This invention will be more fully understood from the following detailed description, taken in connection with the accompanying drawings, which form a part of this application and in which:
Throughout the following detailed description similar reference characters refer to similar elements in all Figures of the drawings.
The detector 10 includes a substrate 12 in which a flow channel 14 is formed. The flow channel 14 has an inlet 15 and an outlet 16.
A plaque 18 of a sensor material is located on the substrate 12 at a predetermined position along the channel 14. Enlarged diagrammatic plan views of the plaque 18 of the sensor material are shown in
The sensor material in the plaque 18 may be any of a variety of materials that reacts upon exposure to differing concentrations of a predetermined target gas by changing at least one of its optical properties. For example, the ability of the sensor material in the plaque 18 to absorb or reflect one or more wavelengths of light in ultraviolet, visible, or infrared regions of the spectrum, as manifested by the intensity of radiation reflected from the material, is an optical property of the material that may be expeditiously monitored. Other useful optical properties include, but are not limited to, fluorescence or chemiluminescent reactivity. Materials used in the prior art detectors discussed earlier are useful as the sensor material(s) for the present invention.
As will be developed, the predetermined amount of the sensor material distributed over the area of the plaque 18 is selected such that a reaction occurs in the sensor material when it is exposed to the target gas in a concentration range of interest in the gas sample. In the preferred instance the plaque is sized such that, aside from minor local variations, the reaction occurs essentially uniformly over substantially the entire surface of the area of the sensor material.
The reaction between the target gas and the sensor material is such that there is a one-to-one relationship between the magnitude of the intensity of at least one optical property and the concentration of the target gas in the gas sample. Thus, the concentration of the target gas in the gas sample is able to be determined from the measured magnitude of the intensity of said at least one optical property after passage of a predetermined volume of gas sample over the given amount of sensor material.
A photometric device generally indicated by the reference character 20 is positioned to detect changes in intensity of the optical property (e.g., reflective intensity) of the sensor material. The photometric device 20 includes a source 22 positioned to direct interrogating radiation at one or more selected wavelengths toward the plaque 18. In practice, as will be developed, it may desirable to use interrogating radiation over a spectrum of wavelengths.
For instance it may be desirable to use a wavelength or a range of wavelengths for which the optical property exhibits the maximum change in intensity upon reaction of the plaque with the target gas.
Radiation reflected from the plaque 18 produces an electronic image 18′ on a suitable electronic imaging device 24, such as a charge coupled diode array. An electronic signal derived from the electronic image 18′ and representative of the reflected intensity from the plaque 18 is generated on a line 26.
The reflected intensity signal 26 is compared by a comparator 28 to a reference intensity signal on a line 30. The reference intensity signal may be derived from the sensor material measured at a time earlier than the time of the analysis in question, as at a time prior to the initial reaction with a target gas.
A signal representative of the measured magnitude of the intensity after passage of the predetermined volume of gas sample over the given amount of sensor material (as compared to the reference intensity signal) is generated from the comparator 28 on a line 34. The signal on the line 34 is used to address a table of calibrated values relating concentration of a target gas to a measured intensity. The table is stored in a memory 36. Information indicating the concentration of the target gas T in the sample is displayed to a viewer over a monitor or other display device 38.
The principles of operation of the gas detector 10 may be more fully understood with reference to
Prior to the introduction into the channel 14 of a predetermined volume of a gas sample G containing some concentration of a target gas T the plaque 18 of sensor material may appear as shown diagrammatically in
Assume the virgin plaque 18 (
However, if the virgin plaque 18 (
If the virgin plaque 18 (
It should be able to be observed that in the region of
In the region of
It should be appreciated that the foregoing discussion of
In accordance with the present invention the magnitude of the change in intensity of an optical property produced by the passage of a predetermined volume of a gas sample over a given amount of sensor material is calibrated to a known concentration of the target gas in a predetermined volume of gas sample. A table of calibrated values relating target concentration to diminution in intensity is stored in the memory 36. Thereafter, in use, changes in the optical property of that given amount of a sensor material may be used to determine an unknown concentration of the target gas in the same predetermined volume of a gas sample.
Because the change in optical property is used to determine the unknown concentration of the target gas, only a relatively small area of sensor material and a relatively short time span are required. This enables a detector 10 embodying the present invention to be implemented in a compact, preferably hand-held device, operative to provide an indication of a concentration of a target gas in a relatively short time.
The detector device 100 includes a housing 102 fabricated of any suitable material, such as a durable plastic, whereby the detector 100 may be used in hostile environments, such as a factory floor. As suggested diagrammatically in
The main functional element of the detector 100 is, as discussed earlier, the substrate 12. The substrate 12 may be preferably fabricated from silicon, although any suitable polymer, glass, or other material may be used. The substrate 12 has one or more channels generally indicated by the reference character 14 formed therein. In the embodiment illustrated in
As best shown in
The plaques 18 of sensor material can be arranged in any desired fashion. Plaques of different sensor materials disposed in one given channel can be reactive with respective different target gases.
