A combined redox-competition and negative-feedback SECM study of self-healing anticorrosive coatings

In this paper, the long-term anticorrosive efficiency of a damaged self-healing coating is studied for the first time using scanning electrochemical microscopy (SECM). In the study an epoxy-coating with embedded-capsules containing a silyl-ester is employed. The properties of the silyl-ester as a healing-agent for the protection of AA2024-T3 were evaluated by complementary SECM experiments operating in negative-feedback and redox-competition modes. The experimental approach here presented allowed for monitoring the early-stages of corrosion activity and subsequent healing mechanisms offered by the release of silyl-ester into a relatively large coating defect. This result was observed by detecting the transition of the oxygen reduction response from a redox-competition mode to a negative-feedback behavior. These measurements demonstrated that the silyl-ester is released efficiently after capsules break upon coating damage, covering relatively large areas and gradually healing the damaged-site hindering the corrosion processes and providing an effective protection for at least one month of immersion in chloride solution.     

Development of a novel self-healing dental nanocomposite containing PUF nanocapsules and nanoclay

The aims of this research were to develop the first self-healing dental nanocomposite and to evaluate mechanical properties (compressive and flexural strength), crack-healing, and self-healing longevity after 90 days of water aging. The principal reasons for failure are microcracks formed by polymerization shrinkage, recurrent dynamic mechanical stress, water sorption, and thermal fatigue. N, N-dihydroxyethyl p-toluidine and triethylene glycol dimethacrylate (DEPT-TEGDMA) nanocapsules were synthesized as they have been proven previously to be biocompatible for dental materials. Nanoclay was used as a filler to improve the mechanical properties of self-healing tooth nanocomposites. Nanocapsules were prepared by in situ emulsion polymerization of poly urea-formaldehyde (PUF) shells. The synthesized PUF shells were characterized by FTIR, SEM, and DLS analyses. The results showed that incorporating nanocapsules at a 7.5% mass fraction into the nanocomposite increased the mechanical properties. A good self-healing efficiency ranging from 54.06 to 58% recovery was obtained. The 90 days of water-aging compared to 1 day did not reduce the self-healing efficiency (p > 0.1), showing water-aging did not damage the nanocapsules.     

Thermo-reversible MWCNTs/epoxy polymer for use in self-healing and recyclable epoxy adhesive

A self-healing and recyclable carbon tube/epoxy adhesive was prepared by epoxy monomer with Diels-Alder(DA) bonds, diethylenetriamine and polyethyleneimine modified multi-wall carbon nanotubes(MWCNTs). The self-healing and recyclable ability was attained by thermally reversible Diels-Alder reaction between furan and maleimide in the epoxy monomer. By controlling the molar ratio of furfuryl glycidyl ether and 4,4′-methylenebis(N-phenylmaleimide), the glass transition temperature and mechanical properties of MWCNTs/epoxy adhesives were varied. The self-healing properties of MWCNTs/epoxy polymers were evaluated by lap shear experiment and the results showed that the MWCNTs/epoxy adhesives exhibited enhanced mechanical properties and excellent self-healing ability under heat stimulus. The healing efficiency was related to the molecule mobility and the conversion of DA reaction between furan and maleimide. The MWCNTs/epoxy adhesives also displayed excellent recyclable ability by transforming into soluble polymer under heating. These materials offer a wide range of possibilities to produce materials with healing and recyclable ability and have the potential to bring great benefits to our daily lives by enhancing the safety, performance, and lifetime of products.     

