CN110527995B - Application of MXene/silane surface composite silane film in metal corrosion protection - Google Patents

Application of MXene/silane surface composite silane film in metal corrosion protection Download PDF

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CN110527995B
CN110527995B CN201910931909.1A CN201910931909A CN110527995B CN 110527995 B CN110527995 B CN 110527995B CN 201910931909 A CN201910931909 A CN 201910931909A CN 110527995 B CN110527995 B CN 110527995B
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silane
mxene
film
metal
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CN110527995A (en
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曹美文
聂焱
马晟焱
石永康
李智超
党梦涛
王生杰
夏永清
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China University of Petroleum East China
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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
    • C23C22/50—Treatment of iron or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—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
    • 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 belongs to the field of metal corrosion protection, and particularly relates to an application of an MXene/silane surface composite silane film in metal corrosion protection. The method comprises the following steps: preparing and hydrolyzing MXene/silane mixed solution, treating the surface of a metal sample, and immersing and curing the metal sample in the mixed silane hydrolysate to form a film. The method adopts the MXene/silane surface composite silane film protection surface treatment technology, overcomes the defect of incompactness of a single silane film, is simple to operate, safe and environment-friendly, and can effectively hinder the diffusion of corrosive media and improve the corrosion resistance of the silane film by doping the MXene.

Description

Application of MXene/silane surface composite silane film in metal corrosion protection
Technical Field
The invention belongs to the field of metal corrosion protection, and particularly relates to an application of an MXene/silane surface composite silane film in metal corrosion protection.
Background
Metal materials are widely used in human life, and corrosion is an important factor causing waste of metal materials. Aluminum alloys and steel materials have excellent characteristics and are widely used in various fields of industrial production. However, aluminum alloys and steel materials generally have poor corrosion resistance, particularly hard aluminum alloys and super hard aluminum alloys. With the improvement of the requirement of people on environmental protection in recent years, the traditional chromate passivation and corrosion prevention technology is gradually eliminated, and a plurality of researchers are always searching for an aluminum alloy surface treatment technology which is environment-friendly, energy-saving, efficient and harmless to human bodies.
Recent research discovers that the silane coupling agent can be firmly attached to the surface of the metal through chemical bonds of Si-O-metal, and silane is crosslinked with each other to form a three-dimensional net-shaped protective film, so that the metal is effectively protected. However, the single silane film is very thin, and some of the silane films have certain defects and poor stability, and once the silane film is mechanically damaged, the silane film is damaged and loses the function of protecting the metal.
In order to solve the problems, researchers modify a silane film by mixing a plurality of silanes and adding some nano materials into a silane solution so as to improve the protective performance and stability of the silane film. The invention patent CN102719821B discloses a composite nano silane film for metal surface corrosion prevention and a film forming method thereof, which comprises the steps of surface treatment, hydrolysis, dipping, drying and the like of a metal piece. The invention combines the activated nano material and the silane, effectively improves the corrosion resistance of the silane film, and the corrosion current is almost zero when the overpotential of the anode polarization curve in 3.5 percent NaCl solution reaches 700 mV. However, when the silane film in the above patent is used for metal surface corrosion prevention, the corrosion protection performance is improved to a limited extent, and the nano material needs to be activated in the application process, the process is complex, the silanol solution needs to be hydrolyzed for a long time, and the method is time-consuming, labor-consuming, high in cost and not beneficial to industrial production.
Disclosure of Invention
In order to overcome the defects of the traditional single silanization treatment in metal corrosion protection and reduce the application cost of the composite silane film, the invention provides the application of the MXene/silane surface composite silane film in metal corrosion protection, the silane film can effectively hinder the diffusion of a corrosion medium in the silane film, the corrosion resistance of the silane film is greatly improved, the process operation is simple, and the industrial popularization is facilitated.
In order to achieve the purpose, the invention provides the application of the MXene/silane surface composite silane film in metal corrosion protection.
Preferably, the silane is selected from gamma-GPS (gamma-glycidoxypropyltrimethoxysilane) or BTSE (1, 2-bis (triethoxysilyl) ethane), and the metal is aluminum alloy or Q235 steel.
