Correlation between the Arrhenius crossover and the glass forming ability in metallic glasses.

PubMed

Wen, Tongqi; Yao, Wenjing; Wang, Nan

2017-10-13

The distinctive characteristic of the metallic glass-forming system is that the variation in viscosity with temperature obeys Vogel-Fulcher-Tammann (VFT) relationship in the undercooled state and Arrhenius relationship in the high temperature region. A dimensionless index has thus been proposed based on the Arrhenius-VFT crossover and the classical nucleation rate and growth rate theory to evaluate the glass-forming ability (GFA). The indicator G(a) is expressed with the combination of T g , the glass transition temperature, T x , the onset crystallization temperature, T l , the liquidus temperature, T 0 , the VFT temperature, and a a constant that could be determined according to the best correlation between G(a) and the critical cooling rate (R c ). Compared with other GFA indexes, G(a) shows the best fit with R c , with the square of the correlation coefficient (R 2 ) being 0.9238 when a = 0.15 for the 23 various alloy systems concerned about. Our results indicate the crossover in the viscosity variation has key effect on GFA and one can use the index G(a) to predict R c and GFA for different alloys effectively.

Computing the Viscosity of Supercooled Liquids: Markov Network Model

PubMed Central

Li, Ju; Kushima, Akihiro; Eapen, Jacob; Lin, Xi; Qian, Xiaofeng; Mauro, John C.; Diep, Phong; Yip, Sidney

2011-01-01

The microscopic origin of glass transition, when liquid viscosity changes continuously by more than ten orders of magnitude, is challenging to explain from first principles. Here we describe the detailed derivation and implementation of a Markovian Network model to calculate the shear viscosity of deeply supercooled liquids based on numerical sampling of an atomistic energy landscape, which sheds some light on this transition. Shear stress relaxation is calculated from a master-equation description in which the system follows a transition-state pathway trajectory of hopping among local energy minima separated by activation barriers, which is in turn sampled by a metadynamics-based algorithm. Quantitative connection is established between the temperature variation of the calculated viscosity and the underlying potential energy and inherent stress landscape, showing a different landscape topography or “terrain” is needed for low-temperature viscosity (of order 107 Pa·s) from that associated with high-temperature viscosity (10−5 Pa·s). Within this range our results clearly indicate the crossover from an essentially Arrhenius scaling behavior at high temperatures to a low-temperature behavior that is clearly super-Arrhenius (fragile) for a Kob-Andersen model of binary liquid. Experimentally the manifestation of this crossover in atomic dynamics continues to raise questions concerning its fundamental origin. In this context this work explicitly demonstrates that a temperature-dependent “terrain” characterizing different parts of the same potential energy surface is sufficient to explain the signature behavior of vitrification, at the same time the notion of a temperature-dependent effective activation barrier is quantified. PMID:21464988

Determination of Wetting Behavior, Spread Activation Energy, and Quench Severity of Bioquenchants

NASA Astrophysics Data System (ADS)

Prabhu, K. Narayan; Fernandes, Peter

2007-08-01

An investigation was conducted to study the suitability of vegetable oils such as sunflower, coconut, groundnut, castor, cashewnut shell (CNS), and palm oils as quench media (bioquenchants) for industrial heat treatment by assessing their wetting behavior and severity of quenching. The relaxation of contact angle was sharp during the initial stages, and it became gradual as the system approached equilibrium. The equilibrium contact angle decreased with increase in the temperature of the substrate and decrease in the viscosity of the quench medium. A comparison of the relaxation of the contact angle at various temperatures indicated the significant difference in spreading of oils having varying viscosity. The spread activation energy was determined using the Arrhenius type of equation. Oils with higher viscosity resulted in lower cooling rates. The quench severity of various oil media was determined by estimating heat-transfer coefficients using the lumped capacitance method. Activation energy for spreading determined using the wetting behavior of oils at various temperatures was in good agreement with the severity of quenching assessed by cooling curve analysis. A high quench severity is associated with oils having low spread activation energy.

Temperature Dependence of the Viscosity of Isotropic Liquids

NASA Astrophysics Data System (ADS)

Jadzyn, J.; Czechowski, G.; Lech, T.

1999-04-01

Temperature dependence of the shear viscosity measured for isotropic liquids belonging to the three homologous series: 4-(trans-4'-n-alkylcyclohexyl) isothiocyanatobenzenes (Cn H2n+1 CyHx Ph NCS; nCHBT, n=0-12), n-alkylcyanobiphenyls (CnH2n+1 Ph Ph CN; nCB, n=2-12) and 1,n-alkanediols (HO(CH2)nOH; 1,nAD, n=2-10) were analysed with the use of Arrhenius equation and its two modifications: Vogel--Fulcher and proposed in this paper. The extrapolation of the isothermal viscosity of 1,n-alkanediols (n=2-10) to n=1 leads to an interesting conclusion concerning the expected viscosity of methanediol, HOCH2OH, the compound strongly unstable in a pure state.

Effect of two viscosity models on lethality estimation in sterilization of liquid canned foods.

PubMed

Calderón-Alvarado, M P; Alvarado-Orozco, J M; Herrera-Hernández, E C; Martínez-González, G M; Miranda-López, R; Jiménez-Islas, H

2016-09-01

A numerical study on 2D natural convection in cylindrical cavities during the sterilization of liquid foods was performed. The mathematical model was established on momentum and energy balances and predicts both the heating dynamics of the slowest heating zone (SHZ) and the lethal rate achieved in homogeneous liquid canned foods. Two sophistication levels were proposed in viscosity modelling: 1) considering average viscosity and 2) using an Arrhenius-type model to include the effect of temperature on viscosity. The remaining thermodynamic properties were kept constant. The governing equations were spatially discretized via orthogonal collocation (OC) with mesh size of 25 × 25. Computational simulations were performed using proximate and thermodynamic data for carrot-orange soup, broccoli-cheddar soup, tomato puree, and cream-style corn. Flow patterns, isothermals, heating dynamics of the SHZ, and the sterilization rate achieved for the cases studied were compared for both viscosity models. The dynamics of coldest point and the lethal rate F0 in all food fluids studied were approximately equal in both cases, although the second sophistication level is closer to physical behavior. The model accuracy was compared favorably with reported sterilization time for cream-style corn packed at 303 × 406 can size, predicting 66 min versus an experimental time of 68 min at retort temperature of 121.1 ℃. © The Author(s) 2016.

Temperature dependence of internal friction in enzyme reactions.

PubMed

Rauscher, Anna Á; Simon, Zoltán; Szöllosi, Gergely J; Gráf, László; Derényi, Imre; Malnasi-Csizmadia, Andras

2011-08-01

Our aim was to elucidate the physical background of internal friction of enzyme reactions by investigating the temperature dependence of internal viscosity. By rapid transient kinetic methods, we directly measured the rate constant of trypsin 4 activation, which is an interdomain conformational rearrangement, as a function of temperature and solvent viscosity. We found that the apparent internal viscosity shows an Arrhenius-like temperature dependence, which can be characterized by the activation energy of internal friction. Glycine and alanine mutations were introduced at a single position of the hinge of the interdomain region to evaluate how the flexibility of the hinge affects internal friction. We found that the apparent activation energies of the conformational change and the internal friction are interconvertible parameters depending on the protein flexibility. The more flexible a protein was, the greater proportion of the total activation energy of the reaction was observed as the apparent activation energy of internal friction. Based on the coupling of the internal and external movements of the protein during its conformational change, we constructed a model that quantitatively relates activation energy, internal friction, and protein flexibility.

Rheological characterisation of concentrated domestic slurry.

PubMed

Thota Radhakrishnan, A K; van Lier, J B; Clemens, F H L R

2018-05-03

The much over-looked element in new sanitation, the transport systems which bridge the source and treatment facilities, is the focus of this study. The knowledge of rheological properties of concentrated domestic slurry is essential for the design of the waste collection and transport systems. To investigate these properties, samples were collected from a pilot sanitation system in the Netherlands. Two types of slurries were examined: black water (consisting of human faecal waste, urine, and flushed water from vacuum toilets) and black water with ground kitchen waste. Rheograms of these slurries were obtained using a narrow gap rotating rheometer and modelled using a Herschel-Bulkley model. The effect of concentration on the slurry are described through the changes in the parameters of the Herschel-Bulkley model. A detailed method is proposed on estimating the parameters for the rheological models. For the black water, yield stress and consistency index follow an increasing power law with the concentration and the behaviour index follows a decreasing power law. The influence of temperature on the viscosity of the slurry is described using an Arrhenius type relation. The viscosity of black water decreases with temperature. As for the black water mixed with ground kitchen waste, it is found that the viscosity increases with concentration and decreases with temperature. The viscosity of black-water with ground kitchen waste is found to be higher than that of black water, which can be attributed to the presence of larger particles in the slurry. Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.

Application of the compensated Arrhenius formalism to fluidity data of polar organic liquids.

PubMed

Petrowsky, Matt; Fleshman, Allison M; Frech, Roger

2013-03-14

The temperature dependence of viscosity (the reciprocal of fluidity) in polar liquids has been studied for over a century, but the available theoretical models have serious limitations. Consequently, the viscosity is often described with empirical equations using adjustable fitting parameters that offer no insight into the molecular mechanism of transport. We have previously reported a novel approach called the compensated Arrhenius formalism (CAF) to describe ionic conductivity, self-diffusion, and dielectric relaxation in terms of molecular and system properties. Here the CAF is applied to fluidity data of pure n-acetates, 2-ketones, n-nitriles, and n-alcohols over the temperature range 5-85 °C. The fluidity is represented as an Arrhenius-like expression that includes a static dielectric constant dependence in the exponential prefactor. The dielectric constant dependence results from the dependence of mass and charge transport on the molecular dipole moment and the solvent dipole density. The CAF is the only self-consistent description of fluid transport in polar liquids written solely in terms of molecular and system parameters. A scaling procedure is used to calculate the activation energy for transport. We find that the activation energies for fluidity of the aprotic liquids are comparable in value, whereas a higher average E(a) value is observed for the n-alcohol data. Finally, we contrast the molecular description of transport presented here with the conventional hydrodynamic model.

Predicting the glass transition temperature and viscosity of secondary organic material using molecular composition

NASA Astrophysics Data System (ADS)

Wong DeRieux, Wing-Sy; Li, Ying; Lin, Peng; Laskin, Julia; Laskin, Alexander; Bertram, Allan K.; Nizkorodov, Sergey A.; Shiraiwa, Manabu

2018-05-01

Secondary organic aerosol (SOA) accounts for a large fraction of submicron particles in the atmosphere. SOA can occur in amorphous solid or semi-solid phase states depending on chemical composition, relative humidity (RH), and temperature. The phase transition between amorphous solid and semi-solid states occurs at the glass transition temperature (Tg). We have recently developed a method to estimate Tg of pure compounds containing carbon, hydrogen, and oxygen atoms (CHO compounds) with molar mass less than 450 g mol-1 based on their molar mass and atomic O : C ratio. In this study, we refine and extend this method for CH and CHO compounds with molar mass up to ˜ 1100 g mol-1 using the number of carbon, hydrogen, and oxygen atoms. We predict viscosity from the Tg-scaled Arrhenius plot of fragility (viscosity vs. Tg/T) as a function of the fragility parameter D. We compiled D values of organic compounds from the literature and found that D approaches a lower limit of ˜ 10 (±1.7) as the molar mass increases. We estimated the viscosity of α-pinene and isoprene SOA as a function of RH by accounting for the hygroscopic growth of SOA and applying the Gordon-Taylor mixing rule, reproducing previously published experimental measurements very well. Sensitivity studies were conducted to evaluate impacts of Tg, D, the hygroscopicity parameter (κ), and the Gordon-Taylor constant on viscosity predictions. The viscosity of toluene SOA was predicted using the elemental composition obtained by high-resolution mass spectrometry (HRMS), resulting in a good agreement with the measured viscosity. We also estimated the viscosity of biomass burning particles using the chemical composition measured by HRMS with two different ionization techniques: electrospray ionization (ESI) and atmospheric pressure photoionization (APPI). Due to differences in detected organic compounds and signal intensity, predicted viscosities at low RH based on ESI and APPI measurements differ by 2-5 orders of magnitude. Complementary measurements of viscosity and chemical composition are desired to further constrain RH-dependent viscosity in future studies.

Relationship between the Macroscopic and Quantum Characteristics of Dynamic Viscosity for Hydrocarbons upon the Compensation Effect

NASA Astrophysics Data System (ADS)

Dolomatov, M. Yu.; Kovaleva, E. A.; Khamidullina, D. A.

2018-05-01

An approach that allows the calculation of dynamic viscosity for liquid hydrocarbons from quantum (ionization energies) and molecular (Wiener topological indices) parameters is proposed. A physical relationship is revealed between ionization and the energies of viscous flow activation. This relationship is due to the contribution from the dispersion component of Van der Waals forces to intermolecular interaction. A two-parameter dependence of the energy of viscous flow activation, energy of ionization, and Wiener topological indices is obtained. The dynamic viscosities of liquid hydrocarbons can be calculated from the kinetic compensation effect of dynamic viscosity, which indicates a relationship between the energy of activation and the Arrhenius pre-exponental factor of the Frenkel-Eyring hole model. Calculation results are confirmed through statistical processing of the experimental data.

Temperature dependence of the positronium yields in polar and nonpolar pure liquids; an experimental test of a phenomenological model

NASA Astrophysics Data System (ADS)

Lévay, B.

2004-08-01

A phenomenological model describing the temperature dependence of the positronium yields ( IPs, %) was tested in pure liquids of different polarity. The investigated solvents were: m-xylene (m-Xy) and iso-octane (i-C8) as aromatic and aliphatic nonpolar hydrocarbons, methanol (MeOH), water and dimethyl formamide as polar solvents with and without OH group. Arrhenius type linear relationship predicted by the model for the ln Q vs 1/ T function, where Q=(100/ IPs-1), was found to be valid in all cases. The slopes of the lines correspond to the activation energy differences (Δ E*= Erec- EPs) between the two main competing reaction pathways in the positron spur, i.e., solvent recombination (e - + M +) and positronium formation (e - + e +). The slopes were positive, i.e., Δ E*<0 and Erec< EPs. For polar liquids, correlation seems to exists between Δ E* and the electron mobility ( μ) or the activation energy of the viscosity ( Eη).

Glass transition and viscosity of P/sub 2/O/sub 5/

DOE Office of Scientific and Technical Information (OSTI.GOV)

Martin, S.W.; Angell, C.A.

1986-12-04

The calorimetric glass transition temperature T/sub g/ for pure anhydrous P/sub 2/O/sub 5/ melted in sealed SiO/sub 2/ ampules at 1000 /sup 0/C has been obtained directly for the first time with differential scanning calorimetry, and the increase in heat capacity at T/sub g/ has been determined. T/sub g/ measured in this way is 57 K higher than the value quoted in the literature, which is probably based on an Arrhenius law extrapolation of viscosity data to eta = 10/sup 13/ P. Combining the high-temperature viscosity data with the common observation that, for oxide glasses, eta = 10/sup 12/ Pmore » at the DSC T/sub g/, the authors find that the P/sub 2/O/sub 5/ viscosity obeys an Arrhenius law over at least 6 decades of eta. Furthermore, the intercept at 1/T = 0 coincides with the common point of T/sub g/ - reduced viscosity plots for a wide variety of liquids recently used in establishing the strong vs. fragile classification of glass-forming liquids. On this basis, P/sub 2/O/sub 5/ behaves as the archetypal strong liquid. However, the value of C/sub p/(liquid)/C/sub p/(glass) at T/sub g/, 1.27, is larger than expected on this basis since other strong liquids show smaller values, e.g., GeO/sub 2/ (1.09) and BeF/sub 2/ (no ..delta..C/sub p/ detected). The dependence of T/sub g/ on heating rate has been determined and shows that enthalpy relaxation in the transition region has, within error, the same activation energy (43.9 kcal/mol) as for viscous flow.« less

Thermophysical Property Measurements of Silicon-Transition Metal Alloys

NASA Technical Reports Server (NTRS)

Banish, R. Michael; Erwin, William R.; Sansoucie, Michael P.; Lee, Jonghyun; Gave, Matthew A.

2014-01-01

Metals and metallic alloys often have high melting temperatures and highly reactive liquids. Processing reactive liquids in containers can result in significant contamination and limited undercooling. This is particularly true for molten silicon and it alloys. Silicon is commonly termed "the universal solvent". The viscosity, surface tension, and density of several silicon-transition metal alloys were determined using the Electrostatic Levitator system at the Marshall Space Flight Center. The temperature dependence of the viscosity followed an Arrhenius dependence, and the surface tension followed a linear temperature dependence. The density of the melts, including the undercooled region, showed a linear behavior as well. Viscosity and surface tension values were obtain for several of the alloys in the undercooled region.

Kinetics of low-temperature transitions and a reaction rate theory from non-equilibrium distributions

PubMed Central

Aquilanti, Vincenzo; Coutinho, Nayara Dantas

2017-01-01

This article surveys the empirical information which originated both by laboratory experiments and by computational simulations, and expands previous understanding of the rates of chemical processes in the low-temperature range, where deviations from linearity of Arrhenius plots were revealed. The phenomenological two-parameter Arrhenius equation requires improvement for applications where interpolation or extrapolations are demanded in various areas of modern science. Based on Tolman's theorem, the dependence of the reciprocal of the apparent activation energy as a function of reciprocal absolute temperature permits the introduction of a deviation parameter d covering uniformly a variety of rate processes, from those where quantum mechanical tunnelling is significant and d < 0, to those where d > 0, corresponding to the Pareto–Tsallis statistical weights: these generalize the Boltzmann–Gibbs weight, which is recovered for d = 0. It is shown here how the weights arise, relaxing the thermodynamic equilibrium limit, either for a binomial distribution if d > 0 or for a negative binomial distribution if d < 0, formally corresponding to Fermion-like or Boson-like statistics, respectively. The current status of the phenomenology is illustrated emphasizing case studies; specifically (i) the super-Arrhenius kinetics, where transport phenomena accelerate processes as the temperature increases; (ii) the sub-Arrhenius kinetics, where quantum mechanical tunnelling propitiates low-temperature reactivity; (iii) the anti-Arrhenius kinetics, where processes with no energetic obstacles are rate-limited by molecular reorientation requirements. Particular attention is given for case (i) to the treatment of diffusion and viscosity, for case (ii) to formulation of a transition rate theory for chemical kinetics including quantum mechanical tunnelling, and for case (iii) to the stereodirectional specificity of the dynamics of reactions strongly hindered by the increase of temperature. This article is part of the themed issue ‘Theoretical and computational studies of non-equilibrium and non-statistical dynamics in the gas phase, in the condensed phase and at interfaces’. PMID:28320904

Kinetics of low-temperature transitions and a reaction rate theory from non-equilibrium distributions.

PubMed

Aquilanti, Vincenzo; Coutinho, Nayara Dantas; Carvalho-Silva, Valter Henrique

2017-04-28

This article surveys the empirical information which originated both by laboratory experiments and by computational simulations, and expands previous understanding of the rates of chemical processes in the low-temperature range, where deviations from linearity of Arrhenius plots were revealed. The phenomenological two-parameter Arrhenius equation requires improvement for applications where interpolation or extrapolations are demanded in various areas of modern science. Based on Tolman's theorem, the dependence of the reciprocal of the apparent activation energy as a function of reciprocal absolute temperature permits the introduction of a deviation parameter d covering uniformly a variety of rate processes, from those where quantum mechanical tunnelling is significant and d  < 0, to those where d  > 0, corresponding to the Pareto-Tsallis statistical weights: these generalize the Boltzmann-Gibbs weight, which is recovered for d  = 0. It is shown here how the weights arise, relaxing the thermodynamic equilibrium limit, either for a binomial distribution if d  > 0 or for a negative binomial distribution if d  < 0, formally corresponding to Fermion-like or Boson-like statistics, respectively. The current status of the phenomenology is illustrated emphasizing case studies; specifically (i) the super -Arrhenius kinetics, where transport phenomena accelerate processes as the temperature increases; (ii) the sub -Arrhenius kinetics, where quantum mechanical tunnelling propitiates low-temperature reactivity; (iii) the anti -Arrhenius kinetics, where processes with no energetic obstacles are rate-limited by molecular reorientation requirements. Particular attention is given for case (i) to the treatment of diffusion and viscosity, for case (ii) to formulation of a transition rate theory for chemical kinetics including quantum mechanical tunnelling, and for case (iii) to the stereodirectional specificity of the dynamics of reactions strongly hindered by the increase of temperature.This article is part of the themed issue 'Theoretical and computational studies of non-equilibrium and non-statistical dynamics in the gas phase, in the condensed phase and at interfaces'. © 2017 The Author(s).

Effect of atmosphere on the surface tension and viscosity of molten LiNbO 3 measured using the surface laser-light scattering method

NASA Astrophysics Data System (ADS)

Nagasaka, Yuji; Kobayashi, Yusuke

2007-09-01

The surface tension and the viscosity of molten LiNbO 3 (LN) having the congruent composition have been measured simultaneously in a temperature range from 1537 to 1756 K under argon gas and dry-air atmospheres. The present measurement technique involves surface laser-light scattering (SLLS) that detects nanometer-order-amplitude surface waves usually regarded as ripplons excited by thermal fluctuations. This technique's non-invasive nature allows it to avoid the experimental difficulties of conventional techniques resulting from the insertion of an actuator in the melt. The results of surface tension measurement obtained under a dry-air atmosphere are about 5% smaller than those obtained under an argon atmosphere near the melting temperature, and the temperature dependence of the surface tension under a dry-air atmosphere is twice that under an argon atmosphere. The uncertainty of surface tension measurement is estimated to be ±2.6% under argon and ±1.9% under dry air. The temperature dependence of viscosity can be well correlated with the results of Arrhenius-type equations without any anomalous behavior near the melting point. The viscosities obtained under a dry-air atmosphere were slightly smaller than those obtained under an argon atmosphere. The uncertainty of viscosity measurement is estimated to be ±11.1% for argon and ±14.3% for dry air. Moreover, we observed the real-time dynamic behavior of the surface tension and the viscosity of molten LN in response to argon and dry-air atmospheres.

Steady shear flow properties of Cordia myxa leaf gum as a function of concentration and temperature.

PubMed

Chaharlang, Mahmood; Samavati, Vahid

2015-08-01

The steady shear flow properties of dispersions of Cordia myxa leaf gum (CMLG) were determined as a function of concentration (0.5-2.5%, w/w), and temperature (10-50 °C). The CMLG dispersions exhibited strong shear-thinning behavior at all concentrations and temperatures. The Power-law (Ostwald-Waele's) and Herschel-Bulkley models were employed to characterize flow behavior of CMLG solutions at 0.1-100 s(-1) shear rate. Non-Newtonian shear-thinning behavior was observed at all temperatures and concentrations. While increase in temperature decreased the viscosity and increased the flow behavior indices, adverse effect was obtained by increasing the concentration. The Power-law model was found the best model to describe steady shear flow behavior of CMLG. The pseudoplasticity of CMLG increased markedly with concentration. An Arrhenius-type model was also used to describe the effect of temperature. The activation energy (Ea) appeared in the range of 5.972-18.104 kJ/mol, as concentration increased from 0.5% to 2.5%, at a shear rate of 10 s(-1). Copyright © 2015 Elsevier B.V. All rights reserved.

The Rheology of a Three Component System: COAL/WATER/#4 Oil Emulsions.

NASA Astrophysics Data System (ADS)

Gilmartin, Barbara Jean

The purpose of this investigation was to study the rheology of a three component system, coal/water/#4 oil emulsions (COW), in which the third component, water, was present in a significant concentration, and to determine the applicability of existing theories from suspension rheology to the three component system studied. In a coal/water/oil emulsion, free coal particles adhere to the surface of the water droplets, preventing their coagulation, while the larger coal particles reside in the matrix of stabilized water droplets. The use of liquid fuels containing coal is a means of utilizing our nation's coal reserves while conserving oil. These fuels can be burned in conventional oil-fired furnaces. In this investigation, a high sulfur, high ash, bituminous coal was used, along with a heavy #4 oil to prepare the emulsions. The coal was ground to a log-normal distribution with an average particle size of 62 microns. A Haake RV3 concentric cylinder viscometer, with a ribbed measuring system, was used to determine the viscosity of the emulsions. A physical pendulum settling device measured the shift in center of mass of the COW as a function of time. The flow behavior of the fuel in pipes was also tested. In interpreting the data from the viscometer and the pipe flow experiments, a power law analysis was used in the region from 30 s('-1) to 200 s('-1). Extrapolation methods were used to obtain the low and high shear behavior of the emulsions. In the shear rate region found in boiler feed systems, COW are shear thinning with a flow behavior index of 0.7. The temperature dependent characteristic of the emulsions studied were similar and followed an Arrhenius type relationship. The viscosity of the COW decreases with increasing coal average particle size and is also a function of the width of the size distribution used. The type of coal used strongly influences the rheology of the fuel. The volatile content and the atomic oxygen to nitrogen ratio of the coal are the most predictive factors in terms of the variation in viscosity of the emulsion with coal type. The viscosity of the oil used is linearly related to the viscosity of the COW. The relative viscosity - concentration relationship for the emulsions was evaluated by an equation developed by Quemada for use in blood rheology: (eta)(,r) = (1 - (phi)/(phi)(,max))('-2). The best fit of the data to the equation was found when the coal plus water concentration was used for (phi). The maximum packing fraction increased with increasing shear rate, reflecting a breaking up of the agglomerates in the system. By using the relative packing fraction of the coal plus oil concentration, the relative viscosity of the emulsions tested at the three shear rates evaluted can be fit to the Quemada relative viscosity equation. In the pipe flow tests, the emulsions showed little time-dependent behavior, however they did exhibit a well effect. A fair correlation was obtained between pipe flow behavior and the results obtained in the viscometer. Coal/water/#4 oil emulsions behave as coal and water in oil systems and can be successfully modeled using theories from suspension rheology.

What can we learn from Einstein and Arrhenius about the optimal flow of our blood?

PubMed

Schuster, Stefan; Stark, Heiko

2014-01-01

The oxygen flow in humans and other higher animals depends on the erythrocyte-to-blood volume ratio, the hematocrit. Since it is physiologically favourable when the flow of oxygen transport is maximum it can be assumed that this situation has been achieved during evolution. If the hematocrit was too low, too few erythrocytes could transport oxygen. If it was too high, the blood would be very viscous, so that oxygen supply would again be reduced. The theoretical optimal hematocrit can be calculated by considering the dependence of blood viscosity on the hematocrit. Different approaches to expressing this dependence have been proposed in the literature. Here, we discuss early approaches in hydrodynamics proposed by Einstein and Arrhenius and show that especially the Arrhenius equation is very appropriate for this purpose. We show that despite considerable simplifications such as neglecting the deformation, orientation and aggregation of erythrocytes, realistic hematocrit values of about 40% can be derived based on optimality considerations. Also the prediction that the ratio between the viscosities of the blood and blood plasma at high shear rates nearly equals Euler's constant (2.718) is in good agreement with observed values. Finally, we discuss possible extensions of the theory. For example, we derive the theoretical optimal hematocrit for persevering divers among marine mammals to be 65%, in excellent agreement with the values observed in several species. These considerations are very important for human and animal physiology since oxygen transport is an important factor for medicine and physical performance. © 2013 Elsevier B.V. All rights reserved.

Sequence and Temperature Dependence of the End-to-End Collision Dynamics of Single-Stranded DNA

PubMed Central

Uzawa, Takanori; Isoshima, Takashi; Ito, Yoshihiro; Ishimori, Koichiro; Makarov, Dmitrii E.; Plaxco, Kevin W.

2013-01-01

Intramolecular collision dynamics play an essential role in biomolecular folding and function and, increasingly, in the performance of biomimetic technologies. To date, however, the quantitative studies of dynamics of single-stranded nucleic acids have been limited. Thus motivated, here we investigate the sequence composition, chain-length, viscosity, and temperature dependencies of the end-to-end collision dynamics of single-stranded DNAs. We find that both the absolute collision rate and the temperature dependencies of these dynamics are base-composition dependent, suggesting that base stacking interactions are a significant contributor. For example, whereas the end-to-end collision dynamics of poly-thymine exhibit simple, linear Arrhenius behavior, the behavior of longer poly-adenine constructs is more complicated. Specifically, 20- and 25-adenine constructs exhibit biphasic temperature dependencies, with their temperature dependences becoming effectively indistinguishable from that of poly-thymine above 335 K for 20-adenines and 328 K for 25-adenines. The differing Arrhenius behaviors of poly-thymine and poly-adenine and the chain-length dependence of the temperature at which poly-adenine crosses over to behave like poly-thymine can be explained by a barrier friction mechanism in which, at low temperatures, the energy barrier for the local rearrangement of poly-adenine becomes the dominant contributor to its end-to-end collision dynamics. PMID:23746521

Perfluoroalkyl phosphonic and phosphinic acids as proton conductors for anhydrous proton-exchange membranes.

PubMed

Herath, Mahesha B; Creager, Stephen E; Kitaygorodskiy, Alex; DesMarteau, Darryl D

2010-09-10

A study of proton-transport rates and mechanisms under anhydrous conditions using a series of acid model compounds, analogous to comb-branch perfluorinated ionomers functionalized with phosphonic, phosphinic, sulfonic, and carboxylic acid protogenic groups, is reported. Model compounds are characterized with respect to proton conductivity, viscosity, proton, and anion (conjugate base) self-diffusion coefficients, and Hammett acidity. The highest conductivities, and also the highest viscosities, are observed for the phosphonic and phosphinic acid model compounds. Arrhenius analysis of conductivity and viscosity for these two acids reveals much lower activation energies for ion transport than for viscous flow. Additionally, the proton self-diffusion coefficients are much higher than the conjugate-base self-diffusion coefficients for these two acids. Taken together, these data suggest that anhydrous proton transport in the phosphonic and phosphinic acid model compounds occurs primarily by a structure-diffusion, hopping-based mechanism rather than a vehicle mechanism. Further analysis of ionic conductivity and ion self-diffusion rates by using the Nernst-Einstein equation reveals that the phosphonic and phosphinic acid model compounds are relatively highly dissociated even under anhydrous conditions. In contrast, sulfonic and carboxylic acid-based systems exhibit relatively low degrees of dissociation under anhydrous conditions. These findings suggest that fluoroalkyl phosphonic and phosphinic acids are good candidates for further development as anhydrous, high-temperature proton conductors.

A Low Viscosity Lunar Magma Ocean Forms a Stratified Anorthitic Flotation Crust With Mafic Poor and Rich Units: Lunar Magma Ocean Viscosity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dygert, Nick; Lin, Jung-Fu; Marshall, Edward W.

Much of the lunar crust is monomineralic, comprising >98% plagioclase. The prevailing model argues the crust accumulated as plagioclase floated to the surface of a solidifying lunar magma ocean (LMO). Whether >98% pure anorthosites can form in a flotation scenario is debated. An important determinant of the efficiency of plagioclase fractionation is the viscosity of the LMO liquid, which was unconstrained. Here we present results from new experiments conducted on a late LMO-relevant ferrobasaltic melt. The liquid has an exceptionally low viscosity of 0.22more » $$+0.11\\atop{-0.19}$$to 1.45 $$+0.46\\atop{-0.82}$$ Pa s at experimental conditions (1,300–1,600°C; 0.1–4.4 GPa) and can be modeled by an Arrhenius relation. Extrapolating to LMO-relevant temperatures, our analysis suggests a low viscosity LMO would form a stratified flotation crust, with the oldest units containing a mafic component and with very pure younger units. Old, impure crust may have been buried by lower crustal diapirs of pure anorthosite in a serial magmatism scenario.« less

Transport properties of glass-forming liquids suggest that dynamic crossover temperature is as important as the glass transition temperature.

PubMed

Mallamace, Francesco; Branca, Caterina; Corsaro, Carmelo; Leone, Nancy; Spooren, Jeroen; Chen, Sow-Hsin; Stanley, H Eugene

2010-12-28

It is becoming common practice to partition glass-forming liquids into two classes based on the dependence of the shear viscosity η on temperature T. In an Arrhenius plot, ln η vs 1/T, a strong liquid shows linear behavior whereas a fragile liquid exhibits an upward curvature [super-Arrhenius (SA) behavior], a situation customarily described by using the Vogel-Fulcher-Tammann law. Here we analyze existing data of the transport coefficients of 84 glass-forming liquids. We show the data are consistent, on decreasing temperature, with the onset of a well-defined dynamical crossover η(×), where η(×) has the same value, η(×) ≈ 10(3) Poise, for all 84 liquids. The crossover temperature, T(×), located well above the calorimetric glass transition temperature T(g), marks significant variations in the system thermodynamics, evidenced by the change of the SA-like T dependence above T(×) to Arrhenius behavior below T(×). We also show that below T(×) the familiar Stokes-Einstein relation D/T ∼ η(-1) breaks down and is replaced by a fractional form D/T ∼ η(-ζ), with ζ ≈ 0.85.

Transport properties of glass-forming liquids suggest that dynamic crossover temperature is as important as the glass transition temperature

PubMed Central

Mallamace, Francesco; Branca, Caterina; Corsaro, Carmelo; Leone, Nancy; Spooren, Jeroen; Chen, Sow-Hsin; Stanley, H. Eugene

2010-01-01

It is becoming common practice to partition glass-forming liquids into two classes based on the dependence of the shear viscosity η on temperature T. In an Arrhenius plot, ln η vs 1/T, a strong liquid shows linear behavior whereas a fragile liquid exhibits an upward curvature [super-Arrhenius (SA) behavior], a situation customarily described by using the Vogel–Fulcher–Tammann law. Here we analyze existing data of the transport coefficients of 84 glass-forming liquids. We show the data are consistent, on decreasing temperature, with the onset of a well-defined dynamical crossover η×, where η× has the same value, η× ≈ 103 Poise, for all 84 liquids. The crossover temperature, T×, located well above the calorimetric glass transition temperature Tg, marks significant variations in the system thermodynamics, evidenced by the change of the SA-like T dependence above T× to Arrhenius behavior below T×. We also show that below T× the familiar Stokes–Einstein relation D/T ∼ η-1 breaks down and is replaced by a fractional form D/T ∼ η-ζ, with ζ ≈ 0.85. PMID:21148100

Describing Temperature-Dependent Self-Diffusion Coefficients and Fluidity of 1- and 3-Alcohols with the Compensated Arrhenius Formalism.

PubMed

Fleshman, Allison M; Forsythe, Grant E; Petrowsky, Matt; Frech, Roger

2016-09-22

The location of the hydroxyl group in monohydroxy alcohols greatly affects the temperature dependence of the liquid structure due to hydrogen bonding. Temperature-dependent self-diffusion coefficients, fluidity (the inverse of viscosity), dielectric constant, and density have been measured for several 1-alcohols and 3-alcohols with varying alkyl chain lengths. The data are modeled using the compensated Arrhenius formalism (CAF). The CAF follows a modified transition state theory using an Arrhenius-like expression to describe the transport property, which consists of a Boltzmann factor containing an energy of activation, Ea, and an exponential prefactor containing the temperature-dependent solution dielectric constant, εs(T). Both 1- and 3-alcohols show the Ea of diffusion coefficients (approximately 43 kJ mol(-1)) is higher than the Ea of fluidity (approximately 35 kJ mol(-1)). The temperature dependence of the exponential prefactor in these associated liquids is explained using the dielectric constant and the Kirkwood-Frölich correlation factor, gk. It is argued that the dielectric constant must be used to account for the additional temperature dependence due to variations in the liquid structure (e.g., hydrogen bonding) for the CAF to accurately model the transport property.

Evaluation of the relevance of the glassy state as stability criterion for freeze-dried bacteria by application of the Arrhenius and WLF model.

PubMed

Aschenbrenner, Mathias; Kulozik, Ulrich; Foerst, Petra

2012-12-01

The aim of this work was to describe the temperature dependence of microbial inactivation for several storage conditions and protective systems (lactose, trehalose and dextran) in relation to the physical state of the sample, i.e. the glassy or non-glassy state. The resulting inactivation rates k were described by applying two models, Arrhenius and Williams-Landel-Ferry (WLF), in order to evaluate the relevance of diffusional limitation as a protective mechanism. The application of the Arrhenius model revealed a significant decrease in activation energy E(a) for storage conditions close to T(g). This finding is an indication that the protective effect of a surrounding glassy matrix can, at least, partly be ascribed to its inherent restricted diffusion and mobility. The application of the WLF model revealed that the temperature dependence of microbial inactivation above T(g) is significantly weaker than predicted by the universal coefficients. Thus, it can be concluded that microbial inactivation is not directly linked with the mechanical relaxation behavior of the surrounding matrix as it was reported for viscosity and crystallization phenomena in case of disaccharide systems. Copyright © 2012. Published by Elsevier Inc.

A Low Viscosity Lunar Magma Ocean Forms a Stratified Anorthitic Flotation Crust With Mafic Poor and Rich Units

NASA Astrophysics Data System (ADS)

Dygert, Nick; Lin, Jung-Fu; Marshall, Edward W.; Kono, Yoshio; Gardner, James E.

2017-11-01

Much of the lunar crust is monomineralic, comprising >98% plagioclase. The prevailing model argues the crust accumulated as plagioclase floated to the surface of a solidifying lunar magma ocean (LMO). Whether >98% pure anorthosites can form in a flotation scenario is debated. An important determinant of the efficiency of plagioclase fractionation is the viscosity of the LMO liquid, which was unconstrained. Here we present results from new experiments conducted on a late LMO-relevant ferrobasaltic melt. The liquid has an exceptionally low viscosity of 0.22-0.19+0.11 to 1.45-0.82+0.46 Pa s at experimental conditions (1,300-1,600°C; 0.1-4.4 GPa) and can be modeled by an Arrhenius relation. Extrapolating to LMO-relevant temperatures, our analysis suggests a low viscosity LMO would form a stratified flotation crust, with the oldest units containing a mafic component and with very pure younger units. Old, impure crust may have been buried by lower crustal diapirs of pure anorthosite in a serial magmatism scenario.

Nonequilibrium viscosity of glass

NASA Astrophysics Data System (ADS)

Mauro, John C.; Allan, Douglas C.; Potuzak, Marcel

2009-09-01

Since glass is a nonequilibrium material, its properties depend on both composition and thermal history. While most prior studies have focused on equilibrium liquid viscosity, an accurate description of nonequilibrium viscosity is essential for understanding the low temperature dynamics of glass. Departure from equilibrium occurs as a glass-forming system is cooled through the glass transition range. The glass transition involves a continuous breakdown of ergodicity as the system gradually becomes trapped in a subset of the available configurational phase space. At very low temperatures a glass is perfectly nonergodic (or “isostructural”), and the viscosity is described well by an Arrhenius form. However, the behavior of viscosity during the glass transition range itself is not yet understood. In this paper, we address the problem of glass viscosity using the enthalpy landscape model of Mauro and Loucks [Phys. Rev. B 76, 174202 (2007)] for selenium, an elemental glass former. To study a wide range of thermal histories, we compute nonequilibrium viscosity with cooling rates from 10-12 to 1012K/s . Based on these detailed landscape calculations, we propose a simplified phenomenological model capturing the essential physics of glass viscosity. The phenomenological model incorporates an ergodicity parameter that accounts for the continuous breakdown of ergodicity at the glass transition. We show a direct relationship between the nonequilibrium viscosity parameters and the fragility of the supercooled liquid. The nonequilibrium viscosity model is validated against experimental measurements of Corning EAGLE XG™ glass. The measurements are performed using a specially designed beam-bending apparatus capable of accurate nonequilibrium viscosity measurements up to 1016Pas . Using a common set of parameters, the phenomenological model provides an accurate description of EAGLE XG™ viscosity over the full range of measured temperatures and fictive temperatures.

Experimental and Theoretical Studies on the Viscosity-Structure Correlation for High Alumina-Silicate Melts

NASA Astrophysics Data System (ADS)

Talapaneni, Trinath; Yedla, Natraj; Pal, Snehanshu; Sarkar, Smarajit

2017-06-01

Blast furnaces are encountering high Alumina (Al2O3 > 25 pct) in the final slag due to the charging of low-grade ores. To study the viscosity behavior of such high alumina slags, synthetic slags are prepared in the laboratory scale by maintaining a chemical composition of Al2O3 (25 to 30 wt pct) CaO/SiO2 ratio (0.8 to 1.6) and MgO (8 to 16 wt pct). A chemical thermodynamic software FactSage 7.0 is used to predict liquidus temperature and viscosity of the above slags. Experimental viscosity measurements are performed above the liquidus temperature in the range of 1748 K to 1848 K (1475 °C to 1575 °C). The viscosity values obtained from FactSage closely fit with the experimental values. The viscosity and the slag structure properties are intent by Fourier Transform Infrared (FTIR) and Raman spectroscopy. It is observed that increase in CaO/SiO2 ratio and MgO content in the slag depolymerizes the silicate structure. This leads to decrease in viscosity and activation energy (167 to 149 kJ/mol) of the slag. Also, an addition of Al2O3 content increases the viscosity of slag by polymerization of alumino-silicate structure and activation energy from 154 to 161 kJ/mol. It is witnessed that the activation energy values obtained from experiment closely fit with the Shankar model based on Arrhenius equation.

Activation energy associated with the electromigration of oligosaccharides through viscosity modifier and polymeric additive containing background electrolytes.

PubMed

Kerékgyártó, Márta; Járvás, Gábor; Novák, Levente; Guttman, András

2016-02-01

The activation energy related to the electromigration of oligosaccharides can be determined from their measured electrophoretic mobilities at different temperatures. The effects of a viscosity modifier (ethylene glycol) and a polymeric additive (linear polyacrylamide) on the electrophoretic mobility of linear sugar oligomers with α1-4 linked glucose units (maltooligosaccharides) were studied in CE using the activation energy concept. The electrophoretic separations of 8-aminopyrene-1,3,6-trisulfonate-labeled maltooligosaccharides were monitored by LIF detection in the temperature range of 20-50°C, using either 0-60% ethylene glycol (viscosity modifier) or 0-3% linear polyacrylamide (polymeric additive) containing BGEs. Activation energy curves were constructed based on the slopes of the Arrhenius plots. With the use of linear polyacrylamide additive, solute size-dependent activation energy variations were found for the maltooligosaccharides with polymerization degrees below and above maltoheptaose (DP 7), probably due to molecular conformation changes and possible matrix interaction effects. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A comparative study on improved Arrhenius-type and artificial neural network models to predict high-temperature flow behaviors in 20MnNiMo alloy.

PubMed

Quan, Guo-zheng; Yu, Chun-tang; Liu, Ying-ying; Xia, Yu-feng

2014-01-01

The stress-strain data of 20MnNiMo alloy were collected from a series of hot compressions on Gleeble-1500 thermal-mechanical simulator in the temperature range of 1173 ∼ 1473 K and strain rate range of 0.01 ∼ 10 s(-1). Based on the experimental data, the improved Arrhenius-type constitutive model and the artificial neural network (ANN) model were established to predict the high temperature flow stress of as-cast 20MnNiMo alloy. The accuracy and reliability of the improved Arrhenius-type model and the trained ANN model were further evaluated in terms of the correlation coefficient (R), the average absolute relative error (AARE), and the relative error (η). For the former, R and AARE were found to be 0.9954 and 5.26%, respectively, while, for the latter, 0.9997 and 1.02%, respectively. The relative errors (η) of the improved Arrhenius-type model and the ANN model were, respectively, in the range of -39.99% ∼ 35.05% and -3.77% ∼ 16.74%. As for the former, only 16.3% of the test data set possesses η-values within ± 1%, while, as for the latter, more than 79% possesses. The results indicate that the ANN model presents a higher predictable ability than the improved Arrhenius-type constitutive model.

Study on elevated-temperature flow behavior of Ni-Cr-Mo-B ultra-heavy-plate steel via experiment and modelling

NASA Astrophysics Data System (ADS)

Gao, Zhi-yu; Kang, Yu; Li, Yan-shuai; Meng, Chao; Pan, Tao

2018-04-01

Elevated-temperature flow behavior of a novel Ni-Cr-Mo-B ultra-heavy-plate steel was investigated by conducting hot compressive deformation tests on a Gleeble-3800 thermo-mechanical simulator at a temperature range of 1123 K–1423 K with a strain rate range from 0.01 s‑1 to10 s‑1 and a height reduction of 70%. Based on the experimental results, classic strain-compensated Arrhenius-type, a new revised strain-compensated Arrhenius-type and classic modified Johnson-Cook constitutive models were developed for predicting the high-temperature deformation behavior of the steel. The predictability of these models were comparatively evaluated in terms of statistical parameters including correlation coefficient (R), average absolute relative error (AARE), average root mean square error (RMSE), normalized mean bias error (NMBE) and relative error. The statistical results indicate that the new revised strain-compensated Arrhenius-type model could give prediction of elevated-temperature flow stress for the steel accurately under the entire process conditions. However, the predicted values by the classic modified Johnson-Cook model could not agree well with the experimental values, and the classic strain-compensated Arrhenius-type model could track the deformation behavior more accurately compared with the modified Johnson-Cook model, but less accurately with the new revised strain-compensated Arrhenius-type model. In addition, reasons of differences in predictability of these models were discussed in detail.

Transient Cooperative Processes in Dewetting Polymer Melts.

PubMed

Chandran, Sivasurender; Reiter, Günter

2016-02-26

We compare the high velocity dewetting behavior, at elevated temperatures, of atactic polystyrene (aPS) and isotactic polystyrene (iPS) films, with the zero shear bulk viscosity (η_{bulk}) of aPS being approximately ten times larger than iPS. As expected, for aPS the apparent viscosity of the films (η_{f}) derived from high-shear dewetting is less than η_{bulk}, displaying a shear thinning behavior. Surprisingly, for iPS films, η_{f} is always larger than η_{bulk}, even at about 50 °C above the melting point, with η_{f}/η_{bulk} following an Arrhenius behavior. The corresponding activation energy of ∼160±10  kJ/mol for iPS films suggests a cooperative motion of segments which are aligned and agglomerated by fast dewetting.

Glass dynamics and anomalous aging in a family of ionic liquids above the glass transition temperature.

PubMed

Shamim, Nabila; McKenna, Gregory B

2010-12-09

The present paper reports the results of a systematic rheological study of the dynamic moduli of 1-butyl 3-methylimidazolium tetrafluoroborate ([Bmim][BF(4)]), 1-butyl 3-methylimidazolium hexafluorophosphate ([Bmim][PF(6)]), and 1-ethyl 3-methylimidazolium ethylsulfate ([Emim][EtSO(4)]) in the vicinity of their respective glass transition temperatures. The results show an anomalous aging in that the dynamic and the low shear rate viscosities decrease with time at temperatures near to, but above, the glass transition temperature, and this is described. The samples that are aged into equilibrium obey the time-temperature superposition principle, and the shift factors and the viscosities follow classic super-Arrhenius behaviors with intermediate fragility values as the glass transition is approached. Similar experiments using a high-purity [Bmim][BF(4)] show that using a higher purity of the ionic liquid, while changing absolute values of the properties, does not eliminate the anomalous aging response. The data are also analyzed in a fashion similar to that used for polymer melts, and we find that these ionic liquids do not follow, for example, the Cox-Merz relationship between the steady shear viscosity and the dynamic viscosity.

A Comparative Study on Improved Arrhenius-Type and Artificial Neural Network Models to Predict High-Temperature Flow Behaviors in 20MnNiMo Alloy

PubMed Central

Yu, Chun-tang; Liu, Ying-ying; Xia, Yu-feng

2014-01-01

The stress-strain data of 20MnNiMo alloy were collected from a series of hot compressions on Gleeble-1500 thermal-mechanical simulator in the temperature range of 1173∼1473 K and strain rate range of 0.01∼10 s−1. Based on the experimental data, the improved Arrhenius-type constitutive model and the artificial neural network (ANN) model were established to predict the high temperature flow stress of as-cast 20MnNiMo alloy. The accuracy and reliability of the improved Arrhenius-type model and the trained ANN model were further evaluated in terms of the correlation coefficient (R), the average absolute relative error (AARE), and the relative error (η). For the former, R and AARE were found to be 0.9954 and 5.26%, respectively, while, for the latter, 0.9997 and 1.02%, respectively. The relative errors (η) of the improved Arrhenius-type model and the ANN model were, respectively, in the range of −39.99%∼35.05% and −3.77%∼16.74%. As for the former, only 16.3% of the test data set possesses η-values within ±1%, while, as for the latter, more than 79% possesses. The results indicate that the ANN model presents a higher predictable ability than the improved Arrhenius-type constitutive model. PMID:24688358

Relaxation mechanisms in glassy dynamics: the Arrhenius and fragile regimes.

PubMed

Hentschel, H George E; Karmakar, Smarajit; Procaccia, Itamar; Zylberg, Jacques

2012-06-01

Generic glass formers exhibit at least two characteristic changes in their relaxation behavior, first to an Arrhenius-type relaxation at some characteristic temperature and then at a lower characteristic temperature to a super-Arrhenius (fragile) behavior. We address these transitions by studying the statistics of free energy barriers for different systems at different temperatures and space dimensions. We present a clear evidence for changes in the dynamical behavior at the transition to Arrhenius and then to a super-Arrhenius behavior. A simple model is presented, based on the idea of competition between single-particle and cooperative dynamics. We argue that Arrhenius behavior can take place as long as there is enough free volume for the completion of a simple T1 relaxation process. Once free volume is absent one needs a cooperative mechanism to "collect" enough free volume. We show that this model captures all the qualitative behavior observed in simulations throughout the considered temperature range.

Study of nanostructural organization of ionic liquids by electron paramagnetic resonance spectroscopy.

PubMed

Merunka, Dalibor; Peric, Mirna; Peric, Miroslav

2015-02-19

The X-band electron paramagnetic resonance spectroscopy (EPR) of a stable, spherical nitroxide spin probe, perdeuterated 2,2,6,6-tetramethyl-4-oxopiperidine-1-oxyl (pDTO) has been used to study the nanostructural organization of a series of 1-alkyl-3-methylimidazolium tetrafluoroborate ionic liquids (ILs) with alkyl chain lengths from two to eight carbons. By employing nonlinear least-squares fitting of the EPR spectra, we have obtained values of the rotational correlation time and hyperfine coupling splitting of pDTO to high precision. The rotational correlation time of pDTO in ILs and squalane, a viscous alkane, can be fit very well to a power law functionality with a singular temperature, which often describes a number of physical quantities measured in supercooled liquids. The viscosity of the ILs and squalane, taken from the literature, can also be fit to the same power law expression, which means that the rotational correlation times and the ionic liquid viscosities have similar functional dependence on temperature. The apparent activation energy of both the rotational correlation time of pDTO and the viscous flow of ILs and squalane increases with decreasing temperature; in other words, they exhibit strong non-Arrhenius behavior. The rotational correlation time of pDTO as a function of η/T, where η is the shear viscosity and T is the temperature, is well described by the Stokes-Einstein-Debye (SED) law, while the hydrodynamic probe radii are solvent dependent and are smaller than the geometric radius of the probe. The temperature dependence of hyperfine coupling splitting is the same in all four ionic liquids. The value of the hyperfine coupling splitting starts decreasing with increasing alkyl chain length in the ionic liquids in which the number of carbons in the alkyl chain is greater than four. This decrease together with the decrease in the hydrodynamic radius of the probe indicates a possible existence of nonpolar nanodomains.

Measurement of the Diffusion Coefficient of Water in RP-3 and RP-5 Jet Fuels Using Digital Holography Interferometry

NASA Astrophysics Data System (ADS)

Li, Chaoyue; Feng, Shiyu; Shao, Lei; Pan, Jun; Liu, Weihua

2018-04-01

The diffusion coefficient of water in jet fuel was measured employing double-exposure digital holographic interferometry to clarify the diffusion process and make the aircraft fuel system safe. The experimental method and apparatus are introduced in detail, and the digital image processing program is coded in MATLAB according to the theory of the Fourier transform. At temperatures ranging from 278.15 K to 333.15 K in intervals of 5 K, the diffusion coefficient of water in RP-3 and RP-5 jet fuels ranges from 2.6967 × 10 -10 m2·s-1 to 8.7332 × 10 -10 m2·s-1 and from 2.3517 × 10 -10 m2·s-1 to 8.0099 × 10-10 m2·s-1, respectively. The relationship between the measured diffusion coefficient and temperature can be well fitted by the Arrhenius law. The diffusion coefficient of water in RP-3 jet fuel is higher than that of water in RP-5 jet fuel at the same temperature. Furthermore, the viscosities of the two jet fuels were measured and found to be expressible in the form of the Arrhenius equation. The relationship among the diffusion coefficient, viscosity and temperature is analyzed according to the classic prediction model, namely the Stokes-Einstein correlation, and this correlation is further revised via experimental data to obtain a more accurate predication result.

A molecular dynamics examination of the relationship between self-diffusion and viscosity in liquid metals.

PubMed

Lü, Yongjun; Cheng, Hao; Chen, Min

2012-06-07

The self-diffusion coefficients D and the viscosities η of elemental Ni, Cu, and Ni-Si alloys have been calculated over a wide temperature range by molecular dynamics simulations. For elemental Ni and Cu, Arrhenius-law variations of D and η with temperature dominate. The temperature dependence of Dη can be approximated by a linear relation, whereas the Stokes-Einstein relation is violated. The calculations of D and η are extended to the regions close to the crystallization of Ni(95)Si(5), Ni(90)Si(10), and the glass transitions of Ni(80)Si(20) and Ni(75)Si(25). The results show that both D and η strongly deviate from the Arrhenius law in the vicinity of phase transitions, exhibiting a power-law divergence. We find a decoupling of diffusion and viscous flow just above the crystallization of Ni(95)Si(5) and Ni(90)Si(10). For the two glass-forming alloys, Ni(80)Si(20) and Ni(75)Si(25), the relation Dη = const is obeyed as the glass transition is approached, indicating a dynamic coupling as predicted by the mode-coupling theory. This coupling is enhanced with increasing Si composition and at 25%, Si spans a wide temperature range through the melting point. The decoupling is found to be related to the distribution of local ordered structure in the melts. The power-law governing the growth of solid-like clusters prior to crystallization creates a dynamic heterogeneity responsible for decoupling.