Plaques of a particular sensor material reactive with a given target gas may be placed in the same or different channels thereby to detect different concentration ranges of the same target gas. In such a case the sensor material may contain different numbers of reactive sites. It should also be noted that if the sensor materials for different concentration ranges are disposed in the same channel some accommodation must be made in calibrating downstream plaque(s) to take into account reactions of the target gas with plaque(s) upstream of a given plaque.
Alternatively, plaques of different sensor materials, each reactive with the same target gas, may be placed in different channels thereby to detect different concentration ranges of the same target gas.
Every plaque 18 presents a predetermined amount of sensor material available for reaction. The sensor material is distributed substantially evenly within the channel that it occupies. The sensor materials can be made available for reaction by being attached to high surface area micro-particles or nano-particles (silica, for example) to produce appropriately sensitive detection. The high surface area structures can be aerogels, clay-assisted agglomerations of micron or nano-scale silica or other oxide materials.
An example of the coupling chemistry that can be used to bind a sensor molecule to a high surface area silica particle is illustrated in
It should be appreciated that although shown as substantially rectangular in configuration the plaque(s) 18 of sensor material may exhibit any desired shape consistent with the particular channel in which the plaque is disposed.
Typically a plaque 18 of sensor material exhibits planar length and width dimensions on the order of one millimeter of less. Preferably, the plaque dimensions are in the range of fifty (50) to one hundred (100) micrometers.
Each channel further includes a respective pretreatment region 119A, 119B and 119B. The pretreatment region is disposed intermediate that channel's detection region 117 and the channel inlet 15. The pretreatment region 119A-119C contains a respective filter or reactive material 122A-122C operative to remove any gases in the gaseous sample that would interfere with the performance of sensor plaques in the channel.
In the arrangement shown each channel communicates at its inlet 15 to an inlet manifold 124. The inlet manifold is connected to a sample supply line 125 as diagrammatically suggested in
It lies within the contemplation of the present invention that each of the channels could be provided with individual inlets and/or outlets. It should also be understood that although the detection region of each channel is shown as substantially linear and the pretreatment region is shown as serpentine, the various regions of the channels and the channels as a whole could exhibit any desired configuration.
As seen in
As shown in
Gas samples to be tested for the presence of a target gas are collected and presented to the substrate 12 by a sampling module 132 (
A predetermined volume of a gaseous sample is introduced into the cartridge by continuously metering a gas sample into the detector cartridge module 128. A predetermined fixed volume may be introduced by metering for a predetermined time interval.
The intensity of an optical property of the plaques 18 of sensor material(s) on the substrate 121 is(are) measured using a photometer module 136. The photometer module 136 is received in the recess 106C provided in the housing 102. The photometer module 136 includes a source 22 operative to direct interrogating radiation through a collimating lens 138 toward the substrate 12.
A particular sensor material responds to the presence of a particular target gas by reflecting different wavelengths of light.
Light reflected from the substrate 12 is gathered by a collection lens 142. The light reflected from each respective plaque 18A, 18B-1, 18B-2, 18C-1, 18C-2 is imaged on predetermined regions 18A′, 18B-1′, 18B-2′, 18C-1′, 18C-2′ of an electronic imaging device 24 such as a charge-coupled diode array 24. Each imaged region 18′ on the surface of the electronic imaging device 24 corresponding to a given plaque of sensor material may contain any predetermined number (one or more) pixel locations.
In order to encompass the spectrum believed necessary for the detection of the various possible target gases the source 22 may be implemented using multiple light emitting diodes that each illuminate the substrate with a predetermined wavelength of light. Signals derived from these various regions of the electronic image plane represent the intensity of light reflected from corresponding plaques of sensor materials on the substrate. Alternatively, a filter wheel is interposed in the optical path between a full range source 22 and the electronic imaging device 24. Particularly, the filter wheel is interposed in the reflected light path between the plaques 18 on the surface of the substrate and the imaging device 24. The use of the multiple light emitting diodes or the filter wheel enhances the signal-to-noise ratio of the reflected signal.
The signal representative of a given plaque 18 of sensor material may be based upon a summation of the intensity values derived from the pixel location(s) on the electronic imaging device 24 corresponding to the given plaque 18. The derived signal is applied to an electronics module 148. The electronics module 148 is received within the recess 106D within the housing. The electronics module 148 includes a computer operating in accordance with a program to effect the functions performed by the functional elements 28 through 36 discussed in connection with
A flow diagram of a computer program 160 executed by a computer within the electronics module 148 is shown in
The output of the electronics module 148 is applied to a human interface or display 38 received in the recess 106E.
