CN110885612B - A kind of epoxy resin/montmorillonite nanocomposite coating for metal surface - Google Patents
A kind of epoxy resin/montmorillonite nanocomposite coating for metal surface Download PDFInfo
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- CN110885612B CN110885612B CN201911208516.4A CN201911208516A CN110885612B CN 110885612 B CN110885612 B CN 110885612B CN 201911208516 A CN201911208516 A CN 201911208516A CN 110885612 B CN110885612 B CN 110885612B
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- montmorillonite
- epoxy resin
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 229910052901 montmorillonite Inorganic materials 0.000 title claims abstract description 112
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 69
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 69
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 42
- 239000011248 coating agent Substances 0.000 title claims abstract description 32
- 238000000576 coating method Methods 0.000 title claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 15
- 239000002184 metal Substances 0.000 title claims abstract description 15
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims abstract description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 6
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 6
- 239000011734 sodium Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 24
- 239000003085 diluting agent Substances 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- -1 hexadecylamine modified montmorillonite Chemical class 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- 239000004952 Polyamide Substances 0.000 claims description 7
- 229920002647 polyamide Polymers 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 150000001412 amines Chemical group 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000000084 colloidal system Substances 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 239000010410 layer Substances 0.000 abstract description 18
- 239000002131 composite material Substances 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 9
- 239000012528 membrane Substances 0.000 abstract description 6
- 239000011229 interlayer Substances 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 22
- 238000005260 corrosion Methods 0.000 description 20
- 230000007797 corrosion Effects 0.000 description 18
- 229910052782 aluminium Inorganic materials 0.000 description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 11
- 239000011780 sodium chloride Substances 0.000 description 11
- 238000000840 electrochemical analysis Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 229910000838 Al alloy Inorganic materials 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229910000077 silane Inorganic materials 0.000 description 5
- 238000001132 ultrasonic dispersion Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Classifications
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
- Epoxy Resins (AREA)
Abstract
本发明涉及一种用于金属表面的环氧树脂/蒙脱石纳米复合涂料，以及利用所述纳米复合涂料制备复合膜的方法。本发明将氯化锂对蒙脱石片层进行剥离以及十六胺对剥离后蒙脱石进行有机改性，使亲水性的蒙脱石转变为亲油性，蒙脱石层间距被撑大，层间作用力变弱，使蒙脱石能够更加均匀分散在聚合物中。环氧树脂/蒙脱石纳米复合膜材料的制备方法简单，无需复杂设备，钠基蒙脱石储量巨大，适合于工业化生产。The invention relates to an epoxy resin/montmorillonite nanocomposite coating for metal surfaces, and a method for preparing a composite film by using the nanocomposite coating. In the invention, the montmorillonite lamellae are peeled off by lithium chloride and the peeled montmorillonite is organically modified by hexadecylamine, so that the hydrophilic montmorillonite is transformed into lipophilic, and the montmorillonite layer spacing is enlarged. , the interlayer force becomes weaker, so that the montmorillonite can be more uniformly dispersed in the polymer. The preparation method of the epoxy resin/montmorillonite nanocomposite membrane material is simple, does not require complicated equipment, and has huge reserves of sodium-based montmorillonite, which is suitable for industrial production.
Description
(I) technical field
The invention relates to an epoxy resin/montmorillonite nano composite coating for a metal surface and a method for preparing a composite film by using the nano composite coating.
(II) background of the invention
The development and development of aluminum alloys have improved the overall performance of aluminum, and therefore, aluminum alloys are widely used in transportation, machine manufacturing, aerospace, electrical components, and the like. The poor corrosion resistance of the aluminum alloy brings certain trouble to the maintenance of the aluminum alloy. Accordingly, many anticorrosion treatment technologies for aluminum alloys, such as chromate, phosphate, molybdate and other passivation treatment technologies, have been developed, but all have serious environmental pollution problems, and the treatment technologies are complex and expensive. With the gradual improvement of environmental protection requirements and the enhancement of environmental consciousness of people, particularly the great reduction of the allowable discharge amount of chromium and phosphorus in various countries, research and development of a new surface treatment process which can effectively improve the binding force between a coating and a metal matrix and is environment-friendly has become a new emerging problem at present.
