WO2011070408A2 - Capteur électrochimique - Google Patents

Capteur électrochimique Download PDF

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Publication number
WO2011070408A2
WO2011070408A2 PCT/IB2010/002641 IB2010002641W WO2011070408A2 WO 2011070408 A2 WO2011070408 A2 WO 2011070408A2 IB 2010002641 W IB2010002641 W IB 2010002641W WO 2011070408 A2 WO2011070408 A2 WO 2011070408A2
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WO
WIPO (PCT)
Prior art keywords
electrochemical sensor
species
sensor according
polymer
encapsulated
Prior art date
Application number
PCT/IB2010/002641
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English (en)
Other versions
WO2011070408A3 (fr
Inventor
Valerie Lafitte
Nathan Lawrence
Original Assignee
Schlumberger Technology B.V.
Schlumberger Holdings Limited
Schlumberger Canada Limited
Services Petroliers Schlumberger
Prad Research And Development Limited
Schlumberger Seaco, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Schlumberger Technology B.V., Schlumberger Holdings Limited, Schlumberger Canada Limited, Services Petroliers Schlumberger, Prad Research And Development Limited, Schlumberger Seaco, Inc. filed Critical Schlumberger Technology B.V.
Priority to EP10835558A priority Critical patent/EP2510344A2/fr
Priority to US13/502,718 priority patent/US9377434B2/en
Publication of WO2011070408A2 publication Critical patent/WO2011070408A2/fr
Publication of WO2011070408A3 publication Critical patent/WO2011070408A3/fr

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/333—Ion-selective electrodes or membranes
    • G01N27/3335—Ion-selective electrodes or membranes the membrane containing at least one organic component
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/18—Water

