Kinetics of interaction of hardened oil-well cement slurries with acidic solutions from isothermal heat-conduction calorimetry

The kinetics of interaction of hydrochloric acid with oil-well cement slurries treated with the silane coupling agents, tetraethyl orthosilicate, 3-(trimethoxysilyl)-1-propanethiol and 3-(chloropropyl)-trimethoxysilane have been investigated isothermal heat-conduction calorimetry at 298.15 K. The Avrami kinetic model gives a better fit to the experimental data than the traditional Lagergren kinetics models. A pore diffusion model suggests acid diffusion only for the standard slurry. The results indicate that isothermal heat-conduction calorimetry is suitable to evaluate the protective role of silane coupling agents on hardened oil-well cement slurries.     

Analysis of cement slurries by inductively coupled plasma optical emission spectrometry with axial viewing

The feasibility of Portland cement analysis by introduction of slurries in an inductively coupled plasma optical emission spectrometer (ICP-OES) with axial viewing has been evaluated. After a fast manual grinding of the cement samples, owing to the pulverized state of this material, 0.1% m/v slurries were prepared in 1% v/v HCl. The calibration was performed adopting two strategies: one based on slurries prepared from different masses (50, 75, 100 and 125 mg) of a Portland cement standard reference material (NIST SRM 1881), and the other one based on aqueous reference solutions. A complete analysis of cement for major (Al, Ca, Fe, Mg and Si), minor and trace elements (Mn, P, S, Sr and Ti) was accomplished. Both strategies led to accurate results for commercial Portland cement samples, except for Si and Ti, for which the calibration with aqueous reference solutions resulted in low values. Applying a paired t-test it was shown that most results were in agreement at a 95% confidence level with a conventional fusion decomposition procedure. The ICP-OES with axial viewing and end-on gas configuration for removal of the recombination plasma zone was effective for cement slurry analysis without any undesirable particle deposition in the pre-optics interface and without severe spectral interferences.     

Application of heat flow calorimetry to the study of oilwell cements

The majority of previous studies of the hydration of cements using heat flow calorimetry have been carried out isothermally. However, with oilwell cements the slurry is mixed on the surface at ambient temperature and then gradually increases in temperature as it is pumped down the well. A Setaram C-80 calorimeter has been used to simulate the temperature ramp in API oilwell cement test schedules. This approach has enabled cementing reactions to be studied for the first time under conditions approaching those encountered in the field, and has shown that the results obtained from isothermal experiments may be misleading.The permission of the British Petroleum Company PLC to publish this paper is gratefully acknowledged.     

Thermal analysis applied for the removal of surfactant from mesoporous molecular sieves MCM-41 synthesized from gold mine tailings slurry

The aim of the current study is to obtain the thermal behavior and kinetic analyses of the removal of surfactant from MCM-41 synthesized from tailings slurry at different heating rates. X-ray diffraction and thermogravimetric analyses were carried out to determine the characterization of the synthesized samples. Kissinger–Akahira–Sunose and Friedman isoconversional kinetic methods were applied for the purpose of determining the kinetic analysis parameters of the decomposition of surfactant from the mesoporous molecular sieves MCM-41 under non-isothermal conditions. For the comparison of these results, MCM-41 was synthesized from a pure silica source. The thermal behaviors of MCM-41 synthesized from tailings slurry do not differ from samples synthesized from pure silica during the decomposition reactions. The kinetic analysis’ results indicate that the decomposition reactions of the synthesized MCM-41 samples had complex reaction mechanisms.     

Hydration of Cement Slurry in The Presence of Spent Cracking Catalyst

The physicochemical properties of spent fluidized bed cracking catalyst and its influence on hydration process of cement slurry were studied. The samples were cement slurries prepared with water/solid=0.5 and additions of used catalyst amounted to 0, 5, 10, 15, 20 and 25%with resp. to the solid. After definite time they were subjected to thermogravimetric analysis (TG, DTG, DTA) and, in order to determine the progress of reaction with water, the heat of hydration was measured by means of isotherm calorimetry. The studies disclosed that the spent cracking catalyst is not merely an inactive filler in cement slurries, but it modifies the course of the hydration process. The spent catalyst is a pozzolana additive and its presence leads to a decrease of calcium hydroxide contents in the system. The spent catalyst affect on the heat of cement hydration. Small amounts additive accelerate the process of binding. This revised version was published online in August 2006 with corrections to the Cover Date.     

