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.

Gas-Phase Acylium Ion Transfer Reactions Mediated by a Proton Shuttle Mechanism

The mechanism and the energy profile of the gas-phase reaction that mimics esterification under acidic conditions have been investigated at different levels of theory. These reactions are known to proceed with rate constants close to the collision limit in the gas-phase and questions have been raised as to whether the typical addition-elimination mechanism via a tetrahedral intermediate can explain the ease of these processes. Because these reactions are common to many organic and biochemical processes it is important to understand the intrinsic reactivity of these systems. Our calculations at different levels of theory reveal that a stepwise mechanism via a tetrahedral species is characterized by energy barriers that are inconsistent with the experimental results. For the thermoneutral exchange between protonated acetic acid and water and the exothermic reaction of protonated acetic acid and methanol our calculations show that these reactions proceed initially by a proton shuttle between the carbonyl oxygen and the hydroxy oxygen of acetic acid mediated by water, or methanol, followed by displacement at the acylium ion center. These findings suggest that the reactions in the gas-phase should be viewed as an acylium ion transfer reaction. (C) 2010 Wiley Periodicals, Inc. Int J Quantum Chem 111: 1596-1606, 2011

Molecular modeling and UV-vis spectroscopic studies on the mechanism of action of reversed chloroquine (RCQ)

Reversed chloroquine (RCQ) is a multiple ligand compound active against chloroquine-sensitive and resistant falciparum malaria. It is composed by a 4-aminoquinoline moiety (like that present in chloroquine (CQ)) joined to imipramine (IMP), a modulating agent that also showed intrinsic antiplasmodial activity against Brazilian Plasmodium falciparum isolates resistant to CQ. Molecular modeling and ultraviolet-visible spectroscopy (UV-vis) studies strongly suggest that the interaction between RCQ and heme is predominant through the quinoline moiety in a mechanism of action similar to that observed for CQ. (C) 2010 Elsevier Ltd. All rights reserved.

In Situ Infrared (FTIR) Study of the Mechanism of the Borohydride Oxidation Reaction on Smooth Pt Electrode

Although Pt has been thoroughly studied regarding its activity for the borohydride oxidation reaction (BOR), the BOR mechanism at Pt remains unclear: Depending on the applied potential, spontaneous BH(4)(-) hydrolysis can compete with the direct BOR. The goal of the present work is to provide more insight into the behavior of smooth Pt electrodes toward the BOR, by coupling in situ infrared reflectance spectroscopy with electrochemistry. The measurements were performed on a Pt electrode in 1 M NaOH/1 M NaBH(4), so as to detect the reaction intermediate species generated as a function of the applied potential. Several bands were monitored in the B-H ((v) over bar approximate to 1180, 1080, and 972 cm(-1)) and B-O ((v) over bar = 1325 and similar to 1425 cm(-1)) bond regions upon increased electrode polarization. These absorption bands, which appear sequentially and were already detected for similar measurements on Au electrodes, are assigned to BH(3), BH(2), and BO(2)(-) species. In light of these experimental data and previous results obtained in our group for Pt- or Au-based electrodes, possible initial elementary steps of the BOR on platinum electrodes are proposed and discussed according to the relevant literature data.

Investigation of the CO tolerance mechanism at several Pt-based bimetallic anode electrocatalysts in a PEM fuel cell

The electrocatalysis of CO tolerance of Pt/C, PtRu/C, PtFe/C, PtMo/C, and PtW/C at a PEM fuel cell anode has been investigated using single cell polarization and online electrochemical mass spectrometry (EMS) measurements, and cyclic voltammetry, X-ray diffraction (XRD), in situ X-ray absorption near edge structure (XANES) analyses of the electrocatalysts. For all bimetallic electrocatalysts, which presented higher CO tolerance, EMS results have shown that the production of CO(2) start at lower hydrogen electrode overpotentials as compared to Pt/C, confirming the occurrence of the so-called bifunctional mechanism. On the other hand, XANES results indicate an increase in the Pt 5d-band vacancies for the bimetallic catalysts, particulary for PtFe/C, this leading to a weakening of the Pt-CO bond, helping to increase the CO tolerance (the so-called electronic effect). For PtMo/C and PtRu/C supplied with H(2)/CO, the formation of CO(2) is observed even when the cell is at open circuit, confirming some elimination of CO by a chemical process, most probably the water gas shift reaction. (C) 2008 Elsevier Ltd. All rights reserved.

