WO2007126371A1 - Method at spectrometry for investigation of samples, where the sample contains at least two elements - Google Patents
Method at spectrometry for investigation of samples, where the sample contains at least two elements Download PDFInfo
- Publication number
- WO2007126371A1 WO2007126371A1 PCT/SE2007/050240 SE2007050240W WO2007126371A1 WO 2007126371 A1 WO2007126371 A1 WO 2007126371A1 SE 2007050240 W SE2007050240 W SE 2007050240W WO 2007126371 A1 WO2007126371 A1 WO 2007126371A1
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- WIPO (PCT)
- Prior art keywords
- elements
- sample
- intensity
- measured
- concentrations
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 31
- 238000011835 investigation Methods 0.000 title description 2
- 238000004611 spectroscopical analysis Methods 0.000 title description 2
- 238000004364 calculation method Methods 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 4
- 238000000441 X-ray spectroscopy Methods 0.000 claims description 3
- 238000011156 evaluation Methods 0.000 claims description 3
- 239000000523 sample Substances 0.000 description 29
- 238000004458 analytical method Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 238000010200 validation analysis Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000004876 x-ray fluorescence Methods 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 235000015108 pies Nutrition 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 241001137251 Corvidae Species 0.000 description 1
- 238000004164 analytical calibration Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
- G01N23/223—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material by irradiating the sample with X-rays or gamma-rays and by measuring X-ray fluorescence
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2223/00—Investigating materials by wave or particle radiation
- G01N2223/07—Investigating materials by wave or particle radiation secondary emission
- G01N2223/076—X-ray fluorescence
Definitions
- the present invention relates to a calibration process in X- ray fluorescence analysis with the aid of solely one sample.
- the present invention solves the problem mentioned above.
- the present invention thus relates to a method of analysing a sample spectrometrically, where the sample contains at least two elements, wherein the method is characterized by placing a sample of known concentrations of known elements in a spectrometer in a first step and measuring the intensity II, 12.... In of the different elements included in the sample, by relating known concentrations Cl, C2... Cn for the elements included in the sample to the measured intensities II, 12... In in a second step such as to calculate a fictive intensity for a 100%-pure element for each of the elements included; calculating calibration constants Kl, K2... Kn for each of the ele- ments as the relationship between measured intensity II, 12...
- the present invention is unique in so much that only one sam- pie containing the elements to be calibrated is required for the calibration of two or more elements.
- the method is also based on the ability to simultaneously calculate the background of the sample from solely one single measurement of the sample, i.e. solely one measurement per element, i.e. one point .
- the calculation according to the above mentioned second step is carried out by using a relationship between the concentration of an element and the intensity to which the concentration gives rise in the spectrometer used.
- the calculation is carried out in the mentioned second step, in which the known concentrations Cl, C2... Cn for the elements present are related to the measured intensities II, 12...
- a fictive intensity for a 100%-pure element for each of the elements is established with the aid of algorithms described in the article "Application of J. E. Fernandez algorithms in the evaluation of X-ray intensities measured on fused glass discs for a set of international standards and a proposed calibration procedure", J. MaIm- qvist; X-RAY SPECTROMETRY; X-Ray Spectrom 2001; 30 : 83-92.
- a sample of known concentrations of known elements is placed in an appropriate spec- trometer and the intensity II, 12... In of the sample is measured with respect to the various elements present in the sample.
- the above example concerns the calibration of Fe and Si for two standards, FElOOl and SIlOOl, which were produced with pure chemicals and contained 100% SiO 2 and 100% Fe 2 O 3 respectively.
- the FESI-sample comprised a mixture of the two ox- ides.
- the known concentrations Cl, C2... Cn of the elements present in the sample are related to the measured intensities II, 12 ... In such as to calculate a fictive intensity for a 100%-pure element for each of the elements present.
- the concentration of an element in a sample is determined generally by the relationship
- C 1 the concentration of the element i
- k x the calibration constant
- I 1 the measured intensity
- M the mathematical correction used in accordance with the present invention.
- the expected theoretical intensity value in the case of a concentration of 100% in respect of the element El is designated lEiioo% ⁇ eor > This can be considered to indicate the sub- quantity of photons registered for the element of all the photons produced with the X-ray tube used in the spectrometer.
