Epoxide polymerization

Summary Poly(propylene oxide), PPO, obtained using diphenylzinc, Ph₂Zn, and using the diphenylzinc-water system at various molar ratios H₂O/Ph₂Zn, were studied through ¹H NMR and IR spectroscopy establishing that the polymerization initiates by coordition of propylene oxide (PO) to a terminal zinc atom of the active species followed by consecutive insertions of PO units at this zinc atom. The PPO obtained showed Ph-and HO-, HO-and HO-end-groups depending on the molar ratio H₂O/Ph²Zn used, and also HO-and PhO-end-groups when oxygen was present in the polymerization system.     

Upgrading coal-derived liquids to diesel fuel

Distilled fractions of a coal-derived liquid from the H-Coal process were upgraded to diesel fuel by catalytic hydrotreatment. The total hydrotreated products were distilled into naphtha (<180°C) and diesel fuel fractions (>180°C) and the diesel fractions were analysed for hydrocarbon-type composition, hydrogen content and some diesel fuel properties. GC—MS-analyses were carried out on the hydrocarbon-type fractions to identify individual chemical compounds. To investigate the effect of different distillation cut points on diesel fuel yield and properties, cut points for one hydrotreated product were varied. The diesel fuel cetane numbers were correlated with percentage hydrogen, total aromatics and saturates. Cetane numbers above 40 were obtained for diesel fuels containing (i) more than 75% saturates, (ii) less than 15% total aromatics and (iii) a hydrogen content above 12.8%. Compounds identified by GC—MS-analyses (in the diesel fractions) were typical aromatic and cycloparaffin compounds. Normal-and iso-paraffin compounds were not detected. By varying the distillation cut point from 135 to 180°C, the cetane number of the residual diesel fraction improved from 37 to 44. This increase is ascribed to the removal of aromatic compounds in the 135–180°C boiling point range.     

Fine-line conductor manufacturing using drop-on demand PZT printingtechnology

An emerging selective metallization process to fabricate fine-line conductors based on drop-on-demand (DOD) ink jet printing and novel nano-particle fluid suspensions (NPFS) was studied. The suspensions consist of 1-10 nm silver or gold particulates that are homogeneously suspended in an organic carrier. A piezo-electric droplet generator driven by a bipolar voltage signal is used to dispense 50-70 μm diameter droplets traveling at 1-3 m/s before impacting a compliant polyimide substrate. The deposit/substrate composite is subsequently processed at 300°C for 15 min to allow for complete evaporation of the carrier and for sintering of the nano-particles, thereby yielding a finished circuit interconnect. Test vehicles created using this technique exhibit features as fine as 120 μm wide and 1 μm thick with resistivities on the order of 3.5×10^-5 Ωcm. The circuitry performed well under environmental conditioning. As expected, repeatability of circuitry fabrication showed sensitivity to the generation of steady, satellite-free droplets. In an effort to generate droplets consistently, it is essential to develop a strong fundamental understanding of the correlation between device excitation parameters and dispensed fluid properties, and to resolve the microrheological behavior of the NPFS when flowing through the droplet generator     

Epoxidation of natural rubber studied by nmr spectroscopy

Epoxidation of natural rubber with peroxyacids in homogeneous solution (CHCl₃, benzene) and in latex occurs without main chain fission or isomerization of the cis configuration. There are two possible modes of addition of oxygen to the double bond, which gives rise to diastereoisomers in dyad structures, as shown by the occurrence of splitting of ¹³C NMR resonances in 100% epoxidized rubber. In partially epoxidized rubber the ¹³C NMR resonances of the methylene carbon atoms have been fully assigned using pulse sequences and lanthanide shift reagents, in terms of triad sequences. Resonances in the olefinic region of the spectrum require assignment in terms of pentad sequences whereas those from the oxirane region are much more closely spaced and are assigned using triads. Intensity measurements on the methylene carbon NMR resonances show that the epoxidation reaction is a random process in both homogeneous solution and in latex particles.     

Melting and crystallization behaviour of elastoplastic semicrystalline copolymers: poly(ether ester)

The melting and crystallization behaviour of an elastoplastic semi-crystalline poly(etherester) has been studied by differential scanning calorimetry. The shape of the melting endotherm is strongly dependent on heating rate and annealing time and results from the sum of simultaneous melting and crystallization phenomena. Samples prepared by different techniques, i.e. by solvent evaporation or by melt extrusion, behave very differently owing to specific crystal morphologies. By applying the Hoffman-Weeks plot, the equilibrium melting temperature has been extrapolated. The Avrami treatment allows the calculation of the index n and of the rate constant K from the isothermal kinetic data.     

TEM study of PLZT ceramics

The microscopic structures of PLZT(7.9/70/30 and x/65/35, x = 7 or 8) ceramics were studied by means of transmission electron microscopy. The presence of micro-regions in PLZTs was first verfied.