CN115074707A - Method for synthesizing double-layer composite film on surface of magnesium alloy in one step and magnesium alloy material obtained by method - Google Patents
Method for synthesizing double-layer composite film on surface of magnesium alloy in one step and magnesium alloy material obtained by method Download PDFInfo
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
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Abstract
The invention belongs to the technical field of magnesium alloy surface treatment, and particularly relates to a method for synthesizing a double-layer composite film on a magnesium alloy surface in one step and a magnesium alloy material obtained by the method. The method comprises the following steps: 1) pretreating the magnesium alloy to obtain the magnesium alloy with a clean surface; 2) immersing the magnesium alloy obtained in the step 1) into a surface treatment solution, heating for hydrothermal reaction, and cleaning and drying the magnesium alloy after the reaction is finished to obtain compact Mg (OH) 2 Bottom film and K with porous support-like microstructure 2 Al 2 Si 4 O 12 ·xH 2 A magnesium alloy sample of the O top film; 3) immersing the magnesium alloy sample obtained in the step 2) into a solution of stearic acid in ethanol for modification treatment, taking out, cleaning and drying to obtain the hard magnesium alloyThe magnesium alloy of the lipid acid modified double-layer composite membrane has excellent corrosion resistance and stable hydrophobicity.
Description
Technical Field
The invention belongs to the technical field of magnesium alloy surface treatment, and particularly relates to a method for synthesizing a double-layer composite film on a magnesium alloy surface in one step and a magnesium alloy material obtained by the method.
Background
The magnesium alloy is used as a degradable green environment-friendly material, has excellent mechanical properties such as small density, high strength, strong ductility and the like, and is widely applied to the fields of medical treatment, automobile industry, aerospace and the like. However, magnesium alloys have poor corrosion resistance and are very susceptible to corrosion in practical applications, and in order to improve the corrosion resistance, many treatments have been proposed, including conversion coating, surface modification, chemical inhibition, and the like. Among them, the conversion coating method is receiving wide attention as the most economical, effective and practical method.
In order to obtain a magnesium alloy corrosion-resistant coating which is simple and environment-friendly in preparation process, excellent in corrosion protection performance and low in manufacturing cost, in recent years, people continuously optimize and improve the preparation method. Zeolites, which have superior properties such as adsorption, ion exchange, acid and alkali resistance, and high temperature resistance, are often used as fillers to enhance the corrosion resistance of the prepared coating, and currently involved methods include a coating method, a sol-gel method, a dip coating method, a hot press method, and an electrodeposition method. However, due to the limitations of the preparation method, the sample prepared by the method often faces the problems of poor adhesion performance of the coating, incomplete coating coverage, complex preparation process or limited improvement of corrosion protection effect, and the like. Calabrese et al prepared a silane sol-gel coating on the surface of a magnesium alloy filled with zeolite, and as the amount of zeolite was increased, the corrosion resistance of the coating was gradually increased, but the adhesion properties of the coating were consequently deteriorated. Rotella et al prepared a coating with good adhesion and controllable thickness by dip-coating with zeolite as filler on the surface of the magnesium alloy after alkaline pretreatment, and the maximum coverage rate reached 97%, but compared with magnesium alloy, the corrosion improvement efficiency was only increased by 8 times, and the corrosion protection performance was only increased to a limited extent. In addition, Banerjee et al use tetrapropylammonium hydroxide (TPAOH) and Structure Directing Agent (SDA) to form a uniform zeolite film on the surface of AZ91D magnesium alloy by in-situ crystallization technology, but the corrosion current density of the prepared sample is only improved by 1 order of magnitude compared with that of a bare magnesium alloy matrix, and the preparation process is complicated, and the used drugs are expensive, thus limiting practical application.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a method for synthesizing a double-layer composite film on the surface of magnesium alloy in one step and a magnesium alloy material obtained by the method.
