Preparation and characterization of poly(butylene terephthalate)/poly(ethylene terephthalate) copolymers via solid‐state and melt polymerization

To increase the T_g in combination with a retained crystallization rate, bis(2‐hydroxyethyl)terephthalate (BHET) was incorporated into poly(butylene terephthalate) (PBT) via solid‐state copolymerization (SSP). The incorporated BHET fraction depends on the miscibility of BHET in the amorphous phase of PBT prior to SSP. DSC measurements showed that BHET is only partially miscible. During SSP, the miscible BHET fraction reacts via transesterification reactions with the mobile amorphous PBT segments. The immiscible BHET fraction reacts by self‐condensation, resulting in the formation of poly(ethylene terephthalate) (PET) homopolymer. ¹H‐NMR sequence distribution analysis showed that self‐condensation of BHET proceeded faster than the transesterification with PBT. SAXS measurements showed an increase in the long period with increasing fraction BHET present in the mixtures used for SSP followed by a decrease due to the formation of small PET crystals. DSC confirmed the presence of separate PET crystals. Furthermore, the incorporation of BHET via SSP resulted in PBT‐PET copolymers with an increased T_g compared to PBT. However, these copolymers showed a poorer crystallization behavior. The modified copolymer chain segments are apparently fully miscible with the unmodified PBT chains in the molten state. Consequently, the crystal growth process is retarded resulting in a decreased crystallization rate and crystallinity. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 882–899, 2007.     

Modelling the velocity of air through beds of cereal grains

The quality of cereal grains in storage will deteriorate toan unacceptable level if they are not kept dry and cool. Tomodel the drying and cooling process, an accurate knowledgeof the airflow distribution is required. In this paper, theequations used to model the air velocity are analysed. To study the flow of air through a typical drying system forstored grain, a two-dimensional rectangular bin is considered,with a single source of air on the bin floor. Two paths ofstudyare undertaken: the first is a linear analysis for low velocities,and following on from this is a nonlinear approach for largervelocities. The linear analysis is used to study a bin witha semi-infinite height, and the drying pattern is studied inthis bin using the air traverse time. Then bins with a finiteheight are analysed: it is shown that, for tall enough bins,the semi-infinite solution is accurate enough. A perturbationanalysis is used to study the semi-infinite bin when the airvelocity is too large for the linear analysis to be accu rate.It is shown that the effect of the nonlinearity is to move theair away from the high-velocity regions towards the areas oflower velocity.     

A horizontal atmospheric temperature sounder: Applications to remote sensing of atmospheric hazards

Several atmospheric hazards, including wind shear, clear-air turbulence, and wake vortices cause special problems for aircraft. These phenomena are usually characterized by a change in temperature relative to ambient, which may be detected by a millimeter wave radiometer operating on an absorption line in the atmosphere. Because of available componentry with excellent performance and relative freedom from interference by water vapor, the family of oxygen absorptions centered near 60 GHz is considered the best atmospheric feature on which the design of such an instrument could be based. This paper describes a multi-channel radiometer operating near 60 GHz which should be capable of detecting the hazards mentioned above as well as other potential dangers such as the passage of strong fronts and other severe weather. It is shown that a carefully designed instrument will be capable of measuring range to a hazard to an accuracy of about 5 percent and temperature difference to an accuracy of approximately half the actual measured difference, depending on range and temperature. An actual design is proposed, and graphs of expected performance are included.     

On a Moving Boundary Problem Aristing in Fluidized Bed Combustion

We consider a model describing the combustion of a coal particlein a fluidized bed, in which attrition plays a dominant role.The model consists of (1) a quasi-linear elliptic equation forthe oxygen concentration, supplemented by boundary conditionson the moving surface representing the burning particle interface,(2) an evolution equation for the carbon consumption, and (3)an equation governing the motion of the interface in terms ofa specified function of the carbon consumption at the interface.We prove a global existence and uniqueness result, togetherwith a priori bounds for the solution; the existence of travellingwaves will also be established.     