Preferably, the application comprises the steps of:
preparing MXene/silane mixed solution and hydrolyzing to obtain mixed silane hydrolysate; fully soaking the surface-treated metal sample in the mixed silane hydrolysate; and taking out the dipped metal sample, removing redundant liquid, and curing in an oven to form a film.
Preferably, the specific operation steps in the preparation of the mixed silane hydrolysate are as follows:
preparing 1-5% silane solution; mixing MXene with the silane solution, and uniformly stirring to obtain a mixed silane solution; adjusting pH to 4.5-6.5 with acetic acid, and performing ultrasonic hydrolysis at 25-35 deg.C for 2-3h to obtain mixed silane hydrolysate.
Preferably, the volume ratio of silane/water/ethanol in the silane solution is 1/5/94, and the concentration of MXene in the mixed silane solution is 1 mg/mL.
Preferably, the surface treatment of the metal comprises the steps of:
cutting the metal into small pieces with preset sizes; sequentially grinding with 800#, 1000#, 1500# and 2000# water grinding sand paper step by step; then polishing to a mirror surface on velvet polishing cloth by using 1.0 mu m of alumina grinding paste; and finally, performing alkali washing on the metal sample, washing with deionized water and drying by blowing to obtain the pretreated metal sample.
Preferably, the alkali washing is normal-temperature alkali washing for 30-60s, and the alkali solution is NaOH solution with the concentration of 3-3.5 wt%.
Preferably, in the full immersion process, the metal sample is immersed in the mixed silane hydrolysate for 1-2min each time, and the immersion is repeated for 3 times.
Preferably, the curing film forming refers to placing the metal sample in an oven at the temperature of 120-150 ℃ for 1-2 h.
Preferably, in 3.5wt% NaCl solution, the self-corrosion current density of the MXene/silane surface composite silane film treatment sample is remarkably reduced to 1/5 of the self-corrosion current density of a single silane film treatment sample;
the MXene/silane surface compounded with the silane film treated sample is soaked in a 3.5wt% NaCl solution for 250 hours at room temperature, and no rust generated by corrosion is observed on the surface;
at 3% CuSO4In the pitting corrosion experiment, the color change time of the MXene/silane surface composite silane film treated sample is prolonged by more than 4 times compared with that of a single silane film treated sample.
Compared with the prior art, the invention has the advantages and positive effects that:
1.MXene is doped on the metal surface to form a physical barrier for resisting corrosion media (water, oxygen and ions), the diffusion speed of the corrosion media to a metal matrix is reduced, and the MXene is combined with silane, so that the metal corrosion protection capability is greatly improved.
2. The process has simple operation steps and short hydrolysis time, does not use toxic and harmful raw materials in the whole process, and is safe and environment-friendly.
3. The raw materials have wide sources and low price, and are beneficial to industrial amplification.
Drawings
FIG. 1 shows the connection of silane on the surface of a metal substrate;
FIG. 2 is a FT-IR infrared analysis spectrum of MXene and MXene/gamma-GPS composite silane solution;
FIG. 3 is a graphical representation of polarization curves of untreated, gamma-GPS silane film treated, and MXene/gamma-GPS composite silane film treated aluminum alloys in a 3.5% NaCl solution;
FIG. 4 is a Bode plot (a), phase angle plot (b) and Nyquist plot (c) of a Bode plot in a 3.5% NaCl solution for untreated, gamma-GPS silane film treated, and MXene/gamma-GPS composite silane film treated aluminum alloys
FIG. 5 is a schematic representation of the copper sulfate titration experiment for the metals in each example: an MXene/gamma-GPS composite film (a) on the aluminum alloy, an MXene/BTSE composite film (b) on the aluminum alloy and an MXene/BTSE composite film (c) on Q235 steel;
FIG. 6 is a schematic of a corrosion test of untreated, gamma-GPS silane film treated and MXene/gamma-GPS composite silane film treated aluminum alloys in a 3.5% NaCl solution for 250 h.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention provides application of an MXene/silane surface composite silane film in metal corrosion protection.
In an alternative embodiment, the silane is selected from gamma-GPS or BTSE and the metal is an aluminum alloy or Q235 steel.