The technical scheme provided by the invention is as follows:
method for synthesizing double-layer composite film on surface of magnesium alloy in one step
A method for synthesizing a double-layer composite film on the surface of magnesium alloy in one step comprises the following steps:
1) pretreating the magnesium alloy to obtain the magnesium alloy with a clean surface;
2) immersing the magnesium alloy obtained in the step 1) into a surface treatment solution, heating for hydrothermal reaction, and cleaning and drying the magnesium alloy after the reaction is finished to obtain compact Mg (OH) 2 Bottom film and K with porous support-like microstructure 2 Al 2 Si 4 O 12 ·xH 2 A magnesium alloy sample of O upper film, x is 3-12, hereinafter abbreviated as M-Z/CH;
3) immersing the magnesium alloy sample obtained in the step 2) into a solution of stearic acid ethanol for modification treatment, then taking out, cleaning and drying to obtain a magnesium alloy with a stearic acid modified double-layer composite membrane, which is abbreviated as M-Z/CH @ SA hereinafter;
wherein, in step 2):
the surface treatment liquid comprises SiO 2 KOH, ethylenediaminetetraacetic acid, Ca (OH) 2 The weight ratio of each component to the solvent deionized water is (0.0184-0.0192):1, (0.069-0.071):1, (0.090-0.092):1, (0.0226-0.0234): 1;
the conditions of the hydrothermal reaction are as follows: heating to 190-210 ℃, preferably 200 ℃, and keeping the temperature for 90-105 min.
Based on the technical scheme, the method can synthesize the double-layer composite film on the surface of the magnesium alloy in one step. The film is mainly dense Mg (OH) 2 Bottom film and K with porous support-like microstructure 2 Al 2 Si 4 O 12 ·xH 2 The corrosion current on the surface of the magnesium alloy modified by stearic acid is reduced by about 3 orders of magnitude compared with that of a Mg matrix, the slow release rate reaches 99.96%, and the contact angle is stabilized at about 125 ℃. The results show that the obtained magnesium alloy has excellent corrosion resistance and stable hydrophobicity. Meanwhile, the preparation process is simple, efficient, environment-friendly and good in application prospect.
The principle of the reaction process is as follows:
the magnesium alloy reacts with the mixed solution, and as shown in FIG. 6, Mg in the sample reacts with ethylenediaminetetraacetic acid (EDTA) in the mixed solution to produce Mg 2+ ，Mg 2+ With OH in alkaline solution - Reaction to produce Mg (OH) 2 And (1) depositing on the surface of the magnesium alloy substrate. Al in the sample is affected in alkaline solution, with OH - React to generate AlO 2- (2). Nano SiO 2 The powder is reacted with OH in solution - Reaction to produce SiO 3 2- And is present in the solution (3). With the increase of the heating time, the surface of the Mg substrate is gradually coated with Mg (OH) 2 Complete coverage and tendency to stabilize (part a, c in FIG. 6), followed by the presence of K in solution + ，SiO 3 2- ，AlO 2 - And H 2 O is reacted (4) to form K 2 Al 2 Si 4 O 12 ·xH 2 O, in Mg (OH) 2 Crystallization gradually occurred on the surface of the layer (portions b and d in FIG. 6).
Mg + +2OH - ＝Mg(OH) 2 (1)
2Al+2OH - +2H 2 O＝2AlO 2 - +3H 2 (2)
SiO 2 +2OH - ＝SiO 3 2- +H 2 O (3)
2K + +2AlO 2 - +4SiO 3 2- +(x+4)H 2 O＝K 2 Al 2 Si 4 O 12 ·xH 2 O+8 OH - (4)
Specifically, in the step 1), the magnesium alloy is an AZ91D magnesium alloy. Compared with other types of magnesium alloys, the AZ91D magnesium alloy has better treatment effect because the alloy directly contains a certain amount of Al element, provides Al atoms in the reaction process and promotes the reaction.
Specifically, in the step 2), SiO used 2 The particle size of (D) is 8000-10000 meshes, preferably 8000 meshes.Too large particle size can result in uneven film morphology and thus poor treatment results.
Specifically, in the step 2), the reaction vessel is a muffle furnace.
Specifically, in the step 3), the magnesium alloy sample obtained in the step 2) is immersed in a solution of stearic acid in ethanol and is kept still for modification treatment, and the keeping still time is 40-60min, preferably 50 min.
The invention also provides the magnesium alloy with the double-layer composite film on the surface, which is prepared by the method.
The magnesium alloy provided by the invention has excellent corrosion resistance and stable hydrophobicity.
Drawings
FIG. 1 is an SEM image of the surface of a sample of M-Z/CH @ SA in section 2.1 of the detailed description, (a, c, e)90min, (b, d, f)105 min.
