Study on the preparation and properties of novel block copolymeric materials based on structurally modified organometallic as well as organic polyamides and polydimethylsiloxane

Some novel ferrocene‐containing polyamide‐based block copolymer materials with telechelic polydimethylsiloxane oligomer and their organic analogues were prepared by solution‐phase polycondensation of ferrocene‐based organometallic and terephthaloyl‐ as well as isophthaloyl‐based organic acyl chlorides with a series of semi‐aromatic diamines having ether linkages together with variable aliphatic character. The corresponding polyamides of the synthesized materials, without polydimethylsiloxane segment, were also prepared for comparison of physicochemical properties. None of the synthesized organometallic and organic block copolymers along with their respective polyamides melted below 300 °C and their structural features were confirmed by their physical properties and spectroscopic studies. The weight‐average molecular weights and molecular parameters of all these materials were determined by the static laser light scattering technique. The materials were soluble in sulfuric acid and partially soluble in common organic solvents, and yet became readily soluble upon N‐trifluoroacetylation. The synthesized materials were further characterized by their water absorption characteristics, X‐ray diffraction studies and surface morphology (SEM and AFM) and thermal (DSC and TG) analyses, and their structure–property relationships were elucidated from these studies. The energies of pyrolysis for these materials were calculated by the Horowitz and Metzger method. © 2012 Society of Chemical Industry     

Genome-Wide Investigation of Multifocal and Unifocal Prostate Cancer—Are They Genetically Different?

Prostate cancer is widely observed to be biologically heterogeneous. Its heterogeneity is manifested histologically as multifocal prostate cancer, which is observed more frequently than unifocal prostate cancer. The clinical and prognostic significance of either focal cancer type is not fully established. To investigate prostate cancer heterogeneity, the genetic profiles of multifocal and unifocal prostate cancers were compared. Here, we report observations deduced from tumor-tumor comparison of copy number alteration data of both focal categories. Forty-one fresh frozen prostate cancer foci from 14 multifocal prostate cancers and eight unifocal prostate cancers were subjected to copy number variation analysis with the Affymetrix SNP 6.0 microarray tool. With the investigated cases, tumors obtained from a single prostate exhibited different genetic profiles of variable degrees. Further comparison identified no distinct genetic pattern or signatures specific to multifocal or unifocal prostate cancer. Our findings suggest that samples obtained from multiple sites of a single unifocal prostate cancer show as much genetic heterogeneity and variability as separate tumors obtained from a single multifocal prostate cancer.     

Photocatalytic degradation of Basic Blue 41 dye under visible light over SrTiO3/Ag3PO4 hetero-nanostructures

In an attempt to develop nanostructured photocatalysts with high performance, SrTiO₃/Ag₃PO₄ hetero-nanostructures were successfully fabricated. The formed binary heterojunctions were composed of SrTiO₃ nanotubes prepared using liquid-phase deposition, and Ag₃PO₄ nanoparticles prepared using a sol–gel method. Synthesis details, including morphology, structure, and optical properties of the prepared photocatalysts, were characterized and comparatively discussed. The results showed that at an optimal ratio of SrTiO₃ to Ag₃PO₄ (20–80), the photocatalytic degradation of Basic Blue 41 under 80-min visible light irradiation is the maximum amount of 99%, which is about 4.4 and 1.5 times higher than that of pristine SrTiO₃ nanorods and Ag₃PO₄ nanoparticles, respectively. It can be due to the synergistic effect of two materials that provide high light absorption and charge carriers’ separation. Finally, a detailed possible mechanism for enhancing the photocatalytic activity of the SrTiO₃/Ag₃PO₄ hetero-nanostructures was proposed.     

Thermodynamic Equilibrium Analysis of Propane Dehydrogenation with Carbon Dioxide and Side Reactions

A thermodynamic analysis of propane dehydrogenation with carbon dioxide was performed using constrained Gibbs free energy minimization method. Different reaction networks corresponding to different catalytic systems, including non-redox and redox oxide catalysts, were simulated. The influences of CO₂/C₃H₈ molar ratio (1–10), temperature (700–1000 K), and pressure (0.5–5 bar) on equilibrium conversion and product composition were studied. In the presence of CO₂ with a molar ratio of CO₂/C₃H₈ = 1, the temperature of dehydrogenation can be 30 K lower than that of dehydrogenation in the presence of steam (H₂O/C₃H₈ = 1) and about 50 K lower than that of simple dehydrogenation without dilution to achieve 60% propane conversion. It was found that the occurrence of dry reforming of propane and coke-forming side reactions could strongly impact the equilibrium product composition of the multireaction system and, therefore, these reactions should be kinetically controlled. Comparison of the simulated reactant conversions with those reported in the literatures revealed that the experimental conversion levels of propane are far below the corresponding equilibrium values due to rapid catalyst deactivation by coke, implying that research efforts should be directed toward formulation of more active and selective catalysts.     

Six-Phase Voltage Source Inverter Driven Induction Motor

A six-phase six-step voltage-fed induction motor is presented. The inverter is a transistorized six-step voltage source inverter, while the motor is a modified standard three-phase squirrel-cage motor. The stator is rewound with two three-phase winding sets displaced from each other by 30 electrical degrees. A model for the system is developed to simulate the drive and predict its performance. The simulation results for steady-state conditions and experimental measurements show very good correlation. It is shown that this winding configuration results in the elimination of all air-gap flux time harmonics of the order (6v ±1, v = 1,3,5,...). Consequently, all rotor copper losses produced by these harmonics as well as all torque harmonics of the order (6v, v = 1,3,5,...) are eliminated. A comparison between-the measured instantaneous torque of both three-phase and six-phase six-step voltage-fed induction machines shows the advantage of the six-phase system over the three-phase system in eliminating the sixth harmonic dominant torque ripple.     

