Photoresponsive peptide and polypeptide systems: part II. Photochromism of poly(l-ornithine) containing various azo-contents in side chains

Poly(L-ornithine)s having various azo-contents in the side chains were synthesized by the water-soluble carbodiimide procedure. The photochemical properties of the polypeptides poly[N^δ-p-(phenylazo)benzoyl-L-ornithine] (PPABLO) containing 3–77 mol% azobenzene were investigated by absorption and circular dichroism spectroscopy in hexafluoro-2-propanol (HFIP) or water, and in HFIP-water or methanol-water solvent mixtures. The photochromism of the dichroic bands of the PPABLOs containing 20–77 mol% azobenzene in the visible and ultraviolet wavelength regions was found to be mostly reversible as a function of irradiation time at different wavelengths due to the photostationary state (above 80% trans-cis photoisomerization) of the azo aromatic moieties. The PPABLO containing 3.2 mol% azobenzene in water exhibited conformational changes from random coil to helix by the addition of methanol or sodium dodecyl sulphate (SDS). The photo-induced conformational change was observed in HFIP-water-SDS solvent mixtures, while no conformational change was seen in water and HFIP-water solvent mixtures.     

Measurement of the tunnel rate in SIS' tunnel junctions as function of bias voltage

Cryogenic detectors with superconducting tunnel junctions can provide an energy resolution improved by at least one order of magnitude compared with standard semiconductor detectors. While the detection principle was already demonstrated many years ago, the past years were dedicated to the transition from the laboratory sample to practical detectors. Our most favored detector design gives rise to tunnel junctions with electrodes of unequal energy gaps. In such hetero tunnel junctions bias conditions can be established which cause a negative signal current. We report the experimental verification of this effect, and we discuss the yield of charge signal of cryogenic detectors based upon superconducting tunnel junctions.     

Cohesive stresses and size effect in quasi-brittle materials

A novel approach to the derivation of Bažant’s size effect law is presented. Contrarily to the original Lagrangian derivation which hinged on energetic consideration, a Newtonian approach based on local stress intensity factors is presented. Through this approach, it is shown that Bažant’s size effect law is the first (and dominant) term in a series expansion for the nominal stress. Furthermore, analytical expressions forB are derived for selected specimen geometries.     

Paste Residence Time in a Spouted Bed Dryer. II: Effect of Spout Operational Conditions

Residence time distributions for an aqueous solution of 10% sodium chloride in a spouted bed dryer of inert particles were determined using the stimulus-response technique. Glass and polyethylene beads with diameters 2.6 and 3.4 mm were used as inert bodies in a cylindrical column of 14.0 cm diameter and 60° conical base. The effects of inert bodies load, air, and paste flow rates on the mean residence times and RTD were determined following 2³ factorial designs. The RTD could be correlated to the perfect mixing cell model with R² varying from 0.8684 to 0.9815. The mean residence times in CSBD varied from 10.8 to 13.9 and 10.7 to 13.3 min for glass and polyethylene beads, respectively. For both inert particles, mean residence times increased with bed height and decreased with paste feed rates. Also, terms of interaction among the factors were significant in some cases, showing a complex behavior of paste residence times. Equations obtained by response surface regression could predict mean residence times on glass and polyethylene beads with deviations lower than ±10%.     

Drying Characteristics of Barley Grain Dried in a Spouted-Bed and Combined IR-Convection Dryers

A study was performed to determine the drying characteristics and quality of barley grain dried in a laboratory scale spouted-bed dryer at 30, 35, 40, and 45°C and an inlet air velocity of 23 m/s^-1, and in an IR-convection dryer under an infrared radiation intensity of 0.048, 0.061, 0.073, and 0.107 W cm^-2 at an air velocity of 0.5 m/s^-1. The results show that the first, relatively short, phase of a sharp decrease in the drying rate was followed by the phase of a slow decrease. The time of barley drying depended on temperature of inlet air in a spouted-bed dryer and on radiation intensities in an IR-convection dryer. Barley drying at 45°C in a spouted-bed dryer was accompanied by the lowest total energy consumption. The average specific energy consumption was lower and the average efficiency of drying was higher for drying in a spouted-bed dryer. The effective diffusivities were in the range 2.20-4.52 × 10^-11 m² s^-1 and 3.04-4.79 × 10^-11 m²/s^-1 for barley dried in a spouted-bed and in an IR-convection dryer, respectively. There were no significant differences in kernel germination energy and capacity between the two drying methods tested.     

