E.s.r. study of annealing and melting effects on the molecular motion of spin trapped chain-end radicals located on the polyethylene surface

E.s.r. spectra of chain-end spin labels on the surface of polyethylene powder were obtained for high and low density polyethylene samples at various stages of heat treatment process. The subsequent crystalline structures of the samples were examined with wide angle and small angle X-ray diffraction spectra. The effects of annealing on the motion of the labels were dependent on annealing temperature and the type of the samples. Higher temperature annealing decreased the rotational correlation times (τ_c) and their activation energy in high density polyethylene but did not affect those of low density polyethylene. Melting decreases the values of τ_c and ΔE for both high an low density polyethylene samples. The cause of these decreases were attributed to the changing of the sites of the chain-end labels. The motion of the labels appeared to be influenced by the local segmental motion of the polymer main chains.     

Surface modification of polyethylene by electrical discharge treatment and the mechanism of autoadhesion

A reexamination of previous studies concerning the electrical (‘corona’) discharge treatment of polyethylene and the resulting enhancement of autoadhesion has been carried out. X-ray photoelectron spectroscopic data provide new insight into the phenomenon by showing surface oxidation to result from treatment in ‘inert’ gases. Treatment in hydrogen is an exception and results in no autoadhesion enhancement even though energy input into the film is more efficient than in air. Autoadhesion theories based on electret formation are rejected; those based on hydrogen bonding are largely up-held and shown to be more generally applicable than at first imagined.     

Electron spin resonance studies of spin-labelled synthetic polymers: 13. Lithiation of copolymers of chloro-and bromostyrenes

The products of the reaction between n-butyllithium, complexed with tetramethylethylenediamine or THF, and chloro- and bromostyrene copolymers were identified by trapping the lithiated sites with 2-methyl-2-nitrosopropane. From the e.s.r. spectra of the resulting nitroxide-labelled polymers it was concluded that bromostyrene units undergo direct lithium—bromine exchange. Styrene—bromostyrene copolymers are therefore useful precursors to labelled polystyrene. Chlorostyrene units, by contrast, react with butyllithium to yield intermediate benzynes to which another molecule of butyllithium adds. The product contains a mixture of lithiated sites, each carrying a n-butyl group ortho to the lithium atom; the resulting nitroxide-labelled polymers are unsuitable for dynamic studies. The observations on halogenated styrene copolymers were complemented by experiments on small model molecules.     

Rheo-optical studies on the deformation mechanism of semi-crystalline polymers. IX. Dynamic birefringence behaviour of a high-density polyethylene film having row nucleated crystalline texture of c-axis orientation

The dynamic birefringence behaviour of a high-density polyethylene film having a row-nucleated crystalline texture of cylindrites oriented along the machine direction of fabrication was investigated over frequency and temperature ranges covering the α mechanical dispersion of this material. The results are discussed in combination with the dynamic X-ray diffraction behaviour of the material so as to explore the structural origins of the α mechanical dispersion, not only for this particular material, but also for bulk-crystallized polyethylene having a spherulitic texture. Two deformation processes contribute to the α₁ mechanism, corresponding to the lower temperature relaxation process in the α mechanical dispersion; i.e. (i) a lamellar detwisting process involving the rotation of crystal grains within the crystal lamellae or of lamellar segments around the crystal b-axis or the lamellar axis, which predominates in the MD (machine direction) specimen, and (ii) lamellar shearing associated with the rotation of the crystal grains or the lamellar segments around the crystal a-axis, which is accentuated in the TD (transverse direction to fabrication) specimen. An additional deformation process, lamellar bending, is also observed in the MD specimen as being likely elastic in the dynamic response, and its contribution is found to be substantial, not to the α dispersion, but rather to the β dispersion of this material. The α₂ mechanism corresponding to the higher temperature relaxation process in the α mechanical dispersion is observed to be more pronounced in the TD than in the MD specimen. The apparent dynamic crystal lattice compliance shows a definite dispersion during activation of the α₂ mechanism, but a slight dispersion during activation the α₁ mechanism, suggesting that the α₂ mechanism must be related to an intracrystal relaxation process whereas the α₁ mechanism must be associated with an intercrystal relaxation process at their boundaries.     

