Fluidos de perfuração aquosos: a contribuição da goma xantana e carboximetilcelulose no controle de filtrado

This study aimed mainly to evaluate the influence of xanthan gum (XG) and carboxymethylcellulose (CMC) in the filtration process of water-based drilling fluids, considering the conformational changes suffered by the polyelectrolyte with the addition of sodium chloride (NaCl) in different concentrations (0.17, 0.34 and 0.51 mol.L-1). It was also evaluated the behavior of the fluid by the addition of calcium carbonate (CaCO3) in pure water and in brine. Seeking a better understanding of the interaction between the polymers used and CaCO3, polymer adsorption analyzes were performed using a depletion method, which yielded a higher percentage of adsorption of Xanthan Gum in this material (29%), which can justify the formation of a thin and waterproof filter cake for drilling fluids containing this polymer. However, the best values of apparent viscosity (20 and 24 mPa.s) and volume of filtrate (8.0 and 8.1 mL) were obtained for the systems consisting of xanthan gum, CMC and CaCO3, in NaCl aqueous solutions concentrations of 0.34 and 0.51 mol.L-1, respectively. The values can be related to the presence of CMC that increases the apparent viscosity and reduces the volume of filtrate. In addition, the CaCO3 added acts as a bridging agent, promoting the formation of a less permeable filter cake

Uso de água produzida na formulação de fluidos de perfuração

Drilling fluids have fundamental importance in the petroleum activities, since they are responsible for remove the cuttings, maintain pressure and well stability, preventing collapse and inflow of fluid into the rock formation and maintain lubrication and cooling the drill. There are basically three types of drilling fluids: water-based, non-aqueous and aerated based. The water-based drilling fluid is widely used because it is less aggressive to the environment and provide excellent stability and inhibition (when the water based drilling fluid is a inhibition fluid), among other qualities. Produced water is generated simultaneously with oil during production and has high concentrations of metals and contaminants, so it’s necessary to treat for disposal this water. The produced water from the fields of Urucu-AM and Riacho da forquilha-RN have high concentrations of contaminants, metals and salts such as calcium and magnesium, complicating their treatment and disposal. Thus, the objective was to analyze the use of synthetic produced water with similar characteristics of produced water from Urucu-AM and Riacho da Forquilha-RN for formulate a water-based drilling mud, noting the influence of varying the concentration of calcium and magnesium into filtered and rheology tests. We conducted a simple 32 factorial experimental design for statistical modeling of data. The results showed that the varying concentrations of calcium and magnesium did not influence the rheology of the fluid, where in the plastic viscosity, apparent viscosity and the initial and final gels does not varied significantly. For the filtrate tests, calcium concentration in a linear fashion influenced chloride concentration, where when we have a higher concentration of calcium we have a higher the concentration of chloride in the filtrate. For the Urucu’s produced water based fluids, volume of filtrate was observed that the calcium concentration influences quadratically, this means that high calcium concentrations interfere with the power of the inhibitors used in the formulation of the filtered fluid. For Riacho’s produced water based fluid, Calcium’s influences is linear for volume of filtrate. The magnesium concentration was significant only for chloride concentration in a quadratic way just for Urucu’s produced water based fluids. The mud with maximum concentration of magnesium (9,411g/L), but minimal concentration of calcium (0,733g/L) showed good results. Therefore, a maximum water produced by magnesium concentration of 9,411g/L and the maximum calcium concentration of 0,733g/L can be used for formulating water-based drilling fluids, providing appropriate properties for this kind of fluid.

Contribuição da poliacrilamida parcialmente hidrolisada em associação com a bentonita em fluidos de perfuração aquosos

In this study, we investigated the effect of addition of partially hydrolyzed polyacrylamide (HPAM) and bentonite in the physicochemical properties of acquous drilling fluids. Two formulations were evaluated: F1 formulation, which was used as reference, containing carboxymethylcellulose (CMC), magnesium oxide (MgO), calcite (calcium carbonate - CaCO3 ), xanthan gum, sodium chloride (NaCl) and triazine (bactericidal); and F2, containig HPAM steady of CMC and bentonite in substituition of calcite. The prepared fluids were characterized by rheological properties, lubricity and fluid loss. Calcite was characterized by granulometry and thermal gravimetric analysis (TGA). The formulation F2 presented filtration control at 93◦C 34 mL while F1 had total filtration. The lubricity coefficient was 0.1623 for F2 and 0.2542 for F1, causing reduction in torque of 25% for F1 and 52 % for F2, compared to water. In the temperature of 49 ◦C and shear rate of 1022 s −1 , the apparent viscosities were 25, 5 and 48 cP for F1 and F2 formulation, respectively, showing greater thermal resistance to F2. With the confirmation of higher thermal stability of F2, factorial design was conducted in order to determine the HPAM and of bentonite concentrations that resulted in the better performance of the fluids. The statistical design response surfaces indicated the best concentrations of HPAM (4.3g/L) and bentonite (28.5 g/L) to achieve improved properties of the fluids (apparent viscosity, plastic viscosity, yield point and fluid loss) with 95% confidence, as well as the correlations between these factors (HPAM and bentonite concentrations). The thermal aging tests indicated that the formulations containing HPAM and bentonite may be used to the maximum temperature until 150 ◦C. The analyze of the filter cake formed after filtration of fluids by X-ray diffraction showed specific interactions between the bentonite and HPAM, explaining the greater thermal stability of F2 compared to the fluid F1, that supports maximum temperature of 93 ◦C.

