CN110527995A - Application of the compound silane film of MXene/ silane surfaces in metal erosion protection - Google Patents

Application of the compound silane film of MXene/ silane surfaces in metal erosion protection Download PDF

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CN110527995A
CN110527995A CN201910931909.1A CN201910931909A CN110527995A CN 110527995 A CN110527995 A CN 110527995A CN 201910931909 A CN201910931909 A CN 201910931909A CN 110527995 A CN110527995 A CN 110527995A
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silane
mxene
film
solution
application according
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CN110527995B (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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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

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

The invention belongs to metal erosion to protect field, in particular to application of a kind of compound silane film of MXene/ silane surfaces in metal erosion protection.The following steps are included: the configuration and hydrolysis of MXene/ silane mixture solution, test button surface treatment, test button impregnates in mixed silanes hydrolyzate and film-forming.The present invention uses the compound silane film protection coating processing technique of MXene/ silane surfaces, solves the unsound defect of single silane film, and easy to operate, safety and environmental protection, and doping MXene can effectively hinder the diffusion of corrosive medium, improve the corrosion resistance of silane film.

Description

Application of the compound silane film of MXene/ silane surfaces in metal erosion protection
Technical field
The invention belongs to metal erosion to protect field, in particular to a kind of compound silane film of MXene/ silane surfaces is in metal Application in corrosion protection.
Background technique
Metal material is widely used in human lives, and corroding is an important factor for causing metal material to waste.Aluminium closes Gold and steel have excellent characteristic, are widely used in industrial every field.But aluminium alloy and corrosion resistance of steel Can be general, especially hard aluminium alloy and extra super duralumin alloy, corrosion resistance are generally poor.As people in recent years are to environmental requirement Raising, traditional chromating aseptic technic is gradually eliminated, and many researchers always search for environmental-friendly, energy saving height Effect and harmless aluminum alloy surface processing technique.
Current research discovery is consolidated by the chemical bond energy of Si-O- metal using silane coupling agent and is attached to metal surface, Three-dimensional netted protecting film is formed further through being cross-linked with each other between silane, to reach effective protection to metal.However it is single Silane film is very thin, and for some there is also certain defect, stability is poor, once mechanically damaged, it will be destroyed, and loses Protect the effect of metal.
To solve the above-mentioned problems, some nanometers are added in researcher through a variety of silane mixtures and in solution of silane Material is modified silane film, to promote its protective performance and stability.Patent of invention CN102719821B discloses one Kind is used for the composite Nano silane film and its film build method of Metal surface anti-corrosion, surface treatment, hydrolysis including metalwork, dipping And drying and other steps.The invention combines the nano material of activation and silane, effectively increases the antiseptic property of silane film, In Corrosion current is still almost nil when 3.5%NaCl solution Anodic polarization curve overpotential reaches 700mV.But the silicon in above-mentioned patent When alkane film is used for Metal surface anti-corrosion, corrosion protection promotion is limited, and needs to carry out nano material in application process Activation, complex process, silanol solution is needed to hydrolyze for a long time, be taken time and effort, at high cost, is unfavorable for industrialized production.
Summary of the invention
The present invention reduces comprehensive silicon to overcome the single silanization treatment of tradition deficiency present in metal erosion protection The application cost of alkane film proposes a kind of application of the compound silane film of MXene/ silane surfaces in metal erosion protection, the silicon Alkane film can effectively hinder diffusion of the corrosive medium in silane film, the corrosion resistance of significant increase silane film, and technique to grasp Make simply, to be conducive to industrialization promotion.
In order to achieve the above object, the present invention provides the compound silane films of MXene/ silane surfaces in metal erosion protection Application.
Preferably, the silane be selected from γ-GPS (γ-glycidyl ether oxygen propyl trimethoxy silicane) or BTSE (1, Bis- (triethoxy silicon substrate) ethane of 2-), the metal is aluminium alloy or Q235 steel.
Preferably, it is described application the following steps are included:
Configuration MXene/ silane mixture solution simultaneously hydrolyzes, and obtains mixed silanes hydrolyzate；By the metal examination after surface treatment Sample is sufficiently impregnated in mixed silanes hydrolyzate；Surplus liquid is removed after test button after dipping is taken out, it is solid in baking oven It is melted into film.