A molecular dynamics examination of the relationship between self-diffusion and viscosity in liquid metals

NASA Astrophysics Data System (ADS)

Lü, Yongjun; Cheng, Hao; Chen, Min

2012-06-01

The self-diffusion coefficients D and the viscosities η of elemental Ni, Cu, and Ni-Si alloys have been calculated over a wide temperature range by molecular dynamics simulations. For elemental Ni and Cu, Arrhenius-law variations of D and η with temperature dominate. The temperature dependence of Dη can be approximated by a linear relation, whereas the Stokes-Einstein relation is violated. The calculations of D and η are extended to the regions close to the crystallization of Ni95Si5, Ni90Si10, and the glass transitions of Ni80Si20 and Ni75Si25. The results show that both D and η strongly deviate from the Arrhenius law in the vicinity of phase transitions, exhibiting a power-law divergence. We find a decoupling of diffusion and viscous flow just above the crystallization of Ni95Si5 and Ni90Si10. For the two glass-forming alloys, Ni80Si20 and Ni75Si25, the relation Dη = const is obeyed as the glass transition is approached, indicating a dynamic coupling as predicted by the mode-coupling theory. This coupling is enhanced with increasing Si composition and at 25%, Si spans a wide temperature range through the melting point. The decoupling is found to be related to the distribution of local ordered structure in the melts. The power-law governing the growth of solid-like clusters prior to crystallization creates a dynamic heterogeneity responsible for decoupling.

Calorimetric indications of a cooperativity onset in the crossover region of dynamic glass transition for benzoin isobutylether

NASA Astrophysics Data System (ADS)

Kahle, S.; Schröter, K.; Hempel, E.; Donth, E.

1999-10-01

Heat capacity spectroscopy (HCS), dielectric spectroscopy, and shear viscosity data are reported for liquid benzoin isobutylether (BIBE). Dielectric and viscosity peculiarities indicate the crossover region of dynamic glass transition at T=(-8±8) °C where the extrapolated Johari Goldstein β relaxation intersects the main transition trace in an Arrhenius plot. Although HCS does not reach the crossover frequency of order ω=2×106 rad/s, the linear decrease of the square root of cooperativity as calculated from HCS data at lower frequencies indicates a cooperativity onset in the crossover temperature-frequency range. As BIBE belongs to another dielectric crossover scenario as the substances where such an onset could previously be observed, it seems that the cooperativity onset is a general property of the crossover region.

A Comparison of Arrhenius and Macromolecular Rate Theory for Predicting Temperature Responses of Soil CO2 Production

NASA Astrophysics Data System (ADS)

Alster, C. J.; Koyama, A.; Johnson, N. G.; von Fischer, J.

2015-12-01

Soil microbes catalyze many key ecosystem functions, including soil respiration, and are thus important for understanding global carbon cycles and other biogeochemical cycles. One important component in predicting rates of respiration is determining how microbial communities respond to temperature. A range of models have been developed for determining temperature sensitivity of soil biological activities, most of which are based on the Arrhenius equation. This equation predicts an exponential increase in rate with temperature, despite field and laboratory results suggesting a temperature optimum below the denaturation point. Recently, Schipper et al. (2014) developed a novel theory, Macromolecular Rate Theory (MMRT), which explains this trend due to heat capacity (CP) changes associated with enzymes. We applied MMRT to respiration data collected using a reciprocal transplant design with soils from three different sites across the U.S. Great Plains to isolate the effects of microbial community type from edaphic factors. We found that MMRT provided a better fit to the data than Arrhenius in 8 out of the 9 soil x inocula combinations. Our analysis revealed that the microbial communities have distinct CP values largely independent of soil type. These results have significant implications for fundamental understanding of microbial enzyme dynamics in soils as well as for ecosystem and global carbon modeling.

Can More Nanoparticles Induce Larger Viscosities of Nanoparticle-Enhanced Wormlike Micellar System (NEWMS)?

PubMed

Zhao, Mingwei; Zhang, Yue; Zou, Chenwei; Dai, Caili; Gao, Mingwei; Li, Yuyang; Lv, Wenjiao; Jiang, Jianfeng; Wu, Yining

2017-09-18

There have been many reports about the thickening ability of nanoparticles on the wormlike micelles in the recent years. Through the addition of nanoparticles, the viscosity of wormlike micelles can be increased. There still exists a doubt: can viscosity be increased further by adding more nanoparticles? To answer this issue, in this work, the effects of silica nanoparticles and temperature on the nanoparticles-enhanced wormlike micellar system (NEWMS) were studied. The typical wormlike micelles (wormlike micelles) are prepared by 50 mM cetyltrimethyl ammonium bromide (CTAB) and 60 mM sodium salicylate (NaSal). The rheological results show the increase of viscoelasticity in NEWMS by adding nanoparticles, with the increase of zero-shear viscosity and relaxation time. However, with the further increase of nanoparticles, an interesting phenomenon appears. The zero-shear viscosity and relaxation time reach the maximum and begin to decrease. The results show a slight increasing trend for the contour length of wormlike micelles by adding nanoparticles, while no obvious effect on the entanglement and mesh size. In addition, with the increase of temperature, remarkable reduction of contour length and relaxation time can be observed from the calculation. NEWMS constantly retain better viscoelasticity compared with conventional wormlike micelles without silica nanoparticles. According to the Arrhenius equation, the activation energy E a shows the same increase trend of NEWMS. Finally, a mechanism is proposed to explain this interesting phenomenon.

A viscometric approach of pH effect on hydrodynamic properties of human serum albumin in the normal form.

PubMed

Monkos, Karol

2013-03-01

The paper presents the results of viscosity determinations on aqueous solutions of human serum albumin (HSA) at isoelectric point over a wide range of concentrations and at temperatures ranging from 5°C to 45°C. On the basis of a modified Arrhenius equation and Mooney's formula some hydrodynamic parameters were obtained. They are compared with those previously obtained for HSA in solutions at neutral pH. The activation energy and entropy of viscous flow and the intrinsic viscosity reach a maximum value, and the effective specific volume, the self-crowding factor and the Huggins coefficient a minimum value in solutions at isoelectric point. Using the dimensionless parameter [η]c, the existence of three ranges of concentrations: diluted, semi-diluted and concentrated, was shown. By applying Lefebvre's relation for the relative viscosity in the semi-dilute regime, the Mark-Houvink-Kuhn-Sakurada (MHKS) exponent was established. The analysis of the results obtained from the three ranges of concentrations showed that both conformation and stiffness of HSA molecules in solutions at isoelectric point and at neutral pH are the same.

Atomic-scale dynamics of a model glass-forming metallic liquid: Dynamical crossover, dynamical decoupling, and dynamical clustering

DOE PAGES

Jaiswal, Abhishek; Egami, Takeshi; Zhang, Yang

2015-04-01

The phase behavior of multi-component metallic liquids is exceedingly complex because of the convoluted many-body and many-elemental interactions. Herein, we present systematic studies of the dynamic aspects of such a model ternary metallic liquid Cu 40Zr 51Al 9 using molecular dynamics simulation with embedded atom method. We observed a dynamical crossover from Arrhenius to super-Arrhenius behavior in the transport properties (diffusion coefficient, relaxation times, and shear viscosity) bordered at T x ~1300K. Unlike in many molecular and macromolecular liquids, this crossover phenomenon occurs in the equilibrium liquid state well above the melting temperature of the system (T m ~ 900K),more » and the crossover temperature is roughly twice of the glass-transition temperature (T g). Below T x, we found the elemental dynamics decoupled and the Stokes-Einstein relation broke down, indicating the onset of heterogeneous spatially correlated dynamics in the system mediated by dynamic communications among local configurational excitations. To directly characterize and visualize the correlated dynamics, we employed a non-parametric, unsupervised machine learning technique and identified dynamical clusters of atoms with similar atomic mobility. The revealed average dynamical cluster size shows an accelerated increase below T x and mimics the trend observed in other ensemble averaged quantities that are commonly used to quantify the spatially heterogeneous dynamics such as the non-Gaussian parameter and the four-point correlation function.« less

Melting properties of Pt and its transport coefficients in liquid states under high pressures

NASA Astrophysics Data System (ADS)

Wang, Pan-Pan; Shao, Ju-Xiang; Cao, Qi-Long

2016-11-01

Molecular dynamics (MD) simulations of the melting and transport properties in liquid states of platinum for the pressure range (50-200 GPa) are reported. The melting curve of platinum is consistent with previous ab initio MD simulation results and the first-principles melting curve. Calculated results for the pressure dependence of fusion entropy and fusion volume show that the fusion entropy and the fusion volume decrease with increasing pressure, and the ratio of the fusion volume to fusion entropy roughly reproduces the melting slope, which has a moderate decrease along the melting line. The Arrhenius law well describes the temperature dependence of self-diffusion coefficients and viscosity under high pressure, and the diffusion activation energy decreases with increasing pressure, while the viscosity activation energy increases with increasing pressure. In addition, the entropy-scaling law, proposed by Rosenfeld under ambient pressure, still holds well for liquid Pt under high pressure conditions.

Viscosity and diffusivity in melts: from unary to multicomponent systems

NASA Astrophysics Data System (ADS)

Chen, Weimin; Zhang, Lijun; Du, Yong; Huang, Baiyun

2014-05-01

Viscosity and diffusivity, two important transport coefficients, are systematically investigated from unary melt to binary to multicomponent melts in the present work. By coupling with Kaptay's viscosity equation of pure liquid metals and effective radii of diffusion species, the Sutherland equation is modified by taking the size effect into account, and further derived into an Arrhenius formula for the convenient usage. Its reliability for predicting self-diffusivity and impurity diffusivity in unary liquids is then validated by comparing the calculated self-diffusivities and impurity diffusivities in liquid Al- and Fe-based alloys with the experimental and the assessed data. Moreover, the Kozlov model was chosen among various viscosity models as the most reliable one to reproduce the experimental viscosities in binary and multicomponent melts. Based on the reliable viscosities calculated from the Kozlov model, the modified Sutherland equation is utilized to predict the tracer diffusivities in binary and multicomponent melts, and validated in Al-Cu, Al-Ni and Al-Ce-Ni melts. Comprehensive comparisons between the calculated results and the literature data indicate that the experimental tracer diffusivities and the theoretical ones can be well reproduced by the present calculations. In addition, the vacancy-wind factor in binary liquid Al-Ni alloys with the increasing temperature is also discussed. What's more, the calculated inter-diffusivities in liquid Al-Cu, Al-Ni and Al-Ag-Cu alloys are also in excellent agreement with the measured and theoretical data. Comparisons between the simulated concentration profiles and the measured ones in Al-Cu, Al-Ce-Ni and Al-Ag-Cu melts are further used to validate the present calculation method.

Investigation of a Coupled Arrhenius-Type/Rossard Equation of AH36 Material.

PubMed

Qin, Qin; Tian, Ming-Liang; Zhang, Peng

2017-04-13

High-temperature tensile testing of AH36 material in a wide range of temperatures (1173-1573 K) and strain rates (10 -4 -10 -2 s -1 ) has been obtained by using a Gleeble system. These experimental stress-strain data have been adopted to develop the constitutive equation. The constitutive equation of AH36 material was suggested based on the modified Arrhenius-type equation and the modified Rossard equation respectively. The results indicate that the constitutive equation is strongly influenced by temperature and strain, especially strain. Moreover, there is a good agreement between the predicted data of the modified Arrhenius-type equation and the experimental results when the strain is greater than 0.02. There is also good agreement between the predicted data of the Rossard equation and the experimental results when the strain is less than 0.02. Therefore, a coupled equation where the modified Arrhenius-type equation and Rossard equation are combined has been proposed to describe the constitutive equation of AH36 material according to the different strain values in order to improve the accuracy. The correlation coefficient between the computed and experimental flow stress data was 0.998. The minimum value of the average absolute relative error shows the high accuracy of the coupled equation compared with the two modified equations.

A physical organogel electrolyte: characterized by in situ thermo-irreversible gelation and single-ion-predominent conduction

PubMed Central

Kim, Young-Soo; Cho, Yoon-Gyo; Odkhuu, Dorj; Park, Noejung; Song, Hyun-Kon

2013-01-01

Electrolytes are characterized by their ionic conductivity (σi). It is desirable that overall σi results from the dominant contribution of the ions of interest (e.g. Li+ in lithium ion batteries or LIB). However, high values of cationic transference number (t+) achieved by solid or gel electrolytes have resulted in low σi leading to inferior cell performances. Here we present an organogel polymer electrolyte characterized by a high liquid-electrolyte-level σi (~101 mS cm−1) with high t+ of Li+ (>0.8) for LIB. A conventional liquid electrolyte in presence of a cyano resin was physically and irreversibly gelated at 60°C without any initiators and crosslinkers, showing the behavior of lower critical solution temperature. During gelation, σi of the electrolyte followed a typical Arrhenius-type temperature dependency, even if its viscosity increased dramatically with temperature. Based on the Li+-driven ion conduction, LIB using the organogel electrolyte delivered significantly enhanced cyclability and thermal stability. PMID:23715177

Shear rheological characterization of motor oils

NASA Technical Reports Server (NTRS)

Bair, Scott; Winer, Ward O.

1988-01-01

Measurements of high pressure viscosity, traction coefficient, and EHD film thickness were performed on twelve commercial automotive engine oils, a reference oil, two unformulated base oils and two unformated base oil and polymer blends. An effective high shear rate inlet viscosity was calculated from film thickness and pressure viscosity coefficient. The difference between measured and effective viscosity is a function of the polymer type and concentration. Traction measurements did not discriminate mileage formulated oils from those not so designated.

Physicochemical, morphological and rheological properties of canned bean pastes "negro Queretaro" variety (Phaseolus vulgaris L.).

PubMed

Martínez-Preciado, A H; Estrada-Girón, Y; González-Álvarez, A; Fernández, V V A; Macías, E R; Soltero, J F A

2014-09-01

Proximate, thermal, morphological and rheological properties of canned "negro Querétaro" bean pastes, as a function of fat content (0, 2 and 3 %) and temperature (60, 70 and 85 °C), were evaluated. Raw and precooked bean pastes were characterized by scanning electron microscopy (SEM) and differential scanning calorimetry (DSC). Well-defined starch granules in the raw bean pastes were observed, whereas a gelatinized starch paste was observed for the canned bean pastes. The DSC analysis showed that the raw bean pastes had lower onset peak temperatures (79 °C, 79.1 °C) and gelatinization enthalpy (1.940 J/g), compared to that precooked bean pastes (70.4 °C, 75.7 °C and 1.314 J/g, respectively) thermal characteristics. Moreover, the dynamic rheological results showed a gel-like behavior for the canned bean pastes, where the storage modulus (G') was frequency independent and was higher than the loss modulus (G″). The non-linear rheological results exhibited a shear-thinning flow behavior, where the steady shear-viscosity was temperature and fat content dependent. For canned bean pastes, the shear-viscosity data followed a power law equation, where the power law index (n) decreased when the temperature and the fat content increased. The temperature effect on the shear-viscosity was described by an Arrhenius equation, where the activation energy (Ea) was in the range from 19.04 to 36.81 KJ/mol. This rheological behavior was caused by gelatinization of the starch during the cooking and sterilization processes, where starch-lipids and starch-proteins complex were formed.

A comparative study of texture and rheology of Argentinian honeys from two regions.

PubMed

Maldonado, Ezequiel; Navarro, Alba S; Yamul, Diego K

2018-06-23

The rheological and textural properties of 26 eastern Argentinian honeys from two different regions (North and Central) were investigated. The viscosity curves of the samples were obtained using a rotational rheometer over a temperature range of 10 to 50°C. The viscosity decreased with temperature and all honeys showed a Newtonian behaviour. The temperature dependence of viscosity was described using the Arrhenius, Williams- Landel-Ferry, Vogel-Taumman-Fulcher and Power Law models. The glass transition temperatures of honeys were measured with differential scanning calorimetry and values ranged from -42.63 to -47.71°C. The glass transition temperature was also predicted with the Williams- Landel-Ferry model and no significant differences were observed with the experimental results. Rheological parameters were obtained by small amplitude oscillation experiments. Results indicated that the viscous modulus was higher than the storage modulus within all the frequency ranges assayed and honeys from the North region were more viscous. Results of the back extrusion test showed that honeys from the Central region are harder and both groups of honeys (North and Central) exhibited the same consistency and adhesivity. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

Investigation of a Coupled Arrhenius-Type/Rossard Equation of AH36 Material

PubMed Central

Qin, Qin; Tian, Ming-Liang; Zhang, Peng

2017-01-01

High-temperature tensile testing of AH36 material in a wide range of temperatures (1173–1573 K) and strain rates (10−4–10−2 s−1) has been obtained by using a Gleeble system. These experimental stress-strain data have been adopted to develop the constitutive equation. The constitutive equation of AH36 material was suggested based on the modified Arrhenius-type equation and the modified Rossard equation respectively. The results indicate that the constitutive equation is strongly influenced by temperature and strain, especially strain. Moreover, there is a good agreement between the predicted data of the modified Arrhenius-type equation and the experimental results when the strain is greater than 0.02. There is also good agreement between the predicted data of the Rossard equation and the experimental results when the strain is less than 0.02. Therefore, a coupled equation where the modified Arrhenius-type equation and Rossard equation are combined has been proposed to describe the constitutive equation of AH36 material according to the different strain values in order to improve the accuracy. The correlation coefficient between the computed and experimental flow stress data was 0.998. The minimum value of the average absolute relative error shows the high accuracy of the coupled equation compared with the two modified equations. PMID:28772767

Growth Kinetics of Extremely Halophilic Archaea (Family Halobacteriaceae) as Revealed by Arrhenius Plots

PubMed Central

Robinson, Jessie L.; Pyzyna, Brandy; Atrasz, Rachelle G.; Henderson, Christine A.; Morrill, Kira L.; Burd, Anna Mae; DeSoucy, Erik; Fogleman, Rex E.; Naylor, John B.; Steele, Sarah M.; Elliott, Dawn R.; Leyva, Kathryn J.; Shand, Richard F.

2005-01-01

Members of the family Halobacteriaceae in the domain Archaea are obligate extreme halophiles. They occupy a variety of hypersaline environments, and their cellular biochemistry functions in a nearly saturated salty milieu. Despite extensive study, a detailed analysis of their growth kinetics is missing. To remedy this, Arrhenius plots for 14 type species of the family were generated. These organisms had maximum growth temperatures ranging from 49 to 58°C. Nine of the organisms exhibited a single temperature optimum, while five grew optimally at more than one temperature. Generation times at these optimal temperatures ranged from 1.5 h (Haloterrigena turkmenica) to 3.0 h (Haloarcula vallismortis and Halorubrum saccharovorum). All shared an inflection point at 31 ± 4°C, and the temperature characteristics for 12 of the 14 type species were nearly parallel. The other two species (Natronomonas pharaonis and Natronorubrum bangense) had significantly different temperature characteristics, suggesting that the physiology of these strains is different. In addition, these data show that the type species for the family Halobacteriaceae share similar growth kinetics and are capable of much faster growth at higher temperatures than those previously reported. PMID:15659670

Surface acetylation of bamboo cellulose: preparation and rheological properties.

PubMed

Cai, Jie; Fei, Peng; Xiong, Zhouyi; Shi, Yongjun; Yan, Kai; Xiong, Hanguo

2013-01-30

In this study, purified bamboo cellulose was used to synthesize cellulose diacetate (B-CDA). The synthesis was controlled by determination of the degree of substitution and insoluble residue content. The product then was characterized by FTIR. The rheological properties of B-CDA solutions in acetone/N,N-dimethylacetamide (DMAc) solvent system were systematically investigated on an advanced rheometer, including the dependence of apparent viscosity η(α), non-Newtonian index n, and structural viscosity index Δη on the concentration and temperature of the solutions. B-CDA-acetone/DMAc solution is a shear-thinning fluid. With increasing solution concentration and decreasing temperature, Δη increased, whereas n decreased, which indicates a deteriorating spinnability. Moreover, the values of the viscous flow activation energy E(η) based on the Arrhenius equation increased when the shear rate γ was enhanced, which indicates that the η(α) of the solution is more sensitive to temperature in the higher γ values. The results are favorable for predicting the B-CDA solution spinnability. Copyright © 2012 Elsevier Ltd. All rights reserved.

Contactless processing of SiGe-melts in EML under reduced gravity.

PubMed

Luo, Yuansu; Damaschke, Bernd; Schneider, Stephan; Lohöfer, Georg; Abrosimov, Nikolay; Czupalla, Matthias; Samwer, Konrad

2016-01-01

The processing of semiconductors based on electromagnetic levitation is a challenge, because this kind of materials shows a poor electrical conductivity. Here, we report the results of measurements of the thermophysical properties obtained recently from highly doped semiconductors Si 1- x Ge x under microgravity conditions in the framework of parabola flight campaigns. Due to the limited time of about 20 s of microgravity especially Ge-rich samples with low melting temperatures were investigated. The measurements were performed contactlessly by video techniques with subsequent digital image processing. Linear and volume thermal expansion coefficients were measured hereby from image data. An anomaly of volume changes near the solidus temperature is visible. Viscosity and surface tension were determined by the oscillating drop technique using optic and electronic data. It was observed that the alloying of Si into Ge increases the surface tension of the melts. The viscosity is following an Arrhenius equation and shows a crossover temperature which separates simple liquid at high temperatures from cooperative liquid at low temperatures.

On the validity of the Arrhenius equation for electron attachment rate coefficients.

PubMed

Fabrikant, Ilya I; Hotop, Hartmut

2008-03-28

The validity of the Arrhenius equation for dissociative electron attachment rate coefficients is investigated. A general analysis allows us to obtain estimates of the upper temperature bound for the range of validity of the Arrhenius equation in the endothermic case and both lower and upper bounds in the exothermic case with a reaction barrier. The results of the general discussion are illustrated by numerical examples whereby the rate coefficient, as a function of temperature for dissociative electron attachment, is calculated using the resonance R-matrix theory. In the endothermic case, the activation energy in the Arrhenius equation is close to the threshold energy, whereas in the case of exothermic reactions with an intermediate barrier, the activation energy is found to be substantially lower than the barrier height.

Relationship of Catalysis and Active Site Loop Dynamics in the (βα)8-Barrel Enzyme Indole-3-glycerol Phosphate Synthase.

PubMed

Schlee, Sandra; Klein, Thomas; Schumacher, Magdalena; Nazet, Julian; Merkl, Rainer; Steinhoff, Heinz-Jürgen; Sterner, Reinhard

2018-03-08

It is important to understand how the catalytic activity of enzymes is related to their conformational flexibility. We have studied this activity-flexibility correlation using the example of indole-3-glycerol phosphate synthase from Sulfolobus solfataricus (ssIGPS), which catalyzes the fifth step in the biosynthesis of tryptophan. ssIGPS is a thermostable representative of enzymes with the frequently encountered and catalytically versatile (βα) 8 -barrel fold. Four variants of ssIGPS with increased catalytic turnover numbers were analyzed by transient kinetics at 25 °C, and wild-type ssIGPS was likewise analyzed both at 25 °C and at 60 °C. Global fitting with a minimal three-step model provided the individual rate constants for substrate binding, chemical transformation, and product release. The results showed that in both cases, namely, the application of activating mutations and temperature increase, the net increase in the catalytic turnover number is afforded by acceleration of the product release rate relative to the chemical transformation steps. Measurements of the solvent viscosity effect at 25 °C versus 60 °C confirmed this change in the rate-determining step with temperature, which is in accordance with a kink in the Arrhenius diagram of ssIGPS at ∼40 °C. When rotational diffusion rates of electron paramagnetic spin-labels attached to active site loop β1α1 are plotted in the form of an Arrhenius diagram, kinks are observed at the same temperature. These findings, together with molecular dynamics simulations, demonstrate that a different degree of loop mobility correlates with different rate-limiting steps in the catalytic mechanism of ssIGPS.

Co-pyrolysis of biomass and plastic wastes: investigation of apparent kinetic parameters and stability of pyrolysis oils

NASA Astrophysics Data System (ADS)

Fekhar, B.; Miskolczi, N.; Bhaskar, T.; Kumar, J.; Dhyani, V.

2018-05-01

This work is dedicated to the co-pyrolysis of real waste high density polyethylene (HDPE) and biomass (rice straw) obtained from agriculture. Mixtures of raw materials were pyrolyzed in their 0%/100%, 30%/70%, 50%/50%, 70%/30%, 100%/0% ratios using a thermograph. The atmosphere was nitrogen, and a constant heating rate was used. Based on weight loss and DTG curves, the apparent reaction kinetic parameters (e.g., activation energy) were calculated using first-order kinetic approach and Arrhenius equation. It was found that decomposition of pure plastic has approximately 280 kJ/mol activation energy, while that of was considerably less in case of biomass. Furthermore, HDPE decomposition takes by one stage, while that of biomass was three stages. The larger amount of raw materials (100 g) were also pyrolyzed in the batch rig at 550°C to obtain products for analysis focussing to their long-term application. Pyrolysis oils were investigated by Fourier transformed infrared spectroscopy and standardized methods, such as density, viscosity, boiling range determination. It was concluded, that higher plastic ratio in raw material had the advantageous effect to the pyrolysis oil long-term application. E.g., the concentration of oxygenated compounds, such as aldehydes, ketones, carboxylic acids or even phenol and its derivate could be significantly decreased, which had an advantageous effect to their corrosion property. Lower average molecular weight, viscosity, and density were measured as a function of plastic content.

The Temperature Optima and Temperature Sensitivity of Soil Respiration Explained By Macromolecular Rate Theory (MMRT).

NASA Astrophysics Data System (ADS)

Schipper, L. A.; O'Neill, T.; Arcus, V. L.

2014-12-01

One of the most fundamental factors controlling all biological and chemical processes is changing temperature. Temperature dependence was originally described by the Arrhenius function in the 19th century. This function provides an excellent description of chemical reaction rates. However, the Arrhenius function does not predict the temperature optimum of biological rates that is clearly evident in laboratory and field measurements. Previously, the temperature optimum of biological processes has been ascribed to denaturation of enzymes but the observed temperature optima in soil are often rather modest, occurring at about 40-50°C and generally less than recognised temperatures for protein unfolding. We have modified the Arrhenius function incorporating a temperature-dependent activation energy derived directly from first principles from thermodynamics of macromolecules. MacroMolecular Rate Theory (MMRT) accounts for large changes in the flexibility of enzymes during catalysis that result in changes in heat capacity (ΔC‡p) of the enzyme during the reaction. MMRT predicts an initially Arrhenius-like response followed by a temperature optimum without the need for enzyme denaturation (Hobbs et al., 2013. ACS Chemical Biology. 8: 2388-2393). Denaturation, of course, occurs at much higher temperatures. We have shown that MMRT fits biogeochemical data collected from laboratory and field studies with important implications for changes in absolute temperature sensitivity as temperature rises (Schipper et al., 2014. Global Change Biology). As the temperature optimum is approached the absolute temperature sensitivity of biological processes decreases to zero. Consequently, the absolute temperature-sensitivity of soil biological processes depends on both the change in ecosystem temperature and the temperature optimum of the biological process. MMRT also very clearly explains why Q10 values decline with increasing temperature more quickly than would be predicted from the Arrhenius function. Temperature optima of many soil biological processes including respiration are very poorly documented but would lead to a better understanding of how soil systems will respond to increasing global temperatures.

Temperature dependence of ion transport: the compensated Arrhenius equation.

PubMed

Petrowsky, Matt; Frech, Roger

2009-04-30

The temperature-dependent conductivity originating in a thermally activated process is often described by a simple Arrhenius expression. However, this expression provides a poor description of the data for organic liquid electrolytes and amorphous polymer electrolytes. Here, we write the temperature dependence of the conductivity as an Arrhenius expression and show that the experimentally observed non-Arrhenius behavior is due to the temperature dependence of the dielectric constant contained in the exponential prefactor. Scaling the experimentally measured conductivities to conductivities at a chosen reference temperature leads to a "compensated" Arrhenius equation that provides an excellent description of temperature-dependent conductivities. A plot of the prefactors as a function of the solvent dielectric constant results in a single master curve for each family of solvents. These data suggest that ion transport in these and related systems is governed by a single activated process differing only in the activation energy for each family of solvents. Connection is made to the shift factor used to describe electrical and mechanical relaxation in a wide range of phenomena, suggesting that this scaling procedure might have broad applications.

Force effects on rotor of squeeze film damper using Newtonian and non-Newtonian fluid

NASA Astrophysics Data System (ADS)

Dominik, Šedivý; Petr, Ferfecki; Simona, Fialová

2017-09-01

This article presents the evaluation of force effects on rotor of squeeze film damper. Rotor is eccentric placed and its motion is translate-circular. The amplitude of rotor motion is smaller than its initial eccentricity. The force effects are calculated from pressure and viscous forces which were gained by using computational modeling. Two types of fluid were considered as filling of damper. First type of fluid is Newtonian (has constant viscosity) and second type is magnetorheological fluid (does not have constant viscosity). Viscosity of non-Newtonian fluid is given using Bingham rheology model. Yield stress is a function of magnetic induction which is described by many variables. The most important variables of magnetic induction are electric current and gap width which is between rotor and stator. Comparison of application two given types of fluids is shown in results.

Arrhenius parameter determination as a function of heating method and cellular microenvironment based on spatial cell viability analysis.

PubMed

Whitney, Jon; Carswell, William; Rylander, Nichole

2013-06-01

Predictions of injury in response to photothermal therapy in vivo are frequently made using Arrhenius parameters obtained from cell monolayers exposed to laser or water bath heating. However, the impact of different heating methods and cellular microenvironments on Arrhenius predictions has not been thoroughly investigated. This study determined the influence of heating method (water bath and laser irradiation) and cellular microenvironment (cell monolayers and tissue phantoms) on Arrhenius parameters and spatial viability. MDA-MB-231 cells seeded in monolayers and sodium alginate phantoms were heated with a water bath for 3-20 min at 46, 50, and 54 °C or laser irradiated (wavelength of 1064 nm and fluences of 40 W/cm(2) or 3.8 W/cm(2) for 0-4 min) in combination with photoabsorptive carbon nanohorns. Spatial viability was measured using digital image analysis of cells stained with calcein AM and propidium iodide and used to determine Arrhenius parameters. The influence of microenvironment and heating method on Arrhenius parameters and capability of parameters derived from more simplistic experimental conditions (e.g. water bath heating of monolayers) to predict more physiologically relevant systems (e.g. laser heating of phantoms) were assessed. Arrhenius predictions of the treated area (<1% viable) under-predicted the measured areas in photothermally treated phantoms by 23 mm(2) using water bath treated cell monolayer parameters, 26 mm(2) using water bath treated phantom parameters, 27 mm(2) using photothermally treated monolayer parameters, and 0.7 mm(2) using photothermally treated phantom parameters. Heating method and cellular microenvironment influenced Arrhenius parameters, with heating method having the greater impact.

Convex Arrhenius plots and their interpretation

PubMed Central

Truhlar, Donald G.; Kohen, Amnon

2001-01-01

This paper draws attention to selected experiments on enzyme-catalyzed reactions that show convex Arrhenius plots, which are very rare, and points out that Tolman's interpretation of the activation energy places a fundamental model-independent constraint on any detailed explanation of these reactions. The analysis presented here shows that in such systems, the rate coefficient as a function of energy is not just increasing more slowly than expected, it is actually decreasing. This interpretation of the data provides a constraint on proposed microscopic models, i.e., it requires that any successful model of a reaction with a convex Arrhenius plot should be consistent with the microcanonical rate coefficient being a decreasing function of energy. The implications and limitations of this analysis to interpreting enzyme mechanisms are discussed. This model-independent conclusion has broad applicability to all fields of kinetics, and we also draw attention to an analogy with diffusion in metastable fluids and glasses. PMID:11158559

On the decoupling of relaxation modes in a molecular liquid caused by isothermal introduction of 2 nm structural inhomogeneities.

PubMed

Ueno, Kazuhide; Angell, C Austen

2011-12-08

To support a new interpretation of the origin of the dynamic heterogeneity observed pervasively in fragile liquids as they approach their glass transition temperatures T(g), we demonstrate that the introduction of ~2 nm structural inhomogeneities into a homogeneous glass former leads to a decoupling of diffusion from viscosity similar to that observed during the cooling of orthoterphenyl (OTP) below T(A,) where Arrhenius behavior is lost. Further, the decoupling effect grows stronger as temperature decreases (and viscosity increases). The liquid is cresol, and the ~2 nm inhomogeneities are cresol-soluble asymmetric derivatized tetrasiloxy-based (polyhedral oligomeric silsesquioxane (POSS)) molecules. The decoupling is the phenomenon predicted by Onsager in discussing the approach to a liquid-liquid phase separation with decreasing temperature. In the present case the observations support the notion of a polyamorphic transition in fragile liquids that is hidden below the glass transition. A similar decoupling can be expected as a globular protein is dissolved in dilute aqueous solutions or in protic ionic liquids. © 2011 American Chemical Society

Temperature and chain length dependence of ultrafast vibrational dynamics of thiocyanate in alkylimidazolium ionic liquids: A random walk on a rugged energy landscape.

PubMed

Brinzer, Thomas; Garrett-Roe, Sean

2017-11-21

Ultrafast two-dimensional infrared spectroscopy of a thiocyanate vibrational probe (SCN - ) was used to investigate local dynamics in alkylimidazolium bis-[trifluoromethylsulfonyl]imide ionic liquids ([Im n,1 ][Tf 2 N], n = 2, 4, 6) at temperatures from 5 to 80 °C. The rate of frequency fluctuations reported by SCN - increases with increasing temperature and decreasing alkyl chain length. Temperature-dependent correlation times scale proportionally to temperature-dependent bulk viscosities of each ionic liquid studied. A multimode Brownian oscillator model demonstrates that very low frequency (<10 cm -1 ) modes primarily drive the observed spectral diffusion and that these modes broaden and blue shift on average with increasing temperature. An Arrhenius analysis shows activation barriers for local motions around the probe between 5.5 and 6.5 kcal/mol that are very similar to those for translational diffusion of ions. [Im 6,1 ][Tf 2 N] shows an unexpected decrease in activation energy compared to [Im 4,1 ][Tf 2 N] that may be related to mesoscopically ordered polar and nonpolar domains. A model of dynamics on a rugged potential energy landscape provides a unifying description of the observed Arrhenius behavior and the Brownian oscillator model of the low frequency modes.

Bianchi Type VI1 Viscous Fluid Cosmological Model in Wesson´s Theory of Gravitation

NASA Astrophysics Data System (ADS)

Khadekar, G. S.; Avachar, G. R.

2007-03-01

Field equations of a scale invariant theory of gravitation proposed by Wesson [1, 2] are obtained in the presence of viscous fluid with the aid of Bianchi type VIh space-time with the time dependent gauge function (Dirac gauge). It is found that Bianchi type VIh (h = 1) space-time with viscous fluid is feasible in this theory, whereas Bianchi type VIh (h = -1, 0) space-times are not feasible in this theory, even in the presence of viscosity. For the feasible case, by assuming a relation connecting viscosity and metric coefficient, we have obtained a nonsingular-radiating model. We have discussed some physical and kinematical properties of the models.

Effect of concentration and temperature on the rheological behavior of collagen solution.

PubMed

Lai, Guoli; Li, Yang; Li, Guoying

2008-04-01

Dynamic viscoelastic properties of collagen solutions with concentrations of 0.5-1.5% (w/w) were characterized by means of oscillatory rheometry at temperatures ranging from 20 to 32.5 degrees C. All collagen solutions showed a shear-thinning flow behavior. The complex viscosity exhibited an exponential increase and the loss tangent decreased with the increase of collagen concentration (C(COL)) when the C(COL)> or =0.75%. Both storage modulus (G') and loss modulus (G'') increased with the increase of frequency and concentration, but decreased with the increase of temperature and behaved without regularity at 32.5 degrees C. The relaxation times decreased with the increase of temperature for 1.0% collagen solution. According to a three-zone model, dynamic modulus of collagen solutions showed terminal-zone and plateau-zone behavior when C(COL) was no more than 1.25% or the stated temperature was no more than 30 degrees C. The concentrated solution (1.5%) behaved being entirely in plateau zone. An application of the time-temperature superposition (TTS) allowed the construction of master curve and an Arrhenius-type TTS principle was used to yield the activation energy of 161.4 kJ mol(-1).

Low Melt Viscosity Resins for Resin Transfer Molding

NASA Technical Reports Server (NTRS)

Harris, Frank W.

2002-01-01

In recent years, resin transfer molding (RTM) has become one of the methods of choice for high performance composites. Its cost effectiveness and ease of fabrication are major advantages of RTM. RTM process usually requires resins with very low melt viscosity (less than 10 Poise). The optimum RTM resins also need to display high thennal-oxidative stability, high glass transition temperature (T(sub g)), and good toughness. The traditional PMR-type polyimides (e.g. PMR-15) do not fit this requirement, because the viscosities are too high and the nadic endcap cures too fast. High T(sub g), low-melt viscosity resins are highly desirable for aerospace applications and NASA s Reusable Launch Vehicle (RLV) program. The objective of this work is to prepare low-melt viscosity polyimide resins for RTM or resin film infusion (RFI) processes. The approach involves the synthesis of phenylethynyl-terminated imide oligomers. These materials have been designed to minimize their melt viscosity so that they can be readily processed. During the cure, the oligomers undergo both chain extension and crosslinking via the thermal polymerization of the phenylethynyl groups. The Phenylethynyl endcap is preferred over the nadic group due to its high curing temperature, which provides broader processing windows. This work involved the synthesis and polymerization of oligomers containing zig-zag backbones and twisted biphenyl structures. Some A-B type precursors which possessed both nitro and anhydride functionality, or both nitro and amine functionality, were also synthesized in order to obtain the well defined oligomers. The resulting zig-zag structured oligomers were then end-capped with 4-phenylethynylphthalic anhydride (PEPA) for further cure. The properties of these novel imide oligomers are evaluated.

Site-Directed Mutations of Thermostable Direct Hemolysin from Grimontia hollisae Alter Its Arrhenius Effect and Biophysical Properties

PubMed Central

Wang, Yu-Kuo; Huang, Sheng-Cih; Wu, Yi-Fang; Chen, Yu-Ching; Lin, Yen-Ling; Nayak, Manoswini; Lin, Yan Ren; Chen, Wen-Hung; Chiu, Yi-Rong; Li, Thomas Tien-Hsiung; Yeh, Bo-Sou; Wu, Tung-Kung

2011-01-01

Recombinant thermostable direct hemolysin from Grimontia hollisae (Gh-rTDH) exhibits paradoxical Arrhenius effect, where the hemolytic activity is inactivated by heating at 60 oC but is reactivated by additional heating above 80 oC. This study investigated individual or collective mutational effect of Tyr53, Thr59, and Ser63 positions of Gh-rTDH on hemolytic activity, Arrhenius effect, and biophysical properties. In contrast to the Gh-rTDH wild-type (Gh-rTDHWT) protein, a 2-fold decrease of hemolytic activity and alteration of Arrhenius effect could be detected from the Gh-rTDHY53H/T59I and Gh-rTDHT59I/S63T double-mutants and the Gh-rTDHY53H/T59I/S63T triple-mutant. Differential scanning calorimetry results showed that the Arrhenius effect-loss and -retaining mutants consistently exhibited higher and lower endothermic transition temperatures, respectively, than that of the Gh-rTDHWT. Circular dichroism measurements of Gh-rTDHWT and Gh-rTDHmut showed a conspicuous change from a β-sheet to α-helix structure around the endothermic transition temperature. Consistent with the observation is the conformational change of the proteins from native globular form into fibrillar form, as determined by Congo red experiments and transmission electron microscopy. PMID:21494434

Site-directed mutations of thermostable direct hemolysin from Grimontia hollisae alter its arrhenius effect and biophysical properties.

PubMed

Wang, Yu-Kuo; Huang, Sheng-Cih; Wu, Yi-Fang; Chen, Yu-Ching; Lin, Yen-Ling; Nayak, Manoswini; Lin, Yan Ren; Chen, Wen-Hung; Chiu, Yi-Rong; Li, Thomas Tien-Hsiung; Yeh, Bo-Sou; Wu, Tung-Kung

2011-03-31

Recombinant thermostable direct hemolysin from Grimontia hollisae (Gh-rTDH) exhibits paradoxical Arrhenius effect, where the hemolytic activity is inactivated by heating at 60 °C but is reactivated by additional heating above 80 °C. This study investigated individual or collective mutational effect of Tyr53, Thr59, and Ser63 positions of Gh-rTDH on hemolytic activity, Arrhenius effect, and biophysical properties. In contrast to the Gh-rTDH wild-type (Gh-rTDH(WT)) protein, a 2-fold decrease of hemolytic activity and alteration of Arrhenius effect could be detected from the Gh-rTDH(Y53H/T59I) and Gh-rTDH(T59I/S63T) double-mutants and the Gh-rTDH(Y53H/T59I/S63T) triple-mutant. Differential scanning calorimetry results showed that the Arrhenius effect-loss and -retaining mutants consistently exhibited higher and lower endothermic transition temperatures, respectively, than that of the Gh-rTDH(WT). Circular dichroism measurements of Gh-rTDH(WT) and Gh-rTDH(mut) showed a conspicuous change from a β-sheet to α-helix structure around the endothermic transition temperature. Consistent with the observation is the conformational change of the proteins from native globular form into fibrillar form, as determined by Congo red experiments and transmission electron microscopy.

Viscotaxis: Microswimmer Navigation in Viscosity Gradients

NASA Astrophysics Data System (ADS)

Liebchen, Benno; Monderkamp, Paul; ten Hagen, Borge; Löwen, Hartmut

2018-05-01

The survival of many microorganisms, like Leptospira or Spiroplasma bacteria, can depend on their ability to navigate towards regions of favorable viscosity. While this ability, called viscotaxis, has been observed in several bacterial experiments, the underlying mechanism remains unclear. We provide a framework to study viscotaxis of biological or synthetic self-propelled swimmers in slowly varying viscosity fields and show that suitable body shapes create viscotaxis based on a systematic asymmetry of viscous forces acting on a microswimmer. Our results shed new light on viscotaxis in Spiroplasma and Leptospira and suggest that dynamic body shape changes exhibited by both types of microorganisms may have an unrecognized functionality: to prevent them from drifting to low viscosity regions where they swim poorly. The present theory classifies microswimmers regarding their ability to show viscotaxis and can be used to design synthetic viscotactic swimmers, e.g., for delivering drugs to a target region distinguished by viscosity.

Remote sensing-based estimation of annual soil respiration at two contrasting forest sites

NASA Astrophysics Data System (ADS)

Huang, Ni; Gu, Lianhong; Black, T. Andrew; Wang, Li; Niu, Zheng

2015-11-01

Soil respiration (Rs), an important component of the global carbon cycle, can be estimated using remotely sensed data, but the accuracy of this technique has not been thoroughly investigated. In this study, we proposed a methodology for the remote estimation of annual Rs at two contrasting FLUXNET forest sites (a deciduous broadleaf forest and an evergreen needleleaf forest). A version of the Akaike's information criterion was used to select the best model from a range of models for annual Rs estimation based on the remotely sensed data products from the Moderate Resolution Imaging Spectroradiometer and root-zone soil moisture product derived from assimilation of the NASA Advanced Microwave Scanning Radiometer soil moisture products and a two-layer Palmer water balance model. We found that the Arrhenius-type function based on nighttime land surface temperature (LST-night) was the best model by comprehensively considering the model explanatory power and model complexity at the Missouri Ozark and BC-Campbell River 1949 Douglas-fir sites. In addition, a multicollinearity problem among LST-night, root-zone soil moisture, and plant photosynthesis factor was effectively avoided by selecting the LST-night-driven model. Cross validation showed that temporal variation in Rs was captured by the LST-night-driven model with a mean absolute error below 1 µmol CO2 m-2 s-1 at both forest sites. An obvious overestimation that occurred in 2005 and 2007 at the Missouri Ozark site reduced the evaluation accuracy of cross validation because of summer drought. However, no significant difference was found between the Arrhenius-type function driven by LST-night and the function considering LST-night and root-zone soil moisture. This finding indicated that the contribution of soil moisture to Rs was relatively small at our multiyear data set. To predict intersite Rs, maximum leaf area index (LAImax) was used as an upscaling factor to calibrate the site-specific reference respiration rates. Independent validation demonstrated that the model incorporating LST-night and LAImax efficiently predicted the spatial and temporal variabilities of Rs. Based on the Arrhenius-type function using LST-night as an input parameter, the rates of annual C release from Rs were 894-1027 g C m-2 yr-1 at the BC-Campbell River 1949 Douglas-fir site and 818-943 g C m-2 yr-1 at the Missouri Ozark site. The ratio between annual Rs estimates based on remotely sensed data and the total annual ecosystem respiration from eddy covariance measurements fell within the range reported in previous studies. Our results demonstrated that estimating annual Rs based on remote sensing data products was possible at deciduous and evergreen forest sites.

Molecular dynamics simulations of quinoline in the liquid phase.

PubMed

Soetens, Jean-Christophe; Ahmad, Norariza; Adnan, Rohana; Millot, Claude

2012-05-17

Molecular dynamics simulations of liquid quinoline have been performed at experimental densities corresponding to the temperature range 276-320 K. The intermolecular potential is a simple effective two-body potential between rigid molecules having 17 atomic Lennard-Jones and electrostatic Coulomb interaction sites. The vaporization enthalpy is overestimated by 8-9% with respect to the experimental value. The translational diffusion coefficient exhibits a small non-Arrhenius behavior with a change in temperatures near 290 and 303 K. The rotational diffusion tensor is rotated around the z axis perpendicular to the molecular plane by an angle of 4-6° with respect to the frame of reference defined by the principal axes of inertia. The rotational diffusion tensor presents a significant anisotropy with D(rot,y)/D(rot,x) ≃ 0.6-0.5 and D(rot,z)/D(rot,x) ≃ 1.6-1.3 between 276 and 320 K when the x axis is defined as the long molecular axis and the y axis is situated nearly along the central C-C bond. The rotational diffusion coefficients, the reorientational correlation times of the C-H vectors, and the T1(13)C NMR relaxation times present a non-Arrhenius break around 288-290 K in agreement with several experimental results. In addition, a non-Arrhenius break can also be observed at 303 K for these properties. It has been found that the structure evolves smoothly in the studied temperature range. Center of mass-center of mass and atom-atom radial distribution functions show a monotonous evolution with temperature. Various types of first-neighbor dimers have been defined, and their population analysis has revealed a continuous monotonous evolution with temperature. Thus, the non-Arrhenius behavior observed for translational and rotational diffusion is correlated with the monotonous evolution of the population of first-neighbor dimers at a microscopic level and not with a sharp structural transition.

Mixing effects in a ternary Hf-Zr-Ni metallic melt

NASA Astrophysics Data System (ADS)

Nowak, B.; Holland-Moritz, D.; Yang, F.; Evenson, Z.; Meyer, A.

2018-03-01

We study the effect of the substitution of Zr by Hf on the dynamical behavior in the Zr36Ni64 melt. A reduced measured self-diffusion coefficient and a higher measured melt viscosity for an increased amount of Hf were observed. The ternary Hf10Zr25Ni65 melt, which exhibits a pronounced deviation from Arrhenius behavior over a studied temperature range of 550 K, can be accurately described by the scaling law of mode-coupling theory (MCT) with almost equal parameters for the self-diffusion and the viscosity. Although we only substitute alloy components with a nearly equal atomic size and the measured overall packing fraction remains almost unchanged, the dynamics in Hf10Zr25Ni65 are slower compared to Zr36Ni64 . This corresponds also to a higher critical temperature Tc and might be induced by different chemical interactions in the melts. The increased Tc results in a significantly smaller difference between liquidus and critical temperature Δ TLC=TL-Tc for the ternary melt in comparison with Zr36Ni64 , which may favor the glass formation in the Hf10Zr25Ni65 melt.

Modeling oil generation with time-temperature index graphs based on the Arrhenius equation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hunt, J.M.; Lewan, M.D.; Hennet, R.J.C.

1991-04-01

The time and depth of oil generation from petroleum source rocks containing type II kerogens can be determined using time-temperature index (TTI) graphs based on the Arrhenius equation. Activation energies (E) and frequency factors (A) used in the Arrhenius equation were obtained from hydrous pyrolysis experiments on rock samples in which the kerogens represent the range of type II kerogen compositions encountered in most petroleum basins. The E and A values obtained were used to construct graphs that define the beginning and end of oil generation for most type II kerogens having chemical compositions in the range of these standards.more » Activation energies of these standard kerogens vary inversely with their sulfur content. The kerogen with the highest sulfur content had the lowest E value and was the fastest in generating oil, whereas the kerogen with the lowest sulfur content had the highest E value and was the slowest in generating oil. These standard kerogens were designated as types IIA, B, C, and D on the basis of decreasing sulfur content and corresponding increasing time-temperature requirements for generating oil. The {Sigma}TTI{sub ARR} values determined graphically with these type II kerogen standards in two basin models were compared with a computer calculation using 2,000 increments. The graphical method came within {plus minus} 3% of the computer calculation. As type II kerogens are the major oil generators in the world, these graphs should have wide application in making preliminary evaluations of the depth of the oil window in exploration areas.« less

Absorbing states in a catalysis model with anti-Arrhenius behavior.

PubMed

de Andrade, M F; Figueiredo, W

2012-04-28

We study a model of heterogeneous catalysis with competitive reactions between two monomers A and B. We assume that reactions are dependent on temperature and follow an anti-Arrhenius mechanism. In this model, a monomer A can react with a nearest neighbor monomer A or B, however, reactions between monomers of type B are not allowed. We assume attractive interactions between nearest neighbor monomers as well as between monomers and the catalyst. Through mean-field calculations, at the level of site and pair approximations, and extensive Monte Carlo simulations, we determine the phase diagram of the model in the plane y(A) versus temperature, where y(A) is the probability that a monomer A reaches the catalyst. The model exhibits absorbing and active phases separated by lines of continuous phase transitions. We calculate the static, dynamic, and spreading exponents of the model, and despite the absorbing state be represented by many different microscopic configurations, the model belongs to the directed percolation universality class in two dimensions. Both reaction mechanisms, Arrhenius and anti-Arrhenius, give the same set of critical exponents and do not change the nature of the universality class of the catalytic models.

Viscosity and Structure of a Late Lunar Magma Ocean Liquid: Implications for the Purity of Ferroan Anorthosites and the Dynamics of a Crystallizing Magma Ocean

NASA Astrophysics Data System (ADS)

Dygert, N. J.; Lin, J. F.; Marshall, E. W., IV; Kono, Y.; Gardner, J. E.

2016-12-01

The current paradigm argues the Moon formed after a giant impact that produced a deep lunar magma ocean (LMO). After a period of turbulent convection, the LMO experienced fractional crystallization, causing the initially peridotitic liquid to evolve to a plagioclase-saturated ferrobasalt. The lunar crust, much of which comprises 93-98% pure anorthosite [1,2], formed by flotation of positively buoyant plagioclase on the residual liquid. A flotation crust would contain some trapped melt; compaction of the melt out of the crust before solidification may be necessary to generate a very pure anorthitic crust. The efficiency of this process depends on the previously unmeasured viscosity of the residual liquid [3]. To characterize the viscosity and thermal equation of state of a late LMO liquid, we conducted experiments at the Advanced Photon Source, Beamline 16-BM-B, Argonne National Laboratory on a nominally anhydrous Ti-rich ferrobasalt [4]. X-ray radiography and diffuse scattering experiments were conducted in a Paris-Edinburgh apparatus in graphite-lined BN capsules, allowing in-situ observation of viscosity and derivation of thermal EoS at P-T conditions relevant to the Moon (1300-1600°C, 0.1-4.4GPa). We calculated viscosities of 0.23-1.45 Pa·s for the melt; based on 11 observations, we find that viscosity is pressure insensitive under the conditions explored. Viscosity can be modeled by an Arrhenius relation with an activation enthalpy of 66 kJ/mol. Composition-dependent predictive models [5] overestimate our observations by roughly a factor of 2. Preliminary analysis suggests no pressure-dependent structural transition over the conditions explored. Late LMO liquids brought to the lunar core-mantle boundary by cumulate mantle overturn may be positively buoyant, implying the seismically attenuating layer around the lunar core contains a denser, higher-Ti melt. Our results suggest that efficient phase segregation in the lunar magma ocean and compaction in the anorthositic flotation crust can produce a high-purity crust under physically reasonable conditions. [1] Warren (1990), AmMin 75, 46-58. [2] Ohtake et al. (2009), Nature 461, 236-240. [3] Piskorz, & Stevenson (2014), Icarus 239, 238-243. [4] Longhi (2003), JGR 108, doi:10.1029/2002JE001941. [5] Giordano et al. (2008), EPSL 271, 123-134.

Relationships between thermal maturity indices calculated using Arrhenius equation and Lopatin method: implications for petroleum exploration

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wood, D.A.

1988-02-01

Thermal maturity can be calculated with time-temperature indices (TTI) based on the Arrhenius equation using kinetics applicable to a range of Types II and III kerogens. These TTIs are compared with TTI calculations based on the Lopatin method and are related theoretically (and empirically via vitrinite reflectance) to the petroleum-generation window. The TTIs for both methods are expressed mathematically as integrals of temperature combined with variable linear heating rates for selected temperature intervals. Heating rates control the thermal-maturation trends of buried sediments. Relative to Arrhenius TTIs, Lopatin TTIs tend to underestimate thermal maturity at high heating rates and overestimate itmore » as low heating rates. Complex burial histories applicable to a range of tectonic environments illustrate the different exploration decisions that might be made on the basis of independent results of these two thermal-maturation models. 15 figures, 8 tables.« less

Temperature sensitivity of soil microbial communities: An application of macromolecular rate theory to microbial respiration

NASA Astrophysics Data System (ADS)

Alster, Charlotte J.; Koyama, Akihiro; Johnson, Nels G.; Wallenstein, Matthew D.; von Fischer, Joseph C.