The epoxy resin is a thermosetting resin with excellent performance, has the advantages of excellent mechanical property, adhesive property, heat resistance, solvent resistance, easy processing, easy molding and the like, and is widely applied. However, since epoxy resins are thermosetting materials having a high degree of crosslinking, they have disadvantages of insufficient toughness, poor impact resistance and easy cracking after curing, and their use has been limited. Therefore, toughening the epoxy resin by various methods is an important subject and has great significance for the research of the epoxy resin. Some conventional toughening methods, such as the addition of elastomers, thermoplastic particles, etc., are based on the cost of reduced strength and heat distortion temperature. With the wide application of nanotechnology, many people think of improving the toughness of epoxy resin by using nanoparticles, but the materials also have the problems of complex preparation process, high production cost and easy agglomeration.
Montmorillonite is a layered silicate mineral with a natural nano structure, and exchangeable ions are arranged between layers. People utilize the cation exchange property of montmorillonite to react montmorillonite with long-chain quaternary ammonium salt, so that hydrophilic montmorillonite is converted into lipophilicity, and the interlayer spacing is enlarged. And then inserting the epoxy resin prepolymer into the montmorillonite layers by utilizing the characteristic of weak interlayer acting force of the montmorillonite, further expanding and stripping the interlayer spacing of the montmorillonite in the epoxy resin curing process, and finally uniformly dispersing the montmorillonite in the polymer in a single-layer form to prepare the epoxy resin prepolymer/montmorillonite intercalation compound with high thixotropy.
The traditional epoxy resin/montmorillonite composite film material is slow in curing and drying speed and long in time, certain tackiness exists at the film-metal interface and the film-air interface, so that the film-air interface is easy to stick and adsorb a series of impurities such as fine dust, scraps, water drops and charged monomers, if the film-air interface is exposed in air for a long time, an anticorrosive film layer on the metal surface looks dirty, and micro current is easily generated between the metal-film layer-impurities to accelerate the corrosion of the metal, so that the anticorrosive effect of the metal surface cannot be achieved.
Therefore, how to prepare the epoxy resin/montmorillonite composite film material enhances the bonding force between the coating and the metal interface, so that the coating is less prone to falling off on the metal surface; the coating and the air interface are smooth and stable, so that the probability of self-corrosion of the film is reduced, the curing and drying speed of the film is accelerated, the coating has good toughness, wear resistance, salt resistance and acid resistance, the corrosion resistance of the coating can be effectively improved, and the coating is an important subject worthy of deep exploration at present.
Disclosure of the invention
The invention aims to solve the problems and provides an epoxy resin/montmorillonite nano composite anticorrosive coating for a metal surface.
The technical scheme adopted by the invention is as follows:
an epoxy resin/montmorillonite nano composite coating for a metal surface mainly comprises the following components in percentage by mass: 80-120 parts of epoxy resin, 12-18 parts of diluent, 40-60 parts of curing agent, 0.1-3 parts of accelerator and 1-5 parts of hexadecylamine modified montmorillonite, wherein the hexadecylamine modified montmorillonite is prepared by the following method:
(1) purification of montmorillonite: mixing original sodium-based montmorillonite and deionized water according to the proportion of 1: 10-30, performing ultrasonic treatment while stirring mechanically for 12-24 h, standing for 48-72 h, taking an intermediate colloid part after layering is obvious, separating the center, taking a precipitate, and drying to obtain purified montmorillonite;
(2) stripping montmorillonite: taking 8-10 mol/L lithium chloride solution as a stripping agent, uniformly mixing the purified montmorillonite and the lithium chloride solution in a hydrothermal reaction kettle, carrying out hydrothermal reaction for 20-28 h at 120-160 ℃, and centrifugally washing a sample until a separation solution does not contain Cl-Drying and grinding to obtain peeled montmorillonite;
(3) preparation of hexadecylamine modified montmorillonite: dissolving montmorillonite in deionized water, and obtaining an exfoliated montmorillonite suspension under magnetic stirring, wherein the mass concentration of montmorillonite in the suspension is 0.1-5%; placing the stripped montmorillonite suspension in a water bath kettle at the temperature of 60-100 ℃, adding hexadecylamine, and mechanically stirring for 120-210 min, wherein the dosage of the hexadecylamine is 0.5-2 g/meq of montmorillonite exchange capacity; and after the reaction is finished, centrifugally washing the product for 2-5 times, drying at 70-80 ℃ for 12-24 h, and grinding to obtain the hexadecylamine modified montmorillonite.