ABSOLUTELY UNSTABLE WAVES IN INVISCID HYDROELASTIC SYSTEMS

The effect of inviscid plug flow on the stability of several hydroelastic systems is investigated by determining the absolute or convective nature of the instability from the linear dispersion relation. The fluid-structure systems consist of plates and membranes with bounded and unbounded flow. A method is proposed to derive systematically in parameter space the boundary between convective and absolute instability, based on the particular symmetries of the dispersion relation as originally noted by Crighton and Oswell. This method is then applied to the case of plates with superimposed tension, thick plates with rotary inertia and walls made of plates or membranes bounding channel flow, oscillating in a sinuous or varicose mode of deformation. A relation is drawn with solutions by previous authors for plates, for pipes and for the Kelvin-Helmholtz instability with surface tension. To illustrate these results some temporal evolutions are calculated by using an integration in the wavenumber space. Based on the large set of new cases solved in the paper some general trends are discussed as to the influence of flow velocity, confinement and structural stiffness on the existence of absolutely unstable waves in inviscid hydroelastic systems.     

Use of measurement uncertainty analysis to assess accuracy of carbon mass balance closure for a cellulase production process

Closing carbon mass balances is a critical and necessary step for verifying the performance of any conversion process. We developed a methodology for calculating carbon mass balance closures for a cellulase production process and then applied measurement uncertainty analysis to calculate 95% confidence limits to assess the accuracy of the results. Cellulase production experiments were conducted in 7-L fermentors using Trichoderma reesei grown on pure cellulose (Solka-floc), glucose, or lactose. All input and output carbon-containing streams were measured and carbon dioxide in the exhaust gas was quantified using a mass spectrometer. On Solka-floc, carbon mass balances ranged from 90 to 100% closure for the first 48 h but increased to 101 to 135% closure from 72 h to the end of the cultivation at 168 h. Carbon mass balance closures for soluble sugar substrates ranged from 92 to 127% over the entire course of the cultivations. The 95% confidence intervals (CIs) for carbon mass balance closure were typically ±11 to 12 percentage points after 48 h of cultivation. Many of the carbon mass balance results did not bracket 100% closure within the 95% CIs. These results suggest that measurement problems with the experimental or analytical methods may exist. This work shows that uncertainty analysis can be a useful diagnostic tool for identifying measurement problems in complex biochemical systems.     

Design of hydrophobic polyoxometalate hybrid assemblies beyond surfactant encapsulation

Grafting of C-6, C-16 and C-18 alkyl chains onto the hydrophilic Mn-Anderson clusters (compounds 2-4) has been achieved. Exchange of the tetrabutyl ammonium (TBA) with dimethyldioctadecyl ammonium (DMDOA) results in the formation of new polyoxometalate (POM) assemblies (compounds 5-6), in which the POM cores are covalently functionalized by hydrophilic alkyl-chains and enclosed by surfactant of DMDOABr. As a result, we have been able to design and synthesize POM-containing hydrophobic materials beyond surfactant encapsulation. In solid state, scanning electron and transmission electron microscopy (SEM and TEM) studies of the TBA salts of compounds 3 and 4 show highly ordered, uniform, reproducible assemblies with unique segmented rodlike morphology. SEM and TEM studies of the DMDOA salts of compounds 5 and 6 show that they form spherical and sea urchin 3D objects in different solvent systems. In solution, the physical properties of compound 5 and 6 (combination of surfactant-encapsulated cluster (SEC) and surface-grafted cluster (SGC)) show a liquid-to-gel phase transition in pure chloroform below 0 degrees C, which are much lower than other reported SECs. By utilizing light scattering measurements, the nanoparticle size for compounds 5 and 6 were measured at 5 degrees C and 30 degrees C, respectively. Other physical properties including differential scanning calorimetry have been reported.     

Commutators with idempotent values on multilinear polynomials in prime rings

Let R be a prime ring of characteristic different from 2, C its extended centroid, d a nonzero derivation of R, f(x ₁, . . . , x _n ) a multilinear polynomial over C, ρ a nonzero right ideal of R and m > 1 a fixed integer such that

$$\qquad \left ([d(f(r_{1},\ldots ,r_{n})),f(r_{1},\ldots ,r_{n})]\right )^{m}=[d(f(r_{1},\ldots ,r_{n})),f(r_{1},\ldots ,r_{n})] $$

for all r ₁, . . . , r _n ∈ρ. Then either [f(x ₁,…,x _n ),x _n+1]x _n+2 is an identity for ρ or d(ρ)ρ = 0.

     

Incorporation of N-heterocyclic cations into proteins with a highly directed chemical modification

N-Heterocyclic cations are incorporated into proteins using 5-(2-bromoethyl)phenanthridinium bromide, which selectively reacts with either cysteine or lysine residues, resulting in ethylphenanthridinium (Phen) or highly stable cyclised dihydro-imidazo-phenanthridinium (DIP) adducts respectively; these modifications have been found to manipulate the observed structure of lysozyme and bovine serum albumin by AFM.