WO2007051445A1 - Temperaturfeste ir-messsonde - Google Patents
Temperaturfeste ir-messsonde Download PDFInfo
- Publication number
- WO2007051445A1 WO2007051445A1 PCT/DE2006/001896 DE2006001896W WO2007051445A1 WO 2007051445 A1 WO2007051445 A1 WO 2007051445A1 DE 2006001896 W DE2006001896 W DE 2006001896W WO 2007051445 A1 WO2007051445 A1 WO 2007051445A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- probe
- optical fiber
- illumination
- light guide
- detection
- Prior art date
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
- G01N21/55—Specular reflectivity
- G01N21/552—Attenuated total reflection
-
- 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
- G01N21/84—Systems specially adapted for particular applications
- G01N21/85—Investigating moving fluids or granular solids
-
- 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
- G01N21/84—Systems specially adapted for particular applications
- G01N21/85—Investigating moving fluids or granular solids
- G01N21/8507—Probe photometers, i.e. with optical measuring part dipped into fluid sample
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/24—Coupling light guides
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/24—Coupling light guides
- G02B6/241—Light guide terminations
Definitions
- the invention relates to an optical fiber-coupled measuring probe, which uses the principle of attenuated total reflection (ATR) and a measuring system with optical fiber coupled ATR probe for process monitoring by means of infrared spectroscopy.
- ATR attenuated total reflection
- waveguide-based MIR immersion probes are their rigid, voluminous construction and their extremely strong adjustment sensitivity.
- optical fibers coupled immersion probes are available, which are very flexible and easy to adjust, but at the same time, due to the light guides used, are very sensitive to temperature.
- the light guides used are based on chalcogenide compounds.
- DE10123254 describes an infrared measuring probe consisting of an ATR diamond element and a silver halide optical fiber optic. The infrared radiation emerging from the light guide is coupled into the probe element via a micro-optic.
- US Pat. No. 5,185,834 shows an ATR measuring probe for infrared spectroscopy with a probe body for 2 internal reflections.
- the probe body is preferably made of ZnSe and has a lens formed on one side.
- the beam-guiding and beam-detecting optical fiber is fixed at a fixed distance to the probe body in an adjustable holder.
- hollow-conductor immersion probes eg from the companies Axiom and Mettler-Toledo
- the infrared radiation is directed via mirror optics to the probe element and from there to the detector.
- the components to be joined are joined together via sealing ring systems.
- IR probes consisting of rigid mirror arm systems are not flexible, they are sensitive to adjustment and only have a very short range.
- fiber-based IR probes are flexible, compact, and have a much wider range.
- the IR probes described in the prior art are only usable over a very narrow temperature range without active cooling. They usually consist of a probe element, an illumination light guide and a detection light guide, both of which are either firmly connected to the probe element or fixed in front of the probe element on the probe head housing.
- Polycrystalline silver halide compounds such as AgCl-AgBr for example, have a Audehnungskostoryen of typically 35 * 10 -6 ⁇ , while eg SiO2-based glass optical fiber, which are used in the near infrared spectral range have an approximately 2 orders of magnitude smaller coefficient of expansion.
- Glass fiber based probes therefore require a completely different packaging technology compared to polycrystalline silver halide light guides.
- Commercially available glass fiber optic probes, which are used in the temperature range up to 18O 0 C, can be permanently and permanently fixed in front of the probe element with high-temperature adhesives based on epoxy resin.
- Silver halides are in contrast to other infrared transparent materials used as optical waveguide materials such as chalcogenide glass optical fibers permanently stable from -150 0 C to 25O 0 C temperature and are therefore suitable for use in this temperature range with suitable packaging.
- the illumination and detection fiber end facing the probe element is supported so as to be resilient upon heating and cooling of the probe head housing, i. can extend and shorten without plastic deformation.
- This is e.g. achieved in that the probe head housing encloses a volume such that the non-destructive extension of the optical fibers, e.g. allowed by elastic deflection of the light guide in the lateral direction.
- a plastic deformation of the light guide leads to a degradation of the transmission properties of the light guide and can be avoided by a sufficiently large dimensioning of the escape volume.
- the light guides are held over a wide temperature range in a defined lateral and axial distance from the probe element. Reproducible measurement results are only possible if the position of the optical fiber ends relative to the probe element does not change during the pursuit of a laboratory reaction. This is realized via a restoring force which acts along the light guide axis.
- Attenuated Total Reflection (ATR) elements transmission and reflection elements are advantageous.
