Incorporation of LDH nanocontainers into plasma electrolytic oxidation coatings on Mg alloy

In-situ incorporation of layered double hydroxides(LDH)nanocontainers into plasma electrolytic oxidation(PEO)coatings on AZ91 Mg alloy has been achieved in the present study.Fumarate was selected as Mg corrosion inhibitor for exchange and intercalation into the nanocontainers,which were subsequently incorporated into the coating.It was found that the thickness and compactness of the coatings were increased in the presence of LDH nanocontainers.The corrosion protection performance of the blank PEO,LDH containing PEO and inhibitor loaded coatings was evaluated by means of polarization test and electrochemical impedance spectroscopy(EIS).The degradation process and corrosion resistance of PEO coating were found to be greatly affected by the loaded inhibitor and nanocontainers by means of ion-exchange when corrosion occurs,leading to enhanced and stable corrosion resistance of the substrate.

Corrosion resistance and mechanisms of smart micro-arc oxidation/epoxy resin coatings on AZ31 Mg alloy: Strategic positioning of nanocontainers

Smart micro-arc oxidation(MAO)/epoxy resin(EP) composite coatings were formed on AZ31 magnesium(Mg) alloy. Mesoporous silica nanocontainers(MSN) encapsulated with sodium benzoate(SB) corrosion inhibitors were strategically incorporated in the MAO micropores and in the top EP layer. The influence of the strategic positioning of the nanocontainers on the corrosion protective performance of coating was investigated. The experimental results and analysis indicated that the superior corrosion resistance of the hybrid coating is ascribed to the protection mechanisms of the nanocontainers. This involves two phenomena:(1) the presence of the nanocontainers in the MAO micropores decreased the distance between MSN@SB and the substrate, demonstrating a low admittance value(^5.18 × 10^(-8)Ω^(-1)), and thus exhibiting significant corrosion inhibition and self-healing function;and(2) the addition of nanocontainers in the top EP layer densified the coating via sealing of the inherent defects, and hence the coating maintained higher resistance even after 90 days of immersion(1.13 × 10^(10)Ω cm^(2)).However, the possibility of corrosion inhibitors located away from the substrate transport to the substrate is reduced, reducing its effective utilization rate. This work demonstrates the importance of the positioning of nanocontainers in the coating for enhanced corrosion resistance,and thereby providing a novel perspective for the design of smart protective coatings through regulating the distribution of nanocontainers in the coatings.

A self-healing coating based on facile pH-responsive nanocontainers for corrosion protection of magnesium alloy

The preparation of pH-responsive nanocontainers by typical silane modification of the mesoporous silica nanoparticle(MSN)surface is usually high-cost,complex,and time-consuming,which remains a great challenge for effective corrosion protection of magnesium alloy.Here,a new strategy to construct pH-responsive nanocontainers(MSN-MBT@LDH)is demonstrated.The nanocontainers consist of corrosion inhibitor(2-mercaptobenzothiazole,MBT)loaded MSN core and layered double hydroxide(LDH)nanosheet shell serving as gatekeepers.The successful loading of MBT and encapsulation by LDH nanosheets were confirmed by a series of characterization such as scanning transmission electron microscopy coupled with energy dispersive X-ray spectroscopy(STEM-EDS)and N2 adsorption/desorption isotherms.The pH-responsive feature of the nanocontainers was demonstrated by determination of the MBT concentration in buffer solutions with different pH values.A smart corrosion protection system on Mg alloy is obtained by incorporating the synthesized nanocontainers into a self-assembled nanophase particle(SNAP)coating.The electrochemical tests and visual observations show that the hybrid coating has the best barrier properties and robustness in corrosion protection in NaCl corrosive solutions in comparison with the control coatings.The present method simplifies the synthesis processes of nanocontainers and eliminates the potential detrimental effect of excess gatekeepers on the coating.The findings provide new insights into the preparation of scalable nanocontainers.The self-healing coatings are expected to have widespread applications for corrosion protection of Mg alloy and other metals.

Smart anticorrosion coating based on stimuli-responsive micro/nanocontainer:a review

Smart coating for corrosion protection of metal materials(steel,magnesium,aluminum and their alloys)has drawn great attention because of their capacity to prevent crack propagation in the protective coating by releasing functional molecules(healing agents or corrosion inhibitors)on demand from delivery vehicle,that is,micro/nanocontainer made up of a shell and core material or a coating layer,in a controllable manner.Herein,we summarize the recent achievements during the last 10 years in the field of the micro/nanocontainer with different types of stimuli-responsive properties,i.e.,pH,electrochemical potential,redox,aggressive corrosive ions,heat,light,magnetic field,and mechanical impact,for smart anticorrosion coating.The state-of-the-art design and fabrication of micro/nanocontainer are emphasized with detailed examples.

Preparation of a TiO_(2)@o-Vanillin@TEOS-APTES Nanocontainer and Its Anti-Corrosion Performance on Steel

A TiO_(2)@o-vanillin@TEOS-APTES nanocontainer was prepared by an experimental process in which,firstly,2-hydroxy-3-methoxybenzaldehyde(o-vanillin)was loaded in a TiO_(2) container to obtain TiO_(2)@o-vanillin.Then,TiO_(2)@o-vanillin was encapsulated by tetraethyl orthosilicate(TEOS).Finally,3-aminopropyl triethoxysilane(APTES)was used to modify the obtained sample.The morphology,structural phase and thermal stability of the TiO_(2)@o-vanillin@TEOS-APTES nanocontainer were analyzed using scanning electron microscopy(SEM),energy dispersive spectroscopy(EDS),Fourier transform infrared spectroscopy(FTIR),X-ray diffractometry(XRD)and thermal gravimetric analysis(TG).The release rate of o-vanillin was investigated using an ultraviolet-visible(UV-vis)spectrometer.The anti-corrosion performances of the epoxy,epoxy@o-vanillin and epoxy@TiO_(2)@o-vanillin@TEOS-APTES coatings on steel sheets were evaluated using an electrochemical method and scarification experiments.The results showed that the impedance value of the epoxy@TiO_(2)@o-vanillin@TEOS-APTES coating was two orders of magnitude higher than that of the blank epoxy coating,and one order of magnitude higher than that of the epoxy@o-vanillin coating.The maximum inhibition rate of the epoxy@TiO_(2)@o-vanillin@TEOS-APTES coating on the steel can reach 97.3%.The scarification experiments confirmed that the epoxy@TiO_(2)@o-vanillin@TEOS-APTES coating had the best anti-corrosion performance.