The production of a table of calibrated values relating concentration to change in intensity may be understood by the following example. Reference characters from
A silicon wafer (12) was wet etched to provide ten channels (e.g., 14A) therein. The wafer was one hundred millimeters (100 mm) in diameter and one-half millimeter (0.5 mm) in thickness. Each channel was approximately ninety millimeters (90 mm) long, four millimeters (4 mm) wide and four-tenths millimeter (0.4 mm) deep. A glass cover (128C) was diamond point machined to create an inlet access hole for each channel. An inlet manifold common to all channels was formed in the wafer. Each channel had a separate outlet port.
A plaque (18) of sensing material was disposed in one channel of interest. The sensing material was obtained from a sealed ammonia 2-50 ppm Dräger CMS™ tube manufactured and sold by Dräger Safety AG & Co. KGaA, Luebeck, Germany. The cover was anodically bonded at elevated temperature onto the surface of the wafer to seal the channels. Suitable inlet and outlet fittings were provided using Nanoport™ compression fittings available from Upchurch Scientific Incorporated, Oak Harbor, Wash. 98277.
The detector was mounted on a sixty-by-sixty centimeter (60 cm×60 cm) optical table and was illuminated using a 31-35-30 visible light source (22) formerly available from Bausch and Lomb, Incorporated, Rochester, N.Y.
A Photometrix™ Quantix KAF 1600 thermoelectrically-cooled charge-coupled diode (CCD) device available from Photometrix, Tucson, Ariz. 85706, was used as an electronic imaging device (24). A collection lens (142) was used to focus the image on the CCD. A one hundred five millimeter (105 mm), f/2.8 AF Micro-Nikkor™ available from Nikon USA, Melville, N.Y. 11747, was used as the collection lens.
Gas lines were connected to the compression fittings for the inlet manifold on the substrate and to the outlet fitting for each channel on the substrate. The outlet fitting for each channel was connected to a Varian DS102 vacuum pump available from Varian Incorporated, Palo Alto, Calif. 94304.
A one (1) liter supply plenum was connected to the inlet manifold.
The one liter (1 l) plenum was purged with nitrogen and evacuated to a base pressure below three (3) Torr three times. The manifold was backfilled with eighteen (18) Torr of a mixture of one hundred parts per million (100 ppm) ammonia in nitrogen and pure nitrogen was added to make a total pressure in the manifold eight hundred fifty (850) Torr, corresponding to an effective concentration of two parts per million (2 ppm) ammonia in nitrogen.
Flow rates through the sensor channel were typically one-half (0.5) Torr-liter per second (TL/s).
Images were recorded in twelve (12) bit grayscale. The illumination intensity, f-stop of the lens, and exposure time of the CCD were adjusted to obtain images with maximum recorded intensities near half of full scale. After image acquisition from the camera was begun the plenum was opened and 0.35 second exposures were taken every two (2) seconds. After thirty frames were acquired (approximately one minute) the plenum was closed.
The diminution in reflected intensity relative to the initial intensity was measured for individual pixels located near the inlet end of the sensing materials over the time of the experiment (as indicated by camera frame).
The results are listed in the following Table.
The calculation of the intensity for data point I was as follows:
If the initial intensity was one-half full scale (where full scale was 212=4096), a diminution of 90 pixels corresponds to ninety-six percent (96%) of the initial intensity.
Data Point I indicated that a quantity Q of ammonia that passed over the sample after two (2) seconds produced a diminution in intensity of ninety (90) units. The quantity Q was on the order of 3.5×1013 molecules of ammonia (the target gas).
Data Point II indicated that the quantity 2Q of ammonia that passed over the sample after four (4) seconds produced a diminution in intensity of three hundred twenty (320) units [eighty-four percent (84%) of the initial intensity].
Data Points III, IV and V respectively indicated that the respective quantities 3Q, 4Q and 5Q of ammonia that passed over the sample after six (6) seconds, eight (8) seconds and ten (10) seconds produced the corresponding diminutions in intensity listed.
From these data it is seen that if the various quantities of ammonia (the target gas) were contained in the same predetermined volume of a gas sample and that gas sample were passed over a given amount of sensor material, a unique corresponding diminution of reflected intensity would occur. The data show that there is a one-to-one correspondence between the ammonia concentration of gas (i.e., the amount of target gas in a predetermined sample volume) and the change in intensity produced thereby. There is a unique specific value of target gas concentration associated with each and every value of intensity.
Thus, a table of calibrated values relating concentration of target gas to a change in intensity of an optical property produced by the passage of a predetermined volume of a gas sample over a given amount of sensor material may be produced.
Those skilled in the art having the benefit of the teachings of the present invention may impart modifications thereto. Such modifications are to be construed as lying within the scope of the present invention, as defined by the appended claims.
This application claims the benefit of U.S. Provisional Application No. 60/791,743, filed on Apr. 13, 2006, which is incorporated in its entirety as a part hereof for all purposes.
Number | Date | Country | |
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60791743 | Apr 2006 | US |