2016-06-01

There is compelling evidence that microbial communities vary widely in their temperature sensitivity and may adapt to warming through time. To date, this sensitivity has been largely characterized using a range of models relying on versions of the Arrhenius equation, which predicts an exponential increase in reaction rate with temperature. However, there is growing evidence from laboratory and field studies that observe nonmonotonic responses of reaction rates to variation in temperature, indicating that Arrhenius is not an appropriate model for quantitatively characterizing temperature sensitivity. Recently, Hobbs et al. (2013) developed macromolecular rate theory (MMRT), which incorporates thermodynamic temperature optima as arising from heat capacity differences between isoenzymes. We applied MMRT to measurements of respiration from soils incubated at different temperatures. These soils were collected from three grassland sites across the U.S. Great Plains and reciprocally transplanted, allowing us to isolate the effects of microbial community type from edaphic factors. We found that microbial community type explained roughly 30% of the variation in the CO2 production rate from the labile C pool but that temperature and soil type were most important in explaining variation in labile and recalcitrant C pool size. For six out of the nine soil × inoculum combinations, MMRT was superior to Arrhenius. The MMRT analysis revealed that microbial communities have distinct heat capacity values and temperature sensitivities sometimes independent of soil type. These results challenge the current paradigm for modeling temperature sensitivity of soil C pools and understanding of microbial enzyme dynamics.

Viscosity of alumina nanoparticles dispersed in car engine coolant

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kole, Madhusree; Dey, T.K.

The present paper, describes our experimental results on the viscosity of the nanofluid prepared by dispersing alumina nanoparticles (<50 nm) in commercial car coolant. The nanofluid prepared with calculated amount of oleic acid (surfactant) was tested to be stable for more than 80 days. The viscosity of the nanofluids is measured both as a function of alumina volume fraction and temperature between 10 and 50 C. While the pure base fluid display Newtonian behavior over the measured temperature, it transforms to a non-Newtonian fluid with addition of a small amount of alumina nanoparticles. Our results show that viscosity of themore » nanofluid increases with increasing nanoparticle concentration and decreases with increase in temperature. Most of the frequently used classical models severely under predict the measured viscosity. Volume fraction dependence of the nanofluid viscosity, however, is predicted fairly well on the basis of a recently reported theoretical model for nanofluids that takes into account the effect of Brownian motion of nanoparticles in the nanofluid. The temperature dependence of the viscosity of engine coolant based alumina nanofluids obeys the empirical correlation of the type: log ({mu}{sub nf}) = A exp(BT), proposed earlier by Namburu et al. (author)« less

A Comparative Study on Johnson Cook, Modified Zerilli-Armstrong and Arrhenius-Type Constitutive Models to Predict High-Temperature Flow Behavior of Ti-6Al-4V Alloy in α + β Phase

NASA Astrophysics Data System (ADS)

Cai, Jun; Wang, Kuaishe; Han, Yingying

2016-03-01

True stress and true strain values obtained from isothermal compression tests over a wide temperature range from 1,073 to 1,323 K and a strain rate range from 0.001 to 1 s-1 were employed to establish the constitutive equations based on Johnson Cook, modified Zerilli-Armstrong (ZA) and strain-compensated Arrhenius-type models, respectively, to predict the high-temperature flow behavior of Ti-6Al-4V alloy in α + β phase. Furthermore, a comparative study has been made on the capability of the three models to represent the elevated temperature flow behavior of Ti-6Al-4V alloy. Suitability of the three models was evaluated by comparing both the correlation coefficient R and the average absolute relative error (AARE). The results showed that the Johnson Cook model is inadequate to provide good description of flow behavior of Ti-6Al-4V alloy in α + β phase domain, while the predicted values of modified ZA model and the strain-compensated Arrhenius-type model could agree well with the experimental values except under some deformation conditions. Meanwhile, the modified ZA model could track the deformation behavior more accurately than other model throughout the entire temperature and strain rate range.

Green-Kubo relation for viscosity tested using experimental data for a two-dimensional dusty plasma

NASA Astrophysics Data System (ADS)

Feng, Yan; Goree, J.; Liu, Bin; Cohen, E. G. D.

2011-10-01

The theoretical Green-Kubo relation for viscosity is tested using experimentally obtained data. In a dusty plasma experiment, micron-sized dust particles are introduced into a partially ionized argon plasma, where they become negatively charged. They are electrically levitated to form a single-layer Wigner crystal, which is subsequently melted using laser heating. In the liquid phase, these dust particles experience interparticle electric repulsion, laser heating, and friction from the ambient neutral argon gas, and they can be considered to be in a nonequilibrium steady state. Direct measurements of the positions and velocities of individual dust particles are then used to obtain a time series for an off-diagonal element of the stress tensor and its time autocorrelation function. This calculation also requires the interparticle potential, which was not measured experimentally but was obtained using a Debye-Hückel-type model with experimentally determined parameters. Integrating the autocorrelation function over time yields the viscosity for shearing motion among dust particles. The viscosity so obtained is found to agree with results from a previous experiment using a hydrodynamical Navier-Stokes equation. This comparison serves as a test of the Green-Kubo relation for viscosity. Our result is also compared to the predictions of several simulations.

Probing static disorder in Arrhenius kinetics by single-molecule force spectroscopy.

PubMed

Kuo, Tzu-Ling; Garcia-Manyes, Sergi; Li, Jingyuan; Barel, Itay; Lu, Hui; Berne, Bruce J; Urbakh, Michael; Klafter, Joseph; Fernández, Julio M

2010-06-22

The widely used Arrhenius equation describes the kinetics of simple two-state reactions, with the implicit assumption of a single transition state with a well-defined activation energy barrier DeltaE, as the rate-limiting step. However, it has become increasingly clear that the saddle point of the free-energy surface in most reactions is populated by ensembles of conformations, leading to nonexponential kinetics. Here we present a theory that generalizes the Arrhenius equation to include static disorder of conformational degrees of freedom as a function of an external perturbation to fully account for a diverse set of transition states. The effect of a perturbation on static disorder is best examined at the single-molecule level. Here we use force-clamp spectroscopy to study the nonexponential kinetics of single ubiquitin proteins unfolding under force. We find that the measured variance in DeltaE shows both force-dependent and independent components, where the force-dependent component scales with F(2), in excellent agreement with our theory. Our study illustrates a novel adaptation of the classical Arrhenius equation that accounts for the microscopic origins of nonexponential kinetics, which are essential in understanding the rapidly growing body of single-molecule data.

Relationship between viscosity of the ankle joint complex and functional ankle instability for inversion ankle sprain patients.

PubMed

Lin, Che-Yu; Kang, Jiunn-Horng; Wang, Chung-Li; Shau, Yio-Wha

2015-03-01

Measurement of viscosity of the ankle joint complex is a novel method to assess mechanical ankle instability. In order to further investigate the clinical significance of the method, this study intended to investigate the relationship between ankle viscosity and severity of functional ankle instability. Cross-sectional study. 15 participants with unilateral inversion ankle sprain and 15 controls were recruited. Their ankles were further classified into stable and unstable ankles. Ankle viscosity was measured by an instrumental anterior drawer test. Severity of functional ankle instability was measured by the Cumberland Ankle Instability Tool. Unstable ankles were compared with stable ankles. Injured ankles were compared with uninjured ankles of both groups. The spearman's rank correlation coefficient was applied to determine the relationship between ankle viscosity and severity of functional ankle instability in unstable ankles. There was a moderate relationship between ankle viscosity and severity of functional ankle instability (r=-0.64, p<0.0001). Unstable ankles exhibited significantly lower viscosity (p<0.005) and more severe functional ankle instability (p<0.0001) than stable ankles. Injured ankles exhibited significantly lower viscosity and more severe functional ankle instability than uninjured ankles (p<0.0001). There was a moderate relationship between ankle viscosity and severity of functional ankle instability. This finding suggested that, severity of functional ankle instability may be partially attributed to mechanical insufficiencies such as the degenerative changes in ankle viscosity following the inversion ankle sprain. In clinical application, measurement of ankle viscosity could be a useful tool to evaluate severity of chronic ankle instability. Copyright © 2014 Sports Medicine Australia. Published by Elsevier Ltd. All rights reserved.

The Arrhenius equation revisited.

PubMed

Peleg, Micha; Normand, Mark D; Corradini, Maria G

2012-01-01

The Arrhenius equation has been widely used as a model of the temperature effect on the rate of chemical reactions and biological processes in foods. Since the model requires that the rate increase monotonically with temperature, its applicability to enzymatic reactions and microbial growth, which have optimal temperature, is obviously limited. This is also true for microbial inactivation and chemical reactions that only start at an elevated temperature, and for complex processes and reactions that do not follow fixed order kinetics, that is, where the isothermal rate constant, however defined, is a function of both temperature and time. The linearity of the Arrhenius plot, that is, Ln[k(T)] vs. 1/T where T is in °K has been traditionally considered evidence of the model's validity. Consequently, the slope of the plot has been used to calculate the reaction or processes' "energy of activation," usually without independent verification. Many experimental and simulated rate constant vs. temperature relationships that yield linear Arrhenius plots can also be described by the simpler exponential model Ln[k(T)/k(T(reference))] = c(T-T(reference)). The use of the exponential model or similar empirical alternative would eliminate the confusing temperature axis inversion, the unnecessary compression of the temperature scale, and the need for kinetic assumptions that are hard to affirm in food systems. It would also eliminate the reference to the Universal gas constant in systems where a "mole" cannot be clearly identified. Unless proven otherwise by independent experiments, one cannot dismiss the notion that the apparent linearity of the Arrhenius plot in many food systems is due to a mathematical property of the model's equation rather than to the existence of a temperature independent "energy of activation." If T+273.16°C in the Arrhenius model's equation is replaced by T+b, where the numerical value of the arbitrary constant b is substantially larger than T and T(reference), the plot of Ln k(T) vs. 1/(T+b) will always appear almost perfectly linear. Both the modified Arrhenius model version having the arbitrary constant b, Ln[k(T)/k(T(reference)) = a[1/ (T(reference)+b)-1/ (T+b)], and the exponential model can faithfully describe temperature dependencies traditionally described by the Arrhenius equation without the assumption of a temperature independent "energy of activation." This is demonstrated mathematically and with computer simulations, and with reprocessed classical kinetic data and published food results.

Depinning transition of a domain wall in ferromagnetic films

DOE PAGES

Xi, Bin; Luo, Meng -Bo; Vinokur, Valerii M.; ...

2015-09-14

Here, we report first principle numerical study of domain wall (DW) depinning in two-dimensional magnetic film, which is modeled by 2D random-field Ising system with the dipole-dipole interaction. We observe non-conventional activation-type motion of DW and reveal the fractal structure of DW near the depinning transition. We determine scaling functions describing critical dynamics near the transition and obtain universal exponents establishing connection between thermal softening of pinning potential and critical dynamics. In addition, we observe that tuning the strength of the dipole-dipole interaction switches DW dynamics between two different universality classes, corresponding to two distinct dynamic regimes characterized by non-Arrheniusmore » and conventional Arrhenius-type DW motions.« less

Effect of CO2 Solubility on Dissolution Rates of Minerals in Porous Media Imbibed with Brine: Actual Efficiency of CO2 Sequestration

NASA Astrophysics Data System (ADS)

Alizadeh Nomeli, M.; Riaz, A.

2016-12-01

A new model is developed for geochemical reactions to access dissolution rate of minerals in saline aquifers with respect to saturated concentration of dissolved CO2 as a function of parameters that are dynamically available during computer program execution such as pressure, temperature, and salinity. A general Arrhenius-type equation, with an explicit dependence on the pH of brine, is employed to determine the rates of mineral dissolution. The amount of dissolved CO2 is determined with the help of an accurate PVTx model for the temperature range of 50-100C and pressures up to 600 bar relevant to the geologic sequestration of CO2. We show how activity coefficients for a given salinity condition alters solubility, pH, and reaction rates. We further evaluate the significance of the pre-exponential factor and the reaction order associated with the modified Arrhenius equation to determine the sensitivity of the reaction rates as a function to the pH of the system. It is found that the model can reasonably reproduce experimental data with new parameters that we obtain from sensitivity studies. Using the new rate equation, we investigate geochemically induced alterations of fracture geometry due to mineral dissolution. Finally, we use our model to evaluate the effects of temperature, pressure, and salinity on the actual efficiency of CO2 storage.

Temperature Sensitivity as a Microbial Trait Using Parameters from Macromolecular Rate Theory

PubMed Central

Alster, Charlotte J.; Baas, Peter; Wallenstein, Matthew D.; Johnson, Nels G.; von Fischer, Joseph C.

2016-01-01

The activity of soil microbial extracellular enzymes is strongly controlled by temperature, yet the degree to which temperature sensitivity varies by microbe and enzyme type is unclear. Such information would allow soil microbial enzymes to be incorporated in a traits-based framework to improve prediction of ecosystem response to global change. If temperature sensitivity varies for specific soil enzymes, then determining the underlying causes of variation in temperature sensitivity of these enzymes will provide fundamental insights for predicting nutrient dynamics belowground. In this study, we characterized how both microbial taxonomic variation as well as substrate type affects temperature sensitivity. We measured β-glucosidase, leucine aminopeptidase, and phosphatase activities at six temperatures: 4, 11, 25, 35, 45, and 60°C, for seven different soil microbial isolates. To calculate temperature sensitivity, we employed two models, Arrhenius, which predicts an exponential increase in reaction rate with temperature, and Macromolecular Rate Theory (MMRT), which predicts rate to peak and then decline as temperature increases. We found MMRT provided a more accurate fit and allowed for more nuanced interpretation of temperature sensitivity in all of the enzyme × isolate combinations tested. Our results revealed that both the enzyme type and soil isolate type explain variation in parameters associated with temperature sensitivity. Because we found temperature sensitivity to be an inherent and variable property of an enzyme, we argue that it can be incorporated as a microbial functional trait, but only when using the MMRT definition of temperature sensitivity. We show that the Arrhenius metrics of temperature sensitivity are overly sensitive to test conditions, with activation energy changing depending on the temperature range it was calculated within. Thus, we propose the use of the MMRT definition of temperature sensitivity for accurate interpretation of temperature sensitivity of soil microbial enzymes. PMID:27909429

Influence of Functional Groups on the Viscosity of Organic Aerosol.

PubMed

Rothfuss, Nicholas E; Petters, Markus D

2017-01-03

Organic aerosols can exist in highly viscous or glassy phase states. A viscosity database for organic compounds with atmospherically relevant functional groups is compiled and analyzed to quantify the influence of number and location of functional groups on viscosity. For weakly functionalized compounds the trend in viscosity sensitivity to functional group addition is carboxylic acid (COOH) ≈ hydroxyl (OH) > nitrate (ONO 2 ) > carbonyl (CO) ≈ ester (COO) > methylene (CH 2 ). Sensitivities to group addition increase with greater levels of prior functionalization and decreasing temperature. For carboxylic acids a sharp increase in sensitivity is likely present already at the second addition at room temperature. Ring structures increase viscosity relative to linear structures. Sensitivities are correlated with analogously derived sensitivities of vapor pressure reduction. This may be exploited in the future to predict viscosity in numerical models by piggybacking on schemes that track the evolution of organic aerosol volatility with age.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wemhoff, A P; Burnham, A K; Nichols III, A L

The reduction of the number of reactions in kinetic models for both the HMX beta-delta phase transition and thermal cookoff provides an attractive alternative to traditional multi-stage kinetic models due to reduced calibration effort requirements. In this study, we use the LLNL code ALE3D to provide calibrated kinetic parameters for a two-reaction bidirectional beta-delta HMX phase transition model based on Sandia Instrumented Thermal Ignition (SITI) and Scaled Thermal Explosion (STEX) temperature history curves, and a Prout-Tompkins cookoff model based on One-Dimensional Time to Explosion (ODTX) data. Results show that the two-reaction bidirectional beta-delta transition model presented here agrees as wellmore » with STEX and SITI temperature history curves as a reversible four-reaction Arrhenius model, yet requires an order of magnitude less computational effort. In addition, a single-reaction Prout-Tompkins model calibrated to ODTX data provides better agreement with ODTX data than a traditional multi-step Arrhenius model, and can contain up to 90% less chemistry-limited time steps for low-temperature ODTX simulations. Manual calibration methods for the Prout-Tompkins kinetics provide much better agreement with ODTX experimental data than parameters derived from Differential Scanning Calorimetry (DSC) measurements at atmospheric pressure. The predicted surface temperature at explosion for STEX cookoff simulations is a weak function of the cookoff model used, and a reduction of up to 15% of chemistry-limited time steps can be achieved by neglecting the beta-delta transition for this type of simulation. Finally, the inclusion of the beta-delta transition model in the overall kinetics model can affect the predicted time to explosion by 1% for the traditional multi-step Arrhenius approach, while up to 11% using a Prout-Tompkins cookoff model.« less

Application of global kinetic models to HMX beta-delta transition and cookoff processes.

PubMed

Wemhoff, Aaron P; Burnham, Alan K; Nichols, Albert L

2007-03-08

The reduction of the number of reactions in kinetic models for both the HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) beta-delta phase transition and thermal cookoff provides an attractive alternative to traditional multi-stage kinetic models due to reduced calibration effort requirements. In this study, we use the LLNL code ALE3D to provide calibrated kinetic parameters for a two-reaction bidirectional beta-delta HMX phase transition model based on Sandia instrumented thermal ignition (SITI) and scaled thermal explosion (STEX) temperature history curves, and a Prout-Tompkins cookoff model based on one-dimensional time to explosion (ODTX) data. Results show that the two-reaction bidirectional beta-delta transition model presented here agrees as well with STEX and SITI temperature history curves as a reversible four-reaction Arrhenius model yet requires an order of magnitude less computational effort. In addition, a single-reaction Prout-Tompkins model calibrated to ODTX data provides better agreement with ODTX data than a traditional multistep Arrhenius model and can contain up to 90% fewer chemistry-limited time steps for low-temperature ODTX simulations. Manual calibration methods for the Prout-Tompkins kinetics provide much better agreement with ODTX experimental data than parameters derived from differential scanning calorimetry (DSC) measurements at atmospheric pressure. The predicted surface temperature at explosion for STEX cookoff simulations is a weak function of the cookoff model used, and a reduction of up to 15% of chemistry-limited time steps can be achieved by neglecting the beta-delta transition for this type of simulation. Finally, the inclusion of the beta-delta transition model in the overall kinetics model can affect the predicted time to explosion by 1% for the traditional multistep Arrhenius approach, and up to 11% using a Prout-Tompkins cookoff model.

Functionality of maize, wheat, teff and cassava starches with stearic acid and xanthan gum.

PubMed

Maphalla, Thabelang Gladys; Emmambux, Mohammad Naushad

2016-01-20

Consumer concerns to synthetic chemicals have led to strong preference for 'clean' label starches. Lipid and hydrocolloids are food friendly chemicals. This study determines the effects of stearic acid and xanthan gum alone and in combination on the functionality of maize, wheat, teff and cassava starches. An increase in viscosity was observed for all starches with stearic acid and xanthan gum compared to the controls with cassava having the least increase. A further increase in viscosity was observed for the cereal starches with combination of stearic acid and xanthan gum. Stearic acid reduced retrogradation, resulting in soft textured pastes. Combination of stearic acid and xanthan gum reduced the formation of type IIb amylose-lipid complexes, syneresis, and hysteresis in cereal starches compared to stearic acid alone. A combination of stearic acid and xanthan gum produce higher viscosity non-gelling starches and xanthan gum addition increases physical stability to freezing and better structural recovery after shear. Copyright © 2015 Elsevier Ltd. All rights reserved.

Sequential allosteric mechanism of ATP hydrolysis by the CCT/TRiC chaperone is revealed through Arrhenius analysis

PubMed Central

Gruber, Ranit; Levitt, Michael; Horovitz, Amnon

2017-01-01

Knowing the mechanism of allosteric switching is important for understanding how molecular machines work. The CCT/TRiC chaperonin nanomachine undergoes ATP-driven conformational changes that are crucial for its folding function. Here, we demonstrate that insight into its allosteric mechanism of ATP hydrolysis can be achieved by Arrhenius analysis. Our results show that ATP hydrolysis triggers sequential ‟conformational waves.” They also suggest that these waves start from subunits CCT6 and CCT8 (or CCT3 and CCT6) and proceed clockwise and counterclockwise, respectively. PMID:28461478

Sequential allosteric mechanism of ATP hydrolysis by the CCT/TRiC chaperone is revealed through Arrhenius analysis.

PubMed

Gruber, Ranit; Levitt, Michael; Horovitz, Amnon

2017-05-16

Knowing the mechanism of allosteric switching is important for understanding how molecular machines work. The CCT/TRiC chaperonin nanomachine undergoes ATP-driven conformational changes that are crucial for its folding function. Here, we demonstrate that insight into its allosteric mechanism of ATP hydrolysis can be achieved by Arrhenius analysis. Our results show that ATP hydrolysis triggers sequential ‟conformational waves." They also suggest that these waves start from subunits CCT6 and CCT8 (or CCT3 and CCT6) and proceed clockwise and counterclockwise, respectively.

Improving Accuracy in Arrhenius Models of Cell Death: Adding a Temperature-Dependent Time Delay.

PubMed

Pearce, John A

2015-12-01

The Arrhenius formulation for single-step irreversible unimolecular reactions has been used for many decades to describe the thermal damage and cell death processes. Arrhenius predictions are acceptably accurate for structural proteins, for some cell death assays, and for cell death at higher temperatures in most cell lines, above about 55 °C. However, in many cases--and particularly at hyperthermic temperatures, between about 43 and 55 °C--the particular intrinsic cell death or damage process under study exhibits a significant "shoulder" region that constant-rate Arrhenius models are unable to represent with acceptable accuracy. The primary limitation is that Arrhenius calculations always overestimate the cell death fraction, which leads to severely overoptimistic predictions of heating effectiveness in tumor treatment. Several more sophisticated mathematical model approaches have been suggested and show much-improved performance. But simpler models that have adequate accuracy would provide useful and practical alternatives to intricate biochemical analyses. Typical transient intrinsic cell death processes at hyperthermic temperatures consist of a slowly developing shoulder region followed by an essentially constant-rate region. The shoulder regions have been demonstrated to arise chiefly from complex functional protein signaling cascades that generate delays in the onset of the constant-rate region, but may involve heat shock protein activity as well. This paper shows that acceptably accurate and much-improved predictions in the simpler Arrhenius models can be obtained by adding a temperature-dependent time delay. Kinetic coefficients and the appropriate time delay are obtained from the constant-rate regions of the measured survival curves. The resulting predictions are seen to provide acceptably accurate results while not overestimating cell death. The method can be relatively easily incorporated into numerical models. Additionally, evidence is presented to support the application of compensation law behavior to the cell death processes--that is, the strong correlation between the kinetic coefficients, ln{A} and E(a), is confirmed.

Are tropical small mammals physiologically vulnerable to Arrhenius effects and climate change?

PubMed

Lovegrove, Barry G; Canale, Cindy; Levesque, Danielle; Fluch, Gerhard; Reháková-Petrů, Milada; Ruf, Thomas

2014-01-01

There is some urgency in the necessity to incorporate physiological data into mechanistic, trait-based, demographic climate change models. Physiological responses at the individual level provide the mechanistic link between environmental changes and individual performances and hence population dynamics. Here we consider the causal relationship between ambient temperature (Ta) and metabolic rate (MR), namely, the Arrhenius effect, which is directly affected by global warming through increases in average global air temperatures and the increase in the frequency and intensity of extreme climate events. We measured and collated data for several small, free-ranging tropical arboreal mammals and evaluated their vulnerability to Arrhenius effects and putative heat stress associated with climate change. Skin temperatures (Tskin) were obtained from free-ranging tarsiers (Tarsius syrichta) on Bohol Island, Philippines. Core body temperature (Tb) was obtained from the greater hedgehog tenrec (Setifer setosus) and the gray brown mouse lemur (Microcebus ravelobensis) from Ankarafantsika, Madagascar. Tskin for another mouse lemur, Microcebus griseorufus, was obtained from the literature. All four species showed evidence of hyperthermia during the daytime rest phase in the form of either Tskin or Tb that was higher than the normothermic Tb during the nighttime active phase. Potentially, tropical arboreal mammals with the lowest MRs and Tb, such as tarsiers, are the most vulnerable to sustained heat stress because their Tb is already close to Ta. Climate change may involve increases in MRs due to Arrhenius effects, especially during the rest phase or during torpor and hibernation. The most likely outcome of increased Arrhenius effects with climate change will be an increase in energy expenditure at the expense of other critical functions such as reproduction or growth and will thus affect fitness. However, we propose that these hypothetical Arrhenius costs can be, and in some species probably are, offset by the use of hyperthermic daily torpor, that is, hypometabolism at high Ta.

The rheological properties of modified microcrystalline cellulose containing high levels of model drugs.

PubMed

Knight, Paul E; Podczeck, Fridrun; Newton, J Michael

2009-06-01

The rheological properties of different types of microcrystalline cellulose (MCC) mixed with model drugs and water have been evaluated to identify the influence of sodium carboxymethylcellulose (SCMC) added to the cellulose during preparation. A ram extruder was used as a capillary rheometer. The mixtures consisted of 20% spheronizing agent (standard grade MCC or modified types with 6% or 8% of low viscosity grade SCMC) and 80% of ascorbic acid, ibuprofen or lactose monohydrate. The introduction of SCMC changed all rheological parameters assessed. It produced more rigid systems, requiring more stress to induce and maintain flow. Degree of non-Newtonian flow, angle of convergence, extensional viscosity, yield and die land shear stress at zero velocity, and static wall friction were increased, but recoverable shear and compliance were decreased. The presence of SCMC did not remove the influence of the type of drug. The mixture of ibuprofen and standard MCC had the lowest values for shear stress as a function of the rate of shear, extensional viscosity, and angle of convergence, but the highest values for recoverable shear and compliance. The findings indicate that the system has insufficient rigidity to form pellets. (c) 2008 Wiley-Liss, Inc.

Complex interactions between diapirs and 4-D subduction driven mantle wedge circulation.

NASA Astrophysics Data System (ADS)

Sylvia, R. T.; Kincaid, C. R.

2015-12-01

Analogue laboratory experiments generate 4-D flow of mantle wedge fluid and capture the evolution of buoyant mesoscale diapirs. The mantle is modeled with viscous glucose syrup with an Arrhenius type temperature dependent viscosity. To characterize diapir evolution we experiment with a variety of fluids injected from multiple point sources. Diapirs interact with kinematically induced flow fields forced by subducting plate motions replicating a range of styles observed in dynamic subduction models (e.g., rollback, steepening, gaps). Data is collected using high definition timelapse photography and quantified using image velocimetry techniques. While many studies assume direct vertical connections between the volcanic arc and the deeper mantle source region, our experiments demonstrate the difficulty of creating near vertical conduits. Results highlight extreme curvature of diapir rise paths. Trench-normal deflection occurs as diapirs are advected downward away from the trench before ascending into wedge apex directed return flow. Trench parallel deflections up to 75% of trench length are seen in all cases, exacerbated by complex geometry and rollback motion. Interdiapir interaction is also important; upwellings with similar trajectory coalesce and rapidly accelerate. Moreover, we observe a new mode of interaction whereby recycled diapir material is drawn down along the slab surface and then initiates rapid fluid migration updip along the slab-wedge interface. Variability in trajectory and residence time leads to complex petrologic inferences. Material from disparate source regions can surface at the same location, mix in the wedge, or become fully entrained in creeping flow adding heterogeneity to the mantle. Active diapirism or any other vertical fluid flux mechanism employing rheological weakening lowers viscosity in the recycling mantle wedge affecting both solid and fluid flow characteristics. Many interesting and insightful results have been presented based upon 2-D, steady-state thermal and flow regimes. We reiterate the importance of 4-D time evolution in subduction models. Analogue experiments allow added feedbacks and complexity improving intuition and providing insight for further investigation.

Fluctuation relations between hierarchical kinetically equivalent networks with Arrhenius-type transitions and their roles in systems and structural biology.

PubMed

Deng, De-Ming; Lu, Yi-Ta; Chang, Cheng-Hung

2017-06-01

The legality of using simple kinetic schemes to determine the stochastic properties of a complex system depends on whether the fluctuations generated from hierarchical equivalent schemes are consistent with one another. To analyze this consistency, we perform lumping processes on the stochastic differential equations and the generalized fluctuation-dissipation theorem and apply them to networks with the frequently encountered Arrhenius-type transition rates. The explicit Langevin force derived from those networks enables us to calculate the state fluctuations caused by the intrinsic and extrinsic noises on the free energy surface and deduce their relations between kinetically equivalent networks. In addition to its applicability to wide classes of network related systems, such as those in structural and systems biology, the result sheds light on the fluctuation relations for general physical variables in Keizer's canonical theory.

Impact of medium-range order on the glass transition in liquid Ni-Si alloys

NASA Astrophysics Data System (ADS)

Lü, Y. J.; Entel, P.

2011-09-01

We study the thermophysical properties and structure of liquid Ni-Si alloys using molecular dynamics simulations. The liquid Ni-5% and 10%Si alloys crystallize to form the face-centered cubic (Ni) at 900 and 850 K, respectively, and the glass transitions take place in Ni-20% and 25%Si alloys at about 700 K. The temperature-dependent self-diffusion coefficients and viscosities exhibit more pronounced non-Arrhenius behavior with the increase of Si content before phase transitions, indicating the enhanced glass-forming ability. These appearances of thermodynamic properties and phase transitions are found to closely relate to the medium-range order clusters with the defective face-centered cubic structure characterized by both local translational and orientational order. This locally ordered structure tends to be destroyed by the addition of more Si atoms, resulting in a delay of nucleation and even glass transition instead.

Dynamic compensation in the central Pacific Ocean

NASA Technical Reports Server (NTRS)

Hinojosa, Juan Homero; Marsh, Bruce D.

1988-01-01

The intermediate-wavelength geoid (lambda similar to 2000 km) and sea-floor topography fields in the central Pacific Ocean were studied in terms of static and dynamic compensation models. Topographic features on the sea-floor with lambda less than 1000 km were found to be compensated both regionally, by the elastic strength of the lithosphere, and locally, by displacing mantle material to reach isostatic adjustment. The larger-scale sea-floor topography and the corresponding geoid anomalies with lambda similar to 2000 km cannot be explained by either local or regional compensation. The topography and the resulting geoid anomaly at this wavelength were modeled by considering the dynamic effects arising from viscous stresses in a layer of fluid with a highly temperature-dependent viscosity for the cases of: (1) surface cooling, and (2) basal heating. In this model, the mechanical properties of the elastic part of the lithosphere were taken into account by considering an activation energy of about 520 kJ/mol in the Arrhenius law for the viscosity. Numerical predictions of the topography, total geoid anomaly, and admittance were obtained, and the results show that the thermal perturbation in the layer, which accounts for the mass deficit, must be located close to the surface to compensate the gravitational effect of the surface deformation. For the case of basal heating, the temperature dependence of viscosity results in a separation of the upper, quasi-rigid lid from the lower mobile fluid, hence inhibiting the development of a compensating thermal perturbation at shallow depths. The results clearly rule out small-scale, upper-mantle convection as the source of these anomalies. Instead, the geophysical observables can be well explained by a shallow, transient thermal perturbation.

Configurational Entropy Approach to the Kinetics of Glasses

PubMed Central

Di Marzio, Edmund A.; Yang, Arthur J. M.

1997-01-01

A kinetic theory of glasses is developed using equilibrium theory as a foundation. After establishing basic criteria for glass formation and the capability of the equilibrium entropy theory to describe the equilibrium aspects of glass formation, a minimal model for the glass kinetics is proposed. Our kinetic model is based on a trapping description of particle motion in which escapes from deep wells provide the rate-determining steps for motion. The formula derived for the zero frequency viscosity η (0,T) is log η (0,T) = B − AF(T)kT where F is the free energy and T the temperature. Contrast this to the Vogel-Fulcher law log η (0,T) = B + A/(T − Tc). A notable feature of our description is that even though the location of the equilibrium second-order transition in temperature-pressure space is given by the break in the entropy or volume curves the viscosity and its derivative are continuous through the transition. The new expression for η (0,T) has no singularity at a critical temperature Tc as in the Vogel-Fulcher law and the behavior reduces to the Arrhenius form in the glass region. Our formula for η (0,T) is discussed in the context of the concepts of strong and fragile glasses, and the experimentally observed connection of specific heat to relaxation response in a homologous series of polydimethylsiloxane is explained. The frequency and temperature dependencies of the complex viscosity η (ω< T), the diffusion coefficient D(ω< T), and the dielectric response ε (ω< T) are also obtained for our kinetic model and found to be consistent with stretched exponential behavior. PMID:27805133

The adhesive strength and initial viscosity of denture adhesives.

PubMed

Han, Jian-Min; Hong, Guang; Dilinuer, Maimaitishawuti; Lin, Hong; Zheng, Gang; Wang, Xin-Zhi; Sasaki, Keiichi

2014-11-01

To examine the initial viscosity and adhesive strength of modern denture adhesives in vitro. Three cream-type denture adhesives (Poligrip S, Corect Cream, Liodent Cream; PGS, CRC, LDC) and three powder-type denture adhesives (Poligrip Powder, New Faston, Zanfton; PGP, FSN, ZFN) were used in this study. The initial viscosity was measured using a controlled-stress rheometer. The adhesive strength was measured according to ISO-10873 recommended procedures. All data were analyzed independently by one-way analysis of variance combined with a Student-Newman-Keuls multiple comparison test at a 5% level of significance. The initial viscosity of all the cream-type denture adhesives was lower than the powder-type adhesives. Before immersion in water, all the powder-type adhesives exhibited higher adhesive strength than the cream-type adhesives. However, the adhesive strength of cream-type denture adhesives increased significantly and exceeded the powder-type denture adhesives after immersion in water. For powder-type adhesives, the adhesive strength significantly decreased after immersion in water for 60 min, while the adhesive strength of the cream-type adhesives significantly decreased after immersion in water for 180 min. Cream-type denture adhesives have lower initial viscosity and higher adhesive strength than powder type adhesives, which may offer better manipulation properties and greater efficacy during application.

Erroneous Arrhenius: Modified Arrhenius model best explains the temperature dependence of ectotherm fitness

PubMed Central

Knies, Jennifer L.; Kingsolver, Joel G.

2013-01-01

The initial rise of fitness that occurs with increasing temperature is attributed to Arrhenius kinetics, in which rates of reaction increase exponentially with increasing temperature. Models based on Arrhenius typically assume single rate-limiting reaction(s) over some physiological temperature range for which all the rate-limiting enzymes are in 100% active conformation. We test this assumption using datasets for microbes that have measurements of fitness (intrinsic rate of population growth) at many temperatures and over a broad temperature range, and for diverse ectotherms that have measurements at fewer temperatures. When measurements are available at many temperatures, strictly Arrhenius kinetics is rejected over the physiological temperature range. However, over a narrower temperature range, we cannot reject strictly Arrhenius kinetics. The temperature range also affects estimates of the temperature dependence of fitness. These results indicate that Arrhenius kinetics only apply over a narrow range of temperatures for ectotherms, complicating attempts to identify general patterns of temperature dependence. PMID:20528477

Erroneous Arrhenius: modified arrhenius model best explains the temperature dependence of ectotherm fitness.

PubMed

Knies, Jennifer L; Kingsolver, Joel G

2010-08-01

The initial rise of fitness that occurs with increasing temperature is attributed to Arrhenius kinetics, in which rates of reaction increase exponentially with increasing temperature. Models based on Arrhenius typically assume single rate-limiting reactions over some physiological temperature range for which all the rate-limiting enzymes are in 100% active conformation. We test this assumption using data sets for microbes that have measurements of fitness (intrinsic rate of population growth) at many temperatures and over a broad temperature range and for diverse ectotherms that have measurements at fewer temperatures. When measurements are available at many temperatures, strictly Arrhenius kinetics are rejected over the physiological temperature range. However, over a narrower temperature range, we cannot reject strictly Arrhenius kinetics. The temperature range also affects estimates of the temperature dependence of fitness. These results indicate that Arrhenius kinetics only apply over a narrow range of temperatures for ectotherms, complicating attempts to identify general patterns of temperature dependence.

Super-Arrhenius diffusion in an undercooled binary Lennard-Jones liquid results from a quantifiable correlation effect.

PubMed

de Souza, Vanessa K; Wales, David J

2006-02-10

On short time scales an underlying Arrhenius temperature dependence of the diffusion constant can be extracted from the fragile, super-Arrhenius diffusion of a binary Lennard-Jones mixture. This Arrhenius diffusion is related to the true super-Arrhenius behavior by a factor that depends on the average angle between steps in successive time windows. The correction factor accounts for the fact that on average, successive displacements are negatively correlated, and this effect can therefore be linked directly with the higher apparent activation energy for diffusion at low temperature.

Hot Deformation Behavior and Flow Stress Prediction of TC4-DT Alloy in Single-Phase Region and Dual-Phase Regions

NASA Astrophysics Data System (ADS)

Liu, Jianglin; Zeng, Weidong; Zhu, Yanchun; Yu, Hanqing; Zhao, Yongqing

2015-05-01

Isothermal compression tests of TC4-DT titanium alloy at the deformation temperature ranging from 1181 to 1341 K covering α + β phase field and β-phase field, the strain rate ranging from 0.01 to 10.0 s-1 and the height reduction of 70% were conducted on a Gleeble-3500 thermo-mechanical simulator. The experimental true stress-true strain data were employed to develop the strain-compensated Arrhenius-type flow stress model and artificial neural network (ANN) model; the predictability of two models was quantified in terms of correlation coefficient ( R) and average absolute relative error (AARE). The R and AARE for the Arrhenius-type flow stress model were 0.9952 and 5.78%, which were poorer linear relation and more deviation than 0.9997 and 1.04% for the feed-forward back-propagation ANN model, respectively. The results indicated that the trained ANN model was more efficient and accurate in predicting the flow behavior for TC4-DT titanium alloy at elevated temperature deformation than the strain-compensated Arrhenius-type constitutive equations. The constitutive relationship compensating strain could track the experimental data across the whole hot working domain other than that at high strain rates (≥1 s-1). The microstructure analysis illustrated that the deformation mechanisms existed at low strain rates (≤0.1 s-1), where dynamic recrystallization occurred, were far different from that at high strain rates (≥1 s-1) that presented bands of flow localization and cracking along grain boundary.

Dynamical properties in supercooling liquid of trehalose aqueous solution studied by Brillouin scattering

NASA Astrophysics Data System (ADS)

Shibata, Tomohiko; Tominaga, Ayane; Takayama, Haruki; Kojima, Seiji

2013-02-01

Brillouin scattering spectroscopy has been applied to study the dynamical properties of glass transition of trehalose aqueous solutions in a high-frequency gigahertz range and in the temperature range (-190°C ≤ T ≤ 100°C). The temperature variations of sound velocity and attenuation were accurately determined using the refractive index measured by a prism-coupling method. The temperature dependence of relaxation time of the structural relaxation process was determined by the Debye model. Its temperature dependence shows Arrhenius behavior in a liquid state. The parameters of Arrhenius law were also determined as a function of trehalose concentration.

Ocean chemistry, ocean warming, and emerging hypoxia: Commentary

NASA Astrophysics Data System (ADS)

Brewer, Peter G.; Peltzer, Edward T.

2016-05-01

For 50 years, ocean scientists have represented deep sea biogeochemical rates as a temperature independent function of depth with form R = R0e-αz where z is depth in km. We show this resembles, but is not an identity for, a form of the classical Arrhenius equation K = Ae-Ea/RT where T is temperature in Kelvins, R is the gas constant (8.314 JK-1mol-1), and A is a preexponential factor. For a deep Sargasso Sea data set, we find oxygen consumption rates are accurately represented by an Arrhenius process with apparent activation energy of 86.5 kJ mol-1, and Q10 = 3.63.

Shelf-life of a 2.5% sodium hypochlorite solution as determined by Arrhenius equation.

PubMed

Nicoletti, Maria Aparecida; Siqueira, Evandro Luiz; Bombana, Antonio Carlos; Oliveira, Gabriella Guimarães de

2009-01-01

Accelerated stability tests are indicated to assess, within a short time, the degree of chemical degradation that may affect an active substance, either alone or in a formula, under normal storage conditions. This method is based on increased stress conditions to accelerate the rate of chemical degradation. Based on the equation of the straight line obtained as a function of the reaction order (at 50 and 70 degrees C) and using Arrhenius equation, the speed of the reaction was calculated for the temperature of 20 degrees C (normal storage conditions). This model of accelerated stability test makes it possible to predict the chemical stability of any active substance at any given moment, as long as the method to quantify the chemical substance is available. As an example of the applicability of Arrhenius equation in accelerated stability tests, a 2.5% sodium hypochlorite solution was analyzed due to its chemical instability. Iodometric titration was used to quantify free residual chlorine in the solutions. Based on data obtained keeping this solution at 50 and 70 degrees C, using Arrhenius equation and considering 2.0% of free residual chlorine as the minimum acceptable threshold, the shelf-life was equal to 166 days at 20 degrees C. This model, however, makes it possible to calculate shelf-life at any other given temperature.

Reliable Viscosity Calculation from Equilibrium Molecular Dynamics Simulations: A Time Decomposition Method.

PubMed

Zhang, Yong; Otani, Akihito; Maginn, Edward J

2015-08-11

Equilibrium molecular dynamics is often used in conjunction with a Green-Kubo integral of the pressure tensor autocorrelation function to compute the shear viscosity of fluids. This approach is computationally expensive and is subject to a large amount of variability because the plateau region of the Green-Kubo integral is difficult to identify unambiguously. Here, we propose a time decomposition approach for computing the shear viscosity using the Green-Kubo formalism. Instead of one long trajectory, multiple independent trajectories are run and the Green-Kubo relation is applied to each trajectory. The averaged running integral as a function of time is fit to a double-exponential function with a weighting function derived from the standard deviation of the running integrals. Such a weighting function minimizes the uncertainty of the estimated shear viscosity and provides an objective means of estimating the viscosity. While the formal Green-Kubo integral requires an integration to infinite time, we suggest an integration cutoff time tcut, which can be determined by the relative values of the running integral and the corresponding standard deviation. This approach for computing the shear viscosity can be easily automated and used in computational screening studies where human judgment and intervention in the data analysis are impractical. The method has been applied to the calculation of the shear viscosity of a relatively low-viscosity liquid, ethanol, and relatively high-viscosity ionic liquid, 1-n-butyl-3-methylimidazolium bis(trifluoromethane-sulfonyl)imide ([BMIM][Tf2N]), over a range of temperatures. These test cases show that the method is robust and yields reproducible and reliable shear viscosity values.

Rheological and interfacial properties at the equilibrium of almond gum tree exudate (Prunus dulcis) in comparison with gum arabic.

PubMed

Mahfoudhi, Nesrine; Sessa, Mariarenata; Ferrari, Giovanna; Hamdi, Salem; Donsi, Francesco

2016-06-01

Almond gum contains an arabinogalactan-type polysaccharide, which plays an important role in defining its interfacial and rheological properties. In this study, rheological and interfacial properties of almond gum and gum arabic aqueous dispersions were comparatively investigated. The interfacial tension of almond gum and gum arabic aqueous dispersions was measured using the pendant drop method in hexadecane. The asymptotic interfacial tension values for almond gum were significantly lower than the corresponding values measured for gum arabic, especially at high concentration. Rheological properties were characterized by steady and oscillatory tests using a coaxial geometry. Almond gum flow curves exhibited a shear thinning non-Newtonian behavior with a tendency to a Newtonian plateau at low shear rate, while gum arabic flow curves exhibited such behavior only at high shear rate. The influence of temperature (5-50  ℃) on the flow curves was studied at 4% (m/m) gum concentration and the Newtonian viscosities at infinite and at zero shear rate, for gum arabic and almond gum, respectively, were accurately fitted by an Arrhenius-type equation. The dynamic properties of the two gum dispersions were also studied. Both gum dispersions exhibited viscoelastic properties, with the viscous component being predominant in a wider range of concentrations for almond gum, while for gum arabic the elastic component being higher than the elastic one especially at higher concentrations.The rheological and interfacial tension properties of almond gum suggest that it may represent a possible substitute of gum arabic in different food applications. © The Author(s) 2015.

The Gassmann-Burgers Model to Simulate Seismic Waves at the Earth Crust And Mantle

NASA Astrophysics Data System (ADS)

Carcione, José M.; Poletto, Flavio; Farina, Biancamaria; Craglietto, Aronne

2017-03-01

The upper part of the crust shows generally brittle behaviour while deeper zones, including the mantle, may present ductile behaviour, depending on the pressure-temperature conditions; moreover, some parts are melted. Seismic waves can be used to detect these conditions on the basis of reflection and transmission events. Basically, from the elastic-plastic point of view the seismic properties (seismic velocity and density) depend on effective pressure and temperature. Confining and pore pressures have opposite effects on these properties, such that very small effective pressures (the presence of overpressured fluids) may substantially decrease the P- and S-wave velocities, mainly the latter, by opening of cracks and weakening of grain contacts. Similarly, high temperatures induce the same effect by partial melting. To model these effects, we consider a poro-viscoelastic model based on Gassmann equations and Burgers mechanical model to represent the properties of the rock frame and describe ductility in which deformation takes place by shear plastic flow. The Burgers elements allow us to model the effects of seismic attenuation, velocity dispersion and steady-state creep flow, respectively. The stiffness components of the brittle and ductile media depend on stress and temperature through the shear viscosity, which is obtained by the Arrhenius equation and the octahedral stress criterion. Effective pressure effects are taken into account in the dry-rock moduli using exponential functions whose parameters are obtained by fitting experimental data as a function of confining pressure. Since fluid effects are important, the density and bulk modulus of the saturating fluids (water and steam) are modeled using the equations provided by the NIST website, including supercritical behaviour. The theory allows us to obtain the phase velocity and quality factor as a function of depth and geological pressure and temperature as well as time frequency. We then obtain the PS and SH equations of motion recast in the velocity-stress formulation, including memory variables to avoid the computation of time convolutions. The equations correspond to isotropic anelastic and inhomogeneous media and are solved by a direct grid method based on the Runge-Kutta time stepping technique and the Fourier pseudospectral method. The algorithm is tested with success against known analytical solutions for different shear viscosities. An example shows how anomalous conditions of pressure and temperature can in principle be detected with seismic waves.

Relationship between structural and dynamic properties of Al-rich Al-Cu melts: Beyond the Stokes-Einstein relation

NASA Astrophysics Data System (ADS)

Jakse, N.; Pasturel, A.

2016-12-01

We perform ab initio molecular dynamics simulations to study structural and transport properties in liquid A l1 -xC ux alloys, with copper composition x ≤0.4 , in relation to the applicability of the Stokes-Einstein (SE) equation in these melts. To begin, we find that self-diffusion coefficients and viscosity are composition dependent, while their temperature dependence follows an Arrhenius-type behavior, except for x =0.4 at low temperature. Then, we find that the applicability of the SE equation is also composition dependent, and its breakdown in the liquid regime above the liquidus temperature can be related to different local ordering around each species. In this case, we emphasize the difficulty of extracting effective atomic radii from interatomic distances found in liquid phases, but we see a clear correlation between transport properties and local ordering described through the structural entropy approximated by the two-body contribution. We use these findings to reformulate the SE equation within the framework of Rosenfeld's scaling law in terms of partial structural entropies, and we demonstrate that the breakdown of the SE relation can be related to their temperature dependence. Finally, we also use this framework to derive a simple relation between the ratio of the self-diffusivities of the components and the ratio of their partial structural entropies.

Subduction and volatile recycling in Earth's mantle

NASA Technical Reports Server (NTRS)

King, S. D.; Ita, J. J.; Staudigel, H.

1994-01-01

The subduction of water and other volatiles into the mantle from oceanic sediments and altered oceanic crust is the major source of volatile recycling in the mantle. Until now, the geotherms that have been used to estimate the amount of volatiles that are recycled at subduction zones have been produced using the hypothesis that the slab is rigid and undergoes no internal deformation. On the other hand, most fluid dynamical mantle flow calculations assume that the slab has no greater strength than the surrounding mantle. Both of these views are inconsistent with laboratory work on the deformation of mantle minerals at high pressures. We consider the effects of the strength of the slab using two-dimensional calculations of a slab-like thermal downwelling with an endothermic phase change. Because the rheology and composition of subducting slabs are uncertain, we consider a range of Clapeyron slopes which bound current laboratory estimates of the spinel to perovskite plus magnesiowustite phase transition and simple temperature-dependent rheologies based on an Arrhenius law diffusion mechanism. In uniform viscosity convection models, subducted material piles up above the phase change until the pile becomes gravitationally unstable and sinks into the lower mantle (the avalanche). Strong slabs moderate the 'catastrophic' effects of the instabilities seen in many constant-viscosity convection calculations; however, even in the strongest slabs we consider, there is some retardation of the slab descent due to the presence of the phase change.

Exploratory Characterization of a Perfluoropolyether Oil as a Possible Viscosity Standard at Deepwater Production Conditions of 533 K and 241 MPa

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baled, Hseen O.; Tapriyal, Deepak; Morreale, Bryan D.

2013-08-29

DuPont’s perfluoropolyether oil Krytox® GPL 102 is a promising candidate for the high-temperature, high-pressure Deepwater viscosity standard (DVS). The preferred DVS is a thermally stable liquid that exhibits a viscosity of roughly 20 mPa∙s at 533 K and 241 MPa; a viscosity value representative of light oils found in ultra-deep formations beneath the deep waters of the Gulf of Mexico. A windowed rolling-ball viscometer designed by our team is used to determine the Krytox® GPL 102 viscosity at pressures to 245 MPa and temperatures of 311 K, 372 K, and 533 K. At 533 K and 243 MPa, the Krytox®more » GPL 102 viscosity is (27.2±1.3)mPa∙s. The rolling-ball viscometer viscosity results for Krytox® GPL 102 are correlated with an empirical 10-parameter surface fitting function that yields an MAPD of 3.9 %. A Couette rheometer is also used to measure the Krytox® GPL 102 viscosity, yielding a value of (26.2±1)mPa∙s at 533 K and 241 MPa. The results of this exploratory study suggest that Krytox®GPL 102 is a promising candidate for the DVS, primarily because this fluoroether oil is thermally stable and exhibits a viscosity closer to the targeted value of 20 mPa ∙ s at 533 K and 241 MPa than any other fluid reported to date. Finally and nonetheless, further studies must be conducted by other researcher groups using various types of viscometers and rheometers on samples of Krytox GPL® 102 from the same lot to further establish the properties of Krytox GPL® 102.« less

Estimating Arrhenius parameters using temperature programmed molecular dynamics.

PubMed

Imandi, Venkataramana; Chatterjee, Abhijit

2016-07-21

Kinetic rates at different temperatures and the associated Arrhenius parameters, whenever Arrhenius law is obeyed, are efficiently estimated by applying maximum likelihood analysis to waiting times collected using the temperature programmed molecular dynamics method. When transitions involving many activated pathways are available in the dataset, their rates may be calculated using the same collection of waiting times. Arrhenius behaviour is ascertained by comparing rates at the sampled temperatures with ones from the Arrhenius expression. Three prototype systems with corrugated energy landscapes, namely, solvated alanine dipeptide, diffusion at the metal-solvent interphase, and lithium diffusion in silicon, are studied to highlight various aspects of the method. The method becomes particularly appealing when the Arrhenius parameters can be used to find rates at low temperatures where transitions are rare. Systematic coarse-graining of states can further extend the time scales accessible to the method. Good estimates for the rate parameters are obtained with 500-1000 waiting times.

Voltage stress effects on microcircuit accelerated life test failure rates

NASA Technical Reports Server (NTRS)

Johnson, G. M.

1976-01-01

The applicability of Arrhenius and Eyring reaction rate models for describing microcircuit aging characteristics as a function of junction temperature and applied voltage was evaluated. The results of a matrix of accelerated life tests with a single metal oxide semiconductor microcircuit operated at six different combinations of temperature and voltage were used to evaluate the models. A total of 450 devices from two different lots were tested at ambient temperatures between 200 C and 250 C and applied voltages between 5 Vdc and 15 Vdc. A statistical analysis of the surface related failure data resulted in bimodal failure distributions comprising two lognormal distributions; a 'freak' distribution observed early in time, and a 'main' distribution observed later in time. The Arrhenius model was shown to provide a good description of device aging as a function of temperature at a fixed voltage. The Eyring model also appeared to provide a reasonable description of main distribution device aging as a function of temperature and voltage. Circuit diagrams are shown.

Spreading properties of cosmetic emollients: Use of synthetic skin surface to elucidate structural effect.

PubMed

Douguet, Marine; Picard, Céline; Savary, Géraldine; Merlaud, Fabien; Loubat-Bouleuc, Nathalie; Grisel, Michel

2017-06-01

The study focuses on the impact of structural and physicochemical properties of emollients on their spreadability. Fifty-three emollients, among which esters, silicones, vegetable and mineral oils, have been characterized. Their viscosity, surface tension, density and spreadability have been measured. Vitro-skin ® , an artificial skin substitute, was used as an artificial porous substrate to measure spreadability. Two different methods have been selected to characterize spreadability, namely contact angle and spreading value. Dynamic contact angle measurements showed that emollient spreadability is first governed by spontaneous spreading and that, in a second phase, absorption and migration into the porous substrate becomes the driver of the extension of the spreading area. Statistical analysis of physicochemical and spreading value data revealed that viscosity has a major impact on the spreading behavior of emollients whatever their chemical type. A special emphasis was placed on the ester family in which chemical diversity is very wide. The results highlighted a difference between "high viscosity esters" for which viscosity is the main factor impacting spreadability and "low viscosity esters" for which structural variations (mono/diester, saturated/unsaturated chain, linear/branched chain) have to be considered in addition to viscosity. Linear regressions were used to express spreading value as a function of viscosity for each of the four emollient families tested (esters, silicones, vegetable and mineral oils). These regressions allowed the development of reliable predictive models as a powerful tool for formulators to forecast spreadability of emollients. Copyright © 2017 Elsevier B.V. All rights reserved.

