EP1963818A1 - Apparatus for permeation or substance passage investigations - Google Patents

Apparatus for permeation or substance passage investigations

Info

Publication number
EP1963818A1
EP1963818A1 EP06828525A EP06828525A EP1963818A1 EP 1963818 A1 EP1963818 A1 EP 1963818A1 EP 06828525 A EP06828525 A EP 06828525A EP 06828525 A EP06828525 A EP 06828525A EP 1963818 A1 EP1963818 A1 EP 1963818A1
Authority
EP
European Patent Office
Prior art keywords
sample
measuring
space
permeation
substance
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.)
Ceased
Application number
EP06828525A
Other languages
German (de)
French (fr)
Inventor
Karin GLOCK-JÄGER
Katrin Pawlik
Thomas Richter
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.)
Innovent eV Technologieentwicklung
Original Assignee
Innovent eV Technologieentwicklung
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 Innovent eV Technologieentwicklung filed Critical Innovent eV Technologieentwicklung
Publication of EP1963818A1 publication Critical patent/EP1963818A1/en
Ceased legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N15/00—Investigating characteristics of particles; Investigating permeability, pore-volume or surface-area of porous materials
    • G01N15/08—Investigating permeability, pore-volume, or surface area of porous materials
    • G01N15/0806—Details, e.g. sample holders, mounting samples for testing
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N15/00—Investigating characteristics of particles; Investigating permeability, pore-volume or surface-area of porous materials
    • G01N15/08—Investigating permeability, pore-volume, or surface area of porous materials
    • G01N15/082—Investigating permeability by forcing a fluid through a sample

Definitions

  • the invention relates to a device for permeation or mass transfer studies, in particular for investigations on materials, such as. Plastic films and packaging, coatings o.a., Which can be operated independently of time and location of the analyzer.
  • the permeation measurement proceeds in two phases.
  • the substrate to be tested is exposed to the permeating medium in a special sample chamber or measuring cell.
  • the substance permeated by this substrate is analyzed for volume, mass and / or composition.
  • the two phases of the permeation measurement are coupled directly to one another, for example by transferring the permeated substance directly from the sample space into the analyzer by means of a carrier gas stream, in order to be analyzed there immediately (eg with an electrochemical measuring cell). with a gas chromatograph or a mass spectrometer).
  • the substance is adsorbed on the surface of the sample, for example the polymer film,
  • the substance is absorbed on the surface of the sample, for example of the polymer film, and thus penetrates into the sample / polymer,
  • the substance is desorbed on the opposite surface of the sample, for example the polymer film.
  • the rate-determining step of a permeation measurement is in most cases the permeation process itself, ie the adsorption and absorption of the substance on the polymer surface, diffusion through the polymer, and desorption of the substance from the opposite polymer surface. Of these individual steps, diffusion is again the slowest step.
  • the permeation process can take minutes, but also hours or even days, especially if there is no artificial additional pressure drop between the two sample chambers (so-called "pressureless processes").
  • JP 2003106971 A discloses a method for measuring the
  • Vapor permeability of a film or film with pores The permeation process is accelerated by application of pressure one side of the movie.
  • the measured variable is the amount of gas per unit of time.
  • US Pat. No. 6,804,989 B2 discloses a method for measuring very low water permeation rates. In this tritium enriched water is used, which is enriched after permeation in a gas stream. For analysis, the radioactivity is measured.
  • US 2002/0152800 A1 discloses a method in which the substrate is reacted with certain Ca or Ba compounds. These react with the diffused water. Detection takes place via transmission and reflection measurements.
  • US Pat. No. 6,043,027 describes measuring the permeation of chemicals through cells with specific corrugated plate assemblies. With such and similar arrangements, e.g. the permeation of drugs through the intestinal wall in the medical field can be measured.
  • the patent DE 697 24 504 T2 discloses a method for the investigation of food packaging, especially organic and inorganic Gassperrfllme.
  • the invention is therefore based on the object, a device for permeation or mass transfer studies, in particular for investigations of polymers, indicate that avoids the disadvantages of the prior art, in particular allows a temporally and locally independent of the analyzer handling. - -
  • the device according to the invention comprises a space which is divided by the sample to be examined into two spaces, a measuring and a sample space, wherein the permeating medium can be introduced into the sample space and from the measuring space to a corresponding one Reaction time to be analyzed, the permeated substance or a part thereof can be removed.
  • the permeation or the passage of material can be temporally and spatially independent of the second phase of permeation, the analysis of the permeated substance in the analyzer, which is not the case with the previously known devices for Permeations horr.
  • ⁇ 1 shows a schematic representation of the device according to the invention.
  • the sample 4 for example a polymer film, a coating or a film, which can be introduced into the measuring cell 1, divides the measuring cell 1 of the device according to the invention into two chambers, the sample chamber 2 and the measuring chamber 3.
  • the sample space 2 is provided with a septum 21.
  • the sample space 2 with permeating substance (s) can be filled.
  • This substance (s) may be solid, liquid and / or volatile or gaseous. It preferably permeates without draining through the sample 4 into the measuring space 3.
  • septum 21 As an alternative to the septum 21, it is also possible to provide a supply line with quick-action closures, screw connections and / or valves, through which the permeating substance (s) can be introduced into the sample space 2 and through which sampling in the sample space 2 is possible (depletion principle).
  • the measuring space 3 can likewise be provided with a further septum 31 or alternatively have a discharge with quick-release closures, screw connections and / or valves.
  • the septum 31 and the supply line the measurement samples are entOSE- and fed to any independent analysis method.
  • the measuring space 3 can be filled, for example, with an absorption medium or a measuring gas.
  • the entire device can be tempered by appropriate means if necessary. Due to the arbitrary configurability of the device according to the invention this is preferably autosamplerposition with appropriate spatial / geometric design.
  • the device according to the invention in contrast to commercial measuring cells, is not firmly connected to the analyzer, a selection is made possible between various, any suitable analytical methods. This has the advantage that the device immediately after sampling by another erfmdungswashe device can be replaced with a new sample.
  • the permeated substance located in the measuring space 3 is not completely taken off, but only part of it is withdrawn through the septum 31 or the discharge, then after a certain period of time during which the permeation process continues, the contents can be withdrawn of the measuring space 3 again and possibly analyzed with further analysis methods. It proves to be particularly advantageous that the device according to the invention can be handled independently of time and place of an analyzer.
  • the complete removal it proves to be particularly advantageous that the device according to the invention can be handled time and place independently of an analyzer.
  • the device according to the invention is, for example, in the testing and characterization of packaging materials,. such as food packaging or PET bottles, in the testing of protective gloves, such as impermeability to Chemicals or minimum permeability to moisture and to investigate the functioning of barrier layers, such as in the field of corrosion protection or in the field of environmental protection, used and allows the analyzer time and place independent handling.
  • packaging materials such as food packaging or PET bottles
  • protective gloves such as impermeability to Chemicals or minimum permeability to moisture
  • barrier layers such as in the field of corrosion protection or in the field of environmental protection, used and allows the analyzer time and place independent handling.
  • the advantage of the present invention is that a completely independent device independent of the analyzer is provided, in which the two phases of a permeation measurement (permeation and analysis) are separated from each other both locally and temporally.
  • the device in which the permeation process takes place no longer necessarily remain in the meter during the entire examination period. This makes it possible for the first time to start the permeation process on several samples (corresponding to the number of individual measuring cells) almost parallel with a large number of individual measuring cells. The sampling can also be done almost simultaneously or in a short time on all subjects.
  • the analyzes can then in principle be made according to the availability of the analyzer (s) even for the individual samples on different devices.
  • liquid substances / substance mixtures by sample in carrier gas 4. liquid substances / substance mixtures by sample in
  • Absorbing medium There is the possibility of selective depletion by permeation, the performance of several analyzes from a measuring cell or the removal of analysis samples of the permeating or penetrating substance both from the sample room and from the measuring room.
  • the measuring space and optionally also the sample space can be partially or completely emptied at a specific time or several times after certain periods, whereby the samples taken thereby can be supplied to one or more different analytical methods.
  • a comprehensive analytical characterization of the sample can be performed at a specific time, and it can be determined by time-shifted sampling profiles that characterize the timing of the permeation or the mass transfer.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Sampling And Sample Adjustment (AREA)

