Study of the compositional heterogeneity of ethylene/1–hexene copolymers produced over supported catalysts of different composition

Separation into narrow MWD fractions (liquid–liquid fractionation) and preparative TREF (temperature rising elution fractionation) with subsequent analysis of fractions by GPC, FTIR, and ¹³C NMR spectroscopy were used to study the comonomer distribution of ethylene/1–hexene copolymers produced over highly active supported titanium‐ and vanadium‐magnesium catalysts (TMC and VMC) and a supported zirconocene catalyst. These catalysts produce PE with different MWD: M_w/M_n values vary from 2.9 for zirconocene catalyst, 4.0 for TMC, and 15 for VMC. 1‐Hexene increases polydispersity to 25 for copolymer produced over VMC and hardly affects MWD of the copolymer produced over TMC and zirconocene catalysts. The most broad short chain branching distribution (SCBD) was found for ethylene/1–hexene copolymers produced over TMC. VMC and supported zirconocene catalyst produce copolymers with uniform profile of SCB content vs. molecular weight in spite of great differences in M_w/M_n values (22 and 2.5 respectively). TREF data showed that majority of copolymer produced over supported zirconocene catalyst was eluted at 70–90°C (about 85 wt %). In the case of VMC copolymer's fractions were eluted in the broad temperature interval (40–100°C). Accordingly, TREF data indicate a more homogeneous SCBD in copolymer, produced over supported zirconocene catalyst. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Copolymerization of ethylene with α-olefins over supported titanium–magnesium catalysts. II. Comonomer as a chain transfer agent

The data on the effect of comonomer (propylene and 1-hexene) on molecular weight (M_w), molecular weight distribution (MWD), and content of terminal double bonds were obtained for ethylene/α-olefin copolymers produced over a supported titanium–magnesium catalyst (TMC) upon polymerization in the absence of hydrogen. The experimental data on the effect of comonomer concentration on M_w of polymers were used to calculate the ratios between the effective rate constants of chain transfer with monomer and the propagation rate constant. It was shown that the effective rate constant of chain transfer with monomers increases in the row of monomers: ethylene < 1-hexene < propylene. Meanwhile, the data on the effect of copolymers on content of terminal double bonds of various types demonstrate that different reactions of chain transfer with comonomer may simultaneously occur during copolymerization. It results in simultaneous formation of terminal vinylidene and trans-vinylene bonds. Therefore, the calculated rate constants of chain transfer with comonomer are complex values, which include the rate constants of chain transfer with comonomer occurring via different mechanisms. The data on MWD, short chain branching (SCB) and terminal double bonds content of different types were obtained by molecular weight fractionation of copolymers followed by the analysis of narrow fractions. The analysis of the data on MWDs of SCB and terminal double bonds shows that active sites of the TMC are considerably heterogeneous with respect to the rates of different chain transfer reactions with monomers. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Lateralization of amygdala activation in fMRI may depend on phase-encoding polarity

Object

Susceptibility artifacts along the phase-encoding (PE) direction impact the activation pattern in the amygdala and may lead to systematic asymmetries. We implemented a triple-echo echo-planar imaging (EPI) sequence, acquiring opposite PE polarities along left?Cright PE direction in a single shot, to investigate its effects on amygdala lateralization.

Materials and Methods

Twelve subjects viewed emotional faces to evoke amygdala activation.

Results and Conclusion

A region of interest analysis revealed that the lateralization of amygdala responses depended on the PE polarity thus representing a pure method artifact. Alternating PE with multi-echo EPI reduced the artifact. Lateralized fMRI activation in areas with magnetic field inhomogeneities need to be interpreted with caution.     

Virtual active touch using randomly patterned intracortical microstimulation

Intracortical microstimulation (ICMS) has promise as a means for delivering somatosensory feedback in neuroprosthetic systems. Various tactile sensations could be encoded by temporal, spatial, or spatiotemporal patterns of ICMS. However, the applicability of temporal patterns of ICMS to artificial tactile sensation during active exploration is unknown, as is the minimum discriminable difference between temporally modulated ICMS patterns. We trained rhesus monkeys in an active exploration task in which they discriminated periodic pulse-trains of ICMS (200 Hz bursts at a 10 Hz secondary frequency) from pulse trains with the same average pulse rate, but distorted periodicity (200 Hz bursts at a variable instantaneous secondary frequency). The statistics of the aperiodic pulse trains were drawn from a gamma distribution with mean inter-burst intervals equal to those of the periodic pulse trains. The monkeys distinguished periodic pulse trains from aperiodic pulse trains with coefficients of variation 0.25 or greater. Reconstruction of movement kinematics, extracted from the activity of neuronal populations recorded in the sensorimotor cortex concurrent with the delivery of ICMS feedback, improved when the recording intervals affected by ICMS artifacts were removed from analysis. These results add to the growing evidence that temporally patterned ICMS can be used to simulate a tactile sense for neuroprosthetic devices.     

