Drying kinetics, quality changes and shrinkage of Two grape varieties of Italy

Two varieties of grapes, white grape and red grape grown in the Campania region of Italy were selected for the study of drying characteristics, moisture diffusion, quality changes (colour) and shrinkage behaviour. Comparisons were made with treated and untreated grapes under constant drying condition of 50o C in a conventional drying system. This temperature was selected to represent farm drying conditions. Grapes were purchased from a local market from the same supplier to maintain the same size of grapes and same properties. An abrasive physical treatment was used as pretreatment. The drying curves were constructed and drying kinetics was calculated using several commonly available models. It was found that treated samples shows better drying characteristics than untreated samples. The objective of this study is to obtain drying kinetics which can be used to optimize the drying operations in grape drying.

Base-induced decomposition of alkyl hydroperoxides in the gas phase. Part 3. Kinetics and dynamics in HO-+CH3OOH, C2H5OOH, and tert-C4H9OOH reactions

The E-CO(2) elimination reactions of alkyl hydroperoxides proceed via abstraction of an (x-hydrogen by a base: X- + (RRHCOOH)-R-1-H-2 -> HX + (RRC)-R-1-C-2=O + HO-. Efficiencies and product distributions for the reactions of the hydroxide anion with methyl, ethyl, and tert-butyl hydroperoxides are studied in the gas phase. On the basis of experiments using three isotopic analogues, HO- + CH3OOH, HO- + CD3OOH, and H18O- + CH3OOH. the overall intrinsic reaction efficiency is determined to be 80% or greater. The E(CO)2 decomposition is facile for these methylperoxide reactions, and predominates over competing proton transfer at the hydroperoxide moiety. The CH3CH2OOH reaction displays a similar E(CO)2 reactivity, whereas proton transfer and the formation of HOO- are the exclusive pathways observed for (CH3)(3)COOH, which has no (x-hydrogen. All results are consistent with the E-CO(2) mechanism, transition state structure, and reaction energy diagrams calculated using the hybrid density functional B3LYP approach. Isotope labeling for HO- + CH3OOH also reveals some interaction between H2O and HO- within the E(CO)2 product complex [H2O center dot center dot center dot CH2=O center dot center dot center dot HO-]. There is little evidence, however. for the formation of the most exothermic products H2O + CH2(OH)O-, which would arise from nuclephilic condensation of CH2=O and HO-. The results suggest that the product dynamics are not totally statistical but are rather direct after the E-CO(2) transition state. The larger HO- + CH3CH2OOH system displays more statistical behavior during complex dissociation.

Thermal stability and decomposition kinetics of styrene-butadiene rubber nanocomposites filled with different particle sized kaolinites

A series of styrene-butadiene rubber (SBR) nanocomposites filledwith different particle sized kaolinites are prepared via a latex blending method. The thermal stabilities of these clay polymer nanocomposites (CPN) are characterized by a range of techniques including thermogravimetry (TG), digital photos, scanning electron microscopy (SEM) and Raman spectroscopy. These CPN show some remarkable improvement in thermal stability compared to that of the pure SBR. With the increase of kaolinite particle size, the residual char content and the average activation energy of kaolinite SBR nanocomposites all decrease; the pyrolysis residues become porous; the crystal carbon in the pyrolysis residues decrease significantly from 58.23% to 44.41%. The above results prove that the increase of kaolinite particle size is not beneficial in improving the thermal stability of kaolinite SBR nanocomposites.

Kinetics of low-pressure, low-temperature graphene growth : toward single-layer, single-crystalline structure

Graphene grown on metal catalysts with low carbon solubility is a highly competitive alternative to exfoliated and other forms of graphene, yet a single-layer, single-crystal structure remains a challenge because of the large number of randomly oriented nuclei that form grain boundaries when stitched together. A kinetic model of graphene nucleation and growth is developed to elucidate the effective controls of the graphene island density and surface coverage from the onset of nucleation to the full monolayer formation in low-pressure, low-temperature CVD. The model unprecedentedly involves the complete cycle of the elementary gas-phase and surface processes and shows a precise quantitative agreement with the recent low-energy electron diffraction measurements and also explains numerous parameter trends from a host of experimental reports. These agreements are demonstrated for a broad pressure range as well as different combinations of precursor gases and supporting catalysts. The critical role of hydrogen in controlling the graphene nucleation and monolayer formation is revealed and quantified. The model is generic and can be extended to even broader ranges of catalysts and precursor gases/pressures to enable the as yet elusive effective control of the crystalline structure and number of layers of graphene using the minimum amounts of matter and energy.

Kinetics of the initial stage of silicon surface oxidation : Deal–Grove or surface nucleation?

