CN101519782A - Corrosion resistant hydrotalcite/polyelectrolyte composite film and preparation method thereof - Google Patents
Corrosion resistant hydrotalcite/polyelectrolyte composite film and preparation method thereof Download PDFInfo
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- CN101519782A CN101519782A CN200910081336A CN200910081336A CN101519782A CN 101519782 A CN101519782 A CN 101519782A CN 200910081336 A CN200910081336 A CN 200910081336A CN 200910081336 A CN200910081336 A CN 200910081336A CN 101519782 A CN101519782 A CN 101519782A
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Abstract
The invention relates to a corrosion resistant hydrotalcite/polyelectrolyte composite film and a preparation method thereof, which belongs to the technical field of metallic corrosion protection. The general chemical formula of the corrosion resistant hydrotalcite/polyelectrolyte composite film is (PEI/PAA)m/(I-LDHs)n/(PAA/AEI)m, wherein the PEI stands for polyethyleneimine, the PAA stands for polyacrylic acid, and the I-LDHs stands for inhibitor layered double hydroxides. The preparation method comprises the following steps: firstly, the inhibitor layered double hydrotalcites is prepared, then the inhibitor layered double hydrotalcites and the polyelectrolyte are helically coated on an alumina substrate or a stainless steel substrate, and finally, the corrosion resistant hydrotalcite/polyelectrolyte composite film is prepared by heating the inhibitor layered double hydrotalcites and the polyelectrolyte helically coated on the alumina substrate or the stainless steel substrate and performing crosslinking treatment to the same two. The invention has the advantages that the film is even and compact, has firm combination force with the substrate and excellent corrosion resistance, mild preparation condition, wide application range and good application prospect and overcomes the defects of loose and porous structure and short corrosion resistant life of the pure hydrotalcite film; and hydrotalcite interlayer inhibitor molecules perform driving inhibition function.
Description
Technical field
The invention belongs to metallic corrosion guard technology field, be specifically related to a kind of corrosion resistant inhibiter intercalated houghite/poly-electrolysis laminated film and preparation method thereof.
Background technology
Metallic corrosion all causes enormous economic loss to the mankind every year, and diminishes the natural resources and enviroment protection, and it is significant therefore to study the corrosion of metal preserver.One of tradition anti-corrosion method is to adopt coating or the coating that contains chromium, but in recent years, sexavalent chrome is because its high pollution and high carcinogenic are limited use by countries in the world.Therefore, development Chrome-free, efficient, the corrosion protection system of environmental protection is extremely urgent.
In recent years, hydrotalcite-based compound (Layered Double Hydroxide is abbreviated as LDHs) is owing to its particular structure character, and cheapness, and advantages such as asepsis environment-protecting are applied to corrosion of metal and protection field.U.S. Pat 2008002115A1 has reported and has utilized laminate to peel off LDHs in metallic surface solvent evaporation film forming that salt-fog test shows that this film had good antiseptic property in 8～24 hours; Chinese patent CN101050539A has reported and has a kind ofly prepared the method for corrosion resistant hydrotalcite film in the Mg alloy surface spin coating, had certain anti-corrosion capability; Chinese patent CN101285185A has reported a kind of method for preparing the erosion resistance hydrotalcite film at aluminium and aluminum alloy surface growth in situ.These methods all adopt the pure water talc materials to construct corrosion prevention film, but hydrotalcite is as a kind of inorganic nano-particle, bonding force is not strong between particle, toughness is relatively poor, cause film forming fine and close inadequately, corrosive medium is easy to permeate rete, the corroding metal matrix, therefore, often there is short defective of anticorrosion life-span in pure water talcum film.
Prolong the life-span of coating, just require the coating porosity defective few, the surface coverage densification.Inorganic/organic hybrid film can be good at satisfying above-mentioned requirements.In addition, coating antiseptic technology and inhibiter technology are combined, construct a kind of active inhibition system, become one of new developing direction in aseptic technic field.Initiatively the inhibition system is to be different from traditional " passive " corrosion protection coating, and this system contains a kind of molecule container to the environmental change sensitivity usually, and inhibiter is stored in wherein.When corrosion took place, the molecule container was sensed the variation of environment, and inhibiter is discharged automatically, stopped or reduce corrosive further taking place.The intercalation of hydrotalcite layers and interlayer ion interchangeability make it become the good material of constructing this quasi-molecule container.
Summary of the invention
The object of the present invention is to provide a kind of corrosion resistant hydrotalcite/polyelectrolyte composite film and preparation method thereof, with inhibiter intercalated houghite and polyelectrolyte spin coating assembling film forming, it is fine and close inadequately to have overcome pure water talcum film, and toughness is relatively poor, the defective that the anticorrosion life-span is short.Simultaneously, by ion exchange method the inhibiter molecule is introduced hydrotalcite layers, as corrosive medium Cl
-When hydrotalcite contacts in the film, ion-exchange takes place, absorb Cl
-And the release inhibiter, thereby play the initiatively effect of inhibition.This film has the antiseptic property excellence, the preparation condition gentleness, and advantage such as applied widely has a good application prospect.
