Apparatus and method for early detection and identification of dilute chemical vapors

• US 4,895,017 A
• Filed: 01/23/1989
• Issued: 01/23/1990
• Est. Priority Date: 01/23/1989
• Status: Expired due to Term

• Current Assignee: The Boeing Co.
• Original Assignee: The Boeing Co.
• Inventors: Pyke, Stephen C., Hager, Harold E.
• Primary Examiner(s): Tokar, Michael J.
• Assistant Examiner(s): Arana, Louis M.
• Application Number:
  US07/300,367
• Time in Patent Office: 365 Days
• Field of Search: 73/23, 73/579, 73/26, 73/27 R, 422/88, 422/98
• US Class Current: 73/24.06
• CPC Class Codes: G01N 2291/0256 Adsorption, desorption, surface mass change, e.g. on biosensors
• CPC Class Codes: G01N 2291/0423 Surface waves, e.g. Rayleigh waves, Love waves
• CPC Class Codes: G01N 29/022 Fluid sensors based on microsensors, e.g. quartz crystal-microbalance [QCM], surface acoustic wave [SAW] devices, tuning forks, cantilevers, flexural plate wave [FPW] devices microdevices per se B81B
• CPC Class Codes: G01N 33/0031 comprising two or more sensors, e.g. a sensor array electrochemical electrode arrays G01N27/27

Abstract

A detector and method for identifying a chemical vapor and determining its concentration in the ambient atmosphere. The chemical detector apparatus (120) preferably includes a plurality of surface acoustic wave (SAW) devices (10), each including a piezoelectric substrate (20), one-half (32) of which is coated with a selected polymer. The polymer characteristically absorbs one or more of a group of chemical vapors. Diffusion of a chemical vapor into the polymer increases its mass and proportionately changes the resonant frequency of the SAW device. A microcomputer control (186) is operative to determine a predicted time constant (or rate) for diffusion and a predicted equilibrium concentration of the chemical vapor within the polymer coating of the SAW device and to identify the chemical vapor and its relative concentration in the ambient atmosphere using the predicted values for these parameters long before the SAW device has reached equilibrium with the chemical vapor.

Claims

1. Apparatus for rapidly detecting and identifying a chemical substance, comprising:

(a) a sensor having a surface exposed to the chemical substance and comprising a material selectively absorptive of a group of chemical substances of which said chemical substance is a member, a physical parameter associated with that surface changing as the quality of the chemical substance absorbed by diffusion into the material changes;

(b) monitoring means, coupled to the sensor, for monitoring the change in the physical parameter associated with said surface due to absorption of the chemical substance, producing an electrical signal indicative of said charge;

(c) analysis means, connected to the monitoring means, for determining a predicted time constant for diffusion of the chemical substance into the material and a predicted equilibrium concentration of the chemical substance in the material as a function of the electrical signal, well before the concentration of the chemical substance in the material asymptotically approaches equilibrium; and

(d) identification means for identifying the chemical substance from said group of chemical substances based on both its predicted time constant for diffusion and predicted equilibrium concentration, which are generally characteristic of the chemical substance and different than those of other chemical substances of the group.

2. The apparatus of claim 1, wherein the identification means are further operative to determine the approximate concentration of the chemical substance in a sample of air to which the material is exposed, as a function of its predicted time constant for diffusion into the material and its predicted equilibrium concentration in the material.

3. The apparatus of claim 1, wherein the sensor comprises a surface acoustic wave device having at least one surface coated with the material selectively absorptive of the group of chemical substances, absorption of said chemical substance into said material changing its mass, said physical parameter comprising the frequency of a surface acoustic wave propagating along the coated surface of the surface acoustic wave device, said frequency decreasing as the mass of the coating increases due to absorption of the chemical substance.

4. The apparatus of claim 3, wherein the material coating said at least one surface of the surface acoustic wave device comprises a polymer.

5. The apparatus of claim 3, wherein a plurality of spaced apart electrodes are disposed on said at least one surface of the surface acoustic wave device, with the material disposed between pairs of the electrodes, said apparatus further comprising means to excite the surface acoustic wave device with a periodically varying signal.

