Surface Reaction Regime Research Articles

New insights into modeling disjoining pressure and wettability alteration by engineered water: Surface complexation based rock composition study

Several laboratory studies observed wettability alteration of carbonate rocks towards a more water-wet state through modifying the composition of injected water. The change in carbonate surface charge was reported as the underlying reason behind this wettability alteration and the corresponding incremental oil recovery by engineered water injection (EWI). Although the reported results of carbonate rock sensitivity to injected water ionic strength, pH, salinity, and concentration of potential determining ions (Ca 2+ , Mg 2+ , and SO 4 2− ), there is still an ambiguity on the way carbonates interact with injected water/ions. This is due to the different mineralogical compositions and electrokinetic properties of carbonates. Therefore, this paper provides more insight into the role of major rock-forming carbonate minerals (calcite and dolomite) in engineered water injection at different water compositions by utilizing surface complexation modeling (SCM). The study utilizes a geochemical simulator to highlight the effect of dolomite surface complexation reactions. After determining the total rock surface charge and surface potential, the disjoining pressure was calculated to estimate the water film thickness and consequently, infer about wettability alteration. The results showed that a successful EWI operation creates three regimes: displacement regime, surface reaction regime, and quasi-equilibrium regime. These regimes can be characterized by the proposed surface complexation technique to calculate/optimize the injection pore volumes needed for each regime, determine the location of EWI effect in the reservoir, and predict the time ranges when EWI will reach to the surface in the form of additional oil recovery. Also, it was found that the surface reaction regime is the most important one where main surface reactions and oil recovery occur. Furthermore, the study utilizes SCM for both calcite and dolomite minerals for the first time highlighting their importance in geochemical reactions of EWI when the rock has dolomite in its composition. Existing SCM considers oil-brine and rock-brine interfaces where only calcite mineral is captured in the rock-brine interface. The latter is based on assuming that the rock composition is pure calcite, which is not necessary the case. The findings of this study confirm that seawater is capable of inducing wettability alteration in carbonates under certain favorable conditions due to adsorption/desorption of the potentially determining ions. • This paper provides novel insight into the role of major rock-forming carbonate minerals (calcite and dolomite) in EWI/LSWI at different water compositions by utilizing the surface complexation reactions. • It is found that in a successful EWI operation, three regimes would be created, i.e. displacement regime, surface reaction regime, and equilibrium regime. • These regimes can be characterized by the proposed technique to calculate/optimize the injection pore volumes needed for each zone. • The developed approach can determine the location of EWI effect in the reservoir, and predict the time ranges when EWI would reach to the surface in the form of additional oil recovery. • This study utilizes SCM for both calcite and dolomite minerals for the first time highlighting their importance in geochemical reactions during EWI when the rock has dolomite as a constituent.

Stimulation of high temperature carbonate gas reservoirs using seawater and chelating agents: Reaction kinetics

The use of hydrochloric acid (HCl) in gas well stimulation of high temperature reservoirs is currently facing different challenges. These challenges include rapid corrosion of the well tubulars, face dissolution, very high and uncontrolled reaction rate, and formation damage in high clay content and iron-rich reservoirs. In this study, water-soluble diethylene triamine penta acetic acid (DTPA) chelating agent is introduced as alternative to eliminate the risk associated with HCl at high temperatures. In addition, the potential of using seawater to replace fresh water in the stimulation process is explored to save the cost of fresh water transportation to deep offshore oil and gas wells. The effect of seawater on the reaction kinetics of DTPA with carbonate rocks under high pressure and high temperature conditions is investigated using the rotating disk apparatus. The reactions of DTPA solution diluted with fresh water (DTPA/DI) and seawater (DTPA/SW) with carbonate rocks were carried out at the same conditions. In the case of fresh water, the reaction is controlled by the surface reaction regime. Adding HCl to adjust DTPA pH did not turn the reaction into a mass transfer controlled reaction like the case of using HCl alone. The heavy matrix of seawater increased the resistance of ions diffusion, which resulted in a low reaction rate and transformed the reaction into a mass transfer limited regime. Corrosion tests were carried out on production and coiled tubing coupons obtained from the gas wells and the results of the new DTPA/SW formulation is compared to the standard HCl formulation. DTPA showed very low corrosion rate of 0.0034 g/cm2 without adding corrosion inhibitors compared to 0.205 g/cm2 of 15 wt% HCl with 3% corrosion inhibitors while the industry limit is 0.0244 g/cm2 in 6 h. The reaction regime of DTPA chelating agent with calcite is identified to be mass transfer limited in seawater and surface reaction limited in fresh water. The rate expression for the dissolution of Ca2+ in DTPA/SW solution is obtained. Coreflooding experiments were performed to determine the optimum injection rate using low permeability Indiana limestone core samples. The optimum injection rate required to stimulate a very deep carbonate gas well was found to be 1.4 bbl/min after scaling up the coreflooding results to field scale. The application of the new DTPA/SW formulation in treating deep gas wells is expected to save the cost of fresh water and eliminate the cost of corrosion inhibitors.