- step 1 an adjustment, calibration, in which the I E iioo % ⁇ eor -value of the elements Fe and Si is ad- justed so that the concentrations of the samples will be 100%.
- CEIIOO% k E i • l ⁇ iMdtt • M
- the concentration of respective elements in the sample last mentioned is calculated as the measured in- tensity multiplied by a respective calibration constant with respect to the elements present in the sample.
- the fifth step is repeated without repeating the first, second and third steps.
- the example given illustrates how calibration with respect to several elements can be achieved with the aid of solely one sample. This is of particular significance in re- spect of multi-element analysis, of which X-ray fluorescence analysis is often an example where it may concern the calibration of perhaps 10 - 50 elements with respect to an analysis method. It will readily be understood that the novel process is time saving and that one of the reasons for this lies in the ability of the process to calculate a background with the use of solely one measurement, i.e. the determination of solely one point/element.
- the inventive process can also be applied in the validation of an analysis method.
- individual especially produced samples used for the calibration process can also be tied to an earlier executed validation of an analysis method, which is beneficial per se as an updating of a validation that can be applied to this individ- ual sample. This is particularly significant in those cases where problems occur with the instrument hardware, such as when changing X-ray tubes, faulty detectors, malfunctioning of a scanner, or other serious faults in the system.
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- Physics & Mathematics (AREA)
- Health & Medical Sciences (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)
- Analysing Materials By The Use Of Radiation (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention is characterized by placing a sample of known concentrations of known elements in a spectrometer in a first step and measuring the intensity II, 12.... In of the different elements included in the sample, by relating known concentrations Cl, C2... Cn for the elements included in the sample to the measured intensities II, 12... In in a second step such as to calculate a fictive intensity for a 100%-pure element for each of the elements included; calculating calibration constants Kl, K2... Kn for each of the elements as the relationship between measured intensity II, 12... In and the calculated intensity of respective 100%-pure elements in a third step; placing a sample of unknown concentrations of said elements in the spectrometer and reading-off the intensity of the different elements in a fourth step; and in a fifth step calculating the concentration of respective elements in the last mentioned sample as the measured intensity multiplied by respective calibration constants for the elements present in the sample.
Description
Method at spectrometry for investigation of samples, where the sample contains at least two elements.
The present invention relates to a calibration process in X- ray fluorescence analysis with the aid of solely one sample.
Present day X-spectrometers are highly developed with many facilities for facilitating the calibration of instrument pa- rameters and the registration of measurements. In all chemical analytical processes the calibration of the instrument to be used is both time consuming and an important part of the process. This applies, for instance, to the calibration of the parameters of the instrument used, the supervision of the calibrations made, or in other words the control of the operational reliability of the instrument used and, not least, the work involved in the validation of the chemical analytical process that has been developed and its documentation. The process proposed enables the work involved to be greatly simplified and the process by which this can be achieved will be described hereinafter for a simple case in which X-ray fluorescence analysis has been applied.
All chemical-analytical methods are based on some physical- chemical property of an element which shall be characterized by measuring this property or established in some other way. In addition, it is necessary in the majority of cases also to determine a background, the reason for which background is often unknown. In other words, it is necessary to establish when calibrating an element at least two properties (two points) . This also applies to determining the concentration of the element with respect to a standard that is used in the validation of an analytical process.
A calibration is thus usually carried out with the aid of one or more samples per element with the subsequent determination/measurement of the background of the element concerned.
A method of how calibration of an element can be carried out with the aid of a glass standard containing a "highly pure" chemical has been described in an earlier article by the invention, "Application of J. E. Fernandez algorithms in the evaluation of X-ray intensities measured on fused glass discs for a set of international standards and a proposed calibration procedure", J. Malmqvist; X-RAY SPECTROMETRY; X-Ray Spectrom 2001; 30 : 83-92. Thus, in the case mentioned there is required one standard for each element to be calibrated. This article shall be included as a part of the present applica- tion.
The present invention solves the problem mentioned above.
