CN105925129A - Self-corrosion potential response type self-repairing anti-corrosion coating, preparation method and application - Google Patents
Self-corrosion potential response type self-repairing anti-corrosion coating, preparation method and application Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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Abstract
The invention discloses a self-corrosion potential response type self-repairing anti-corrosion coating and belongs to the field of the metal anti-corrosion technology. The self-corrosion potential response type self-repairing anti-corrosion coating is composed of an epoxy-silane composite coating and a mesoporous silica nano-container doped in the epoxy-silane composite coating. The preparation process includes the steps that an epoxy-silane composite coating substrate is prepared; the mesoporous silica nano-container is prepared; the mesoporous silica nano-container is dispersed in the epoxy-silane composite coating and then attached to the surface of a basic material, and the self-corrosion potential response type self-repairing anti-corrosion coating is formed after high-temperature drying. The self-corrosion potential response type self-repairing anti-corrosion coating is high in sensitivity and short in response time, microcell corrosion on the surface of metal can be actively and rapidly detected, corrosion inhibitor molecules are released and adsorbed on the surfaces of corrosion microcells to generate a self-repairing effect, and good application prospects are achieved in the metal anti-corrosion technology. The invention further discloses a preparation method and application of the self-corrosion potential response type self-repairing anti-corrosion coating.
Description
Technical field
Corrosion-inhibiting coating of the present invention and preparation method, be especially a kind of corrosion potential response type selfreparing corrosion-inhibiting coating, its preparation method and application, belong to technical field of metal anti-corrosion.
Background technology
At present, metal erosion is one of single incident maximum on national economy impact.Metal erosion at every moment threatens the security of the lives and property of the mankind, designs and develops effective corrosion protection technology extremely urgent.Being applied in industrial metal material numerous, the light alloy material with magnesium alloy as representative is little due to its density, and specific strength is high, and the advantages such as processing characteristics is excellent are widely used in various engineer equipment.But owing to the thermodynamic stability of magnesium alloy is low, chemical property is active, and in actual application, magnesium alloy materials is very easy to suffer corrosion failure.Compared to other metal materials, the susceptibility-to-corrosion of magnesium alloy makes the research and development of its anti-corrosion protection measure increasingly difficult.
In order to realize the permanent anticorrosion of magnesium alloy, extend magnesium alloy materials the use cycle, use coating protection method be most economical effectively.The coating technology reaching now ripe application is chrome conversion coating, but, Cr VI element has high carcinogenic and strong toxicity, is all limiting the use of this technique, the most at last total ban in current worldwide.At present, the design principle of the substitute technology of chrome conversion coating should be: environmental friendliness, good compactness, obstructing capacity and can automatically repair the self-repair function in corrosion failure region.German mark this-Planck colloidal interface institute H. M hwald professor seminar on the authoritative journals such as Advanced Materials, delivered many selfreparing sol-gel coatings about Subjective and Objective pH-stimuli responsive (Adv. Mater. 2006; 18; 1672 1678 etc.): by scattered for intelligent nano container coat inside; intelligent nano container can experience the microcell environmental pH change caused by corrosion; thus discharge the corrosion inhibition for metal agent molecule of inside, adsorb and form protecting film layer on affected area surface.The change of corrosion area pH value is mainly by the hydrolysis of metal ion, start to pH value to change to need the regular hour from corrosion process, thus, shortening the response time for environmental stimuli can reach selfreparing effect quickly, improves the protection effect that coating is overall further.Stimulating compared to pH, more structurally sound stimulating factor is the corrosion potential of metal, and when corrosion starts to occur, metal corrosion potential i.e. synchronizes to reduce.Thus, the coating of energy responded metal corrosion potential can faster complete self-repair procedure, but the research of the current responsive materials for corrosion potential is also in the blank stage, and this material has great potentiality in corrosion protection application.
Summary of the invention
It is an object of the invention to overcome prior art defect, it is provided that a kind of coating is highly sensitive, and metal corrosion potential changes corrosion potential response type selfreparing corrosion-inhibiting coating, its preparation method and the application that can produce the most accurately response.
In order to solve above-mentioned technical problem, the corrosion potential response type selfreparing corrosion-inhibiting coating that the present invention provides, by epoxy-silane composite coating be entrained in the mesoporous silicon dioxide nano container within epoxy-silane composite coating and form.
In the present invention, the enclosed inside inhibitor molecular of described mesoporous silicon dioxide nano container, the surface modification cystine linkage-N,N'-dimethyl-.gamma..gamma.'-dipyridylium molecule of mesoporous silicon dioxide nano container holds axle, and using water solublity post [5] aromatic hydrocarbons as macrocycle molecule valve cover.
