EP0672835B1 - Micro fluid diode - Google Patents
Micro fluid diode Download PDFInfo
- Publication number
- EP0672835B1 EP0672835B1 EP95101737A EP95101737A EP0672835B1 EP 0672835 B1 EP0672835 B1 EP 0672835B1 EP 95101737 A EP95101737 A EP 95101737A EP 95101737 A EP95101737 A EP 95101737A EP 0672835 B1 EP0672835 B1 EP 0672835B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fluid
- micro
- silicon
- diode
- capillaries
- 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.)
- Expired - Lifetime
Links
Images
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F15—FLUID-PRESSURE ACTUATORS; HYDRAULICS OR PNEUMATICS IN GENERAL
- F15C—FLUID-CIRCUIT ELEMENTS PREDOMINANTLY USED FOR COMPUTING OR CONTROL PURPOSES
- F15C4/00—Circuit elements characterised by their special functions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
- B01F25/30—Injector mixers
- B01F25/31—Injector mixers in conduits or tubes through which the main component flows
- B01F25/314—Injector mixers in conduits or tubes through which the main component flows wherein additional components are introduced at the circumference of the conduit
- B01F25/3142—Injector mixers in conduits or tubes through which the main component flows wherein additional components are introduced at the circumference of the conduit the conduit having a plurality of openings in the axial direction or in the circumferential direction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F33/00—Other mixers; Mixing plants; Combinations of mixers
- B01F33/30—Micromixers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L3/00—Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
- B01L3/50—Containers for the purpose of retaining a material to be analysed, e.g. test tubes
- B01L3/502—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures
- B01L3/5027—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T137/00—Fluid handling
- Y10T137/206—Flow affected by fluid contact, energy field or coanda effect [e.g., pure fluid device or system]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T137/00—Fluid handling
- Y10T137/206—Flow affected by fluid contact, energy field or coanda effect [e.g., pure fluid device or system]
- Y10T137/2224—Structure of body of device
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T137/00—Fluid handling
- Y10T137/8593—Systems
- Y10T137/87571—Multiple inlet with single outlet
- Y10T137/87652—With means to promote mixing or combining of plural fluids
Definitions
- the invention relates to a micro-fluid diode that is only permeable to fluid in one direction directional coupling of submicroliter amounts of one fluid medium into another standing or flowing target fluid in a closed system.
- Appropriate Requirements exist when dosing, mixing and injecting fluids in the sub-microliter range for applications in particular in the field of biomedical engineering and chemical microsensor technology.
- Liquid is a widely used procedure in the field of medical technology and Flow injection analysis. It is known to be by injecting through a rubber septum [P. W. Alexander et al., Analyst 107 (1982) 1335] or using rotary injection valves [M. D. Luque de Castro et al., Analyst 109 (1984) 413] or based on the hydrodynamic injection [J. Ruzicka et al., Anal. Chim. Acta, 145 (1983) 1].
- the devices that use these techniques and are currently commercially available are based exclusively on costly precision mechanical manufacturing technologies.
- the aim of the invention is to avoid adhering to the micromechanical valves Problems a technical solution for coupling a dosing fluid into a standing one or flowing target fluid can be found, which has a high dosing accuracy in the Has submicroliter range and maximum security against penetration of the target fluid into the dosing fluid.
- the object is achieved by a micro-fluid diode which is only permeable to fluid in one direction and which consists of one or a system of a plurality of microcapillaries which are open on both sides and are in direct contact on the output side with the target fluid and whose input side facing the metering fluid is provided by an air or gas cushion is separated from the metering fluid so that the target fluid that expands in the capillaries is prevented from advancing due to the surface tension with the formation of a meniscus.
- the metering fluid is applied to this meniscus discontinuously, preferably as a self-supporting fluid jet, and is coupled into the target fluid as a result of diffusion or convection processes.
- the micro-fluid diode according to the invention is preferably integrated into a microtechnical flow channel, whereby it reliably prevents the liquid (target fluid) standing or flowing in the flow channel from escaping and at the same time ensures the entry of a second liquid (metering fluid) to be applied to the micro-fluid diode from the outside.
- a coupling surface for the introduction of microdrops of a metering fluid is formed by the large number of open capillaries directed outwards.
- the gas-liquid interface at each end of the microcapillaries is a mandatory prerequisite for the maintenance of the micro-fluid diode function at all times for the component functions and thus part of the component.
- the microcapillaries have three-dimensional dimensions in the ⁇ m range and, due to the high precision requirements for their geometry, are preferably manufactured by anisotropic etching on ⁇ 100> or ⁇ 110> silicon substrates.
- the length of each individual microcapillary is to be dimensioned such that the target fluid extends up to the capillary ends, and there, under the influence of the surface tension and the acting fluidic gravity pressures, forms a defined liquid-gas interface in the form of a meniscus at each microcapillary end.
- each meniscus With the formation of each meniscus, the process of spreading the liquid in the corresponding microcapillary is completed and the coupling surface is thus brought into a reproducible state.
- This state represents the prevailing equilibrium between the static gravity pressures and, in the event that the target fluid moves in the flow channel, the dynamic hydrostatic pressures. As long as the equilibrium conditions of the pressures are met, the desired directional dependence exists on all menisci of the entire coupling area. This means that the target fluid moved or standing in the flow channel does not leave the microcapillaries in the direction of the droplet chamber, but a metering fluid sprayed through the gas space of the droplet chamber onto any meniscus can get into the interior of the microcapillary and thus the flow channel.