Conditions of viscosity measurement for detecting irradiated peppers

NASA Astrophysics Data System (ADS)

Hayashi, Toru; Todoriki, Setsuko; Okadome, Hiroshi; Kohyama, Kaoru

1995-04-01

Viscosity of gelatinized suspensions of black and white peppers decreased depending upon dose. The viscosity was influenced by gelatinization and viscosity measurement conditions. The difference between unirradiated pepper and an irradiated one was larger at a higher pH and temperature for gelatinization. A viscosity parameter normalized with the starch content of pepper sample and the viscosity of a 5% suspension of corn starch could get rid of the influence of the conditions for viscosity measurement such as a type of viscometer, shear rate and temperature.

Sweetness and other sensory properties of model fruit drinks: Does viscosity have an impact?

PubMed

Brandenstein, Cai V S; Busch-Stockfisch, Mechthild; Fischer, Markus

2015-03-15

The impact of thickening agents and viscosity levels on sensory perception was studied in model fruit drinks. Four formulations were prepared that varied in the sweetener blend (erythritol, maltitol and/or steviol glycosides). Locust bean gum and its blends with either xanthan or carrageenan were used to adjust viscosity levels (20, 40, and 70 mPa s). The ranges of viscosity and sweetness level were selected to represent a typical concentration range in commercially available beverages. An increase in viscosity resulted in significant increases in pulpiness, sliminess and perceived viscosity (P-values ≤ 0.001), which were not dependent on sweeteners or hydrocolloid type. Taste perception remained largely unchanged irrespective of the hydrocolloid used. The impact of viscosity on sweetness and taste perception was much smaller in the concentrations used than has been generally reported. The effect of the type of hydrocolloid on the perception of taste attributes was greater than that of viscosity. © 2014 Society of Chemical Industry.

Dynein-deficient flagella respond to increased viscosity with contrasting changes in power and recovery strokes.

PubMed

Wilson, Kate S; Gonzalez, Olivia; Dutcher, Susan K; Bayly, Philip V

2015-09-01

Changes in the flagellar waveform in response to increased viscosity were investigated in uniflagellate mutants of Chlamydomonas reinhardtii. We hypothesized that the waveforms of mutants lacking different dynein arms would change in different ways as viscosity was increased, and that these variations would illuminate the feedback pathways from force to dynein activity. Previous studies have investigated the effects of viscosity on cell body motion, propulsive force, and power in different mutants, but the effect on waveform has not yet been fully characterized. Beat frequency decreases with viscosity in wild-type uniflagellate (uni1) cells, and outer dynein arm deficient (oda2) mutants. In contrast, the inner dynein arm mutant ida1 (lacking I1/f) maintains beat frequency at high viscosity but alters its flagellar waveform more than either wild-type or oda2. The ida1 waveform is narrower than wild-type, primarily due to an abbreviated recovery stroke; this difference is amplified at high viscosity. The oda2 mutant in contrast, maintains a consistent waveform at high and low viscosity with a slightly longer power stroke than wild-type. Analysis of the delays and shear displacements between bends suggest that direct force feedback in the outer dynein arm system may initiate switching of dynein activity. In contrast, I1/f dynein appears to delay switching, most markedly at the initiation of the power stroke, possibly by controlling inter-doublet separation. © 2015 Wiley Periodicals, Inc.

Dynein-deficient flagella respond to increased viscosity with contrasting changes in power and recovery strokes

PubMed Central

Wilson, Kate S.; Gonzalez, Olivia; Dutcher, Susan K.; Bayly, P.V.

2015-01-01

Changes in the flagellar waveform in response to increased viscosity were investigated in uniflagellate mutants of Chlamydomonas reinhardtii. We hypothesized that the waveforms of mutants lacking different dynein arms would change in different ways as viscosity was increased, and that these variations would illuminate the feedback pathways from force to dynein activity. Previous studies have investigated the effects of viscosity on cell body motion, propulsive force, and power in different mutants, but the effect on waveform has not yet been fully characterized. Beat frequency decreases with viscosity in wild-type uniflagellate (uni1) cells, and outer dynein arm deficient (oda2) mutants. In contrast, the inner dynein arm mutant ida1 (lacking I1/f) maintains beat frequency at high viscosity but alters its flagellar waveform more than either wild-type or oda2. The ida1 waveform is narrower than wild-type, primarily due to an abbreviated recovery stroke; this difference is amplified at high viscosity. The oda2 mutant in contrast, maintains a consistent waveform at high and low viscosity with a slightly longer power stroke than wild-type. Analysis of the delays and shear displacements between bends suggest that direct force feedback in the outer dynein arm system may initiate switching of dynein activity. In contrast, I1/f dynein appears to delay switching, most markedly at the initiation of the power stroke, possibly by controlling inter-doublet separation. PMID:26314933

Blood pressure directly correlates with blood viscosity in diabetes type 1 children but not in normals.

PubMed

Vázquez, Beatriz Y Salazar; Vázquez, Miguel A Salazar; Jáquez, Manuel Guajardo; Huemoeller, Antonio H Bracho; Intaglietta, Marcos; Cabrales, Pedro

2010-01-01

To determine the relationship between mean arterial blood pressure (MAP) and blood viscosity in diabetic type 1 children and healthy controls to investigate whether MAP is independent of blood viscosity in healthy children, and vice versa. Children with diabetes type 1 treated by insulin injection were studied. Controls were healthy children of both sexes. MAP was calculated from systolic and diastolic pressure measurements. Blood viscosity was determined indirectly by measuring blood hemoglobin (Hb) content. The relationship between Hb, hematocrit (Hct) and blood viscosity was determined in a subgroup of controls and diabetics selected at random. 21 (10.6+/-2.5 years) type 1 diabetic children treated with insulin and 25 healthy controls age 9.6+/-1.7 years were studied. Hb was 13.8+/-0.8 g/dl in normal children vs. 14.3+/-0.9 g/dl in the diabetic group (p<0.05). MAP was 71.4+/-8.2 in the normal vs. 82.9+/-7.2 mmHg in the diabetic group (p<0.001). Glucose was 89.3+/-10.6 vs. 202.4+/-87.4 mg/dl respectively. Diabetics had a positive MAP/Hb correlation (p=0.007), while normals showed a non significant (p=0.2) negative correlation. The blood viscosity/Hb relationship was studied in a subgroup of 8 healthy controls and 8 diabetic type 1 children. There was no significant difference in Hb and Hct between groups. Diabetics showed a trend of increasing blood viscosity (+7%, p=0.15). Normal children compensate for the increase in vascular resistance due to increased blood viscosity (increased Hb and Hct) while diabetic children do not, probably due to endothelial dysfunction.

Near-wall k-epsilon turbulence modeling

NASA Technical Reports Server (NTRS)

Mansour, N. N.; Kim, J.; Moin, P.

1987-01-01

The flow fields from a turbulent channel simulation are used to compute the budgets for the turbulent kinetic energy (k) and its dissipation rate (epsilon). Data from boundary layer simulations are used to analyze the dependence of the eddy-viscosity damping-function on the Reynolds number and the distance from the wall. The computed budgets are used to test existing near-wall turbulence models of the k-epsilon type. It was found that the turbulent transport models should be modified in the vicinity of the wall. It was also found that existing models for the different terms in the epsilon-budget are adequate in the region from the wall, but need modification near the wall. The channel flow is computed using a k-epsilon model with an eddy-viscosity damping function from the data and no damping functions in the epsilon-equation. These computations show that the k-profile can be adequately predicted, but to correctly predict the epsilon-profile, damping functions in the epsilon-equation are needed.

Uniqueness of solutions for Keller-Segel system of porous medium type coupled to fluid equations

NASA Astrophysics Data System (ADS)

Bae, Hantaek; Kang, Kyungkeun; Kim, Seick

2018-04-01

We prove the uniqueness of Hölder continuous weak solutions via duality argument and vanishing viscosity method for the Keller-Segel system of porous medium type equations coupled to the Stokes system in dimensions three. An important step is the estimate of the Green function of parabolic equations with lower order terms of variable coefficients, which seems to be of independent interest.

A comparative study of high-viscosity cement percutaneous vertebroplasty vs. low-viscosity cement percutaneous kyphoplasty for treatment of osteoporotic vertebral compression fractures.

PubMed

Sun, Kai; Liu, Yang; Peng, Hao; Tan, Jun-Feng; Zhang, Mi; Zheng, Xian-Nian; Chen, Fang-Zhou; Li, Ming-Hui

2016-06-01

The clinical effects of two different methods-high-viscosity cement percutaneous vertebroplasty (PVP) and low-viscosity cement percutaneous kyphoplasty (PKP) in the treatment of osteoporotic vertebral compression fractures (OVCFs) were investigated. From June 2010 to August 2013, 98 cases of OVCFs were included in our study. Forty-six patients underwent high-viscosity PVP and 52 patients underwent low-viscosity PKP. The occurrence of cement leakage was observed. Pain relief and functional activity were evaluated using the Visual Analog Scale (VAS) and Oswestry Disability Index (ODI), respectively. Restoration of the vertebral body height and angle of kyphosis were assessed by comparing preoperative and postoperative measurements of the anterior heights, middle heights and the kyphotic angle of the fractured vertebra. Nine out of the 54 vertebra bodies and 11 out of the 60 vertebra bodies were observed to have cement leakage in the high-viscosity PVP and low-viscosity PKP groups, respectively. The rate of cement leakage, correction of anterior vertebral height and kyphotic angles showed no significant differences between the two groups (P>0.05). Low-viscosity PKP had significant advantage in terms of the restoration of middle vertebral height as compared with the high-viscosity PVP (P<0.05). Both groups showed significant improvements in pain relief and functional capacity status after surgery (P<0.05). It was concluded that high-viscosity PVP and low-viscosity PKP have similar clinical effects in terms of the rate of cement leakage, restoration of the anterior vertebral body height, changes of kyphotic angles, functional activity, and pain relief. Low-viscosity PKP is better than high-viscosity PVP in restoring the height of the middle vertebra.

Thermal therapy in urologic systems: a comparison of arrhenius and thermal isoeffective dose models in predicting hyperthermic injury.

PubMed

He, Xiaoming; Bhowmick, Sankha; Bischof, John C

2009-07-01

The Arrhenius and thermal isoeffective dose (TID) models are the two most commonly used models for predicting hyperthermic injury. The TID model is essentially derived from the Arrhenius model, but due to a variety of assumptions and simplifications now leads to different predictions, particularly at temperatures higher than 50 degrees C. In the present study, the two models are compared and their appropriateness tested for predicting hyperthermic injury in both the traditional hyperthermia (usually, 43-50 degrees C) and thermal surgery (or thermal therapy/thermal ablation, usually, >50 degrees C) regime. The kinetic parameters of thermal injury in both models were obtained from the literature (or literature data), tabulated, and analyzed for various prostate and kidney systems. It was found that the kinetic parameters vary widely, and were particularly dependent on the cell or tissue type, injury assay used, and the time when the injury assessment was performed. In order to compare the capability of the two models for thermal injury prediction, thermal thresholds for complete killing (i.e., 99% cell or tissue injury) were predicted using the models in two important urologic systems, viz., the benign prostatic hyperplasia tissue and the normal porcine kidney tissue. The predictions of the two models matched well at temperatures below 50 degrees C. At higher temperatures, however, the thermal thresholds predicted using the TID model with a constant R value of 0.5, the value commonly used in the traditional hyperthermia literature, are much lower than those predicted using the Arrhenius model. This suggests that traditional use of the TID model (i.e., R=0.5) is inappropriate for predicting hyperthermic injury in the thermal surgery regime (>50 degrees C). Finally, the time-temperature relationships for complete killing (i.e., 99% injury) were calculated and analyzed using the Arrhenius model for the various prostate and kidney systems.

Which side of the balance determines the frequency of vaso-occlusive crises in children with sickle cell anemia: Blood viscosity or microvascular dysfunction?

PubMed

Charlot, Keyne; Romana, Marc; Moeckesch, Berenike; Jumet, Stéphane; Waltz, Xavier; Divialle-Doumdo, Lydia; Hardy-Dessources, Marie-Dominique; Petras, Marie; Tressières, Benoît; Tarer, Vanessa; Hue, Olivier; Etienne-Julan, Maryse; Antoine-Jonville, Sophie; Connes, Philippe

2016-01-01

Vascular resistance and tissue perfusion may be both affected by impaired vascular function and increased blood viscosity. Little is known about the effects of vascular function on the occurrence of painful vaso-occlusive crises (VOC) in children with sickle cell anemia (SCA). The aim of the present study was to determine which side of the balance (blood viscosity or vascular function) is the most deleterious in SCA and increases the risk for frequent hospitalized VOC. Microvascular function, microcirculatory oxygenation and blood viscosity were determined in a group of 22 SCA children/adolescents at steady state and a group of 13 healthy children/adolescents. Univariate analyses demonstrated blunted microvascular reactivity during local thermal heating test and decreased microcirculatory oxygenation in SCA children compared to controls. Multivariate analysis revealed that increased blood viscosity and decreased microcirculatory oxygenation were independent risk factors of frequent VOC in SCA. In contrast, the level of microvascular dysfunction does not predict VOC rate. In conclusion, increased blood viscosity is usually well supported in healthy individuals where vascular function is not impaired. However, in the context of SCA, microvascular function is impaired and any increase of blood viscosity or decrease in microcirculatory oxygenation would increase the risks for frequent VOC. Copyright © 2015 Elsevier Inc. All rights reserved.

Temperature dependence of feedyard ammonia emissions: The Arrhenius equation

USDA-ARS?s Scientific Manuscript database

Ammonia emissions from beef cattle feedyards exhibit an annual pattern-like temperature. This suggests that ammonia emissions may obey the Arrhenius temperature relationship. Our objective was to determine the Arrhenius relationship between mean monthly ammonia emissions from cattle feedyards and me...

Properties of Particle Size Distribution from Milled White Nixtamalized Corn Kernels as a Function of Steeping Time

PubMed Central

Fernández-Muñoz, J. L.; Zapata-Torrez, M.; Márquez-Herrera, A.; Sánchez-Sinencio, F.; Mendoza-Álvarez, J. G.; Meléndez-Lira, M.; Zelaya-Ángel, O.

2016-01-01

This paper focuses on the particle size distribution (PSD) changes during nixtamalized corn kernels (NCK) as a function of the steeping time (ST). The process to obtain powder or corn flour from NCK was as follows: (i) the NCK with different STs were wet-milled in a stone mill, (ii) dehydrated by a Flash type dryer, and (iii) pulverized with a hammer mill and sieved with a 20 mesh. The powder was characterized by measuring the PSD percentage, calcium percentage (CP), peak viscosity at 90°C (PV), and crystallinity percentage (CP). The PSD of the powder as a function of ST was determined by sieving in Ro-TAP equipment. By sieving, five fractions of powder were obtained employing meshes 30, 40, 60, 80, and 100. The final weight of the PSD obtained from the sieving process follows a Gaussian profile with the maximum corresponding to the average particle obtained with mesh 60. The calcium percentage as a function of ST follows a behavior similar to the weight of the PSD. The study of crystallinity versus the mesh number shows that it decreases for smaller mesh number. A similar behavior is observed as steeping time increases, except around ST = 8 h where the gelatinization of starch is observed. The trend of increasing viscosity values of the powder samples occurs when increasing ST and decreasing particle size. The ST significantly changes the crystallinity and viscosity values of the powder and, in both cases, a minimum value is observed in the region 7–9 h. The experimental results show that the viscosity increases (decreases) if the particle size decreases (increases). PMID:27375921

A Classical Phase Space Framework For the Description of Supercooled Liquids and an Apparent Universal Viscosity Collapse

NASA Astrophysics Data System (ADS)

Weingartner, Nicholas; Pueblo, Chris; Nogueira, Flavio; Kelton, Kenneth; Nussinov, Zohar

A fundamental understanding of the phenomenology of the metastable supercooled liquid state remains elusive. Two of the most pressing questions in this field are how to describe the temperature dependence of the viscosity, and determine whether or not the dynamical behaviors are universal. To address these questions, we have devised a simple first-principles classical phase space description of supercooled liquids that (along with a complementary quantum approach) predicts a unique functional form for the viscosity which relies on only a single parameter. We tested this form for 45 liquids of all types and fragilities, and have demonstrated that it provides a statistically significant fit to all liquids. Additionally, by scaling the viscosity of all studied liquids using the single parameter, we have observed a complete collapse of the data of all 45 liquids to a single scaling curve over 16 decades, suggesting an underlying universality in the dynamics of supercooled liquids. In this talk I will outline the basic approach of our model, as well as demonstrate the quality of the model performance and collapse of the data.

A nanoscale perspective on the effects of transverse microprestress on drying creep of nanoporous solids

NASA Astrophysics Data System (ADS)

Sinko, Robert; Bažant, Zdeněk P.; Keten, Sinan

2018-01-01

The Pickett effect describes the excess non-additive strain developed during drying of a nanoporous solid material under creep. One explanation for its origins, developed using micromechanical models, is the progressive relaxation of internally developed microprestress. However, these models have not explicitly considered the effects of this microprestress on nanoscale energy barriers that govern the relative motion and displacement between nanopore walls during deformation. Here, we evaluate the nanoscale effects of transverse microprestresses on the drying creep behaviour of a nanoscale slit pore using coarse-grained molecular dynamics. We find that the underlying energy barrier depends exponentially on the transverse microprestress, which is attributed to changes in the effective viscosity and degree of nanoconfinement of molecules in the water interlayer. Specifically, as the transverse microprestress is relaxed (i.e. its magnitude decreases), the activation energy barrier is reduced, thereby leading to an acceleration of the creep behaviour and a stronger Pickett effect. Based on our simulation results, we introduce a new microprestress-dependent energy term into our existing Arrhenius model, which describes the relative displacement of pore walls as a function of the underlying activation energy barriers. Our findings further verify the existing micromechanical theories for the origin of the Pickett effect and establish a quantitative relationship between the transverse microprestress and the intensity of the Pickett effect.

Characterization of rheological and structural properties of a gum from Balangu seeds.

PubMed

Salehi, Mohammad; Tabarsa, Mehdi; Amraie, Milad; Anvari, Mohammad; Rezaei, Masoud; Smith, Brennan M

2018-05-07

With the growing interest in all-natural foods, there has been increased study of sustainable natural sources of polysaccharides with suitable functional properties. Lallemantia royleana seed polysaccharide is one such material. Water-soluble polysaccharides were isolated from L. royleana seed to evaluate their chemical structure and rheological properties. The polysaccharide was consisted of neutral (62.9% w/w) and acidic (16.7% w/w) sugars. The backbone of the isolated rhamnoarabinogalactan was composed of (1 → 4)-linked galactopyranose residues. The weight average molecular weight (M w ) of the polysaccharide was 0.777 × 10 6  g/mol. Rheological behavior of extracted gum was studied at different concentrations (0.1-2.0%; w/v) and temperatures of 5-50 °C. The extracted gum showed typical non-Newtonian and shear thinning behavior at all concentrations and temperatures. However, higher apparent viscosity was observed with increasing gum concentration or decreasing temperature. The quantification of flow activation energy using Arrhenius model showed a decrease from 29,931 to 8339 kJ/mol -1 . The mechanical spectra indicated viscoelastic behavior of the gum in all samples. Dynamic moduli increased with increased frequency and G' was always greater than G″, indicating a weak gel system. The results of this study will help to increase potential applications of L. royleana polysaccharide in various food formulations. Copyright © 2017. Published by Elsevier B.V.

Seismic Rheological Model and Reflection Coefficients of the Brittle-Ductile Transition

NASA Astrophysics Data System (ADS)

Carcione, José M.; Poletto, Flavio

2013-12-01

It is well established that the upper—cooler—part of the crust is brittle, while deeper zones present ductile behaviour. In some cases, this brittle-ductile transition is a single seismic reflector with an associated reflection coefficient. We first develop a stress-strain relation including the effects of crust anisotropy, seismic attenuation and ductility in which deformation takes place by shear plastic flow. Viscoelastic anisotropy is based on the eigenstrain model and the Zener and Burgers mechanical models are used to model the effects of seismic attenuation, velocity dispersion, and steady-state creep flow, respectively. The stiffness components of the brittle and ductile media depend on stress and temperature through the shear viscosity, which is obtained by the Arrhenius equation and the octahedral stress criterion. The P- and S-wave velocities decrease as depth and temperature increase due to the geothermal gradient, an effect which is more pronounced for shear waves. We then obtain the reflection and transmission coefficients of a single brittle-ductile interface and of a ductile thin layer. The PP scattering coefficient has a Brewster angle (a sign change) in both cases, and there is substantial PS conversion at intermediate angles. The PP coefficient is sensitive to the layer thickness, unlike the SS coefficient. Thick layers have a well-defined Brewster angle and show higher reflection amplitudes. Finally, we compute synthetic seismograms in a homogeneous medium as a function of temperature.

Acoustic and sonochemical methods for altering the viscosity of oil during recovery and pipeline transportation.

PubMed

Abramov, Vladimir O; Abramova, Anna V; Bayazitov, Vadim M; Mullakaev, Marat S; Marnosov, Alexandr V; Ildiyakov, Alexandr V

2017-03-01

Reduction of oil viscosity is of great importance for the petroleum industry since it contributes a lot to the facilitation of pipeline transportation of oil. This study analyzes the capability of acoustic waves to decrease the viscosity of oil during its commercial production. Three types of equipment were tested: an ultrasonic emitter that is located directly in the well and affects oil during its production and two types of acoustic machines to be located at the wellhead and perform acoustic treatment after oil extraction: a setup for ultrasonic hydrodynamic treatment and a flow-through ultrasonic reactor. In our case, the two acoustic machines were rebuilt and tested in the laboratory. The viscosity of oil was measured before and after both types of acoustic treatment; and 2, 24 and 48h after ultrasonic treatment and 1 and 4h after hydrodynamic treatment in order to estimate the constancy of viscosity reduction. The viscosity reduction achieved by acoustic waves was compared to the viscosity reduction achieved by acoustic waves jointly with solvents. It was shown, that regardless of the form of powerful acoustic impact, a long lasting decrease in viscosity can be obtained only if sonochemical treatment is used. Using sonochemical treatment based on ultrasonic hydrodynamic treatment a viscosity reduction by 72,46% was achieved. However, the reduction in viscosity by 16%, which was demonstrated using the ultrasonic downhole tool in the well without addition of chemicals, is high enough to facilitate the production of viscous hydrocarbons. Copyright © 2016 Elsevier B.V. All rights reserved.

Estimating Arrhenius parameters using temperature programmed molecular dynamics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Imandi, Venkataramana; Chatterjee, Abhijit, E-mail: abhijit@che.iitb.ac.in

2016-07-21

Kinetic rates at different temperatures and the associated Arrhenius parameters, whenever Arrhenius law is obeyed, are efficiently estimated by applying maximum likelihood analysis to waiting times collected using the temperature programmed molecular dynamics method. When transitions involving many activated pathways are available in the dataset, their rates may be calculated using the same collection of waiting times. Arrhenius behaviour is ascertained by comparing rates at the sampled temperatures with ones from the Arrhenius expression. Three prototype systems with corrugated energy landscapes, namely, solvated alanine dipeptide, diffusion at the metal-solvent interphase, and lithium diffusion in silicon, are studied to highlight variousmore » aspects of the method. The method becomes particularly appealing when the Arrhenius parameters can be used to find rates at low temperatures where transitions are rare. Systematic coarse-graining of states can further extend the time scales accessible to the method. Good estimates for the rate parameters are obtained with 500-1000 waiting times.« less

The effect of glycosaminoglycan enzymes and proteases on the viscosity of alpaca seminal plasma and sperm function.

PubMed

Kershaw-Young, C M; Stuart, C; Evans, G; Maxwell, W M C

2013-05-01

In order to advance the development of cryopreservation and other assisted reproductive technologies in camelids it is necessary to eliminate the viscous component of the seminal plasma without impairing sperm function. It has been postulated that glycosaminoglycans (GAGs) or proteoglycans are responsible for this viscosity. This study investigated the effect of the GAG enzymes hyaluronidase, chondroitinase ABC and keratanase and the proteases papain and proteinase K on seminal plasma viscosity and sperm function in order to aid identification of the cause of seminal plasma viscosity and propose methods for the reduction of viscosity. Sperm motility, DNA integrity, acrosome integrity and viability were assessed during 2h incubation. All enzymes reduced seminal plasma viscosity compared to control (P<0.001) although papain was most effective, completely eliminating viscosity within 30 min of treatment. Sperm motility and DNA integrity was not affected by enzyme treatment. The proportion of viable, acrosome intact sperm was reduced in all enzyme treated samples except those treated with papain (P<0.001). These findings suggest that proteins, not GAGs are the main cause of alpaca seminal plasma viscosity. Papain treatment of alpaca semen may be a suitable technique for reduction of seminal plasma viscosity prior to sperm cryopreservation. Copyright © 2013 Elsevier B.V. All rights reserved.

A new method to simulate the effects of viscous fingering on miscible displacement processes in porous media

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vossoughi, S.; Green, D.W.; Smith, J.E.

Dispersion and viscous fingering are important parameters in miscible displacement. Effects of dispersion on concentration profiles in porous media can be simulated when the viscosity ratio is favorable. The capability to simulate viscous fingering is limited. This paper presents a new method to simulate effects of viscous fingering on miscible displacement processes in porous media. The method is based on the numerical solution of a general form of the convection-dispersion equation. In this equation the convection term is represented by a fractional flow function. The fractional flow function is derived from Darcy's law by using a concentration-dependent average viscosity andmore » relative flow area to each fluid at any point in the bed. The method was extended to the description of a polymer flood by including retention and inaccessible PV. A Langmuir-type model for polymer retention in the rock was used. The resulting convection-dispersion equation for displacement by polymer was solved numerically by the use of a finite-element method with linear basis functions and Crank-Nicholson derivative approximation. History matches were performed on four sets of laboratory data to verify the model: (1) an unfavorable viscosity ratio displacement, (2) stable displacement of glycerol by polymer solution, (3) unstable displacement of brine by a slug of polymer solution, and (4) a favorable viscosity ratio displacement. In general, computed results from the model matched laboratory data closely. Good agreement of the model with experiments over a significant range of variables lends support to the analysis.« less

Determination of the Arrhenius Activation Energy Using a Temperature-Programmed Flow Reactor.

ERIC Educational Resources Information Center

Chan, Kit-ha C.; Tse, R. S.

1984-01-01

Describes a novel method for the determination of the Arrhenius activation energy, without prejudging the validity of the Arrhenius equation or the concept of activation energy. The method involves use of a temperature-programed flow reactor connected to a concentration detector. (JN)

Arrhenius equation for modeling feedyard ammonia emissions using temperature and diet crude protein

USDA-ARS?s Scientific Manuscript database

Temperature controls many processes of ammonia volatilization. For example, urea hydrolysis is an enzymatically catalyzed reaction described by the Arrhenius equation. Diet crude protein (CP) controls ammonia emission by affecting N excretion. Objectives were to use the Arrhenius equation to model a...

Fragility correlates thermodynamic and kinetic properties of glass forming liquids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reddy, C.Narayana; Viswanatha, R.; Chethana, B.K.

2015-03-15

Graphical abstract: The suggested new fragility parameter correlates viscosity and configurational entropy. - Highlights: • A new fragility function, F=ΔT/ΔC{sub p}×C{sub p}{sup l}/T{sub g} has been proposed. • A three parameter viscosity function using the new F reproduces Angell fragility plot. • A new ΔC{sub p} function is derived which directly relates Adam–Gibbs function with the fragility based viscosity function. - Abstract: In our earlier communication we proposed a simple fragility determining function, ([NBO]/V{sub m}{sup 3}T{sub g}), which we have now used to analyze several glass systems using available thermal data. A comparison with similar fragility determining function, ΔC{sub p}/C{submore » p}{sup l}, introduced by Chryssikos et al. in their investigation of lithium borate glasses has also been performed and found to be more convenient quantity for discussing fragilities. We now propose a new function which uses both ΔC{sub p} and ΔT and which gives a numerical fragility parameter, F whose value lies between 0 and 1 for glass forming liquids. F can be calculated through the use of measured thermal parameters ΔC{sub p}, C{sub p}{sup l}, T{sub g} and T{sub m}. Use of the new fragility values in reduced viscosity equation reproduces the whole range of viscosity curves of the Angell plot. The reduced viscosity equation can be directly compared with the Adam–Gibbs viscosity equation and a heat capacity function can be formulated which reproduces satisfactorily the ΔC{sub p} versus ln(T{sub r}) curves and hence the configurational entropy.« less

The effect of hydroxyl functional groups and molar mass on the viscosity of non-crystalline organic and organic-water particles

NASA Astrophysics Data System (ADS)

Grayson, James W.; Evoy, Erin; Song, Mijung; Chu, Yangxi; Maclean, Adrian; Nguyen, Allena; Upshur, Mary Alice; Ebrahimi, Marzieh; Chan, Chak K.; Geiger, Franz M.; Thomson, Regan J.; Bertram, Allan K.

2017-07-01

The viscosities of three polyols and three saccharides, all in the non-crystalline state, have been studied. Two of the polyols (2-methyl-1,4-butanediol and 1,2,3-butanetriol) were studied under dry conditions, the third (1,2,3,4-butanetetrol) was studied as a function of relative humidity (RH), including under dry conditions, and the saccharides (glucose, raffinose, and maltohexaose) were studied as a function of RH. The mean viscosities of the polyols under dry conditions range from 1.5 × 10-1 to 3.7 × 101 Pa s, with the highest viscosity being that of the tetrol. Using a combination of data determined experimentally here and literature data for alkanes, alcohols, and polyols with a C3 to C6 carbon backbone, we show (1) there is a near-linear relationship between log10 (viscosity) and the number of hydroxyl groups in the molecule, (2) that on average the addition of one OH group increases the viscosity by a factor of approximately 22 to 45, (3) the sensitivity of viscosity to the addition of one OH group is not a strong function of the number of OH functional groups already present in the molecule up to three OH groups, and (4) higher sensitivities are observed when the molecule has more than three OH groups. Viscosities reported here for 1,2,3,4-butanetetrol particles are lower than previously reported measurements using aerosol optical tweezers, and additional studies are required to resolve these discrepancies. For saccharide particles at 30 % RH, viscosity increases by approximately 2-5 orders of magnitude as molar mass increases from 180 to 342 g mol-1, and at 80 % RH, viscosity increases by approximately 4-5 orders of magnitude as molar mass increases from 180 to 991 g mol-1. These results suggest oligomerization of highly oxidized compounds in atmospheric secondary organic aerosol (SOA) could lead to large increases in viscosity, and may be at least partially responsible for the high viscosities observed in some SOA. Finally, two quantitative structure-property relationship models (Sastri and Rao, 1992; Marrero-Morejón and Pardillo-Fontdevila, 2000) were used to predict the viscosity of alkanes, alcohols, and polyols with a C3-C6 carbon backbone. Both models show reasonably good agreement with measured viscosities for the alkanes, alcohols, and polyols studied here except for the case of a hexol, the viscosity of which is underpredicted by 1-3 orders of magnitude by each of the models.

Investigating mixing and emptying for aqueous liquid content from the stomach using a coupled biomechanical-SPH model.

PubMed

Harrison, Simon M; Cleary, Paul W; Sinnott, Matthew D

2018-05-18

The stomach is a critical organ for food digestion but it is not well understood how it operates, either when healthy or when dysfunction occurs. Stomach function depends on the timing and amplitude of wall contractions, the fill level and the type of gastric content. Using a coupled biomechanical-Smoothed Particle Hydrodynamics (B-SPH) model, we investigate how gastric discharge is affected by the contraction behaviour of the stomach wall and the viscosity of the content. The results of the model provide new insights into how the content viscosity and the number of compression waves down the length of the stomach affect the mixing within and the discharge rate of the content exiting from the stomach to the duodenum. This investigation shows that the B-SPH model is capable of simulating complicated stomach behaviour. The rate of gastric emptying is found to increase with a smaller period in between contractile waves and to have a nonlinear relationship with content viscosity. Increased resistance to flow into the duodenum is also shown to reduce the rate of emptying. The degree of gastric mixing is found to be insensitive to changes in the period between contractile waves for fluid with a viscosity of water but to be substantially affected by the viscosity of the gastric content.

Mineral Bionization - Surface Chemical Modeling of the Emergence of Life

NASA Astrophysics Data System (ADS)

Arrhenius, G.

2001-12-01

The earliest stages in entering an RNA-world require natural mechanisms that are capable of selective concentration of simple aldehydes from dilute solution in the environment (4), furthermore phosphorylation of the sequestered aldehydes (2) and their catalytic condensation to form, selectively, tetrose- (threose) or pentose- (ribose) phosphate (3); the latter representing the R in RNA. A variety of common positively charged sheet structure minerals (mixed valence double layer metal hydroxide minerals such as hydrotalcite and green rust) have proven to be remarkably capable of performing these crucial tasks under simplified natural conditions (1). These prebiotic model reactions have demonstrated plausible closure of the gap, previously thought to preclude the natural formation of nucleoside phosphates, the backbone components of the information carrying genetic material. Pioneering research by other workers (5) has demonstrated the feasibility of necessary further steps in the chain toward functional RNA; mineral (montmorillonite) catalyzed oligomerization of nucleotides, the formation of complementary RNA strands (6) and the enzymatic activity of RNA (ribozymes). These contributions have placed the initially conjectural concept of an initial RNA-world on an experimental footing. Remaining problems include the initial transfer of information to spontaneously forming RNA, sufficient to convey biofunctionallity (7). Also in this central problem mineral surface interactions may be speculated to play a natural role; a question that is open to experimental verification. References. 1. Pitsch, S.; Eschenmoser, A.; Gedulin, B.; Hui, S. and Arrhenius, G. Origins Life Evol. Biosphere, 1994, 24 (5), 389. 2. Kolb, V.; Zhang, S.; Xu, Y.; Arrhenius, G. Origins Life Evol. Biosphere, 1997, 27, 485. 3. Krishnamurthy, R.; Pitsch, S.; Arrhenius, G. Origins Life Evol. Biosphere, Origins Life Evol. Biosphere 1999, 29, 139 4. Pitsch, S.; Krishnamurthy, R.; Arrhenius, G. Helv. Chim. Acta. 2000, 83, 2398. 5. Ferris, J. P.; Ertem, G. J. J. Am. Chem. Soc. 1993, 115, 1270. 6. Orgel ,L.E. J. Theoretical Biol. 1986, 123, 127-149 7. Arrhenius, G; Life out of Chaos. In Palyi et al. eds. Fundamentals of Life, Elsevier, Paris, 2001

Modeling the rheological behavior of thermosonic extracted guava, pomelo, and soursop juice concentrates at different concentration and temperature using a new combination model

PubMed Central

Abdullah, Norazlin; Yusof, Yus A.; Talib, Rosnita A.

2017-01-01

Abstract This study has modeled the rheological behavior of thermosonic extracted pink‐fleshed guava, pink‐fleshed pomelo, and soursop juice concentrates at different concentrations and temperatures. The effects of concentration on consistency coefficient (K) and flow behavior index (n) of the fruit juice concentrates was modeled using a master curve which utilized the concentration‐temperature shifting to allow a general prediction of rheological behaviors covering a wide concentration. For modeling the effects of temperature on K and n, the integration of two functions from the Arrhenius and logistic sigmoidal growth equations has provided a new model which gave better description of the properties. It also alleviated the problems of negative region when using the Arrhenius model alone. The fitted regression using this new model has improved coefficient of determination, R 2 values above 0.9792 as compared to using the Arrhenius and logistic sigmoidal models alone, which presented minimum R 2 of 0.6243 and 0.9440, respectively. Practical applications In general, juice concentrate is a better form of food for transportation, preservation, and ingredient. Models are necessary to predict the effects of processing factors such as concentration and temperature on the rheological behavior of juice concentrates. The modeling approach allows prediction of behaviors and determination of processing parameters. The master curve model introduced in this study simplifies and generalized rheological behavior of juice concentrates over a wide range of concentration when temperature factor is insignificant. The proposed new mathematical model from the combination of the Arrhenius and logistic sigmoidal growth models has improved and extended description of rheological properties of fruit juice concentrates. It also solved problems of negative values of consistency coefficient and flow behavior index prediction using existing model, the Arrhenius equation. These rheological data modeling provide good information for the juice processing and equipment manufacturing needs. PMID:29479123

Dynamic topography and gravity anomalies for fluid layers whose viscosity varies exponentially with depth

NASA Technical Reports Server (NTRS)

Revenaugh, Justin; Parsons, Barry

1987-01-01

Adopting the formalism of Parsons and Daly (1983), analytical integral equations (Green's function integrals) are derived which relate gravity anomalies and dynamic boundary topography with temperature as a function of wavenumber for a fluid layer whose viscosity varies exponentially with depth. In the earth, such a viscosity profile may be found in the asthenosphere, where the large thermal gradient leads to exponential decrease of viscosity with depth, the effects of a pressure increase being small in comparison. It is shown that, when viscosity varies rapidly, topography kernels for both the surface and bottom boundaries (and hence the gravity kernel) are strongly affected at all wavelengths.

SQUID picovoltometry of single crystal Bi2Sr2CaCu2O(8+delta) - Observation of the crossover from high-temperature Arrhenius to low-temperature vortex-glass behavior

NASA Astrophysics Data System (ADS)

Safar, H.; Gammel, P. L.; Bishop, D. J.; Mitzi, D. B.; Kapitulnik, A.

1992-04-01

A SQUID voltmeter has been used to measure current-voltage curves in untwinned crystals of Bi2Sr2CaCu2O(8+delta) as a function of temperature and magnetic field. The data show a clear crossover from high-temperature Arrhenius behavior to a critical region associated with the low-temperature three-dimensional vortex-glass phase transition. The critical exponents v(z - 1) = 7 +/- 1 in this system are in accord with theoretical models and previous measurements in YBa2Cu3O7. The width of the critical region collapses below 2 T, reflecting the changing role of dimensionality with field.

A comprehensive model to determine the effects of temperature and species fluctuations on reaction rates in turbulent reacting flows

NASA Technical Reports Server (NTRS)

Foy, E.; Ronan, G.; Chinitz, W.

1982-01-01

A principal element to be derived from modeling turbulent reacting flows is an expression for the reaction rates of the various species involved in any particular combustion process under consideration. A temperature-derived most-likely probability density function (pdf) was used to describe the effects of temperature fluctuations on the Arrhenius reaction rate constant. A most-likely bivariate pdf described the effects of temperature and species concentrations fluctuations on the reaction rate. A criterion is developed for the use of an "appropriate" temperature pdf. The formulation of models to calculate the mean turbulent Arrhenius reaction rate constant and the mean turbulent reaction rate is considered and the results of calculations using these models are presented.

Application of SH surface acoustic waves for measuring the viscosity of liquids in function of pressure and temperature.

PubMed

Kiełczyński, P; Szalewski, M; Balcerzak, A; Rostocki, A J; Tefelski, D B

2011-12-01

Viscosity measurements were carried out on triolein at pressures from atmospheric up to 650 MPa and in the temperature range from 10°C to 40°C using ultrasonic measuring setup. Bleustein-Gulyaev SH surface acoustic waves waveguides were used as viscosity sensors. Additionally, pressure changes occurring during phase transition have been measured over the same temperature range. Application of ultrasonic SH surface acoustic waves in the liquid viscosity measurements at high pressure has many advantages. It enables viscosity measurement during phase transitions and in the high-pressure range where the classical viscosity measurement methods cannot operate. Measurements of phase transition kinetics and viscosity of liquids at high pressures and various temperatures (isotherms) is a novelty. The knowledge of changes in viscosity in function of pressure and temperature can help to obtain a deeper insight into thermodynamic properties of liquids. Copyright © 2011 Elsevier B.V. All rights reserved.

On the penetration of a hot diapir through a strongly temperature-dependent viscosity medium

NASA Technical Reports Server (NTRS)

Daly, S. F.; Raefsky, A.

1985-01-01

The ascent of a hot spherical body through a fluid with a strongly temperature-dependent viscosity has been studied using an axisymmetric finite element method. Numerical solutions range over Peclet numbers of 0.1 - 1000 from constant viscosity up to viscosity variations of 100,000. Both rigid and stress-free boundary conditions were applied at the surface of the sphere. The dependence of drag on viscosity variation was shown to have no dependence on the stress boundary condition except for a Stokes flow scaling factor. A Nusselt number parameterization based on the stress-free constant viscosity functional dependence on the Peclet number scaled by a parameter depending on the viscosity structure fits both stress-free and rigid boundary condition data above viscosity variations of 100. The temperature scale height was determined as a function of sphere radius. For the simple physical model studied in this paper pre-heating is required to reduce the ambient viscosity of the country rock to less than 10 to the 22nd sq cm/s in order for a 10 km diapir to penetrate a distance of several radii.

Pressure Modeling of Char-Forming and Laminated Materials.

DTIC Science & Technology

1983-06-01

flame spread rates for various types of materials. For instance, the PMMA fuel used for the laminated wall fires in the present study has a pyroly - sis...thermal conduction and pyroly - sis with one-step Arrhenius kinetics. This numerical procedure is documented in detail in Appendix A, which is taken from

Symmetric flows for compressible heat-conducting fluids with temperature dependent viscosity coefficients

NASA Astrophysics Data System (ADS)

Wan, Ling; Wang, Tao

2017-06-01

We consider the Navier-Stokes equations for compressible heat-conducting ideal polytropic gases in a bounded annular domain when the viscosity and thermal conductivity coefficients are general smooth functions of temperature. A global-in-time, spherically or cylindrically symmetric, classical solution to the initial boundary value problem is shown to exist uniquely and converge exponentially to the constant state as the time tends to infinity under certain assumptions on the initial data and the adiabatic exponent γ. The initial data can be large if γ is sufficiently close to 1. These results are of Nishida-Smoller type and extend the work (Liu et al. (2014) [16]) restricted to the one-dimensional flows.

Characterization of oscillator circuits for monitoring the density-viscosity of liquids by means of piezoelectric MEMS microresonators

NASA Astrophysics Data System (ADS)

Toledo, J.; Ruiz-Díez, V.; Pfusterschmied, G.; Schmid, U.; Sánchez-Rojas, J. L.

2017-06-01

Real-time monitoring of the physical properties of liquids, such as lubricants, is a very important issue for the automotive industry. For example, contamination of lubricating oil by diesel soot has a significant impact on engine wear. Resonant microstructures are regarded as a precise and compact solution for tracking the viscosity and density of lubricant oils. In this work, we report a piezoelectric resonator, designed to resonate with the 4th order out-of-plane modal vibration, 15-mode, and the interface circuit and calibration process for the monitoring of oil dilution with diesel fuel. In order to determine the resonance parameters of interest, i.e. resonant frequency and quality factor, an interface circuit was implemented and included within a closed-loop scheme. Two types of oscillator circuits were tested, a Phase-Locked Loop based on instrumentation, and a more compact version based on discrete electronics, showing similar resolution. Another objective of this work is the assessment of a calibration method for piezoelectric MEMS resonators in simultaneous density and viscosity sensing. An advanced calibration model, based on a Taylor series of the hydrodynamic function, was established as a suitable method for determining the density and viscosity with the lowest calibration error. Our results demonstrate the performance of the resonator in different oil samples with viscosities up to 90 mPa•s. At the highest value, the quality factor measured at 25°C was around 22. The best resolution obtained was 2.4•10-6 g/ml for the density and 2.7•10-3 mPa•s for the viscosity, in pure lubricant oil SAE 0W30 at 90°C. Furthermore, the estimated density and viscosity values with the MEMS resonator were compared to those obtained with a commercial density-viscosity meter, reaching a mean calibration error in the best scenario of around 0.08% for the density and 3.8% for the viscosity.

Effect of polycarboxylate ether comb-type polymer on viscosity and interfacial properties of kaolinite clay suspensions.

PubMed

Zhang, Ling; Lu, Qingye; Xu, Zhenghe; Liu, Qingxia; Zeng, Hongbo

2012-07-15

The interactions between kaolinite clay particles and a comb-type polymer (polycarboxylate ether or PCE), so-called PCE super-plasticizer, were investigated through viscosity and surface forces measurements by a rheometer and a Surface Forces Apparatus (SFA). The addition of PCE shows a strong impact on the viscosity of concentrated kaolinite suspensions in alkaline solutions (pH=8.3) but a weak effect under acidic conditions (pH=3.4). In acidic solutions, the high viscosity measured is attributed to the strong electrostatic interaction between negatively charged basal planes and positively charged edge surfaces of clay particles. Under the alkaline condition, the suspension viscosity was found to first increase significantly and then decrease with increasing PCE dosages. The results from surface forces measurement show that PCE molecules at low dosages can bridge the kaolinite particles in the concentrated suspensions via hydrogen bonding, leading to the formation of a kaolinite-PCE "network" and hence an increased suspension viscosity. At high PCE dosages, clay particles are fully covered by PCE molecules, leading to a more dispersed kaolinite suspensions and hence lower suspension viscosity due to steric repulsion between the adsorbed PCE molecules. The insights derived from measuring viscosity and interfacial properties of kaolinite suspensions containing varying amount of comb-type super-plasticizer PCE at different pH provide the foundation for many engineering applications and optimizing industrial processes. Copyright © 2012 Elsevier Inc. All rights reserved.

Impaired protein conformational landscapes as revealed in anomalous Arrhenius prefactors.

PubMed

Nagel, Zachary D; Dong, Ming; Bahnson, Brian J; Klinman, Judith P

2011-06-28

A growing body of data supports a role for protein motion in enzyme catalysis. In particular, the ability of enzymes to sample catalytically relevant conformational substates has been invoked to model kinetic and spectroscopic data. However, direct experimental links between rapidly interconverting conformations and the chemical steps of catalysis remain rare. We report here on the kinetic analysis and characterization of the hydride transfer step catalyzed by a series of mutant thermophilic alcohol dehydrogenases (ht-ADH), presenting evidence for Arrhenius prefactor values that become enormously elevated above an expected value of approximately 10(13) s(-1) when the enzyme operates below its optimal temperature range. Restoration of normal Arrhenius behavior in the ht-ADH reaction occurs at elevated temperatures. A simple model, in which reduced temperature alters the ability of the ht-ADH variants to sample the catalytically relevant region of conformational space, can reproduce the available data. These findings indicate an impaired landscape that has been generated by the combined condition of reduced temperature and mutation at a single, active-site hydrophobic side chain. The broader implication is that optimal enzyme function requires the maintenance of a relatively smooth landscape that minimizes low energy traps.

Impaired protein conformational landscapes as revealed in anomalous Arrhenius prefactors

PubMed Central

Nagel, Zachary D.; Dong, Ming; Bahnson, Brian J.; Klinman, Judith P.

2011-01-01

A growing body of data supports a role for protein motion in enzyme catalysis. In particular, the ability of enzymes to sample catalytically relevant conformational substates has been invoked to model kinetic and spectroscopic data. However, direct experimental links between rapidly interconverting conformations and the chemical steps of catalysis remain rare. We report here on the kinetic analysis and characterization of the hydride transfer step catalyzed by a series of mutant thermophilic alcohol dehydrogenases (ht-ADH), presenting evidence for Arrhenius prefactor values that become enormously elevated above an expected value of approximately 1013 s-1 when the enzyme operates below its optimal temperature range. Restoration of normal Arrhenius behavior in the ht-ADH reaction occurs at elevated temperatures. A simple model, in which reduced temperature alters the ability of the ht-ADH variants to sample the catalytically relevant region of conformational space, can reproduce the available data. These findings indicate an impaired landscape that has been generated by the combined condition of reduced temperature and mutation at a single, active-site hydrophobic side chain. The broader implication is that optimal enzyme function requires the maintenance of a relatively smooth landscape that minimizes low energy traps. PMID:21670258

The effect of carbon-chain oxygenation in the carbon-carbon dissociation.

PubMed

Dos Santos, Lisandra Paulino; Baptista, Leonardo

2018-06-01

Currently, there is a trend of moving away from the use of fossil fuels to the use of biofuels. This modification changes the molecular structure of gasoline and diesel constituents, which should impact pollutant emissions and engine efficiency. An important property of automotive fuels is the resistance to autoignition. The goal of the present work is to evaluate thermochemical and kinetic parameters that govern the carbon-carbon bond dissociation and relate these parameters, in conjunction with molecular properties, to autoignition resistance. Three model reactions were investigated in the present work: dissociation of ethane, ethanol, and ethanal. All studies were conducted at the multiconfigurational level of theory, and the rate coefficients were evaluated from 300 to 2000 K. The comparison of dissociation energies and Arrhenius expressions indicates that autoignition resistance is related to the kinetic control of dissociation reactions and it is possible to relate the higher octane number of ethanol based fuels to the kinetics parameters of carbon-carbon bond fission. Graphical abstract Effect of the functional group in the Arrhenius parameters of the C-C dissociation. Arrhenius curves calculated at NEVPT2(6,6)/6-311G(2df,2pd).

Chemoviscosity modeling for thermosetting resin systems, 4

NASA Technical Reports Server (NTRS)

Hou, T. H.; Huang, Joan Y. Z.

1989-01-01

An experimental study on the changes of chemorheological properties has been conducted and analyzed on commercial Hercules 3501-6 resin system cured under several isothermal conditions between 375 and 435 K. For the cure temperatures equal to or greater than 385 K, the storage modulus curing curves, G prime (t), exhibited abrupt changes in slope which occurred at various times depending on the curing temperatures and were attributed to the onset of gelation reactions. The crossover points between G prime (t) and G double prime (t) curves were observed for curing temperatures equal to or greater than 400 K. The gelation and the crossover points obtained from the chemorheological measurements, therefore, defined two characteristic resin states during cure. Approximately the same value for the degree of cure was reached by the advancement of the reaction at each of these states. The temperature dependency of the viscosities for the characteristic resin states and the rate constants of increase in moduli at different stages of curing were analyzed. Various G prime (t) and G double prime (t) isothermal curing curves were also shown to be capable of being superimposed on one another by the principle of time-temperature superposition. The resultant shift factors a sub t(t) and a Eta(T) were shown to follow the Arrhenius type relationship. Values of the activation energy suggested that the reaction kinetics, instead of the diffusion mechanism, was the limiting step in the overall resin advancement for the cure at temperatures equal to or greater than 385 K.

Anisotropic Bianchi Type-I and Type-II Bulk Viscous String Cosmological Models Coupled with Zero Mass Scalar Field

NASA Astrophysics Data System (ADS)

Venkateswarlu, R.; Sreenivas, K.

2014-06-01

The LRS Bianchi type-I and type-II string cosmological models are studied when the source for the energy momentum tensor is a bulk viscous stiff fluid containing one dimensional strings together with zero-mass scalar field. We have obtained the solutions of the field equations assuming a functional relationship between metric coefficients when the metric is Bianchi type-I and constant deceleration parameter in case of Bianchi type-II metric. The physical and kinematical properties of the models are discussed in each case. The effects of Viscosity on the physical and kinematical properties are also studied.

Shear Viscosity Coefficient of 5d Liquid Transition Metals

NASA Astrophysics Data System (ADS)

Thakor, P. B.; Sonvane, Y. A.; Gajjar, P. N.; Jani, A. R.

2011-07-01

In the present paper we have calculated shear viscosity coefficient (η) of 5 d liquid transition metals. To calculate effective pair potential ν(r) and pair distribution function g(r) we have used our own newly constructed model potential and Percus- Yevick hard sphere (PYHS) structure factor S(q) respectively. We have also investigated the effect of different correction function like Hartree (H), Taylor (T) and Sarkar et al. (S) on shear viscosity coefficient (η). Our newly constructed model potential successfully explains the shear viscosity coefficient (η) of 5 d liquid transition metals.

[Sputum viscosity and pulmonary function measurements during a one-week parenteral treatment with a standardized oxidation product of oil of turpentine and terpin hydrate].

PubMed

Löllgen-Horres, I; Löllgen, H

1976-01-01

In 23 patients with chronic obstructive lung diseases, viscosity, airway resistance, arterial blood gases and acid-base balance, and sputum aspect were measured before and after one-week treatment with Ozothin, a substance from oxidation products of ol. terebinth. and terpinum hydratum. Within this time, viscosity of the sputum was reduced, airway resistance decreased, and arterial oxygen pressure slightly increased, whereas arterial carbon dioxide tension obvious change of sputum aspect could be observed. Correlation calculations revealed no significant relations between viscosity and the above cited lung function values. The results indicate that administration of Ozothin may liquefy viscous secretion and reduce sputum viscosity.

Computation and analysis of the transverse current autocorrelation function, Ct(k,t), for small wave vectors: A molecular-dynamics study for a Lennard-Jones fluid

NASA Astrophysics Data System (ADS)

Vogelsang, R.; Hoheisel, C.

1987-02-01

Molecular-dynamics (MD) calculations are reported for three thermodynamic states of a Lennard-Jones fluid. Systems of 2048 particles and 105 integration steps were used. The transverse current autocorrelation function, Ct(k,t), has been determined for wave vectors of the range 0.5<||k||σ<1.5. Ct(k,t) was fitted by hydrodynamic-type functions. The fits returned k-dependent decay times and shear viscosities which showed a systematic behavior as a function of k. Extrapolation to the hydrodynamic region at k=0 gave shear viscosity coefficients in good agreement with direct Green-Kubo results obtained in previous work. The two-exponential model fit for the memory function proposed by other authors does not provide a reasonable description of the MD results, as the fit parameters show no systematic wave-vector dependence, although the Ct(k,t) functions are somewhat better fitted. Similarly, the semiempirical interpolation formula for the decay time based on the viscoelastic concept proposed by Akcasu and Daniels fails to reproduce the correct k dependence for the wavelength range investigated herein.

