Dynamics of ion beam modification of polymer films

Thin polymer films were irradiated in a high vacuum environment with energetic (～2 MeV) ions. The emitted molecular species were studied with a quadrupole mass spectrometer during bombardment. The emitted species are predominantly small molecules. The efficiency of emission depends strongly upon the electronic energy loss of the incident ions in the film and, hence, upon the velocity and atomic number of the incident ion. The emission efficiency of all species decreases with increasing damage in the film. By pulsing the ion beam, the time dependence of irradiation induced emission of molecular species from the films has been studied. Emission delays of hundreds of milliseconds are observed in some cases. These delays are found to depend upon the emitted species as well as the host film and seem to be associated with diffusion of the species in the films.     

Stabilization of foams and emulsions by mixtures of surface active food-grade particles and proteins

Surface active biopolymers such as proteins can form films with particularly high interfacial elasticities and viscosities and these molecules are widely exploited as foaming and emulsifying agents in foods. Solid particles of the correct size and wetting characteristics can also be extremely effective stabilizers of foams and emulsions, although the underlying mechanism of stabilization is somewhat different. Relatively little is known about what happens when both surface active polymers and surface active particles are present together. This work presents recent findings on the effects of mixtures of proteins plus novel food-compatible surface active particles. The proteins include caseins and whey proteins. The surface active particles prepared include cellulose + ethyl cellulose complexes, hydrophobically-modified starch granule particles and stable (non-spreading) protein-stabilized oil droplets. Interfacial shear rheology of adsorbed films was measured via a biconical bob apparatus and interfacial dilatational rheology was measured via a Langmuir trough type apparatus. The corresponding stability of bubbles to coalescence and disproportionation was assessed in separate experiments. Stability of oil-in-water emulsions was assessed via measurement of particle size distributions as function of time and visual assessment of the tendency to creaming and oiling off. In general, it is shown that the surface active particles on their own exhibit much lower measures of interfacial elasticity and viscosity than the proteins, but in combination with the proteins they appear to enhance the interfacial viscoelasticity considerably, with concomitant increases in bubble and emulsion droplet stability. There is little evidence of attractive interactions between the particles and the proteins, so a possible explanation of the increased stability is that the proteins increase the accumulation of particles at the interface, giving rise to increased jamming of particles at the interface.     

Sex pheromone of cranberry fruitworm,Acrobasis vaccinii riley (Lepidoptera: Pyralidae)

The following compounds and (approximate ratios) were identified in sex pheromone gland extracts of femaleAcrobasis vaccinii Riley by comparison of gas chromatography-mass spectrometric traces with those of synthetic standards: (E,Z)-, (Z,E)-, (Z,Z), and (E,E)-8, 10-pentadecadien-l-ol acetates (100:1:2:12), a dodecen-l-ol acetate (8), (Z)-8-, (Z)-9-, and (E)-9-pentadecen-l-ol acetates (3:23:4), two heptadecen-l-ol acetates (4:4), tetradecyl, pentadecyl, hexadecyl, and heptadecyl acetates (3:15:10:8), dodecan-l-ol (6), tetradecan-l-ol (5), and hexadecan-l-ol (23). The amount of (E,Z)-8, 10-pentadecadien-l-ol acetate (E8,Z10–15:Ac) in the extract was about 0.5 ng/female. Electroantennographic analysis of gas chromatographic fractions of female sex pheromone gland extract showed that the fraction containingE8,Z10–15:Ac elicited the greatest response. Alone,E8,Z10–15:Ac failed to elicit upwind flight of males in flight-tunnel tests, and traps baited with it did not catch males in field experiments. WhenE8,Z10–15:Ac was combined with (E)-9-pentadecen-l-ol acetate (100:4), male upwind flight response in flight-tunnel tests was equivalent to those obtained with extract of female sex pheromone glands (synthetic, 62%; natural, 51%), but the percent of males flying upwind that contacted the source was lower (synthetic, 47%; natural, 88%). The lower percent of source contact elicited by the synthetic pheromone could be a result of the difference in isomer ratios of 8,10–15:Ac in the natural and synthetic pheromone or could indicate that the synthetic pheromone is incomplete. Traps baited with the 100:4 combination caught large numbers of males in field experiments.     

Solvent screening for non‐aqueous extraction of Alberta oil sands

Non‐aqueous extraction of bitumen from oil sands has the potential to reduce fresh water demand of the extraction process and eliminate tailings ponds. In this study, different light hydrocarbon solvents, including aromatics, cycloalkanes, biologically derived solvents and mixtures of solvents were compared for extraction of bitumen from Alberta oil sands at room temperature and ambient pressure. The solvents are compared based on bitumen recovery, the amount of residual solvent in the extracted oil sands tailings and the content of fine solids in the extracted bitumen. The extraction experiments were carried out in a multistage process with agitation in rotary mixers and vibration sieving. The oil sands tailings were dried under ambient conditions, and their residual solvent contents were measured by a purge and trap system followed by gas chromatography. The elemental compositions of the extraction tailings were measured to calculate bitumen recovery. Supernatants from the extraction tests were centrifuged to separate and measure the contents of fine solid particles. Except for limonene and isoprene, the tested solvents showed good bitumen recoveries of around 95%. The solvent drying rates and residual solvent contents in the extracted oil sands tailings correlated to solvent vapour pressure. The contents of fine solids in the extracted bitumen (supernatant) were below 2.9% for all solvents except n‐heptane‐rich ones. Based on these findings, cyclohexane is the best candidate solvent for bitumen extraction, with 94.4% bitumen recovery, 5 mg of residual solvent per kilogram of extraction tailings and 1.4 wt% fine solids in the recovered bitumen. © 2012 Canadian Society for Chemical Engineering     

