Thermal analysis of styrene–alkyl methacrylate polymers. I. Glass transition temperatures

The glass transition temperatures (T_g's) of several polystyrenes and styrene–alkyl methacrylate copolymers and terpolymers were measured using thermomechanical analysis (TMA) and differential scanning calorimetry (DSC). The polymers studied had number-average molecular weights from 3000 to 250,000 g/mole. The results indicate that the composition dependence of the T_g's for the copolymers and terpolymers can be satisfactorily described by a general Fox equation. In general, the measured T_g's of the copolymer and terpolymer samples depend more on the steric effects of the constituent pendent groups than on their molecular weights. The chain flexibility rather than the size of the pendent group is the determining factor in the glass transition properties of the styrene polymers.     

Alarm pheromone system of leaf-footed bugLeptoglossus zonatus (Heteroptera: Coreidae)

The alarm pheromone system ofLeptoglossus zonatus (Dallas) adults was shown to be composed of hexyl acetate, hexanol, hexanal, and hexanoic acid. Single components tested in the field elicited dispersive behavior of over 70% of adults. 2-(E)-Hexenal, found in the secretion of nymphs, but not in the exudates of adults, was also active against adults. In addition, first-instar nymphs responded to the four components of the alarm pheromone of adults as well as to 2-(E)-hexenal, a component of their own alarm pheromone system. Adults and nymphs possess different alarm pheromone systems, which are not specific to their own life stage. That hemipteran alarm pheromone systems are not species-specific was supported by the fact that both adult and nymphL. zonatus responded to butanoic acid, an alarm pheromone of Alydidae, which was not found in this Coreidae species.     

X-ray crystal structure of the dye 2-cyano-4-bromo-4′-N,N-diethylaminoazobenzene

The crystal structure and molecular conformation of 2-cyano-4-bromo-4′-N,N-diethylaminoazobenzene (C₁₇H₁₇N₄Br, mol. wt. = 357·2 a.m.u) has been determined from X-ray diffraction data; triclinic, P$\text{1}$ (No. 2), a = 10·132(11) Å, b = 12·216(16) Å, c = 6·966(11) Å, α = 104·21(9)°, β = 92·67(12)°, γ = 97·22(7)°, V = 826·5(9) ų, Z = 2, D_c = 1·436 g cm^?3, F(000) = 378, λ(MoKα) = 0·71069 Å, μ(MoKα) = 26·0 cm^?1. The structure was solved by the multiple solution direct method and refined by full-matrix least-squares to R = 0·059 for 1538 independent observed reflections. The azobenzene skeleton is planar to within 0·06 Å. Most significant bonding data are: NN, 1·290(8) Å; BrC, 1·866(6) Å; mean CN (azo) 1·380(8) Å; NNC, 113·6(4) and 115·3(4)°; NCC (cis relative to NN) 125·9(4)° and 126·7(4)°; NCC (trans) 116·8°(5)° and 116·1(4)°.     

Caving performance through the integration of microseismic activity and numerical modeling at DOZ-PT Freeport, Indonesia

This article describes an undergoing research at PT Freeport,Indonesia,in which the main goal is to use the microseismic information recorded as a result of mining to analyze cave propagation and stress performance on the actual production and fixed in-frastructure.At the moment,several numerical experiments have been conducted to correlate the mining activity with the microseis-mic events using the data collected during year 2005 and 2006.As a result of the preliminary analysis a micro-and a macrocracking envelop were proposed on the basis of computation of stress behavior at the location of the events.Stresses have been computed us-ing standard elastic continuous boundary element models.The correlation between the average source radius and the stress perform-ance has provided a method to propose a macrocracking criterion.Several techniques have been tested to nucleate the microseismic activity around different geological features.This last attempt was aimed to look at potential overstresses induced over the undercut and extraction level drifts.A method was devised to integrate the microseismicity into a 3-dimensional ride distribution model.This model has shown to be very effective to quantify the overstress induced as a result of computing volumetric microseismieity density.The volumetric microseismic model showed to induce overstress up to 10 MPa over a period of two months.The future work will concentrate on the calibration of the integrated model with actual damage observations made at the current mining infrastructure.     

