The Solid State Postcondensation of PET, 3

Summary: It was demonstrated that it is possible to produce prepolymers with a number‐average degree of polymerisation on the order of 5–40 directly in a liquid‐liquid dispersion in less than three hours. It was also shown that prepolymers made via this route and rapidly crystallised by the addition of a dispersant at ambient temperature are more porous than prepolymers made in an industrial liquid melt process.

SEM micrograph of prepolymers pLL‐PTA with \overline {DP} _{\rm n} = 28, d_p ∈ 63–125 μm.     

Polyurethane‐infiltrated carbon foams: A coupling of thermal and mechanical properties

The thermal and mechanical properties of polyurethane‐infiltrated carbon foam of various densities were investigated. By combining the high thermal conductivity of the carbon foam with the mechanical toughness of the pure polyurethane, a mechanically tough composite (relative to the unfilled foam) that could be used at higher temperatures than the polyurethane's degradation was formed. Both the tensile strength and the modulus increased by an order of magnitude for the composites compared to unfilled foam, while the compressive and shear strengths and moduli of the composites approached values exhibited by pure polyurethane. At both 300 and 400°C, the rectangular blocks of pure polyurethane lost their mechanical integrity due to decomposition in air. Thermogravimetric analysis confirms substantial initial weight loss above 290°C. Filled carbon foam blocks, however, maintain their mechanical integrity at both 300 and 400°C indefinitely, although the bulk of the rectangular block mass is polyurethane. Three different carbon foam densities are examined. As expected, the higher density foams show greater heat transfer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2348–2355, 2003     

Catalytic olefin polymerisation at short times: Studies using specially adapted reactors

Despite the fact that the very early stages (several tens of seconds) of catalysed olefin polymerisation processes appear negligibly short with respect to the residence time of most industrial reactors, they are critical in terms of catalyst activation, obtaining good particle morphology, and avoiding irreparable problems caused by particle overheating. The different types of reactors that have been used over the course of the past few years are discussed in this feature article. It is shown that despite the difficulties encountered in finding the perfect experimental tool for this purpose, different configurations of stopped flow reactors can be used successfully to explore different aspects of what happens to the catalyst (supported and molecular) during these critical moments of polymerisation. © 2012 Canadian Society for Chemical Engineering     

Horizontal reactive distillation for multicomponent chiral resolution

A novel horizontal reactive distillation apparatus and a new overall process scheme are proposed for continuous multicomponent chiral resolution via reversible enantioselective acylation of a chiral (racemic) substrate by a chiral (racemic) acyl donor. The process enables simultaneous production of up to four enantiomers with enhanced chiral purity. Kinetic studies, miniplant experiments, and process simulation results are described for a model lipase‐catalyzed reaction: (R)‐enantioselective transesterification of (R,S)‐1‐n‐butoxy‐2‐propanol with (R,S)‐1‐methoxy‐2‐acetoxypropane to produce (R)‐1‐n‐butoxy‐2‐acetoxypropane, (R)‐1‐methoxy‐2‐propanol, and the two unreacted (S)‐enantiomers of the (R,S)‐reagents. A horizontal, compartmentalized reactive distillation vessel is specified instead of a conventional reactive distillation column to provide longer liquid‐phase residence time needed for adequate conversion. Low vapor‐traffic pressure drop allows operation under vacuum at reduced temperatures for good enzyme stability and enantioselectivity. The general technology has potential as a means to producing a wide range of chiral synthons used in asymmetric syntheses of chiral pharmaceuticals and other biologically active products. © 2013 American Institute of Chemical Engineers AIChE J, 59: 2603–2620, 2013     

Measurement of Aerosol Organic Compounds Using a Novel Collection/Thermal-Desorption PTR-ITMS Instrument

We report the development and characterization of a proton-transfer-reaction ion trap mass spectrometer for the speciated measurement of organic compounds in atmospheric aerosols and show results from its first field deployment. The instrument uses an aerosol collection inlet to accumulate aerosol mass followed by rapid thermal desorption to volatilize the organic compounds for in situ analysis. We have performed laboratory studies to characterize instrument performance and the instrument was deployed aboard a NOAA research vessel during the Texas Air Quality Study 2006/Gulf of Mexico Atmospheric Composition and Climate Study (TexAQS 2006/GoMACCS) in August–September 2006. The laboratory-determined detection limit for glutaric acid in mixed glutaric acid/NH ₄ HSO ₄ test aerosols was 0.22 ng collected mass, which corresponds to an estimated detection limit of 12 ng m^?3 for a 10 min sample based on the instrument sample flow rate of 1.8 L min^?1. During TexAQS 2006/GoMACCS, signals well above the detection limit were observed at a number of mass to charge ratios, mostly occurring during an extended period of active pollution photochemistry, but also including detection of possible primary emissions of aerosol-phase pyridine.     