The chemical constitution general formula of hydrotalcite/polyelectrolyte composite film is (PEI/PAA)
m/ (I-LDHs)
n/ (PAA/PEI)
m, wherein PEI is a polymine, and PAA is a polyacrylic acid, and I-LDHs is the inhibiter intercalated houghite, and m and n represent the assembling number of plies of polyelectrolyte and inhibiter intercalated houghite, 3≤m≤5,1≤n≤10 respectively.The chemical constitution of inhibiter intercalated houghite is [M
2+ 1-xAl
3+ x(OH)
2]
X+(I
N- X/n) mH
2O, wherein main body laminate divalent metal M
2+Be Zn
2+, Ni
2+, Mg
2+, Co
2+In a kind of; Trivalent metal cation is Al
3+1-x and x be respectively+molar fraction of divalent and+3 valence metal ions, and 0.2≤x≤0.4; I
N-Be the hydrotalcite layers inhibitor anion, can be the vanadic acid root, molybdate, wolframate radical, borate etc., preferred vanadic acid root and borate.
Concrete processing step is as follows:
A. the preparation of inhibiter intercalated houghite:
With M
2+Nitrate and Al
3+Nitrate according to M
2+/ Al
3+Amount of substance is than being dissolved in CO for the ratio of 2:1～4:1
2Redistilled water (promptly through 2 distillatory distilled water) in, be made into mixing salt solution, make M
2+Concentration be 0.4～2.1mol/L; NaOH is dissolved in CO
2Redistilled water in, be mixed with the alkaline solution that concentration is 0.5～2.0mol/L; Above-mentioned two kinds of solution are poured in the colloidal mill react, the gained slurries wash the sample that obtains to pH=7～7.5 120～180 ℃ of following hydrothermal crystallizings 8～24 hours; The sample of gained obtains nitrate radical intercalated houghite powder after 60～80 ℃ drying was also ground in 12～24 hours down.Main body laminate divalent metal M wherein
2+Be Zn
2+, Ni
2+, Mg
2+, Co
2+, in a kind of; Trivalent metal cation is Al
3+Preparation contains the CO that goes of vanadic acid root, molybdate, wolframate radical or borate inhibitor anion again
2Whose solution is that to adjust the pH value be 5～6 for the HNO3 of 1～2mol/L with concentration.Then, the nitrate radical intercalated houghite that makes is joined in the above-mentioned solution, stir, exchange 48～72 hours down, adopt and remove CO at 50～80 ℃
2Deionized water wash to pH=7～7.5, obtain the inhibiter intercalated houghite.According to the hydrotalcite quality: remove CO
2Water is the ratio formulated suspension of 1.0～3.0g/L, and ultra-sonic dispersion 1～2 hour obtains inhibiter intercalated houghite colloidal sol.
B. the surface treatment of substrate: substrate is immersed in ultrasonic cleaning in the washing lotion, uses N then
2Dry up and be horizontally fixed on the spin coater sample table.The washing lotion and the purging method that adopt are: after substrate is used 300# waterproof abrasive paper and 800# waterproof abrasive paper uniform grinding surface successively, use deionized water and acetone ultrasonic cleaning 10～15 minutes more successively, to remove the impurity and the greasy dirt on surface.If substrate is aluminium flake and aluminum alloy sheet, be 1～5% NaOH aqueous solution soaking 2～10 minutes with massfraction more then, remove surperficial zone of oxidation.
C. the spin coating of inhibiter intercalated houghite and polyelectrolyte assembling:
Step 1: using microsyringe is 50～100 μ L/cm according to dripping volume/chip area
2Ratio, dripping concentration is 1.0～1.5g/L polymine (PEI) aqueous solution, with 500～1000 rev/mins rotating speed prerotations 10～20 seconds, treat that solution is paved with substrate surface after, again with 3000～6000 rev/mins speed rotation 30～60 seconds; Drip equivalent 1.0～1.5g/L polyacrylic acid (PAA) aqueous solution again, press the same terms spin coating, the membrane structure that obtains is (PEI/PAA)
1Repeat above-mentioned steps m time, the membrane structure that obtains is (PEI/PAA)
m
Step 2: on step 1 spin coating assembling film basis, using microsyringe is 50～100 μ L/cm according to dripping volume/chip area
2Ratio, dripping concentration is the inhibiter intercalated houghite colloidal sol of 1.0～3.0g/L, with 500～1000 rev/mins rotating speed prerotations 10～20 seconds, after treating that solution is paved with substrate surface, rotated 30～60 seconds with 3000～6000 rev/mins speed again, repeat above-mentioned steps n time, the membrane structure that obtains is (PEI/PAA)
m/ (I-LDHs)
n
Step 3: on step 2 spin coating assembling film basis, according to the order repeating step 1 of PEI behind the first PAA, the membrane structure that finally obtains is (PEI/PAA)
m/ (I-LDHs)
n/ (PAA/PEI)
m
Step 4: at last the film that makes was promptly obtained corrosion resistant hydrotalcite/polyelectrolyte composite film in 10～12 hours at 100～120 ℃ of following heat cross-linkings.
