Preparation and Characterization of Water-borne Polyurethane Based on Benzotriazole as Pendant Group with Different N-Alkylated Chain Extenders and Its Application in Anticorrosion.

A series of novel anti-corrosive coatings were synthesized successfully. Water-borne polyurethane (WPU) was synthesized using polyethylene glycol and modified by grafting benzotriazole (BTA) as a pendant group (WPU-g-BTA) and N-alkylated amines (ethylene diamine (A), diethylene triamine (B), triethylene tetramine (C)) as side-chain extenders. Fourier-transform infrared spectroscopy, thermogravimetry, and dynamic mechanical analyses were used to characterize the structural and thermomechanical properties of the samples. A gas permeability analyzer (GPA) was used to evaluate molecular barrier properties. The corrosion inhibition performance of WPU-g-BTA-A, WPU-g-BTA-B, and WPU-g-BTA-C coatings in 3.5 wt% NaCl solution was determined by electrochemical measurements. WPU-g-BTA-C coating synthesized with a high cross-linking density showed superior anticorrosive performance. The as-prepared coatings exhibited a very low icorr value of 0.02 µA.cm-2, a high Ecorr value of -0.02 V, as well as excellent inhibition efficiency (99.972%) and impedance (6.33 Ω) after 30 min of exposure.

Self-assembly behavior of amphiphilic poly(amidoamine) dendrimers with a shell of aniline pentamer.

A series of amphiphilic poly(amidoamine) dendrimers (PAMAM, G2-G5) composed of a hydrophilic core and a hydrophobic shell of aniline pentamer (AP) were synthesized and characterized. The modified dendrimers self-assembled to vesicular aggregates in water with the critical aggregation concentration (CAC) decreased in the order of G2 > G3 > G4 > G5. It was found that the modified dendrimers self-organized into spherical aggregates with a bilayer vesicular structures and that the dendrimers in higher generation have more order structure, which may be attributed to the crystallization induced by the compacted effect of AP segments. In addition, larger spherical vesicles were observed under acidic and alkaline conditions, as compared with sizes of aggregates in neutral medium. At low pH, the tertiary amine groups of PAMAM-AP were transformed to ammonium salts; the polarons were formed from AP units by doping with strong acids, thereby leading to the stability of vesicular aggregates being better than that in double distilled water. Nevertheless, in high pH environment, the deprotonation of PAMAM-AP caused the enhancement of π-π interactions, resulting in generation of twins or multilayered vesicles.

Comparatively electrochemical studies at different operational temperatures for the effect of layered silicate and spherical silica on the anticorrosion efficiency of PANI nanocomposite coatings.

In this paper, a series of PANI nanocomposites have been successfully prepared by in situ oxidative polymerization. The as-prepared PANI nanocomposites were subsequently characterized by WAXRD patterns and TEM. It should be noted that the nanocomposite coating containing 3 wt-% of organophilic clay loading was found to exhibit an observable enhanced corrosion protection on cold-rolled steel (CRS) electrode at higher operational temperature of 50 degrees C, which was even better than that of uncoated and electrode-coated with PANI or PANI nanocomposites with 3 wt-% of amino-modified silica nanoparticles alone at room temperature of 30 degrees C based on the electrochemical parameter evaluations (e.g., E(corr), R(p), I(corr), R(corr) and impedance). The vapor permeability property at three different operational temperatures of PANI and PANI nanocomposite membranes were investigated by vapor permeability analyzer (VPA). Effect of material composition on the molecular weight, optical properties and surface hydrophobicity of neat PANI and PANI nanocomposite, in the form of membrane and solution, were studied by gel permeation chromatography (GPC), ultraviolet-visible absorption spectra and contact-angle measurements, respectively. Finally, electrical conductivity at three different operational temperatures of PANI and PANI nanocomposite powder-pressed pellets was also investigated through the measurements of standard four-point-probe technique.

Enhancement in insulation and mechanical properties of PMMA nanocomposite foams infused with multi-walled carbon nanotubes.

In this study, PMMA/CNTs composite materials with carboxyl-multi walled carbon nanotubes (c-MWNTs) or untreated MWNTs were prepared via in-situ bulk polymerization. The as-prepared PMMA/CNTs composite materials were then characterized by Fourier-Transformation infrared (FTIR) spectroscopy, and transmission electron microscopy (TEM). The molecular weights of PMMA extracted from PMMA/CNTs composite materials and bulk PMMA were determined by gel permeation chromatography (GPC) with THF used as the eluant. The PMMA/CNTs composite materials were used to produce foams by a batch process in an autoclave using nitrogen as foaming agent. The cellular microstructure, insulation and compressive mechanical properties of PMMA/CNTs composite foams were also investigated in detail. Compared to neat PMMA foam, the presence of CNTs increases in cell density and reduces cell size. The insulation and compressive mechanical properties of PMMA/CNTs composite foams were found to improve substantially those of neat PMMA foam. In particular, 22.6% decrease in thermal conductivity, 19.7% decrease in dielectric constant and 160% increase in compressive modulus were observed with the addition of 0.3 wt% carboxyl-multi walled carbon nanotubes (c-MWNTs).

