GB2259767A - Laser Raman measuring cell - Google Patents
Laser Raman measuring cell Download PDFInfo
- Publication number
- GB2259767A GB2259767A GB9214803A GB9214803A GB2259767A GB 2259767 A GB2259767 A GB 2259767A GB 9214803 A GB9214803 A GB 9214803A GB 9214803 A GB9214803 A GB 9214803A GB 2259767 A GB2259767 A GB 2259767A
- Authority
- GB
- United Kingdom
- Prior art keywords
- sample chamber
- measuring cell
- laser raman
- windows
- laser
- 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.)
- Granted
Links
- 238000001069 Raman spectroscopy Methods 0.000 title claims abstract description 36
- 230000005855 radiation Effects 0.000 claims abstract description 12
- 210000003298 dental enamel Anatomy 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002320 enamel (paints) Substances 0.000 claims description 7
- 239000010935 stainless steel Substances 0.000 claims description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 3
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 10
- 238000011835 investigation Methods 0.000 abstract description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 239000004411 aluminium Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052594 sapphire Inorganic materials 0.000 description 3
- 239000010980 sapphire Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 230000002285 radioactive effect Effects 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000010905 molecular spectroscopy Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012812 sealant material Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000000699 topical effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052722 tritium Inorganic materials 0.000 description 1
- 238000003466 welding Methods 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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
-
- 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
-
- 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
- G01J3/44—Raman spectrometry; Scattering spectrometry ; Fluorescence 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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N2021/651—Cuvettes therefore
-
- 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
Landscapes
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The cell (5) for analytical investigation of gases comprises a basic body member made of metal including a vacuum- tight sample chamber (4) coated with black enamel; at least two windows (3, 6, 8, 11) permeable to Laser and Raman radiation seal the sample chamber in a vacuum-tight manner and are offset in relation to one another in one plane at an angle of 90 DEG ; and one or more connections (14) for evacuating and filling the sample chamber with a gaseous sample. <IMAGE>
Description
1) r, c -.' 1 LASER RAMAN MEASURING CELL The present invention relates to
a Laser Raman measuring cell for analytical investigation of gases or gas mixtures, and in particular to a Laser Raman measuring cell having a considerably reduced proportion of scattered light.
Raman spectroscopy is a spectroscopy of scattered radiation which is observed when light is radiated, generally at right angles to the direction of observation, into a Raman-active medium. However, in the analysis of gases in particular, the Raman lines are generally extremely weak. Raman spectroscopy has only achieved analytical importance since laser radiation has become available as a light-source.
Laser Raman spectroscopy (LRS) is suitable f or analytical detection of a plurality of gasesf particularly of those with symmetrical molecules without dipole moment, which cannot be detected by infrared spectroscopy (Frenesius, Z. Anal. Chem., vol. 327, 1987f pages 335 to 337). Laser Raman spectroscopy is particularly suitable for analysis of hydrogen and, in this case above all, for determining the content of hydrogen isotopes. The Raman lines of each of the possible isotope compounds H2, D2f T2 HD, HT and DT can be resolved by conventional spectrometers.
Analysis of hydrogen isotopes is described in the publication of T. Uda, K. Okuno, S. Olhira and Y. Naruse entitled "Application Study of Laser Raman Spectroscopy to In Situ Gas Analysis for Fusion Fuel Processing Systems" in the conference report of the 9th Topical Meeting on the Technology of Fusion Energy, Oak Brook, Illinois, USA, (Oct. 1990). A cuboid glass body with square cross-section, surrounding a sample chamber of about 6 cm3, is used. A connector nozzle of glass is cast in place in the centre of one of the sides, through which the sample chamber can be evacuated and f illed. The laser light falls through one of the square sides into the sample chamber. The Raman radiation is passed through the side opposite the connector nozzle, into a monochromator.
For several reasons, this measuring cell represents a provisional solution. The glass connector nozzle has to be connected to a vacuumtight metallic fitting. Further, the glass surfaces through which the laser or Raman light is coupled or uncoupled consist of optical windows. Optical windows can only be used when the glass surf aces f rom which the cell is constructed are glued together, in which case organic adhesives would have to be used which can react with the glass, or fused together, in which case the optical quality of the windows would be impaired. In either case finishing work can only be carried out on the outer surfaces of the windows. Further, the cell appears unsuitable for measurements at high pressure.
