913 resultados para Phase rule and equilibrium.
Resumo:
This article is the result of experimental studies of the rheologv, viscosities, surface tensions, and atomization of water-methanol and diesel emulsions. The Span 80 and Tween 60 are employed to make three emulsifying agents, Y01, Y02, and Y03, with viscosity of 1.32-1.5 Pa s and HLB values of 5.36, 4.83, and 4.51, respectively. In the water-in-oil emulsions, the aqueous phase is between 10% and 50%; the agent concentration added is 0.8-8.0%. The viscosity of the emulsions is 0.003-0.02 Pa s, and the surface tens ion is 0.04-0.1 N/m. The types and concentrations of agents significantly influence the viscosity of the emulsions, and the higher concentration of the aqueous phase (<50%) in creases the viscosities of the emulsions, especially for higher agent concentration. Interfacial membrane and HLB values of the agents can explain all these phenomena. Higher aqueous phase concentration and agent viscosity results in larger Sauter mean diameter.
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The phase behavior of liquid crystalline in the ternary system of dodecyl dimethyl ammonium hydroxyl propyl sulfonate(DDAHPS)/1-pentanol(C5H11OH)/water deuteron (D2O) has been investigated by polarizing optical microscopy, H-2 NMR spectroscopy methods. The results indicate that two kinds of liquid crystals (the lamellar, and the hexagonal) exist in the liquid crystalline phase region. In this paper, we also use the polarized Raman spectroscopy method to measure the values of the order/disorder parameters and the values of the environment polarity parameters for the samples selected from the liquid crystalline phase region, and compare these two parameters of the samples with those of solid state DDAHPS and liquid state pentan-1-ol.
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Molecular dynamics (MD) simulations and first-principles calculations are carried out to analyze the stability of both newly discovered and previously known phases of ZnO under loading of various triaxialities. The analysis focuses on a graphite-like phase (FIX) and a body-centered-tetragonal phase (BCT-4) that were observed recently in [0 1 (1) over bar 0]- and [0 0 0 1]-oriented nanowires respectively under uniaxial tensile loading as well as the natural state of wurtzite (WZ) and the rocksalt (RS) phase which exists under hydrostatic pressure loading. Equilibrium critical stresses for the transformations are obtained. The WZ -> HX transformation is found to be energetically favorable above a critical tensile stress of 10 GPa in [0 1 (1) over tilde 0] nanowires. The BCT-4 phase can be stabilized at tensile stresses above 7 GPa in [0 0 0 1] nanowires. The RS phase is stable at hydrostatic pressures above 8.2 GPa. The identification and characterization of these phase transformations reveal a more extensive polymorphism of ZnO than previously known. A crystalline structure-load triaxiality map is developed to summarize the new understanding. (c) 2007 Elsevier Ltd. All rights reserved.
Wave propagation and the frequency domain Green's functions in viscoelastic Biot/squirt (BISQ) media
Resumo:
In this paper, we examine the characteristics of elastic wave propagation in viscoelastic porous media, which contain simultaneously both the Biot-flow and the squirt-flow mechanisms (BISQ). The frequency-domain Green's functions for viscoelastic BISQ media are then derived based on the classic potential function methods. Our numerical results show that S-waves are only affected by viscoelasticity, but not by squirt-flows. However, the phase velocity and attenuation of fast P-waves are seriously influenced by both viscoelasticity and squirt-flows; and there exist two peaks in the attenuation-frequency variations of fast P-waves. In the low-frequency range, the squirt-flow characteristic length, not viscoelasticity, affects the phase velocity of slow P-waves, whereas it is opposite in the high-frequency range. As to the contribution of potential functions of two types of compressional waves to the Green's function, the squirt-flow length has a small effect, and the effects of viscoelastic parameter are mainly in the higher frequency range. Crown Copyright (C) 2006 Published by Elsevier Ltd. All rights reserved.