- the unhindered entry of the second liquid into the flow channel via the meniscus of the first liquid takes place via diffusion and / or convection mechanisms.
- the flow velocity in the flow channel is exactly zero or the microcapillaries of the micro fluid diode are chosen long enough, only the diffusion component comes into play when the metering and target fluids are mixed. All flow velocities other than zero in the channel lead directly to the formation of convection components in the microcapillary, which are also superimposed by diffusion components.
- the rate of inflow of the metering fluid through the microcapillaries of the coupling surface into the flow channel can be adjusted by choosing their geometric dimensions.
- the figure shows the sectional view of the planar construction of a complete MFD component containing the actual inventive micro fluid diode (hereinafter referred to as MFD).
- the MFD is a chip-shaped component 1 made entirely of ⁇ 100> or ⁇ 110> silicon. It is etched on one side as a lattice structure 6 and on the other side as a continuous flow channel 9.
- the MFD chip 1 is mounted with the spacer chip 2, which is also made of silicon, in the glass-silicon flow cell 3 in such a way that a target fluid 7 can move past the MFD unhindered, thereby forming 6 small micromenisci in the lattice structure.
- the lattice structure forms the coupling surface of the microfluidic diode in the direction of the spacer chip 2.
- the entire component of the MFD comprises the stack arrangement of fluidic flow cell 3, 4 with flow channel 7, 9 and channel stopper 8, the MFD chip 1 with its microcapillary array 6 and the spacer chip 2, which is connected to the adjacent gas or air cushion over the microcapillary array.
- the spacer chip 2, which forms the droplet chamber, is also produced by anisotropic etching in ⁇ 100> silicon. If the flow channel 7 is now flowed through by the target fluid, it wets the microcapillaries and spreads up to their opposite opening, where it forms a target fluid meniscus 6 independently of the flow speed depending on its surface tension and the system-internal gravity pressures, the total field of the capillary openings providing a coupling area for one Dosing fluid forms. If the metering fluid 5 is now sprayed onto this coupling surface 6 by means of a microtechnical pump, it can pass through the MFD arrangement 1 and directly reach the flow channel of the target fluid.
- the micro fluid diode according to the invention provides a new element for microfluid handling without mechanical valves.
- the construction of the micro fluid diode according to the invention is much simpler than that of the micromechanical valves, so that in addition to the smaller space requirement, the production is more cost-effective.
- they can be used to implement a new concept for coupling unsupported fluid jets into a flowing target fluid located in a closed system.
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Engineering & Computer Science (AREA)
- Fluid Mechanics (AREA)
- Physics & Mathematics (AREA)
- Theoretical Computer Science (AREA)
- Mechanical Engineering (AREA)
- Micromachines (AREA)
- Automatic Analysis And Handling Materials Therefor (AREA)
- Reciprocating Pumps (AREA)
- Bipolar Transistors (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Thermistors And Varistors (AREA)
Abstract
Description
Die Erfindung betrifft eine nur in einer Richtung fluiddurchlässige Mikro-Fluiddiode zur gerichteten Einkopplung von Submikrolitermengen eines Fluidmediums in ein anderes stehendes oder strömendes, in einem geschlossenen System befindliches Zielfluid. Entsprechende Anforderungen bestehen beim Dosieren, Mischen und Injizieren von Fluiden im Submikroliter-Bereich für Anwendungen insbesondere im Bereich der Biomedizintechnik und der chemischen Mikrosensorik.The invention relates to a micro-fluid diode that is only permeable to fluid in one direction directional coupling of submicroliter amounts of one fluid medium into another standing or flowing target fluid in a closed system. Appropriate Requirements exist when dosing, mixing and injecting fluids in the sub-microliter range for applications in particular in the field of biomedical engineering and chemical microsensor technology.
Die Einkopplung einer Flüssigkeit in eine andere, in einem geschlossenen System befindliche Flüssigkeit ist eine weit verbreitete Prozedur im Bereich der Medizintechnik und der Fließinjektionsanalyse. Sie wird bekannterweise durch Injizieren durch ein Gummiseptum [P. W. Alexander et al., Analyst 107 (1982) 1335] oder mit Hilfe von Rotationsinjektionsventilen [M. D. Luque de Castro et al., Analyst 109 (1984) 413] oder auf der Basis der hydrodynamischen Injektion [J. Ruzicka et al., Anal. Chim. Acta, 145 (1983) 1] realisiert. Die diese Techniken nutzenden, und derzeit kommerziell verfügbaren Geräte basieren ausschließlich auf kostenaufwendigen feinmechanischen Fertigungstechnologien. Bekannt sind weiterhin Entwicklungsarbeiten, die sich mit piezoelektrisch angetriebenen mikromechanischen Ventilen auf der Basis der Silizium-Technologie, insbesondere für den Einsatz in chemischen Mikroanalysatoren befassen [Van der Schoot et al., A Silicon Integrated Miniature Chemical Analysis System, Sensors and Actuators B6 (1992) 57-60]. Der Problemkreis diesbezüglich ist gegenwärtig noch nicht vollständig erfaßbar, da die Entwicklung noch ganz am Anfang steht. Momentan erkennbar sind folgende Probleme. Mechanische Ventile können nicht absolut schließen. Die Dosiergenauigkeit ist dadurch eingeschränkt. Das zweite Problem ist der große Platzbedarf von solchen mikromechanischen Elementen. Das dritte Problem ist die aufwendige Herstellungstechnologie, da Ventilstrukturen kompliziert sind.The coupling of one liquid into another, in a closed system Liquid is a widely used procedure in the field of medical technology and Flow injection analysis. It is known to be by injecting through a rubber septum [P. W. Alexander et al., Analyst 107 (1982) 1335] or using rotary injection valves [M. D. Luque de Castro et al., Analyst 109 (1984) 413] or based on the hydrodynamic injection [J. Ruzicka et al., Anal. Chim. Acta, 145 (1983) 1]. The devices that use these techniques and are currently commercially available are based exclusively on costly precision mechanical manufacturing technologies. Known are still development work dealing with piezoelectrically driven micromechanical Valves based on silicon technology, especially for use in chemical microanalysers [Van der Schoot et al., A Silicon Integrated Miniature Chemical Analysis System, Sensors and Actuators B6 (1992) 57-60]. Of the The problem area in this regard is currently not fully comprehensible, since the Development is just beginning. The following problems are currently recognizable. Mechanical valves cannot close absolutely. The dosing accuracy is thereby limited. The second problem is the large space requirement of such micromechanical Elements. The third problem is the complex manufacturing technology there Valve structures are complicated.