- ATR elements must be used regularly under elevated probe head temperature conditions. Active cooling not only cools the temperature-sensitive optical fibers but also the probe element and thus the measuring environment. Since ATR measurements take place only in a few microns thick layer around the ATR element, these measurements would give false results with active cooling. ATR measurements at elevated or reduced temperature thus make only without active Cooling sense.
- the IR probe according to the invention provides unadulterated measurement data without active cooling in the temperature range -15O 0 C to 25O 0 C.
- polycrystalline silver halide light guides having a core-shell structure are used. These light conductors are sufficiently flexible and can be used permanently in the temperature range from -150 0 C to 250 0 C.
- Light guides with a rectangular cross-section are particularly advantageous because they can be better adapted to the cross-sectional area of the probe element and also can contact each other flat and be attached. A flat attachment improves the reproducibility of the measured data.
- core light guides Light guides with a pure core structure, so-called core light guides, have a higher numerical aperture and thus a generally higher beam throughput than core-sheath light guides.
- core light guides provide significantly better measurement results with regard to the signal-to-noise ratio in the spectral range from 2 ⁇ m to 8 ⁇ m wavelength.
- the use of monocrystalline light guide sections, at least in the tempered region of the probe head, allows the use of the IR probe in the temperature range up to 35O 0 C.
- the two optical fiber ends are connected without optical gap fixed to the probe element.
- the gap-free coupling can be realized via a layer whose refractive index lies between the refractive index of the probe element and the light guide.
- the illumination and detection light guides are firmly connected in front of the probe element, but not with the probe head housing, this improves the reproducibility of the radiation coupling between the light guide and the probe element, since no relative displacement can occur between the two light guides.
- Detection and illumination light guides are stored in a defined position in front of the probe element via a restoring force.
- the light guides must be fixed at a point on the probe head housing which is outside the expansion area and behind the restoring force-generating element.
- the illumination and / or the detection light guide over its entire length only at a point between Eintial. Outcoupling and probe element connected to the surrounding sheath, wherein the surrounding sheath may be the probe head housing, the flexible optical protective sleeves or the optical fiber connector.
- the surrounding sheath may be the probe head housing, the flexible optical protective sleeves or the optical fiber connector.
- the restoring force is generated by elastic bending of the illumination and detection light guide in the rigid probe head housing.
- the probe head housing must be designed so that there is sufficient space for a further elastic deformation of the light guide, as a result of the temperature expansion, up to the maximum possible temperature available.
- IR probes are preferably assembled in a continuous rigid housing.
- the probe body is a very slender, elongated, e.g. cylindrical shape has, in particular at a length to diameter ratio of the probe body of more than 25. If the optical fiber behind the elongated probe body in a flexible protective tube with a length of at least 0.3m and an inner diameter of more than or twice the optical fiber diameter , no expansion volume exceeding the outer diameter of the slender probe body needs to be provided.
- Such IR measuring probes can preferably also be assembled in a continuous rigid tube.
- reaction temperatures in the range of -15O 0 C and 250 0 C are possible.
- the IR measuring probes used must not only be stable in this temperature range, but also provide reproducible measurement data.
- the length of silver halide Lichtlehern coefficient of expansion: 40 * 10 ⁇ -6) changes over a length of 20cm in the range of about 3.5mm, ie the expansion volume in the probe body must be designed accordingly.
- a temperature stability above 250 ° C. can be achieved if the optical fibers in the region of the probe head are made up in a vacuum-tight or gas-tight manner.
- the signal to noise of the ER probe can be significantly improved if the IR radiation via a microlens, which is formed on the optical fiber end of the coupling and / or detection light guide, is coupled into or out of the probe element.
- a particularly high beam throughput is achieved if at least the Einkoppellichtleiterende is provided with a lens whose focal length is more than 0.3 times the optical beam path between the input and Detetationsuchtleiterende.
- the IR measuring probe according to the invention can be connected very easily with the aid of conventional IR optics to any FTIR spectrometer, dispersive IR spectrometer, IR filter spectrometer or IR laser light sources.
- the high beam throughput and the optical properties, such as numerical aperture and fiber diameter, the light guides require no special device-specific adjustments.
- the IR measuring probe according to the invention can be connected to an IR detector element or to a laser or filtered light source without additional coupling optics. As a result, the beam throughput is significantly improved. In addition, eliminates at least one optical component, which in addition to the costs of the
- Highly sensitive IR detector elements are cooled to liquid nitrogen temperature. A direct coupling of the detection optical fiber is then particularly low loss when the detection optical fiber in front of the detector element
- Fig. 1 is a cross section through the probe head housing (12) of the inventive IR-measuring probe, in which Fig the course of the optical fiber at room temperature and Fig. Ib shown. Ia at 250 0 C.