MXene has the general formula Mn+1XnTx(n-1-3) in which M is a transition metal Ti, X is C, and Tx represents a surface functional group — OH, and has characteristics of high conductivity, capability of intercalating various organic and inorganic ions, capability of performing a rapid redox reaction on the surface thereof, and the like. In the embodiment, MXene and the silane film interact with each other, so that the stability of the composite silane film is greatly improved, a physical barrier for resisting corrosion media (water, oxygen and ions) can be quickly formed on the surface of the metal, the diffusion speed of the corrosion media to the metal substrate is reduced, the corrosion potential is moved in the positive direction, the self-corrosion current density is obviously reduced, and the corrosion tendency of the metal substrate is obviously reduced. The silane can be selected from gamma-GPS or BTSE, and no matter which silane is used, after the silane and MXene form a composite silane film, the corrosion resistance of the silane to aluminum alloy or Q235 steel is much stronger than that of a single silane film.
In an alternative embodiment, the application comprises the steps of:
preparing MXene/silane mixed solution and hydrolyzing to obtain mixed silane hydrolysate; fully soaking the surface-treated metal sample in the mixed silane hydrolysate; and taking out the dipped metal sample, removing redundant liquid, and curing in an oven to form a film. In the embodiment, the operation process steps are simple and reasonable, and the formed composite silane film has good stability.
In an alternative embodiment, the specific operation steps in the preparation of the mixed silane hydrolysate are as follows:
preparing 1-5% silane solution; mixing MXene with the silane solution, and uniformly stirring to obtain a mixed silane solution; adjusting pH to 4.5-6.5 with acetic acid, and performing ultrasonic hydrolysis at 25-35 deg.C for 2-3h to obtain mixed silane hydrolysate.
In the above examples, acetic acid was used to adjust the pH to 4.5-6.5, which favours the silane hydrolysis reaction under mildly acidic conditions. In addition, MXene and the silane solution are fully mixed by means of ultrasonic hydrolysis, and a sufficient amount of hydroxyl groups are generated in the silane mixed solution.
The volume ratio of silane to water to ethanol in the silane solution is 1/5/94, and the concentration of MXene in the mixed silane solution is 1 mg/mL. In the embodiment, water with 5 times of the volume of the silane can fully hydrolyze the silane to generate enough hydroxyl, ethanol is non-toxic, harmless and volatile, and in the selected materials, gamma-GPS and BTSE are hydrophobic silane, so that the cavity defect of the film can be greatly reduced due to the high ethanol content; in this embodiment, the ratio of γ -GPS and BTSE to water and ethanol may be appropriately adjusted, but ethanol is mainly used.
In an alternative embodiment, the surface treatment of the metal comprises the steps of:
cutting the metal into small pieces with preset sizes; sequentially grinding with 800#, 1000#, 1500# and 2000# water grinding sand paper step by step; then polishing to a mirror surface on velvet polishing cloth by using 1.0 mu m of alumina grinding paste; and finally, performing alkali washing on the metal sample, washing with deionized water and drying by blowing to obtain the pretreated metal sample.
In the above embodiment, for convenience of test operation and convenience of detection, the size of the aluminum alloy sample is 10mm × 10mm × 1mm, and it can be understood that, in practical application, a person skilled in the art can adjust the shape and size of the aluminum alloy according to practical situations, and the performance of the silane film on corrosion protection of the aluminum alloy is not affected.
In a preferred embodiment, the alkali washing is normal-temperature alkali washing for 30-60s, and the alkali solution is NaOH solution with the concentration of 3-3.5 wt%.
In an alternative embodiment, in the full immersion process, the metal sample is immersed in the mixed silane hydrolysate for 1-2min each time, and the immersion is repeated for 3 times. In the embodiment, a mode of multiple times of impregnation is adopted, the time of each time of impregnation is short, the production efficiency can be improved, and the uniformity and the completeness of the metal surface impregnation can be ensured.
In an alternative embodiment, the curing to form the film refers to placing the metal sample in an oven at the temperature of 120-150 ℃ for 1-2 h. Within the temperature range, a layer of compact and uniform silane film can be quickly formed on the surface of the metal.