The Molecular Chaperone Hsp70 Family Members Function by a Bidirectional Heterotrophic Allosteric Mechanism

The Hsp70 family is one of the most important and conserved molecular chaperone families. It is well documented that Hsp70 family members assist many cellular processes involving protein quality control, as follows: protein folding, transport through membranes, protein degradation, escape from aggregation, intracellular signaling, among several others. The Hsp70 proteins act as a cellular pivot capable of receiving and distributing substrates among the other molecular chaperone families. Despite the high identity of the Hsp70 proteins, there are several homologue Hsp70 members that do not have the same role in the cell, which allow them to develop and participate in such large number of activities. The Hsp70 proteins are composed of two main domains: one that binds ATP and hydrolyses it to ADP and another which directly interacts with substrates. These domains present bidirectional heterotrophic allosteric regulation allowing a fine regulated cycle of substrate binding and release. The general mechanism of the Hsp70s cycle is under the control of ATP hydrolysis that modulates the low (ATP-bound state) and high (ADP-bound state) affinity states of Hsp70 for substrates. An important feature of the Hsp70s cycle is that they have several co-chaperones that modulate their cycle and that can also interact and select substrates. Here, we review some known details of the bidirectional heterotrophic allosteric mechanism and other important features for Hsp70s regulating cycle and function.

Nuclear magnetic resonance water relaxation time changes in bananas during ripening: a new mechanism

BACKGROUND: Nuclear magnetic resonance studies of banana fragments during ripening show an increase on the water transverse relaxation time (T(2)) and a decrease in water self-diffusion coefficient (D). As T(2) and D are normally directly correlated, we studied these two properties in intact bananas during ripening, in an attempt to rule out the effect of injury on the apparent discrepancies in the behavior of T(2) and D. RESULTS: The results show that injury in bananas causes a decrease in T(2) of the water in vacuoles (T(2vac)). They also show that T(2vac) increased and D decreased during ripening, ruling out the injury effect. To explain the apparent discrepancies, we propose a new hypothesis for the increase in T(2) values, based on the reduction of Fe(3+) ions to Fe(2+) by galacturonic acid, produced by the hydrolysis of pectin and a decrease in internal oxygen concentration during ripening. CONCLUSION: As injury alters T(2) values it is necessary to use intact bananas to study relaxation times during ripening. The novel interpretation for the increase in T(2vac) based on reduction of Fe(+3) and O(2) concentration is an alternative mechanism to that based on the hydrolysis of starch in amyloplasts. (C) 2010 Society of Chemical Industry

Formation Mechanism via a Heterocoagulation Approach of FePt Nanoparticles Using the Modified Polyol Process

Herein, we report a new approach of an FePt nanoparticle formation mechanism studying the evolution of particle size and composition during the synthesis using the modified polyol process. One of the factors limiting their application in ultra-high-density magnetic storage media is the particle-to-particle composition, which affects the A1-to-L1(0) transformation as well as their magnetic properties. There are many controversies in the literature concerning the mechanism of the FePt formation, which seems to be the key to understanding the compositional chemical distribution. Our results convincingly show that, initially, Pt nuclei are formed due to reduction of Pt(acac)(2) by the diol, followed by heterocoagulation of Fe cluster species formed from Fe(acac)(3) thermal decomposition onto the Pt nuclei. Complete reduction of heterocoagulated iron species seems to involve a CO-spillover process, in which the Pt nuclei surface acts as a heterogeneous catalyst, leading to the improvement of the single-particle composition control and allowing a much narrower compositional distribution. Our results show significant decreases in the particle-to-particle composition range, improving the A1-to-L1(0) phase transformation and, consequently, the magnetic properties when compared with other reported methods.