The nucleation-initiated oxidation of a Si surface at very low temperatures in plasmas is demonstrated experimentally, in contrast to the Deal-Grove mechanism, which predicts Si oxidation at a Si/SiO interface and cannot adequately describe the formation of SiO nanodots and oxidation rates at very low (several nanometers) oxide thickness. Based on the experimental results, an alternative oxidation scenario is proposed and supported by multiscale numerical simulations suggesting that saturation of micro- and nanohillocks with oxygen is a trigger mechanism for initiation of Si surface oxidation. This approach is generic and can be applied to describe the kinetics of low-temperature oxidation of other materials. © 2009 American Institute of Physics.

Growth kinetics of carbon nanowall-like structures in low-temperature plasmas

The results of a hybrid numerical simulation of the growth kinetics of carbon nanowall-like nanostructures in the plasma and neutral gas synthesis processes are presented. The low-temperature plasma-based process was found to have a significant advantage over the purely neutral flux deposition in providing the uniform size distribution of the nanostructures. It is shown that the nanowall width uniformity is the best (square deviations not exceeding 1.05) in high-density plasmas of 3.0× 1018 m-3, worsens in lower-density plasmas (up to 1.5 in 1.0× 1017 m-3 plasmas), and is the worst (up to 1.9) in the neutral gas-based process. This effect has been attributed to the focusing of ion fluxes by irregular electric field in the vicinity of plasma-grown nanostructures on substrate biased with -20 V potential, and differences in the two-dimensional adatom diffusion fluxes in the plasma and neutral gas-based processes. The results of our numerical simulations are consistent with the available experimental reports on the effect of the plasma process parameters on the sizes and shapes of relevant nanostructures.

Including nonequilibrium interface kinetics in a continuum model for melting nanoscaled particles

The melting temperature of a nanoscaled particle is known to decrease as the curvature of the solid-melt interface increases. This relationship is most often modelled by a Gibbs--Thomson law, with the decrease in melting temperature proposed to be a product of the curvature of the solid-melt interface and the surface tension. Such a law must break down for sufficiently small particles, since the curvature becomes singular in the limit that the particle radius vanishes. Furthermore, the use of this law as a boundary condition for a Stefan-type continuum model is problematic because it leads to a physically unrealistic form of mathematical blow-up at a finite particle radius. By numerical simulation, we show that the inclusion of nonequilibrium interface kinetics in the Gibbs--Thomson law regularises the continuum model, so that the mathematical blow up is suppressed. As a result, the solution continues until complete melting, and the corresponding melting temperature remains finite for all time. The results of the adjusted model are consistent with experimental findings of abrupt melting of nanoscaled particles. This small-particle regime appears to be closely related to the problem of melting a superheated particle.

Adsorption thermodynamics and kinetics study for the self-assembly of 1,8,15,22-tetraaminophthalocyanatocobalt(II) on glassy carbon surface

Spontaneous adsorption of 1,8,15,22-tetraaminophthalocyanatocobalt(II) (4α-CoIITAPc) on glassy carbon (GC) electrode leads to the formation of a stable self-assembled monolayer (SAM). Since the SAM of 4α-CoIITAPc is redox active, its adsorption on GC electrode was followed by cyclic voltammetry. SAM of 4α-CoIITAPc on GC electrode shows two pairs of well-defined redox peaks corresponding to CoIII/CoII and CoIIIPc−1/CoIIIPc−2. The surface coverage (Γ) value, calculated by integrating the charge under CoII oxidation, was used to study the adsorption thermodynamics and kinetics of 4α-CoIITAPc on GC surface. Cyclic voltammetric studies show that the adsorption of 4α-CoIITAPc on GC electrode has reached the saturation coverage (Γs) within 3 h. The Γs value for the SAM of 4α-CoIITAPc on GC electrode was found to be 2.37 × 10−10 mol cm−2. Gibbs free energy (ΔGads) and adsorption rate constant (kad) for the adsorption of 4α-CoIITAPc on GC surface were found to be −16.76 kJ mol−1 and 7.1 M−1 s−1, respectively. The possible mechanism for the self-assembly of 4α-CoIITAPc on GC surface is through the addition of nucleophilic amines to the olefinic bond on the GC surface in addition to a meager contribution from π stacking. The contribution of π stacking was confirmed from the adsorption of unsubstituted phthalocyanatocobalt(II) (CoPc) on GC electrode. Raman spectra for the SAM of 4α-CoIITAPc on carbon surface shows strong stretching and breathing bands of Pc macrocycle, pyrrole ring and isoindole ring. Raman and CV studies suggest that 4α-CoIITAPc is adopting nearly a flat orientation or little bit tilted orientation.

