CN113444364A - Layer-by-layer self-assembly pH response type silicon dioxide nano container, preparation thereof and application thereof in composite silane film - Google Patents
Layer-by-layer self-assembly pH response type silicon dioxide nano container, preparation thereof and application thereof in composite silane film Download PDFInfo
- Publication number
- CN113444364A CN113444364A CN202110856664.8A CN202110856664A CN113444364A CN 113444364 A CN113444364 A CN 113444364A CN 202110856664 A CN202110856664 A CN 202110856664A CN 113444364 A CN113444364 A CN 113444364A
- Authority
- CN
- China
- Prior art keywords
- layer
- pei
- pss
- silicon dioxide
- assembly
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 194
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 103
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 40
- 238000001338 self-assembly Methods 0.000 title claims abstract description 28
- 230000004044 response Effects 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000005260 corrosion Methods 0.000 claims abstract description 63
- 230000007797 corrosion Effects 0.000 claims abstract description 62
- 239000003112 inhibitor Substances 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002105 nanoparticle Substances 0.000 claims abstract description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000008367 deionised water Substances 0.000 claims abstract description 23
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- 239000007790 solid phase Substances 0.000 claims abstract description 15
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012964 benzotriazole Substances 0.000 claims abstract description 14
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 12
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 25
- 229910052681 coesite Inorganic materials 0.000 claims description 22
- 229910052906 cristobalite Inorganic materials 0.000 claims description 22
- 229910052682 stishovite Inorganic materials 0.000 claims description 22
- 229910052905 tridymite Inorganic materials 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 9
- 238000005119 centrifugation Methods 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims 1
- 229920000867 polyelectrolyte Polymers 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 238000000151 deposition Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 239000000843 powder Substances 0.000 abstract 1
- 230000001988 toxicity Effects 0.000 abstract 1
- 231100000419 toxicity Toxicity 0.000 abstract 1
- 229920002873 Polyethylenimine Polymers 0.000 description 37
- 238000000576 coating method Methods 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 13
- 230000008569 process Effects 0.000 description 12
- 239000012153 distilled water Substances 0.000 description 11
- 238000001179 sorption measurement Methods 0.000 description 8
- 239000012528 membrane Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 229910000838 Al alloy Inorganic materials 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 6
- 238000001132 ultrasonic dispersion Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000011253 protective coating Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010349 cathodic reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- -1 hydroxyl ions Chemical class 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 2
- 238000000527 sonication Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 230000000711 cancerogenic 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
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical class [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002088 nanocapsule Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- IZRJPHXTEXTLHY-UHFFFAOYSA-N triethoxy(2-triethoxysilylethyl)silane Chemical compound CCO[Si](OCC)(OCC)CC[Si](OCC)(OCC)OCC IZRJPHXTEXTLHY-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/02—Polyamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Silicon Compounds (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
The invention relates to a layer-by-layer self-assembly pH response type silicon dioxide nano container, a preparation method thereof and application thereof in a composite silane film, wherein the preparation method of the nano container comprises the following steps: firstly, mixing cetyl trimethyl ammonium bromide, deionized water, ethanol, ethyl orthosilicate and ammonia water, centrifuging to obtain a solid phase, and then obtaining hollow silicon dioxide nanoparticles in a calcining mode; mixing the dispersed powder with a benzotriazole solution, and repeatedly evacuating by using a vacuum pump to obtain corrosion inhibitor-loaded particles; and depositing a polyelectrolyte shell on the outer layer of the obtained particles in an LbL mode to obtain the layer-by-layer self-assembled pH response type silicon dioxide nano container. The obtained sample is added into a mixed silane solution of BTSE and KH-560 for application. The composite silane film prepared by the invention has a potential self-healing effect, and compared with the traditional metal anti-corrosion agent, the composite silane film is low in toxicity, small in pollution in the production process, green and environment-friendly.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and relates to a layer-by-layer self-assembly pH response type silicon dioxide nano container, a preparation method thereof and application thereof in a composite silane film.
Background
Corrosion is an extremely important problem that humans have attempted to understand and control since the beginning of the use of metal objects. The corrosion degradation process of the material is not only very complex, but also has great economic significance. Aluminum alloys are widely used in the aircraft industry for their optimal weight and strength, and exhibit resistance to general corrosion due to their formation of natural, inert, and protective oxide layers. However, because of the inclusion of intermetallic inclusions, localized pitting is likely to occur, thereby destroying the structural integrity of the alloy. Currently, its corrosion protection is accomplished by pre-deposition treatments, primers and top coats. The most effective corrosion inhibition is widely dependent on the hexavalent chromium compounds contained in the protective coating. However, chromate and other chromium-containing compounds have limited worldwide use due to their toxic and carcinogenic properties, which requires the search for environmentally friendly alternatives that exhibit high performance corrosion protection. .
