Study on the Effect of Carboxyl Terminated Butadiene Acrylonitrile (CTBN) Copolymer Concentration on the Decomposition Kinetics Parameters of Blends of Glycidyl Epoxy and Non-Glycidyl Epoxy Resin

The degradation of the epoxy system was studied for the prepared six blend samples with the incorporation of 0 wt% - 25 wt% carboxyl terminated butadiene acrylonitrile (CTBN) copolymer, on a dynamic basis using Thermo gravimetric analysis (TGA) technique under a nitrogen atmosphere. The blends were prepared by physical mixing and were cured with diamine. The degradation of each sample followed second-order degradation kinetics, which was calculated by Coats-Redfern equation using best-fit analysis. This was further confirmed by linear regression analysis. The validity of data was checked by t-test statistical analysis. From this value of reaction order, activation energy (E), and pre-exponential factor (Z) were calculated. It was found that the activation energy increased with the addition of liquid elastomer.

Microsatellite instability,MMR gene expression and proliferation kinetics in colorectal cancer with famillial predisposition

INTRODUCTIONGenetic instability is a conunon property of manyhuman cancers,including those of HNPCC.A novel form of genetic instability involving somaticalterations,such as deletions and insertions insimple repeated sequences,has been found.Microsatellitcs are relatively short runs of tandemlyrepeated sequences scattered throughout

Kinetics and Vapor Pressure Studies of bis(<i>N</i>-alkyl-2-hydroxonapthaldimine)nickel (II) (<i>N</i>-R = methyl to pentyl) Complexes

The complexes of bis[N-alkyl-2-hydroxonapthaldimine]nickel(II) (N-alkyl = methyl, ethyl, propyl, butyl or pentyl) were synthesized and their volatilization in N2 atmosphere was demonstrated by the TG-based transpiration technique. The equilibrium vapor pressure of the complexes over a temperature span of 470 - 590 K was determined by adapting a horizontal dual arm single furnace thermoanalyser as a transpiration apparatus. It yielded as 153.1 (±1.9), 122.9 (±0.3), 147.6 (±10.7), 151.8 (±10.9) and 114.7 (±5.3) k·Jmol–1 respectively. The entropies of vaporization for these complexes as calculated from the intercept of the linear fit expressions were found to be 319.7 (±3.9), 229.9 (±5.8), 317.8 (±17.2), 319.7 (±19.1) and 254.6 (±9.6) Jmo–1·K–1 respectively. The non-isothermal vaporization activation energy was determined from Arrhenius and Coats-Redfern methods.

On Single Compartment Pharmacokinetic Model Systems that Obey Michaelis-Menten Kinetics and Systems that Obey Krebs Cycle Kinetics

The integration of Michaelis-Menten kinetics results in a trancedental equation. The results are not in a form that is readily usable. A more usable form of the model solutions is developed. This was accomplished by using Taylor series expansion of dimensionless concentration u in terms of its derivatives. The infinite series expression for dimensionless concentration is given. It can be seen that for times t < , the Taylor series expression evaluated near the origin up to the third derivative is a reasonable representation of the integrated solution. More terms in the Taylor series expression can be added to suit the application. It can vary with the apparent volume, dosage, enzyme concentration, Michaelis constant and the desired accuracy level needed. The single compartment model solution was obtained by the method of Laplace transform. It can be seen from Figure 2 that the dimensionless drug concentration in the compartment goes through a maxima. The curve is convex throughout the absorption and elimination processes. The drug gets completely depleted after a said time. The curve is asymmetrical with a right skew. The systems under absorption with elimination that obey the kinetics that can be represented by a set of reactions in circle were considered. A system of simple reactions in circle was taken into account. The concentration profile of the reactants were obtained by the method of Laplace transforms. The conditions when subcritical damped oscillations can be expected are derived. A model was developed for cases when absorption kinetics exhibit subcritical damped oscillations. The solution was developed by the method of Laplace transforms. The solution for dimensionless concentration of the drug in single compartment for different values of rate constants and dimensionless frequency are shown in Figures 6-9. The drug profile reaches a maximum and drops to zero concen-tration after a said time. The fluctuations in concentration depends on the dimensionless frequency resulting from the subcritical damped oscillations during absorption. At low frequencies the fluctuations are absent. As the frequency is increased the fluctuations in concentration are pronounced. The fre-quency of fluctuations were found to increase with increase in frequency of oscillations during ab-sorption.

