Kinetics of formalization of poly(vinyl acetate)

Kinetic information on the formation of poly(vinyl formal) by the reaction of poly(vinyl acetate) and formaldehyde in presence of aqueous acid has been derived from the spectroscopic analysis of polymer samples after different periods of reaction. The hydroxyl content of poly(vinyl formal) is found to be nearly independent of reaction time and only slightly affected by temperature while the fall of acetate content and the increase in formal content are most rapid in the initial period and are largely influenced by temperature. The rate expression formulated on the assumption that the formalization reaction is of first order with respect to both poly(vinyl acetate) and formaldehyde explains the observed variation of polymer composition with reaction time. The activation energy for the reaction is found to be 17.3 kcal/mol.

Kinetics of hydrogen evolution on a stainless steel electrode

The kinetic parameters for the hydrogen evolution reaction on a stainless steel substrate have been obtained from a study of the steady-state polarization curves as well as the galvanostatic transients. The high Tafel slope obtained in the steady-state polarization measurements was ascribed to the presence of an oxide film present on the surface of the stainless steel electrode.

Field-Effect and Frequency Dependent Transport in Semiconductor-Enriched Single-Wall Carbon Nanotube Network Device

The electrical and optical response of a field-effect device comprising a network of semiconductor-enriched single-wall carbon nanotubes, gated with sodium chloride solution is investigated. Field-effect is demonstrated in a device that uses facile fabrication techniques along with a small-ion as the gate electrolyte-and this is accomplished as a result of the semiconductor enhancement of the tubes. The optical transparency and electrical resistance of the device are modulated with gate voltage. A time-response study of the modulation of optical transparency and electrical resistance upon application of gate voltage suggests the percolative charge transport in the network. Also the ac response in the network is investigated as a function of frequency and temperature down to 5 K. An empirical relation between onset frequency and temperature is determined.

Oestrogen-induced synthesis of thiamin-binding protein in immature chicks. Kinetics of induction, hormonal specificity and modulation

A specific radioimmunoassay procedure was developed to monitor the plasma concentrations of thiamin-binding protein, a minor yolk constituent of the chicken egg. By using this sensitive assay, the kinetics of oestrogen-induced elaboration of this specific protein in immature chicks was investigated. After a single injection of the steroid hormone, with an initial lag period of 4–5h the thiamin-binding protein rapidly accumulated in the plasma, attaining peak concentrations around 75h and declining thereafter. A 4-fold amplification of the response was noticed during the secondary stimulation, and this increased to 9-fold during the tertiary stimulation with the steroid hormone. The magnitude of the response was dependent on the hormone dose, and the initial latent period and the duration of the ascending phase of induction were unchanged for the hormonal doses tested during both the primary and secondary stimulations. The circulatory half-life of the protein was 6h as calculated from the measurement of the rate of disappearance of the exogenously administered 125I-labelled protein. Simultaneous administration of progesterone, dihydrotestosterone or corticosterone did not alter the pattern of induction. On the other hand, hyperthyroidism markedly decreased the oestrogenic response, whereas propylthiouracil-induced hypothyroidism had the opposite effect. The anti-oestrogen E- and Z-clomiphene citrates, administered 30min before oestrogen, effectively blocked the hormonal induction. α-Amanitin and cycloheximide administered along with or shortly after the sex steroid severely curtailed the protein elaboration. A comparison of the kinetics of induction of thiamin- and riboflavin-binding proteins by oestrogen revealed that, beneath an apparent similarity, a clear-cut difference exists between the two vitamin-binding proteins, particularly with regard to hormonal dose-dependent sensitivity of induction and the half-life in circulation. The steroid-mediated elaboration of the two yolk proteins thus appears to be not strictly co-ordinated, despite several common regulatory features underlying their induction.

Field Emission Properties of Carbon Nanotube Arrays with Defects and Impurities

It has been found experimentally that the results related to the collective field emission performance of carbon nanotube (CNT) arrays show variability. The emission performance depends on the electronic structure of CNTs (especially their tips). Due to limitations in the synthesis process, production of highly pure and defect free CNTs is very difficult. The presence of defects and impurities affects the electronic structure of CNTs. Therefore, it is essential to analyze the effect of defects on the electronic structure, and hence, the field emission current. In this paper, we develop a modeling approach for evaluating the effect of defects and impurities on the overall field emission performance of a CNT array. We employ a concept of effective stiffness degradation for segments of CNTs, which is due to structural defects. Then, we incorporate the vacancy defects and charge impurity effects in our Green's function based approach. Simulation results indicate decrease in average current due to the presence of such defects and impurities.