6. The apparatus of claim 5, wherein the monitoring means comprise a high speed counter connected to determine the frequency of the surface acoustic wave propagating through the material, at a sampling rate that is substantially faster than an expected time for the concentration of chemical substance in the material to reach equilibrium, said electrical signal indicating the change in frequency due to absorption of the chemical substance in the material coating said at least one surface of the acoustic wave device.

7. The apparatus of claim 1, wherein the analysis means comprise a Kalman filter for determining the predicted time constant for diffusion of the chemical substance into said material and the predicted equilibrium concentration of the chemical substance in said material according to an approximation based on:

space="preserve" listing-type="equation">M=0.9A(1-e.sup.-Kt)[(1-e.sup.-Bt)+1/9(1-e.sup.-9Bt)]

where

M=the mass/unit area of chemical substance absorbed by the material;

t=time that material is exposed to the chemical substance;

A=the equilibrium absorption/unit area of chemical substance;

B=a rate constant, which is related to a chemical substance diffusion coefficient and is the reciprocal of the time constant for diffusion; and

K=a constant that depends on rate of flow of chemical substance over the material coating.

8. The apparatus of claim 1, wherein the analysis means are operative to determine the predicted time constant for diffusion and the predicted percent of the time required for the concentration of chemical substance in the material to reach equilibrium.

9. The apparatus of claim 1, further comprising a chemical substance concentrator, for increasing the relative concentration of the chemical substance to which the surface is exposed.

10. The apparatus of claim 1, wherein the identification means comprise logic means for comparing the predicted time constant for diffusion and predicted equilibrium concentration determined by the analysis means to those listed in a look-up table identifying specific members of the group of chemical substances as a function of their characteristic time constant for diffusion and equilibrium concentration in said material.

11. The apparatus of claim 1, further comprising a plurality of other sensors, each having a surface exposed to the chemical substance and each comprising a different material selectively absorptive of a different group of chemical substances, said identification means being operative to identify the chemical substance as a function of predicted rates of diffusion and predicted equilibrium concentrations determined by the analysis means for all of the sensors.

12. The apparatus of claim 1, wherein the sensor comprises a chemical field effect transistor including a semiconductor coated with the material, the diffusion of chemical substance into the material modulating the flow of free charge carriers therewithin, said physical parameter comprising the conductivity between a source and a drain of the chemical field effect transistor due to a localized field in the material caused by absorption of the chemical vapor.

13. The apparatus of claim 1, wherein the sensor comprises a chemical resistor which changes impedance as the chemical substance diffuses into the material, and wherein the physical parameter comprises the resistance of the chemical resistor.

14. A method for detecting and identifying a particular chemical substance from a group of chemical substances, comprising the steps of:

(a) exposing a surface to the chemical substance, said surface comprising a material selectively absorptive of said group of chemical substances;

(b) sensing a physical parameter associated with the surface, which changes due to absorption of the chemical substance by the material comprising said surface;

(c) producing an electrical signal indicative of the change in the physical parameter associated with said surface due to absorption of the chemical substance;

(d) determining a predicted time constant for diffusion of the chemical substance into the surface and a predicted equilibrium concentration of the chemical substance within the material as a function of the electrical signal, well before the concentration asymptotically reaches equilibrium; and

(e) identifying the chemical substance from said group of chemical substances, based on both its predicted time constant for diffusion and predicted equilibrium concentration, which are generally characteristic of the chemical substance and different than those of other chemical substances of the group.

15. The method of claim 14, further comprising the step of determining the approximate concentration of the chemical substance in a sample of air to which the material is exposed, as a function of its predicted time constant for diffusion into the material and its predicted equilibrium concentration in the material.

16. The method of claim 14, wherein a surface acoustic wave device has at least one surface coated with the material selectively absorptive of the group of chemical substances, absorption of the chemical substance into the material changing its mass, said physical parameter comprising the frequency of a surface acoustic wave propagating along the coated surface of the surface acoustic wave device, said frequency decreasing as the mass of the coating increases due to absorption of the chemical substance.

17. The method of claim 16, wherein the material coating said at least one surface of the surface acoustic wave device comprises a polymer.

18. The method of claim 16, wherein a plurality of spaced apart electrodes are disposed on said at least one surface of the surface acoustic wave device, with the material disposed between pairs of the electrodes, further comprising the step of exciting said pairs of electrodes with a periodically varying signal.