Wear of coated and uncoated PCBN cutting tool used in turning and milling

This licentiate thesis has the main focus on evaluation of the wear of coated and uncoated polycrystalline cubic boron nitride cutting tool used in cutting operations against hardened steel. And to exam the surface finish and integrity of the work material used. Harder work material, higher cutting speed and cost reductions result in the development of harder and more wear resistance cutting tools. Although PCBN cutting tools have been used in over 30 years, little work have been done on PVD coated PCBN cutting tools. Therefore hard turning and hard milling experiments with PVD coated and uncoated cutting tools have been performed and evaluated. The coatings used in the present study are TiSiN and TiAlN. The wear scar and surface integrity have been examined with help of several different characterization techniques, for example scanning electron microscopy and Auger electron spectroscopy.   The results showed that the PCBN cutting tools used displayed crater wear, flank wear and edge micro chipping. While the influence of the coating on the crater and flank wear was very small and the coating showed a high tendency to spalling. Scratch testing of coated PCBN showed that, the TiAlN coating resulted in major adhesive fractures. This displays the importance of understanding the effect of different types of lapping/grinding processes in the pre-treatment of hard and super hard substrate materials and the amount and type of damage that they can create. For the cutting tools used in turning, patches of a adhered layer, mainly consisting of FexOy were shown at both the crater and flank. And for the cutting tools used in milling a tribofilm consisting of SixOy covered the crater. A combination of tribochemical reactions, adhesive wear and mild abrasive wear is believed to control the flank and crater wear of the PCBN cutting tools. On a microscopic scale the difference phases of the PCBN cutting tool used in turning showed different wear characteristics. The machined surface of the work material showed a smooth surface with a Ra-value in the range of 100-200 nm for the turned surface and 100-150 nm for the milled surface. With increasing crater and flank wear in combination with edge chipping the machined surface becomes rougher and showed a higher Ra-value. For the cutting tools used in milling the tendency to micro edge chipping was significant higher when milling the tools steels showing a higher hard phase content and a lower heat conductivity resulting in higher mechanical and thermal stresses at the cutting edge.

Towards a Methodology for Coordination Mechanism Selection in Open Systems

Agent-oriented software engineering (AOSE) is a promising approach to developing applications for dynamic open systems. If well developed, these applications can be opportunistic, taking advantage of services implemented by other developers at appropriate times. However, methodologies are needed to aid the development of systems that are both flexible enough to be opportunistic and tightly defined by the application requirements. In this paper, we investigate how developers can choose the coordination mechanisms of agents so that the agents will best fulfil application requirements in an open system.

Adaptive device with underlying mechanism defined by a programming language

An adaptive device is made up of an underlying mechanism, for instance, an automaton, a grammar, a decision tree, etc., to which is added an adaptive mechanism, responsible for allowing a dynamic modification in the structure of the underlying mechanism. This article aims to investigate if a programming language can be used as an underlying mechanism of an adaptive device, resulting in an adaptive language.

Mechanism of Muscle Vibrations During Stimulated and Voluntary Isometric Contractions of Mammalian Skeletal Muscle

When a muscle contracts it produces vibrations. The origin of these vibrations is not known in detail. The purpose of this study was to determine the mechanism associated with muscle vibrations. Mechanisms which have been proposed in the literature were described as theories (cross-bridge cycling, vibrating string and unfused motor unit theories). Specific predictions were derived from each theory, and tested in three conceptually different studies. In the first study, the influence of recruitment strategies of motor units (MUs) on the vibromyographic (VMG) signal was studied in the in-situ cat soleus using electrical stimulation of the soleus nerve. VMG signals increased with increasing recruitment and decreased with increasing firing rates of MUs. Similar results were obtained for the human rectus femoris (RF) muscle using percutaneous electrical stimulation of the femoral nerve. The influence of MU activation on muscle vibrations was studied in RF by analyzing VMG signals at different percentages (0-100%) of the maximal voluntary contraction (MVC). In our second study, we tested the effects of changing the material properties of the in-situ cat soleus (through muscle length changes) on the VMG signal. The magnitude of the VMG signal was higher for intermediate muscle lengths compared to the longest and the shortest muscle lengths. The decreased magnitude of the VMG signal at the longest and at the shortest muscle lengths was associated with increased passive stiffness and with decreased force transients during unfused contractions, respectively. In the third study, the effect of fatigue on muscle vibrations was studied in human RF and vastus lateralis (VL) musc1es during isometric voluntary contractions at a leveI of 70% MVC. A decrease in the VMG signal magnitude was observed in RF (presumably due to derecruitment of MUs) and an increase in VL (probably related to the enhancement of physiological tremor, which may have occurred predorninantly in a mediolateral direction) with fatigue. The unfused MU theory, which is based on the idea that force transients produced by MUs during unfused tetanic contraction is the mechanism for muscle vibrations, was supported by the results obtained in the above three studies.