Adopt day island proper Tianjin XRD-6000 type X-ray diffractometer (XRD) and German Bruker Vector22 type Fourier transform infrared spectrometer (FT-IR) that precursor nitrate radical intercalated houghite and inhibiter intercalated houghite sample are carried out qualitative analysis.Fig. 1 is the XRD spectra of nitrate radical intercalation zinc-aluminium hydrotalcite and ten vanadic acid root intercalation zinc-aluminium hydrotalcites among the embodiment 1.By XRD figure as can be known, after ten vanadic acid roots entered hydrotalcite layers through ion-exchange, its interlamellar spacing increased to 1.19nm by the 0.86nm of precursor; Fig. 2 is the FT-IR spectrogram of nitrate radical intercalation zinc-aluminium hydrotalcite and ten vanadic acid root intercalation zinc-aluminium hydrotalcites among the embodiment 1,960,814,744,560 and 512cm
-1The characteristic absorption band of ten vanadic acid roots, wherein 960cm have appearred in the place
-1The symmetrical stretching vibration of the corresponding V=O key in the spectrum peak at place, and 800～500cm
-1The symmetry and the antisymmetric stretching vibration of the corresponding V-O-V key of the bands of a spectrum at place, above-mentioned sign prove successfully synthetic ten vanadic acid root intercalation zinc-aluminium hydrotalcites.
Adopt Japanese Hitachi S4700 type scanning electronic microscope (SEM) to characterize hydrotalcite/polyelectrolyte composite film surface and section pattern.Fig. 3 is (PEI/PAA) of preparation among the embodiment 1
3/ (V
10O
28-LDHs)
3/ (PAA/PEI)
3The SEM photo of laminated film, the very smooth densification of visible surface; The laminated film section is carried out SEM characterize, its thickness is 214 ± 30nm, and visible film thickness is extremely thin.
Adopt Shanghai occasion China CHI660c type electrochemical workstation that hydrotalcite/polyelectrolyte composite film is carried out the polarization curve test.Fig. 4 is (PEI/PAA) of preparation among the embodiment 1
3/ (V
10O
28-LDHs)
3/ (PAA/PEI)
3Laminated film and the aluminium substrate polarization curve in 0.5mol/L NaCl neutral solution, as seen from the figure, surface-assembled the aluminium substrate of laminated film, its corrosion electric current density is from original 8.6 * 10
-5Ampere drops to 3.8 * 10 for every square centimeter
-7Every square centimeter of ampere shows that its anti-corrosion capability significantly improves.
Adopt the IM6e type electrochemical workstation of German Zahner that hydrotalcite/polyelectrolyte composite film is carried out the electrochemical impedance test.Fig. 5 is (PEI/PAA) of preparation among the embodiment 1
3/ (V
10O
28-LDHs)
3/ (PAA/PEI)
3Laminated film soaks the alternating-current impedance spectrogram of different time in 0.05mol/L NaCl neutral solution.As seen from the figure, the resistance value of laminated film still kept 4.3 * 10 after 7 days
-5Ohms per square centimetre was declined by less than an order of magnitude with comparing originally, showed that film can keep good Corrosion Protection in a long time.
According among standard GB/T 5270-2005 to the evaluation method of metallic surface adhesion layer bonding strength, adopted stroke lattice laboratory method that the bonding strength of hydrotalcite/polyelectrolyte composite film has been carried out qualitative evaluation.Film in the test result demonstration stroke lattice zone and substrate show that without any obscission laminated film and matrix bond are good.
Of the present inventionly be a little, the film forming even compact, firm with substrate caking power, have excellent Corrosion Protection, it is loose porous to have solved pure water talcum membrane structure, the defective that the anticorrosion life-span is short; Hydrotalcite layers inhibiter molecule plays the initiatively effect of inhibition; And the preparation condition gentleness, the scope of application is extensive, has a good application prospect.
Description of drawings
Fig. 1. the X-ray diffraction spectrogram of synthetic nitrate radical intercalation zinc-aluminium hydrotalcite and ten vanadic acid root intercalation zinc-aluminium hydrotalcites under embodiment 1 condition.X-coordinate-angle 2 θ, unit for the degree (°); Ordinate zou-intensity, unit is counting per second (cps).The X-ray diffraction spectrogram of curve (a)-nitrate radical intercalation zinc-aluminium hydrotalcite; The X-ray diffraction spectrogram of curve (b)-ten vanadic acid root intercalation zinc-aluminium hydrotalcite.