Definitions

  • This invention relates to electrochemical sensors for determining
  • Fields in which the invention may be utilised include, although are not restricted to, the analysis of aqueous fluid at the Earth's surface, including aqueous fluid which is about to be pumped to a subterranean location and also the analysis of subterranean fluids which may be in an aquifer, in a hydrocarbon reservoir or in a carbon dioxide sequestration facility.
  • a particularly challenging context is the analysis of downhole fluids, that is to say fluids encountered at underground locations accessed by a wellbore.
  • analysis of downhole fluids can be an important aspect of determining the quality and economic value of a hydrocarbon formation.
  • Knowledge of downhole formation (produced) water chemistry can be applied to save costs and increase production at all stages of oil and gas exploration and production. Measurements obtained downhole can be important for a number of key processes of hydrocarbon production, including:
  • pH -log[concentration of H + ]
  • C0 2 C0 2
  • H 2 S may change significantly while tripping to the surface. The change occurs mainly due to a difference in temperature and pressure between downhole and surface environment. In case of samples taken downhole, this change may also happen due to degassing of a sample (seal failure), mineral precipitation in a sampling bottle, and (especially in case of H 2 S) - a chemical reaction with the sampling chamber.
  • pH, H 2 S, and C0 2 are among the most critical parameters for corrosion and scale assessment. Consequently it is of considerable importance to determine their downhole values and there have been a number of proposals for analytical sensors to be used downhole.
  • An electrochemical sensor may then comprise electrodes and one or more electrochemically active species able to undergo electrochemical reaction in response to electrical potential applied to the electrodes, where that electrochemical reaction is modified by the presence of an analyte species.
  • An electrochemical pH sensor is disclosed in US 5223117, where the sensor was intended for use in a number of applications including biomedical sensing. Two electrochemically active species were attached to a gold substrate which provided an electrode. Both of these attached species were redox systems. One of the attached species was hydroquinone whose redox potential is sensitive to the
  • sensors intended to be suitable for use downhole, incorporating electrodes and electrochemically active species are described in WO 2005/066618 and WO 2007/034131. These documents envisage immobilizing redox systems on a conductive carbon substrate. In the latter document, two redox systems were incorporated chemically into a copolymer made from vinyl ferrocene and vinyl anthracene so that the two redox systems were present as side chains from the hydrocarbon backbone of the polymer. This fixed their proportions relative to each other. However, problems have been found to arise when redox systems are attached to macromolecules. The vast majority of polymers have transition temperatures above which the physical properties of the polymer alter. There is a loss of physical stability, which can be profoundly detrimental to the ability of a polymer to act as a sensor.
  • the present invention is concerned with an electrochemical analytical procedure involving a chemical which participates in electrochemical reaction, characterized in that the chemical is encapsulated with polymer particles.
  • the present invention provides an electrochemical sensor comprising at least one electrode and one or more electrochemically active species able to undergo electrochemical reaction in response to electrical potential applied to the electrode(s), said reaction being modified by the presence of an analyte species, characterised in that at least one said electrochemically active species is encapsulated within polymer particles.
  • the invention also includes equipment such as a wireline tool, incorporating such a sensor. This equipment may be configured and intended for use downhole.
  • Electrodes which are required when carrying out the electrochemical reaction may be provided separately, or may be incorporated into the sensor.
  • the polymer particles in which the encapsulated electrochemically active species is immobilized could be free to move about within a quantity of electrolyte in contact with the electrodes. However, it is preferred that they are immobilized relative to the sensor. So the sensor may comprise a solid substrate, which may be a body part of the sensor, to which the encapsulated electrochemically active species is
  • the sensor may provide an electrically insulating solid substrate to which the encapsulated species is immobilised, with the sensor having a conductive electrode in proximity to the encapsulated species.
  • the sensor may have an electrode which is formed by a conductive solid body on which at least one encapsulated
  • electrochemically active species is immobilised.
  • An electrode may be provided by a solid, electrically conductive substrate on which at least one encapsulated electrochemically active species is immobilised.
  • This invention is not limited to a specific electrochemical reaction or category of reaction.
  • the electrochemical change may be oxidation and/or reduction and such a redox reaction may be a change in oxidation state brought about by electron transfer.
  • the one or more electrochemically active species may therefore be one or more redox systems, i.e. molecules capable of undergoing oxidation and reduction reactions, preferably reversible oxidation and reduction reactions, brought about through application of electrical potential.
  • the encapsulating polymer may be chosen such that it incorporates aromatic groups and/or heteroatoms which facilitate electron transfer to and from the encapsulated species. [0017] It is desirable that the encapsulating polymer is at least partially amorphous and is below its glass transition temperature when it is at a location, notably at a subterranean location, where measurements are to be made. Accordingly, in a further aspect, this invention provides a method of measuring an analyte concentration in a fluid, which may be a wellbore fluid, comprising exposing a sensor embodying the invention to the fluid, where the encapsulating polymer in the sensor has a glass transition temperature above the temperature of the fluid.
  • the method will then generally also include operating the sensor by applying electrical potential and observing current flow.
  • Glass transition temperature denoted Tg
  • Tg Glass transition temperature
  • Many polymers have a solid appearance at ambient temperature, but are in fact wholly or partially in an amorphous glassy state.
