Synthesis and characterization of aramid composites reinforced with silanized graphene platelets.

The synthesis and characterization of aramid composites reinforced with graphene platelets are reported. Hydroxy-functionalised graphene platelets were modified with two sol-gel binders (aminopropyl- or aminophenyl-trialkoxysilanes) and then chemically linked with aramid chains. The effect of the two sol-gel binders on the physiochemical and mechanical properties was evaluated. Chemical changes during the sol-gel reaction and subsequent amidation process in the nano-composite preparation were evaluated by the XPS and FTIR analyses. Thin films of these composites with different proportions of graphene were prepared. Morphology of the hybrids prepared was studied by the SEM technique. Properties of the composite films were studied by dynamical mechanical thermal (DMT) analysis to measure their glass transition temperature (T g) and storage modulus. These properties have been compared with previously reported values using pristine graphene (Gr) as a filler. The increase in thermal mechanical properties on addition of silanized graphene (SiGr) showed a large shift in the T g and more increase in storage modulus by chemically binding SiGr sheets on the aramid chains. Aminophenyl-trialkoxysilane was found to give better results due to the presence of phenyl groups which were more rigid than propyl groups present in aminopropyl-trialkoxysilane. The effect of chemical bonding and the possible π-π secondary bond interactions between the matrix and graphene platelets on the properties of the resulting hybrids are discussed.

Heterogeneous Hybrid Nanocomposite Based on Chitosan/Magnesia Hybrid Films: Ecofriendly and Recyclable Solid Catalysts for Organic Reactions.

Chitosan/magnesia hybrid films (CS-Mg) have been prepared via sol-gel process and employed as heterogeneous catalysts. An in situ generation of a magnesia network in the chitosan matrix was performed through hydrolysis/condensation reactions of magnesium ethoxide. The synthesized hybrid films were characterized using various analytical techniques, such as X-ray photo-electron spectroscopy (XPS), field emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM). The hybrid films display excellent catalytic activities in Michael and Knoevenagel reactions via one pot or solvent-free approaches under microwave irradiation conditions. Chitosan/magnesia hybrid films, catalysed pyrimidine, benzochromene, coumarin and arylidene-malononitriles derivatives formation reactions occurred with highly efficient yields of 97%, 92%, 86% and 95% respectively. Due to the fact that the films are durable and insoluble in common organic solvents, they were easily separated and can be recycled up to five times without a considerable loss of their catalytic activity.

Antibiotic resistance and drug modification: Synthesis, characterization and bioactivity of newly modified potent ciprofloxacin derivatives.

Development of new derivatives of commercial antibiotics using different organic reagents and testing these derivatives against different microorganisms are the main goals of this article. Thus, the antibiotic ciprofloxacin, CF, was acylated via reaction with ethyl cyanoacetate and ethyl acetoacetate in basic medium to give the cyanoacetylpiprazinyl dihydroquinoline derivative 3, and oxobutanoylpiprazinyl dihydroquinoline derivative 5, respectively. On the other hand, N-alkylated derivatives 8-10, were prepared through the reaction of CF with chloroacetonitrile, chloroacetyl acetone and chloroacetone in the presence of carbonate salt. In basic medium, both 3 and 10 were coupled with benzenediazonium chloride to afford hydrazono derivatives, which were then cyclized to give 4-(dihydropyridazinecarbonyl)piperazinyl-1,4-dihydroquinoline. Furthermore, compounds 3 and 10 were reacted with benylidenemalononitrile to produce 4H-pyan and pyrido[1,2-a]pyrazine derivatives, respectively. Both 3 and 10 were reacted with DMFDMA to give enaminone derivatives. These enaminones were cyclized to aminopyrimidine derivatives by reacting with urea or thiourea. X-ray, elemental analysis and spectral data were used to illustrate and confirm the structures of the isolated compounds. The bioactivities of the novel compounds were investigated against different gram-positive and gram-negative bacteria. In addition, these novel antibiotic derivatives were tested against ciprofloxacin-resistant bacteria isolated from patients aged 65-74 years. This study reveals that most of the modified drugs show high to moderate antibacterial activity. Additionally, these drugs show good effects against ciprofloxacin-resistant bacteria.