The epoxy resin is E51 epoxy resin and/or E44 epoxy resin.
The epoxy resin is bisphenol A type epoxy resin and/or bisphenol F type epoxy resin.
Preferably, the accelerator is an amine accelerator, the curing agent is 650 low molecular weight polyamide, and the diluent is one or more of No. 600 diluent, No. 660 diluent, No. 669 diluent and No. 690 diluent.
More preferably, the nanocomposite coating comprises the following components in percentage by mass: 95-100 parts of epoxy resin, 15 parts of diluent, 50 parts of curing agent, 3 parts of accelerator and 3 parts of hexadecylamine modified montmorillonite.
The invention also relates to a method for preparing a composite membrane by using the nano composite coating, which comprises the following steps: adding epoxy resin, hexadecylamine modified montmorillonite and a diluent into a container, uniformly stirring, heating to 60-80 ℃, preserving heat, stirring for 1-3 h, performing ultrasonic dispersion at 60-80 ℃ for 5-15 min, and performing vacuum defoaming for 5-15 min; and cooling to 20-30 ℃, adding a curing agent and an accelerant into the mixture, fully and uniformly stirring, coating 2-3 layers on the surface of the aluminum sheet, and curing at room temperature for 24-72 hours to obtain the epoxy resin/montmorillonite nano composite film.
Metal surfaces are usually pretreated, including polishing, acidification, phosphating and silane coating; in particular, the method comprises the following steps of,
sequentially polishing the sample by using 80# and 800# abrasive paper, and removing oil by using acetone;
during acidification, placing the sample in 1-2% hydrochloric acid solution, soaking for 5-15 min, taking out, washing with deionized water, and drying at 60-80 ℃;
during phosphorization, a 800# abrasive paper is used for polishing a sample and is placed into zinc phosphorization liquid, the sample is taken out after being soaked for 20-40 min, and the sample is washed by deionized water and dried at 60-80 ℃;
when preparing a silane film, polishing a sample by 800# abrasive paper, preparing a silane hydrolysis solution by using a silane coupling agent (KH-550), ethanol and deionized water according to a certain proportion, adjusting the pH value of the solution by using ammonia water, magnetically stirring for 20-40 min, and standing for a period of time until the hydrolysis is balanced for later use; and (3) putting the phosphatized sample into a silane hydrolysis solution at room temperature for 5-20 min, taking out, drying, curing at 100-140 ℃ for 40-80 min, and taking out to obtain the silane film.
The coating can be used for surface corrosion prevention of aluminum alloy.
Compared with the prior art (the method disclosed in patent CN 109796845A), the beneficial effects of the invention are mainly reflected in that:
(1) the invention uses ultrasonic mechanical agitation to purify the original montmorillonite, and can obtain montmorillonite colloid nano particles (figures 3e and 3f) which have smaller particle size and thinner lamella than those in patent CN109796845A (figures 3c and 3d) so as to facilitate the subsequent stripping modification.
(2) According to the method, the lithium chloride is used for stripping montmorillonite sheets and the hexadecylamine is used for organically modifying the stripped montmorillonite, so that the hydrophilic montmorillonite is converted into oleophilic montmorillonite, the montmorillonite can be stripped and modified into thinner sheets than that disclosed in the patent CN109796845A, the interlaminar acting force of the montmorillonite is weakened, and the montmorillonite can be uniformly dispersed in the polymer.
(3) According to the invention, through an improved montmorillonite organic modification method, the flexibility, plasticity and corrosion resistance of the epoxy resin/montmorillonite nano composite film are improved, and the impedance of the prepared epoxy resin/montmorillonite nano composite coating is 1-4 orders of magnitude higher than that of the epoxy resin/montmorillonite nano composite coating prepared in the patent CN 109796845A.
(4) The preparation method of the epoxy resin/montmorillonite nano composite film material is simple, does not need complex equipment, has huge sodium-based montmorillonite reserves, and is suitable for industrial production.
