EP2182212B1 - Mikropumpe mit Betätigung durch Tropfen - Google Patents

Mikropumpe mit Betätigung durch Tropfen Download PDF

Info

Publication number
EP2182212B1
EP2182212B1 EP09173788A EP09173788A EP2182212B1 EP 2182212 B1 EP2182212 B1 EP 2182212B1 EP 09173788 A EP09173788 A EP 09173788A EP 09173788 A EP09173788 A EP 09173788A EP 2182212 B1 EP2182212 B1 EP 2182212B1
Authority
EP
European Patent Office
Prior art keywords
microchannel
electrode
droplet
drop
micropump according
Prior art date
Legal status (The legal status 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 status listed.)
Not-in-force
Application number
EP09173788A
Other languages
English (en)
French (fr)
Other versions
EP2182212A1 (de
Inventor
Yves Fouillet
Guillaume Delapierre
Olivier Fuchs
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Original Assignee
Commissariat a lEnergie Atomique CEA
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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 Commissariat a lEnergie Atomique CEA, Commissariat a lEnergie Atomique et aux Energies Alternatives CEA filed Critical Commissariat a lEnergie Atomique CEA
Publication of EP2182212A1 publication Critical patent/EP2182212A1/de
Application granted granted Critical
Publication of EP2182212B1 publication Critical patent/EP2182212B1/de
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F04—POSITIVE - DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS FOR LIQUIDS OR ELASTIC FLUIDS
    • F04B—POSITIVE-DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS
    • F04B19/00—Machines or pumps having pertinent characteristics not provided for in, or of interest apart from, groups F04B1/00 - F04B17/00
    • F04B19/006—Micropumps
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F04—POSITIVE - DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS FOR LIQUIDS OR ELASTIC FLUIDS
    • F04B—POSITIVE-DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS
    • F04B43/00—Machines, pumps, or pumping installations having flexible working members
    • F04B43/02—Machines, pumps, or pumping installations having flexible working members having plate-like flexible members, e.g. diaphragms
    • F04B43/04—Pumps having electric drive
    • F04B43/043—Micropumps