A new method to simulate the effects of viscous fingering on miscible displacement processes in porous media

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vossoughi, S.; Green, D.W.; Smith, J.E.

This paper presents a new method to simulate the effects of viscous fingering on miscible displacement processes in porous media. The method is based on the numerical solution of a general form of the convection-dispersion equation. In this equation the convection term is represented by a fractional flow function. The fractional flow function is derived from Darcy's law using a concentration-dependent, average viscosity and relative flow area to each fluid at any point in the bed. The method was extended to the description of a polymer flood by including retention and inaccessible pore volume. A Langmuir-type model for polymer retentionmore » in the rock was used. The resulting convection-dispersion equation for displacement by polymer was then solved numerically by the use of a finite element method with linear basis functions and Crank-Nicholson derivative approximation. History matches were performed on four sets of laboratory data to verify the model. These were: an unfavorable viscosity ratio displacement, stable displacement of glycerol by polymer solution, unstable displacement of brine by a slug of polymer solution, and a favorable viscosity ratio displacement. In general, computed results from the model matched laboratory data closely. Good agreement of the model with experiments over a significant range of variables lends support to the analysis.« less

Bulk viscosity of the Lennard-Jones fluid for a wide range of states computed by equilibrium molecular dynamics

NASA Astrophysics Data System (ADS)

Hoheisel, C.; Vogelsang, R.; Schoen, M.

1987-12-01

Accurate data for the bulk viscosity ηv have been obtained by molecular dynamics calculations. Many thermodynamic states of the Lennard-Jones fluid were considered. The Green-Kubo integrand of ηv is analyzed in terms of partial correlation functions constituting the total one. These partial functions behave rather differently from those found for the shear viscosity or the thermal conductivity. Generally the total autocorrelation function of ηv shows a steeper initial decay and a more pronounced long time form than those of the shear viscosity or the thermal conductivity. For states near transition to solid phases, like the pseudotriple point of argon, the Green-Kubo integrand of ηv has a significantly longer ranged time behavior than that of the shear viscosity. Hence, for the latter states, a systematic error is expected for ηv using equilibrium molecular dynamics for its computation.

A wrinkling-based method for investigating glassy polymer film relaxation as a function of film thickness and temperature.

PubMed

Chung, Jun Young; Douglas, Jack F; Stafford, Christopher M

2017-10-21

We investigate the relaxation dynamics of thin polymer films at temperatures below the bulk glass transition T g by first compressing polystyrene films supported on a polydimethylsiloxane substrate to create wrinkling patterns and then observing the slow relaxation of the wrinkled films back to their final equilibrium flat state by small angle light scattering. As with recent relaxation measurements on thin glassy films reported by Fakhraai and co-workers, we find the relaxation time of our wrinkled films to be strongly dependent on film thickness below an onset thickness on the order of 100 nm. By varying the temperature between room temperature and T g (≈100 °C), we find that the relaxation time follows an Arrhenius-type temperature dependence to a good approximation at all film thicknesses investigated, where both the activation energy and the relaxation time pre-factor depend appreciably on film thickness. The wrinkling relaxation curves tend to cross at a common temperature somewhat below T g , indicating an entropy-enthalpy compensation relation between the activation free energy parameters. This compensation effect has also been observed recently in simulated supported polymer films in the high temperature Arrhenius relaxation regime rather than the glassy state. In addition, we find that the film stress relaxation function, as well as the height of the wrinkle ridges, follows a stretched exponential time dependence and the short-time effective Young's modulus derived from our modeling decreases sigmoidally with increasing temperature-both characteristic features of glassy materials. The relatively facile nature of the wrinkling-based measurements in comparison to other film relaxation measurements makes our method attractive for practical materials development, as well as fundamental studies of glass formation.

A wrinkling-based method for investigating glassy polymer film relaxation as a function of film thickness and temperature

NASA Astrophysics Data System (ADS)

Chung, Jun Young; Douglas, Jack F.; Stafford, Christopher M.

2017-10-01

We investigate the relaxation dynamics of thin polymer films at temperatures below the bulk glass transition Tg by first compressing polystyrene films supported on a polydimethylsiloxane substrate to create wrinkling patterns and then observing the slow relaxation of the wrinkled films back to their final equilibrium flat state by small angle light scattering. As with recent relaxation measurements on thin glassy films reported by Fakhraai and co-workers, we find the relaxation time of our wrinkled films to be strongly dependent on film thickness below an onset thickness on the order of 100 nm. By varying the temperature between room temperature and Tg (≈100 °C), we find that the relaxation time follows an Arrhenius-type temperature dependence to a good approximation at all film thicknesses investigated, where both the activation energy and the relaxation time pre-factor depend appreciably on film thickness. The wrinkling relaxation curves tend to cross at a common temperature somewhat below Tg, indicating an entropy-enthalpy compensation relation between the activation free energy parameters. This compensation effect has also been observed recently in simulated supported polymer films in the high temperature Arrhenius relaxation regime rather than the glassy state. In addition, we find that the film stress relaxation function, as well as the height of the wrinkle ridges, follows a stretched exponential time dependence and the short-time effective Young's modulus derived from our modeling decreases sigmoidally with increasing temperature—both characteristic features of glassy materials. The relatively facile nature of the wrinkling-based measurements in comparison to other film relaxation measurements makes our method attractive for practical materials development, as well as fundamental studies of glass formation.

Study on the temperature-dependent coupling among viscosity, conductivity and structural relaxation of ionic liquids.

PubMed

Yamaguchi, Tsuyoshi; Yonezawa, Takuya; Koda, Shinobu

2015-07-15

The frequency-dependent viscosity and conductivity of three imidazolium-based ionic liquids were measured at several temperatures in the MHz region, and the results are compared with the intermediate scattering functions determined by neutron spin echo spectroscopy. The relaxations of both the conductivity and the viscosity agree with that of the intermediate scattering function at the ionic correlation when the relaxation time is short. As the relaxation time increases, the relaxations of the two transport properties deviate to lower frequencies than that of the ionic structure. The deviation begins at a shorter relaxation time for viscosity than for conductivity, which explains the fractional Walden rule between the zero-frequency values of the shear viscosity and the molar conductivity.

Photoinduced aging and viscosity evolution in Se-rich Ge-Se glasses

NASA Astrophysics Data System (ADS)

Gueguen, Yann; King, Ellyn A.; Keryvin, Vincent; Sangleboeuf, Jean-Christophe; Rouxel, Tanguy; Bureau, Bruno; Lucas, Pierre

2013-08-01

We propose here to investigate the non-equilibrium viscosity of Ge-Se glasses under and after light irradiation. Ge10Se90 and Ge20Se80 fibers have been aged in the dark and under ambient light, over months. During aging, both the relaxation of enthalpy and the viscosity have been investigated. The viscosity was measured by shear relaxation-recovery tests allowing the measurement of non-equilibrium viscosity. When Ge10Se90 glass fibers are aged under irradiation, a relatively fast fictive temperature decrease is observed. Concomitantly, during aging under irradiation, the non-equilibrium viscosity increases and reaches an equilibrium after two months of aging. This viscosity increase is also observed in Ge20Se80 fibers. Nevertheless, this equilibrium viscosity is far below the viscosity expected at the configurational equilibrium. As soon as the irradiation ceases, the viscosity increases almost instantaneously by about one order of magnitude. Then, if the fibers are kept in the dark, their viscosity slowly increases over months. The analysis of the shear relaxation functions shows that the aging is thermorheologically simple. On the other side, there is no simple relaxation between the shear relaxation functions measured under irradiation and those measured in the dark. These results clearly suggest that a very specific photoinduced aging process occurs under irradiation. This aging is due to photorelaxation. Nevertheless, the viscosity changes are not solely correlated to photoaging and photorelaxation. A scenario is proposed to explain all the observed viscosity evolutions under and after irradiation, on the basis of photoinduced transient defects.

Checking the statistical theory of liquids by ultraacoustic measurements

NASA Technical Reports Server (NTRS)

Dima, V. N.

1974-01-01

The manner of theoretically obtaining radial distribution functions 9(r) for n-hexane as a function of temperature is described. With the aid of function g(r) the coefficient of dynamic viscosity and the coefficient of volumetric viscosity for temperatures ranging from 213 K to 273 K were calculated. With the aid of the two coefficients of viscosity the coefficient of absorption of ultrasounds in n-hexane referred to the square of the frequency was determined. The same values were measured experimentally. Comparison of theory with experiments resulted in satisfactory agreement.

Shear viscosity coefficient of liquid lanthanides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Patel, H. P., E-mail: patel.harshal2@gmail.com; Thakor, P. B., E-mail: pbthakore@rediffmail.com; Prajapati, A. V., E-mail: anand0prajapati@gmail.com

2015-05-15

Present paper deals with the computation of shear viscosity coefficient (η) of liquid lanthanides. The effective pair potential v(r) is calculated through our newly constructed model potential. The Pair distribution function g(r) is calculated from PYHS reference system. To see the influence of local field correction function, Hartree (H), Tailor (T) and Sarkar et al (S) local field correction function are used. Present results are compared with available experimental as well as theoretical data. Lastly, we found that our newly constructed model potential successfully explains the shear viscosity coefficient (η) of liquid lanthanides.

Shear viscosity coefficient of liquid lanthanides

NASA Astrophysics Data System (ADS)

Patel, H. P.; Sonvane, Y. A.; Thakor, P. B.; Prajapati, A. V.

2015-05-01

Present paper deals with the computation of shear viscosity coefficient (η) of liquid lanthanides. The effective pair potential v(r) is calculated through our newly constructed model potential. The Pair distribution function g(r) is calculated from PYHS reference system. To see the influence of local field correction function, Hartree (H), Tailor (T) and Sarkar et al (S) local field correction function are used. Present results are compared with available experimental as well as theoretical data. Lastly, we found that our newly constructed model potential successfully explains the shear viscosity coefficient (η) of liquid lanthanides.

A Biochemist's View of Ecosystem Rates and their Response to Changing Temperature

NASA Astrophysics Data System (ADS)

Arcus, V. L.

2017-12-01

Enzyme kinetics lie at the heart of biochemistry and the Michaelis-Menten equation that defines the relationship between substrate and rate is over 100 years old. About 80 years ago Eyring and Polyani formulated Transistion State Theory (TST) which describes the temperature-dependence of chemical reaction rates and the precise relationship between activation energy and the rate. TST provided a robust theoretical foundation for the Arrhenius equation and together, these equations are the foundation equations for the biochemist. Can these equations provide any insights into rates at larger scales, such as organism growth rates and those rates that interest ecosystem scientists (e.g. heterotrophic respiration, gross primary production)? Let us begin by considering a microbial cell. Microbial growth (i.e. cell division) requires the coordinated kinetics of thousands of enzymes including DNA/RNA polymerases, ribosomes, biosynthetic enzymes - all under a regime of highly complex regulatory effects. There is no a priori reason to expect that Michaelis-Menten kinetics and TST will adequately describe this vastly complex process. Indeed, Lloyd and Taylor showed 23 years ago that soil respiration is not well described by the Arrhenius function. More recently, Heskel and colleagues showed that leaf respiration is also not well described by the Arrhenius function. It is the same case for rates of photosynthesis. Despite this failure of the basic equations of biochemistry to map to biological rates at greater scales, what insights can biochemistry provide to ecosystem science? As nearly all of biological metabolism is mediated through enzyme kinetics, I will begin with the Michaelis-Menten equation under regimes of low and high substrate concentrations. This simplified view can provide surprising insights into processes at larger scales. I will also consider the relationship between the activation energy and the reaction rate. Many, many ecosystem-rate papers focus on the activation energy and thus, it is important to understand this relationship. Finally, I will consider the Arrhenius and TST equations and their failure for ecosystem processes and the reasons for this failure. Understanding the failure is a first step towards a resolution to this long-standing problem in ecosystem science.

Calculating electronic tunnel currents in networks of disordered irregularly shaped nanoparticles by mapping networks to arrays of parallel nonlinear resistors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aghili Yajadda, Mir Massoud

2014-10-21

We have shown both theoretically and experimentally that tunnel currents in networks of disordered irregularly shaped nanoparticles (NPs) can be calculated by considering the networks as arrays of parallel nonlinear resistors. Each resistor is described by a one-dimensional or a two-dimensional array of equal size nanoparticles that the tunnel junction gaps between nanoparticles in each resistor is assumed to be equal. The number of tunnel junctions between two contact electrodes and the tunnel junction gaps between nanoparticles are found to be functions of Coulomb blockade energies. In addition, the tunnel barriers between nanoparticles were considered to be tilted at highmore » voltages. Furthermore, the role of thermal expansion coefficient of the tunnel junction gaps on the tunnel current is taken into account. The model calculations fit very well to the experimental data of a network of disordered gold nanoparticles, a forest of multi-wall carbon nanotubes, and a network of few-layer graphene nanoplates over a wide temperature range (5-300 K) at low and high DC bias voltages (0.001 mV–50 V). Our investigations indicate, although electron cotunneling in networks of disordered irregularly shaped NPs may occur, non-Arrhenius behavior at low temperatures cannot be described by the cotunneling model due to size distribution in the networks and irregular shape of nanoparticles. Non-Arrhenius behavior of the samples at zero bias voltage limit was attributed to the disorder in the samples. Unlike the electron cotunneling model, we found that the crossover from Arrhenius to non-Arrhenius behavior occurs at two temperatures, one at a high temperature and the other at a low temperature.« less

Comparison of sarcoplasmic reticulum Ca2+-adenosine triphosphatase from vitamin E-deficient dystrophic rabbit skeletal muscle with iron-ascorbate-treated and untreated enzyme.

PubMed

Nirdnoy, W; Komaratat, P; Wilairat, P

1988-02-01

Sarcoplasmic reticulum Ca2+-ATPase from rabbit skeletal muscle has an Arrhenius curve of enzyme activity with a discontinuity at about 20 degrees C. Preparations treated with FeSO4 and ascorbic acid and from a vitamin E-deficient dystrophic rabbit have 22% of the normal activity and a linear Arrhenius curve (Promkhatkaew, D., Komaratat, P., & Wilairat, P. (1985) Biochem. Int. 10, 937-943). All three preparations were cross-linked to the same extent by dimethyl suberimidate and copper-phenanthroline reagent at temperatures above and below the temperature of the Arrhenius discontinuity. Both iron-ascorbate-treated Ca2+-ATPase and that from a vitamin E-deficient animal had 50% of the normal sulfhydryl content, but the disulfide and free amino contents were unaltered. These observations suggest that loss of sulfhydryl groups through lipid peroxidation, both in vivo and in vitro, resulted in reduction of Ca2+-ATPase activity and loss of the break in the Arrhenius plot. Changes in Ca2+-ATPase polypeptide aggregational state could not account for the discontinuity in the Arrhenius curve as revealed by the similar extent of cross-linking of the three enzyme preparations at temperatures above and below the temperature of the Arrhenius discontinuity.

Photoinduced aging and viscosity evolution in Se-rich Ge-Se glasses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gueguen, Yann; Sangleboeuf, Jean-Christophe; Rouxel, Tanguy

We propose here to investigate the non-equilibrium viscosity of Ge-Se glasses under and after light irradiation. Ge{sub 10}Se{sub 90} and Ge{sub 20}Se{sub 80} fibers have been aged in the dark and under ambient light, over months. During aging, both the relaxation of enthalpy and the viscosity have been investigated. The viscosity was measured by shear relaxation-recovery tests allowing the measurement of non-equilibrium viscosity. When Ge{sub 10}Se{sub 90} glass fibers are aged under irradiation, a relatively fast fictive temperature decrease is observed. Concomitantly, during aging under irradiation, the non-equilibrium viscosity increases and reaches an equilibrium after two months of aging. Thismore » viscosity increase is also observed in Ge{sub 20}Se{sub 80} fibers. Nevertheless, this equilibrium viscosity is far below the viscosity expected at the configurational equilibrium. As soon as the irradiation ceases, the viscosity increases almost instantaneously by about one order of magnitude. Then, if the fibers are kept in the dark, their viscosity slowly increases over months. The analysis of the shear relaxation functions shows that the aging is thermorheologically simple. On the other side, there is no simple relaxation between the shear relaxation functions measured under irradiation and those measured in the dark. These results clearly suggest that a very specific photoinduced aging process occurs under irradiation. This aging is due to photorelaxation. Nevertheless, the viscosity changes are not solely correlated to photoaging and photorelaxation. A scenario is proposed to explain all the observed viscosity evolutions under and after irradiation, on the basis of photoinduced transient defects.« less

Mathematical models for prediction of rheological parameters in vinasses derived from sugar cane

NASA Astrophysics Data System (ADS)

Chacua, Leidy M.; Ayala, Germán; Rojas, Hernán; Agudelo, Ana C.

2016-04-01

The rheological behaviour of vinasses derived from sugar cane was studied as a function of time (0 and 600 s), soluble solids content (44 and 60 °Brix), temperature (10 and 50°C), and shear rate (0.33 and 1.0 s-1). The results indicated that vinasses were time-independent at 25°C, where shear stress values ranged between 0.01 and 0.08 Pa. Flow curves showed a shear-thinning rheological behaviour in vinasses with a flow behaviour index between 0.69 and 0.89, for temperature between 10 and 20°C. With increasing temperature, the flow behaviour index was modified, reaching values close to 1.0. The Arrhenius model described well the thermal activation of shear stress and the consistency coefficient as a function of temperature. Activation energy from the Arrhenius model ranged between 31 and 45 kJ mol-1. Finally, the consistency coefficient as a function of the soluble solids content and temperature was well fitted using an exponential model (R2 = 0.951), showing that the soluble solids content and temperature have an opposite effect on consistency coefficient values.

A Simple BODIPY-Based Viscosity Probe for Imaging of Cellular Viscosity in Live Cells

PubMed Central

Su, Dongdong; Teoh, Chai Lean; Gao, Nengyue; Xu, Qing-Hua; Chang, Young-Tae

2016-01-01

Intracellular viscosity is a fundamental physical parameter that indicates the functioning of cells. In this work, we developed a simple boron-dipyrromethene (BODIPY)-based probe, BTV, for cellular mitochondria viscosity imaging by coupling a simple BODIPY rotor with a mitochondria-targeting unit. The BTV exhibited a significant fluorescence intensity enhancement of more than 100-fold as the solvent viscosity increased. Also, the probe showed a direct linear relationship between the fluorescence lifetime and the media viscosity, which makes it possible to trace the change of the medium viscosity. Furthermore, it was demonstrated that BTV could achieve practical applicability in the monitoring of mitochondrial viscosity changes in live cells through fluorescence lifetime imaging microscopy (FLIM). PMID:27589762

A Simple BODIPY-Based Viscosity Probe for Imaging of Cellular Viscosity in Live Cells.

PubMed

Su, Dongdong; Teoh, Chai Lean; Gao, Nengyue; Xu, Qing-Hua; Chang, Young-Tae

2016-08-31

Intracellular viscosity is a fundamental physical parameter that indicates the functioning of cells. In this work, we developed a simple boron-dipyrromethene (BODIPY)-based probe, BTV, for cellular mitochondria viscosity imaging by coupling a simple BODIPY rotor with a mitochondria-targeting unit. The BTV exhibited a significant fluorescence intensity enhancement of more than 100-fold as the solvent viscosity increased. Also, the probe showed a direct linear relationship between the fluorescence lifetime and the media viscosity, which makes it possible to trace the change of the medium viscosity. Furthermore, it was demonstrated that BTV could achieve practical applicability in the monitoring of mitochondrial viscosity changes in live cells through fluorescence lifetime imaging microscopy (FLIM).

Magnetic field tunable dielectric dispersion in successive field-induced magnetic phases of the geometrically frustrated magnet CuFeO2 up to 28 T

NASA Astrophysics Data System (ADS)

Tamatsukuri, H.; Mitsuda, S.; Hiroura, K.; Nakajima, T.; Fujihala, M.; Yamano, M.; Toshioka, Y.; Kaneko, C.; Takehana, K.; Imanaka, Y.; Terada, N.; Kitazawa, H.

2018-06-01

We find magnetic-field-dependent dielectric dispersions specific to successive field-induced magnetic phases of a geometrically frustrated magnet CuFeO2 up to 28 T. The dielectric dispersions in the three field-induced collinear-commensurate magnetic phases are well described by the superposition of Debye-type relaxations, and the number of contributions to the Debye-type dispersions differs in these phases. In contrast, the dielectric dispersions in the noncollinear-incommensurate phase, known as a spin-driven ferroelectric phase, cannot be simply described by the Debye-type relaxations. In addition, we find that the temperature dependence of the Debye relaxation frequencies follows the Arrhenius law, and that the activation energies derived from the Arrhenius equation also depend on the magnetic field. Considering the magnetostriction effect in combination with elongation/contraction of spins resulting from the application of a magnetic field, we show that the number of Debye relaxation components is equivalent to the number of states of local Fe3O clusters determined by oxygen displacement within a triangular Fe lattice. Based on this correspondence, we propose a possible explanation that excess charges resulting from a lack of stoichiometry hop over the double-well potentials within each local Fe3O cluster, like small polarons.

A singularity free approach to post glacial rebound calculations

NASA Technical Reports Server (NTRS)

Fang, Ming; Hager, Bradford H.

1994-01-01

Calculating the post glacial response of a viscoelastic Earth model using the exponential decay normal mode technique leads to intrinsic singularities if viscosity varies continuously as a function of radius. We develop a numerical implementation of the Complex Real Fourier transform (CRFT) method as an accurate and stable procedure to avoid these singularities. Using CRFT, we investigate the response of a set of Maxwell Earth models to surface loading. We find that the effect of expanding a layered viscosity structure into a continuously varying structure is to destroy the modes associated with the boundary between layers. Horizontal motion is more sensitive than vertical motion to the viscosity structure just below the lithosphere. Horizontal motion is less sensitive to the viscosity of the lower mantle than the vertical motion is. When the viscosity increases at 670 km depth by a factor of about 60, the response of the lower mantle is close to its elastic limit. Any further increase of the viscosity contrast at 670 km depth or further increase of viscosity as a continuous function of depth starting from 670 km depth is unlikely to be resolved.

Uncertainty quantification of reaction mechanisms accounting for correlations introduced by rate rules and fitted Arrhenius parameters

DOE PAGES

Prager, Jens; Najm, Habib N.; Sargsyan, Khachik; ...

2013-02-23

We study correlations among uncertain Arrhenius rate parameters in a chemical model for hydrocarbon fuel-air combustion. We consider correlations induced by the use of rate rules for modeling reaction rate constants, as well as those resulting from fitting rate expressions to empirical measurements arriving at a joint probability density for all Arrhenius parameters. We focus on homogeneous ignition in a fuel-air mixture at constant-pressure. We also outline a general methodology for this analysis using polynomial chaos and Bayesian inference methods. Finally, we examine the uncertainties in both the Arrhenius parameters and in predicted ignition time, outlining the role of correlations,more » and considering both accuracy and computational efficiency.« less

Diffusion and plasticity at high temperature

NASA Astrophysics Data System (ADS)

Philibert, J.

1991-06-01

High temperature plastic deformation requires atomic migration whatever the mechanism of deformation. The constitutive equations contain a diffusion coefficient and the deformation rate follows an Arrhenius law. This paper will only discuss the case of viscous creep in order to elucidate the nature of the diffusion processes and the expression of the diffusion coefficient involved in alloys or compounds. La déformation plastique à haute température met en jeu des migrations atomiques, quel que soit le mécanisme de déformation. Les lois de comportement contiennent donc un coefficient de diffusion et la vitesse de déformation obéit à une loi d'Arrhenius. Dans cet article, qui ne conceme qu'un seul type de déformation, lefluage visqueux, on s'efforce de préciser la nature des processus de diffusion et du coefficient de diffusion mis en jeu dans le cas des alliages et des composés.

Model free simulations of a high speed reacting mixing layer

NASA Technical Reports Server (NTRS)

Steinberger, Craig J.

1992-01-01

The effects of compressibility, chemical reaction exothermicity and non-equilibrium chemical modeling in a combusting plane mixing layer were investigated by means of two-dimensional model free numerical simulations. It was shown that increased compressibility generally had a stabilizing effect, resulting in reduced mixing and chemical reaction conversion rate. The appearance of 'eddy shocklets' in the flow was observed at high convective Mach numbers. Reaction exothermicity was found to enhance mixing at the initial stages of the layer's growth, but had a stabilizing effect at later times. Calculations were performed for a constant rate chemical rate kinetics model and an Arrhenius type kinetics prototype. The Arrhenius model was found to cause a greater temperature increase due to reaction than the constant kinetics model. This had the same stabilizing effect as increasing the exothermicity of the reaction. Localized flame quenching was also observed when the Zeldovich number was relatively large.

Changes in the flagellar bundling time account for variations in swimming behavior of flagellated bacteria in viscous media

NASA Astrophysics Data System (ADS)

Qu, Zijie; Temel, Fatma; Henderikx, Rene; Breuer, Kenneth

2017-11-01

The motility of bacteria E.coli in viscous fluids has been widely studied, although conflicting results on the effect of viscosity on swimming speed abound. The swimming mode of wild-type E.coli is idealized as a run-and-tumble sequence in which periods of straight swimming at a constant speed are randomly interrupted by a tumble, defined as a sudden change of direction with a very low speed. Using a tracking microscope, we follow cells for extended time and find that the swimming behavior of a single cell can exhibit a variety of behaviors including run-and-tumble and ``slow-random-walk'' in which the cells move at relatively low speed without the characteristic run. Although the characteristic swimming speed varies between individuals and in different polymer solutions, we find that the skewness of the speed distribution is solely a function of viscosity, and uniquely determines the ratio of the average speed to the characteristic run speed. Using Resistive Force Theory and the cell-specific measured characteristic run speed, we show that differences in the swimming behavior observed in solutions of different viscosity are due to changes in the flagellar bundling time, which increases as the viscosity rises, due to lower rotation rate of the flagellar motor. National Science Foundation.

Grain boundary oxidation and an analysis of the effects of oxidation on fatigue crack nucleation life

NASA Technical Reports Server (NTRS)

Oshida, Y.; Liu, H. W.

1988-01-01

The effects of preoxidation on subsequent fatigue life were studied. Surface oxidation and grain boundary oxidation of a nickel-base superalloy (TAZ-8A) were studied at 600 to 1000 C for 10 to 1000 hours in air. Surface oxides were identified and the kinetics of surface oxidation was discussed. Grain boundary oxide penetration and morphology were studied. Pancake type grain boundary oxide penetrates deeper and its size is larger, therefore, it is more detrimental to fatigue life than cone-type grain boundary oxide. Oxide penetration depth, a (sub m), is related to oxidation temperature, T, and exposure time, t, by an empirical relation of the Arrhenius type. Effects of T and t on statistical variation of a (sub m) were analyzed according to the Weibull distribution function. Once the oxide is cracked, it serves as a fatigue crack nucleus. Statistical variation of the remaining fatigue life, after the formation of an oxide crack of a critical length, is related directly to the statistical variation of grain boundary oxide penetration depth.

Grain boundary oxidation and an analysis of the effects of pre-oxidation on subsequent fatigue life

NASA Technical Reports Server (NTRS)

Oshida, Y.; Liu, H. W.

1986-01-01

The effects of preoxidation on subsequent fatigue life were studied. Surface oxidation and grain boundary oxidation of a nickel-base superalloy (TAZ-8A) were studied at 600 to 1000 C for 10 to 1000 hours in air. Surface oxides were identified and the kinetics of surface oxidation was discussed. Grain boundary oxide penetration and morphology were studied. Pancake type grain boundary oxide penetrates deeper and its size is larger, therefore, it is more detrimental to fatigue life than cone-type grain boundary oxide. Oxide penetration depth, a (sub m), is related to oxidation temperature, T, and exposure time, t, by an empirical relation of the Arrhenius type. Effects of T and t on statistical variation of a (sub m) were analyzed according to the Weibull distribution function. Once the oxide is cracked, it serves as a fatigue crack nucleus. Statistical variation of the remaining fatigue life, after the formation of an oxide crack of a critical length, is related directly to the statistical variation of grain boundary oxide penetration depth.

Shear flow simulations of biaxial nematic liquid crystals

NASA Astrophysics Data System (ADS)

Sarman, Sten

1997-08-01

We have calculated the viscosities of a biaxial nematic liquid crystal phase of a variant of the Gay-Berne fluid [J. G. Gay and B. J. Berne, J. Chem. Phys. 74, 3316 (1981)] by performing molecular dynamics simulations. The equations of motion have been augmented by a director constraint torque that fixes the orientation of the directors. This makes it possible to fix them at different angles relative to the stream lines in shear flow simulations. In equilibrium simulations the constraints generate a new ensemble. One finds that the Green-Kubo relations for the viscosities become linear combinations of time correlation function integrals in this ensemble whereas they are complicated rational functions in the conventional canonical ensemble. We have evaluated these Green-Kubo relations for all the shear viscosities and all the twist viscosities. We have also calculated the alignment angles, which are functions of the viscosity coefficients. We find that there are three real alignment angles but a linear stability analysis shows that only one of them corresponds to a stable director orientation. The Green-Kubo results have been cross checked by nonequilibrium shear flow simulations. The results from the different methods agree very well. Finally, we have evaluated the Miesowicz viscosities [D. Baalss, Z. Naturforsch. Teil A 45, 7 (1990)]. They vary by more than 2 orders of magnitude. The viscosity is consequently highly orientation dependent.

Is trabecular bone permeability governed by molecular ordering-induced fluid viscosity gain? Arguments from re-evaluation of experimental data in the framework of homogenization theory.

PubMed

Abdalrahman, T; Scheiner, S; Hellmich, C

2015-01-21

It is generally agreed on that trabecular bone permeability, a physiologically important quantity, is governed by the material׳s (vascular or intertrabecular) porosity as well as by the viscosity of the pore-filling fluids. Still, there is less agreement on how these two key factors govern bone permeability. In order to shed more light onto this somewhat open issue, we here develop a random homogenization scheme for upscaling Poiseuille flow in the vascular porosity, up to Darcy-type permeability of the overall porous medium "trabecular bone". The underlying representative volume element of the macroscopic bone material contains two types of phases: a spherical, impermeable extracellular bone matrix phase interacts with interpenetrating cylindrical pore channel phases that are oriented in all different space directions. This type of interaction is modeled by means of a self-consistent homogenization scheme. While the permeability of the bone matrix equals to zero, the permeability of the pore phase is found through expressing the classical Hagen-Poiseuille law for laminar flow in the format of a "micro-Darcy law". The upscaling scheme contains pore size and porosity as geometrical input variables; however, they can be related to each other, based on well-known relations between porosity and specific bone surface. As two key results, validated through comprehensive experimental data, it appears (i) that the famous Kozeny-Carman constant (which relates bone permeability to the cube of the porosity, the square of the specific surface, as well as to the bone fluid viscosity) needs to be replaced by an again porosity-dependent rational function, and (ii) that the overall bone permeability is strongly affected by the pore fluid viscosity, which, in case of polarized fluids, is strongly increased due to the presence of electrically charged pore walls. Copyright © 2014 Elsevier Ltd. All rights reserved.

Low VOC Barrier Coating for Industrial Maintenance

DTIC Science & Technology

2007-11-01

Color - VOC - Total Solids (wt) - Total Solids (volume) - Percent Pigment - Stormer Viscosity - Brookfield Viscosity - Pot Life...17 NTPEP LVBC Testing (R 31-02) ●Formula - Color - VOC - Total Solids (wt) - Total Solids (volume) - Percent Pigment - Stormer ...Consistency of Paints Measuring Krebs Unit (KU) Viscosity Using the Stormer -Type Viscometer D 610 Test Method for Evaluating Degree of

The Effect of the Melt Viscosity and Impregnation of a Film on the Mechanical Properties of Thermoplastic Composites

PubMed Central

Kim, Jong Won; Lee, Joon Seok

2016-01-01

Generally, to produce film-type thermoplastic composites with good mechanical properties, high-performance reinforcement films are used. In this case, films used as a matrix are difficult to impregnate into tow due to their high melt viscosity and high molecular weight. To solve the problem, in this paper, three polypropylene (PP) films with different melt viscosities were used separately to produce film-type thermoplastic composites. A film with a low melt viscosity was stacked so that tow was impregnated first and a film with a higher melt viscosity was then stacked to produce the composite. Four different composites were produced by regulating the pressure rising time. The thickness, density, fiber volume fraction (Vf), and void content (Vc) were analyzed to identify the physical properties and compare them in terms of film stacking types. The thermal properties were identified by using differential scanning calorimetry (DSC) and dynamical mechanical thermal analysis (DMTA). The tensile property, flexural property, interlaminar shear strength (ILSS), and scanning electron microscopy (SEM) were performed to identify the mechanical properties. For the films with low molecular weight, impregnation could be completed fast but showed low strength. Additionally, the films with high molecular weight completed impregnation slowly but showed high strength. Therefore, appropriate films should be used considering the forming process time and their mechanical properties to produce film-type composites. PMID:28773572

Characteristics of Chemical and Functional Properties of Modified Cassava Flour (Manihot esculenta) by Autoclaving-Cooling Cycles Method

NASA Astrophysics Data System (ADS)

Cecep Erwan Andriansyah, Raden; Rahman, Taufik; Herminiati, Ainia; Rahman, Nurhaidar; Luthfiyanti, Rohmah

2017-12-01

The modified cassava flour can be made using the method of the autoclaving cooling cycle (AAC). The stability of the warming can be seen from the decreasing value of breakdown viscosity, while the stability of the stirring process can be seen by the decreasing value of setback viscosity. The stages of research include: (1) the making of cassava flour, (2) the making of modified cassava flour by the method of treatment of ACC with a variety of flour concentration and autoclaving time, (3) chemical analysis of the moisture, ash, fat, protein, carbohydrate; The functional properties of the pasting characteristics to the initial temperature of the pasting, peak viscosity, hot paste viscosity, breakdown viscosity, cold paste viscosity and setback viscosity. The result shows that cassava flour modified by treatment of flour concentration 16% and autoclaving time 41 minutes having pasting code and pasting viscosity which is resistant to high temperature. Flour with this character is flour that is expected to maintain the texture of processed products with a paste form that remains stable. Utilization of modified cassava flour by the ACC method can be applied to the pasting product such as noodle and spaghetti, hoping to support for food diversification program to reduce dependence on wheat flour in Indonesia.

Modeling and prediction of relaxation of polar order in high-activity nonlinear optical polymers

NASA Astrophysics Data System (ADS)

Guenthner, Andrew J.; Lindsay, Geoffrey A.; Wright, Michael E.; Fallis, Stephen; Ashley, Paul R.; Sanghadasa, Mohan

2007-09-01

Mach-Zehnder optical modulators were fabricated using the CLD and FTC chromophores in polymer-on-silicon optical waveguides. Up to 17 months of oven-ageing stability are reported for the poled polymer films. Modulators containing an FTC-polyimide had the best over all aging performance. To model and extrapolate the ageing data, a relaxation correlation function attributed to A. K. Jonscher was compared to the well-established stretched exponential correlation function. Both models gave a good fit to the data. The Jonscher model predicted a slower relaxation rate in the out years. Analysis showed that collecting data for a longer period relative to the relaxation time was more important for generating useful predictions than the precision with which individual model parameters could be estimated. Thus from a practical standpoint, time-temperature superposition must be assumed in order to generate meaningful predictions. For this purpose, Arrhenius-type expressions were found to relate the model time constants to the ageing temperatures.

BODIPY-Based Two-Photon Fluorescent Probe for Real-Time Monitoring of Lysosomal Viscosity with Fluorescence Lifetime Imaging Microscopy.

PubMed

Li, Ling-Ling; Li, Kun; Li, Meng-Yang; Shi, Lei; Liu, Yan-Hong; Zhang, Hong; Pan, Sheng-Lin; Wang, Nan; Zhou, Qian; Yu, Xiao-Qi

2018-05-01

The viscosity of lysosome is reported to be a key indicator of lysosomal functionality. However, the existing mechanical methods of viscosity measurement can hardly be applied at the cellular or subcellular level. Herein, a BODIPY-based two-photon fluorescent probe was presented for monitoring lysosomal viscosity with high spatial and temporal resolution. By installing two morpholine moieties to the fluorophore as target and rotational groups, the TICT effect between the two morpholine rings and the main fluorophore scaffold endowed the probe with excellent viscosity sensitivity. Moreover, Lyso-B succeeded in showing the impact of dexamethasone on lysosomal viscosity in real time.

Conformations of gelatin in trivalent chromium salt solutions: Viscosity and dynamic light scattering study

NASA Astrophysics Data System (ADS)

Qiao, Congde; Zhang, Jianlong; Kong, Aiqun

2017-02-01

An investigation of the influences of pH, salt type, and salt concentration on the conformations of gelatin molecules in trivalent chromium salt solutions was performed by viscosity and dynamic light scattering (DLS) techniques. It was found that the viscosity behaviors as polyelectrolytes or polyampholytes depended on the charge distribution on the gelatin chains, which can be tuned by the value of pH of the gelatin solution. The intrinsic viscosity of gelatin in basic chromium sulfate aqueous solution at pH = 2.0 first decreased and then increased with increasing Cr(OH)SO4 concentration, while a monotonic decrease of the intrinsic viscosity of gelatin was observed in CrCl3 solution. However, the intrinsic viscosity of gelatin at pH = 5.0 was found to be increased first and then decreased with an increase in salt concentration in Cr(OH)SO4 solution, as well as in CrCl3 solution. We suggested that the observed viscosity behavior of gelatin in trivalent chromium salt solutions was attributed to the comprehensive effects of shielding, overcharging, and crosslinking (complexation) caused by the introduction of the different counterions. In addition, the average hydrodynamic radius ( R h ) of gelatin molecules in various salt solutions was determined by DLS. It was found that the change trend of R h with salt concentration was the same as the change of intrinsic viscosity. Based on the results of the viscosity and DLS, a possible mechanism for the conformational transition of gelatin chains with external conditions including pH, salt concentration, and salt type is proposed.

Arrhenius analysis of the electrophorus electricus acetylcholinesterase-catalyzed hydrolysis of acetylthiocholine.

PubMed

Oakes, Jesse; Nguyen, Tina; Britt, B Mark

2003-06-01

Ellman's method was used to determine the Michaelis-Menten parameters for the hydrolysis of acetylthiocholine by Electrophorus electricus acetylcholinesterase from 12 to 37 degrees C. Arrhenius analysis revealed that the activation energy for formation of the enzyme/substrate complex is 22.2 +/- 1.1 kJ/mole. The Arrhenius plot of k(cat) is markedly curved and attributed to comparable rates of acylation and deacylation due to the absence of evidence for a temperature-dependent enzyme conformational change by differential scanning calorimetry.

Viscous effects on the Rayleigh-Taylor instability with background temperature gradient

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gerashchenko, Sergiy; Livescu, Daniel

Here we studied the growth rate of the compressible Rayleigh-Taylor instability in the presence of a background temperature gradient, Θ, using a normal mode analysis. The effect of Θ variation is examined for three interface types corresponding to the combinations of the viscous properties of the fluids (inviscid-inviscid, viscous-viscous, and viscous-inviscid) at different Atwood numbers, At, and when at least one of the fluids' viscosity is non-zero, as a function of the Grashof number. For the general case, the resulting ordinary differential equations are solved numerically; however, dispersion relations for the growth rate are presented for several limiting cases. Anmore » analytical solution is found for the inviscid-inviscid interface and the corresponding dispersion equation for the growth rate is obtained in the limit of large Θ. For the viscous-inviscid case, a dispersion relation is derived in the incompressible limit and Θ=0. Compared to Θ=0 case, the role of Θ<0 (hotter light fluid) is destabilizing and becomes stabilizing when Θ>0 (colder light fluid). The most pronounced effect of Θ ≠ 0 is found at low At and/or at large perturbation wavelengths relative to the domain size for all interface types. On the other hand, at small perturbation wavelengths relative to the domain size, the growth rate for the Θ<0 case exceeds the infinite domain incompressible constant density result. The results are applied to two practical examples, using sets of parameters relevant to Inertial Confinement Fusion coasting stage and solar corona plumes. The role of viscosity on the growth rate reduction is discussed together with highlighting the range of wavenumbers most affected by viscosity. The viscous effects further increase in the presence of background temperature gradient, when the viscosity is temperature dependent.« less

Viscous effects on the Rayleigh-Taylor instability with background temperature gradient

DOE PAGES

Gerashchenko, Sergiy; Livescu, Daniel

2016-07-28

Here we studied the growth rate of the compressible Rayleigh-Taylor instability in the presence of a background temperature gradient, Θ, using a normal mode analysis. The effect of Θ variation is examined for three interface types corresponding to the combinations of the viscous properties of the fluids (inviscid-inviscid, viscous-viscous, and viscous-inviscid) at different Atwood numbers, At, and when at least one of the fluids' viscosity is non-zero, as a function of the Grashof number. For the general case, the resulting ordinary differential equations are solved numerically; however, dispersion relations for the growth rate are presented for several limiting cases. Anmore » analytical solution is found for the inviscid-inviscid interface and the corresponding dispersion equation for the growth rate is obtained in the limit of large Θ. For the viscous-inviscid case, a dispersion relation is derived in the incompressible limit and Θ=0. Compared to Θ=0 case, the role of Θ<0 (hotter light fluid) is destabilizing and becomes stabilizing when Θ>0 (colder light fluid). The most pronounced effect of Θ ≠ 0 is found at low At and/or at large perturbation wavelengths relative to the domain size for all interface types. On the other hand, at small perturbation wavelengths relative to the domain size, the growth rate for the Θ<0 case exceeds the infinite domain incompressible constant density result. The results are applied to two practical examples, using sets of parameters relevant to Inertial Confinement Fusion coasting stage and solar corona plumes. The role of viscosity on the growth rate reduction is discussed together with highlighting the range of wavenumbers most affected by viscosity. The viscous effects further increase in the presence of background temperature gradient, when the viscosity is temperature dependent.« less

Inference of reaction rate parameters based on summary statistics from experiments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Khalil, Mohammad; Chowdhary, Kamaljit Singh; Safta, Cosmin

Here, we present the results of an application of Bayesian inference and maximum entropy methods for the estimation of the joint probability density for the Arrhenius rate para meters of the rate coefficient of the H 2/O 2-mechanism chain branching reaction H + O 2 → OH + O. Available published data is in the form of summary statistics in terms of nominal values and error bars of the rate coefficient of this reaction at a number of temperature values obtained from shock-tube experiments. Our approach relies on generating data, in this case OH concentration profiles, consistent with the givenmore » summary statistics, using Approximate Bayesian Computation methods and a Markov Chain Monte Carlo procedure. The approach permits the forward propagation of parametric uncertainty through the computational model in a manner that is consistent with the published statistics. A consensus joint posterior on the parameters is obtained by pooling the posterior parameter densities given each consistent data set. To expedite this process, we construct efficient surrogates for the OH concentration using a combination of Pad'e and polynomial approximants. These surrogate models adequately represent forward model observables and their dependence on input parameters and are computationally efficient to allow their use in the Bayesian inference procedure. We also utilize Gauss-Hermite quadrature with Gaussian proposal probability density functions for moment computation resulting in orders of magnitude speedup in data likelihood evaluation. Despite the strong non-linearity in the model, the consistent data sets all res ult in nearly Gaussian conditional parameter probability density functions. The technique also accounts for nuisance parameters in the form of Arrhenius parameters of other rate coefficients with prescribed uncertainty. The resulting pooled parameter probability density function is propagated through stoichiometric hydrogen-air auto-ignition computations to illustrate the need to account for correlation among the Arrhenius rate parameters of one reaction and across rate parameters of different reactions.« less

Inference of reaction rate parameters based on summary statistics from experiments

DOE PAGES

Khalil, Mohammad; Chowdhary, Kamaljit Singh; Safta, Cosmin; ...

2016-10-15

Here, we present the results of an application of Bayesian inference and maximum entropy methods for the estimation of the joint probability density for the Arrhenius rate para meters of the rate coefficient of the H 2/O 2-mechanism chain branching reaction H + O 2 → OH + O. Available published data is in the form of summary statistics in terms of nominal values and error bars of the rate coefficient of this reaction at a number of temperature values obtained from shock-tube experiments. Our approach relies on generating data, in this case OH concentration profiles, consistent with the givenmore » summary statistics, using Approximate Bayesian Computation methods and a Markov Chain Monte Carlo procedure. The approach permits the forward propagation of parametric uncertainty through the computational model in a manner that is consistent with the published statistics. A consensus joint posterior on the parameters is obtained by pooling the posterior parameter densities given each consistent data set. To expedite this process, we construct efficient surrogates for the OH concentration using a combination of Pad'e and polynomial approximants. These surrogate models adequately represent forward model observables and their dependence on input parameters and are computationally efficient to allow their use in the Bayesian inference procedure. We also utilize Gauss-Hermite quadrature with Gaussian proposal probability density functions for moment computation resulting in orders of magnitude speedup in data likelihood evaluation. Despite the strong non-linearity in the model, the consistent data sets all res ult in nearly Gaussian conditional parameter probability density functions. The technique also accounts for nuisance parameters in the form of Arrhenius parameters of other rate coefficients with prescribed uncertainty. The resulting pooled parameter probability density function is propagated through stoichiometric hydrogen-air auto-ignition computations to illustrate the need to account for correlation among the Arrhenius rate parameters of one reaction and across rate parameters of different reactions.« less

Teachers' Perceptions of the Teaching of Acids and Bases in Swedish Upper Secondary Schools

ERIC Educational Resources Information Center

Drechsler, Michal; Van Driel, Jan

2009-01-01

We report in this paper on a study of chemistry teachers' perceptions of their teaching in upper secondary schools in Sweden, regarding models of acids and bases, especially the Bronsted and the Arrhenius model. A questionnaire consisting of a Likert-type scale was developed, which focused on teachers' knowledge of different models, knowledge of…

Models for viscosity and shear localization in bubble-rich magmas

NASA Astrophysics Data System (ADS)

Vona, Alessandro; Ryan, Amy G.; Russell, James K.; Romano, Claudia

2016-09-01

Bubble content influences magma rheology and, thus, styles of volcanic eruption. Increasing magma vesicularity affects the bulk viscosity of the bubble-melt suspension and has the potential to promote non-Newtonian behavior in the form of shear localization or brittle failure. Here, we present a series of high temperature uniaxial deformation experiments designed to investigate the effect of bubbles on the magma bulk viscosity. The starting materials are cores of natural rhyolitic obsidian synthesized to have variable vesicularity (ϕ = 0- 66%). The foamed cores were deformed isothermally (T = 750 °C) at atmospheric conditions using a high-temperature uniaxial press under constant displacement rates (strain rates between 0.5- 1 ×10-4 s-1) and to total strains of 10-40%. The viscosity of the bubble-free melt (η0) was measured by micropenetration and parallel plate methods to establish a baseline for experiments on the vesicle rich cores. At the experimental conditions, rising vesicle content produces a marked decrease in bulk viscosity that is best described by a two-parameter empirical equation: log10 ⁡ηBulk =log10 ⁡η0 - 1.47[ ϕ / (1 - ϕ) ] 0.48. Our parameterization of the bubble-melt rheology is combined with Maxwell relaxation theory to map the potential onset of non-Newtonian behavior (shear localization) in magmas as a function of melt viscosity, vesicularity, and strain rate. For low degrees of strain (i.e. as in our study), the rheological properties of vesicular magmas under different flow types (pure vs. simple shear) are indistinguishable. For high strain or strain rates where simple and pure shear viscosity values may diverge, our model represents a maximum boundary condition. Vesicular magmas can behave as non-Newtonian fluids at lower strain rates than unvesiculated melts, thereby, promoting shear localization and (explosive or non-explosive) magma fragmentation. The extent of shear localization in magma influences outgassing efficiency, thereby, affecting magma ascent and the potential for explosivity.

Application of SEAWAT to select variable-density and viscosity problems

USGS Publications Warehouse

Dausman, Alyssa M.; Langevin, Christian D.; Thorne, Danny T.; Sukop, Michael C.

2010-01-01

SEAWAT is a combined version of MODFLOW and MT3DMS, designed to simulate three-dimensional, variable-density, saturated groundwater flow. The most recent version of the SEAWAT program, SEAWAT Version 4 (or SEAWAT_V4), supports equations of state for fluid density and viscosity. In SEAWAT_V4, fluid density can be calculated as a function of one or more MT3DMS species, and optionally, fluid pressure. Fluid viscosity is calculated as a function of one or more MT3DMS species, and the program also includes additional functions for representing the dependence of fluid viscosity on temperature. This report documents testing of and experimentation with SEAWAT_V4 with six previously published problems that include various combinations of density-dependent flow due to temperature variations and/or concentration variations of one or more species. Some of the problems also include variations in viscosity that result from temperature differences in water and oil. Comparisons between the results of SEAWAT_V4 and other published results are generally consistent with one another, with minor differences considered acceptable.

Relaxation-based viscosity mapping for magnetic particle imaging.

PubMed

Utkur, M; Muslu, Y; Saritas, E U

2017-05-07

Magnetic particle imaging (MPI) has been shown to provide remarkable contrast for imaging applications such as angiography, stem cell tracking, and cancer imaging. Recently, there is growing interest in the functional imaging capabilities of MPI, where 'color MPI' techniques have explored separating different nanoparticles, which could potentially be used to distinguish nanoparticles in different states or environments. Viscosity mapping is a promising functional imaging application for MPI, as increased viscosity levels in vivo have been associated with numerous diseases such as hypertension, atherosclerosis, and cancer. In this work, we propose a viscosity mapping technique for MPI through the estimation of the relaxation time constant of the nanoparticles. Importantly, the proposed time constant estimation scheme does not require any prior information regarding the nanoparticles. We validate this method with extensive experiments in an in-house magnetic particle spectroscopy (MPS) setup at four different frequencies (between 250 Hz and 10.8 kHz) and at three different field strengths (between 5 mT and 15 mT) for viscosities ranging between 0.89 mPa · s-15.33 mPa · s. Our results demonstrate the viscosity mapping ability of MPI in the biologically relevant viscosity range.

Structure–property reduced order model for viscosity prediction in single-component CO 2 -binding organic liquids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cantu, David C.; Malhotra, Deepika; Koech, Phillip K.

2016-01-01

CO2 capture from power generation with aqueous solvents remains energy intensive due to the high water content of the current technology, or the high viscosity of non-aqueous alternatives. Quantitative reduced models, connecting molecular structure to bulk properties, are key for developing structure-property relationships that enable molecular design. In this work, we describe such a model that quantitatively predicts viscosities of CO2 binding organic liquids (CO2BOLs) based solely on molecular structure and the amount of bound CO2. The functional form of the model correlates the viscosity with the CO2 loading and an electrostatic term describing the charge distribution between the CO2-bearingmore » functional group and the proton-receiving amine. Molecular simulations identify the proton shuttle between these groups within the same molecule to be the critical indicator of low viscosity. The model, developed to allow for quick screening of solvent libraries, paves the way towards the rational design of low viscosity non-aqueous solvent systems for post-combustion CO2 capture. Following these theoretical recommendations, synthetic efforts of promising candidates and viscosity measurement provide experimental validation and verification.« less

Relaxation-based viscosity mapping for magnetic particle imaging

NASA Astrophysics Data System (ADS)

Utkur, M.; Muslu, Y.; Saritas, E. U.

2017-05-01

Magnetic particle imaging (MPI) has been shown to provide remarkable contrast for imaging applications such as angiography, stem cell tracking, and cancer imaging. Recently, there is growing interest in the functional imaging capabilities of MPI, where ‘color MPI’ techniques have explored separating different nanoparticles, which could potentially be used to distinguish nanoparticles in different states or environments. Viscosity mapping is a promising functional imaging application for MPI, as increased viscosity levels in vivo have been associated with numerous diseases such as hypertension, atherosclerosis, and cancer. In this work, we propose a viscosity mapping technique for MPI through the estimation of the relaxation time constant of the nanoparticles. Importantly, the proposed time constant estimation scheme does not require any prior information regarding the nanoparticles. We validate this method with extensive experiments in an in-house magnetic particle spectroscopy (MPS) setup at four different frequencies (between 250 Hz and 10.8 kHz) and at three different field strengths (between 5 mT and 15 mT) for viscosities ranging between 0.89 mPa · s-15.33 mPa · s. Our results demonstrate the viscosity mapping ability of MPI in the biologically relevant viscosity range.

Response to Oil Sands Products Assessment

DTIC Science & Technology

2015-09-01

volume of the spill, its duration, and the viscosity and density of the crude oil involved. The denser components of a Dilbit spill would be difficult...C-4 Figure ‎C-2. Viscosity change for the three types of diluted bitumen. ......................................................... C...specific gravity) approaching or even exceeding the density of water. As a result of their high viscosity , bitumen cannot be produced by conventional

Experimental Study on the Viscosity and Adhesive Performance of Exogenous Liquid Fibrin Glue

PubMed Central

HAYASHI, Takuro; HASEGAWA, Mitsuhiro; INAMASU, Joji; ADACHI, Kazuhide; NAGAHISA, Shinya; HIROSE, Yuichi

2014-01-01

Exogenous fibrin glue (FG) is highly suitable for neurosurgical procedures, because of its viscosity and adhesive properties. Several FGs are commercially available, but only few reports detail their differences. In the present study, we investigated the viscosity and adhesive performance of two types of FG: one is derived from blood donated in Europe and the United States (CSL Behring's Beriplast®, BP) and the other is derived from blood donated in Japan (the Chemo-Sero-Therapeutic Research Institute's Bolheal®, BH). The viscosity test that measured fibrinogen viscosity revealed that BP had significantly higher viscosity than BH. Similarly, the dripping test showed that BP traveled a significantly shorter drip distance in the vertical direction than BH, although the transverse diameter of the coagulated FG did not differ statistically significantly. In the tensile strength test, BP showed superior adhesion performance over BH. The histological study of the hematoxylin-eosin-stained specimens in both groups showed favorable adhesion. Although further studies are required on its manufacturing and usage methods, FG shows differences in viscosity and adhesive performance according to the blood from which it is derived. We conclude that it is desirable to select the type and usage method of FG according to the characteristics of the surgical operation in question. Our findings suggest that FG produced from the blood donated in Europe and the United States might be more suitable for use in surgical procedures that demand an especially high degree of viscosity and rapid adhesive performance. PMID:25367586

Experimental study on the viscosity and adhesive performance of exogenous liquid fibrin glue.

