EP0808452A1 - Detecteur optique - Google Patents
Detecteur optiqueInfo
- Publication number
- EP0808452A1 EP0808452A1 EP96939894A EP96939894A EP0808452A1 EP 0808452 A1 EP0808452 A1 EP 0808452A1 EP 96939894 A EP96939894 A EP 96939894A EP 96939894 A EP96939894 A EP 96939894A EP 0808452 A1 EP0808452 A1 EP 0808452A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- layer
- optical sensor
- sensor element
- optical
- element according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/41—Refractivity; Phase-affecting properties, e.g. optical path length
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
-
- 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
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
- Y10T428/2495—Thickness [relative or absolute]
- Y10T428/24967—Absolute thicknesses specified
- Y10T428/24975—No layer or component greater than 5 mils thick
-
- 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
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249955—Void-containing component partially impregnated with adjacent component
-
- 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
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249955—Void-containing component partially impregnated with adjacent component
- Y10T428/249956—Void-containing component is inorganic
-
- 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
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249955—Void-containing component partially impregnated with adjacent component
- Y10T428/249958—Void-containing component is synthetic resin or natural rubbers
-
- 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
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249978—Voids specified as micro
- Y10T428/249979—Specified thickness of void-containing component [absolute or relative] or numerical cell dimension
-
- 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
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249978—Voids specified as micro
- Y10T428/24998—Composite has more than two layers
Definitions
- the invention relates to an optical sensor element for the detection of organic compounds, in particular hydrocarbons, which e.g. can be used in environmental and health protection.
- Hydrocarbons can pollute the environment and endanger human health. The measurement of hydrocarbons is therefore an important task.
- Usual methods for the detection of hydrocarbons are chromatography, IR absorption processors, optoacoustic measurement processes, thermal conductivity measurements, heat tone measurements in the event of catalytic decomposition of the hydrocarbons or electrolytic conductivity measurements.
- the first three measuring methods are complex in terms of equipment and can practically only be carried out in laboratories.
- the other methods are suitable for the design of measuring probes that can be used at different locations in the environment or in industrial processes. Their service life is short under corrosive environmental conditions. Because their functionality is based on electrical principles, they can only be used in explosive environments with explosion protection precautions and the measuring or amplification electronics must be located in the immediate vicinity of the measuring probes.
- fiber-optic sensors generally do not require any additional explosion protection measures and, because of the extremely low-attenuation and interference-free measurement signal transmission over fiber optic cables, larger distances up to the kilometer range between the measurement location and electronic signal evaluation can be realized ("remote sensing").
- the intensity measurements on optical fibers used with this sensor principle are a little suitable means of ensuring a stable and quantitatively reliable determination of the substance concentration to be detected, since any changes in the light intensity of the light source or of the fiber feed lines to the sensor falsify the measurement signal.
- an optical fiber which has a core made of quartz glass and an optical cladding made of silicone [JP Conzen, et al: Characterization of a Fiber-Optic Evanescent Wave Absorbance Sensor for Nonpolar Organic Compounds "; Applied Spectroscopy Vol. 47, 6 (1993) 753 or C. Ronot, et al: "Detection of chemical vapors with a specifically coated optical fiber sensors; Sensors and Actuators B, 11 (1993) 375-381].
- the silicone jacket protects the fiber core from water and other polar substances. However, organic compounds, such as hydrocarbon compounds, can diffuse into the silicone jacket. Changes in refractive index, swelling and optical absorption changes can be the result.
- optical sensor signals are also possible over long distances via optical fibers if the measurement information is transmitted as a spectrally coded optical signal, changes in the measurement information being made measurable as spectral shifts of maxima or minima of the light intensity.
- An example of such a principle is a fiber-optic moisture sensor [EP 0536 656 AI] and an associated method for signal evaluation [EP 0538 664 A2].
