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.     

Critical slowing down in lead magnesium niobate–zirconate ceramic

Dielectric relaxation behaviour of (1 − x)PMN − xPZ, for x = 0.10, 0.30 and 0.40 have been studied. The nature of relaxational behaviour was found to change with PZ concentration. A crossover from a static freezing to critical slowing down like behaviour is observed with increase in Zr⁴⁺ concentration. We have used Glazounov and Tangastev criterion to distinguish freezing and critical slowing down like behaviour.     

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.     

Modelling of effects of ultrastructural morphology on the hygroelastic properties of wood fibres

Wood fibres constitute the structural framework of e.g. wood, paper, board and composites, where stiffness and dimensional stability are of importance. An analytical modelling approach has been used for prediction of hygroelastic response, and assessment of the stresses in thick-walled cylinder models of wood fibres. A wood fibre was idealised as a multilayered hollow cylinder made of orthotropic material with helical orientation. The hygroelastic response of the layered assembly due to axisymmetric loading and moisture content changes was obtained by solving the corresponding boundary value problem of elasticity. A simple solution scheme based on the state space approach and the transfer matrix method was employed. This was combined with an analytical ultrastructural homogenisation method, used to link hygroelastic properties of constituent wood polymers to properties of each layer. Predicted hygroelastic response captured experimentally measured behaviour. Fibres that were constrained not to twist showed a stiffer response than fibres allowed twisting under uniaxial loading. It was also shown that the ultrastructure, i.e. the microfibril angle, will control the hygroexpansion in the same way as it controls the compliance of the cell wall. Qualitative failure trends comparable with experimental observations could be established with stress analysis and a simple plane-stress failure criterion.     

Synthesis and characterization of morphologically different high purity gallium oxide nanopowders

High purity gallium oxide nanopowders have been synthesized by using a simple precipitation technique with calcination at elevated temperature. From the X-ray pattern, the phase purity of the synthesized powders was confirmed as β-Ga₂O_3. Elemental quantification (stoichiometry) of Ga₂O₃ was also examined from the X-ray energy dispersive analysis (EDAX). Based on the recorded Fourier Transform Infrared (FTIR) spectrum of Ga₂O_3, the IR bands due to Ga–O bond and crystal lattice vibrations have been identified in the wavenumber range 400–4,000 cm⁻¹. From the measured SEM images, it is obvious to notice that the pH value has been playing a dominant role in obtaining morphologically different gallium oxide nanopowders. Thermogravimetric analysis reveals 8.3% of weight loss when the sample was heated to the temperature of 1,100 °C from the room temperature, which also shows a crystalline phase transformation. It is very interesting to report that a broad blue emission at 455 nm has been measured from the synthesized gallium oxide nanopowders.     

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.     

Modeling of precipitation hardening in Mg-based alloys

This work deals with the development of Mg-based alloys with enhanced properties at elevated temperatures. This is achieved by precipitation of binary phases such as MgZn₂ and Mg₂Sn during the aging of these alloys. The aim of the present work is to develop and calibrate a model for precipitation hardening in Mg-based alloys, as different types of precipitates form simultaneously. The modified Langer-Schwartz approach, while taking into account nucleation, growth and coarsening of the new phase precipitations, was used for the analysis of precipitates’ evolution and precipitation hardening during aging of Mg-based alloys. Two strengthening mechanisms associated with particle-dislocation interaction (shearing and bypassing) were considered to be operating simultaneously due to particle size-distribution. Parameters of the model, R _N i and k _{σ i} , were found by fitting of calculated densities and average sizes of precipitates with ones estimated from experiments. The effective diffusion coefficients of phase formation processes, which determine the strengthening kinetics, were estimated from the hardness maximum positions on the aging curves.