In the present invention, comprise the following steps:
1) epoxy-silane composite coating, is prepared；
2) mesoporous silicon dioxide nano container, is prepared:
21), by meso-porous nano silicon dioxide microsphere and 3-sulfydryl trimethoxy silane back flow reaction in dry toluene, mesoporous silicon dioxide nano container-1 after cleaning-drying, is obtained；
22), by step 21) the mesoporous silicon dioxide nano container that obtains-1 and N-methyl-N '-bromoethyl-4,4 ' bipyridyls are back flow reaction in anhydrous DMF, obtains mesoporous silicon dioxide nano container-2 after cleaning-drying；
23), by step 22) the mesoporous silicon dioxide nano container-2 that obtains is dispersed in the buffer solution containing inhibitor molecular, stir, centrifugal after obtain mesoporous silicon dioxide nano container-3 and be dried；
24), by step 23) the silica nanometer container-3 that obtains is dispersed in the buffer solution containing inhibitor molecular and macrocycle molecule water solublity post [5] aromatic hydrocarbons, centrifugal after stirring obtains solid cleaning-drying, finally gives mesoporous silicon dioxide nano container；
3), by step 2) mesoporous silicon dioxide nano container is dispersed in epoxy-silane composite coating prepared by step 1), is then attached to substrate surface, forms corrosion potential response type selfreparing corrosion-inhibiting coating after high temperature drying.
In the present invention, the detailed process of described step 1) is: by silane coupler ethanol dilution, diluted by epoxy resin acetone, adds cross-linking agent after two kinds of diluent mixing.
In the present invention, described silane coupler is one or both in tetraethyl orthosilicate, 3-glycidyl ether propyl trimethoxy silicane and 3-aminopropyl triethoxysilane；Described cross-linking agent one in diethyl triamine and triethylene tetramine.
In the present invention, described step 21) detailed process be:
Mesoporous silicon dioxide nano microsphere is scattered in water-toluene; in the case of nitrogen is protected, solution is heated to 80-100 DEG C; it is subsequently adding 3-sulfydryl trimethoxy silane; it is centrifuged after back flow reaction and obtains solid product, after cleaning, at 80 DEG C, obtain mesoporous silicon dioxide nano container-1 after vacuum drying；The mass ratio of described mesoporous silicon dioxide nano microsphere, 3-sulfydryl trimethoxy silane and toluene is 1:1.055:86.7.
In the present invention, described step 22) detailed process be:
221), by step 22) the mesoporous silicon dioxide nano container-1 that obtains is scattered in anhydrous DMF, stirs after solution is heated to 100-120 DEG C under conditions of nitrogen is protected；
222), by N-methyl-N '-bromoethyl-4,4 ' bipyridyls are dissolved in anhydrous DMF, are then gradually dropped step 221) solution in, being centrifuged after back flow reaction and obtain solid product, after cleaning, at 80-100 DEG C, vacuum drying obtains mesoporous silicon dioxide nano container-3.
In the present invention, described reflux time is 12-36h；
Described buffer solution is sodium dihydrogen phosphate-disodium hydrogen phosphate or disodium hydrogen phosphate-citric acid solution, and pH value is 7.0-7.2；
Described inhibitor molecular is one or more in caffeine, paeonol or BTA；
Described inhibitor molecular concentration in buffer solution is 30-150 mg/mL.
In the present invention, described inhibitor molecular concentration in buffer solution is 100 mg/mL.
Present invention also offers the application in guardrail wires of the above-mentioned corrosion potential response type selfreparing corrosion-inhibiting coating.
The principle of the present invention is: use fine and close, adhesion is strong epoxy-silane composite coating to be attached to Mg alloy surface, effectively intercepts the infiltration of corrosive medium, and coating itself is not susceptible to peeling with metal.Meanwhile, water solublity post [5] aromatic hydrocarbons-N,N'-dimethyl-.gamma..gamma.'-dipyridylium supramolecular system is connected to by cystine linkage the surface of meso-porous nano silica dioxide granule, blocks meso-hole structure, inhibitor molecular is encapsulated in the inside of meso-porous nano silica dioxide granule.Once face coat lost efficacy and causes metal surface to start corrosion, and the corrosion potential of metal can cut off cystine linkage and make water solublity post [5] aromatic hydrocarbons-N,N'-dimethyl-.gamma..gamma.'-dipyridylium supramolecular system cast out meso-porous nano silica surface aside, thus realizes the quick release of corrosion inhibiter.The inhibitor molecular discharged can form one layer of fine and close molecular film and adsorb the Mg alloy surface in damage, so can effectively stop corrosion area to spread.
