Pore formation during dehydration of polycrystalline gypsum observed and quantified in a time-series synchrotron radiation based X-ray micro-tomography experiment

We conducted an in-situ X-ray micro-computed tomography heating experiment at the Advanced Photon Source (USA) to dehydrate an unconfined 2.3 mm diameter cylinder of Volterra Gypsum. We used a purpose-built X-ray transparent furnace to heat the sample to 388 K for a total of 310 min to acquire a three-dimensional time-series tomography dataset comprising nine time steps. The voxel size of 2.2 μm3 proved sufficient to pinpoint reaction initiation and the organization of drainage architecture in space and time. We observed that dehydration commences across a narrow front, which propagates from the margins to the centre of the sample in more than four hours. The advance of this front can be fitted with a square-root function, implying that the initiation of the reaction in the sample can be described as a diffusion process. Novel parallelized computer codes allow quantifying the geometry of the porosity and the drainage architecture from the very large tomographic datasets (20483 voxels) in unprecedented detail. We determined position, volume, shape and orientation of each resolvable pore and tracked these properties over the duration of the experiment. We found that the pore-size distribution follows a power law. Pores tend to be anisotropic but rarely crack-shaped and have a preferred orientation, likely controlled by a pre-existing fabric in the sample. With on-going dehydration, pores coalesce into a single interconnected pore cluster that is connected to the surface of the sample cylinder and provides an effective drainage pathway. Our observations can be summarized in a model in which gypsum is stabilized by thermal expansion stresses and locally increased pore fluid pressures until the dehydration front approaches to within about 100 μm. Then, the internal stresses are released and dehydration happens efficiently, resulting in new pore space. Pressure release, the production of pores and the advance of the front are coupled in a feedback loop.

The Law of Real Property Mortgages [2nd. Ed.]

This book examines the principles and practice of real estate mortgages in an easily accessible text referenced to all the Australian States. It specifically deals with the major theoretical and practical aspects of the land mortgage, including vitiating factors in formation, mortgagees’ powers and duties and mortgagors’ rights – both statutory and other – as well as assignment, insurance and discharge. It focuses exclusively on real estate mortgages and provides a thorough account of the law through analysis of the plethora of court decisions and statutory provisions in this area. Duncan and Dixon analyse the substance of the mortgage transaction from creation through to rights of enforcement. In its detailed consideration of the rights and obligations of mortgagors and mortgagees, it covers topics such as priorities and tacking, insurance, variation and assignment, rights of discharge, entry into possession, foreclosure and power of sale. In addition, the book contains a separate chapter on factors that may affect the validity and enforcement of a mortgage, together with separate consideration of a mortgagee’s right to enforce a guarantee provided on behalf of a mortgagor, and the rights and liabilities associated with a receivership regime initiated by

Questions and Answers : Contract Law [5th ed.]

LexisNexis Questions & Answers - Contract Law provides an understanding of contract law and gives a clear and systematic approach to analysing and answering problem and exam questions. Each chapter commences with a summary of the relevant cases and identification of the key issues. Each question is followed by a suggested answer plan, a sample answer and comments on how the answer might be assessed by an examiner. The author also offers advice on common errors to avoid and practical hints and tips on how to achieve higher marks.

Gibbs Energy of Formation of Cobalt Divanadium Tetroxide

The Gibbs energy of formation of V2O3-saturated spinel CoV2O4 has been measured in the temperature range 900–1700 K using a solid state galvanic cell, which can be represented as Pt, Co + CoV2O4 + V2O3/(CaO) ZrO2/Co + CoO, Pt. The standard free energy of formation of cobalt vanadite from component oxides can be represented as CoO (rs) + V2O3 (cor) → CoV2O4 (sp), ΔG° = −30,125 − 5.06T (± 150) J mole−1. Cation mixing on crystallographically nonequivalent sites of the spinel is responsible for the decrease in free energy with increasing temperature. A correlation between “second law” entropies of formation of cubic 2–3 spinels from component oxides with rock salt and corundum structures and cation distribution is presented. Based on the information obtained in this study and trends in the stability of aluminate and chromite spinels, it can be deduced that copper vanadite is unstable.

