WO2005100955A1 - Procede et appareil permettant de determiner des specimen liquides faiblement absorbant et/ou a faible diffusion - Google Patents
Procede et appareil permettant de determiner des specimen liquides faiblement absorbant et/ou a faible diffusion Download PDFInfo
- Publication number
- WO2005100955A1 WO2005100955A1 PCT/HU2005/000038 HU2005000038W WO2005100955A1 WO 2005100955 A1 WO2005100955 A1 WO 2005100955A1 HU 2005000038 W HU2005000038 W HU 2005000038W WO 2005100955 A1 WO2005100955 A1 WO 2005100955A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- light
- sample
- opening
- hollow body
- hollow
- 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
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
- G01N21/47—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
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
- G01J3/02—Details
- G01J3/0205—Optical elements not provided otherwise, e.g. optical manifolds, diffusers, windows
- G01J3/0254—Spectrometers, other than colorimeters, making use of an integrating sphere
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
- G01J3/28—Investigating the spectrum
- G01J3/42—Absorption spectrometry; Double beam spectrometry; Flicker spectrometry; Reflection spectrometry
-
- 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
- G01N21/03—Cuvette constructions
- G01N21/031—Multipass arrangements
-
- 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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2201/00—Features of devices classified in G01N21/00
- G01N2201/06—Illumination; Optics
- G01N2201/065—Integrating spheres
Definitions
- the invention relates generally to a method and apparatus for determining the absorption off weakly absorbing and/or scattering liquid samples.
- the invention relates to a method for determining the absorption of weakly absorbing and/or scattering liquid samples comprising the steps of
- the invention also relates to an apparatus for determining the absorption of weakly absorbing and/or scattering liquid samples
- a hollow measuring body having a wall with reflecting surface and at least one opening for receiving the sample and an opening or window not coated with reflecting lining for illuminating the hollow body and for collecting light from the hollow body the opening or window being associated with a light source and with a detector for receiving the collected light.
- spectrophotometry is a convenient and reliable technique for measuring moderately absorbing optically clear samples.
- the sample absorbs weakly and/or is not optically clear either lack of sensitivity or losses due to scattering the accuracy of the measurements will decrease and the determination of the absorbance properties will not be possible.
- Other im- portant applications include the detection of weakly allowed or forbidden transitions, flash- or chemically induced absorbance transients in dilute systems.
- the absorbance spectra of turbid samples are determined by placing a cuvette containing the sample inside an Ulbricht's integrating sphere, the internal surface of which is coated with a diffusely reflecting material and multiple reflections direct a fraction of the transmitted and scattered light to a detector ( Figure 1).
- the absorption spectrum of the sample can be determined by measuring the intensity of the detected light as a function of the wavelength of the measuring beam.
- a photometer sphere using this principle is disclosed in US 4,310,246. This procedure thus eliminates scattering artifacts in the measured absorbance spectra.
- this method is applicable only for moderately absorbing samples.
- Ketskemety et al. 1969, 1970 An important development, allowing a sensitivity enhancement of more than lOOx and the elimination of the scattering artifacts, was the introduction of a spherical cuvette the outer surface of which, apart from two windows serving as entrance and exit of the monitoring beam and the opening for filling/emptying, was coated by reflective or diffusely reflective material (Ketskemety et al. 1969, 1970). However, as pointed out by Ketskemety and
- Our invention aims at the elimination of principal drawbacks of these systems and elabora- tion of a correction procedure for retrieving the true absorption spectra, and adapting these techniques to the modern versions of spectrophotometers, laser technology, and extending their use in flash photometry and other forms of transient spectroscopy.
- an improved method comprising:
- the mathematical model takes into account the geometry and material constant of the cell, and absorbance of the sample.
- an apparatus for determining the absorption of weakly absorbing and/or scattering samples is suggested the improvement of which comprises:
- the apparatus further comprises a hollow body which is made of two parts each of them having a spherical wall with a reflecting surface and at least one opening for receiving the sample and a light conducting means for illuminating the hollow body and for collecting light from the hollow body wherein the two parts are fitted together to build a uniform spherical liollow body.