Three dimensional discrete element modeling of granular media under cyclic constant volume loading: A micromechanical perspective

Discrete element modeling is employed to investigate the micromechanics of two granular assemblies subjected to constant-volume cyclic loading. For this purpose, two assemblies of spherical particles are modeled at the same confining pressure but with two different void ratios. The cyclic behaviors of the assemblies are inspected and the micromechanical parameters and their variations during cyclic loading are carefully observed and analyzed. The evolution of contact force networks with the progression of the loading cycles confirms that the contact force networks are hysteretic and their formation depends on the previous strain conditions of the assemblies. The distributions of the contact normals and their normal forces are also investigated to obtain a quantitative insight of the changes in the contact force networks. The probability distributions of the normal and tangential forces during cyclic loading are similar to the results of previous experimental studies that were conducted on two-dimensional specimens of granular materials. In addition, variations of the fabric tensors, which were calculated for strong contacts, are studied to trace the changes of the structural anisotropy of the specimens. The results suggest that the structural anisotropy of the specimens increases dramatically when they approach the state of liquefaction and that the degree of anisotropy is more profound in the strong contacts. Finally, the displacements of the particles during specific loading cycles are calculated to determine the relation between the movements of the particles and the changes in the macro-scale behavior of the two assemblies. The results of this study elaborate the origin of liquefaction phenomena with respect to the microstructure of the granular soils, showing the role of different mode of contacts failure in micro-scale (sliding and rolling) on the overall observed behavior of granular soils with two different relative densities, moreover the importance of strong and weak contacts in cyclic constant-volume loading of the media. It also emphasizes on the variation of structural anisotropy in undrained cyclic loading of granular media and its relationship with common soil behavior in macro-scale during liquefaction failure.     

A new thermodynamic function for phase‐splitting at constant temperature,moles, and volume

We introduce a new thermodynamic function for phase‐split computations at constant temperature, moles, and volume. The new volume function F_i introduced in this work is a natural choice under these conditions. Phase equilibrium conditions in terms of the volume functions are derived using the Helmholtz free energy. We present a numerical algorithm to investigate two‐phase equilibrium based on the fixed point iteration and Newton method. We demonstrate usefulness and powerful features of the new thermodynamic function for a number of examples in two‐phase equilibrium calculations. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Efficient and robust three‐phase split computations

The combination of successive substitution and the Newton method provides a robust and efficient algorithm to solve the nonlinear isofugacity and mass balance equations for two‐phase split computations. The two‐phase Rachford–Rice equation may sometimes introduce complexity, but the Newton and bisection methods provide a robust solution algorithm. For three‐phase split calculations, the literature shows that the computed three‐phase region is smaller than measured data indicate. We suggest that an improved solution algorithm for the three‐phase Rachford–Rice equations can address the problem. Our proposal is to use a two‐dimensional bisection method to provide good initial guesses for the Newton algorithm used to solve the three‐phase Rachford–Rice equations. In this work, we present examples of various degree of complexity to demonstrate powerful features of the combined bisection‐Newton method in three‐phase split calculations. To the best of our knowledge, the use of the bisection method in two variables has not been used to solve the three‐phase Rachford–Rice equations in the past. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Structural modeling of petroleum fractions based on mixture viscosity and Watson K factor

Two procedures have been developed for structural modeling of petroleum fractions based on mixture viscosity and Watson K factor. The representative molecules of paraffinic, naphthenic and aromatic hydrocarbons, based upon Ruzicka’s structural model, have been determined for lube-oil cut SAE 10 from Tehran oil refinery. Unlike previous methods, the newly developed procedures do not require time-consuming and costly laboratory data such as true boiling point profile. Good agreement between predictions of the new models and experimental results has been observed. Moreover, the proposed methods take less run-time than previous models due to less experimental and computational complexities. The results indicate that Ruzicka’s procedure, based on vapor pressure, is only applicable for light hydrocarbon mixtures, while the new methods can be applied for structural modeling of a wide range of petroleum fractions. Furthermore, as a result of this study, the application of a vapor pressure constraint leads to a higher degree of accuracy than the earlier suggested constraint, partial pressure, by Ruzicka.     

On the dispersion of CNTs in polyamide 6 matrix via solution methods: assessment through electrical, rheological, thermal and morphological analyses

In this study, polyamide 6 (PA 6)/multi-walled carbon nanotube (MWCNT) nanocomposites were prepared by different solution methods based on phase inversion, drop-casting and simple evaporation processes. Optical microscopy and field emission scanning electron microscopy techniques were used to investigate the dispersion states of the nanotubes in PA 6 matrix. The results indicated that the dispersion state of MWCNTs in the nanocomposites prepared by the phase inversion-based method was better than those in the nanocomposites prepared by the other two methods. Electrical, rheological, differential scanning calorimetry and thermo-gravimetric analysis measurements showed that the PA 6/MWCNTs nanocomposites prepared by the phase inversion-based method had higher electrical conductivity, storage modulus, crystallization temperature and thermal stability in comparison with those prepared by the other two methods, attributed to the better dispersion state of MWCNTs. These results confirmed achievement of a good dispersion state of MWCNTs within PA 6 matrix by the phase inversion-based efficient approach.