(IV) description of the drawings
FIG. 1 is an XRD pattern of the organically modified montmorillonite according to the present invention.
FIG. 2 is an FTIR chart of the organically modified montmorillonite of the present invention.
FIG. 3 is an SEM image of montmorillonite. Wherein 3a and 3b are original montmorillonite, 3c and 3d are purified montmorillonite in patent CN109796845A, 3e and 3f are purified montmorillonite obtained by ultrasonic mechanical stirring, and 3g and 3h are hexadecylamine modified montmorillonite obtained by modification.
FIG. 4 shows the results of the analysis of the original aluminum flakes in 1.0mol/L NaCl solution and 0.5mol/L H solution2SO4Tafel polarization profile in solution.
FIG. 5 the original aluminum flakes in 1.0mol/L NaCl solution and 0.5mol/L H solution2SO4EIS impedance plot in solution.
FIG. 6 is a Tafel polarization curve of the epoxy/montmorillonite nanocomposite films prepared in examples 1, 2 and 3 in a 1.0mol/L NaCl solution.
FIG. 7 shows that the epoxy resin/montmorillonite nanocomposite films prepared in examples 1, 2 and 3 are at 0.5mol/L H2SO4Tafel polarization profile in solution.
FIG. 8 is an EIS impedance diagram of the epoxy resin/montmorillonite nanocomposite film prepared in examples 1, 2 and 3 in a 1.0mol/L NaCl solution.
FIG. 9 shows that the epoxy resin/montmorillonite nanocomposite films prepared in examples 1, 2 and 3 are at 0.5mol/L H2SO4EIS impedance plot in solution.
(V) detailed description of the preferred embodiments
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto:
preparation of hexadecylamine modified montmorillonite:
dissolving original sodium-based montmorillonite and deionized water at a ratio of 1:20 in 2000mL beaker, performing ultrasonic treatment (200W, 100%) while stirring mechanically (20Kr/min) for 12h, standing for 72h, centrifuging the mesocolloid part (8000r/min, 6min) after the layering is obvious, and drying the precipitate in the centrifuge tube with the beaker for later use to obtain purified montmorillonite (FIG. 3e, 3f, thickness of about 0.12 μm). At 8 mol. L-1Uniformly mixing 2g of purified montmorillonite and 70mL of lithium chloride solution in a 100mL hydrothermal reaction kettle by using a lithium chloride solution as a stripping agent, carrying out hydrothermal reaction for 24h at 140 ℃, and centrifugally washing a sample until a separation solution does not contain Cl-(addition of AgNO)3No precipitation occurred), dried and ground to obtain a exfoliated montmorillonite sample.
Dissolving 5g of exfoliated montmorillonite (the cation exchange capacity of the exfoliated montmorillonite is 116meq/100g) in deionized water, preparing an exfoliated montmorillonite suspension with the mass fraction of 2% under magnetic stirring, placing the montmorillonite suspension in a water bath kettle at 100 ℃, then adding 2.85g of hexadecylamine which is 2 times of the montmorillonite exchange capacity into the solution, mechanically stirring for 210min, centrifugally washing the product for multiple times after the reaction is finished, the centrifugal rotation speed is 8000r/min, the centrifugal time is 8min each time, then drying for 24h at 80 ℃, and finally grinding to obtain the hexadecylamine modified montmorillonite.
In the embodiment, the epoxy resin is one or more of E51, E44, bisphenol A type epoxy resin and bisphenol F type epoxy resin of the Barring petrochemical company; the diluent is an active diluent 600, 660, 669 or 690 of Wuxi Guanghong chemical raw materials Co; the curing agent is low molecular polyamide 650 of Danbao resin Co., Ltd, and the accelerator is amine accelerator DMP-30 of Runkang chemical Co., Ltd, Changzhou city.
Example 1:
preparation of epoxy resin/montmorillonite nanocomposite film: adding 100 parts of epoxy resin E51, 3 parts of organic modified montmorillonite and 15 parts of active diluent 669 into a 250mL three-neck flask, uniformly stirring, heating to 80 ℃, keeping the temperature and stirring for 2h, performing ultrasonic dispersion at 80 ℃ for 10min, and performing vacuum defoaming for 10 min; and cooling to the temperature close to room temperature, adding 50 parts of curing agent polyamide 650 and 3 parts of accelerant DMP-30 into the mixture, fully and uniformly stirring, coating 1 layer on the surface of the aluminum sheet, and curing for 48 hours at room temperature to prepare the epoxy resin/montmorillonite nano composite material.