In order to more clearly and specifically describe the application of the MXene/silane surface composite silane film in metal corrosion protection provided by the embodiments of the present invention, the following description will be made with reference to specific examples.
Comparative example 1:
cutting the aluminum alloy and the Q235 steel into 10mm multiplied by 1mm, respectively grinding by using No. 800, No. 1000, No. 1500 and No. 2000 water grinding abrasive paper step by step, then polishing to a mirror surface by using 1.0 mu m aluminum oxide grinding paste on velvet polishing cloth, then washing by 3 wt% NaOH at normal temperature for 30s, taking out, washing by using a large amount of deionized water, drying by using a blower, putting into a 120 ℃ oven for 120min, curing, and taking out.
Comparative example 2:
firstly, preparing a gamma-GPS silane solution with the concentration of 1%, wherein the gamma-GPS/water/ethanol is 1/5/94(v/v/v), adjusting the pH value to 4.5 by using acetic acid, and ultrasonically hydrolyzing for 2h at 35 ℃. Cutting the size of aluminum alloy and Q235 steel into 10mm multiplied by 1mm, respectively grinding with No. 800, No. 1000, No. 1500, No. 2000 water mill abrasive paper step by step, then polishing to a mirror surface on velvet polishing cloth by using 1.0 μm aluminum oxide grinding paste, then washing with 3 wt% NaOH at normal temperature for 30s, taking out, washing with a large amount of deionized water and drying with a blower, then immersing the sample in prepared silane hydrolysate for 1min and repeating for 3 times, taking out and blowing off redundant liquid, and placing in a 120 ℃ oven for 120min to solidify into a film, thus obtaining the silane film.
Comparative example 3:
the silane membrane was prepared in the same manner as in comparative example 2 except that the γ -GPS silane solution was replaced with BTSE silane solution.
Example 1:
firstly, preparing a gamma-GPS silane solution with the concentration of 1%, wherein the gamma-GPS/water/ethanol is 1/5/94(v/v/v), mixing a certain amount of MXene with the gamma-GPS silane solution, stirring the solution to control the concentration of MXene to be 1mg/mL, adjusting the pH value to be 4.5 by using acetic acid, and ultrasonically hydrolyzing for 2h at the temperature of 35 ℃. Cutting the size of the aluminum alloy into 10mm multiplied by 1mm, respectively grinding the aluminum alloy by using No. 800, No. 1000, No. 1500 and No. 2000 water grinding abrasive paper step by step, then polishing the aluminum alloy on velvet polishing cloth by using 1.0 mu m aluminum oxide grinding paste to a mirror surface, then washing the polished aluminum alloy by 3 wt% NaOH at normal temperature for 30s, taking out the polished aluminum alloy, washing the polished aluminum alloy by using a large amount of deionized water, drying the polished aluminum alloy by using a blower, immersing the sample in prepared silane hydrolysate for 1min, repeating the operation for 3 times, taking out the sample, blowing off redundant liquid, and putting the sample into a 120 ℃ oven for 120min to solidify into a.
Example 2
Firstly, preparing a 5% BTSE silane solution, wherein the BTSE/water/ethanol concentration is 1/5/94(v/v/v), mixing a certain amount of MXene with the BTSE silane solution, stirring the solution to control the concentration of MXene to be 1mg/mL, adjusting the pH value to be 4.5 by using acetic acid, and ultrasonically hydrolyzing for 2h at 35 ℃. Cutting the size of the aluminum alloy into 10mm multiplied by 1mm, respectively grinding the aluminum alloy by using No. 800, No. 1000, No. 1500 and No. 2000 water grinding abrasive paper step by step, then polishing the aluminum alloy on velvet polishing cloth by using 1.0 mu m aluminum oxide grinding paste to a mirror surface, then washing the polished aluminum alloy by 3 wt% NaOH at normal temperature for 30s, taking out the polished aluminum alloy, washing the polished aluminum alloy by using a large amount of deionized water, drying the polished aluminum alloy by using a blower, immersing the sample in prepared silane hydrolysate for 1min, repeating the operation for 3 times, taking out the sample, blowing off redundant liquid, and putting the sample into a 120 ℃ oven for 120min to solidify into a film, thus obtaining the composite silane film.