Preferably, in mixed silanes hydrolyzate preparation specific steps are as follows:
Configure the solution of silane of 1-5% concentration；It takes MXene to mix with above-mentioned solution of silane, stirs evenly to obtain mixed silanes Solution；With second acid for adjusting pH to 4.5-6.5,25-35 DEG C of ultrasonic hydrolysis 2-3h obtains mixed silanes hydrolyzate.
Preferably, silane/water/ethyl alcohol volume ratio is 1/5/94 in the solution of silane, in the mixed silanes solution The concentration of MXene is 1mg/mL.
Preferably, metallic surface processing the following steps are included:
Metal is cut into the fritter of predetermined size；Successively beaten step by step with 800#, 1000#, 1500#, 2000# silicon carbide paper Mill；Then mirror surface is polished to using 1.0 μm of alumina lap cream on velvet polishing cloth；Test button is finally subjected to alkali cleaning, Deionized water is rinsed and is dried up, and metal pretreated sample is obtained.
Preferably, the alkali cleaning is room temperature alkali cleaning 30-60s, aqueous slkali is NaOH solution, concentration 3-3.5wt%.
Preferably, it is described be sufficiently impregnated during, test button impregnates 1-2min in mixed silanes hydrolyzate every time, Repeated impregnations 3 times.
Preferably, the film-forming, which refers to, is placed in 1-2h in 120-150 DEG C of baking oven for test button.
Preferably, in the NaCl solution of 3.5wt%, the compound silane film process sample of MXene/ silane surfaces Corrosion current density significantly reduces, and reaches the 1/5 of the corrosion current density of single silane film process sample；
The sample of the compound silane film process of MXene/ silane surfaces soaking at room temperature 250h in the NaCl solution of 3.5wt%, The rusty stain that corrosion generates is not observed in surface；
In 3%CuSO4Spot corrosion experiment in, the sample of the compound silane film process of MXene/ silane surfaces than single silane film at The sample Coloring Time of reason extends 4 times or more.
Compared with prior art, the advantages and positive effects of the present invention are:
1, the metal surface that is entrained in of MXene forms a kind of physical barriers for resisting corrosive medium (water, oxygen, ion), Diffusion velocity of the corrosive medium to metallic matrix is reduced, is combined with silane, greatly improves metal erosion protective capacities.
2, technological operation step is simple, and hydrolysis time is short, and whole without using poisonous and harmful raw material, safety and environmental protection.
3, raw material sources are extensive, cheap, are conducive to industrialization amplification.
Detailed description of the invention
Fig. 1 is connection type of the silane in metal base surface；
Fig. 2 is the FT-IR infrared analysis map of the compound solution of silane of MXene and MXene/ γ-GPS；
Fig. 3 is untreated, γ-GPS silane film process and the compound silane film process of MXene/ γ-GPS aluminium alloy Polarization curve schematic diagram in 3.5%NaCl solution；
Fig. 4 is the aluminium alloy of untreated, γ-GPS silane film process and the compound silane film process of MXene/ γ-GPS The phase angle figure (b) and Nyquist figure (c) of Bode figure (a), Bode figure in 3.5%NaCl solution
Fig. 5 is the copper sulphate titration experiments schematic diagram of metal in each embodiment: MXene/ γ-GPS composite membrane on aluminium alloy (a), MXene/BTSE composite membrane (b) and MXene/BTSE composite membrane (c) on Q235 steel on aluminium alloy；
Fig. 6 is the aluminium alloy of untreated, γ-GPS silane film process and the compound silane film process of MXene/ γ-GPS The corrosion test schematic diagram of 250h in 3.5%NaCl solution.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects It encloses.
The embodiment of the invention provides application of the compound silane film of MXene/ silane surfaces in metal erosion protection.
In an alternative embodiment, the silane is selected from γ-GPS or BTSE, and the metal is aluminium alloy or Q235 steel.
MXene general formula is Mn+1XnTx(n=1-3), wherein M is transition metal Ti, and X is C, and Tx indicates surface functional group-OH, It is special that quick redox reaction etc. can be carried out with high conductivity, embeddable various organic and inorganic ions and on its surface Property.In above-described embodiment, MXene and silane membrane interaction greatly promote the stability of compound silane film, can be in metal surface A kind of physical barriers for resisting corrosive medium (water, oxygen, ion) are quickly formed, diffusion of the corrosive medium to metallic matrix is reduced Speed keeps corrosion potential forward direction mobile, and corrosion current density is substantially reduced, so that the tendency for corroding metallic matrix is bright It is aobvious to reduce.The silane can choose γ-GPS or BTSE, either any silane, after forming compound silane film with MXene, It is all more much better than than single silane film to the corrosion protection of aluminium alloy or Q235 steel.