Síntese, caracterização e estudo da associação em meio aquoso de copolímeros responsivos de carboximetilcelulose-g-Jeffamine®

This thesis presents the synthesis, characterization and study of the associative behaviour in aqueous media of new responsive graft copolymers, based on carboxymethylcellulose as the water-soluble backbone and Jeffamine® M-2070 e Jeffamine® M-600 (commercial polyetheramines) as the thermoresponsive grafts with high cloud point temperatures in water. The synthesis was performed on aqueous medium, by using 1-ethyl-3- (3-(dimethylamino)-propyl)carbodiimide hydrochloride and N-hydroxysuccinimide as activators of the reaction between carboxylategroupsfrom carboxymethylcellulose and amino groups from polyetheramines. The grafting reaction was confirmed by infrared spectroscopy and the grafting percentage by 1H NMR. The molar mass of the polyetheramines was determined by 1H NMR, whereas the molar mass of CMC and graft copolymers was determined by static light scattering. The salt effect on the association behaviour of the copolymers was evaluated in different aqueous media (Milli-Q water, 0.5M NaCl, 0.5M K2CO3 and synthetic sea water), at different temperatures, through UV-vis, rheology and dynamic light scattering. None of the copolymers solutions, at 5 g/L, turned turbid in Milli-Q water when heated from 25 to 95 °C, probably because of the increase in hydrophibicity promoted by CMC backbone. However, they became turbid in the presence of salts, due to the salting out effect, where the lowest cloud point was observed in 0.5M K2CO3, which was attributed to the highest ionic strength in water, combined to the ability of CO3 2- to decrease polymer-solvents interactions. The hydrodynamic radius and apparent viscosity of the copolymers in aqueous medium changed as a function of salts dissolved in the medium, temperature and copolymer composition. Thermothickening behaviour was observed in 0.5M K2CO3 when the temperature was raised from 25 to 60°C. This performance can be attributed to intermolecular associations as a physical network, since the temperature is above the cloud point of the copolymers in this solvent.

