The present invention pertains to detection of fluids. Particularly, the invention pertains to plasma structures, and more particularly to the application of the structures as sensors for the identification and quantification of fluid components. The term “fluid” may be used as a generic term that includes gases and liquids as species. For instance, air, gas, water and oil are fluids.
Aspects of structures and processes related to fluid analyzers may be disclosed in U.S. Pat. No. 6,393,894 B1, issued May 28, 2002, to Ulrich Bonne et al., and entitled “Gas Sensor with Phased Heaters for Increased Sensitivity,” which is incorporated herein by reference.
Related art fluid composition analyzers may be selective and sensitive but lack the capability to identify the one or more components of a sample mixture with unknown components, besides being generally bulky and costly. The state-of-the-art combination analyzers GC-GC and GC-MS (gas chromatograph—mass spectrometer) approach the desirable combination of selectivity, sensitivity and smartness, yet are bulky, costly, slow and unsuitable for battery-powered applications. In GC-AED (gas chromatograph—atomic emission detector), the AED alone uses more than 100 watts, uses water cooling, has greater than 10 MHz microwave discharges and are costly.
Micro gas chromatography (μGC) detectors should be fast responding (<1 ms), sensitive but not selective to specific compounds, of simple construction and low-cost, compact, and low-power (˜mW). Presently available or conceived μGC detectors are either not very sensitive, such as thermal conductivity sensors (>10 to 100 ppm of analyte); too selective to specific compounds such as fluorescence and electron-capture detectors; relatively high-cost such as the typical price tags in year 2003 of about $600, $3000 and upwards for many GC detectors; prone to drift due to soiled optics as micro-discharge devices (MDDs) monitored via spectral analysis; or relatively high-power such as the AEDs (atomic emission detectors) which consume over 100 W.
Related art NOx (and to an extent NH3, SOx, COx, O2, VOC, and the like) sensors to monitor and/or control such emissions from (internal and external) combustion processes are not suited for use in unsupervised, stationary or automotive combustion systems. They are either too costly (chemiluminescence (CL) and even multi-layered ZrO2 sensors), too bulky (chemiluminescence and IR absorption if the detection limit is to be near 5 ppm), too fragile (CL and IR long-path cell) or not stable enough (SnO2/WO3 and wet-electrochemical sensors) or too costly especially for automotive applications. Other known problems of optical sensors is their high maintenance cost, as needed to keep the optics clean, and the short life of the electrical contacts to any electrical-powered sensor exposed to harsh combustion exhaust conditions
Related art optical gas sensors (NO, CO, NH3, SO2, CH4, . . . , CWA) based on spectral analysis of glow discharge emission are not suited for compact, low-cost, wide-wavelength-range packaged systems because they lack a rugged, low-cost and compact multi-channel analyzer. They are either too costly and bulky (e.g., FTIR or conventional dispersive spectrometers, or even new, compact palm-top-size spectrometers), too fragile (spectrometers), not transmissive enough (narrow band-pass filters need fairly good collimation of light to avoid band broadening, i.e., need low aperture operation resulting in low-light transmission) or not versatile enough (small number of channels with individual, narrow band-pass filters). Also, a problem of these optical sensors is their high maintenance cost, such as keeping their optics clean.
The invention may be a sensor system having a discharge gap formed by electrodes. A fluid to be sensed may enter the vicinity of a discharge at the gap. An optical coupling may include a waveguide proximate to the discharge gap. Cleanliness of the optical coupling and one or more electrodes may be maintained by the discharge. A processor may be coupled to the waveguide. The electrodes and waveguide may have various configurations and arrangements.
a are cross-section diagrams of sensors revealing electrode enclosures;
a and 18b are top views of an optical fiber and a pair of electrodes separated by a number of optical fibers;
a is a side cross-section and top view of two electrodes separated by an optical fiber; and
b is a side cross-section and top view of two concentric electrodes separated by a light waveguide.
The present optical spectral/molecular emission-based NO (and other chemicals) sensor system may be a low power, low-mass and compact (the emissive glow discharge plasma of each element may be 10 to 100 microns in diameter). The system may have its plasma operate at about 1100 degrees C. Also, the system may be low-cost, rugged (no precision optical alignments needed) and maintain operational stability various kinds of environments. With adequate air filtering, sensor system operation may occur without noble gas purging, such as for exhaust gas composition measurements, along with high temperature plasma self-cleaning, signal processing and advantageous low-cost, compact and rugged packaging.