Numerical stability of the classical and the modified Saul'yev's finite-difference methods

Stability criteria a modified Saul'yev's explicit method for parabolic partial differential equations are derived and compared with those of classical Saul'yev's explicit method and Crank-Nicholson's implicit method. The two Saul'yev methods operated in the averaging mode are found to be unconditionally stable with respect to the heat equation. However, when lower order terms are included in the linear test equation, the modified method is shown to have a greater stability region than the classical method, while the Crank-Nicholson method maintains its stability unconditionally. Results of numerical experiments confirm the validity of the derived criteria.     

13C and 1H n.m.r. dynamic study of poly(γ-benzyl-l-glutamate) poly(β-benzyl-l-aspartate) and poly(l-alanine) in solution

¹H T₁ relaxation times were measured in solutions of poly (γ-benzyl-l-glutamate), PBLG, and poly(β-benzyl-^l-aspartate), PBLA, and ¹³C T₁ relaxation times, NOE factors and line widths in solutions of the two polypeptides and of poly(l-alanine), PLA, over a broad range of solvent composition (CDCI₃—trifluoroacetic acid) including the helix—coil transition. PBLG was also studied through temperature-induced inverted helix—coil transition. Most relaxation parameters change smoothly over the studied range, and the observed changes correspond to increase of mobility with increasing content of trifluoroacetic acid and with increasing temperature except for PBLG which undergoes an inverted helix—coil transition with temperature. Analysis of experimental data by means of the isotropic model yielded, for the backbone carbons of all three polypeptides, τ_eff ～ 2 × 10^?8 sec in the helix and τ_eff ～ 1 × 10^?9 sec in the coil form. For the side-chain carbons, τ_eff decreases in the range 10^?9 ? 10^?10 sec with increasing distance from the backbone, with τ_eff values consistently lower in the coil form. Results of analysis by means of a model with two correlation times are discussed.     

The electrochemistry of silver in koh at elevated temperatures—III. Potentiostatic study

The electrochemistry of polycrystalline silver in 1 mol kg^?1 KOH at temperatures between 295 K and 478 K has been studied using potentiostatic polarization. At potentials corresponding to silver dissolution and to the early stages of Ag₂O formation, the transient current data at all the temperatures studied exhibit regions that are linearly dependent on the inverse square root of time. This dependence indicates mass transport to be a rate limiting step in these processes. Log (steady-state current) vs potential data show that at all temperatures silver undergoes an active-to-passive transition. However, the potential of the transition shifts to less positive values and the passive current increases with increasing temperature. In the region of formation of surface oxide phases, the transients exhibit maxima due to nucleation and growth phenomena. The effect of temperature on the transients is similar to the effect of overpotential; in both cases, the time taken to reach the maximum current decreases.     

PtSiO2: II. Characterization of the gel and the platinum particles by X-Ray diffraction

Modern techniques for analysis of X-ray diffraction profiles have been applied to several of the platinum-silica gel catalysts described in Part I to determine average platinum crystallite size, percentage exposed, crystallite shape, size distribution, lattice parameter, residual stresses and strains, presence or absence of faulting, and mean-square amplitude of vibration. In addition the surface area of the gel was determined with small-angle scattering (SAS). There is good agreement between the percentage exposed of platinum measured by gas adsorption in Part I and the results reported here, calculated from crystallite sizes, indicating the crystallite size is the true platinum particle size. Crystallites to sizes as small as ≈25 Å have been examined. Furthermore, the crystallites are equiaxed in shape (and definitely not cuboidal) and are strain and defect free, except in the case where the average size is near the pore size of the gel. Size distributions are sharper when the catalyst preparation is by impregnation rather than by ion exchange. The size distributions indicate that there is coalescence of some surface species during preparation rather than coarsening (Ostwald ripening). The meansquare amplitude of vibration of platinum increases by ≈30% as the particles decrease in size from ≈100 to ≈25 Å. There is no change in the lattice parameter greater than ≈0.1%. The gel surface areas determined by SAS are in agreement with those determined in Part I by physisorbtion of nitrogen.     

