is 6. according to claim 1 to carry out Protective treatment method of aluminum alloy surface with nano modification silicon systems composite passivation film,
Characterized in that, described inertia nano particle is fume colloidal silica, preferably specific surface area is：150~250m2/ g, addition
It is 5mg/L-25mg/L to measure, and acetic acid adjusts the pH value 3-6 of hydrolyzate, and hydrolysis temperature is 25-45 DEG C.
It is 7. according to claim 1 to carry out Protective treatment method of aluminum alloy surface with nano modification silicon systems composite passivation film,
Characterized in that, described solvent solution is alcohol/aqueous solution, the volume ratio of wherein alcohol/aqueous solution is（5-15)：(45-35).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611196910.7A CN106756968A (en) | 2016-12-22 | 2016-12-22 | Protective treatment method of aluminum alloy surface is carried out with nano modification silicon systems composite passivation film |
Applications Claiming Priority (1)
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| CN107475706A (en) * | 2017-06-26 | 2017-12-15 | 安徽雷萨重工机械有限公司 | A kind of surface treatment method for lifting aluminium alloy and using characteristic |
| CN107829086A (en) * | 2017-11-08 | 2018-03-23 | 安徽腾龙泵阀制造有限公司 | A kind of anticorrosion treatment technology of pump aluminium alloy part |
| CN108456878A (en) * | 2018-03-08 | 2018-08-28 | 东北大学 | A kind of nano grain surface Modified lift conversion film performance methodology |
| CN109706335A (en) * | 2019-02-25 | 2019-05-03 | 江苏港缆新材料科技有限公司 | A kind of processing technology of the almag of corrosion resistance |
| CN110923685A (en) * | 2019-12-10 | 2020-03-27 | 湖州织里宝丰铝业有限公司 | Surface passivation treatment process for aluminum alloy profile |
| CN113088188A (en) * | 2021-03-31 | 2021-07-09 | 上海应用技术大学 | Hydrophobic nanoparticle-based super-hydrophobic silane membrane and preparation and application thereof |
| CN113182777A (en) * | 2021-04-25 | 2021-07-30 | 合肥聚能电物理高技术开发有限公司 | Preparation method of beryllium and aluminum or aluminum alloy component |
| CN115462384A (en) * | 2022-08-02 | 2022-12-13 | 山东大学 | DCOIT slow-release nanocapsule taking silicon dioxide as carrier as well as preparation method and application thereof |
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| CN107475706A (en) * | 2017-06-26 | 2017-12-15 | 安徽雷萨重工机械有限公司 | A kind of surface treatment method for lifting aluminium alloy and using characteristic |
| CN107829086A (en) * | 2017-11-08 | 2018-03-23 | 安徽腾龙泵阀制造有限公司 | A kind of anticorrosion treatment technology of pump aluminium alloy part |
| CN108456878A (en) * | 2018-03-08 | 2018-08-28 | 东北大学 | A kind of nano grain surface Modified lift conversion film performance methodology |
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| CN110923685A (en) * | 2019-12-10 | 2020-03-27 | 湖州织里宝丰铝业有限公司 | Surface passivation treatment process for aluminum alloy profile |
| CN113088188A (en) * | 2021-03-31 | 2021-07-09 | 上海应用技术大学 | Hydrophobic nanoparticle-based super-hydrophobic silane membrane and preparation and application thereof |
| CN113182777A (en) * | 2021-04-25 | 2021-07-30 | 合肥聚能电物理高技术开发有限公司 | Preparation method of beryllium and aluminum or aluminum alloy component |
| CN115462384A (en) * | 2022-08-02 | 2022-12-13 | 山东大学 | DCOIT slow-release nanocapsule taking silicon dioxide as carrier as well as preparation method and application thereof |
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