DISSOLUTION KINETICS OF PHOSPHATE ORE IN ACIDIC SOLUTIONS

The dissolution kinetics of Florida and Jordan phosphate ore was studied in diluted nitric acid (0.2, 0.5, 1.0 mol ·L-1), and in phosphoric acid (55 wt% H3PO4) aqueous solutions. It was found that the hydrogen ions concentration is a controlling factor, but the calcium ions concentration can not affect the dissolution rate in the range of 0.0 and 2.0 wt% Ca2+. The effects of temperature, stirring intensity and the size of ore particles were also investigated. The transfer of hydrogen ion depends on the diffusion, while the calcium ions transfer is assumed to be depended on mechanically stripping. The shrinking core model with hydrogen ions diffusion control match the experimental results.

Investigation on the effect of oxalic acid, succinic acid and aspartic acid on the gas hydrate formation kinetics

Gas hydrate reserves are potential source of clean energy having low molecular weight hydrocarbons trapped in water cages.In this work,we report how organic compounds of different chain lengths and hydrophilicities when used in small concentration may modify hydrate growth and either act as hydrate inhibitors or promoters.Hydrate promoters foster the hydrate growth kinetics and are used in novel applications such as methane storage as solidified natural gas,desalination of sea water and gas separation.On the other hand,gas hydrate inhibitors are used in oil and gas pipelines to alter the rate at which gas hydrate nucleates and grows.Inhibitors such as methanol and ethanol which form strong hydrogen bond with water have been traditionally used as hydrate inhibitors.However,due to relatively high volatility a significant portion of these inhibitors ends up in gas stream and brings further complexity to the safe transportation of natural gas.In this study,organic additives such as oxalic acid,succinic acid and L-aspartic acid(all three)having––COOH group(s)with aspartic acid having an additional––NH2 group,are investigated for gas hydrate promotion/inhibition behavior.These compounds are polar in nature and thus have significant solubility in liquid water;the presence of weak acidic and water loving(carboxylic/amine groups)moieties makes these organic acids an excellent candidate for further study.This study would pave ways to identify a novel(read better)promoter/inhibitor for gas hydrate formation.Suitable thermodynamic conditions were generated in a stirred tank reactor coupled with cooling system;comparison of gas hydrate formation kinetics with and without additives were carried out to identify the effect of these acids on the formation and growth of hydrates.The possible mechanisms by which these additives inhibit or promote the hydrate growth are also discussed.

Kinetics and mechanism of the low-energy β-a phase transition of the second kind in 2,4-dinitroanisole

In this work, comprehensive studies of 2,4-dinitroanisole(2,4DNAN) were carried out using powder thermorentgenography of the internal standard. The time of the complete polymorphic transition in the solid phase β→a in 2,4DNAN under various combinations of conditions has been determined. It has been established that, regardless of the season of manufacture of the substance, when it is stored for 8-9months, with a change in ambient temperature from minus 30℃ to plus 30℃, a complete polymorphic transition β→a occurs. When stored in conditions below minus 5℃, polymorphic transition does not occur. When stored in conditions above plus 30℃ in a closed container, polymorphic transition occurs within 3 weeks. The polymorphic transition is accompanied by a decrease in density by 1.3%-1.5% and an increase in melting temperature by 10-12℃, depending on the degree of purity of the starting substance. The activation energy of the molecular rearrangement was 68-70 k J/mol(16.5 ± 3 kcal/mol). The mechanism of polymorphic transition has been evaluated, which is presumably based on internal homodiffusion and energy transfer to the surface of the mass of powder particles and the product. The average activation energy of the polymorphic transition process was 110 ± 6.2 k J/mol(26.2 kcal/mol). In an open container, reactions proceed by a homogeneous mechanism, and in a closed container by a heterogeneous mechanism involving the gas phase.

Kinetics of Manganese Oxides Dissolution in Sulphuric Acid Solutions Containing Oxalic Acid

The kinetics of the interaction of MnO2, Mn2O3, and Mn3O4, with sulphuric acid solutions and the effect of oxalic acid on this process are studied. As the sulphuric acid concentration is increased from 0.1 to 5 N, the dissolution rate of Mn2O3, Mn3O4 to MnO2 and Mn2+ ions decreases, whereas it increases with the concentration of Mn2+ ions. Upon the addition of H2Ox, the complete dissolution of Mn3O4 occurs more quickly. The reaction order with respect to the H+ and O x2- ions is +0.5 ± 0.1. A mechanism of MnO2 dissolution promotion by?O x2- is proposed. The dissolution rate was found to depend on the concentrations of?MnHOx - ions and was highest at pH 1.6 ± 0.2. A rate law and mechanism are suggested for manganese oxides dissolution.