Mit der Erfindung soll unter Vermeidung der den mikromechanischen Ventilen anhaftenden Probleme eine technische Lösung zur Einkopplung eines Dosierfluides in ein stehendes oder strömendes Zielfluid gefunden werden, welches eine hohe Dosiergenauigkeit im Submikroliterbereich aufweist und höchste Sicherheit gegen ein Eindringen des Zielfluids in das Dosierfluid bietet.The aim of the invention is to avoid adhering to the micromechanical valves Problems a technical solution for coupling a dosing fluid into a standing one or flowing target fluid can be found, which has a high dosing accuracy in the Has submicroliter range and maximum security against penetration of the target fluid into the dosing fluid.
Die Aufgabe wird erfindungsgemäß durch eine nur in einer Richtung fluiddurchlässige
Mikro-Fluiddiode gelöst, welche aus einer, oder einem System von mehreren beidseitig
offenen Mikrokapillaren besteht, welche ausgangsseitig mit dem Zielfluid in direktem
Kontakt stehen, und deren dem Dosierfluid zugewandte Eingangsseite durch ein Luft- bzw.
Gaspolster vom Dosierfluid so getrennt ist, daß das in den Kapillaren emporspreitende
Zielfluid infolge der Oberflächenspannung unter Ausbildung eines Meniskus am Weiterdringen
gehindert wird. Das Dosierfluid wird diskontinuierlich, vorzugsweise als freitragender
Fluidstrahl auf diesen Meniskus aufgebracht und infolge Diffusions- bzw. Konvektionsvorgängen
in das Zielfluid eingekoppelt.
Die erfindungsgemäße Mikro-Fluiddiode wird vorzugsweise in einen mikrotechnischen
Strömungskanal integriert, wobei sie den Austritt der im Strömungskanal stehenden oder
strömenden Flüssigkeit ( Zielfluid ) sicher verhindert und gleichzeitig den Eintritt einer
von außen auf die Mikro-Fluiddiode aufzubringenden zweiten Flüssigkeit ( Dosierfluid )
gewährleistet. Bei der erfindungsgemäßen Anordnung einer siebartigen Struktur von
Mikrokapillaren an einen Strömungskanal wird durch die große Anzahl der nach außen
gerichteten offenen Kapillaren eine Einkopplungsfläche für den Eintrag von Mikrotropfen
eines Dosierfluides gebildet. Die Gas-Flüssigkeits-Grenzfläche an jedem Ende der Mikrokapillaren
ist dabei für die Aufrechterhaltung der Mikro-Fluiddiodenfunktion zu jedem
Moment zwingende Voraussetzung für die Bauelementefunktionen und somit Teil des
Bauelementes.
Die Mikrokapillaren haben dreidimensionale Abmessungen im µm-Bereich und werden
aufgrund der hohen Präzisionsanforderungen an deren Geometrie vorzugsweise durch
anisotropes Ätzen an <100>- oder <110>-Siliciumsubstraten gefertigt. Die Länge jeder
einzelnen Mikrokapillare ist so zu bemessen, daß das Zielfluid bis zu den Kapillarenden
emporspreitet, und dort unter dem Einfluß der Oberflächenspannung und den einwirkenden
fluidischen Schweredrücken an jedem Mikrokapillarende eine definierte Flüssigkeits-Gas-Grenzfläche
in Form eines Meniskus ausbildet. Mit der Ausbildung jedes Meniskus wird
der Vorgang des Spreitens der Flüssigkeit in der entsprechenden Mikrokapillare abgeschlossen
und so die Einkopplungsfläche in einen reproduzierbaren Zustand versetzt.
Dieser Zustand repräsentiert das herrschende Gleichgewicht zwischen den statischen
Schweredrücken und für den Fall das sich das Zielfluid im Strömungskanal bewegt, der
dynamischen hydrostatischen Drücke. Solange die Gleichgewichtsbedingungen der Drücke
erfüllt sind, existiert die gewünschte Richtungsabhänigkeit an allen Menisken der gesamten
Einkopplungsfläche. Dies bedeutet, daß das im Strömungskanal bewegte oder stehende
Zielfluid die Mikrokapillaren in Richtung Tröpfchenkammer nicht verlassen, sehr wohl
aber ein durch den Gasraum der Tröpfchenkammer auf einen beliebigen Meniskus gespritztes
Dosierfluid in das Innere der Mikrokapillare und somit des Strömungskanales
gelangen kann. Der ungehinderte Eintritt der zweiten Flüssigkeit über den Meniskus der
ersten Flüssigkeit in den Strömungskanal erfolgt über Diffusions- und/oder Konvektionsmechanismen.