Fig. 2. the infrared spectrum of synthetic nitrate radical intercalation zinc-aluminium hydrotalcite and ten vanadic acid root intercalation zinc-aluminium hydrotalcites under embodiment 1 condition.X-coordinate-wave number, unit is cm
-1Ordinate zou-intensity, unit is absolute units (a.u.).The infrared spectrum of curve (a)-nitrate radical intercalation zinc-aluminium hydrotalcite; The infrared spectrum of curve (b)-ten vanadic acid root intercalation zinc-aluminium hydrotalcite.
Fig. 3. (PEI/PAA) for preparing under embodiment 1 condition
3/ (V
10O
28-LDHs)
3/ (PAA/PEI)
3The SEM photo of laminated film.The SEM photo on figure (a)-surface; The SEM photo of figure (b)-section.
Fig. 4. (PEI/PAA) for preparing under embodiment 1 condition
3/ (V
10O
28-LDHs)
3/ (PAA/PEI)
3The polarization curve of laminated film and aluminium substrate.X-coordinate-strength of current, unit is every square centimeter of (Amps/cm of ampere
2); Ordinate zou-current potential, unit are volt (V).The polarization curve of curve (a)-aluminium substrate; The polarization curve of spin coating assembling laminated film on curve (b)-aluminium substrate.
Fig. 5. (PEI/PAA) for preparing under embodiment 1 condition
3/ (V
10O
28-LDHs)
3/ (PAA/PEI)
3Laminated film soaks the alternating-current impedance spectrogram of different time.X-coordinate-frequency, unit is hertz (Hz); Left side ordinate zou-impedance, unit is ohms per square centimetre (Ohms/cm
2); Right ordinate zou-phasing degree, unit for degree (°).The alternating-current impedance spectrogram of curve (a)-1 day laminated film of immersion; The alternating-current impedance spectrogram of curve (b)-7 days laminated films of immersion.
Embodiment:
Embodiment 1
Take by weighing 28.56g Zn (NO
3)
26H
2O and 9.00g Al (NO
3)
39H
2O is dissolved in 150mL and removes CO
2In the water, be mixed with mixing salt solution, other gets 9.12g NaOH and is dissolved in 150mL and removes CO
2In the water, rapidly alkaline solution and mixing salt solution were poured in the colloidal mill into reaction under the room temperature 1 minute, the gained slurries wash the sample that obtains to pH=7 120 ℃ of following hydrothermal crystallizings 8 hours.The sample of gained obtains nitrate radical intercalation zinc-aluminium hydrotalcite (Zn/Al=2) powder after 60 ℃ drying was also ground in 24 hours down; Take by weighing 0.1g nitrate radical intercalation zinc-aluminium hydrotalcite powder and 4.0g NaVO
3Join 100mL and remove CO
2In the water, be the HNO of 1.0mol/L with concentration
3Regulate pH=5, at 70 ℃ of down logical N
2Carried out ion-exchange 48 hours, and adopted and remove CO
2Deionized water wash to pH=7, obtain ten vanadic acid root intercalation zinc-aluminium hydrotalcites (Zn/Al=2).According to hydrotalcite quality/go CO
2Water is the ratio formulated suspension of 1.0g/L, and ultra-sonic dispersion 2 hours obtains ten vanadic acid root intercalation zinc-aluminium hydrotalcite colloidal sols.
After aluminium flake used 300# waterproof abrasive paper and 800# waterproof abrasive paper uniform grinding surface successively, using deionized water and acetone ultrasonic cleaning 10 minutes more successively, is 5% NaOH aqueous solution soaking 2 minutes with massfraction then, uses N at last
2Dry up and be horizontally fixed on the spin coater sample table.
At first, using microsyringe is 100 μ L/cm according to dripping volume/chip area
2Ratio, dripping concentration is 1.0g/L polymine (PEI) aqueous solution, with 1000 rev/mins rotating speed prerotations 10 seconds, treat that solution is paved with the aluminium substrate surface after, again with 2000 rev/mins speed rotation 60 seconds; Drip equivalent 1.0g/L polyacrylic acid (PAA) aqueous solution again, press the same terms spin coating.Repeat above-mentioned steps 3 times, the membrane structure that obtains is (PEI/PAA)
3Then, on above-mentioned spin coating assembling film basis, be 100 μ L/cm according to dripping volume/chip area again
2Ratio, dripping concentration was the ten vanadic acid root intercalation zinc-aluminium hydrotalcite colloidal sols of 1.0g/L, with 1000 rev/mins rotating speed prerotations 10 seconds, after treating that solution is paved with the aluminium flake surface, rotated 60 seconds with 2000 rev/mins speed, repeat above-mentioned steps 3 times, the membrane structure that obtains is (PEI/PAA)
3/ (V
10O
28-LDHs)
3At last, on above-mentioned spin coating assembling film basis, repeat the first step according to the order of PEI behind the first PAA with the same terms, the membrane structure that finally obtains is (PEI/PAA)
3/ (V
10O
28-LDHs)
3/ (PAA/PEI)
3The film for preparing was promptly obtained corrosion resistant hydrotalcite/polyelectrolyte composite film in 10 hours at 120 ℃ of following heat cross-linkings.