Definitions

  • the present invention relates to the general field of microfluidics and, more particularly, to that of micropumps, and relates to a drop-operated micropump.
  • Micropumps provide controlled flow of fluid, particularly in a microchannel, and are involved in many microfluidic systems.
  • micropumps may be present in lab-on-a-chip, medical substance injection systems, or the electronic cooling circuits of electronic chips.
  • micropumps can be actuated in various ways, for example using a piezoelectric, electrostatic, thermopneumatic or even electromagnetic device.
  • a presentation of these different actuators can be found in the document DJ Laser and JG Santiago entitled “A review of micropumps", J. Micromech. Microeng., 14 (2004), R35-R64 .
  • actuators have certain drawbacks such as the presence of deformable membranes or valves, the use of high voltages, for example for piezoelectric or electrostatic devices, or a significant electrical consumption, for example with thermopneumatic or electromagnetic devices.
  • Another approach which avoids at least partly the disadvantages mentioned above, is to actuate the micropump by electrowetting, and more precisely by electrowetting on dielectric.
  • the document WO206 / 086620A describes a micropump according to the preamble of claim 1.
  • the patent application WO2002 / 07503A1 describes a micropump, illustrated in Fig. 1 , comprising a substrate in which is formed a microchannel 10, and an actuating device for ensuring the flow of a fluid F1 in the microchannel 10.
  • the operating principle of the actuating device is based on the displacement by electrowetting a conductive liquid L1 in the microchannel 10 from a tank 41.
  • the actuating device comprises a linear array of displacement electrodes 31 (1), 31 (2), 31 (3) ... integrated in the substrate and arranged in the microchannel 10 from the tank 41.
  • a counter-electrode 43 is disposed in the tank 41 and provides electrical contact with the conductive liquid L1.
  • the displacement electrodes are covered with a hydrophobic dielectric layer (not shown).
  • a voltage generator (not shown) is connected to the displacement electrode array 31 and to the counter-electrode 43, and makes it possible to apply a voltage U between the electrodes.
  • the conductive liquid L1 forms with the fluid F1 filling the microchannel 10 an interface I1.
  • the displacement electrode 31 (i) located opposite the interface I1 is activated, using switching means (not shown) whose closure establishes a contact between this electrode and the voltage source via a conductor common, the liquid under voltage L1, dielectric layer and activated electrode 31 (i) acts as a capacitance.
  • the liquid L1 behaves like a conductor insofar as the frequency of the bias voltage is substantially lower than a cutoff frequency.
  • the latter which depends in particular on the electrical conductivity of the liquid, is typically of the order of a few tens of kilohertz (see for example the article of Mugele and Baret entitled “Electrowetting: from basics to applications", J. Phys. Condens. Matter, 17 (2005), R705-R774 ).
  • the frequency is preferably substantially greater than the frequency corresponding to the hydrodynamic response time of the liquid, which depends on the physical parameters such as the surface tension, the viscosity or the size of the microchannel, and which is of the order a few tens or hundreds of Hertz.
  • the response of the liquid then depends on the rms value of the voltage, since the contact angle depends on the voltage U 2 , according to the relation (1).
  • micropump according to the prior art has certain disadvantages.
  • the pressure force exerted by the liquid on the fluid is proportional to cos ⁇ ( U ).
  • ⁇ ( U ) the smaller the angle ⁇ ( U ), the greater the pressure force and the greater the flow rate.
  • the contact angle decreases with the increase of the polarization voltage U to a saturation angle which is usually between about 30 ° and 80 °. The pressure force, and thus the fluid flow rate, are then limited by this saturation angle.
  • the displacement length of the liquid in the microchannel corresponds to that of the operating electrode array. Also, moving the liquid along the entire length of the microchannel requires extending the electrode array all along the microchannel. The manufacture is then made particularly complex, especially in the case where the microchannel has a non-rectangular transverse shape, for example circular, or if it has changes of direction.
  • the object of the present invention is to provide a micropump whose pressure force is not limited by the electrowetting saturation angle, while having a simplified manufacturing.
  • the invention relates to a micropump for moving a fluid in a microchannel.
  • the microchannel comprises an inlet orifice and has a hydrophilic wall extending from said inlet orifice
  • the micropump comprises means for moving a drop of liquid by electrowetting on a hydrophobic surface until contacting said drop with said hydrophilic wall, whereby said drop is introduced by wetting into said microchannel through said inlet port, causing said fluid to move.
  • the pressure force exerted by the liquid on the fluid in the microchannel is not limited by the electrowetting saturation angle, as in the micropump according to the prior art.
  • electrowetting makes it possible to bring drops of liquid to the inlet orifice of the microchannel, but is not the driving phenomenon of the micropump.
  • Fluid flow is achieved by introducing the drop of liquid into the microchannel through the inlet port. This naturally occurs because of the difference in wettability to which the drop is subjected. Indeed, when the drop is brought into contact with the hydrophilic wall through the inlet port, it wets at the same time the hydrophobic surface and the hydrophilic wall of the microchannel. The difference in wettability between these two surfaces causes the migration of the entire drop of the hydrophobic surface towards the hydrophilic wall. The drop of liquid is then introduced into the microchannel and simultaneously "pushes" the fluid.
  • the realization of the micropump is simplified since it is no longer necessary to have the electrowetting electrodes along the entire length of the microchannel.
  • said drop forms a contact angle on said hydrophilic wall substantially less than that formed by electrowetting on said hydrophobic surface.
  • Said displacement means preferably comprise at least one displacement electrode and a counter-electrode in electrical contact with the drop, and a voltage generator for applying a potential difference between one or more displacement electrodes and said counter-electrode.
  • Said displacement electrodes may be arranged along a determined path.
  • a so-called contacting displacement electrode is advantageously arranged so that a drop of liquid covering it is in contact with said hydrophilic wall through said inlet orifice.
  • Said displacement means may comprise a single displacement electrode, which is then said contacting electrode.
  • Said hydrophilic wall may have a nanotextured or microtextured surface.
  • Said hydrophilic wall may be of hydrophilic material.
  • Said hydrophilic wall may comprise a layer of a hydrophilic material.
  • said hydrophilic wall extends over the entire length of the microchannel.