The inorganic protective coating prepared by the sol-gel method has good corrosion inhibition performance, and the silane and siloxane-based film not only has good adhesive force to metal substrates and organic surface coatings, but also has good barrier performance due to a compact-Si-O-Si-network. But it does not prevent the penetration of the aggressive substances to the metal surface when micro-cracks or small defects are present in the coating. The addition of nanoparticles can reduce the tendency of the protective film to form holes and cracks, contributing to the formation of a passive barrier to corrosion. The method can also improve the mechanical stability and thickness of the silane layer. However, these systems only act as passive physical barriers and cannot actively prevent the propagation of corrosion in case of partial failure of the coating.
The addition of inorganic or organic corrosion inhibitors to the sol-gel coating is a viable approach to reduce the corrosion rate when the protective coating is damaged, thereby achieving active self-healing properties. However, too high a concentration of inhibitor or undesirable solubility can reduce the integrity and physical barrier properties of the coating matrix. Therefore, it is of great importance to control the release rate of the corrosion inhibitor.
In order to meet the special requirements of different occasions, the release rate of the corrosion inhibitor is controlled by adopting the coating technology of the corrosion inhibitor more and more. Many coating techniques have been proposed, studied and utilized, including emulsion polymerization coating, polyelectrolyte self-assembly techniques, porous metal oxide adsorption techniques, and the like. The main idea of these embedding methods is to load the corrosion inhibitor molecules into microcapsules or nanocapsules, the release process of which is mainly diffusion-controlled. The above prior art has not only the disadvantage of complicated operation steps, but also the possibility of having a certain negative impact on the stability of the coating.
Disclosure of Invention
The invention aims to provide a layer-by-layer self-assembly pH response type silicon dioxide nano container, a preparation method thereof and application thereof in a composite silane film so as to realize long-term corrosion protection and the like on various metals.
The invention carries out the loading of the corrosion inhibitor on the silicon dioxide nanometer micro-container, and encapsulates the corrosion inhibitor in an LBL mode, so that the coating has the self-healing performance and plays an active role in the anticorrosion application of metal.
The purpose of the invention can be realized by the following technical scheme:
one of the technical schemes of the invention provides a preparation method of a layer-by-layer self-assembly pH response type silicon dioxide nano container, which comprises the following steps:
(1) taking deionized water, Cetyl Trimethyl Ammonium Bromide (CTAB) and ethanol, stirring and mixing, adding Tetraethoxysilane (TEOS), stirring and reacting for a period of time, adding ammonia water into the obtained solution, providing an alkaline environment, reacting for a period of time at room temperature, centrifuging and collecting a solid phase, washing and drying, and calcining to obtain hollow mesoporous silica nanoparticles;
(2) adding hollow mesoporous silica nanoparticles into a Benzotriazole (BTA) solution, ultrasonically dispersing, stirring for a certain time, vacuumizing overnight, and centrifugally collecting a solid phase to obtain corrosion inhibitor-loaded silica nanoparticle;
(3) adding the obtained silica particle nano-particles loaded with the corrosion inhibitor into deionized water for ultrasonic dispersion, adding a Polyethyleneimine (PEI) aqueous solution, reacting for a certain time, centrifugally washing in distilled water for 3 times, and collecting a solid phase to obtain SiO2/PEI；
(4) The obtained SiO2/PEI is added into deionized water for ultrasonic dispersion, and then poly (4-styrene sodium sulfonate) (PSS) aqueous solution is addedCentrifugally washing in distilled water for 3 times after reacting for a certain time, and collecting solid phase to obtain SiO2/PEI/PSS；
(5) Repeating the step (3) and the step (4) to obtain SiO2The target product is PEI/PSS/PEI/PSS.
Further, in the step (1), the volume ratio of the deionized water, CTAB, ethanol, TEOS and ammonia water is (50-60) mL, (0.10-0.20) g, (0.5-1.5) mL:1mL, and optionally 55mL:0.16g:26mL:1mL:1 mL.
Further, in the step (1), the stirring reaction time is 3-7 min; optionally for 5 min.
Further, in the step (1), the reaction time is 2-5h at room temperature; and can be selected to be 3 h.
Further, in the step (1), the calcination temperature is 530-570 ℃; optionally 550 deg.c.
Further, in the step (1), the calcining time is 3-7 h; optionally 5 h.
Further, in the step (2), the adding amount ratio of the hollow mesoporous silica nanoparticles to the benzotriazole solution is (0.05-0.15) g (30-70) mL; optionally 0.1g:50 mL.
Further, in the step (2), the concentration of the benzotriazole solution is 8-12mg/mL, and optionally 10 mg/mL;
further, in the step (2), the stirring time is 10-15h, and optionally 12 h.
Further, in the step (3), the volume ratio of the deionized water to the PEI aqueous solution is (15-25) to (2-5), and optionally 20: 3.
Further, in step (3), the concentration of the PEI aqueous solution is 1-3mg/mL, optionally 2 mg/mL.
Further, in the step (3), the reaction time is 10-20 min;
further, in the step (4), the volume ratio of the deionized water to the PSS aqueous solution is (15-25mL): (2-5 mL); further, in the step (4), SiO2The addition amount of PEI is the amount obtained in step (3).
