Calibration card for photoluminescent oxygen sensors with zero point maintained with a metal-air battery

• US 8,241,911 B2
• Filed: 11/19/2010
• Issued: 08/14/2012
• Est. Priority Date: 11/07/2008
• Status: Active Grant

• Current Assignee: MOCON, Inc. (Ametek Incorporated)
• Original Assignee: MOCON, Inc. (Ametek Incorporated)
• Inventors: Ascheman, Timothy A., Mayer, Daniel W., Tuomela, Stephen D.
• Primary Examiner(s): Wallenhorst, Maureen
• Application Number:
  US12/950,018
• Publication Number:
  US 20110154881A1
• Time in Patent Office: 634 Days
• Field of Search: 436/8, 436/9, 436/127, 436/136, 436/138, 436/164, 436/166, 436/167, 436/169, 436/172, 436/174, 436/181, 422/400, 422/420, 422/82.05, 422/82.08, 422/83, 422/86, 422/88, 422/500, 422/547, 422/551, 73/10.1, 73/10.2, 73/10.3, 73/10.6, 356/436, 356/437, 356/440, 206/703, 324/426, 136/290, 136/291
• US Class Current: 436/9
• CPC Class Codes: G01N 2021/6432 Quenching
• CPC Class Codes: G01N 2021/6439 with indicators, stains, dyes, tags, labels, marks
• CPC Class Codes: G01N 2021/6441 with two or more labels
• CPC Class Codes: G01N 2021/7786 Fluorescence
• CPC Class Codes: G01N 21/274 Calibration, base line adjustment, drift correction
• CPC Class Codes: G01N 21/278 Constitution of standards
• CPC Class Codes: G01N 21/6408 with measurement of decay time, time resolved fluorescence
• CPC Class Codes: G01N 21/643 non-biological material
• CPC Class Codes: G01N 31/22 using chemical indicators G01N31/02 takes precedence
• CPC Class Codes: H01M 12/06 with one metallic and one gaseous electrode
• CPC Class Codes: H01M 50/216 adapted for button or coin cells
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y10T 436/10 Composition for standardization, calibration, simulation, stabilization, preparation or preservation; processes of use in preparation for chemical testing
• CPC Class Codes: Y10T 436/100833 Simulative of a gaseous composition
• CPC Class Codes: Y10T 436/20 Oxygen containing
• CPC Class Codes: Y10T 436/207497 Molecular oxygen
• CPC Class Codes: Y10T 436/25875 Gaseous sample or with change of physical state

Abstract

A calibration card and method of using the card to calibrate an analytical instrument capable of reading a photoluminescent oxygen probe. The card includes at least (a) a first mass of an oxygen sensitive photoluminescent dye retained within a hermetically sealed space so as to isolate the dye from environmental oxygen, and in fluid communication with an activated metal-air battery whereby any oxygen permeating into the hermetically sealed space is quickly consumed by the battery, and (b) a second mass of an oxygen sensitive photoluminescent dye in fluid communication with the environment whereby the second mass of photoluminescent dye is exposed to an environmental concentration of oxygen.

Claims

1. A calibration card for use in calibrating an optical oxygen sensor, comprising (i) a first mass of an oxygen sensitive photoluminescent dye retained within a hermetically sealed space so as to isolate the dye from environmental oxygen and thereby define a permeation rate of oxygen from the surrounding air into the sealed space, and in fluid communication with an activated metal-air battery whereby any oxygen in the hermetically sealed space is consumed by the battery, and (ii) a second mass of an oxygen sensitive photoluminescent dye in fluid communication with the environment whereby the second mass of photoluminescent dye is exposed to an environmental concentration of oxygen.

2. The calibration card of claim 1, wherein the card has a length of about 4 to 20 cm, a width of about 4 to 20 cm, and a thickness of less than 1 cm.

3. The calibration card of claim 2, wherein the first mass of oxygen sensitive photoluminescent dye is isolated from environmental oxygen by sandwiching the first mass of oxygen sensitive photoluminescent dye between an oxygen barrier support layer and an oxygen barrier cover layer.

4. The calibration card of claim 3, wherein the cover layer is a transparent layer of polyethylene terephthalate.

5. The calibration card of claim 3, wherein the first and second masses of oxygen sensitive photoluminescent dye are sandwiched between the oxygen barrier support layer and the oxygen barrier cover layer, with the second mass of oxygen sensitive photoluminescent dye in fluid communication with the environment via at least one hole through at least one of the support layer and the cover layer.