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The lytropic liquid crystals in dodecanic acid diethanolamine (DAD)/n-butanol (C4OH)/octane (n-C8H18)/deuteron (D2O) system were studied to determine the phase regions and were investigated by H-2-NMR spectroscopy,optical polarizing microscope and small-angle X-ray diffraction (SAXD) methods. The results indicate that the lamellar, hexagonal and cubic liquid crystals all exist in the above system. Keeping the weight ratio of DAD and C4OH constant,the microphase structure, H-2 quadruple splitting and the interlayer spacing are all changed with the addition of deuteron.
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We generalise and extend the work of Iñarra and Laruelle (2011) by studying two person symmetric evolutionary games with two strategies, a heterogenous population with two possible types of individuals and incomplete information. Comparing such games with their classic homogeneous version vith complete information found in the literature, we show that for the class of anti-coordination games the only evolutionarily stable strategy vanishes. Instead, we find infinite neutrally stable strategies. We also model the evolutionary process using two different replicator dynamics setups, each with a different inheritance rule, and we show that both lead to the same results with respect to stability.
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This paper uses a structural approach based on the indirect inference principle to estimate a standard version of the new Keynesian monetary (NKM) model augmented with term structure using both revised and real-time data. The estimation results show that the term spread and policy inertia are both important determinants of the U.S. estimated monetary policy rule whereas the persistence of shocks plays a small but significant role when revised and real-time data of output and inflation are both considered. More importantly, the relative importance of term spread and persistent shocks in the policy rule and the shock transmission mechanism drastically change when it is taken into account that real-time data are not well behaved.
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A critical review on the mechanism and models on the bubble-to-slug transition of two-phase gas-liquid flows are presented in the present paper. It is shown that the most possible mechanism controlled the bubble-to-slug transition is the bubble coalescence. Focusing on the bubble-to-slug transition for the low-Re two-phase flow, a simple Monte Carlo method is used to simulate the influence of the initial bubble size on the bubble-to-slug transition. Some secondary factors, such as the liquid viscosity, the surface tension, and the relative slip between the two phases, are ignored in the present study. It is found that the locus of the dimensionless rate of collision is a universal curve. Based on this curve, it is determined that the bubble initial size can affect the phase distribution and flow pattern when its dimensionless value is in the range from 0.03 to 0.4. A simple relationship between the critical void fraction and the initial bubble size is proposed, which agrees very well with the experimental data.
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The spray of emulsified fuel, composed of diesel fuel, water and methanol can make micro-explosion under high temperature conditions, and the viscosity and the atomization characteristics of emulsion have significant effects on the micro- explosion of emulsions. To clarify the combustion mechanism of water-in-oil emulsion sprays, combustion bomb experiments were carried out, and the droplet group micro- explosions in W/O fuel emulsion sprays in a high-pressure, high-temperature bomb were observed clearly by a multi-pulsed, off-axis, image-plane ruby laser holocamera and continuously by a high-speed CCD camera.The viscosity and atomization characteristics of emulsions were also studied experimentally. The experimental results show that the higher concentration of the aqueous phase (water-methanol) (<50%) increases the viscosity of the emulsions, especially for higher agent concentration, and higher aqueous phase concentration and higher viscosity results in lager Sauter Mean Diameter (SMD). The experiment results also show that the different kinds of emulsifying agents, with different Hydrophile-Lipophile Balance (HLB) values, have significant influence on the viscosity of the emulsions.
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We conduct experiments to investigate the effects of different majority requirements on bargaining outcomes in small and large groups. In particular, we use a Baron-Ferejohn protocol and investigate the effects of decision rules on delay (number of bargaining rounds needed to reach agreement) and measures of "fairness" (inclusiveness of coalitions, equality of the distribution within a coalition). We find that larger groups and unanimity rule are associated with significantly larger decision making costs in the sense that first round proposals more often fail, leading to more costly delay. The higher rate of failure under unanimity rule and in large groups is a combination of three facts: (1) in these conditions, a larger number of individuals must agree, (2) an important fraction of individuals reject offers below the equal share, and (3) proposers demand more (relative to the equal share) in large groups.