Abstract

The invention relates to an apparatus for permeation or substance passage investigations, in particular for investigations on materials, for example polymers, plastic films, packaging, coatings, paper, wood (veneer) or the like, which can be operated independently of the analysing device in terms of time and location. The object of the invention of specifying an apparatus for permeation or substance passage investigations, in particular for investigations on polymers, which avoids the disadvantages of the prior art, in particular can be handled independently of the analysing device in terms of time and location, is achieved by virtue of the fact that the apparatus comprises a measuring cell (1), a sample space (2), a measuring space (3) and a sample (4), wherein the sample (4) divides the measuring cell (1) into a sample space (2) and a measuring space (3) in such a manner that permeation or substance passage can take place solely through the sample.

Description

P2231 Patentanwälte Bock Bieber Donath, Hans-Knöll-Str. 1 , 07745 JenaP2231 Patent Attorneys Bock Bieber Donath, Hans-Knöll-Str. 1, 07745 Jena
Vorrichtung für Permeations- oder StoffdurchgangsuntersuchungenDevice for permeation or mass transfer studies
Die Erfindung betrifft eine Vorrichtung für Permeations- oder Stoffdurchgangsuntersuchungen, insbesondere für Untersuchungen an Materialien, wie bspw. Kunststoff-Folien und -Verpackungen, Beschichtungen o.a., die zeitlich und örtlich unabhängig vom Analysengerät betrieben werden kann.The invention relates to a device for permeation or mass transfer studies, in particular for investigations on materials, such as. Plastic films and packaging, coatings o.a., Which can be operated independently of time and location of the analyzer.
Es ist bekannt, dass die Permeationsmessung in zwei Phasen verläuft. In der ersten Phase wird das zu prüfende Substrat in einer speziellen Probenkammer oder Messzelle dem permeierenden Medium ausgesetzt. In der zweiten Phase wird die durch dieses Substrat permeierte Substanz hinsichtlich ihres Volumens, ihrer Masse und/oder Zusammensetzung analysiert.It is known that the permeation measurement proceeds in two phases. In the first phase, the substrate to be tested is exposed to the permeating medium in a special sample chamber or measuring cell. In the second phase, the substance permeated by this substrate is analyzed for volume, mass and / or composition.
Gemäß des Standes der Technik sind die beiden Phasen der Permeationsmessung unmittelbar miteinander gekoppelt, indem bspw. die permeierte Substanz mittels eines Trägergasstromes direkt aus dem Probenraum in das Analysengerät, überführt wird, um dann dort sofort analysiert zu werden (bspw. mit einer eletrochemischen Messzelle, mit einem Gaschromatographen oder einem Massenspektrometer).According to the prior art, the two phases of the permeation measurement are coupled directly to one another, for example by transferring the permeated substance directly from the sample space into the analyzer by means of a carrier gas stream, in order to be analyzed there immediately (eg with an electrochemical measuring cell). with a gas chromatograph or a mass spectrometer).
Die Permeation an sich erfolgt dabei in folgenden vier Schritten:The permeation itself takes place in the following four steps:
1. die Substanz wird auf der Oberfläche der Probe, bspw. des Polymerfilms, adsorbiert,1. the substance is adsorbed on the surface of the sample, for example the polymer film,
2. die Substanz wird auf der Oberfläche der Probe, bspw. des Polymerfilms, absorbiert und dringt damit in die Probe / das Polymer ein,2. the substance is absorbed on the surface of the sample, for example of the polymer film, and thus penetrates into the sample / polymer,
3. die Substanz diffundiert durch die Probe / das Polymer bis zur gegenüberliegenden Grenzfläche,3. the substance diffuses through the sample / polymer to the opposite interface,
4. die Substanz wird auf der gegenüberliegenden Oberfläche der Probe, bspw. des Polymerfilms, desorbiert.4. The substance is desorbed on the opposite surface of the sample, for example the polymer film.
Der geschwindigkeitsbestimmende Schritt einer Permeationsmessung ist in den meisten Fällen der Permeationsvorgang selbst, d.h. die Adsorption und Absorption der Substanz auf der Polymeroberfläche, die Diffusion durch das Polymer sowie die Desorption der Substanz von der gegenüberliegenden Polymeroberfläche. Von diesen einzelnen Schritten ist wiederum die Diffusion der langsamste Schritt. Der Permeationsvorgang kann Minuten, aber auch Stunden oder gar Tage dauern, insbesondere dann, wenn kein künstliches zusätzliches Druckgefalle zwischen den beiden Probenräumen besteht (s.g. „drucklose Verfahren").The rate-determining step of a permeation measurement is in most cases the permeation process itself, ie the adsorption and absorption of the substance on the polymer surface, diffusion through the polymer, and desorption of the substance from the opposite polymer surface. Of these individual steps, diffusion is again the slowest step. The permeation process can take minutes, but also hours or even days, especially if there is no artificial additional pressure drop between the two sample chambers (so-called "pressureless processes").
Damit sind die bisherigen Verfahren zur Permeationsmessung sehr zeitaufwendig und nur bedingt geeignet für eine Hochdurchsatz- Analytik.Thus, the previous methods for Permeationsmessung are very time consuming and only partially suitable for high-throughput analysis.
Bisher sind folgende Methoden der Permeationsmessungen bekannt:So far, the following methods of permeation measurements are known:
■ volumetrische Messung nach DIN 53380-1 (Gaspermeation) ■ manometrische Messung nach DIN 53380-2 ■ volumetric measurement according to DIN 53380-1 (gas permeation) ■ manometric measurement according to DIN 53380-2
■ gravimetrische Messung nach DIN 53122- 1. ■ gravimetric measurement according to DIN 53122-1.
Der Nachteil all dieser Messungen ist, dass die beiden Phasen derThe disadvantage of all these measurements is that the two phases of the
Permeationsmessung unmittelbar miteinander gekoppelt sind und die Messzellen nicht unabhängig vom Analysengerät sind. Dies ist insbesondere bei den drucklosen Verfahren nachteilig, da die Einzelmessung lange Zeiträume in Anspruch nimmt.Permeationsmessung are coupled directly to each other and the measuring cells are not independent of the analyzer. This is particularly disadvantageous in the unpressurized method, since the individual measurement takes long periods of time.
Da im Zuge der Entwicklung von Polymerfolien und Sperrschichten für die Verpackungs- und Elektronikindustrie, den Arbeitsschutz usw. dieAs in the development of polymer films and barrier layers for the packaging and electronics industry, occupational safety, etc. the
Ansprüche ständig steigen, geht der Trend hin zu immer niedrigerenClaims are constantly rising, the trend is towards ever lower
