Bulk free radical polymerizations of methyl methacrylateunder non-isothermal conditions and with intermediate additionof initiator: Experiments and modeling

Experimental data on the monomer conversion, x_m, and the weight average molecular weight, M_w, have been generated under several isothermal and non-isothermal conditions for the polymerization of methyl methacrylate in a rheometer-reactor assembly. The non-isothermal results, in particular, can be used to provide more stringent tests of kinetic models than isothermal data alone. A simple empirical model has been used to describe this system that accounts for the gel (Trommsdorff) and glass effects. The model involves only x_m and the temperature, and is quite general. The model parameters are tuned using only three sets of isothermal data. Good agreement is found between the experimental results and model predictions for a whole variety of experimental conditions, including non-isothermal operation and with intermediate addition of initiator. Because of its generality, this model is quite suitable for use for on-line optimizing control as well as for describing industrial reactors.     

Simulation of an industrial nylon 6 tubular reactor

A commonly used energy-efficient nylon 6 reactor is simulated under steady-state conditions. The effects of various operating conditions and parameters, e.g., feed composition, temperature and flow rate, heat transfer coefficients, and reactor dimensions, on the temperature and molecular weight profiles are studied. A temperature maximum is observed in the reactor under usual conditions of operation. The maximum value of the temperature is sensitive to the feed conditions, and one has to ensure that degradation reactions speeded up at high temperatures do not affect product characteristics. The model and the numerical technique used are fairly simple and account for most of the important features of industrial reactors. Hence, these can be used in the development of digital-control algorithms in the future.     

A novel microfluidic switch for pH control using Chitosan based hydrogels

We report a novel pH-sensitive hydrogel based micro-valve for metered flow that has applications in a laboratory made “Intelligent valving system”. The hydrogel solution was prepared through Chitosan and poly vinyl alcohol in acetic acid and crystallized using gluteraldehyde as the crosslinking agent in the form of thin wafers and it was found to be very sensitive to pH changes. The pore structure of hydrogel was investigated through Field Emission Scanning Electron Microscopy and thin wafers of the gel were physically placed inside PDMS microchannels. Flow metering in these channels was observed by controlled expansion of the hydrogel plug till complete valving was realized. This valving device was further precisely characterized with micro Particle Image Velocimetry using a solution containing fluorescent polymeric micro beads. The principle advantage of this hydrogel device is the smaller range of pH (varying between pH 3 and 7) over which the valving response is observed.     

Scientific basis for establishing country greenhouse gas estimates for rice-based agriculture: An Indian case study

A comprehensive scientific assessment of CH₄ budget estimation for Indian rice paddies, based on a decade of measurements in India, is presented. Indian paddy cultivation areas contain soils that have low to medium levels of soil organic carbon. The average seasonally integrated CH₄ flux (E _sif) values calculated from these measurements were 15.3 ± 2.6 g m^–2 for continuously flooded (CF), 6.9 ± 4.3 g m^–2 for intermittently flooded (IF) single aeration (SA) and 2.2 ± 1.5 g m^–2 for IF multiple aeration (MA) rice ecosystems. For CF and IF (MA) rice ecosystems having high soil organic carbon, without organic amendments, the CH₄ flux (E _sif) may be increased by 1.7 times relative to low soil organic carbon, whereas it may enhance by 5.3 for CF if amended organically. Organic amendment and high soil organic carbon paddy areas do not alter the methane budget estimates for India (3.6±1.4 TgY^–1) much, due to their small paddy harvested area. Methane estimated using average emission factors (E _sif) for all paddy water regimes, which include harvested areas having soils with high organic carbon and organic amendments, may give a budget of 5 TgY^–1 for India.     

Chlorosis in sugarcane: Associated soil properties,leaf mineral composition,and crop response to iron and manganese

Attempts were made to find out the nature and cause of a widespread sugarcane chlorosis in a cane growing area. Soils from chlorotic and nonchlorotic fields did not differ markedly in pH, CaCO₃, electrical conductivity, organic C, and soil test P, Zn, Cu, and Mn levels, but the chlorotic field soils had relatively more NH₄OAc-extractable K and less clay and DTPA-extractable Fe. Chlorotic and green leaf blades contained about the same concentration of P, S, Mg, Fe, Zn, Cu, and Mo, but the former leaf blades had more K and less Ca and HCl soluble Fe than the green ones. Green leaves of plants that seemed to have naturally recovered in chlorotic fields were higher in Mn. A foliage spray with 2.5% FeSO₄.7H₂O solution resulted in greening of leaves and a field experiment showed marked crop response to Fe and some response to Mn. The results thus suggest that the chlorosis is due to a lime-induced Fe-deficiency with the possibility of some role of Mn in Fe nutrition in calcareous soil conditions.Deceased 22 September 1988     

