Estimation of kinetic and electric parameters of liquid feed passive DMFCs

The study of polarization curves is an important part for evaluating the performance of passive direct methanol fuel cells (DMFCs). This study must be essentially followed by other experiments to gain knowledge of important kinetic and electrical parameters such as exchange current density, charge transfer coefficients, ohmic resistance, etc. This experimentation include in-situ characterization techniques such as electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), and current interrupt (CI) technique which are expensive to carry out. Hence, this study develops a semi-analytical model for estimating exchange current density, charge transfer coefficients and ohmic resistance directly from the polarization curves. In addition, a simple “3/4-Point method” is introduced, utilizes the polarization curves for the estimation of kinetic and electric parameters. The triad (proposed model, 3/4-Point method and polarization/EIS experiment) are compared and exhibited similar trends, thereby validating it as a tool for estimation of a large class of parameters. The model is comprehensive as it is valid throughout the polarization curves, thereby avoiding the need for multiple strategies in different regions of the polarization curves to calculate various parameters. The model can serve to know the values of these parameters by-hand before other experimentations which involves high cost and sophisticated experimental conditions.     

Correlation of Arrhenius parameters for UHMWPE synthesis with ethylene solubility characteristics in different polymerization media

The effect of different polymerization media like n‐hexane, cyclohexane, isooctane, n‐decane, toluene, varsol, and light normal paraffin (LNP) on the kinetics of the slurry polymerization of ethylene using a highly active Ziegler Natta (ZN) catalyst for synthesizing UHMWPE was studied. Attempts have been made to determine the solubility of ethylene in the above polymerization media in a very basic manner and to correlate same with the process activation energy based on the Arrhenius plots. The ethylene solubility seemed to depend on the number of carbon atoms in the media, besides other parameters like geometry, dipole moment, etc. It is obvious and well understood that the monomer (ethylene) concentration has a direct bearing on the polymerization kinetics, which influenced the activation energy (Ea) besides other parameters like catalyst/cocatalyst concentration, temperature, etc which were kept constant during the study. The role of the catalyst system in controlling the activation energy was also further exemplified by employing a different ZN catalyst system wherein higher activation energy was observed. This was ascribed to restricted activation pathways for the catalyst under the comparable experimental conditions employed. As soon as better activation pathways for the catalyst were enabled the activation energy dropped down remarkably. The Ea for the synthesis of ultra‐high molecular weight polyethylene (UHMWPE) using traditional MgCl₂ supported Ti catalyst was found to be 5–12 kcal/mol which compared well with the values obtained by other researchers using other similar catalyst systems for different ethylene polymerization processes. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Friedel–Crafts green alkylation of xylenes with tert-butanol over mesoporous superacid UDCaT-5

Friedel–Crafts green alkylation of xylenes with tert-butanol was investigated in the presence of mesoporous superacidic catalysts named as UDCaT-4, UDCaT-5 and UDCaT-6. The catalysts are modified versions of zirconia showing high catalytic activity, stability and reusability. The catalytic activity is in the order: UDCaT-5 (most active) > UDCaT-6 > UDCaT-4 > sulfated zirconia (least active). Synergistic effect of very high sulfur content present (9% (w/w) S) and preservation of tetragonal phase in UDCaT-5, in comparison with sulfated zirconia (4% (w/w) S), were responsible for higher catalytic activity. The performance of UDCaT-5 in alkylation of xylenes was studied with tert-butanol with reference to selectivity and stability. Alkylation of m-xylene over UDCaT-5 gives 96% conversion of tert-butanol with 82% selectivity towards 5-tert-butyl-m-xylene (5-TBMX) under optimum reaction conditions. The formation of products is correlated with the acidity of the catalyst. The reactions were conducted in liquid phase at relatively low reaction temperatures (130–160 °C). A systematic investigation of the effects of various operating parameters was done to describe the reaction pathway. The reaction was carried out without any solvent in order to make the process cleaner and greener. An overall second order kinetic equation was used to fit the experimental data, under the assumption that both xylene and tert-butanol are weakly adsorbed. An independent study of dehydration of tert-butanol (TBA) was also done. Alkylation of o-xylene and p-xylene with tert-butanol was also studied. The overall process is green and clean.     