Permeationsraten, was im Gegenzug immer längere Permeationszeiten zur Folge hat. Darüber hinaus werden immer empfindlicherePermeation rates, which in turn has always longer permeation times result. In addition, becoming more sensitive
Messmethoden erforderlich, so dass der zuvor stehende Nachteil der bisherigen Permeationsmessungen zukünftig noch stärker zum Tragen kommt.Measuring methods required, so that the disadvantage of the previous Permeationsmessungen before has come to an even greater extent in the future.
Die Schrift JP 2003106971 A offenbart ein Verfahren zur Messung derJP 2003106971 A discloses a method for measuring the
Dampfdurchlässigkeit eines Films oder eines Films mit Poren. Der Permeationsvorgang wird beschleunigt durch Anwendung von Druck auf einer Seite des Films. Messgröße ist jeweils die Gasmenge pro Zeiteinheit.Vapor permeability of a film or film with pores. The permeation process is accelerated by application of pressure one side of the movie. The measured variable is the amount of gas per unit of time.
Aus dem Patent US 6,804,989 B2 ist eine Methode zur Messung sehr geringer Wasserpermeationsraten bekannt. Bei dieser wird tritiumangereichertes Wasser verwendet, welches nach der Permeation in einem Gasstrom angereichert wird. Zur Analyse wird die Radioaktivität gemessen.US Pat. No. 6,804,989 B2 discloses a method for measuring very low water permeation rates. In this tritium enriched water is used, which is enriched after permeation in a gas stream. For analysis, the radioactivity is measured.
Die Schrift US 2002/ 0152800 Al offenbart eine Methode, bei der das Substrat mit bestimmten Ca- oder Ba-Verbindungen zur Reaktion gebracht wird. Diese reagieren mit dem diffundierten Wasser. Die Detektion erfolgt über Transmissions- und Reflexionsmessungen.The document US 2002/0152800 A1 discloses a method in which the substrate is reacted with certain Ca or Ba compounds. These react with the diffused water. Detection takes place via transmission and reflection measurements.
Das US-Patent 6,043,027 beschreibt die Messung der Permeation von Chemikalien durch Zellen mit speziellen Wellplattenanordnungen. Mit solchen und ähnlichen Anordnungen kann z.B. die Permeation von Drogen durch die Darmwand im medizinischen Bereich gemessen werden.US Pat. No. 6,043,027 describes measuring the permeation of chemicals through cells with specific corrugated plate assemblies. With such and similar arrangements, e.g. the permeation of drugs through the intestinal wall in the medical field can be measured.
Das Patent DE 697 24 504 T2 offenbart eine Methode zur Untersuchung von Lebensmittelverpackungen, speziell organischer und anorganischer Gassperrfllme.The patent DE 697 24 504 T2 discloses a method for the investigation of food packaging, especially organic and inorganic Gassperrfllme.
All die zuvor stehenden Schriften offenbaren unterschiedliche Vorrichtungen und Methoden, um die Permeation von Wasser bzw. Feuchtigkeit und flüchtigen, flüssigen Substanzen zu messen. In jedem Fall ist die Probenkammer, in der der Permeationsvorgang stattfindet, direkt mit der Analyse gekoppelt. Damit sind die genannten Verfahren insbesondere für niedrige Permeationsraten zeitaufwendig.All of the above references disclose various apparatus and methods for measuring the permeation of water and moisture and volatile liquid substances. In any case, the sample chamber in which the permeation process takes place is directly coupled to the analysis. Thus, the methods mentioned are time-consuming, in particular for low permeation rates.
Weiterhin ist aus der Schrift EP 0 425 809 A2 bekannt, dass die Permeation von Fremdmolekülen in einen Festkörper bestimmbar ist, indem die eindiffundierende Menge von Fremdmolekülen ermittelt wird. Der Nachteil dieser Messmethode ist, dass nur das Eindringen von Fremdmolekülen in eine Probe, jedoch nicht das Durchdringen durch die Probe bestimmbar ist.Furthermore, it is known from document EP 0 425 809 A2 that the permeation of foreign molecules into a solid can be determined by determining the amount of foreign molecules which diffuses in. The disadvantage of this measuring method is that only the penetration of foreign molecules into a sample, but not the penetration through the sample can be determined.
Der Erfindung liegt daher die Aufgabe zugrunde, eine Vorrichtung für Permeations- oder Stoffdurchgangsuntersuchungen, insbesondere für Untersuchungen an Polymeren, anzugeben, die die Nachteile des Standes der Technik vermeidet, insbesondere eine vom Analysengerät zeitlich und örtlich unabhängige Handhabung ermöglicht. - -The invention is therefore based on the object, a device for permeation or mass transfer studies, in particular for investigations of polymers, indicate that avoids the disadvantages of the prior art, in particular allows a temporally and locally independent of the analyzer handling. - -
Gemäß der Erfindung wird diese Aufgabe durch die kennzeichnenden Merkmale des ersten Patentanspruchs gelöst und durch vorteilhafte Ausgestaltungen gemäß den Unteransprüchen ergänzt.According to the invention, this object is solved by the characterizing features of the first claim and supplemented by advantageous embodiments according to the subclaims.
Das Wesen der Erfindung besteht darin, dass die erfindungsgemäße Vorrichtung einen Raum umfasst, der durch die zu untersuchende Probe in zwei Räume, einen Mess- und einen Probenraum, geteilt wird, wobei in den Probenraum das permeierende Medium einbringbar und aus dem Messraum nach einer entsprechenden Reaktionszeit die zu analysierende, permeierte Substanz oder ein Teil davon entnehmbar ist.The essence of the invention is that the device according to the invention comprises a space which is divided by the sample to be examined into two spaces, a measuring and a sample space, wherein the permeating medium can be introduced into the sample space and from the measuring space to a corresponding one Reaction time to be analyzed, the permeated substance or a part thereof can be removed.
Durch diesen Aufbau der erfindungsgemäßen Vorrichtung kann die Permeation oder der Stoffdurchgang zeitlich und örtlich unabhängig von der zweiten Phase der Permeationsmessung, der Analyse der permeierten Substanz im Analysengerät, erfolgen, was bei den bisher bekannten Geräten zur Permeationsmessung nicht der Fall ist.By this construction of the device according to the invention, the permeation or the passage of material can be temporally and spatially independent of the second phase of permeation, the analysis of the permeated substance in the analyzer, which is not the case with the previously known devices for Permeationsmessung.
Die Erfindung wird nachstehend an Hand der Zeichnung und des Ausführangsbeispiels näher erläutert.The invention will be explained in more detail below with reference to the drawing and the Ausführangsbeispiels.
Dabei zeigt Figur ■ 1 eine schematische Darstellung der erfindungsgemäßen Vorrichtung.In this figure ■ 1 shows a schematic representation of the device according to the invention.
