Aromatic polyesters containing pendent 4-(phenylsulfonyl)phenyl groups: synthesis and characterization

A new bisphenol, 1,1-bis-[(4-hydroxyphenyl)-1-(4-phenylsulfonyl)phenyl)]ethane (DPSBP) was synthesized starting from diphenylsulfide and was characterized by spectroscopic methods. DPSBP was polycondensed with isophthalic acid chloride (IPC), terephthalic acid chloride (TPC) and a mixture of IPC and TPC (50:50 mol%) by phase-transfer catalysed interfacial polymerization method to obtain aromatic polyesters containing pendent 4-(phenylsulfonyl)phenyl groups. A series of copolyesters was also obtained by polycondensation of varying molar proportions of DPSBP and bisphenol-A (BPA) with TPC. (Co)polyesters exhibited inherent viscosities in the range 0.56–1.57 dLg^?1 and number average molecular weights (Mn) were in the range 28,650–80,230 g/mol. Polyesters dissolved readily in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran and aprotic polar solvents such as N-methylpyrrolidone, and N,N-dimethylacetamide. Tough, transparent and flexible films of polyesters could be cast from their chloroform solutions. X-Ray diffraction studies indicated amorphous nature of aromatic polyesters. Polyesters showed T_g values in the range 223–257 °C while T₁₀ values were in the range of 469–484 °C indicating their excellent thermal stability.     

Composition effects of thermal barrier coating ceramics on their interaction with molten Ca–Mg–Al–silicate (CMAS) glass

Systematic studies have been performed to investigate the composition effects of ZrO₂-based thermal barrier coating (TBC) ceramics on their interactions with molten Ca–Mg–Al–silicate (CMAS) glass. Porous ceramic pellets (～15% porosity), instead of actual TBCs, are used in these model studies, where the penetration of molten CMAS into the pellets is investigated. This study involves a total of six compositions of ZrO₂-based ceramics: two containing low solute (Y³⁺ or Gd³⁺) concentration, three with high concentration of solute (Y³⁺, Gd³⁺ or Yb³⁺), and one containing a combined intermediate concentration of Y³⁺+Al³⁺+Ti⁴⁺ solutes. While both the type of the solute and its concentration in the ZrO₂-based TBC ceramics have been found to influence the extent of molten CMAS penetration into the pellets, the solute concentration has the most dramatic effect. In particular, molten CMAS penetration is almost completely suppressed in porous TBC ceramic pellets containing a high concentration of Y³⁺ solute (Y₂Zr₂O₇). Possible mechanisms governing these effects are presented, together with a discussion of guidelines for the chemical design of CMAS-resistant zirconate TBC ceramics. Generally, for a TBC ceramic to be highly effective against CMAS attack it must interact vigorously with the molten CMAS, which must result in the rapid crystallization of the refractory oxide phase(s) that form a sealing layer, arresting further penetration of the molten CMAS. The porous ceramic pellets approach used here could be developed into rapid-screening methodologies for the discovery of CMAS-resistant TBC ceramic compositions, and to study the effect of composition of CMAS glasses on their interactions with TBC ceramics of specific compositions.     

Evaluation of stamping lubricants at various temperature levels using the ironing test

Lubricants are employed in stamping operations in order to (a) improve the material flow into the die cavity, (b) reduce wear and galling in the die and (c) obtain good surface finish of the part. Process conditions such as high temperatures and pressures could cause the lubricant to fail, thus resulting in galling or tearing of the part, damage to the tooling, and lost production. Therefore, selection of an appropriate lubricant based on the process conditions is important in the stamping industry. Several benchmark tests emulating stamping operations have been developed and are used to evaluate the performance of candidate lubricants. The major drawback of most of these tests is their inability to emulate high contact pressures and sliding velocities, which are crucial parameters for lubricity, especially in the case of high-speed progressive or transfer die operations involving ironing. Moreover, most of these tests are conducted at room temperature, while in reality; the process temperature can reach as high as 200 °C. The ironing tribotest developed at the Engineering Research Center for Net Shape Manufacturing (ERC/NSM) induces high contact pressures and temperatures, thus emulating the conditions in a production environment. Application of the test to screen candidate lubricants for stamping operations involving the ironing process is discussed in this paper.     

Partitioning,solubility and solubilization of limonene into water or short-chain phosphatidylcholine solutions

Using headspace solid-phase microextraction (HS–SPME), equilibrium distributions could be determined for hydrophobic solutes in closed systems containing vapor and aqueous solution, either in the absence or presence of two short-chain phospholipids, dihexanoyl-phosphatidylcholine (diC₆PC) and diheptanoyl-phosphatidylcholine (diC₇PC). Without phospholipid, HS–SPME with short extraction times was used to measure water–vapor partition coefficients for d-limonene at five temperatures within 15–40°C, with results in good agreement with existing literature. The temperature dependence of yielded the enthalpy of volatilization 34.5 kJ/mol for limonene. At 25°C, solubility values for d-limonene, 1-octanol, and n-decane were obtained using similar measurements above aqueous solutions of various solute concentrations. Short-time HS–SPME extraction of limonene in closed vials containing diC₆PC or diC₇PC micelles was also used to evaluate distributions of solute between vapor, aqueous dissolution, and micelles, for various surfactant concentrations at 15–40°C. Resulting vapor phase concentrations were analyzed using a mass balance and measured values, to obtain micelle–water partition coefficients and critical micelle concentrations. in diC₆PC solutions (1–2 mM⁻¹) weakly increased with temperature, but decreased significantly with increased temperature for diC₇PC micelles (2–4 mM⁻¹). Solubilization in short-chain PC micelles has previously received little attention, and our results show that the extent of partitioning into these diacyl (i.e., two-tailed) lipids is comparable to that for single-tailed anionic or nonionic surfactants.     