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DNA recognition is an essential biological process responsible for the regulation of cellular functions including protein synthesis and cell division and is implicated in the mechanism of action of some anticancer drugs. Studies directed towards defining the elements responsible for sequence specific DNA recognition through the study of the interactions of synthetic organic ligands with DNA are described.
DNA recognition by poly-N-methylpyrrolecarboxamides was studied by the synthesis and characterization of a series of molecules where the number of contiguous N-methylpyrrolecarboxamide units was increased from 2 to 9. The effect of this incremental change in structure on DNA recognition has been investigated at base pair resolution using affinity cleaving and MPE•Fe(II) footprinting techniques. These studies led to a quantitative relationship between the number of amides in the molecule and the DNA binding site size. This relationship is called the n + 1 rule and it states that a poly-N methylpyrrolecarboxamide molecule with n amides will bind n + 1 base pairs of DNA. This rule is consistent with a model where the carboxamides of these compounds form three center bridging hydrogen bonds between adjacent base pairs on opposite strands of the helix. The poly-N methylpyrrolecarboxamide recognition element was found to preferentially bind poly dA•poly dT stretches; however, both binding site selection and orientation were found to be affected by flanking sequences. Cleavage of large DNA is also described.
One approach towards the design of molecules that bind large sequences of double helical DNA sequence specifically is to couple DNA binding subunits of similar or diverse base pair specificity. Bis-EDTA-distamycin-fumaramide (BEDF) is an octaamide dimer of two tri-N methylpyrrolecarboxamide subunits linked by fumaramide. DNA recognition by BEDF was compared to P7E, an octaamide molecule containing seven consecutive pyrroles. These two compounds were found to recognize the same sites on pBR322 with approximately the same affinities demonstrating that fumaramide is an effective linking element for Nmethylpyrrolecarboxamide recognition subunits. Further studies involved the synthesis and characterization of a trimer of tetra-N-methylpyrrolecarboxamide subunits linked by β-alanine ((P4)_(3)E). This trimerization produced a molecule which is capable of recognizing 16 base pairs of A•T DNA, more than a turn and a half of the DNA helix.
DNA footprinting is a powerful direct method for determining the binding sites of proteins and small molecules on heterogeneous DNA. It was found that attachment of EDTA•Fe(II) to spermine creates a molecule, SE•Fe(II), which binds and cleaves DNA sequence neutrally. This lack of specificity provides evidence that at the nucleotide level polyamines recognize heterogeneous DNA independent of sequence and allows SE•Fe(II) to be used as a footprinting reagent. SE•Fe(II) was compared with two other small molecule footprinting reagents, EDTA•Fe(II) and MPE•Fe(II).
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In this thesis, a method to retrieve the source finiteness, depth of faulting, and the mechanisms of large earthquakes from long-period surface waves is developed and applied to several recent large events.
In Chapter 1, source finiteness parameters of eleven large earthquakes were determined from long-period Rayleigh waves recorded at IDA and GDSN stations. The basic data set is the seismic spectra of periods from 150 to 300 sec. Two simple models of source finiteness are studied. The first model is a point source with finite duration. In the determination of the duration or source-process times, we used Furumoto's phase method and a linear inversion method, in which we simultaneously inverted the spectra and determined the source-process time that minimizes the error in the inversion. These two methods yielded consistent results. The second model is the finite fault model. Source finiteness of large shallow earthquakes with rupture on a fault plane with a large aspect ratio was modeled with the source-finiteness function introduced by Ben-Menahem. The spectra were inverted to find the extent and direction of the rupture of the earthquake that minimize the error in the inversion. This method is applied to the 1977 Sumbawa, Indonesia, 1979 Colombia-Ecuador, 1983 Akita-Oki, Japan, 1985 Valparaiso, Chile, and 1985 Michoacan, Mexico earthquakes. The method yielded results consistent with the rupture extent inferred from the aftershock area of these earthquakes.