Example 3
Firstly, preparing a 5% BTSE silane solution, wherein the BTSE/water/ethanol concentration is 1/5/94(v/v/v), mixing a certain amount of MXene with the BTSE silane solution, stirring the solution to control the concentration of MXene to be 1mg/mL, adjusting the pH value to be 4.5 by using acetic acid, and ultrasonically hydrolyzing for 2h at 35 ℃. And (2) grinding the Q235 steel by using No. 800, No. 1000, No. 1500 and No. 2000 water grinding abrasive paper step by step, polishing the polished velvet cloth to a mirror surface by using 1.0 mu m of alumina abrasive paste, washing the polished velvet cloth by 3 wt% NaOH at normal temperature for 30s, taking out the polished velvet cloth, washing the polished velvet cloth by using a large amount of deionized water, drying the polished velvet cloth by using a blower, immersing the sample in prepared silane hydrolysate for 1min, repeating the step for 3 times, taking out the sample, blowing off redundant liquid, and putting the sample into a 120-DEG C oven for 120min to be cured into a film, thus obtaining the composite silane film.
And (3) performance testing:
1. infrared Spectrum testing
And performing Fourier infrared spectrum analysis on the prepared MXene and MXene/gamma-GPS composite silane solution. As shown in fig. 2: in the spectrum of MXene/gamma-GPS composite silane solution, 840cm-1、905cm-1、1200cm-1Corresponding to a C-O-C bond, 1713cm-1C ═ O bonds probably associated with epoxide epoxidation, 1080cm-1At the Si-O-C bond to 2931cm-1Of (C is a-CH)3Evidence of the presence of unhydrolyzed Si-O-CH3The existence of gamma-GPS is proved, 1260cm-1Production of Si-OH for hydrolysis, 1101cm-13390cm of Si-O-Si formed for crosslinking-1Also shows a broad peak of-OH bonds, which demonstrate that the crosslinked structure of silane as shown in fig. 1, the formed crosslinked film plays a protective role; 997cm-1Is a Ti-O-Si bond, and is supposed to be formed by connecting MXene and gamma-GPS, so that the MXene is doped in the silane film to improve the protective performance of the silane film.
2. Determination of polarization curves
Samples of untreated (comparative example 1), gamma-GPS silane solution treated (comparative example 2), MXene/gamma-GPS composite silane solution treated (example 1) aluminum alloys were encapsulated with epoxy resin to a bare area of 1cm2. The polarization curve was tested in 3.5 w% NaCl using a three electrode system and the resulting polarization curve is shown in FIG. 3, with the parameters listed in Table 1.
As can be seen from FIG. 3, the corrosion potential of the silane film formed by doping MXene is shifted in the positive direction, and obviously, the MXene doping forms a physical barrier against corrosion media (water, oxygen and ions) on the surface of the aluminum alloy, so that the diffusion speed of the corrosion media to the metal matrix is reduced, and the corrosion tendency of the aluminum alloy matrix is obviously reduced. Table 1 shows that the self-corrosion current density of the MXene doped composite silane film is minimal and reduced by 2 orders of magnitude relative to the untreated sample, where the corrosion resistance of the composite silane film is the most excellent.
TABLE 1 fitting parameters of polarization curves of various treatment modes of aluminum alloys in 3.5% NaCl solution
Figure BDA0002220429820000081
3. Electrochemical impedance spectroscopy
All Electrochemical Impedance (EIS) tests in this experiment were performed on CHI660E electrochemical workstation manufactured by Chenghua instruments, Inc., using 3.5wt% NaCl solution as a conductive medium, and the test temperature was room temperature. Adopting a three-electrode system, wherein the auxiliary electrode is a platinum sheet electrode with the diameter of 10mm, the reference electrode is a Saturated Calomel Electrode (SCE), the sample to be detected is a working electrode, and the area of the working electrode is 1cm2. Before the electrochemical AC impedance spectrum is tested, the corrosion potential change of the working electrode is observed, after the corrosion potential change is stabilized, the corrosion potential change is measured under the open-circuit potential, the excitation signal is a sine wave with the amplitude of 10mv, and the frequency range is 10-2-10- 5Hz. After the impedance data are collected, the data are processed by Z-View software.