Assessment of Bioaerosol Generation and Sampling Efficiency Based on Pantoea agglomerans

This study was conducted to evaluate the effect of aerosol generation, relative humidity, and method of sampling on the culturability of the vegetative bacteria Pantoea agglomerans (P. agglomerans) formerly known as Erwinia herbicola. This research has relevance both for the use of this organism as a biowarfare simulant and for bioaerosol exposure assessment and public health. The culturability of P. agglomerans was tested using a test chamber against two generating systems (Collison and Bubble nebulizers), two sampling systems (the all-glass impinger (AGI-30), and the BioSampler), three collection media (water, TSB, and PBS) and across a range of humidities. Results indicated that the Bubble nebulizer was 15% more efficient in generating viable P. agglomerans counts (p ≤ 0.05). No difference was observed in overall efficiency between sampling methods (p > 0.05). However, as a collection media, PBS was observed to yield higher (p ≤ 0.01) viable counts compared to sterile deionized water. Relative humidity was found to strongly influence airborne P. agglomerans culturability. Culturable P. agglomerans was below the limit of detection for RH < 15% and then increased in a log-linear fashion to humidities of 75%. This research will help identify optimal means for evaluation of environmentally sensitive airborne bacteria for purposes of exposure assessment and public health as well as homeland security.     

Soot Particle Studies—Instrument Inter-Comparison—Project Overview

An inter-comparison study of instruments designed to measure the microphysical and optical properties of soot particles was completed. The following mass-based instruments were tested: Couette Centrifugal Particle Mass Analyzer (CPMA), Time-of-Flight Aerosol Mass Spectrometer—Scanning Mobility Particle Sizer (AMS-SMPS), Single Particle Soot Photometer (SP2), Soot Particle-Aerosol Mass Spectrometer (SP-AMS) and Photoelectric Aerosol Sensor (PAS2000CE). Optical instruments measured absorption (photoacoustic, interferometric, and filter-based), scattering (in situ), and extinction (light attenuation within an optical cavity). The study covered an experimental matrix consisting of 318 runs that systematically tested the performance of instruments across a range of parameters including: fuel equivalence ratio (1.8 ≤ φ ≤ 5), particle shape (mass-mobility exponent ( D _fm ), 2.0 ≤ D _fm ≤ 3.0), particle mobility size (30 ≤ d _m ≤ 300 nm), black carbon mass (0.07 ≤ m _BC ≤ 4.2 fg) and particle chemical composition. In selected runs, particles were coated with sulfuric acid or dioctyl sebacate (DOS) (0.5 ≤ Δ r _ve ≤ 201 nm) where Δ r _ve is the change in the volume equivalent radius due to the coating material. The effect of non-absorbing coatings on instrument response was determined. Changes in the morphology of fractal soot particles were monitored during coating and denuding processes and the effect of particle shape on instrument response was determined. The combination of optical and mass based measurements was used to determine the mass specific absorption coefficient for denuded soot particles. The single scattering albedo of the particles was also measured. An overview of the experiments and sample results are presented.     

Spatial Measurements of Ultrafine Particles Using an Engine Exhaust Particle SizerTM within a Local Community Downwind of a Major International Trade Bridge in Buffalo,New York

Ultrafine particles (UFP) can be defined as having at least one dimension that is less than 100 nanometers. Because of their dimensions, they exhibit unique properties that affect atmospheric transport, exposures, and possibly health endpoints. Freshly generated Diesel particulate matter (DPM) is predominantly in the ultrafine particle size range size range, which in practice is defined by the detection characteristics of the sampling instrument. During two seasons, an Engine Exhaust Particle Sizer^TM (TSI, St. Paul, MN) detects particles over a range of 5.6–560 nm was used to continuously measure real-time particle size distributions along several streets that extend from the Peace Bridge (PB), a major international trade bridge, into a the nearby adjacent neighborhood that has reported a high prevalence rate of asthma (Lwebuga-Mukasa 2000). The Peace Bridge connects Buffalo, NY, USA to Fort Erie, ON, Canada. During summer 2004, one minute average particle number concentrations were continuously monitored along neighborhood streets near the Peace Bridge Complex (PBC) plaza out to about 2 km. Ultrafine particle counts as a function of bridge traffic showed downwind UFP levels at 300 m ranging from 60,000–70,000 p/cm³. Upwind background UFP levels at the shore line of Lake Erie were typically 8,000–10,000 p/cm³ under similar traffic and meteorological conditions. During winter 2006, additional measurements were conducted in front of several homes that were part of a separate indoor-outdoor exposure study (McAuley et al. 2010 McAuley, T. R., Fisher, R., Zhou, X., Jaques, P. A. and Ferro, A. R. 2010. Relationships of Outdoor and Indoor Ultrafine Particles at Residences Downwind of a Major International Border Crossing in Buffalo, NY.. Indoor Air, 20: 298–308. [Crossref] , [Google Scholar]). Sampling at the homes was done during the weekdays when heavy diesel truck traffic was highest. Results showed that most of the UFP number concentrations fell between 10–20 nm in front of homes with UFP levels ranging from 59,000 p/cm³ at couple hundred m downwind to 81,000 p/cm³ several hundred m directly downwind of the Peace Bridge under similar diesel trucks traffic and meteorological conditions.