PubMed

Hayashi, Takuro; Hasegawa, Mitsuhiro; Inamasu, Joji; Adachi, Kazuhide; Nagahisa, Shinya; Hirose, Yuichi

2014-01-01

Exogenous fibrin glue (FG) is highly suitable for neurosurgical procedures, because of its viscosity and adhesive properties. Several FGs are commercially available, but only few reports detail their differences. In the present study, we investigated the viscosity and adhesive performance of two types of FG: one is derived from blood donated in Europe and the United States (CSL Behring's Beriplast(®), BP) and the other is derived from blood donated in Japan (the Chemo-Sero-Therapeutic Research Institute's Bolheal(®), BH). The viscosity test that measured fibrinogen viscosity revealed that BP had significantly higher viscosity than BH. Similarly, the dripping test showed that BP traveled a significantly shorter drip distance in the vertical direction than BH, although the transverse diameter of the coagulated FG did not differ statistically significantly. In the tensile strength test, BP showed superior adhesion performance over BH. The histological study of the hematoxylin-eosin-stained specimens in both groups showed favorable adhesion. Although further studies are required on its manufacturing and usage methods, FG shows differences in viscosity and adhesive performance according to the blood from which it is derived. We conclude that it is desirable to select the type and usage method of FG according to the characteristics of the surgical operation in question. Our findings suggest that FG produced from the blood donated in Europe and the United States might be more suitable for use in surgical procedures that demand an especially high degree of viscosity and rapid adhesive performance.

Convection Models for Ice-Water System: Dynamical Investigation of Phase Transition

NASA Astrophysics Data System (ADS)

Allu Peddinti, D.; McNamara, A. K.

2012-12-01

Ever since planetary missions of Voyager and Galileo revealed a dynamically altered surface of the icy moon Europa, a possible subsurface ocean under an icy shell has been speculated and surface features have been interpreted from an interior dynamics perspective. The physics of convection in a two phase water-ice system is governed by a wide set of physical parameters that include melting viscosity of ice, the variation of viscosity due to pressure and temperature, temperature contrast across and tidal heating within the system, and the evolving thickness of each layer. Due to the extreme viscosity contrast between liquid water and solid ice, it is not feasible to model the entire system to study convection. However, using a low-viscosity proxy (higher viscosity than the liquid water but much lower than solid ice) for the liquid phase provides a convenient approximation of the system, and allows for a relatively realistic representation of convection within the ice layer while also providing a self-consistent ice layer thickness that is a function of the thermal state of the system. In order to apply this method appropriately, we carefully examine the upper bound of viscosity required for the low-viscosity proxy to adequately represent the liquid phase. We identify upper bounds on the viscosity of the proxy liquid such that convective dynamics of the ice are not affected by further reductions of viscosity. Furthermore, we investigate how the temperature contrast across the system and viscosity contrast between liquid and ice control ice layer thickness. We also investigate ice shell thickening as a function of cooling, particularly how viscosity affects the conduction-to-convection transition within the ice shell. Finally, we present initial results that investigate the effects that latent heat of fusion (due to the ice-water phase transition) has on ice convection.

Chemical demulsification of tanker crude emulsions. Memorandum report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Little, R.C.

1980-02-13

The chemical demulsification of tanker crude emulsions was studied as a function of oil type (light vs. heavy crude), demulsifier concentrations, and temperature. Aerosol OT shows promise as a chemical demulsifier of tanker crude emulsions provided that ambient temperatures are not too cold and that an appropriate concentration range is used for specific oil. The evaporation rates and viscosities of the six crudes studied are also reported in the text.

Impact of Types of Moisturizer and Humidity on the Residual Weight and Viscosity of Liquid and Gel Oral Moisturizers.

PubMed

Murakami, Mamoru; Nishi, Yasuhiro; Fujishima, Kei; Nishio, Misaki; Minemoto, Yoko; Kanie, Takahito; Nishimura, Masahiro

2016-10-01

Oral moisturizers need to be selected based on their material properties. The purpose of this study was to investigate the effects of moisturizer type and humidity on the residual weight and viscosity of oral moisturizers. The weight and viscosity of 17 oral moisturizers (7 liquid and 10 gel) at baseline and after 8 hours were measured using an incubator maintained at 37°C at either 85% or 40% relative humidity (RH). The rate of change in weight (RCW) and the rate of change in viscosity (RCV) were calculated. Data were analyzed with two-way analysis of variance (ANOVA) and Scheffe's test to evaluate the effect of the type of moisturizer (liquid or gel) and humidity (85% or 40% RH) on RCW and RCV. Pearson's correlation coefficient was used to evaluate the relationship between RCW and RCV. Two-way ANOVA results indicated that the type of moisturizer and RH had a significant effect on RCW and RCV (p < 0.05); however, the interaction between them was not significant. The results of multiple comparisons showed that gel moisturizers had a significantly lower RCW and higher RCV than liquid moisturizers (p < 0.05). The RCW and RCV at 40% RH were significantly higher than those at 85% RH (p < 0.05). There was no correlation between RCW and RCV in the liquid moisturizer group, but a significant negative correlation was found in the gel moisturizer group (pp = 0.01). Because viscosity of gel moisturizers increases as weight decreases, selecting gel moisturizers with a minimal change in weight and viscosity would be preferable in the case of a long-time application and severe dry mouth. © 2015 by the American College of Prosthodontists.

Conductivity studies of PEG based polymer electrolyte for applications as electrolyte in ion batteries

NASA Astrophysics Data System (ADS)

Patil, Ravikumar V.; Praveen, D.; Damle, R.

2018-05-01

Development of lithium ion batteries employing solid polymer electrolytes as electrolyte material has led to efficient energy storage and usage in many portable devices. However, due to a few drawbacks like lower ionic conductivity of solid polymer electrolytes (SPEs), studies on SPEs for improvement in conductivity still have a good scope. In the present paper, we report the conductivity studies of a new SPE with low molecular weight poly ethylene glycol (PEG) as host polymer in which a salt with larger anion Lithium trifluro methane sulphonate (LTMS). XRD studies have revealed that the salt completely dissociates in the polymer giving a good stable electrolyte at lower salt concentration. Conductivity of the SPEs has been studied as a function of temperature and we reiterate that the conductivity is a thermally activated process and follows Arrhenius type behavior.

Towards adjoint-based inversion of time-dependent mantle convection with nonlinear viscosity

NASA Astrophysics Data System (ADS)

Li, Dunzhu; Gurnis, Michael; Stadler, Georg

2017-04-01

We develop and study an adjoint-based inversion method for the simultaneous recovery of initial temperature conditions and viscosity parameters in time-dependent mantle convection from the current mantle temperature and historic plate motion. Based on a realistic rheological model with temperature-dependent and strain-rate-dependent viscosity, we formulate the inversion as a PDE-constrained optimization problem. The objective functional includes the misfit of surface velocity (plate motion) history, the misfit of the current mantle temperature, and a regularization for the uncertain initial condition. The gradient of this functional with respect to the initial temperature and the uncertain viscosity parameters is computed by solving the adjoint of the mantle convection equations. This gradient is used in a pre-conditioned quasi-Newton minimization algorithm. We study the prospects and limitations of the inversion, as well as the computational performance of the method using two synthetic problems, a sinking cylinder and a realistic subduction model. The subduction model is characterized by the migration of a ridge toward a trench whereby both plate motions and subduction evolve. The results demonstrate: (1) for known viscosity parameters, the initial temperature can be well recovered, as in previous initial condition-only inversions where the effective viscosity was given; (2) for known initial temperature, viscosity parameters can be recovered accurately, despite the existence of trade-offs due to ill-conditioning; (3) for the joint inversion of initial condition and viscosity parameters, initial condition and effective viscosity can be reasonably recovered, but the high dimension of the parameter space and the resulting ill-posedness may limit recovery of viscosity parameters.

A study of overflow simulations using MPAS-Ocean: Vertical grids, resolution, and viscosity

NASA Astrophysics Data System (ADS)

Reckinger, Shanon M.; Petersen, Mark R.; Reckinger, Scott J.

2015-12-01

MPAS-Ocean is used to simulate an idealized, density-driven overflow using the dynamics of overflow mixing and entrainment (DOME) setup. Numerical simulations are carried out using three of the vertical coordinate types available in MPAS-Ocean, including z-star with partial bottom cells, z-star with full cells, and sigma coordinates. The results are first benchmarked against other models, including the MITgcm's z-coordinate model and HIM's isopycnal coordinate model, which are used to set the base case used for this work. A full parameter study is presented that looks at how sensitive overflow simulations are to vertical grid type, resolution, and viscosity. Horizontal resolutions with 50 km grid cells are under-resolved and produce poor results, regardless of other parameter settings. Vertical grids ranging in thickness from 15 m to 120 m were tested. A horizontal resolution of 10 km and a vertical resolution of 60 m are sufficient to resolve the mesoscale dynamics of the DOME configuration, which mimics real-world overflow parameters. Mixing and final buoyancy are least sensitive to horizontal viscosity, but strongly sensitive to vertical viscosity. This suggests that vertical viscosity could be adjusted in overflow water formation regions to influence mixing and product water characteristics. Lastly, the study shows that sigma coordinates produce much less mixing than z-type coordinates, resulting in heavier plumes that go further down slope. Sigma coordinates are less sensitive to changes in resolution but as sensitive to vertical viscosity compared to z-coordinates.

Ion transport mechanism in glasses: non-Arrhenius conductivity and nonuniversal features.

PubMed

Murugavel, S; Vaid, C; Bhadram, V S; Narayana, C

2010-10-28

In this article, we report non-Arrhenius behavior in the temperature-dependent dc conductivity of alkali ion conducting silicate glasses well below their glass transition temperature. In contrast to the several fast ion-conducting and binary potassium silicate glasses, these glasses show a positive deviation in the Arrhenius plot. The observed non-Arrhenius behavior is completely reproducible in nature even after prolonged annealing close to the glass transition temperature of the respective glass sample. These results are the manifestation of local structural changes of the silicate network with temperature and give rise to different local environments into which the alkali ions hop, revealed by in situ high-temperature Raman spectroscopy. Furthermore, the present study provides new insights into the strong link between the dynamics of the alkali ions and different sites associated with it in the glasses.

Application of the compensated Arrhenius formalism to explain the dielectric constant dependence of rates for Menschutkin reactions.

PubMed

Petrowsky, Matt; Glatzhofer, Daniel T; Frech, Roger

2013-11-21

The dependence of the reaction rate on solvent dielectric constant is examined for the reaction of trihexylamine with 1-bromohexane in a series of 2-ketones over the temperature range 25-80 °C. The rate constant data are analyzed using the compensated Arrhenius formalism (CAF), where the rate constant assumes an Arrhenius-like equation that also contains a dielectric constant dependence in the exponential prefactor. The CAF activation energies are substantially higher than those obtained using the simple Arrhenius equation. A master curve of the data is observed by plotting the prefactors against the solvent dielectric constant. The master curve shows that the reaction rate has a weak dependence on dielectric constant for values approximately less than 10 and increases more rapidly for dielectric constant values greater than 10.

Communication: On the origin of the non-Arrhenius behavior in water reorientation dynamics.

PubMed

Stirnemann, Guillaume; Laage, Damien

2012-07-21

We combine molecular dynamics simulations and analytic modeling to determine the origin of the non-Arrhenius temperature dependence of liquid water's reorientation and hydrogen-bond dynamics between 235 K and 350 K. We present a quantitative model connecting hydrogen-bond exchange dynamics to local structural fluctuations, measured by the asphericity of Voronoi cells associated with each water molecule. For a fixed local structure the regular Arrhenius behavior is recovered, and the global anomalous temperature dependence is demonstrated to essentially result from a continuous shift in the unimodal structure distribution upon cooling. The non-Arrhenius behavior can thus be explained without invoking an equilibrium between distinct structures. In addition, the large width of the homogeneous structural distribution is shown to cause a growing dynamical heterogeneity and a non-exponential relaxation at low temperature.

A micro-macro constitutive model for finite-deformation viscoelasticity of elastomers with nonlinear viscosity

NASA Astrophysics Data System (ADS)

Zhou, Jianyou; Jiang, Liying; Khayat, Roger E.

2018-01-01

Elastomers are known to exhibit viscoelastic behavior under deformation, which is linked to the diffusion processes of the highly mobile and flexible polymer chains. Inspired by the theories of polymer dynamics, a micro-macro constitutive model is developed to study the viscoelastic behaviors and the relaxation process of elastomeric materials under large deformation, in which the material parameters all have a microscopic foundation or a microstructural justification. The proposed model incorporates the nonlinear material viscosity into the continuum finite-deformation viscoelasticity theories which represent the polymer networks of elastomers with an elastic ground network and a few viscous subnetworks. The developed modeling framework is capable of adopting most of strain energy density functions for hyperelastic materials and thermodynamics evolution laws of viscoelastic solids. The modeling capacity of the framework is outlined by comparing the simulation results with the experimental data of three commonly used elastomeric materials, namely, VHB4910, HNBR50 and carbon black (CB) filled elastomers. The comparison shows that the stress responses and some typical behaviors of filled and unfilled elastomers can be quantitatively predicted by the model with suitable strain energy density functions. Particularly, the strain-softening effect of elastomers could be explained by the deformation-dependent (nonlinear) viscosity of the polymer chains. The presented modeling framework is expected to be useful as a modeling platform for further study on the performance of different type of elastomeric materials.

The calculation of the viscosity from the autocorrelation function using molecular and atomic stress tensors

NASA Astrophysics Data System (ADS)

Cui, S. T.

The stress-stress correlation function and the viscosity of a united-atom model of liquid decane are studied by equilibrium molecular dynamics simulation using two different formalisms for the stress tensor: the atomic and the molecular formalisms. The atomic and molecular correlation functions show dramatic difference in short-time behaviour. The integrals of the two correlation functions, however, become identical after a short transient period whichis significantly shorter than the rotational relaxation time of the molecule. Both reach the same plateau value in a time period corresponding to this relaxation time. These results provide a convenient guide for the choice of the upper integral time limit in calculating the viscosity by the Green-Kubo formula.

Indirect color prediction of amorphous carbohydrate melts as a function of thermal history.

PubMed

van Sleeuwen, Rutger M T; Gosse, Anaїck J; Normand, Valery

2013-07-01

Glassy carbohydrate microcapsules are widely used for the encapsulation of flavors in food applications, and are made using various thermal processes (for example, extrusion). During manufacturing, these carbohydrate melts are held at elevated temperatures and color can form due to nonenzymatic browning reactions. These reactions can negatively or positively affect the color and flavor of microcapsules. The rate of color formation of maltodextrin and maltodextrin/sucrose melts at elevated temperatures was determined spectrophotometrically and was found to follow pseudo zero-order kinetics. The effect of temperature was adequately modeled by an Arrhenius relationship. Reaction rate constants and Arrhenius parameters were determined for individual wavelengths in the visible range (360 to 700 nm at 1 nm intervals). Transient processes (temperature changes with time) were modeled as a sequence of small isothermal events, and the equivalent thermal history at a reference temperature calculated using the Arrhenius relationship. Therefore, spectral transmittance curves could be predicted with knowledge of the time/temperature relationship. Validation was conducted by subjecting both melts to a transient thermal history. Experimental transmittance spectrum compared favorably against predicted values. These spectra were optionally converted to any desirable color space (for example, CIELAB, XYZ, RGB) or derived parameter (for example, Browning Index). The tool could be used to better control nonenzymatic browning reactions in industrial food processes. © 2013 Institute of Food Technologists®

Polyfunctional dispersants for controlling viscosity of phyllosilicates

DOEpatents

Chaiko, David J.

2006-07-25

This invention provides phyllosilicates and polyfunctional dispersants which can be manipulated to selectively control the viscosity of phyllosilicate slurries. The polyfunctional dispersants used in the present invention, which include at least three functional groups, increase the dispersion and exfoliation of phyllosilicates in polymers and, when used in conjunction with phyllosilicate slurries, significantly reduce the viscosity of slurries having high concentrations of phyllosilicates. The functional groups of the polyfunctional dispersants are capable of associating with multivalent metal cations and low molecular weight organic polymers, which can be manipulated to substantially increase or decrease the viscosity of the slurry in a concentration dependent manner. The polyfunctional dispersants of the present invention can also impart desirable properties on the phyllosilicate dispersions including corrosion inhibition and enhanced exfoliation of the phyllosilicate platelets.

Calculated viscosity-distance dependence for some actively flowing lavas

NASA Technical Reports Server (NTRS)

Pieri, David

1987-01-01

The importance of viscosity as a gauge of the various energy and momentum dissipation regimes of lava flows has been realized for a long time. Nevertheless, despite its central role in lava dynamics and kinematics, it remains among the most difficult of flow physical properties to measure in situ during an eruption. Attempts at reconstructing the actual emplacement viscosities of lava flows from their solidified topographic form are difficult. Where data are available on the position of an advancing flow front as a function of time, it is possible to calculate the effective viscosity of the front as a function of distance from the vent, under the assumptions of a steady state regime. As an application and test of an equation given, relevant parameters from five recent flows on Mauna Loa and Kilauea were utilized to infer the dynamic structure of their aggregate flow front viscosity as they advanced, up to cessation. The observed form of the viscosity-distance relation for the five active Hawaiian flows examined appears to be exponential, with a rapid increase just before the flows stopped as one would expect.

Measuring temperature-dependent activation energy in thermally activated processes: a 2D Arrhenius plot method.

PubMed

Li, Jian V; Johnston, Steven W; Yan, Yanfa; Levi, Dean H

2010-03-01

Thermally activated processes are characterized by two key quantities, activation energy (E(a)) and pre-exponential factor (nu(0)), which may be temperature dependent. The accurate measurement of E(a), nu(0), and their temperature dependence is critical for understanding the thermal activation mechanisms of non-Arrhenius processes. However, the classic 1D Arrhenius plot-based methods cannot unambiguously measure E(a), nu(0), and their temperature dependence due to the mathematical impossibility of resolving two unknown 1D arrays from one 1D experimental data array. Here, we propose a 2D Arrhenius plot method to solve this fundamental problem. Our approach measures E(a) at any temperature from matching the first and second moments of the data calculated with respect to temperature and rate in the 2D temperature-rate plane, and therefore is able to unambiguously solve E(a), nu(0), and their temperature dependence. The case study of deep level emission in a Cu(In,Ga)Se(2) solar cell using the 2D Arrhenius plot method reveals clear temperature dependent behavior of E(a) and nu(0), which has not been observable by its 1D predecessors.

Measurement and correlation of jet fuel viscosities at low temperatures

NASA Technical Reports Server (NTRS)

Schruben, D. L.

1985-01-01

Apparatus and procedures were developed to measure jet fuel viscosity for eight current and future jet fuels at temperatures from ambient to near -60 C by shear viscometry. Viscosity data showed good reproducibility even at temperatures a few degrees below the measured freezing point. The viscosity-temperature relationship could be correlated by two linear segments when plotted as a standard log-log type representation (ASTM D 341). At high temperatures, the viscosity-temperature slope is low. At low temperatures, where wax precipitation is significant, the slope is higher. The breakpoint between temperature regions is the filter flow temperature, a fuel characteristic approximated by the freezing point. A generalization of the representation for the eight experimental fuels provided a predictive correlation for low-temperature viscosity, considered sufficiently accurate for many design or performance calculations.

ATMOSPHERIC CHEMISTRY FOR ASTROPHYSICISTS: A SELF-CONSISTENT FORMALISM AND ANALYTICAL SOLUTIONS FOR ARBITRARY C/O

DOE Office of Scientific and Technical Information (OSTI.GOV)

Heng, Kevin; Tsai, Shang-Min; Lyons, James R., E-mail: kevin.heng@csh.unibe.ch

2016-01-10

We present a self-consistent formalism for computing and understanding the atmospheric chemistry of exoplanets from the viewpoint of an astrophysicist. Starting from the first law of thermodynamics, we demonstrate that the van’t Hoff equation (which describes the equilibrium constant), Arrhenius equation (which describes the rate coefficients), and procedures associated with the Gibbs free energy (minimization, rescaling) have a common physical and mathematical origin. We address an ambiguity associated with the equilibrium constant, which is used to relate the forward and reverse rate coefficients, and restate its two definitions. By necessity, one of the equilibrium constants must be dimensionless and equatemore » to an exponential function involving the Gibbs free energy, while the other is a ratio of rate coefficients and must therefore possess physical units. We demonstrate that the Arrhenius equation takes on a functional form that is more general than previously stated without recourse to tagging on ad hoc functional forms. Finally, we derive analytical models of chemical systems, in equilibrium, with carbon, hydrogen, and oxygen. We include acetylene and are able to reproduce several key trends, versus temperature and carbon-to-oxygen ratio, published in the literature. The rich variety of behavior that mixing ratios exhibit as a function of the carbon-to-oxygen ratio is merely the outcome of stoichiometric book-keeping and not the direct consequence of temperature or pressure variations.« less

Atmospheric Chemistry for Astrophysicists: A Self-consistent Formalism and Analytical Solutions for Arbitrary C/O

NASA Astrophysics Data System (ADS)

Heng, Kevin; Lyons, James R.; Tsai, Shang-Min

2016-01-01

We present a self-consistent formalism for computing and understanding the atmospheric chemistry of exoplanets from the viewpoint of an astrophysicist. Starting from the first law of thermodynamics, we demonstrate that the van’t Hoff equation (which describes the equilibrium constant), Arrhenius equation (which describes the rate coefficients), and procedures associated with the Gibbs free energy (minimization, rescaling) have a common physical and mathematical origin. We address an ambiguity associated with the equilibrium constant, which is used to relate the forward and reverse rate coefficients, and restate its two definitions. By necessity, one of the equilibrium constants must be dimensionless and equate to an exponential function involving the Gibbs free energy, while the other is a ratio of rate coefficients and must therefore possess physical units. We demonstrate that the Arrhenius equation takes on a functional form that is more general than previously stated without recourse to tagging on ad hoc functional forms. Finally, we derive analytical models of chemical systems, in equilibrium, with carbon, hydrogen, and oxygen. We include acetylene and are able to reproduce several key trends, versus temperature and carbon-to-oxygen ratio, published in the literature. The rich variety of behavior that mixing ratios exhibit as a function of the carbon-to-oxygen ratio is merely the outcome of stoichiometric book-keeping and not the direct consequence of temperature or pressure variations.

Molecular Dynamics Simulations of the Temperature Induced Unfolding of Crambin Follow the Arrhenius Equation.

PubMed

Dalby, Andrew; Shamsir, Mohd Shahir

2015-01-01

Molecular dynamics simulations have been used extensively to model the folding and unfolding of proteins. The rates of folding and unfolding should follow the Arrhenius equation over a limited range of temperatures. This study shows that molecular dynamic simulations of the unfolding of crambin between 500K and 560K do follow the Arrhenius equation. They also show that while there is a large amount of variation between the simulations the average values for the rate show a very high degree of correlation.

Molecular Dynamics Simulations of the Temperature Induced Unfolding of Crambin Follow the Arrhenius Equation.

PubMed Central

Dalby, Andrew; Shamsir, Mohd Shahir

2015-01-01

Molecular dynamics simulations have been used extensively to model the folding and unfolding of proteins. The rates of folding and unfolding should follow the Arrhenius equation over a limited range of temperatures. This study shows that molecular dynamic simulations of the unfolding of crambin between 500K and 560K do follow the Arrhenius equation. They also show that while there is a large amount of variation between the simulations the average values for the rate show a very high degree of correlation. PMID:26539292

Incremental viscosity by non-equilibrium molecular dynamics and the Eyring model

NASA Astrophysics Data System (ADS)

Heyes, D. M.; Dini, D.; Smith, E. R.

2018-05-01

The viscoelastic behavior of sheared fluids is calculated by Non-Equilibrium Molecular Dynamics (NEMD) simulation, and complementary analytic solutions of a time-dependent extension of Eyring's model (EM) for shear thinning are derived. It is argued that an "incremental viscosity," ηi, or IV which is the derivative of the steady state stress with respect to the shear rate is a better measure of the physical state of the system than the conventional definition of the shear rate dependent viscosity (i.e., the shear stress divided by the strain rate). The stress relaxation function, Ci(t), associated with ηi is consistent with Boltzmann's superposition principle and is computed by NEMD and the EM. The IV of the Eyring model is shown to be a special case of the Carreau formula for shear thinning. An analytic solution for the transient time correlation function for the EM is derived. An extension of the EM to allow for significant local shear stress fluctuations on a molecular level, represented by a gaussian distribution, is shown to have the same analytic form as the original EM but with the EM stress replaced by its time and spatial average. Even at high shear rates and on small scales, the probability distribution function is almost gaussian (apart from in the wings) with the peak shifted by the shear. The Eyring formula approximately satisfies the Fluctuation Theorem, which may in part explain its success in representing the shear thinning curves of a wide range of different types of chemical systems.

Reducing blood viscosity with magnetic fields

NASA Astrophysics Data System (ADS)

Tao, R.; Huang, K.

2011-07-01

Blood viscosity is a major factor in heart disease. When blood viscosity increases, it damages blood vessels and increases the risk of heart attacks. Currently, the only method of treatment is to take drugs such as aspirin, which has, however, several unwanted side effects. Here we report our finding that blood viscosity can be reduced with magnetic fields of 1 T or above in the blood flow direction. One magnetic field pulse of 1.3 T lasting ˜1 min can reduce the blood viscosity by 20%-30%. After the exposure, in the absence of magnetic field, the blood viscosity slowly moves up, but takes a couple of hours to return to the original value. The process is repeatable. Reapplying the magnetic field reduces the blood viscosity again. By selecting the magnetic field strength and duration, we can keep the blood viscosity within the normal range. In addition, such viscosity reduction does not affect the red blood cells’ normal function. This technology has much potential for physical therapy.

Dynamical influences on the moment of inertia tensor from lateral viscosity variations inferred from seismic tomographic models

NASA Technical Reports Server (NTRS)

Zhang, Shuxia; Yuen, David A.

1994-01-01

We have investigated the influences of lateral variations of viscosity on the moment of inertia tensor from viscous flows due to the density anomalies in the mantle inferred from seismic tomographic models. The scaling relations between the density and the seismic anomalies is taken as either a constant or a function increasing with depth in accord with the recent high-pressure experimental studies. The viscosity is taken as an exponential function of the 3D density anomaly. In models with an isoviscous background, the effects on the perturbed moment of inertia tensor from the lateral viscosity variations are smaller than those due to variations in the radial viscosity profiles. In mantle models with a background viscosity increasing with depth, the influences of the lateral viscosity variations are significant. The most striking feature in the latter case is that the two off-diagonal elements delta I(sub xz) and delta I(sub yz) in the inertia tensor exhibit greatest sensitivity to lateral variations of the viscosity. While the other elements of the inertia change by only about a few tens of percent in the range of lateral viscosity contrast considered (less than 300), delta I(sub xz) and delta I(sub yz) can vary up to 40 times even with a change in sign, depending on the radial viscosity stratification and the location of the strongest lateral variations. The increase in the velocity-density scaling relation with depth can reduce the influences of the lateral viscosity variations, but it does not change the overall sensitive nature of delta I(sub xz) and delta I(sub yz). This study demonstrates clearly that the lateral viscosity variations, especially in the upper mantle, must be considered in the determination of long-term polar wander, since the variations in the delta I(sub xz) and delta I(sub yz) terms are directly responsible for exciting rotational movements.

Measuring and Overcoming Limits of the Saffman-Delbrück Model for Soap Film Viscosities

PubMed Central

Vivek, Skanda; Weeks, Eric R.

2015-01-01

We observe tracer particles diffusing in soap films to measure the two-dimensional (2D) viscous properties of the films. Saffman-Delbrück type models relate the single-particle diffusivity to parameters of the film (such as thickness h) for thin films, but the relation breaks down for thicker films. Notably, the diffusivity is faster than expected for thicker films, with the crossover at h/d = 5.2 ± 0.9 using the tracer particle diameter d. This indicates a crossover from purely 2D diffusion to diffusion that is more three-dimensional. We demonstrate that measuring the correlations of particle pairs as a function of their separation overcomes the limitations of the Saffman-Delbrück model and allows one to measure the viscosity of a soap film for any thickness. PMID:25822262

Bacterial accumulation in viscosity gradients

NASA Astrophysics Data System (ADS)

Waisbord, Nicolas; Guasto, Jeffrey

2016-11-01

Cell motility is greatly modified by fluid rheology. In particular, the physical environments in which cells function, are often characterized by gradients of viscous biopolymers, such as mucus and extracellular matrix, which impact processes ranging from reproduction to digestion to biofilm formation. To understand how spatial heterogeneity of fluid rheology affects the motility and transport of swimming cells, we use hydrogel microfluidic devices to generate viscosity gradients in a simple, polymeric, Newtonian fluid. Using video microscopy, we characterize the random walk motility patterns of model bacteria (Bacillus subtilis), showing that both wild-type ('run-and-tumble') cells and smooth-swimming mutants accumulate in the viscous region of the fluid. Through statistical analysis of individual cell trajectories and body kinematics in both homogeneous and heterogeneous viscous environments, we discriminate passive, physical effects from active sensing processes to explain the observed cell accumulation at the ensemble level.

Measuring and overcoming limits of the Saffman-Delbrück model for soap film viscosities.

PubMed

Vivek, Skanda; Weeks, Eric R

2015-01-01

We observe tracer particles diffusing in soap films to measure the two-dimensional (2D) viscous properties of the films. Saffman-Delbrück type models relate the single-particle diffusivity to parameters of the film (such as thickness h) for thin films, but the relation breaks down for thicker films. Notably, the diffusivity is faster than expected for thicker films, with the crossover at h/d = 5.2 ± 0.9 using the tracer particle diameter d. This indicates a crossover from purely 2D diffusion to diffusion that is more three-dimensional. We demonstrate that measuring the correlations of particle pairs as a function of their separation overcomes the limitations of the Saffman-Delbrück model and allows one to measure the viscosity of a soap film for any thickness.

The Development of the Arrhenius Equation.

ERIC Educational Resources Information Center

Laidler, Keith J.

1984-01-01

Traces the development of the Arrhenius equation from its beginning, examining the more important alternate proposals and the work that supported them. Aside from its historical interest, this examination affords insight into how scientific progress is made. (JN)

Interactive Classroom Graphics--Simulating Non-Linear Arrhenius Plots.

ERIC Educational Resources Information Center

Ben-Zion, M.; Hoz, S.

1980-01-01

Describes two simulation programs using an interactive graphic display terminal that were developed for a course in physical organic chemistry. Demonstrates the energetic conditions that give rise to deviations from linearity in the Arrhenius equation. (CS)

Hall viscosity of hierarchical quantum Hall states

NASA Astrophysics Data System (ADS)

Fremling, M.; Hansson, T. H.; Suorsa, J.

2014-03-01

Using methods based on conformal field theory, we construct model wave functions on a torus with arbitrary flat metric for all chiral states in the abelian quantum Hall hierarchy. These functions have no variational parameters, and they transform under the modular group in the same way as the multicomponent generalizations of the Laughlin wave functions. Assuming the absence of Berry phases upon adiabatic variations of the modular parameter τ, we calculate the quantum Hall viscosity and find it to be in agreement with the formula, given by Read, which relates the viscosity to the average orbital spin of the electrons. For the filling factor ν =2/5 Jain state, which is at the second level in the hierarchy, we compare our model wave function with the numerically obtained ground state of the Coulomb interaction Hamiltonian in the lowest Landau level, and find very good agreement in a large region of the complex τ plane. For the same example, we also numerically compute the Hall viscosity and find good agreement with the analytical result for both the model wave function and the numerically obtained Coulomb wave function. We argue that this supports the notion of a generalized plasma analogy that would ensure that wave functions obtained using the conformal field theory methods do not acquire Berry phases upon adiabatic evolution.

Gas phase chemistry in gallium nitride CVD: Theoretical determination of the Arrhenius parameters for the first Ga-C bond homolysis of trimethylgallium.

PubMed

Schmid, Rochus; Basting, Daniel

2005-03-24

Experimental evidence suggests that the energy of activation for the first homolytic Ga-C bond fission of GaMe3 of Ea = 249 kJ/mol, measured by Jacko and Price in a hot-wall tube reactor, is affected by surface catalytic effects. In this contribution, the rate constant for this crucial step in the gas-phase pyrolysis of GaMe3 has been calculated by variational transition state theory. By a basis set extrapolation on the MP2/cc-pVXZ level and a correlation correction from CCSD(T)/cc-pVDZ level, a theoretical "best estimate" for the bond energy of Delta H(289K) = 327.2 kJ/mol was derived. For the VTST calculation on the B3LYP/cc-pVDZ level, the energies were corrected to reproduce this bond energy. Partition functions of the transitional modes were approximated by a hindered rotor approximation to be valid along the whole reaction coordinate defined by the Ga-C bond length. On the basis of the canonical transition state theory, reaction rates were determined using the maxima of the free energy Delta G++. An Arrhenius-type rate law was fitted to these rate constants, yielding an apparent energy of activation of Ea = 316.7 kJ/mol. The preexponential factor A = 3.13 x 10(16) 1/s is an order of magnitude larger than the experimental results because of a larger release of entropy at the transition state as compared to that of the unknown surface catalyzed mechanism.

Osmotic and Chill Activation of Glycine Betaine Porter II in Listeria monocytogenes Membrane Vesicles

PubMed Central

Gerhardt, Paul N. M.; Tombras Smith, Linda; Smith, Gary M.

2000-01-01

Listeria monocytogenes is a foodborne pathogen known for its tolerance to conditions of osmotic and chill stress. Accumulation of glycine betaine has been found to be important in the organism's tolerance to both of these stresses. A procedure was developed for the purification of membranes from L. monocytogenes cells in which the putative ATP-driven glycine betaine permease glycine betaine porter II (Gbu) is functional. As is the case for the L. monocytogenes sodium-driven glycine betaine uptake system (glycine betaine porter I), uptake in this vesicle system was dependent on energization by ascorbate-phenazine methosulfate. Vesicles lacking the gbu gene product had no uptake activity. Transport by this porter did not require sodium ion and could be driven only weakly by artificial gradients. Uptake rates could be manipulated under conditions not affecting secondary transport but known to affect ATPase activity. The system was shown to be both osmotically activated and cryoactivated. Under conditions of osmotic activation, the system exhibited Arrhenius-type behavior although the uptake rates were profoundly affected by the physical state of the membrane, with breaks in Arrhenius curves at approximately 10 and 18°C. In the absence of osmotic activation, the permease could be activated by decreasing temperature within the range of 15 to 4°C. Kinetic analyses of the permease at 30°C revealed Km values for glycine betaine of 1.2 and 2.9 μM with Vmax values of 2,200 and 3,700 pmol/min · mg of protein under conditions of optimal osmotic activation as mediated by KCl and sucrose, respectively. PMID:10762257

Artificial viscosity in Godunov-type schemes to cure the carbuncle phenomenon

NASA Astrophysics Data System (ADS)

Rodionov, Alexander V.

2017-09-01

This work presents a new approach for curing the carbuncle instability. The idea underlying the approach is to introduce some dissipation in the form of right-hand sides of the Navier-Stokes equations into the basic method of solving Euler equations; in so doing, we replace the molecular viscosity coefficient by the artificial viscosity coefficient and calculate heat conductivity assuming that the Prandtl number is constant. For the artificial viscosity coefficient we have chosen a formula that is consistent with the von Neumann and Richtmyer artificial viscosity, but has its specific features (extension to multidimensional simulations, introduction of a threshold compression intensity that restricts additional dissipation to the shock layer only). The coefficients and the expression for the characteristic mesh size in this formula are chosen from a large number of Quirk-type problem computations. The new cure for the carbuncle flaw has been tested on first-order schemes (Godunov, Roe, HLLC and AUSM+ schemes) as applied to one- and two-dimensional simulations on smooth structured grids. Its efficiency has been demonstrated on several well-known test problems.

Shock-wave structure for a polyatomic gas with large bulk viscosity

NASA Astrophysics Data System (ADS)

Kosuge, Shingo; Aoki, Kazuo

2018-02-01

The structure of a standing plane shock wave in a polyatomic gas is investigated on the basis of kinetic theory, with special interest in gases with large bulk viscosities, such as CO2 gas. The ellipsoidal statistical model for a polyatomic gas is employed. First, the shock structure is computed numerically for various upstream Mach numbers and for various (large) values of the ratio of the bulk viscosity to the shear viscosity, and different types of profiles, such as the double-layer structure consisting of a thin upstream layer with a steep change and a much thicker downstream layer with a mild change, are obtained. Then, an asymptotic analysis for large values of the ratio is carried out, and an analytical solution that describes the different types of profiles obtained by the numerical analysis, such as the double-layer structure, correctly is obtained.

Influence of functionalized nanoparticles on conformational stability of type I collagen for possible biomedical applications.

PubMed

Kandamchira, Aswathy; Selvam, Sangeetha; Marimuthu, Nidhin; Janardhanan, Sreeram Kalarical; Fathima, Nishter Nishad

2013-12-01

Collagen-nanoparticle interactions are vital for many biomedical applications including drug delivery and tissue engineering applications. Iron oxide nanoparticles synthesized using starch template according to our earlier reported procedures were functionalized by treating them with Gum Arabic (GA), a biocompatible polysaccharide, so as to enhance the interaction between nanoparticle surfaces and collagen. Viscosity, circular dichroism (CD) and Fourier transform infrared spectroscopy (FTIR) techniques have been used to study the collagen-nanoparticle interactions. The relative viscosity for collagen-nanoparticle conjugate was found to increase with increase in concentration of the nanoparticle within the concentration range investigated, which is due to the aggregation of protein onto the surface of nanoparticle. The CD spectra for the collagen-nanoparticle at different concentration ratios do not have much variation in the Rpn values (ratio of positive peak intensity over negative peak intensity) after functionalization with GA. The variation of molar ellipticity values for collagen-nanoparticle is due to the glycoprotein present in GA. The collagen triple helical structure is maintained after interaction with nanoparticles. The FTIR spectra of native collagen, Coll-Fs (nanoparticle without functionalization) and Coll-FsG (nanoparticle functionalized with GA) show clearly the amide I, II, III bands, with respect to collagen. The ability of polysaccharide stabilized/functionalized nanoparticles to maintain the collagen properties would help in its biomedical applications. © 2013.

Simultaneous effects of single wall carbon nanotube and effective variable viscosity for peristaltic flow through annulus having permeable walls

NASA Astrophysics Data System (ADS)

Shahzadi, Iqra; Nadeem, S.; Rabiei, Faranak

The current article deals with the combine effects of single wall carbon nanotubes and effective viscosity for the peristaltic flow of nanofluid through annulus. The nature of the walls is assumed to be permeable. The present theoretical model can be considered as mathematical representation to the motion of conductive physiological fluids in the existence of the endoscope tube which has many biomedical applications such as drug delivery system. The outer tube has a wave of sinusoidal nature that is travelling along its walls while the inner tube is rigid and uniform. Lubrication approach is used for the considered analysis. An empirical relation for the effective variable viscosity of nanofluid is proposed here interestingly. The viscosity of nanofluid is the function of radial distance and the concentration of nanoparticles. Exact solution for the resulting system of equations is displayed for various quantities of interest. The outcomes show that the maximum velocity of SWCNT-blood nanofluid enhances for larger values of viscosity parameter. The pressure gradient in the more extensive part of the annulus is likewise found to increase as a function of variable viscosity parameter. The size of the trapped bolus is also influenced by variable viscosity parameter. The present examination also revealed that the carbon nanotubes have many applications related to biomedicine.

Green-Kubo relations for the viscosity of biaxial nematic liquid crystals

NASA Astrophysics Data System (ADS)

Sarman, Sten

1996-09-01

We derive Green-Kubo relations for the viscosities of a biaxial nematic liquid crystal. In this system there are seven shear viscosities, three twist viscosities, and three cross coupling coefficients between the antisymmetric strain rate and the symmetric traceless pressure tensor. According to the Onsager reciprocity relations these couplings are equal to the cross couplings between the symmetric traceless strain rate and the antisymmetric pressure. Our method is based on a comparison of the microscopic linear response generated by the SLLOD equations of motion for planar Couette flow (so named because of their close connection to the Doll's tensor Hamiltonian) and the macroscopic linear phenomenological relations between the pressure tensor and the strain rate. In order to obtain simple Green-Kubo relations we employ an equilibrium ensemble where the angular velocities of the directors are identically zero. This is achieved by adding constraint torques to the equations for the molecular angular accelerations. One finds that all the viscosity coefficients can be expressed as linear combinations of time correlation function integrals (TCFIs). This is much simpler compared to the expressions in the conventional canonical ensemble, where the viscosities are complicated rational functions of the TCFIs. The reason for this is, that in the constrained angular velocity ensemble, the thermodynamic forces are given external parameters whereas the thermodynamic fluxes are ensemble averages of phase functions. This is not the case in the canonical ensemble. The simplest way of obtaining numerical estimates of viscosity coefficients of a particular molecular model system is to evaluate these fluctuation relations by equilibrium molecular dynamics simulations.

Kinetics of the Reactions of Cl((sup 2)P(sub J)) and Br((sup 2)P(sub 3/2)) with O3

NASA Technical Reports Server (NTRS)

Nicovich, J. M.; Kreutter, K. D.; Wine, P. H.

1997-01-01

A laser flash photolysis-resonance fluorescence technique has been employed to study the kinetics of the important stratospheric reactions Cl((sup 2)P(sub J)) + O3 yields ClO + O2 and Br((sup 2)P(sub 3/2)) + O3 yields BrO + O2 as a function of temperature. The temperature dependence observed for the Cl((sup 2)P(sub J)) + O3 reaction is nonArrhenius, but can be adequately described by the following two Arrhenius expressions (units are cu cm/(molecule.s), errors are 2 sigma and represent precision only): k(sub 1)(T) = (1.19 +/- 0.21) x 10(exp -11) exp[(-33 +/- 37)/T] for T = 189-269 K and k(sub 1)(T) = (2.49 +/- 0.38) x 10(exp -11) exp[(-233 +/- 46)/T] for 269-385 K. At temperatures below 230 K, the rate coefficients determined in this study are faster than any reported previously. Incorporation of our values for k(sub 1)(T) into stratospheric models would increase calculated ClO levels and decrease calculated HCI levels; hence the calculated efficiency of ClO catalyzed ozone destruction would increase. The temperature dependence observed for the Br((sup 2)P(sub 3/2)) + O3 reaction is adequately described by the following Arrhenius expression (units are cu cm/(molecule.s), errors are 2 sigma and represent precision only): k(sub 2)(T) = (1.50 +/- 0.16) x 10(exp -11)exp[(-775 +/- 30)/T for 195-392 K. While not in quantitative agreement with Arrhenius parameters reported in most previous studies, our results almost exactly reproduce the average of all earlier studies and therefore will not affect the choice of k(sub 2)(T) for use in modeling stratospheric BrO2 chemistry.

Viscosity and compressibility of diacylglycerol under high pressure

NASA Astrophysics Data System (ADS)

Malanowski, Aleksander; Rostocki, A. J.; Kiełczyński, P.; Szalewski, M.; Balcerzak, A.; Kościesza, R.; Tarakowski, R.; Ptasznik, S.; Siegoczyński, R. M.

2013-03-01

The influence of high pressure on viscosity and compressibility of diacylglycerol (DAG) oil has been presented in this paper. The investigated DAG oil was composed of 82% of DAGs and 18% TAGs (triacylglycerols). The dynamic viscosity of DAG was investigated as a function of the pressure up to 400 MPa. The viscosity was measured by means of the surface acoustic wave method, where the acoustic waveguides were used as sensing elements. As the pressure was rising, the larger ultrasonic wave attenuation was observed, whereas amplitude decreased with the liquid viscosity augmentation. Measured changes of physical properties were most significant in the pressure range near the phase transition. Deeper understanding of DAG viscosity and compressibility changes versus pressure could shed more light on thermodynamic properties of edible oils.

The viscosity of magmatic silicate liquids: A model for calculation

NASA Technical Reports Server (NTRS)

Bottinga, Y.; Weill, D. F.

1971-01-01

A simple model has been designed to allow reasonably accurate calculations of viscosity as a function of temperature and composition. The problem of predicting viscosities of anhydrous silicate liquids has been investigated since such viscosity numbers are applicable to many extrusive melts and to nearly dry magmatic liquids in general. The fluidizing action of water dissolved in silicate melts is well recognized and it is now possible to predict the effect of water content on viscosity in a semiquantitative way. Water was not incorporated directly into the model. Viscosities of anhydrous compositions were calculated, and, where necessary, the effect of added water and estimated. The model can be easily modified to incorporate the effect of water whenever sufficient additional data are accumulated.

Viscosity of colloidal suspensions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cohen, E.G.D.; Schepper, I.M. de

Simple expressions are given for the effective Newtonian viscosity as a function of concentration as well as for the effective visco-elastic response as a function of concentration and imposed frequency, of monodisperse neutral colloidal suspensions over the entire fluid range. The basic physical mechanisms underlying these formulae are discussed. The agreement with existing experiments is very good.

Volatile flavor analysis and sensory evaluation of custard desserts varying in type and concentration of carboxymethyl cellulose.

PubMed

van Ruth, Saskia M; de Witte, Leontien; Uriarte, Amaya Rey

2004-12-29

The influence of type and concentration of carboxymethyl cellulose (CMC) on flavor and textural properties of custard desserts was examined. A synthetic strawberry flavor mixture was used to flavor the custards; it comprised 15 volatile flavor compounds. The viscosity of the custards was determined using rheometric measurements. Static headspace gas chromatography and in-nose proton transfer reaction-mass spectrometry analyses were conducted to determine the custards' volatile flavor properties. Perceived odor, flavor, and textural properties were assessed in sensory analysis experiments using magnitude estimation against a fixed modulus. Both type and concentration of CMC altered the viscosity of the custards. Softer custards had higher static headspace flavor concentrations. On the contrary, firmer custards demonstrated higher in-nose flavor concentrations. In sensory analysis, firmer custards showed higher thickness and lower sweetness intensities than their low-viscosity counterparts. The thickness perception corresponded to the viscosity of the custards. Removal of sucrose from the custards affected sweetness intensity only and not the intensity of other attributes. Therefore, the influence of the viscosity of the custards on the release of sweet-tasting components is held responsible for the effect on perceived sweetness intensity. Odor intensities were generally higher for the low-viscosity custard, whereas fruity flavor intensities were higher for the firmer custards. Odor intensities correlated with static headspace concentrations and flavor intensities related reasonably well with in-nose concentrations. Opening and closing of the nasal cavity is regarded as an important factor determining the discrepancy between static and in-nose measurements.

Thermal quenching of the yellow luminescence in GaN

NASA Astrophysics Data System (ADS)

Reshchikov, M. A.; Albarakati, N. M.; Monavarian, M.; Avrutin, V.; Morkoç, H.

2018-04-01

We observed varying thermal quenching behavior of the yellow luminescence band near 2.2 eV in different GaN samples. In spite of the different behavior, the yellow band in all the samples is caused by the same defect—the YL1 center. In conductive n-type GaN, the YL1 band quenches with exponential law, and the Arrhenius plot reveals an ionization energy of ˜0.9 eV for the YL1 center. In semi-insulating GaN, an abrupt and tunable quenching of the YL1 band is observed, where the apparent activation energy in the Arrhenius plot is not related to the ionization energy of the defect. In this case, the ionization energy can be found by analyzing the shift of the characteristic temperature of PL quenching with excitation intensity. We conclude that only one defect, namely, the YL1 center, is responsible for the yellow band in undoped and doped GaN samples grown by different techniques.

Significant difference in the dynamics between strong and fragile glass formers.

PubMed

Furukawa, Akira; Tanaka, Hajime

2016-11-01

Glass-forming liquids are often classified into strong glass formers with nearly Arrhenius behavior and fragile ones with super-Arrhenius behavior. We reveal a significant difference in the dynamics between these two types of glass formers through molecular dynamics simulations: In strong glass formers, the relaxation dynamics of density fluctuations is nondiffusive, whereas in fragile glass formers it exhibits diffusive behavior. We demonstrate that this distinction is a direct consequence of the fundamental difference in the underlying elementary relaxation process between these two dynamical classes of glass formers. For fragile glass formers, a density-exchange process proceeds the density relaxation, which takes place locally at the particle level in normal states but is increasingly cooperative and nonlocal as the temperature is lowered in supercooled states. On the other hand, in strong glass formers, such an exchange process is not necessary for density relaxation due to the presence of other local relaxation channels. Our finding provides a novel insight into Angell's classification scheme from a hydrodynamic perspective.

Margin adaptation of indirect composite inlays fabricated on flexible dies.

PubMed

Price, R B; Gerrow, J D

2000-03-01

Indirect composite restorations can be made in 1 appointment using a flexible die. Interactions between different impression materials and flexible die materials may affect the accuracy of fit and margin adaptation of the restoration. This study compared the margin adaptation of composite inlays made using the following 5 impression/flexible die material combinations; condensation silicone/polyvinyl siloxane (CS/PVS), wash viscosity polyvinyl siloxane/medium or heavy viscosity polyvinyl siloxane (PVS/PVS), irreversible hydrocolloid impression/medium viscosity polyvinyl siloxane (IH/PVS), wash viscosity polyvinyl siloxane impression/polyether (PVS/PE), with composite inlays made using a control system of a wash viscosity polyvinyl siloxane impression and a type IV stone die. For each test and control system, 10 impressions were made of a class II composite inlay preparation in a metal master die. One die was made from each impression and one composite inlay was made and finished on each die (a total of 60 inlays). Inlays were placed on the master die and the margin opening at the buccal, distal, and gingival sites was recorded with a measuring microscope (x40 magnification). The overall mean +/- SD margin openings of inlays made from the systems were as follows: PVS wash/PVS heavy viscosity 149.5 +/- 107. 4 microm; PVS wash/PVS medium viscosity 87.4 +/- 63.0 microm; IH/PVS medium viscosity 76.7 +/- 48.9 microm; CS/PVS 73.3 +/- 48.7 microm, PVS wash viscosity/PE 64.0 +/- 44.3 microm, PVS wash viscosity/stone 53.9 +/- 48.3 microm. Composite inlays made using the PVS wash viscosity/PVS heavy viscosity system had significantly larger distal, gingival, and overall mean margin openings than all other inlays (ANOVA and Fisher PLSD test; P =.05). The separating medium required between some impression and die materials did not work consistently. Composite inlays fabricated on dies made of material different than the impression material had mean buccal, distal, gingival, and overall margin openings < or =100 microm. Composite inlays made on the CS/PVS, IH/PVS medium viscosity, PVS wash viscosity/PE flexible dies, and control PVS wash viscosity/stone dies had statistically similar (P =.05) mean buccal, distal, gingival, and overall mean margin openings that were < or =100 microm. Composite inlays made on dies that were made of the same type of material as the impression material (PVS/PVS) had mean gingival margin openings >100 microm that were significantly larger than all other systems tested (P =.05).

Uncovering the role of the flexible C-terminal tail: A model study with Strep-tagged GFP.

PubMed

Lassalle, Michael W; Kondou, Shinobu

2016-06-01

Recently, it has been recognized that, much like an electric current in an electric circuit, dynamic disruptions from flexible, unstructured regions distal to the active region are transferred through the contact network to the active site and influence protein stability and/or function. As transmembrane proteins frequently possess the β-barrel structure, studies of proteins with this topology are required. The unstructured lid segments of the β-barrel GFP protein are conserved and could play a role in the backbone stabilization required for chromophore function. A study of the disordered C-terminus and the function within the lid is necessary. In this study, we entirely truncated the flexible C-terminal tail and investigated the N-terminal Strep-tagged GFP by fluorescence spectroscopy, and the temperature- and GdnHCl-induced unfolding by circular dichroism. The introduction of the unstructured Strep-tag itself changed the unfolding pathway. Truncating the entire flexible tail did not decrease the fluorescence intensity to a large extent; however, the protein stability changed dramatically. The temperature for half-denaturation T 1/2 changed significantly from 79 °C for the wild-type to 72.8 °C for the mutant. Unfolding kinetics at different temperatures have been induced by 4 M GdnHCl, and the apparent Arrhenius activation energy decreased by 40% as compared to the wild-type.

Arrhenius curves of hydrogen transfers: tunnel effects, isotope effects and effects of pre-equilibria

PubMed Central

Limbach, Hans-Heinrich; Miguel Lopez, Juan; Kohen, Amnon

2006-01-01

In this paper, the Arrhenius curves of selected hydrogen-transfer reactions for which kinetic data are available in a large temperature range are reviewed. The curves are discussed in terms of the one-dimensional Bell–Limbach tunnelling model. The main parameters of this model are the barrier heights of the isotopic reactions, barrier width of the H-reaction, tunnelling masses, pre-exponential factor and minimum energy for tunnelling to occur. The model allows one to compare different reactions in a simple way and prepare the kinetic data for more-dimensional treatments. The first type of reactions is concerned with reactions where the geometries of the reacting molecules are well established and the kinetic data of the isotopic reactions are available in a large temperature range. Here, it is possible to study the relation between kinetic isotope effects (KIEs) and chemical structure. Examples are the tautomerism of porphyrin, the porphyrin anion and related compounds exhibiting intramolecular hydrogen bonds of medium strength. We observe pre-exponential factors of the order of kT/h≅1013 s−1 corresponding to vanishing activation entropies in terms of transition state theory. This result is important for the second type of reactions discussed in this paper, referring mostly to liquid solutions. Here, the reacting molecular configurations may be involved in equilibria with non- or less-reactive forms. Several cases are discussed, where the less-reactive forms dominate at low or at high temperature, leading to unusual Arrhenius curves. These cases include examples from small molecule solution chemistry like the base-catalysed intramolecular H-transfer in diaryltriazene, 2-(2′-hydroxyphenyl)-benzoxazole, 2-hydroxy-phenoxyl radicals, as well as in the case of an enzymatic system, thermophilic alcohol dehydrogenase. In the latter case, temperature-dependent KIEs are interpreted in terms of a transition between two regimes with different temperature-independent KIEs. PMID:16873127

Arrhenius curves of hydrogen transfers: tunnel effects, isotope effects and effects of pre-equilibria.

