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.     

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.     

Vibrating Wire Thermometry in Superfluid 3He

We report systematic measurements of the response of a Vibrating Wire Resonator (VWR) in normal and superfluid liquid ³He. Special attention has been paid to the hydrodynamic regime of the superfluid B-phase, where the response parameters of the VWR do not follow a simple law. We show that a simple interpolation between the region where first order slip-corrections can be applied and the ballistic regime is insufficient. Measuring an empirical effective viscosity, we propose a temperature calibration method which allows the use of VWRs as a secondary thermometer at intermediate and high pressures in the temperature range 0.2 T _c < T < 50 mK.     

Repulsive Flux Pinning Force in NbTi/Nb Superconductor/Superconductor Multilayers

Flux pinning characteristics have been investigated for the Nb _x Ti_100-x /Nb(x = 65, 50 and 28) and Nb ₂₈ Ti ₇₂/Nb ₆₅ Ti ₃₅ superconductor(S)/superconductor(S^′) multilayers. The maximum of the pinning force F _{p⊥ max} perpendicular to the layer plane as a function of the structure modulation length λ has a peak in the quasi-two-dimensional region (λ～20 nm). The maximum. values of the F _{p⊥ max} versus λ curve are proportional to the difference of the GL coherence length (ξ _GL ) between the superconductive sublayers S and S^′. The results suggest that the large F _{p⊥ max} in the S/S^′ multilayer is caused by the repulsive pinning force due to Nb layers with larger ξ _GL .