Non-Isothermal crystallization of isotactic polypropylene in dotriacontane. II: Effects of dilution,cooling rate,and nucleating agent addition on growth rate

Non-isothermal crystallization growth rates of nucleated and non-nucleated isotactic polypropylene (iPP) in dotriacontane were determined experimentally by thermal optical microscopy. Adipic acid was used as the nucleating agent. The non-isothermal growth rates of the nucleated and non-nucleated systems were compared with experimentally determined isothermal growth rates. The Lauritzen and Hoffman growth rate equation, originally developed for isothermal crystallization, was modified to describe the non-isothermal growth. The modified Lauritzen-Hoffman equation was used to predict isothermal growth rates from non-isothermal crystallization for the nucleated and non-nucleated polymer-diluent mixtures. This study is the first to deal with polymer-diluent-nucleating agent systems vital to membrane production.     

Identification of new components from anal glands ofTapinoma simrothi pheonicium

In addition to 2-methyl-4-heptanone, 6-methyl-5-hepten-2-one, and iridodials, the anal gland exudate of the dolichoderine ant,Tapinoma simrothi, contains 4-heptanone and 4-hydroxy-4-methyl-2-pentanone. The secretion functions as an alarm pheromone.     

Influence of polymer molecular weight on selected thermodynamic properties of polymer/solvent systems and the application of the UNIFAC theory

The intrinsic viscosities of eleven narrow molecular weight distribution polystyrene samples ranging from number-average molecular weight 1820 to 1 292 000 have been determined in pure solvents of tetrahydrofuran and chloroform with a Ubbelohde No. 1 viscometer at 25°C. By combining the original and modified Fox-Flory viscosity treatments, respectively, with the Flory-Huggins Lattice theory, the interaction parameters were calculated. With the aid of original and modified UNIFAC methods the solvent activity, clustering function of the solvent, and the interaction parameter were computed and compared with the experimental data. It was established that the influence imposed by the polymer molecular weight on the activity of the solvent, the clustering function of solvent, and interaction parameter is insignificant. The modified UNIFAC method satisfactorily predicted the solvent activity as illustrated by previous investigators. However, both UNIFAC methods failed to predict the interaction parameter.     

Chemistry of mandibular and Dufour's gland secretions of ants in genusMyrmecocystus

Males of several species ofMyrmecocystus produce mandibular gland secretions that contain 2,4-dimethyl-2-hexenoic acid and a variety of monoterpenes that include neral, geranial, citronellol, limonene, and 2,6-dimethyl-5-hepten-1-ol. Other components identified include methyl anthranilate, octanal, octanol, octyl octanoate, and 2-hexyl-2-decenal. Methyl salicylate has been identified as a mandibular gland constituent of workers of several species in addition to mellein and monoterpenes such as cymene, limonene, and the isomers of citral. The Dufour's gland secretions of workers and females of 14 species contain typical formicine alkanes (e.g., undecane), 2-alkanols (e.g., 2-tridecanol), and 2-alkanones (e.g., 2-tridecanone). Two species in the subgenusEremnocystus produce secretions that are distinguished by the presence of significant quantities of tridecyl esters. The functions of these compounds as well as their possible chemosystematic significance in the genusMyrmecocystus are discussed.     

Recombinant human erythrocyte cytochrome b5

The gene encoding the human erythrocyte form of cytochrome b5 (97 residues in length) has been prepared by mutagenesis of an expression vector encoding lipase-solubilized bovine liver microsomal cytochrome b5 (93 residues in length) (Funk et al., 1990). Efficient expression of this gene in Escherichia coli has provided the first opportunity to obtain this protein in quantities sufficient for physical and functional characterization. Comparison of the erythrocytic cytochrome with the trypsin-solubilized bovine liver cytochrome b5 by potentiometric titration indicates that the principal electrostatic difference between the two proteins results from two additional His residues present in the human erythrocytic protein. The midpoint reduction potential of this protein determined by direct electrochemistry is -9 +/- 2 mV vs SHE at pH 7.0 (mu = 0.10 M, 25.0 degrees C), and this value varies with pH in a fashion that is consistent with the presence of a single ionizable group that changes pKa from 6.0 +/- 0.1 in the ferricytochrome to 6.3 +/- 0.1 in the ferrocytochrome with delta H degrees = -3.2 +/- 0.1 kcal/mol and delta S degrees = -11.5 +/- 0.3 eu (pH 7.0, mu = 0.10). The 1D 1H NMR spectrum of the erythrocytic ferricytochrome indicates that 90% of the protein binds heme in the "major" orientation and 10% of the protein binds heme in the "minor" orientation (pH 7.0, 25 degrees C) with delta H degrees = -2.9 +/- 0.3 kcal/mol and delta S degrees = -5.4 +/- 0.9 eu for this equilibrium.     

