Identification of lift-off mechanism failure for salt drill-in drilling fluid containing polymer filter cake through adsorption/desorption studies

Drilling fluid`s contact with the productive zone of horizontal or complex wells can reduce well productivity by fluid invasion in the borehole wall. Salted drilling drill-in fluid containing polymers has often been applied in horizontal or complex petroleum wells in the poorly consolidated sandstone reservoirs of the Campos basin, Rio de Janeiro, Brazil. This fluid usually consists of natural polymers such as starch and xanthan gum, which are deposited as a filter cake on the wellbore wall during the drilling. Therefore, the identification of a lift-off mechanism failure, which can be detachment or blistering and pinholing, will enable formulation improvements. increasing the chances of success during filter cake removal in open hole operations. Likewise, knowledge of drill-in drilling fluid adsorption/desorption onto sand can help understand the filter cake-rock adhesion mechanism and consequently filter cake lift-off mechanism failures. The present study aimed to identify the lift-off failure mechanism for this type of fluid filter cake studying adsorption/desorption onto SiO(2) using solutions of natural polymers, lubricants, besides the fluid itself. Ellipsometry was employed to measure this process. The adsorption/desorption studies showed that the adsorbed layer of drilling fluid onto the walls of the rock pores is made up of clusters of polymers, linked by hydrogen bonds, which results in a force of lower cohesion compared to the electrostatic interaction between silica and polymers. Consequently, it was found that the most probable filter cake failure mechanism is rupture (blistering and pinholing), which results in the formation of ducts within the filter cake. (C) 2009 Elsevier B.V. All rights reserved.

Flocculation, filtration and selective flocculation studies on haematite ore fines using starch

The flocculation and filtration characteristics of typical Indian iron ore fines have been studied using starch as flocculant in the presence of an inorganic electrolyte, namely calcium chloride. The effect of various parameters such as pH, starch and calcium chloride concentrations and pulp density on the settling and filtration rates, turbidity of the supernatant and on residual starch and calcium ion concentrates has been investigated through a statistical design and analysis approach and subsequently optimised on a laboratory scale. The adsorption mechanisms of starch onto haematite have been elucidated through adsorption density measurements, infrared and X-ray photoelectron spectroscopic techniques. The rheological property of the polymer solutions of relevance to flocculations has also been investigated. Further, the role of metal ion-starch interactions in the bulk solution, has been studied. In order to understand the nature of polymer adsorption at the double-layer, electrokinetic studies have been carried out with the iron ore mineral samples using starch and calcium chloride. Based on the above findings, selective floculaation tests on artificial mixtures of iron ore minerals have been carried out to determine the separation efficiencies from the view point of alumina and silica removal from haematite as well as the control of alumina: silica ratio in Indian iron ores.

Kontrollierte Fällung von amorphem Calciumcarbonat durch homogene Carbonatfreisetzung

