Terpolymers. II. Mechanical properties and transition temperatures of terpolymers of vinyl stearate,vinyl acetate,and vinyl chloride

Vinyl stearate was studied as a major internal plasticizer in terpolymers containing vinyl acetate and vinyl chloride. The terpolymers were prepared by systematically replacing vinyl acetate by close increments of vinyl stearate starting with combinations of vinyl acetate and vinyl chloride, in increments, over all compositions. For comparison of properties, a complete range of copolymers of vinyl stearate and vinyl chloride, as well as mixtures of poly(vinyl chloride) and di-2-ethylhexyl phthalate (DOP) were also made. The external plasticizer was more efficient in reducing the glass temperature than was vinyl stearate. The decline in T_g with weight fraction of plasticizer was linear for the copolymers and terpolymers but concave downward with the liquid diluent. The linear decline was shown to involve mere additivity of the free volume contributed by each side-chain methylene (or methyl) group in both vinyl esters to reducing T_g. The mechanism of the diluent system was more complex. However, the magnitude of the reduction of tensile modulus at a given weight fraction of DOP could be equaled or exceeded by the same amount of vinyl stearate, by increasing the vinyl acetate content of the base copolymer to 40 mole-% or more. Unfortunately, the ultimate strengths and elongations of internally plasticized systems were reduced more than those of the mixtures at comparable compositions. Vinyl stearate was found to markedly retard photolytic degradation compared to both vinyl acetate and the external plasticizer in unstabilized samples having nearly the same thermal treatment. The effect was greater than could be ascribed to dilution by the long alkyl group. The production of a stearoyl radical more stable than the radicals initiating dehydrochlorination is suggested as a possible mechanism.     

Mechanical properties and transition temperatures of copolymers of N-n-alkylacrylamides and vinylidene chloride

Mechanical and solution properties, melting transitions, torsional stiffness temperatures, T_f, and selected modulus-temperature curves are presented for copolymers of the N-n-alkylacrylamides with vinylidene chloride. Copolymers were prepared at 60°C across the range of compositions, using as comonomers N-n-butyl-, octyl-, dodecyl- and oleyl-acrylamide, which have amorphous side-chains, and N-n-octadecyl acrylamide and n-octadecyl acrylate whose side-chains are crystalline. The mechanical properties reflected the effect of the decline in backbone crystallinity and the simultaneous development of strong intermolecular interactions in the amorphous stage. Copolymers were stiff or showed brittle failure across the compositional range except when intermolecular forces were reduced (with n-octadrcyl acrylate) and side-chain crystallization eliminated (with N-oleylacrylamide). These systems and the n-dodecylacrylamide copolymers had yield strengths less than brittle strengths and substantial elongations. Backbone crystallinity was eliminated at about 15 mole % amide and side-chain crystallinity vanished at less than 10 mole % of the amide in the N-n-octadecylacrylamide series. No depression in side-chain melting point occurred with dilution by segments of vinylidene chloride. Over-all decline in the flex-temperature was the normal monotonic function of composition except that values increased in magnitude at high vinylidene chloride contents, the effect presumably being caused by the presence of crystallinity. An empirical equation was developed which permitted the calculation of T_f for any N-n-alkylacrylamide composition with any number of carbon atoms in the side-chain, above 3.     

Coal liquefaction in nitrogen compounds

Model compound studies have shown that 1,2,3,4-tetrahydroquinoline is an exceptionally good coal solvent. In the pure compound, subbituminous coal conversion to THF-soluble products approaches 100% under relatively mild reaction conditions. The effectiveness of tetrahydroquinoline for coal conversion appears to be related to its concentration relative to coal. The unique behaviour of tetrahydroquinoline is ascribed to its being a highly active H-donor; the fact that it is regenerable under reaction conditions by the reaction of hydrogen and quinoline; and that its polarity allows penetration of the coal structure and aids in dispersion of the dissolved coal. It has been found that, during reaction with coal, tetrahydroquinoline and other nitrogen compounds undergo extensive condensation reactions which result in an increase in the nitrogen content of the high boiling and non-distillable liquefaction products.     

Viscometric determination of the molecular weight of polymers in the low molecular weight region

In order to overcome the difficulty of the determination of the molecular weight of a polymer in the low molecular weight region by viscometry using the Mark–Houwink–Sakurada (MHS) equation, we have proposed the Dondos–Benoit relationship [η]^?1 = A₂ + AM^?1/2, for a number of polymer–solvent systems, for which we give the numerical values of the parameters A₁ and A₂. Furthermore, we suggest a method for the determination of the above parameters using the MHS constants a and k.     

Effect of theθ-α-Al2O3 transformation on the oxidation behavior ofβ-NiAl + Zr

Isothermal oxidation of NiAl + Zr has been performed over the temperature range of 800–1200°C and studied by TGA, XRD, and SEM. A discontinuous decrease in growth rate of two orders of magnitude was observed at 1000° C due to the formation of -Al₂O₃ from -Al₂O₃. This transformation also resulted in a dramatic change in the surface morphology of the scales, as a whisker topography was changed into a weblike network of oxide ridges and radial transformation cracks. It is believed that the ridges are evidence for a shortcircuit outward aluminum diffusion growth mechanism that has been documented in a number of¹⁸O tracer studies.     