Adopting CHI660 type electrochemical workstation of Shanghai Chenghua company to perform salt resistance (1.0mol/L NaCl solution) and acid resistance (0.5mol/L H) on the epoxy resin/montmorillonite nano composite membrane2SO4Solution) corrosion electrochemical test, the results are shown in fig. 6, 7, 8 and 9, from which it can be seen that the aluminum sheets coated with 1 layer of the montmorillonite/epoxy resin composite film are 1.0mol/L NaCl and 0.5mol/L H2SO4The corrosion potential in the solution is-1.28V and-1.23V respectively, and the corrosion current density is 1.74 multiplied by 10 respectively-6A·cm-2And 2.18X 10-6A·cm-2The resistances are respectively 2.50 multiplied by 104Ω·cm-2And 2.50X 104Ω·cm-2. The film layer is thin, bubbles are easily generated in the electrochemical test process, and the anti-corrosion effect is poor.
Example 2:
preparation of epoxy resin/montmorillonite nanocomposite film: adding 100 parts of epoxy resin E51, 3 parts of organic modified montmorillonite and 15 parts of active diluent 669 into a 250mL three-neck flask, uniformly stirring, heating to 80 ℃, keeping the temperature and stirring for 2h, performing ultrasonic dispersion at 80 ℃ for 10min, and performing vacuum defoaming for 10 min; and cooling to the temperature close to room temperature, adding 50 parts of curing agent polyamide 650 and 3 parts of accelerant DMP-30 into the mixture, fully and uniformly stirring, coating 2 layers on the surface of the aluminum sheet, and curing for 48 hours at room temperature to prepare the epoxy resin/montmorillonite nano composite material.
The epoxy resin/montmorillonite nano-composite is prepared by adopting CHI660 type electrochemical workstation of Shanghai Chenghua companyThe membrane was salt (1.0mol/L NaCl solution) and acid (0.5mol/L H) tolerant2SO4Solution) corrosion electrochemical test, the results are shown in fig. 6, 7, 8 and 9, from which it can be seen that the aluminum sheets coated with 2 layers of the montmorillonite/epoxy resin composite film are 1.0mol/L NaCl and 0.5mol/L H2SO4The corrosion potential in the solution is-1.39V and-1.25V respectively, and the corrosion current density is 6.61X 10 respectively-7A·cm-2And 1.81X 10-6A·cm-2The resistances are respectively 7.00X 105Ω·cm-2And 1.49X 105Ω·cm-2. The film layer coated with the 2 layers has better anticorrosion effect than the film layer coated with the 1 layer, and bubbles generated in the electrochemical test process are less.
Example 3:
preparation of epoxy resin/montmorillonite nanocomposite film: adding 100 parts of epoxy resin E51, 3 parts of organic modified montmorillonite and 15 parts of active diluent 669 into a 250mL three-neck flask, uniformly stirring, heating to 80 ℃, keeping the temperature and stirring for 2h, performing ultrasonic dispersion at 80 ℃ for 10min, and performing vacuum defoaming for 10 min; and cooling to the temperature close to room temperature, adding 50 parts of curing agent polyamide 650 and 3 parts of accelerant DMP-30 into the mixture, fully and uniformly stirring, coating 3 layers on the surface of the aluminum sheet, and curing for 48 hours at room temperature to prepare the epoxy resin/montmorillonite nano composite material.
Adopting CHI660 type electrochemical workstation of Shanghai Chenghua company to perform salt resistance (1.0mol/L NaCl solution) and acid resistance (0.5mol/L H) on the epoxy resin/montmorillonite nano composite membrane2SO4Solution) corrosion electrochemical test, the results are shown in fig. 6, 7, 8 and 9, from which it can be seen that the aluminum sheets coated with 3 layers of the montmorillonite/epoxy resin composite film are 1.0mol/L NaCl and 0.5mol/L H2SO4The corrosion potential in the solution is-1.42V and-1.33V respectively, and the corrosion current density is 6.61X 10 respectively-7A·cm-2And 1.00X 10-6A·cm-2The resistances are respectively 8.30 multiplied by 106Ω·cm-2And 1.00X 107Ω·cm-2. The film coated with the 3 layers is smooth and stable, bubbles are hardly generated in the electrochemical test process, and the corrosion resistance is good.
