New polymer synthesis. XXX. Synthesis and thermal behavior of new organometallic polyketones and copolyketones based on diferrocenylidenecycloheptanone

A new interesting category of organometallic polyketones and copolyketones was synthesized via Friedel–Crafts reactions through the polymerization of 2,7‐bis[(2‐ferrocenyl)methylene] cycloheptanone ( II ) with different diacid chlorides. The model compound was synthesized by reacting monomer II with benzoyl chloride and characterized by ¹H‐NMR, IR, and elemental analyses. The polyketones and copolyketones were insoluble in most organic solvents but easily soluble in concentrated H₂SO₄. The thermal properties of these polyketones and copolyketones were evaluated and correlated to their structural units by TGA and DTG measurements and had inherent viscosity of 0.32–0.65 dI g^?1. Moreover, the electrical conductivity of polyketone Va and copolyketone VI was investigated above the temperature range (300–500 K) and followed an Arrhenius equation with activation energy 2.09 eV. Also, the morphological properties of selected example of polyketones were detected by scanning electron microscopy. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2394–2401, 2005     

Effects of cobalt and potassium doping on thermal stability and electrical properties of radiation grafted acrylic acid onto poly(tetrafluoroethylene ethylene) copolymer films

Grafted copolymer of poly(tetrafluoroethylene ethylene) (ET) with acrylic acid (AAc) was prepared by direct radiation method. The obtained films were modified by treating with small amounts of Co²⁺ and K⁺ ions (1.0 wt %). The effects of such treatment on the thermal stability and electrical conductivity of these films were studied. Cobalt treatment did not much affect the thermal degradation of the films. The results obtained revealed that k⁺ treatment enhanced the thermal degradation of ET‐g‐PAAc, which started 273 K lower than that observed in the case of the untreated and Co²⁺‐treated films. Potassium and cobalt treatment of the investigated films increased their electrical conductivity (σ) and decreased the activation energy ΔE_σ. The increase in σ values was, however, more pronounced in the case of K⁺‐treated film. These results were discussed in terms of the effective increase in the hydrophilicity of the films, especially those treated with potassium. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 867–871, 2005     

Microwave-Assisted Synthesis of the Flexible Iron-based MIL-88B Metal–Organic Framework for Advanced Energetic Systems

The 3D metal–organic framework (MOF), MIL-88B, built from the trivalent metal ions and the ditopic 1,4-Benzene dicarboxylic acid linker (H₂BDC), distinguishes itself from the other MOFs for its flexibility and high thermal stability. MIL-88B was synthesized by a rapid microwave-assisted solvothermal method at high power (850 W). The iron-based MIL-88B [Fe₃.O.Cl.(O₂C–C₆H₄–CO₂)₃] exposed oxygen and iron content of 29% and 24%, respectively, which offers unique properties as an oxygen-rich catalyst for energetic systems. Upon dispersion in an organic solvent and integration into ammonium perchlorate (AP) (the universal oxidizer for energetic systems), the dispersion of the MOF particles into the AP energetic matrix was uniform (investigated via elemental mapping using an EDX detector). Therefore, MIL-88B(Fe) could probe AP decomposition with the exclusive formation of mono-dispersed Fe₂O₃ nanocatalyst during the AP decomposition. The evolved nanocatalyst can offer superior combustion characteristics. XRD pattern for the MIL-88B(Fe) framework TGA residuals confirmed the formation of α-Fe₂O₃ nanocatalyst as a final product. The catalytic efficiency of MIL-88B(Fe) on AP thermal behavior was assessed via DSC and TGA. AP solely demonstrated a decomposition enthalpy of 733 J g^?1, while AP/MIL-88B(Fe) showed a 66% higher decomposition enthalpy of 1218 J g^?1; the main exothermic decomposition temperature was decreased by 71 °C. Besides, MIL-88B(Fe) resulted in a decrease in AP decomposition activation energy by 23% and 25% using Kissinger and Kissinger–Akahira–Sunose (KAS) models, respectively.

     

Stress relaxation in carbon black loaded butyl rubber

The dependence of equilibrium force (F^*) on the strain ratio (α) of carbon black loaded butyl rubber was studied. The relation between elastic constant and volume fraction of carbon black was found in good agreement with that obtained by Guth and Gold relation at low concentrations using the shape factor (f = 6.5). The relaxation time and viscosity (η) were calculated by using stress relaxation of these samples at different compression strains. The same agreement was observed in the relation between viscosity and volume fraction of carbon black concentration. The results are discussed according to the dispersion mechanism of carbon black in rubber. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1067–1076, 2000     

Vanadia-based coatings of self-repairing functionality for advanced magnesium Elektron ZE41 Mg–Zn–rare earth alloy

A smart vanadia protective coating of self-repairing functionality that has proven to provide superior corrosion resistance for several magnesium and aluminum alloys has successfully been designed by our group. A newly developed series of magnesium alloys, namely ZE41 alloy, has recently been proposed for automotive, electronics and aerospace applications. The advanced ZE41 alloy possesses very low density, high specific strength, and good castability and weldability characteristics compared to aluminum and steel based alloys. However, the corrosion resistance of ZE41 alloy in the presence of corrosive chloride environment is relatively low. The possibility of utilizing such coatings to add self-repairing functionalities to ZE41 alloy was discussed in this paper. The electrochemical corrosion behavior of the vanadia coatings over ZE41 alloy was investigated in 3.5% NaCl solution using EIS, linear polarization and cyclic voltammetry techniques. The optimum conditions for obtaining protective vanadia coatings of self-repairing abilities and improved localized corrosion resistance were determined. Surface examination of the coatings was investigated using SEM-EDS and macroscopic imaging.     