Gibbs energies of formation of rare earth oxysulfides

The standard Gibbs energy change accompanying the conversion of rare earth oxides to oxysulfides by reaction of rare earth oxides with diatomic sulfur gas has been measured in the temperature range 870 to 1300 K using the solid state cell: Pt/Cu+Cu2S/R2O2S+R2O3‖(CaO)ZrO2‖Ni+NiO, Pt where R=La, Nd, Sm, Gd, Tb, and Dy. The partial pressure of diatomic sulfur over a mixture of rare earth oxide (R2O3) and oxysulfide (R2O2S) is fixed by the dissociation of Cu2S to Cu in a closed system. The buffer mixture of Cu+Cu2S is physically separated from the rare earth oxide and oxysulfide to avoid complications arising from interaction between them. The corresponding equilibrium oxygen partial pressure is measured with an oxide solid electrolyte cell. Gibbs energy change for the conversion of oxide to the corresponding oxysulfide increases monotonically with atomic number of the rare earth element. Second law enthalpy of formation also shows a similar trend. Based on this empirical trend Gibbs energies of formation of oxysulfides of Pr, Eu, Ho, and Er are estimated as a function of temperature.

Dynamics of loop formation in a semiflexible polymer

The dynamics of loop formation by linear polymer chains has been a topic of several theoretical and experimental studies. Formation of loops and their opening are key processes in many important biological processes. Loop formation in flexible chains has been extensively studied by many groups. However, in the more realistic case of semiflexible polymers, not much results are available. In a recent study [K. P. Santo and K. L. Sebastian, Phys. Rev. E 73, 031923 (2006)], we investigated opening dynamics of semiflexible loops in the short chain limit and presented results for opening rates as a function of the length of the chain. We presented an approximate model for a semiflexible polymer in the rod limit based on a semiclassical expansion of the bending energy of the chain. The model provided an easy way to describe the dynamics. In this paper, using this model, we investigate the reverse process, i.e., the loop formation dynamics of a semiflexible polymer chain by describing the process as a diffusion-controlled reaction. We make use of the ``closure approximation'' of Wilemski and Fixman [G. Wilemski and M. Fixman, J. Chem. Phys. 60, 878 (1974)], in which a sink function is used to represent the reaction. We perform a detailed multidimensional analysis of the problem and calculate closing times for a semiflexible chain. We show that for short chains, the loop formation time tau decreases with the contour length of the polymer. But for longer chains, it increases with length obeying a power law and so it has a minimum at an intermediate length. In terms of dimensionless variables, the closing time is found to be given by tau similar to L-n exp(const/L), where n=4.5-6. The minimum loop formation time occurs at a length L-m of about 2.2-2.4. These are, indeed, the results that are physically expected, but a multidimensional analysis leading to these results does not seem to exist in the literature so far.

Drop formation in non-newtonian liquids under pulsed conditions

Drop formation from single nozzles under pulsed flow conditions in non-Newtonian fluids following the power law model has been studied. An existing model has been modified to explain the experimental data. The flow conditions employed correspond to the mixer—settler type of operation in pulsed sieve-plate extraction columns. The modified model predicts the drop sizes satisfactorily. It has been found that consideration of non-Newtonian behaviour is important at low pulse intensities and its significance decreases with increasing intensity of pulsation. Further, the proposed model for single orifices has been tested to predict the sizes of drops formed from a sieve-plate distributor having four holes, and has been found to predict the sizes fairly well in the absence of coalescence.