FIG. 2 is an XRD diffraction pattern of the M-Z/CH @ SA film in section 2.2 of the detailed description.
FIG. 3 is a plot of the surface infrared spectrum of the M-Z/CH @ SA film in section 2.2 of the specific embodiment.
FIG. 4 is an XPS survey scan of the M-Z/CH @ SA film in section 2.2 of the detailed description.
FIG. 5 is an XPS narrow scan spectrum of an M-Z/CH @ SA film in section 2.2 of the detailed description, (a) region K2p (b) region O1s (C) region C1s (d) region Mg1s (e) region Si2p (f) region Ca2 p.
FIG. 6 is a schematic diagram of the hydrothermal reaction of the present invention.
FIG. 7 is a dynamic potential polarization curve of the AZ91D magnesium alloy, M-Z/CH sample versus M-Z/CH @ SA sample and in a 3.5 wt.% NaCl solution in section 2.3 of the detailed description.
FIG. 8 is a Nyquist plot for each sample in section 2.3 of the detailed description in a 3.5 wt% NaCl aqueous solution.
FIG. 9 is a Bode plot of | Z | versus frequency for each sample in section 2.3 of the detailed description in a 3.5 wt% NaCl aqueous solution.
FIG. 10 is a Baud plot of phase angle versus frequency for each sample in section 2.3 of the detailed description in a 3.5 wt% NaCl aqueous solution.
FIG. 11 is an equivalent circuit model of AZ91D magnesium alloy in section 2.3 in 3.5 wt% NaCl aqueous solution in accordance with an embodiment
FIG. 12 is an equivalent circuit model of the M-Z/CH @ SA sample in section 2.3 of the detailed description in a 3.5 wt% NaCl aqueous solution.
FIG. 13 is an image of the M-Z/CH sample film in section 2.4 of the detailed description after image polishing with droplet contact (parts a, b); M-Z/CH @ SA sample films static water contact angle image (section c, d) with droplet contact image.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
1.1 materials
The material is AZ91D magnesium alloy (89.1% -90.8% Mg, 8.5-9.5% Al, 0.45-0.9% Zn, 0.17-0.4% Mn), purchased from North China Tengshite Metal materials Co., Ltd (Paschen platform), and the AZ91D magnesium alloy is cut into the specification of 40mm × 20mm × 5 mm. Absolute ethyl alcohol (C) 2 H 6 O, AR) was purchased from Fuyu Fine chemical Co., Ltd, Tianjin, 8000 mesh nanometer SiO 2 The powder was purchased from Shanghai Yangtze chemical Co., Ltd, Potassium hydroxide (KOH, AR), calcium hydroxide (Ca (OH) 2 AR), ethylenediaminetetraacetic acid (EDTA, AR) and stearic acid (98%) were provided by shanghai jen chemical technology limited. The high temperature box furnace (KSL-1700X) used in the heating process is purchased from Kagaku crystal materials technology Co., Ltd (Anhui, Kagaku).
1.2 methods
And respectively polishing the AZ91D magnesium alloy sheet by using 500-mesh and 1000-mesh SiC abrasive paper, and then sequentially putting the SiC abrasive paper into deionized water and absolute ethyl alcohol for ultrasonic cleaning for 10 minutes to remove impurities on the surface of the magnesium alloy and water-insoluble fat-soluble substances.
8000 mesh nano SiO 2 Adding 0.94g of powder, 1.75g of KOH solid and 4.55g of Ethylene Diamine Tetraacetic Acid (EDTA) into a beaker filled with 25ml of deionized water, and uniformly stirring by ultrasound to obtain a solution A; taking Ca (OH) 2 Pellets 1.15g and 1.75g KOH solids were added to another 25ml deionisedUltrasonically stirring in a beaker of water to dissolve the water to obtain a solution B; and then mixing and uniformly stirring the solution A and the solution B, adding the mixed solution and the pretreated AZ91D magnesium alloy sheet into a reaction kettle lining with the volume of 100ml, and heating in a muffle furnace at the heating temperature and the heat preservation temperature of 200 ℃ for 90-105 min. And taking out the sample after the reaction kettle is completely cooled, washing the sample by using a large amount of deionized water, and drying to obtain the M-Z/CH sample.