Thermal Mechanical Properties of Graphene Nano-Composites with Kevlar-Nomex Copolymer: A Comparison of the Physical and Chemical Interactions.

This paper reports the preparation of Kevlar-Nomex copolymer nano-composites with exfoliated pristine and functionalized graphene sheets (Grs). The graphene oxide (GrO) platelets were amidized by the reaction of amine-terminated aramid (Ar) with the functional groups present on the GrO surface to prepare the nano-composites films with different loadings of GrO. Chemical changes involved during the oxidation and subsequent amidation were monitored by Raman, FTIR and XP spectroscopic analyses. Morphology of the composite films was studied by atomic force and scanning electron microscopies. Viscoelastic properties of the hybrid films were studied for their glass transition temperature (Tg) and storage modulus by dynamical mechanical thermal analysis (DMTA). A higher shift in glass transition temperature was obtained by chemically binding the aramid copolymer chains on the functionalized Gr sheets. The increase in tensile strength and modulus at various loadings of GrO are compared with the composites using pristine Gr. The effect of interfacial interactions between the matrix chains and the reinforcement on the properties of these hybrids have been explained.

Aramid-Zirconia Nanocomposite Coating With Excellent Corrosion Protection of Stainless Steel in Saline Media.

Resistance to stainless steel corrosion in marine-based industries requires more research into materials with an improved surface and enhanced protection by utilizing surface coatings. Herein, a thermally stable aramid-zirconia nanocomposite has been successfully prepared using the sol-gel method to produce a zirconia network-structure bonded to the polymer chain. Using thermal gravimetric analysis (TGA), the residue mass of zirconia retained after the thermal degradation of aramid-zirconia film was determined and found to be 10% by mass. The investigated nanocomposite (using 10% zirconia) was coated on the stainless-steel surface through a facile and effective spin coating method and its protection was examined in saline solution (3.5% NaCl). The aramid-zirconia nanocomposite coating (Ar-Zr10) was found to provide an outstanding corrosion resistance to steel surfaces which led to protecting it against the corrosive marine environment. The electrochemical impedance (EIS) measurements were carried out to evaluate steel resistance against dissolution in chloride solution in the absence and presence of the investigated coatings showed a corrosion protection efficiency of 99.3% using Ar-Zr10 compared to 92.1% using pure aramid. Moreover, the potentiodynamic polarization (PDP) plots showed a pronounced decrease in the corrosion current values which confirmed the formation of a passive layer which mitigated the corrosion reaction and ions diffusion. The water contact angle of stainless-steel coated with pure aramid and the aramid-zirconia was found to be 84.2° and 125°, respectively, confirming the hydrophobic nature of the hybrid coating Ar-Zr10. On the other hand, the results achieved through the electrochemical and surface techniques were used to clarify the protection mechanism. The aramid-zirconia nanocomposite coating showed a remarkable protection performance by controlling the charge transfer at the interface between the steel alloy and the electrolyte which prevented the alloy dissolution.

To what extent do polymeric stabilizers affect nanoparticles characteristics?

Colloidal synthesis of nanoparticles using polymeric stabilizers as a template of a structure directing agent provided a plethora of opportunities in fabricating nanoparticles (NPs) with controlled size, shape, composition and structural characteristics. To understand the complete potency of polymeric stabilizers during the synthesis of nanoparticles, the relationship between polymer characteristics such as structure, molecular weight and concentration and nanoparticles characteristics is discussed in depth. This review portrays the use of polymers to attain nanostructured materials via covalent and non-covalent approaches. These polymers can also serve as surfaces modifier as well as the growth regulators during the synthesis of nanomaterials. The effect provided by polymers that directs the formation of nanomaterials into desired forms is otherwise hard to achieve. We especially spotlight on the approaches for tuning the characteristic properties of nanoparticles via cautious choice of the polymer system with special focus to stimuli-responsive polymers. This review mainly focusses on answering the main challenging question; what is the ideal polymeric stabilizer system to obtain specific morphology, size and phase structure of nanoparticles? Such vital information will enable rational design of nanoparticles to meet specific needs for different applications.