In der Vergangenheit haben Untersuchung an biologischen und Modell-Systemen gezeigt, dass amorphes Calciumcarbonat als instabiles Zwischenprodukt bei der Bildung kristalliner Strukturen aus CaCO3 auftritt. Über dessen Rolle im Fällungsprozess von CaCO3 ist nicht viel bekannt und es wird davon ausgegangen, dass es als CaCO3-Speicher für die nachfolgenden kristallinen Produkte dient. Der genaue Reaktionsablauf, der zur Bildung von amorphem Calciumcarbonat (ACC) führt, ist nicht bekannt. Ziel dieser Arbeit war die Entwicklung einer Fällungstechnik, die die Beobachtung der Bildungskinetik von ACC durch Lichtstreuung ermöglicht. In Fällungsexperimenten wird gezeigt, dass die Fällung unter nicht-turbulenten Bedingungen zur Bildung von amorphem Calciumcarbonat führt. Hinsichtlich der Basen- und Alkylcarbonatmenge, die äquivalent oder im Überschuss zur Calciumionenkonzentration eingesetzt wird, entstehen zwei verschiedene Fällungsprodukte. In Bezug auf ihre chemische Zusammensetzung, thermische und mechanische Eigenschaften werden diese charakterisiert. In beiden Fällen wird ein amorphes CaCO3 mit einem Wassergehalt von 0,5 mol/L pro Mol CaCO3 erhalten. Die in situ Generierung von Carbonat führt zur Bildung von sphärischem amorphem Calciumcarbonat, das eine gewisse Tendenz zur Koazervation zeigt. Die bei gleichem Reaktionsumsatz beobachtete Temperaturabhängigkeit des Partikelradius konnten wir unter Annahme einer Mischungslücke mit unterer kritischer Mischungstemperatur interpretieren. Für die Bildung von amorphem Calciumcarbonat schlagen wir daher einen Mechanismus via binodaler flüssig-flüssig Entmischung vor. Nach einer kurzen Keimbildungsperiode können flüssige Tröpfchen aus wasserhaltigem CaCO3 wachsen und dann infolge von stetigem Wasserverlust glasartig erstarren und so amorphes Calciumcarbonat bilden. Bekräftigt wird dieses Modell durch die Wachstumskinetik, die mittels Lichtstreuung und SAXS verfolgt worden ist. In den Fällungsversuchen sind je nach Reaktionsbedingungen, zwei verschiedene Zeitgesetze des Teilchenwachstums erkennbar: Bei schneller Freisetzung von Carbonat liegt ein parabolischer Verlauf des Radienwachstums vor; hingegen führt eine langsame Freisetzung von Carbonat zu einem linearen Wachstum der Radien. Diese Abhängigkeiten lassen sich im Rahmen der bekannten Kinetik einer flüssig-flüssig Entmischung deuten. Ferner wird der Einfluss von doppelthydrophilen Blockcopolymeren (PEO-PMAA) auf die Teilchengröße und die Kinetik der Bildung von amorphem Calciumcarbonat untersucht. Zum Einsatz kommen zwei verschiedene Blockcopolymere, die sich in der Länge des PEO-Blocks unterscheiden. Im Fällungsexperiment führt das in sehr kleinen Konzentrationen vorliegende Blockcopolymere zur Stabilisierung von kleineren Partikeln. Das Blockcopolymer mit der längeren PEO-Einheit weist eine größere Effizienz auf. Die Ergebnisse lassen sich durch Annahme von Adsorption des Polymers an der Oberfläche interpretieren. Der Einfluss der doppelthydrophilen Blockcopolymere auf die Bildung von ACC deutet darauf, dass amorphes Calciumcarbonat eine komplexere Rolle als lediglich die eines Calciumcarbonatspeichers für das spätere Wachstum kristalliner Produkte einnimmt. Für die Wirkung von Polymerzusätzen muss somit nicht nur die Wechselwirkung mit den gegen Ende gebildeten Kristalle betrachtet werden, sondern auch der Einfluss, den das Polymer auf die Bildung des amorphen Calciumcarbonats hat. Die hier neu entwickelte Methode bietet die Möglichkeit, auch für komplexere Polymere, wie z.B. extrahierte Proteine, den Einfluss auf die Bildung der amorphen Vorstufe zu untersuchen.

Dynamic interfacial tension of aqueous solutions of PVAAs and its role in liquid-liquid dispersion stabilization

In liquid-liquid dispersion systems, the dynamic change of the interfacial properties between the two immiscible liquids plays an important role in both the emulsification process and emulsion stabilization. In this paper, experimentally measured dynamic interfacial tensions of 1-chlorobutane in the aqueous solutions of various random copolymers of polyvinyl acetate and polyvinyl alcohol (PVAA) are presented. Theoretical analyses on these results suggest that the adsorption of the polymer molecules is controlled neither by the bulk diffusion process nor the activation energy barrier for the adsorption but the conformation of polymer molecules. Based on the concept of critical concentration of condensation for polymer adsorption, as well as the observation that the rate at which the dynamic interfacial tension changes does not correlate to the PVAA's ability to stabilize a single drop, it is postulated that the main stabilization mechanism for the PVAAs is by steric hindrance, not the Gibbs-Marangoni effect offered by the small molecule surfactants.

Ocular biotribology and contact lens lubrication mechanisms

The work described in this thesis is concerned with mechanisms of contact lens lubrication. There are three major driving forces in contact lens design and development; cost, convenience, and comfort. Lubrication, as reflected in the coefficient of friction, is becoming recognised as one of the major factors affecting the comfort of the current generation of contact lenses, which have benefited from several decades of design and production improvements. This work started with the study of the in-eye release of soluble macromolecules from a contact lens matrix. The vehicle for the study was the family of CIBA Vision Focus® DAILIES® daily disposable contact lenses which is based on polyvinyl alcohol (PVA). The effective release of linear soluble PVA from DAILIES on the surface of the lens was shown to be beneficial in terms of patient comfort. There was a need to develop a novel characterisation technique in order to study these effects at surfaces; this led to the study of a novel tribological technique, which allowed the friction coefficients of different types of contact lenses to be measured reproducibly at genuinely low values. The tribometer needed the ability to accommodate the following features: (a) an approximation to eye lid load, (b) both new and ex-vivo lenses, (c) variations in substrate, (d) different ocular lubricants (including tears). The tribometer and measuring technique developed in this way was used to examine the surface friction and lubrication mechanisms of two different types of contact lenses: daily disposables and silicone hydrogels. The results from the tribometer in terms of both mean friction coefficient and the friction profiles obtained allowed various mechanisms used for surface enhancement now seen in the daily disposable contact lens sector to be evaluated. The three major methods used are: release of soluble macromolecules (such as PVA) from the lens matrix, irreversible surface binding of a macromolecule (such as polyvinyl pyrrolidone) by charge transfer and the simple polymer adsorption (e.g. Pluoronic) at the lens surface. The tribological technique was also used to examine the trends in the development of silicone hydrogel contact lenses. The focus of the principles in the design of silicone hydrogels has now shifted from oxygen permeability, to the improvement of surface properties. Presently, tribological studies reflect the most effective in vitro method of surface evaluation in relation to the in-eye comfort.