Germanium-silicon alloy and core-shell nanocrystals by gas phase synthesis.

In this work we present a novel route to synthesize well defined germanium-silicon alloy (GexSi1-x) and core-shell nanocrystals (NCs) employing monosilane (SiH4) and monogermane (GeH4) as precursors in a continuously operated two-stage hot-wall aerosol reactor setup. The first hot-wall reactor stage (HWR I) is used to produce silicon (Si) seed particles from SiH4 pyrolysis in Argon (Ar). The resulting seeding aerosol is fed into the second reactor stage (HWR II) and a mixture of SiH4 and GeH4 is added. The ratio of the precursors in the feed, their partial pressures, the synthesis temperature in HWR II and the overall pressure are varied depending on the desired morphology and composition. Alloy particle production is achieved in the heterogeneous surface reaction regime, meaning that germanium (Ge) and Si are deposited on the seed surface simultaneously. The NCs can be synthesized with any desired composition, whilst maintaining a mean diameter around 30 nm with a geometric standard deviation (GSD) around 1.25. The absorption behavior and the related fundamental optical band gap energy in dependence on the alloy composition are exemplarily presented. They prove the possibility to tailor NC properties for electronical and opto-electronical applications. In the homogeneous gas phase reaction regime facetted Ge-Si core-shell structures are accessible. The Ge deposition on the seeds precedes the Si deposition due to different gas phase reaction kinetics of the precursors. The Si layer grows epitaxially on the Ge core and is around 5 nm thick.

A kinetic model of nano‐CaO reactions with CO2 in a sorption complex catalyst

AbstractThis article describes the reactive kinetics of nano‐CaO with CO2 in a sorption complex catalyst. Based on an observation of nano‐CaO reaction with CO2 has a fast surface reaction regime and followed by a slow diffusion‐controlled regime, a criterion has been proposed to divide the fast surface reaction regime and the slow diffusion‐controlled reaction regime. The kinetics of the fast surface reaction was studied, and a new ion reaction mechanism was proposed. A surface reaction‐controlled kinetic model with a Boltzmann equation, X = Xu−Xu/[1+exp((t−t0)k/Xu)], was developed. Experiments using nano‐CaO to react with CO2 in a fast surface reaction regime within a sorption complex catalyst were performed using thermogravimetric analysis at 773–873 K under a N2 atmosphere with 0.010–0.020 MPa CO2. The activation energy of the kinetic model for carbonation is 30.2 kJ/mol, and the average relative deviation of the sorption ratio is less than 9.8%. © 2011 American Institute of Chemical Engineers AIChE J, 2012

MOCVD and characterization of Hf-silicate thin films using HTB and TEMAS

Hafnium silicate (HfSixOy) films were deposited by metal-organic chemical vapor deposition (MOCVD) using a combination of precursors: hafnium tetra-tert-butoxide [Hf(OC(CH3)3)4, HTB] and tetrakis-ethylmethylamino silane [Si(N(C2H5)(CH3))4, TEMAS]. The activation energy was independent on the ratio of precursor amounts in the surface reaction regime. The grown films showed Hf-rich characteristics and the impurity concentrations were less than 1at.% (below detection limits). Hafnium silicate films were amorphous up to 700°C annealing. Hf/(Hf+Si) composition ratio and dielectric constant (k) of the Hf-silicate films decreased by increasing the growth temperature above 270°C.

Anisotropic wet etching on birefringent calcite crystal

In this paper, a mechanism for wet etching on birefringent calcite crystal is discussed. By altering the etchant type, its concentration and the stirring speed, the etching mechanism can be confined within the surface reaction regime, resulting in anisotropic etching. Acetic acid can be used to form V shapes defined by the {1011} planes with an intersecting angle of 51 degree. V-groove and blazed grating, with a grating period as small as 2 μm, were successfully fabricated. Such gratings can be used as transmission and reflection devices in the visible and infrared ranges. In addition, a transmission polarization dependent device can also be made by covering the calcite with index matching material.

The influence of filament material on radical production in hot wire chemical vapor deposition of a-Si:H

The choice of filament material has an influence on the decomposition of silane during the hot wire chemical vapor deposition of amorphous and microcrystalline silicon films. In this paper, the Si radicals produced from W, Re, Mo and Ta filament materials are probed by laser-based single photon ionization as a function of hot wire temperature. The apparent activation energy of the Si radical production in the surface reaction regime from Ta (140–180 kcal/mol) and Mo (120–160 kcal/mol) are found to be close to the corresponding Si thermal desorption energies from these surfaces, suggesting that the Si production is controlled by the desorption process from the bare metal. On the other hand, the Si activation energies from W and Re (60 kcal/mol) are lower than the related desorption energies, suggesting silicon desorption from a silicon layer formed on the surfaces. Kinetic modeling supports this desorption mechanism. In addition to the Si radical study, the corresponding film deposition is detected in situ by multiple internal reflection infrared spectroscopy, from which growth rates are estimated. The results show similar activation energies for both the growth rate and Si formation from the various filaments, implying that Si radical production and subsequent film growth are dominated by the same elementary reactions at low pressure.