  • a dielectric material layer is preferably disposed between said hydrophobic surface and said electrodes.
  • the microchannel comprises a connecting portion defining an upstream portion and a downstream portion, said connecting portion having a section transversely larger than that of the upstream portion.
  • the size of the connecting portion is preferably between 5 and 50 times that of the upstream portion.
  • a second fluid may be located downstream of the first fluid so as to form therewith an interface located in said coupling portion.
  • the upstream portion may comprise a first upstream portion extending from the inlet orifice and a plurality of second elementary upstream portions arranged in parallel each communicating with said first upstream portion.
  • Each second elementary upstream portion may communicate with said connection portion.
  • Each second elementary upstream portion may be at least partially filled with said fluid.
  • the micropump advantageously comprises means for forming said droplet on said hydrophobic surface, by electrowetting.
  • the drop forming means may comprise a plurality of drop forming electrodes, one of which is adjacent to a displacement electrode.
  • a second hydrophobic surface may be arranged facing the first hydrophobic surface so as to form a closed or confined device for said drop.
  • a first embodiment of the invention is shown schematically on the Figures 2A and 2B , in top view.
  • the micropump comprises a microchannel 10 at least partially filled with a fluid F1 and an actuating device for ensuring the flow of said fluid F1 in the microchannel 10.
  • the Figure 2A shows a direct orthonormal frame ( i , j , k ).
  • a droplet 51 can be moved in a plane substantially parallel to the plane ( i , j ).
  • the longitudinal axis of the microchannel 10 is defined as being the median line of the microchannel.
  • the longitudinal axis may be rectilinear or curved, and have changes of direction.
  • the microchannel 10 may have a convex polygonal cross section, for example square, rectangular, hexagonal, a square section being a particular case of the more general rectangular shape. It can also have a circular cross section.
  • the term microchannel is taken here in a general sense and includes in particular the case particular microtube whose section is circular.
  • the microchannel may also be the catheter of a drug delivery system.
  • the term "height" refers to the transverse characteristic size of the microchannel 10. In the case of a microtube, the height refers to the diameter.
  • the microchannel 10 comprises an inlet orifice 11 allowing the passage of a liquid L1 from the outside inside the microchannel 10.
  • the inlet orifice 11 is located at one end of the microchannel 10.
  • the microchannel 10 comprises a hydrophilic wall 12 which extends from said inlet orifice 11 over a portion of the transverse contour, or preferably over the entire transverse contour.
  • the hydrophilic wall 12 may extend over a length defined along the longitudinal axis of the microchannel, or preferably extend over the entire length of the microchannel.
  • the device for actuating the micropump ensures the flow of the fluid F1 in the microchannel 10.
  • It comprises means for moving at least one drop 51 of liquid L1, by electrowetting, on a hydrophobic surface to the inlet orifice 11 of the microchannel 10.
  • the displacement means here comprise a single displacement electrode 31 integrated in or disposed on a support substrate 21, and covered with the hydrophobic surface.
  • the displacement electrode 31, called the contacting electrode, is arranged so that a droplet 51 of liquid L1 covering it is in contact with the hydrophilic wall 12 through said inlet orifice 11.
  • a series of displacement electrodes may be arranged in a determined path ending in a contacting electrode 31 arranged to contact a drop 51 covering it with the hydrophilic wall 12 through the inlet orifice 11 of the microchannel 10.
  • the verbs "to cover”, “to be located on” and “to be disposed of” do not necessarily imply direct contact here.
  • the droplet 51 of liquid can cover the displacement electrode 31 without direct contact, a hydrophobic surface being disposed here between the drop 51 and the electrode 31.
  • the means of displacement of the drops are here in a so-called open configuration, or not confined, to the extent that said drops of liquid are not confined between two support substrates, or two hydrophobic surfaces, parallel between they but rest solely on the support substrate 21.
  • the inlet orifice 11 is disposed substantially opposite the displacement electrode 31. More specifically, the inlet axis through the orifice 11, here following i, is substantially parallel to the plane ( i , j ) of the displacement electrode 31. Other arrangements are possible, as shown in FIG. figure 5 (described in detail below), where the inlet port 11 is formed substantially in the same plane as the displacement electrode 31.
  • the input axis through the orifice, here following k is substantially perpendicular to the plane ( i , j ) of the displacement electrode 31.
  • the inlet orifice 11 is surrounded by the displacement electrode 31, so that a drop 51 which covers the electrode 31 is brought into contact with said hydrophilic wall 12 through said inlet orifice 11.
  • the hydrophobic surface may be a layer of a hydrophobic material.
  • a layer of a dielectric material is disposed between the displacement electrode (s) 31 and the hydrophobic surface.
  • the dielectric and hydrophobic layers may be a single layer combining these two functions, for example a parylene layer.
  • a counter electrode (not shown) is provided to provide electrical contact with liquid drop 51. It is arranged at least facing the displacement electrode 31.
  • This counter-electrode can be either a catenary, a wire buried between the dielectric layer and the hydrophobic layer, or a planar electrode integrated into a hood of the micropump (a such hood is described later). In the latter case, an electrically conductive hydrophobic layer may cover the counter-electrode.
  • the displacement electrode 31 and the counterelectrode may be connected to a continuous voltage generator (not shown) or, preferably, alternative, to move the drop 51 by electrowetting, as previously described.
  • the frequency is advantageously between 100 Hz and 10 kHz, preferably of the order of 1 kHz, so as to maintain the conductive electrical properties of the liquid and to exceed the hydrodynamic response time of the droplet.
  • the response of the drop 51 then depends on the rms value of the applied voltage.
  • the rms value can vary between a few volts and a few hundred volts, for example 200V. Preferably, it is of the order of a few tens of volts.
  • the micropump has means for forming drops 51 by electrowetting from a tank 41 containing said liquid L1.
  • the drop forming means preferably comprise at least three forming electrodes 42 (1), 42 (2), 42 (3) integrated in or deposited on said support substrate 21 and covered with said hydrophobic surface.
  • said dielectric layer is also disposed between the hydrophobic surface and the formation electrodes 42.
  • a first forming electrode 42 (1) is disposed substantially facing or near the tank 41 containing the liquid.