In Chapter 2, the depths and source mechanisms of nine large shallow earthquakes were determined. We inverted the data set of complex source spectra for a moment tensor (linear) or a double couple (nonlinear). By solving a least-squares problem, we obtained the centroid depth or the extent of the distributed source for each earthquake. The depths and source mechanisms of large shallow earthquakes determined from long-period Rayleigh waves depend on the models of source finiteness, wave propagation, and the excitation. We tested various models of the source finiteness, Q, the group velocity, and the excitation in the determination of earthquake depths.
The depth estimates obtained using the Q model of Dziewonski and Steim (1982) and the excitation functions computed for the average ocean model of Regan and Anderson (1984) are considered most reasonable. Dziewonski and Steim's Q model represents a good global average of Q determined over a period range of the Rayleigh waves used in this study. Since most of the earthquakes studied here occurred in subduction zones Regan and Anderson's average ocean model is considered most appropriate.
Our depth estimates are in general consistent with the Harvard CMT solutions. The centroid depths and their 90 % confidence intervals (numbers in the parentheses) determined by the Student's t test are: Colombia-Ecuador earthquake (12 December 1979), d = 11 km, (9, 24) km; Santa Cruz Is. earthquake (17 July 1980), d = 36 km, (18, 46) km; Samoa earthquake (1 September 1981), d = 15 km, (9, 26) km; Playa Azul, Mexico earthquake (25 October 1981), d = 41 km, (28, 49) km; El Salvador earthquake (19 June 1982), d = 49 km, (41, 55) km; New Ireland earthquake (18 March 1983), d = 75 km, (72, 79) km; Chagos Bank earthquake (30 November 1983), d = 31 km, (16, 41) km; Valparaiso, Chile earthquake (3 March 1985), d = 44 km, (15, 54) km; Michoacan, Mexico earthquake (19 September 1985), d = 24 km, (12, 34) km.
In Chapter 3, the vertical extent of faulting of the 1983 Akita-Oki, and 1977 Sumbawa, Indonesia earthquakes are determined from fundamental and overtone Rayleigh waves. Using fundamental Rayleigh waves, the depths are determined from the moment tensor inversion and fault inversion. The observed overtone Rayleigh waves are compared to the synthetic overtone seismograms to estimate the depth of faulting of these earthquakes. The depths obtained from overtone Rayleigh waves are consistent with the depths determined from fundamental Rayleigh waves for the two earthquakes. Appendix B gives the observed seismograms of fundamental and overtone Rayleigh waves for eleven large earthquakes.
Resumo:
This document contains three papers examining the microstructure of financial interaction in development and market settings. I first examine the industrial organization of financial exchanges, specifically limit order markets. In this section, I perform a case study of Google stock surrounding a surprising earnings announcement in the 3rd quarter of 2009, uncovering parameters that describe information flows and liquidity provision. I then explore the disbursement process for community-driven development projects. This section is game theoretic in nature, using a novel three-player ultimatum structure. I finally develop econometric tools to simulate equilibrium and identify equilibrium models in limit order markets.
In chapter two, I estimate an equilibrium model using limit order data, finding parameters that describe information and liquidity preferences for trading. As a case study, I estimate the model for Google stock surrounding an unexpected good-news earnings announcement in the 3rd quarter of 2009. I find a substantial decrease in asymmetric information prior to the earnings announcement. I also simulate counterfactual dealer markets and find empirical evidence that limit order markets perform more efficiently than do their dealer market counterparts.
