Structure of trans-1,4-polybutadiene synthesized with a new catalyst system

Abstract

The structure, phase composition, and temperature behavior of two trans-1,4-polybutadienes (TPBs) were studied by means of x-ray scattering and differential scanning calorimetry (DSC) techniques. The two samples examined were (1) PB synthesized using an immobilized titanium-magnesium catalyst and (2) a random copolymer based on PB prepared with a homogeneous vanadium-containing catalyst used as a reference material. It was found that the nascent structure of the first PB involves three phases: crystalline, mesomorphic (low-temperature form), and amorphous. In the vicinity of 65°C, a first-order phase transition occurs. The system becomes biphasic and contains the high-temperature form of the mesophase, as well as the amorphous phase, component. Above 165°C, the polymer melts to form a single-phase isotropic melt with a structure typical of liquids. The lateral dimension of crystallites reversibly changes at the crystal-mesophase transition. It is suggested that during annealing of the mesophase formed by cooling of the isotropic melt, the chains acquire an extended conformation. Loss of regularity of the structure of macromolecules of TPB causes a reduction of phase transition temperatures, an increase of the imperfection of the crystalline phase, and a contraction of the temperature range of existence of the mesophase.     

Data for scaling-up hydrothermal waste water treatment process

Abstract

Hydrothermal oxidation of wastes is developed as an alternative technique in order to limit the toxic end-product formation, the waste volume and the energy supply. We are now working on the transfer of this technology, and so on the determination of data for scaling-up the hydrothermal oxidation process. The main data concern the knowledge of reactive pathway, the determination of reaction kinetic and thermal parameter. Kinetic and thermal data have been determined for the hydrothermal oxidation of acetic acid as well as the reactive pathway of hydrothermal oxidation of a C, H, O, N compound, the fenuron (C₆H₅-NH-CO-N(CH₃)₂).     

High pressure: a tool to improve the enzymatic production of glycosides

Naringinase, an enzyme complex that expresses α -l-rhamnosidase and β -d-glucosidase activities in native state, can be used to deglycosylate natural glycosides. The selective inactivation of one of these activities will allow the biosynthesis of different bioactive compounds in a simple, effective and cheap way. In this work, pressure and temperature were the tools used to selectively inactivate the activities expressed by naringinase. The main goal was the identification of pressure–temperature conditions to acquire conditions for the maximization of enzymatic hydrolysis of substrates with different numbers of glycosidic residues. α -l-Rhamnosidase was 32-fold more resistant against inactivation at 250 MPa than at atmospheric pressure. The best pressure condition to reduce β -d-glucosidase inactivation at 75°C was 173 MPa, while in the case of α -l-rhamnosidase inactivation at 85°C, it was above 250 MPa. Moreover, a selective inactivation of β -d-glucosidase activity of naringinase was attained, allowing an easy and cheap method with which to produce prunin and other expensive glycosides. The present work highlights the effect of high pressure on enzyme protection against thermal inactivation, demonstrating its potential as a powerful tool in biosynthesis.     

High pressure neutron-scattering experiments on phospholipid model biomembranes

Abstract

By use of neutron small-angle scattering (SANS) the structural properties of saturated and unsaturated phosphatidylcholine model biomembrane systems have been investigated in the temperature range from 0°C to 70°C and at pressures up to 3.5 kbar. The effect of chemical constitution of the hydrocarbon chains of the lipids and the effect of cholesterol on the thermotropic and barotropic phase behaviour is discussed.     

Interaction of food packaging material and selected food components under high pressure

Abstract

Interactions between ethanolic solutions of p-cymene and acetophenone and different polymer packaging materials. were studied at 500 MPa and 25° C. p-Cymene solution, filled into low-density polyethylene bags, lost 30% of its aroma concentration after 24 h at 500 MPa compared to a 60% loss at atmospheric pressure. The decrease was strongest within the first 15 min. Using LDPE/HDPE/LDPE bags, losses were 20% and 30%, resp. Applying the “bag in the bag” method, p-cymene concentrations measured inside and outside the inner bag has shown sorption by the pressurized film to be one third of that by the non-pressurized. In PET/AI/LDPE bags impermeable to p-cymene, sorption was confined to the inner LDPE layer and caused higher loss in the non-pressurized sample. Acetophenone has not been found to interact with the polymer during pressure treatment, while at atmospheric pressure sorption loss in aroma concentration was nearly 70% after 60 h.     