19. The method of claim 18, wherein the step of sensing the physical parameter comprises the step of determining the frequency of the surface acoustic wave propagating through the material, at a sampling rate that is substantially faster than an expected time for the concentration of chemical substance in the material to reach equilibrium, and wherein the electrical signal indicates the change in frequency due to absorption of the chemical substance in the material coating said at least one surface of the acoustic wave device.

20. The method of claim 14, wherein a Kalman filter is used for determining the predicted time constant for diffusion and the predicted equilibrium concentration of the chemical substance in said material according to an approximation based on:

space="preserve" listing-type="equation">M=0.9A(1-e.sup.-Kt)[(1-e.sup.-Bt)+1/9(1-e.sup.-9Bt)]

where

M=the mass/unit area of chemical substance absorbed by the material;

t=time that material is exposed to the chemical substance;

A=the equilibrium absorption/unit area of chemical substance;

B=a rate constant, which is related to a chemical substance diffusion coefficient and is the reciprocal of the time constant for diffusion; and

K=a constant that depends on rate of flow of the chemical substance over the material coating.

21. The method of claim 14, wherein the step of determining the predicted time constant for diffusion and the predicted equilibrium concentration of the chemical substance in the material is completed in about ten percent of the time required for the concentration of chemical substance in the material to reach equilibrium.

22. The method of claim 14, further comprising the step of increasing the relative concentration of chemical substance to which the surface is exposed.

23. The method of claim 14, wherein the step of identifying the chemical substance comprises the step of comparing the predicted time constant for diffusion and the predicted equilibrium concentration with those listed in a look-up table identifying specific members of the group of chemical substances as a function of their characteristic time constant for diffusion and equilibrium concentration in said material.

24. The method of claim 14, further comprising the step of exposing other surfaces comprising different materials that are each selectively absorptive of a group of chemical substances, determining the predicted rates of diffusion and predicted equilibrium concentrations of the chemical substance in the materials of each of the other surfaces, and identifying the chemical substance as a function of all the predicted rates of diffusion and predicted concentrations of the chemical substance in the materials comprising all the surfaces.

25. The method of claim 14, wherein the physical parameter comprises the conductivity between a source and a drain of a chemical field effect transistor that includes the material into which the chemical substance diffuses, thereby modulating the flow of free charge carriers between the source and drain.

26. The method of claim 14, wherein the physical parameter comprises the resistance of a chemical resistor.

27. A method for rapidly identifying an unknown chemical substance that is one of a group of chemical substances, comprising the steps of:

(a) exposing the chemical substance to a surface of a sensor that includes a material selected for its affinity to absorb a chemical substance from said group of chemical substances, said sensor effecting an electrical signal that changes as the chemical substance diffuses into the material as a function of the quantity of the chemical substance absorbed therein;

(b) monitoring the sensor for changes in the electrical signal indicative of the diffusion of the chemical substance into the material;

(c) predicting the time constant for diffusion of said chemical substance into the material of the sensor and its equilibrium concentration in the material, at a time substantially prior to chemical substance reaching its equilibrium concentration in the material; and

(d) identifying the chemical substance as a function of both its predicted time constant for diffusion and its predicted equilibrium concentration in the material of the sensor.

28. The method of claim 27, further comprising the step of determining the approximate concentration of the chemical substance in a sample as a function of its predicted time constant for diffusion and predicted equilibrium concentration in the material.

29. The method of claim 27, wherein the material of the sensor is absorptive of other chemical substances from the group of chemical substances, the step of identifying the chemical substance as a function of its predicted time constant for diffusion and equilibrium concentration comprising the step of stochastically selecting a most probable chemical substance having a characteristic time constant for diffusion and equilibrium concentration in the material substantially the same as the predicted time constant for diffusion and predicted equilibrium concentration.

30. The method of claim 29, further comprising the steps of:

(a) exposing surfaces of other sensors, each including different materials selected for their ability to absorb chemical substances from different groups of chemical substances, said sensors effecting electrical signals that change as a function of the quantity of chemical substances absorbed therein;

(b) monitoring the other sensors for changes in their electrical signals indicative of the diffusion of the chemical substances into their respective different materials;

(c) predicting the rates of chemical diffusion of the chemical substances into the different materials, at a time substantially prior to their reaching equilibrium concentration; and

(d) identifying the chemical substance as a function of the predicted rates of diffusion and predicted equilibrium concentration in the materials of all the sensors.