Amylopectin structure and crystallinity explains variation in digestion kinetics of starches across botanic sources in an in vitro pig model

Background: Starch is the main source of energy in commonly used pig diets.Besides effects related to the extent of starch digestion,also several effects related to variation in digestion rate have recently been demonstrated in non-ruminants.Different rates of starch digestion in animals and in in vitro models have been reported,depending on the botanic origin of starch.Starches from different botanic sources differ widely in structural and molecular properties.Predicting the effect of starch properties on in vitro digestion kinetics based on existing literature is hampered by incomplete characterization of the starches,or by a selective choice of starches from a limited number of botanic sources.This research aimed to analyse the relationships between starch properties and in vitro digestion kinetics of pure starches isolated from a broad range of botanic origins,which are used in non-ruminant diets or have a potential to be used in the future.Therefore we studied starch digestion kinetics of potato,pea,corn,rice,barley,and wheat starches,and analysed the granule diameter,number of pores,type and amount of crystalline structure,amylose content and amylopectin side-chain length of all starches.Results: Multivariate analysis revealed strong correlations among starch properties,leading us to conclude that effects of most starch characteristics are strongly interrelated.Across all analysed botanic sources,crystalline type and amylopectin chain length showed the strongest correlation with in vitro digestion kinetics.Increased percentages of A–type crystalline structure and amylopectin side chains of DP 6–24 both increased the rate of digestion.In addition,within,but not across,(clusters of) botanic sources,a decrease in amylose content and increase in number of pores correlated positively with digestion kinetics.Conclusion: The type of crystalline structure and amylopectin chain length distribution of starch correlate significantly with digestion kinetics of starches across botanic sources in an in vitro pig model.Variation in digestion kinetics across botanic sources is not additively explained by other starch properties measured,but appears to be confined within botanical sources.

Kinetics and Dissolution Mechanisms of Oolitic Limestone Under Burial Condition

In order to study the control factors and mechanism of oolitic limestone reservoir being corroded by organic acid produced in burial stage,the reactions of acetic acid(pH=3) with oolitic limestone were investigated using the rotating-disk Corrosion Reactor System(CRS).The effects of disk rotational speed, temperature and system pressure were examined. Scanning Electron Microscope attached with Energy Dispersive X-Ray Analyzer(SEM-EDX) was

Higher-order approximate solutions of fractional stochastic point kinetics equations in nuclear reactor dynamics

Stochastic point kinetics equations(SPKEs) are a system of Ito? stochastic differential equations whose solution has been obtained by higher-order approximation.In this study, a fractional model of SPKEs has been analyzed. The efficiency of the proposed higher-order approximation scheme has been discussed in the results section. The solutions of SPKEs in the presence of Newtonian temperature feedback have also been provided to further discuss the physical behavior of the fractional model.

Experimental study on thermal decomposition kinetics of natural ageing AP/HTPB base bleed composite propellant

The kinetics of the thermal decomposition for a naturally ageing ammonium perchlorate(AP) and hydroxyl-terminated-polybutadiene(HTPB) base bleed composite propellant were investigated using a differential scanning calorimetry(DSC). The naturally ageing AP/HTPB base bleed propellant samples have been stored in a sealed plastic bag at room temperature(5-25 ℃) for more than 20 years. The experimental DSC results were obtained by placing samples(each about 1.5 mg) in a sealed pan under non-isothermal condition under different heating rates, 5.0, 10.0, 15.0, 20.0 and 30.0 ℃·min^(-1). The activation energy and pre-exponential factor were estimated based on the relationship between the exothermic peak temperature and the heating rate by Ozawa and Kissinger methods, respectively. The decomposition kinetic parameters is lower the values under laboratorial aging condition.

Spectrum behavior for the nonlinear fractional point reactor kinetics model

The nonlinear fractional point reactor kinetics equation in the presence of Newtonian temperature reactivity feedback with a multi-group of delayed neutrons,which describes the spectrum behavior of neutron density into the homogenous nuclear reactors, is developed. This system is one of the most important stiff coupled nonlinear fractional differentials for nuclear reactor dynamics. The generalization of Taylor's formula that involves Caputo fractional derivatives is developed in an attempt to overcome the difficulty of the stiffness of the nonlinear fractional differential model. Moreover, the general fractional derivatives are calculated analytically throughout this work. Furthermore, the local and global estimated errors were analyzed, which suggest that the error quantification should take into account the possible grow in time of the error. This observation provides a motivation for going beyond more classical local-in-time concepts of error(local truncation error). The neutron density response with time is analyzed for the anomalous diffusion, sub-diffusion, and super-diffusion processes.

