Apparatus for sensing volatile organic chemicals in fluids

• US 6,902,701 B1
• Filed: 10/09/2001
• Issued: 06/07/2005
• Est. Priority Date: 10/09/2001
• Status: Active Grant

• Current Assignee: National Technology & Engineering Solutions Of Sandia LLC (Honeywell International Inc.)
• Original Assignee: Sandia Corporation (Martin Marietta Corporation)
• Inventors: Kottenstette, Richard, Manginell, Ronald P., Hughes, Robert C., Patel, Sanjay V., Jenkins, Mark W.
• Primary Examiner(s): Warden, Jill
• Assistant Examiner(s): SINES, BRIAN J
• Application Number:
  US09/974,327
• Time in Patent Office: 1,337 Days
• Field of Search: 422/50, 422/56, 422/82.01, 422/82.02, 422/57, 422/61, 422/68.1, 422/69, 422/83, 422/88, 422/98, 73/10.1, 73/10.2, 73/232, 73/530.1, 436/43, 436/174, 436/178, 295/92, 295/921
• US Class Current: 422/83
• CPC Class Codes: G01N 1/405 by adsorption or absorption
• CPC Class Codes: G01N 27/128 Microapparatus
• CPC Class Codes: Y10T 29/49 Method of mechanical manufacture
• CPC Class Codes: Y10T 29/49002 Electrical device making
• CPC Class Codes: Y10T 436/11 Automated chemical analysis
• CPC Class Codes: Y10T 436/25 including sample preparation
• CPC Class Codes: Y10T 436/255 including use of a solid sorbent, semipermeable membrane, or liquid extraction

Abstract

A chemical-sensing apparatus is formed from the combination of a chemical preconcentrator which sorbs and concentrates particular volatile organic chemicals (VOCs) and one or more chemiresistors that sense the VOCs after the preconcentrator has been triggered to release them in concentrated form. Use of the preconcentrator and chemiresistor(s) in combination allows the VOCs to be detected at lower concentration than would be possible using the chemiresistor(s) alone and further allows measurements to be made in a variety of fluids, including liquids (e.g. groundwater). Additionally, the apparatus provides a new mode of operation for sensing VOCs based on the measurement of decay time constants, and a method for background correction to improve measurement precision.

Claims

1. An apparatus for sensing an analyte in a fluid, comprising:

(a) a chemical preconcentrator further comprising a substrate, a sorptive material and a heating element both located on a thinned portion of the substrate, with the sorptive material acting to absorb or adsorb the analyte from the fluid over time, and with the heating element upon electrical activation releasing the analyte from the sorptive material in concentrated form; and

(b) at least one chemiresistor located proximate to the chemical preconcentrator and spatially separated therefrom and having an electrical resistance that changes in response to exposure to the concentrated analyte, thereby sensing the analyte.

2. The apparatus of claim 1 further including a resistance measurement unit for measuring a change in the electrical resistance of the chemiresistor upon exposure to the concentrated analyte.

3. The apparatus of claim 1 wherein the sorptive material comprises a polymer or sol-gel coating.

4. The apparatus of claim 3 wherein the sorptive material further comprises fine-grain particles of activated charcoal or carbon molecular sieve material.

5. The apparatus of claim 1 wherein the heating element comprises a resistive heating element.

10. The apparatus of claim 1 wherein each chemiresistor comprises a chemiresistive material disposed between at least one pair of spaced-apart electrodes.

11. The apparatus of claim 10 wherein the chemiresistive material comprises a plurality of electrically-conductive particles suspended in a polymer host material.

13. The apparatus of claim 11 wherein the electrically-conductive particles comprise carbon.

14. The apparatus of claim 11 wherein the electrically-conductive particles comprise a metal.

15. The apparatus of claim 11 wherein the polymer comprises a polymer selected from the group consisting of poly(n-vinyl pyrrolidone), poly(vinyl alcohol), poly(ethylene-vinyl acetate) and poly(isobutylene).

6. An apparatus for sensing an analyte in a fluid, comprising:

(a) a chemical preconcentrator formed on a substrate and further comprising, a sorptive material and a heating element both located on a thinned portion of the substrate, with the sorptive material acting to absorb or adsorb the analyte from the fluid over time, and with the heating element upon electrical activation releasing the analyte from the sorptive material in concentrated form; and

(b) at least one chemiresistor formed on the same substrate proximate to the chemical preconcentrator and spatially separated therefrom and having an electrical resistance that changes in response to exposure to the concentrated analyte, thereby sensing the analyte.

