Synthesis of highly isotactic poly 1-hexene using Fe-doped Mg(OEt)2/TiCl4/ED Ziegler–Natta catalytic system

In this article, polymerization of 1-hexene with FeCl_3-doped Mg(OET)₂/TiCl₄/electron donor (ED) catalytic system is presented. For this purpose, first a number of TiCl₄ catalysts supported on Mg(OEt)₂ and Fe-doped Mg(OEt)₂ supports were prepared with ethylbenzoate or dibutylphthalate as the internal EDs. After successive catalysts synthesis, they were employed in 1-hexene polymerization using cyclohexyl methyl dimethoxysilane as external ED as well as without it. The catalysts activity and molecular weight distribution (MWD) of poly 1-hexenes (PHs) were influenced strongly by both FeCl₃ doping and donor presence so that a remarkable increase in the catalyst activity was seen in doped catalysts. Deconvolution of MWD curves revealed that increase in the type of active centers by introducing FeCl₃ into the support should be responsible for the broadening of MWD of PHs. ¹³CNMR analysis indicated that while isotacticity does not change considerably by Fe doping, EDs increase its amount as high as 8–21%. Second, the stereoselective behavior of active Ti species in doped and undoped catalysts was fully explored by molecular modeling using density functional theory (DFT) method. Finally, with the aid of rheological measurements, the processability of polymers were evaluated and then the gel permeation chromatography (GPC) results were approved through the values obtained from model fitting as well as changes in moduli crossover modulus.     

Effects of aluminium nitride silane-treatment on the mechanical and thermal properties of polybenzoxazine matrix

A new kind of polymer composite, produced from the typical polybenzoxazine and 0–30 wt-% native and silane-treated aluminium nitride (T-AlN), was investigated. The mechanical tests revealed a significant increase in the microhardness and flexural properties upon adding the T-AlN particles compared to that obtained from the untreated ones. By adding 0–30 wt-% T-AlN, the tensile moduli were accurately reproduced by the Halpin-Tsai and Nielsen models. At 30 wt-% T-AlN, dynamic mechanical analysis showed a significant increase in the storage moduli and the glass transition temperature (T_g), reaching 3.2?GPa and 217°C, respectively. The thermal stability of these materials was significantly improved upon the addition of the T-AlN fillers. These improvements are attributed to the high thermal and mechanical properties of the fillers and their good dispersion and adhesion in and to the matrix as revealed by a morphological analysis.     

Removal of ciprofloxacin from aqueous solution by a continuous flow electro-coagulation process

This study deals with the performance and modeling of the electro-coagulation process for ciprofloxacin (CIP) removal by using aluminum electrode as anode in a continuous electrochemical reactor. The initial pH, temperature, current density, time and flow rate were selected as independent variables in response surface methodology (RSM) involving a five-level central composite design (CCD), while CIP removal efficiency was considered as the response function. The result of optimization showed that the maximum amount of CIP removal efficiency (88%) presented at the optimal condition of pH=5.6, t=100min, T=25.5 °C, I=5.6mA/cm² and V=25.9 mL/min. In addition, the mineralization of the CIP was investigated by chemical oxygen demand (COD) and total organic carbon (TOC) measurements that showed 77% COD removal and 49%TOC removal.     

Synthesis and architecture study of a reactive polybutadiene polyamine as a toughening agent for epoxy resin

In this study, a novel reactive toughener for the epoxy resin was developed and compared with traditional hydroxyl‐terminated polybutadiene (HTPB). For this purpose, the highly reactive aliphatic amine‐terminated polybutadiene (ATPB) was synthesized at ambient conditions by nucleophilic substitution amination. The characterizations of the product were provided by Fourier transform infrared and ¹H NMR spectroscopy. According to the mechanical test results, incorporation of ATPB into epoxy networks can significantly toughen the epoxy matrix. The addition of 10 phr ATPB increased the critical stress intensity factor (K_IC) and critical strain energy release rate (G_IC) of the epoxy from 0.85 to 2.16 MPa m^1/2 and from 0.38 to 3.02 kJ m^?2, respectively. Furthermore, unlike HTPB, the presence of the ATPB did not deteriorate the tensile strength of the matrix. The toughening and failure mechanisms were discussed based on the epoxy network morphological characteristics. The reduction in cross‐linking density and glass transition temperature of the epoxy system upon modification with liquid rubbers was confirmed by dynamic mechanical analysis. This article opens up the possibility of utilizing reactive flexible diamines with polybutadiene backbone as effective toughening agents for thermoset polymers. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44061.     

Influence of sintering temperature on microstructural changes of ceramic Raschig ring

The thermal behavior of Illitic-kaolinitic clay for manufacturing of low porosity ceramic Raschig rings was characterized during the sintering process. The samples were shaped by extrusion method and fired at different temperatures from 1,100 to 1,300 °C. The main physical-chemical transformations were studied by evaluating changes in shrinkage, water absorption, porosity, mechanical strength, microstructure and mineralogical compositions. The optimum sintering condition was found to obtain maximum mechanical strength. Chemical resistance of ceramic Raschig rings also was determined according standard method. It was shown that the better chemical resistance could be attributed to the different mineralogical compositions, in particular with presence of mullite phase.     

