Synthesis and characterization of two-armed poly(ɛ-caprolactone) polymers initiated by the Schiff's base complexes of copper(II) and nickel(II)

Two-armed poly(?-caprolactone) (TAPCL) polymers were successfully synthesized via the ring opening polymerization (ROP) of ?-caprolactone (?-CL) using the Schiff's base complexes [Cu(SAEE)₂] (1) and [Ni(SAEE)₂] (2), which have two hydroxyl functional groups, as the two-site initiators and tin(II) 2-ethylhexanoate (Sn(Oct)₂) as the catalyst in bulk at 115 °C. The Schiff's base complexes (1 and 2) were synthesized by utilizing the concentrated template synthesis method starting from salicyl aldehyde, 2-(2-aminoethoxy) ethanol and related metal acetate salts. The synthesized TAPCL polymers were characterized by GPC, FTIR, UV–vis, and electron paramagnetic resonance (EPR). The molecular weights of TAPCL polymers linearly increased with increasing molar ratio of the monomer to the initiator. The results obtained from FTIR, UV–vis, and EPR studies indicated that TAPCL polymers had the Schiff's base complexes at the junction point of PCL arms. The crystallization behavior of TAPCL was studied by using differential scanning calorimetry (DSC) and polarizing optical microscopy (POM). Thermal behavior of TAPCL was also investigated by thermogravimetrical analysis (TGA).     

Stability of the δ-TeO2 phase in the binary and ternary TeO2 glasses

The stability of δ-TeO₂ phase was studied in binary TeO₂–WO₃, TeO₂–CdO and ternary TeO₂–WO₃–CdO glasses. The samples were prepared by heating high purity powder mixtures of TeO₂, WO₃ and/or CdO to 800 °C in a platinum crucible with a closed lid, holding for 30 min and quenching in water bath. Differential thermal analysis (DTA), X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques were used to characterize the thermal, phase and microstructural properties of the δ-TeO₂ phase. The addition of CdO into the tellurite glasses increased the stability range of the δ-TeO₂ phase up to higher temperature values and expanded the compositional δ-TeO₂ formation range. The formation of δ-TeO₂ phase in the binary systems was observed for samples containing 5–10 mol% WO₃ and 5–15 mol% CdO. However, for the ternary TeO₂–WO₃–CdO system the formation of δ-TeO₂ phase was determined in a wider compositional range.     

The effect of temperature on the pulsed current processing behaviour and structural characteristics of porous ZSM-5 and zeolite Y monoliths

Hierachically porous monoliths of ZSM-5 and Y zeolites have been prepared by pulsed current processing (PCP). The densification behaviour and structural characteristics during rapid thermal treatment of the zeolites have been determined and related to the influence of the Si:Al ratio on the thermal stability of the zeolites. Monoliths of macroscopic shape can be prepared with an insignificant loss of surface area and micropore volume when the PCP-treatment was performed at temperatures below a critical maximum PCP temperature (T_PCP). Full-profile fittings of the powder X-ray diffraction patterns showed that the lattice strain of zeolite Y increases rapidly above the critical T_PCP while the ZSM-5 zeolites undergo a phase transition from orthorhombic to monoclinic. The use of a novel ceramic processing route for the production of the zeolite monoliths that do not significantly influence the structural characteristics and surface area of the starting materials has a potential to be of importance in catalysis and gas separation applications.     

Inclusions in commercial low and medium carbon ferromanganese

The microstructures of commercial low and medium carbon ferromanganese have been studied by optical microscopy and electron microprobe techniques. Element analysis and mapping have been performed on impurities in the matrix and nonmetallic inclusions present. The results show that the most common nonmetallic inclusion is managanese oxide, followed by complex compounds of managanese oxide, silicon oxide, and manganese sulfide. The different inclusions have been assessed according to the SS 111116 method. It follows that over 85 pct of the present nonmetallic inclusions are manganese oxides and that the amount of manganese oxide inclusions is inversely proportional to the carbon content in standard refined ferromanganese.     

Revisiting and Extending Interface Penalties for Multi-domain Summation-by-Parts Operators

A general interface procedure is presented for multi-domain collocation methods satisfying the summation-by-parts (SBP) spatial discretization convention. Unlike more traditional operators (e.g. FEM) applied to the advection-diffusion equation, the new procedure penalizes the solution and the first p derivatives across the interface. The combined interior/interface operators are proven to be pointwise stable, and conservative, although accuracy deteriorates for p≥2. Penalties between two different sets of variables are compared (motivated by FEM primal and flux formulations), and are shown to be equivalent for certain choices of penalty parameters. Extensive validation studies are presented using two classes of high-order SBP operators: (1) central finite difference, and (2) Legendre spectral collocation.     