Die in die Messzelle 1 einführbare Probe 4, bspw. ein Polymerfilm, eine Beschichtung oder eine Folie, teilt die Messzelle 1 der erfindungsgemäßen Vorrichtung in zwei Räume, den Probenraum 2 und den Messraum 3. Besonders vorteilhaft ist der Probenraum 2 mit einem Septum 21 versehen.The sample 4, for example a polymer film, a coating or a film, which can be introduced into the measuring cell 1, divides the measuring cell 1 of the device according to the invention into two chambers, the sample chamber 2 and the measuring chamber 3. Particularly advantageously, the sample space 2 is provided with a septum 21.
Durch dieses Septum 21 ist der Probenraum 2 mit permeierender Substanz(en) befüllbar. Diese Substanz(en) kann fest, flüssig und/oder flüchtig oder gasförmig sein. Sie permeiert vorzugsweise dracklos durch die Probe 4 in den Messraum 3.Through this septum 21, the sample space 2 with permeating substance (s) can be filled. This substance (s) may be solid, liquid and / or volatile or gaseous. It preferably permeates without draining through the sample 4 into the measuring space 3.
Bei Bedarf kann über das Septum 21- auch eine Probennahme im Probenraum 2 erfolgen (Abreicherungsprinzip).If required, it is also possible to take a sample in the sample space 2 via the septum 21- (depletion principle).
Alternativ zu dem Septum 21 kann auch eine Zuleitung mit Schnellverschlüssen, Verschraubungen und/oder Ventilen vorgesehen sein, durch die die permeierende Substanz(en) in den Probenraum 2 einbringbar und durch die eine Probennahme im Probenraum 2 möglich ist (Abreicherungsprinzip).As an alternative to the septum 21, it is also possible to provide a supply line with quick-action closures, screw connections and / or valves, through which the permeating substance (s) can be introduced into the sample space 2 and through which sampling in the sample space 2 is possible (depletion principle).
Der Messraum 3 kann erfindungsgemäß ebenfalls mit einem weiteren Septum 31 versehen sein bzw. alternativ dazu eine Ableitung mit Schnellverschlüssen, Verschraubungen und/oder Ventilen aufweisen. Durch das Septum 31 bzw. die Zuleitung sind die Messproben entnehm- und einer beliebigen unabhängigen Analysenmethode zufuhrbar.According to the invention, the measuring space 3 can likewise be provided with a further septum 31 or alternatively have a discharge with quick-release closures, screw connections and / or valves. Through the septum 31 and the supply line, the measurement samples are entnehm- and fed to any independent analysis method.
Der Messraum 3 kann bspw. mit einem Absorptionsmedium oder einem Messgas befüllt werden.The measuring space 3 can be filled, for example, with an absorption medium or a measuring gas.
Im Rahmen der Erfindung liegt auch, dass die gesamte Vorrichtung bei Bedarf durch entsprechende Einrichtungen temperierbar ist. Durch die beliebige Gestaltbarkeit der erfindungsgemäßen Vorrichtung ist diese bei entsprechender räumlicher/geometrischer Gestaltung vorzugsweise autosamplerfähig.Within the scope of the invention is also that the entire device can be tempered by appropriate means if necessary. Due to the arbitrary configurability of the device according to the invention this is preferably autosamplerfähig with appropriate spatial / geometric design.
Da die erfindungsgemäße Vorrichtung im Gegensatz zu kommerziellen Messzellen nicht fest mit dem Analysengerät verbunden ist, wird eine Auswahl zwischen verschiedenen, beliebigen geeigneten Analysenmethoden ermöglicht. Das hat den Vorteil, dass die Vorrichtung unmittelbar nach der Probennahme durch eine weitere erfmdungsgemäße Vorrichtung mit einer neuen Probe ersetzt werden kann.Since the device according to the invention, in contrast to commercial measuring cells, is not firmly connected to the analyzer, a selection is made possible between various, any suitable analytical methods. This has the advantage that the device immediately after sampling by another erfmdungsgemäße device can be replaced with a new sample.
Wird bei der Verwendung der erfindungsgemäßen Vorrichtung während der Probenahme die im Messraum 3 befindliche permeierte Substanz nicht vollständig, sondern nur ein Teil durch das Septum 31 oder die Ableitung entnommen, so kann nach Ablauf einer gewissen Zeit, in der der Permeationsvorgang weiter fortschreitet, der Inhalt des Messraumes 3 erneut und ggf. mit weiteren Analysenmethoden analysiert werden. Dabei erweist es sich als besonders vorteilhaft, dass die erfindungsgemäße Vorrichtung zeitlich und örtlich unabhängig von einem Analysengerät handhabbar ist.If during use of the device according to the invention the permeated substance located in the measuring space 3 is not completely taken off, but only part of it is withdrawn through the septum 31 or the discharge, then after a certain period of time during which the permeation process continues, the contents can be withdrawn of the measuring space 3 again and possibly analyzed with further analysis methods. It proves to be particularly advantageous that the device according to the invention can be handled independently of time and place of an analyzer.
Ebenfalls ist es möglich und erfindungsgemäß, nach Ablauf einer gewissen Zeit den Inhalt des Messraums vollständig zur Analyse zu entnehmen und durch frisches Messgas bzw. Absorptionsmedium zu ersetzen. Auch dann kann nach Ablauf einer gewissen Zeit, in der der Permeationsvorgang weiter fortschreitet, der Inhalt des Messraumes 3 erneut und ggf. mit weiteren Analysenmethoden analysiert werden.It is also possible and according to the invention, after a certain time, to completely remove the contents of the measuring space for analysis and to replace them with fresh measuring gas or absorption medium. Even then, after a certain time has elapsed, during which the permeation process continues to progress, the content of the measuring space 3 can be analyzed again and, if necessary, with further analysis methods.
Auch in diesem Fall der vollständigen Entnahme erweist es sich als besonders vorteilhaft, dass die erfindungsgemäße Vorrichtung zeitlich und örtlich unabhängig von einem Analysengerät handhabbar ist.Also in this case, the complete removal, it proves to be particularly advantageous that the device according to the invention can be handled time and place independently of an analyzer.
Als besonders vorteilhaft erweist sich weiterhin die Tatsache, dass mit der erfindungsgemäßen Vorrichtung erstmals die kombinierte Anwendung verschiedener Analysenmethoden möglich ist, weil alle Komponenten der Probe aus einer Messzelle bestimmbar sind.The fact that with the device according to the invention the combined use of different analysis methods is possible for the first time is also particularly advantageous because all components of the sample can be determined from a measuring cell.