Nonswellable hydrogels with robust micro/nano-structures and durable superoleophobic surfaces under seawater

Hydrogels, composed mainly of water trapped in three dimensional cross-linked polymer networks, have been widely utilized to construct underwater superoleophobic surfaces. However, the swelling nature and instability of hydrogels under complex marine environment will weaken their underwater superoleophobicity. Herein, we synthesize structured poly(2-hydroxyethylmethacrylate)(PHEMA) hydrogels by using sandpaper as templates. The robust non-swelling of PHEMA hydrogel ensures that micro/nano-structures on the surface of PHEMA hydrogels can be well maintained. Moreover, when roughness Ra of about 3~4 μm, the surface has superior oil-repellency. Additionally, even after immersing in seawater for one-month, their breaking strength and toughness can be well kept. The non-swellable hydrogels with long-term stable under seawater superoleophobicity will promote the development of robust superoleophobic materials in marine antifouling coatings,biomedical devices and oil/water separation.     

Preparation and characterization of electrophoretically deposited high-temperature superconductor coatings

The high-temperature superconductor, YBa₂Cu₃O_7–x (x = 0.1–0.2) [YBCO], was prepared using an optimized calcination and sintering process. Thin layers of a few microns of this material were deposited on a silver substrate by applying a simplified electrophoretic deposition technique in a suspension of the fine, < 10 m, superconductor powder in a non-aqueous liquid. To get a uniform and strongly adherent coating, the deposition process is repeated several times, followed by an appropriate sintering procedure. The initially prepared YBCO powder and the coatings produced were characterized for their superconducting properties by X-ray diffraction analysis (XRD), magnetization measurements with a Superconducting Quantum Interference Device (SQUID) and electrical resistivity measurements. By scanning electron microscopy (SEM) and electron probe microanalysis (EPMA) the grain size of the YBCO film, its thickness and impurity content, respectively, were estimated.     

荧光二氧化硅纳米胶囊的制备及性能研究

开发出一种简单、重复性好的合成路线得到了中空的荧光二氧化硅纳米胶囊(SiO_2(NCs)),制备的荧光SiO_2(NCs)分散性好,尺寸均匀.此外,探讨了球形荧光SiO_2(NCs)对抗癌药物的负载能力.     

Behaviour of surface-treated mica and other pigments with lamellar particles in anticorrosive coatings

The paper deals with using lamellar pigments for anticorrosive barrier coatings. By depositing a ferric oxide layer on a muscovite particle a pigment is obtained, which being applied to coatings improves the mechanical properties thereof, resistance to UV radiation and acts as an anticorrosion barrier. The optimum concentration of lamellar surface-treated muscovite in the coatings amounts to 20 vol. %.     

Preparation and characterization of porous cordierite for potential use in cellular ceramics

Cordierite porous ceramics Z, X, and K were prepared using three mixtures of clay minerals: Z from kaolinite, talc, and aluminum hydroxide, X from kaolinite, talc, vermiculite, and aluminum hydroxide, and K from kaolinite, talc, and magnesium oxide. Ceramics were different in porosity, specific surface area, cordierite polymorphs, and secondary crystalline phases. Vermiculite influenced textural architecture of calcined cordierite ceramics X and predestinated crystallization of the high-temperature hexagonal α-cordierite with secondary minerals enstatite, spinel and corundum. Ceramics Z contained low-temperature orthorhombic β-cordierite, enstatite, and corundum, K was diphase of β-cordierite and forsterite. Total pore area (TPA) and specific surface area (SSA) of X, in spite of the higher porosity and the pore size distribution in the range of 300–1000 nm, were smaller in comparison with TPA and SSA of Z. Ceramics K retained high porosity, two maxima at 300–1000 nm and 50–200 nm in the pores size distribution, and the highest TPA and SSA compared to those observed in ceramics Z and X. Presented at the 8th Conference on Solid State Chemistry, 6-11 July 2008, Bratislava, Slovak Republic.     