The present invention thus relates to a method of analysing a sample spectrometrically, where the sample contains at least two elements, wherein the method is characterized by placing a sample of known concentrations of known elements in a spectrometer in a first step and measuring the intensity II, 12.... In of the different elements included in the sample, by relating known concentrations Cl, C2... Cn for the elements included in the sample to the measured intensities II, 12... In in a second step such as to calculate a fictive intensity for a 100%-pure element for each of the elements included; calculating calibration constants Kl, K2... Kn for each of the ele- ments as the relationship between measured intensity II, 12... In and the calculated intensity of respective 100%-pure elements in a third step; placing a sample of unknown concentrations of said elements in the spectrometer and reading-off the intensity of the different elements in a fourth step; and
in a fifth step calculating the concentration of respective elements in the last mentioned sample as the measured intensity multiplied by respective calibration constants for the elements present in the sample.
The present invention will be described in more detail below, partly with reference to a table illustrated in Figure 1.
The present invention is unique in so much that only one sam- pie containing the elements to be calibrated is required for the calibration of two or more elements.
In addition to knowing the concentrations of the elements present in the single sample produced, the method is also based on the ability to simultaneously calculate the background of the sample from solely one single measurement of the sample, i.e. solely one measurement per element, i.e. one point .
There is given below an example with a starting point from the above mentioned as to how two such standards (FElOOl and SIlOOl) can be calibrated. As will be seen from Figure 1, line 1, there remains FElOOl that contains 100% Fe2O3. SIlOOl contains 100% SiO2, see line 2 in Figure 1.
This is used for determining the composition of a sample containing the two elements FESI, see Figure 1, line 4.
In the MultiScat program that has been used and that is based on the J. E. Fernandez algorithms mentioned above, there has been developed a method of calculating the calibration constants for the elements concerned, i.e. for Fe and Si. This process is carried out with the estimated concentrations and the measured intensities of the FESI-sample, whereafter new
calibration constants were calculated. The concentrations of the two 100% samples were then calculated with the aid of these constants.
As will be evident from Figure 1, these concentrations differed slightly from 100% but lie within the accuracy that can be expected with regard to carrying out the measurements concerned.
According to one preferred embodiment the calculation according to the above mentioned second step is carried out by using a relationship between the concentration of an element and the intensity to which the concentration gives rise in the spectrometer used.
According to one preferred embodiment of the embodiment just mentioned, the calculation is carried out in the mentioned second step, in which the known concentrations Cl, C2... Cn for the elements present are related to the measured intensities II, 12... In so that a fictive intensity for a 100%-pure element for each of the elements is established with the aid of algorithms described in the article "Application of J. E. Fernandez algorithms in the evaluation of X-ray intensities measured on fused glass discs for a set of international standards and a proposed calibration procedure", J. MaIm- qvist; X-RAY SPECTROMETRY; X-Ray Spectrom 2001; 30 : 83-92.
In the above mentioned first step a sample of known concentrations of known elements is placed in an appropriate spec- trometer and the intensity II, 12... In of the sample is measured with respect to the various elements present in the sample.
The above example concerns the calibration of Fe and Si for two standards, FElOOl and SIlOOl, which were produced with pure chemicals and contained 100% SiO2 and 100% Fe2O3 respectively. The FESI-sample comprised a mixture of the two ox- ides.
It is pointed out that the inventive method is in no way restricted to the elements mentioned but that the invention can be applied for analysing all sorts of elements.
In the second step mentioned above, the known concentrations Cl, C2... Cn of the elements present in the sample are related to the measured intensities II, 12 ... In such as to calculate a fictive intensity for a 100%-pure element for each of the elements present.
The concentration of an element in a sample is determined generally by the relationship
C1 = Ic1 • I1 • M, (1)
where C1 = the concentration of the element i, kx = the calibration constant, I1 = the measured intensity and M is the mathematical correction used in accordance with the present invention.
The expected theoretical intensity value in the case of a concentration of 100% in respect of the element El is designated lEiioo%τeor> This can be considered to indicate the sub- quantity of photons registered for the element of all the photons produced with the X-ray tube used in the spectrometer. There is made in step 1 an adjustment, calibration, in which the IEiioo%τeor-value of the elements Fe and Si is ad-
justed so that the concentrations of the samples will be 100%.
In the third step mentioned above calibration constants Kl, K2... Kn is calculated for each of the elements as the relationship between the measured intensity II, 12... In and the calculated intensity for respective 100%-pure elements.
With the calibration constant defined as kEi = lEiioo%τeor / IεiM&tt the concentration of El is obtained by using the algorithm in step 1 for the element El at a 100% concentration.