In an alternative embodiment, it is described application the following steps are included:
Configuration MXene/ silane mixture solution simultaneously hydrolyzes, and obtains mixed silanes hydrolyzate；By the metal examination after surface treatment Sample is sufficiently impregnated in mixed silanes hydrolyzate；Surplus liquid is removed after test button after dipping is taken out, it is solid in baking oven It is melted into film.In above-described embodiment, the compound silane membrane stability of operating procedure simple and reasonable steps, formation is good.
In an alternative embodiment, in mixed silanes hydrolyzate preparation specific steps are as follows:
Configure the solution of silane of 1-5% concentration；It takes MXene to mix with above-mentioned solution of silane, stirs evenly to obtain mixed silanes Solution；With second acid for adjusting pH to 4.5-6.5,25-35 DEG C of ultrasonic hydrolysis 2-3h obtains mixed silanes hydrolyzate.
In the above-described embodiments, it is anti-to be conducive to silane hydrolyzate under mildly acidic conditions with second acid for adjusting pH value to 4.5-6.5 The generation answered.Furthermore it by way of ultrasonic hydrolysis, is on the one hand sufficiently mixed MXene with solution of silane, on the other hand makes silicon The hydroxyl of alkane mixed solution generation sufficient amount.
Silane/water/ethyl alcohol volume ratio is 1/5/94 in the solution of silane, and MXene's is dense in the mixed silanes solution Degree is 1mg/mL.In the above-described embodiments, the water of 5 times of silane volumes can make silane be fully hydrolyzed the enough hydroxyls of generation, second Alcohol is not only nontoxic, volatile, and γ-GPS and BTSE is hydrophobic silane in selection, and ethanol content height can make the sky of film Chamber defect greatly reduces；The ratio of γ-GPS, BTSE and water and ethyl alcohol can be with appropriate adjustment in the present embodiment, but with ethyl alcohol is It is main.
In an alternative embodiment, metallic surface processing the following steps are included:
Metal is cut into the fritter of predetermined size；Successively beaten step by step with 800#, 1000#, 1500#, 2000# silicon carbide paper Mill；Then mirror surface is polished to using 1.0 μm of alumina lap cream on velvet polishing cloth；Test button is finally subjected to alkali cleaning, Deionized water is rinsed and is dried up, and metal pretreated sample is obtained.
In above-described embodiment, in order to which test operation is convenient and convenient for detection, the size of aluminum alloy specimen is 10mm × 10mm × 1mm, it is to be understood that in practical application, those skilled in the art can according to the actual situation to the shape of aluminium alloy and Size is adjusted, and has no effect on the performance that silane film of the present invention protects corrosion of aluminium alloy.
In a preferred embodiment, the alkali cleaning is room temperature alkali cleaning 30-60s, and aqueous slkali is NaOH solution, concentration 3- 3.5wt%.
In an alternative embodiment, it is described be sufficiently impregnated during, test button soaks every time in mixed silanes hydrolyzate Stain 1-2min, repeated impregnations 3 times.In above-described embodiment by the way of repeatedly impregnating, the time impregnated every time is shorter, not only may be used To improve production efficiency, and it can guarantee the uniform complete of metal surface dipping.
In an alternative embodiment, the film-forming, which refers to, is placed in 1-2h in 120-150 DEG C of baking oven for test button.On It states in temperature range, metal surface can quickly form the silane film of one layer of dense uniform.
The compound silane film of MXene/ silane surfaces provided by the embodiment of the present invention is introduced in detail in gold in order to become apparent from Belong to the application in corrosion protection, is described below in conjunction with specific embodiment.
Comparative example 1:
The size of aluminium alloy and Q235 steel is cut into 10mm × 10mm × 1mm, uses 800#, 1000#, 1500#, 2000# respectively Silicon carbide paper is polished step by step, then is carried out being polished to mirror surface using 1.0 μm of alumina lap cream on velvet polishing cloth, then be passed through 3wt%NaOH room temperature alkali cleaning 30s is rinsed with a large amount of deionized waters after taking-up and is dried up with hair dryer, is put into 120 DEG C of baking ovens It is taken out after 120min solidification.