There is a brief description of a further measuring cell for the LRS of hydrogen isotopes in the publication 11Raman Line Positions in Molecular Hydrogen: H2, HD, HT, D2, DT and T211 by D. Kirk Veirs and Gerd M. Rosenblatt, Journal of Molecular Spectroscopy 121, 401419 (1987). It is merely known from this publication that the measuring cell is made of aluminium and contains coated windows which are sealed by metallic 0rings. The sample chamber volume is given as 1.3 cm3
More specific details on this cell are contained in the publication of Dean H. W. Carstens, "An Apparatus f or Studies of Hydrogen Isotope Exchange over Metals using Laser-Raman Spectroscopyll, Los Alamos National Laboratory, LA-11884-MS, UC-704 (Oct. 1990). According to this document the measuring cell comprises a block of aluminium, in which a hole f or the laser beam is bored along the longitudinal axis. Attached at the ends of the block are coated quartz glass windows sealed by 0rings. Additional and larger windows at right angles to the laser beam enable observation of the Raman light.
A measuring cell whose sample chamber consists of aluminium appears less suitable for LRS as a high background results during measurement because of the diffuse reflections, particularly in the case of small sample volumes.
Small sample volumes are particularly required for measuring cells into which highly toxic, aggressive or radioactive gases are introduced. With small sample volumes the proportion of scattered light increases sharply, so that a high background results during measurement.
A Laser Raman measuring cell of the type already mentioned is known from the publication Rev. Sci. Instrum. vol. 57, 1986, pages 2507 to 2511.
In this measuring cell the proportion of scattered light arising from diffuse reflections is reduced by screens and guide plates and by a black coating in the sample chamber, produced by anodic oxidation. Anodic oxidation is usable on few materials, but particularly on aluminium. In order to provide black coloration in the coating, organic dyestuffs and/or organic salts must be used, which are not stable in laser light.
A further measuring cell of the type already mentioned, yet without a black coating in the sample chamber, is known from US-PS 4,676,639.
In this measuring cell the diffuse scattered light is minimised by screens alone.
There is known from DE 23 63 180 C2 a reactionkinetic measuring apparatus containing a measuring cell of stainless steel, whose core consists of a black plastic material in order to reduce diffuse scattered light. In this case the core surrounds the sample chamber. The black plastic (polyacetal resin) also has poor stability in scattered laser light.
A further Laser Raman measuring cell is described in the 11Zeitschrift filr Naturforschung, vol. 28a, 1973, bk. 1, pages 27 to 30. This measuring cell consists of stainless steel and contains no measures to minimise diffuse scattered light.
The object of the present invention is to provide a measuring cell suitable for LRS in which the proportion of scattered light is considerably reduced. In the connected-up state, the measuring cell is to be vacuum-tight or ultra-high-vacuum-tight. The gas sample is not to come into contact with unstable, particularly organic materials. Further, the construction is to permit the use of optical windows of high quality.
According to the present invention there is provided a Laser Raman measuring cell comprising: a basic body member made of metal including a vacuum-tight sample chamber covered with a black enamel coating; at least two windows permeable to Laser and Raman radiation, said windows sealing the sample chamber vacuum-tight and being disposed in a plane relative to one another which is offset through 900; and one or more connections for evacuating the sample chamber and filling the sample chamber with a gaseous sample.
The measuring cell according to the preferred embodiment of the present invention comprises a metallic basic body member made of stainless steel which contains a sample chamber for the gases to be measured which is coated in black enamel. The proportion of scattered light arising from diffuse reflections in the sample chamber is particularly effectively reduced by black enamel. Enamelling can be applied later to the previous ly-manuf actured basic body member, so that the latter can be manufactured in the conventional manner. A further advantage of the enamel coating is that the sample chamber is then inert against most gases, which is of particular importance when gas samples containing radioactive tritium are used.
Black enamel has been known per se f or a long time, i. e. from Ullmann 1 s Enzyklopadie der technischen Chemie, vol. 6, 3rd ed., Urban & Schwarzenberg, MUekenBerlin, 1955, pages 478 to 492. However, it has not previously been used for coating the sample chamber of a Laser Raman measuring cell.
In its simplest embodiment the measuring cell contains two windows which seal the sample chamber in a vacuum-tight or ultra-high-vacuum-tight manner, and are off set to one another in one plane through an angle of 900. The laser bean is coupled through the first window into the sample chamber and the Raman radiation is passed through the second window, disposed at right angles to the first window, into a monochromator.
An improved embodiment contains a further window, which in turn is disposed at right angles to the second window and thus lies opposite the first window.
