WO2008014901A1 - Optische messsonde zur prozessüberwachung - Google Patents
Optische messsonde zur prozessüberwachung Download PDFInfo
- Publication number
- WO2008014901A1 WO2008014901A1 PCT/EP2007/006494 EP2007006494W WO2008014901A1 WO 2008014901 A1 WO2008014901 A1 WO 2008014901A1 EP 2007006494 W EP2007006494 W EP 2007006494W WO 2008014901 A1 WO2008014901 A1 WO 2008014901A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- measuring probe
- light
- region
- optical measuring
- distal
- Prior art date
Links
- 239000000523 sample Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 38
- 230000008569 process Effects 0.000 title claims abstract description 38
- 230000003287 optical effect Effects 0.000 title claims abstract description 18
- 238000012544 monitoring process Methods 0.000 title claims abstract description 8
- 238000005259 measurement Methods 0.000 claims description 18
- 238000011010 flushing procedure Methods 0.000 claims description 17
- 238000011156 evaluation Methods 0.000 claims description 9
- 238000001228 spectrum Methods 0.000 claims description 9
- 230000008878 coupling Effects 0.000 claims description 5
- 238000010168 coupling process Methods 0.000 claims description 5
- 238000005859 coupling reaction Methods 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000010926 purge Methods 0.000 claims 2
- 239000000463 material Substances 0.000 description 10
- 239000013307 optical fiber Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 239000000835 fiber Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004886 process control Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000012369 In process control Methods 0.000 description 1
- 238000003841 Raman measurement Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010965 in-process control Methods 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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
- G01N21/47—Scattering, i.e. diffuse reflection
- G01N21/4738—Diffuse reflection, e.g. also for testing fluids, fibrous materials
- G01N21/474—Details of optical heads therefor, e.g. using optical fibres
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B23/00—Telescopes, e.g. binoculars; Periscopes; Instruments for viewing the inside of hollow bodies; Viewfinders; Optical aiming or sighting devices
- G02B23/24—Instruments or systems for viewing the inside of hollow bodies, e.g. fibrescopes
- G02B23/2476—Non-optical details, e.g. housings, mountings, supports
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B23/00—Telescopes, e.g. binoculars; Periscopes; Instruments for viewing the inside of hollow bodies; Viewfinders; Optical aiming or sighting devices
- G02B23/24—Instruments or systems for viewing the inside of hollow bodies, e.g. fibrescopes
- G02B23/2476—Non-optical details, e.g. housings, mountings, supports
- G02B23/2492—Arrangements for use in a hostile environment, e.g. a very hot, cold or radioactive environment
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B23/00—Telescopes, e.g. binoculars; Periscopes; Instruments for viewing the inside of hollow bodies; Viewfinders; Optical aiming or sighting devices
- G02B23/24—Instruments or systems for viewing the inside of hollow bodies, e.g. fibrescopes
- G02B23/26—Instruments or systems for viewing the inside of hollow bodies, e.g. fibrescopes using light guides
-
- 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
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
- G01N21/15—Preventing contamination of the components of the optical system or obstruction of the light path
-
- 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
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/359—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using near infrared light
-
- 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
Definitions
- the present invention relates to an optical measuring probe for process monitoring, in particular for reflection measurements on solids, emulsions and suspensions.
- optical probes are frequently used in the field of process devices, with the aid of which the concentration, substance identity, turbidity and purity of educts, intermediates and products (solids , Emulsions and suspensions) in real time.
- Optical probes offer the advantage that they work without sampling, permit the simultaneous determination of the concentration of several analytes and can also be used in unfavorable environments (toxic, corrosive, radioactive, potentially explosive, sterile, contaminated).
- These probes are typically fiber optic elements which have their distal end, which has the light entrance aperture, in the process device, i. are more or less in the vicinity of or in direct contact with the analytes and with its proximal end to an evaluation device, e.g. an NIR spectrometer coupled.
- reflection measurements of the process material with the aid of a light source of known spectrum are carried out with these probes, the light of which is often coupled into the measuring location via a separate light guide arranged in the measuring probe.
- the systems mentioned comprise one or more fiber-optic measuring probes and an evaluation device such as an NIR spectrometer, for example, and are offered by Bayer under the trade name "Spectrobay.” Another supplier is Sentronic. Due to the extreme chemical, thermal and mechanical conditions that prevail in said process devices, said probes must be extremely robust and resistant, at least in the region of their distal ends. As a rule, they therefore have a fiber-optic core and a flexible metallic reinforcement. To provide the necessary strength, currently available, generic probes have a diameter of at least 8 mm, which continues into the distal region of the probe.
- the object of the present invention is therefore to provide an optical measuring probe for the real-time process control according to the above introduction, which is less susceptible to false readings due to deposits and contamination.