The electrochemistry of silver in KOH at elevated temperatures—IV. AC impedance study

The ac impedance properties of silver in 1 mol kg^?1 KOH were studied under potentiostatic conditions over the temperature range 295–478 K. Measurements were obtained over the frequency range 0.5 Hz–5 kHz, and were analyzed in terms of equivalent in terms of equivalent circuits. It was shown that provision for surface roughness is required for a satisfactory explanation of the impedance data. Values for the double layer capacity and the concentration AgO^? ions at the electrode surface could generally then be obtained. At potentials corresponding to the formation of Ag₂O, it is demonstrated that both diffusion in solution and diffusion in the oxide film are operative. At elevated temperatures, the rate of growth of Ag₂O centres is controlled partly by diffusion in the oxide and party by a reaction step at the growing interfaces of the centers. The subsequent formation of Ag₂O₂, at all temperatures in the range studied, is interpreted on the basis of an electrocrystallisation impedance.     

A basic study of catalyst aging in the H-coal process

Samples of CoMo/Al₂O₃ catalysts used in an H-coal process demonstration run were studied to determine causes of catalyst deactivation. Physical and surface properties of the aged and regenerated catalysts were examined. Model compounds were used to assess four catalyst activity functions, viz., hydrodesulfurization (HDS), hydrogenation, cracking and hydrodeoxygenation (HDO). Other tests were performed to study the effects of coke and metals separately on the four catalyst activity functions.Catalyst coke content and metals deposits first increased rapidly, then more gradually with exposure time in the process run. Surface area and pure volume markedly decreased with exposure time. Catalyst activities of aged catalysts showed a rapid decline with exposure time. One-day exposure to coal resulted in significant losses in HDS and hydrogenation activities and nearly complete loss in cracking and HDO activities. Although metal deposits caused some permanent catalyst deactivation, coke had a much greater effect. Regenerated catalysts showed less recovery of catalytic activity as processing time increased. These results agreed well with product inspections from the process run.Oxygen chemisorption on aged—regenerated catalysts decreased with catalyst exposure time, indicating a significant loss of active sites. However, ESCA results showed no evidence of extensive sintering of the active MoS₂ phase. Permanent deactivation of the longer-time exposed catalysts can be ascribed, at least partly, to lateral growth of the active molybdenum sulfide phase. In addition, some loss in cobalt promotion occurred early in the process, which may account for the rapid loss in HDS and HDO activity in regenerated catalysts.     

Theoretical study of the inactivation of phosphatase during spray drying of skim-milk

A theoretical calculation is presented of the drying history of skim-milk droplets under spray drying conditions. From the unsteady state diffusion equation the water concentration distribution is calculated as a function of time; simultaneously the thermal degradation of the enzyme alkaline phosphatase is calculated and integrated over the particle. Effects accounted for are the temperature and concentration dependence of the water diffusion coefficient and of the degradation rate constant, and the shrinkage due to water loss. Droplet geometries considered are the “solid sphere” model (fully liquid droplets) and the “hollow sphere” model (with air bubble in the centre). The effect on final phosphatase retention of the following process variables was investigated: dissolved solids content of the feed, air temperature, particle size, and gas bubble size.     

Anodic oxidation of some phenols related to lignin — II. Oxidation of isoeugenol methylether and 4-propylveratrole in acetonitrile

The anodic oxidation of isoeugenol methylether and 4-propylveratrole has been studied in unbuffered acetonitrile solution and in solutions buffered with pyridine and 2,6-lutidine using cyclic voltammetry, steady-state measurements on rotating electrodes, coulometry, esr, uv-spectroscopy, nonlinear galvanostatics and preparative electrolysis. Reaction mechanism, which account for the experimental results, are presented and discussed.     