Continuous Distribution Kinetics for Photopolymerization of Alkyl Methacrylates

The photopolymerization of methyl,ethyl,butyl, and hexyl methacrylates in solution was studied. The effect of initial initiator and monomer concentrations on the time evolution of polymer concentration (M) over bar (n) and PDI was examined. The reversible chain addition and beta-scission, and primary radical termination steps were included in the mechanism along with the classical steps. The rate equations were derived using continuous distribution kinetics and solved numerically to fit the experimental data. The regressed rate coefficients compared well with the literature data. The model predicted the instantaneous increase in (M) over bar (n) and PDI to steady state values. The rate coefficients exhibited a linear increase with the size of alkyl chain of the alkyl methacrylates.

Crystallization kinetics of SrBi2B2O7 glasses by non-isothermal methods

Transparent glasses of SrBi2B2O7 (SBBO) were fabricated via the conventional melt-quenching technique. The amorphous and the glassy nature of the as-quenched samples were, respectively, confirmed by X-ray powder diffraction (XRD) and differential scanning calorimetry (DSC). The glass transition (T (g)) and the crystallization parameters [crystallization activation energy (E (cr)) and Avrami exponent (n)] were evaluated under non-isothermal conditions using DSC. There was a close agreement between the activation energies for the crystallization process determined by Augis and Bennet and Kissinger methods. The variation of local activation energy [E (c)(x)] that was determined by Ozawa method, decreased with the fraction of crystallization (x). The Avrami exponent (n(x)) increased with the increase in fraction of crystallization (x) suggesting that there was a change over in the crystallization process from the surface to the bulk.

High Resolution Surface Imaging Using a Carbon Nanotube Array with Pointed Height distribution

In this paper we discuss a new technique to image the surfaces of metallic substrates using field emission from a pointed array of carbon nanotubes (CNTs). We consider a pointed height distribution of the CNT array under a diode configuration with two side gates maintained at a negative potential to obtain a highly intense beam of electrons localized at the center of the array. The CNT array on a metallic substrate is considered as the cathode and the test substrate as the anode. Scanning the test Substrate with the cathode reveals that the field emission current is highly sensitive to the surface features with nanometer resolution. Surface features of semi-circular, triangular and rectangular geometries (projections and grooves) are considered for simulation. This surface scanning/mapping technique can be applied for surface roughness measurements with nanoscale accuracy. micro/nano damage detection, high precision displacement sensors, vibrometers and accelerometers. among other applications.

Anomalous reaction-diffusion as a model of nonexponential DNA escape kinetics

We show that data from recent experiments carried out on the kinetics of DNA escape from alpha-hemolysin nanopores [M. Wiggin, C. Tropini, C. T. Cossa, N. N. Jetha, and A. Marziali, Biophys. J. 95, 5317 (2008)] may be rationalized by a model of chain dynamics based on the anomalous diffusion of a particle moving in a harmonic well in the presence of a delta function sink. The experiments of Wiggin found, among other things, that the occasional occurrence of unusually long escape times in the distribution of chain trapping events led to nonexponential decays in the survival probability, S(t), of the DNA molecules within the nanopore. Wiggin ascribed this nonexponentiality to the existence of a distribution of trapping potentials, which they suggested was theresult of stochastic interactions between the bases of the DNA and the amino acids located on the surface of the nanopore. Based on this idea, they showed that the experimentally determined S(t) could be well fit in both the short and long time regimes by a function of the form (1+t/tau)(-alpha) (the so called Becquerel function). In our model, S(t) is found to be given by a Mittag-Leffler function at short times and by a generalized Mittag-Leffler function at long times. By suitable choice of certain parameter values, these functions are found to fit the experimental S(t) even better than the Becquerel function. Anomalous diffusion of DNA within the trap prior to escape over a barrier of fixed height may therefore provide a second, plausible explanation of the data, and may offer fresh perspectives on similar trapping and escape problems.

A germanium/single-walled carbon nanotube composite paper as a free-standing anode for lithium-ion batteries

Paper-like free-standing germanium (Ge) and single-walled carbon nanotube (SWCNT) composite anodes were synthesized by the vacuum filtration of Ge/SWCNT composites, which were prepared by a facile aqueous-based method. The samples were characterized by X-ray diffraction, field emission scanning electron microscopy, and transmission electron microscopy. Electrochemical measurements demonstrate that the Ge/SWCNT composite paper anode with the weight percentage of 32% Ge delivered a specific discharge capacity of 417 mA h g-1 after 40 cycles at a current density of 25 mA g-1, 117% higher than the pure SWCNT paper anode. The SWCNTs not only function as a flexible mechanical support for strain release, but also provide excellent electrically conducting channels, while the nanosized Ge particles contribute to improving the discharge capacity of the paper anode.

