Determination of Surface Functional Groups in Lignocellulosic Materials by Chemical Derivatization and ESCA Analysis

Simple and convenient methods for determining surface chemical composition of lignocellulosic materials are described. The methods are based on vapor phase fluorine surface derivatization with either trifluoro acetic anhydride (TFAA), tri-fluoro ethanol (TFE) or pentafluorophenyl hydrazine (PFPH) and subsequent Electron Spectroscopy for Chemical Analysis (ESCA). Model cellulosic surfaces with well defined functionalities were used to optimize the derivatization reaction conditions. Detection and accessibility of surface hydroxyl functional groups were investigated in cotton and regenerated cellulose as models. Carboxymethyl cellulose (CMC) was used as a model surface for detection and quantification of carboxylic acid groups. Theoretical conversion curves for derivatization reactions were calculated and used to evaluate the extent of the reactions on the model surfaces. It was found that the conversion was higher for the regenerated cellulose and CMC than for cotton. The protocols developed using the model surfaces were applied to a case study on wood fibers with different degrees of complexity, namely dissolving and chemithermomechanical (CTMP) pulp. Untreated and oxygen-plasma modified pulps were compared with respect to the surface composition of functional groups. According to the derivatization reactions, functionalities containing oxygen were significantly increased on the plasma-treated samples. The effect of the treatment was found to be dependent on the type of pulp. Fluorine derivatization is shown to be an unambiguous method for clear assessment of the chemical functionalities of cellulosic surfaces.     

ToF-SIMS analysis of a fluorocarbon-grafted PET with a gold cluster ion source

Cluster ions have been recognized as a superb primary species in time of flight secondary ion mass spectroscopy (ToF-SIMS) compared with monatomic primary ions, as they significantly enhance the secondary ion yields from bulk samples. Self-assembled monolayers provide an important system for studying the fundamental mechanism involved in the yield enhancement.We used a gold cluster ion source to analyze a new type of self-assembled monolayer: a fluorocarbon-grafted polyethylene terephthalate. In addition to the structure details, which helped to understand the grafting mechanism, ToF-SIMS analysis revealed that fluorocarbon secondary ion yield enhancements by cluster ions were due to the enhanced sputter efficiency. A larger information depth may also be expected from the enhancement. Both mathematical definitions of damage cross-section and disappearance cross-section were revisited under a new context. Another cross-section parameter, sputter cross-section, was introduced to differentiate the beam induced sputter process from damage process.     

Design and Experimental Characterization of Low‐Volume PM10/2.5/1.0 Trichotomous Sampler Inlet

This paper presents the development and laboratory evaluation of a PM10/2.5/1.0 trichotomous sampling inlet that consists of two main parts: a previously designed PM10 size‐selective inlet part and a PM2.5/1.0 two‐stage virtual impactor, which was newly fabricated and attached serially to the PM10 size selective inlet part. Particles are collected in three locations through the trichotomous sampling inlet to provide for not only particle concentration measurements of PM10, PM2.5 and PM1.0, but also those of PM2.5–10 and PM1.0–2.5.     

Baer orderings with noninvariant valuation ring

We construct division algebras with involution containing a Baer ordering with noninvariant order ring. This gives a negative answer to a question of Holland, whether the order ring is always invariant under inner automorphisms. Furthermore, we give examples of any index. Previously, the only known examples of division algebras containing Baer orderings were of index 2 ⁿ or of indexp forp a prime of the form 4m + 3. Supported in part by the National Science Foundation.     

Buckling of sandwich wide columns

The paper deals with the theoretical prediction of buckling loads for sandwich columns with metallic and laminated facings and foam or honeycomb core. The loading is a uniform axial compression, applied statically (very slowly) and suddenly with constant magnitude and infinite duration (step loading). The effect of length and boundary conditions is assessed and results are presented for the following cases: for a cantilever column, a simply supported column and a clamped column, for several lengths. Several fiber materials are used in the laminated facings. Two types of core were examined: alloy-foam or hexagonal glass/phenolic honeycomb. The facings are Boron/Epoxy, Graphite/Epoxy and Kevlar/Epoxy laminates with 0° orientation with respect to the column axis and a metallic one made out of aluminum. These various materials are employed to provide comparative data that can be used in design. Results, for the static case are generated by computer codes as well as by the use of closed form theoretical solutions. For the dynamic case, results are generated by the DYNA3D code.     

Local search algorithms for the min-max loop layout problem

In the min-max loop layout problem, machines are to be arranged around a loop of conveyor belt. The ordering of the machines dictates the number of circuits of the conveyor belt required to manufacture each of several products. The goal is to find an ordering of the machines that minimises the maximum number of circuits required for the manufacture of any of the products. Since the problem is strongly NP-hard, the study of heuristic methods is of interest. This paper proposes iterated descent and tabu search algorithms, and a randomised insertion algorithm. Results of extensive computational tests show that all of our algorithms outperform a previously known algorithm that applies a greedy heuristic to the solution of a linear programming relaxation. The best quality solutions are obtained with iterated descent. This adds further evidence to the belief that iterated descent can produce high quality solutions to a variety of combinatorial optimisation problems. Moreover, unlike some other local search algorithms, iterated descent does not require much tuning in order to be competitive.     

Tight-binding method modelling of photonic crystal waveguides

We present here a tight-binding-like modelling of two-dimensional (2D) photonic crystals (PCs). Adopted from solid-state physics, the concept of generalized Wannier functions is used to construct a localized state basis that allows a parameter-free ab initio study of defects in PCs. We demonstrate here for a 2D triangular lattice of dielectric rods in air, the existence of this localized basis and the possibility to study large scale complex dielectric structures deviating from periodicity. Specific numerical simulations on a split waveguide embedded in this triangular lattice are performed, and they demonstrate the superiority of this method over plane wave based techniques.     

Combining PSMs with hard OR methods: the philosophical and practical challenges

Combinations of problem structuring methods with hard OR methodologies are seldom described in the literature. This paper will reflect on the barriers to such combinations that can be seen at the philosophical level—paradigm incommensurability—and cognitive level—type of personality and difficulty of switching paradigm. This paper examines the combination of Soft Systems Methodology and Discrete Event Simulation within an Intermediate Care case study. The paper will argue, by way of the practical application, that these problems are not insurmountable and that the result can be seen as interplay of the soft and hard paradigms. The idea of yin and yang is proposed as a metaphor for this process.     

The α-arylation of α-bromo- and α-chloroenones using palladium-catalysed cross-coupling

The palladium-catalysed cross-coupling reaction of various arylboronic acids with α-bromoenones and α-chloroenones offers an operationally simple approach to the synthesis of both cyclic and acyclic α-arylenones.     

Aryl pyrrolidinones via radical 1,4-aryl migration and 5-endo-trig cyclisation of N-(2-bromoallyl)arylcarboxamides

Radical reaction of a series of N-(2-bromoallyl)arylcarboxamides led to the production of 4-arylpyrrolidin-2-ones and directly reduced materials in comparable yields. A cascade process, involving sequential 5-exo-trig spirocyclisation, β-scission, and 5-endo-trig cyclisation of the resulting acyl radical, is proposed to explain the pyrrolidinone products.