  • a second forming electrode 42 (2) is adjacent to the first 42 (1) and followed by a third electrode 42 (3).
  • the third electrode 42 (3) is preferably adjacent to the displacement electrode 31.
  • the drop forming means have in common with the displacement means against the electrode and the voltage generator described above.
  • the counter-electrode is then arranged so as to be opposite the formation electrodes 42.
  • Switching means are provided for successively activating the different electrodes 42 (1), 42 (2), 42 (3), 31 and thus ensuring, on the one hand, the formation of a drop and, on the other hand, its displacement to the inlet orifice 11 of the microchannel 10.
  • FIGS. 3A to 3C illustrate an example of forming a drop by electrowetting from a tank 41 containing said liquid L1, in the case of an open configuration.
  • the patent application WO2006 / 070162 filed in the name of the Applicant, describes in detail the principle of drop formation used herein, and also gives an example of droplet formation in confined configuration.
  • said reservoir 41 may be a reservoir electrode at which a reservoir drop 53 of liquid L1 is disposed.
  • This reservoir electrode defines a liquid holding micro-reservoir, and may be similar or identical to the reservoir electrode 46 described later with reference to the second embodiment of the invention.
  • Said reservoir electrode 41 may have a circular shape as on the Figures 2A and 2B , square as on the Figure 4A , or any other form.
  • FIGS. 3A to 3C Three electrodes 42 (1), 42 (2), 42 (3) are shown on the FIGS. 3A to 3C .
  • this liquid segment 52 is cut in two parts by deactivating the electrode 42 (2). A drop 51 is thus obtained, as shown in FIG. figure 3C .
  • a series of electrodes 42 (1), 42 (2), 42 (3) are thus used to stretch liquid L1 from the reservoir drop 53 into a liquid segment 52 (FIG. figure 3B ) then to cut this liquid segment 52 ( figure 3C ) and form a drop 51 which can be moved by the moving means.
  • micropump The operation of the micropump according to the first embodiment of the invention is as follows, with reference to Figures 2A and 2B .
  • the drop forming means are activated so as to electromagnetically form a drop 51 of liquid L1 on the hydrophobic surface, as described above.
  • the displacement means are activated to move the drop 51 formed by electrowetting up to the inlet orifice 11, and thus bring it into contact with the hydrophilic wall 12.
  • the drop When the drop is in contact with the hydrophilic wall 12 through the inlet orifice 11, it is introduced spontaneously by wetting in the More precisely, the drop migrates from the hydrophobic surface of the actuating device to the hydrophilic wall 12 of the microchannel 10. In doing so, it "pushes" the fluid F1 contained in the microchannel 10 and thus ensures the controlled flow of the microchannel 10. this one.
  • a second drop 51 can be brought to the inlet port 11 by electrowetting and then introduced by wetting in the microchannel 10. More precisely, the second drop 51 coalesces with the liquid L1 already present in the microchannel 10 from the In this case, a drop of larger volume is obtained, one part wetting the hydrophobic surface and the other part wetting the hydrophilic wall 12. The phenomenon remains the same. The new drop will move to dewake the hydrophobic surface and further wet the hydrophilic wall 12 of the microchannel 10. And in doing so, it "pushes" the fluid F1 and thus ensures the flow thereof.
  • the micropump according to the invention therefore has the advantage of not being limited by the saturation angle of electrowetting.
  • the driving force is then the wetting force that appears spontaneously when the liquid drop 51 is in contact with the hydrophilic wall 12 of the microchannel 10.
  • This wetting force depends on the contact angle formed by the liquid L1 on the hydrophilic wall . This can be very small, for example of the order of, or less than, 10 °.
  • the pressure force and therefore the fluid flow in the microchannel are then greater than in the micropump according to the prior art.
  • the flow of the fluid F1 is ensured as the microchannel 10 is supplied with drops of liquid 51 by the displacement means.
  • the liquid L1 can extend in the microchannel 10 over the entire length of the hydrophilic wall 12. It is thus not necessary to have displacement electrodes 31 along the microchannel 10. The manufacture of the micropump is then particularly simplified. .
  • a second embodiment of the invention is shown on the Figures 4A and 4B where the first is a view from above and the second a longitudinal section of the first along an axis II.
  • the means for forming and moving drops contain the drop of liquid.
  • a second hydrophobic surface 26 is disposed facing the first hydrophobic surface 22 and substantially parallel thereto, and integrated in or disposed on an upper cover 25.
  • a droplet 51 may be formed by the drop forming means and displaced by the displacement means between the first and second hydrophobic surfaces 22, 26.
  • the counter-electrode 43 is integrated in the cover 25 or disposed thereon, and covered by the second hydrophobic surface 26.
  • the means for forming a drop are advantageously similar to those described in the patent application. W02006 / 070162 filed in the name of the plaintiff.
  • a well 27 is formed in the upper cover 25.
  • This well 27 is placed at least partially in front of a transfer electrode 47, the latter being integrated with the substrate 21 or disposed thereon.
  • the drop forming electrodes 42 are then placed followed by at least one displacement electrode, here a single so-called contacting electrode 31.
  • dielectric layer if it is distinct from the hydrophobic layer 22, is not represented on the Figures 4A and 4B .
  • the transfer electrode 47 makes it possible to pump the liquid from the reservoir (not shown) communicating with the well, and to bring it close to the reservoir electrode 46.
  • this reservoir electrode can be accumulated a certain amount of liquid. It is represented as having a square or rectangular shape on the Figure 4A but its form can be any. Of Preferably, it can accumulate at least three to four times the volume of the drops 51 to be dispensed, and preferably at least 10 times or 20 times the volume of each drop dispensed 51.
  • the distance between the two substrates 21, 25 is substantially constant (as can be seen in FIG. Figure 4B ), it is actually the surface of the electrode 46 which is at least three to four times equal, or at least 10 or 20 times equal to the area of each of the drop forming electrodes 42.
  • the transfer electrode when it is activated, makes it possible to bring a portion of liquid located in the well 27 close to the reservoir electrode 46.
  • the transfer electrode 47 can be reactivated, and then the reservoir electrode 46, so as to continue to accumulate liquid in this reservoir zone.
  • the transfer electrode 47 is not activated, the liquid defined by the reservoir electrode 46 is not in contact with the well 27.
  • the formation of drops that can be made from the The liquid stored above the reservoir electrode 46 can therefore be calibrated while using a well 27, and independently of the pressure therein, to fill the component.
  • the two hydrophobic surfaces 22, 26 form two substantially parallel planes and do not constitute a microchannel.