- the light conducting means is applied to the hollow measuring body at the opening for filling and/or emptying the body with the sample.
- the light conducting means applied to the hollow measuring body at the opening for filling and/or emptying the body with the sample may be a bifurcated light guide.
- the hollow body may also be a cuvette hav- ing substantially planar side walls and a bottom wall with reflecting surface at least on two opposite side walls; one opening for receiving the sample and at least one window not coated with reflecting lining for illuminating the hollow body and for collecting light from the hollow body the window being associated with a light conducting means and a detector for receiving the collected light.
- FIG-. 1 is a schematic view of a conventional integrating sphere
- FIG-. 2 is a schematic view of an integrating sphere according to the invention.
- FIG-. 3 is a schematic view of a multipath cuvette according to the invention.
- FIG-. 4 is a schematic view of assembling the parts of the integrating sphere for performing a measurement according to the invention
- FIG. 5 is a schematic view of three single-beam photometer arrangements
- FIG. 6 is a schematic view of a double-beam photometer arrangement
- FIG. 7 is a schematic view of a dual-wavelength photometer arrangement
- FIG. 8 is a schematic view of a double-beam photometer arrangement with a chopper and one monochromator.
- the conventional arrangement of an integrating sphere (such as used by Ketskemety et al. described above in more detail) as shown in Fig. 1 has been modified according to the invention as shown in Fig. 2.
- One improvement of the conventional arrangement used by Ketskemety et al. involves the use of a proper inner or outer coating as a diffusely or specularly ⁇ reflecting surface.
- a protective dielectric overcoating is applied to the reflective coating layer on the inner or outer wall of the hollow body.
- the reflecting surface is accomplished by a reflective layer of any reflective metal such as silver or aluminium.
- the dielectric layer may be a composite layer of two dielectric layers with a different index of refraction.
- the two layers are applied as a pair of alternating layers in a number of up to 10 or up to one hundred pairs.
- the use of inner layers results in a higher sensitivity. Because of the direct and permanent contact with the liquid sample the protec- tive layer should provide a suitable protection against mechanical and chemical erosion as well . When using outer layers the sensitivity will be lower because of the losses caused by tbe wall of the hollow measuring body but only mechanical protection is required as no chemical agents contact the layers permanently.
- a light conducting means (a light guide) is applied between the opening for filling the cavity with the liquid sample (or emptying) and the light source or illuminating the liquid sample inside the cavity.
- a transparent surface can also be used for illuminating the liquid sample inside the cavity.
- the illuminating light guide need not to be removed while filling or emptying the integrating sphere.
- Another light guide is used between a second opening or transparent surface (window) and the detector.
- the light illuminating the liquid sample generates a homogenous photon gas distribution inside the cavity.
- This can be achieved by using a diffuser at the light entrance of the cavity.
- the diffuser may be a multifaceted prism which is attached to the end of the light guide facing the hollow body.
- the sensitivity of absorption measurements can be increased by a factor of up to three orders of magnitude using the integrating sphere according to the invention due to the multiple reflections of monitoring beam inside the sphere.
- the measuring light can be continuous or pulsed (e.g. train of flashes).
- the multipath cuvette of Hegguist and Naqvi can be improved by depositing min-ors, with dielectric overcoat, on the internal or external surface of the cuvette (Fig. 3). By this means, unwanted optical effects (absorption, reflection, refraction, polarization distortion, etc.) at the walls can be eliminated.
- For non-scattering sample much longer pathways can be obtained by using a well-collimated beam, such as emerging from a laser, and optimizing the entrance and exit windows and the angle of incidence. Proper design of the exit beam would permit the use of polychromators and multichannel detectors, which makes the instrument easy to use and/or to adopt it to commercially available diode array spectropho- tometers or flash photolysis instruments.
- Fig. 4 shows shcematically the steps of assembling the parts of the apparatus according to the invention.