Comparative electrochemical studies at different operational temperatures for the effect of nanoclay platelets on the anticorrosion efficiency of organo-soluble polyimide/clay nanocomposite coatings.

A organic soluble polyimide (SPI) prepared from 4,4'-Oxydianiline and 4,4'-(4,4'-Isopropylidenediphenoxy)bis(phthalic anhydride) was mixed with organo-modified montmorillonite (MMT) in N,N-Dimethylacetamide. The organic soluble polyimide-clay nanocomposite (PCN) materials were characterized by Fourier-Transformation infrared (FTIR), spectroscopy, wide-angle X-ray diffraction (WAXRD) patterns and transmission electron microscopy (TEM). It should be noted that the nanocomposite coating containing 3 wt% of clay loading was found to exhibit an observable enhanced corrosion protection on cold-rolled stell (CRS) electrode at higher operational temperature of 50 degrees C, which was even better than that of uncoated and electrode-coated with SPI alone at room temperature of 30 degrees C based on the electrochemical parameter evaluations. In this work, all electrochemical measurements were performed at a double-wall jacketed cell, covered with a glass plate, through which water was circulated from a thermostat to maintain a constant operational temperature of 30, 40 and 50 +/- 0.5 degrees C. Moreover, a series of electrochemical parameters shown in Tafel, Nyquist and Bode plots were all used to evaluate PCN coatings at three different operational temperatures in 5 wt% aqueous NaCl electrolyte. The molecular barrier properties at three different operational temperatures of SPI and PCN membranes were investigated by gas permeability analyzer (GPA) and vapor permeability analyzer (VPA).

Effect of vinyl-modified silica and raw silica particles on the properties of as-prepared polymer-silica nanocomposite foams.

In this study, the first comparative studies for the effect of vinyl-modified silica (VMS) and raw silica (RS) particles on the physical properties of as-prepared polymer-silica nanocomposite (PSN) foams are presented. First of all, the VMS particles were synthesized by performing conventional acid-catalyzed sol-gel reactions of TEOS in the presence/absence of MSMA molecules. The as-prepared VMS particles were then characterized through Fourier Transform Infrared (FTIR), solid-state 13C-nuclear magnetic resonance (13C-NMR) and 29Si-NMR spectroscopy. Subsequently, a series of PSN materials have been prepared through bulk polymerization of MMA monomers in the presence of VMS and RS particles with BPO as initiator. The dispersion capability of silica particles in polymer matrix was further observed by transmission electron microscopy (TEM) studies. The PSN foams can be further obtained by performing batch-foaming process on as-prepared bulky PSN materials with N2 as foaming agent. The cell structure analysis of the PSN foams was subsequently examined by the scanning electron microscopy (SEM) images. Gel permeation chromatography (GPC) was used to determine the molecular weights of as-prepared samples. It should be noted that the incorporated VMS and RS particles served as heterogeneous nucleation agent in polymer matrix under foaming process to reduce the cell size and increase the cell density of the PSN foams. Furthermore, the VMS particles exhibited a better dispersion capability of silica particles in PMMA matrix as compared to that of RS particles, leading to the PSN foams with smaller cell size and higher cell density. Effect of material composition on the thermal transport properties, thermal stability and mechanical strength of PSN foams were investigated by transient plane source (TPS) technique, thermal gravimetric analysis (TGA) and dynamic mechanical analysis (DMA), respectively.

Effect of amino-modified silica nanoparticles on the corrosion protection properties of epoxy resin-silica hybrid materials.