  • a glass is a liquid which is undercooled (sometimes termed supercooled) significantly below its true melting point and which has an extremely high viscosity. In a glass, most diffusive processes other than the movement of some very small molecules, take place at extremely low rates, such as microns per year.
  • Tg glass transition temperature
  • Tg of the encapsulating polymer is well above ambient temperature at the surface.
  • a Tg of at least 60°C may be preferred, and possibly at least 80°C or even at least 100°C or 120°C.
  • Encapsulation of one material within another in the present case encapsulation of an electrochemically active species within a polymer, can lead to particles in which the said species is distributed within a particle of the polymer, for instance as a plurality of small islands of the electrochemically active species surrounded by a continuous matrix of the polymer.
  • encapsulation can lead to core-shell type particles in which a core of the electrochemically active species is encapsulated within a shell of the polymer.
  • Both core-shell and islands-in-matrix type particles may be used in this invention, although islands-in-matrix type particles may be preferred as giving a higher surface area of the encapsulated electrochemically active species.
  • electrochemically active species can be successfully encapsulated by processes which involve evaporation of solvent from an emulsified phase. Moreover, such processes are repeatable from batch to batch, allow the size of particles to be controlled and give an acceptably narrow distribution of particle size.
  • Hydrophobic electrochemically active species, soluble in organic solvent can be encapsulated within a polymer using a technique comprising steps of (i) dissolving the electrochemically active species and encapsulating polymer in a water-immiscible organic solvent,
  • step (ii) dispersing the resulting solution in an aqueous phase to form an oil-in-water emulsion in which the disperse phase is the solution formed in step (i), (iii) stirring or otherwise agitating that emulsion while causing or allowing
  • Hydrophilic, water-soluble electrochemically active species can be encapsulated by a double emulsion technique. This comprises steps of
  • electrochemically active species to be encapsulated suspended within these droplets, and (iv) stirring or otherwise agitating that emulsion while causing or allowing evaporation of the organic solvent, thereby forming particles in which the electrochemically active species is enclosed by the polymer.
  • the particle size is dependant on factors which include the choice of encapsulating polymer and the initial concentration of polymer in organic solvent, because these factors affect the viscosity of the disperse phase, from which organic solvent evaporates. A higher viscosity of this disperse phase leads to larger disperse droplets which in turn leads to larger particles.
  • the droplet size of the disperse phase (and hence the particle size of the resulting polymer particles enclosing the electrochemically active species) can be controlled through the amount of shear applied to stir or agitate the emulsion while solvent evaporates. So, after choosing the encapsulating polymer and the other features of the composition, the significant parameters influencing particle size are the mixing condition and speed.
  • Particle size distribution may be such that di 0 is not less than 1 micron, and possibly not less than 20 micron while d 90 is not more than 500 micron, possibly not more than 300 micron.
  • a sensor embodying this invention may comprise two or more
  • electrochemically active species with different sensitivities to analyte ions There could example be one redox system which is sensitive to an analyte and a second redox system which is insensitive to that analyte and serves as an internal reference.
  • a combination of two redox systems is anthraquinone as a pH sensitive redox system and ferrocene as a pH-independent reference.
  • Another possibility is that there could be one species sensitive to one analyte and a second, different species sensitive to another analyte: for instance one species sensitive to hydrogen ion concentration, for measuring pH and a second species sensitive to the bisulfide (HS ⁇ ) ion, for measuring hydrogen sulfide concentration.
  • electrochemically active species there is more than one electrochemically active species present, it is possible that they could be encapsulated within separate polymer particles, but it is also possible that the two species could be mixed together and then encapsulated. It is also within the scope of this invention that one electrochemically active species which is present is encapsulated while another is not.
  • the encapsulated electrochemically active species must of course be positioned where it (or they) can participate in electrochemical reaction.
  • the particles of the encapsulated electrochemically active species may be immobilised on an electrically conductive solid body which is the working electrode, with that electrode and at least one other electrode immersed in a conductive solution, which could be an aqueous solution containing dissolved electrolyte.
  • This working electrode should not be chemically degraded by the fluid to which it is exposed.
  • Noble metals have traditionally been used for electrodes, and may possibly be used in this invention, especially if the sensor is to be used to measure pH in a context where hydrogen sulfide is absent.
  • the substrate is provided by elemental carbon, which is not susceptible to attack by sulfides or thiol groups.
  • CNT carbon nanotube
  • SWCNTs Single-walled carbon nanotubes
  • MWCNTs Multi-walled carbon nanotubes
  • Polymer particles may be immobilised on a hard surface by abrasion of the surface followed by rubbing the polymer particles onto the surface and into the surface abrasions.
  • polymer particles with reactive functional groups at a surface might be chemically immobilised onto an electrode.
  • the polymer particles may be mixed with conductive carbon powder, mixed with a liquid to form a paste and the mixture packed into a holder which is part of the sensor and which exposes a surface at which there are both polymer particles and carbon particles.
  • the carbon particles provide the working electrode and there must be an electrical connection to them.
  • An insulating body of the sensor may provide the holder and support an electrical connection to the paste packed into the holder.
  • the sensor might be constructed such that the electrochemical reaction can be followed by voltammetry.
  • the sensor may then constitute at least part of a potentiometric cell with the electrodes and the encapsulated species in contact with the solution.