Particle Size Effect on the Packaging Performance of YAG:Ce Phosphors in White LEDs

The synthesis of cerium-doped yttrium aluminum garnet (YAG:Ce) phosphor of different sizes with uniform size distribution was carried out using solid-state reaction followed by grinding and sieving method. The effect of particle size distribution of YAG:Ce phosphors on the photoluminescence (PL) properties was investigated. The results demonstrate that the uniform size distribution and particle size affects the packaging performance in white light emitting diode (LED) applications. The YAG:Ce phosphors with different particle sizes were packaged in white LEDs using different amounts of each phosphors in order to get similar efficiency as that of commercially available YAG:Ce phosphors. It was observed that minimum amount of phosphor material is required for smaller particle size for getting the similar efficiency as that exhibited by commercially available YAG:Ce phosphors. The results are particularly interesting in view of reducing the cost of current LEDs by lowering the amount of phosphors without compromising the efficiencies of final LED package. A systematic study of YAG:Ce phosphors on the packing performance in white LEDs is reported.     

Recyclable Amberlyst-70 as a Catalyst for Biginelli Reaction: An Efficient One-Pot Green Protocol for the Synthesis of 3,4-Dihydropyrimidin-2(1H)-ones

An environmentally benign aqueous protocol for the synthesis of 3,4-dihydropyrimidin-2(1H)-ones using Amberlyst-70 as a recyclable catalyst has been developed. The use of resinous, nontoxic, thermally stable and inexpensive Amberlyst-70, as a recyclable heterogeneous catalyst, makes the process simple with negligible chemical waste. Thus renders this method an environmentally acceptable synthetic tool for Biginelli reaction.     

Estimation of critical stability parameters by asymptotic analysis in multilayer extrusion

In industrial coextrusion operations, multiple layers are frequently brought in contact with each other at different temperatures to “match” viscosities and to reduce interfacial instability. Here, a linear stability analysis of multilayer plane Poiseuille flow is carried out for real, specific polymer melts in terms of process parameters, such as temperatures and flow rates. However, heat transfer across the layers is neglected as a first approximation. Previously, it was observed that below a certain Reynolds number and above a certain relaxation time, the flow-rate ratio (or the depth ratio), above which the flow is stable to all wavelengths, can be estimated by the long-wavelength asymptotic analysis (1,3). The Reynolds numbers for the industrial flows are smaller, and the relaxation times are larger than the corresponding critical values by several orders of magnitude. Therefore, the critical stability parameters can be estimated in the present study for industrial cases using the asymptotic stability analysis at long wavelengths. Although a large number of earlier parametric studies of model fluids indicate the influence of various theological parameters, only the viscosity stratification plays an important role in the interfacial instability within the operating range of industrial coextrusion processes.     

Environmental-barrier coating ceramics for resistance against attack by molten calcia-magnesia-aluminosilicate (CMAS) glass: Part I,YAlO3 and γ-Y2Si2O7

The high-temperature (1500?°C) interactions of two promising dense, polycrystalline EBC ceramics, YAlO₃ (YAP) and γ-Y₂Si₂O₇, with a calcia-magnesia-aluminosilicate (CMAS) glass have been explored as part of a model study. Despite the fact that the optical basicities of both the EBC ceramics and the CMAS are similar, they both react with the CMAS. In the case of the Si-free YAlO₃, the reaction zone is small and it comprises three regions of reaction-crystallization products, including Y-Ca-Si apatite solid-solution (ss) and Y₃Al₅O₁₂ (YAG)(ss). In contrast, only Y-Ca-Si apatite(ss) forms in the case of Si-containing γ-Y₂Si₂O₇, and the reaction zone is an order-of-magnitude thicker. These CMAS interactions are analyzed in detail, and are found to be strikingly different than those observed in Y-free EBC ceramics (β-Yb₂Si₂O₇ and β-Sc₂Si₂O₇) in the accompanying Part II paper. This is attributed to the presence of the Y in the YAlO₃ and γ-Y₂Si₂O₇ EBC ceramics.     

Analyzing collective behavior from blogs using swarm intelligence

With the rapid growth of the availability and popularity of interpersonal and behavior-rich resources such as blogs and other social media avenues, emerging opportunities and challenges arise as people now can, and do, actively use computational intelligence to seek out and understand the opinions of others. The study of collective behavior of individuals has implications to business intelligence, predictive analytics, customer relationship management, and examining online collective action as manifested by various flash mobs, the Arab Spring (2011) and other such events. In this article, we introduce a nature-inspired theory to model collective behavior from the observed data on blogs using swarm intelligence, where the goal is to accurately model and predict the future behavior of a large population after observing their interactions during a training phase. Specifically, an ant colony optimization model is trained with behavioral trend from the blog data and is tested over real-world blogs. Promising results were obtained in trend prediction using ant colony based pheromone classier and CHI statistical measure. We provide empirical guidelines for selecting suitable parameters for the model, conclude with interesting observations, and envision future research directions.