In-Situ Preparation of Aramid-Multiwalled CNT Nano-Composites: Morphology, Thermal Mechanical and Electric Properties.

In this work in-situ polymerization technique has been used to chemically link the functionalized multiwalled carbon nanotubes (CNTs) with aramid matrix chains. Phenylene diamine monomers were reacted in the first stage with the carboxylic acid functionalized CNTs and then amidized in-situ using terephthaloyl chloride generating chemically bonded CNTs with the matrix. Various proportions of the CNTs were used to prepare the hybrid materials. The functionalization procedure was studied by Fourier transform infrared (FTIR) spectroscopy and composite morphology investigated by scanning electron microscopy (SEM). Thermal mechanical properties of these hybrids, together with those where pristine CNTs with similar loadings were used, are compared using tensile and dynamic mechanical analysis (DMA). The tensile strength and temperature involving α-relaxations on CNT loading increased with CNT loading in both systems, but much higher values, i.e., 267 MPa and 353 °C, respectively, were obtained in the chemically bonded system, which are related to the nature of the interface developed as observed in SE micrographs. The water absorption capacity of the films was significantly reduced from 6.2 to 1.45% in the presence pristine CNTs. The inclusion of pristine CNTs increased the electric conductivity of the aramid films with a minimum threshold value at the loading of 3.5 wt % of CNTs. Such mechanically strong and thermally stable aramid and easily processable composites can be suitable for various applications including high performance films, electromagnetic shielding and radar absorption.

Controlled Synthesis of ZrO2 Nanoparticles with Tailored Size, Morphology and Crystal Phases via Organic/Inorganic Hybrid Films.

In this investigation, well defined mesoporous zirconia nanoparticles (ZrO2 NPs) with cubic, tetragonal or monoclinic pure phase were synthesized via thermal recovery (in air) from chitosan (CS)- or polyvinyl alcohol (PVA)-ZrOx hybrid films, prepared using sol-gel processing. This facile preparative method was found to lead to an almost quantitative recovery of the ZrOx content of the film in the form of ZrO2 NPs. Impacts of the thermal recovery temperature (450, 800 and 1100 °C) and polymer type (natural bio-waste CS or synthetic PVA) used in fabricating the organic/inorganic hybrid films on bulk and surface characteristics of the recovered NPs were probed by means of X-ray diffractometry and photoelectron spectroscopy, FT-IR and Laser Raman spectroscopy, transmission electron and atomic force microscopy, and N2 sorptiometry. Results obtained showed that the method applied facilates control over the size (6-30 nm) and shape (from loose cubes to agglomerates) of the recovered NPs and, hence, the bulk crystalline phase composition and the surface area (144-52 m2/g) and mesopore size (23-10 nm) and volume (0.31-0.11 cm3/g) of the resulting zirconias.

Stabilizing poly(vinyl chloride) using its blends with poly(methyl methacarylate): pyrolysis GC/MS studies.

Binary blends of poly(vinyl chloride) (PVC) with poly(methyl methacarylate) (PMMA) of various compositions were prepared through solution blending. Thermogravimetric and pyrolysis studies of these blends were carried out and the volatile products were separated and quantitatively analyzed by GC/MS. Harmful pyrolysis products from PVC like HCl and different aromatic hydrocarbons are significantly suppressed in presence of a small amount of PMMA. The stabilization effect on PVC was found to be the most significant with 10 wt.%. PMMA contents in the matrix. Mechanism of the stabilization has been explained by the interaction of micro- and macro-radicals resulting from PMMA with PVC, which stabilize the unzipping of polymer chains by a reversible blocking mechanism and increase the amount of cross-linked residue retained above 500 °C.