Durch die Möglichkeit des Austausches der erfindungsgemäßen, geräteunabhängigen Vorrichtung kann selbst bei langwierigen Perrneationsprozessen bzw. niedrigen Permeationsraten eine große Probenmenge pro Zeiteinheit analysiert und eine effiziente Auslastung der Messtechnik erreicht werden.Due to the possibility of exchanging the apparatus-independent device according to the invention, a large amount of sample per unit of time can be analyzed and an efficient utilization of the measuring technique can be achieved even with lengthy perforation processes or low permeation rates.
Die erfindungsgemäße Vorrichtung ist bspw. bei der Prüfung und Charakterisierung von Verpackungsmaterialien, . wie bspw. Lebensmittelverpackungen oder PET-Flaschen, bei der Prüfung von Arbeitsschutzhandschuhen, wie bspw. auf Undurchlässigkeit für Chemikalien oder Mindestdurchlässigkeit an Feuchtigkeit und zur Untersuchung der Funktionsweise von Sperrschichten, wie bspw. auf dem Gebiet des Korrosionsschutzes oder auf dem Gebiet des Umweltschutzes, einsetzbar und ermöglicht eine vom Analysengerät zeitlich und örtlich unabhängige Handhabung.The device according to the invention is, for example, in the testing and characterization of packaging materials,. such as food packaging or PET bottles, in the testing of protective gloves, such as impermeability to Chemicals or minimum permeability to moisture and to investigate the functioning of barrier layers, such as in the field of corrosion protection or in the field of environmental protection, used and allows the analyzer time and place independent handling.
Der Vorteil der vorliegenden Erfindung ist, dass eine völlig eigenständige und vom Analysengerät unabhängige Vorrichtung bereit gestellt wird, bei - der - bewusst die beiden -Phasen- einer Permeationsmessung (Permeation und Analyse) sowohl örtlich als auch zeitlich voneinander getrennt werden. Somit muss die Vorrichtung, in der der Permeationsvorgang stattfindet, nicht mehr zwingend während der gesamten Untersuchungsdauer im Messgerät verbleiben. Damit wird es erstmals möglich, mit einer Vielzahl von Einzelmesszellen nahezu parallel den Permeationsvorgang an mehreren Proben (entsprechend der Anzahl an Einzelmesszellen) zu starten. Die Probennahme kann ebenso nahezu gleichzeitig oder in kurzer Folge an allen Probanden erfolgen. Die Analysen können dann prinzipiell nach der Verfügbarkeit der/des Analysengerate(s) sogar für die einzelnen Proben an verschiedenen Geräten erfolgen.The advantage of the present invention is that a completely independent device independent of the analyzer is provided, in which the two phases of a permeation measurement (permeation and analysis) are separated from each other both locally and temporally. Thus, the device in which the permeation process takes place, no longer necessarily remain in the meter during the entire examination period. This makes it possible for the first time to start the permeation process on several samples (corresponding to the number of individual measuring cells) almost parallel with a large number of individual measuring cells. The sampling can also be done almost simultaneously or in a short time on all subjects. The analyzes can then in principle be made according to the availability of the analyzer (s) even for the individual samples on different devices.
Während des eigentlichen Permeationsvorgangs ist das entsprechende Analysengerät damit nicht mehr blockiert, sondern kann effektiv für andere Untersuchungen genutzt werden. Organisiert man Bestückung der erfindungsgemäßen Vorrichtung und die Analysen jeweils zeitlich versetzt, wird deutlich, welche Zeitersparnis erreicht wird bzw. dass der Probendurchsatz pro Zeiteinheit mit dieser erfindungsgemäßen Vorrichtung erhöht werden kann, wobei die Permeation oder der Stoffdurchgang wie folgt untersucht werden kann: 1. gasförmiger Substanzen/Substanzgemische durch Probe in Trägergas,During the actual permeation process, the corresponding analyzer is thus no longer blocked, but can be effectively used for other investigations. Organized assembly of the device according to the invention and the analyzes each time offset, it becomes clear which time savings can be achieved or that the sample throughput per unit time can be increased with this device according to the invention, wherein the permeation or mass transfer can be examined as follows: 1. gaseous Substances / substance mixtures by sample in carrier gas,
2. gasförmiger Substanzen/Substanzgemische durch Probe in Absorptionsmedium,2. gaseous substances / substance mixtures by sample in absorption medium,
3. flüssiger Substanzen/Substanzgemische durch Probe in Trägergas, 4. flüssiger Substanzen/Substanzgemische durch Probe in3. liquid substances / substance mixtures by sample in carrier gas, 4. liquid substances / substance mixtures by sample in
Absorptionsmedium. Dabei besteht die Möglichkeit der selektiven Abreicherung durch Permeation, der Durchführung mehrerer Analysen aus einer Messzelle bzw. der Entnahme von Analyseproben der permeierenden oder penetrierenden Substanz sowohl aus Probenraum als auch aus Messraum.Absorbing medium. There is the possibility of selective depletion by permeation, the performance of several analyzes from a measuring cell or the removal of analysis samples of the permeating or penetrating substance both from the sample room and from the measuring room.
Bei der erfindungsgemäßen Vorrichtung kann vorteilhafter Weise der Messraum und ggf. auch der Probenraum zu einem bestimmten Zeitpunkt oder mehrfach nach bestimmten Zeiträumen jeweils teilweise oder komplett entleert werden, wobei die dabei entnommenen Proben dadurch jeweils einer oder mehreren verschiedenen Analysenmethoden zugeführt werden können.In the case of the device according to the invention, advantageously, the measuring space and optionally also the sample space can be partially or completely emptied at a specific time or several times after certain periods, whereby the samples taken thereby can be supplied to one or more different analytical methods.
Damit kann eine umfangreiche analytische Charakterisierung der Probe zu einem bestimmten Zeitpunkt durchgeführt werden, und es können durch zeitlich versetzte Probenahmen Profile ermittelt werden, die den zeitlichen Ablauf der Permeation oder des Stoffdurchgangs charakterisieren.Thus, a comprehensive analytical characterization of the sample can be performed at a specific time, and it can be determined by time-shifted sampling profiles that characterize the timing of the permeation or the mass transfer.
Alle in der Beschreibung und den nachfolgenden Ansprüchen dargestellten Merkmale können sowohl einzeln als auch in beliebiger Kombination miteinander erfindungswesentlich sein. All features described in the description and the following claims may be essential to the invention both individually and in any combination with one another.
Bezugszeichenreference numeral
1 Messzelle1 measuring cell
Probenraum 1 SeptumSample room 1 septum
3 Messraum 1 Septum3 measuring room 1 septum
Probe sample