- the first step on the left
- two hemispheres are provided with equal dimensions.
- One of the hemispheres (upper part) is also provided with a filling/emptying opening attached to a short filling/emptying pipe.
- Both the upper and the lower part is provided with a diffusely or specularly reflecting layer and a protective dielectric overcoat on the inside or outside surface.
- the two parts are fitted together facing each other with the hollow side and attached to each other permanently by gluing, sealing or the like.
- the integrating sphere is then filled up with the sample through the filling aperture.
- a bifurcated light guide is being mounted onto the sphere.
- a diffuser prism is attached to the penetrating (common) end of the light guide in order to foster a homogenous distribution of the photon gas in the cavity.
- one end of the bifurcated light guide is connected to a light source for illuminating the liquid sample inside the cavity and the other end of the light guide is connected to a detector for receiving the reflected and/or scattered light.
- the illumination can be continuous or pulsed (e.g. trains of flashes) .
- Fig. 5A-5C shows schematic diagrams of three different single-beam photometer arrangements: a conventional photometer arrangement with one monochromator (Fig. 5A); with a polychromator and diode-array (Fig. 5B); and with double-monochromator (Fig. 5C).
- Fig 5A Single-beam spectrophotometer has a light source L with the necessary collimation optics C, a dispersing element (a prism or a diffraction grating) and aperture or slit to select a narrow bandwidth quasi-monochromatic light.
- the light is directed into the integrating sphere IS with the aid of a light guide.
- a photo detector D photomultiplier or photodiode measures the absolute intensity of outgoing light.
- the photo detector D is connected to a data acquisition and analysis unit.
- the data acquisition and analysis unit also serves as a controller for the light source L and the monochromator M.
- Light-induced absorption changes could also be measured using e.g. a flash lamp or other actinic illumination, which is directed into the cavity by an additional light guide (grey line).
- the same opening can serve for injecting different reagents.
- Fig. 5B Similar arrangement as described above.
- a broadband illumination is used and the spectral resolution is provided by the combination of a polychromator and a diode array on the detection side.
- the illumination can be a continuous light source or a flash lamp. In this latter case the detector performs intensity measurements synchronously with light emission from the flash lamp.
- the necessary synchiOnity is controlled by the data acquisition and analysis unit, which is connected to the diode array and the light source. Light-induced absorption changes can also be measured using e.g. an additional flash between two monitoring flashes (dashed vertical line). Again, the light is directed to and from the sphere with a light guide.
- Fig. 5C With this arrangement one can perform three different types of measurements, (i) The conventional absorption spectrum can be measured on non-fluorescing samples by the simultaneous scanning of the two monochromators Ml and M2 on the illu ination and the detection side, respectively. In this case the monochromators are set to the same wave- lengths).
- the emission spectrum of a fluorescent sample can be measured if the wavelength of the illuminating light is fixed (by setting Ml) within a specific range where the sample can absorb it and the monochromator on the detection side (M2) scans through the wavelength range where the fluorescent sample emits light, (iii) The excitation spectrum of a fluorescent sample can be measured if the detection wavelength is fixed (by setting M-2) to a specific value where the sample emits fluorescent light and the wavelength of the illuminating light is scanned through the range where the sample can absorb it.
- the data acquisition and analysis unit (signal processing and control unit) is connected to the monochromators Ml, M2 and the detector D.
- Fig. 6 shows a schematic drawing of a double-beam photometer arrangement.
- the light of light source L passes through collimator lenses CI, C2 and a monochromator M before reaching at a beam splitter B.
- the beam-splitter B divides the measuring beam-, which is then directed into the sample and the reference path, respectively. Since the two beams are not combined after passing through the sample and the reference, two detectors Dl, D2 are needed to measure the intensities.
- an attenuator which can be either another integrating sphere or a neutral density filter
- the intensity of the sample and reference beam could be brought into similar ranges. This makes the intensity measurements more reliable because the same sensitivity range of the detectors could be applied for the sample and the reference beams.