  • the displacement of a drop 51 does not cause overall displacement of the surrounding fluid in the same direction. This one bypasses the drop 51 in its displacement. It is thus possible to bring a drop 51 to the inlet orifice 11 without introducing the surrounding fluid into the microchannel.
  • the micropump according to this embodiment of the invention makes it possible to precisely control the flow of the fluid F1 in the microchannel 10.
  • the fluid F1 is "pushed" by the drop 51 of liquid over a distance that depends in particular the volume of the drop 51.
  • the formation of a calibrated volume drop makes it possible to move the fluid F1 over a precise distance.
  • the distance between the two hydrophobic surfaces 22, 26 is of the order of a few hundred micrometers, preferably 100 microns.
  • the drops 51 obtained have a volume between a few nanoliters to a few microliters, for example 64nl.
  • the drop reservoir 53 located at the reservoir electrode 46 may be formed during the production of the micropump.
  • the drop forming means do not comprise wells communicating with a reservoir, nor transfer electrode, but only a drop reservoir located at the reservoir electrode. It is then advantageous for the cover 25 to include a cavity at the reservoir electrode 46, in order to accommodate a reservoir drop of a large volume.
  • the space located at the reservoir electrode 46, or said cavity can communicate with the outside, so that liquid can be introduced, for example manually with a pipette, to reform or replenish the droplet. tank.
  • the support substrate 21 and the cover 25 may be made of silicon or glass, polycarbonate, polymer or ceramic.
  • the microchannel 10 is, for example, produced by lithography and selective etching. Depending on the desired dimensions, it is possible to use dry etching (gas attack, for example SF 6 , in a plasma). Engraving can be wet too. For glass (mainly SiO 2 ) or silicon nitrides, can use hydrofluoric or phosphoric acid etchings (these etchings are selective but isotropic). Engraving can be performed by laser ablation or ultrasound. Micromachining can also be used, in particular for polycarbonate.
  • the microchannel 10 may also be a soft fused silica capillary.
  • the height of the microchannel 10 is typically between a few tens of nanometers and 200 .mu.m, and preferably between 1 .mu.m and 100 .mu.m, preferably 30 .mu.m.
  • the length of the microchannel 10 can be from a few hundred microns to a few centimeters, for example 50cm.
  • the displacement and forming electrodes 31, 42, as well as the transfer electrode 47 and the reservoir electrolyte 46, and the counter electrode 43, may be produced by depositing a thin layer of a metal chosen from Au , Al, ITO, Pt, Cu, Cr ... or an Al-Si alloy ... using conventional microtechnologies of microelectronics, for example by photolithography.
  • the electrodes 31, 42, 46, 47 are then etched in a suitable pattern, for example by wet etching.
  • the thickness of the electrodes 31, 42, 46, 47 may be between 10 nm and 1 ⁇ m, and preferably be of the order of 300 nm.
  • the length of the electrodes 31 and 42 can be between a few micrometers to a few millimeters, preferably between 50 .mu.m and 1 mm, preferably 800 .mu.m.
  • the surface of these electrodes depends on the size of the drops to be formed and moved.
  • the spacing between adjacent electrodes may be between 1 ⁇ m and 20 ⁇ m.
  • the displacement and drop-forming electrodes 31 and 42 may have a substantially square or rectangular shape, as shown in the figures.
  • the inter-electrode spacing may have a curved or angular shape.
  • the edge of an electrode may have a sawtooth shape substantially parallel to the edge of the neighboring electrode having a corresponding shape. This form of electrodes facilitates the passage of the drop of liquid from one electrode to another.
  • the reservoir electrode 46 may have a comb or half-star shape, or even a tip, to ensure an electrode surface gradient.
  • the transfer electrode 47 has a shape adapted to that of the reservoir electrode 46.
  • a dielectric layer may cover the various electrodes 31, 42, 46, 47. It may be made of Si 3 N 4 , SiO 2 , SiN, barium strontium titanate (BST) or other high-permittivity materials such as HFO 2 , Al 2 O 3 , Ta 2 O 5 [29], Ta 2 O 5 -TiO 2 , SrTiO 3 or Ba 1-x Sr x TiO 3 .
  • the thickness of this layer may be between 100 nm and 3 ⁇ m, generally between 100 nm and 1 ⁇ m, preferably 300 nm.
  • the dielectric layer of SiO 2 can be obtained by thermal oxidation.
  • PECVD Plasma assisted vapor phase
  • LPCVD low pressure vapor deposition
  • the hydrophobic surface 22 may be deposited on the dielectric layer.
  • a Teflon deposit by dipping or spray or SiOC deposited by plasma can be achieved.
  • Hydrophobic silane deposition in the vapor or liquid phase can be carried out. Its thickness will be between 100 nm and 5 ⁇ m, preferably 1 ⁇ m. This layer makes it possible in particular to reduce or even to avoid the effects of hysteresis of the wetting angle.
  • a hydrophobic layer 26 covers the counter electrode 43.
  • the microchannel 10 is at least partially filled with F1 fluid, preferably insulating, which may be air, a mineral oil or silicone, a perfluorinated solvent, such as FC-40 or FC-70, or an alkane such as undecane.
  • F1 fluid preferably insulating, which may be air, a mineral oil or silicone, a perfluorinated solvent, such as FC-40 or FC-70, or an alkane such as undecane.
  • the liquid L1 is electrically conductive and may be an aqueous solution loaded with ions, for example Cl - , K + , Na + , Ca 2+ , Mg 2+ , Zn 2+ , Mn 2+.
  • the liquid may also be mercury, gallium, eutectic gallium, or ionic liquids of the type bmim PF6, bmim BF4 or tmba NTf2.
  • the drops 51 of liquid have a volume between a few nanoliters and a few microliters, for example about 64nl.
  • the fluid F1 is immiscible with the conductive liquid L1.
  • the hydrophilic character of said wall 12 may be obtained by using a naturally hydrophilic material for the substrate 21 in which the microchannel 10 is formed, such as aluminum, silica or hydrogel.
  • the substrate may also be a hydrated porous medium, such as hydrated Nafion.
  • the hydrophilic wall 12 may also comprise a layer of silica.
  • the silica layer can be obtained by thermal oxidation of the silicon.
  • the surface of the hydrophilic wall 12 may also be microtextured or nanotextured, so as to amplify the wetting effects and increase the capillarity force, as described in the publication of J. Bico et al. entitled “Wetting of textured surfaces” Colloids and Surfaces A, Physicochem. Eng. Aspects, 206 (2002), 41-46 .
  • a surface is called nanotextured (or microtextured) when it has a relief whose characteristic scale is from a few nanometers (or micrometers) to a few hundred nanometers (or micrometers).
  • the textured surface may have an array of roughnesses, for example nicks, pads or nanometric or micrometric grooves.
  • a film of liquid is then present between the roughnesses.
  • the thickness of this so-called impregnation film is comparable to the height of the roughness but remains negligible compared to the characteristic size of the drop.
  • the drop is placed, in fine, on a wet substrate which is a sort of patchwork of solid and liquid.
  • the wall has an important hydrophilic character.