Further, in step (4), the concentration of the aqueous solution of PSS is 1-3mg/mL, optionally 2 mg/mL.
Further, in the step (4), the reaction time is 10-20 min;
further, in the step (5), the concentration of the PEI and the PSS aqueous solution is 2 mg/mL;
the second technical scheme of the invention provides a layer-by-layer self-assembly pH response type silicon dioxide nano container, and the nano container is prepared by the preparation method.
The third technical scheme of the invention provides application of a layer-by-layer self-assembly pH response type silicon dioxide nano container, and the silicon dioxide nano container is used for preparing a composite silane film.
Further, when the composite silane film is prepared, the specific process comprises the following steps:
adding SiO2/PEI/PSS/PEI/PSS into composite silane comprising 1, 2-bis (triethoxysilyl) ethane (BTSE) and gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane (KH-560), soaking the metal substrate serving as a working electrode into the composite silane solution, taking out after a certain time, drying and curing to obtain the composite silane film attached to the working electrode.
Further, SiO2The addition amount ratio of the/PEI/PSS/PEI/PSS to the composite silane is (30-70) mg, (180-220) mL; and optionally 50 mg/200 mL.
Further, the volume ratio of KH-560 to BTSE is 1.5-2.5: 1; optionally 2: 1.
Further, the metal substrate is an aluminum alloy.
Further, the soaking time of the working electrode is 3-7min, optionally 5 min.
Further, the temperature for drying and curing is 75-85 ℃;
further, the drying time is 1-3h, and 2h can be selected.
The fourth technical scheme of the invention provides application of the composite silane film of the layer-by-layer self-assembled pH response type silicon dioxide nano container, and the composite silane film is used for surface anticorrosion treatment of metal materials.
Ethyl orthosilicate, ethanol and water are used as starting agents, and CTAB is used as a structure guiding agent. The size of the silica nano-particles is controlled by changing the ratio of the ammonia water to the tetraethoxysilane, and the structure directing agent is removed by high-temperature calcination to form a mesoporous structure, so that the possibility of loading benzotriazole is provided. The reservoirs with storage/release properties adjustable by nanometer thickness were prepared by deposition on the surface of silica nanoparticles by layer-by-layer self-assembly (LBL) with oppositely charged polyelectrolytes, i.e. PEI, PSS. Silanes are hybrid molecules, with a hydrolyzable functional group forming a covalent bond with the metal substrate, and an organic functional group on the other end that is compatible with the organic coating system. Silanol molecules generated after silane hydrolysis react with hydroxyl on the surface of a substrate to form Si-O-M bonds, and in addition, silanol molecules react with each other to generate oligosiloxane, and a Si-O-Si network structure is formed after cross-linking, so that the permeation of surrounding aggressive substances can be hindered, and short-time barrier protection is provided. Silane films can provide a physical barrier by retarding the penetration of water and electrolyte into the metal substrate. However, there are some cracks and defects in the silane film, which can lead to electrolyte absorption and thus corrosion. The layer-by-layer self-assembly pH response type silicon dioxide nano container not only has corrosion inhibition performance, but also has self-healing performance. The silane coupling agent of the doped layer-by-layer self-assembly pH response type silicon dioxide nano container is used for carrying out surface treatment on the metal substrate, so that the defect is overcome.
The nano container prepared by the invention can quickly respond to the change of environmental factors in the local corrosion process, immediately release the corrosion inhibitor, and form protective molecules on the corroded metal surface through the chemical adsorption or physical adsorption process to inhibit corrosion expansion. There is an additional increase in pH due to cathodic reactions at the intermetallic surface. Depending on the pH, the aluminum and magnesium ions can immediately react with hydroxyl ions to form insoluble hydroxide precipitates or soluble hydroxyl complexes. The nano container prepared by the invention can quickly respond to the change of environmental factors in the local corrosion process, immediately release the corrosion inhibitor, and form protective molecules on the corroded metal surface through the chemical adsorption or physical adsorption process to inhibit corrosion expansion. There is an additional increase in pH due to cathodic reactions at the intermetallic surface. Depending on the pH, the aluminum and magnesium ions can immediately react with hydroxyl ions to form insoluble hydroxide precipitates or soluble hydroxyl complexes. Thus, modification of the container with a polyelectrolyte shell is a method to achieve controlled release of the encapsulated corrosion inhibitor and prevent its accidental leakage from the coating. Local pH changes may affect the polyelectrolyte shell, in particular its opening and the release of corrosion inhibitors, thereby achieving healing of the corroded area. This effect is self-regulating, and the release of the corrosion inhibitor occurs just in the region of the pH change, triggering a self-healing process. When the pH value is restored to the initial value, the shell is closed, and the release of the corrosion inhibitor is stopped.
