Network topology and the theory of rubber elasticity

The earliest investigations on rubber elasticity, commencing in the 19th century, were necessarily limited to phenomenological interpretations. The realisation that polymers consist of very long molecular chains. commencing c. 1930, gave impetus to the molecular theory of rubber elasticity (1932-). according to which the high deformability of an elastomer, and the elastic force generated by deformation, stem from the configurations accessible to long molecular chains. Theories of rubber elasticity put forward from 1934-1946 relied on the assumption that the junctions of the rubber network undergo displacements that are affine in macroscopic strain. The theory of James and Guth (1947) dispensed with this premise, and demonstrated instead that the mean positions of the junctions of a ‘phantom’ network consisting of Gaussian chains devoid of material properties are affine in the strain. The vital significance of the distinction between the actual distribution of chain vectors in a network and their distribution if the junctions would be fixed at their mean positions went unnoticed for nearly 30 years. Experimental investigations, commencing with the incisive work of Gee in 1946. revealed large departures from the relationship of stress to strain predicted by the theories cited. This discrepancy prompted extensive studies, theoretical and experimental, during succeeding years. Inquiry into the fundamentals of polymer networks, formed for example by interlinking very long polymer molecules, exposed the need to take account of network imperfections, typically consisting of chains attached at only one end to a network junction. Various means were advocated to make corrections for these imperfections. The cycle rank ζ of the network has been shown (1976) to be the fundamental measure of its connectivity, regardless of the junction functionality and pattern of imperfections. Often overlooked is the copious interpenetration of the chains comprising typical elastomeric networks. Theories that attempt to represent such networks on a lattice are incompatible with this universal feature. Moreover, the dense interpenetration of chains may limit the ability of junctions in real networks to accommodate the fluctuations envisaged in the theory of phantom networks. It was suggested in 1975 that departures from the form predicted for the elastic equation of state are due to constraints on the fluctuations of junctions whose effect diminishes with deformation and with dilation. Formulation of a self-consistent theory based on this suggestion required recognition of the non-affine connection between the chain vector distribution function and the macroscopic strain in a real network, which may partake of characteristics of a phantom network in some degree. Implementation of the idea was achieved through postulation of domains of constraint affecting the equilibrium distribution of fluctuations of network junctions from their mean positions. This led in due course to a theory that accounts for the relationship of stress to strain virtually throughout the ranges of strain accessible to measurement. The theory establishes connections between structure and elastic properties. This is achieved with utmost frugality in arbitrary parameters.     

Three ways to implement interfacial techniques: application tomeasurements of chromatic dispersion, birefringence, and nonlinearsusceptibilities

Depending on the spectal width of the source illuminating an interferometer, measurement procedures can utilize either the whole interferogram, or only the fringe envelope, or only the fringe quick oscillations. With an ultraband spectrum source, a simplified adaptation of the methods of Fourier transform spectroscopy yields the variations of the test-fiber propagation constant over the whole wavelength-interval of the source. Chromatic dispersion can then be computed from a single interferogram. With narrower spectrum sources, only the fringe envelopes are utilized and yield measurements of mode delay, with application to chromatic and polarization mode dispersion. In this case, however, interferograms at several wavelengths are necessary. With even narrower spectrum sources, the fringe quick oscillations provide measurements of phase shifts, related to changes in the mode propagation constant, when outside perturbations are applied to the test fiber. A direct method for measuring the third-order nonlinear susceptibilities is discussed. In this case the outside perturbation is an intense pump laser field     

Boosting nitrification by membrane-attached biofilm.

Nitrification is a key step for reliable biological nitrogen removal. In order to enhance nitrification in the activated sludge (AS) process, membrane-attached biofilm (MAB) was incorporated in a conventional activated sludge tank. Simultaneous organic carbon removal and nitrification of the MAB incorporated activated sludge (AS + MAB) process was investigated with continuous wastewater treatment. The effluent TOC concentration of AS and the AS + MAB processes were about 6.3 mg/L and 7.9 mg/L, respectively. The TOC removal efficiency of both AS and AS + MAB were above 95% during the wastewater treatment, indicating excellent organic carbon removal performance in both processes. Little nitrification occurred in the AS process. On the contrary, successful nitrification was obtained with the AS + MAB process with nitrification efficiency of about 90%. The volumetric and surface nitrification rates were about 0.14 g/Ld and 6.5 g/m2d, respectively. The results clearly demonstrated that nitrification in the conventional AS process was boosted by MAB. Furthermore, the microfaunal population in the AS + MAB process was different from that in the AS process. The high concentration of rotifers in the AS + MAB process was expected to decrease the generation of excess sludge in the process.     

Quantitative determination of aflatoxin B1 in chick liver

A method for the rapid and quantitative determination of aflatoxin B1 from small quantities of liver, around 1-2 g, is described. The extraction procedure involves acidification to pH 2 of the aqueous liver homogenates, extraction with chloroform: acetone and HPLC-fluorimetric detection after derivatization with trifluoroacetic acid. Quantitative recovery of aflatoxin B1 from chick liver was achieved and detection at levels of 0.2-1 ppb was proved feasible. The aflatoxin B1 concentration in chick liver after oral administration is also shown.     

High performance biofilm process for treating wastewater discharged from coal refining plants containing nitrogen, cyanide and thiocyanate.