Embodiment 2
Take by weighing 15.384g Mg (NO
3)
26H
2O and 11.253g Al (NO
3)
39H
2O is dissolved in 50mL and removes CO
2In the water, be mixed with mixing salt solution, other gets 6.84g NaOH and is dissolved in 50mL and removes CO
2In the water, rapidly alkaline solution and mixing salt solution were poured in the colloidal mill into reaction under the room temperature 1 minute, the gained slurries wash the sample that obtains to pH=7.5 140 ℃ of following hydrothermal crystallizings 10 hours.The sample of gained obtains nitrate radical intercalation magnesium aluminum-hydrotalcite (Mg/Al=2) powder after 70 ℃ drying was also ground in 20 hours down; Take by weighing 0.1g nitrate radical intercalation magnesium aluminum-hydrotalcite powder and 4.0g NaVO
3Join 100mL and remove CO
2In the water, be the HNO of 1.0mol/L with concentration
3Regulate pH=5, at 50 ℃ of down logical N
2Carried out ion-exchange 72 hours, centrifugation is also washed to pH=7.5.Adopt and remove CO
2Deionized water wash to pH=7.5, obtain ten vanadic acid root intercalation magnesium aluminum-hydrotalcites (Mg/Al=2).According to hydrotalcite quality/go CO
2Water is the ratio formulated suspension of 2.0g/L, and ultra-sonic dispersion 1 hour obtains ten vanadic acid root intercalation magnesium aluminum-hydrotalcite colloidal sols.
After aluminium flake used 300# waterproof abrasive paper and 800# waterproof abrasive paper uniform grinding surface successively, using deionized water and acetone ultrasonic cleaning 15 minutes more successively, is 1% NaOH aqueous solution soaking 10 minutes with massfraction then, uses N at last
2Dry up and be horizontally fixed on the spin coater sample table.
At first, using microsyringe is 50 μ L/cm according to dripping volume/chip area
2Ratio, dripping concentration is 2.0g/L polymine (PEI) aqueous solution, with 800 rev/mins rotating speed prerotations 15 seconds, treat that solution is paved with the aluminium flake surface after, again with 3000 rev/mins speed rotation 60 seconds; Drip equivalent 2.0g/L polyacrylic acid (PAA) aqueous solution again, press the same terms spin coating.Repeat above-mentioned steps 4 times, the membrane structure that obtains is (PEI/PAA)
4Then, on above-mentioned spin coating assembling film basis, be 50 μ L/cm according to dripping volume/chip area again
2Ratio, dripping concentration was the ten vanadic acid root intercalation magnesium aluminum-hydrotalcite colloidal sols of 2.0g/L, with 800 rev/mins rotating speed prerotations 15 seconds, after treating that solution is paved with the aluminium flake surface, rotated 60 seconds with 3000 rev/mins speed, repeat above-mentioned steps 5 times, the membrane structure that obtains is (PEI/PAA)
4/ (V
10O
28-LDHs)
5At last, on above-mentioned spin coating assembling film basis, repeat the first step according to the order of PEI behind the first PAA with the same terms, the membrane structure that finally obtains is (PEI/PAA)
4/ (V
10O
28-LDHs)
5/ (PAA/PEI)
4The film for preparing was promptly obtained corrosion resistant hydrotalcite/polyelectrolyte composite film in 12 hours at 100 ℃ of following heat cross-linkings.
Embodiment 3
Take by weighing 23.220g Co (NO
3)
26H
2O and 10.010g Al (NO
3)
39H
2O is dissolved in 100mL and removes CO
2In the water, be mixed with mixing salt solution, other gets 8.117g NaOH and is dissolved in 100mL and removes CO
2In the water, rapidly alkaline solution and mixing salt solution were poured in the colloidal mill into reaction under the room temperature 1 minute, the gained slurries wash the sample that obtains to pH=7 160 ℃ of following hydrothermal crystallizings 12 hours.The sample of gained obtains nitrate radical intercalation cobalt aluminum hydrotalcite (Co/Al=3) powder after 80 ℃ drying was also ground in 12 hours down; Take by weighing 0.1g nitrate radical intercalation cobalt aluminum hydrotalcite powder and 4.0g NaVO
3Join 100mL and remove CO
2In the water, be the HNO of 1.5mol/L with concentration
3Regulate pH=5.5, at 60 ℃ of down logical N
2Carried out ion-exchange 60 hours, and adopted and remove CO
2Deionized water wash to pH=7, obtain ten vanadic acid root intercalation cobalt aluminum hydrotalcites (Co/Al=3).According to hydrotalcite quality/go CO
2Water is the ratio formulated suspension of 1.5g/L, and ultra-sonic dispersion 1 hour obtains ten vanadic acid root intercalation cobalt aluminum hydrotalcite colloidal sols.