Für den Fall, daß die Strömungsgeschwindigkeit im Strömungskanal genau
Null ist oder die Mikrokapillaren der Mikro-Fluiddiode lang genug gewählt werden,
kommt allein die Diffusionskomponente bei der Vermischung von Dosier- und Zielfluid
zum Tragen. Alle von Null verschiedenen Strömungsgeschwindigkeiten im Kanal führen
direkt zur Ausprägung von Konvektionskomponenten in der Mikrokapillare, die ebenfalls
von Diffusionskomponenten überlagert werden. Die Einströmgeschwindigkeit des Dosierfluides
über die Mikrokapillaren der Einkopplungsfläche in den Strömungskanal läßt sich
durch Wahl deren geometrischer Abmessungen einstellen.According to the invention, the object is achieved by a micro-fluid diode which is only permeable to fluid in one direction and which consists of one or a system of a plurality of microcapillaries which are open on both sides and are in direct contact on the output side with the target fluid and whose input side facing the metering fluid is provided by an air or gas cushion is separated from the metering fluid so that the target fluid that expands in the capillaries is prevented from advancing due to the surface tension with the formation of a meniscus. The metering fluid is applied to this meniscus discontinuously, preferably as a self-supporting fluid jet, and is coupled into the target fluid as a result of diffusion or convection processes.
The micro-fluid diode according to the invention is preferably integrated into a microtechnical flow channel, whereby it reliably prevents the liquid (target fluid) standing or flowing in the flow channel from escaping and at the same time ensures the entry of a second liquid (metering fluid) to be applied to the micro-fluid diode from the outside. In the arrangement according to the invention of a sieve-like structure of microcapillaries on a flow channel, a coupling surface for the introduction of microdrops of a metering fluid is formed by the large number of open capillaries directed outwards. The gas-liquid interface at each end of the microcapillaries is a mandatory prerequisite for the maintenance of the micro-fluid diode function at all times for the component functions and thus part of the component.
The microcapillaries have three-dimensional dimensions in the µm range and, due to the high precision requirements for their geometry, are preferably manufactured by anisotropic etching on <100> or <110> silicon substrates. The length of each individual microcapillary is to be dimensioned such that the target fluid extends up to the capillary ends, and there, under the influence of the surface tension and the acting fluidic gravity pressures, forms a defined liquid-gas interface in the form of a meniscus at each microcapillary end. With the formation of each meniscus, the process of spreading the liquid in the corresponding microcapillary is completed and the coupling surface is thus brought into a reproducible state. This state represents the prevailing equilibrium between the static gravity pressures and, in the event that the target fluid moves in the flow channel, the dynamic hydrostatic pressures. As long as the equilibrium conditions of the pressures are met, the desired directional dependence exists on all menisci of the entire coupling area. This means that the target fluid moved or standing in the flow channel does not leave the microcapillaries in the direction of the droplet chamber, but a metering fluid sprayed through the gas space of the droplet chamber onto any meniscus can get into the interior of the microcapillary and thus the flow channel. The unhindered entry of the second liquid into the flow channel via the meniscus of the first liquid takes place via diffusion and / or convection mechanisms. In the event that the flow velocity in the flow channel is exactly zero or the microcapillaries of the micro fluid diode are chosen long enough, only the diffusion component comes into play when the metering and target fluids are mixed. All flow velocities other than zero in the channel lead directly to the formation of convection components in the microcapillary, which are also superimposed by diffusion components. The rate of inflow of the metering fluid through the microcapillaries of the coupling surface into the flow channel can be adjusted by choosing their geometric dimensions.
Der besondere Vorteil dieser Anordnung besteht darin, daß fluidische Einströmungs- oder Mischstellen realisiert werden können, die auf den Einsatz konventioneller Ventile-Pumpe-Anordnungen verzichten können, welche bislang durch mechanisch aufeinanderliegende Lippendichtungen mit plastischen oder elastischen Dichtungsmaterialien hergestellt wurden. Solche Anordnungen sind in makrotechnischen Konstruktionen aufwendig und in mikrotechischen Bauelementen nur unter Inkaufnahme wesentlicher Nachteile nutzbar. So sind die aus der Literatur bekannten Anordnungen, die sich an den makrotechischen Konstruktionsprinzipien orientieren, generell mit Leckraten behaftet. Gerade für den Einsatz in Mikrosystemen der Umwelt- und biomedizinischen Technik ist aber durch die notwendige Applizierung von hochkonzentrierten Wirkstoffen im Pikoliter- bis Nanoliterbereich das Auftreten von Leckraten nicht mehr tolerierbar. The particular advantage of this arrangement is that fluidic inflow or Mixing points can be realized using conventional valve-pump arrangements can do without, which was previously due to mechanically superimposed Lip seals were made with plastic or elastic sealing materials. Such arrangements are complex in macro-technical constructions and in microtech Components can only be used if significant disadvantages are accepted. That's how they are Arrangements known from the literature, which are based on the macrotech construction principles orient, generally with leak rates. Especially for use in microsystems of environmental and biomedical technology is due to the necessary application of highly concentrated active ingredients in the picoliter to nanoliter range Leakage rates no longer tolerable.