Gibbs energy of formation of orthorhombic CaZrO3

The Gibbs free energy of formation of the orthorhombic form of CaZrO3(o) from monoclinic ZrO2(m) and periclase CaO(p) has been determined as a function of temperature in the range 950-1225 K, using an electrochemical cell incorporating single-crystal CaF2 as the solid electrolyte. The results are corrected for the small solid solubility of CaO in ZrO2. For the reaction, ZrO2(m) + CaO(p) --> CaZrO3(o), DELTAG(phi) = -31590 -13.9T(+/- 180) J mol-1. The ''second-law'' enthalpy of formation of CaZrO3 obtained from the results of this study at a mean temperature of 1090 K is in excellent agreement with the high-temperature solution calorimetric measurements of Muromachi and Navrotsky at 1068 K (J. Solid State Chem., 72 (1988) 244), and the average value of the bomb and acid solution calorimetric studies of Lvova and Feodosev (Zh. Fiz. Khim., 38 (1964) 28), Korneev et al. (Izv. Akad. Nauk SSSR, Neorg. Mater., 7 (1971) 886) and Brown and Bennington (Thermochim. Acta, 106 (1986) 183). The standard entropy of CaZrO3(o) at 298.15 K from the free energy data is 96.4 (+/- 3.5) J K-1 mol-1. The results of this study are discussed in comparison with high-temperture e.m.f. measurements reported in the literature on cubic zirconia solid solutions.

A critical assessment of the standard molar gibbs free energy of formation of NiWO4

Three independent studies have been reported on the free energy of formation of NiWO4. Results of these measurements are analyzed by the �third-law� method, using thermal functions for NiWO4 derived from both low and high temperature heat capacity measurements. Values for the standard molar enthalpy of formation of NiWO4 at 298·15 K obtained from �third-law� analysis are compared with direct calorimetric determinations. Only one set of free energy measurements is found to be compatible with calorimetric enthalpies of formation. The selected value for ?f H m 0 (NiWO4, cr, 298·15 K) is the average of the three calorimetric measurements, using both high temperature solution and combustion techniques, and the compatible free energy determination. A new set of evaluated data for NiWO4 is presented.

Gibbs free energies of formation of ZnAl2O4 and ZnCr2O4

The standard free energies of formation of zinc aluminate and chromite were determined by measuring the oxygen potential over a solid CuZn alloy, containing 10 at.−% Zn, in equilibrium with ZnO, ZnAl2O4+Al2O3(χ) and ZnCr2O4+Cr2O3, in the temperature range 700–900°C. The oxygen potential was monitored by means of a solid oxide galvanic cell in which a Y2O3 ThO2 pellet was sandwiched between a CaOZrO2 crucible and tube. The temperature dependence of the free energies of formation of the interoxidic compounds can be represented by the equations, The heat of formation of the spinels calculated from the measurements by the “Second Law method” is found to be in good agreement with calorimetrically determined values. Using an empirical correlation for the entropy of formation of cubic spinel phases from oxides with rock-salt and corundum structures and the measured high temperature cation distribution in ZnAl2O4, the entropy of transformation of ZnO from wurtzite to rock-salt structure is evaluated.

Measurement of Gibbs energies of formation of CoF2 and MnF2 using a new composite dispersed solid electrolyte

Gibbs energies of formation of CoF2 and MnF2 have been measured in the temperature range from 700 to 1100 K using Al2O3-dispersed CaF2 solid electrolyte and Ni+NiF2 as the reference electrode. The dispersed solid electrolyte has higher conductivity than pure CaF2 thus permitting accurate measurements at lower temperatures. However, to prevent reaction between Al2O3 in the solid electrolyte and NiF2 (or CoF2) at the electrode, the dispersed solid electrolyte was coated with pure CaF2, thus creating a composite structure. The free energies of formation of CoF2 and MnF2 are (± 1700) J mol−1; {fx37-1} The third law analysis gives the enthalpy of formation of solid CoF2 as ΔH° (298·15 K) = −672·69 (± 0·1) kJ mol−1, which compares with a value of −671·5 (± 4) kJ mol−1 given in Janaf tables. For solid MnF2, ΔH°(298·15 K) = − 854·97 (± 0·13) kJ mol−1, which is significantly different from a value of −803·3 kJ mol−1 given in the compilation by Barinet al.