Self-healing polyamide reverse osmosis membranes with temperature-responsive intelligent nanocontainers for chlorine resistance

Improving the performance of reverse osmosis membranes remains great challenge to ensure excellent NaCl rejection while maintaining high water permeability and chlorine resistance. Herein, temperature-responsive intelligent nanocontainers are designed and constructed to improve water permeability and chlorine resistance of polyamide membranes. The nanocontainer is synthesized by layer-by-layer self-assembly with silver nanoparticles as the core, sodium alginate and chitosan as the repair materials, and polyvinyl alcohol as the shell. When the polyamide layer is damaged by chlorine attack, the polyvinyl alcohol shell layer dissolves under temperature stimulation of 37 ℃, releasing inner sodium alginate and chitosan to repair broken amide bonds. The polyvinyl alcohol shell responds to temperature in line with actual operating environment, which can effectively synchronize the chlorination of membranes with temperature response and release inner materials to achieve self-healing properties. With adding temperature-responsive intelligent nanocontainers, the NaCl rejection of thin film composite membrane decreased by 15.64%, while that of thin film nanocomposite membrane decreased by only 8.35% after 9 chlorination cycles. Effective repair treatment and outstanding chlorine resistance as well as satisfactory stability suggest that temperature-responsive intelligent nanocontainer has great potential as membrane-doping material for the targeted repair of polyamide reverse osmosis membranes.

Ultra-Thin Double-Walled Carbon Nanotubes： A Novel Nanocontainer for Preparing Atomic Wires

Double-walled carbon nanotubes （DWCNTs） with high graphitization have been synthesized by hydrogen arc discharge. The obtained DWCNTs have a narrow distribution of diameters of both the inner and outer tubes, and more than half of the DWCNTs have inner diameters in the range 0.6-1.0 nm. Field electron emission from a DWCNT cathode to an anode has been measured, and the emission current density of DWCNTs reached 1 A/cm2 at an applied field of about 4.3 V/~tm. After high-temperature treatment of DWCNTs, long linear carbon chains （C-chains） can be grown inside the ultra-thin DWCNTs to form a novel C-chain@DWCNT nanostructure, showing that these ultra-thin DWCNTs are an appropriate nanocontainer for preparing truly one-dimensional nanostructures with one-atom-diameter.

Engineering a tubular mesoporous silica nanocontainer with well-preserved clay shell from natural halloysite

The in situ synthesis of mesoporous nanotubes from natural minerals remains a great challenge. Herein, we report the successful synthesis of mesoporous silica nanotubes （MNTs） with a varying inner-shell thickness and a preserved clay outer shell from natural-halloysite nanotubes （HNTs）. After the enlargement of the lumen diameter of the tubular aluminosilicate clay by acid leaching, uniform mesopores were introduced by a modified pseudomorphic transformation approach, while the clay outer shell was well-preserved. Using density functional theory calculations, the atomic structure evolution and the energetics during A1 leaching and Si-OH condensation were studied in detail. After the leaching of A1 ions from the HNTs, local structural changes from Al（Oh） to A1（V） at a medium leaching level and to AI（Td） at a high leaching level were confirmed. The calculated hydroxylation energy of two kinds of silica components in the acid-leached HNTs （the distorted two-dimensional silica source in the inner shell and the intact aluminosilicate structure in the outer shell） was 0.5 eV lower or 1.0 eV higher than that of bulk silica, which clarifies the different behavior of the silica components in the hydrothermal process. The successful synthesis of reactive MNTs from HNTs introduces a new strategy for the synthesis of mesoporous nanocontainers with a special morphology using natural minerals. In particular, MNT samples with numerous reactive AI（V） species and a specific surface area up to 583 m^2/g （increased by a factor of 10） are promising drugloading nanocontainers and nanoreactors.

Trigger and response mechanisms for controlled release of corrosion inhibitors from micro/nanocontainers interpreted using endogenous and exogenous stimuli:A review

Metallic corrosion can lead to both economic losses and environmental pollution due to undesired chemical and biochemical reactions.Furthermore,there are a number of drawbacks associated with different corrosion prevention and mitigation techniques.In view of these challenges,corrosion inhibitor-based smart micro/nanocontainers(CISCs)with stimuli-responsive functionality emerge as an important alternative technical approach in dealing with metallic corrosion.The development of CISCs involves controlled release corrosion inhibitors and self-healing coatings.This review focuses on the trigger and response mechanisms of controlling the discharge of corrosion inhibitors from micro/nanocontainers(a core-shell or layered structure)into aqueous solution under endogenous(pH,redox,and ion-exchange).exogenous(temperature,magnetic field,and light),and multiple stimuli.When these CISCs are embedded into coating materials,the self-healing effect of the coating can manifest to protect various types of metals.In this review effort,different types of CISCs are classified for the first time into the following three categories:inorganic,organic,and organic-inorganic hybrid.We also discuss application scope,future perspectives,and research strategies for CISCs in the hopes of increasing the life of corrosion protection and providing inspiration in related fields.