The silane films of comparative example 1, comparative example 2 and example 1 were subjected to impedance spectroscopy (fig. 4), and the Nyquist plot shows that the MXene/γ -GPS composite film exhibited a larger capacitive arc than the γ -GPS silane film and the untreated sample; the Bode plot shows that the impedance of the MXene/gamma-GPS composite film in the low frequency range is almost 7 times that of the gamma-GPS silane film, and is approximately 1.2 orders of magnitude higher than that of the untreated aluminum alloy. The phase angle plot of the Bode plot also shows a broad plateau in the mid-to high frequency region, formed by the MXene/γ -GPS composite film, which represents excellent impedance properties of the composite film.
4、3％CuSO4Pitting test
Refer to the national standard GB5936-86 3% CuSO4Copper sulfate titration solution with the concentration of 3% is prepared in pitting experiment. The liquid transferring gun sucks 2.5 mu L of copper sulfate pitting liquid to drop on the liquid surface, and after the copper sulfate pitting liquid contacts the surface of the membrane layer, divalent copper ions in the copper sulfate pitting liquid can permeate through the surface membrane layer to perform a reduction reaction with metals such as aluminum, magnesium and the like in the base material, so that the copper sulfate pitting liquid is changed from blue to red. And comparing the difference of the color changing time to judge the corrosion resistance of the silane film under different process conditions.
Comparative examples 1-3 and examples 1-3 were subjected to discoloration time experiments and compared separately, as shown in fig. 5, and MXene doping all resulted in a greatly extended color change time. The color change time of the MXene/gamma-GPS composite membrane on the aluminum alloy is prolonged from 200s to 800s compared with that of the gamma-GPS membrane alone, the color change time of the MXene/BTSE composite membrane on the aluminum alloy is prolonged from 60s to 250s compared with that of the BTSE membrane alone, and the color change time of the MXene/BTSE composite membrane on the Q235 steel is prolonged from 10s to 150s compared with that of the BTSE membrane alone. Thus, the MXene flaky two-dimensional material can effectively reduce the transmission rate of particles and slow down the time for a corrosive medium to enter a matrix, and the corrosion resistance of the metal matrix is greatly improved no matter the MXene flaky two-dimensional material is matched with gamma-GPS or BTSE for use.
5. Corrosion resistance test
The untreated (comparative example 1), gamma-GPS silane solution treated (comparative example 2), MXene/gamma-GPS composite silane solution treated (example 1) aluminum alloy was soaked in 3.5 w% NaCl solution at room temperature for 250h, and the surface thereof is shown in FIG. 6. The surface etching condition of the untreated sample is general corrosion; after the single silane film is soaked for 250 hours, corrosion rust generated by the corrosion of the single silane film by sodium chloride can be clearly seen on the surface; no corrosion rust was observed in MXene doped silane films after prolonged immersion in a corrosive medium. Therefore, the MXene lamellar structure can effectively block the diffusion of a corrosive medium after being combined with silane, so that the time of directly exposing the matrix to the corrosive medium is prolonged, and the conclusion is drawn that the corrosion resistance of the silane film is enhanced by the MXene doping.

Claims (8)

  1. The application of the MXene/silane surface composite silane film in metal corrosion protection is characterized in that the MXene/silane surface composite silane film is prepared by the following method:
    preparing MXene/silane mixed solution and hydrolyzing to obtain mixed silane hydrolysate;
    fully soaking the surface-treated metal sample in the mixed silane hydrolysate;
    taking out the dipped metal sample, removing redundant liquid, and curing in an oven to form a film;
    the general formula of MXene is Mn+1XnTxWherein n =1-3, wherein M is a transition metal Ti, X is C, TxRepresents a surface functional group-OH;
    wherein, the preparation steps of the mixed silane hydrolysate are as follows:
    preparing 1-5% silane solution;
    mixing MXene with the silane solution, and uniformly stirring to obtain a mixed silane solution;
    adjusting pH to 4.5-6.5 with acetic acid, and performing ultrasonic hydrolysis at 25-35 deg.C for 2-3h to obtain mixed silane hydrolysate.