Measurement of the Gibbs energy of formation of URh3 using an oxide solid electrolyte

The Gibbs' energy offormation of the intermetallic compound URh3has been measured in the temperature range 980 to 1320 K using an oxide solid state cell incorporating yttria-doped thoria as the solid electrolyte and a mixture of manganese and manganese oxide as the reference electrode. The cell can be represented as Pt, Mn + MnO I (Y203)Th02 I Rh + URh3 + U02 + x' Rh, Pt The reversible emf of the cell was a linear function of temperature E = 15.60 +0.0237 T (±0.8) mY. Using auxiliary thermodynamic data for MnO and U02+ x the Gibbs' energy of formation of URh3 from component metals has been computed. The results can be expressed by the equation L'.G?< URh3 > = -316240 + 13.22 T (± 3000) J mol-1. The "third-law" enthalpy of formation of URh3at 298 K is -293.2 (± 4) kJ mol-1, significantly more negative than the value of -181.5 kJ mol-1 calculated using Miedema's model.

Electrochemical determination of the Gibbs energy of formation of MgAl2O4

The standard Gibbs energy of formation of the spinel MgAl2O4 from component oxides, MgO and α-Al2O3, has been determined in the temperature range 900 to 1250 K using a solid-state cell incorporating single-crystal CaF2 as the solid electrolyte. The cell can be represented as—Pt,O2,MgO+MgF2|CaF2|MgF2+MgAl2O4+α-Al2O3,O2,Pt—The standard Gibbs energy of formation from binary oxides, computed from the reversible emf, can be represented by the expression—capdeltaG°f,ox=−23600 − 5.91T(±150) J/mol—The ‘second-law’ enthalpy of formation of MgAl2O4 obtained in this study is in good agreement with high-temperature solution calorimetric studies reported in the literature.

Numerical study of the impact of inoculant and grain transport on macrosegregation and microstructure formation during solidification of an Al-22%Cu alloy

We investigate the impact of the nucleation law for nucleation on Al-Ti-B inoculant particles, of the motion of inoculant particles and of the motion of grains on the predicted macrosegregation and microstructure in a grain-refined Al-22 wt.% Cu alloy casting. We conduct the study by numerical simulations of a casting experiment in a side-cooled 76×76×254 mm sand mould. Macrosegregation and microstructure formation are studied with a volume-averaged two-phase model accounting for macroscopic heat and solute transport, melt convection, and transport of inoculant particles and equiaxed grains. On the microscopic scale it accounts for nucleation on inoculant particles with a given size distribution (and corresponding activation undercooling distribution)and for the growth of globular solid grains. The growth kinetics is described by accounting for limited solute diffusion in both liquid and solid phases and for convective effects. We show that the consideration of a size distribution of the inoculants has a strong impact on the microstructure(final grain size) prediction. The transport of inoculants significantly increases the microstructure heterogeneities and the grain motion refines the microstructure and reduces the microstructure heterogeneities.

Numerical Solution for Polymer Transient Flows in a Circle Bounded Composite Formation

A new numerical model for transient flows of polymer solution in a circular bounded composite formation is presented in this paper. Typical curves of the wellbore transient pressure are yielded by FEM. The effects of non-Newtonian power-law index, mobility and boundary distance have been considered. It is found that for the mobility ratio larger than 1, which is favorable for the polymer flooding, the pressure derivative curve in log-log form rises up without any hollow. On the other hand, if the pressure derivative curve has a hollow and then is raised up, we say that the polymer flooding fails. Finally, the new model has been extended to more complicated boundary case.