6. The calibration card of claim 1, wherein the oxygen sensitive photoluminescent dye in both the first and second masses are the same.

7. The calibration card of claim 1, wherein the activated battery has an oxygen consumption rate resulting from self-discharge that exceeds the permeation rate of oxygen into the sealed space containing the first mass of photoluminescent dye from the surrounding air.

8. The calibration card of claim 1, wherein the battery continuously powers a load having a resistance of at least 500,000 ohms, whereby the battery is effective for continuously consuming oxygen from the hermetically sealed space containing the first mass of photoluminescent dye.

9. The calibration card of claim 1, wherein the battery continuously powers a load having a resistance of at least 1,000,000 ohms, whereby the battery is effective for continuously scavenging oxygen from the hermetically sealed space containing the first mass of photoluminescent dye.

10. The calibration card of claim 1, wherein the battery continuously powers a load having a resistance selected to limit a rate of oxygen consumable by the battery as between (1) the permeation rate of oxygen into the sealed space containing the first mass of photoluminescent dye from the surrounding air, and (2) ten times this rate.

11. The calibration card of claim 1, wherein the battery continuously powers a load having a resistance selected to limit a rate of oxygen consumable by the battery as between (1) the permeation rate of oxygen into the sealed space containing the first mass of photoluminescent dye from the surrounding air, and (2) twice this rate.

12. The calibration card of claim 1 wherein the metal-air battery is a zinc-air button battery.

13. The calibration card of claim 1, wherein the card contains first indicia tagging the first mass of oxygen sensitive photoluminescent dye as an oxygen sensitive photoluminescent dye exposed to limited oxygen, and second indicia tagging the second mass of oxygen sensitive photoluminescent dye as oxygen sensitive photoluminescent dye exposed to an environmental concentration of oxygen.

14. The calibration card of claim 13, wherein the first indicia comprises at least the designation “

0%”

or “

zero”

, and the second indicia comprises at least the designation “

21%”

or “

air”

.

15. A method of calibrating an optical oxygen sensor having a calibration mode, comprising the steps of:

(a) obtaining a calibration card according to claim 1 with the first mass of oxygen sensitive photoluminescent dye exposed to a known near-zero concentration of oxygen and the second mass of oxygen sensitive photoluminescent dye exposed to a known environmental concentration of oxygen,

(b) setting the optical oxygen sensor to calibration mode, and

(c) sequentially taking an oxygen concentration reading from each of the masses of oxygen sensitive photoluminescent dye such that the oxygen concentration reading is correlated with the known oxygen concentration to which the mass of oxygen sensitive photoluminescent dye is exposed.

16. The method of claim 15, wherein step (c) comprises at least the step of taking an oxygen concentration reading from each of the masses of oxygen sensitive photoluminescent dye in a predetermined sequence.

17. The method of claim 15, wherein step (c) comprises at least the steps of:

(1) sensing the oxygen concentration to which one of the masses of oxygen sensitive photoluminescent dye is exposed using the optical sensor in calibration mode, (2) providing the optical sensor with data indicating which of the masses of oxygen sensitive photoluminescent dye on the calibration card was sensed, and (3) sensing the oxygen concentration to which the other mass of oxygen sensitive photoluminescent dye is exposed using the optical sensor in calibration mode.

18. The method of claim 15, wherein step (c) comprises at least the steps of:

(1) sensing the oxygen concentration to which one of the masses of oxygen sensitive photoluminescent dye is exposed using the optical sensor in calibration mode, (2) providing the optical sensor with data indicating the known oxygen concentration to which the one mass of oxygen sensitive photoluminescent dye is exposed, (3) sensing the oxygen concentration to which the other mass of oxygen sensitive photoluminescent dye is exposed using the optical sensor in calibration mode, and (4) providing the optical sensor with data indicating the known oxygen concentration to which the other mass of oxygen sensitive photoluminescent dye is exposed.

19. The method of claim 15, wherein the first mass of oxygen sensitive photoluminescent dye is sandwiched between an oxygen barrier support layer and an oxygen barrier transparent cover layer.

20. The method of claim 15, wherein the activated battery has an oxygen consumption rate resulting from self-discharge that exceeds the permeation rate of oxygen into the sealed space containing the first mass of photoluminescent dye from the surrounding air.