- an optical measuring probe for process monitoring comprising a distal end arranged in the region of a process device with a light entry opening and a proximal end coupled to an evaluation device.
- the evaluation device may be e.g. photometer or spectrometer, in particular a Fourier transform NIR or IR spectrometer, a grating or AOTF spectrometer, or a spectrometer based on a CCD or a photodiode array.
- the Auwert shark can e.g. also be a photomultiplier.
- the evaluation can extend from the UV to the IR range.
- the evaluation device may be a Raman spectrometer.
- a shaft is arranged, which comprises a light-conducting connection between the two ends.
- the measuring probe has a reduced outside diameter in its distal region relative to the shaft and / or the proximal end. knife on.
- a conical transition can be provided between the shaft and the distal region of the measuring probe with a reduced outer diameter.
- the probe provides only a small area in the area of the process device for depositing contaminants, and the forces which the moving process material has to apply in order to tear away any deposits that may be adhering are reduced to the lowest possible level.
- the distal region of the measuring probe arranged in the region of the process device has an outer diameter of 2 mm, while the shank and the proximal region each have an outer diameter of 12 mm.
- a reduction of the area at which process goods can deposit is achieved by a factor of 36.
- an optical fiber bundle in addition to the actual optical fibers a lamination and a i.d.R. flexible reinforcement on.
- the latter two components are responsible for the mechanical stability, the flexibility and possibly the tightness of the optical fiber bundle and contribute significantly to the outer diameter of the optical fiber bundle.
- the measuring probe according to the invention dispenses with the flexible jacket in its distal region and, instead, has a rigid sheath, possibly tapered at least in some sections, in this area. In this way, the outside diameter of the measuring probe can be drastically reduced in this area, without sacrificing mechanical stability, flexibility or tightness.
- the measuring probe has a flushing device with a flushing channel arranged in the region of the shaft and a flushing opening arranged in the region of the distal end.
- the rinsing opening is preferably arranged adjacent to the light entry opening. With the aid of this rinsing device deposits, which adhere despite the reduced area in the region of the distal end of the measuring probe, can be removed by rinsing.
- a coupling is provided with the aid of which the flushing medium can be introduced into the flushing device.
- flushing medium liquids such as water or solvents, gases such as air or inert gases (N 2 , Ar, Xe) or conveyable solid materials such as powder or microgranules can be used.
- gases such as air or inert gases (N 2 , Ar, Xe)
- conveyable solid materials such as powder or microgranules
- the choice of flushing medium depends on the process conditions and the compatibility of the flushing medium with the process material. It is also possible to use educts, intermediates or products used in the process in question as flushing medium. These may also be in liquid, gaseous or recoverable solid form. In this way, if appropriate, the rinsing medium can be an integral and quantitatively included component of a process, in particular of a production process.
- the rinsing device is designed so that rinsing can take place permanently, at fixed intervals or when cleaning is required.
- the measurement signal generated by the measuring probe and monitored by the evaluation device is used as an indicator for any contamination of the distal region of the measuring probe.
- the rinsing device is preferably designed such that rinsing can take place in a pulse-like manner and / or with high pressure.
- the light-conducting connection of the measuring probe according to the invention is preferably an optical waveguide or fiber-optic bundle of optical fibers.
- Fiber optic bundles of optical fibers have been used for some time and are available in various designs.
- the choice of the glass used for the fibers and the arrangement of the fibers can be adapted to the process conditions and the electromagnetic spectrum used.
- the measuring probe is designed for reflection measurements. This type of measurement method allows inline product touching and non-destructive measurement. Likewise it can be provided that the measuring probe is designed for fluorescence measurements and / or Raman measurements as well as turbidity measurements.
- the probe has a further photoconductive connection for coupling measuring light of a light source with a known spectrum and a light exit opening in the distal region of the probe has up.
- the light exit opening in the region of the distal end of the measuring probe is preferably arranged adjacent to the light entry opening; Frequently, a plurality of light exit openings are arranged around a centrally arranged light entry opening.
- This second light-conducting connection is likewise preferably a light guide or fiber-optic light guide bundle.
- a coupling can be provided, with the aid of which measurement light from a light source can be coupled into the light-conducting connection.
- This type of embodiment is particularly suitable for the use of the measuring probe for reflection measurements.
- the light of a light source with a known spectrum is projected onto the process material, so that changes in the composition of the process material and the like can be deduced from the change in the spectrum of the reflected light.
- this type of embodiment is also suitable for Raman or fluorescence measurements.
- an excitation light of known spectrum is projected onto the process material via the light exit opening, and the device evaluates the scattered light or emission spectrum recorded by the light entry opening.
- the measuring probe is designed for reflection measurements in the NIR range.