Compared with prior art, the beneficial effects of the present invention is: the compactness extent of epoxy prepared by the present invention-silane composite coating is high, can effectively intercept the infiltration of corrosive medium, and it is strong with the adhesion of metal material surface, difficult drop-off or peeling off phenomenon.Corrosion potential response type selfreparing corrosion-inhibiting coating is highly sensitive, response time is short, can be aggressive and quickly detect the microcell of metal surface and corrode and discharge inhibitor molecular absorption and be produced from repairing effect on corrosion microcell surface, have a good application prospect in anti-corrosion of metal.
Accompanying drawing explanation
Fig. 1 is the structural representation of the corrosion potential response type selfreparing corrosion-inhibiting coating of the present invention；
Fig. 2 is the release profiles of the mesoporous silicon dioxide nano container of the present invention；
Fig. 3 is corrosion potential response type selfreparing corrosion-inhibiting coating (A sample), the electrochemical impedance test spectrogram of blank coating sample (B sample) without mesoporous silicon dioxide nano container；
Fig. 4 is corrosion potential response type selfreparing corrosion-inhibiting coating (A sample), blank coating sample (B sample) without mesoporous silicon dioxide nano container soak 15 days in the NaCl solution that concentration is 0.5 M after Corrosion results figure.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail.
As it is shown in figure 1, corrosion potential response type selfreparing corrosion-inhibiting coating of the present invention, for being coated in the surface of magnesium alloy 1.It is by epoxy-silane composite coating 2 and is entrained in the mesoporous silicon dioxide nano container 3 within epoxy-silane composite coating and forms.Wherein, the surface of magnesium alloy 1 is sticked to using epoxy-silane composite coating 2 as skeleton.The skeleton of mesoporous silicon dioxide nano container 3 is the meso-porous nano silicon dioxide microsphere that specific surface area is big, load capacity is strong.Mesoporous silicon dioxide nano container 3 enclosed inside has inhibitor molecular, surface to be modified with cystine linkage-N,N'-dimethyl-.gamma..gamma.'-dipyridylium molecule to hold axle, and using water solublity post [5] aromatic hydrocarbons as macrocycle molecule valve cover.Macrocycle molecule valve cover is the ring dress molecule of pentagonal prism structure, and it is enclosed within the strand on chondritic surface, and this nested structure serves " valve function " of the mesoporous internal binding molecule of closure.
On the surface of above-mentioned mesoporous silicon dioxide nano container, hold axle by cystine linkage-N,N'-dimethyl-.gamma..gamma.'-dipyridylium molecule and form valve, the change of response corrosive environment with water solublity post [5] aromatic hydrocarbons, effectively control the release of corrosion inhibiter (e.g., caffeine), improve the utilization rate of corrosion inhibiter.Cystine linkage-N,N'-dimethyl-.gamma..gamma.'-dipyridylium molecule holds axle two ingredients: wherein N,N'-dimethyl-.gamma..gamma.'-dipyridylium unit occurs the most nested with water solublity post [5] aromatic hydrocarbons by π pi accumulation effect and electrostatic attraction effect, the mesoporous inside of nano container so by inhibitor molecular, can be encapsulated in.Second component units is cystine linkage, during cystine linkage generation reduction reaction, fracture generates sulfydryl, the corrosion potential of magnesium can cut off cystine linkage, nano container surface cast out aside by the nested structure making water solublity post [5] aromatic hydrocarbons and N,N'-dimethyl-.gamma..gamma.'-dipyridylium unit, thus realizes the inhibitor molecular response release for magnesium alloy corrosion potential.
The preparation method of corrosion potential response type selfreparing corrosion-inhibiting coating is as follows:
Embodiment 1
1, epoxy-silane composite coating substrate is prepared
3g 3-aminopropyl triethoxysilane is dissolved in the ethanol of 12.7mL, 34.9g epoxychloropropane the-the third diphenol copolymerization epoxy resin is dissolved in 40 mL acetone, 3.8 g triethylene tetramine stirrings will be added after two kinds of solution mix homogeneously.