- the actual moisture-sensitive element called fiber-optic moisture sensor is an optical narrow-band filter, consisting of a stack of optical layers of inorganic dielectric substances with alternating high and low optical refractive index.
- the optical layer thicknesses always correspond to multiples of a quarter or half of an average working wavelength of the measuring light to be determined. It has long been known that such layers, if they are produced by vacuum evaporation, are porous and can absorb water in the presence of water vapor in the environment [H. Koch: Optical investigations on water vapor sorption in vapor deposition layers "phys. Stat. Sol. 12 (1965) 533-543]. The absorption of water changes the optical refractive indices of the individual layers and the filter spectrum of the layer stack shifts to longer wavelengths.
- the spectral shifts of the filter spectra can be measured very precisely even over large optical fiber sections, and fiber-optic moisture sensors equipped with such layer packets can be evaluated very reliably.
- the invention is based on the object of specifying an optical sensor element for the detection of organic compounds, in particular hydrocarbons, which enables their selective detection using components which produce spectral shifts.
- the object is achieved by the characterizing features of the first claim.
- Fig. La and Fig. Lb represent possible surface assignments and their
- FIG. 2 shows a possible application of a layer package according to the invention as a sensor head of a fiber-optic detector that works in reflection mode
- FIG. 2a shows a more detailed schematic representation of the layer package according to FIG. 2 and FIG extensive layer package according to the invention, which is read out in transmission by, for example, a CCD camera.
- a spectral band filter with several optical thin layers with a thickness of ⁇ / 4 or ⁇ / 2 or a multiple thereof, which alternately have a high (%) and a low refraction (n n ) with respect to the average working wavelength used Measuring light are arranged. It is immaterial in the context of the invention whether the spectral band filter is designed as a transmission or reflection filter, edge filter, narrow band filter, etc.
- a variable optical thickness including the product of refractive index and geometric Thickness is to be understood
- said layer 31 according to the invention is to consist of a dielectric inorganic material, for example one or more metal oxides, which, due to the production process, is provided with pores P of a maximum size of up to a few 10 nm. These pore sizes ensure that the layer appears optically homogeneous and essentially no light scattering occurs.
- This layer is covered on both sides by alternately high n ⁇ and low refractive n n thin layers in the form of a reflection filter.
- the reflection filter layers on the detecting side (on the right in FIG. 2a) likewise have pores which are connected to the pores of layer 31 and allow the substance to be detected to enter.
- the pores of the layer 31, the pore surfaces and also the layer surface of which are inherently very hydrophilic are coated with molecules which make the character of the surface highly hydrophobic.
- This assignment is achieved, for example, by silanization.
- Suitable for this purpose are, for example, organosilane compounds with the general chemical formula R z SiX (4. Z ⁇ with (1 ⁇ z ⁇ 4).
- X stands for a hydrolyzable group, for example an alkoxy group or a halogen, for example chlorine
- R stands for non-hydrolyzable organic radical which is intended to give the pore surface a special functional property, in the sense of the invention, in particular a hydrophobic property ..
- alkoxy groups are methoxy - (- 0 CH 3 ) and ethoxy - (0 CH 2 CH 3 ) - Group:
- the hydrolyzable groups X react chemically with the hydrogen of the hydroxyl groups on the metal oxide surface and are split off, whereupon the silicon with its functional group R is chemically bonded to the metal oxide surface mentioned type are indicated in Figures la and lb.
- the organosilane compound used is methylchlorosilane, for example (C ⁇ SiC ⁇ .
- methylchlorosilanes boil between 57 ° C and 70 ° C, it is preferable to work slightly above these temperatures and to allow the steam to react with the pore surfaces a thin film of methylpolysuoxane is deposited in the interior of the pores, while the released hydrogen chloride evaporates.