Preparation and characterization of implantable sensors with nitric oxide release coatings

The widespread use of miniaturized chemical sensors to monitor clinically important analytes such as PO₂, PCO₂, pH, electrolytes, glucose and lactate in a continuous, real-time manner has been seriously hindered by the erratic analytical results often obtained when such devices are implanted in vivo. One major factor that has influenced the analytical performance of indwelling sensors is the biological response they elicit when in contact with blood or tissue (e.g. thrombus formation on the device surface, inflammatory response, encapsulation, etc.). Nitric oxide (NO) has been shown to be a potent inhibitor of platelet adhesion and activation as well as a promoter of wound healing in tissue. Herein, we review recent work aimed at the development of hydrophobic NO-releasing polymers that can be employed to coat catheter-type amperometric oxygen sensors without interfering with the analytical performance of these devices. Such modified sensors are shown to exhibit greatly enhanced hemocompatibility and improved analytical performance when implanted within porcine carotid and femoral arteries for up to 16 h. Further, results from preliminary studies also demonstrate that prototype fluorescent oxygen sensors, catheter-style potentiometric carbon dioxide sensors and subcutaneous needle-type enzyme-based amperometric glucose sensors can also be fabricated with new NO-release outer coatings without compromising the analytical response characteristics of these devices. The NO-release strategy may provide a solution to the lingering biocompatibility problems encountered when miniature chemical sensors are implanted in vivo.     

Preparation and characterization of polymer single crystals for use as adsorbent

Single crystals of polyoxymethylene are flat, homogeneous, and essentially uncharged and offer a large specific surface area. Since they can be prepared reproducibly and in large amounts, they constitute a suitable model substrate in systematic adsorption studies. The crystallization procedure is discussed in some detail. The thickness of the crystals is obtained from EM and SAXS measurements, the results being in excellent mutual agreement. Combining this thickness with the crystal density the geometrical surface area is found to be 150 m²/g. This is compared with the surface area obtained by BET analysis of nitrogen adsorption (30 m²/g) and with the surface area that follows from adsorption of polyoxyethylated nonyl phenols from aqueous solution (60 m²/g). The discrepancy in the results is explained in terms of different degrees of aggregation of POM crystals in the dry state and in suspension. Finally, some preliminary results of albumin and sodium polystyrene sulfonate adsorption are discussed.     

Preparation,characterization and in vitro anticoagulation of emodin-eluting controlled biodegradable stent coatings

In this study, emodin-eluting poly(lactide-co-glycolide) (PLGA) coating stents and emodin-loaded PLGA films were prepared to explore the potential application of emodin-eluting stent for treating cardiovascular disease. Fourier transform infrared spectra (FTIR) showed all characteristic adsorption peaks of emodin in emodin-loaded PLGA film in comparison to pure emodin. The balloon expansion experiment and surface morphology observation suggested that the integrated emodin-eluting coatings were successfully obtained on the stainless steel surfaces and the coatings had the ability to withstand the strains imparted during balloon experiment. The drug release profile revealed the nearly linear release curve without obvious burst release for different doses of emodin-eluting stents. As compared with stainless steel and PLGA, in vitro platelet adhesion and APTT (activated partial thromboplastin time) tests revealed better blood compatibility of emodin-eluting stent. In conclusion, the results of the present study showed that the emodin-eluting stent has a potential application for treating cardiovascular disease.     

Preparation, characterization and electrochemical corrosion studies on environmentally friendly waterborne polyurethane/Na-MMT clay nanocomposite coatings