Preparing stearic acid-ethanol solution by taking 4g of stearic acid and 30ml of absolute ethanol, putting the M-Z/CH sample into the stearic acid-ethanol solution, standing for 50min, taking out, washing and airing to finally prepare the M-Z/CH @ SA sample.
1.3 sample characterization
The surface morphology of the samples was studied by scanning electron microscopy (SEM, SU5000, HITACHI, 5.0KV, tokyo, japan). The chemical composition and valence state of the sample were measured using x-ray photoelectron spectroscopy (XPS, 250Xi, Thermo scientific, Waltham, Massachusetts, America) and an Al K α x-ray source (h v. 1486.6 eV). A Fourier transform infrared spectrometer (FTIR, IRaffinity-1S, Shimadzu corporation, 4000- -1 Tokyo, japan) and an X-ray diffractometer (XRD, smartlab9, Rigaku; target: CuKa; 40kv, 150 ma; wavelength: 1.54056, tokyo, japan) studied the phase structure of the samples. The static Contact Angle (CA) was measured with a contact angle measuring instrument (SDC-200, san cheng dingding precision instruments ltd) and an average contact angle was obtained by measuring 6 μ L droplets (deionized water) at 4 different positions of the sample, respectively.
1.4 evaluation of Corrosion Properties
To study the corrosion resistance of the films, measurements were performed using a CS2350H electrochemical workstation (marthan koste instruments ltd, wuhan, china) using a conventional three-electrode setup with a platinum plate as auxiliary electrode, a reference electrode being an Ag/AgCl (saturated KCl) electrode, and a 3.5 wt% aqueous NaCl solution as electrolyte to evaluate the corrosion resistance of the material. The test material is used as a working electrode, and the exposed area is 1cm 2 The test was performed at room temperature. Extracting by using Tafel extrapolation method and CView softwareThe corrosion potential (Ecorr) and the corrosion current density (Icorr) are taken, and the polarization resistance (Rp, omega cm) is calculated 2 ) The initial potential of the potential scan was-0.5V, the end potential was 1V, the potential interval for data acquisition was 0.5mV, and the sample was contacted with the solution for 30 minutes before the test to ensure stability of the sample surface.
2.1 characterization of M-Z/CH @ SA films
FIG. 1 shows SEM images of the surface of (90-105min) M-Z/CH @ SA samples prepared at different heating times based on the method in section 1.2. From the SEM macroscopic images (parts a and b in fig. 1), it can be observed that irregular protrusions are randomly distributed on the surface of the sample, and compared with the sample (part a in fig. 1) heated for 90min, the sample (part b in fig. 1) heated for 105min has larger surface protrusions, and some protrusions are connected with each other, and the whole surface has more obvious fluffy feeling. In the high power image, a dense and relatively flat film is generated on the surface of the sample after heating for 90min, and a plurality of slender microstructures with ciliated characteristics are attached to the surface of the film and tightly attached to the surface of the film (part c of fig. 1). With increasing heating time, 105min of the sample surface was spread over the porous characteristic support-like microstructure (section d of fig. 1), while it was observed that a large number of elongated ciliated microstructures were interspersed in the porous support-like microstructure, which also explains why the sample exhibited a pronounced plush feel in SEM macroscopic images. The result shows that with the reaction, a layer of compact and relatively flat film is firstly generated on the surface of a sample, then a large number of slender ciliated microstructures are attached to the surface of the film, and with the increase of the reaction time, the slender ciliated microstructures are continuously generated and are mutually interlaced, and finally a layer of porous supporting microstructures is formed on the film. Randomly distributed irregular protrusions on the sample surface were polymerized from the columnar crystals and the elongated cilia structure (part e of fig. 1), and after heating for 105min, the elongated cilia-like microstructures covered these protrusions completely and also formed surface irregular protrusions (part f of fig. 1) that also had porous supporting-like microstructures.