2, mesoporous silicon dioxide nano container is prepared
0.5g cetyl trimethylammonium bromide (CTAB) is dispersed in 240mL deionized water, is subsequently adding the sodium hydroxide solution that 1.75 mL concentration are 2 mol/L, is incubated half h under the conditions of 80 DEG C.Under conditions of rotating speed is 700rpm, in reaction system, drips 2.5mL tetraethyl orthosilicate (TEOS), reacts 2h.Reaction terminates rear filtered while hot, by the abundant wash products of hot water, is vacuum dried at 80 DEG C.
Weigh the 200 dried solid products of mg, after being fully ground, add 50 mL methanol and the mixed solution of 3 mL concentrated hydrochloric acid, fully after ultrasonic disperse, back flow reaction 7 h under the conditions of 70 DEG C, centrifugation, fully cleans with water and methanol, and at 80 DEG C, vacuum drying obtains mesoporous silicon dioxide nano microsphere (MCM-41).
100 mg mesoporous silicon dioxide nano microspheres are well-dispersed in 20 mL dry toluenes; in the case of nitrogen is protected, system is heated to 80 DEG C; it is subsequently adding 100 μ L 3-sulfydryl trimethoxy silanes; it is centrifuged after back flow reaction 12 h and obtains solid product; after fully cleaning with dry toluene and methanol, at 80 DEG C, vacuum drying obtains the mesoporous silicon dioxide nano container-1(MSNs-SH with sulfydryl as end group).
Weighing 100 mg mesoporous silicon dioxide nano container-1 with sulfydryl as end group, after 80 DEG C of vacuum drying 12h, system, in the 20 anhydrous DMFs of mL, is heated to 100 DEG C under conditions of nitrogen is protected, then stirs 30 min by ultrasonic disperse.Weighing 100 mg N-methyl-N '-bromoethyl-4,4 ' bipyridyl is dissolved in 2.5 mL
In anhydrous DMF, this solution is gradually dropped containing in the reaction system of the mesoporous silicon dioxide nano container-1 with sulfydryl as end group, back flow reaction 12 h.After reaction terminates, being centrifuged and obtain solid product, after fully cleaning with anhydrous DMF and methanol, at 80 DEG C, vacuum drying obtains the mesoporous silicon dioxide nano container-2(MSNs-Py with N,N'-dimethyl-.gamma..gamma.'-dipyridylium as end group).
Weigh 150 mg caffeine to be dissolved in the sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution of 5mL pH=7,50 mg mesoporous silicon dioxide nano container-2 with N,N'-dimethyl-.gamma..gamma.'-dipyridylium as end group is disperseed in this solution, this system is centrifugal after being stirred at room temperature three days under sealing condition obtains solid, after drying；This solid is dispersed again in sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution that 5 mL contain 50 mg water solublity post [5] aromatic hydrocarbons and 50 mg caffeine.Three days it are stirred at room temperature under sealing condition.After end, it is centrifuged and obtains solid product, fully clean three times with the sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution of pH=7, be dried to obtain final mesoporous silicon dioxide nano container.
3, preparation is doped with the epoxy-silane composite coating of mesoporous silicon dioxide nano container
The mesoporous silicon dioxide nano container for preparing in grinding steps 2 also weighs 20 mg and adds 8 mL epoxies-silane composite coating substrate, is sufficiently stirred for dispersion.
Choose AZ31B magnesium alloy, in acetone soln the most ultrasonic, use 200 mesh, 400 mesh the most respectively, 1200 mesh and 1500 mesh sand paper are once polished, EtOH Sonicate is dried after cleaning in N2 atmosphere, hangs and immerses in the coated substrate containing mesoporous silicon dioxide nano container with the speed of 1.8 cm/min, after soaking 2min, lift with the speed of 2cm/min again, then repeat this lifting step twice, by this magnesium alloy sample under the conditions of 100 DEG C, be dried 90min.
Embodiment 2
1, epoxy-silane composite coating substrate is prepared
1.5 g tetraethyl orthosilicates are dissolved in 6.3 mL ethanol solution, 17.5 g epoxychloropropane the-the third diphenol copolymerization epoxy resin are dissolved in 20 mL acetone, by these two kinds of solution ethyl ester mixing, be then added thereto to 1.9 g diethyl triamine, stir.
2, mesoporous silicon dioxide nano container is prepared
0.5g cetyl trimethylammonium bromide (CTAB) is dispersed in 240mL deionized water, and being subsequently adding 1.75 mL concentration is the sodium hydroxide solution of 2mol/L, is incubated half h under the conditions of 80 DEG C.Under conditions of rotating speed is 700rpm, in reaction system, drips 2.5mL tetraethyl orthosilicate (TEOS), reacts 2h.Reaction terminates rear filtered while hot, by the abundant wash products of hot water, is vacuum dried at 80 DEG C.