Die Herstellung definierter und gegenüber Schweredruckschwankungen im Strömungskanal relativ unempfindlicher Gas-Flüssigkeits-Grenzflächen im Bereich der Tröpfchenkammer, hier in Form des Meniskus an der Mikro-Fluiddiode zum Einsatz kommend, sind eine ebenso einfache wie wirkungsvolle Konstruktionsform, die auch zum Aufbau von Anordnungen geeignet sind, welche hinsichtlich ihrer Wirkungen mit konventionellen Ventil-Pumpe-Anordnungen vergleichbar sind, dabei ideal keine Leckraten aufweisen.The production of defined and against gravitational pressure fluctuations in the flow channel relatively insensitive gas-liquid interfaces in the area of the droplet chamber, used here in the form of the meniscus on the micro fluid diode are one construction form that is as simple as it is effective, and that can also be used to set up arrangements which are suitable in terms of their effects with conventional valve-pump arrangements are comparable, ideally have no leakage rates.
Nachfolgend wird die Erfindung anhand des in der Zeichnung dargestellten Ausführungsbeispieles näher erläutert.The invention based on the embodiment shown in the drawing explained in more detail.
Die Figur zeigt die Schnittarstellung der planaren Konstruktion eines die eigentliche erfindungsgemäße
Mikro-Fluiddiode (im weiteren MFD) enthaltenden kompletten MFD-Bauelementes.
Die MFD ist ein vollständig aus <100>- oder <110>-Silicium hergestelltes
chipförmiges Bauelement 1. Sie wird einseitig als Gitterstruktur 6 und anderseitig als
fortgesetzter Strömungskanal 9 geätzt. Das MFD-Chip 1 wird mit dem ebenfalls aus
Silicium bestehenden Spacerchip 2 so in die Glas-Silicium-Durchflußzelle 3 montiert, daß
sich ein Zielfluid 7 ungehindert an der MFD vorbei bewegen kann und dabei in der
Gitterstruktur 6 kleine Mikromenisken ausbildet. Die Gitterstruktur bildet in Richtung des
Spacerchips 2 die Einkopplungsfläche der Mikrofluiddiode. Die Herstellung des MFD-Chips
1 erfolgt durch zweiseitiges anisotropes Ätzen in KOH-Lösung. Dabei entstehen ein
Strömungskanal 9 im MFD-Chip 1 der Geometrie L:B:H= 1000 µm : 500 µm : 250 µm,
sowie die Mikrokapillaren der Geometrie L:B:H= 50 µm : 50 µm : 150 µm. Die Geometrie
des Strömungskanales in der durch anodisches Bonden hergestellten Glas-Silicium-Durchflußzelle
3, 4 beträgt B:H = 500 µm : 250 µm.
Das gesamte Bauelement der MFD umfaßt die durch Waferbonden oder Kleben miteinander
verbundene Stapelanordnung aus fluidischer Durchflußzelle 3, 4 mit Strömungskanal
7, 9 und Kanalstopper 8, dem MFD-Chip 1 mit seinem Mikrokapillarenarray 6 und dem
Spacerchip 2, der das angrenzende Gas- oder Luftpolster über dem Mikrokapillarenarray
bildet. Auch der Spacerchip 2, welcher die Tröpfchenkammer bildet, wird durch anisotropes
Ätzen in <100>-Silicium hergestellt.
Wird nun der Strömungskanal 7 vom Zielfluid durchströmt, benetzt dieses die Mikrokapillaren
und spreitet zu deren gegenüberliegender Öffnung empor, wo es unabhänig von der
Strömungsgeschwindigkeit in Abhänigkeit von seiner Oberflächensspannung und den
systeminneren Schweredrücken einen Zielfluidmeniskus 6 ausbildet, wobei das Gesamtfeld
der Kapillaröffnungen eine Einkopplungsfläche für ein Dosierfluid bildet. Wird nun das
Dosierfluid 5 mittels einer mikrotechnischen Pumpe auf diese Einkopplungsfläche 6 gespritzt,
kann es die MFD-Anordnung 1 durchlaufen und direkt den Strömungskanal des
Zielfluides erreichen.The figure shows the sectional view of the planar construction of a complete MFD component containing the actual inventive micro fluid diode (hereinafter referred to as MFD). The MFD is a chip-
The entire component of the MFD comprises the stack arrangement of
If the
Mit der erfindungsgemäßen Mikro-Fluiddiode wird ein neues Element zum Mikrofluidhandling
ohne mechanische Ventile bereitgestellt. Die Konstruktion der erfindungsgemäßen
Mikro-Fluiddiode ist wesentlich einfacher als die der mikromechanischen Ventile,
so daß neben dem kleineren Platzbedarf die Herstellung kostengünstiger ist.
Im besonderen läßt sich mit deren Hilfe ein neues Konzept zur Einkopplung von freitragenden
Fluidstrahlen in ein strömendes, in einem geschlossenen System befindliches
Zielfluid realisieren.The micro fluid diode according to the invention provides a new element for microfluid handling without mechanical valves. The construction of the micro fluid diode according to the invention is much simpler than that of the micromechanical valves, so that in addition to the smaller space requirement, the production is more cost-effective.
In particular, they can be used to implement a new concept for coupling unsupported fluid jets into a flowing target fluid located in a closed system.
Claims (3)
- Micro fluid diode (1) to directionally inject a dosing fluid (5) into another standing or flowing target fluid (7) found in a contained system, particularly in the submicrolitre range, distinguished by a planar arrangement of a microcapillary open at both ends or a system of microcapillaries (6) open at both ends and arranged closely beside each other, which at the outlet end are in direct contact with the target fluid and at the input side are separated by an air or gas buffer from the dosing fluid, which is to be fed intermittently, forming a curved meniscus in accordance with the surface tension.