After aluminum alloy sheet used 300# waterproof abrasive paper and 800# waterproof abrasive paper uniform grinding surface successively, using deionized water and acetone ultrasonic cleaning 10 minutes more successively, is 2% NaOH aqueous solution soaking 5 minutes with massfraction then, uses N at last
2Dry up and be horizontally fixed on the spin coater sample table.
At first, using microsyringe is 80 μ L/cm according to dripping volume/chip area
2Ratio, dripping concentration is 1.5g/L polymine (PEI) aqueous solution, with 500 rev/mins rotating speed prerotations 20 seconds, treat that solution is paved with the aluminum alloy sheet surface after, again with 6000 rev/mins speed rotation 30 seconds; Drip equivalent 1.5g/L polyacrylic acid (PAA) aqueous solution again, press the same terms spin coating.Repeat above-mentioned steps 5 times, the membrane structure that obtains is (PEI/PAA)
5Then, on above-mentioned spin coating assembling film basis, be 80 μ L/cm according to dripping volume/chip area again
2Ratio, dripping concentration was the ten vanadic acid root intercalation cobalt aluminum hydrotalcite colloidal sols of 1.5g/L, with 500 rev/mins rotating speed prerotations 20 seconds, after treating that solution is paved with the aluminium flake surface, rotated 30 seconds with 6000 rev/mins speed, repeat above-mentioned steps 10 times, the membrane structure that obtains is (PEI/PAA)
5/ (V
10O
28-LDHs)
10At last, on above-mentioned spin coating assembling film basis, repeat the first step according to the order of PEI behind the first PAA with the same terms, the membrane structure that finally obtains is (PEI/PAA)
5/ (V
10O
28-LDHs)
10/ (PAA/PEI)
5The film for preparing was promptly obtained corrosion resistant hydrotalcite/polyelectrolyte composite film in 11 hours at 110 ℃ of following heat cross-linkings.
Embodiment 4
Take by weighing 38.68g Ni (NO
3)
26H
2O and 24.99g Al (NO
3)
39H
2O is dissolved in 250mL and removes CO
2In the water, be mixed with mixing salt solution, other gets 15.20g NaOH and is dissolved in 250mL and removes CO
2In the water, rapidly alkaline solution and mixing salt solution were poured in the colloidal mill into reaction under the room temperature 1 minute, the gained slurries wash the sample that obtains to pH=7.5 180 ℃ of following hydrothermal crystallizings 24 hours.The sample of gained obtains nitrate radical intercalation nickel aluminum hydrotalcite (Ni/Al=2) powder after 80 ℃ drying was also ground in 16 hours down; Take by weighing 0.1g nitrate radical intercalation nickel aluminum hydrotalcite powder and 4.0gNaVO
3Join 100mL and remove CO
2In the water, be the HNO of 2.0mol/L with concentration
3Regulate pH=5, at 80 ℃ of down logical N
2Carried out ion-exchange 48 hours, and adopted and remove CO
2Deionized water wash to pH=7.5, obtain ten vanadic acid root intercalation nickel aluminum hydrotalcites (Ni/Al=2).According to hydrotalcite quality/go CO
2Water is the ratio formulated suspension of 1.5g/L, and ultra-sonic dispersion 2 hours obtains ten vanadic acid root intercalation nickel aluminum hydrotalcite colloidal sols.
After stainless steel substrates used 300# waterproof abrasive paper and 800# waterproof abrasive paper uniform grinding surface successively, use deionized water and acetone ultrasonic cleaning 15 minutes more successively.Use N then
2Dry up and be horizontally fixed on the spin coater sample table.