- a surface covering produced in this way has a pronounced affinity for non-polar or low-polar molecules, as a result of which wetting occurs with such compounds, but water is repelled. Since the pore surfaces clad according to the invention are strongly concave, there are vapor pressure reductions in the wetting liquid, the greater the greater the wettability and the smaller the pores. From a gas mixture which contains, for example, condensable non-polar vapors, e.g. Containing organic solvent vapors, or other condensable hydrocarbon compounds, the lowering of the D-mipfdnickern leads to the fact that these vapors can condense in the pores. The cavity of various pores, which was originally filled with gas or steam, is now filled with liquid. This increases the optical refractive index of the porous layer and thus its optical thickness.
- condensable non-polar vapors e.g. Containing organic solvent vapors, or other condensable hydrocarbon compounds
- these layers are to be designed in such a way that at least the mirror layers on one side are also porous and all pores of the middle porous and sensitive layer which essentially determines the working wavelength have access to the outside through which the steam molecules from the environment into the pores and can get back again.
- These mirror layers can be made from dielectric substances with an optical thickness corresponding to a quarter of the light wavelength or from optically partially transparent metallic substances.
- the spectrally filtering layer system 3 on the detector head 2 can be firmly connected to the end faces of optical fibers 1 or can be applied directly to these, the optical fibers 1 illuminating I [ ⁇ ] of the layer system 3 and returning the filtered light I [ ⁇ (C)], where C stands for the concentration of the substance to be detected, are used for an optical evaluation unit, which is shown with a broken line in FIG. 2. It is also within the scope of the invention to design the spectrally filtering layer system 3, 31 as an extended spatial plate, which is applied to a transparent carrier 4 (as shown in FIG. 3), and to remove the spectral evaluation spatially, for example using a CCD -Camera 5 to accomplish.
- organosilane compounds other than those described can also be used in the context of the invention, either to increase the temperature resistance of the siloxane films, or to change the polar character or to increase the selectivity of the interaction with special molecules.
- the dielectric inorganic base substance for the porous layer it is also possible to use organic substances whose molecules form cage-shaped cavities, such as cyclodextrins, the selectivity towards certain molecules being achievable by matching the size of these molecules with the sizes of the molecular cages.
- this pore surface acquires a property which decisively determines the attachability of substances depending on their polar or non-polar molecular character, that is to say their wettability.
- methyl groups used in the example above
- other groups preferably bound to silicon, are of course also used, e.g. Phenyl or A-minogroups to increase the selectivity of the sensors towards certain hydrocarbons, amines etc. to modify.
- Phenyl or A-minogroups to increase the selectivity of the sensors towards certain hydrocarbons, amines etc. to modify.
- a phenyl group significantly increases the desired hydrophobic effect and is still stable even up to temperatures of approx. 300 ° C.
- a porous, dielectric organic layer is used for the layer with variable optical thickness, which inherently has a non-polar surface character.
- a porous polymer layer can be produced, for example, from a mixture of polymerizable monomers and an inert organic solvent, which is applied to a substrate.
- a porous layer is formed by polymerization and subsequent removal of the inert solvent. Because of their excellent optical transmission properties, methyl methacrylate (MMA) or triethylene glycol di-methacrylate (TGMA) can be used as monomeric starting materials, and octane can be used as an inert solvent be used. Benzoyl peroxide can serve as the polymerization initiator.
- MMA methyl methacrylate
- TGMA triethylene glycol di-methacrylate
- Benzoyl peroxide can serve as the polymerization initiator.
- a porous polymer layer with the desired non-polar and hydrophobic surface is formed, so that vaporous substances with non-polar molecules can condense depending on their vapor pressure in the pores of the appropriate size.
- the size and number of pores can be influenced in a targeted manner by the mixture ratio of the mixture and the polymerization conditions.
- the thickness of the layer can be selected in a predeterminable manner in order to achieve optical effects according to the use. For this purpose it can also be combined with other layers to form layer systems.
- the pores can, of course, in particular if they are to be larger, also be produced by an "exposure process” (e.g. with electron beams) which is common in microlithography and subsequent development. PMMA layers customary in electron beam lithography are suitable for this.