Batch gravitational sedimentation of slurries

We investigated the batch settling behavior of the kaolin slurry and the UK ball clay slurry at various initial solids fractions (phi(0)s) using a computerized axial tomography scanner (CATSCAN). The spatio-temporal evolutions of solids fractions in the consolidating sediments were continuously monitored. Since the interface between the sediment and the supernatant of the investigated slurries was blurred, an averaging procedure was employed to estimate their null-stress solids fractions (phi(g)s). Besides the rather slow settling for the high-phi(0) slurries, the basic settling characteristics resemble each other regardless of whether phi(0)>phi(g) or vice versa. The above-mentioned experimental data reveal that the investigated slurries are neither purely elastic nor purely plastic in rheological behavior. On contrary to most model works a blurred supernatant-sediment interface makes difficulty in the gel point determination. During initial settling the high-phi(0) slurries clearly exhibit a finite yield stress to resist deformation. That is, the slurries are plastic fluids. However, the network structure in the slurries deteriorates gradually in the subsequent settling stage while the final, equilibrated sediment reveals a continuous distribution in solids fraction. Restated, the final sediment possesses as a purely elastic characteristic. The model parameters of theory by Buscall and White were regressed by the dynamic consolidating sediment data, while those by Tiller and Leu were obtained using the final equilibrated sediment data. Calculations from both models reveal that ball clay slurry is more compressible than is the kaolin slurry. The high-phi(S0) slurry would yield the less compressible sediment.     

Adsorption and desorption kinetics of benzene derivatives on mesoporous carbons

Adsorption and desorption of benzoic and salicylic acids and phenol from a series of synthesized mesoporous carbons is measured and analyzed. Equilibrium adsorption isotherms are best described by the Langmuir–Freundlich isotherm. Intraparticle diffusion and McKay’s pore diffusion models, as well as mixed 1,2-order (MOE), integrated Langmuir kinetic equation (IKL), Langmuir–Freundlich kinetic equation and recently derived fractal-like MOE (f-MOE) and IKL models were compared and used to analyze adsorption kinetic data. New generalization of Langmuir kinetics (gIKL), MOE and f-MOE were used to describe desorption kinetics. Analysis of adsorption and desorption half-times shows simple relation to the size of carbon pores.     

Oilwell cements: NMR contribution to establish the phase diagram pressure/temperature of the mixture H2O / Ca3SiO5

Cement slurry is always used to support the casing of oilwells. This slurry is pumped down the steel casing of the well and then placed in the annular space between the casing and the surrounding rock. Nowadays wells are becoming deeper and deeper so the setting conditions of the cement paste are crucial. The pressure and temperature limit conditions can reach 1 000 bar and 250 °C at the bottom of the well. Hydration of synthetic tricalcium silicate Ca₃SiO₅ – the main component of oil well cements – was performed at high temperature under high pressure to simulate the oilwell conditions. The objective of the study is the establishment of the phase diagram of the ternary system – SiO₂, CaO, H₂O – according to the parameters: pressure, temperature and Ca/Si ratio. In this study, NMR is largely used to identify and to quantify the synthesized silicate hydrates, with two setting conditions (6 days at 120 °C under 400 bar and 6 days at 200 °C under 600 bar). Mechanical tests were performed to evaluate the compression strength of those silicate hydrates synthesized under such drastic conditions and to verify that they were still efficient binders.     

