Diffusion-reaction modelling of the degradation of oil-well cement exposed to carbonated brine

The essential aspects of a diffusion-reaction model in development for the degradation process of oil-well cement exposed to carbonated brine are presented in this paper. The formulation consists of two main diffusion/reaction field equations for the concentrations of aqueous calcium and carbon species in the hardened cement paste pore solution, complemented by a number of chemical kinetics and chemical equilibrium equations. The volume fraction distribution of the solid constituents of the hardened cement paste and the reaction products evolve with the progress of the reaction, determining the diffusivity properties of the material. A sensitivity analysis of some parameters of the model is presented to illustrate the capabilities to reproduce realistically some aspects of the degradation process.The essential aspects of a diffusion-reaction model in development for the degradation process of oil-well cement exposed to carbonated brine are presented in this paper. The formulation consists of two main diffusion/reaction field equations for the concentrations of aqueous calcium and carbon species in the hardened cement paste pore solution, complemented by a number of chemical kinetics and chemical equilibrium equations. The volume fraction distribution of the solid constituents of the hardened cement paste and the reaction products evolve with the progress of the reaction, determining the diffusivity properties of the material. A sensitivity analysis of some parameters of the model is presented to illustrate the capabilities to reproduce realistically some aspects of the degradation process

Diffusion-reaction modelling of the degradation of oil-well cement exposed to carbonated brine

The essential aspects of a diffusion-reaction model in development for the degradation process of oil-well cement exposed to carbonated brine are presented in this paper. The formulation consists of two main diffusion/reaction field equations for the concentrations of aqueous calcium and carbon species in the hardened cement paste pore solution, complemented by a number of chemical kinetics and chemical equilibrium equations. The volume fraction distribution of the solid constituents of the hardened cement paste and the reaction products evolve with the progress of the reaction, determining the diffusivity properties of the material. A sensitivity analysis of some parameters of the model is presented to illustrate the capabilities to reproduce realistically some aspects of the degradation process.The essential aspects of a diffusion-reaction model in development for the degradation process of oil-well cement exposed to carbonated brine are presented in this paper. The formulation consists of two main diffusion/reaction field equations for the concentrations of aqueous calcium and carbon species in the hardened cement paste pore solution, complemented by a number of chemical kinetics and chemical equilibrium equations. The volume fraction distribution of the solid constituents of the hardened cement paste and the reaction products evolve with the progress of the reaction, determining the diffusivity properties of the material. A sensitivity analysis of some parameters of the model is presented to illustrate the capabilities to reproduce realistically some aspects of the degradation process

Diffusion-reaction modelling of the degradation of oil-well cement exposed to carbonated brine

The essential aspects of a diffusion-reaction model in development for the degradation process of oil-well cement exposed to carbonated brine are presented in this paper. The formulation consists of two main diffusion/reaction field equations for the concentrations of aqueous calcium and carbon species in the hardened cement paste pore solution, complemented by a number of chemical kinetics and chemical equilibrium equations. The volume fraction distribution of the solid constituents of the hardened cement paste and the reaction products evolve with the progress of the reaction, determining the diffusivity properties of the material. A sensitivity analysis of some parameters of the model is presented to illustrate the capabilities to reproduce realistically some aspects of the degradation process.The essential aspects of a diffusion-reaction model in development for the degradation process of oil-well cement exposed to carbonated brine are presented in this paper. The formulation consists of two main diffusion/reaction field equations for the concentrations of aqueous calcium and carbon species in the hardened cement paste pore solution, complemented by a number of chemical kinetics and chemical equilibrium equations. The volume fraction distribution of the solid constituents of the hardened cement paste and the reaction products evolve with the progress of the reaction, determining the diffusivity properties of the material. A sensitivity analysis of some parameters of the model is presented to illustrate the capabilities to reproduce realistically some aspects of the degradation process

Energy transfer between colloids via critical interactions

We report the observation of a temperature-controlled synchronization of two Brownian-particles in a binary mixture close to the critical point of the demixing transition. The two beads are trapped by two optical tweezers whose distance is periodically modulated. We notice that the motion synchronization of the two beads appears when the critical temperature is approached. In contrast, when the fluid is far from its critical temperature, the displacements of the two beads are uncorrelated. Small changes in temperature can radically change the global dynamics of the system. We show that the synchronisation is induced by the critical Casimir forces. Finally, we present the measure of the energy transfers inside the system produced by the critical interaction.Comment: 8 pages, 7 figure