MDD may be used for optical transmission surface cleaning and for maintaining electrode isolation in an MDD detector application; that is, the same plasma discharge may be used to keep the observation window clean, by plasma-etching away any combustion-product deposits such as condensable tars and carbon-soot. The same or a similar glow discharge may maintain cleanliness and (more importantly) the required electrical isolation of the soot-sensor electrodes of soot sensors. One may co-locate a spectral-emissive and a soot sensor in one package. In other words, it is compatible and easy to integrate with soot sensor systems.
The silica chip may be eliminated and the discharge may be operated between two free-standing electrodes. The same plasma discharge may maintain the required electrical insulation of the non-grounded micro-discharge electrode (magnified view of one example electrode tip in
With little power, an electrostatic field across the impactor “baffles” or between the “fins” of the cyclone element can improve the capture and retention of the smaller particles. Housing with louvers (and cyclonic and impactor particle separators) may be less costly than the sensor system frit. Integrated particle removal via cyclone and impactor plate may occur with low Δp to sample gas flow (
Smart positioning between the end of the optical fiber and the photodiode may be used to detect optical fiber light components of small angles, as required by the chosen bandpass filter width.
The present system may be more compact, rugged and lower cost than chemiluminescence-based sensor systems. It may be more stable than metal-oxide or catalyst-based and conventional optical sensor systems and less energy consuming than ZrO2-based sensor systems. The present system may be more tolerant to temperature change than other sensor systems, and more manufacturable than multi-layer ZrO2, metal oxide or catalyst based sensor systems.
The present system may be lower cost than previous MDD-based NOx sensor systems. It may permit observation of NO spectral emissions in the IR. Also, it may allow co-planar design with one MDD as source and another as detector.
Concerns about water condensation may be obviated with removal or preferably made harmless via sensor heating. Another sensor may be packaged into the same housing of the system to reduce cost, total bulkiness and incorporate plasma-cleaning synergies.
Spectral analysis of the MDD emission may rely on a scanning, narrow band-pass, MEMS Fabry-Perot (FP) filter, i.e., it is compact, versatile (having many channels), highly effective light intensity (despite the high mirror-etalon reflectivity if many (100 to 1000) MDDs are operated in parallel) and low-maintenance because the FP-filter operates in a sealed environment, and the only other optical surface exposed to sample gas is self-cleaned by the MDD.
A micro discharge device (MDD) 11 is shown in systems 10, 20 and 30 of
The glow discharge device 11 may be a part of system 10 as illustrated in
Glow discharge 18 may be about 10 to 500 microns in diameter. The discharge may be started and sustained with about a 100 to 400 volt AC/DC power supply in series with about a 1 to 15 Meg-ohm resistor 19, which generates the spectral band emissions shown in
Optical fibers 21 may be optically connected to the glow discharge device 11 at optical interface or window 25 and be used with filters 22 for NO at 247.2 or 258.8±1.4 nm, a reference N2 at 336.9 or 357.5±2 nm, other band pass filters for O2, CH, C2, CO, SO2, as needed, and off-NO and N2 at 251.2±2.5 and 362.3±4 nm, respectively. The optical filters 22 may be deposited at the flattened ends of the optical fibers 21, which would have narrow band pass half-width of about three nm (to match the ˜2.8 nm NO emission half bandwidth (HBW)) to 20 nm. Also shown in
For operation, device 11 may be designed to force the micro discharge 18 to glow close to and impinge on the side of the observation fibers 21, as shown in
Significant elements of the system 10 in
λφ=λo(ne2−sin2 φ)0.5/ne.
This influence of the index, n, on λφ is illustrated by the data in the table of
The concern about the influence of temperature is based on the fact that λo tends to shift to longer wavelength with increasing temperature (and vice versa) due to the thermal expansion of the coating materials, as suggested here.
λT=λo+α ΔT,
with α˜0.01−0.2 nm/deg. C.