Optical monitoring of technological parameters during molecular-beam epitaxy

It is shown that one can use low-coherence tandem interferometry to measure the substrate temperature during the course of molecular-beam epitaxy in the case of oblique incidence of the probing light onto the surface. The temperature conditions in the Ob??-M installation for growing heteroepitaxial structures of cadmium and mercury tellurides and in the RIBER SIVA-21 installation for the growth of silicon-germanium structures are investigated. Calibration curves relating the readings of the standard thermocouple fixed within the heater to the true substrate temperature in the range 0?C500°C are created.     

Magnetoabsorption in narrow-gap HgCdTe epitaxial layers in the terahertz range

The magnetoabsorption and photoconductivity spectra are investigated in the terahertz (THz) range at a temperature of T = 4.2 K for n-Hg_{1 ? x} Cd _x Te bulk epitaxial layers of various compositions (both semiconductor and semimetallic) grown by molecular-beam epitaxy. Within the framework of the Kane 8 · 8 model, the electron and hole Landau levels are calculated. It is shown that, in contrast to the results of previous investigations, all observed resonance lines are related to transitions between the Landau levels of free carriers (the cyclotron resonance in the conduction band and the transitions between heavy-hole and electron Landau levels), which is evidence of the high purity and structural perfection of the samples. The possibility of using zero-gap Hg_{1 ? x} Cd _x Te solid solutions as THz photodetectors tunable by magnetic field is shown.     

Analysis of the frequency characteristics of the spin-injection emitter in the terahertz range using a diffraction grating

A method for the measurement and identification of the radiation frequencies of the spin-injection oscillator in the terahertz frequency range using a diffraction grating is developed and experimentally implemented. For the system consisting of a ferromagnetic rod (Fe) and nanosized ferromagnetic film (Fe₃O₄ with a thickness of up to 100 nm), the thermal and dynamic components of the radiation that is induced by the current flow are separated. The diffraction peaks at a frequency of about 9.6 THz and a band of 37% at a level of 3 dB and at a frequency of 43.5 THz are demonstrated. It is shown that the intensity of each signal is significantly higher than the thermal background level.     

Thieno[3,2‐b]thiophene‐diketopyrrolopyrrole Containing Polymers for Inverted Solar Cells Devices with High Short Circuit Currents

The synthesis and characterization four diketopyrrolopyrrole containing conjugated polymers for use in organic photovoltaics is presented. Excellent energy level control is demonstrated through heteroatomic substitution whilst maintaining similar solid state properties as shown by X‐ray diffraction and atomic force microscopy. Inverted solar cells were fabricated with the best devices having short circuit currents exceeding 16 mA cm^?2 and efficiencies of over 5% irrespective of whether [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PC₆₀BM) or [6,6]‐phenyl‐C₇₁‐butyric acid methyl ester (PC₇₀BM) is used. Transient absorption spectroscopy on the bulk heterojunction blends shows efficient charge photo‐generation, with the variations in short circuit current correlated to the energetic offset between polymer and fullerene.     

Study on polybenzoxazinone membrane in pervaporation processes

Poly(benz‐3,1‐oxazinone‐4) was prepared by thermal cyclization of its hydrolytically stable precursor polyamic acid. Both polymer and its precursor were investigated as membrane materials. Thermogravimetric analysis and contact angle measurements were carried out for characterization of peculiarity of membrane compositions and analysis of membrane surface. Pervaporation of water–isopropanol mixture was studied in the wide range of feed composition. To interpret the pervaporation transport properties of the membranes, swelling experiments were performed, kinetic curves of sorption and desorption were plotted, and basic sorption and diffusion parameters were analyzed. It was established that poly(benz‐3,1‐oxazinone‐4) membrane is extremely effective in dehydration of water–isopropanol mixture and shows high separation factor. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4024–4031, 2013     

Self-propelled automatic chassis of Lunokhod-1: History of creation in episodes

This report reviews the most important episodes in the history of designing the self-propelled automatic chassis of the first mobile extraterrestrial vehicle in the world, Lunokhod-1. The review considers the issues in designing moon rovers, their essential features, and the particular construction properties of their systems, mechanisms, units, and assemblies. It presents the results of exploiting the chassis of Lunokhod-1 and Lunokhod-2. Analysis of the approaches utilized and engineering solutions reveals their value as well as the consequences of certain defects.