Weigh the 200 dried solid products of mg, after being fully ground, add 50 mL methanol and the mixed solution of 3 mL concentrated hydrochloric acid, fully after ultrasonic disperse, back flow reaction 7 h under the conditions of 70 DEG C, centrifugation, fully cleans with water and methanol, and at 80 DEG C, vacuum drying obtains mesoporous silicon dioxide nano microsphere (MCM-41).
100 mg mesoporous silicon dioxide nano microspheres are well-dispersed in 20 mL dry toluenes; in the case of nitrogen is protected, system is heated to 80 DEG C; it is subsequently adding 100 μ L 3-sulfydryl trimethoxy silanes; it is centrifuged after back flow reaction 24 h and obtains solid product; after fully cleaning with dry toluene and methanol, at 80 DEG C, vacuum drying obtains the mesoporous silicon dioxide nano container-1 with sulfydryl as end group.
Weighing 100mg mesoporous silicon dioxide nano container-1 with sulfydryl as end group, after 80 DEG C of vacuum drying 12h, system, in the anhydrous DMF of 20mL, is heated to 100 DEG C under conditions of nitrogen is protected, then stirs 30min by ultrasonic disperse.Weighing 100 mg N-methyl-N '-bromoethyl-4,4 ' bipyridyl is dissolved in 2.5 mL
In anhydrous DMF, this solution is gradually dropped in the reaction system containing MSNs-SH, back flow reaction 24 h.After reaction terminates, being centrifuged and obtain solid product, after fully cleaning with anhydrous DMF and methanol, at 100 DEG C, vacuum drying obtains the mesoporous silicon dioxide nano container-2 with N,N'-dimethyl-.gamma..gamma.'-dipyridylium as end group.
Weigh 150 mg paeonol (HMAP) and be dissolved in 5
In the sodium dihydrogen phosphate-citric acid solution of mL pH=7, by 50 mg
MSNs-Py disperses in this solution, and this system is centrifugal after being stirred at room temperature three days under sealing condition obtains solid, after drying；This solid is scattered in the buffer solution that 5 mL contain 50 mg water solublity post [5] aromatic hydrocarbons and 50 mg paeonol.Three days it are stirred at room temperature under sealing condition.After reaction terminates, it is centrifuged and obtains solid product, fully clean three times with the disodium hydrogen phosphate-citric acid solution of pH=7, be dried to obtain final mesoporous silicon dioxide nano container.
3, preparation is doped with the coating of mesoporous silicon dioxide nano container
The mesoporous silicon dioxide nano container for preparing in grinding steps 2 also weighs 20 mg and adds 8 mL epoxies-silane composite coating substrate, is sufficiently stirred for dispersion.
Choose AZ31B magnesium alloy, in acetone soln the most ultrasonic, use 200 mesh, 400 mesh the most respectively, 1200 mesh and 1500 mesh sand paper are once polished, EtOH Sonicate is dried after cleaning in N2 atmosphere, hangs and immerses in the coated substrate containing mesoporous silicon dioxide nano container with the speed of 1.8 cm/min, after soaking 2 min, lift with the speed of 2cm/min again, then repeat this lifting step twice, by this magnesium alloy sample under the conditions of 100 DEG C, be dried 90min.
4, the controllable release of binding molecule
In order to study the mesoporous silicon dioxide nano container of doping releasing effect under additional reduction potential (simulation magnesium alloy corrosion potential) environment in this coating, test as follows: weigh this mesoporous silicon dioxide nano container 2 mg, drop coating is on platinum electrode, apply the recovery voltage of-2.3V, after energising a period of time, the voltage of logical+2.3 V again, circulation repeats above-mentioned galvanization three times.After energising terminates every time, the release profiles of this nano container is recorded by ultraviolet-uisible spectrophotometer, the binding molecule content discharged in obtaining system by the ultraviolet-visible spectrum standard curve of paeonol, concrete operations are: accurately weigh 2 mg encapsulation products and be dispersed in water, then drop coating is on the platinum electrode that test area is 0.5 cm2, drop coating is had the platinum electrode of nano container and an other blank platinum electrode, the saturated KCl of Ag-AgCl() electrode composition three-electrode system, being immersed in survey volume is 5 mL, in the disodium hydrogen phosphate-sodium dihydrogen phosphate buffer of pH=7, apply the recovery voltage of-2.3V, after energising 30min, the voltage of logical+2.3 V again, conduction time is 30 min, circulation repeats above-mentioned galvanization three times.After energising terminates every time, monitored by ultraviolet-uisible spectrophotometer and record the absorbance at 274 nm, obtaining the release profiles of this nano container, as shown in Figure 2.Meanwhile, the nano container additionally weighing 2 mg is immersed in 5 mL, in the disodium hydrogen phosphate-sodium dihydrogen phosphate buffer of pH=7, the most ultrasonic 3 h, cross ultraviolet-uisible spectrophotometer and test the absorbance at 274 nm, obtain total adsorbance of inhibitor molecular.