PubMed

Limbach, Hans-Heinrich; Miguel Lopez, Juan; Kohen, Amnon

2006-08-29

In this paper, the Arrhenius curves of selected hydrogen-transfer reactions for which kinetic data are available in a large temperature range are reviewed. The curves are discussed in terms of the one-dimensional Bell-Limbach tunnelling model. The main parameters of this model are the barrier heights of the isotopic reactions, barrier width of the H-reaction, tunnelling masses, pre-exponential factor and minimum energy for tunnelling to occur. The model allows one to compare different reactions in a simple way and prepare the kinetic data for more-dimensional treatments. The first type of reactions is concerned with reactions where the geometries of the reacting molecules are well established and the kinetic data of the isotopic reactions are available in a large temperature range. Here, it is possible to study the relation between kinetic isotope effects (KIEs) and chemical structure. Examples are the tautomerism of porphyrin, the porphyrin anion and related compounds exhibiting intramolecular hydrogen bonds of medium strength. We observe pre-exponential factors of the order of kT/h congruent with 10(13) s-1 corresponding to vanishing activation entropies in terms of transition state theory. This result is important for the second type of reactions discussed in this paper, referring mostly to liquid solutions. Here, the reacting molecular configurations may be involved in equilibria with non- or less-reactive forms. Several cases are discussed, where the less-reactive forms dominate at low or at high temperature, leading to unusual Arrhenius curves. These cases include examples from small molecule solution chemistry like the base-catalysed intramolecular H-transfer in diaryltriazene, 2-(2'-hydroxyphenyl)-benzoxazole, 2-hydroxy-phenoxyl radicals, as well as in the case of an enzymatic system, thermophilic alcohol dehydrogenase. In the latter case, temperature-dependent KIEs are interpreted in terms of a transition between two regimes with different temperature-independent KIEs.

Using Mars Orbiter Laser Altimeter (MOLA) Data to Assess Impact Crater Modification in the Arrhenius Region of Mars

NASA Technical Reports Server (NTRS)

Garvin, J. B.; Grosfils, E. B.; Sakimoto, S. E. H.

2000-01-01

This study combines MOLA altimetry with photographic imagery to begin assessing the extent to which sedimentary and volcanic processes have affected impact crater morphology in the Arrhenius region of Mars.

Transition from Arrhenius to non-Arrhenius temperature dependence of structural relaxation time in glass-forming liquids: continuous versus discontinuous scenario.

PubMed

Popova, V A; Surovtsev, N V

2014-09-01

The temperature dependences of α relaxation time τ(α)(T) of three glass-forming liquids (salol, o-terphenyl, and α-picoline) were investigated by a depolarized light scattering technique. A detailed description of τ(α)(T) near T(A), the temperature of the transition from the Arrhenius law at high temperatures to a non-Arrhenius behavior of τ(α)(T) at lower temperatures, was done. It was found that this transition is quite sharp. If the transition is described as switching from the Arrhenius law to the Vogel-Fulcher-Tammann law, it occurs within the temperature range of about 15 K or less. Most of the known expressions for τ(α)(T) cannot describe this sharp transition. Our analysis revealed that this transition can be described either as a discontinuous transition in the spirit of the frustration-limited domain theory [D. Kivelson, G. Tarjus, X. Zhao, and S. A. Kivelson, Phys. Rev. E 53, 751 (1996)], implying a phase transition, or by a phenomenological expression recently suggested [B. Schmidtke, N. Petzold, R. Kahlau, M. Hofmann, and E. A. Rössler, Phys. Rev. E 86, 041507 (2012)], where the activation energy includes the term depending exponentially on temperature.

Anion-Functionalized Task-Specific Ionic Liquids: Molecular Origin of Change in Viscosity upon CO2 Capture.

PubMed

Li, Ailin; Tian, Ziqi; Yan, Tianying; Jiang, De-en; Dai, Sheng

2014-12-26

The structure and dynamics of a task-specific ionic liquid (TSIL), trihexyl(tetradecyl)phosphonium imidazolate, before and after absorbing CO(2) were studied with a molecular dynamics (MD) simulation. This particular ionic liquid is one of several newly discovered azole-based TSILs for equimolar CO(2) capture. Unlike other TSILs whose viscosity increases drastically upon reaction with CO(2), its viscosity decreases after CO(2) absorption. This unique behavior was confirmed in our MD simulation. We find that after CO(2) absorption the translational dynamics of the whole system is accelerated, accompanied by an accelerated rotational dynamics of the cations. Radial distribution function and spatial distribution function analyses show that the anions become asymmetric after reaction with CO(2), and this causes the imbalance of the interaction between the positive and negative regions of the ions. The interaction between the phosphorus atom of the cation and oxygen atoms of the carboxyl group on the anion is enhanced, while that between the phosphorus atom and the naked nitrogen atom of the anion is weakened. The ion-pair correlation functions further support that the weakened interaction leads to faster dissociation of cation-anion pairs, thereby causing an accelerated dynamics. Hence, the asymmetry of anions influences the dynamics of the system and affects the viscosity. This insight may help design better TSILs with decreased viscosity for CO(2) capture.

Compositional dependence of lower crustal viscosity

NASA Astrophysics Data System (ADS)

Shinevar, William J.; Behn, Mark D.; Hirth, Greg

2015-10-01

We calculate the viscosity structure of the lower continental crust as a function of its bulk composition using multiphase mixing theory. We use the Gibbs free-energy minimization routine Perple_X to calculate mineral assemblages for different crustal compositions under pressure and temperature conditions appropriate for the lower continental crust. The effective aggregate viscosities are then calculated using a rheologic mixing model and flow laws for the major crust-forming minerals. We investigate the viscosity of two lower crustal compositions: (i) basaltic (53 wt % SiO2) and (ii) andesitic (64 wt % SiO2). The andesitic model predicts aggregate viscosities similar to feldspar and approximately 1 order of magnitude greater than that of wet quartz. The viscosity range calculated for the andesitic crustal composition (particularly when hydrous phases are stable) is most similar to independent estimates of lower crust viscosity in actively deforming regions based on postglacial isostatic rebound, postseismic relaxation, and paleolake shoreline deflection.

Rheological Modification of Reduced Fat Chocolate Induced by the Addition of Limonene

NASA Astrophysics Data System (ADS)

Do, T.-A. Line; Vieira, Joselio; Hargreaves, Jeremy; Wolf, Bettina; Mitchell, John

2008-07-01

The objective of this study is to understand how the addition of limonene, a low molecular weight hydrophobic compound, to chocolate, leads to a decrease in the viscosity of molten chocolate. Chocolate is a fat (cocoa butter) based dispersion of solids (sugar, cocoa and milk solids). We showed that, by mixing with cocoa butter, limonene decreases the viscosity of chocolate by decreasing the viscosity of its continuous phase, liquid cocoa butter. To understand the functionality of limonene in decreasing the viscosity of cocoa butter (triacylglyceride melt), additional mixtures of cocoa butter and limonene were prepared and their viscosity was measured. The dependence of the viscosity on the ratio of cocoa butter to limonene analyzed using Kay's equation seems to indicate that limonene mixes with and within the cocoa butter triacylglycerides, diluting the fat and leading to a decrease in the overall fat viscosity.

Some effects of swirl on turbulent mixing and combustion

NASA Technical Reports Server (NTRS)

Rubel, A.

1972-01-01

A general formulation of some effects of swirl on turbulent mixing is given. The basis for the analysis is that momentum transport is enhanced by turbulence resulting from rotational instability of the fluid field. An appropriate form for the turbulent eddy viscosity is obtained by mixing length type arguments. The result takes the form of a corrective factor that is a function of the swirl and acts to increase the eddy viscosity. The factor is based upon the initial mixing conditions implying that the rotational turbulence decays in a manner similar to that of free shear turbulence. Existing experimental data for free jet combustion are adequately matched by using the modifying factor to relate the effects of swirl on eddy viscosity. The model is extended and applied to the supersonic combustion of a ring jet of hydrogen injected into a constant area annular air stream. The computations demonstrate that swirling the flow could: (1) reduce the burning length by one half, (2) result in more uniform burning across the annulus width, and (3) open the possibility of optimization of the combustion characteristics by locating the fuel jet between the inner wall and center of the annulus width.

Rheological properties of molten Kilauea Iki basalt containing suspended crystals. Revision 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Weed, H.C.; Ryerson, F.J.; Piwinskii, A.J.

1984-01-01

In order to model the flow behavior of molten silicate suspensions, such as magmas and slags, the rheological behavior must be known as a function of the concentration of suspended crystals, melt composition, and external conditions. We have determined the viscosity and crystallization sequence for a Kilauea Iki basalt between 1250/sup 0/C and 1149/sup 0/C at 100 kPa total pressure and fO/sub 2/ corresponding to the quartz-fayalite-magnetite buffer in an iron-saturated Pt30Rh rotating cup viscometer of the Couette type. The apparent viscosity varies from 9 to 879 Pa.s. The concentration of suspended cyrstals varies from 18 volume percent at 1250/supmore » 0/C to 59 volume percent at 1149/sup 0/C. The molten silicate suspension shows power-law behavior: log tau yx = A/sub 0/ + A/sub 1/ log du/dx, where tau/sub yx/ is the shear stress and (du/dx) the shear rate. Since A/sub 1/ less than or equal to 1, the apparent viscosity decreases with increasing shear rate and the system is pseudoplastic. 15 refs., 4 figs., 5 tabs.« less

Deexcitation Dynamics of Superhydrogenated Polycyclic Aromatic Hydrocarbon Cations after Soft-x-Ray Absorption

NASA Astrophysics Data System (ADS)

Reitsma, G.; Boschman, L.; Deuzeman, M. J.; González-Magaña, O.; Hoekstra, S.; Cazaux, S.; Hoekstra, R.; Schlathölter, T.

2014-08-01

We have investigated the response of superhydrogenated gas-phase coronene cations upon soft x-ray absorption. Carbon (1s)⟶π⋆ transitions were resonantly excited at hν =285 eV. The resulting core hole is then filled in an Auger decay process, with the excess energy being released in the form of an Auger electron. Predominantly highly excited dications are thus formed, which cool down by hydrogen emission. In superhydrogenated systems, the additional H atoms act as a buffer, quenching loss of native H atoms and molecular fragmentation. Dissociation and transition state energies for several H loss channels were computed by means of density functional theory. Using these energies as input into an Arrhenius-type cascade model, very good agreement with the experimental data is found. The results have important implications for the survival of polyaromatic hydrocarbons in the interstellar medium and reflect key aspects of graphene hydrogenation.

Water hammer prediction and control: the Green's function method

NASA Astrophysics Data System (ADS)

Xuan, Li-Jun; Mao, Feng; Wu, Jie-Zhi

2012-04-01

By Green's function method we show that the water hammer (WH) can be analytically predicted for both laminar and turbulent flows (for the latter, with an eddy viscosity depending solely on the space coordinates), and thus its hazardous effect can be rationally controlled and minimized. To this end, we generalize a laminar water hammer equation of Wang et al. (J. Hydrodynamics, B2, 51, 1995) to include arbitrary initial condition and variable viscosity, and obtain its solution by Green's function method. The predicted characteristic WH behaviors by the solutions are in excellent agreement with both direct numerical simulation of the original governing equations and, by adjusting the eddy viscosity coefficient, experimentally measured turbulent flow data. Optimal WH control principle is thereby constructed and demonstrated.

Structure-activity relationship for hydrophobic salts as viscosity-lowering excipients for concentrated solutions of monoclonal antibodies.

PubMed

Guo, Zheng; Chen, Alvin; Nassar, Roger A; Helk, Bernhard; Mueller, Claudia; Tang, Yu; Gupta, Kapil; Klibanov, Alexander M

2012-11-01

To discover, elucidate the structure-activity relationship (SAR), and explore the mechanism of action of excipients able to drastically lower the viscosities of concentrated aqueous solutions of humanized monoclonal antibodies (MAbs). Salts prepared from hydrophobic cations and anions were dissolved into humanized MAbs solutions. Viscosities of the resulting solutions were measured as a function of the nature and concentration of the salts and MAbs. Even at moderate concentrations, some of the salts prepared herein were found to reduce over 10-fold the viscosities of concentrated aqueous solutions of several MAbs at room temperature. To be potent viscosity-lowering excipients, the ionic constituents of the salts must be hydrophobic, bulky, and aliphatic. A mechanistic hypothesis explaining the observed salt effects on MAb solutions' viscosities was proposed and verified.

Flow behaviour and constitutive modelling of a ferritic stainless steel at elevated temperatures

NASA Astrophysics Data System (ADS)

Zhao, Jingwei; Jiang, Zhengyi; Zu, Guoqing; Du, Wei; Zhang, Xin; Jiang, Laizhu

2016-05-01

The flow behaviour of a ferritic stainless steel (FSS) was investigated by a Gleeble 3500 thermal-mechanical test simulator over the temperature range of 900-1100 °C and strain rate range of 1-50 s-1. Empirical and phenomenological constitutive models were established, and a comparative study was made on the predictability of them. The results indicate that the flow stress decreases with increasing the temperature and decreasing the strain rate. High strain rate may cause a drop in flow stress after a peak value due to the adiabatic heating. The Zener-Hollomon parameter depends linearly on the flow stress, and decreases with raising the temperature and reducing the strain rate. Significant deviations occur in the prediction of flow stress by the Johnson-Cook (JC) model, indicating that the JC model cannot accurately track the flow behaviour of the FSS during hot deformation. Both the multiple-linear and the Arrhenius-type models can track the flow behaviour very well under the whole hot working conditions, and have much higher accuracy in predicting the flow behaviour than that of the JC model. The multiple-linear model is recommended in the current work due to its simpler structure and less time needed for solving the equations relative to the Arrhenius-type model.

Blood viscosity monitoring during cardiopulmonary bypass based on pressure-flow characteristics of a Newtonian fluid.

PubMed

Okahara, Shigeyuki; Zu Soh; Takahashi, Shinya; Sueda, Taijiro; Tsuji, Toshio

2016-08-01

We proposed a blood viscosity estimation method based on pressure-flow characteristics of oxygenators used during cardiopulmonary bypass (CPB) in a previous study that showed the estimated viscosity to correlate well with the measured viscosity. However, the determination of the parameters included in the method required the use of blood, thereby leading to high cost of calibration. Therefore, in this study we propose a new method to monitor blood viscosity, which approximates the pressure-flow characteristics of blood considered as a non-Newtonian fluid with characteristics of a Newtonian fluid by using the parameters derived from glycerin solution to enable ease of acquisition. Because parameters used in the estimation method are based on fluid types, bovine blood parameters were used to calculate estimated viscosity (ηe), and glycerin parameters were used to estimate deemed viscosity (ηdeem). Three samples of whole bovine blood with different hematocrit levels (21.8%, 31.0%, and 39.8%) were prepared and perfused into the oxygenator. As the temperature changed from 37 °C to 27 °C, the oxygenator mean inlet pressure and outlet pressure were recorded for flows of 2 L/min and 4 L/min, and the viscosity was estimated. The value of deemed viscosity calculated with the glycerin parameters was lower than estimated viscosity calculated with bovine blood parameters by 20-33% at 21.8% hematocrit, 12-27% at 31.0% hematocrit, and 10-15% at 39.8% hematocrit. Furthermore, deemed viscosity was lower than estimated viscosity by 10-30% at 2 L/min and 30-40% at 4 L/min. Nevertheless, estimated and deemed viscosities varied with a similar slope. Therefore, this shows that deemed viscosity achieved using glycerin parameters may be capable of successfully monitoring relative viscosity changes of blood in a perfusing oxygenator.

Viscosity of Common Seed and Vegetable Oils

NASA Astrophysics Data System (ADS)

Wes Fountain, C.; Jennings, Jeanne; McKie, Cheryl K.; Oakman, Patrice; Fetterolf, Monty L.

1997-02-01

Viscosity experiments using Ostwald-type gravity flow viscometers are not new to the physical chemistry laboratory. Several physical chemistry laboratory texts (1 - 3) contain at least one experiment studying polymer solutions or other well-defined systems. Several recently published articles (4 - 8) indicated the continued interest in using viscosity measurements in the teaching lab to illustrate molecular interpretation of bulk phenomena. Most of these discussions and teaching experiments are designed around an extensive theory of viscous flow and models of molecular shape that allow a full data interpretation to be attempted. This approach to viscosity experiments may not be appropriate for all teaching situations (e.g., high schools, general chemistry labs, and nonmajor physical chemistry labs). A viscosity experiment is presented here that is designed around common seed and vegetable oils. With the importance of viscosity to foodstuffs (9) and the importance of fatty acids to nutrition (10), an experiment using these common, recognizable oils has broad appeal.

Molecular basis of high viscosity in concentrated antibody solutions: Strategies for high concentration drug product development.

PubMed

Tomar, Dheeraj S; Kumar, Sandeep; Singh, Satish K; Goswami, Sumit; Li, Li

2016-01-01

Effective translation of breakthrough discoveries into innovative products in the clinic requires proactive mitigation or elimination of several drug development challenges. These challenges can vary depending upon the type of drug molecule. In the case of therapeutic antibody candidates, a commonly encountered challenge is high viscosity of the concentrated antibody solutions. Concentration-dependent viscosity behaviors of mAbs and other biologic entities may depend on pairwise and higher-order intermolecular interactions, non-native aggregation, and concentration-dependent fluctuations of various antibody regions. This article reviews our current understanding of molecular origins of viscosity behaviors of antibody solutions. We discuss general strategies and guidelines to select low viscosity candidates or optimize lead candidates for lower viscosity at early drug discovery stages. Moreover, strategies for formulation optimization and excipient design are also presented for candidates already in advanced product development stages. Potential future directions for research in this field are also explored.

Contribution to viscosity from the structural relaxation via the atomic scale Green-Kubo stress correlation function.

PubMed

Levashov, V A

2017-11-14

We studied the connection between the structural relaxation and viscosity for a binary model of repulsive particles in the supercooled liquid regime. The used approach is based on the decomposition of the macroscopic Green-Kubo stress correlation function into the correlation functions between the atomic level stresses. Previously we used the approach to study an iron-like single component system of particles. The role of vibrational motion has been addressed through the demonstration of the relationship between viscosity and the shear waves propagating over large distances. In our previous considerations, however, we did not discuss the role of the structural relaxation. Here we suggest that the contribution to viscosity from the structural relaxation can be taken into account through the consideration of the contribution from the atomic stress auto-correlation term only. This conclusion, however, does not mean that only the auto-correlation term represents the contribution to viscosity from the structural relaxation. Previously the role of the structural relaxation for viscosity has been addressed through the considerations of the transitions between inherent structures and within the mode-coupling theory by other authors. In the present work, we study the structural relaxation through the considerations of the parent liquid and the atomic level stress correlations in it. The comparison with the results obtained on the inherent structures also is made. Our current results suggest, as our previous observations, that in the supercooled liquid regime, the vibrational contribution to viscosity extends over the times that are much larger than the Einstein's vibrational period and much larger than the times that it takes for the shear waves to propagate over the model systems. Besides addressing the atomic level shear stress correlations, we also studied correlations between the atomic level pressure elements.

Contribution to viscosity from the structural relaxation via the atomic scale Green-Kubo stress correlation function

NASA Astrophysics Data System (ADS)

Levashov, V. A.

2017-11-01

We studied the connection between the structural relaxation and viscosity for a binary model of repulsive particles in the supercooled liquid regime. The used approach is based on the decomposition of the macroscopic Green-Kubo stress correlation function into the correlation functions between the atomic level stresses. Previously we used the approach to study an iron-like single component system of particles. The role of vibrational motion has been addressed through the demonstration of the relationship between viscosity and the shear waves propagating over large distances. In our previous considerations, however, we did not discuss the role of the structural relaxation. Here we suggest that the contribution to viscosity from the structural relaxation can be taken into account through the consideration of the contribution from the atomic stress auto-correlation term only. This conclusion, however, does not mean that only the auto-correlation term represents the contribution to viscosity from the structural relaxation. Previously the role of the structural relaxation for viscosity has been addressed through the considerations of the transitions between inherent structures and within the mode-coupling theory by other authors. In the present work, we study the structural relaxation through the considerations of the parent liquid and the atomic level stress correlations in it. The comparison with the results obtained on the inherent structures also is made. Our current results suggest, as our previous observations, that in the supercooled liquid regime, the vibrational contribution to viscosity extends over the times that are much larger than the Einstein's vibrational period and much larger than the times that it takes for the shear waves to propagate over the model systems. Besides addressing the atomic level shear stress correlations, we also studied correlations between the atomic level pressure elements.

Addition of simultaneous heat and solute transport and variable fluid viscosity to SEAWAT

USGS Publications Warehouse

Thorne, D.; Langevin, C.D.; Sukop, M.C.

2006-01-01

SEAWAT is a finite-difference computer code designed to simulate coupled variable-density ground water flow and solute transport. This paper describes a new version of SEAWAT that adds the ability to simultaneously model energy and solute transport. This is necessary for simulating the transport of heat and salinity in coastal aquifers for example. This work extends the equation of state for fluid density to vary as a function of temperature and/or solute concentration. The program has also been modified to represent the effects of variable fluid viscosity as a function of temperature and/or concentration. The viscosity mechanism is verified against an analytical solution, and a test of temperature-dependent viscosity is provided. Finally, the classic Henry-Hilleke problem is solved with the new code. ?? 2006 Elsevier Ltd. All rights reserved.

Time-Dependent Effect of Refrigeration on Viscosity and Conversion Kinetics of Dental Adhesive Resins

PubMed Central

Faria-e-Silva, André L; Piva, Evandro; Moraes, Rafael R

2010-01-01

Objectives: This study evaluated the effect of refrigeration at 4°C and post-refrigeration times (immediate, 5, 10, 15, or 20 min) on the viscosity and conversion kinetics of adhesive bonding resins. Methods: Scotchbond Dual-Cure (3M ESPE) and Clearfil SE Bond (Kuraray) were tested. Control samples were kept at 25°C for 24 h. At each post-refrigeration time, the temperature was checked with a K-type thermocouple. Viscosity measurements as a function of temperature were performed using a cone-plate viscometer. Real-time polymerization was monitored by infrared spectroscopy. Degree of conversion (DC) was calculated for each second during polymerization, and the rate of polymerization analyzed. Data were separately submitted to two-way ANOVA and Tukey’s test (P<.05). Results: Clearfil presented faster increase in temperature after exposure to room temperature than Scotchbond. A continuous decrease in viscosity (Pa.s) was observed for both Scotchbond (0.49, 0.34, 0.30, 0.26, 0.23, 0.23) and Clearfil (0.38, 0.37, 0.34, 0.25, 0.24, 0.22). For Scotchbond, higher final DC was detected for the control (62.7%) compared with the immediate (53.3%) and 5 min (54.7%) groups. For Clearfil, the control sample (81.4%) showed higher DC than all refrigerated groups (68.8–69.5%). Clearfil always showed significantly higher DC than Scotchbond. Conclusions: Refrigeration presented a significant time- and material-dependent effect on the viscosity and polymerization kinetics of the bonding resins. Under clinical conditions, adhesive agents should be removed from the refrigerator at least 20 min before being used. PMID:20396445

Rheology of composite solid propellants during motor casting

NASA Technical Reports Server (NTRS)

Klager, K.; Rogers, C. J.; Smith, P. L.

1978-01-01

Results of casting studies are reviewed so as to define the viscosity criteria insuring the fabrication of defect-free grains. The rheology of uncured propellants is analyzed showing that a realistic assessment of a propellant's flow properties must include measurement of viscosity as a function of shear stress and time after curing agent. Methods for measuring propellant viscosity are discussed, with particular attention given to the Haake-Rotovisko rotational viscometer. The effects of propellant compositional and processing variables on apparent viscosity are examined, as are results relating rheological behavior to grain defect formation during casting.

Viscosity, conductivity, and electrochemical property of dicyanamide ionic liquids

NASA Astrophysics Data System (ADS)

Yuan, Wen-Li; Yang, Xiao; He, Ling; Xue, Ying; Qin, Song; Tao, Guo-Hong

2018-03-01

The instructive structure-property relationships of ionic liquids (ILs) can be put to task-specific design of new functionalized ILs. The dicyanamide (DCA) ILs are typical CHN type ILs which are halogen free, chemical stable, low-viscous and fuel-rich. The transport properties of DCA ionic liquids are significant for their applications as solvents, electrolytes and hypergolic propellants. This work systematically investigates several important transport properties of four DCA ILs ([C4mim][N(CN)2], [C4m2im][N(CN)2], N4442[N(CN)2], and N8444[N(CN)2]) including viscosity, conductivity, and electrochemical property at different temperatures. The melting points, temperature-dependent viscosities and conductivities reveal the structure-activity relationship of four DCA ILs. From the Walden plots, the imidazolium cations exhibit stronger cation–anion attraction than the ammonium cations. DCA ILs have relatively high values of electrochemical windows (EWs), which indicates that the DCA ILs are potential candidates for electrolytes in electrochemical applications. The cyclic voltammograms of Eu(III) in these DCA ILs at GC working electrode at various temperatures 303–333 K consists of quasi-reversible waves. The electrochemical properties of the DCA ILs are also dominated by the cationic structures. The current intensity (ip), the diffusion coefficients (Do), the charge transfer rate constants (ks) of Eu(III) in DCA ILs all increased with the molar conductivities increased. The cationic structure-transport property relationships of DCA ILs were constructed for designing novel functionalized ILs to fulfill specific demands.

Physicochemical and Thermal Properties of Extruded Instant Functional Rice Porridge Powder as Affected by the Addition of Soybean or Mung Bean.

PubMed

Mayachiew, Pornpimon; Charunuch, Chulaluck; Devahastin, Sakamon

2015-12-01

Legumes contain protein, micronutrients, and bioactive compounds, which provide various health benefits. In this study, soybean or mung bean was mixed in rice flour to produce by extrusion instant functional legume-rice porridge powder. The effects of the type and percentage (10%, 20%, or 30%, w/w) of legumes on the expansion ratio of the extrudates were first evaluated. Amino acid composition, color, and selected physicochemical (bulk density, water absorption index, and water solubility index), thermal (onset temperature, peak temperature, and transition enthalpy), and pasting (peak viscosity, trough viscosity, and final viscosity) properties of the powder were determined. The crystalline structure and formation of amylose-lipid complexes and the total phenolics content (TPC) and antioxidant activity of the powder were also measured. Soybean-blended porridge powder exhibited higher TPC, 2,2-diphenyl-1-picrylhydrazyl radical scavenging capacity, ferric reducing antioxidant power, amino acid, and fat contents than the mung bean-blended porridge powder. Incorporating either legume affected the product properties by decreasing the lightness and bulk density, while increasing the greenness and yellowness and the peak temperature and transition enthalpy. Expansion capacity of the extrudates increased with percentage of mung bean in the mixture but decreased as the percentage of soybean increased. Amylose-lipid complexes formation was confirmed by X-ray diffraction analysis results. Addition of soybean or mung bean resulted in significant pasting property changes of the porridge powder. © 2015 Institute of Food Technologists®

Viscosity, Conductivity, and Electrochemical Property of Dicyanamide Ionic Liquids

PubMed Central

Yuan, Wen-Li; Yang, Xiao; He, Ling; Xue, Ying; Qin, Song; Tao, Guo-Hong

2018-01-01

The instructive structure-property relationships of ionic liquids (ILs) can be put to task-specific design of new functionalized ILs. The dicyanamide (DCA) ILs are typical CHN type ILs which are halogen free, chemical stable, low-viscous, and fuel-rich. The transport properties of DCA ionic liquids are significant for their applications as solvents, electrolytes, and hypergolic propellants. This work systematically investigates several important transport properties of four DCA ILs ([C4mim][N(CN)2], [C4m2im][N(CN)2], N4442[N(CN)2], and N8444[N(CN)2]) including viscosity, conductivity, and electrochemical property at different temperatures. The melting points, temperature-dependent viscosities and conductivities reveal the structure-activity relationship of four DCA ILs. From the Walden plots, the imidazolium cations exhibit stronger cation–anion attraction than the ammonium cations. DCA ILs have relatively high values of electrochemical windows (EWs), which indicates that the DCA ILs are potential candidates for electrolytes in electrochemical applications. The cyclic voltammograms of Eu(III) in these DCA ILs at GC working electrode at various temperatures 303–333 K consists of quasi-reversible waves. The electrochemical properties of the DCA ILs are also dominated by the cationic structures. The current intensity (ip), the diffusion coefficients (Do), the charge transfer rate constants (ks) of Eu(III) in DCA ILs all increased with the molar conductivities increased. The cationic structure-transport property relationships of DCA ILs were constructed for designing novel functionalized ILs to fulfill specific demands. PMID:29600245

A Rapid Capillary-Pressure Driven Micro-Channel to Demonstrate Newtonian Fluid Behavior of Zebrafish Blood at High Shear Rates.

PubMed

Lee, Juhyun; Chou, Tzu-Chieh; Kang, Dongyang; Kang, Hanul; Chen, Junjie; Baek, Kyung In; Wang, Wei; Ding, Yichen; Carlo, Dino Di; Tai, Yu-Chong; Hsiai, Tzung K

2017-05-16

Blood viscosity provides the rheological basis to elucidate shear stress underlying developmental cardiac mechanics and physiology. Zebrafish is a high throughput model for developmental biology, forward-genetics, and drug discovery. The micro-scale posed an experimental challenge to measure blood viscosity. To address this challenge, a microfluidic viscometer driven by surface tension was developed to reduce the sample volume required (3μL) for rapid (<2 min) and continuous viscosity measurement. By fitting the power-law fluid model to the travel distance of blood through the micro-channel as a function of time and channel configuration, the experimentally acquired blood viscosity was compared with a vacuum-driven capillary viscometer at high shear rates (>500 s -1 ), at which the power law exponent (n) of zebrafish blood was nearly 1 behaving as a Newtonian fluid. The measured values of whole blood from the micro-channel (4.17cP) and the vacuum method (4.22cP) at 500 s -1 were closely correlated at 27 °C. A calibration curve was established for viscosity as a function of hematocrits to predict a rise and fall in viscosity during embryonic development. Thus, our rapid capillary pressure-driven micro-channel revealed the Newtonian fluid behavior of zebrafish blood at high shear rates and the dynamic viscosity during development.

Experimental Evidence of Volcanic Earthquakes Induced by Different Fluid Types

NASA Astrophysics Data System (ADS)

Clarke, J. A.; Adam, L.; Sarout, J.; van Wijk, K.; Dautriat, J. D.; Kennedy, B.

2017-12-01

Low Frequency volcanic seismicity has long been associated with resonance in fluid-filled cracks or conduits driven by pressure perturbations at depth. In volcano monitoring, fluid movement, fracturing and the conduit geometry are interpreted based on field observations, laboratory experiments, and numerical models. Fluids in a volcanic environment include gasses, brine and magmas with different viscosities. Magma viscosity is a key influence on eruptive behaviour. For example, increasing magma viscosity is known to favour explosive eruptions. How different fluids affect volcano seismicity is not well understood. Here, we explore the effects of fluid type on volcano seismic signals. Frequency content in the signal, frequency of the events, source mechanism and quality factor are studied. We simulate volcano tectonic (fracturing) and volcano seismic (fluid movement) signatures in a controlled laboratory environment using a range of rock samples, fluid types and pressure conditions. The viscosity of the fluids spans six orders of magnitude, representing realistic volcanic fluids. Microseismicity is generated by venting pressurised fluids through pre-generated fracture networks in cylindrical rock core samples and detected by an array of 18 ultrasonic transducers. We fracture samples of two lithologies: 1) low porosity impermeable granite samples and 2) a permeable volcanic ash tuff sample. Permeability and porosity in the granites are due to a fracture network, while in the tuff a high porosity matrix ( 40 %) and a fracture network interact. The fluids used are nitrogen gas, water, and mixtures of water and glycerol. We generate and detect a myriad of seismic event types, some of which resemble well-known families of volcano-tectonic, low-frequency, hybrid and tremor-type seismicity. Samples with fluids of lower density and viscosity generate a higher number of seismic events. We will present an integrated analysis of the event types, frequency content, source locations and mechanisms. In addition, we explore the importance of seismic wave attenuation by studying the relationship between wave path and event frequency content.

Hypothesis for thermal activation of the caspase cascade in apoptotic cell death at elevated temperatures

NASA Astrophysics Data System (ADS)

Pearce, John A.

2013-02-01

Apoptosis is an especially important process affecting disease states from HIV-AIDS to auto-immune disease to cancer. A cascade of initiator and executioner capsase functional proteins is the hallmark of apoptosis. When activated the various caspases activate other caspases or cleave structural proteins of the cytoskeleton, resulting in "blebbing" of the plasma membrane forming apoptotic bodies that completely enclose the disassembled cellular components. Containment of the cytosolic components within the apoptotic bodies differentiates apoptosis from necroptosis and necrosis, both of which release fragmented cytosol and other cellular constituents into the intracellular space. Biochemical models of caspase activation reveal the extensive feedback loops characteristic of apoptosis. They clearly explain the failure of Arrhenius models to give accurate predictions of cell survival curves in hyperthermic heating protocols. Nevertheless, each of the individual reaction velocities can reasonably be assumed to follow Arrhenius kinetics. If so, the thermal sensitivity of the reaction velocity to temperature elevation is: ∂k/∂T = Ea [k/RT2]. Particular reaction steps described by higher activation energies, Ea, are likely more thermally-sensitive than lower energy reactions and may initiate apoptosis in the absence of other stress signals. Additionally, while the classical irreversible Arrhenius formulation fails to accurately represent many cell survival and/or dye uptake curves - those that display an early stage shoulder region - an expanded reversible model of the law of mass action equation seems to prove effective and is directly based on a firm theoretical thermodynamic foundation.

Characterization of n-Type and p-Type Long-Wave InAs/InAsSb Superlattices

NASA Astrophysics Data System (ADS)

Brown, A. E.; Baril, N.; Zuo, D.; Almeida, L. A.; Arias, J.; Bandara, S.

2017-09-01

The influence of dopant concentration on both in-plane mobility and minority carrier lifetime in long-wave infrared InAs/InAsSb superlattices (SLs) was investigated. Unintentially doped ( n-type) and various concentrations of Be-doped ( p-type) SLs were characterized using variable-field Hall and photoconductive decay techniques. Minority carrier lifetimes in p-type InAs/InAsSb SLs are observed to decrease with increasing carrier concentration, with the longest lifetime at 77 K determined to be 437 ns, corresponding to a measured carrier concentration of p 0 = 4.1 × 1015 cm-3. Variable-field Hall technique enabled the extraction of in-plane hole, electron, and surface electron transport properties as a function of temperature. In-plane hole mobility is not observed to change with doping level and increases with reducing temperature, reaching a maximum at the lowest temperature measured of 30 K. An activation energy of the Be-dopant is determined to be 3.5 meV from Arrhenius analysis of hole concentration. Minority carrier electrons populations are suppressed at the highest Be-doping levels, but mobility and concentration values are resolved in lower-doped samples. An average surface electron conductivity of 3.54 × 10-4 S at 30 K is determined from the analysis of p-type samples. Effects of passivation treatments on surface conductivity will be presented.

Longitudinal and bulk viscosities of Lennard-Jones fluids

NASA Astrophysics Data System (ADS)

Tankeshwar, K.; Pathak, K. N.; Ranganathan, S.

1996-12-01

Expressions for the longitudinal and bulk viscosities have been derived using Green Kubo formulae involving the time integral of the longitudinal and bulk stress autocorrelation functions. The time evolution of stress autocorrelation functions are determined using the Mori formalism and a memory function which is obtained from the Mori equation of motion. The memory function is of hyperbolic secant form and involves two parameters which are related to the microscopic sum rules of the respective autocorrelation function. We have derived expressions for the zeroth-, second-and fourth- order sum rules of the longitudinal and bulk stress autocorrelation functions. These involve static correlation functions up to four particles. The final expressions for these have been put in a form suitable for numerical calculations using low- order decoupling approximations. The numerical results have been obtained for the sum rules of longitudinal and bulk stress autocorrelation functions. These have been used to calculate the longitudinal and bulk viscosities and time evolution of the longitudinal stress autocorrelation function of the Lennard-Jones fluids over wide ranges of densities and temperatures. We have compared our results with the available computer simulation data and found reasonable agreement.

The relationship between plate velocity and trench viscosity in Newtonian and power-law subduction calculations

NASA Technical Reports Server (NTRS)

King, Scott D.; Hager, Bradford H.

1990-01-01

The relationship between oceanic trench viscosity and oceanic plate velocity is studied using a Newtonian rheology by varying the viscosity at the trench. The plate velocity is a function of the trench viscosity for fixed Rayleigh number and plate/slab viscosity. Slab velocities for non-Newtonian rheology calculations are significantly different from slab velocities from Newtonian rheology calculations at the same effective Rayleigh number. Both models give reasonable strain rates for the slab when compared with estimates of seismic strain rate. Non-Newtonian rheology eliminates the need for imposed weak zones and provides a self-consistent fluid dynamical mechanism for subduction in numerical convection models.

High Accuracy Fuel Flowmeter, Phase 1

NASA Technical Reports Server (NTRS)

Mayer, C.; Rose, L.; Chan, A.; Chin, B.; Gregory, W.

1983-01-01

Technology related to aircraft fuel mass - flowmeters was reviewed to determine what flowmeter types could provide 0.25%-of-point accuracy over a 50 to one range in flowrates. Three types were selected and were further analyzed to determine what problem areas prevented them from meeting the high accuracy requirement, and what the further development needs were for each. A dual-turbine volumetric flowmeter with densi-viscometer and microprocessor compensation was selected for its relative simplicity and fast response time. An angular momentum type with a motor-driven, spring-restrained turbine and viscosity shroud was selected for its direct mass-flow output. This concept also employed a turbine for fast response and a microcomputer for accurate viscosity compensation. The third concept employed a vortex precession volumetric flowmeter and was selected for its unobtrusive design. Like the turbine flowmeter, it uses a densi-viscometer and microprocessor for density correction and accurate viscosity compensation.

Fluid displacement between two parallel plates: a non-empirical model displaying change of type from hyperbolic to elliptic equations

NASA Astrophysics Data System (ADS)

Shariati, M.; Talon, L.; Martin, J.; Rakotomalala, N.; Salin, D.; Yortsos, Y. C.

2004-11-01

We consider miscible displacement between parallel plates in the absence of diffusion, with a concentration-dependent viscosity. By selecting a piecewise viscosity function, this can also be considered as ‘three-fluid’ flow in the same geometry. Assuming symmetry across the gap and based on the lubrication (‘equilibrium’) approximation, a description in terms of two quasi-linear hyperbolic equations is obtained. We find that the system is hyperbolic and can be solved analytically, when the mobility profile is monotonic, or when the mobility of the middle phase is smaller than its neighbours. When the mobility of the middle phase is larger, a change of type is displayed, an elliptic region developing in the composition space. Numerical solutions of Riemann problems of the hyperbolic system spanning the elliptic region, with small diffusion added, show good agreement with the analytical outside, but an unstable behaviour inside the elliptic region. In these problems, the elliptic region arises precisely at the displacement front. Crossing the elliptic region requires the solution of essentially an eigenvalue problem of the full higher-dimensional model, obtained here using lattice BGK simulations. The hyperbolic-to-elliptic change-of-type reflects the failing of the lubrication approximation, underlying the quasi-linear hyperbolic formalism, to describe the problem uniformly. The obtained solution is analogous to non-classical shocks recently suggested in problems with change of type.

Elevated 1-h post-challenge plasma glucose levels in subjects with normal glucose tolerance or impaired glucose tolerance are associated with whole blood viscosity.

PubMed

Marini, Maria Adelaide; Fiorentino, Teresa Vanessa; Andreozzi, Francesco; Mannino, Gaia Chiara; Perticone, Maria; Sciacqua, Angela; Perticone, Francesco; Sesti, Giorgio

2017-08-01

It has been suggested that glucose levels ≥155 mg/dl at 1-h during an oral glucose tolerance test (OGTT) may predict development of type 2 diabetes and cardiovascular events among adults with normal glucose tolerance (NGT 1 h-high). Studies showed a link between increased blood viscosity and type 2 diabetes. However, whether blood viscosity is associated with dysglycemic conditions such as NGT 1 h-high, impaired glucose tolerance (IGT) or impaired fasting glucose (IFG) is unsettled. 1723 non-diabetic adults underwent biochemical evaluation and OGTT. A validated formula based on hematocrit and total plasma proteins was employed to estimate whole blood viscosity. Subjects were categorized into NGT with 1 h glucose <155 mg/dL (NGT-1 h-low), NGT-1 h-high, IFG and/or IGT. Hematocrit and blood viscosity values appeared significantly higher in individuals with NGT 1 h-high, IFG and/or IGT as compared to NGT 1 h-low subjects. Blood viscosity was significantly correlated with age, waist circumference, blood pressure, HbA1c, fasting, 1- and 2-h post-challenge insulin levels, total cholesterol and low-density lipoprotein, triglycerides, fibrinogen, white blood cell, and inversely correlated with high-density lipoprotein and insulin sensitivity. Of the four glycemic parameters, 1-h post-challenge glucose showed the strongest correlation with blood viscosity (β = 0.158, P < 0.0001) in a multivariate regression analysis model including several atherosclerosis risk factors. Our results demonstrate a positive relationship between blood viscosity and 1-h post-challenge plasma glucose. They also suggest that a subgroup of NGT individuals with 1-h post-challenge plasma >155 mg/dl have increased blood viscosity comparable to that observed in subjects with IFG and/or IGT.

Titin Based Viscosity in Ventricular Physiology: An Integrative Investigation of PEVK-Actin Interactions

PubMed Central

Chung, Charles S; Methawasin, Methajit; Nelson, O Lynne; Radke, Michael H; Hidalgo, Carlos G; Gotthardt, Michael; Granzier, Henk L

2011-01-01

Viscosity is proposed to modulate diastolic function, but only limited understanding of the source(s) of viscosity exists. In-vitro experiments have shown that the proline-glutamic acid-valine-lysine (PEVK) rich element of titin interacts with actin, causing a viscous force in the sarcomere. It is unknown whether this mechanism contributes to viscosity in-vivo. We tested the hypothesis that PEVK-actin interaction causes cardiac viscosity and is important in-vivo via an integrative physiological study on a unique PEVK-knockout (KO) model. Both skinned cardiomyocytes and papillary muscle fibers were isolated from wildtype (WT) and PEVK KO mice and passive viscosity was examined using stretch-hold-release and sinusoidal analysis. Viscosity was reduced by ~60% in KO myocytes and ~50% in muscle fibers at room temperature. The PEVK-actin interaction was not modulated by temperature or diastolic calcium, but was increased by lattice compression. Stretch-hold and sinusoidal frequency protocols on intact isolated mouse hearts showed a smaller, 30–40% reduction in viscosity, possibly due to actomyosin interactions, and showed that microtubules did not contribute to viscosity. Transmitral Doppler echocardiography similarly revealed a 40% decrease in LV chamber viscosity in the PEVK KO in-vivo. This integrative study is the first to quantify the influence of a specific molecular (PEVK-actin) viscosity in-vivo and shows that PEVK-actin interactions are an important physiological source of viscosity. PMID:21708170

ΛCDM model with dissipative nonextensive viscous dark matter

NASA Astrophysics Data System (ADS)

Gimenes, H. S.; Viswanathan, G. M.; Silva, R.

2018-03-01

Many models in cosmology typically assume the standard bulk viscosity. We study an alternative interpretation for the origin of the bulk viscosity. Using nonadditive statistics proposed by Tsallis, we propose a bulk viscosity component that can only exist by a nonextensive effect through the nonextensive/dissipative correspondence (NexDC). In this paper, we consider a ΛCDM model for a flat universe with a dissipative nonextensive viscous dark matter component, following the Eckart theory of bulk viscosity, without any perturbative approach. In order to analyze cosmological constraints, we use one of the most recent observations of Type Ia Supernova, baryon acoustic oscillations and cosmic microwave background data.

α-Pinene secondary organic aerosol at low temperature: chemical composition and implications for particle viscosity

NASA Astrophysics Data System (ADS)

Huang, Wei; Saathoff, Harald; Pajunoja, Aki; Shen, Xiaoli; Naumann, Karl-Heinz; Wagner, Robert; Virtanen, Annele; Leisner, Thomas; Mohr, Claudia

2018-02-01

Chemical composition, size distributions, and degree of oligomerization of secondary organic aerosol (SOA) from α-pinene (C10H16) ozonolysis were investigated for low-temperature conditions (223 K). Two types of experiments were performed using two simulation chambers at the Karlsruhe Institute of Technology: the Aerosol Preparation and Characterization (APC) chamber, and the Aerosol Interaction and Dynamics in the Atmosphere (AIDA) chamber. Experiment type 1 simulated SOA formation at upper tropospheric conditions: SOA was generated in the AIDA chamber directly at 223 K at 61 % relative humidity (RH; experiment termed cold humid, CH) and for comparison at 6 % RH (experiment termed cold dry, CD) conditions. Experiment type 2 simulated SOA uplifting: SOA was formed in the APC chamber at room temperature (296 K) and < 1 % RH (experiment termed warm dry, WD) or 21 % RH (experiment termed warm humid, WH) conditions, and then partially transferred to the AIDA chamber kept at 223 K, and 61 % RH (WDtoCH) or 30 % RH (WHtoCH), respectively. Precursor concentrations varied between 0.7 and 2.2 ppm α-pinene, and between 2.3 and 1.8 ppm ozone for type 1 and type 2 experiments, respectively. Among other instrumentation, a chemical ionization mass spectrometer (CIMS) coupled to a filter inlet for gases and aerosols (FIGAERO), deploying I- as reagent ion, was used for SOA chemical composition analysis. For type 1 experiments with lower α-pinene concentrations and cold SOA formation temperature (223 K), smaller particles of 100-300 nm vacuum aerodynamic diameter (dva) and higher mass fractions (> 40 %) of adducts (molecules with more than 10 carbon atoms) of α-pinene oxidation products were observed. For type 2 experiments with higher α-pinene concentrations and warm SOA formation temperature (296 K), larger particles ( ˜ 500 nm dva) with smaller mass fractions of adducts (< 35 %) were produced. We also observed differences (up to 20 °C) in maximum desorption temperature (Tmax) of individual compounds desorbing from the particles deposited on the FIGAERO Teflon filter for different experiments, indicating that Tmax is not purely a function of a compound's vapor pressure or volatility, but is also influenced by diffusion limitations within the particles (particle viscosity), interactions between particles deposited on the filter (particle matrix), and/or particle mass on the filter. Highest Tmax were observed for SOA under dry conditions and with higher adduct mass fraction; lowest Tmax were observed for SOA under humid conditions and with lower adduct mass fraction. The observations indicate that particle viscosity may be influenced by intra- and inter-molecular hydrogen bonding between oligomers, and particle water uptake, even under such low-temperature conditions. Our results suggest that particle physicochemical properties such as viscosity and oligomer content mutually influence each other, and that variation in Tmax of particle desorptions may have implications for particle viscosity and particle matrix effects. The differences in particle physicochemical properties observed between our different experiments demonstrate the importance of taking experimental conditions into consideration when interpreting data from laboratory studies or using them as input in climate models.

Rheological properties of molten flax- and Tencel{sup ®}-polypropylene composites: Influence of fiber morphology and concentration

DOE Office of Scientific and Technical Information (OSTI.GOV)

Abdennadher, Ahmed; Vincent, Michel; Budtova, Tatiana, E-mail: Tatiana.Budtova@mines-paristech.fr

The rheological properties of short fiber reinforced polypropylene were investigated. Flax and Tencel{sup ®} are two cellulose based fibers used in this study. Flax fibers are extracted from the bast of plants. They are composed of thin elementary fibers and rigid thick bundles made of elementary fibers “glued” together. Tencel{sup ®} is a man-made cellulosic fiber spun from cellulose solution, with a uniform diameter, thin, and flexible. First, fiber dimensions before and after compounding were analyzed. Both types of fibers were broken during compounding. Flax shows larger length and diameter than Tencel{sup ®}, but aspect ratio of flax is smaller.more » The reason is that after compounding flax remained in bundles. Dynamic viscosity, elastic and viscous moduli were studied as a function of fiber type, concentration (from 0 to 30 wt. %), and composite temperature (from 180 to 200 °C). All Tencel{sup ®}-based composites showed higher apparent yield stress, viscosity, and moduli compared to flax-based composites at the same fiber concentrations. The results are analyzed in terms of the influence of fiber type, aspect ratio, and flexibility. The importance of considering fiber morphology is demonstrated as far as it controls fiber flexibility and fiber-fiber interactions.« less

Kinetic and Thermodynamics studies for Castor Oil Extraction Using Subcritical Water Technology.

PubMed

Abdelmoez, Wael; Ashour, Eman; Naguib, Shahenaz M; Hilal, Amr; Al Mahdy, Dalia A; Mahrous, Engy A; Abdel-Sattar, Essam

2016-06-01

In this work both kinetic and thermodynamics of castor oil extraction from its seeds using subcritical water technique were studied. It was found that the extraction process followed two consecutive steps. In these steps, the oil was firstly extracted from inside the powder by diffusion mechanism. Then the extracted oil, due to extending the extraction time under high temperature and pressure, was subjected to a decomposition reaction following first order mechanism. The experimental data correlated well with the irreversible consecutive unimolecular-type first order mechanism. The values of both oil extraction rate constants and decomposition rate constants were calculated through non-linear fitting using DataFit software. The extraction rate constants were found to be 0.0019, 0.024, 0.098, 0.1 and 0.117 min(-1), while the decomposition rate constants were 0.057, 0.059, 0.014, 0.019 and 0.17 min(-1) at extraction temperatures of 240, 250, 260, 270 and 280°C, respectively. The thermodynamic properties of the oil extraction process were investigated using Arrhenius equation. The values of the activation energy, Ea, and the frequency factor, A, were 73 kJ mol(-1) and 946, 002 min(-1), respectively. The physicochemical properties of the extracted castor oil including the specific gravity, viscosity, acid value, pH value and calorific value were found to be 0.947, 7.487, 1.094 mg KOH/g, 6.1, and 41.5 MJ/Kg, respectively. Gas chromatography analysis showed that ricinoleic acid (83.6%) appears as the predominant fatty acid in the extracted oil followed by oleic acid (5.5%) and linoleic acid (2.3%).

On the Mechanism of Microwave Flash Sintering of Ceramics

PubMed Central

Bykov, Yury V.; Egorov, Sergei V.; Eremeev, Anatoly G.; Kholoptsev, Vladislav V.; Plotnikov, Ivan V.; Rybakov, Kirill I.; Sorokin, Andrei A.

2016-01-01

The results of a study of ultra-rapid (flash) sintering of oxide ceramic materials under microwave heating with high absorbed power per unit volume of material (10–500 W/cm3) are presented. Ceramic samples of various compositions—Al2O3; Y2O3; MgAl2O4; and Yb(LaO)2O3—were sintered using a 24 GHz gyrotron system to a density above 0.98–0.99 of the theoretical value in 0.5–5 min without isothermal hold. An analysis of the experimental data (microwave power; heating and cooling rates) along with microstructure characterization provided an insight into the mechanism of flash sintering. Flash sintering occurs when the processing conditions—including the temperature of the sample; the properties of thermal insulation; and the intensity of microwave radiation—facilitate the development of thermal runaway due to an Arrhenius-type dependency of the material’s effective conductivity on temperature. The proper control over the thermal runaway effect is provided by fast regulation of the microwave power. The elevated concentration of defects and impurities in the boundary regions of the grains leads to localized preferential absorption of microwave radiation and results in grain boundary softening/pre-melting. The rapid densification of the granular medium with a reduced viscosity of the grain boundary phase occurs via rotation and sliding of the grains which accommodate their shape due to fast diffusion mass transport through the (quasi-)liquid phase. The same mechanism based on a thermal runaway under volumetric heating can be relevant for the effect of flash sintering of various oxide ceramics under a dc/ac voltage applied to the sample. PMID:28773807

Experimental Evidence for Hydrogen Tunneling when the Isotopic Arrhenius Prefactor (AH/AD) is Unity

PubMed Central

Sharma, Sudhir C.; Klinman, Judith P.

2009-01-01

The temperature dependence of the kinetic isotope effect (KIE) is one of the major tools used for the investigation of hydrogen tunneling in condensed phase. Hydrogen transfer reactions displaying isotopic Arrhenius prefactor ratios (AH/AD) of unity are generally ascribed to a semi-classical mechanism. Here, we have identified a double mutant of soybean lipoxygenase (SLO-1, an enzyme previously shown to follow quantum mechanical hydrogen tunneling), that displays an AH/AD of unity and highly elevated (non-classical) KIEs. This observation highlights the shortcoming of assigning a hydrogen transfer reaction to a semi-classical model based solely on an Arrhenius prefactor ratio. PMID:19061319

Arrhenius' law in turbulent media and an equivalent tunnel effect. [in binary exchange chemical reactions

NASA Technical Reports Server (NTRS)

Tsuge, S.; Sagara, K.