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

Adsorption of anionic dyes on a reversibly swelling cationic superabsorbent polymer

A cationic monomer 2-(methacryloyloxy)ethyl]trimethylammonium chloride was polymerized using N,N'-methylenebisacrylamide as the crosslinker to obtain a cationic superabsorbent polymer (SAP). This SAP was characterized by Fourier transform-infrared spectroscopy, and the equilibrium swelling capacity was determined by swelling in water. The SAP was subjected to cyclic swelling/deswelling in water and NaCl solution. The conductivity of the swelling medium was monitored during the swelling/deswelling and was related to the swelling/deswelling characteristics of the SAP. The adsorption of five anionic dyes of different classes on the SAP was carried out and was found to follow the first-order kinetics. The Langmuir adsorption isotherms were found to fit the equilibrium adsorption data. The dye adsorption capacity of the SAP synthesized in this study was higher than that obtained for other hydrogels reported in the literature. (c) 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013

ELECTROACTIVE COATINGS OF DICYANO-BIS(1,10-PHENANTHROLINE)IRON(II) ATTACHED TO NAFION POLYMER FILM-MODIFIED ELECTRODES VIA ADSORPTION

A dicyano-bis(1,10-phenanthroline)iron(II) modified elecrode was prepared. The voltammetric and the spectroelectrochemical behavior of this electrode were investigated. The influence of pH and the amount of Nafion and dicyano-bis(1,10-phenanthroline) iron(II) (DBPI) used in the electrode preparation on the electrochemical behavior is presented.

Adsorption, lubrication, and wear of lubricin on model surfaces : polymer brush-like behavior of a glycoprotein

Using a surface force apparatus, we have measured the normal and friction forces between layers of the human glycoprotein lubricin, the major boundary lubricant in articular joints, adsorbed from buffered saline solution on various hydrophilic and hydrophobic surfaces: i), negatively charged mica, ii), positively charged poly-lysine and aminothiol, and iii), hydrophobic alkanethiol monolayers. On all these surfaces lubricin forms dense adsorbed layers of thickness 60–100 nm. The normal force between two surfaces is always repulsive and resembles the steric entropic force measured between layers of end-grafted polymer brushes. This is the microscopic mechanism behind the antiadhesive properties showed by lubricin in clinical tests. For pressures up to ∼6 atm, lubricin lubricates hydrophilic surfaces, in particular negatively charged mica (friction coefficient μ = 0.02–0.04), much better than hydrophobic surfaces (μ > 0.3). At higher pressures, the friction coefficient is higher (μ > 0.2) for all surfaces considered and the lubricin layers rearrange under shear. However, the glycoprotein still protects the underlying substrate from damage up to much higher pressures. These results support recent suggestions that boundary lubrication and wear protection in articular joints are due to the presence of a biological polyelectrolyte on the cartilage surfaces.

Surface charge of polymer coated SPIONs influences the serum protein adsorption, colloidal stability and subsequent cell interaction in vitro

It is known that the nanoparticle-cell interaction strongly depends on the physicochemical properties of the investigated particles. In addition, medium density and viscosity influence the colloidal behaviour of nanoparticles. Here, we show how nanoparticle-protein interactions are related to the particular physicochemical characteristics of the particles, such as their colloidal stability, and how this significantly influences the subsequent nanoparticle-cell interaction in vitro. Therefore, different surface charged superparamagnetic iron oxide nanoparticles were synthesized and characterized. Similar adsorbed protein profiles were identified following incubation in supplemented cell culture media, although cellular uptake varied significantly between the different particles. However, positively charged nanoparticles displayed a significantly lower colloidal stability than neutral and negatively charged particles while showing higher non-sedimentation driven cell-internalization in vitro without any significant cytotoxic effects. The results of this study strongly indicate therefore that an understanding of the aggregation state of NPs in biological fluids is crucial in regards to their biological interaction(s).