Measuring kinetic energy changes in the mesoscale with low acquisition rates

We describe a new technique to estimate the mean square velocity of a Brownian particle from time series of the position of the particle sampled at frequencies several orders of magnitude smaller than the momentum relaxation frequency. We apply our technique to determine the mean square velocity of single optically trapped polystyrene microspheres immersed in water. The velocity is increased applying a noisy electric field that mimics a higher kinetic temperature. Therefore, we are able to measure the average kinetic energy change in isothermal and non-isothermal quasistatic processes. Moreover, we show that the dependence of the mean square time-averaged velocity on the sampling frequency can be used to quantify properties of the electrophoretic mobility of a charged colloid. Our method could be applied to detect temperature gradients in inhomogeneous media and to characterize the complete thermodynamics of microscopic heat engines.Comment: 9 pages, 5 figure

Biochemical noise in single DNA molecule studied by optical trapping technique

Tesina realitzada en col.laboració amb l'IFCONoise spectra from single DNA molecules in their natural aqueous environment at different grades of stretching are presented. A DNA molecule is anchored between two dielectric beads. One of the beads is fixed to the surface and the other is optically trapped. The stiffness of each stage is calculated and compared with the previous results to verify the presence of one and only one single molecule. The results are compared with the preceding bibliography and are focused in the study of the spectral response which is not deeply studied yet

Zero-thickness interface model with chemical degradation by acid attack

Carbon dioxide (CO2) storage in abandoned oil/gas reservoirs is considered a viable alternative to reduce greenhouse gas emissions to the atmosphere. An important element of the risk associated with long-term CO2 storage is the loss of integrity of the cement seals of the abandoned wells in the reservoir. Among others, one possible cause of loss of integrity is the degradation of the oil-well cement due to the acid attack of the carbonated brine in the reservoir. In previous studies, the authors have developed a diffusion-reaction model for simulating this degradation process. In order to study possible coupled Chemo-Mechanical (CM) mechanisms, this model will be coupled with an existing mechanical model. For this purpose, in this paper, an existing constitutive law for zero-thickness interface, based on the theory of elasto-plasticity with concepts of fracture mechanics, is modified to incorporate the effect of chemical degradation on the mechanical strength parameters. Preliminary results obtained with this new constitutive law are presented, in order to illustrate the main aspects of the proposed constitutive law, as well as a possible C-M degradation mechanism that should be considered in the long-term safety assessment of CO2 geological storage projects

Arcsine Laws in Stochastic Thermodynamics

We show that the fraction of time a thermodynamic current spends above its average value follows the arcsine law, a prominent result obtained by L\'evy for Brownian motion. Stochastic currents with long streaks above or below their average are much more likely than those that spend similar fractions of time above and below their average. Our result is confirmed with experimental data from a Brownian Carnot engine. We also conjecture that two other random times associated with currents obey the arcsine law: the time a current reaches its maximum value and the last time a current crosses its average value. These results apply to, inter alia, molecular motors, quantum dots and colloidal systems.Comment: 11 pages, 11 figure

Adiabatic processes realized with a trapped Brownian particle

We experimentally realize quasistatic adiabatic processes using a single optically-trapped micro- sphere immersed in water whose effective temperature is controlled by an external random electric field. A full energetic characterization of adiabatic processes that preserve either the position dis- tribution or the full phase space volume is presented. We show that only in the latter case the exchanged heat and the change in the entropy of the particle vanish when averaging over many repetitions. We provide analytical expressions for the distributions of the fluctuating heat and en- tropy, which we verify experimentally. We show that the heat distribution is asymmetric for any non-isothermal quasistatic process. Moreover, the shape of the distribution of the system entropy change in the adiabatic processes depends significantly on the number of degrees of freedom that are considered for the calculation of system entropy

Inferring broken detailed balance in the absence of observable currents

Identifying dissipation is essential for understanding the physical mechanisms underlying nonequilibrium processes. {In living systems, for example, the dissipation is directly related to the hydrolysis of fuel molecules such as adenosine triphosphate (ATP)}. Nevertheless, detecting broken time-reversal symmetry, which is the hallmark of dissipative processes, remains a challenge in the absence of observable directed motion, flows, or fluxes. Furthermore, quantifying the entropy production in a complex system requires detailed information about its dynamics and internal degrees of freedom. Here we introduce a novel approach to detect time irreversibility and estimate the entropy production from time-series measurements, even in the absence of observable currents. We apply our technique to two different physical systems, namely, a partially hidden network and a molecular motor. Our method does not require complete information about the system dynamics and thus provides a new tool for studying nonequilibrium phenomena.Comment: 14 pages, 6 figure