Such an embodiment permits a so-called 11multipass11 measuring arrangement, in which the laser beam is reflected by mirrors and thus multiplies radiation through the sample chamber.
The preferred embodiment contains four windows, arranged in pairs opposite one another. In this embodiment the Raman light shining through the fourth window can be reflected by a further mirror, so that double the Raman light intensity passes into the monochromator.
The windows used may, for example, be sapphire or quartz glass windows, preferably with an evenness of less than 1 lambda, better still with an evenness of less than 1110 lambda.
Particularly preferred are optical windows manufactured by a diffusion welding process. Such windows comprise, for example, a quartz glass or sapphire pane secured by a metallic ring, for example of tantalum or titanium. The metallic ring is welded to the pane with the aid of an aluminium alloy as a connecting material at high pressure at a temperature of approximately 5000C. In the case of windows produced in this way, the optical quality of the quartz glass or of the sapphire is maintained; moreover, an ultra-highvacuum-tight measuring cell can be constructed with such windows without the use of organic sealant materials.
o C The sample chamber is most simply f ormed by bores originating from the openings f or the windows, extending perpendicularly to the window surface and intersecting one another in the interior of the basic body member.
Stainless steel is preferred as a material f or the basic body member, because it is easily provided with a strongly-bonded and dense enamel coating. An enamel coating melted from a frit with the principal ingredients Si02 B2031 Zr02, P203, alkaline metal and alkaline earth metal oxides, has proved particularly suitable for coating a basic body member made of stainless steel.
Particularly preferred composition:
Si02 B203 Zr02 P203 Na20 K20 Li20 CaO BaO MnO CUO coo is a f rit with the 20.0% 17.0% 10.0% 22.0% 6.0% 2. 0% 2. 0% 1.5% 16.5% 2.0% 0.5% 0.5% In order to produce the enamel coating, enamel frit together with a suitable binding agent, is applied, e.g. with a paintbrush, to the surface of the sample chamber. During subsequent firing the enamel coating formsf and the binding agent evaporates. it is recommended that all the edges of the sample chamber be rounded off by means of enamelling.
electroerosion before A preferred embodiment of the present invention will now be described by way of example with reference to the accompanying drawing in which the preferred embodiment of the present invention in a measuring arrangement is shown.
A laser beam 1 is radiated by a mirror 2 through the window 3 into the sample chamber 4 of the measuring cell 5. The beam leaving the sample chamber 4 through the window 6 is reflected at mirrors 7 and 2. Raman radiation is passed through window 8 and through slot 9 into the monochromator 10. The Raman radiation leaving the sample chamber 4 through the window 11 is reflected by mirror 12, and likewise passes into the monochromator 10.
The measuring cell comprises a basic body member made of stainless steel in which crucif orm bores f orm the sample chamber 4. The sample chamber is coated with black enamel 13. The diameter of the bores f or the Raman radiation is slightly larger than the diameter for the laser radiation (1lmm compared to 9mm). The bores are expanded at their outer end to receive the windows 3, 6, 8, 11. The windows are secured by UHV f langes (not illustrated) such as ConflatR- (CF-) flanges (Trade Mark of the Varian Company), and sealed with the aid of flat seals of copper. The sample chamber 4 is evacuated and filled with a gas sample through connections 14.
Claims (6)
- Laser Raman measuring cell comprising:a basic body member made of metal including a vacuum-tight sample chamber covered with a black enamel coating; at least two windows permeable to Laser and Raman radiation, said windows sealing the sample chamber vacuum-tight and being disposed in a plane relative to one another which is offset through 900; and one or more connections for evacuating the sample chamber and filling the sample chamber with a gaseous sample.
- 2. Laser Raman measuring cell according to claim 1, wherein three windows are provided.
- 3. Laser Raman measuring cell according to claim 1, wherein four windows are provided.
- 4. Laser Raman measuring cell according to claims 1, 2 or 3, wherein the sample chamber is formed by cylindrical bores disposed vertically relative to the window surfaces and intersect in the interior of the basic body member.
- 5. Laser Raman measuring cell according to any of claims 1 to 4, wherein the metal of the basic body member is stainless steel.