Physical and chemical kinetics of structural build-up of cement suspensions

Abstract : The structural build-up of fresh cement-based materials has a great impact on their structural performance after casting. Accordingly, the mixture design should be tailored to adapt the kinetics of build-up given the application on hand. The rate of structural build-up of cement-based suspensions at rest is a complex phenomenon affected by both physical and chemical structuration processes. The structuration kinetics are strongly dependent on the mixture’s composition, testing parameters, as well as the shear history. Accurate measurements of build-up rely on the efficiency of the applied pre-shear regime to achieve an initial well-dispersed state as well as the applied stress during the liquid-solid transition. Studying the physical and chemical mechanisms of build-up of cement suspensions at rest can enhance the fundamental understanding of this phenomenon. This can, therefore, allow a better control of the rheological and time-dependent properties of cement-based materials. The research focused on the use of dynamic rheology in investigating the kinetics of structural build-up of fresh cement pastes. The research program was conducted in three different phases. The first phase was devoted to evaluating the dispersing efficiency of various disruptive shear techniques. The investigated shearing profiles included rotational, oscillatory, and combination of both. The initial and final states of suspension’s structure, before and after disruption, were determined by applying a small-amplitude oscillatory shear (SAOS). The difference between the viscoelastic values before and after disruption was used to express the degree of dispersion. An efficient technique to disperse concentrated cement suspensions was developed. The second phase aimed to establish a rheometric approach to dissociate and monitor the individual physical and chemical mechanisms of build-up of cement paste. In this regard, the non-destructive dynamic rheometry was used to investigate the evolutions of both storage modulus and phase angle of inert calcium carbonate and cement suspensions. Two independent build-up indices were proposed. The structural build-up of various cement suspensions made with different cement contents, silica fume replacement percentages, and high-range water reducer dosages was evaluated using the proposed indices. These indices were then compared to the well-known thixotropic index (Athix.). Furthermore, the proposed indices were correlated to the decay in lateral pressure determined for various cement pastes cast in a pressure column. The proposed pre-shearing protocol and build-up indices (phases 1 and 2) were then used to investigate the effect of mixture’s parameters on the kinetics of structural build-up in phase 3. The investigated mixture’s parameters included cement content and fineness, alkali sulfate content, and temperature of cement suspension. Zeta potential, calorimetric, spectrometric measurements were performed to explore the corresponding microstructural changes in cement suspensions, such as inter-particle cohesion, rate of Brownian flocculation, and nucleation rate. A model linking the build-up indices and the microstructural characteristics was developed to predict the build-up behaviour of cement-based suspensions The obtained results showed that oscillatory shear may have a greater effect on dispersing concentrated cement suspension than the rotational shear. Furthermore, the increase in induced shear strain was found to enhance the breakdown of suspension’s structure until a critical point, after which thickening effects dominate. An effective dispersing method is then proposed. This consists of applying a rotational shear around the transitional value between the linear and non-linear variations of the apparent viscosity with shear rate, followed by an oscillatory shear at the crossover shear strain and high angular frequency of 100 rad/s. Investigating the evolutions of viscoelastic properties of inert calcite-based and cement suspensions and allowed establishing two independent build-up indices. The first one (the percolation time) can represent the rest time needed to form the elastic network. On the other hand, the second one (rigidification rate) can describe the increase in stress-bearing capacity of formed network due to cement hydration. In addition, results showed that combining the percolation time and the rigidification rate can provide deeper insight into the structuration process of cement suspensions. Furthermore, these indices were found to be well-correlated to the decay in the lateral pressure of cement suspensions. The variations of proposed build-up indices with mixture’s parameters showed that the percolation time is most likely controlled by the frequency of Brownian collisions, distance between dispersed particles, and intensity of cohesion between cement particles. On the other hand, a higher rigidification rate can be secured by increasing the number of contact points per unit volume of paste, nucleation rate of cement hydrates, and intensity of inter-particle cohesion.

Changes in physical and chemical parameters of the traditional portuguese product água-mel during the production process

Changes in physical and chemical parameters (viscosity, total soluble solids and Hunter color parameters L*, a*, b*, chroma and hue angle) of água-mel were investigated throughout processing. Kinetic parameters for color change of heatprocessed água-mel were monitored. A zero-order kinetic model was applied to changes in L* and b*, while a* and C* were described using a first-order kinetic model. The heating process changed all three color parameters (L*, a*, b*), causing a shift toward the darker colors. Parameters L* decreased, while a*, b*, C* and hue angle (°h) increased during heating. Regarding changes in total soluble solids and in apparent viscosity, both fitted first-order kinetics. A direct relationship was found between the changes in these two parameters. The increase in both total soluble solids and viscosity affected a*, b* and C*. In addition, a flow diagram for the Portuguese água-mel production process has been established.

Anomalous Viscosity Reduction and Hydrodynamic Interactions of Polymeric Nanocolloids in Polymers

One of the central dogmas of fluid physics is the no-slip boundary condition, whose validity has come under scrutiny, especially in the fields of micro and nanofluidics. Although various studies show the violation of the no-slip condition its effect on flow of colloidal particles in viscous media has been rarely explored. Here we report unusually large reduction of effective viscosity experienced by polymeric nano colloids moving through a highly viscous and confined polymer, well above its glass transition temperature. The extent of reduction in effective interface viscosity increases with decreasing temperature and polymer film thickness. Concomitant with the reduction in effective viscosity we also observe apparent divergence of the wave vector dependent hydrodynamic interaction function of these colloids with an anomalous power law exponent of similar to 2 at the lowest temperatures and film thickness studied. Such strong hydrodynamic interactions are not expected for polymeric colloidal motion in polymer melts. We suggest hydrodynamics, especially slip present at the colloid-polymer interface which determines the observed reduction in interface viscosity and presence of strong hydrodynamic interactions.