Wastewater discharge from coal refining plants contains a number of biologically toxic compounds; 2000-2500 mg/l of COD of which 40% is composed of phenol, 100-400 mg/l of thiocyanate, 10-40 mg/l of cyanide, 100-250 mg/l of NH4+-N and 150-300 mg/l of total nitrogen. In order to treat this kind of high strength wastewater, we have developed a high performance biofilm process using fluidizing bio-carriers of the tube chip type. The fluidizing biofilm carriers are made of a composite of polyethylene and several inorganic materials, whose density is controlled at 0.97-0.98 g/ml. The fluidizing biofilm carriers show sound fluidization characteristics inside bioreactors. The wastewater is treated using three consecutive series reactors in oxic-anoxic-oxic arrangement. Each reactor is charged with the fluidizing biofilm carriers of 50 vol%. Furthermore, newly cultured active microorganisms for the thiocyanate biodegradation are added in the biofilm process. At total hydraulic retention time of 2.2 days, this process can achieve steady state removal efficiencies: COD, 99%; thiocyanate, 99%; NH4+-N, 99% and total nitrogen, 90%.     

Solution of Helmholtz equation by Trefftz method

The application of the Trefftz method for calculating wave forces on offshore structures is presented. Indirect and direct formulations using complete and non-singular systems of Trefftz functions for the Helmholtz equation are posed in this paper. An effective technique using different interpolation functions for the velocity potential and wave force are suggested to improve the computational accuracy of the wave force. The numerical examples show that the present method is highly efficient and accurate.     

Organic matter release in low temperature thermal treatment of biological sludge for reduction of excess sludge production.

Thermal treatment applied in association with a biological system allows for a significant reduction in excess sludge production (approximately 50%). In general, heat treatment is described as a sludge disintegration technique. This paper offers a thorough study on the impact of heat treatment, at temperatures below 100 degrees C, on the solubilisation of the sludge COD and its biodegradability. Discontinuous heating experiments were performed on activated and digested sludge. At all temperatures tested the released COD for digested sludge was systematically higher than that for activated sludge (15 and 40%, respectively, at 95 degrees C for 40 min of contact time). For the first 30 min, a 1st order kinetic, with respect to the residual COD, was systematically found. In the range of 40-95 degrees C, digested sludge had a lower activation energy than activated sludge (26 kcal/mol compared to 70-160 kcal/mol). COD solubilisation is thus more positively influenced by temperature in the case of activated sludge. This may be due to the significant difference in the ratio of protein/carbohydrate in digested and activated sludge (1-5 and 0.2-0.7, respectively). The increase in the COD/TKN ratio in the solubilised fraction after thermal treatment of activated sludge suggests a preferential solubilisation of proteins over carbohydrates. Respirometric tests performed on the solubilised COD showed that whatever the sludge origin, only 40-50% of released COD is biodegradable at a conventional hydraulic retention time (i.e., 24 h). Hence, heat treatment would act more through organic matter solubilisation rather than by a biodegradability increase.     

Novel tiO2 nanocatalysts for wastewater purification: tapping energy from the sun.

Water treatment using TiO2 semiconductor as a durable heterogeneous photocatalyst has been the focus of environmentalists in recent years. Currently, we developed an inexpensive and highly efficient approach for synthesizing nitrogen-doped TiO2 with lower band-gap energy that can respond to visible light. Doping on the molecular scale led to an enhanced nitrogen concentration of up to 21.8%. Reflectance measurements showed the synthesized N-doped TiO2 nanoparticles are catalytically active with the absorbance that extends into the visible region up to 600 nm. The water purification potential of this new class of compound was evaluated by studying the photodegradation of Acid Orange 7 (AO7) and E. coli. Experiments were conducted to compare the photocatalytic activities of N-doped TiO2 nanocatalysts and commercially available Degussa P25 power under identical solar light exposure. N-doped TiO2 demonstrated superior photocatalytic activities in both chemical compound degradation and bactericidal reactions. The result of this study shows the potential of applying new generations of catalyst for wastewater purification and disinfection.     

Anaerobic biodecolorization of textile reactive anthraquinone and phthalocyanine dyebaths under hypersaline conditions.

The biological decolorization of two industrial, spent textile reactive dyebaths was investigated using a suspended-growth, halophilic mixed culture fed with glucose. Dyebath I contained mainly Reactive Blue 19 (RB19), an anthraquinone dye, whereas dyebath II contained mainly Reactive Blue 21 (RB21), a phthalocyanine dye. Batch assays under anaerobic conditions with the two neutralized dyebaths resulted in 87 and 37% extent of decolorization for dyebaths I and II, respectively. The rate of glucose utilization and the extent of acetate production were impacted in the presence of each dyebath as compared to the control culture. However, dyebath decolorization occurred despite moderate culture inhibition. Reuse of a biologically renovated RB19-containing dyebath in the dyeing process resulted in reproducible but not identical cotton fabric shades as compared to a standard dyeing (i.e., control) using fresh water. This difference is attributed to a variable degree of RB19 aggregation during the dyeing process and is not related to the efficiency of the biodecolorization process. Further improvement of the redyeing efficiency will lead to the development of an in-plant, closed-loop decolorization system resulting in significant water conservation and minimization of textile pollutants such as salt and dyes.     

Linearity stablized fiber-optic thermometer using pseudo-heterodyne phase detection

A temperature sensor using a fiber-optic Fabry-Perot interferometer is described. A pseudo-heterodyne detection scheme is adopted to read the light phase difference in the Fabry-Perot interference output. A higher harmonic components comparison method is used to stabilize the system and to increase detection linearity. This system realizes not only highly sensitive temperature sensing with good linearity and minimal adjusting error, but also application to the sensing of other physical quantities such as vibrations. Additionally, the signal-to-noise ratio and distortion of the detected signal are investigated as functions of fiber end reflectivity. These results will be useful in designing a high performance fiber-optic Fabry-Perot thermometer.