In chapter three, I examine Community-Driven Development. Community-Driven Development is considered a tool empowering communities to develop their own aid projects. While evidence has been mixed as to the effectiveness of CDD in achieving disbursement to intended beneficiaries, the literature maintains that local elites generally take control of most programs. I present a three player ultimatum game which describes a potential decentralized aid procurement process. Players successively split a dollar in aid money, and the final player--the targeted community member--decides between whistle blowing or not. Despite the elite capture present in my model, I find conditions under which money reaches targeted recipients. My results describe a perverse possibility in the decentralized aid process which could make detection of elite capture more difficult than previously considered. These processes may reconcile recent empirical work claiming effectiveness of the decentralized aid process with case studies which claim otherwise.
In chapter four, I develop in more depth the empirical and computational means to estimate model parameters in the case study in chapter two. I describe the liquidity supplier problem and equilibrium among those suppliers. I then outline the analytical forms for computing certainty-equivalent utilities for the informed trader. Following this, I describe a recursive algorithm which facilitates computing equilibrium in supply curves. Finally, I outline implementation of the Method of Simulated Moments in this context, focusing on Indirect Inference and formulating the pseudo model.
Resumo:
Superprotonic phase transitions and thermal behaviors of three complex solid acid systems are presented, namely Rb3H(SO4)2-RbHSO4 system, Rb3H(SeO4)2-Cs3H(SeO4)2 solid solution system, and Cs6(H2SO4)3(H1.5PO4)4. These material systems present a rich set of phase transition characteristics that set them apart from other, simpler solid acids. A.C. impedance spectroscopy, high-temperature X-ray powder diffraction, and thermal analysis, as well as other characterization techniques, were employed to investigate the phase behavior of these systems.
Rb3H(SO4)2 is an atypical member of the M3H(XO4)2 class of compounds (M = alkali metal or NH4+ and X = S or Se) in that a transition to a high-conductivity state involves disproportionation into two phases rather than a simple polymorphic transition [1]. In the present work, investigations of the Rb3H(SO4)2-RbHSO4 system have revealed the disproportionation products to be Rb2SO4 and the previously unknown compound Rb5H3(SO4)4. The new compound becomes stable at a temperature between 25 and 140 °C and is isostructural to a recently reported trigonal phase with space group P3̅m of Cs5H3(SO4)4 [2]. At 185 °C the compound undergoes an apparently polymorphic transformation with a heat of transition of 23.8 kJ/mol and a slight additional increase in conductivity.
The compounds Rb3H(SeO4)2 and Cs3H(SeO4)2, though not isomorphous at ambient temperatures, are quintessential examples of superprotonic materials. Both adopt monoclinic structures at ambient temperatures and ultimately transform to a trigonal (R3̅m) superprotonic structure at slightly elevated temperatures, 178 and 183 °C, respectively. The compounds are completely miscible above the superprotonic transition and show extensive solubility below it. Beyond a careful determination of the phase boundaries, we find a remarkable 40-fold increase in the superprotonic conductivity in intermediate compositions rich in Rb as compared to either end-member.
The compound Cs6(H2SO4)3(H1.5PO4)4 is unusual amongst solid acid compounds in that it has a complex cubic structure at ambient temperature and apparently transforms to a simpler cubic structure of the CsCl-type (isostructural with CsH2PO4) at its transition temperature of 100-120 °C [3]. Here it is found that, depending on the level of humidification, the superprotonic transition of this material is superimposed with a decomposition reaction, which involves both exsolution of (liquid) acid and loss of H2O. This reaction can be suppressed by application of sufficiently high humidity, in which case Cs6(H2SO4)3(H1.5PO4)4 undergoes a true superprotonic transition. It is proposed that, under conditions of low humidity, the decomposition/dehydration reaction transforms the compound to Cs6(H2-0.5xSO4)3(H1.5PO4)4-x, also of the CsCl structure type at the temperatures of interest, but with a smaller unit cell. With increasing temperature, the decomposition/dehydration proceeds to greater and greater extent and unit cell of the solid phase decreases. This is identified to be the source of the apparent negative thermal expansion behavior.