Dexamethasone treatment alters kinetics properties of liver mitochondrial F₀.F₁-ATPase and membrane lipid profiles in developing and adult rats

Dexamethasone—a potent synthetic glucocorticoid—has multiple diagnostic and therapeutic applications in wide range of age groups. However, the side-effects of dexamethasone (Dex) treatment including those on development are becoming increasingly apparent. Since the developmental processes are energy-dependent, we examined the effects of chronic Dex treatment on kinetics properties of liver mitochondrial F0.F1-ATPase and mitochondrial membrane lipid profiles in rats belonging to different developmental age groups (2, 3, 4 and 5 weeks) and in adults (~8 weeks). The animals were treated with a subcutaneous dose of 2 mg of Dex/kg body weight (or saline as vehicle) for three alternative days (at around 7.00 A.M.) prior to the day of sacrifice. Dex treatment resulted in significant reduction in F0.F1-ATPase activity in developmental age groups and in adults as compared to their age-matched vehicle-treated control group. The substrate kinetics analysis of F0.F1-ATPase resolved Km and Vmax values in 3 components in all the control age groups;whereas Dex treatment significantly altered the Km and Vmax values or abolished the entire components in age-specific manner. Dex treatment significantly lowered the energy of activation and altered phase transition temperature (TtoC) in all the developmental age groups and in adults. Dex treatment significantly increased the contents of total phospholipid (TPL), individual phospholipids classes and cholesterol (CHL) in all the developmental age groups whereas opposite pattern was observed in adults. The mitochondrial membrane became more fluidized in the developing age groups (2, 4 and 5 weeks);whereas no change was observed in 3-week and adult groups following Dex treatment. In present study, our data demonstrate comprehensive deleterious effects of chronic Dex treatment on liver mitochondrial membrane structure and F0.F1-ATPase functional properties with respect to energy metabolism. At the same time, our data also warns against excessive repeated use of antenatal DEX in treatments in growing and adult human patients.

Non-Isothermal Degradation Kinetics of Hybrid Copolymers Containing Thermosensitive and Polypeptide Blocks

Novel, self-associating hybrid copolymers were synthesized via controlled ring-opening polymerization of N-carboxyanhydride of Z-L-lysine (Z-L-Lys-NCA), initiated by amino-functional macroinitiators. A poly(N-isopropylacry-lamide) (PNIPAm)-based macroinitiator containing 10 mol% of polyoxyethylene grafts and a terminal primary amine group in the form of ammonium hydrochloride (PNIPAm-g-PEО) was synthesized and used to initiate the ammonium- mediated ring-opening polymerization of NCA described by Dimitrov and Schlaad [1]. Thus, hybrid copolymers ((PNIPAm-g-PEO)-b-PLys) with controlled molar-mass characteristics and functionality were obtained. The potential applications of PNIPAm-based copolymers in the systems for controlled drug release, immobilization of enzymes and protein purification have aroused great interest in the studies of their properties and behaviour. The thermal stability and thermodynamic properties of the copolymers obtained were studied. The differential thermal analysis of polyfunctional hybrid copolymers (PNIPAm-g-PEO)-b-PLys) showed that thermooxidative destruction occurs in two stages: primary, of the unstable fragments (grafted chains of PEO);and secondary, of the main polymer chains of poly(N-isopropylacry-lamide) and poly(L-lysine). The kinetics of thermal degradation was evaluated and the values of the activation energy of the degradation process, changes of Gibbs free energy, enthalpy and entropy for the formation of the activated complex were also calculated.