As shown in Figure 2, when reduction potential is applied in delivery systme, within the time of 0-0.5h, the inhibitor molecular paeonol having 12.6% is discharged in solution, this is because cystine linkage generation reduction reaction is cut to sulfydryl, water solublity post [5] aromatic hydrocarbons-N,N'-dimethyl-.gamma..gamma.'-dipyridylium supramolecular system is made to cast out nanometer vessel surface aside, it is achieved that the release of internal load paeonol.In oxidizing potential is applied to delivery systme, within the time of 0.5-1 h, inhibitor molecular paeonol concentration in delivery systme is almost without changing, this is because the reversibility of cystine linkage, water solublity post [5] aromatic hydrocarbons-N,N'-dimethyl-.gamma..gamma.'-dipyridylium supramolecular system is connected to nano container surface by cystine linkage again, has blocked the paeonol molecule of mesoporous inside.Through the loop test in three cycles, have the paeonol of 80.4% and be discharged in test system.
The above results shows that this nano container can realize the controllable release to molecular encapsulation.
Embodiment 3
1, epoxy-silane composite coating substrate is prepared
0.75 g tetraethyl orthosilicate and 0.75 g 3-glycidyl ether propyl trimethoxy silicane are dissolved in 6.3 mL ethanol solution, 17.5 g epoxychloropropane the-the third diphenol copolymerization epoxy resin are dissolved in 20 mL acetone, by these two kinds of solution ethyl ester mixing, then it is added thereto to 1.9 g diethyl triamine, stirs.
2, mesoporous silicon dioxide nano container is prepared
0.5g cetyl trimethylammonium bromide (CTAB) is dispersed in 240mL deionized water, is subsequently adding the sodium hydroxide solution that 1.75 mL concentration are 2 mol/L, is incubated half h under the conditions of 80 DEG C.Under conditions of rotating speed is 700rpm, in reaction system, drips 2.5 mL tetraethyl orthosilicates (TEOS), reacts 2
h.Reaction terminates rear filtered while hot, by the abundant wash products of hot water, is vacuum dried at 80 DEG C.
Weigh the dried solid product of 200mg, after being fully ground, add 50mL methanol and the mixed solution of 3mL concentrated hydrochloric acid, fully after ultrasonic disperse, back flow reaction 7h under the conditions of 70 DEG C, centrifugation, fully cleans with water and methanol, and at 80 DEG C, vacuum drying obtains mesoporous silicon dioxide nano microsphere (MCM-41).
100 mg mesoporous silicon dioxide nano microspheres are well-dispersed in 20 mL dry toluenes; in the case of nitrogen is protected, system is heated to 100 DEG C; it is subsequently adding 100 μ L 3-sulfydryl trimethoxy silanes; it is centrifuged after back flow reaction 36 h and obtains solid product; after fully cleaning with dry toluene and methanol, at 80 DEG C, vacuum drying obtains the mesoporous silicon dioxide nano container-1 with sulfydryl as end group.
Weighing 100 mg mesoporous silicon dioxide nano container-1 with sulfydryl as end group, after 80 DEG C of vacuum drying 12h, system, in the 20 anhydrous DMFs of mL, is heated to 120 DEG C under conditions of nitrogen is protected, then stirs 30 min by ultrasonic disperse.Weigh 100
Mg N-methyl-N '-bromoethyl-4,4 ' bipyridyls are dissolved in the 2.5 anhydrous DMFs of mL, are gradually dropped in the reaction system containing MSNs-SH by this solution, back flow reaction 36 h.After reaction terminates, being centrifuged and obtain solid product, after fully cleaning with anhydrous DMF and methanol, at 80 DEG C, vacuum drying obtains the mesoporous silicon dioxide nano container-2 with N,N'-dimethyl-.gamma..gamma.'-dipyridylium as end group.