- a dielectric layer is used for the layer 31 with a variable optical thickness which explicitly has no recognizable pore structures, but which is able, for example, to use non-polar hydrocarbon To solve connections or those with a small molecular dipole moment and to take them up, as a result of which changes in the optical refractive index and / or the thickness of the layer 31 occur.
- water cannot be dissolved in any significant concentration in these layers.
- the layer or layers should be able to be integrated into an optical filter layer system or an optical filter layer system should be able to be built from them.
- such layers consist of siloxanes, for example dimethypolysuoxane (DMPS), and of polytetrafluoroethylene (for example Teflon AF).
- DMPS dimethypolysuoxane
- Teflon AF polytetrafluoroethylene
- Hydrocarbon compounds in particular chlorinated hydrocarbons, are readily soluble in both substances, but water is hardly.
- DMPS with optical refractive indices of 1, 4 and slightly above can perform the role of an optically high refractive index layer and Teflon AF with a refractive index of about 1.3 that of an optically low-refractive layer, so that optical filter layer systems can be constructed with alternating sequences of these layers with optical thicknesses to be determined which correspond to a quarter or a half of an optical working wavelength.
- optically effective thicknesses change in these layers when hydrocarbon molecules are dissolved in these layers due to the associated changes in refractive index and thickness, there are shifts in the optical working wavelengths of the filters, at which maximum transmission or reflection takes place. These spectral shifts can be evaluated with great precision and reliability.
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Plasma & Fusion (AREA)
- Engineering & Computer Science (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
Abstract
L'invention concerne un détecteur optique pour identifier des composés organiques, notamment des hydrocarbures. L'invention a pour objet de définir un tel détecteur qui permette la détection sélective des substances mentionnées en utilisant des sous-groupes produisant des déplacements spectraux. Pour ce faire, il est proposé d'utiliser un filtre à bande spectrale contenant au moins une couche d'une épaisseur optique modifiable de μ/4 ou de μ/2 ou bien d'un multiple de ces valeurs. Cette couche possède des propriétés hydrophobes et contient des groupes d'affinité organiques dont le choix peut être adapté à la substance à détecter.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19545414A DE19545414C2 (de) | 1995-12-06 | 1995-12-06 | Optisches Sensorelement |
DE19545414 | 1995-12-06 | ||
PCT/EP1996/005155 WO1997021092A1 (fr) | 1995-12-06 | 1996-11-22 | Detecteur optique |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0808452A1 true EP0808452A1 (fr) | 1997-11-26 |
Family
ID=7779279
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP96939894A Withdrawn EP0808452A1 (fr) | 1995-12-06 | 1996-11-22 | Detecteur optique |
Country Status (4)
Country | Link |
---|---|
US (1) | US6007904A (fr) |
EP (1) | EP0808452A1 (fr) |
DE (1) | DE19545414C2 (fr) |
WO (1) | WO1997021092A1 (fr) |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999056109A1 (fr) * | 1998-04-27 | 1999-11-04 | Gottlieb Amos J | Article et procede servant a effectuer la mesure optique et spectroscopique d'un gaz dissous |
US7449146B2 (en) * | 2002-09-30 | 2008-11-11 | 3M Innovative Properties Company | Colorimetric sensor |