Low frequency ac conduction and dielectric relaxation behavior of solution grown and uniaxially stretched poly(vinylidene fluoride) films

The measurements of ac conductivity [σ_m(ω)], dielectric constant [?′(ω)] and loss [?″(ω)] have been performed on solution grown (thickness ∼85 μm) and uniaxially stretched (thickness ∼25, 45 and 80 μm) films of poly(vinylidene fluoride) (PVDF) in the frequency range 0.1 kHz-10 MHz and in the temperature range 77-400 K. The σ_m(ω) can be described by the relation σ(ω) = Aω^s, where s is close to unity and decreases with increase in temperature. Three relaxations, observed in the present investigation, have been designated as the α_c-, the α_a- and the β-relaxations appearing from high temperature side to the low temperature side. The α_c-relaxation could not be observed in the case of uniaxially stretched poly(vinylidene fluoride) films. The α_c- and α_a-relaxations are associated with the molecular motions in the crystalline regions and micro-Brownian motion in the amorphous regions of the main polymer chain, respectively, whereas the β-relaxation is attributed to the rotation of side group dipoles or to the local oscillations of the frozen main polymer chain.     

Prediction of properties of rubber by using artificial neural networks

Different rubber formulations were designed using nitrile rubber and a mixed crosslinking system consisting of sulfur/accelerator and electron beam radiation. Based on the experimental results, an artificial neural network (ANN) was constructed to simulate the mechanical properties and volume fraction of rubber. The ANN could predict accurately the above properties for a series of nitrile rubber compounds. However, the number of training data played a key role in the ANN predictive quality. In addition, the more complex the nonlinear relation between input and output was, the larger was the number of training dataset required. The predicted results were further validated using another mathematical model. The constructed ANN was verified with a completely different styrene butadiene rubber system. The prediction was found to be extremely good. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2227–2237, 2006     

Graft copolymerization of acrylonitrile and methacrylonitrile onto gelatin by mutual irradiation method

In order to improve upon certain properties of gelatin graft copolymerization of acrylonitrile (AN) and methacrylonitrile (MAN) onto gelatin has been studied in aqueous medium using γ rays as a source of initiation. Optimum conditions for affording maximum percentage of grafting have been evaluated as a function of various reaction parameters. The grafted polyacrylonitrile (PAN) was isolated from the graft copolymer by acid hydrolysis, and the average molecular weight (M_v) of the isolated polymer has been determined viscometrically. The graft copolymers were characterized by IR spectroscopic methods and thermogravimetric analysis (TGA). Acrylonitrile was found to be more reactive than methacrylonitrile toward graft copolymerization. © 1994 John Wiley & Sons, Inc.     

Infrared study of salt free and salt treated cellulose pyrolysis under nitrogen atmosphere

The pyrolysis under nitrogen of salt free and salt treated cellulose was studied by infrared spectroscopy. The results confirm the unzipping mechanism suggested by DTA and TGA studies, and show this mechanism to apply to the untreated and salt treated samples. The results also show the unzipping to stop at the stage of char formation. The onset of this stage was found to occur after the volatilization of only 45–50% of the initial sample of the borax treated cellulose, compared with 65–70% of the KCl treated cellulose and 80–85% of the untreated cellulose.     

Target following with motion prediction for unmanned surface vehicle operating in cluttered environments

The capability of following a moving target in an environment with obstacles is required as a basic and necessary function for realizing an autonomous unmanned surface vehicle (USV). Many target following scenarios involve a follower and target vehicles that may have different maneuvering capabilities. Moreover, the follower vehicle may not have prior information about the intended motion of the target boat. This paper presents a trajectory planning and tracking approach for following a differentially constrained target vehicle operating in an obstacle field. The developed approach includes a novel algorithm for computing a desired pose and surge speed in the vicinity of the target boat, jointly defined as a motion goal, and tightly integrates it with trajectory planning and tracking components of the entire system. The trajectory planner generates a dynamically feasible, collision-free trajectory to allow the USV to safely reach the computed motion goal. Trajectory planning needs to be sufficiently fast and yet produce dynamically feasible and short trajectories due to the moving target. This required speeding up the planning by searching for trajectories through a hybrid, pose-position state space using a multi-resolution control action set. The search in the velocity space is decoupled from the search for a trajectory in the pose space. Therefore, the underlying trajectory tracking controller computes desired surge speed for each segment of the trajectory and ensures that the USV maintains it. We have carried out simulation as well as experimental studies to demonstrate the effectiveness of the developed approach.