In this paper, a series of organic-inorganic hybrid materials consisting of epoxy resin frameworks and dispersed nanoparticles of amino-modified silica (AMS) were successfully prepared. First of all, the AMS nanoparticles were synthesized by carrying out the conventional acid-catalyzed sol-gel reactions of tetraethyl orthosilicate (TEOS) in the presence of (3-aminopropyl)-trimethoxysilane (APTES) molecules. The as-prepared AMS nanoparticles were then characterized by FTIR, 13C-NMR and 29Si-NMR spectroscopy. Subsequently, a series of hybrid materials were prepared by performing in-situ thermal ring-opening polymerization reactions of epoxy resin in the presence of as-prepared AMS nanoparticles and raw silica (RS) particles. The as-prepared epoxy-silica hybrid materials with AMS nanoparticles were found to show better dispersion capability than that of RS particles existed in hybrid materials based on the morphological observation of transmission electron microscopy (TEM). The hybrid materials containing AMS nanoparticles in the form of coating on cold-rolled steel (CRS) were found to be much superior in corrosion protection over those of hybrid materials with RS particles when tested by a series of electrochemical measurements of potentiodynamic and impedance spectroscopy in 5 wt% aqueous NaCI electrolyte. The increase of corrosion protection effect of hybrid coatings may have probably resulted from the enhancement of the adhesion strength of the hybrid coatings on CRS coupons, which may be attributed to the formation of Fe-O-Si covalent bond at the interface of coating/CRS system based on the FTIR-RAS (reflection absorption spectroscopy) studies. The better dispersion capability of AMS nanoparticles in hybrid materials were found to lead more effectively enhanced molecular barrier property, mechanical strength, surface hydrophobicity and optical clarity as compared to that of RS particles, in the form of coating and membrane, based on the measurements of molecular permeability analysis, dynamic mechanical analysis, contact angle measurements and ultraviolet-visible transmission spectra, respectively.

Discotic liquid crystals as novel corrosion-resistant coatings.

A discotic liquid crystal (DLC), HBC-C12, coating was successfully applied to improve the corrosion resistance of an iron surface. The iron surface with the DLC-coating exhibited improved corrosion resistance in various environments, including exposure to air and solutions with different pH values. To the best of our knowledge, studies regarding corrosion protection using DLCs have never been reported.

In situ gelation of PEG-PLGA-PEG hydrogels containing high loading of hydroxyapatite: in vitro and in vivo characteristics.

Thermosensitive hydrogels are renowned carriers that are used to deliver a variety of drugs with the aim of combating diseases. In this study, the injectability of thermosensitive hydrogels comprised of poly(ethylene glycol)-poly(lactic acid-co-glycolic acid)-poly(ethylene glycol) (PEG-PLGA-PEG, PELGE) and hydroxyapatite (HA) were examined for their ability to deliver bone morphological protein 2 (BMP-2). The physicochemical characteristics of PELGE, HA, and PELGE/HA hydrogel composites were investigated by (1)H NMR, GPC, FTIR, XRD, SEM, and TEM. The rheological properties, injectability, in vitro degradation, and in vivo biocompatibility were investigated. The hydrogel with a weight ratio of 4:6 of polymer to HA was found to be resistant to auto-catalyzed degradation of acidic monomers (LA, GA) for a period of 70 days owing to the presence of alkaline HA. Injectability was quantitatively determined by the ejected weight of the hydrogel composite at room temperature and was a close match to the weight amount predetermined by the syringe pump. The results not only revealed that the PELGE/HA hydrogel composite presented a minor tissue response in the subcutis of ICR mice at eight weeks, but they also indicated an acceptable tolerance of the hydrogel composite in animals. Thus, PELGE/HA hydrogel composite is expected to be a promising injectable orthopedic substitute because of its desirable thermosensitivity and injectability.

Nanocasting technique to prepare lotus-leaf-like superhydrophobic electroactive polyimide as advanced anticorrosive coatings.

Nanocasting technique was used to obtain a biomimetic superhydrophobic electroactive polyimide (SEPI) surface structure from a natural Xanthosoma sagittifolium leaf. An electroactive polyimide (EPI) was first synthesized through thermal imidization. An impression of the superhydrophobic Xanthosoma sagittifolium leaf was then nanocasted onto the surface of the EPI so that the resulting EPI was superhydrophobic and would prevent corrosion. Polydimethylsiloxane (PDMS) was then used as a negative template to transfer the impression of the superhydrophobic surface of the biomimetic EPI onto a cold-rolled steel (CRS) electrode. The superhydrophobic electroactive material could be used as advanced coatings that protect metals against corrosion. The morphology of the surface of the as-synthesized SEPI coating was investigated using scanning electron microscopy (SEM). The surface showed numerous micromastoids, each decorated with many nanowrinkles. The water contact angle (CA) for the SEPI coating was 155°, which was significantly larger than that for the EPI coating (i.e., CA = 87°). The significant increase in the contact angle indicated that the biomimetic morphology effectively repelled water. Potentiodynamic and electrochemical impedance spectroscopic measurements indicated that the SEPI coating offered better protection against corrosion than the EPI coating did.