Lignin and Other Aromatic Substances Released from Spruce Wood During Pressurized Hot-Water Extraction,Part 2: Structural Characterization

Extraction of ground spruce sapwood with pressurized hot water in an accelerated solvent extractor (ASE) at 170°C during 20, 60, and 100 min resulted in isolation of galactoglucomannans and aromatic substances, including lignin. The isolated lignin preparations were characterized by spectrometric (UV, FT-IR, ¹H NMR, liquid and solid-state ¹³C NMR), chromatographic (RP-HPLC, HP-SEC, GC-FID, and GC-MS), conventional pyrolysis, thermally assisted hydrolysis, and methylation techniques in tandem with GC-MS, and classical wet chemistry (methoxyl groups, total and phenolic hydroxyl groups, derivatization followed by reductive cleavage—DFRC). The content of β-O-4 bonds in isolated lignins was similar to that in MWL and their proportion decreased with extraction time. The oxidation of isolated lignins and content of total hydroxyl groups were significantly increased with extraction time. The lignin structure underwent condensation and demethylation reactions during hot-water extraction. The induction of new phenylcoumaran substructures was proposed in isolated lignins.     

Minimal dissipation theory and shear bands in biaxial tests

True biaxial tests of granular materials are investigated by applying the principle of minimal dissipation and comparing to two dimensional contact dynamics simulations. It is shown that the macroscopic steady state manifested by constant stress ratio and constant volume is the result of the ever changing microscopic structure which minimizes the dissipation rate. The shear band angle in the varying shear band structures is found to be constant. We also show that introducing friction on the walls reduces the degeneracy of the optimal shear band structures to one for a wide range of parameters which gives a non-constant stress ratio curve with varying aspect ratio that can be calculated.     

Nanometer-thick films of titanium oxide acting as electrolyte in the polymer electrolyte fuel cell

0-18 nm-thick titanium, zirconium and tantalum oxide films are thermally evaporated on Nafion 117 membranes, and used as thin spacer electrolyte layers between the Nafion and a 3 nm Pt catalyst film. Electrochemical characterisation of the films in terms of oxygen reduction activity, high frequency impedance and cyclic voltammetry in nitrogen is performed in a fuel cell at 80 °C and full humidification. Titanium oxide films with thicknesses up to 18 nm are shown to conduct protons, whereas zirconium oxide and tantalum oxide block proton transport already at a thickness of 1.5 nm. The performance for oxygen reduction is higher for a bi-layered film of 3 nm platinum on 1.5 or 18 nm titanium oxide, than for a pure 3 nm platinum film with no spacer layer. The improvement in oxygen reduction performance is ascribed to a higher active surface area of platinum, i.e. no beneficial effect of combining platinum with zirconium, tantalum or titanium oxides on the intrinsic oxygen reduction activity is seen. The results suggest that TiO₂ may be used as electrolyte in fuel cell electrodes, and that low-temperature proton exchange fuel cells could be possible using TiO₂ as electrolyte.     

Utilization of Heavy Metal Molten Salts in the ARIES-RS Fusion Reactor

ARIES-RS is one of the major magnetic fusion energy reactor designs that uses a blanket having vanadium alloy structure cooled by lithium [1, 2]. It is a deuterium–tritium (DT) fusion driven reactor, having a fusion power of 2170 MW [1, 2]. This study presents the neutronic analysis of the ARIES-RS fusion reactor using heavy metal molten salts in which Li₂BeF₄ as the main constituent was mixed with increased mole fractions of heavy metal salt (ThF₄ or UF₄) starting by 2 mol.% up to 12 mol.%. Neutron transport calculations were carried out with the help of the SCALE 4.3 system by solving the Boltzmann transport equation with the XSDRNPM code in 238 neutron groups and a S ₈–P ₃ approximation. According to the numerical results, tritium self-sufficiency was attained for the coolants, Flibe with 2% UF₄ or ThF₄ and 4% UF₄. In addition, higher energy multiplication values were found for the salt with UF₄ compared to that with ThF₄. Furthermore, significant amount of high quality nuclear fuel was produced to be used in external reactors.