2.2 surface composition analysis
Based on the method in section 1.2, and all with a heating time of 105minM-Z/CH @ SA films were prepared under the conditions described. FIG. 2 is an XRD diffraction pattern of the M-Z/CH @ SA sample showing characteristic peaks at 18.5 °, 32.9 °, 38.0 °, 50.8 °, 58.7 °, 62.1 °, 68.2 °, 68.9 °, 72.1 °, corresponding to Mg (OH), respectively 2 The peak shape of (001) (100) (101) (102) (110) (111) (103) (200) (201) in PDF (044-1482) of (1) is narrower, the intensity is higher, and the grain size is larger. The sample also showed characteristic peaks at 10.7 °, 12.4 °, 16.5 °, 17.6 °, 19.8 °, 20.7 °, 21.6 °, 27.4 °, 28.0 °, 30.2 °, 32.8 °, 35.2 ° from K 2 Al 2 Si 4 O 12 ·xH 2 O (PDF 016) 0692, which is determined by the (110) (002) (112) (022) (211) (103) (220) (310) (311) (321) (303) (323) crystal face, has lower height and intensity of each diffraction peak and wider peak area, and shows that K contained in the film layer is contained 2 Al 2 Si 4 O 12 ·xH 2 The grains of the O substance are small. In addition, the sample showed characteristic peaks at 18.2 °, 34.2 °, 36.9 °, 50.9 °, 64.7 °, 72.1 ° belonging to Ca (OH) 2 (PDF 089-2779) has (001) (011) (002) (110) (103) (202) crystal face, and the characteristic peaks at 30.2 DEG and 60.5 DEG consist of SiO 2 (PDF 015-0026) determined by the (110) (211) plane, the peak patterns of these two substances are not obvious, indicating Ca (OH) 2 And SiO 2 The two substances are loaded in a low amount, are crystallized weakly and are distributed in the membrane in a dispersed manner.
The chemical composition of the surface of the M-Z/CH @ SA sample was analyzed using Fourier transform Infrared Spectroscopy (FTIR) as shown in FIG. 3, where a represents stearic acid and b represents the M-Z/CH @ SA sample, as shown in section a of FIG. 3, at a wave number of 2916cm -1 And 2848cm -1 Nearby occurrence of-CH 2 -and CH 3 -C-H stretching vibration absorption peak with wave number of 1703cm -1 The position (A) corresponds to the absorption peak of stretching vibration of carbonyl (C ═ O) in the-COOH group. M-Z/CH @ SA sample modified with stearic acid at 2916cm -1 And 2848cm -1 The C-H bond stretching vibration absorption peak corresponding to the peak value at the wave number does not have peak shift and is 1700-1725 cm -1 The free-COOH band in the wavenumber range disappeared and was 1576cm -1 The (C ═ O) vibration absorption peak of the carboxylate is correspondingly appeared nearbyA peak shift phenomenon occurs. And at wave number 934cm -1 the-OH bending vibration is greatly reduced. Thus, the CH in stearic acid 3 (CH 2 ) 12 The COO-functional group reacts with the sample surface and stearic acid is successfully modified to the M-Z/CH @ SA sample surface.
To further examine the chemical composition of the film and determine its properties, samples were analyzed by XPS, and FIG. 4 shows an XPS survey scan of M-Z/CH @ SA films in which elements such as K, O, C, Mg, Si, Ca, etc. are present.
The narrow scan spectra of K2p, O1s, C1s, Mg1s, Si2p and Ca2p are shown in sections a, b, C, d, e, f in fig. 5. The narrow scan spectrum of the characteristic element K2p is shown in part (a) of FIG. 5, the binding energies of the K2p3/2 peak and the K2p1/2 peak are concentrated in 293.2eV and 296eV, and are mainly represented by an oxidation state signal of potassium, the O1s consists of two characteristic peaks (part b of FIG. 5), the first group of peaks is carbon-oxygen double bonds (C ═ O) and has a characteristic binding energy between 531.5eV and 532eV, and is mainly represented by a chemical state of silicate, and the other group of peaks is located between 533eV and is attributed to a carbon-oxygen single bond (C-O) and a hydroxyl group (-OH). The C1s peaks can be divided into three groups of characteristic peaks (part C in fig. 5), the first group of peaks being carbon-carbon single bonds (C-C) and characterized by a binding energy of 284.8eV, the second group of peaks having a binding energy of-286 eV associated with carbon-oxygen single bonds (C-O), and the third group of peaks located at-288.5 eV due to carboxyl groups (O-C ═ O). The narrow scanning spectrum of the characteristic element Mg1s is shown in part (d) of figure 5, and is divided into two characteristic peaks, wherein the first group of peaks is positioned at 1303eV and represents Mg simple substance, the second group of peaks is positioned at 1304.5eV and represents oxidation state signals of Mg, and the main component of the narrow scanning spectrum is Mg (OH) according to XRD result analysis 2 . The characteristic peak of Si2p lies at-102 eV, which represents the chemical state of silicate (part e in FIG. 5). The characteristic peaks for Ca2p1/2 and Ca2p3/2 were at 351eV and-347.5 eV, respectively, and were shown as the oxidation state of Ca (FIG. 5 f). The experimental result shows that the surface film layer of the M-Z/CH @ SA sample mainly contains Mg (OH) according to the analysis result of XRD 2 And K 2 Al 2 Si 4 O 12 ·xH 2 O。