Compared with the prior art, the invention has the following advantages:
(1) the layer-by-layer self-assembly pH response type silicon dioxide nano container prepared by the invention is used for preparing a composite silane film, and the composite silane film has a potential self-healing effect and can actively inhibit corrosion expansion;
(2) the coating structure of the invention has simple design, simple and convenient operation and low cost, and is beneficial to large-scale batch production;
(3) compared with the traditional metal corrosion inhibitor, the composite silane film prepared by the invention has the advantages of low toxicity, small pollution in the production process and environmental protection;
(4) the composite silane film prepared by the invention has high yield and stability, and is suitable for further research and development work.
Drawings
FIG. 1 is a diagram showing nitrogen adsorption-desorption and pore size distribution of a silica nano-container according to the present invention;
FIG. 2 is a line graph showing the release rate of the corrosion inhibitor of the present invention as a function of time.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
In the following examples, unless otherwise specified, all the conventional commercially available raw materials or conventional processing techniques in the art are indicated.
Example 1
A preparation method of a layer-by-layer self-assembly pH response type silicon dioxide nano container comprises the following steps:
(1) the silicon dioxide nano-container (namely the hollow mesoporous silicon dioxide nano-particles) is synthesized by a hard membrane plate method, and the well-dispersed silicon dioxide microspheres are obtained by a method with simple process and low cost.
The specific process is as follows: stirring and mixing 55mL of deionized water, 0.16g of CTAB, 26mL of ethanol and 1mL of TEOS for 5min, then adding 1mL of ammonia water, stirring for 3h at room temperature, centrifuging to collect a solid phase, repeatedly washing with the deionized water and the ethanol, drying, and calcining for 5h at 550 ℃ to remove a hard membrane plate, thereby obtaining the hollow mesoporous silica nanoparticle.
As shown in FIG. 1, which is a nitrogen adsorption-desorption diagram and a pore size distribution diagram of hollow silica nanoparticles, the specific surface area is 1275.5403m2The volume of the pores is 1.2765ml/g, the average diameter of the pores is 3.8975nm as measured by BJH desorption, and the pore size distribution is narrow. The above shows that the synthesized silica nanocontainer has a hollow mesoporous shell structure, which ensures high loading and releasing capacity of the corrosion inhibitor.
(2) Preparation of corrosion inhibitor-loaded mesoporous silica nanoparticles
BTA is implemented by a diffusion effect. 0.1g of the silica nanocontainer was mixed with the corrosion inhibitor solution (i.e. 50mL of 10mg/mL BTA solution), dispersed ultrasonically, stirred for 12h and then evacuated overnight with a vacuum pump. Centrifugally separating the silica suspension to remove excessive corrosion inhibitor, centrifugally separating to obtain a solid phase product, and drying. Repeating the steps for four times to balance the adsorption of the corrosion inhibitor, thereby obtaining the mesoporous silica nano-particles loaded with the corrosion inhibitor.
(3) Preparation of layer-by-layer self-assembly pH response type silicon dioxide nano container
Adding the negatively charged mesoporous silica nano particles loaded with the corrosion inhibitor into 20mL of deionized water, performing ultrasonic dispersion, adding 3mL of 2mg/mL of positively charged PEI, and after fifteen minutes, adding SiO2PEI samples were washed 3 times by centrifugation in distilled water. Adding 20mL of distilled water into the obtained solid phase, and performing ultrasonic dispersion on the solid phaseThen 3mL of 2mg/mL negatively charged PSS was added, and fifteen minutes later, SiO2the/PEI/PSS samples were washed 3 times by centrifugation in distilled water. This procedure was repeated twice to obtain a composition having SiO2The layer-by-layer self-assembly pH response type silicon dioxide nanometer container with the structure of/PEI/PSS/PEI/PSS.
As shown in FIG. 2, a line graph of the release rate of the corrosion inhibitor of the obtained layer-by-layer self-assembled pH-responsive silica nano container changing with time shows that the polyelectrolyte shell has stronger permeability under alkaline conditions, and the corrosion inhibitor is hardly released under neutral conditions.
Example 2
Prepared as described in example 1 above with SiO2Layer-by-layer self-assembly pH response type silicon dioxide nano container with/PEI/PSS/PEI/PSS structure for preparing composite silane membrane
And (2) soaking the metal substrate working electrode in a composite silane solution containing the mesoporous silica nanoparticles loaded with the corrosion inhibitor, taking out the working electrode after 5min, drying and curing, wherein the drying temperature is 80 ℃, and the drying time is 2h, so as to obtain the composite silane film attached to the working electrode. The metal substrate here is an aluminum alloy.
A three-electrode system (the three-electrode system takes a platinum wire as a counter electrode, calomel as a reference electrode and a metal substrate attached with a composite silane membrane as a working electrode) is immersed in 3.5 wt% of sodium chloride solution, and data are measured by an electrochemical workstation, so that the composite silane membrane of the layer-by-layer self-assembled pH response type silicon dioxide nano container is proved to have better corrosion resistance.