Preparation of macroporous methacrylate monolithic material with convective flow properties for bioseparation : Investigating the kinetics of pore formation and hydrodynamic performance

The preparation of macroporous methacrylate monolithic material with controlled pore structures can be carried out in an unstirred mould through careful and precise control of the polymerisation kinetics and parameters. Contemporary synthesis conditions of methacrylate monolithic polymers are based on existing polymerisation schemes without an in-depth understanding of the dynamics of pore structure and formation. This leads to poor performance in polymer usage thereby affecting final product recovery and purity, retention time, productivity and process economics. The unique porosity of methacrylate monolithic polymer which propels its usage in many industrial applications can be controlled easily during its preparation. Control of the kinetics of the overall process through changes in reaction time, temperature and overall composition such as cross-linker and initiator contents allow the fine tuning of the macroporous structure and provide an understanding of the mechanism of pore formation within the unstirred mould. The significant effect of temperature of the reaction kinetics serves as an effectual means to control and optimise the pore structure and allows the preparation of polymers with different pore size distributions from the same composition of the polymerisation mixture. Increasing the concentration of the cross-linking monomer affects the composition of the final monoliths and also decreases the average pore size as a result of pre-mature formation of highly cross-linked globules with a reduced propensity to coalesce. The choice and concentration of porogen solvent is also imperative. Different porogens and porogen mixtures present different pore structure output. Example, larger pores are obtained in a poor solvent due to early phase separation.

Reduced intensity conditioning for allogeneic hematopoietic stem cell transplant determines the kinetics of acute Graft-Versus-Host Disease

Background Preparative myeloablative conditioning regimens for allogeneic hematopoietic stem-cell transplantation (HSCT) may control malignancy and facilitate engraftment but also contribute to transplant related mortality, cytokine release, and acute graft-versus-host disease (GVHD). Reduced intensity conditioning (RIC) regimens have decreased transplant related mortality but the incidence of acute GVHD, while delayed, remains unchanged. There are currently no in vivo allogeneic models of RIC HSCT, limiting studies into the mechanism behind RIC-associated GVHD. Methods We developed two RIC HSCT models that result in delayed onset GVHD (major histocompatibility complex mismatched (UBI-GFP/BL6 [H-2b]→BALB/c [H-2d]) and major histocompatibility complex matched, minor histocompatibility mismatched (UBI-GFP/BL6 [H-2b]→BALB.B [H-2b])) enabling the effect of RIC on chimerism, dendritic cell (DC) chimerism, and GVHD to be investigated. Results In contrast with myeloablative conditioning, we observed that RIC-associated delayed-onset GVHD is characterized by low production of tumor necrosis factor-α, maintenance of host DC, phenotypic DC activation, increased T-regulatory cell numbers, and a delayed emergence of activated donor DC. Furthermore, changes to the peritransplant milieu in the recipient after RIC lead to the altered activation of DC and the induction of T-regulatory responses. Reduced intensity conditioning recipients suffer less early damage to GVHD target organs. However, as donor cells engraft, activated donor DC and rising levels of tumor necrosis factor-α are associated with a later onset of severe GVHD. Conclusions Delineating the mechanisms underlying delayed onset GVHD in RIC HSCT recipients is vital to improve the prediction of disease onset and allow more targeted interventions for acute GVHD.

Effect of functionalized kaolinite on the curing kinetics of cycloaliphatic epoxy/anhydride system

Silane grafted kaolinite (KGS) was prepared through grinding kaolinite and then grafting with 3-aminopropyltriethoxysilane. The influence of KGS on the curing kinetics of cycloaliphatic epoxy resin was studied by non-isothermal differential scanning calorimetry at different heating rates. The reaction activation energy (Ea) was determined based on the Flynn–Wall–Ozawa method. The results of dynamic differential scanning calorimetry (DSC) kinetic analysis show that the surface hydroxyl groups of clay decreases the Ea from 70.6 kJ mol− 1 to 62.8 kJ mol− 1 and accelerates the curing reaction of the epoxy resin. The silane grafting reactions consume the surface hydroxyl groups of kaolinite and lead to a decrease in the catalytic efficiency of KGS in the curing of epoxy resin.

Kinematics and kinetics of the Nordic hamstring curl

This thesis describes, for the first time, the forces involved in the Nordic hamstring exercise, its reliability and the biomechanical effects of extra loading during the movement. The results provide practitioners with valuable information to enhance hamstring injury prevention and rehabilitation programs.

Stochastic linear multistep methods for the simulation of chemical kinetics

In this paper, we introduce the Stochastic Adams-Bashforth (SAB) and Stochastic Adams-Moulton (SAM) methods as an extension of the tau-leaping framework to past information. Using the theta-trapezoidal tau-leap method of weak order two as a starting procedure, we show that the k-step SAB method with k >= 3 is order three in the mean and correlation, while a predictor-corrector implementation of the SAM method is weak order three in the mean but only order one in the correlation. These convergence results have been derived analytically for linear problems and successfully tested numerically for both linear and non-linear systems. A series of additional examples have been implemented in order to demonstrate the efficacy of this approach.