2.3 Corrosion protection
M-Z/CH @ SA films were prepared based on the method in section 1.2, all with a heating time of 105 min. FIG. 7 showsThe dynamic potential polarization curves of the AZ91D magnesium alloy, the M-Z/CH sample and the M-Z/CH @ SA sample in a 3.5 wt% NaCl solution were obtained, and Table 1 below shows the corrosion potentials (E) measured by Tafel extrapolation corr ) And corrosion current density (I) corr ) Also given is the corrosion inhibition efficiency (eta) of the membrane calculated from formula (1), wherein I 0 corr Corrosion current density of Mg base, I corr Is the corrosion current density of the sample.
As shown in Table 1, the corrosion current density (I) of the AZ91D magnesium substrate 0 corr ) Is 3.1503X 10 -5 A/cm 2 Corrosion potential (E) corr ) was-1.1996V. Corrosion Current Density (I) of M-Z/CH and M-Z/CH @ SA samples corr ) And corrosion potential (E) corr ) Are respectively 7.1812X 10 -8 A/cm 2 ，1.4086×10 -8 A/cm 2 and-0.93089V, -0.89433V. According to the electrochemical theory, a material with better corrosion resistance, I corr And E corr All with lower positive values. I of M-Z/CH sample compared to AZ91D magnesium alloy corr About 2.5 orders of magnitude lower, I for the M-Z/CH @ SA sample corr Reduced by about 3 orders of magnitude, and E of the two corr Are all less positive than the Mg matrix, but where E for the M-Z/CH @ SA samples corr The positive values are lower. The results show that the corrosion resistance of the magnesium alloy is obviously improved by the experimentally prepared M-Z/CH and M-Z/CH @ SA samples, the film corrosion inhibition rate of the M-Z/CH sample is 99.77%, the corrosion inhibition rate of the modified M-Z/CH @ SA sample film layer is more 99.96%, and meanwhile, the I is corr And E corr The positive values of (A) are also lowest, and therefore, the M-Z/CH @ SA samples have the best corrosion protection performance.
TABLE 1 electrochemical data of polarization curves obtained from samples
To characterize the corrosion resistance of the samples, the Nyquist plots, the Baud plots of | Z | versus frequency, and the Baud plots of phase angle versus frequency for the M-Z/CH samples, the M-Z/CH @ SA samples, and the AZ91D magnesium alloy in 3.5 wt% aqueous NaCl are given in FIGS. 8, 9, and 10, with the fit data connected by curves and scatter points being the measured data points.
In the Nyquist plot (FIG. 8), the capacitor semi-circle diameter is related to the charge transfer resistance, the larger capacitor semi-circle diameter indicates that the sample has better corrosion resistance, and the capacitor semi-circle diameter of the magnesium alloy is about 250 Ω -cm -2 In contrast, the capacitor semi-circle diameters of the M-Z/CH sample and the M-Z/CH @ SA sample are both much higher than that of the magnesium alloy substrate, and compared with the M-Z/CH sample, the capacitor semi-circle diameter of the modified M-Z/CH @ SA sample is higher and is about 1 multiplied by 10 6 Ω·cm -2 About 4 orders of magnitude higher than the magnesium alloy matrix. The M-Z/CH @ SA sample is shown to have excellent corrosion resistance. This is also seen in the bode plot of | Z | versus frequency (FIG. 9), where generally the higher the | Z | value, the better the corrosion resistance, and the data show that the | Z | value is an integer 3.5 orders of magnitude higher for the M-Z/CH @ SA sample compared to the magnesium alloy matrix and 1 order of magnitude higher for the M-Z/CH sample. The high phase angle in the high frequency domain indicates good rejection and the large modulus in the low frequency domain indicates enhanced corrosion resistance, as shown in fig. 10, the Z/CH @ SA sample exhibits a higher phase angle in both the high frequency and low frequency domains. The results show that the M-Z/CH @ SA sample has excellent corrosion protection performance.