- Light-induced absorption changes can also be measured if one is using another light guide to direct the actinic light (e.g. train of flashes) into the sphere (grey line).
- the data acquisition and analysis unit is connected to the detectors Dl, D2 and the light source L.
- Fig. 7 shows a schematic diagram of a dual-wavelength photometer.
- the light of the light source L passes through a collimator lens C and is projected onto a rotating mirror or chopper CH, which alternately directs the beam through the two monochromators Ml, M2 several times per second.
- the difference in the absorbance of a sample is measured at two selected wavelengths provided by the two monochromators Ml and M2.
- Dual- wavelength spectroscopy i automatically performed by alternating two incident light beams of different wavelengths.
- One beam is fixed at a specific wavelength while the other is scanned over a given wavelength range.
- Light-induced absorption changes can also be measured if a further light guide is used to direct the actinic light (e.g.
- the date acqui sition and analysis unit is connected to the detector D, the monochromators Ml, M2 , the rotating mirror CH and the light source L in order to control them according to a measuring program.
- Fig. 8 shows a schematic diagram of a double-beam photometer arrangement with a chop- per CH and one monochromator M.
- the light passes through collimator lenses CI, C2, a monochromator M and a beam chopper CH, which alternately directs the beam through the sample or an attenuator several times per second.
- an attenuator in the reference pathway the intensity of the sample and the reference beam can be set in similar range and this makes easier the intensity measurement because the same sensitivity range can be applied in the detector D for measuring light intensity of the sample and reference beam.
- Light- or chemically-induced absorption changes can also be measured as in other arrangements, e.g. using a flash, which is guided into the sphere by an additional light guide (grey line).
- the measuring procedure requires a correction of this distortion in order to provide correct absorption spectra.
- the method according to the invention also involves a mathematical correction procedure, the empirically determined parameters of which depend on the geometry and material constant of the cell, and on the absorbance of the sample. We have found at least two simple relations w-hich fit the data extremely well, and permit us to convert the measured absorbance to the true value. Let A * ( ⁇ ; C) denote the measured absorbance at wavelength ⁇ and a solute concentration
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- General Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
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Abstract
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| HUP0400816 | 2004-04-19 | ||
| HU0400816A HU0400816D0 (en) | 2004-04-19 | 2004-04-19 | Method and apparatus for determining the absorption of weakly absorbing solutions and scattering particles of liquid samples |
| HU0401709A HU227140B1 (en) | 2004-08-19 | 2004-08-19 | Method and apparatus for determining the absorbtion of weakly absorbing and/or scattering samples |
| HUP0401709 | 2004-08-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2005100955A1 true WO2005100955A1 (fr) | 2005-10-27 |
Family
ID=89985450
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/HU2005/000038 Ceased WO2005100955A1 (fr) | 2004-04-19 | 2005-04-18 | Procede et appareil permettant de determiner des specimen liquides faiblement absorbant et/ou a faible diffusion |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO2005100955A1 (fr) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102890071A (zh) * | 2011-07-18 | 2013-01-23 | 中国科学院理化技术研究所 | 一种测量激光工作介质散射系数与吸收系数的装置 |