21. The method of claim 15, wherein the battery continuously powers a load having a resistance of at least 100,000 ohms, whereby the battery is effective for continuously consuming oxygen from the hermetically sealed space containing the first mass of photoluminescent dye.

22. The method of claim 15, wherein the battery continuously powers a load having a resistance of at least 500,000 ohms, whereby the battery is effective for continuously scavenging oxygen from the hermetically sealed space containing the first mass of photoluminescent dye.

23. The method of claim 15, wherein the battery continuously powers a load having a resistance selected to limit a rate of oxygen consumable by the battery as between (1) the permeation rate of oxygen into the sealed space containing the first mass of photoluminescent dye from the surrounding air, and (2) ten times this rate.

24. The method of claim 15, wherein the battery continuously powers a load having a resistance selected to limit a rate of oxygen consumable by the battery as between (1) the permeation rate of oxygen into the sealed space containing the first mass of photoluminescent dye from the surrounding air, and (2) twice this rate.

25. The method of claim 15, wherein the calibration card contains first indicia tagging the first mass of oxygen sensitive photoluminescent dye as an oxygen sensitive photoluminescent dye exposed to limited oxygen, and second indicia tagging the second mass of oxygen sensitive photoluminescent dye as oxygen sensitive photoluminescent dye exposed to an environmental concentration of oxygen.

26. A calibration card for use in calibrating an analytical instrument capable of reading a photoluminescent oxygen probe from which the concentration of oxygen in a sample communicating with the probe can be determined, wherein the probe comprises an oxygen-sensitive photoluminescent dye embedded within an oxygen-permeable carrier matrix, the calibration card comprising:

(a) a first probe isolated from environmental oxygen and in fluid communication with an activated metal-air battery effective for scavenging oxygen from the first probe, whereby the concentration of oxygen in communication with the first probe can be reduced and maintained near zero, and

(b) a second probe in fluid communication with the environment for allowing the second probe to communicate with an environmental concentration of oxygen.

27. The calibration card of claim 26 wherein the oxygen-sensitive photoluminescent dye is a transition metal complex selected from the group consisting of a ruthenium bipyridyl, a ruthenium diphenylphenanotroline, a platinum porphyrin, a palladium porphyrin, a phosphorescent complex of a tetrabenzoporphyrin, a chlorin, a porphyrin-ketone, an aza-porphyrin and a long-decay luminescent complex of iridium(III) or osmium(III).

28. The calibration card of claim 26 wherein the oxygen-permeable carrier matrix is selected from the group consisting of silicone, polystryrene, polycarbonate, and polysulfone.

29. The calibration card of claim 26 wherein the first and second probes are applied as a coating onto an oxygen barrier support layer.

30. The calibration card of claim 29 wherein the oxygen barrier support layer is selected from the group consisting of polyethylene terephthalate, polyvinyl chloride, polyethylene and polypropylene.

31. The calibration card of claim 29 wherein the oxygen barrier support layer is biaxially oriented polyethylene terephthalate.

32. The calibration card of claim 26 wherein the first and second probes are covered by a transparent cover layer.

33. The calibration card of claim 26, wherein the card contains (i) first indicia tagging the first probe to a calibration value of a probe exposed to a near zero concentration of oxygen, and (ii) second indicia tagging the second probe to a calibration value of a probe exposed to an environmental concentration of oxygen.

34. A method of calibrating an analytical instrument having a calibration mode and capable of reading a photoluminescent oxygen probe or plurality of photoluminescent oxygen probes from which the concentration of oxygen in a sample or set of samples communicating with the probe can be determined, comprising the steps of:

(a) obtaining a calibration card according to claim 26,

(b) exposing the second probe to a medium having a known concentration of oxygen,

(c) setting the analytical instrument to calibration mode,

(d) taking a reading from the first probe with the analytical instrument,

(e) correlating the value of the reading to a zero oxygen concentration,

(f) taking a reading from the second probe with the analytical instrument, and

(g) correlating the value of the reading to the known oxygen concentration to which the second probe is exposed.

35. The method of claim 34 wherein the steps of taking a reading from the first and second probes are performed in a predetermined sequence.

36. The method of claim 34 further comprising the step of providing the analytical instrument with data indicating which probe on the calibration card was read first.

37. The method of claim 34 further comprising the step of providing the analytical instrument with data indicating the oxygen concentration of the medium to which the second probe is exposed.

38. The method of claim 34 wherein readings and correlations are based upon photoluminescence lifetime.