Polymerization of pyrrole on cellulose fibres using a FeCl3 impregnation- pyrrole polymerization sequence

Polypyrrole was polymerized on the surface of cellulose fibres using a sequence of fibre impregnation in FeCl₃ solutions, thickening and re-dispersion in a pyrrole solution. ζ-Potential and adsorption isotherms of the FeCl₃-cellulose systems showed that the adsorption of iron III was associated with the formation of free Fe³⁺ cations in the impregnation liquor. Moreover, under the test conditions applied, the amount of adsorbed iron III was not sufficient to promote the polymerization of a adequate amount of pyrrole on the fibre surface. Optimization of the polymerization reaction required that the FeCl₃ concentration in the impregnation liquor be increased to approximately 1 mol/l with a subsequent decrease of pH to approximately1.8. Based on scanning electron (SEM) micrographs and the low cellulose polymerization degree measured after pyrrole polymerization, we concluded that the decrease in the electric resistance of bulky polypyrrole/cellulose compounds was associated with a not negligible degradation of the cellulose fibres due to acid hydrolysis and the subsequent impossibility to prepare hand sheets with modified fibres due to the insufficient strength of the wet fibre network. The results of this investigation bring into question the use of FeCl₃-pyrrole-cellulose systems for the elaboration of conducting paper sheets with good and stable mechanical properties.     

Rapid hydrogen peroxide release in cell suspensions ofCapsicum spp. elicited by fungal preparations

The release of H₂O₂ by plant cell suspensions elicited with crude hyphal wall preparations has been studied in a complex of plant genotypes (two cvs ofCapsicum annuum and one of C.frutescens) and fungus species(Phytophthora capsici, Ph. parasitica andVerticillium dahliae), representing several combinations of compatibility and both host and nonhost resistance. Production of H₂O₂ was revealed as peroxidasedependent and catalase-inhibited fluorescence quenching of an extracellular probe (Pyranine). All the plant genotypes responded to at least one elicitor, but the cell sensitivity showed a great age-dependent variability. Riboflavine and Mn²⁺ added in the incubation medium acted to some extent as primers for activated cell response, as well as a high Na⁺ concentration. Cell rest condition, however, was not removed. Some quantitative features of responsive plant/elicitor combinations (dose-response relation and lasting time) have been recorded. The complex PO/H₂O₂ of elicited cells could perform detectable lignin-like polymerization of an exogenous natural substrate (coniferyl alcohol). The time-course of pyranine oxidation and lignin-like polymer formation could be recorded by adopting a fluorimetric procedure that allowed sequential observations on the same cell sample. In one instance, the cell reaction seemed associated with thein planta host/parasite incompatibility.     

Crystallization and characterization of crystallites in charge stabilized suspensions

For three different types of polymer latex particles with widely different particle charges the structure of suspensions before and after crystallization is investigated. A liquid-like ordered state was achieved by shear melting crystal-like ordered samples. The structure factors S(Q) of the liquid-like suspensions are analyzed in terms of the resealed mean spherical approximation (RMSA) of Hansen and Hayter. The Bragg diffraction pattern of the crystallized samples shows that the structure is b.c.c. It is found that the particle number concentration n and the distance of nearest neighbours in corresponding liquid- and crystal-like states differ by less than 4 %.

In the second part of the paper, Bragg diffraction was used to determine the crystallite size distribution in samples of different particle concentration.     