Comparative example 2:
γ-GPS the solution of silane of 1% concentration is configured first, and wherein γ-GPS/ water/ethyl alcohol is 1/5/94 (v/v/v), is used Second acid for adjusting pH is 4.5,35 DEG C of ultrasonic hydrolysis 2h.The size of aluminium alloy and Q235 steel is cut into 10mm × 10mm × 1mm, uses respectively 800#, 1000#, 1500#, 2000# silicon carbide paper are polished step by step, and 1.0 μm of alumina laps are then used on velvet polishing cloth Cream carries out being polished to mirror surface, then through 3wt%NaOH room temperature alkali cleaning 30s, is rinsed after taking-up with a large amount of deionized waters and uses blowing Sample is immersed 1min in the hydrolyzed silane solution of configuration later and is repeated 3 times by machine drying, and surplus liquid is blown away in taking-up, is put into 120 DEG C 120min film-forming in baking oven, can be obtained silane film.
Comparative example 3:
Silane membrane preparation method is identical as comparative example 2, and γ-GPS solution of silane is only changed to BTSE solution of silane.
Embodiment 1:
γ-GPS the solution of silane of 1% concentration is configured first, and wherein γ-GPS/ water/ethyl alcohol is 1/5/94 (v/v/v), is taken A certain amount of MXene is mixed with γ-GPS solution of silane, and the concentration that agitating solution controls MXene is 1mg/mL, is adjusted with acetic acid PH is 4.5,35 DEG C of ultrasonic hydrolysis 2h.The size of aluminium alloy is cut into 10mm × 10mm × 1mm, uses 800#, 1000# respectively, 1500#, 2000# silicon carbide paper are polished step by step, are then polished on velvet polishing cloth using 1.0 μm of alumina lap cream Mirror surface is rinsed with a large amount of deionized waters after taking-up and is dried up with hair dryer then through 3wt%NaOH room temperature alkali cleaning 30s, later will Sample immerses 1min in the hydrolyzed silane solution of configuration and is repeated 3 times, and surplus liquid is blown away in taking-up, is put into 120min in 120 DEG C of baking ovens Compound silane film can be obtained in film-forming.
Embodiment 2
The BTSE solution of silane of 5% concentration is configured first, and wherein BTSE/ water/ethyl alcohol is 1/5/94 (v/v/v), is taken certain MXene and the BTSE solution of silane of amount mix, and the concentration that agitating solution controls MXene is 1mg/mL, are with second acid for adjusting pH 4.5,35 DEG C of ultrasonic hydrolysis 2h.The size of aluminium alloy is cut into 10mm × 10mm × 1mm, uses 800#, 1000#, 1500# respectively, 2000# silicon carbide paper is polished step by step, then carries out being polished to mirror surface using 1.0 μm of alumina lap cream on velvet polishing cloth, Then it through 3wt%NaOH room temperature alkali cleaning 30s, is rinsed after taking-up with a large amount of deionized waters and is dried up with hair dryer, later by sample It immerses 1min in the hydrolyzed silane solution of configuration to be repeated 3 times, surplus liquid is blown away in taking-up, is put into 120min in 120 DEG C of baking ovens and is solidified Film forming, can be obtained compound silane film.
Embodiment 3
The BTSE solution of silane of 5% concentration is configured first, and wherein BTSE/ water/ethyl alcohol is 1/5/94 (v/v/v), is taken certain MXene and the BTSE solution of silane of amount mix, and the concentration that agitating solution controls MXene is 1mg/mL, are with second acid for adjusting pH 4.5,35 DEG C of ultrasonic hydrolysis 2h.Q235 steel uses 800#, 1000#, 1500# respectively, and 2000# silicon carbide paper polishes step by step, then exists It carries out being polished to mirror surface using 1.0 μm of alumina lap cream on velvet polishing cloth, then through 3wt%NaOH room temperature alkali cleaning 30s, take It is rinsed after out with a large amount of deionized waters and is dried up with hair dryer, sample is immersed to 1min in the hydrolyzed silane solution of configuration later and is repeated 3 times, surplus liquid is blown away in taking-up, is put into 120min film-forming in 120 DEG C of baking ovens, compound silane film can be obtained.