Oligomer Content of α-Pinene Secondary Organic Aerosol

The quantity, extraction efficiency, and molecular composition of non-volatile oligomeric species in SOA generated by the reaction of α-pinene with ozone were studied. Two different methods of determining the total particulate mass in the reaction chamber were compared and found to be in good agreement when changes in the partitioning of semi-volatile compounds to the particle phase during measurement were properly handled. Almost all of the non-volatile organic carbon formed by the reaction was collected and recovered by extraction with organic solvents; recoveries with water extraction were somewhat lower. The identities of compounds extracted by the various solvents were determined using electrospray ionization Fourier transform ion cyclotron resonance (ESI-FTICR) mass spectrometry. Over 80% of the peaks weighted by mass and intensity were the same in the spectra of samples obtained from different extraction solvents. Standard addition plots were used to determine the amounts of two commercially available monomer compounds in the SOA extracts. When the response factors for those compounds were applied to other monomers detected in the mass spectra, the weight percent of monomers was estimated to be slightly less than 50%, with the remaining mass (over 50%) assigned to oligomers. The oligomer content is sufficiently large that it should be taken into account when modeling the formation and properties of laboratory SOA.     

Fe(TSPc)-Catalysed Benzylic Oxidation and Subsequent Dealkylation of a Non-Phenolic Lignin Model

Abstract

The mechanism by which the phthalocyanine complex trisodium tetra-4-sulfonatophthalocyanineiron(JJJ) (Fe(TSPc)) promotes oxidation and dealkylation of non-phenolic benzyl alcohol units in lignin under alkaline conditions was investigated using simple lignin model compounds. The iron complex effectively oxidised benzylic hydroxyl groups in 2-hydroxyethyl apocynol (5), with the extent of oxidation increasing with the amount of Fe(TSPc) added. To a limited extent, Fe(TSPc) also catalysed the oxidation of 5 by small amounts of oxygen in the reaction mixture. However, the extent of oxidation did not increase on adding excess air or oxygen, as greater amounts of oxygen also increased complex degradation. Phenolic products were formed in these reactions in the presence of Fe(TSPc), but at a rate slower than that of the benzylic oxidation. Further experiments indicated that the phenolic products were formed by base-promoted loss of the ether group at C4 and that such dealkylation occurred more readily in oxidised products.     

An Electrostatic Lens for Focusing Charged Particles in a Mass Spectrometer

The ability to transmit particles into the ablation region of an aerosol mass spectrometer determines in part the lower size limit for particles that can be analyzed. A large fraction of small particles (< 100 nm) are lost due to processes such as Brownian diffusion that broaden the particle beam. In this work, electrostatic focusing is used to overcome the limits of aerodynamic focusing in the analysis of nanometer-sized particles by aerosol mass spectrometry. A simple tube lens is used to focus charged particles into the ablation laser beam path. The diameter of the focused beam is smaller than the fundamental aerodynamic limit imposed by Brownian motion. Measured enhancements of the hit rate for particles between 21 and 33 nm diameter are between 3 and 6. These values are lower limits for the true enhancements. The lens is also energy selective and can be used to select the mass (size) of the particles being analyzed.     

Engineered clay products for the paper industry

The need for kaolin pigments by the paper industry with controlled optical and physical properties have significantly changed the type of filler and coating clays available to the paper industry. Processing equipment now used in the production of kaolin products is much more sophisticated and controllable than in the past. Better understanding of the mineralogy and the physical and chemical properties of kaolins, in addition to improved processing techniques, has allowed the kaolin processors to produce engineered or tailored grades that meet particular needs of the user. Particle size and shape, brightness, gloss, opacity, and viscosity can be altered and controlled to meet specific requirements of the paper coater. Examples of several types of engineered products available for use by the paper industry are discussed.     

Characterization of Liquid Developers for Continuous Tone Electrography

The relatively small particle sizes and lack of threshold development forces make liquid development a particularly suitable candidate for the development of continuously varying surface charge densities in pictorial electrography. The characterization of such developers has been pursued by studying their response to continuous and discrete surface charge density wedges on a computer-controlled test fixture. Results have been interpreted in terms of standard models of liquid development, and in most cases allow the extraction of the effective area coverage provided by the developer per unit of input surface charge density (the imagewise pattern of charge deposited by whatever electrographic writing device is employed). Examples of materials displaying linear and nonlinear responses to varying surface charge densities will be shown.     

Preparation and characterization of novel nanometer-scale platinum electrodes

Observation of the oxidation–reduction processes occurring at the nanoelectrode–solution interface demonstrates how electrochemical behavior depends upon nanoelectrode size. The use of a modified form of pulsed laser ablation as an improved method to synthesize nanometer-scaled electrode materials easily and consistently is reported. This method of fabrication enables platinum metal nanoparticles averaging 3 nm in diameter and approximately 5.0 × 10¹¹ particles/cm² to be deposited onto silicon substrates using optimum ablation parameters. A platinum silicide phase exists at the interface of the platinum and silicon as a result of the ablation process. Electrochemical results demonstrate the presence of a large number of isolated platinum particles (1.1 × 10⁷ particles/cm²), separated by an average edge to edge distance of 14 nm, which are electrochemically active nanoelectrodes.