- Micro fluid diode (1) as in claim 1, a distinguishing feature of which is that its components are composed of silicon, glass, ceramics, metal or a combination of these materials and produced by means of microscopic processes and micro systems engineering building and connecting means.
- Micro fluid diode (1) as in claim 1, a distinguishing feature of which is that it is produced of silicon with <100> - <110> - orientation.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4405005 | 1994-02-17 | ||
DE4405005A DE4405005A1 (en) | 1994-02-17 | 1994-02-17 | Micro fluid diode |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0672835A1 EP0672835A1 (en) | 1995-09-20 |
EP0672835B1 true EP0672835B1 (en) | 1999-05-12 |
Family
ID=6510442
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP95101737A Expired - Lifetime EP0672835B1 (en) | 1994-02-17 | 1995-02-09 | Micro fluid diode |
Country Status (7)
Country | Link |
---|---|
US (1) | US5730187A (en) |
EP (1) | EP0672835B1 (en) |
JP (1) | JP3786421B2 (en) |
AT (1) | ATE180044T1 (en) |
DE (2) | DE4405005A1 (en) |
DK (1) | DK0672835T3 (en) |
WO (1) | WO1995022696A1 (en) |
Families Citing this family (54)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19530886C1 (en) * | 1995-08-11 | 1996-10-02 | Inst Bioprozess Analysenmesst | Sterile sampling appts., esp. for bio-technical processes |
DE19611270A1 (en) * | 1996-03-22 | 1997-09-25 | Gesim Ges Fuer Silizium Mikros | Micro-mixer for very small volumes of liquids or suspensions |
US6033544A (en) * | 1996-10-11 | 2000-03-07 | Sarnoff Corporation | Liquid distribution system |
US5964997A (en) * | 1997-03-21 | 1999-10-12 | Sarnoff Corporation | Balanced asymmetric electronic pulse patterns for operating electrode-based pumps |
US6117396A (en) * | 1998-02-18 | 2000-09-12 | Orchid Biocomputer, Inc. | Device for delivering defined volumes |
JP2981547B1 (en) * | 1998-07-02 | 1999-11-22 | 農林水産省食品総合研究所長 | Cross-flow type microchannel device and method for producing or separating emulsion using the device |
JP3012608B1 (en) * | 1998-09-17 | 2000-02-28 | 農林水産省食品総合研究所長 | Microchannel device and method for producing emulsion using the same |
WO2000022436A1 (en) * | 1998-10-13 | 2000-04-20 | Biomicro Systems, Inc. | Fluid circuit components based upon passive fluid dynamics |
US6637463B1 (en) | 1998-10-13 | 2003-10-28 | Biomicro Systems, Inc. | Multi-channel microfluidic system design with balanced fluid flow distribution |
US6601613B2 (en) | 1998-10-13 | 2003-08-05 | Biomicro Systems, Inc. | Fluid circuit components based upon passive fluid dynamics |
US6591852B1 (en) | 1998-10-13 | 2003-07-15 | Biomicro Systems, Inc. | Fluid circuit components based upon passive fluid dynamics |
US6360775B1 (en) | 1998-12-23 | 2002-03-26 | Agilent Technologies, Inc. | Capillary fluid switch with asymmetric bubble chamber |
US6561208B1 (en) * | 2000-04-14 | 2003-05-13 | Nanostream, Inc. | Fluidic impedances in microfluidic system |
US6481453B1 (en) * | 2000-04-14 | 2002-11-19 | Nanostream, Inc. | Microfluidic branch metering systems and methods |
US6296452B1 (en) | 2000-04-28 | 2001-10-02 | Agilent Technologies, Inc. | Microfluidic pumping |
US6615856B2 (en) * | 2000-08-04 | 2003-09-09 | Biomicro Systems, Inc. | Remote valving for microfluidic flow control |
JP3511238B2 (en) | 2000-10-13 | 2004-03-29 | 独立行政法人食品総合研究所 | Microsphere manufacturing method and manufacturing apparatus |
EP1334279A1 (en) | 2000-11-06 | 2003-08-13 | Nanostream, Inc. | Uni-directional flow microfluidic components |
US6649078B2 (en) | 2000-12-06 | 2003-11-18 | The Regents Of The University Of California | Thin film capillary process and apparatus |
US20020186263A1 (en) * | 2001-06-07 | 2002-12-12 | Nanostream, Inc. | Microfluidic fraction collectors |
US20030015425A1 (en) * | 2001-06-20 | 2003-01-23 | Coventor Inc. | Microfluidic system including a virtual wall fluid interface port for interfacing fluids with the microfluidic system |
US7211442B2 (en) * | 2001-06-20 | 2007-05-01 | Cytonome, Inc. | Microfluidic system including a virtual wall fluid interface port for interfacing fluids with the microfluidic system |
US20020195343A1 (en) * | 2001-06-20 | 2002-12-26 | Coventor, Inc. | Microfabricated separation device employing a virtual wall for interfacing fluids |
US20020197733A1 (en) * | 2001-06-20 | 2002-12-26 | Coventor, Inc. | Microfluidic system including a virtual wall fluid interface port for interfacing fluids with the microfluidic system |
US7179423B2 (en) | 2001-06-20 | 2007-02-20 | Cytonome, Inc. | Microfluidic system including a virtual wall fluid interface port for interfacing fluids with the microfluidic system |
EP1314479A3 (en) * | 2001-11-24 | 2004-03-24 | GeSIM Gesellschaft für Silizium-Mikrosysteme mbH | Device for the transfer of liquid samples |
US6932502B2 (en) * | 2002-05-01 | 2005-08-23 | Hewlett-Packard Development Company, L.P. | Mixing apparatus |
US20050032238A1 (en) * | 2003-08-07 | 2005-02-10 | Nanostream, Inc. | Vented microfluidic separation devices and methods |
KR100540143B1 (en) * | 2003-12-22 | 2006-01-10 | 한국전자통신연구원 | Microfluidic control device and method for controlling microfluidic |