  • a working electrode also termed a measuring electrode, which may be carbon with the encapsulated electrochemically active species immobilised on it.
  • a counter electrode and there may also be a reference electrode, with the three electrodes being in contact with an electrolyte solution which may be aqueous or non-aqueous.
  • the electrodes may be separate from each other but it may be convenient that a sensor incorporates the working electrode, the counter electrode and any reference electrode within a single structure.
  • Sensors embodying this invention may be employed in a diverse range of applications, including equipment for testing aqueous fluids at the Earth's surface.
  • an area of application which is of particular interest to us is in devices for testing subterranean fluids, in particular devices to be used downhole in a well.
  • Downhole measurement tools for oilfield applications are known as such.
  • An electro-chemical technique using a sensor in accordance with the present invention can be applied for example as part of a production logging tool or an open hole formation tester tool for use in a well drilled for oil or gas.
  • the invention may be used in providing a downhole real-time water sample validation or downhole pH or sulfide measurement which in turn can be used for predicting mineral scale and for corrosion assessment.
  • Such tools may be devices lowered into a well by means of a cable, such as wireline or slickline, or may be tools carried into a well by coiled tubing, or even tools which are positioned downhole for a longer period.
  • Downhole measurement tools are also used in wells drilled to monitor groundwater or to access subterranean aquifers.
  • a sensor in accordance with the invention can be utilised in such tools, notably in providing real time measurement of pH and/or oxygen content.
  • Fig 1 is a diagrammatic cross-section of a sensor with a carbon paste electrode containing polymer particles
  • Fig 2 shows the electrode in a potentiometric cell
  • Fig 3 shows the cyclic voltammetric signal obtained with a carbon paste electrode comprising particles in which t-butylferrocene sulfonate was encapsulated with polysulfone;
  • Fig 4 shows the corresponding signals obtained when t-butylferrocene sulfonate was encapsulated with two other polymers
  • Fig 5A shows the square wave voltammetric response obtained in three buffer solutions with a carbon paste electrode comprising particles in which anthraquinone sulfonate was encapsulated with polysulfone;
  • Fig 5B shows peak potential plotted against against pH for the voltammetry signals shown in Figure 5A;
  • Fig 6 shows the square wave voltammetric response obtained in two buffer solutions with a carbon paste electrode comprising two types of particles
  • Fig 7 shows cyclic voltammetric signals obtained with a carbon paste electrode and a progressively increasing concentration of sulfide in the test solution.
  • Fig 8 is a diagrammatic cross section of a sensor unit embodying the invention.
  • Fig 9 is a diagrammatic illustration of a wireline tool incorporating the sensor unit of Fig 8;
  • Fig 10 is a diagrammatic illustration of a cable-suspended tool for testing water. Detailed Description and Examples
  • Example 1 Encapsulation of hydrophobic redox chemical
  • Anthraquinone (0.03gm) and encapsulating polymer (0.20gm) were dissolved in 10 ml dichloromethane. These amounts were calculated to lead to polymer particles containing containing 12-13wt% anthraquinone.
  • Polyvinyl alcohol (0.375gm) was dissolved in de-ionised water (150gm) using a mechanical stirrer with four vertical blades (Heidolph RZ2050 electronic, 320 rpm) for about 30 min and the solution of dye and polymer in dichloromethane was then added to it, dropwise, to form an emulsion of the dichloromethane solution in the water.
  • This emulsion was stirred at 320 rpm for 2 hours, the time for the dichloromethane solvent to evaporate.
  • the resulting suspension of particles was then poured into 600 ml of de-ionised water and stirred for another 2 hours.
  • These particles were then recovered by vacuum filtration on a cellulose nitrate membrane filter of 0.45 micron pore size and washed thoroughly with water until no coloration of the filtrate water was observed.
  • the particles were then dried for 2 days in a vacuum desiccator and stored in a refrigerator at 4°C.
  • Median particle sizes were determined using a Malvern Mastersizer. All the particles prepared in this example were found to have median particle sizes d 50 within a range from 50 to 250 micron. Scanning electron microscopy showed the particles to be spherical with a smooth surface.
  • Example 2 Encapsulation of hydrophilic redox chemicals.
  • Anthraquinone-2-sulfonic acid, sodium salt (more conveniently referred to as anthraquinone sulfonate) from Sigma-Aldrich Chemicals was encapsulated with polysulfone by the following procedure.
  • a saline solution of polyvinyl alcohol was prepared by dissolving polyvinyl alcohol (0.375gm) in water (150gm) containing 3wt% sodium chloride using a four bladed mechanical stirrer (Heidolph RZ2050 electronic, 320 rpm) for about 30 min.
  • Encapsulating polymer (0.20gm) was dissolved in 3.7 ml dichloromethane and added to a solution of anthraquinone sulfonate (0.03gm) in water (0.20 ml). The amounts of materials were calculated to lead eventually to particles containing 12- 13wt% anthraquinone sulfonate. The resulting mixture was stirred using a magnetic stirrer at its maximum rate for 10 min to form a water-in-oil emulsion which was then added dropwise to the saline solution of polyvinyl alcohol over about 3 hours with continued stirring to form a water-in-oil-in-water double emulsion.
  • This double emulsion was then poured into 600 ml of water containing 3wt% sodium chloride and stirred at 320rpm for another hour.
  • the dichloromethane solvent evaporated, the dispersed droplets were converted to particles comprising anthraquinone sulfonate encapsulated within polysulfone.
  • the particles were recovered by vacuum filtration on a cellulose nitrate membrane filter of 0.45 micron pore size and washed three times with water. The particles were then dried under vacuum and stored in a refrigerator.
  • Example 1 polysulfone ferrocene
  • Example 1 polysulfone
  • a potentiostat 19 which is able to apply a variable potential difference between the working electrode provided by the sensor 15 and the counter electrode 17.
  • the potentiostat 19 was used to carry out voltammetry experiments, measuring and recording the current flow as the applied potential was varied. Suitable potentiostats are available from Eco Chemie BV, Utrecht, Netherlands. In these experiments the counter electrode was a 1mm diameter platinum wire and the reference electrode was a standard calomel electrode.