7. An apparatus for sensing an analyte in a fluid, comprising:

(a) a chemical preconcentrator further comprising a substrate, a sorptive material and a heating element both located on a thinned portion of the substrate, with the sorptive material acting to absorb or adsorb the analyte from the fluid over time, and with the heating element upon electrical activation releasing the analyte from the sorptive material in concentrated form; and

(b) at least one chemiresistor located proximate to the chemical preconcentrator on another substrate and having an electrical resistance that changes in response to exposure to the concentrated analyte, thereby sensing the analyte.

8. The apparatus of claim 7 wherein the substrates are located one above the other with the chemiresistor facing the sorptive material of the chemical preconcentrator.

9. The apparatus of claim 7 wherein the substrates are located proximate to each other and are substantially coplanar.

12. An apparatus for sensing an analyte in a fluid, comprising:

(a) a chemical preconcentrator further comprising a substrate, a sorptive material and a heating element both located on a thinned portion of the substrate, with the sorptive material acting to absorb or adsorb the analyte from the fluid over time, and with the heating element upon electrical activation releasing the analyte from the sorptive material in concentrated form; and

(b) at least one chemiresistor located proximate to the chemical preconcentrator, with each chemiresistor comprising a chemiresistive material disposed between at least one pair of spaced-apart electrodes, with the chemiresistive material further comprising a plurality of electrically-conductive particles suspended in a polymer host material, with the electrically-conductive particles comprising 20-40 percent by volume of the chemiresistive material, and with each chemiresistor having an electrical resistance that chances in response to exposure to the concentrated analyte, thereby sensing the analyte.

16. A chemical-sensing apparatus, comprising:

(a) a chemical preconcentrator further comprising a substrate with a sorptive material being located on a thinned portion of the substrate for sorbing a chemical species of interest from a fluid over time and subsequently releasing the chemical species of interest upon heating of the sorptive material; and

(b) at least one chemiresistor located proximate to the chemical preconcentrator and spatially separated therefrom for sensing the chemical species upon heating of the sorptive material.

17. The apparatus of claim 16 further including a resistance measurement unit for measuring the resistance of each chemiresistor to determine the presence or concentration of the chemical species.

18. The apparatus of claim 16 wherein the fluid comprises a gas or vapor.

19. The apparatus of claim 16 wherein the fluid comprises a liquid.

20. The apparatus of claim 16 wherein the sorptive material comprises activated charcoal or a carbon molecular sieve material.

21. The apparatus of claim 20 wherein the sorptive material further comprises a polymer or sol-gel host material wherein the activated charcoal or the carbon molecular sieve material is embedded.

22. The apparatus of claim 16 wherein the chemiresistor comprises a plurality of electrically-conductive particles suspended in a polymer host material.

23. The apparatus of claim 22 wherein the electrically-conductive particles comprise carbon.

24. The apparatus of claim 22 wherein the electrically-conductive particles comprise a metal.

25. The apparatus of claim 22 wherein the polymer host material comprises a polymer selected from the group consisting of poly(n-vinyl pyrrolidone), poly(vinyl alcohol), poly(ethylene-vinyl acetate) and poly(isobutylene).

26. A method for increasing the sensitivity for detection of an analyte in a fluid using at least one chemiresistor, comprising steps for:

(a) providing a sorptive material on a thinned portion of a substrate and sorbing the analyte from the fluid into the sorptive material; and

(b) heating the sorptive material in the proximity of the chemiresistor which is located on another substrate or beside the sorptive material on the same substrate and thereby generating a concentrated whiff of the analyte for detection by the chemiresistor.

27. The method of claim 26 wherein the step for sorbing the analyte from the fluid into the sorptive material is performed at a location distal to the chemiresistor.

28. The method of claim 27 further including a step for placing the chemiresistor and sorptive material within a common housing prior to the step for heating the sorptive material.

29. The method of claim 26 wherein the fluid comprises a liquid.

30. The method of claim 26 wherein the fluid comprises a gas or vapor.

31. The method of claim 26 further including steps for measuring a resistance of the chemiresistor immediately prior to the step for heating the sorptive material, and comparing the resistance of the chemiresistor immediately prior to the step for heating the sorptive material with the resistance measured upon heating of the sorptive material, thereby providing a background-corrected measurement of the analyte.

32. The method of claim 26 further including a step for characterizing the analyte by measuring a decay time constant for a change in resistance of the chemiresistor after exposure to the concentrated whiff of the analyte.

33. A chemical-sensing apparatus, comprising:

(a) a chemical preconcentrator having a sorptive material further comprising a polymer or sol-gel host material wherein activated charcoal or a carbon molecular sieve material is embedded, with the sorptive material sorbing a chemical species of interest from a fluid over time and subsequently releasing the chemical species of interest upon heating of the sorptive material; and

(b) at least one chemiresistor located proximate to the chemical preconcentrator for sensing the chemical species of interest upon heating of the sorptive material.