Asymptotic Models for Studying Kinetics of Formation of Compact Objects with Strong Internal Bonds

An asymptotic method has been developed for investigation of kinetics of formation of compact objects with strong internal bonds. The method is based on the uncertainty relation for a coordinate and a momentum in space of sizes of objects (clusters) with strongly pronounced collective quantum properties resulted from exchange interactions of various physical nature determined by spatial scales of the processes under consideration. The proposed phenomenological approach has been developed by analogy with the all-known ideas about coherent states of quantum mechanical oscillator systems for which a product of coordinate and momentum uncertainties (dispersions) accepts the value, which is minimally possible within uncertainty relations. With such an approach the leading processes are oscillations of components that make up objects, mainly: collective nucleon oscillations in a nucleus and phonon excitations in a mesostructure crystal lattice. This allows us to consider formation and growth of subatomic and mesoscopic objects in the context of a single formalism. The proposed models adequately describe characteristics of formation processes of nuclear matter clusters as well as mesoscopic crystals having covalent and quasi-covalent bonds between atoms.

The Fractal (BSf) Kinetics Equation and Its Approximations

We discuss the Brouers-Sotolongo fractal (BSf) kinetics model. This formalism interpolates between the first and second order kinetics. But more importantly, it introduces not only a fractional order n but also a fractal time parameter a which characterizes the time variation of the rate constant. This exponent appears in non-exponential relaxation and complex reaction models as demonstrated by the extended use of the Weibull and Hill kinetics which are the two most popular approximations of the BSf (n, a) kinetic equation as well in non-Debye relaxation formulas. We show that the use of nonlinear programs allows an easy and precise fitting of the data yielding the BSf parameters which have simple physical interpretations.

Revealing the Uncertainty and Absolute Certainty Principles in the Kinetics of Objects Formation

The paper presents some examples revealing the uncertainty and absolute certainty principles in kinetics of objects formation that are different in their physical nature and in space scales: sub-stances of microcosm, nanoparticles and mesostructures, astrophysical and cosmological objects. Under the proposed kinetic approach, the uncertainty principle covers a wider spectrum of processes of approaching to equilibrium and object formation, than the absolute certainty principle. It refers, in particular, to nano-range-of-problems and mesoscopics as well as to cosmology. Both principles predict formation of objects that are not well-known or, at least, well-described so far. Among these are neutron-rich super-heavy and giant nuclei, biologic and organic-silicon mesoobjects, cosmological objects with the sizes considerably exceeding the size of a light sphere.

Improvement of Fe(Ii)-Adsorption Capacity of Feooh-Coated Brick in Solutions, and Kinetics Aspects

The adsorbent, iron oxy-hydroxide coated brick, was used in the present work for removal of iron(II) from aqueous solutions. The adsorption performances of this composite were significantly improved when brick pellets (as a support material) were pre-treated in a 6 M HCl solution at 90°C for 6 hours, when compared to untreated ones and those pre-washed in a 1M HCl solution at RT for 1 day. This phenomenon was attributed to larger surface areas measured for modified brick by BET, thus enabling a better FeOOH deposition. The ability of this new composite to better adsorb Fe2+ ions from synthetic solutions was evidenced from fixed-bed column experiments: data were compared to those obtained from raw brick and iron oxides - coated sand columns. The adsorption mechanism followed better pseudosecond-order reaction kinetics, suggesting a chemisorption process, and the rate constant increased with a temperature increase, revealing the endothermic nature of Fe(II) adsorption. Furthermore, the equilibrium data fitted the Langmuir isotherm model with a maximum monolayer sorption capacity Qmax = 0.669 mg/g and a Langmuir constant KL = 0.659 L/mg at room temperature. The activation energy (Ea) of Fe(II) adsorption and the changes in entropy (ΔS), enthalpy (ΔH) and free energy (ΔG) of activation were determined, with values suggesting the involvement of an activated chemical adsorption and an associative mechanism.

Dissolution mechanism and kinetics ofβ(Mg_(17)Al_(12))phases in AZ91 magnesium alloy

In this study,the phase transformations,crystallization kinetics and dissolution mechanism ofβphase(Mg_(17)Al_(12))in magnesium alloy AZ91 were investigated by optical microscopy,X-ray diffraction,differential scanning calorimetry and differential dilatometry.The results indicate that this AZ91 alloy undergoes a phase transformation during aging,a discontinuous precipitation of theβphase(Mg_(17)Al_(12))at 150℃at the grain boundaries and another continuous at 350℃within the grains.The activation energy of the dissolution reaction of theβphase(Mg_(17)Al_(12))under non-isothermal conditions is 116.781 kJ/mol,while it is 129.7383 kJ/mol under isothermal conditions.The Avrami coefficient,n,relevant for the dissolution kinetics of theβphase(Mg_(17)Al_(12))is 1.152 and 1.211 in the non-isothermal and isothermal conditions respectively.The numerical coefficients m and Avrami n are 0.993 and 1.152.