CORRELATION OF DISPERSION STABILITY WITH SURFACTANT CONCENTRATION AND ABRASIVE PARTICLE SIZE FOR CHEMICAL MECHANICAL POLISHING (CMP) SLURRIES

The preparation of stable colloidal slurries is often difficult in industries where many chemical components are added into the slurries. A critically acclaimed example of such an industry is the chemical mechanical polishing (CMP) industry which involves polishing slurries with several chemical additives. In the present work, the stabilization of a slurry used for CMP of metals is investigated in detail. This high ionic strength slurry has been stabilized using an optimaJ combination of sodium dodecyl sulfate (anionic surfactant) and Tween 80 (nonionic surfactant). The amount of surfactant needed to impart stability has been investigated in this study for two different sizes of abrasive particles. It has been found that the amount of surfactant needed to stabilize the slurry increases as the total surface area per gram of panicles increases. Slurry stabilization has been correlated with particle size measurements. It has been found that the average panicle size of the slurry decreases as the stability of the slurry increases. Stable slurries have been found to have particle sizes close to those of the particles before agglomeration. It is proposed that the stabilized CMP slurries can lead to reduced defects in wafers by preventing agglomeration of panicles.     

Multistep adsorption of anionic dyes on silica/chitosan hybrid. 1. Comparative kinetic data from liquid- and solid-phase models

In this work, a hybrid silica/chitosan was synthesized and characterized by nitrogen elemental analysis and thermal analysis (TG, DTG, DTA, and DSC) and BET surface area. The hybrid was used in adsorption studies of two anionic dyes from aqueous solutions. A rise of temperature accelerates mass transfer of dyes into the hybrid. However, the maximum adsorption capacities reach similar values from 25 to 55 degrees C. The kinetic data were first evaluated in relation to the decrease of the time-related residual concentration of the dyes in solution, where the second-order model has presented the best fitting. The solid-phase interaction of dye data presents a rough fitting to the traditional first-order Lagergren kinetic model. However, a modified Avrami kinetic equation was successfully fitted to the kinetic quantities, where from five to seven kinetic regions were found. A pore-diffusion model has also demonstrated that the diffusion is the rate-controlling interaction mechanism. However, the experimental-calculated comparative values are the best way to evaluate a specific aqueous- or solid-phase kinetic model.     

Abrasive properties of nano silica particles prepared by a sol–gel method for polishing silicon wafers

Abrasive properties of cocoon shaped silica particles fabricated by a sol–gel method have been studied. Since silicon wafers are polished with slurry by the mechanism of Chemical Mechanical Polishing, polishing rates may depend on various chemical and mechanical factors, such as particle concentration in slurry, slurry pH and kinds of basic compounds for controlling the slurry pH. The silicon wafer was polished by slurry continuously fed on a pad, and the polishing rate was estimated as a weight loss of the wafer. For studying the effects of the various factors on the rate, the slurries were prepared by adding the silica particles, basic compounds or salts, and the polishing rates of the slurry were measured. The effects of the various factors were made clear as follows: For the effect of particle concentration, the rates increased with increasing of the concentrations up to 1.0 wt.%. And for the effect of the slurry pH, slurries added basic compounds, such as KOH, NaOH, ammonia, were tested, and it was found that increasing of the slurry pH brought increases of the polishing rates. KOH-containing slurry of pH 13.2 had the fastest rate, 3.6 times as fast as the standard slurry with pH 9.4. For the effect of the adding of salts, it was indicated that the salts, such as KCl, NaCl, NH₄Cl, NaNO₃ and K₂SO₄ increased the polishing rates, and that KCl-containing slurry of 0.36 mol/l had the highest polishing rate, 3.4 times as fast as that of the standard slurry containing no salts.     

The fluorescence enhancement effect of the Tb-Gd-guanosine-5′-triphosphate-phen system and its analytical application

The simplified generalized standard additions method (GSAM) was investigated as an alternative method for the ICP-OES analysis of solid materials, introduced into the plasma in the form of slurries. The method is an expansion of the conventional standard additions method. It is based on the principle of varying both the sample mass and the amount of standard solution added. The relationship between the sample mass, standard solution added and signal intensity is assumed to be linear. Concentration of the analyte can be found either geometrically from the slope of the two-dimensional response plane in a three-dimensional space or mathematically from the ratio of the parameters estimated by multiple linear regression. The analysis of a series of certified reference materials (CRMs) (cement CRM-BCS No 353, gypsum CRM-Gyp A and basic slag CRM No 382/I) introduced into the plasma in the form of slurry is described. The slurries contained glycerol and hydrochloric acid and were placed in an ultrasonic bath to ensure good dispersion. Table curve 3D software was used to fit the data. Results obtained showed that the method could be successfully applied to the analysis of cement, gypsum and slag samples, without the need to dissolve them. In this way, we could avoid the use of hazardous chemicals (concentrated acids), incomplete dissolution and loss of some volatiles. The application of the simplified GSAM for the analysis did not require a CRM with similar chemical and mineralogical properties for the calibration of the instrument.     