A study of solid circulation rate in a circulating fluidized bed

An experimental investigation under cold condition was made to study the effects of some operating/design parameters and non-mechanical L valve configuration on the solid circulation rate in a 4.5 m tall, 0.15 m diameter circulating fluidized bed with riser flow rate varying from 1400 litres/min to 2000 litres/min and bed inventory from 15 kg to 25 kg of sand of average sizes 200 μm, 400 μm and 500 μm. Solid circulation rate was estimated by measuring velocity of sand particle travelling through a vertical Perspex tube section at the bottom of the return leg. It was found to be in the range of 2.8 to 12.3kg/m²s, 0.07 to 9.1kg/m²s and 0.12 to 2.23kg/m²s for sand sizes of 200 μm, 400 μm and 500 μm, respectively for a horizontal L valve. Two mathematical correlations have been developed from the experimental results to predict solid circulation rate as a function of riser flow rate, aeration flow rate, total bed inventory and particle size used.     

A New Variable Diffusion Drying Model for the Second Falling Rate Period of Paddy Dried in a Rapid Bin Dryer

The objectives of this article is to propose a new drying model for the second falling rate period known as the variable diffusion controlled period that follows after the first falling rate period and to propose a new method to determine the second critical moisture content that separates these two periods. Experimental work on paddy drying at minimum fluidization velocity was carried out in a rapid bin dryer. The effects of operating temperatures (60-120°C) and bed depths (2-6 cm) on the paddy drying characteristics were investigated. It was found that the normalized drying rate of paddy was proportional to the normalized moisture content in the first falling rate period but in the second falling rate period, the normalized drying rate of the material varies exponentially with the normalized moisture content. The different relationship between the normalized drying rate and the normalized moisture content in the first and second falling rate periods indicate that two different mechanism of moisture transport are at work. The new exponential model of the second falling rate period and the linear model of the first falling rate period were found to fit the experimental data very well. Derivation from variable diffusion equation shows that the linear model is the result of constant diffusion coefficient whereas the new exponential model is the result of linear diffusion coefficient. This also implies that the first falling rate period is a constant diffusion controlled period and the second falling rate period is a variable diffusion controlled period. In addition, drying kinetics data of a drying process that fits the exponential model over a very slow drying period will show that the drying process is under the effect of a linear diffusion coefficient. It was also found that the proposed new method to determine the second critical moisture content that distinguishes between the first and second falling rate periods by using a sudden change in the value of the drying rate gradient to a much lower value at that point is more rigorous and yet simpler than the method of determining the specific location of the receding drying boundary since it is based on the behavior of the actual drying kinetic data.     

Effects of α‐form or β‐form nuclei on polymorphic crystalline morphology of poly(butylene adipate)

The effects of α‐form and β‐form nuclei on polymorphic morphology of poly(butylene adipate) (PBA) upon recrystallization from the molten state up to various T_max values were examined by differential scanning calorimetry (DSC), wide‐angle X‐ray diffraction (WAXD) and polarized light microscopy (PLM). In this study, PBA with complex melting and polymorphism behaviour was used as a model for examining different types and extents of residual nuclei. As the PBA initially containing the sole α‐crystal was brought to a molten state of various T_max, the extents of trace α‐form crystal nuclei varied and were dependent on T_max. Furthermore, it did not matter whether, initially, the PBA contained α‐ or β‐form crystals (or both) because only a single type of α‐nuclei could be left upon treatment to the molten liquid state at T_max. Therefore, only the α‐crystal in PBA had ‘memory capacity’ in the molten liquid state while the β‐crystal did not. This was so because the latter had been completely transformed into the solid state prior to being heated into a liquid. PBA crystallized before α‐nuclei could be packed into α‐crystal, regardless of the crystallization temperature (T_c). For recrystallization from molten PBA without any nuclei, the crystalline polymorphism was correspondingly influenced by T_c. Copyright © 2005 Society of Chemical Industry     

Flow stress of high density polyethylene and nylon 66 at high rates of strain

Measurement of the flow stress of high density polyethylene (HDPE) and nylon 66 at strain rates of 10³ s^?1 using a split Hopkinson pressure bar technique is discussed. The flow stress at a strain of 10% has been determined for both polymers at 20°C. The intrinsic errors involved in this technique are briefly reviewed. The results indicate that the flow stress of HDPE and nylon 66 were 50MPa and 150MPa, respectively, at strain rates of about 10³s^?1.