US20040062682A1 (en) * | 2002-09-30 | 2004-04-01 | Rakow Neal Anthony | Colorimetric sensor |
AU2003294535A1 (en) * | 2002-12-20 | 2004-07-14 | Fiso Technologies Inc. | Polarisation interferometric method and sensor for detecting a chemical substance |
US20070286546A1 (en) * | 2003-03-11 | 2007-12-13 | Jean-Francois Masson | Surface Initiated Thin Polymeric Films for Chemical Sensors |
US7556774B2 (en) * | 2005-12-21 | 2009-07-07 | 3M Innovative Properties Company | Optochemical sensor and method of making the same |
US7767143B2 (en) | 2006-06-27 | 2010-08-03 | 3M Innovative Properties Company | Colorimetric sensors |
US8067110B2 (en) * | 2006-09-11 | 2011-11-29 | 3M Innovative Properties Company | Organic vapor sorbent protective device with thin-film indicator |
US7906223B2 (en) | 2006-09-11 | 2011-03-15 | 3M Innovative Properties Company | Permeable nanoparticle reflector |
US20080285165A1 (en) * | 2007-05-14 | 2008-11-20 | Wu Kuohua Angus | Thin film filter system and method |
KR101544633B1 (ko) * | 2008-06-30 | 2015-08-17 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | 노출 표시 장치 |
EP2433112A4 (fr) | 2009-05-22 | 2015-05-13 | 3M Innovative Properties Co | Capteur colorimétrique multicouche |
US8537358B2 (en) | 2009-05-22 | 2013-09-17 | 3M Innovative Properties Company | Multilayer colorimetric sensor arrays |
CN110068545A (zh) * | 2018-01-22 | 2019-07-30 | 中昊晨光化工研究院有限公司 | 用于四氟乙烯生产系统的微量水传感器及水分检测装置 |
CA3218768A1 (fr) * | 2021-05-11 | 2022-11-17 | Farshad RAJABIPOUR | Systeme de capteur integre pour la mesure et la surveillance de la resistivite electrique d'une solution interstitielle dans des materiaux et des structures en beton |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0097695B1 (fr) * | 1981-12-30 | 1989-04-19 | Mta Központi Fizikai Kutato Intezete | Procede de fabrication d'un miroir a interference sensible a l'humidite, et procede et dispositif de mesure de l'humidite utilisant ce miroir |
US4641524A (en) * | 1985-08-15 | 1987-02-10 | Kms Fusion, Inc. | Optical humidity sensor |
JPS62108133A (ja) * | 1985-11-06 | 1987-05-19 | Fujitsu Ltd | 湿度センサ |
DE3832185A1 (de) * | 1988-09-22 | 1990-03-29 | Fedor Dipl Phys Dr Mitschke | Feuchtesensor und messanordnung zur messung der feuchte |
DE4133126C2 (de) * | 1991-10-05 | 1996-11-07 | Ultrakust Electronic Gmbh | Feuchtesensor |
DE4133125C1 (fr) * | 1991-10-05 | 1993-02-18 | Ultrakust Electronic Gmbh, 8375 Gotteszell, De | |
DE4200088C2 (de) * | 1992-01-04 | 1997-06-19 | Nahm Werner | Verfahren und Vorrichtung zum optischen Nachweis einer An- oder Einlagerung mindestens einer stofflichen Spezies in oder an mindestens einer dünnen Schicht |
EP0598341B1 (fr) * | 1992-11-17 | 1998-09-23 | Hoechst Aktiengesellschaft | Capteur optique pour la détection d'espèces chimiques |
EP0598340B1 (fr) * | 1992-11-17 | 2012-06-13 | O.S.P. Inc. | Utilisation d'un film de copolymère sur un substrat pour détecter des substances chimiques |
-
1995
- 1995-12-06 DE DE19545414A patent/DE19545414C2/de not_active Expired - Fee Related
-
1996
- 1996-11-22 EP EP96939894A patent/EP0808452A1/fr not_active Withdrawn
- 1996-11-22 WO PCT/EP1996/005155 patent/WO1997021092A1/fr not_active Application Discontinuation
- 1996-11-22 US US08/860,771 patent/US6007904A/en not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
---|
See references of WO9721092A1 * |
Also Published As
Publication number | Publication date |
---|---|
WO1997021092A1 (fr) | 1997-06-12 |
DE19545414C2 (de) | 2002-11-14 |
US6007904A (en) | 1999-12-28 |
DE19545414A1 (de) | 1997-06-12 |
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