Determination of trace elements in plant materials by slurry sampling graphite furnace AAS — some analytical problems

Summary The analytical conditions of cadmium, lead, nickel and cobalt determination in plant material by slurry sampling graphite furnace atomic absorption spectrometry (GFAAS) are presented. The results of stability tests for slurries prepared in different ways are also shown. The ratio of the amount of analyte found in the liquid phase to the total amount of analyte in the slurries is investigated. The determination results are calculated from aqueous standard calibration graphs (cobalt and nickel) or by the standard addition method (cadmium and lead). Statistical evaluation of the results from the certified materials indicate that the slurry method is both accurate and comparable in precision to the conventional wet-ashing procedure.Presented at the 5th International Colloquium on Solid Sampling, with Atomic Spectroscopy, May 18–20, 1992; Geel, Belgium. Papers edited by R. F. M. Herber, Amsterdam     

Adsorption of Bismarck Brown by Iron Oxide Nanosphere and Its Modified Form

In the present study, adsorption of Bismarck Brown (BB) dye onto iron oxide nanospheres (IONs) and modified IONs by HCl from aqueous solution was investigated. The IONs was synthesized by solvothermal method and then modified by HCl. The high magnetic properties of both adsorbents lead to facial separation from aqueous solution by an external magnet. The results show that the modification of adsorbent cause higher adsorption capacity for removal of BB from aqueous solution. The prepared adsorbents were characterized by SEM, XRD, FTIR, and ATR-IR techniques. The adsorption kinetic and equilibrium data were fitted with different models. The results show that the equilibrium and kinetic data were best fitted with Langmuir–Freundlich isotherm and fractal-like pseudo-second-order kinetic model, respectively. The effects of pH and temperature have also been investigated.     

外加无机电解质对煤浆性质调控作用的研究

考察了数种无机电解质对煤浆分散体系流变特性的影响。结果发现，煤浆的流变特性不仅与电解质种类有关，还取决于煤质特征。某些煤适，适量的无机电解质可使浆体的屈报胀塑料转化为屈服假塑性。     

Slurry sampling of sediments and coals for the determination of Sn by HG-GF AAS with retention in the graphite tube treated with Th or W as permanent modifiers

A method for the determination of Sn in slurry samples of sediment and coal by hydride generation graphite furnace electrothermal atomic absorption spectrometry (HG-GF AAS) is proposed. The slurries were prepared by mixing the ground sample (particle size 50 m) with 2.0 mol L^–1 HCl for the sediment samples or with 2.0 mol L^–1 HCl+1.0% v/v HF in a saturated boric acid medium for the coal samples. The slurry was placed in an ultrasonic bath for 30 min, before and after standing for 24 h, with occasional manual stirring. The graphite tube was treated with 0.5 mg of Th or W as a permanent modifier. Sn determination was carried out by electrothermal atomic absorption spectrometry at the optimized retention temperatures of 450 and 300°C for Th and W treatment, respectively. With this coupling, kinetic interference in the formation of the hydrides is avoided, and excellent detection limits can be obtained by using peak height. For the chemical vapor generation device, an optimized volume of 2 mL of sample slurry and an optimized NaBH₄ concentration of 5% m/v were employed. The vapor produced was transported and retained on the graphite tube surface, which was further heated for Sn atomization. The accuracy of the method was verified by analyzing five certified sediments and three coals. By using the external calibration against aqueous standard solutions, the results obtained were in agreement with the certified values only for the sediment samples. For the coal samples, an addition calibration curve, obtained for one certified coal, was necessary to achieve accurate results. The obtained limits of detection were 0.03 g g^–1 for sediment and 0.09 g g^–1 for coal with Th as permanent modifier. The relative standard deviations were lower than 15%, demonstrating an adequate precision for slurry analysis. Sediment and coal samples from Santa Catarina, Brazil, were also analyzed.     