This may shift λo by 10 nm for only a 100 degree C. rise in temperature and α=0.1 nm/deg. C., if the above information is correct. One would expect a value for α′˜10−6−10−5/deg. C. or α˜2·10−4−2·10−3 nm/deg. C.
It may be useful to calculate the maximum diameter, d, possible for a single-mode optical fiber, which also may have a more limited acceptance angle, which could keep the band-pass half-width of an associated interference filter small. For single mode optical fiber operation, the quantity V<2.405, where V=(πd/λ) {n(core)2−n(clad)2)}0.5, so that the d<2.405·λ·{n(core)2−n(clad)2)}0.5, which for an example based on sapphire (n=1.6) optical fibers, operation near 300 nm, and a Δn˜0.3 would require that d<673 nm. For single-mode fibers, the numerical aperture (=sine of largest acceptance angle, which is half-angle of the cone within which the light is totally internally reflected by the fiber core), NA=0.15 for single mode fiber and 0.3 for multi-mode fibers.
NA=sin(qmax)=(n12−n22)0.5.
Manufacturing costs may be low due to inexpensive parts and assembly as preliminarily noted here. The parts may include one grounded and one insulated wire in a tube 33 (glass, quartz, sapphire) to support the plasma in a spark-plug-like environmental package 44 as shown in
NOx sensing via MDD may have been done by others, with noble gas purge in one micro channel leading to the MDD, but has not been done without such purge, directing only the sample gas to the MDD. Features of the sensing system in
There may be self-cleaning of the optical surface 33 on the MDD side and facing the optical fiber, i.e., window 25 of
Additional design features related to quasi state-of-the-art PM filters may include mechanisms for overcoming concerns about water condensation (removal or made harmless via sensor heating), and packaging the soot sensor electrode into this same housing to reduce cost, total bulkiness and plasma-cleaning synergies.
Another implementation of glow discharge device 11 is system 20 shown in
Filter 26 may be a Fabry-Perot (FP) based MEMS spectrometer for MDD emission analysis. Light pipe 34 may be optically coupled to a Pyrex or quartz window 36 of filter 26. Window 36 may be a UV blocking filter. As shown in
During operation of filter 26, one may envision that only one (and not many in parallel) tine (=transmission peak of the Fabry-Perot comb-filter) of about 1 nm to 3 nm half width does the scanning, while the others may be designed to be outside of the scanning area. The table in
As the FP-spacing layer 38 of cavity 37 is dithered by a given amount, the Δλ line-width band-pass may scan around the band center by ± the tine spacing in cm−1 or nm, or between the shown band limits in nm. The computed Fabry-Perot band width and spectral position (and including the response of the AlGaN detector array) for the last row in the table in
Features of system 20 in
One may consider the known influence of f-number on achievable FP-filter 26 finesse, which may be even more constraining here. However, one may design the FP-filter 26 to be less sensitive to temperature-induced drift of the wavelength band-pass, but also limited by the temperature range rating of the discharge device 11.
The sensor system 20 may be based on the following: plasma micro discharge device (MDD) for gas sensing via spectral emission analysis of unknown gas mixture samples, using non-dispersive (Fabry-Perot-based) spectral analysis (rather than a dispersive spectrometric analysis) or interference filters; the Fabry-Perot (FP) wavelength scan performed via a MEMS-based FP-filter design; new use of the above assembly (of MDD and FP-based spectral filter) as high speed gas chromatography peak (GC) analyzer, and independently, as stand alone gas sensor for NO, O2, SO2, . . . in one unit; new use of above assembly (MDD+FP+GC), whereby the GC is a μGC or a μGC-μGC or a μGC-μGC-MDD gas mixture analyzer, of low probability for false positives, Pfp; and a design of the MDD in which the discharge self-cleans the window 25 and operates without a noble gas purge.
Successful implementation of systems 10 and 20 may enable the achievement of low false positive probabilities when using this discharge device 11 and detector as part of a GC-CG-MDD micro-analyzer, as represented by PHASED.