At first, using microsyringe is 50 μ L/cm according to dripping volume/chip area
2Ratio, dripping concentration is 2.0g/L polymine (PEI) aqueous solution, with 1000 rev/mins rotating speed prerotations 15 seconds, treat that solution is paved with the aluminium flake surface after, again with 2000 rev/mins speed rotation 60 seconds; Drip equivalent 2.0g/L polyacrylic acid (PAA) aqueous solution again, press the same terms spin coating.Repeat above-mentioned steps 3 times, the membrane structure that obtains is (PEI/PAA)
3Then, on above-mentioned spin coating assembling film basis, be 50 μ L/cm according to dripping volume/chip area again
2Ratio, dripping concentration was the ten vanadic acid root intercalation nickel aluminum hydrotalcite colloidal sols of 2.0g/L, with 1000 rev/mins rotating speed prerotations 15 seconds, after treating that solution is paved with the aluminium flake surface, rotated 60 seconds with 2000 rev/mins speed, repeat above-mentioned steps 5 times, the membrane structure that obtains is (PEI/PAA)
3/ (V
10O
28-LDHs)
5At last, on above-mentioned spin coating assembling film basis, repeat the first step according to the order of PEI behind the first PAA with the same terms, the membrane structure that finally obtains is (PEI/PAA)
3/ (V
10O
28--LDHs)
5/ (PAA/PEI)
3The film for preparing was promptly obtained corrosion resistant hydrotalcite/polyelectrolyte composite film in 12 hours at 120 ℃ of following heat cross-linkings.
Embodiment 5
Take by weighing 28.56g Zn (NO
3)
26H
2O and 9.00g Al (NO
3)
39H
2O is dissolved in 150mL and removes CO
2In the water, be mixed with mixing salt solution, other gets 9.12g NaOH and is dissolved in 150mL and removes CO
2In the water, rapidly alkaline solution and mixing salt solution were poured in the colloidal mill into reaction under the room temperature 1 minute, the gained slurries wash the sample that obtains to pH=7 120 ℃ of following hydrothermal crystallizings 8 hours.The sample of gained obtains nitrate radical intercalation zinc-aluminium hydrotalcite (Zn/Al=2) powder after 60 ℃ drying was also ground in 24 hours down; Take by weighing 0.1g nitrate radical intercalation zinc-aluminium hydrotalcite powder and 12.6g Na
2B
4O
7Join 100mL and remove CO
2In the water, be the HNO of 1.0mol/L with concentration
3Regulate pH=5, at 70 ℃ of down logical N
2Carried out ion-exchange 48 hours, and adopted and remove CO
2Deionized water wash to pH=7, obtain borate intercalation zinc-aluminium hydrotalcite (Zn/Al=2).According to hydrotalcite quality/go CO
2Water is the ratio formulated suspension of 1.0g/L, and ultra-sonic dispersion 1.5 hours obtains borate intercalation zinc-aluminium hydrotalcite colloidal sol.
After stainless steel substrates used 300# waterproof abrasive paper and 800# waterproof abrasive paper uniform grinding surface successively, use deionized water and acetone ultrasonic cleaning 10 minutes more successively.Use N then
2Dry up and be horizontally fixed on the spin coater sample table.
At first, using microsyringe is 100 μ L/cm according to dripping volume/chip area
2Ratio, dripping concentration is 1.0g/L polymine (PEI) aqueous solution, with 1000 rev/mins rotating speed prerotations 10 seconds, treat that solution is paved with the aluminium substrate surface after, again with 2000 rev/mins speed rotation 60 seconds; Drip equivalent 1.0g/L polyacrylic acid (PAA) aqueous solution again, press the same terms spin coating.Repeat above-mentioned steps 3 times, the membrane structure that obtains is (PEI/PAA)
3Then, on above-mentioned spin coating assembling film basis, be 100 μ L/cm according to dripping volume/chip area again
2Ratio, drip dripping 100 μ L concentration was the borate intercalation zinc-aluminium hydrotalcite colloidal sol of 1.0g/L, with 1000 rev/mins rotating speed prerotations 10 seconds, after treating that solution is paved with the aluminium flake surface, rotated 60 seconds with 2000 rev/mins speed, repeat above-mentioned steps 3 times, the membrane structure that obtains is (PEI/PAA)
3/ (B
4O
7-LDHs)
3At last, on above-mentioned spin coating assembling film basis, repeat the first step according to the order of PEI behind the first PAA with the same terms, the membrane structure that finally obtains is (PEI/PAA)
3/ (B
4O
7-LDHs)
3/ (PAA/PEI)
3The film for preparing was promptly obtained corrosion resistant hydrotalcite/polyelectrolyte composite film in 10 hours at 120 ℃ of following heat cross-linkings.
Claims (6)
1, a kind of corrosion resistant hydrotalcite/polyelectrolyte composite film is characterized in that, the chemical constitution general formula of film is (PEI/PAA)
m/ (I-LDHs)
n/ (PAA/PEI)
m, wherein PEI is a polymine, and PAA is a polyacrylic acid, and I-LDHs is the inhibiter intercalated houghite, and m and n represent the number of plies of polyelectrolyte and inhibiter intercalated houghite respectively, 3≤m≤5,1≤n≤10.