Claims

Patentansprüche claims
1. Vorrichtung für Permeations- oder Stoffdurchgangsuntersuchungen bestehend aus einer Messzelle (1), einem Probenraum (2), einem1. Device for permeation or substance flow tests consisting of a measuring cell (1), a sample chamber (2), a
5 Messraum (3) und einer Probe (4), dadurch gekennzeichnet, dass die5 measuring space (3) and a sample (4), characterized in that the
Probe (4) in die Messzelle (1) einbringbar ist und diese nach ihrem Einbringen in einen Probenraum (2) und einen Messraum (3) derart teilt, dass eine Peπneation oder ein Stoffdurchgang mindestens eines Mediums / mindestens einer perrneierenden. Substanz ausschließlich W durch die Probe hindurch erfolgen kann.Sample (4) in the measuring cell (1) can be introduced and these after their introduction into a sample chamber (2) and a measuring space (3) so divides that a Peπneation or a passage of at least one medium / at least one perrneierenden. Substance W can only be done through the sample.
2. Vorrichtung gemäß Anspruch 1 , dadurch gekennzeichnet, dass die Probe (4) ein Festkörper ist.2. Device according to claim 1, characterized in that the sample (4) is a solid.
15 3. Vorrichtung gemäß Anspruch 3, dadurch gekennzeichnet, dass der Festkörper ein Polymerfllm, eine Beschichtung, eine Folie, Papier oder Holz ist.3. The device according to claim 3, characterized in that the solid is a Polymerfllm, a coating, a film, paper or wood.
4. Vorrichtung gemäß Anspruch 1, dadurch gekennzeichnet, dass der 0 Probenraum (2) ein Septum (21) besitzt, durch das der Probenraum (2) mit permeierenden Medium / permeierender Substanz(en) befüllbar ist und /oder durch das eine Probennahme im Probenraum (2) möglich ist.4. The device according to claim 1, characterized in that the sample space (2) has a septum (21) through which the sample space (2) can be filled with permeating medium / permeating substance (s) and / or by sampling in the Sample space (2) is possible.
5 5. Vorrichtung gemäß Anspruch 1, dadurch gekennzeichnet, dass der Probenraum (2) eine Zuleitung mit Schnellverschlüssen, Verschraubungen und/oder Ventilen besitzt, durch die das permeierende Medium / die permeirenden Medien in den Probenraum (2) einbringbar ist /sind und /oder durch die eine 0 Probennahme im Probenraum (2).5. The device according to claim 1, characterized in that the sample space (2) has a supply line with quick-release closures, screw connections and / or valves, through which the permeating medium / the permeating media in the sample space (2) can be introduced / / and / or by the 0 sampling in the sample room (2).
6. Vorrichtung gemäß Anspruch 1, dadurch gekennzeichnet, dass das Medium / die permeierende Substanz(en) fest, flüssig und/oder flüchtig oder gasförmig ist / sind und 56. The device according to claim 1, characterized in that the medium / the permeating substance (s) is / are solid, liquid and / or volatile or gaseous and / or 5
7. Vorrichtung gemäß Anspruch 6, dadurch gekennzeichnet, dass das Medium / die permeierende Substanz(en) drucklos durch die Probe (4) in den Messraum (3) permeabel sind. 7. The device according to claim 6, characterized in that the medium / the permeating substance (s) are without pressure through the sample (4) in the measuring space (3) permeable.
8. Vorrichtung gemäß Anspruch 1, dadurch gekennzeichnet, dass der Messraum (3) ein Septum (31) besitzt, durch das Messproben entnehm- und einer beliebigen unabhängigen Analysenmethode zuführbar sind.8. The device according to claim 1, characterized in that the measuring space (3) has a septum (31), can be supplied by the measuring samples and any arbitrary independent analysis method can be fed.
9. Vorrichtung gemäß Anspruch 1, dadurch gekennzeichnet, dass der Messraum (3) eine Ableitung mit Schnellverschlüssen, Verschraubungen und/oder Ventilen besitzt, durch die Messproben entnehm- und einer beliebigen unabhängigen Analysenmethode zuführbar sind.9. The device according to claim 1, characterized in that the measuring chamber (3) has a derivative with quick-release fasteners, fittings and / or valves, are removed by the measurement samples and any arbitrary independent analysis method can be fed.
10. Vorrichtung nach einem oder mehrerer der zuvor stehenden Ansprüche, dadurch gekennzeichnet, dass die gesamte Vorrichtung temperierbar ist.10. Device according to one or more of the preceding claims, characterized in that the entire device is temperature-controlled.
11. Verwendung der Vorrichtung nach einem oder mehrerer der zuvor stehenden Ansprüche, wobei der Messraum (3) und / oder der Probenraum (2) zu einem bestimmten Zeitpunkt oder mehrfach nach bestimmten Zeiträumen jeweils teilweise entleert oder komplett entleert werden. 11. Use of the device according to one or more of the preceding claims, wherein the measuring space (3) and / or the sample space (2) are each partially emptied or completely emptied at a certain time or several times after certain periods.
EP06828525A 2005-11-25 2006-11-15 Apparatus for permeation or substance passage investigations Ceased EP1963818A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005057031A DE102005057031B4 (en) 2005-11-25 2005-11-25 Device for permeation or mass transfer studies
PCT/DE2006/002020 WO2007059738A1 (en) 2005-11-25 2006-11-15 Apparatus for permeation or substance passage investigations