All test results show that the silicon dioxide microsphere has high loading rate, pH responsiveness, good stability, high yield, simple and convenient coating preparation process operation, low cost, energy conservation and contribution to large-scale popularization and research.
Comparative example 1:
compared with example 1, most of them are the same except that the amounts of deionized water, ethanol, TEOS, CTAB and ammonia water are changed.
In this case, the size, wall thickness, pore volume, pore diameter, specific surface area, and the like of the obtained silica nanocontainer were changed.
Comparative example 2:
compared to example 1, most of them are the same except that deposition of PEI, PSS is omitted.
At this time, the resulting silica nanocontainer cannot respond according to a change in pH, but directly releases BTA.
Comparative example 3:
compared with the embodiment 2, the method is mostly the same, except that the addition of the layer-by-layer self-assembly pH response type silicon dioxide nano container is omitted.
In this case, the condition for self-repairing the silane film cannot be satisfied, that is, when the metal is corroded, only the silane film on the surface is easily broken down.
Comparative example 4:
compared to example 2, most of them are the same except that the complex silane solution is omitted and a single silane solution (BTSE) is used.
At this time, stability and corrosion resistance of the silane film are reduced, and the time for forming siloxane is shortened.
Example 3
Compared with example 1, most of them are the same, except that the preparation process of the hollow mesoporous silica nanoparticle in this example is as follows:
stirring and mixing 50mL of deionized water, 0.10g of CTAB, 20mL of ethanol and 0.5mL of TEOS for 3min, then adding 1mL of ammonia water, stirring for 2h at room temperature, centrifuging to collect a solid phase, repeatedly washing with the deionized water and the ethanol, drying, and calcining for 3h at 530 ℃ to remove a hard membrane plate, thus obtaining the hollow mesoporous silica nanoparticle.
Example 4
Compared with example 1, most of them are the same, except that the preparation process of the hollow mesoporous silica nanoparticle in this example is as follows:
stirring and mixing 60mL of deionized water, 0.20g of CTAB, 30mL of ethanol and 1.5mL of TEOS for 7min, then adding 1mL of ammonia water, stirring for 5h at room temperature, centrifuging to collect a solid phase, repeatedly washing with the deionized water and the ethanol, drying, and calcining for 7h at 570 ℃ to remove a hard membrane plate, thus obtaining the hollow mesoporous silica nanoparticle.
Example 5
Compared with example 1, most of them are the same, except that the preparation process of the mesoporous silica nanoparticle loaded with the corrosion inhibitor in this example is as follows:
0.05g of surface-modified silicon dioxide nanoparticles was mixed with a corrosion inhibitor solution (i.e. 30mL of 8mg/mL BTA solution), dispersed ultrasonically, stirred for 10h and then evacuated overnight with a vacuum pump. Centrifugally separating the silica suspension to remove excessive corrosion inhibitor, centrifugally separating to obtain a solid phase product, and drying. Repeating the steps for four times to balance the adsorption of the corrosion inhibitor, thereby obtaining the mesoporous silica nano-particles loaded with the corrosion inhibitor.
Example 6
Compared with example 1, most of them are the same, except that the preparation process of the mesoporous silica nanoparticle loaded with the corrosion inhibitor in this example is as follows:
0.15g of surface-modified silicon dioxide nanoparticles was mixed with a corrosion inhibitor solution (i.e. 70mL of 12mg/mL BTA solution), dispersed ultrasonically, stirred for 10h and then evacuated overnight with a vacuum pump. Centrifugally separating the silica suspension to remove excessive corrosion inhibitor, centrifugally separating to obtain a solid phase product, and drying. Repeating the steps for four times to balance the adsorption of the corrosion inhibitor, thereby obtaining the mesoporous silica nano-particles loaded with the corrosion inhibitor.
Example 7
Compared with the embodiment 1, the method is mostly the same, except that the preparation process of the layer-by-layer self-assembly pH response type silicon dioxide nano container in the embodiment is as follows:
adding mesoporous silica nano particles loaded with corrosion inhibitor into 15mL of deionized water, performing ultrasonic dispersion, adding 2mL of 1mg/mL of PEI with positive charge, and after 10 minutes, adding SiO2PEI samples were washed 3 times by centrifugation in distilled water. The resulting solid phase was dispersed by sonication with 15mL of distilled water, followed by 2mL of 1mg/mL negatively charged PSS, and after 10 minutes, SiO2the/PEI/PSS samples were washed 3 times by centrifugation in distilled water. This process was repeated twiceTo obtain the SiO of the layer-by-layer self-assembly pH response type silicon dioxide nano container2/PEI/PSS/PEI/PSS。
Example 8
Compared with the embodiment 1, the method is mostly the same, except that the preparation process of the layer-by-layer self-assembly pH response type silicon dioxide nano container in the embodiment is as follows:
adding the obtained mesoporous silica nano particles loaded with the corrosion inhibitor into 25mL of deionized water, performing ultrasonic dispersion, adding 5mL of 3mg/mL of PEI with positive electricity, and after 20 minutes, adding SiO2PEI samples were washed 3 times by centrifugation in distilled water. The resulting solid phase was dispersed by sonication with 25mL of distilled water, followed by 5mL of 3mg/mL negatively charged PSS, and after 20 minutes, SiO2the/PEI/PSS samples were washed 3 times by centrifugation in distilled water. The process is repeated twice to obtain the SiO of the layer-by-layer self-assembly pH response type silicon dioxide nano container2/PEI/PSS/PEI/PSS。
Example 9
Compared with example 1, most of the components are the same, except that the preparation process of the composite silane film in the example is as follows:
a metal substrate (aluminum alloy) working electrode is soaked in 180mL of composite silane solution (the composite silane solution consists of BTSE and KH-560, the volume ratio of the BTSE to the KH-560 is 1.5:1) containing 30mg of SiO2/PEI/PSS/PEI/PSS of the silicon dioxide nanocontainer in the embodiment 1, after 3min, the working electrode is taken out and dried and cured, the drying temperature is 75 ℃, and the drying time is 1h, so that the composite silane film attached to the working electrode is obtained.