Performance test:
1, examination of infrared spectrum
FTIR spectrum analysis is carried out to the compound solution of silane of the MXene and MXene/ γ-GPS of configuration.Such as Fig. 2 institute Show: in the spectrogram of the compound solution of silane of MXene/ γ-GPS, 840cm-1、905cm-1、1200cm-1Corresponding to C-O-C key, 1713cm-1C=O key may be related with epoxy epoxidation, 1080cm-1Locate Si-O-C key and 2931cm-1- the CH at place3Prove exist Unhydrolysed Si-O-CH3, all demonstrate the presence of γ-GPS, 1260cm-1The Si-OH, 1101cm generated for hydrolysis-1For crosslinking The Si-O-Si of formation, 3390cm-1The also broad peak of display-OH key, these keys demonstrate the crosslinked with silicane structure shown such as Fig. 1, shape At cross linking membrane play protective action；997cm-1It is Ti-O-Si key, thus it is speculated that be that MXene connect to be formed with γ-GPS, to make MXene is entrained in the protective performance that silane film is promoted in silane film.
2, determination of polarization curve
Untreated (comparative example 1), (comparative example 2) of the processing of γ-GPS solution of silane, MXene/ γ-GPS is multiple (embodiment 1) aluminum alloy sample for closing solution of silane processing is packaged with epoxy resin, bare area 1cm2.In 3.5w% Polarization curve test is carried out using three-electrode system in NaCl, obtains polarization curve such as Fig. 3, each parameter of polarization curve is listed in table 1.
From figure 3, it can be seen that the silane film corrosion potential that doping MXene is formed is all positive mobile, it is clear that the doping of MXene A kind of physical barriers for resisting corrosive medium (water, oxygen, ion) are formed in aluminum alloy surface, reduce corrosive medium to Metal Substrate The diffusion velocity of body, so that the tendency for corroding aluminum matrix alloy is substantially reduced.The comprehensive silicon of the display doping of table 1 MXene Alkane film corrosion current density is minimum, and reduces 2 orders of magnitude relative to untreated sample, and compound silane film at this time is resistance to Corrosive nature is most excellent.
The fitting parameter of the various processing modes of 1 aluminium alloy of table polarization curve in 3.5%NaCl solution
3, electrochemical impedance spectrum analysis
All electrochemical impedance (EIS) tests are in the CHI660E of Shanghai Chen Hua Instrument Ltd. production in this experiment It is carried out on electrochemical workstation, using 3.5wt%NaCl solution as conducting medium, test temperature is room temperature.Using three-electrode system, Auxiliary electrode is diameter 10mm platinum plate electrode, and reference electrode is saturated calomel electrode (SCE), and print to be measured is working electrode, work Making electrode area is 1cm2.Before electrochemical alternate impedance spectrum starts test, the variation of working electrode corrosion potential is first observed, to It is measured under open circuit potential again after stablizing, and pumping signal is the sine wave of amplitude 10mv, frequency range 10-2-10- 5Hz.After impedance data is collected, data processing is carried out with Z-View software.
Silane film in comparative example 1, comparative example 2 and embodiment 1 is subjected to impedance spectrum (Fig. 4) analysis, Nyquist figure is shown MXene/ γ-GPS composite membrane shows bigger capacitive reactance arc compared with γ-GPS silane film and untreated sample；Bode figure is shown MXene/ γ-GPS composite membrane is higher than untreated aluminium alloy in 7 times that the impedance of low-frequency range is almost γ-GPS silane film Nearly 1.2 orders of magnitude are gone out.The phase angle figure of Bode figure is also shown at the wide platform peak in one, medium-high frequency area, this is by MXene/ What γ-GPS composite membrane was formed, it is excellent to represent the composite membrane impedance behavior.
4,3%CuSO4Spot corrosion experiment
Referring to national standard GB5936-86 " 3%CuSO4Spot corrosion experiment " compound concentration be 3% copper sulphate titrating solution.Liquid-transfering gun 2.5 μ L copper sulphate spot corrosion drops are drawn in liquid surface, copper sulphate spot corrosion liquid behind contacting film layer surface, cupric therein from Son can penetrate the metals such as aluminium, the magnesium in superficial film and substrate and reduction reaction occurs, and become copper sulphate spot corrosion liquid from blue It is red.The difference of comparison Coloring Time is the corrosion resistance that can determine whether silane film under different technology conditions.