In this study, we present the first practical evaluation for the corrosion protection effect of waterborne polyurethane (WPU)/Na⁺-montmorillonite (Na⁺-MMT) clay nanocomposite coating. Typically, a series of waterborne polyurethane (WPU)/Na⁺-montmorillonite (Na⁺-MMT) clay nanocomposite materials have been successfully prepared by effectively dispersing the inorganic nanolayers of commercially purified Na⁺-MMT clay in WPU matrix through direct aqueous solution dispersion technique. First of all, WPU was prepared by polymerizing PCL, DMPA and H₁₂MDI, followed by characterized by nuclear magnetic resonance (¹H NMR), Fourier transform infrared (FTIR) and gel permeation chromatography (GPC). Subsequently, the as-prepared PU/Na⁺-MMT clay nanocomposite (Na⁺-PCN) materials were subsequently characterized by FTIR, X-ray diffraction (XRD) patterns and transmission electron microscopy (TEM).PCN materials in the form of coating at low Na⁺-MMT clay loading up to 3 wt% coated on the cold-rolled steel (CRS) coupons were found to exhibit superior corrosion protection effect over those of neat WPU based on a series of electrochemical measurements of corrosion potential, polarization resistance, corrosion current and impedance in 5 wt% aqueous NaCl electrolyte. Effects of the material composition on the gas permeability, thermal stability and optical clarity of neat WPU along with a series of Na⁺-PCN materials, in the form of coating and free-standing film, were also studies by gas permeability analyzer (GPA), thermogravimetric (TGA), differential scanning calorimetry (DSC) and ultraviolet UV-visible transmission spectroscopy, respectively. As control experiments, a series of PU/organo-MMT nanocomposite (denoted by organo-PCN) materials were also prepared for comparative studies.     

Preparation of dually, pH- and thermo-responsive nanocapsules in inverse miniemulsion

pH- and thermo-sensitive nanocapsules were successfully synthesized via inverse miniemulsion copolymerization of N-isopropyl acrylamide (NIPAM), N,N'-methylene bisacrylamide (MBA), and a functional monomer, 4-vinyl pyridine (4-VP). The size and size distribution of nanocapsules were measured by dynamic light scattering (DLS). The particle morphology was observed by transmission electron microscopy (TEM). The final morphology of particles was strongly influenced by the hydrophobicity of functional monomers. The use of a hydrophilic functional monomer, acrylic acid, led to the formation of solid particles, while the use of the more hydrophobic functional monomer, 4-VP, resulted in the formation of nanocapsules. The particle morphology, size, and size distribution were investigated in terms of the content of 4-VP, MBA, and the type and content of surfactant. The pH- and thermo-sensitivities were characterized by measuring the size variation with the change of temperature and pH. The organic-inorganic nanocapsules were prepared by coating a layer of silica particles on the surface of the sensitive nanocapsules.     

Preparation, characterization, and electrocatalytic properties of hybrid coatings of hexacyanometalate-doped-cationic films

Electrochemically active hybrid coatings based on cationic films, didodecyldimethylammonium bromide (DDAB), and poly(diallyldimethylammonium chloride) (PDDAC) are prepared on electrode surface by cycling the film-covered electrode repetitively in a pH 6.5 solution containing Fe(CN)₆ ³⁻ and Ru(CN)₆ ⁴⁻ anions. Modified electrodes exhibited stable and reversible voltammetric responses corresponding to characteristics of Fe(CN)₆ ^3−/4− and Ru(CN)₆ ^4−/3− redox couples. The cyclic voltammetric features of hybrid coatings resemble that of electron transfer process of surface-confined redox couple. Electrochemical quartz crystal microbalance results show that more amounts of electroactive anionic complexes partitioned into DDAB coating than those doped into PDDAC coating from the same doping solution. Peak potentials of hybrid film-bound redox couples showed a negative shift compared to those at bare electrode and this shift was more pronounced in the case of DDAB. Finally, the advantages of hybrid coatings in electrocatalysis are demonstrated with sulfur oxoanions.     

Synthesis and characterization of novel biocompatible nanocapsules encapsulated lily fragrance

In this study, novel biocompatible nanocapsules encapsulated lily fragrance (LF-NPs) were development. And, the LF-NPs are expect to have many potential applications to our daily life, such as cosmetic decorative, food industry, antibacterial, medical industry, tobacco industry, textile industry, home life, and so on.     