  • Example 3 A sensor as illustrated in Fig 1 incorporating a carbon paste electrode containing particles comprising t-butylferrocene sulfonate encapsulated within polysulfone (PSU) was subjected to cyclic voltammetry in pH 7 buffer solution. The resulting signal is shown in Figure 3. An oxidation wave along with a corresponding reduction wave were observed at +0.50 V and +0.10 V respectively. Analysis of the peak to peak separation for the encapsulated particle showed that it is similar to that of t-butylferrocene sulfonate dissolved directly in aqueous media as reported by Tustin et al Journal of Organometallic Chemistry vol 692 pp 5173-5182 (2007). This therefore indicates that hydrogen ions were diffusing through the polysulfone layer.
  • a sensor as illustrated in Fig 1 incorporating a carbon paste electrode containing particles comprising anthraquinone sulfonate encapsulated within polysulfone (PSU) was subjected to square wave voltammetry in buffer solutions at pH 4, 7 and 9.
  • the resulting signals are shown in Figure 5A. These signals show a well resolved oxidation wave whose potential varies with pH from -0.31 V (pH 4) to +0.60 V (pH 9).
  • a plot of oxidative peak potential as a function of pH (Figure 5B) was found to be linear with a gradient of 58 mV/pH unit consistent with an n electron, n proton oxidation process where n is likely to be 2. This indicates that the hydrogen ions can pass through the polymer layer to the encapsulated particle and therefore the redox chemistry of the encapsulated species mimics that of the species in solution.
  • a mixture of particles comprising ferrocene encapsulated within polysulfone and particles comprising anthraquinone sulfonate encapsulated within polysulfone was mixed with graphite and used to make a sensor of the kind illustrated in Fig 1 with a carbon paste working electrode in which both these kinds of particles were present.
  • This electrode was examined by square wave voltammetry as in Example 5 using buffer solutions at pH 7 and pH 9. The resulting signals are shown in Figure 6. It can be clearly seen that at each pH two redox active waves are observed, the first at lower pH
  • anthraquinone sulfonate varies with pH whilst the second at higher pH (ferrocene) is independent of pH.
  • ferrocene a pH sensor.
  • the pH independent species serves as an internal reference and the variation in potential of the pH dependent peak provides a measure of pH.
  • a sensor as illustrated in Fig 1 incorporating a carbon paste electrode containing particles comprising t-butylferrocene sulfonate encapsulated within polysulfone (PSU) was subjected to cyclic voltammetry in pH 7 buffer solution.
  • PSU polysulfone
  • increasing amounts of sulfide were added to the test solution so that the sulfide concentration ranged from zero to 0.5mM sulfide.
  • the signals obtained are shown in Figure 7. It can be seen that the current flow increased progressively with the concentration of sulfide and the peak of the oxidation wave shifted from +0.3 volts to +0.4 volts.
  • Fig 8 illustrates in cross section a sensor unit embodying the invention. It has a main body 32 which is cylindrical. This body is intended to be accommodated inside a cylindrical cavity in a wellbore tool or other structure and is encircled by two sealing rings 34 to provide a seal between the body 32 and the cavity accommodating it.
  • the body 32 supports a working electrode 40, and a counter electrode 42. Electrical connections to the electrodes are indicated at 46. Immobilised at the exposed surface 41 of the electrode 40 are particles of polymer encapsulating redox systems such as those described in Examples 3 to 7 above. This surface 41 and an end portion of the counter electrode 42 are in contact with an electrolyte retained by a membrane 44 within a cavity 48 at the end of the body 32.
  • This membrane 44 separates the electrolyte from the fluid under test, but is permeable to the species such as hydrogen (H + ) ions and bisulfide (HS ⁇ ) whose concentration is to be measured. Depending on the nature of the fluid under test, it may be possible to dispense with the membrane 44 and allow the surface 41 and counter electrode 42 to contact the test fluid directly.
  • H + hydrogen
  • HS ⁇ bisulfide
  • Fig 9 diagrammatically illustrates a wireline tool with a generally cylindrical body 52 suspended at the lower end of a wireline 54.
  • the body 52 is provided with centralisers 56 for positioning it within a wellbore.
  • the body 52 may house a variety of devices for making measurements on the wellbore, the surrounding geological formation and on fluid within the wellbore.
  • a sensor unit 60 such as that of Fig 8. This is fitted into a cavity within the body 52 so that the end 49 of the sensor unit 60 is exposed to the fluid within the wellbore.
  • the tool body 52 also encloses a unit 62 for supplying voltage to the electrodes of the sensor unit 60, measuring the current which flows and communicating the results to the surface via the wireline cable.
  • a wireline tool such as that diagrammatically illustrated by Fig 9 could be configured and used to determine the producing zones of an oil production well.
  • the tool is suspended from the wireline cable which is used to lower and raise the tool within the well.
  • the tool is pushed or pulled using coiled tubing from the surface, or a tractor powered and controlled by cable from the surface.
  • a wireline tool could be configured and used to investigate an underground body of water contacted by a well drilled into an aquifer.
  • a sensor in accordance with this invention could also be incorporated into a wide variety of other tools and equipment. Possibilities include use in tools which are located permanently downhole, use in tools which are conveyed downhole at the head of coiled tubing, use in underground, undersea or surface pipeline equipment to monitor liquid flowing in the pipeline, and use in various kinds of process plant at the Earth's surface.
  • a sensor in accordance with this invention may well be used outside the oil and gas industry. Use in water treatment can be envisaged, as can use in a wide variety of other areas of science and industry.
  • Fig 10 illustrates a tool for investigating subterranean water.
  • This tool also has a cylindrical body 52 which is suspended from a cable 55.
  • a sensor unit 60 is accommodated within the body so that its end 49 is exposed to the subterranean water.
  • the tool also encloses also encloses a unit 62 for supplying voltage to the electrodes of the sensor unit 60, measuring the current which flows and transmitting the results to the surface.