Volumetric properties, viscosity and refractive index of the protic ionic liquid, pyrrolidinium octanoate, in molecular solvents

Densities ([rho]) and viscosities ([eta]) of binary mixtures containing the Protic Ionic Liquid (PIL), pyrrolidinium octanoate with five molecular solvents: water, methanol, ethanol, n-butanol, and acetonitrile are determined at the atmospheric pressure as a function of the temperature and within the whole composition range. The refractive index of all mixtures (nD) is measured at 298.15†K. The excess molar volumes VE and deviation from additivity rules of viscosities [eta]E and refractive index [Delta][phi]n, of pyrrolidinium octanoate solutions were then deduced from the experimental results as well as apparent molar volumes V[phi]i, partial molar volumes and thermal expansion coefficients [alpha]p. The excess molar volumes VE are negative over the entire mole fraction range for mixture with water, acetonitrile, and methanol indicating strong hydrogen-bonding interaction for the entire mole fraction. In the case of longest carbon chain alcohols (such as ethanol and n-butanol)†+†pyrrolidinium octanoate solutions, the VE variation as a function of the composition describes an S shape. The deviation from additivity rules of viscosities is negative over the entire composition range for the acetonitrile, methanol, ethanol, and butanol, and becomes less negative with increasing temperature. Whereas, [eta]E of the {[Pyrr][C7CO2]†+†water} binary mixtures is positive in the whole mole fraction range and decreases with increasing temperature. the excess Gibbs free energies of activation of viscous flow ([Delta]G*E) for these systems were calculated. The deviation from additivity rules of refractive index [Delta][phi]n are positive over the whole composition range and approach a maximum of 0.25 in PIL mole fraction for all systems. The magnitude of deviation for [Delta][phi]n describes the following order: water†>†methanol†>†acetonitrile†>†ethanol. Results have been discussed in terms of molecular interactions and molecular structures in these binary mixtures.

Density, conductivity, viscosity, and excess properties of (pyrrolidinium nitrate-based Protic Ionic Liquid + propylene carbonate) binary mixture

Density, ?, viscosity, ?, and conductivity, s, measurements of binary mixtures containing the pyrrolidinium nitrate Protic Ionic Liquid (PIL) and propylene carbonate (PC), are determined at the atmospheric pressure as a function of the temperature from (283.15 to 353.15) K and within the whole composition range. The temperature dependence of both the viscosity and conductivity of each mixture exhibits a non-Arrhenius behaviour, but is correctly fitted by using the Vogel–Tamman–Fulcher (VTF) equation. In each case, the best-fit parameters, such as the pseudo activation energy, View the MathML source and ideal glass transition temperature, T0 are then extracted. The excess molar volumes VE, and viscosity deviations from the ideality, ??, of each investigated mixture were then deduced from the experimental results, as well as, their apparent molar volumes, V?, thermal expansion coefficients ap, and excess Gibbs free energies (?G*E) of activation of viscous flow. The VE, apE, ?? values are negative over the whole composition range for each studied temperature therein. According to the Walden rule, the ionicity of each mixture was then evaluated as a function of the temperature from (283.15 to 353.15) K and of the composition. Results have been then discussed in terms of molecular interactions and molecular structures in this binary mixture.

A Correlation between the Dynamic Viscosity and Crystallisation of Felodipine from its Amorphous Polymer Solid Dispersion

Purpose Previously, it has been reported that molecular mobility determines the rate of molecular approach to crystal surfaces, while entropy relates to the probability of that approaching molecule having the desirable configuration for further growth of the existing crystal; and the free energy dictates the probability of that molecule not returning to the liquid phase1. If we plot the crystal growth rate and viscosity of a supercooled liquid in a log-log format, the relationship between the two is linear, indicating the influence viscosity has upon crystal growth rate. However, such approximation has been derived from pure drug compounds and it is apparent that further understanding of crystallization from drug-polymer solid dispersion is required in order to stabilise drugs embedded within amorphous polymeric solid dispersions. Methods Mixtures of felodipine and polymer (HPMCAS-HF, PVPK15 and Soluplus®) at specified compositions were prepared using a Restch MM200 ball mill. To examine crystal growth within amorphous solid dispersions, samples were prepared by melting 5-10 mg of ball milled mixture at 150°C for 3-5 minutes on a glass slip pre-cleaned with methanol and acetone. All prepared samples were confirmed to be crystal free by visual observation using a polarised light microscope (Olympus BX50). Prepared samples were stored at 0% RH (P2O5), inside desiccators, maintained in ovens at 80°C. For the dynamic viscosity measurement, approximately 100-200mg ball milled mixture was heated on the base plate of a rotational rheometer at 150°C for 5 minutes and the top plate was lowered to a defined gap to form a good contact with the material. The sandwiched amorphous material was heated to 80°C and the viscosity was measured. Results The equation was used to probe the correlation of viscosity to crystal growth rate. In comparison to the value of xi in log-log equation reported from pure drug compound, a value of 1.63 was obtained for FD-polymer solid dispersions irrespective of the polymer involved. &#8733 Conclusion The high xi value suggests stronger viscosity dependence may exist for amorphous FD once incorporated with amorphous polymer.