Drought Severity Assessment Based on Bivariate Probability Analysis

Conventionally drought severity is assessed based on drought indices. Recently the Reconnaissance Drought Index (RDI) was proposed to assess drought severity based on the precipitation to potential evapotranspiration ratio (P/PET). In this paper RDI is studied as a bivariate index under a set of assumptions and simplifications. The paper presents a simple computational procedure for estimating the P/PET ratio for selected reference periods varying from 3 to 12 months, for any return period of drought. Alternatively, based on this procedure, the severity of any drought episode is rationally assessed. A bivariate probability analysis is employed based on the assumption that P and PET values are normally distributed and often negatively correlated. Examples for the application of the proposed procedure are presented using data from several meteorological stations in Greece. It is shown that the assumption of normality of both P and PET holds for long periods at all examined stations.     

Components for the implementation of free-space optical crossbars

We describe an optical system developed to form the basis of a 64 × 64 free-space optical matrix-matrix crossbar switch. The design and performance of each of the main optical components is discussed: lenses, diffractive optical elements, and polarizing beamsplitters, together with the optomechanical hardware design. For these components, throughput levels of -6.9 dB have been achieved, which is compatible with full system operation at 10(-12) bit error rates at ≥270 Mbits s(-1).     

Quantile map: Simultaneous visualization of patterns in many distributions with application to tandem mass spectrometry

High-throughput experiments have become more and more prevalent in biomedical research. The resulting high-dimensional data have brought new challenges. Effective data reduction, summarization and visualization are important keys to initial exploration in data mining. In this paper, we introduce a visualization tool, namely a quantile map, to present information contained in a probabilistic distribution. We demonstrate its use as an effective visual analysis tool through the application of a tandem mass spectrometry data set. Information of quantiles of a distribution is presented in gradient colors by concentric doughnuts. The width of the doughnuts is proportional to the Fisher information of the distribution to present unbiased visualization effect. A parametric empirical Bayes (PEB) approach is shown to improve the simple maximum likelihood estimate (MLE) approach when estimating the Fisher information. In the motivating example from tandem mass spectrometry data, multiple probabilistic distributions are to be displayed in two-dimensional grids. A hierarchical clustering to reorder rows and columns and a gradient color selection from a Hue-Chroma-Luminance model, similar to that commonly applied in heatmaps of microarray analysis, are adopted to improve the visualization. Both simulations and the motivating example show superior performance of the quantile map in summarization and visualization of such high-throughput data sets.     

Infinitesimal Perturbation Analysis in Networks of Stochastic Flow Models: General Framework and Case Study of Tandem Networks with Flow Control

This paper presents a general algorithmic framework for computing the IPA derivatives of sample performance functions defined on networks of fluid queues. The underlying network-model consists of bi-layered hybrid dynamical systems with continuous-time dynamics at the lower layer and discrete-event dynamics at the upper layer. The linearized system, computed from the sample path via a discrete-event process, yields fairly simple algorithms for the IPA derivatives. As an application-example, the paper discusses loss and workload performance functions in a tandem network with congestion control, subjected to signal delays.     

A Biologically-Inspired Micro Aerial Vehicle

This paper introduces a novel framework for the design, modeling and control of a Micro Aerial Vehicle (MAV). The vehicle’s conceptual design is based on biologically-inspired principles and emulates a dragonfly (Odonata–Anisoptera). We have taken inspiration from the flight mechanism features of the dragonfly and have developed indigenous designs in creating a novel version of a Flapping Wing MAV (FWMAV). The MAV design incorporates a complex mechanical construction and a sophisticated multi-layered, hybrid, linear/non-linear controller to achieve extended flight times and improved agility compared to other rotary wing and FWMAV Vertical Take Off and Landing (VTOL) designs. The first MAV prototype will have a ballpark weight including sensor payload of around 30 g. The targeted lifting capability is about twice the weight. The MAV features state of the art sensing and instrumentation payload, which includes integrated high-power on-board processors, 6DoF inertial sensors, 3DoF compasses, GPS, embedded camera and long-range telemetry capability. A 3-layer control mechanism has been developed to harness the dynamics and attain complete navigational control of the MAV. The inner-layer is composed of a ‘quad hybrid-energy controller’ and two higher layers are at present, implementing a linear controller; the latter will be replaced eventually with a dynamic adaptive non-linear controller. The advantages of the proposed design compared to other similar ones include higher energy efficiency and extended flight endurance. The design features elastic storage and re-use of propulsion energy favoring energy conservation during flight. The design/modeling of the MAV and its kinematics & dynamics have been tested under simulation to achieve desired performance. The potential applications for such a high endurance vehicle are numerous, including air-deployable mass surveillance and reconnaissance in cluster and swarm formations. The efficacy of the design is demonstrated through a simulation environment. The dynamics are verified through simulations and a general linear controller coupled with an energy based non-linear controller is shown to operate the vehicle in a stable regime. In accordance with specified objectives a prototype is being developed for flight-testing and demonstration purposes.