Schnell-Methode zur Umsetzung von Kohlenwasserstoffen zu Wasserstoff für die Isotopenanalyse

Es wird eine weiterentwickeltes, isotopenanalytisches Verfahren zur probenchemischen Umsetzung von Kohlenwasserstoffen mit Chromium zu Wasserstoff bei 1300 K vorgestellt. Die erzielten Testergebnisse zeigen anhand der gemessenen δD-Werte, daβ Quarzöfen bei diesen Temperaturen noch keine die Isotopenmeβwerte beeinflussende Diffusion von Wasserstoff durch die Wandung zulassen. Auβerdem erfolgte die Reaktion nahezu spontan und vollständig, was die Methode zeitlich sehr effektiv macht.

A modified isotope analytical method is presented for the chemical reaction of hydrocarbons with chromium at 1300 K to form hydrogen. The test results obtained (i.e. the measured δD-values) show that at this temperature quartz heating tubes do not allow hydrogen to diffuse through the wail, which fact would influence the isotopic composition. Furthermore the reaction proceeds nearly spontaneously and quantitatively, which yields an effective method, especially with respect to time.     

Thermoluminescence characterization of the irradiated minerals extracted from nopal

The mineral fraction from dehydrated nopal leaves (Opuntia ficus indica) belonging to the Cactaceae family was extracted and selected by sizes of 10 and 74 μm and exposed to ⁶⁰Co gamma radiation at different doses in the range 70 Gy–20 kGy. The glow-curves from these polyminerals show a thermoluminescence (TL) band with one very intense peak at a temperature around 150 °C and a second one emerging in the high temperature region, moving in a large zone of temperature values according to the preparation used and the level of irradiation. The XRD analysis shows a composition of both biominerals as whewellite and weddellite and a mineral fraction as anorthoclase and quartz. The main TL characteristics of the polymineral content of the nopal was analyzed, i.e. the TL response at different doses and fading during storage at room temperature. The activation energy of the traps responsible for the TL emission was also investigated and a possible continuous distribution of traps is discussed. A review of the scientific literature shows that this is the first time that a TL study on nopal ionized by irradiation has been carried out.     

A mathematical model of hotspot condensed phase ignition in the presence of a competitive endothermic reaction

We consider the propagation of a combustion front resulting from the gasless combustion of a condensed state fuel. The propagation of the front, essentially a premixed laminar flame, is supported by an exothermic reaction subject to possible heat loss through a competitive endothermic reaction. The dynamics of the endothermic process inducing the heat loss strongly depend on the temperature and the local fuel concentration. Through an analysis based on high activation energy, the steady-state values of the final burnt temperature as well as the burning velocity are obtained, and the control parameters are identified. Using a linear perturbation method, we assess the stability of the propagating front and obtain a condition for oscillatory behaviour. The critical parameter values for the transition from steady to oscillatory burning speeds are identified. The results represent a generalization of those obtained by Matkowsky and Sivashinsky to include the effects of heat loss induced by a competitive endothermic reaction.     

High pressure infiltration sintering behavior of WC-Co alloys

In this paper, two average tungsten carbide particle sizes of 2, 0.5?μm are placed respectively, in contact with a WC-16Co substrate, pressed at the pressure of 4.5–5.5?GPa, and heated to temperatures ranging from 1350°C to 1500°C in a large-volume cubic press. During the process Co was forced out of the WC-16Co substrate into the compressed powder. The resulting infiltrated samples were characterized using X-ray diffraction (XRD), scanning electron microscope (SEM), Vickers hardness and cutting performance tests. The results of XRD confirmed that the sintered bulks have WC and Co phases. The scanning electron microscopy (SEM) analysis reveals that the WC grains in well-sintered alloys are round in shape and cobalt with lower content is uniformly dispersed in the WC grain boundaries. The sintered sub-micron WC-Co alloy with a cobalt content of 3.8?wt% exhibits a prominent combination of high hardness value of 23.1?GPa and a large fracture toughness value of 8.6?MPa?m^½. The high-speed cutting tests indicating its cutting performance is significantly superior to the commercial YG6X (WC-6?wt%Co with WC grain size of 0.5?μm).     

Phonon frequency shift and effect of correlation on the electron-phonon interaction in heavy fermion systems

The electron-phonon interaction in the periodic Anderson model (PAM) is considered. The PAM incorporates the effect of onsite Coulomb interaction (U) between f-electrons. The influence of Coulomb correlation U on the phonon response of the system is studied by evaluating the phonon spectral function for various parameters of the model. The numerical evaluation of the spectral function is carried out in the long wavelength limit at finite temperatures keeping only linear terms in U. The observed behaviour is found to agree well with the general features obtained experimentally for some heavy fermion (HF) systems.