Natural rubber filled SiC and B4C ceramic composites as a new NTC thermistors and piezoresistive sensor materials

A novel electrically conductive composite for NTC thermistor and piezoresistive sensor was successfully fabricated by homogeneously dispersing conductive SiC and B₄C in an insulating natural rubber (NR) matrix. The morphology of the composites was investigated by means of scanning electron microscopy, cross linking density (n), volume fraction of rubber (V_r), and interparticle distance among conductive phases (r_p). The influence of the filler concentrations on the mechanical properties such as modulus of elasticity (E); hardness shore A (H), and elongation at break (EB) were studied in details. The dependences of volume resistivity of NR based composites filled with B₄C and SiC as a function of fillers concentration was investigated. Temperature dependencies of volume resistivity were also measured to examine the possible application of the composites to polymer linear negative temperature (NTC) thermistors. Furthermore, the temperature dependencies of dielectric constant of the composites were studied. For practical application, the thermal stability of the composites was examined by means of resistivity temperature and pressure hysteresis cycle. In parallel, the conduction mechanism of conductivity of the composites was interpreted in terms of the computed the activation and hopping energy. The applicability of the composites to piezoresistive sensor was examined too. The good mechanical properties and thermal stability of NR composites behavior can be utilized for fabricating various electronic devices as NTC thermistors and piezoresistive sensor (i.e. transducers in pressure sensors). POLYM. COMPOS., 29:109–118, 2008. © 2007 Society of Plastics Engineers     

Compatibilization of low‐density polyethylene/plasticized starch blends by reactive compounds and electron beam irradiation

Blends based on various compositions of low‐density polyethylene (LDPE) and plasticized starch (PLST) were prepared by melt extrusion and molding in the form of sheets under hot press. The rheology properties during mixing were studied in terms of torque and temperature against mixing time. The structural properties of LDPE/PLST blends before and after electron beam irradiation was characterized by IR spectroscopy, tensile mechanical testing, and scanning electron microscopy (SEM). The torque‐time curves during the mixing process showed that the values of torque in the first region of mixing for pure LDPE or LDPE/PLST blends are higher in the presence of the compatibilizer PEMA than that in the presence of EVA. In addition, the stability of mixing was attained after a short time in the presence of PEMA. The IR spectroscopy suggests that the compatibilization by EVA and PEMA compounds proceeds through the formation of hydrogen bonding during mixing and this compatibility was improved after electron beam irradiation. The stress–strain curves of pure LDPE and its blends with PLST showed the behavior of tough polymers with yielding properties. The SEM micrographs of the fracture surfaces give supports to the effect of EVA and PEMA as compatibilizers and the effect of electron beam irradiation. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Electrochemical assessment of inhibitive behavior of some antibacterial drugs on 316 stainless steel in acidic medium

In this work, the inhibitive effect of some antibacterial drugs against the corrosion of 316 stainless steel in 1M HCl has been studied by weight loss, potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). The inhibiting effect explained by adsorption of the additives on steel surface. The inhibition efficiency increases with increasing the inhibitors concentrations and decreases with increasing the temperature. The data obtained fit well to Langmuir adsorption isotherm and the kinetic-thermodynamic model. The results of polarization studies indicate that the investigated antibacterial drugs are mixed type inhibitors. Increasing the inhibition efficiency of the investigated inhibitors with the addition of iodide ions indicates that iodide ions play important role in the adsorption process. The efficiencies obtained from the different electrochemical techniques were in good agreement which prove the validity of these tools in the measurements of the tested inhibitors.     

Loss of nitrogen from urea applied to rainfed wheat in varying rainfall zones in northern Syria

Fertilizer-applied Nitrogen (N) may be lost from the soil by various mechanisms, i.e., runoff, leaching, denitrification, and volatilization. The latter process is of primary concern in calcareous soils of arid and semi-arid regions, especially when urea is used. In this field study from northern Syria, urea alone, urea with either an incorporated urease inhibitor, phenylphosphorodiamidate, or an experimental bran-wax coating were evaluated on wheat for two cropping seasons at two experimental stations with varying average seasonal rainfall (340 mm, 270 mm). Loss of N was assessed with ¹⁵N by mass balance, i.e., the amount of N applied minus the crop N uptake and N remaining in the soil. Crop yields and N uptake were related to seasonal rainfall. Losses of N, apparently as volatilized NH₃, were relatively low at both sites, i.e., 11–18%. However, compared to the unmodified urea, neither the incorporated urease inhibitor nor the bran-wax coating had any effect on yields, N uptake or N loss. While urea hydrolysis is normally rapid, it may be delayed by dry conditions at the soil surface; similarly, unusually cold periods may delay nitrification following hydrolysis. Thus, under the cool-season conditions of rainfed cropping in the Middle East, efficient use of urea is not likely to be achieved by modification of the urea but by conventional management practices that ensure pre-plant soil incorporation or topdressing during early spring rains.