- the NIR range Near Infrared
- This wavelength range is particularly well suited for reflective measurements of substrate composition, since many of the molecules of interest absorb particularly well in the NIR range.
- NIR reflection measurements are therefore widely used in process control in the food industry, and chemical and pharmaceutical.
- FIG. 1 shows an optical measuring probe 10 for process monitoring with a distal end 11 having a light entry opening 12 arranged in the region of a process device whose wall is shown in dashed lines. is coupled to a not shown spectrometer.
- a shaft 14 is arranged, which comprises a light-conducting connection between the two ends.
- the light-conducting connection is a fiber-optic light guide or a light guide bundle with a lamination and a flexible metal reinforcement.
- the measuring probe has a reduced outer diameter in its distal region 11 relative to the shaft 14.
- the probe provides only a small area in the area of the process device for depositing contaminants, and the forces which the moving process material has to apply in order to tear away any deposits that may be adhering are reduced to the lowest possible level.
- the measuring probe has a flushing device 15 with a flushing channel arranged in the region of the shaft and a flushing opening 16 arranged in the region of the distal end 11.
- flushing medium while liquids such as water or solvents, gases such as air or inert gases (N 2 , Ar, Xe) or conveyable solid materials such as powder or microgranules can be used.
- gases such as air or inert gases (N 2 , Ar, Xe) or conveyable solid materials such as powder or microgranules
- starting materials, intermediates or products used in the process in question can be used as flushing medium.
- the probe also has its own light guide 17 for coupling measuring light and a plurality of Lichtaustrittsöffhungen 18 arranged around the centrally arranged light inlet opening.
- the probe can be set up for reflection, Raman, turbidity or fluorescence measurements.
- measuring light of a light source having a known spectrum is irradiated onto the process material via the light guide 17 and the light exit opening, and the reflected light or the fluorescence emitted by the excitation is received via the light entry opening 12 and via the light-conducting connection to an evaluation device , especially in spectrometers, passed.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Astronomy & Astrophysics (AREA)
- Optics & Photonics (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002659561A CA2659561A1 (en) | 2006-08-02 | 2007-07-20 | Optical measurement probe for process monitoring |
AU2007280793A AU2007280793B2 (en) | 2006-08-02 | 2007-07-20 | Optical measuring probe for process monitoring |
US12/375,496 US8238698B2 (en) | 2006-08-02 | 2007-07-20 | Optical measuring probe for process monitoring |
EP07786241A EP2049883A1 (de) | 2006-08-02 | 2007-07-20 | Optische messsonde zur prozessüberwachung |
JP2009522140A JP5190455B2 (ja) | 2006-08-02 | 2007-07-20 | プロセスモニター用光学的測定プローブ |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102006035996.8 | 2006-08-02 | ||
DE102006035996A DE102006035996A1 (de) | 2006-08-02 | 2006-08-02 | Optische Messsonde zur Prozessüberwachung |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2008014901A1 true WO2008014901A1 (de) | 2008-02-07 |
Family
ID=38565945
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2007/006494 WO2008014901A1 (de) | 2006-08-02 | 2007-07-20 | Optische messsonde zur prozessüberwachung |
Country Status (9)
Country | Link |
---|---|
US (1) | US8238698B2 (de) |
EP (1) | EP2049883A1 (de) |
JP (1) | JP5190455B2 (de) |
CN (2) | CN101495851A (de) |
AU (1) | AU2007280793B2 (de) |
CA (1) | CA2659561A1 (de) |
DE (1) | DE102006035996A1 (de) |
TW (1) | TWI443324B (de) |
WO (1) | WO2008014901A1 (de) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101717367B1 (ko) | 2015-08-19 | 2017-03-16 | 엘에스산전 주식회사 | 정적 무효전력 보상 장치 및 그 동작 방법 |
EP3571490B1 (de) * | 2017-01-17 | 2022-12-28 | Hach Lange GmbH | Trübungsmessung, vorrichtung zum eindicken von schlämmen, und verfahren zur trübungsmessung einer flüssigen probe mittels eines trübungssensors |