Example 10
Compared with example 1, most of the components are the same, except that the preparation process of the composite silane film in the example is as follows:
a metal substrate (aluminum alloy) working electrode is soaked in 200mL of composite silane solution (the composite silane solution consists of BTSE and KH-560, the volume ratio of the BTSE to the KH-560 is 2.0:1) containing 50mg of SiO2/PEI/PSS/PEI/PSS of the silicon dioxide nanocontainer in the embodiment 1, after 5min, the working electrode is taken out and dried and cured, the drying temperature is 80 ℃, and the drying time is 2h, so that the composite silane film attached to the working electrode is obtained.
Example 11
Compared with example 1, most of the components are the same, except that the preparation process of the composite silane film in the example is as follows:
a metal substrate (aluminum alloy) working electrode is soaked in 220mL of composite silane solution (the composite silane solution consists of BTSE and KH-560, the volume ratio of the BTSE to the KH-560 is 2.5:1) containing 70mg of SiO2/PEI/PSS/PEI/PSS of the silicon dioxide nanocontainer in the embodiment 1, after 7min, the working electrode is taken out and dried and cured, the drying temperature is 85 ℃, and the drying time is 3h, so that the composite silane film attached to the working electrode is obtained.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A preparation method of a layer-by-layer self-assembly pH response type silicon dioxide nano container is characterized by comprising the following steps:
(1) uniformly mixing deionized water, CTAB and ethanol, adding TEOS, stirring for reaction, continuously adding ammonia water, reacting at room temperature, centrifuging, washing, drying and calcining to obtain hollow mesoporous silica nanoparticles;
(2) dispersing hollow mesoporous silica nanoparticles in a benzotriazole solution, stirring, centrifuging and collecting a solid phase to obtain corrosion inhibitor-loaded silica nanoparticle;
(3) dispersing the obtained silica particle nano particles loaded with the corrosion inhibitor into deionized water, adding a PEI aqueous solution, reacting, centrifuging and washing to obtain SiO2/PEI；
(4) The obtained SiO2PEI is dispersed in deionized water, then PSS aqueous solution is added,after reaction, the SiO is obtained by centrifugation and washing2/PEI/PSS；
(5) Then SiO is used2The PEI/PSS is taken as a raw material, and the steps (3) and (4) are repeated to obtain SiO2The target product is PEI/PSS/PEI/PSS.
2. The method for preparing the layer-by-layer self-assembly pH-responsive silica nanocontainer according to claim 1, wherein in the step (1), the addition amount ratio of the deionized water to CTAB to ethanol to TEOS is (50-60) mL, (0.10-0.20) g, (20-30) mL, (0.5-1.5) mL;
stirring for reaction for 3-7min, and reacting for 2-5h at room temperature;
the calcination temperature is 530 ℃ and 570 ℃, and the calcination time is 3-7 h.
3. The method for preparing a layer-by-layer self-assembly pH-responsive silica nanocontainer according to claim 1, wherein in the step (2), the ratio of the addition amounts of the hollow mesoporous silica nanoparticles and the benzotriazole solution is (0.05-0.15) g (30-70) mL, wherein the concentration of the benzotriazole solution is 8-12 mg/mL;
the stirring time is 10-15 h.
4. The method for preparing a layer-by-layer self-assembled pH-responsive silica nanocontainer according to claim 1, wherein in the step (3), the volume ratio of the deionized water to the PEI aqueous solution is (15-25): 2-5), and the concentration of the PEI aqueous solution is 1-3 mg/mL;
the reaction time is 10-20 min.
5. The method for preparing a layer-by-layer self-assembly pH-responsive silica nanocontainer according to claim 1, wherein in the step (4), the volume ratio of the deionized water to the PSS aqueous solution is (15-25) mL (2-5) mL, and the concentration of the PSS aqueous solution is 1-3 mg/mL;
the reaction time is 10-20 min.