Publications (1)

Publication Number Publication Date
EP1963818A1 true EP1963818A1 (en) 2008-09-03

Family

ID=37775191

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06828525A Ceased EP1963818A1 (en) 2005-11-25 2006-11-15 Apparatus for permeation or substance passage investigations

Country Status (4)

Country Link
US (1) US20090133475A1 (en)
EP (1) EP1963818A1 (en)
DE (1) DE102005057031B4 (en)
WO (1) WO2007059738A1 (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2009041632A1 (en) * 2007-09-28 2011-01-27 株式会社アルバック Apparatus and method for measuring water vapor permeability
US8729472B2 (en) 2010-09-10 2014-05-20 Saint-Gobain Performance Plastics Corporation Systems and methods for permeability rate testing of barrier films
FR2997763B1 (en) * 2012-11-06 2015-01-16 Commissariat Energie Atomique DEVICE AND METHOD FOR ESTIMATING A GAS STREAM IN AN ENCLOSURE CONTINUED IN LOW GAS DEPRESSION
KR20140142541A (en) * 2013-06-04 2014-12-12 삼성전기주식회사 Moisture transmission testing instrument
DE102020115601A1 (en) 2020-06-12 2021-12-16 VON ARDENNE Asset GmbH & Co. KG Method and device
CN115479880A (en) * 2022-10-17 2022-12-16 大连理工大学 Method for measuring permeability coefficient of high-density polyethylene film in process of blocking volatile organic compounds

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6298713B1 (en) * 2000-05-10 2001-10-09 Bausch & Lomb Incorporated Method for determination of water transport in biocompatible materials
WO2004040006A1 (en) * 2002-10-28 2004-05-13 Transform Pharmaceuticals, Inc. Transdermal assay with magnetic clamp
US20050063862A1 (en) * 2003-09-24 2005-03-24 3M Innovative Properties Company System, kit, and method for measuring membrane diffusion

