Catalytic oxidation of methanol over molybdenum oxide–tungsten oxide

The vapour phase oxidation of methanol to formaldehyde over molybdenum oxide, tungsten oxide and their mixtures has been investigated in an integral flow reactor at atmospheric pressure. The effect of several process variables on the conversion and yield were determined. A high conversion of 95.6% methanol with nearly 95% selectivity was obtained at 430°C. A rate expression has been derived from the kinetics of the reaction.     

The Structure of the Irreversibly Bound Adhesion Promoter-Substrate Interfacial Layer of γ-Aminopropylsilanetriol on Crystalline Si, as Measured by XPS and FTIR

The irreversibly bound interfacial layer deposited by the γ-aminopropysilanetriol adhesion promoter onto a crystalline silicon substrate, which remains even after profuse washing, was found by XPS to have resulted from the fragmentation and rearrangement of the original γ-aminopropylsilanetriol molecule. A mechanism is proposed, involving the homolytic scission of the terminal N-C bond. One of the subsequent reactions is believed to involve hydrogen loss by abstraction and the formation of a terminal vinyl group, which bonds to the substrate. Support for this mechanism is found in IR spectroscopy of this layer.     

The role of the surface free energy in the selection of a suitable excipient in the course of a wet-granulation method

Pellets containing metronidazole were produced in a centrifugal granulator, with hydroxypropylcellulose (Klucel LF®) as binding agent, and corn starch, microcrystalline cellulose (Vivapur 101®) and lactose as excipients. The wettability of the pharmaceutical powders was assessed by means of contact angle measurements, and the dispersive and polar surface energies were determined. The spreading coefficients, the work of adhesion and the work of cohesion were calculated and correlated with the pellet properties (friability, bulk and tapped density, and porosity). The aim was to investigate the role of the surface free energy of one- and two-component powder compositions in pellet production. The interactions between the particles were found to be connected with the measured pellet parameters. It was concluded that, in the course of the growth of the pellets, the particle sizes of the pharmaceutical powders and the interactions between them are important. If the work of cohesion of the binder is lower than the work of cohesion of the substrate and the work of adhesion, then the optimal amount of the binding agent is that which coats the particles uniformly in minimal quantity and in continuous layer.     

Fractionation of partially stereoregular poly(propylene oxide)

Partially stereoregular poly(propylene oxide) samples were synthesized via reactions catalysed by a preformed analytically defined trimethylaluminium hydrolysate. These samples were fractionated into two contrastingly different fractions.

1. (i) D-polymers: This fraction constituted the major part (up to 90%). It mainly contained cyclic low molecular weight oligomers (MW < 1000). The linear chains found in D-polymers had hydroxyl end groups. No double bonds could be detected spectroscopically.

2. (ii) K-polymers: This fraction was high molecular weight stereoregular polymer. Stepwise thermal precipitation from dilute isooctane solution of K-polymers yielded a succession of fractions which differed in melting point. It appears that the phase equilibria during the thermal precipitations were not controlled by the molecular weights of species.

The behavior of a swarm of particles moving in a viscous fluid

A significant bulk flow is thought to occur if a part of the body of a suspension, which has a different density from the density of the remainder of the suspension, is large enough in space however slight the difference may be. As a typical case, the slow motion of a swarm of particles in a viscous fluid was studied both theoretically and experimentally. Under a certain condition, the suspended particles formed a drop of suspension, in which the suspended particles and fluid moved as one body in the same way. The falling velocity of a spherical swarm of particles, which was called a drop of suspension, was measured and compared with a new theoretical prediction presented in this paper.It may be also noted that the theoretical model may be applicable to the flow due to density difference by means of replacement of the continuous mass by the damped mass which is regarded as consisting of particles.     

Orientational crystallization and orientational drawing as strengthening methods for polyethylene

This paper reports on the theoretical and experimental studies of structure formation and strengthening (stiffening) of flexible-chain polymers. Two techniques of strengthening relying on the melt extrusion, i.e., orientational crystallization (crystallization initiated by melt extension) and drawing (uniaxial stretching of a crystallized polymer) are analysed by theory. The experiments involved preparation and study of melt extruded films and film fibers of linear polyethylene formed by the two techniques mentioned above. The effect of the degree of orientation and other parameters of the formation processes on the mechanical characteristics and the factors limiting the ultimate values of these characteristics are discussed. It is shown that multistage drawing succeeds in achieving a higher tensile strength and elastic modulus (1.2 and 35 GPa, respectively) than the orientational crystallization, which gives 0.8 and 15 GPa. The strengthening by drawing is accompanied by microcrack formation. In contrast, no discontinuities are observed in orientationally crystallized samples up to their ultimate extension.     

DRY-RO membranes from cellulose acetate carbamates

Cellulose acetate carbamates (CACs) are the polymers which result when organic isocyanates are reacted with the free hydroxyl groups of cellulose acetate (CA). CACs are more hydrolytically stable and exhibit physical properties which are superior to those of their CA mixed ester analogs. Two synthetic approaches to CACs have been utilized in this study: (1) preformation, i.e., separate synthesis of such polymers prior to their inclusion in solutions for membrane casting; and (2) in situ formation, i.e., the inclusion of blocked isocyanates in standard dry process casting solutions of CA followed by thermal activation of the resultant dry membranes leading to regeneration of free isocyanate and subsequent CAC formation. Preformed CAC polymers have been prepared utilizing phenyl-, 3-chloropropyl-, 3-bromopropyl-, and 3-bromopropyl-(isothio)-, isocyanates. Polymers containing omega-halocarbamate moieties were quaternized with dimethylbenzylamine to produce ionogenic (QCAC) polymers containing quaternary ammonium groups. DRY-RO membranes from the QCACs exhibit flux/rejection values varying between 6–8 gfd at 98% rejection and 20 gfd at 90% rejection (0.5% NaCl feed at 400 psi and 25°C). In situ formation of CAC membranes has been effected with tolylene- and hexamethylene-diisocyantes, with quaternized isocyanate monomers employed for the preformed CAC polymers, and with specially tailored diisocyanates containing ionogenic groups. Crosslinking rendered all of the membranes acetone insoluble. Inasmuch as in situ formation substitutes the easy synthesis of blocked isocyanate monomers for the more difficult separate synthesis of preformed CAC polymers, it is anticipated that the former will replace the latter.     

The chlorine/carbon electrode in a silver chloride melt in the temperature range 475–820°C—I: The mechanism and rate of the reaction and the heat of activation

The kinetics of the chlorine evolution on carbon from a silver chloride melt have been studied at several temperatures using the steady state method and galvanostatic methods. Measurements with the double pulse method show that the charge transfer reaction is fast. The Tafel curves indicate that two parallel desorption reactions have about the same rate. The apparent heat of activation have been determined for the various reaction steps.