Comparative example 1-3 and embodiment 1-3 is subjected to Coloring Time experiment, and is compared respectively, as shown in figure 5, MXene's mixes It is miscellaneous to greatly prolong the color change time.Wherein, γ-is used alone using MXene/ γ-GPS composite membrane ratio on aluminium alloy The Coloring Time of GPS film extends to 800s by 200s, uses MXene/BTSE composite membrane ratio exclusive use BTSE film on aluminium alloy Coloring Time 250s is extended to by 60s, the discoloration on Q235 steel using MXene/BTSE composite membrane than BTSE film is used alone Time extends to 150s by 10s.It can be seen that the two-dimensional material of this sheet of MXene, can effectively reduce the transmission rate of particle, slows down Corrosive medium enters the time of matrix, be either used cooperatively with γ-GPS or BTSE, equal significant increase metallic matrix Corrosion resistance.
5, corrosion-resistant test
Untreated (comparative example 1), (comparative example 2) of the processing of γ-GPS solution of silane, MXene/ γ-GPS is multiple (embodiment 1) aluminium alloy of conjunction solution of silane processing soaking at room temperature 250h, surface such as Fig. 6 institute in the NaCl solution of 3.5w% Show.Untreated sample surfaces etch situation is general corrosion；After 250h impregnates, surface can understand to be seen single silane film It is chlorinated sodium out and corrodes the corrosion rusty stain that single silane film generates；And the silane film of MXene is adulterated in corrosive medium through too long Corrosion rusty stain is not observed in time immersion yet.To can effectively hinder to corrode after demonstrating MXene lamellar structure in conjunction with silane The diffusion of medium, the time for making matrix be directly exposed to corrosive medium extend, therefore by drawing a conclusion above, MXene's mixes It is miscellaneous to enhance silane film corrosion resistance.

Claims (10)

  1. Application of the compound silane film of 1.MXene/ silane surfaces in metal erosion protection.
  2. 2. application according to claim 1, which is characterized in that the silane is selected from γ-GPS or BTSE, and the metal is Aluminium alloy or Q235 steel.
  3. 3. application according to claim 1, which comprises the following steps:
    Configuration MXene/ silane mixture solution simultaneously hydrolyzes, and obtains mixed silanes hydrolyzate；
    Test button after surface treatment is sufficiently impregnated in mixed silanes hydrolyzate；
    Surplus liquid is removed after test button after dipping is taken out, the film-forming in baking oven.
  4. 4. application according to claim 3, which is characterized in that concrete operation step in the mixed silanes hydrolyzate preparation It is as follows:
    Configure the solution of silane of 1-5% concentration；
    It takes MXene to mix with above-mentioned solution of silane, stirs evenly to obtain mixed silanes solution；
    With second acid for adjusting pH to 4.5-6.5,25-35 DEG C of ultrasonic hydrolysis 2-3h obtains mixed silanes hydrolyzate.
  5. 5. application according to claim 4, which is characterized in that silane/water/ethyl alcohol volume ratio is 1/ in the solution of silane 5/94, the concentration of MXene is 1mg/mL in the mixed silanes solution.
  6. 6. application according to claim 3, which is characterized in that metallic surface processing the following steps are included:
    Metal is cut into the fritter of predetermined size；
    Successively polished step by step with 800#, 1000#, 1500#, 2000# silicon carbide paper；
    Then mirror surface is polished to using 1.0 μm of alumina lap cream on velvet polishing cloth；
    Test button is finally subjected to alkali cleaning, deionized water is rinsed and dried up, and metal pretreated sample is obtained.
  7. 7. application according to claim 6, which is characterized in that the alkali cleaning is room temperature alkali cleaning 30-60s, and aqueous slkali is NaOH solution, concentration 3-3.5wt%.
  8. 8. application according to claim 3, which is characterized in that it is described be sufficiently impregnated during, test button mixing silicon Impregnate 1-2min in alkane hydrolyzate every time, repeated impregnations 3 times.
  9. 9. application according to claim 3, which is characterized in that the film-forming, which refers to, is placed in 120- for test button 1-2h in 150 DEG C of baking ovens.
  10. 10. application according to claim 1 or 2, which is characterized in that in the NaCl solution of 3.5wt%, the MXene/ The corrosion current density of the compound silane film process sample of silane surfaces significantly reduces, and reaches single silane film process sample oneself The 1/5 of corrosion electric current density；
    The sample of the compound silane film process of MXene/ silane surfaces soaking at room temperature 250h, surface in the NaCl solution of 3.5wt% The rusty stain that corrosion generates is not observed；
    In 3%CuSO4In spot corrosion experiment, the sample of the compound silane film process of MXene/ silane surfaces is than single silane film process Sample Coloring Time extends 4 times or more.
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