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.     

Mixing mechanisms of vortex ring formed by gravity slumping motion

 This paper is concerned with an experimental investigation of the mixing inside the vortex ring formed by the gravity slumping motion of a dense cloud in a less dense atmosphere. The dynamics of the spreading and instantaneous structures of the turbulent flow were examined by visualization, single and multi-point measurements of velocity and concentration for two heavy gases, carbondioxide (CO₂) and dichlorodifluoromethane (CCl₂F₂), in a configuration in that heavy gas, initially trapped in a reservoir, was released with the rise of a shutter into calm air of a sector-shaped dispersion channel. Visualization of the cloud as a whole showed a spreading motion in which an advancing frontal structure was followed by a stratified flow with a layer of dense fluid of higher velocities near the wall and, on top of it, a layer of dilute fluid whose concentration is controlled by the mixing mechanisms within the head. During the course of spreading, there was always a phase in which the head attained to a constant speed of advance, which occurred as 0.13 m/s for CO₂ and 0.48 m/s for CCl₂F₂. It was interesting to observe for CO₂ that the phase of constant speed took place in between two acceleration phases; the former was due to the initial slumping of the cloud at the exit of the reservoir, and the latter was attributed to the collapse of the head on the transition to the passive dispersion phase. Instantaneous two-dimensional velocity field, measured with particle image velocimeter (PIV), showed that the cloud overran the ambient air which caused the approaching dense fluid deflected away from the wall with significant vertical velocities and downstream-moving separation, and the air trapped under the head resulted in the density inversion which introduced further intricacy to the turbulent structure of the head. Instabilities at the upper free shear layer due to density and velocity discontinuity rolled into periodic array of vortices which engulfed a considerable amount of air as they were convected backwards over the head, but the incorporation of heavy and light fluids was completed with the appearance of microscales after the collapse on the stratified layer. Analyses of the cloud head at different downstream locations also revealed that its size remained unchanged when the speed of advance was constant, allowing the rate of change of the cloud volume being modeled with the rate of spreading. Contours of concentration obtained from digitized PIV pictures confirmed the kinematic features of the mixing revealed by the velocity field and that the concentration values within the large structures were higher than those at the upper part of the stratified layer. Motivated by the experimental observations, a semi-empirical analysis was presented to describe the results and based on local values of the Richardson and Reynolds numbers. Received: 4 October 1995 / Accepted: 4 July 1996     

Solubility of carbon dioxide in aqueous solutions of sodium chloride: Experimental results and correlation

The solubility of carbon dioxide in aqueous solutions of sodium chloride was measured in the temperature range from 40 to 160°C, up to 6 mol-kg salt solutions and total pressures up to 10 MPa. Pitzer's⁽¹⁾ equations as well as the Chen and Evans⁽²⁾ model were used to correlate the new data. Results are reported and compared to literature data and correlations.     

Fracture strength of class II slot cavities restored with polymerizable restorative materials

This study compared the fracture strength of Class II slot cavities restored with polymerizable restorative materials. Sixty, caries-free, posterior teeth were divided into five groups of 12 teeth. The Class II slot cavities were prepared. The teeth were restored with two packable composites (Filtek P60, Surefil), a microhybrid composite (Filtek Z250)and two ormocer (Definite, Admira). The restorations were then subjected to fracture resistance tests. The marginal ridges of the restorations were loaded at an angle of 13.5° to the long axis of the tooth in an Universal Testing Machine until failure. Analysis of mean forces indicated that, Filtek P60, Surefil and Filtek Z250 exhibited better performance than Definite and Admira. The tested resin composites differed in their mechanical properties. This study suggested that fracture behavior were highly influenced by the filler system. Overall, Filtek P60, Surefil, Filtek Z250, demonstrated good fracture resistance. Copyright © 2003 John Wiley & Sons, Ltd.     

Fluctuation measurements in a supersonic boundary layer implying in-situ calibration of the hot-wire anemometer

A calibration technique for the constant-temperature hot-wire anemometer is presented, which is based on traversing the probe through the boundary layer of a flat plate while simultaneously performing fluctuation measurements. The free stream Mach number was M = 2.54, and the Reynolds number Re_d, based on wire diameter, ranged from 9 to 23. A comparison of the sensitivity values obtained with the aid of such a calibration procedure — under the condition of neglecting low temperature loadings (t<0.6) — agrees well with sensitivities determined with free-stream data-The use of a modified transfer function for correcting the power spectra of flow perturbations revealed a conformity of wide parts of the corrected spectra with the Kolmogorov decay. The fluctuation levels of total temperature and mass flux were computed for the boundary layer of a flat plate. This work was presented at the International Conference on the Methods of Aerophysical Research ICMAR 2007, which was held in Novosibirsk on 5–10 February 2007.     

Bi5O7Br and its structural relation to α‐Bi5O7I

Pentabismuth heptoxide bromide, Bi₅O₇Br, crystallizes in the space group Cmca. Its structure is compared with the closely related Ibca structure of α‐Bi₅O₇I. The change in the space group is assumedly the result of a compromise between the different spatial needs of Br and I and the rigidity of the {³_∞}[Bi, O] frameworks into which they are embedded. A detailed procedure for the synthesis of Bi₅O₇Br is given.     

Preliminary analyses of natural radionuclides in selected Turkish power plant lignites

This preliminary study presents the experimental results concerning the concentrations of selected radionuclides (²³⁸U, ²³²K, ²²⁶Ra, ²³²Th) in Af?in-Elbistan, Çan, Çay?rhan, Erzurum, Göynük, Kangal, Orhaneli, Saray, Seyitömer, Soma, Tunçbilek, Yata?an and Yeniköy lignites, which are primarily utilized as fuel for thermal power plants in Turkey. Gamma-spectrometry of 39 representative lignite samples gave results with the following concentration ranges: 8 to 296 Bq/kg for ²³⁸U, 3 to 79 Bq/kg for ²³²Th, 17 to 360 Bq/kg for 40K, and 5 to 130 Bq/kg for ²²⁶Ra. The ²³⁸U results reported here are higher than other literature values for various world coals, earth's crust and world average.     

Antimicrobial activity studies of the binuclear metal complexes derived from tridentate Schiff base ligands

Three novel tridentate Schiff base ligands derived fromthe 3-hydroxysalicylaldehyde (H₂L¹), 4-hydroxysalicylaldehyde (H₂L²) and 5-bromosalicylaldehyde (H₂L³) with a new amine N-(pyridyl)-2-hydroxy-3-methoxy-5-aminobenzylamine (2) have been prepared. The ligands and their metal complexes have been characterized by elemental analyses, conductivity and magnetic susceptibility measurements, i.r., electronic absorption and ¹H and ¹³C n.m.r. spectroscopy. All complexes are binuclear and, in some, the H₂O molecules are coordinated to the metal ion. Antimicrobial activities of the ligands and their complexes have been tested against to the Bacillus subtilis IMG 22 (bacteria), Micrococcus luteus LA 2971 (bacteria) Saccharamyces cerevisiae WET 136 (yeast), and Candida albicans CCM 314 (yeast). Thermal properties of all complexes have been studied by t.g. and d.t.a techniques.