Family Cites Families (47)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2400481A (en) * 1944-03-25 1946-05-21 George J Brabender Apparatus for testing water-vapor permeability
US2498198A (en) * 1946-12-14 1950-02-21 Socony Vacuum Oil Co Inc Method of measuring permeability
US2705418A (en) * 1950-12-30 1955-04-05 Socony Vacuum Oil Co Inc Apparatus for measuring charateristics of core samples under compressive stresses
US3286509A (en) * 1964-09-22 1966-11-22 St Regis Paper Co Apparatus for measuring water vapor permeability
US3604246A (en) * 1965-09-14 1971-09-14 Minnesota Mining & Mfg Permeability testing apparatus and method
US3580067A (en) * 1967-11-02 1971-05-25 Dow Chemical Co Method of determining the rate of vapor transmission through sheet materials
US3590634A (en) * 1969-05-05 1971-07-06 Stanford Research Inst Instrument for determining permeation rates through a membrane
US3839899A (en) * 1971-09-24 1974-10-08 Mobil Oil Corp Method and apparatus for determining parameters of core samples
US3926561A (en) * 1974-05-13 1975-12-16 Meloy Lab Gas analysis employing semi-permeable membrane
DE3110183C2 (en) * 1981-03-17 1983-12-01 Franz Dr.-Ing. 1000 Berlin Wallner Membrane osmometer
US4389878A (en) * 1981-05-01 1983-06-28 The Dow Chemical Company Dynamic gas transmission measuring apparatus
US4468951A (en) * 1983-01-21 1984-09-04 Garcia David B Permeation testing apparatus
US4557138A (en) * 1984-06-06 1985-12-10 Dumitriu Valcea Eugene J Large-scale cold cup apparatus for vapor barriers resistance (permeance) testing
US5081863A (en) * 1985-05-31 1992-01-21 Modern Controls, Inc. Apparatus for measuring transmission of volatile substances through films
JPS62119433A (en) * 1985-11-20 1987-05-30 Fuji Electric Co Ltd Hydrogen transmission coefficient measuring apparatus for film
US4771004A (en) * 1986-08-29 1988-09-13 Iprx, Inc. Method for in vitro determination of transdermal absorption
US4791822A (en) * 1987-05-20 1988-12-20 Stim Lab, Inc. Cell assembly for determining conductivity and permeability
DE3933382C2 (en) * 1989-10-06 1994-03-10 Audi Ag Method for determining permeation behavior
FR2656695B1 (en) * 1989-12-28 1993-04-02 Inst Francais Du Petrole DEVICE AND METHOD FOR EVALUATING THE FITNESS OF A BODY TO OPPOSE THE PASSING OF A PRODUCT AND THEIR APPLICATION TO THE EVALUATION OF DYSMIGRATION.
US5198109A (en) * 1992-03-23 1993-03-30 Hanson Research Corp. Diffusion cell
JPH06273309A (en) * 1993-03-19 1994-09-30 Mitsubishi Kasei Corp Gas permeability measuring equipment for resin film
WO1996001994A1 (en) * 1994-07-11 1996-01-25 Tekmar Company Modular vial autosampler
US5563333A (en) * 1995-01-20 1996-10-08 Haines; Hiemi K. Method and apparatus for core flooding studies
US5551284A (en) * 1995-02-23 1996-09-03 Wenkert; William Portable instrument and method for measuring the air permeability of plant leaves
US5513515A (en) * 1995-05-15 1996-05-07 Modern Controls, Inc. Method for measuring permeability of a material
US5659130A (en) * 1996-04-03 1997-08-19 Industrual Technology Research Institute Simple device for testing chemical permeation
ATE248881T1 (en) * 1996-04-05 2003-09-15 Toray Industries GAS BARRIER FILM
US5837888A (en) * 1997-05-14 1998-11-17 Modern Controls, Inc. Process for measuring vapor transmission through materials
US5962250A (en) * 1997-10-28 1999-10-05 Glaxo Group Limited Split multi-well plate and methods
US5817924A (en) * 1998-01-21 1998-10-06 Modern Controls, Inc. Method and apparatus for measuring oxygen transmission through contact lenses
WO2000009988A2 (en) * 1998-08-11 2000-02-24 The Penn State Research Foundation Rapid method to experimentally measure the gas permeability of micro-perforated films
KR100338346B1 (en) * 2000-05-24 2002-05-30 박호군 Membrane filtration equipment and method for simultaneously and continuously monitoring time-based membrane fouling
US6640615B1 (en) * 2001-01-26 2003-11-04 Darrell R. Morrow System for determining the integrity of a package or packaging material based on its transmission of a test gas
JP4209194B2 (en) * 2001-03-29 2009-01-14 コーニンクレッカ フィリップス エレクトロニクス エヌ ヴィ Permeability measurement and inspection method and measurement and inspection apparatus
US6598463B2 (en) * 2001-05-02 2003-07-29 Du Pont Method for determining gas accumulation rates
EP1395418B1 (en) * 2001-05-23 2005-11-23 Novartis AG Basket for holding an ophtalmic lens
US6766682B2 (en) * 2001-10-19 2004-07-27 Desert Cryogenics Llc Precise measurement system for barrier materials
US7364905B2 (en) * 2001-11-29 2008-04-29 Techelan, Llc Apparatus and method for high throughput analysis of compound-membrane interactions
US6788399B2 (en) * 2001-11-30 2004-09-07 Bausch & Lomb Incorporated Ophthalmic article inspection system
US6804989B2 (en) * 2002-10-31 2004-10-19 General Atomics Method and apparatus for measuring ultralow water permeation
DE10344992A1 (en) * 2003-09-27 2005-05-19 Bayerische Motoren Werke Ag Test method and device for air-permeable materials
US6981403B2 (en) * 2003-10-31 2006-01-03 Mocon, Inc. Method and apparatus for measuring gas transmission rates of deformable or brittle materials
US6935159B2 (en) * 2003-11-19 2005-08-30 University Of Waterloo Centrifugal permeameter
US7257990B2 (en) * 2005-04-25 2007-08-21 General Atomics Accelerated ultralow moisture permeation measurement
US7555934B2 (en) * 2006-09-07 2009-07-07 3M Innovative Properties Company Fluid permeation testing apparatus employing mass spectrometry
US7526917B1 (en) * 2008-08-11 2009-05-05 Hoffman John C Gas diffusion vacuum device
US8074491B2 (en) * 2009-02-11 2011-12-13 Seagate Technology Llc Monitoring gas leakage rates from hermetically sealed devices

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6298713B1 (en) * 2000-05-10 2001-10-09 Bausch & Lomb Incorporated Method for determination of water transport in biocompatible materials
WO2004040006A1 (en) * 2002-10-28 2004-05-13 Transform Pharmaceuticals, Inc. Transdermal assay with magnetic clamp
US20050063862A1 (en) * 2003-09-24 2005-03-24 3M Innovative Properties Company System, kit, and method for measuring membrane diffusion

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO2007059738A1 *

Also Published As

Publication number Publication date
DE102005057031B4 (en) 2011-04-21
DE102005057031A1 (en) 2007-05-31
WO2007059738A1 (en) 2007-05-31
US20090133475A1 (en) 2009-05-28

Similar Documents

Publication Publication Date Title
WO2007059738A1 (en) Apparatus for permeation or substance passage investigations
DE112010005878T5 (en) Method for testing the hygroscopicity of tobaccos
DE1909843B2 (en) Method and device for the continuous quantitative analysis of a gaseous component contained in liquid samples
EP2951573A1 (en) Device for measuring residual oil
DE602004011795T2 (en) METHOD FOR INTRODUCING STANDARD GAS INTO A SAMPLING VESSEL
DE202010017827U1 (en) Device for the preparation of substances for qualitative and quantitative analyzes
EP1007938A1 (en) Device and method for sampling in liquid phases using a diffusion body and an analyte-binding phase
DE19502674C1 (en) Ion mobility spectrometer with internal gas chromatography column
DE2141244A1 (en) Sample valve for a device for the detection of a gas mixture
EP1287329A2 (en) Method for the determination of product- and substrate-concentrations in a medium
WO2024083479A1 (en) Medium for quantitatively removing water from a gas stream, device for this purpose, and use of said medium
DE2000074A1 (en) Analytical method and device suitable for it
WO2009118122A2 (en) Device for preparing a gas flow for introduction thereof into a mass spectrometer
DE60123523T2 (en) Transport device for the analysis of hydrocarbon constituents
EP3093658B1 (en) Gas analysis device and method
DE10235662A1 (en) Method and device for determining the isotope ratios of 18O and 16O as well as 15N and 14N
DE102015222769A1 (en) Method for balancing an optical fluid sensor
EP3292563A1 (en) Online mass spectrometer for real-time detection of volatile components from the gas and liquid phase for process analysis
EP0483613B1 (en) Method and apparatus for the qualitative and/or quantitative monitoring of liquid raw materials
EP1718963B1 (en) Method and device for characterizing osi materials
DE19957513B4 (en) Method for measuring changes in the gas composition in reaction processes
DE102008015145A1 (en) Method for recalibrating sensors and calibrating other sensors
DE102017009147A1 (en) Filtration device, method for assembling a modular filtration device and method for characterizing a filter medium and / or medium to be filtered
EP1464947A2 (en) Method and device for determining material emissions of test pieces
DE102022116897A1 (en) System and method for detecting internal leakage of a fuel cell stack

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

17P Request for examination filed

Effective date: 20080611

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 HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20150609

REG Reference to a national code

Ref country code: DE

Ref legal event code: R003

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

Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED

18R Application refused

Effective date: 20160115