Effect of diacid stabilizers on kinetics of hydrolytic polymerization of ϵ‐caprolactam in industrial reactors

The rate constants in hydrolytic polymerization of ε‐caprolactam are dependent on the concentration of carboxylic acid groups in the reaction medium. Therefore, the use of diacid stabilizers for regulating molecular weight are likely to have favorable effect on the kinetics of polymerization compared to monoacid stabilizers, which are traditionally used in such polymerizations. To understand the kinetics of polymerization in the presence of diacid stabilizer compared to monoacid stabilizer, mathematical kinetic models were developed using the end group approach. These models were used to quantify the effect of both stabilizers on nylon‐6 synthesis in a closed isothermal batch reactor at different temperatures in the range of 245–265°C. The kinetic model for the diacid‐stabilized system was then extended to an industrial VK tube reactor using the process model developed earlier for the monoacid stabilized system. Both the mathematical modeling and experimental results showed that the presence of diacid stabilizer could significantly enhance the overall kinetics of the reaction compared to the monoacid stabilized system and in turn, resulted in reduction of the polymerization time by about 20–25%. The study suggests that diacid stabilizers may be used preferably over monoacid stabilizers in synthesis of nylon‐6 to reduce the cost of polymerization. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Characterization of Open Volume Regions in a Simulated Cu-Zr Metallic Glass

Optimizing the structural reliability of bulk metallic glass (BMG) components demands a detailed understanding of the atomic structure of the glass, particularly the defects that control plastic flow. These defects are thought to be associated with regions of low atomic density, which facilitate the required diffusion-like atomic rearrangement processes. In the present article, the distribution of low-density regions in a simulated Cu-Zr glass is studied with two different techniques. Using a hard-sphere model, the interstitial volume distribution was obtained by constructing Voronoi polyhedra around each atom and inserting spheres into the unoccupied regions at the vertices. The volumes of touching spheres were summed and corrected for any overlap to obtain the size distribution of the unoccupied sites. The resulting distribution is in good agreement with Cohen and Turnbull’s free volume model and provides insight into how a single free volume site may be described. However, this model depends significantly on the somewhat arbitrary selection of the hard-sphere atomic radii and may not give a realistic indication of the shape or connectivity of the low atomic-density regions. Recent experimental studies of the open volume distribution using positron annihilation spectroscopy probe the electron and not the atomic density. We therefore propose a novel method to identify low-density regions from ab initio calculated radially averaged electron-density distributions, which allows a more physical and less ambiguous identification of low-density areas and, at the same time, connects atomic and electron distributions. Our results show that the qualitative volume distribution from the electron-density model agrees well with the hard-sphere model, while allowing a more physical quantitative analysis. This article is based on a presentation given in the symposium entitled “Bulk Metallic Glasses IV,” which occurred February 25–March 1, 2007 during the TMS Annual Meeting in Orlando, Florida under the auspices of the TMS/ASM Mechanical Behavior of Materials Committee.     

Application-aware dynamic spectrum access

Dynamic Spectrum Access (DSA) allows unlicensed wireless devices to opportunistically access unoccupied licensed spectrum bands. DSA yields efficient spectrum utilization which can greatly improve wireless networking performance. In this paper, we advocate application-awareness to effectively manage the side-effects of DSA that can offset its benefits by adversely impacting application QoS. Simple application hints are found to be able to serve as key inputs in evaluating current spectrum conditions relative to application needs, leading to an informed DSA mechanism that minimizes the impact of undesirable DSA side-effects. Towards this goal, we propose a wireless service architecture called Context-Aware Spectrum Agility (CASA). The key elements of CASA are: (a) semantic dependency equations that provide the relationship between application-layer QoS state and lower-layer DSA parameters, (b) CASA Algorithm that adapts DSA parameters and activities to better suit application needs, and, (c) a low overhead interface to provide application context to DSA. CASA has been explicitly designed with the goals of practical deployment, low overhead operation, and is compatible with any DSA protocol. Compared to state-of-art DSA, the deployment of CASA along with DSA protocols is shown to improve QoS metrics, such as delay and jitter, by an average of 30 and 64%, respectively. CASA is also found to match the application QoS demands for more than 90% of the duration of a communication session—a 300+% improvement over conventional application-agnostic DSA.     