Micropolarizer fabricated from CaCO3 by anisotropic wet etching.

A micropolarizer is fabricated on a birefringent crystal, calcite, by anisotropic wet etching. This device consists of a v-groove grating on calcite, covered by an index-matching material. The grating is fabricated by acid wet etching. When its acid concentration and stirring speed are altered, the etching mechanism can be controlled within the surface-reaction regime. This results in anisotropic etching, which produces a v-groove grating on a calcite surface. This v-groove grating can be fabricated to have a period as small as 2 microm. To the best of our knowledge, this type of v-groove calcite grating is reported for the first time. Although the transmission efficiency of this device is wavelength dependent, a broadband micropolarizer can be made by gluing together two devices with periods of 12 and 16 microm.

Effect of Filament Material on the Decomposition of SiH4 in Hot Wire CVD of Si-Based Films

AbstractThe choice of filament material has an effect on the decomposition of silane during the hot wire chemical vapor deposition (HW-CVD) of amorphous and microcrystalline silicon films. The Si radicals produced from W, Re, Mo and Ta filament materials have been probed by laserbased single photon ionization (SPI) as a function of hot wire temperature. The Si radical profiles are shown to demonstrate two distinct regimes: a regime below 1600°C-1800°C (depending on filament material) limited by surface reaction at the filament in which Si concentration increases monotonically; and a mass transfer limited regime above 1600°C-1800°C where Si intensity saturates. The apparent activation energy of Si radical production in the surface reaction regime from Ta (140-170 kcal/mol) is found to be close to the corresponding Si thermal desorption energy from a Ta surface, suggesting that the Si production is controlled by the desorption process from the bare metal. On the other hand, the Si activation energies from W and Re (30-60 kcal/mol) are lower than the related desorption energies, suggesting that other rate limiting reactions play a role for these materials. The apparent activation energy for the Mo surface (60-90 kcal/mol) is intermediate between the other metal values. In addition to the Si radical study, corresponding film deposition is detected in situ by multiple internal reflection infrared (MIR-IR) spectroscopy. The IR measurements have been used to estimate the growth rate of a-Si:H deposited on a Ge substrate. The results show similar activation energies for both the growth rate and the Si formation from a W filament, implying that Si radical production and subsequent film growth may be dominated by the same elementary reactions within the decomposition and film growth processes at low pressure.

Kinetic Monte Carlo investigation of pit formation at the CaCO 3(101̄4) surface-water interface

On the basis of quantitative information derived from atomic-force microscopy (AFM) studies of shallow pit formation at the CaCO 3(101̄4) surface-water interface in the surface-reaction regime, we have developed a kinetic Monte Carlo (KMC) model which reproduces quantitatively the experimental behaviour of the time-evolution of the pits. This allows the rates of all the important elementary atomistic processes involved in the dissolution to be obtained, rates not readily obtainable directly from AFM data. The KMC model also provides important insight into the evolution of very small pits, which in principle can be resolved using AFM, but which in practice are very difficult to observe because of the low probability of their occurrence in the microscope scan area. The KMC simulations show that the growing pits exhibit two different growth regimes, in agreement with the predictions of a simple terrace-ledge-kink (TLK) model. For very small pits the linear pit size increases exponentially with time and the pit edges accelerate (double-kink self-annihilation regime). Having attained a certain pit size (∼25 nm for a temperature of 300 K), thereafter the pit sizes increase linearly with time, the pit edges maintaining a constant velocity (kink-kink annihilation regime). A comparison of the quantitative predictions of the TLK model with KMC simulations shows that, in spite of its simplicity, the TLK model provides a satisfactory semi-quantitative description of the pit evolution. The KMC model presented provides the starting point for the development of a more comprehensive model of the calcite-water interface which will include the effects of adsorbates and other variations in interface conditions. Published by Elsevier Science B.V.

Interplay between step velocity and morphology during the dissolution of CaCO3 surface

The interplay between the velocity and morphology of steps during the dissolution of the cleaved CaCO3(101̄4) surface in aqueous solution has been studied using atomic force microscopy (AFM). The experimental results were analyzed based on the terrace-ledge-kink model. Real-time AFM images show that, in the surface reaction regime, steps not only retreat at constant velocities which depend only on the atomic structure of the step, but also preserve a straight-edge morphology during the course of dissolution. The straight step morphology suggests that the nucleation of kinks is balanced by the annihilation of the kinks at the step during the dissolution. This result, along with the constant step velocity, can be explained in terms of a kink-kink annihilation process.