JP4520166B2 (en) * | 2004-02-02 | 2010-08-04 | 独立行政法人農業・食品産業技術総合研究機構 | Resin microchannel substrate and manufacturing method thereof |
JP4700003B2 (en) * | 2004-08-12 | 2011-06-15 | 独立行政法人農業・食品産業技術総合研究機構 | Micro channel array |
US8685711B2 (en) | 2004-09-28 | 2014-04-01 | Singulex, Inc. | Methods and compositions for highly sensitive detection of molecules |
US7572640B2 (en) * | 2004-09-28 | 2009-08-11 | Singulex, Inc. | Method for highly sensitive detection of single protein molecules labeled with fluorescent moieties |
US9040305B2 (en) * | 2004-09-28 | 2015-05-26 | Singulex, Inc. | Method of analysis for determining a specific protein in blood samples using fluorescence spectrometry |
WO2006047757A1 (en) * | 2004-10-26 | 2006-05-04 | Massachusetts Institute Of Technology | Systems and methods for transferring a fluid sample |
CA3086149A1 (en) | 2006-04-04 | 2007-10-11 | Singulex, Inc. | Highly sensitive system and methods for analysis of troponin |
US7838250B1 (en) | 2006-04-04 | 2010-11-23 | Singulex, Inc. | Highly sensitive system and methods for analysis of troponin |
EP3156799B1 (en) | 2006-04-04 | 2024-01-24 | Novilux, LLC | Analyzer and method for highly sensitive detection of analytes |
KR101419312B1 (en) * | 2006-09-01 | 2014-07-14 | 도소 가부시키가이샤 | Microchannel structure and fine-particle production method using the same |
EP2111551A1 (en) * | 2006-12-20 | 2009-10-28 | Applied Biosystems, LLC | Devices and methods for flow control in microfluidic structures |
US20090087860A1 (en) * | 2007-08-24 | 2009-04-02 | Todd John A | Highly sensitive system and methods for analysis of prostate specific antigen (psa) |
CN103543094B (en) | 2007-12-19 | 2017-06-09 | 神谷来克斯公司 | Single Molecule Detection scanning analysis device and application method |
US20090234202A1 (en) * | 2008-03-05 | 2009-09-17 | Goix Philippe J | Method and compositions for highly sensitive detection of molecules |
GB2464183A (en) * | 2008-09-19 | 2010-04-14 | Singulex Inc | Sandwich assay |
WO2010144358A1 (en) | 2009-06-08 | 2010-12-16 | Singulex, Inc. | Highly sensitive biomarker panels |
CA2798149A1 (en) | 2010-05-06 | 2011-11-10 | Singulex, Inc | Methods for diagnosing, staging, predicting risk for developing and identifying treatment responders for rheumatoid arthritis |
CN103240023B (en) * | 2013-05-09 | 2015-01-07 | 四川大学 | Method for triggering droplet fusion through micro scalpel |
US11085039B2 (en) | 2016-12-12 | 2021-08-10 | xCella Biosciences, Inc. | Methods and systems for screening using microcapillary arrays |
CA3046827A1 (en) | 2016-12-12 | 2018-06-21 | xCella Biosciences, Inc. | Methods and systems for screening using microcapillary arrays |
CA3048904A1 (en) | 2016-12-30 | 2018-07-05 | xCella Biosciences, Inc. | Multi-stage sample recovery system |
EP3871774A1 (en) * | 2017-04-24 | 2021-09-01 | miDiagnostics NV | A channel and a capillary trigger valve comprising the same |
EP4090464A1 (en) | 2020-01-17 | 2022-11-23 | F. Hoffmann-La Roche AG | Microfluidic device and method for automated split-pool synthesis |
CN115003415A (en) | 2020-01-22 | 2022-09-02 | 豪夫迈·罗氏有限公司 | Microfluidic bead capture device and method for next generation sequencing library preparation |
EP4228793A1 (en) | 2020-10-15 | 2023-08-23 | Kapa Biosystems, Inc. | Electrophoretic devices and methods for next-generation sequencing library preparation |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3777344A (en) * | 1969-05-28 | 1973-12-11 | Cava Ind | Method of fabricating fluidic elements by assembling together a plurality of plastic strips |
US3865136A (en) * | 1971-04-29 | 1975-02-11 | Eke Verschuur | Oil/water pipeline inlet with oil supply via a large chamber |
US4027407A (en) * | 1975-11-24 | 1977-06-07 | Kiss Sandor G | Jet flow alternator |
US4761077A (en) * | 1987-09-28 | 1988-08-02 | Barrett, Haentjens & Co. | Mixing apparatus |
DE4003063A1 (en) * | 1990-01-24 | 1991-07-25 | Hopf Rolf | Conventional valve replacement method - using piezoelectric or ferroelectric material, deformed by applied voltage to open or close holes or slits to modulate fluid flow |
US5094594A (en) * | 1990-04-23 | 1992-03-10 | Genomyx, Incorporated | Piezoelectric pumping device |
US5165440A (en) * | 1991-12-30 | 1992-11-24 | Conoco Inc. | Process and apparatus for blending viscous polymers in solvent |
-
1994
- 1994-02-17 DE DE4405005A patent/DE4405005A1/en not_active Withdrawn
-
1995
- 1995-02-09 DK DK95101737T patent/DK0672835T3/en active
- 1995-02-09 AT AT95101737T patent/ATE180044T1/en not_active IP Right Cessation
- 1995-02-09 DE DE59505877T patent/DE59505877D1/en not_active Expired - Fee Related
- 1995-02-09 EP EP95101737A patent/EP0672835B1/en not_active Expired - Lifetime
- 1995-02-17 JP JP52150895A patent/JP3786421B2/en not_active Expired - Lifetime
- 1995-02-17 US US08/696,990 patent/US5730187A/en not_active Expired - Lifetime
- 1995-02-17 WO PCT/DE1995/000200 patent/WO1995022696A1/en active Application Filing
Also Published As
Publication number | Publication date |
---|---|