A Simple maxwell Based Model in Order to Represent the frequency-dependent viscosity measured by ultrasound

A previous work showed that viscosity values measured high frequency by ultrasound agreed with the values at low frequency by the rotational viscometer when conditions are met, such as relatively low frequency viscosity. However, these conditions strongly reduce the range of the measurement cell. In order to obtain a measurement range and sensitivity high frequency must used, but it causes a frequency-dependent decrease on the viscosity values. This work introduces a new simple in order to represent this frequency-dependent behavior.model is based on the Maxwell model for viscoelastic , but using a variable parameter. This parameter has physical meaning because it represents the linear behavior the apparent elasticity measured along with the viscosity by .Automotive oils SAE 90 and SAE 250 at 22.5±0.5oC viscosities at low frequency of 0.6 and 6.7 Pa.s, respectively,tested in the range of 1-5 MHz. The model was used in to fit the obtained data using an algorithm of non-linear in Matlab. By including the viscosity at low frequency an unknown fitting parameter, it is possible to extrapolate its . Relative deviations between the values measured by the and extrapolated using the model for the SAE 90 and SAE 250 oils were 5.0% and 15.7%, respectively.©2008 IEEE.

The new insight into dynamic crossover in glass forming liquids from the apparent enthalpy analysis

One of the most intriguing phenomena in glass forming systems is the dynamic crossover (T(B)), occurring well above the glass temperature (T(g)). So far, it was estimated mainly from the linearized derivative analysis of the primary relaxation time τ(T) or viscosity η(T) experimental data, originally proposed by Stickel et al. [J. Chem. Phys. 104, 2043 (1996); J. Chem. Phys. 107, 1086 (1997)]. However, this formal procedure is based on the general validity of the Vogel-Fulcher-Tammann equation, which has been strongly questioned recently [T. Hecksher et al. Nature Phys. 4, 737 (2008); P. Lunkenheimer et al. Phys. Rev. E 81, 051504 (2010); J. C. Martinez-Garcia et al. J. Chem. Phys. 134, 024512 (2011)]. We present a qualitatively new way to identify the dynamic crossover based on the apparent enthalpy space (H(a)(') = dlnτ/d(1/T)) analysis via a new plot lnH(a)(') vs. 1∕T supported by the Savitzky-Golay filtering procedure for getting an insight into the noise-distorted high order derivatives. It is shown that depending on the ratio between the "virtual" fragility in the high temperature dynamic domain (m(high)) and the "real" fragility at T(g) (the low temperature dynamic domain, m = m(low)) glass formers can be splitted into two groups related to f < 1 and f > 1, (f = m(high)∕m(low)). The link of this phenomenon to the ratio between the apparent enthalpy and activation energy as well as the behavior of the configurational entropy is indicated.

Submucosal gland secretions in airways from cystic fibrosis patients have normal [Na+] and pH but elevated viscosity

Fluid and macromolecule secretion by submucosal glands in mammalian airways is believed to be important in normal airway physiology and in the pathophysiology of cystic fibrosis (CF). An in situ fluorescence method was applied to measure the ionic composition and viscosity of freshly secreted fluid from airway glands. Fragments of human large airways obtained at the time of lung transplantation were mounted in a humidified perfusion chamber and the mucosal surface was covered by a thin layer of oil. Individual droplets of secreted fluid were microinjected with fluorescent indicators for measurement of [Na+], [Cl−], and pH by ratio imaging fluorescence microscopy and viscosity by fluorescence recovery after photobleaching. After carbachol stimulation, 0.1–0.5 μl of fluid accumulated in spherical droplets at gland orifices in ≈3–5 min. In gland fluid from normal human airways, [Na+] was 94 ± 8 mM, [Cl−] was 92 ± 12 mM, and pH was 6.97 ± 0.06 (SE, n = 7 humans, more than five glands studied per sample). Apparent fluid viscosity was 2.7 ± 0.3-fold greater than that of saline. Neither [Na+] nor pH differed in gland fluid from CF airways, but viscosity was significantly elevated by ≈2-fold compared to normal airways. These results represent the first direct measurements of ionic composition and viscosity in uncontaminated human gland secretions and indicate similar [Na+], [Cl−], and pH to that in the airway surface liquid. The elevated gland fluid viscosity in CF may be an important factor promoting bacterial colonization and airway disease.