Enhanced reliability of high-density wiring (HDW) substrates through new base substrate and dielectric materials

Flame retardant glass/epoxy composite (FR4) has been extensively used as a substrate material for microelectronic packaging due to its cost effectiveness and overall performance. However, to be able to fabricate high-density wiring with microvias, and embed capacitors, inductors, resistors, and RF and optoelectronic waveguides into a single substrate, we need materials other than FR4 as a base substrate to meet the stringent warpage requirements during fabrication. Typically, these base substrate materials should have a high modulus and good planarity in addition to having a coefficient of thermal expansion (CTE) that is close to that of silicon so that flip-chips can be attached directly to the substrate without the need for an underfill. Although low-CTE and high modulus base substrate materials can result in low warpage and can eliminate the need for an underfill, they can potentially cause delamination and cracking in the interlayer dielectric. This is due to the high CTE mismatch between the base substrate and a typical polymer dielectric. This paper aims to explore a combination of a base substrate material and an interlayer dielectric material such that the warpage is minimal, the dielectric will not crack or delaminate, and the flip-chip solder joints, assembled without an underfill, will not crack prematurely during qualification regimes or operating conditions. Non-linear finite element models with a design-of-simulations approach are used in arriving at optimized thermo-mechanical properties for the base substrate and the dielectric materials to enhance the overall reliability of the integrated substrate with flip-chip assembly. It is seen that an aluminum nitride base substrate with resin-coated foil C provides the best combination against dielectric cracking, high warpage, and solder joint fatigue. The results from the models have also been validated with experimental data.     

Chlorocarboxylation of polyethylene,IV. Radical scavenging action of maleic anhydride

Radical scavenging action of maleic anhydride (MA) is observed during chlorocarboxylation of polyethylene (PE) (CCPE). Reduction in the rate of chlorination is observed in the presence of MA in the CCPE process as compared to the rate of chlorination of PE (CPE) alone. Reduction in the rate of chlorination is due to the competitive nature of CCPE process and the radical scavenging action of MA. Radical scavenging action arises as a result of the formation of MA excimers of very short half life and their interactions with solvent. Other reactions responsible for scavenging action may also exist and are discussed. The kinetics of the scavenging process is studied by considering number of sites (N?_0Cl), (N?_Cl + N?_MA) occupied during CPE and CCPE processes, respectively. The temperature dependence of the apparent rate constant k_SCV is investigated and reveals that activation energy and pre-exponential factor are of the order of 10.3 kcal/mol and 9.1 s^-1, respectively.     

Biodiesel production from mahua (Madhuca indica) oil having high free fatty acids

A technique to produce biodiesel from mahua oil (Madhuca indica) having high free fatty acids (19% FFA) has been developed. The high FFA level of mahua oil was reduced to less than 1% by a two-step pretreatment process. Each step was carried out with 0.30–0.35 v/v methanol-to-oil ratio in the presence of 1% v/v H₂SO₄ as an acid catalyst in 1-hour reaction at 60°C. After the reaction, the mixture was allowed to settle for an hour and methanol–water mixture that separated at the top was removed. The second step product at the bottom was transesterified using 0.25 v/v methanol and 0.7% w/v KOH as alkaline catalyst to produce biodiesel. The fuel properties of mahua biodiesel were found to be comparable to those of diesel and conforming to both the American and European standards.     

In situ preparation of N doped orthorhombic Nb2O5 nanoplates /rGO composites for photocatalytic hydrogen generation under sunlight

The synthesis of nitrogen doped orthorhombic niobium oxide nanoplates/reduced graphene oxide composites (NNb₂O₅/rGO) and their photocatalytic activity towards hydrogen generation from water and H₂S under natural sunlight has been demonstrated, uniquely. Nanostructured NNb₂O₅/rGO is synthesized by in situ wet chemical method using urea as a source of nitrogen and optimized by varying percentage of graphene oxide (GO). X?ray diffraction (XRD) study reveals that NNb₂O₅ have orthorhombic crystal structure with crystalline size, 35 nm. Further, X?ray photoelectron spectroscopy (XPS) confirm the presence of nitrogen and rGO in NNb₂O₅/rGO nanocomposite. Morphological features of (NNb₂O₅/rGO) were examined by FE?SEM and FE?TEM showed Nb₂O₅ nanoplates of diameter 25–40 nm anchored on 2D rGO. Diffuse reflectance spectra depicts the extended absorbance in the visible region with band gap of 2.2 eV. Considering the band gap in the visible region, the photocatalytic hydrogen generation from water and H₂S has been performed. The 1 wt % rGO hybridized NNb₂O₅ (S2) exhibited superior photocatalytic hydrogen generation (537 μmol/h) from water and (1385 μmol/h) from H₂S under sunlight. The improved photocatalytic activity is attributed due to an extended absorbance in the visible region, modified electronic structure upon doping and formation of well defined NNb₂O₅/rGO interface, provides large surface area, accelerates the supression of electron and hole pairs recombination rate. In our opinion, this works may provides facile route for energy efficient and economic approach for fabrication of NNb₂O₅/rGO nanocomposites as a visible light active photocatalyst.     