Contribution of intermolecular interactions to constructing supramolecular architecture: Synthesis, structure and Hirshfeld surface analysis of a new hybrid of polyoxomolybdate and ((1H-tetrazole-5-yl) methyl)morpholine

A new soluble organic–inorganic hybrid based on polyoxomolybdate, [C₆H₁₂N₅O]₃[(PO₄)Mo₁₂O₃₆]·6H₂O (1), has been successfully synthesized and characterized by using elemental analysis, IR, UV spectroscopies, ¹H NMR technique, and single-crystal X-ray diffraction. According to the results of X-ray crystallography the anion [(PO₄)Mo₁₂O₃₆]³⁻ has a typical Keggin structure and the Mo–O distances of Mo–O–Mo bonds are alternately short and long in the polyoxoanion structure. Hirshfeld surface analyses, especially d_norm surface and fingerprint plots, are used for decoding intermolecular interactions in the crystal network and contribution of component units for the construction of the 3D architecture. The results indicate that in 1 the hydrogen bond interaction play a main role in the construction of the 3D architecture, especially the CHO interaction which overruns the classic NHO, NHO hydrogen bond interactions; van der Waals force between the peripheral atoms of component units cannot be ignored.     

Synthesis and properties of polybenzoxazine modified polyurethanes as a new type of electrical insulators with improved thermal stability

A new class of electrical insulating materials with improved thermal stability was prepared from combination of polybenzoxazine with epoxy terminated polyurethane prepolymer (EPU). EPU was prepared by the reaction of glycidol with NCO‐terminated urethane prepolymer. The prepolymer was prepared from polycaprolactone polyol (molecular weight 1000), and hexamethylene diisocyanate. Bisphenol‐A and aniline were used for preparation of benzoxazine monomer. Mode of reactions and optimum curing condition were determined by DSC and FTIR analysis. Upon these analysis as well as DMTA findings, formation of interpenetrating polymer networks was suggested for blends consisted different weight ratios of two components. Viscoelastic behavior, mechanical, thermal, and electrical properties of the prepared samples was studied and their relation to the chemical structure and composition of blends were elucidated. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Toward A Mechanistic Understanding of Re-Infiltration in Naturally Fractured Reservoirs with Surfactant-Aided Gravity Drainage Process

Surfactant-aided gravity drainage is an improved oil recovery technique for water-invaded zone in fractured carbonate reservoirs, which are mostly oil-wet or mixed-wet rocks. The re-infiltration mechanism in water-invaded zone has a considerable effect on oil vertical movement in gravity drainage processes. In this work, a mechanistic understanding of re-infiltration in surfactant-aided gravity drainage, in comparison to oil–water gravity drainage is presented using an experimentally and numerically validated model. A column model is constructed from three matrix blocks. These blocks are separated from each other by horizontal fractures. A storage tank is considered on top of the model to store depleted oil from matrix blocks. The stacked-blocks model for re-infiltration is validated and verified to simulate water and chemical flooding using a mesh independency study and experimental flooding data in a composite core experiment. Using this model, several analyses are performed to investigate effects of rock and fluid properties, rock saturation functions, wettability alteration, surfactant adsorption, and capillary continuity on re-infiltration.     

Regenerable Sorbents for High-Temperature Desulfurization of Syngas from Biomass Gasification

Single-metal high-temperature solid sorbents for syngas cleaning using Mn, Ca, Fe, Cu, or Mo supported on γ-Al₂O₃ were synthesized, characterized, and tested in a fixed-bed reactor. H₂S and SO₂ concentrations in the gas after treatment at T = 400 to 700 °C were compared with thermodynamic calculations. The Mn-based sorbent showed the best ability to achieve a low sulfur residual in the gas, especially at temperatures above 600 °C. Sorbents with Fe, Cu, and Mo gave SO₂ formation in the initial phase, but this could be avoided by a pre-reduction treatment of the sorbent material.     

Microstructural properties,thermal insulation and thermal degradation behavior of boron-containing monolithic novolac xerogels

Enhancement of thermal stability-insulation performance of hyper porous materials is the premier issue to design of novel porous thermal protection systems. Boron-containing monolithic novolac xerogels (BCNXs) were synthesized using sol–gel networking of novolac resin with hexamethylenetetramine (HMTA) and boric acid at the solvent saturated vapor atmosphere (SSVA). The aim was to elucidate the effect of higher crosslinking density and thermal stable boron containing chemical bonds on the microstructure, thermal conductivity, and thermal oxidation stability of novolac xerogels. The results of FESEM and BET analysis showed that the microstructural characteristics of xerogels are significantly depend on the HMTA and boric acid concentration. The thermogravimetric results were analyzed using characteristic kinetic temperature (CKT)-characteristic kinetic temperature range (CKTR) approximations. The effect of micromorphology of xerogels on the thermal conductivity was investigated. The effective thermal conductivity of samples were in the range of 0.031–0.048 W/m K.