Kinetics and mechanism of hot corrosion of γ-Y 2Si 2O 7 in thin-film Na 2SO 4 molten salt

γ-Y 2Si 2O 7 is a promising candidate material both for hightemperature structural applications and as an environmental/thermal barrier coating material due to its unique properties such as high melting point, machinability, thermal stability, low linear thermal expansion coefficient (3.9×10 -6/K, 200°-1300°C), and low thermal conductivity (<3.0 W/ṁK above 300°C). The hot corrosion behavior of γ-Y 2Si 2O 7 in thin-film molten Na 2SO 4 at 850°-1000°C for 20 h in flowing air was investigated using a thermogravimetric analyzer (TGA) and a mass spectrometer (MS). γ-Y 2Si 2O 7 exhibited good resistance against Na 2SO 4 molten salt. The kinetic curves were well fitted by a paralinear equation: the linear part was caused by the evaporation of Na2SO4 and the parabolic part came from gas products evolved from the hotcorrosion reaction. A thin silica film formed under the corrosion scale was the key factor for retarding the hot corrosion. The apparent activation energy for the corrosion of γ-Y 2Si 2O 7 in Na 2SO 4 molten salt with flowing air was evaluated to be 255 kJ/mol.

Design Optimization of Field Emission From A Stacked Carbon Nanotube Array

Fluctuation of field emission in carbon nanotubes (CNTs) is riot desirable in many applications and the design of biomedical x-ray devices is one of them. In these applications, it is of great importance to have precise control of electron beams over multiple spatio-temporal scales. In this paper, a new design is proposed in order to optimize the field emission performance of CNT arrays. A diode configuration is used for analysis, where arrays of CNTs act as cathode. The results indicate that the linear height distribution of CNTs, as proposed in this study, shows more stable performance than the conventionally used unifrom distribution.

Kinetics of photocatalytic reduction of NO by CO with Pd2+-Ion-Substituted Nano-TiO2

The objective of the present study is to develop the reaction mechanism and kinetics of photoreduction of NO by CO. For this purpose, the reactions were conducted in the presence of Pd-ion-substituted nano-TiO2, Ti1-xPdxO2-delta, which was synthesized via a solution combustion method. The photocatalytic activity was investigated with unsubstituted TiO2, 1% Pd/TiO2(imp), and Ti1-xPdxO2-delta (where x = 0.05-0.3). No appreciable NO conversion was observed over unsubstituted TiO2, although, despite competitive adsorption of NO and CO on the Pd2+ sites, there was a significant reduction of NO over Ti1-xPdxO2-delta. The kinetic model showed that the enhanced catalytic activity is due to the NO photodissociation at the oxide-ion vacancy.

Electromechanical interactions in a carbon nanotube based thin film field emitting diode

Carbon nanotubes (CNTs) have emerged as promising candidates for biomedical x-ray devices and other applications of field emission. CNTs grown/deposited in a thin film are used as cathodes for field emission. In spite of the good performance of such cathodes, the procedure to estimate the device current is not straightforward and the required insight towards design optimization is not well developed. In this paper, we report an analysis aided by a computational model and experiments by which the process of evolution and self-assembly (reorientation) of CNTs is characterized and the device current is estimated. The modeling approach involves two steps: (i) a phenomenological description of the degradation and fragmentation of CNTs and (ii) a mechanics based modeling of electromechanical interaction among CNTs during field emission. A computational scheme is developed by which the states of CNTs are updated in a time incremental manner. Finally, the device current is obtained by using the Fowler–Nordheim equation for field emission and by integrating the current density over computational cells. A detailed analysis of the results reveals the deflected shapes of the CNTs in an ensemble and the extent to which the initial state of geometry and orientation angles affect the device current. Experimental results confirm these effects.

Kinetics of Pressureless Infiltration of Al-Mg Melts into Porous Alumina Preforms

Effective “hydrodynamic” radii governing infiltration kinetics of reactive Al-Mg melts into alumina preforms were found to be three orders of magnitude smaller than the average pore size of the packed bed and also smaller compared with the kinetics for a nonreactive system. A sinusoidal capillary model was developed to predict flow kinetics within the packed bed. For the reactive system, two factors were ascribed for additional melt retardation: (1) different intrinsic wettabilities of the two liquids on alumina, thereby leading to significantly different “effective” local contact angles; and (2) local solute depletion from the meniscus, which was incorporated as a time-dependent contact angle.