Weighing 750 mg phenylpropyl alcohol triazoles to be dissolved in the sodium dihydrogen phosphate-citric acid solution of 5 mL pH=7, disperseed in this solution by 50 mg MSNs-Py, this system is centrifugal after being stirred at room temperature three days under sealing condition obtains solid, after drying；This solid is scattered in the buffer solution that 5 mL contain 50 mg water solublity post [5] aromatic hydrocarbons and 50 mg phenylpropyl alcohol triazoles.Three days it are stirred at room temperature under sealing condition.After reaction terminates, it is centrifuged and obtains solid product, fully clean three times with the disodium hydrogen phosphate-citric acid solution of pH=7, be dried to obtain final mesoporous silicon dioxide nano container.
3, preparation is doped with the coating of mesoporous silicon dioxide nano container
The mesoporous silicon dioxide nano container for preparing in grinding steps 2 also weighs 20 mg and adds 8 mL epoxies-silane composite coating substrate, is sufficiently stirred for dispersion.
Choose AZ31B magnesium alloy, in acetone soln the most ultrasonic, use 200 mesh, 400 mesh the most respectively, 1200 mesh and 1500 mesh sand paper are once polished, EtOH Sonicate is dried after cleaning in N2 atmosphere, hangs and immerses in the coated substrate containing mesoporous silicon dioxide nano container with the speed of 1.8 cm/min, after soaking 2 min, lift with the speed of 2cm/min again, then repeat this lifting step twice, by this magnesium alloy sample under the conditions of 100 DEG C, be dried 90 minutes.This sample is labeled as A sample
4, the preparation blank coating sample without mesoporous silicon dioxide nano container
0.75 g tetraethyl orthosilicate and 0.75 g 3-glycidyl ether propyl trimethoxy silicane are dissolved in 6.3 mL ethanol solution, 17.5 g epoxychloropropane the-the third diphenol copolymerization epoxy resin are dissolved in 20 mL acetone, by these two kinds of solution ethyl ester mixing, then it is added thereto to 1.9 g diethyl triamine, stirs.
Choose AZ31B magnesium alloy, in acetone soln the most ultrasonic, use 200 mesh, 400 mesh the most respectively, 1200 mesh and 1500 mesh sand paper are once polished, EtOH Sonicate is dried after cleaning in N2 atmosphere, hangs and immerses in coated substrate with the speed of 1.8 cm/min, after soaking 2 min, lift with the speed of 2cm/min again, then repeat this lifting step twice, by this magnesium alloy sample under the conditions of 100 DEG C, be dried 90 min.This sample is labeled as B sample.
5, immersion corrosion test
A sample, B sample are immersed in the NaCl solution that concentration is 0.5 M simultaneously, observe corrosion condition.Result is as it is shown on figure 3, after 15 days, the corrosion condition of B sample is more serious, large area corrosion area occurs；A sample is owing to can discharge corrosion inhibiter protection metal doped with mesoporous silicon dioxide nano container, thus obvious corrosion area does not occur.
6, the electrochemical impedance spectroscopy test of the magnesium alloy sample of coating protection
A sample, B sample are respectively placed in Princeton
In 2273 electrochemical workstation test devices, exposing test area is 0.5 cm2, and in test device, concentration is the NaCl solution of 0.1 M.Result is as shown in Figure 4, B sample is along with the growth of soak time, the impedance platform of intermediate frequency zone constantly declines this physical barrier effect lasts that represent coating and weakens, and the impedance modulus at low-limit frequency is used to evaluate the degree of corrosion activity, along with the increase of soak time is also constantly reducing, it means that metallic substrates there occurs corrosion reaction.A sample is along with the growth of soak time, and the impedance platform of intermediate frequency zone is also declining, but the impedance modulus of low frequency range can also maintain 107 orders of magnitude, illustrates that metallic substrates can be played a protective role by inhibitor molecular effectively that contain in A sample.
Above-mentioned being illustrated technical solution of the present invention using magnesium alloy as base material, the corrosion potential response type selfreparing corrosion-inhibiting coating of the present invention can apply common guardrail wires, exterior door etc. to carry out anticorrosion.
The above is only the preferred embodiment of the present invention, it is noted that for those skilled in the art, can also make some improvement under the premise without departing from the principles of the invention, and these improvement also should be regarded as protection scope of the present invention.
Claims (10)
1. a corrosion potential response type selfreparing corrosion-inhibiting coating, it is characterised in that: by epoxy-silane composite coating be entrained in the mesoporous silicon dioxide nano container within epoxy-silane composite coating and form.
