LLDPE’s grown with Metallocene and Ziegler–Natta catalysts: events in the melt and FTIR analysis

LLDPE samples synthesized with Ziegler–Natta (ZN) and Metallocene (MT) catalysts have been analyzed to investigate a potential catalyst-dependent morphology and to find an explanation for the difficult processing of MT. Slow calorimetry at v = 0.02 K/min and IR at RT and in the melt are used. The differences between MT and ZN are assigned to their different composition, MT not having the linear segments, which are present in ZN. Slow calorimetry is effectively a drawing process of the melt with chain orientation followed by decay. The later event, characterized by an endotherm, ΔH _network, occurs at higher temperatures for MT, the presence of a regular distribution of methyl groups slowing down the process. The rocking, gauche, bending and stretching regions of the IR spectra are analyzed. The nascent MT has more strained bands in the rocking region. The wagging region reveals the more homogeneous environment of MT through the maximum absorbance at 1,368 cm⁻¹. Decomposition of bands is made for the rocking and wagging regions. The orthorhombic crystallinity, α_c (FTIR), measures the sum of long- and short-range orthorhombic order, the latter being obtained by α_c (FTIR)-α_c (X-rays). The values of α_c (FTIR) for MT and ZN are very similar in conditions of equilibrium. The justifications for the molecular origin of ΔH _network are presented: (i) the slow relaxation of long chains strained and oriented in the melt measured by other techniques, (ii) The correlation, for gels of a linear sample, made in different solvents, between the maximum drawability, λ_max, and ΔH _network in a slow T-ramp. The range is 80–270 for λ_max and 40–120 J/g for ΔH _network. (iii) The comparison of two traces of the same sample, between 140 °C and 270 °C, show that comparable events in the melt appear in the integrated absorbance and in the slow calorimetry signal. Analysis on thin films of the little-studied CH₂ stretching region reveals that their extinction coefficient, ε, and the shape of the bands are highly sensitive to the sample history, ε diminishing by a large factor in slowly crystallized samples. Events in the slow T-ramp, followed by a fast crystallization, on the other hand, leads to materials with standard characteristics. Slow calorimetry traces display more events (endothermic and exothermic) for MT than for ZN, a finding consistent with more flow irregularities during processing. Equilibrium conditions and better processing could be reached for MT by extending time in the melt or using higher temperatures.     

Probing the thermal decomposition process of layered double hydroxides through in situ <Superscript>57</Superscript>Fe Mössbauer and in situ X-ray diffraction experiments

The thermal decomposition properties of Mg–Fe hydrotalcites were studied through in situ ⁵⁷Fe Mössbauer spectroscopy and in situ X-ray diffraction. Abrupt changes in the quadrupolar splitting measured in the Mössbauer spectra revealed a phase transition from the starting lamellar structure to a new crystalline arrangement. By analyzing the Mössbauer parameters we show that the material is highly disordered in the 300–400 °C temperature range. This hypothesis is confirmed by the X-ray results whose diffractograms indicated the collapse of the lamellar structure and the formation of a solid solution.     

Effect of gamma irradiation on the optical properties of CR-39 polymer

The UV-Visible absorption spectra of virgin and gamma irradiated (20–800 kGy) CR-39 polymer have been deduced by using Shimadzu Double beam Double Monochromator UV-Visible Spectrophotometer (UV-2550). The existence of the peaks, their shifting and broadening as a result of gamma irradiation has been discussed. Finally the indirect and direct band gap in virgin and gamma irradiated CR-39 has been determined. The values of indirect band gap have been found to be lower than the corresponding values of direct band gap.     

Dielectric and thermal characteristics of gel grown single crystals of ytterbium tartrate trihydrate

Dielectric and thermal characteristics of gel grown single crystals of ytterbium tartrate trihydrate have been carried out. The dielectric constant has been measured as a function of frequency in the range 2 kHz–1 MHz and temperature range 30–300 °C. The dielectric constant increases with temperature, attains a peak near 215 °C, and then decreases as the temperature exceeds 215 °C. The dielectric anomaly at 215 °C is suggested to be due to phase transition brought about in the material. The dielectric behaviour of the material is correlated with the results on thermal analysis. Thermogravimetric and differential thermal analysis have been used to study the thermal characteristics of the material. The experimental results show that the material is thermally stable up to 200 °C. The decomposition process occurs in two stages until ytterbium oxide is formed at 700 °C. The non-isothermal kinetic parameters e.g., activation energy and the frequency factor have been evaluated for each stage of thermal decomposition by using the integral method, applying the Coats–Redfern approximation.     

Hydrogen adsorption studies in micro-size cobalt dots

Hydrogen desorption curves were obtained from a sample composed of a square arrangement of Co dots with average diameter of 4.4 μm, separated by a distance of 11.6 μm. A macroscopic sample of Co dots grown on a 2.5 × 2.5 cm Si substrate was made by standard lithographic techniques and used in these experiments. Thermal programmed desorption (TPD) was performed under ultra-high vacuum conditions. Hydrogen TPD curves were obtained from a 1 × 1 cm Co dots samples displaying a maximum of intensity at 425 K. Hydrogen TPD curve was also obtained from 1 cm× 1 cm samples of Co films and Co foils for comparison. The hydrogen TPD curves have decreasing intensity from the Co foils to the Co dots and finally to the Co films. This indicates that there are more sites for hydrogen adsorption on the Co dots than in the Co films. This is a surprising result because there is approximately 8.7 times less Co atoms exposed in the Co dots that in the Co film sample. A desorption energy of 27 kcal/mol was obtained for the Co dots suggesting that hydrogen is adsorbed on an hcp hollow site of the Co dot crystalline structure.     

Effects of hot-carrier stress on high performance polycrystalline silicon thin film transistor with a single perpendicular grain boundary

This paper is a report on the effect of a single perpendicular grain boundary on the hot-carrier and high current stability in high performance polycrystalline silicon (poly-Si) thin film transistors (TFTs). Under a hot carrier stress condition (Vg = Vth + 1 V, Vd = 12 V), the poly-Si TFT with a single grain boundary is superior to the poly-Si without any grain boundary because of the smaller free carriers available for electric conduction. The shift of transconductance in poly-Si TFT with a single grain boundary is less than 5% after hot carrier stress during a period of 1000 s. The shift of transconductance is about 25% in the case of the poly-Si TFTs without a grain boundary in the channel. On high current stress, the poly-Si TFT without the grain boundary is less degraded than the poly-Si TFT with the grain boundary because the concentrated electric field near the drain junction is lower.     

Temperature waves in a horizontal liquid layer cooled from above

Waves in a thermal boundary layer were obtained by numerically modeling the natural thermogravitational convection in the infinite horizontal layer of a liquid cooled from above. The waves are generated via a mechanism related to the loss of stability and periodic separation of the upper, heavier and cooler liquid layer (penetrative convection).     

Surface barrier diode based on zinc selenide with a passivating zinc oxide film

We propose a method of fabricating surface barrier diodes with overlapped metal junction, which provides for a significant decrease in the reverse currents and an increase in the breakdown voltage.