Abstract

L'invention porte sur un capteur électrochimique détectant la présence ou mesurant la concentration d'un analyte comprenant au moins une électrode et au moins une espèce électrochimiquement active apte à subir une réaction électrochimique en réponse à un potentiel électrique appliqué à l'électrode, ladite réaction étant modifiée par la présence de l'analyte. Ce capteur possède la nouvelle caractéristique consistant en ce qu'au moins l'une desdites espèces électrochimiquement actives est encapsulée dans des particules de polymère. Ces particules sont de préférence formées à partir d'un polymère amorphe ayant une température de transition vitreuse supérieure à la température du fluide auquel le capteur est exposé. Le polymère d'encapsulation protège l'espèce analyte d'une dégradation, mais un petit analyte tel qu'un ion d'hydrogène ou bisulfure peut passer à travers le polymère et subir une réaction au niveau de l'espèce active.
PCT/IB2010/002641 2009-12-09 2010-10-14 Capteur électrochimique WO2011070408A2 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP10835558A EP2510344A2 (fr) 2009-12-09 2010-10-14 Capteur électrochimique
US13/502,718 US9377434B2 (en) 2009-12-09 2010-10-14 Electro-chemical sensor

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GB0921511.2 2009-12-09
GB0921511.2A GB2476057B (en) 2009-12-09 2009-12-09 Electro-chemical sensor

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WO2011070408A2 true WO2011070408A2 (fr) 2011-06-16
WO2011070408A3 WO2011070408A3 (fr) 2011-10-27

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EP2510344A2 (fr) 2012-10-17
US20120268134A1 (en) 2012-10-25
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US9377434B2 (en) 2016-06-28
GB0921511D0 (en) 2010-01-20
WO2011070408A3 (fr) 2011-10-27

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