- the light guides used are silver halide light guides with a core diameter of 0.9 mm and a cladding diameter of 1 mm.
- Illumination (13) and detection light guides (14) are located in the probe head housing (12), at one end of which the probe element (11), a 90 ° diamond ATR prism with a rectangular cross-sectional area, is enclosed.
- the bias must be chosen so strong that the end faces (15 and 16) of the illumination (13) and detection light guide (14) even at -150 0 C still on the diamond prism (11) are pressed.
- Behind the probe head housing (12) extend illumination (20) and detection light guide (21) in a flexible protective tube (19).
- T 250 ° C.
- the illumination (13) and detection light conductors (14) expand by about 2.5 mm and deviate into the expansion volume (17) of the probe head housing.
- the end faces (15 and 16) are held in the position in front of the probe element.
- a preferred embodiment of the optical fiber end faces (26 and 27) and the positioning auxiliary surfaces (28) in front of the probe element (11) is shown.
- Probe element focused coupled and via a lens on the
- Detection fiber end (27) collected.
- the coupling lens (26) focuses the
- the radiation is the entire onsllichtleiter transferred into the Deteku 'in the center of the diamond prism.
- the lens on the detection light guide transforms the incident radiation into low-modal radiation, which can then be transmitted very efficiently in the detection light guide.
- the four cone-shaped positioning auxiliary surfaces (28) ensure that the illumination and the detection fiber end are mounted self-aligning and also in the plane perpendicular to the light guide axis (22) have a defined position and can not escape laterally during vibration or other mechanical shocks.
- FIG. 3 shows a further preferred embodiment of the IR measuring probe.
- T room temperature
- the optical fibers Upon heating of the unbent portion of the probe head housing (31), the optical fibers elastically expand into the curved portion of the probe head housing.
- the inner diameter of the bent part is 3mm and its length is 50cm. It consists of a plastically deformable tube section that can be deformed between 100mm (semi-circular) and infinity (straight) in each bend radius, ie the straight section of the probe head housing can assume any position between vertically upwards, horizontally and vertically downwards.
- the outer diameter of the straight probe body portion (33) is 3mm and its length is 200mm.
- the detection light guide end (36) is coupled in a plastic bend over a 90 ° pipe flange (35) to a liquid nitrogen cooled [R detector element (37).
- the Einkoppellichtleiter has behind the splice (38) has a flexible length of Im before he opens in a fiber connector over which the IR probe can be connected to an IR light source or an IR spectrometer.
- Fig. Ia is a sectional view through a probe head of the inventive IR probe at room temperature
- Fig. Ib is a sectional view through a probe head of the IR measurement probe according to the invention at a maximum temperature of 25O 0 C
- Fig. 2a is a detailed sectional view through a preferred embodiment of the probe head tip.
- Fig. 2b View of the probe head tip from direction A.
- FIG. 3 shows a sectional drawing through an IR measuring probe according to the invention with a permanently connected nitrogen-cooled IR detector
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- General Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Optics & Photonics (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
- Radiation Pyrometers (AREA)
- Optical Couplings Of Light Guides (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE112006003624T DE112006003624A5 (de) | 2005-10-30 | 2006-10-27 | Temperaturfeste IR-Messsonde |
EP06805493A EP1943501A1 (de) | 2005-10-30 | 2006-10-27 | Temperaturfeste ir-messsonde |
JP2008536926A JP2009513956A (ja) | 2005-10-30 | 2006-10-27 | 温度耐性を有するir計測ソンデ |
US12/092,201 US20080292238A1 (en) | 2005-10-30 | 2006-10-27 | Temperature-Resistant Ir Measurement Probe |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102005052223.8 | 2005-10-30 | ||