6. A layer-by-layer self-assembled pH-responsive silica nanocontainer prepared by the method of any one of claims 1 to 5.
7. The use of the layer-by-layer self-assembled pH-responsive silica nanocontainer of claim 6 for preparing composite silane films.
8. The application of the layer-by-layer self-assembly pH response type silicon dioxide nano container as claimed in claim 7, wherein the specific process for preparing the composite silane film is as follows:
taking silicon dioxide nano container SiO2Adding PEI/PSS/PEI/PSS into silane, soaking the metal substrate in the composite silane, taking out, drying and curing to obtain the composite silane film attached to the metal substrate.
9. The use of the layer-by-layer self-assembled pH-responsive silica nanocontainer of claim 8, wherein SiO is2The addition amount ratio of/PEI/PSS/PEI/PSS to the composite silane is (30-70) mg (180-220) mL.
10. The application of the layer-by-layer self-assembly pH-responsive silica nanocontainer according to claim 8, wherein the silane is prepared by compounding BTSE and KH-560 according to a volume ratio of 1.5-2.5: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110856664.8A CN113444364A (en) | 2021-07-28 | 2021-07-28 | Layer-by-layer self-assembly pH response type silicon dioxide nano container, preparation thereof and application thereof in composite silane film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110856664.8A CN113444364A (en) | 2021-07-28 | 2021-07-28 | Layer-by-layer self-assembly pH response type silicon dioxide nano container, preparation thereof and application thereof in composite silane film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113444364A true CN113444364A (en) | 2021-09-28 |
Family
ID=77817628
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110856664.8A Pending CN113444364A (en) | 2021-07-28 | 2021-07-28 | Layer-by-layer self-assembly pH response type silicon dioxide nano container, preparation thereof and application thereof in composite silane film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113444364A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115073757A (en) * | 2022-04-18 | 2022-09-20 | 浙江大学温州研究院 | Corrosion inhibitor load BTA @ ZIF-8/SiO with core/shell structure 2 Method for preparing composite powder |
| CN115483501A (en) * | 2022-11-01 | 2022-12-16 | 上海电气国轩新能源科技(南通)有限公司 | Sodium ion battery diaphragm preparation method and sodium ion battery |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005110592A1 (en) * | 2004-05-17 | 2005-11-24 | Yki, Ytkemiska Institutet Ab | Mesoporous particles loaded with active substance |
| EP1832629A1 (en) * | 2006-03-10 | 2007-09-12 | MPG Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. | Corrosion inhibiting pigment comprising nanoreservoirs of corrosion inhibitor |
| CN101717930A (en) * | 2009-12-25 | 2010-06-02 | 华烁科技股份有限公司 | Environment-friendly nano water-based silane treatment agent capable of improving anti-corrosion performance of metal surface |
| EP2202280A1 (en) * | 2008-11-24 | 2010-06-30 | Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. | Corrosion inhibting coatings controllable by electromagnetic irradiation and methods for corrosion inhibition using the same |
| CN102259871A (en) * | 2011-05-20 | 2011-11-30 | 上海大学 | Method for synthesizing mesoporous silicon dioxide nanotube by layer-by-layer (LBL) method |
| CN102784598A (en) * | 2012-06-25 | 2012-11-21 | 浙江赛凡新材料有限公司 | Method for preparing self-repairing nanocomposite sol used for long-lasting anticorrosion of metal plate |
| CN105440884A (en) * | 2015-12-12 | 2016-03-30 | 青岛农业大学 | Preparation of waterborne epoxy resin self-repairing anticorrosion coating and application thereof |
| CN105925129A (en) * | 2016-05-19 | 2016-09-07 | 江苏固格澜栅防护设施有限公司 | Self-corrosion potential response type self-repairing anti-corrosion coating, preparation method and application |
| CN109127329A (en) * | 2018-07-13 | 2019-01-04 | 武汉理工大学 | A method of bionical superslide surface is prepared using polyelectrolyte/self-assembly |
-
2021
- 2021-07-28 CN CN202110856664.8A patent/CN113444364A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005110592A1 (en) * | 2004-05-17 | 2005-11-24 | Yki, Ytkemiska Institutet Ab | Mesoporous particles loaded with active substance |
| EP1832629A1 (en) * | 2006-03-10 | 2007-09-12 | MPG Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. | Corrosion inhibiting pigment comprising nanoreservoirs of corrosion inhibitor |
| EP2202280A1 (en) * | 2008-11-24 | 2010-06-30 | Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. | Corrosion inhibting coatings controllable by electromagnetic irradiation and methods for corrosion inhibition using the same |
| CN101717930A (en) * | 2009-12-25 | 2010-06-02 | 华烁科技股份有限公司 | Environment-friendly nano water-based silane treatment agent capable of improving anti-corrosion performance of metal surface |