, film according to claim 1, it is characterized in that the chemical constitution of inhibiter intercalated houghite is [M
2+
1-xAl
3+ x(OH)
2]
X+(I
N- X/n) mH
2O, wherein, divalent metal M
2+Be Zn
2+, Ni
2+, Mg
2+, Co
2+In a kind of; Trivalent metal cation is Al
3+1-x and x be respectively+molar fraction of divalent and+3 valence metal ions, and 0.2≤x≤0.4; I
N-Be the hydrotalcite layers inhibitor anion.
3, film according to claim 2 is characterized in that, described inhibitor anion is vanadic acid root, molybdate, wolframate radical or borate.
4, film according to claim 2 is characterized in that, described inhibitor anion is vanadic acid root or borate.
5, a kind of method for preparing the described corrosion resistant hydrotalcite/polyelectrolyte composite film of claim 1 is characterized in that, processing step is:
A. the preparation of inhibiter intercalated houghite:
With M
2+Nitrate and Al
3+Nitrate according to M
2+/ Al
3+Amount of substance is than being dissolved in CO for the ratio of 2:1～4:1
2Redistilled water in, be made into mixing salt solution, make M
2+Concentration be 0.4～2.1mol/L; NaOH is dissolved in CO
2Redistilled water in, be mixed with the alkaline solution that concentration is 0.5～2.0mol/L; Above-mentioned two kinds of solution are poured in the colloidal mill react, the gained slurries wash the sample that obtains to pH=7～7.5 120～180 ℃ of following hydrothermal crystallizings 8～24 hours; The sample of gained obtains nitrate radical intercalated houghite powder after 60～80 ℃ drying was also ground in 12～24 hours down; Preparation contains the CO that goes of vanadic acid root, molybdate, wolframate radical or borate inhibitor anion again
2The aqueous solution is the HNO of 1～2mol/L with concentration
3Adjusting the pH value is 5～6; Then, the nitrate radical intercalated houghite that makes is joined in the above-mentioned solution, stir, exchange 48～72 hours down, adopt and remove CO at 50～80 ℃
2Deionized water wash to pH=7～7.5, obtain the inhibiter intercalated houghite; According to the hydrotalcite quality: remove CO
2Water is the ratio formulated suspension of 1.0～3.0g/L, and ultra-sonic dispersion 1～2 hour obtains inhibiter intercalated houghite colloidal sol;
B. the surface treatment of substrate: substrate is immersed in ultrasonic cleaning in the washing lotion, uses N then
2Dry up and be horizontally fixed on the spin coater sample table;
C. the spin coating of inhibiter intercalated houghite and polyelectrolyte assembling:
Step 1: using microsyringe is 50～100 μ L/cm according to dripping volume/chip area
2Ratio, dripping concentration is 1.0～1.5g/L polymine (PEI) aqueous solution, with 500～1000 rev/mins rotating speed prerotations 10～20 seconds, treat that solution is paved with substrate surface after, again with 3000～6000 rev/mins speed rotation 30～60 seconds; Drip equivalent 1.0～1.5g/L polyacrylic acid (PAA) aqueous solution again, press the same terms spin coating, the membrane structure that obtains is (PEI/PAA)
1Repeat above-mentioned steps m time, the membrane structure that obtains is (PEI/PAA)
m
Step 2: on step 1 spin coating assembling film basis, be 50～100 μ L/cm according to dripping volume/chip area again
2Ratio, dripping concentration is the inhibiter intercalated houghite colloidal sol of 1.0～3.0g/L, with 500～1000 rev/mins rotating speed prerotations 10～20 seconds, after treating that solution is paved with substrate surface, rotated 30～60 seconds with 3000～6000 rev/mins speed again, repeat above-mentioned steps n time, the membrane structure that obtains is (PEI/PAA)
m/ (I-LDHs)
n
Step 3: on step 2 spin coating assembling film basis, according to the order repeating step 1 of PEI behind the first PAA, the membrane structure that finally obtains is (PEI/PAA)
m/ (I-LDHs)
n/ (PAA/PEI)
m
Step 4: at last the film that makes was promptly obtained corrosion resistant hydrotalcite/polyelectrolyte composite film in 10～12 hours at 100～120 ℃ of following heat cross-linkings.
6, in accordance with the method for claim 3, it is characterized in that: the described substrate of step c is aluminium flake, aluminum alloy sheet or stainless steel substrates; The washing lotion and the purging method that adopt are:
After substrate used 300# waterproof abrasive paper and 800# waterproof abrasive paper uniform grinding surface successively, use deionized water and acetone ultrasonic cleaning 10～15 minutes more successively, to remove the impurity and the greasy dirt on surface; If substrate is aluminium flake and aluminum alloy sheet, be 1 ~ 5% NaOH aqueous solution soaking 2～10 minutes with massfraction more then, remove surperficial zone of oxidation.
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