Optical and surface characterization of amorphous boron nitride thin films for use as blood compatible coatings

The aim of this work is the investigation of the haemocompatibility properties of homogeneous and amorphous boron nitride (a-BN) thin films, through the adsorption of two basic blood plasma proteins, human serum albumin (HSA) and fibrinogen (Fib). The a-BN thin films were grown onto c-Si(100) substrates under different values of substrate bias voltage, employing the radio frequency (RF) magnetron sputtering technique. For the consideration of the optical, compositional and structural properties of the films, Spectroscopic Ellipsometry (SE) in the Vis–UV spectral region was used, while for the study of surface topography and surface charge distribution as well as of the wetting properties of the a-BN thin films, Atomic Force Microscopy (AFM), Electric Force Microscopy (EFM) and Contact Angle measurements were additionally employed. The properties of the thin films were correlated with their haemocompatibility, through the estimation of the ratio of HSA/Fib surface concentration. The sp³ content of the samples does not seem to correlate with the haemocompatibility of the a-BN thin films. However, the surface properties determine the thrombogenicity potential of the studied samples. More precisely, the a-BN films with a less negatively charged surface exhibit the smallest possibility of clot formation, possibly due to the interactions between the charged chains of the Fib molecules and the a-BN surface, while slight changes in the surface roughness do not affect their haemocompatibility properties. The wetting properties determine the thickness of the adsorbed Fib as well as the ratio of HSA/Fib surface concentration.     

Electrochemical and spectroscopic characterization of organic compound uptake in silica core-shell nanocapsules

Oil-filled silica nanocapsules consisting of a hydrophobic liquid core and a silicate shell have been shown to efficiently extract hydrophobic compounds from aqueous media. With a view toward quantifying the selectivity of these systems, a series of electrochemical and spectroscopic measurements was performed. Uptake and kinetics experiments were carried out through electrochemical measurements by using solutions of lipophilic electroactive molecules of different sizes and with different affinities for silica. Other solutions with fluorescent probes were used for spectrophotometry measurements. In this work we report the environment where the lipophilic compounds studied end up after absorption and the kinetics of their uptake by the oil-filled silica nanocapsules with different shell thicknesses.     

Preparation of highly dispersed core/shell-type titania nanocapsules containing a single Ag nanoparticle

Core/shell-type titania nanocapsules containing a single Ag nanoparticle were prepared. Ag nanoparticles were prepared using the reduction of silver nitrate with hydrazine in the presence of cetyltrimethylammonium bromide (CTAB) as protective agent. The sol-gel reaction of titanium tetraisopropoxide (TTIP) was used to prepare core/shell-type titania nanocapsules with CTAB-coated Ag nanoparticles as the core. TEM observations revealed that the size of the core (Ag particle) and the thickness of the shell (titania) of the core/shell particles obtained are about 10 nm and 5-10 nm, respectively. In addition, the nanocapsules were found to be dispersed in the medium as individual particles without aggregation. Moreover, titania coating caused the surface plasmon absorption of Ag nanoparticles to shift toward the longer wavelength side.     

Needle-type ultra micro silver/silver chloride reference electrode for use in micro-electrochemistry.

A needle-type ultra micro silver/silver chloride reference electrode having a micro capillary with outer and inner diameters of 1.0 microm and 0.5 +/- 0.2 microm, respectively, was constructed. This micro reference electrode can be stuck into a living cell, and is applicable to use in very small environments, such as an electrochemical cell of an electrochemical scanning tunneling microscope or the detection portion of a micro-TAS. Excellent stability and repeatability of the micro reference electrode potential could be obtained by filling the micro capillary with agar gel containing 3.33 mol/L potassium chloride as a salt bridge, by covering the bare part of the silver wire on which silver chloride was deposited, and by electromagnetic shielding of the measurement cell and wire lead from the electromagnetic waves. The electrode showed stable potential for 7 days after its fabrication using 3.3 mol/L potassium chloride aqueous solution containing silver chloride as an internal electrolyte solution. The electrode exhibited constant electrode potential and excellent stability in test solutions of pH 5-9. The electrode potential of a commercial pH glass electrode measured against the micro reference electrode in standard pH buffer solutions was in good accordance with the Nernst equation.