  • a layer or a chemical film is usually deposited on the wall 12, the thickness of which may vary between a few nanometers and a few hundred microns.
  • a silanization of a metal oxide or semiconductor surface for example SiO 2 , HfO 2 , ITO, TiO 2 , SnO 2
  • polymers for example PDMS, COC
  • a hydrophilic surface In order to be as hydrophilic as possible, the silanes preferably carry an ionic group such as, for example, a carboxylate, a phosphate, a phosphonate, an imidazolium, a protonated amine, a quaternary amine or a sulphonate.
  • an ionic group such as, for example, a carboxylate, a phosphate, a phosphonate, an imidazolium, a protonated amine, a quaternary amine or a sulphonate.
  • the group conferring the hydrophilic property may be of the same type as that described above.
  • the preparation of such compounds and their use on surfaces are described in particular in the publication of F. Durmaz et al. entitled "New phosphates / phosphonates; A modular approach to functional sams, European Cells and Materials, Vol. 6, Suppl. 1, 2003, 55 .
  • Polymer families make it possible to obtain a hydrophilic and resistant layer of a few hundred nanometers, such as polyhydroxystyrenes.
  • the patent application WO2007 / 053326 also describes hydrophilic groups, for example silanols, introduced into a polymer matrix to be deposited to form the hydrophilic layer.
  • a third embodiment of the invention is shown on the figure 5 in top view.
  • the microchannel 10 may comprise a second fluid F2 disposed downstream of the first fluid F1 so as to form therewith an interface 12.
  • the first and second fluids F1, F2 are immiscible between them.
  • the interface I2 is located in a connection portion 17.
  • the connecting portion 17 defines an upstream portion 13 extending from the inlet orifice 11 to the connecting portion 17, and a downstream portion 16 extending downstream of the connecting portion 17.
  • the height of the connecting portion 17 is substantially greater than that of the upstream portion 13 of the microchannel.
  • the height is of the order of 5 to 50 times the height of the upstream portion 13, preferably 10 times.
  • the height of the upstream 13 and downstream 16 portions is constant.
  • the downstream portion 16 may have an identical height, greater or less than that of the connecting portion 17. In the example of the figure 4 , the downstream portion 16 has a height substantially identical to that of the upstream portion 13.
  • connecting portion 17 reduces the effects of the hysteresis of the contact angle that oppose the flow of fluids. Indeed, these are inversely proportional to the height of the connecting portion 17.
  • the means for forming and moving the drops are here in confined configuration, as described in the second embodiment and as shown in FIG. figure 5 . Alternatively, they may be in an open configuration, as described in the first embodiment.
  • This third embodiment of the invention has the advantage of delivering a calibrated flow rate of fluid F2 at the outlet of the downstream portion 16 of the microchannel.
  • a fourth embodiment of the invention is shown on the figure 6 in longitudinal section.
  • the inlet orifice 11 is disposed in the same plane as the displacement electrode 31 and surrounded by it.
  • the input axis of the orifice, here following k, is substantially orthogonal to the plane of the electrode of displacement, here (i, j).
  • a drop 51 which covers the displacement electrode is brought into contact with the hydrophilic wall 12 through the inlet orifice 11.
  • a connecting portion 17 is disposed between an upstream portion 13 and a downstream portion 16 of the microchannel.
  • the upstream portion 13 comprises a first upstream portion 14 and a second upstream portion 15.
  • the first upstream portion 14 extends from the inlet port 11.
  • the second upstream portion 15 extends from the first upstream portion 14 to the connecting portion 17.
  • the downstream portion 16 corresponds to a third portion 16 of the microchannel.
  • the second upstream portion 15 comprises a plurality of second upstream channel elemental upstream portions 15 'arranged in parallel, each communicating with the first upstream portion 14 and with the connecting portion 17.
  • the second elementary portions 15 ' may be arranged in a hexagonal network and have a diameter of the order of a few tens of microns, preferably 30 microns.
  • each second elementary portion 15 ' has a circular cross section, hexagonal or having a shape of the same type.
  • the second elementary portions 15 ' can be obtained by plasma etching of the RIE type of the substrate 21.
  • the second elementary portions 15 ' are filled with liquid L1 and / or first fluid F1.
  • the second elementary portions 15 ' may be of a number of hundreds, and have a height (diameter) of a few tens of microns, preferably 30 microns, and a length of a few hundred microns, preferably 700 microns.
  • the means for forming and moving the drops are here in confined configuration, as described in the second embodiment and as shown in FIG. figure 6 . Alternatively, they may be in an open configuration, as described in the first embodiment.
  • a variant of the fourth embodiment of the invention is represented on the figure 7 in longitudinal section.
  • two elementary micropumps each of which is substantially identical to that described in the fourth embodiment, are arranged in parallel and are interconnected on the one hand by a common well 27 filled with liquid L1, and on the other hand by a junction connecting the downstream portions 16-1 and 16-2. More specifically, the two downstream portions 16-1 and 16-2 are connected by a junction 18 so as to form only a portion 19.
  • the two micropumps may have means for controlling the electrodes for forming and moving drops that are independent of one another.
  • the second fluids F2-1 and F2-2 manipulated by the two micropumps may be different.
  • each second fluid F2-1 and F2-2 can be controlled from the control means of the electrodes.
  • the first fluids F1-1 and F1-2 are advantageously identical.
  • the elementary micropumps may not be interconnected at their respective downstream portion 16, to provide an independent exemption of their respective second fluid F2.
  • the phenomenon of direct electrowetting can be realized.
  • the capacity intervening is not that of the dielectric layer but that of a double electric layer forming in the conductive liquid L1 on the surface of the electrodes 31, 41.
  • the applied voltages must remain sufficiently low to avoid electrochemical phenomena such as the electrolysis of water.
  • the thickness e involved in the relationship connecting the contact angle ⁇ to the applied voltage U, described above, is that of the double layer, which is of the order of a few nanometers.
  • the zwitterions used may be amine sulfonates, amine phosphates, amine carbonates, or amine carboxylates, and in particular, trialkylammonium alkane sulfonates, alkyl imidazole alkanesulfonates or alkyl alkanesulfonates pyridine.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Micromachines (AREA)
  • Structures Of Non-Positive Displacement Pumps (AREA)
  • Electrophonic Musical Instruments (AREA)
  • Bidet-Like Cleaning Device And Other Flush Toilet Accessories (AREA)
  • Percussion Or Vibration Massage (AREA)