Studies of a Supported Titanium Catalyst System Using Magnesium Dichloride–Alcohol Adduct

Magnesium dichloride reacts with aliphatic alcohols [ROH; R = n-C₂H₅, n-C₃H₇, i-C₃H₇, n-C₄H₉, i-C₄H₉, t-C₄H₉, n-C₅H₁₁, n-C₆H₁₃, C₆H₁₂(C₂H₅)] to form well-defined solid adducts. Compositional analysis of adducts indicates that the stoichiometric ratio of magnesium dichloride to alcohol depends on length of alkyl group and nature of isomeric alcohol. Magnesium dichloride-2-ethyl-l-hexanol adduct was treated with diphenyldichlorosilane in the presence of dibutylphthalate to obtain active magnesium dichloride support. The titanation process of active magnesium dichloride gives supported magnesium–titanium catalyst (Mg–Ti). The catalyst was characterized by compositional analysis and specific surface area measurements. Performance of the catalyst for polymerization of propene was evaluated with triethylaluminum (TEAL) and phenyltriethoxysilane (PES) as cocatalyst. The yield and isotacticity of the polymer is governed by polymerization parameters such as Si/A1 ratio and polymerization time.     

A hybrid neural network–genetic algorithm approach for permutation flow shop scheduling

The objective of this paper is to find a sequence of jobs for the permutation flow shop to minimise the makespan. The shop consists of 10 machines. A feed-forward back-propagation artificial neural network (ANN) is used to solve the problem. The network is trained with the optimal sequences for five-, six- and seven-job problems. This trained network is then used to solve a problem with a greater number of jobs. The sequence obtained using the neural network is used to generate the initial population for the genetic algorithm (GA) using the random insertion perturbation scheme (RIPS). The makespan of the sequence obtained by this approach (ANN-GA-RIPS) is compared with that obtained using GA starting with a random population (ANN-GA). It was found that the ANN-GA-RIPS approach performs better than ANN-GA starting with a random population. The results obtained are compared with those obtained using the Nawaz, Enscore and Ham (NEH) heuristic and upper bounds of Taillard's benchmark problems. ANN-GA-RIPS performs better than the NEH heuristic and the results are found to be within 5% of the upper bounds.     

Mechanical properties of modified biofiller‐polypropylene composites

This article reports the mechanical, thermal, and morphological properties of polypropylene (PP)‐chicken eggshell (ES) composites. Mechanical properties like tensile strength, tensile modulus, izod impact strength, flexural modulus of PP composites with normal (unmodified) eggshell and chemically treated ES [modified ES (MES) with isophthalic acid] have been investigated. PP–calcium carbonate (CaCO₃) composites, at the same filler loadings, were also prepared and used as reference. The results showed that PP composites with chemically MES had better mechanical properties compared to the unmodified ES and CaCO₃ composites. An increase of about 3–18% in tensile modulus, 4–44% in izod impact strength and 1.5–26% in flexural modulus at different filler loading was observed in MES composites as compared to unmodified ES composites. Scanning electron microscopy (SEM) micrographs of fractured tensile specimens confirmed better interfacial adhesion of MES with polymer matrix resulting into lower voids and plastic deformation resulting in improved mechanicals of the composites. TEM micrographs showed acicular needle shaped morphology for modified ES and have contributed to better dispersion which is the prime reason for enhancement of all the mechanical properties. At higher filler loading, the modulus of MES composite was found to be higher by 5% as compared to commercial CaCO₃ composites. POLYM. COMPOS., 35:708–714, 2014. © 2013 Society of Plastics Engineers