1978-01-01

The indeterminacy inherent to the formal extension of Arrhenius' law to reactions in turbulent flows is shown to be surmountable in the case of a binary exchange reaction with a sufficiently high activation energy. A preliminary calculation predicts that the turbulent reaction rate is invariant in the Arrhenius form except for an equivalently lowered activation energy. This is a reflection of turbulence-augmented molecular vigor, and causes an appreciable increase in the reaction rate. A similarity to the tunnel effect in quantum mechanics is indicated. The anomaly associated with the mild ignition of oxy-hydrogen mixtures is discussed in this light.

Toothpaste lava: Characteristics and origin of a lava structural type transitional between pahoehoe and aa

NASA Astrophysics Data System (ADS)

Rowland, Scott K.; Walker, George P. L.

1987-08-01

Toothpaste lava, an important basalt structural type which illustrates the transition from pahoehoe to aa, is particularly well displayed on the 1960 Kapoho lava of Kilauea Volcano. Its transitional features stem from a viscosity higher than that of pahoehoe and a rate of flow slower than that of aa. Viscosity can be quantified by the limited settling of olivine phenocrysts and rate of flow by field observations related to the low-angle slope on which the lava flowed. Much can be learned about the viscosity, rheologic condition, and flow velocity of lavas long after solidification by analyses of their structural characteristics, and it is possible to make at least a semiquantitative assessment of the numerical values of these parameters.

Supplementation of laying-hen feed with palm tocos and algae astaxanthin for egg yolk nutrient enrichment.

PubMed

Walker, Laurie A; Wang, Tong; Xin, Hongwei; Dolde, David

2012-02-29

Adding supplements to hen feed can increase egg nutritional value. Astaxanthin, tocotrienols, and tocopherols are potent antioxidants that provide health benefits to humans. We hypothesized that the addition of these nutrients to hen feed would result in an increased nutrient content in egg yolk with minimum changes in functional properties. Laying hens (Hy-Line W-36 breed) were fed four diets with different supplementation levels of palm toco concentrate and algae biomass containing astaxanthin for 8 weeks. Egg yolks were analyzed for physical, chemical, and functional properties. The feed with the highest nutrient concentration was also studied for stability of these antioxidants using the Arrhenius approach. No significant differences were observed in functional properties except for emulsification capacity and sensory characteristics among eggs from different diet treatments. Changes in egg yolk color reached the maximum values at day 8. Incorporation of tocopherols and tocotrienols increased until day 8, astaxanthin incorporation increased until day 10, and all decreased thereafter. Feed nutrients resulted in a dose-response relationship of these compounds in the egg yolk. The transfer efficiency ranged from 0 to 9.9% for tocotrienols and tocopherols and from 7.6 to 14.9% for astaxanthin at their peak values. Results of the Arrhenius accelerated stability study showed significant differences in the shelf life of various nutrients, and these results can be used to properly formulate and store the feed materials.

Knee stiffness and viscosity: New implementation and perspectives in prosthesis development

PubMed Central

Bohinc, Klemen; Vantur, Nejc; Torkar, Drago; Lampe, Tomaž; Hribernik, Marija; Jakovljević, Miroljub

2017-01-01

The pendulum test is a method applied to measure passive resistance of the knee. A new and simple pendulum test with instrumentation based on infrared camera was used to evaluate knee stiffness and viscosity on a female human cadaver. The stiffness and viscosity were calculated based on the kinetic data. During the measurements, the periarticular and intraarticular soft tissue of the knee was gradually removed to determine the stiffness and viscosity as a function of the tissue removal rate. The measurements showed that the removal of tissue around the joint reduces the damping of leg oscillation, and therefore decreases the stiffness and viscosity. The contribution to knee joint damping was 10% for the skin, 20% for ligaments, and 40% for muscles and tendons. Tissue removal has a very large impact on the knee stiffness and viscosity. PMID:28422623

Quantitative characterization of the viscosity of a microemulsion

NASA Technical Reports Server (NTRS)

Berg, Robert F.; Moldover, Michael R.; Huang, John S.

1987-01-01

The viscosity of the three-component microemulsion water/decane/AOT has been measured as a function of temperature and droplet volume fraction. At temperatures well below the phase-separation temperature the viscosity is described by treating the droplets as hard spheres suspended in decane. Upon approaching the two-phase region from low temperature, there is a large (as much as a factor of four) smooth increase of the viscosity which may be related to the percolation-like transition observed in the electrical conductivity. This increase in viscosity is not completely consistent with either a naive electroviscous model or a simple clustering model. The divergence of the viscosity near the critical point (39 C) is superimposed upon the smooth increase. The magnitude and temperature dependence of the critical divergence are similar to that seen near the critical points of binary liquid mixtures.

The effect of shear and extensional viscosity on atomization in medical inhaler.

PubMed

Broniarz-Press, L; Ochowiak, M; Matuszak, M; Włodarczak, S

2014-07-01

The paper contains the results of experimental studies of water, aqueous solutions of glycerol and aqueous solutions of glycerol-polyethylene oxide (PEO) atomization process in a medical inhaler obtained by the use of the digital microphotography method. The effect of the shear and extensional viscosity on the drop size, drop size histogram and mean drop diameter has been analyzed. The obtained results have shown that the drop size increases with the increase in shear and extensional viscosity of liquid atomized. Extensional viscosity has a greater impact on the spraying process. It has been shown that the change in liquid viscosity leads to significant changes in drop size distribution. The correlation for Sauter mean diameter as function of the shear and extensional viscosity was proposed. Copyright © 2014 Elsevier B.V. All rights reserved.

Knee stiffness and viscosity: New implementation and perspectives in prosthesis development.

PubMed

Bohinc, Klemen; Vantur, Nejc; Torkar, Drago; Lampe, Tomaž; Hribernik, Marija; Jakovljević, Miroljub

2017-05-20

The pendulum test is a method applied to measure passive resistance of the knee. A new and simple pendulum test with instrumentation based on infrared camera was used to evaluate knee stiffness and viscosity on a female human cadaver. The stiffness and viscosity were calculated based on the kinetic data. During the measurements, the periarticular and intraarticular soft tissue of the knee was gradually removed to determine the stiffness and viscosity as a function of the tissue removal rate. The measurements showed that the removal of tissue around the joint reduces the damping of leg oscillation, and therefore decreases the stiffness and viscosity. The contribution to knee joint damping was 10% for the skin, 20% for ligaments, and 40% for muscles and tendons. Tissue removal has a very large impact on the knee stiffness and viscosity.

Density, Electrical Conductivity and Viscosity of Hg(0.8)Cd(0.2)Te Melt

NASA Technical Reports Server (NTRS)

Li, C.; Scripa, R. N.; Ban, H.; Su, C.-H.; Lehoczky, S. L.

2004-01-01

The density, viscosity, and electrical conductivity of Hg(0.8)Cd(0.2)Te melt were measured as a function of temperature. A pycnometric method was used to measure the melt density in the temperature range of 1072 to 1122 K. The viscosity and electrical conductivity were determined using a transient torque method from 1068 to 1132 K. The density result from this study is within 0.3% of the published data. However, the current viscosity result is approximately 30% lower than the existing data. The electrical conductivity of Hg(0.8)Cd(0.2)Te melt as a function of temperature, which is not available in the literature, is also determined. The analysis of the temperature dependent electrical conductivity and the relationship between the kinematic viscosity and density indicated that the structure of the melt appeared to be homogeneous when the temperature was above 1090 K. A structural transition occurred in the Hg(0.8)Cd(0.2)Te melt as the temperature was decreased to below 1090 K

Density, Electrical Conductivity and Viscosity of Hg(sub 0.8)Cd(sub 0.2)Te Melt

NASA Technical Reports Server (NTRS)

Li, C.; Scripa, R. N.; Ban, H.; Lin, B.; Su, C.-H.; Lehoczky, S. L.

2004-01-01

The density, viscosity, and electrical conductivity of Hg(sub 0.8)Cd(sub 0.2)Te melt were measures as a function of temperature. A pycnometric method was used to measure the melt density in the temperature range of 1072 to 1122 K. The viscosity and electrical conductivity were determined using a transient torque method from 1068 to 1132 K. The density result from this study is within 0.3% of the published data. However, the current viscosity result is approximately 30% lower than the existing data. The electrical conductivity of Hg(sub 0.8)Cd(sub 0.2)Te melt as a function of temperature, which is not available in the literature, is also determined. The analysis of the temperature dependent electrical conductivity and the relationship between the kinematic viscosity and density indicated that the structure of the melt appeared to be homogeneous when the temperature was above 1090 K. A structural transition occurred in the Hg(sub 0.8)Cd(sub 0.2)Te melt as the temperature was decreased to below 1090 K.

Blackbody infrared radiative dissociation of oligonucleotide anions.

PubMed

Klassen, J S; Schnier, P D; Williams, E R

1998-11-01

The dissociation kinetics of a series of doubly deprotonated oligonucleotide 7-mers [d(A)7(2-), d(AATTAAT)2-, d(TTAATTA)2-, and d(CCGGCCG)2-] were measured using blackbody infrared radiative dissociation in a Fourier-transform mass spectrometer. The oligonucleotides dissociate first by cleavage at the glycosidic bond leading to the loss of a neutral nucleobase, followed by cleavage at the adjacent (5') phosphodiester bond to produce structurally informative a-base and w type ions. From the temperature dependence of the unimolecular dissociation rate constants, Arrhenius activation parameters in the zero-pressure limit are obtained for the loss of base. The measured Arrhenius parameters are dependent on the identity of the nucleobase. The process involving the loss of an adenine base from the dianions, d(A)7(2-), d(AATTAAT)2-, and d(TTAATTA)2- has an average activation energy (Ea) of approximately 1.0 eV and a preexponential factor (A) of 10(10) s-1. Both guanine and cytosine base loss occurs for d(CCGGCCG)2-. The average Arrhenius parameters for the loss of cytosine and guanine are Ea = 1.32 +/- 0.03 eV and A = 10(13.3 +/- 0.3) s-1. No loss of thymine was observed for mixed adenine-thymine oligonucleotides. Neither base loss nor any other fragmentation reactions occur for d(T)7(2-) over a 600 s reaction delay at 207 degrees C, a temperature close to the upper limit accessible with our instrument. The Arrhenius parameters indicate that the preferred cleavage sites for mixed oligonucleotides of similar mass-to-charge ratio will be strongly dependent on the internal energy of the precursor ions. At low internal energies (effective temperatures below 475 K), loss of adenine and subsequent cleavage of the adjacent phosphoester bonds will dominate, whereas at higher energies, preferential cleavage at C and G residues will occur. The magnitude of the A factors < or = 10(13) s-1 measured for the loss of the three nucleobases (A, G, and C) is indicative of an entropically neutral or disfavored process as the rate limiting step for this reaction.

Blackbody Infrared Radiative Dissociation of Oligonucleotide Anions

PubMed Central

Klassen, John S.; Schnier, Paul D.; Williams, Evan R.

2005-01-01

The dissociation kinetics of a series of doubly deprotonated oligonucleotide 7-mers [ d(A)72-, d(AATTAAT)2−, d(TTAATTA)2−, and d(CCGGCCG)2−] were measured using blackbody infrared radiative dissociation in a Fourier-transform mass spectrometer. The oligonucleotides dissociate first by cleavage at the glycosidic bond leading to the loss of a neutral nucleobase, followed by cleavage at the adjacent (5′) phosphodiester bond to produce structurally informative a-base and w type ions. From the temperature dependence of the unimolecular dissociation rate constants, Arrhenius activation parameters in the zero-pressure limit are obtained for the loss of base. The measured Arrhenius parameters are dependent on the identity of the nucleobase. The process involving the loss of an adenine base from the dianions, d(A)72-, d(AATTAAT)2−, and d(TTAATTA)2− has an average activation energy (Ea) of ~1.0 eV and a preexponential factor (A) of 1010 s−1. Both guanine and cytosine base loss occurs for d(CCGGCCG)2−. The average Arrhenius parameters for the loss of cytosine and guanine are Ea = 1.32 ± 0.03 eV and A = 1013.3±0.3 s−1. No loss of thymine was observed for mixed adenine–thymine oligonucleotides. Neither base loss nor any other fragmentation reactions occur for d(T)72- over a 600 s reaction delay at 207 °C, a temperature close to the upper limit accessible with our instrument. The Arrhenius parameters indicate that the preferred cleavage sites for mixed oligonucleotides of similar mass-to-charge ratio will be strongly dependent on the internal energy of the precursor ions. At low internal energies (effective temperatures below 475 K), loss of adenine and subsequent cleavage of the adjacent phosphoester bonds will dominate, whereas at higher energies, preferential cleavage at C and G residues will occur. The magnitude of the A factors ≤1013 s−1 measured for the loss of the three nucleobases (A, G, and C) is indicative of an entropically neutral or disfavored process as the rate limiting step for this reaction. PMID:9794082

Geometry of torn boudin-An indicator of relative viscosity

NASA Astrophysics Data System (ADS)

Samanta, Susanta Kumar; Basu Majumder, Debojyoti; Sarkar, Goutam

2017-11-01

The present study determines the role of viscosity on the development of rectangular torn boudin and its various types, defined by the curvature of their exterior and face margins. Numerical modeling was performed with the help of Finite Element Method considering Maxwell visco-elastic materials in commercial code ANSYS. Seven different viscosities were used and interchanged among the boudin, inter-boudin and matrix materials to understand the effect of viscosity ratios, specifically of relative viscosity of inter-boudin material. Results show that the viscosity of inter-boudin material has significant control on the shape of torn boudins apart from the viscosity ratio of boudin to matrix material. Bone-shaped boudin develops only when the inter-boudin is more competent than boudin and it becomes more prominent when matrix is also competent than boudin, but incompetent than inter-boudin. When boudins are stiffer than inter-boudin, barrel-shaped and fish-head boudins with concave faces develop. Exterior or face margins remain almost straight when boudin is relatively rigid compared to its surrounding matrix materials, or when there is no or very little viscosity contrast between boudin and inter-boudin material even in case of large boudin-matrix viscosity contrast. Therefore, the relative viscosity among the boudin, inter-boudin and matrix materials can be estimated qualitatively by studying the shape of boudin in the field.

A Hermite-based lattice Boltzmann model with artificial viscosity for compressible viscous flows

NASA Astrophysics Data System (ADS)

Qiu, Ruofan; Chen, Rongqian; Zhu, Chenxiang; You, Yancheng

2018-05-01

A lattice Boltzmann model on Hermite basis for compressible viscous flows is presented in this paper. The model is developed in the framework of double-distribution-function approach, which has adjustable specific-heat ratio and Prandtl number. It contains a density distribution function for the flow field and a total energy distribution function for the temperature field. The equilibrium distribution function is determined by Hermite expansion, and the D3Q27 and D3Q39 three-dimensional (3D) discrete velocity models are used, in which the discrete velocity model can be replaced easily. Moreover, an artificial viscosity is introduced to enhance the model for capturing shock waves. The model is tested through several cases of compressible flows, including 3D supersonic viscous flows with boundary layer. The effect of artificial viscosity is estimated. Besides, D3Q27 and D3Q39 models are further compared in the present platform.

Viscous effects on the Rayleigh-Taylor instability with background temperature gradient

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gerashchenko, S.; Livescu, D., E-mail: livescu@lanl.gov

The growth rate of the compressible Rayleigh-Taylor instability is studied in the presence of a background temperature gradient, Θ, using a normal mode analysis. The effect of Θ variation is examined for three interface types corresponding to the combinations of the viscous properties of the fluids (inviscid-inviscid, viscous-viscous, and viscous-inviscid) at different Atwood numbers, At, and when at least one of the fluids' viscosity is non-zero, as a function of the Grashof number. For the general case, the resulting ordinary differential equations are solved numerically; however, dispersion relations for the growth rate are presented for several limiting cases. An analyticalmore » solution is found for the inviscid-inviscid interface and the corresponding dispersion equation for the growth rate is obtained in the limit of large Θ. For the viscous-inviscid case, a dispersion relation is derived in the incompressible limit and Θ = 0. Compared to Θ = 0 case, the role of Θ < 0 (hotter light fluid) is destabilizing and becomes stabilizing when Θ > 0 (colder light fluid). The most pronounced effect of Θ ≠ 0 is found at low At and/or at large perturbation wavelengths relative to the domain size for all interface types. On the other hand, at small perturbation wavelengths relative to the domain size, the growth rate for the Θ < 0 case exceeds the infinite domain incompressible constant density result. The results are applied to two practical examples, using sets of parameters relevant to Inertial Confinement Fusion coasting stage and solar corona plumes. The role of viscosity on the growth rate reduction is discussed together with highlighting the range of wavenumbers most affected by viscosity. The viscous effects further increase in the presence of background temperature gradient, when the viscosity is temperature dependent.« less

Challenges in Determining Intrinsic Viscosity Under Low Ionic Strength Solution Conditions.

PubMed

Pindrus, Mariya A; Shire, Steven J; Yadav, Sandeep; Kalonia, Devendra S

2017-04-01

To determine the intrinsic viscosity of several monoclonal antibodies (mAbs) under varying pH and ionic strength solution conditions. An online viscosity detector attached to HPLC (Viscotek®) was used to determine the intrinsic viscosity of mAbs. The Ross and Minton equation was used for viscosity prediction at high protein concentrations. Bulk viscosity was determined by a Cambridge viscometer. At 15 mM ionic strength, intrinsic viscosity of the mAbs determined by the single-point approach varied from 5.6 to 6.4 mL/g with changes in pH. High ionic strength did not significantly alter intrinsic viscosity, while a significant increase (up to 24.0 mL/g) was observed near zero mM. No difference in bulk viscosity of mAb3 was observed around pH 6 as a function of ionic strength. Data analysis revealed that near zero mM ionic strength limitations of the single-point technique result in erroneously high intrinsic viscosity. Intrinsic viscosity is a valuable tool that can be used to model baseline viscosity at higher protein concentrations. However, it is not predictive of solution non-ideality at higher protein concentrations. Furthermore, breakdown of numerous assumptions limits the applicability of experimental techniques near zero mM ionic strength conditions. For molecules and conditions studied, the single-point approach produced reliable intrinsic viscosity results at 15 mM. However, this approach must be used with caution near zero mM ionic strength. Data analysis can be used to reveal whether determined intrinsic viscosity is reliable or erroneously high.

Low Molecular Weight Polymethacrylates as Multi-Functional Lubricant Additives

DOE PAGES

Cosimbescu, Lelia; Vellore, Azhar; Shantini Ramasamy, Uma; ...

2018-04-24

In this study, low molecular weight, moderately polar polymethacrylate polymers are explored as potential multi-functional lubricant additives. The performance of these novel additives in base oil is evaluated in terms of their viscosity index, shear stability, and friction-and-wear. The new compounds are compared to two benchmarks, a typical polymeric viscosity modifier and a fully-formulated oil. Results show that the best performing of the new polymers exhibit viscosity index and friction comparable to that of both benchmarks, far superior shear stability to either benchmark (as much as 15x lower shear loss), and wear reduction significantly better than a typical viscosity modifiermore » (lower wear volume by a factor of 2-3). The findings also suggest that the polarity and molecular weight of the polymers affect their performance which suggests future synthetic strategies may enable this new class of additives to replace multiple additives in typical lubricant formulations.« less

Enhanced t -3/2 long-time tail for the stress-stress time correlation function

NASA Astrophysics Data System (ADS)

Evans, Denis J.

1980-01-01

Nonequilibrium molecular dynamics is used to calculate the spectrum of shear viscosity for a Lennard-Jones fluid. The calculated zero-frequency shear viscosity agrees well with experimental argon results for the two state points considered. The low-frequency behavior of shear viscosity is dominated by an ω 1/2 cusp. Analysis of the form of this cusp reveals that the stress-stress time correlation function exhibits a t -3/2 "long-time tail." It is shown that for the state points studied, the amplitude of this long-time tail is between 12 and 150 times larger than what has been predicted theoretically. If the low-frequency results are truly asymptotic, they imply that the cross and potential contributions to the Kubo-Green integrand for shear viscosity exhibit a t -3/2 long-time tail. This result contradicts the established theory of such processes.

Estimation of shear viscosity based on transverse momentum correlations

NASA Astrophysics Data System (ADS)

STAR Collaboration; Sharma, Monika; STAR Collaboration

2009-11-01

Event anisotropy measurements at RHIC suggest the strongly interacting matter created in heavy ion collisions flows with very little shear viscosity. Precise determination of “shear viscosity-to-entropy” ratio is currently a subject of extensive study [S. Gavin and M. Abdel-Aziz, Phys. Rev. Lett. 97 (2006) 162302]. We present preliminary results of measurements of the evolution of transverse momentum correlation function with collision centrality of Au+Au interactions at s=200 GeV. We compare two differential correlation functions, namely inclusive [J. Adams et al. (STAR Collaboration), Phys. Rev. C 72 (2005) 044902] and a differential version of the correlation measure C˜ introduced by Gavin et al. [S. Gavin and M. Abdel-Aziz, Phys. Rev. Lett. 97 (2006) 162302; M. Sharma and C. A. Pruneau, Phys. Rev. C 79 (2009) 024905.]. These observables can be used for the experimental study of the shear viscosity per unit entropy.

Low Molecular Weight Polymethacrylates as Multi-Functional Lubricant Additives

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cosimbescu, Lelia; Vellore, Azhar; Shantini Ramasamy, Uma

In this study, low molecular weight, moderately polar polymethacrylate polymers are explored as potential multi-functional lubricant additives. The performance of these novel additives in base oil is evaluated in terms of their viscosity index, shear stability, and friction-and-wear. The new compounds are compared to two benchmarks, a typical polymeric viscosity modifier and a fully-formulated oil. Results show that the best performing of the new polymers exhibit viscosity index and friction comparable to that of both benchmarks, far superior shear stability to either benchmark (as much as 15x lower shear loss), and wear reduction significantly better than a typical viscosity modifiermore » (lower wear volume by a factor of 2-3). The findings also suggest that the polarity and molecular weight of the polymers affect their performance which suggests future synthetic strategies may enable this new class of additives to replace multiple additives in typical lubricant formulations.« less

The Burgers/squirt-flow seismic model of the crust and mantle

NASA Astrophysics Data System (ADS)

Carcione, José M.; Poletto, Flavio; Farina, Biancamaria

2018-01-01

Part of the crust shows generally brittle behaviour while areas of high temperature and/or high pore pressure, including the mantle, may present ductile behaviour. For instance, the potential heat source of geothermal fields, overpressured formations and molten rocks. Seismic waves can be used to detect these conditions on the basis of reflection and transmission events. Basically, from the elastic-plastic point of view the seismic properties (seismic velocity, quality factor and density) depend on effective pressure and temperature. Confining and pore pressures have opposite effects on these properties, and high temperatures may induce a similar behaviour by partial melting. In order to model these effects, we consider a poro-viscoelastic model based on the Burgers mechanical element and the squirt-flow model to represent the properties of the rock frame to describe ductility in which deformation takes place by shear plastic flow, and to model local and global fluid flow effects. The Burgers element allows us to model the effects of the steady-state creep flow on the dry-rock frame. The stiffness components of the brittle and ductile media depend on stress and temperature through the shear viscosity, which is obtained by the Arrhenius equation and the octahedral stress criterion. Effective pressure effects are taken into account in the dry-rock moduli by using exponential functions whose parameters are obtained by fitting experimental data as a function of confining pressure. Since fluid effects are important, the density and bulk modulus of the saturating fluids (water at sub- and supercritical conditions) are modeled by using the equations provided by the NIST website. The squirt-flow model has a single free parameter represented by the aspect ratio of the grain contacts. The theory generalizes a preceding theory based on Gassmann (low-frequency) moduli to the more general case of the presence of local (squirt) flow and global (Biot) flow, which contribute with additional attenuation mechanisms to the wave propagation.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johnson, Kyle J.; Glynos, Emmanouil; Maroulas, Serafeim-Dionysios

Incorporating nanoparticles (NPs) within a polymer host to create polymer nanocomposites (PNCs) while having the effect of increasing the functionality (e.g.: sensing, energy conversion) of these materials, introduces additional complications with regard to the processing-morphology-function behavior. A primary challenge is to understand and control the viscosity of a PNC with decreasing film thickness confinement for nanoscale applications. Using a combination of X-ray photon correlation spectroscopy (XPCS) and X-ray standing wave based resonance enhanced XPCS to study the dynamics of neat poly-2-vinyl pyridine (P2VP) chains and the nanoparticle dynamics, respectively, we identified a new mechanism that dictates the viscosity of PNCmore » films in the nanoscale regime. We show that while the viscosities of neat P2VP films as thin as 50 nm remained the same as the bulk, PNC films containing P2VP brush-coated gold NPs, spaced 50 nm apart, exhibited unprecedented increases in viscosities of over an order of magnitude. For thicker films or more widely separated NPs, the chain dynamics and viscosities were equal to the bulk values. These results -NP proximities and suppression of their dynamics -suggest a new mechanism by which the viscosities of polymeric liquids could be controlled for 2D and 3D nanoscale applications.« less

The Contribution of Red Blood Cell Dynamics to Intrinsic Viscosity and Functional ATP Release

NASA Astrophysics Data System (ADS)

Forsyth, Alison; Abkarian, Manouk; Wan, Jiandi; Stone, Howard

2010-11-01

In shear flow, red blood cells (RBCs) exhibit a variety of behaviors such as rouleaux formation, tumbling, swinging, and tank-treading. The physiological consequences of these dynamic behaviors are not understood. In vivo, ATP is known to signal vasodilation; however, to our knowledge, no one has deciphered the relevance of RBC microrheology to the functional release of ATP. Previously, we correlated RBC deformation and ATP release in microfluidic constrictions (Wan et al., 2008). In this work, a cone-plate rheometer is used to shear a low hematocrit solution of RBCs at varying viscosity ratios (λ) between the inner cytoplasmic hemoglobin and the outer medium, to determine the intrinsic viscosity of the suspension. Further, using a luciferin-luciferase enzymatic reaction, we report the relative ATP release at varying shear rates. Results indicate that for λ = 1.6, 3.8 and 11.1, ATP release is constant up to 500 s-1, which suggests that the tumbling-tanktreading transition does not alter ATP release in pure shear. For lower viscosity ratios, λ = 1.6 and 3.8, at 500 s-1 a change in slope occurs in the intrinsic viscosity data and is marked by an increase in ATP release. Based on microfluidic observations, this simultaneous change in viscosity and ATP release occurs within the tank-treading regime.

Hierarchical viscosity of aqueous solution of tilapia scale collagen investigated via dielectric spectroscopy between 500 MHz and 2.5 THz

PubMed Central

Kawamata, H.; Kuwaki, S.; Mishina, T.; Ikoma, T.; Tanaka, J.; Nozaki, R.

2017-01-01

Aqueous solutions of biomolecules such as proteins are very important model systems for understanding the functions of biomolecules in actual life processes because interactions between biomolecules and the surrounding water molecules are considered to be important determinants of biomolecules’ functions. Globule proteins have been extensively studied via dielectric spectroscopy; the results indicate three relaxation processes originating from fluctuations in the protein molecule, the bound water and the bulk water. However, the characteristics of aqueous solutions of collagens have rarely been investigated. In this work, based on broadband dielectric measurements between 500 MHz and 2.5 THz, we demonstrate that the high viscosity of a collagen aqueous solution is due to the network structure being constructed of rod-like collagen molecules surrounding free water molecules and that the water molecules are not responsible for the viscosity. We determine that the macroscopic viscosity is related to the mean lifetime of the collagen-collagen interactions supporting the networks and that the local viscosity of the water surrounded by the networks is governed by the viscosity of free water as in the bulk. This hierarchical structure in the dynamics of the aqueous solution of biomolecules has been revealed for the first time. PMID:28345664

Towards a Quantitative Analysis of the Temperature Dependence of Electron Attachment Processes

DTIC Science & Technology

2016-06-24

from an Arrhenius law should become pronounced when the temperature range would be extended considerably. Such experiments then were done as reported...in Ref. 13. Indeed marked deviations from the Arrhenius law became visible and, in addition, very good agreement with predictions from our “kinetic

Why Are Some Reactions Slower at Higher Temperatures?

ERIC Educational Resources Information Center

Revell, Laura E.; Williamson, Bryce E.

2013-01-01

It is well understood by most chemistry students at advanced undergraduate levels that chemical reactions generally follow the Arrhenius law of temperature dependence with positive activation energies, proceeding faster at elevated temperatures. It is much less widely known that the rates of some Arrhenius-compliant reactions are retarded by…

ENERGETICS AND CHEMICAL KINETICS OF POLYSTYRENE SURFACE DEGRADATION IN INERT AND CHEMICALLY REACTIVE ENVIRONMENTS.

DTIC Science & Technology

gases were passed to emerge at the heated surface, permitted these data to be gathered in chemically reactive environments. Correlation of all these data...in both inert and chemically reactive environments, was possible both on the basis of an energy balance struck at the regressing surface and an...Arrhenius type of chemical kinetic description of the surface degradation process. Although expected, this represents the first demonstration that both

Entropy Viscosity and L1-based Approximations of PDEs: Exploiting Sparsity

DTIC Science & Technology

2015-10-23

AFRL-AFOSR-VA-TR-2015-0337 Entropy Viscosity and L1-based Approximations of PDEs: Exploiting Sparsity Jean-Luc Guermond TEXAS A & M UNIVERSITY 750...REPORT DATE (DD-MM-YYYY) 09-05-2015 2. REPORT TYPE Final report 3. DATES COVERED (From - To) 01-07-2012 - 30-06-2015 4. TITLE AND SUBTITLE Entropy ...conservation equations can be stabilized by using the so-called entropy viscosity method and we proposed to to investigate this new technique. We

Correlation between the Temperature Dependence of Intrsinsic Mr Parameters and Thermal Dose Measured by a Rapid Chemical Shift Imaging Technique

PubMed Central

Taylor, Brian A.; Elliott, Andrew M.; Hwang, Ken-Pin; Hazle, John D.; Stafford, R. Jason

2011-01-01

In order to investigate simultaneous MR temperature imaging and direct validation of tissue damage during thermal therapy, temperature-dependent signal changes in proton resonance frequency (PRF) shifts, R2* values, and T1-weighted amplitudes are measured from one technique in ex vivo tissue heated with a 980-nm laser at 1.5T and 3.0T. Using a multi-gradient echo acquisition and signal modeling with the Stieglitz-McBride algorithm, the temperature sensitivity coefficient (TSC) values of these parameters are measured in each tissue at high spatiotemporal resolutions (1.6×1.6×4mm3,≤5sec) at the range of 25-61 °C. Non-linear changes in MR parameters are examined and correlated with an Arrhenius rate dose model of thermal damage. Using logistic regression, the probability of changes in these parameters is calculated as a function of thermal dose to determine if changes correspond to thermal damage. Temperature calibrations demonstrate TSC values which are consistent with previous studies. Temperature sensitivity of R2* and, in some cases, T1-weighted amplitudes are statistically different before and after thermal damage occurred. Significant changes in the slopes of R2* as a function of temperature are observed. Logistic regression analysis shows that these changes could be accurately predicted using the Arrhenius rate dose model (Ω=1.01±0.03), thereby showing that the changes in R2* could be direct markers of protein denaturation. Overall, by using a chemical shift imaging technique with simultaneous temperature estimation, R2* mapping and T1-W imaging, it is shown that changes in the sensitivity of R2* and, to a lesser degree, T1-W amplitudes are measured in ex vivo tissue when thermal damage is expected to occur according to Arrhenius rate dose models. These changes could possibly be used for direct validation of thermal damage in contrast to model-based predictions. PMID:21721063

Viscosity of particulate soap films: approaching the jamming of 2D capillary suspensions.

PubMed

Timounay, Yousra; Rouyer, Florence

2017-05-14

We compute the effective viscosity of particulate soap films thanks to local velocity fields obtained by Particle Image Velocimetry (PIV) during film retraction experiments. We identify the jamming of these 2D capillary suspensions at a critical particle surface fraction (≃0.84) where effective viscosity diverges. Pair correlation function and number of neighbors in contact or close to contact reveal the cohesive nature of this 2D capillary granular media. The experimental 2D dynamic viscosities can be predicted by a model considering viscous dissipation at the liquid interfaces induced by the motion of individual particles.

Measurement of Xenon Viscosity as a Function of Low Temperature and Pressure

NASA Technical Reports Server (NTRS)

Grisnik, Stanley P.

1998-01-01

The measurement of xenon gas viscosity at low temperatures (175-298 K) and low pressures (350 torr-760 torr) has been performed in support of Hall Thruster testing at NASA Lewis Research Center. The measurements were taken using the capillary flow technique. Viscosity measurements were repeatable to within 3%. The results in this paper are in agreement with data from Hanley and Childs and suggest that the data from Clarke and Smith is approximately 2% low. There are no noticeable pressure effects on xenon absolute viscosity for the pressure range from 350 torr to 760 torr.

Impact of viscosity variation and micro rotation on oblique transport of Cu-water fluid.

PubMed

Tabassum, Rabil; Mehmood, R; Nadeem, S

2017-09-01

This study inspects the influence of temperature dependent viscosity on Oblique flow of micropolar nanofluid. Fluid viscosity is considered as an exponential function of temperature. Governing equations are converted into dimensionless forms with aid of suitable transformations. Outcomes of the study are shown in graphical form and discussed in detail. Results revealed that viscosity parameter has pronounced effects on velocity profiles, temperature distribution, micro-rotation, streamlines, shear stress and heat flux. It is found that viscosity parameter enhances the temperature distribution, tangential velocity profile, normal component of micro-rotation and shear stress at the wall while it has decreasing effect on tangential component of micro-rotation and local heat flux. Copyright © 2017 Elsevier Inc. All rights reserved.

Rheological behaviors of an exopolysaccharide from fermentation medium of a Cordyceps sinensis fungus (Cs-HK1).

PubMed

Sun, Fengyuan; Huang, Qilin; Wu, Jianyong

2014-12-19

The rheological behaviors of an exopolysaccharide (EPS) from a Cordyceps sinensis fungus fermentation were investigated. The intrinsic viscosity of 1986 ± 55 mL/g indicated an extended and rigid chain for EPS. Shear-thinning behavior was observed and became apparent with increasing concentration. According to cross model, two critical transition concentrations (c(*) and c(**)) from dilute solution to semidilute and then to concentrated domain were 0.45 and 6.14 mg/mL. Flow activation energy was calculated by Arrhenius equation and decreased with increasing concentration, indicating a lower sensitivity to temperature. From dynamic frequency sweep, EPS system was classified to three regions including dilution solution (1.25mg/mL), entanglement network (3.75 and 5.00 mg/mL) and weak gel (≥ 7.50 mg/mL). Notably, the increase in η(*) at high frequencies was attributed to a large flow resistance depended on the rigid chain of EPS. Based on Winter-Chambon criterion, EPS formed gel at 2.6 mg/mL (cgel) and showed typical weak gel from temperature ramp and repetitive strain sweep. Copyright © 2014 Elsevier Ltd. All rights reserved.

Lamins at the crossroads of mechanosignaling

PubMed Central

Osmanagic-Myers, Selma; Dechat, Thomas

2015-01-01

The intermediate filament proteins, A- and B-type lamins, form the nuclear lamina scaffold adjacent to the inner nuclear membrane. B-type lamins confer elasticity, while A-type lamins lend viscosity and stiffness to nuclei. Lamins also contribute to chromatin regulation and various signaling pathways affecting gene expression. The mechanical roles of lamins and their functions in gene regulation are often viewed as independent activities, but recent findings suggest a highly cross-linked and interdependent regulation of these different functions, particularly in mechanosignaling. In this newly emerging concept, lamins act as a “mechanostat” that senses forces from outside and responds to tension by reinforcing the cytoskeleton and the extracellular matrix. A-type lamins, emerin, and the linker of the nucleoskeleton and cytoskeleton (LINC) complex directly transmit forces from the extracellular matrix into the nucleus. These mechanical forces lead to changes in the molecular structure, modification, and assembly state of A-type lamins. This in turn activates a tension-induced “inside-out signaling” through which the nucleus feeds back to the cytoskeleton and the extracellular matrix to balance outside and inside forces. These functions regulate differentiation and may be impaired in lamin-linked diseases, leading to cellular phenotypes, particularly in mechanical load-bearing tissues. PMID:25644599

Chemical and Functional Properties of Chia Seed (Salvia hispanica L.) Gum

PubMed Central

Segura-Campos, Maira Rubi; Ciau-Solís, Norma; Rosado-Rubio, Gabriel; Chel-Guerrero, Luis; Betancur-Ancona, David

2014-01-01

Chia (Salvia hispanica L.) constitutes a potential alternative raw material and ingredient in food industry applications due to its dietary fiber content. Gum can be extracted from its dietary fiber fractions for use as an additive to control viscosity, stability, texture, and consistency in food systems. The gum extracted from chia seeds was characterized to determine their quality and potential as functional food additives. The extracted chia gum contained 26.2% fat and a portion was submitted to fat extraction, producing two fractions: gum with fat (FCG) and gum partly defatted (PDCG). Proximal composition and physicochemical characterization showed these fractions to be different (P < 0.05). The PDCG had higher protein, ash, and carbohydrates content than the FCG, in addition to higher water-holding (110.5 g water/g fiber) and water-binding capacities (0.84 g water/g fiber). The FCG had greater oil-holding capacity (25.7 g oil/g fiber) and water absorption capacity (44 g water/g fiber). In dispersion trials, the gums exhibited a non-Newtonian fluid behavior, specifically shear thinning or pseudoplastic type. PDCG had more viscosity than FCG. Chia seed is an excellent natural source of gum with good physicochemical and functional qualities, and is very promising for use in food industry. PMID:26904622

Application of Light-Emitting Diodes and Photodiodes Coupled to Optic Fibers to Study the Dependence of Liquid Viscosity on Temperature

ERIC Educational Resources Information Center

Victoria, L.; Arenas, A.

2004-01-01

A device designed to demonstrate the dependence of viscosity on temperature and to check the validity of the exponential relationship is described. The device has the advantage of versatility as it can be adapted to different types of viscosimeters.

Viscosity of two-dimensional strongly coupled dusty plasma modified by a perpendicular magnetic field

NASA Astrophysics Data System (ADS)

Feng, Yan; Lin, Wei; Murillo, M. S.

2017-11-01

Transport properties of two-dimensional (2D) strongly coupled dusty plasmas have been investigated in detail, but never for viscosity with a strong perpendicular magnetic field; here, we examine this scenario using Langevin dynamics simulations of 2D liquids with a binary Yukawa interparticle interaction. The shear viscosity η of 2D liquid dusty plasma is estimated from the simulation data using the Green-Kubo relation, which is the integration of the shear stress autocorrelation function. It is found that, when a perpendicular magnetic field is applied, the shear viscosity of 2D liquid dusty plasma is modified substantially. When the magnetic field is increased, its viscosity increases at low temperatures, while at high temperatures its viscosity diminishes. It is determined that these different variational trends of η arise from the different behaviors of the kinetic and potential parts of the shear stress under external magnetic fields.

Molecular basis of high viscosity in concentrated antibody solutions: Strategies for high concentration drug product development

PubMed Central

Tomar, Dheeraj S.; Kumar, Sandeep; Singh, Satish K.; Goswami, Sumit; Li, Li

2016-01-01

ABSTRACT Effective translation of breakthrough discoveries into innovative products in the clinic requires proactive mitigation or elimination of several drug development challenges. These challenges can vary depending upon the type of drug molecule. In the case of therapeutic antibody candidates, a commonly encountered challenge is high viscosity of the concentrated antibody solutions. Concentration-dependent viscosity behaviors of mAbs and other biologic entities may depend on pairwise and higher-order intermolecular interactions, non-native aggregation, and concentration-dependent fluctuations of various antibody regions. This article reviews our current understanding of molecular origins of viscosity behaviors of antibody solutions. We discuss general strategies and guidelines to select low viscosity candidates or optimize lead candidates for lower viscosity at early drug discovery stages. Moreover, strategies for formulation optimization and excipient design are also presented for candidates already in advanced product development stages. Potential future directions for research in this field are also explored. PMID:26736022

Highly branched polyethylenes as lubricant viscosity and friction modifiers

DOE PAGES

Robinson, Joshua W.; Zhou, Yan; Qu, Jun; ...

2016-10-08

A series of highly branched polyethylene (BPE) were prepared and evaluated in a Group I base oil as potential viscosity and friction modifiers. The performance of these BPEs supports the expected dual functionality. Changes in polarity, topology, and molecular weight of the BPEs showed significant effects on the lubricants' performance with respect to viscosity index and friction reduction. In conclusion, this study provides scientific insights into polymer design for future lubricant development activities.

The Intrinsic Reactivity of ATP and the Catalytic Proficiencies of Kinases Acting on Glucose, N-Acetylgalactosamine, and Homoserine

PubMed Central

Stockbridge, Randy B.; Wolfenden, Richard

2009-01-01

To evaluate the rate enhancements produced by representative kinases and their thermodynamic basis, rate constants were determined as a function of changing temperature for 1) the spontaneous methanolysis of ATP and 2) reactions catalyzed by kinases to which different mechanisms of action have been ascribed. For each of these enzymes, the minor effects of changing viscosity indicate that kcat/Km is governed by the central chemical events in the enzyme-substrate complex rather than by enzyme-substrate encounter. Individual Arrhenius plots, obtained at intervals between pH 4.8 and 11.0, yielded ΔH‡ and TΔS‡ for the nonenzymatic methanolysis of ATP2−, ATP3−, and ATP4− in the absence of Mg2+. The addition of Mg2+ led to partly compensating changes in ΔH‡ and TΔS‡, accelerating the nonenzymatic methanolysis of ATP 11-fold at pH 7 and 25 °C. The rate enhancements produced by yeast hexokinase, homoserine kinase, and N-acetylgalactosamine kinase (obtained by comparison of their kcat/Km values in the presence of saturating phosphoryl acceptor with the second order rate constant for methanolysis of MgATP) ranged between 1012- and 1014-fold. Their nominal affinities for the altered substrates in the transition state were 2.1 × 10−16 m for N-acetylgalactosamine kinase, 7.4 × 10−17 m for homoserine kinase, and 6.4 × 10−18 m for hexokinase. Compared with nonenzymatic phosphoryl transfer, all three kinases were found to produce major reductions in the entropy of activation, in accord with the likelihood that substrate juxtaposition and desolvation play prominent roles in their catalytic action. PMID:19531469

Effect of Heat (Arrhenius Effect) on Crude Hemolysin of Vibrio parahaemolyticus

PubMed Central

Miwatani, Toshio; Takeda, Yoshifumi; Sakurai, Jun; Yoshihara, Akiko; Taga, Sekiko

1972-01-01

Crude hemolysins prepared from various strains of Vibrio parahaemolyticus, which give positive Kanagawa phenomenon, were partly inactivated by heating at 60 C, but not inactivated significantly by heating at 80 to 90 C. The similar phenomenon has been reported as the Arrhenius effect in staphylococcal alpha toxin. Images PMID:4638496

Effect of temperature on microbial growth rate - thermodynamic analysis, the arrhenius and eyring-polanyi connection

USDA-ARS?s Scientific Manuscript database

The objective of this work is to develop a new thermodynamic mathematical model for evaluating the effect of temperature on the rate of microbial growth. The new mathematical model is derived by combining the Arrhenius equation and the Eyring-Polanyi transition theory. The new model, suitable for ...

Application of the compensated arrhenius formalism to dielectric relaxation.

PubMed

Petrowsky, Matt; Frech, Roger

2009-12-17

The temperature dependence of the dielectric rate constant, defined as the reciprocal of the dielectric relaxation time, is examined for several groups of organic solvents. Early studies of linear alcohols using a simple Arrhenius equation found that the activation energy was dependent on the chain length of the alcohol. This paper re-examines the earlier data using a compensated Arrhenius formalism that assumes the presence of a temperature-dependent static dielectric constant in the exponential prefactor. Scaling temperature-dependent rate constants to isothermal rate constants so that the dielectric constant dependence is removed results in calculated energies of activation E(a) in which there is a small increase with chain length. These energies of activation are very similar to those calculated from ionic conductivity data using compensated Arrhenius formalism. This treatment is then extended to dielectic relaxation data for n-alkyl bromides, n-nitriles, and n-acetates. The exponential prefactor is determined by dividing the temperature-dependent rate constants by the Boltzmann term exp(-E(a)/RT). Plotting the prefactors versus the static dielectric constant places the data on a single master curve for each group of solvents.

Origin of the Non-Arrhenius Behavior of the Rates of Enzymatic Reactions.

PubMed

Roy, Subhendu; Schopf, Patrick; Warshel, Arieh

2017-07-13

The origin of the non-Arrhenius behavior of the rate constant for hydride transfer enzymatic reactions has been a puzzling problem since its initial observation. This effect has been used originally to support the idea that enzymes work by dynamical effects and more recently to suggest an entropy funnel model. Our analysis, however, has advanced the idea that the reason for the non-Arrhenius trend reflects the temperature dependence of the rearrangements of the protein polar groups in response to the change in the charge distribution of the reacting system during the transition from the ground state (GS) to the transition state (TS). Here we examine the validity of our early proposal by simulating the catalytic reaction of alcohol dehydrogenase (ADH) and determine the microscopic origin of the entropic and enthalpic contributions to the activation barrier. The corresponding analysis establishes the origin of the non-Arrhenius behaviors and quantifies our original suggestion that the classical effect is due to the entropic contributions of the environment. We also find that the quantum effects reflect in part the temperature dependence of the donor-acceptor distance.

Correlation between Fragility and the Arrhenius Crossover Phenomenon in Metallic, Molecular, and Network Liquids.

PubMed

Jaiswal, Abhishek; Egami, Takeshi; Kelton, K F; Schweizer, Kenneth S; Zhang, Yang

2016-11-11

We report the observation of a distinct correlation between the kinetic fragility index m and the reduced Arrhenius crossover temperature θ_{A}=T_{A}/T_{g} in various glass-forming liquids, identifying three distinguishable groups. In particular, for 11 glass-forming metallic liquids, we universally observe a crossover in the mean diffusion coefficient from high-temperature Arrhenius to low-temperature super-Arrhenius behavior at approximately θ_{A}≈2 which is in the stable liquid phases. In contrast, for fragile molecular liquids, this crossover occurs at much lower θ_{A}≈1.4 and usually in their supercooled states. The θ_{A} values for strong network liquids spans a wide range higher than 2. Intriguingly, the high-temperature activation barrier E_{∞} is universally found to be ∼11k_{B}T_{g} and uncorrelated with the fragility or the reduced crossover temperature θ_{A} for metallic and molecular liquids. These observations provide a way to estimate the low-temperature glassy characteristics (T_{g} and m) from the high-temperature liquid quantities (E_{∞} and θ_{A}).

Non-Arrhenius temperature dependence of the island density of one-dimensional Al chains on Si(100): A kinetic Monte Carlo study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Albia, Jason R.; Albao, Marvin A., E-mail: maalbao@uplb.edu.ph

Classical nucleation theory predicts that the evolution of mean island density with temperature during growth in one-dimensional systems obeys the Arrhenius relation. In this study, kinetic Monte Carlo simulations of a suitable atomistic lattice-gas model were performed to investigate the experimentally observed non-Arrhenius scaling behavior of island density in the case of one-dimensional Al islands grown on Si(100). Previously, it was proposed that adatom desorption resulted in a transition temperature signaling the departure from classical predictions. Here, the authors demonstrate that desorption above the transition temperature is not possible. Instead, the authors posit that the existence of a transition temperaturemore » is due to a combination of factors such as reversibility of island growth, presence of C-defects, adatom diffusion rates, as well as detachment rates at island ends. In addition, the authors show that the anomalous non-Arrhenius behavior vanishes when adatom binds irreversibly with C-defects as observed in In on Si(100) studies.« less

Correlation between Fragility and the Arrhenius Crossover Phenomenon in Metallic, Molecular, and Network Liquids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jaiswal, Abhishek; Egami, Takeshi; Kelton, K. F.

2016-11-10

In this paper, we report the observation of a distinct correlation between the kinetic fragility index m and the reduced Arrhenius crossover temperature θ A = T A/T g in various glass-forming liquids, identifying three distinguishable groups. In particular, for 11 glass-forming metallic liquids, we universally observe a crossover in the mean diffusion coefficient from high-temperature Arrhenius to low-temperature super-Arrhenius behavior at approximately θ A ≈ 2 which is in the stable liquid phases. In contrast, for fragile molecular liquids, this crossover occurs at much lower θ A ≈ 1.4 and usually in their supercooled states. The θ A valuesmore » for strong network liquids spans a wide range higher than 2. Intriguingly, the high-temperature activation barrier E ∞ is universally found to be ~11k BT g and uncorrelated with the fragility or the reduced crossover temperature θ A for metallic and molecular liquids. Finally, these observations provide a way to estimate the low-temperature glassy characteristics (T g and m) from the high-temperature liquid quantities (E ∞ and θ A).« less

Systematic errors in transport calculations of shear viscosity using the Green-Kubo formalism

NASA Astrophysics Data System (ADS)

Rose, J. B.; Torres-Rincon, J. M.; Oliinychenko, D.; Schäfer, A.; Petersen, H.

2018-05-01

The purpose of this study is to provide a reproducible framework in the use of the Green-Kubo formalism to extract transport coefficients. More specifically, in the case of shear viscosity, we investigate the limitations and technical details of fitting the auto-correlation function to a decaying exponential. This fitting procedure is found to be applicable for systems interacting both through constant and energy-dependent cross-sections, although this is only true for sufficiently dilute systems in the latter case. We find that the optimal fit technique consists in simultaneously fixing the intercept of the correlation function and use a fitting interval constrained by the relative error on the correlation function. The formalism is then applied to the full hadron gas, for which we obtain the shear viscosity to entropy ratio.

Overflow Simulations using MPAS-Ocean in Idealized and Realistic Domains

NASA Astrophysics Data System (ADS)

Reckinger, S.; Petersen, M. R.; Reckinger, S. J.

2016-02-01

MPAS-Ocean is used to simulate an idealized, density-driven overflow using the dynamics of overflow mixing and entrainment (DOME) setup. Numerical simulations are benchmarked against other models, including the MITgcm's z-coordinate model and HIM's isopycnal coordinate model. A full parameter study is presented that looks at how sensitive overflow simulations are to vertical grid type, resolution, and viscosity. Horizontal resolutions with 50 km grid cells are under-resolved and produce poor results, regardless of other parameter settings. Vertical grids ranging in thickness from 15 m to 120 m were tested. A horizontal resolution of 10 km and a vertical resolution of 60 m are sufficient to resolve the mesoscale dynamics of the DOME configuration, which mimics real-world overflow parameters. Mixing and final buoyancy are least sensitive to horizontal viscosity, but strongly sensitive to vertical viscosity. This suggests that vertical viscosity could be adjusted in overflow water formation regions to influence mixing and product water characteristics. Also, the study shows that sigma coordinates produce much less mixing than z-type coordinates, resulting in heavier plumes that go further down slope. Sigma coordinates are less sensitive to changes in resolution but as sensitive to vertical viscosity compared to z-coordinates. Additionally, preliminary measurements of overflow diagnostics on global simulations using a realistic oceanic domain are presented.

Mafic-crystal distributions, viscosities, and lava structures of some Hawaiian lava flows

NASA Astrophysics Data System (ADS)

Rowland, Scott K.; Walker, George P. L.

1988-09-01

The distribution patterns of mafic phenocrysts in some Hawaiian basalt flows are consistent with simple in situ gravitational settling. We use the patterns to estimate the crystal settling velocity and hence viscosity of the lava, which in turn can be correlated with surface structures. Numerical modeling generates theoretical crystal concentration profiles through lava flow units of different thicknesses for differing settling velocities. By fitting these curves to field data, crystal-settling rates through the lavas can be estimated, from which the viscosities of the flows can be determined using Stokes' Law. Lavas in which the crystal settling velocity was relatively high (on the order of 5 × 10 -4 cm/sec) show great variations in phenocryst content, both from top to bottom of the same flow unit, and from one flow unit to another. Such lava is invariably pahoehoe, flow units of which are usually less than 1 m thick. Lavas in which the crystal-settling velocity was low show a small but measurable variation in phenocryst content. These lavas are part of a progression from a rough pahoehoe to toothpaste lava to a'a. Toothpaste lava is characterized by spiny texture as well as the ability to retain surface grooves during solidification, and flow units are usually thicker than 1 m. In the thickest of Hawaiian a'a flows, those of the distal type, no systematic crystal variations are observed, and high viscosity coupled with a finite yield strength prevented crystal settling. The amount of crystal settling in pahoehoe indicates that the viscosity ranged from 600 to 6000 Pa s. The limited amount of settling in toothpaste lava indicates a viscosity greater than this value, approaching 12,000 Pa s. We infer that distal-type a'a had a higher viscosity still and also possessed a yield strength.

The effect of ilmenite viscosity on the dynamics and evolution of an overturned lunar cumulate mantle

NASA Astrophysics Data System (ADS)

Zhang, Nan; Dygert, Nick; Liang, Yan; Parmentier, E. M.

2017-07-01

Lunar cumulate mantle overturn and the subsequent upwelling of overturned mantle cumulates provide a potential framework for understanding the first-order thermochemical evolution of the Moon. Upwelling of ilmenite-bearing cumulates (IBCs) after the overturn has a dominant influence on the dynamics and long-term thermal evolution of the lunar mantle. An important parameter determining the stability and convective behavior of the IBC is its viscosity, which was recently constrained through rock deformation experiments. To examine the effect of IBC viscosity on the upwelling of overturned lunar cumulate mantle, here we conduct three-dimensional mantle convection models with an evolving core superposed by an IBC-rich layer, which resulted from mantle overturn after magma ocean solidification. Our modeling shows that a reduction of mantle viscosity by 1 order of magnitude, due to the presence of ilmenite, can dramatically change convective planform and long-term lunar mantle evolution. Our model results suggest a relatively stable partially molten IBC layer that has surrounded the lunar core to the present day.