Example 4:
this example is a comparative example in which the method of preparing an organically modified montmorillonite and an epoxy resin/montmorillonite composite film is described in patent CN 109796845A.
Preparation of organic modified montmorillonite: dissolving original sodium-based montmorillonite Na-MMT and deionized water in a ratio of 1:20 in a 2000mL beaker, mechanically stirring for 12h, standing for 72h, taking a mesocolloid part after layering is obvious, centrifuging for 6000-8000 r/min for 5min, and drying the precipitate in a centrifuge tube by using the beaker for later use to obtain purified montmorillonite (figure 3e and figure 3f, the thickness is about 0.28 mu m); then, taking 8mol/L lithium chloride solution as a stripping agent, uniformly mixing 3g of purified montmorillonite and lithium chloride solution in a 100mL hydrothermal reaction kettle, carrying out hydrothermal reaction at 150-160 ℃ for 24h, centrifugally washing a sample until the separation solution does not contain Cl-, drying and grinding to obtain stripped montmorillonite E-MMT; drying the stripped montmorillonite E-MMT for 36h for later use, adding 200mL of distilled water, 200mL of 95% ethanol, 0.03mol of hexadecylamine and 3mL of hydrochloric acid into a 1000mL three-neck flask, stirring, heating to 70-80 ℃, adding 15g of montmorillonite, keeping the temperature, stirring and refluxing for 18h, then carrying out high-speed centrifugal separation on the obtained turbid liquid, carrying out 6000-8000 r/min and 5min, and washing with 1:1 ethanol-distilled water for several times until the separated liquid does not contain Cl-And finally, drying the separated substance at room temperature in vacuum to obtain the organic modified montmorillonite.
Preparation of epoxy resin/montmorillonite nanocomposite film: adding 100 parts of epoxy resin E51, 3 parts of organic modified montmorillonite and 15 parts of active diluent 669 into a 250mL three-neck flask, uniformly stirring, heating to 80 ℃, keeping the temperature and stirring for 2h, performing ultrasonic dispersion at 80 ℃ for 10min, and performing vacuum defoaming for 10 min; and cooling to the temperature close to room temperature, adding 50 parts of curing agent polyamide 650 and 3 parts of accelerant DMP-30 into the mixture, fully and uniformly stirring, coating 1, 2 and 3 layers on the surface of the aluminum sheet, and curing for 48 hours at room temperature to prepare the epoxy resin/montmorillonite nanocomposite.
Adopting CHI660 type electrochemical workstation of Shanghai Chenghua company to perform salt resistance (1.0mol/L NaCl solution) and acid resistance (0.5mol/L H) on the epoxy resin/montmorillonite nano composite membrane2SO4Solution) corrosion electrochemical test, the results are shown in table 1; examples 1, 2 and 3 epoxy resins were preparedThe corrosion resistance of the/montmorillonite nanocomposite film is shown in fig. 6, 7, 8 and 9, and the results are summarized in table 2.
As can be seen from the comparison between table 2 and table 1 with fig. 1, 2 and 3, the present invention can peel montmorillonite into thinner sheets by improving the organic modification process of montmorillonite, so that the montmorillonite is better and uniformly dispersed in the epoxy resin, and the flexibility, plasticity and corrosion resistance of the epoxy resin/montmorillonite nanocomposite film are increased. Compared with example 4 (comparative example), the impedance of the prepared epoxy resin/montmorillonite nano composite coating is 1-4 orders of magnitude larger, and meanwhile, the salt resistance of the epoxy resin/montmorillonite nano composite coating is better than the acid resistance of the epoxy resin/montmorillonite nano composite coating as can be seen from a Tafel polarization curve and an EIS impedance spectrum.
Table 1: EXAMPLE 4 Corrosion electrochemical Properties of epoxy/montmorillonite nanocomposite films made by the method
Table 2: examples 1, 2 and 3 methods of making epoxy/montmorillonite nanocomposite films having electrochemical corrosion properties
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