DK0672835T3 (en) | 1999-11-29 |
ATE180044T1 (en) | 1999-05-15 |
JP3786421B2 (en) | 2006-06-14 |
JPH09509466A (en) | 1997-09-22 |
DE4405005A1 (en) | 1995-08-24 |
US5730187A (en) | 1998-03-24 |
EP0672835A1 (en) | 1995-09-20 |
DE59505877D1 (en) | 1999-06-17 |
WO1995022696A1 (en) | 1995-08-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0672835B1 (en) | Micro fluid diode | |
EP1108149B1 (en) | Miniaturized fluid flow switch | |
DE19648695C2 (en) | Device for the automatic and continuous analysis of liquid samples | |
EP1320686B1 (en) | Micro valve normally in a closed position | |
DE60201580T2 (en) | DEVICE FOR CONNECTING CAPILLARY TUBES WITH A MICROFLUIDIC SYSTEM | |
EP2205869B1 (en) | Membrane pump | |
WO2011091943A1 (en) | Micro-fluidic component for manipulating a fluid, and microfluidic chip | |
DE4422743A1 (en) | Micropump | |
DE112005000445T5 (en) | Microchemical system | |
EP1331538A1 (en) | Piezo-electrically controlled micro actuator for fluids | |
EP2731721B1 (en) | Microfluidic device and method for producing a microfluidic device | |
EP0725267A2 (en) | Electrically controlled micro-pipette | |
DE60201017T2 (en) | MICRO-CHANNEL DEVICE AND METHOD | |
DE102011078770B4 (en) | Microfluidic device, microfluidic system and method of transporting fluids | |
EP0672834B1 (en) | Micro fluid manipulator | |
DE4405004A1 (en) | Chemical micro-analyzer | |
WO2006069730A1 (en) | Device for pumping fluids method for production thereof and pipette with said device | |
DE4223067A1 (en) | Micromechanical flow limiter with multilayer structure, e.g. for medical infusion system - has intermediate diaphragm layer which deflects w.r.t. amount of flowing medium, and blocks flow for large flow amounts | |
EP1161294B1 (en) | Active micromixer | |
DE19611270A1 (en) | Micro-mixer for very small volumes of liquids or suspensions | |
EP0943076B1 (en) | Micromechanically produced flow-restriction device | |
DE102010031757A1 (en) | Microfluidic system and manufacturing method for a microfluidic system | |
DE102022125010A1 (en) | Microfluidic component | |
DE10335492B4 (en) | Method for selectively connecting microstructured parts | |
DE102012201714A1 (en) | Method for manufacturing micro fluid system used in e.g. medical field, involves providing connecting element with respect to the position on the primary polymer layer |
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 CH DE DK FR GB IT LI NL SE |
|
17P | Request for examination filed |
Effective date: 19960222 |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
17Q | First examination report despatched |
Effective date: 19980731 |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH DE DK FR GB IT LI NL SE |
|
REF | Corresponds to: |
Ref document number: 180044 Country of ref document: AT Date of ref document: 19990515 Kind code of ref document: T |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REF | Corresponds to: |
Ref document number: 59505877 Country of ref document: DE Date of ref document: 19990617 |
|
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 19990810 |
|
ET | Fr: translation filed | ||
REG | Reference to a national code |
Ref country code: CH Ref legal event code: NV Representative=s name: BOVARD AG PATENTANWAELTE |
|
REG | Reference to a national code |
Ref country code: DK Ref legal event code: T3 |
|
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 |
|
26N | No opposition filed | ||
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20021203 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20021230 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20030109 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20030131 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 20030203 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20030205 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 20030207 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DK Payment date: 20030212 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20030822 Year of fee payment: 9 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20040209 Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20040209 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20040210 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20040228 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20040229 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20040229 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20040301 |
|
BERE | Be: lapsed |
Owner name: FORSCHUNGSZENTRUM *ROSSENDORF E.V. Effective date: 20040228 |
|
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 NON-PAYMENT OF DUE FEES Effective date: 20040901 Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20040901 |
|
REG | Reference to a national code |
Ref country code: DK Ref legal event code: EBP |
|
EUG | Se: european patent has lapsed | ||
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20040209 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20041029 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 20040901 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 20050209 |