| CN105181602A (zh) * | 2015-09-11 | 2015-12-23 | 深圳世绘林科技有限公司 | 一种基于光学积分球的光谱测量装置 |
| JP2018013469A (ja) * | 2016-07-08 | 2018-01-25 | 大起理化工業株式会社 | 反射光検出装置 |
| CN107677686A (zh) * | 2017-09-28 | 2018-02-09 | 京东方科技集团股份有限公司 | 光线透过窗集成装置及采用该装置的设备 |
| WO2018070882A1 (fr) * | 2016-10-11 | 2018-04-19 | Darby Brendan Liam | Appareil spectromètre permettant de mesurer des spectres d'un échantillon liquide à l'aide d'une cavité d'intégration |
| US10670521B2 (en) | 2015-02-10 | 2020-06-02 | University Court Of The University Of St Andrews | System, devices and methods using an integrated sphere light collector |
| CN114509408A (zh) * | 2020-11-17 | 2022-05-17 | 上海微电子装备(集团)股份有限公司 | 一种散射测量装置及方法 |
| US12203848B2 (en) | 2020-01-31 | 2025-01-21 | ODx Innovations Limited | Apparatus, system and method for measuring properties of a sample |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1191784A1 (ru) * | 1983-12-22 | 1985-11-15 | Институт медико-биологических проблем | Устройство дл исследовани веществ методом импульсного радиолиза |
| US4645340A (en) * | 1983-06-01 | 1987-02-24 | Boston University | Optically reflective sphere for efficient collection of Raman scattered light |
| RU2125267C1 (ru) * | 1993-04-29 | 1999-01-20 | Данфосс А/С | Устройство и способ анализа текучей среды |
| GB2394542A (en) * | 2002-10-22 | 2004-04-28 | Mark Johnson | Diffuse light detection system |
-
2005
- 2005-04-18 WO PCT/HU2005/000038 patent/WO2005100955A1/fr not_active Ceased
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4645340A (en) * | 1983-06-01 | 1987-02-24 | Boston University | Optically reflective sphere for efficient collection of Raman scattered light |
| SU1191784A1 (ru) * | 1983-12-22 | 1985-11-15 | Институт медико-биологических проблем | Устройство дл исследовани веществ методом импульсного радиолиза |
| RU2125267C1 (ru) * | 1993-04-29 | 1999-01-20 | Данфосс А/С | Устройство и способ анализа текучей среды |
| GB2394542A (en) * | 2002-10-22 | 2004-04-28 | Mark Johnson | Diffuse light detection system |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102890071B (zh) * | 2011-07-18 | 2015-01-21 | 中国科学院理化技术研究所 | 一种测量激光工作介质散射系数与吸收系数的装置 |
| CN102890071A (zh) * | 2011-07-18 | 2013-01-23 | 中国科学院理化技术研究所 | 一种测量激光工作介质散射系数与吸收系数的装置 |
| US10670521B2 (en) | 2015-02-10 | 2020-06-02 | University Court Of The University Of St Andrews | System, devices and methods using an integrated sphere light collector |
| US10677727B2 (en) | 2015-02-10 | 2020-06-09 | University Court Of The University Of St Andrews | Scattered light integrating collector |
| CN105181602A (zh) * | 2015-09-11 | 2015-12-23 | 深圳世绘林科技有限公司 | 一种基于光学积分球的光谱测量装置 |
| JP2018013469A (ja) * | 2016-07-08 | 2018-01-25 | 大起理化工業株式会社 | 反射光検出装置 |
| WO2018070882A1 (fr) * | 2016-10-11 | 2018-04-19 | Darby Brendan Liam | Appareil spectromètre permettant de mesurer des spectres d'un échantillon liquide à l'aide d'une cavité d'intégration |
| US10983045B2 (en) | 2016-10-11 | 2021-04-20 | Victoria Link Limited | Spectrometer apparatus for measuring spectra of a liquid sample using an integrating cavity |
| AU2017343368B2 (en) * | 2016-10-11 | 2022-10-27 | Marama Labs Limited | A spectrometer apparatus for measuring spectra of a liquid sample using an integrating cavity |
| CN107677686A (zh) * | 2017-09-28 | 2018-02-09 | 京东方科技集团股份有限公司 | 光线透过窗集成装置及采用该装置的设备 |
| CN107677686B (zh) * | 2017-09-28 | 2021-01-26 | 京东方科技集团股份有限公司 | 光线透过窗集成装置及采用该装置的设备 |
| US12203848B2 (en) | 2020-01-31 | 2025-01-21 | ODx Innovations Limited | Apparatus, system and method for measuring properties of a sample |
| CN114509408A (zh) * | 2020-11-17 | 2022-05-17 | 上海微电子装备(集团)股份有限公司 | 一种散射测量装置及方法 |
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