Corrosion potential response type selfreparing corrosion-inhibiting coating the most according to claim 1, it is characterized in that: the enclosed inside inhibitor molecular of described mesoporous silicon dioxide nano container, the surface of mesoporous silicon dioxide nano container is modified cystine linkage-N,N'-dimethyl-.gamma..gamma.'-dipyridylium molecule and is held axle, and using water solublity post [5] aromatic hydrocarbons as macrocycle molecule valve cover.
3. the preparation method of corrosion potential response type selfreparing corrosion-inhibiting coating described in claim 1, it is characterised in that comprise the following steps:
1) epoxy-silane composite coating, is prepared；
2) mesoporous silicon dioxide nano container, is prepared:
21), by meso-porous nano silicon dioxide microsphere and 3-sulfydryl trimethoxy silane back flow reaction in dry toluene, mesoporous silicon dioxide nano container-1 after cleaning-drying, is obtained；
22), by step 21) the mesoporous silicon dioxide nano container that obtains-1 and N-methyl-N '-bromoethyl-4,4 ' bipyridyls are back flow reaction in anhydrous DMF, obtains mesoporous silicon dioxide nano container-2 after cleaning-drying；
23), by step 22) the mesoporous silicon dioxide nano container-2 that obtains is dispersed in the buffer solution containing inhibitor molecular, stir, centrifugal after obtain mesoporous silicon dioxide nano container-3 and be dried；
24), by step 23) the silica nanometer container-3 that obtains is dispersed in the buffer solution containing inhibitor molecular and macrocycle molecule water solublity post [5] aromatic hydrocarbons, centrifugal after stirring obtains solid cleaning-drying, finally gives mesoporous silicon dioxide nano container；
3), by step 2) mesoporous silicon dioxide nano container is dispersed in epoxy-silane composite coating prepared by step 1), is then attached to substrate surface, forms corrosion potential response type selfreparing corrosion-inhibiting coating after high temperature drying.
The preparation method of corrosion potential response type selfreparing corrosion-inhibiting coating the most according to claim 3, the detailed process that it is characterized in that described step 1) is: by silane coupler ethanol dilution, epoxy resin acetone is diluted, after two kinds of diluent mixing, adds cross-linking agent.
The preparation method of corrosion potential response type selfreparing corrosion-inhibiting coating the most according to claim 4, it is characterised in that: described silane coupler is one or both in tetraethyl orthosilicate, 3-glycidyl ether propyl trimethoxy silicane and 3-aminopropyl triethoxysilane；Described cross-linking agent one in diethyl triamine and triethylene tetramine.
The preparation method of corrosion potential response type selfreparing corrosion-inhibiting coating the most according to claim 3, it is characterised in that described step 21) detailed process be:
Mesoporous silicon dioxide nano microsphere is scattered in water-toluene; in the case of nitrogen is protected, solution is heated to 80-100 DEG C; it is subsequently adding 3-sulfydryl trimethoxy silane; it is centrifuged after back flow reaction and obtains solid product, after cleaning, at 80 DEG C, obtain mesoporous silicon dioxide nano container-1 after vacuum drying；The mass ratio of described mesoporous silicon dioxide nano microsphere, 3-sulfydryl trimethoxy silane and toluene is 1:1.055:86.7.
The preparation method of corrosion potential response type selfreparing corrosion-inhibiting coating the most according to claim 3, it is characterised in that described step 22) detailed process be:
221), by step 22) the mesoporous silicon dioxide nano container-1 that obtains is scattered in anhydrous DMF, stirs after solution is heated to 100-120 DEG C under conditions of nitrogen is protected；
222), by N-methyl-N '-bromoethyl-4,4 ' bipyridyls are dissolved in anhydrous DMF, are then gradually dropped step 221) solution in, being centrifuged after back flow reaction and obtain solid product, after cleaning, at 80-100 DEG C, vacuum drying obtains mesoporous silicon dioxide nano container-3.
The preparation method of corrosion potential response type selfreparing corrosion-inhibiting coating the most according to claim 3, it is characterised in that: described reflux time is 12-36h；
Described buffer solution is sodium dihydrogen phosphate-disodium hydrogen phosphate or disodium hydrogen phosphate-citric acid solution, and pH value is 7.0-7.2；
Described inhibitor molecular is one or more in caffeine, paeonol or BTA；
Described inhibitor molecular concentration in buffer solution is 30-150 mg/mL.
The preparation method of corrosion potential response type selfreparing corrosion-inhibiting coating the most according to claim 8, it is characterised in that: described inhibitor molecular concentration in buffer solution is 100 mg/mL.
10. corrosion potential response type selfreparing corrosion-inhibiting coating application in guardrail wires described in claim 1.
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