Effect of hydrocolloids and emulsifiers on the rheological,microstructural and quality characteristics of eggless cake

Effect of hydrocolloids like Arabic (AR), guar (GR), xanthan (XN), carrageenan (CG) and hydroxypropylmethylcellulose (HPMC) in combination with emulsifiers such as glycerol monostearate (GMS) and sodium stearoyl-2-lactylate (SSL) on the rheological, microstructural and quality characteristics of eggless cake was studied. Addition of GR to wheat flour in the presence of SSL increased peak viscosity, while in the presence of GMS all hydrocolloids excepting XN increased the peak viscosity. The set back value decreased with the addition of hydrocolloids. Addition of hydrocolloids to wheat flour as well as in the presence of GMS and SSL increased the eggless cake batter viscosity, specific gravity, and XN showed the highest value. Among different hydrocolloids tried, only HPMC improved the eggless cake making characteristics of wheat flour. Use of HPMC increased the overall quality score of eggless cake with GMS to the maximum extent followed in decreasing order by CG and XN. Addition of all the hydrocolloids increased the overall quality of eggless cake with SSL and highest improvement was brought about by HPMC. Microstructure studies of eggless cake crumb with hydrocolloids showed that the starch granules appeared wrapped by XN and HPMC. In eggless cake with combination of HPMC and SSL the protein matrix appeared more uniform.     

Dynamic Orthogonal Switching of a Thermoresponsive Self‐Organized Helical Superstructure

Controllable manipulation of self‐organized dynamic superstructures of functional molecular materials by external stimuli is an enabling enterprise. Herein, we have developed a thermally driven, self‐organized helical superstructure, i.e., thermoresponsive cholesteric liquid crystal (CLC), by integrating a judiciously chosen thermoresponsive chiral molecular switch into an achiral liquid crystalline medium. The CLC in lying state, in both planar and twisted nematic cells, exhibits reversible in‐plane orthogonal switching of its helical axis in response to the combined effect of temperature and electric field. Consequently, the direction of the cholesteric grating has been observed to undergo 90° switching in a single cell, enabling non‐mechanical beam steering along two orthogonal directions. The ability to reversibly switch the cholesteric gartings along perpendicular directions by appropriately adjusting temperature and electric field strength could facilitate their applications in 2D beam steering, spectrum scanning, optoelectronics and beyond.     

Kinetic,Mechanistic and Spectral Investigation of Ruthenium(III) Catalysed Oxidation of Atenolol by Alkaline Diperiodatonickelate(IV) (Stopped Flow Technique)

The kinetics of ruthenium(III) catalysed oxidation of atenolol by diperiodatonickelate(IV) (DPN) in alkaline medium at a constant ionic strength of 1.0 mol dm^–3 has been studied spectrophotometrically using a rapid kinetic accessory. The reaction exhibits 1:1 stoichiometry (DPN:atenolol). The reaction shows first order dependence on [DPN] and [Ruthenium(III)] and apparent less than unit order dependence each in atenolol and alkali concentrations. Addition of periodate has no effect on the rate of reaction. Effect of added products, ionic strength and dielectric constant of the reaction medium have been investigated. The main products were identified by IR, NMR, fluorimetry and mass spectral studies. The results suggest the formation of a complex between the atenolol and ruthenium(III) species which reacts with one mole of diperiodatonickelate(IV) species in a rate determining step, resulting in the formation of a free radical, which in a subsequent fast step yields the products. The reaction constants involved in the mechanism were evaluated. The activation parameters were computed with respect to the slow step of the mechanism and discussed.     