DE102017113371A1 (de) | 2017-06-19 | 2018-12-20 | Rational Aktiengesellschaft | Gargerät mit Garraum und Verfahren zum Reinigen des Gargerätes |
JP7171765B2 (ja) * | 2018-05-22 | 2022-11-15 | ワットロー・エレクトリック・マニュファクチャリング・カンパニー | デュアルシーリングと圧縮要素を備えた光ファイバープローブ |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3970394A (en) * | 1974-07-22 | 1976-07-20 | Harris Corporation | Densitometer head with fiber optics |
EP0336045A1 (de) * | 1988-03-04 | 1989-10-11 | Heraeus Surgical, Inc. | Vorrichtung zum Transportieren eines Laserstrahles für ein medizinisches Laser-System |
JP2000234953A (ja) * | 1999-02-16 | 2000-08-29 | Ishikawajima Harima Heavy Ind Co Ltd | 光学プローブ組立体 |
US20030090667A1 (en) * | 2001-11-13 | 2003-05-15 | Sick Ag | Gas permeable probe for use in an optical analyzer for an exhaust gas stream flowing through a duct or chimney |
WO2005003740A1 (de) * | 2003-07-07 | 2005-01-13 | Basf Coatings Ag | Remissionssensor zur messung flüssiger pigmentpräparationen oder fester pigmentierter oberflächen |
US20050054900A1 (en) * | 2003-07-21 | 2005-03-10 | Vanderbilt University | Ophthalmic orbital surgery apparatus and method and image-guided navigation system |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5278412A (en) * | 1992-08-18 | 1994-01-11 | Nirsystems Incorporated | System for measuring the moisture content of powder and fiber optic probe therefor |
US5657404A (en) * | 1995-05-25 | 1997-08-12 | Eastman Chemical Company | Robust spectroscopic optical probe |
GB0021975D0 (en) * | 2000-09-07 | 2000-10-25 | Optomed As | Filter optic probes |
JP2006125848A (ja) * | 2004-10-26 | 2006-05-18 | Takuma Co Ltd | レーザ式分析計 |
US7476618B2 (en) * | 2004-10-26 | 2009-01-13 | Asm Japan K.K. | Selective formation of metal layers in an integrated circuit |
-
2006
- 2006-08-02 DE DE102006035996A patent/DE102006035996A1/de not_active Withdrawn
-
2007
- 2007-07-20 JP JP2009522140A patent/JP5190455B2/ja not_active Expired - Fee Related
- 2007-07-20 AU AU2007280793A patent/AU2007280793B2/en not_active Ceased
- 2007-07-20 CN CNA2007800287298A patent/CN101495851A/zh active Pending
- 2007-07-20 WO PCT/EP2007/006494 patent/WO2008014901A1/de active Application Filing
- 2007-07-20 CN CN201210459337XA patent/CN103018204A/zh active Pending
- 2007-07-20 EP EP07786241A patent/EP2049883A1/de not_active Ceased
- 2007-07-20 CA CA002659561A patent/CA2659561A1/en not_active Abandoned
- 2007-07-20 US US12/375,496 patent/US8238698B2/en not_active Expired - Fee Related
- 2007-08-01 TW TW096128144A patent/TWI443324B/zh not_active IP Right Cessation
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3970394A (en) * | 1974-07-22 | 1976-07-20 | Harris Corporation | Densitometer head with fiber optics |
EP0336045A1 (de) * | 1988-03-04 | 1989-10-11 | Heraeus Surgical, Inc. | Vorrichtung zum Transportieren eines Laserstrahles für ein medizinisches Laser-System |
JP2000234953A (ja) * | 1999-02-16 | 2000-08-29 | Ishikawajima Harima Heavy Ind Co Ltd | 光学プローブ組立体 |
US20030090667A1 (en) * | 2001-11-13 | 2003-05-15 | Sick Ag | Gas permeable probe for use in an optical analyzer for an exhaust gas stream flowing through a duct or chimney |
WO2005003740A1 (de) * | 2003-07-07 | 2005-01-13 | Basf Coatings Ag | Remissionssensor zur messung flüssiger pigmentpräparationen oder fester pigmentierter oberflächen |
US20050054900A1 (en) * | 2003-07-21 | 2005-03-10 | Vanderbilt University | Ophthalmic orbital surgery apparatus and method and image-guided navigation system |
Non-Patent Citations (1)
Title |
---|
JÖRG-PETER CONZEN, TIM STADELMANN: "Fiber Optic Probes for the Process Technology", 2004, BRUKER OPTIK GMBH, XP002455274 * |
Also Published As
Publication number | Publication date |
---|---|
US8238698B2 (en) | 2012-08-07 |
CN101495851A (zh) | 2009-07-29 |
CN103018204A (zh) | 2013-04-03 |
CA2659561A1 (en) | 2008-02-07 |
JP2009545730A (ja) | 2009-12-24 |
TWI443324B (zh) | 2014-07-01 |
AU2007280793A1 (en) | 2008-02-07 |
JP5190455B2 (ja) | 2013-04-24 |
DE102006035996A1 (de) | 2008-02-07 |
TW200825403A (en) | 2008-06-16 |
US20090201493A1 (en) | 2009-08-13 |
AU2007280793B2 (en) | 2013-03-21 |
EP2049883A1 (de) | 2009-04-22 |
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