Claims (16)

  1. Mikropumpe, umfassend einen Mikrokanal (10) zum Verlagern eines Fluids (F1) in dem Mikrokanal (10), wobei der Mikrokanal (10) eine Eingangsöffnung (11) umfasst und eine Wand (12) aufweist, und wobei die Mikropumpe Mittel zur Verlagerung eines Tropfens (51) einer Flüssigkeit (L1) durch Elektrobenetzung an einer hydrophoben Oberfläche (22) umfasst, bis der Tropfen (51) in Kontakt mit der Wand gelangt,
    dadurch gekennzeichnet, dass die Wand (12) hydrophil ist (10), und dass sie sich ausgehend von der Eingangsöffnung derart erstreckt, dass der Tropfen (51) durch die Eingangsöffnung (11) hindurch mittels Benetzung in den Mikrokanal (10) eintritt, was die Verlagerung des Fluids (F1) bewirkt.
  2. Mikropumpe nach Anspruch 1, dadurch gekennzeichnet, dass der Tropfen (51) einen Kontaktwinkel an der hydrophilen Wand (12) bildet, der wesentlich kleiner als jener ist, der durch Elektrobenetzung an der hydrophoben Oberfläche (22) gebildet wird.
  3. Mikropumpe nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die Mittel zur Verlagerung wenigstens eine Verlagerungselektrode (31) sowie eine Gegenelektrode umfassen, die in elektrischem Kontakt mit dem Tropfen (51) ist, sowie einen Spannungsgenerator zum Anlegen einer Potentialdifferenz zwischen einer oder mehreren Verlagerungselektroden (31) und der Gegenelektrode.
  4. Mikropumpe nach Anspruch 3, dadurch gekennzeichnet, dass die Mittel zur Verlagerung eine Verlagerungselektrode (31) umfassen, die derart angeordnet ist, dass ein sie bedeckender Flüssigkeitstropfen (51) durch die Eingangsöffnung (11) hindurch in Kontakt mit der hydrophilen Wand (12) ist.
  5. Mikropumpe nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die hydrophile Wand (12) eine nanotexturierte oder mikrotexturierte Oberfläche aufweist.
  6. Mikropumpe nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die hydrophile Wand (12) aus einem hydrophilen Material gebildet ist oder eine Schicht aus einem hydrophilen Material umfasst.
  7. Mikropumpe nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass die hydrophile Wand (12) sich über die gesamte Länge des Mikrokanals (10) erstreckt.
  8. Mikropumpe nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass der Mikrokanal (10) einen Anschlussbereich (17) umfasst, der einen stromaufwärtigen Bereich (13) sowie einen stromabwärtigen Bereich (16) definiert, wobei der Anschlussbereich (17) einen Querschnitt aufweist, der wesentlich größer als jener des stromaufwärtigen Bereichs (13) ist.
  9. Mikropumpe nach Anspruch 8, dadurch gekennzeichnet, dass die Größe des Anschlussbereichs (17) zwischen 5 und 50 Mal jener des stromaufwärtigen Bereichs (13) ist.
  10. Mikropumpe nach Anspruch 8 oder 9, dadurch gekennzeichnet, dass ein zweites Fluid (F2) stromabwärts des ersten Fluids (F1) derart angeordnet ist, dass mit diesem letztgenannten zusammen eine Grenzfläche (12) gebildet wird, die in dem Anschlussbereich (17) lokalisiert ist.
  11. Mikropumpe nach einem der Ansprüche 8 bis 10 dadurch gekennzeichnet, dass der stromaufwärtige Bereich (13) einen ersten stromaufwärtigen Bereich (14) umfasst, der sich ausgehend von der Eingangsöffnung (11) erstreckt, sowie eine Mehrzahl von zweiten stromaufwärtigen Elementarbereichen (15'), die parallel angeordnet sind und jeweils mit dem ersten stromaufwärtigen Bereich (14) kommunizieren.
  12. Mikropumpe nach Anspruch 11, dadurch gekennzeichnet, dass jeder zweite stromaufwärtige Elementarbereich (15') mit dem Anschlussbereich (17) kommuniziert.
  13. Mikropumpe nach Anspruch 12, dadurch gekennzeichnet, dass jeder zweite stromaufwärtige Elementarbereich (15') wenigstens teilweise mit dem Fluid (F1) gefüllt ist.
  14. Mikropumpe nach einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, dass sie ferner Mittel zur Bildung des Tropfens (51) an der hydrophoben Oberfläche (22) mittels Elektrobenetzung umfasst.
  15. Mikropumpe nach Anspruch 14, dadurch gekennzeichnet, dass die Mittel zur Verlagerung wenigstens eine Verlagerungselektrode (31) umfassen, und die Mittel zur Bildung von Tropfen eine Mehrzahl von Tropfenbildungselektroden (42) umfassen, von denen eine einer Verlagerungselektrode (31) benachbart ist.
  16. Mikropumpe nach Anspruch 14 oder 15, dadurch gekennzeichnet, dass eine zweite hydrophobe Oberfläche (26) der ersten hydrophoben Oberfläche (22) derart gegenüberliegend angeordnet ist, dass für den Tropfen (51) eine geschlossene oder begrenzte Vorrichtung gebildet wird.
EP09173788A 2008-10-28 2009-10-22 Mikropumpe mit Betätigung durch Tropfen Not-in-force EP2182212B1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR0857310A FR2937690B1 (fr) 2008-10-28 2008-10-28 Micropome a actionnement par gouttes