Performance of R-N(R′)-R″ functionalised poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) monolithic sorbent for plasmid DNA adsorption

High-throughput plasmid DNA (pDNA) manufacture is obstructed predominantly by the performance of conventional stationary phases. For this reason, the search for new materials for fast chromatographic separation of pDNA is ongoing. A poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) (GMA-EGDMA) monolithic material was synthesised via a thermal-free radical reaction, functionalised with different amino groups from urea, 2-chloro-N,N-diethylethylamine hydrochloride (DEAE-Cl) and ammonia in order to investigate their plasmid adsorption capacities. Physical characterisation of the monolithic polymer showed a macroporous polymer having a unimodal pore size distribution pivoted at 600 nm. Chromatographic characterisation of the functionalised polymers using pUC19 plasmid isolated from E. coli DH5α-pUC19 showed a maximum plasmid adsorption capacity of 18.73 mg pDNA/mL with a dissociation constant (KD) of 0.11 mg/mL for GMA-EGDMA/DEAE-Cl polymer. Studies on ligand leaching and degradation demonstrated the stability of GMA-EGDMA/DEAE-Cl after the functionalised polymers were contacted with 1.0 M NaOH, which is a model reagent for most 'cleaning in place' (CIP) systems. However, it is the economic advantage of an adsorbent material that makes it so attractive for commercial purification purposes. Economic evaluation of the performance of the functionalised polymers on the grounds of polymer cost (PC)/mg pDNA retained endorsed the suitability of GMA-EGDMA/DEAE-Cl polymer.

Adsorption and Desorption Kinetics of Anionic Dyes on Doped Polyaniline

In this study, we report an approach for the adsorption and desorption of anionic (sulfonated) dyes from aqueous solution by doped polyaniline. In this study, we have synthesized PANI with two dopants, namely, p-toluenesulfonic acid (PTSA) and camphorsulfonic acid (CSA), and used these to adsorb various dyes. It was found that the doped PANI selectively adsorbs anionic dyes and does not adsorb cationic dyes. The adsorption of anionic dyes causes the variation in electrical conductivity of PANI, indicating its potential as a conductometric sensor for these dyes at very low concentration. The adsorbed dyes were desorbed from the polymer by using a basic aqueous solution. The adsorption and desorption kinetics of the dye in the presence of doped PANI were also determined.

Studies on adsorption of guar gum onto biotite mica

The interaction of guar gum with biotite mica has been investigated through adsorption, flotation and electrokinetic measurements. The adsorption densities of guar gum increase with increase of pH and the isotherms exhibit Langmuirian behaviour. Pretreatment of mica with a complexing agent such as EDTA results in a decrease in the adsorption density, highlighting the contribution of metal ions to the adsorption process. An increase in the surface face-to-edge ratio lends to an increase in the adsorption density. The flotation recoveries decrease as a function of pH, complementing the adsorption results. However, polymer depressant ability is reduced in the case of EDTA treated mica, consequent to reduction of metallic sites. Electrokinetic measurements portray conformational rearrangements of macromolecules with the loading, resulting in the shift of the shear plane, further away from the interface. Dissolution experiments indicate release of metal ions from mica, while co-precipitation tests confirm polymer-metal ion interaction in the bulk solution. The adsorption process is governed by hydrogen bonding as well as chemical interaction between guar gum and the surface metal hydroxide groups of mica. (C) 1997 Published by Elsevier Science Ltd.

Injection-molded high-density polyethylene-hydroxyapatite-aluminum oxide hybrid composites for hard-tissue replacement: Mechanical, biological, and protein adsorption behavior

In this article, we report the mechanical and biocompatibility properties of injection-molded high-density polyethylene (HDPE) composites reinforced with 40 wt % ceramic filler [hydroxyapatite (HA) and/or Al2O3] and 2 wt % titanate as a coupling agent. The mechanical property measurements revealed that a combination of a maximum tensile strength of 18.7 MPa and a maximum tensile modulus of about 855 MPa could be achieved with the injection-molded HDPE20 wt % HA20 wt % Al2O3 composites. For the same composite composition, the maximum compression strength was determined to be 71.6 MPa and the compression modulus was about 660 MPa. The fractrography study revealed the uniform distribution of ceramic fillers in the semicrystalline HDPE matrix. The cytocompatibility study with osteoblast-like SaOS2 cells confirmed extensive cell adhesion and proliferation on the injection-molded HDPE20 wt % HA20 wt % Al2O3 composites. The cell viability analysis with the 3(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay revealed a statistically significant difference between the injection-molded HDPE20 wt % HA20 wt % Al2O3 composites and sintered HA for various culture durations of upto 7 days. The difference in cytocompatibility properties among the biocomposites is explained in terms of the difference in the protein absorption behavior. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012