  2. 2. Use according to claim 1, wherein the silane is selected from gamma-GPS or BTSE and the metal is an aluminium alloy or Q235 steel.
  3. 3. The use according to claim 1, wherein the silane/water/ethanol volume ratio in the silane solution is 1/5/94, and the concentration of MXene in the mixed silane solution is 1 mg/mL.
  4. 4. Use according to claim 1, characterized in that the surface treatment of the metal comprises the following steps:
    cutting the metal into small pieces with preset sizes;
    sequentially grinding with 800#, 1000#, 1500# and 2000# water grinding sand paper step by step;
    then polishing to a mirror surface on velvet polishing cloth by using 1.0 mu m of alumina grinding paste;
    and finally, performing alkali washing on the metal sample, washing with deionized water and drying by blowing to obtain the pretreated metal sample.
  5. 5. The use according to claim 4, wherein the alkaline washing is normal temperature alkaline washing for 30-60s, and the alkaline solution is NaOH solution with a concentration of 3-3.5 wt%.
  6. 6. The use of claim 1, wherein in the full immersion process, the metal sample is immersed in the mixed silane hydrolysate for 1-2min each time, and the immersion is repeated for 3 times.
  7. 7. The application of claim 1, wherein the curing to form the film is performed by placing the metal sample in an oven at 120-150 ℃ for 1-2 h.
  8. 8. The use according to claim 1, wherein the self-corrosion current density of the MXene/silane surface complex silane film treated sample is significantly reduced to 1/5 of the self-corrosion current density of a single silane film treated sample in 3.5wt% NaCl solution;
    the MXene/silane surface compounded with the silane film treated sample is soaked in a 3.5wt% NaCl solution for 250 hours at room temperature, and no rust generated by corrosion is observed on the surface;
    at 3% CuSO4In the pitting corrosion experiment, the color change time of the MXene/silane surface composite silane film treated sample is prolonged by more than 4 times compared with that of a single silane film treated sample.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003515675A (en) * 1999-12-04 2003-05-07 ローベルト ボツシユ ゲゼルシヤフト ミツト ベシユレンクテル ハフツング Method for producing a composite layer using a plasma radiation source
CN106929863A (en) * 2017-03-09 2017-07-07 王鑫 A kind of method for lifting aluminum alloy surface silane film properties
CN108384448A (en) * 2017-05-17 2018-08-10 东华大学 A kind of composite Nano corrosion-inhibiting coating of imitative clam shell feature and preparation method thereof
CN108610511A (en) * 2018-04-25 2018-10-02 华南理工大学 A kind of functionalization two-dimensional layer transition metal carbide material f-MXene and preparation method thereof and the application in rubber
CN109439188A (en) * 2018-11-15 2019-03-08 北京林业大学 A kind of super-hydrophobic photo-thermal coating and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1553144B1 (en) * 2004-01-09 2016-08-10 Merck Patent GmbH Colored interference pigments having metallic luster, preparing method and use of same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003515675A (en) * 1999-12-04 2003-05-07 ローベルト ボツシユ ゲゼルシヤフト ミツト ベシユレンクテル ハフツング Method for producing a composite layer using a plasma radiation source
CN106929863A (en) * 2017-03-09 2017-07-07 王鑫 A kind of method for lifting aluminum alloy surface silane film properties
CN108384448A (en) * 2017-05-17 2018-08-10 东华大学 A kind of composite Nano corrosion-inhibiting coating of imitative clam shell feature and preparation method thereof
CN108610511A (en) * 2018-04-25 2018-10-02 华南理工大学 A kind of functionalization two-dimensional layer transition metal carbide material f-MXene and preparation method thereof and the application in rubber
CN109439188A (en) * 2018-11-15 2019-03-08 北京林业大学 A kind of super-hydrophobic photo-thermal coating and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Improving the mechanical properties, UV and hydrothermal aging resistance of PIPD fiber using MXene (Ti3C2(OH)(2)) nanosheets";Taloub et al.;《COMPOSITES PART B-ENGINEERING》;20190415;第163卷;第260-271页 *

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