CEIIOO% = kEi • lεiMdtt • M
With kEi inserted there is obtained CEnoo% = lEiioo%τeor »M, where lEiioo%τeor represents the new transformed calibration constant.
With the new transformed calibration constant inserted in (1) there is now obtained the general relationship
Q-Ii = lE1100%Teor • Ii • M, (2)
In the fourth step mentioned above a sample that includes unknown concentrations of said element is placed in the spec- trometer and the intensity of the various elements is read off.
With the aid of the two obtained calibration constants lFeAioo%τeor and Isiftioo%τeor the concentrations of Fe and Si are calculated with respect to the FESI-sample, see Figure 1, line 4.
In a fifth step the concentration of respective elements in the sample last mentioned is calculated as the measured in-
tensity multiplied by a respective calibration constant with respect to the elements present in the sample.
With the aid of the calibration constants, the concentrations with respect to the two samples FElOOl and SIlOOl are calculated, the result of this calculation being evident from Figure 1, lines 6 and 7.
According to a preferred embodiment applied when further sam- pies that contain the same elements as an analysed sample are to be analysed, the fifth step is repeated without repeating the first, second and third steps.
The benefits afforded by the proposed calibrating process are described below.
However, the example given illustrates how calibration with respect to several elements can be achieved with the aid of solely one sample. This is of particular significance in re- spect of multi-element analysis, of which X-ray fluorescence analysis is often an example where it may concern the calibration of perhaps 10 - 50 elements with respect to an analysis method. It will readily be understood that the novel process is time saving and that one of the reasons for this lies in the ability of the process to calculate a background with the use of solely one measurement, i.e. the determination of solely one point/element.
The inventive process can also be applied in the validation of an analysis method. With the aid of the inventive process individual especially produced samples used for the calibration process can also be tied to an earlier executed validation of an analysis method, which is beneficial per se as an updating of a validation that can be applied to this individ-
ual sample. This is particularly significant in those cases where problems occur with the instrument hardware, such as when changing X-ray tubes, faulty detectors, malfunctioning of a scanner, or other serious faults in the system.
Although the invention has been described with reference to a number of embodiments it will be understood that the inventive process is not strictly bound to the aforesaid algorithms but that other modified algorithms can be used without departing from the scope of the invention described in the accompanying claims.
The present invention shall not therefore be considered restricted to the embodiments described above, since variations and modifications can be made within the scope of the accompanying claims.
Claims
1. A method of analysing a sample spectrometrically, where the sample contains at least two elements, wherein the method is characterized by placing a sample of known concentrations of known elements in a spectrometer in a first step and measuring the intensity II, 12.... In of the different elements included in the sample, by relating known concentrations Cl, C2... Cn for the elements included in the sample to the measured intensities II, 12... In in a second step such as to calculate a fictive intensity for a 100%-pure element for each of the elements included; calculating calibration constants Kl, K2... Kn for each of the elements as the relationship between measured intensity II, 12... In and the calculated intensity of respective 100%-pure elements in a third step; placing a sample of unknown concentrations of said elements in the spectrometer and reading-off the intensity of the different elements in a fourth step; and in a fifth step calculating the concentration of respective elements in the last mentioned sample as the measured intensity multiplied by respective calibration constants for the elements present in the sample.
2. A method according to claim 1, characterized by carrying out the calculation according to the second step by using a relationship between the concentration of an element and the intensity of the concentration given in the spectrometer used.
3. A method according to claim 2, characterized in that the calculation in said second step in which the known concentrations Cl, C2... Cn for the elements present in the sample is related to the measured intensities II, 12... In such that a fictive intensity for a 100%-pure element is established for each of the elements with the aid of algorithms described in the article "Application of J. E. Fernandez algorithms in the evaluation of X-ray intensities measured on fused glass discs for a set of international standards and a proposed calibration procedure", J. Malmqvist; X-RAY SPECTROMETRY; X-Ray Spectrom 2001; 30 : 83-92.