FIGS. 11 and 12 are equivalent circuit models (ECs) of AZ91D magnesium alloy and Z/CH @ SA samples, respectively. In the circuit, the solution resistance is Rs, the film resistance is Rh and Rf, the charge transfer resistance is Rct, and a pure capacitor is replaced by a Constant Phase Element (CPE) due to the complex and uneven surface structure of a sample, so that the circuit is a non-ideal capacitor set for circuit fitting, and the constant phase element has a better fitting effect in an equivalent circuit compared with the pure capacitor. The experimental data show that the Rct of the magnesium alloy matrix is 572.5 omega, compared with the Rct of the M-Z/CH @ SA sample being 4.7941 multiplied by 10 6 Omega, which is much higher than the magnesium alloy matrix. The M-Z/CH @ SA samples also proved to have excellent propertiesThe specific corrosion protection performance, detailed fit data are shown in table 2.
TABLE 2 equivalent Circuit fitting results
2.4 wettability of hydrophobic films
In order to explore the membrane protection mechanism, the wettability of the surfaces of an M-Z/CH sample (heated for 105min) and an M-Z/CH @ SA sample (heated for 105min) is researched, and the test shows that deionized water droplets are absorbed by a membrane at the moment of contacting the surfaces of the M-Z/CH sample (part a in figure 13), and the result shows that the surfaces of the M-Z/CH sample which is not modified by stearic acid have strong adsorption force on water, and the surface membrane is super-hydrophilic. This also results in the sample, when exposed to a solution containing corrosive media, being absorbed by the membrane and spreading across the sample along the membrane. To prove the guess, the M-Z/CH sample after the corrosion performance test in 3.5 wt% NaCl solution was taken, the sample was polished, and the surface film was removed to expose the magnesium alloy substrate. The red marked area is the area (part b in fig. 13) where the sample and the corrosive medium are in direct contact during the corrosion performance test, and it can be observed that the sample has pitting not only in the area in direct contact but also in the area not in direct contact. The results show that when the corrosion performance test is carried out, the aqueous solution containing NaCl is really adsorbed and diffused by the surface film of the M-Z/CH sample, so that the sample is corroded wholly. Thus, while the film of the M-Z/CH sample does improve the corrosion protection properties of the Mg matrix, the superhydrophilicity of the film prevents the sample from corrosion protection.
In FIG. 13 (c, part d) is a contact angle image of the surface of the M-Z/CH @ SA sample, the M-Z/CH @ SA sample modified with stearic acid exhibits a distinct hydrophobic character, and the average contact angle obtained using a contact angle measuring instrument is 125 ° when measured at 4 different locations on the M-Z/CH @ SA sample. The modified M-Z/CH @ SA sample has the advantages that the surface has hydrophobicity, so that the solution containing corrosive media is prevented from being adsorbed and diffused on the membrane, the direct contact between the corrosive media in the solution and the sample is greatly limited, and the M-Z/CH @ SA sample has more excellent corrosion protection effect compared with the M-Z/CH @ SA sample before modification.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (6)
1. A method for synthesizing a double-layer composite film on the surface of magnesium alloy in one step is characterized by comprising the following steps:
1) pretreating the magnesium alloy to obtain the magnesium alloy with a clean surface;
2) immersing the magnesium alloy obtained in the step 1) into a surface treatment solution, heating for hydrothermal reaction, and cleaning and drying the magnesium alloy after the reaction is finished to obtain compact Mg (OH) 2 Bottom film and K with porous support-like microstructure 2 Al 2 Si 4 O 12 ·xH 2 O a magnesium alloy sample of the top film, x is 3 to 12;
3) immersing the magnesium alloy sample obtained in the step 2) into a solution of stearic acid and ethanol for modification treatment, taking out, cleaning and drying to obtain the magnesium alloy with the stearic acid modified double-layer composite membrane;
wherein, in step 2):
the surface treatment liquid comprises SiO 2 KOH, ethylenediaminetetraacetic acid, Ca (OH) 2 The weight ratio of each component to the solvent deionized water is (0.0184-0.0192):1, (0.069-0.071):1, (0.090-0.092):1, (0.0226-0.0234): 1;
the conditions of the hydrothermal reaction are as follows: heating to 190-210 ℃ and keeping the temperature for 90-105 min.