Visual enhancement of digital ultrasound images using multiscale wavelet domain

Ultrasonography has been considered as one of the most powerful techniques for imaging organs and soft tissue structures in the human body. The main disadvantage of medical ultrasonography is the poor quality of images, which are affected by multiplicative speckle noise. In this paper, we present a novel method for despeckling medical ultrasound images. The primary goal of speckle reduction is to remove the speckle without losing much detail contained in an image. To achieve this goal, we make use of the wavelet transform and apply multi-resolution analysis to localize an image into different frequency components or useful subbands and then effectively reduce the speckle in the subbands according to the local statistics within the bands. The main advantage of the wavelet transform is that the image fidelity after reconstruction is visually lossless. The objective of the paper is to investigate the proper selection of wavelet filters and thresholding schemes which yields optimal visual enhancement of ultrasound images, in particular. We employ the wavelet shrinkage denoising techniques with different wavelet bases and decomposition levels on the individual subbands to achieve the best acceptable speckle reduction while maintaining the fidelity of the image and also examine the effects of different thresholding techniques as well as shrinkage rules for denoising ultrasound images. The proposed method consists of the log transformed original ultrasound image being subjected to wavelet transform, which is then denoised by a thresholding technique using a shrinkage rule. Experimental results show that the subband decomposition of ultrasound images, using Bior6.8 and level 3 with soft thresholding based on Bayes shrinkage rule, performs better than other techniques. The performance is measured in terms of Variance, Mean Square Error (MSE), Signal-to-Noise Ratio (SNR), Peak SNR (PSNR) and Correlation Coefficient (CC). The results of wavelet shrinkage techniques are compared with common speckle filters. We observe that the proposed method achieves better visual enhancement of ultrasound images which would lead to more accurate image analysis by the medical experts.     

Heat and mass transfer of two immiscible flows of Jeffrey fluid in a vertical channel

In this article, we examined the effect of heat and mass transfer flow of two immiscible Jeffrey fluids in a vertical channel. The highly nonlinear coupled ordinary differential equations are evaluated using regular perturbation parameters, for small values of perturbation parameter. The effect of Jeffrey's parameter on the flow and the effects of various physical parameters entering into the problem on dimensionless velocity, temperature, and concentration distribution is illustrated graphically. We observe that the Jeffrey parameter, thermal, and mass Grashof number enhance the fluid flow, while the chemical reaction parameter suppresses the fluid flow, also it is established that the Nusselt number is boosted by enhancing the thermal and mass Grashof number. We observed that the results are in very good agreement with the results obtained for a viscous fluid.     

Healing of cutaneous wounds in a freshwater teleost, Labeo rohita: scanning electron microscopical investigation

In this study, healing of cutaneous wounds in Labeo rohita using scanning electron microscope is reported. Wound area could be divided into three regions. Immediately after infliction of wound, edges retract exposing underlying tissues in wound gap (Region I). Simultaneously, at region close to wound edge (Region II), mucous goblet cell openings are observed with copious mucous secretions. Within 1 h, Region I gets covered by mucous secretions, and epidermis at edges starts migrating. Opposing fronts gradually advance and by 4-6 h come in contact to epithelialize wound gap. Zone of contact of fronts is demarcated by epidermal ridge, which is relatively prominent at 8 h. It gradually diminishes and is not distinguished at 24 h and afterward. At 1-4 h, microridges on epithelial cell surfaces appear irregularly arranged, widely spaced, short with abrupt ends at Region I; relatively extensive at Region II; and similar to those in controls at region surrounding Region II (Region III). At 12 h and afterward, microridges appear similar to those in controls at Regions I and II. At 1-2 h, isolated swollen epithelial cells, often in process of detachment and exfoliation at surface, are observed at Regions I and II. Such cells are infrequent at 8 h and afterward. Region I covered by migrated epidermis appears trough like at 4 h to 2 days, level of which gradually rises and at Day 4, surface of epidermis appears at a level similar to that at Regions II and III. Changes have been associated with the imbalance of osmotic homeostasis due to disruption of barrier between internal and external environment of skin.     

Effect of Piezoviscous Dependency and Couple Stress on Squeeze Film Lubrication Between Parallel Stepped Plates

Theoretical analysis of the effect of piezoviscous dependency and couple stress on squeeze film lubrication between parallel stepped plates is presented in this article. According to the Stokes microcontinuum theory of couple stress fluids, the modified Reynolds equation is derived by considering viscosity variation along the film thickness. The standard perturbation technique is used to solve the nonlinear Reynolds equation and an approximate analytical solution for the film pressure is obtained. It is found that the effect of couple stresses and pressure-dependent viscosity variation increases the load-carrying capacity and lengthens the squeeze film time.