4. A method according to claim 1, 2 or 3, characterized in that when further samples that contain the same elements as an analysed sample shall be analysed, the fifth step is repeated without repeating the first, second and third steps.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP07748401A EP2013610A4 (en) | 2006-04-28 | 2007-04-12 | Method at spectrometry for investigation of samples, where the sample contains at least two elements |
| JP2009507641A JP2009535619A (en) | 2006-04-28 | 2007-04-12 | Method in spectroscopy for the investigation of samples containing at least two elements |
| US12/298,685 US8119415B2 (en) | 2006-04-28 | 2007-04-17 | X-ray fluorescence method for a composition analysis of a sample containing at least two elements |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE0600946A SE0600946L (en) | 2006-04-28 | 2006-04-28 | Procedure in spectrometry for examination of samples, in which the sample contains at least two elements |
| SE0600946-8 | 2006-04-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2007126371A1 true WO2007126371A1 (en) | 2007-11-08 |
Family
ID=38116182
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/SE2007/050240 WO2007126371A1 (en) | 2006-04-28 | 2007-04-12 | Method at spectrometry for investigation of samples, where the sample contains at least two elements |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US8119415B2 (en) |
| EP (1) | EP2013610A4 (en) |
| JP (1) | JP2009535619A (en) |
| SE (1) | SE0600946L (en) |
| WO (1) | WO2007126371A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2380010A1 (en) * | 2009-01-19 | 2011-10-26 | Multiscat AB | Method for spectrometry for investigation of samples containing at least two elements. |
| WO2017018923A1 (en) * | 2015-07-28 | 2017-02-02 | Multiscat Ab | Method for calibrating an x-ray fluorescence spectrometer |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2594638C1 (en) * | 2015-02-04 | 2016-08-20 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Иркутский государственный университет" | Method for x-ray fluorescent analysis of samples with undefined filler components |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0400396A2 (en) * | 1989-05-16 | 1990-12-05 | Mitsubishi Materials Corporation | Metals assay apparatus and method |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2513094B2 (en) * | 1991-06-19 | 1996-07-03 | 株式会社島津製作所 | X-ray fluorescence intensity correction method in X-ray fluorescence analysis method |
| JPH1090204A (en) * | 1996-09-18 | 1998-04-10 | Fujitsu Ltd | Standard sample used for total reflection fluorescent x-ray analysis, and method for preparing it |
| JP2000074858A (en) * | 1998-09-01 | 2000-03-14 | Fuji Electric Co Ltd | Method for quantitating palladium palladium catalyst |
| JP3612245B2 (en) * | 1999-08-26 | 2005-01-19 | 株式会社東芝 | Method for analyzing impurity concentration of substrate |
| JP2002116160A (en) * | 2000-10-06 | 2002-04-19 | Matsushita Battery Industrial Co Ltd | Method of measuring impurity concentration of cadmium telluride powder and method of making film of cadmium telluride |
| JP2003107020A (en) * | 2001-10-02 | 2003-04-09 | Shimadzu Corp | Fluorescent x-ray analysis method for thin film |
-
2006
- 2006-04-28 SE SE0600946A patent/SE0600946L/en not_active IP Right Cessation
-
2007
- 2007-04-12 WO PCT/SE2007/050240 patent/WO2007126371A1/en active Application Filing
- 2007-04-12 EP EP07748401A patent/EP2013610A4/en not_active Withdrawn
- 2007-04-12 JP JP2009507641A patent/JP2009535619A/en active Pending
- 2007-04-17 US US12/298,685 patent/US8119415B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0400396A2 (en) * | 1989-05-16 | 1990-12-05 | Mitsubishi Materials Corporation | Metals assay apparatus and method |
Non-Patent Citations (5)
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2380010A1 (en) * | 2009-01-19 | 2011-10-26 | Multiscat AB | Method for spectrometry for investigation of samples containing at least two elements. |
| EP2380010A4 (en) * | 2009-01-19 | 2013-07-03 | Multiscat Ab | Method for spectrometry for investigation of samples containing at least two elements. |
| WO2017018923A1 (en) * | 2015-07-28 | 2017-02-02 | Multiscat Ab | Method for calibrating an x-ray fluorescence spectrometer |
Also Published As
| Publication number | Publication date |
|---|---|
| SE529264C2 (en) | 2007-06-12 |
| JP2009535619A (en) | 2009-10-01 |
| EP2013610A1 (en) | 2009-01-14 |
| SE0600946L (en) | 2007-06-12 |
| US8119415B2 (en) | 2012-02-21 |
| EP2013610A4 (en) | 2011-10-05 |
| US20090177411A1 (en) | 2009-07-09 |
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