Publications (2)

Publication Number Publication Date
EP2182212A1 EP2182212A1 (de) 2010-05-05
EP2182212B1 true EP2182212B1 (de) 2012-02-29

Family

ID=40474704

Family Applications (1)

Application Number Title Priority Date Filing Date
EP09173788A Not-in-force EP2182212B1 (de) 2008-10-28 2009-10-22 Mikropumpe mit Betätigung durch Tropfen

Country Status (4)

Country Link
US (1) US20100104459A1 (de)
EP (1) EP2182212B1 (de)
AT (1) ATE547627T1 (de)
FR (1) FR2937690B1 (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2930457B1 (fr) * 2008-04-24 2010-06-25 Commissariat Energie Atomique Procede de fabrication de microcanaux reconfigurables
DE102011115622A1 (de) * 2010-12-20 2012-06-21 Technische Universität Ilmenau Mikropumpe sowie Vorrichtung und Verfahren zur Erzeugung einer Fluidströmung
RU2578262C2 (ru) * 2011-08-31 2016-03-27 Джонсон Энд Джонсон Вижн Кэа, Инк. Жидкостные менисковые линзы с улучшенным составом на основе физиологического раствора

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6565727B1 (en) * 1999-01-25 2003-05-20 Nanolytics, Inc. Actuators for microfluidics without moving parts
US8529743B2 (en) 2000-07-25 2013-09-10 The Regents Of The University Of California Electrowetting-driven micropumping
US6673453B2 (en) 2001-06-12 2004-01-06 Biocoat Incorporated Coatings appropriate for medical devices
US7329545B2 (en) * 2002-09-24 2008-02-12 Duke University Methods for sampling a liquid flow
US6911132B2 (en) * 2002-09-24 2005-06-28 Duke University Apparatus for manipulating droplets by electrowetting-based techniques
US20080135411A1 (en) * 2004-06-16 2008-06-12 Whitehead Lorne A Microfluidic Transport By Electrostatic Deformation of Fluidic Interfaces
US7299639B2 (en) 2004-06-22 2007-11-27 Intel Corporation Thermoelectric module
DE602005024418D1 (de) * 2004-08-26 2010-12-09 Life Technologies Corp Elektrobenetzende abgabevorrichtungen und dazugehörige verfahren
FR2879946B1 (fr) * 2004-12-23 2007-02-09 Commissariat Energie Atomique Dispositif de dispense de gouttes
US7976286B2 (en) * 2005-01-25 2011-07-12 The Regents Of The University Of California Method and apparatus for pumping liquids using directional growth and elimination bubbles
US7454988B2 (en) * 2005-02-10 2008-11-25 Applera Corporation Method for fluid sampling using electrically controlled droplets
JP4593507B2 (ja) * 2005-03-30 2010-12-08 ナノフュージョン株式会社 電気浸透流ポンプ及び液体供給装置
FR2887305B1 (fr) * 2005-06-17 2011-05-27 Commissariat Energie Atomique Dispositif de pompage par electromouillage et application aux mesures d'activite electrique
KR100781739B1 (ko) * 2005-09-28 2007-12-03 삼성전자주식회사 전기습윤에서 액적의 접촉각 변위 및 변화속도 증가방법 및상기 방법에 의해 형성된 액적을 적용한 액적제어장치
US7455912B2 (en) 2005-10-28 2008-11-25 Ppg Industries Ohio, Inc. Compositions containing a silanol functional polymer and related hydrophilic coating films
FR2896803B1 (fr) 2006-02-01 2010-12-10 Commissariat Energie Atomique Nouveaux composes silanes et leur utilisation pour fonctionnaliser des supports solides et immobiliser sur ces supports des molicules biologiques
US20080186801A1 (en) * 2007-02-06 2008-08-07 Qisda Corporation Bubble micro-pump and two-way fluid-driving device, particle-sorting device, fluid-mixing device, ring-shaped fluid-mixing device and compound-type fluid-mixing device using the same

Also Published As

Publication number Publication date
FR2937690B1 (fr) 2010-12-31
EP2182212A1 (de) 2010-05-05
US20100104459A1 (en) 2010-04-29
FR2937690A1 (fr) 2010-04-30
ATE547627T1 (de) 2012-03-15

Similar Documents

Publication Publication Date Title
EP2318136A1 (de) Verfahren und vorrichtung zur handhabung und überwachung von flüssigkeitstropfen
EP1827694B1 (de) Tropfenspendervorrichtung
EP2143948A2 (de) Mikrofluidisches System zur Verdrängung eines Flüssigkeits
WO2006134307A1 (fr) Dispositif de pompage par electromouillage et application aux mesures d'activite electrique
EP2161449B1 (de) Mikropumpe für kontinuierliche mikrofluidische Förderung
EP1376846B1 (de) Vorrichtung zum Austragen kleiner Volumen Flüssigkeit einer Mikrokettenlinie entlang
EP2282827B1 (de) Vorrichtung zur Trennung von Biomolekülen aus einer Flüssigkeit
EP2609993B1 (de) Nano- und mikro-fluidische Vorrichtung für die Trennung und Konzentration von in einem Fluid vorhandenen Partikeln
EP1567269B1 (de) Mikrofluides system mit stabilisierter flüssig-flüssig-grenzfläche
FR2887030A1 (fr) Dispositif planaire avec adressage de puits automatise par electromouillage dynamique
FR2866493A1 (fr) Dispositif de controle du deplacement d'une goutte entre deux ou plusieurs substrats solides
EP2182212B1 (de) Mikropumpe mit Betätigung durch Tropfen
EP3347128A1 (de) Trägersubstrat für flüssigkeitsprobe, anordnung mit solch einem substrat und verwendung davon
EP2268404A1 (de) Verfahren zur herstellung neukonfigurierbarer mikrokanäle
CN113070113B (zh) 芯片结构、成膜方法、纳米孔测序装置及应用
WO2003097238A1 (fr) Dispositif de depot localise et controle activement d'au moins une solution biologique.
FR3055429A1 (fr) Dispositif a actionnement electrostatique
FR2978437A1 (fr) Dispositif microfluidique comportant une chambre pour stocker un liquide
FR2887705A1 (fr) Dispositif de pompage ou de centrifugation des gouttes deplacees par electromouillage
FR2884243A1 (fr) Dispositif et procede de commutation par electromouillage
WO2014207183A1 (fr) Dispositif de separation d'une suspension
WO2005123257A1 (fr) Microdispositif et procede de separation d’emulsion
FR2853565A1 (fr) Microdispositif de transfert collectif d'une pluralite de liquide
Hsu et al. Formation, transportation, and evaporation of encapsulated droplets
WO2006027532A1 (fr) Dispositif de transfert d'elements contenus dans un liquide

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

17P Request for examination filed

Effective date: 20101011

17Q First examination report despatched

Effective date: 20110617

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 547627

Country of ref document: AT

Kind code of ref document: T

Effective date: 20120315

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: FRENCH

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602009005602

Country of ref document: DE

Effective date: 20120426

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20120229

LTIE Lt: invalidation of european patent or patent extension

Effective date: 20120229

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120229

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120229

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120529

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120629

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120229

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120629

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120229

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120530

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120229

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 547627

Country of ref document: AT

Kind code of ref document: T

Effective date: 20120229

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120229

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120229

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120229

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120229

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120229

Ref country code: IE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120229

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120229

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120229

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120229

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120229

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120229

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120229

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20121011

Year of fee payment: 4

Ref country code: FR

Payment date: 20121205

Year of fee payment: 4

26N No opposition filed

Effective date: 20121130

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602009005602

Country of ref document: DE

Effective date: 20121130

BERE Be: lapsed

Owner name: COMMISSARIAT A L'ENERGIE ATOMIQUE ET AUX ENERGIES

Effective date: 20121031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120609

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20121031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120529

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20121031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120229

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120229

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120229

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20121022

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20131022

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20091022

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20131031

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20131022

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20131031

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20140630

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602009005602

Country of ref document: DE

Effective date: 20140501

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140501

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20131031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120229