- 6. Laser Raman cell according to any of claims 1 to 5, wherein a frit used to produce the black enamel has the principal ingredients Si02, B203, Zr02, P203, alkaline metal and alkaline earth metal oxides.7 Laser Raman cell according to claim 6, wherein - 10 the composition of the frit is as follows:Si02 B203 Zr02 P203 Na20 K20 Li20 CaO BaO MnO CUO coo 8. Laser Raman measuring hereinbefore described with accompanying drawing.1 20.0% 17.0% 10.0% 22.0% 6.0% 2. OP-o' 2.0% 1.5% 16.5% 2.0% 0.5% 0.5% cell substantially as reference to the 1 -1
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19914127712 DE4127712C2 (en) | 1991-08-22 | 1991-08-22 | Laser Raman measurement cell |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB9214803D0 GB9214803D0 (en) | 1992-08-26 |
| GB2259767A true GB2259767A (en) | 1993-03-24 |
| GB2259767B GB2259767B (en) | 1995-06-14 |
Family
ID=6438785
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB9214803A Expired - Fee Related GB2259767B (en) | 1991-08-22 | 1992-07-13 | Laser raman measuring cell |
Country Status (3)
| Country | Link |
|---|---|
| DE (1) | DE4127712C2 (en) |
| FR (1) | FR2680571A1 (en) |
| GB (1) | GB2259767B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009101418A1 (en) * | 2008-02-12 | 2009-08-20 | Starna Scientific Limited | Reference cell |
| WO2013087656A1 (en) * | 2011-12-16 | 2013-06-20 | Glaxo Group Limited | Apparatus for testing samples using raman radiation |
| US10094781B2 (en) | 2014-04-14 | 2018-10-09 | General Electric Company | Methods and systems to analyze a gas-mixture |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4320943C2 (en) * | 1993-06-24 | 2001-02-15 | Lavision Gmbh | Method for characterizing the operation of internal combustion engines by measuring the gas composition in the combustion chamber by Raman spectroscopy |
| CN110231330A (en) * | 2019-05-31 | 2019-09-13 | 南方科技大学 | Method for measuring metabolic activity of ammonia oxidizing archaea by using single cell Raman spectroscopy |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4676639A (en) * | 1986-01-22 | 1987-06-30 | Biomaterials International, Inc. | Gas cell for raman scattering analysis by laser means |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2363180C2 (en) * | 1973-12-19 | 1984-05-10 | Max Planck Gesellschaft zur Förderung der Wissenschaften e.V., 3400 Göttingen | Reaction kinetic measuring device |
-
1991
- 1991-08-22 DE DE19914127712 patent/DE4127712C2/en not_active Expired - Fee Related
-
1992
- 1992-07-13 GB GB9214803A patent/GB2259767B/en not_active Expired - Fee Related
- 1992-07-22 FR FR9209029A patent/FR2680571A1/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4676639A (en) * | 1986-01-22 | 1987-06-30 | Biomaterials International, Inc. | Gas cell for raman scattering analysis by laser means |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009101418A1 (en) * | 2008-02-12 | 2009-08-20 | Starna Scientific Limited | Reference cell |
| GB2457449B (en) * | 2008-02-12 | 2011-06-15 | Starna Scient Ltd | Reference cell |
| WO2013087656A1 (en) * | 2011-12-16 | 2013-06-20 | Glaxo Group Limited | Apparatus for testing samples using raman radiation |
| CN104115002A (en) * | 2011-12-16 | 2014-10-22 | 葛兰素集团有限公司 | Apparatus for testing samples using Raman radiation |
| JP2015500492A (en) * | 2011-12-16 | 2015-01-05 | グラクソ グループ リミテッドＧｌａｘｏ Ｇｒｏｕｐ Ｌｉｍｉｔｅｄ | Apparatus for testing samples with Raman radiation |
| AU2012350656B2 (en) * | 2011-12-16 | 2015-04-30 | Glaxo Group Limited | Apparatus for testing samples using Raman radiation |
| US9261404B2 (en) | 2011-12-16 | 2016-02-16 | Glaxo Group Limited | Apparatus for testing samples using raman radiation |
| US10094781B2 (en) | 2014-04-14 | 2018-10-09 | General Electric Company | Methods and systems to analyze a gas-mixture |
| US10495578B2 (en) | 2014-04-14 | 2019-12-03 | General Electric Company | Methods and systems to analyze a gas-mixture |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4127712A1 (en) | 1993-02-25 |
| DE4127712C2 (en) | 1993-10-07 |
| FR2680571A1 (en) | 1993-02-26 |
| GB9214803D0 (en) | 1992-08-26 |
| GB2259767B (en) | 1995-06-14 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19980713 |