Ratcheting in a nonlinear viscoelastic adhesive

Uniaxial time-dependent creep and cycled stress behavior of a standard and toughened film adhesive were studied experimentally. Both adhesives exhibited progressive accumulation of strain from an applied cycled stress. Creep tests were fit to a viscoelastic power law model at three different applied stresses which showed nonlinear response in both adhesives. A third order nonlinear power law model with a permanent strain component was used to describe the creep behavior of both adhesives and to predict creep recovery and the accumulation of strain due to cycled stress. Permanent strain was observed at high stress but only up to 3% of the maximum strain. Creep recovery was under predicted by the nonlinear model, while cycled stress showed less than 3% difference for the first cycle but then over predicted the response above 1000 cycles by 4–14% at high stress. The results demonstrate the complex response observed with structural adhesives, and the need for further analytical advancements to describe their behavior.     

Modeling the microstructural changes during hot tandem rolling of AA5XXX aluminum alloys: Part I. Microstructural evolution

A comprehensive mathematical model of the hot tandem rolling process for aluminum alloys has been developed. Reflecting the complex thermomechanical and microstructural changes effected in the alloys during rolling, the model incorporated heat flow, plastic deformation, kinetics of static recrystallization, final recrystallized grain size, and texture evolution. The results of this microstructural engineering study, combining computer modeling, laboratory tests, and industrial measurements, are presented in three parts. In this Part I, laboratory measurements of static recrystallization kinetics and final recrystallized grain size are described for AA5182 and AA5052 aluminum alloys and expressed quantitatively by semiempirical equations. In Part II, laboratory measurements of the texture evolution during static recrystallization are described for each of the alloys and expressed mathematically using a modified form of the Avrami equation. Finally, Part III of this article describes the development of an overall mathematical model for an industrial aluminum hot tandem rolling process which incorporates the microstructure and texture equations developed and the model validation using industrial data. The laboratory measurements for the microstructural evolution were carried out using industrially rolled material and a state-of-the-art plane strain compression tester at Alcan International. Each sample was given a single deformation and heat treated in a salt bath at 400 °C for various lengths of time to effect different levels of recrystallization in the samples. The range of hot-working conditions used for the laboratory study was chosen to represent conditions typically seen in industrial aluminum hot tandem rolling processes, i.e., deformation temperatures of 350 °C to 500 °C, strain rates of 0.5 to 100 seconds and total strains of 0.5 to 2.0. The semiempirical equations developed indicated that both the recrystallization kinetics and the final recrystallized grain size were dependent on the deformation history of the material i.e., total strain and Zener-Hollomon parameter (Z), where and time at the recrystallization temperature.     

Epitaxially grown graphene based gas sensors for ultra sensitive NO2 detection

Epitaxially grown single layer and multi layer graphene on SiC devices were fabricated and compared for response towards NO₂. Due to electron donation from SiC, single layer graphene is n-type with a very low carrier concentration. The choice of substrate is demonstrated to enable tailoring of the electronic properties of graphene, with a SiC substrate realising simple resistive devices tuned for extremely sensitive NO₂ detection. The gas exposed uppermost layer of the multi layer device is screened from the SiC by the intermediate layers leading to a p-type nature with a higher concentration of charge carriers and therefore, a lower gas response. The single layer graphene device is thought to undergo an n-p transition upon exposure to increasing concentrations of NO₂ indicated by a change in response direction. This transition is likely to be due to the transfer of electrons to NO₂ making holes the majority carriers.     

New method for selectivity enhancement of SiC field effect gas sensors for quantification of NO x

A silicon carbide based enhancement type metal insulator field effect transistor with porous gate metallization has been investigated as a total NO _x sensor operated in a temperature cycling mode. This operating mode is quite new for gas sensors based on the field effect but promising results have been reported earlier. Based on static investigations we have developed a suitable T-cycle optimized for NO _x detection and quantification in a mixture of typical exhaust gases (CO, C₂H₄, and NH₃). Significant features describing the shape of the sensor response have been extracted and evaluated with multivariate statistics (e.g. linear discriminant analysis) allowing quantification of NO _x . Additional cleaning-cycles every 30?min improve the stability of the sensor further. With this kind of advanced signal processing the influence of sensor drift and cross sensitivity to ambient gases can be reduced effectively. Measurements have proven that different concentrations of NO _x can be detected even in a changing mixture of other typical exhaust gases under dry and humid conditions. In addition to that, unknown concentrations of NO _x can be detected based on a small set of training data. It can be concluded that the performance of GasFETs for NO _x determination can be enhanced considerably with temperature cycling and appropriate signal processing.     

Film Blowing of Layered Silicate Nanocomposites

Bubble formation and stability in the film blowing processing of in situ polymerized and melt-compounded polyamide 6-based layered silicate nanocomposites (LSNs) are correlated to their underlying rheology, structure, and crystallization behavior. The layered silicates enhance melt elasticity, induce γ -form crystallinity, and increase crystallization rates without having any significant effect on the extent of crystallinity. A bubble stability quantification method employed to assess the level of instability during the film blowing process finds the in situ polymerized LSNs to be more stable than PA6, while melt-compounded LSNs do not display such an improved processability. All of the LSN films produced by film blowing possess superior mechanical properties compared to neat nylon 6, despite their relatively rougher film surfaces.