Random copolymers at a selective interface: Many chains with excluded volume interactions

We investigate numerically, using the bond-fluctuation model, the adsorption of many random AB-copolymers with excluded volume interactions at the interface between two solvents. We find two regimes, controlled by the total number of polymers. In the first (dilute) regime, the copolymers near the interface extend parallel to it, while in the second regime they extend perpendicular to it. The density at the interface and the density in the bulk depend differently on the total number of copolymers: In the first regime the density at the interface increases more rapidly than in the bulk, whereas the opposite is true in the second regime. Received 4 March 1998 and Received in final form 22 September 1998     

A comparison of automated and manual techniques for measurement of electrospun fibre diameter

Electrospinning is a fibre manufacturing process, and fibre diameter is a fundamental property. We compare diameter measurements made by human operators against two automated algorithms (FibreQuant™ and SEMAnalyser™). The effects of scanning electron microscopy preparation by iridium, gold and carbon coating on fibre diameter are also examined.A human takes 2.2 h to make 150 measurements. Automated analysis produces 9000 measurements less than 5 minutes. The automated method produces results without researcher bias and with greater consistency, but will occasionally include incorrect measurements because of the simple heuristics used. The manual method used by human operators shows larger variation in reported averages and is labour intensive.Before obtaining scanning electron microscopy images, the fibre samples require a conductive coating to prevent charging and burning of the fibres; the effects of SEM preparation methods such as iridium, gold and carbon coating showed that iridium coating had the least impact on fibre diameter.     

Fibre homogenisation

In this article we present a novel method for studying the asymptotic behaviour, with order-sharp error estimates, of the resolvents of parameter-dependent operator families. The method is applied to the study of differential equations with rapidly oscillating coefficients in the context of second-order PDE systems and the Maxwell system. This produces a non-standard homogenisation result that is characterised by ‘fibre-wise’ homogenisation of the related Floquet-Bloch PDEs. These fibre-homogenised resolvents are shown to be asymptotically equivalent to a whole class of operator families, including those obtained by standard homogenisation methods.     

Recombination of hydrogen atoms on fine-grain graphite

The probability of recombination of hydrogen atoms on surfaces of fine-grain graphite EK98 was investigated as a function of surface roughness. The source of hydrogen atoms used in this experiment was weakly ionised plasma created with an inductively coupled radiofrequency generator at pressures from 30 Pa to 175 Pa in hydrogen. Hydrogen atom density was measured by means of fibre optic catalytic probes. The recombination coefficient of the graphite samples was determined by observing their impact on the spatial distribution of the atom density in a closed side-arm of the reactor. Smith's diffusion model was used to calculate the values of the recombination coefficient. The measured recombination coefficient was found to increase much faster than the measured effective surface. This discrepancy is explained by the fact that on a surface which is not perfectly flat, there is a finite probability for multiple collisions. Impinging atoms collide more than once with the surface before they are reflected into the surface, which results in a larger probability of recombination.     

Mixed Measures of Convex Cylinders and Quermass Densities of Boolean Models

Translative integral formulas for curvature measures of convex bodies were obtained by Schneider and Weil by introducing mixed measures of convex bodies. These results can be extended to arbitrary closed convex sets since mixed measures are locally defined. Furthermore, iterated versions of these formulas due to Weil were used by Fallert to introduce quermass densities for (non-stationary and non-isotropic) Poisson processes of convex bodies and respective Boolean models. In the present paper, we first compute the special form of mixed measures of convex cylinders and prove a translative integral formula for them. After adapting some results for mixed measures of convex bodies to this setting we then use this integral formula to obtain quermass densities for (non-stationary and non-isotropic) Poisson processes of convex cylinders. Furthermore, quermass densities of Boolean models of convex cylinders are expressed in terms of mixed densities of the underlying Poisson process generalizing classical formulas by Davy and recent results by Spiess and Spodarev.      

Spatial Statistics of Stochastic Fiber Networks

From the known statistics of fiber-fiber contacts in random fiber networks, an analytic estimate is obtained for the variance of local porosity in random fiber suspensions and evolving filtrate networks. The variance of local porosity, and hence the distribution of projected areal density, seem to depend on fiber geometry only through the cube of mean diameter. Also, the coefficient of variation of local flow rate perpendicular to the plane of the pad is, to a first approximation, independent of the mode of flow. Analytic estimates are obtained also for the effect of fiber clumping on the variance of local porosity of pads for small inspection zones.