2. The method for synthesizing the double-layer composite film on the surface of the magnesium alloy in one step according to claim 1, which is characterized in that: in the step 1), the magnesium alloy is AZ91D magnesium alloy.
3. The method as claimed in claim 1The method for synthesizing the double-layer composite film on the surface of the magnesium alloy by one step is characterized by comprising the following steps of: in step 2), SiO used 2 The particle size of (1) is 8000-10000 meshes.
4. The method for synthesizing the double-layer composite film on the surface of the magnesium alloy in one step according to claim 1, which is characterized in that: in the step 2), the reaction vessel is a muffle furnace.
5. The method for synthesizing the double-layer composite film on the surface of the magnesium alloy in one step according to claim 1, which is characterized in that: in the step 3), the magnesium alloy sample obtained in the step 2) is immersed in a solution of stearic acid and kept stand for modification treatment, and the standing time is 40-60 min.
6. A magnesium alloy having a double-layer composite film on the surface thereof, prepared by the method according to any one of claims 1 to 5.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060234072A1 (en) * | 2005-04-14 | 2006-10-19 | Ilya Ostrovsky | Process for forming a well visible non-chromate conversion coating for magnesium and magnesium alloys |
| US20110003143A1 (en) * | 2008-02-25 | 2011-01-06 | Central Glass Company, Limited | Organosol Containing Magnesium Fluoride Hydroxide, and Manufacturing Method Therefor |
| CN103556141A (en) * | 2013-11-06 | 2014-02-05 | 桂林理工大学 | Preparation method of sol-gel membrane having anticorrosion function on surface of magnesium alloy |
| CN112323116A (en) * | 2020-11-06 | 2021-02-05 | 中国石油大学(华东) | Preparation method of magnesium alloy super-hydrophobic coating based on zeolite imidazole ester framework |
-
2022
- 2022-04-14 CN CN202210392073.4A patent/CN115074707B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060234072A1 (en) * | 2005-04-14 | 2006-10-19 | Ilya Ostrovsky | Process for forming a well visible non-chromate conversion coating for magnesium and magnesium alloys |
| US20110003143A1 (en) * | 2008-02-25 | 2011-01-06 | Central Glass Company, Limited | Organosol Containing Magnesium Fluoride Hydroxide, and Manufacturing Method Therefor |
| CN103556141A (en) * | 2013-11-06 | 2014-02-05 | 桂林理工大学 | Preparation method of sol-gel membrane having anticorrosion function on surface of magnesium alloy |
| CN112323116A (en) * | 2020-11-06 | 2021-02-05 | 中国石油大学(华东) | Preparation method of magnesium alloy super-hydrophobic coating based on zeolite imidazole ester framework |
Non-Patent Citations (8)
| Title |
|---|
| JIYUAN ZHU ET AL.: "Improvement on corrosion resistance of micro-arc oxidized AZ91D magnesium alloy by a pore-sealing coating" * |
| 尚伟;陈白珍;石西昌;温玉清;黄安生;: "镁合金表面复合膜的制备及其耐蚀性" * |
| 张新宇;唐聿明;赵旭辉;左禹;: "硬脂酸添加剂对AZ91D镁合金阳极氧化膜耐蚀性的影响" * |
| 方露;何青青;胡吉明;张鉴清;: "二维层状双金属氢氧化物(LDHs)在金属腐蚀防护中应用的研究进展" * |
| 温玉清;尚伟;李晓晓;蒋秀娟;: "pH值对镁合金表面氧化硅溶胶凝胶成膜及膜层性能的影响" * |
| 王志虎;张菊梅;白力静;张国君;: "AZ31镁合金微弧氧化陶瓷层表面Mg(OH)_2膜层的制备及耐蚀性" * |
| 王志虎;张菊梅;白力静;张国君;: "水热处理对AZ31镁合金微弧氧化陶瓷层组织结构及耐蚀性的影响" * |
| 逯平;方铭中;曹路;许鑫华;: "不同镁合金支架材料MAO/PLLA复合膜研究" * |
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