References
[1] L.A. Cowan, R.M. Morcos, N. Hatada, A. Navrotsky, S.M. Haile, Solid State Ionics 179 (2008) (9-10) 305.
[2] M. Sakashita, H. Fujihisa, K.I. Suzuki, S. Hayashi, K. Honda, Solid State Ionics 178 (2007) (21-22) 1262.
[3] C.R.I. Chisholm, Superprotonic Phase Transitions in Solid Acids: Parameters affecting the presence and stability of superprotonic transitions in the MHnXO4 family of compounds (X=S, Se, P, As; M=Li, Na, K, NH4, Rb, Cs), Materials Science, California Institute of Technology, Pasadena, California (2003).
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This thesis explores the design, construction, and applications of the optoelectronic swept-frequency laser (SFL). The optoelectronic SFL is a feedback loop designed around a swept-frequency (chirped) semiconductor laser (SCL) to control its instantaneous optical frequency, such that the chirp characteristics are determined solely by a reference electronic oscillator. The resultant system generates precisely controlled optical frequency sweeps. In particular, we focus on linear chirps because of their numerous applications. We demonstrate optoelectronic SFLs based on vertical-cavity surface-emitting lasers (VCSELs) and distributed-feedback lasers (DFBs) at wavelengths of 1550 nm and 1060 nm. We develop an iterative bias current predistortion procedure that enables SFL operation at very high chirp rates, up to 10^16 Hz/sec. We describe commercialization efforts and implementation of the predistortion algorithm in a stand-alone embedded environment, undertaken as part of our collaboration with Telaris, Inc. We demonstrate frequency-modulated continuous-wave (FMCW) ranging and three-dimensional (3-D) imaging using a 1550 nm optoelectronic SFL.
We develop the technique of multiple source FMCW (MS-FMCW) reflectometry, in which the frequency sweeps of multiple SFLs are "stitched" together in order to increase the optical bandwidth, and hence improve the axial resolution, of an FMCW ranging measurement. We demonstrate computer-aided stitching of DFB and VCSEL sweeps at 1550 nm. We also develop and demonstrate hardware stitching, which enables MS-FMCW ranging without additional signal processing. The culmination of this work is the hardware stitching of four VCSELs at 1550 nm for a total optical bandwidth of 2 THz, and a free-space axial resolution of 75 microns.
We describe our work on the tomographic imaging camera (TomICam), a 3-D imaging system based on FMCW ranging that features non-mechanical acquisition of transverse pixels. Our approach uses a combination of electronically tuned optical sources and low-cost full-field detector arrays, completely eliminating the need for moving parts traditionally employed in 3-D imaging. We describe the basic TomICam principle, and demonstrate single-pixel TomICam ranging in a proof-of-concept experiment. We also discuss the application of compressive sensing (CS) to the TomICam platform, and perform a series of numerical simulations. These simulations show that tenfold compression is feasible in CS TomICam, which effectively improves the volume acquisition speed by a factor ten.
We develop chirped-wave phase-locking techniques, and apply them to coherent beam combining (CBC) of chirped-seed amplifiers (CSAs) in a master oscillator power amplifier configuration. The precise chirp linearity of the optoelectronic SFL enables non-mechanical compensation of optical delays using acousto-optic frequency shifters, and its high chirp rate simultaneously increases the stimulated Brillouin scattering (SBS) threshold of the active fiber. We characterize a 1550 nm chirped-seed amplifier coherent-combining system. We use a chirp rate of 5*10^14 Hz/sec to increase the amplifier SBS threshold threefold, when compared to a single-frequency seed. We demonstrate efficient phase-locking and electronic beam steering of two 3 W erbium-doped fiber amplifier channels, achieving temporal phase noise levels corresponding to interferometric fringe visibilities exceeding 98%.