| CN102259871A (en) * | 2011-05-20 | 2011-11-30 | 上海大学 | Method for synthesizing mesoporous silicon dioxide nanotube by layer-by-layer (LBL) method |
| CN102784598A (en) * | 2012-06-25 | 2012-11-21 | 浙江赛凡新材料有限公司 | Method for preparing self-repairing nanocomposite sol used for long-lasting anticorrosion of metal plate |
| CN105440884A (en) * | 2015-12-12 | 2016-03-30 | 青岛农业大学 | Preparation of waterborne epoxy resin self-repairing anticorrosion coating and application thereof |
| CN105925129A (en) * | 2016-05-19 | 2016-09-07 | 江苏固格澜栅防护设施有限公司 | Self-corrosion potential response type self-repairing anti-corrosion coating, preparation method and application |
| CN109127329A (en) * | 2018-07-13 | 2019-01-04 | 武汉理工大学 | A method of bionical superslide surface is prepared using polyelectrolyte/self-assembly |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115073757A (en) * | 2022-04-18 | 2022-09-20 | 浙江大学温州研究院 | Corrosion inhibitor load BTA @ ZIF-8/SiO with core/shell structure 2 Method for preparing composite powder |
| CN115073757B (en) * | 2022-04-18 | 2023-06-23 | 浙江大学温州研究院 | Corrosion inhibitor load BTA@ZIF-8/SiO with core/shell structure 2 Preparation method of composite powder |
| CN115483501A (en) * | 2022-11-01 | 2022-12-16 | 上海电气国轩新能源科技(南通)有限公司 | Sodium ion battery diaphragm preparation method and sodium ion battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhou et al. | Epoxy composite coating with excellent anticorrosion and self-healing performances based on multifunctional zeolitic imidazolate framework derived nanocontainers | |
| JP5693819B2 (en) | Corrosion Inhibitor Pigment Containing Corrosion Inhibitor Nano Leather Bar | |
| Zhong et al. | Novel pH-responsive self-healing anti-corrosion coating with high barrier and corrosion inhibitor loading based on reduced graphene oxide loaded zeolite imidazole framework | |
| Manoj et al. | Self-healing and superhydrophobic coatings for corrosion inhibition and protection | |
| CN113444364A (en) | Layer-by-layer self-assembly pH response type silicon dioxide nano container, preparation thereof and application thereof in composite silane film | |
| Xiao et al. | A pH-responsive cerium-imidazole decorated ZIF-8 to achieve self-healing barrier property for epoxy coating on Al alloy by controlled release | |
| CN111234566A (en) | Acid-base double-response hollow mesoporous silica composite nano container, self-repairing anticorrosive coating and preparation method of self-repairing anticorrosive coating | |
| CN111057442B (en) | Preparation method of hollow mesoporous silica \ APS \ graphene oxide nano container | |
| Yeole et al. | The effect of carbon nanotubes loaded with 2-mercaptobenzothiazole in epoxy-based coatings | |
| CN105970192B (en) | The preparation method and application of intelligent corrosion-inhibiting coating | |
| Li et al. | Synthesis of stabilized dispersion covalently-jointed SiO2@ polyaniline with core-shell structure and anticorrosion performance of its hydrophobic coating for Mg-Li alloy | |
| CN114163860A (en) | ZIF-8 structure-based nano container and sol-gel coating and preparation method thereof | |
| CN105524497A (en) | Super-hydrophobic self-repairing intelligent nano coating and preparation method thereof | |
| Liu et al. | Self-healing and corrosion-sensing coatings based on pH-sensitive MOF-capped microcontainers for intelligent corrosion control | |
| Zhao et al. | A smart anticorrosion coating based on hollow silica nanocapsules with inorganic salt in shells | |
| WO2022078211A1 (en) | Passivator having self-repair function, and preparation method and application thereof | |
| Bao et al. | ZnPA@ ZIF-8 nanoparticles: synthesis, sustained release properties and anticorrosion performance | |
| CN113801538A (en) | Metal organic framework/epoxy coating and preparation method and application thereof | |
| Cheng et al. | Three birds with one stone: Contemporaneously boosting passive, active and self-healing properties for long-term anticorrosion coatings | |
| Wang et al. | Intelligent anticorrosion coating based on mesostructured BTA@ mCeO2/g-C3N4 nanocomposites for inhibiting the filiform corrosion of Zn-Mg-Al coated steel | |
| Pourhashem et al. | Investigating the effects of chitosan solution and chitosan modified TiO2 nanotubes on the corrosion protection performance of epoxy coatings | |
| Li et al. | Preparation of intelligent corrosion resistant coatings based on pH-responsive silica nanocontainers | |
| CN113337210A (en) | Corrosion inhibitor-loaded pH-responsive silicon dioxide nano container composite silane film and preparation and application thereof | |
| Zhao et al. | Enhancement of active anti-corrosion properties of waterborne epoxy resin by mussel bionic modified halloysite nanotube | |
| CN114591671A (en) | Preparation method and application of polypyrrole @ ZIF-8 modified epoxy resin anticorrosive paint |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210928 |
|
| RJ01 | Rejection of invention patent application after publication |