Effect of HTPB structure on prepolymer characteristics and on mechanical properties of polybutadiene-based polyurethanes

Oligobutadiene-based prepolymers and polyurethanes (PU) were prepared from hydroxyl terminated polybutadiene (HTPB), three diisocyanates (aromatic, alicyclic and aliphatic) and two chain extenders (containing hydroxyl or amino groups). The free NCO content in the prepolymers varied systematically and the characteristic of these products were interpreted in terms of NCO group reactivity, propagation reactions and HTPB functionality. The mechanical properties of the polyurethane elastomers derived from the prepolymers were discussed in terms of hard and soft segment structures.     

An NMR study of the dissociation of N,N′-(2-propyloximino)-4,4′-methylenebis(phenylcarbamate) and its crosslinking of polymers containing labile hydrogens. II

Nuclear magnetic resonance spectroscopy has been used to study the dissociation and reaction of N,N′-(2-propyloximino)-4,4′-methylenebis(phenylcarbamate), as a crosslinking agent for polymers containing labile hydrogens. The crosslinking of poly(acrylic acid), polyacrylamide, and poly(vinyl alcohol) was found to result upon heating each to 150°C for 10 min with this component at 2–10 wt %.     

ABSORPTION AND DESORPTION TO AND FROM LIQUID FILMS ON INCLINED PLANES

Two published theoretical models are examined and applied to experimental results for absorption and desorption. The system used was CO₂/H₂O and studies were made for liquid film flow down inclined planes. Experimental results give “Reduced” values of mass ransfer rates.

Interferometric studies give interfacial concentration, penetration and film depths, and take-up of carbon dioxide. In the case of desorption the interferograms are distorted by “deflections.”

All the experimental values for absorption and desorption differ from those calculated from theoretical models.

Desorption is not a mirror image of absorption, and it is approximately 75% of the transfer rate of absorption over a wide operating range.

A comparison is made of the behaviour of static pools and flowing liquid films.     

Fabrication of hybrid proton-exchange membranes using a brandnew high temperature ionic liquid as charge transporting and clay modifier

The search for more compatibility between ionic liquids (ILs) and polymer matrices in proton-exchange membrane fuel cells (PEMFCs) is one of the ways in which IL leaking from proton-exchange membranes could be minimized. In this work, it is presented the synthesis of an aromatic high temperature ionic liquid (HTIL), which, incorporated into an aromatic matrix such as sulfonated polyether ether ketone (sPEEK), is expected to diminish the IL leaking that normally affects PEMFC. Phenylethylammonium trifluoromethane sulfonate (PhetaTfO) was successfully synthesized and characterized. Its melting point of 88°C makes it to classify as a HTIL and it was employed as modifier of natural Montmorillonite, forming the phenylethylammonium intercalated montmorillonite (MmtPheta) and thus, ternary membranes containing PhetaTfO, MmtPheta, and sPEEK were prepared and characterized. Immersion tests demonstrated a higher compatibility of PhetaTfO with matrix when compared to the reference DemaTfO, which was reflected in up to 30% lower IL loss by the synthesized IL than the DemaTfO; X-rays diffraction (XRD) patterns demonstrated that the modified clay was properly dispersed inside the membranes, while dynamic mechanical analyses (DMA) results indicated a strong plasticizer effect along the increase of PhetaTfO content inside the membrane, while at the same time, the conductivity increased in an exponential manner, which permitted to identify an empiric exponential equation to evaluate the effect of concentration on ionic conductivity. The maximum conductivity obtained at IL concentrations of around 38 wt% was 0.2 mS/cm. It could expect high ionic conductivities of 10 mS/cm when the concentration of this IL is 60%; nevertheless, in order to achieve that, crosslinking treatments should be done to give the membranes enough mechanical resistance.     

Spatial navigation model based on chaotic attractor networks

We present a model of spatial navigation based on the non-convergent dynamics of brain activity. The system includes a hippocampal module that processes global spatial information and a cortical module that deals with local sensory information. We test the model using several spatial navigation paradigms: goal finding, shortcutting and detouring. Computer simulations show that the performance of the agent qualitatively matches that of animals and related models. This new approach provides a novel interpretation of how the brain accomplishes spatial navigation.