Adsorption of acid dyes from aqueous solutions onto acid-activated bentonite

The adsorption of two dyes, namely, Acid Red 57 (AR57) and Acid Blue 294 (AB294), onto acid-activated bentonite in aqueous solution was studied in a batch system with respect to contact time, pH, and temperature. Acidic pH was favorable for the adsorption of these dyes. The surface characterization of acid-activated bentonite was performed using the FTIR technique. The pseudo-first-order and pseudo-second-order kinetic models and the intraparticle diffusion model were used to describe the kinetic data and the rate constants were evaluated. The dynamic data fitted the pseudo-second-order kinetic model well and also followed the intraparticle diffusion model up to 90 min, but diffusion is not the only rate controlling step. The Langmuir and Freundlich adsorption models were applied to describe the equilibrium isotherms and the isotherm constants were determined. The Freundlich model agrees very well with experimental data. The activation energies of adsorption were also evaluated for the adsorption of AR57 and AB294 onto activated bentonite.     

Flow injection flame atomic absorption analysis of Fe and Mn in cement samples

Summary A new procedure has been developed for the determination of Fe and Mn in cements. It consists in dispersing 50 mg of the solid sample in 25 ml of 0.15 mol/l HNO₃ and 0.12 mol/l HCl solution. Acid slurries are heated at 50°C for 10 min and then different volumes of the slurry are injected into a water carrier stream. This previous acid treatment leaches the elements to be determined and permits the use of acid solutions as standards. For the Mn determination, the use of a single line flow injection manifold provides a limit of detection of 0.03 mgl^–1 and a dynamic range up to 6 mgl^–1. For the determination of Fe, the on-line dispersion of samples, using a well stirred mixing chamber, increases the dynamic range up to a concentration of 125 mgl^–1 and provides a limit of detection of 1 mgl^–1. The procedure has been applied to the analysis of real cement samples and a certified reference material. Results were in agreement with those obtained by a reference procedure involving the alkaline fusion of samples and batch analysis by flame atomic absorption spectrometry.     

Trichloroethylene Dechlorination by Copper-contained Zero-valent Iron Slurry

Zero valent iron technology has been widely used for treating contaminated wastewater these years. However, it always results in inefficiency in the processes of drying and storage due to oxidation and passivation. This could be avoided by in situ synthesized zero valent iron slurry in an emergency if it possesses the same performance as zero valent iron. In this study, iron slurry was synthesized and directly used for dechlorinating trichloroe- thylene to measure its degradation efficiencies and properties. Results show that 2%（mass ratio） copper-contained zero-valent iron slurry exhibits the optimal performance compared with the other iron slurries. Batch experiments in- dicate that factors such as the concentration of trichloroethylene, pH, dissolved oxygen and equilibrium to a certain extent affect the reduction oftrichloroethylene by 2%（mass ratio） copper-contained zero-valent iron slurry. Persistent, high-efficiency degradation performance could last 7 cycles. These demonstrate that the application of coppercontained zero-valent iron slurry in treating trichloroethylene-contained wastewater is realistic.     

Molecular dynamics and kinetic study of carbon coagulation in the release wave of detonation products

We present a combined molecular dynamics and kinetic study of a carbon cluster aggregation process in thermodynamic conditions relevant for the detonation products of oxygen deficient explosives. Molecular dynamics simulations with the LCBOPII potential under gigapascal pressure and high temperatures indicate that (i) the cluster motion in the detonation gas is compatible with Brownian diffusion and (ii) the coalescence probability is 100% for two clusters entering the interaction cutoff distance. We used these results for a subsequent kinetic study with the Smoluchowski model, with realistic models applied for the physical parameters such as viscosity and cluster size. We found that purely aggregational kinetics yield too fast clustering, with moderate influence of the model parameters. In agreement with previous studies, the introduction of surface reactivity through a simple kinetic model is necessary to approach the clustering time scales suggested by experiments (1000 atoms after 100 ns, 10 000 atoms after 1 μs). However, these models fail to reach all experimental criteria simultaneously and more complex modelling of the surface process seems desirable to go beyond these current limitations.