Electrochemistry of ferrocene in anionic,cationic and nonionic micellar solutions. Effet of the micelle solubilization of the half-wave potentials

The redox properties of the ferrocene/ferricinium Fc/Fc⁺ couple were studied in aqueous 0.1 M NaCl solution of sodium dodecylsulphate (SDS), N-cetyltrimethylammonium bromide (CTAB) and polyoxyethylene-23 lauryl ether (Brij 35). Solubilities of ferrocene were measured by spectrophotometry and by limiting current measurements in direct current voltammetry. The reversible half-wave potentials were determined by cyclic and differential pulse voltammetry. The results are discussed on the basis of the micelle solubilization equilibrium of both the reductant Fc and the oxidant Fc⁺. Indeed, diffusion coefficient ratios of the oxidant to the reductant, measured by coulometry, show that the micelle solubilization of the electrogenerated ferricinium cation Fc⁺ must also be considered in the nonionic and the anionic micellar solutions. Thus in every solution studied, a standard potential of Fc/Fc⁺ in water may be obtained from the experimental values of the half-wave potentials, the partition coefficients of Fc and Fc⁺ and the ratio of their diffusion coefficients. The behaviour of ferrocene in the SDS solutions and the effect produced by the addition of pentanol seem to confirm that SDS forms micelles with a less ordered structure than the other surfactants studied. The invariance of the half-wave potentials of ferrocene in pure SDS solutions whatever the surfactant and ferrocene concentrations suggests the use of this solute-solvent couple as a reference potential system.     

The electrochemical oxidation of lead in various H2OH2SO4 mixtures—II. Ring-disc electrode study

The rotating ring-disc electrode technique was used to study the generation of soluble Pb(II) species during the anodic oxidation of the lead electrode in various H₂OSO₄ media. The concentration range extended from 0.06 to 10.3 M H₂SO₄. For every concentration it was possible to detect a small cathodic ring current variation which was attributable to the reduction of Pb(II) to Pb. Quantitative measurements of the collection efficiency showed that the small cycle life of the lead-acid battery in 5.6 M H₂SO₄ cannot be ascribed to the dissolution step.     

Electrooxidation of terpenes—I. Synthesis of dihydrocarvone and 1-hydroxyneodihydrocarveol by anodic oxidation of limonene

The oxidation of (+) and (?) limonene, 1, in THF-H₂O (25:1), NaClO₄ on a graphite electrode gives, with a relative stereoselectivity, (+) and (?) dihydrocarvone, 5 and (+) and (?) 1-hydroxyneodihydrocarveol, 7, respectively as the major products. A logical route for this oxidation via a protonated epoxide as intermediate is proposed.     

Electrochemical kinetic study of the Fe3+Fe2+ system in oxalate medium

The overall processes were determined for the reduction of Fe³⁺ to Fe²⁺, in an oxalate medium and at oxalate concentrations of less than 0.5M. The coordination numbers of the oxidized and reduced species were calculated, together with the number of intervening protons that depend on the oxalate concentration and the pH.In addition, the species that reduces at the electrode is determined, together with the intensity equations for each process.     

Distribution of aliphatic and aromatic carbons in H-Coal liquids by quantitative 13C FT-n.m.r. spectroscopy

Three H-Coal liquids, ASO, ASB, and VSO, have been characterized by quantitative FT-n.m.r. spectroscopy. FT-parameters were chosen to allow determination of aromatic:aliphatic carbon ratios to within 1% and 2% error of the theoretical and the absolute number of aromatic and aliphatic carbons in a simulated coal liquid, respectively. The aromaticity, f_a, the C_ar:C_al ratio and, the absolute number of both the aromatic and the aliphatic carbons on a per mol basis, have been derived for each H-Coal liquid using c.m.r. in combination with other physical data. By analysis of the chemical shifts of the c.m.r. spectra, the carbon distributions in the H-Coal liquids have been estimated and compared in terms of six structural types. The molecular parameters thus derived are reasonable correlated with the average molecular structures proposed as working hypothesis for the molecular characterization of the three H-Coal liquids.