DE102005052223A DE102005052223B3 (de) | 2005-10-30 | 2005-10-30 | Temperaturfeste Infrarot-Messsonde |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2007051445A1 true WO2007051445A1 (de) | 2007-05-10 |
Family
ID=37696021
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/DE2006/001896 WO2007051445A1 (de) | 2005-10-30 | 2006-10-27 | Temperaturfeste ir-messsonde |
Country Status (7)
Country | Link |
---|---|
US (1) | US20080292238A1 (de) |
EP (1) | EP1943501A1 (de) |
JP (1) | JP2009513956A (de) |
KR (1) | KR20080066825A (de) |
CN (1) | CN101300477A (de) |
DE (2) | DE102005052223B3 (de) |
WO (1) | WO2007051445A1 (de) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102009010541A1 (de) | 2009-02-25 | 2010-09-02 | Mmt Micro Mechatronic Technologies Gmbh | Sonde für die Infrarot-Spektroskopie |
JP2011027639A (ja) * | 2009-07-28 | 2011-02-10 | Mitsutoyo Corp | 誘電体形状の非接触測定用プローブ及び非接触測定装置 |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102007058611A1 (de) * | 2007-12-04 | 2009-06-10 | Endress + Hauser Conducta Gesellschaft für Mess- und Regeltechnik mbH + Co. KG | ATR-Sonde |
KR101167229B1 (ko) * | 2010-12-01 | 2012-07-23 | 한국기초과학지원연구원 | 렌즈 일체형 광섬유쌍 프로브 및 그 제조방법 |
CN103635785B (zh) * | 2011-02-15 | 2016-11-02 | 勒克思马克斯科技公司 | 整合cmos-ftir测定及拉曼测定的光谱仪及其方法 |
KR101455460B1 (ko) * | 2012-08-30 | 2014-10-28 | 현대제철 주식회사 | 시편의 전기화학적 측정 장치 |
CN107941871B (zh) * | 2017-11-04 | 2020-01-10 | 安徽师范大学 | 一种聚吡咯/银@溴化银核壳纳米线阵列材料、制备方法及其应用 |
CN110687077B (zh) * | 2019-11-20 | 2022-07-29 | 广东省海洋工程装备技术研究所 | 光纤探头以及测量海冰厚度的装置 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2255652A (en) * | 1991-05-06 | 1992-11-11 | Sirti Spa | Fibre-optic connector with half-casings forming annular cavity |
DE19856591A1 (de) * | 1998-12-08 | 2000-06-21 | Basf Ag | Vorrichtung zur spektroskopischen Analyse eines fluiden Mediums mittels abgeschwächter Reflexion |
DE10123294A1 (de) * | 2001-05-13 | 2002-11-14 | Anne Kuepper | Messsonde für Abgeschwächte Totalreflexion |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5185834A (en) * | 1991-03-04 | 1993-02-09 | Specac Ltd. | Optical fiber probes for remote analysis |
EP0624785B1 (de) * | 1992-10-07 | 1998-11-25 | Sumitomo Electric Industries, Ltd. | Optisches element für den infrarotbereich und messvorrichtung |
US5585634A (en) * | 1994-09-29 | 1996-12-17 | Foster-Miller, Inc. | Attenuated total reflectance sensing |
US5923808A (en) * | 1997-06-23 | 1999-07-13 | Melling; Peter J. | Mid-infrared fiber-optic spectroscopic probe for use at elevated temperatures |
-
2005
- 2005-10-30 DE DE102005052223A patent/DE102005052223B3/de not_active Expired - Fee Related
-
2006
- 2006-10-27 JP JP2008536926A patent/JP2009513956A/ja active Pending
- 2006-10-27 WO PCT/DE2006/001896 patent/WO2007051445A1/de active Application Filing
- 2006-10-27 CN CNA2006800408940A patent/CN101300477A/zh active Pending
- 2006-10-27 KR KR1020087012809A patent/KR20080066825A/ko not_active Application Discontinuation
- 2006-10-27 DE DE112006003624T patent/DE112006003624A5/de not_active Withdrawn
- 2006-10-27 US US12/092,201 patent/US20080292238A1/en not_active Abandoned
- 2006-10-27 EP EP06805493A patent/EP1943501A1/de not_active Withdrawn
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2255652A (en) * | 1991-05-06 | 1992-11-11 | Sirti Spa | Fibre-optic connector with half-casings forming annular cavity |
DE19856591A1 (de) * | 1998-12-08 | 2000-06-21 | Basf Ag | Vorrichtung zur spektroskopischen Analyse eines fluiden Mediums mittels abgeschwächter Reflexion |
DE10123294A1 (de) * | 2001-05-13 | 2002-11-14 | Anne Kuepper | Messsonde für Abgeschwächte Totalreflexion |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102009010541A1 (de) | 2009-02-25 | 2010-09-02 | Mmt Micro Mechatronic Technologies Gmbh | Sonde für die Infrarot-Spektroskopie |
JP2011027639A (ja) * | 2009-07-28 | 2011-02-10 | Mitsutoyo Corp | 誘電体形状の非接触測定用プローブ及び非接触測定装置 |
Also Published As
Publication number | Publication date |
---|---|
JP2009513956A (ja) | 2009-04-02 |
KR20080066825A (ko) | 2008-07-16 |
DE102005052223B3 (de) | 2007-06-14 |
US20080292238A1 (en) | 2008-11-27 |
EP1943501A1 (de) | 2008-07-16 |
DE112006003624A5 (de) | 2008-10-02 |
CN101300477A (zh) | 2008-11-05 |
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