The sensing systems 10 and 20 may offer the following advantages over previously proposed or offered exhaust gas composition sensing systems. They are more compact, rugged and lower cost than chemiluminescence-based sensor systems. They are more stable than metal-oxide or catalyst-based and conventional optical sensor systems. They are less energy consuming than ZrO2-based NO and O2 sensor systems and more temperature change tolerant than other ZrO2—NO/O2 sensor systems. They are more manufacturable than multi-layer ZrO2, metal oxide or catalyst based sensor systems. They are compatible and easy to integrate with a soot sensor system.
System 30 of
One sensor system is depicted in
Light may be conveyed from discharge 56 through fiber 63 to optical filters 22. Fiber 63 may be a silica fiber having an outside diameter of about 20-200 microns. The filters 22 may have a delta wavelength of about 2-5 nm. The filtered light may proceed on to be detected by photo diodes, phototransistors or generically “light detectors” 23, on a one filter to detector basis, respectively. Electrical conductors may connect the detectors 23 to terminals 115 of connector 64. Terminals 115 may be connected to a processor 24 (as shown in
A mode of failure could be via contact problems between the electrical leads 62 fed through or around the silica chip 54 and those embedded in the spark plug package 57. Alternatively, there may be a simple spark plug housing package 57 which includes a pair of self-supporting discharge electrodes 53, or the ends of leads 62 which may be electrodes, a discharge 56 that maintains the optical fiber 63 inlet surface 64 clean, and without a MDD silica chip 54. The electrodes may be kept clean also. This cleaning of surface 64 and electrodes may occur without the presence of a noble gas. The leads 62 may be extended from connector 64 to electrodes 53. The length of the leads 62 and waveguide 63 may be about 10 to 40 cm.
To avoid contact problems with the electrodes 53 and leads 62,
There may be an elimination of potential performance problems caused by less than the ideal and clean optical interface between the silica chip 54 and the optical fiber 63, and a reduction of the losses in transmission through the interface between the silica chip 54 and fiber 63.
During operation, successful system designs may cause the micro discharge 56 to glow close to and impinge on the side of the observation optical surfaces, such as those of the silica fiber 63, chip and/or window. The mild discharge sputter action may be intended to maintain a high level of optical transmission of the optical transmission surface, despite the known tendency of combustion exhaust gases to darken optical surfaces they come in contact with, in a short time, due to a deposition of tarry and soot-containing materials. Such is the cleaning action of discharge plasmas. Excessive discharge action may etch the material of surfaces close to the glow discharge, while insufficient action (i.e., power) may create deposits.
A capillary electrode discharge (CED) approach may be used to generate atmospheric plasmas, and surface cleaning such as the removal of organic material on glass substrates. Helium or hydrogen (He or H2) may be used as an ignition and discharge gas and oxygen (O2) be added as a reactive gas. Low frequency AC power supply with a sine wave voltage (20 kHz to 20 GHz) may be used to generate plasmas under atmospheric pressure. The electrodes may be composed of a 10 micron thick capillary dielectric and have a diameter of about 300 microns. He/O2 plasmas generated in the space of a few mm between the capillary electrode and the substrate (ground) may be uniform and very stable. The optical emission spectroscopy and the I-V characteristic of the discharges may be used to characterize the capillary electrode discharges. A removal of organic materials such as photoresist, in addition to He/O2 plasmas, the effects of other gases like those of He additive gases such as CF4, Ar, and N2, may be implemented. Cleaning rate of organic material on glass higher than 100 Å/min may be observed after exposure to He/O2 plasmas. There may be some effects of various gas mixtures in addition to those of He/O2 on the cleaning rate of organic material and surface chemical composition of the remaining residue as might be measured by x-ray photoelectron spectroscopy.
a shows a sensor 81 having the same kind of structural and electrical parts as sensor system 80, except that the former has a housing that is somewhat different. Structure 82 may have an input of fluid 65 from the sides and a procession of the fluid through a number of impactor plates and into the micro discharge 56 area, and an exit out through the end or top of housing or structure 82. On the other hand, structure 82 may be designed to have both an input and output of fluid at the top of it. Systems 60, 70, 80 and 81 may be used to sense other fluids besides exhaust gases 65.
There may be ruggedized MDD sensor systems.
a and 18b show arrangements 111 and 112, respectively, with a single 40 to 70 micron diameter 117 optical fiber 95 with cladding of a small thickness, and four of such fibers 95 having positions and being fastened between two larger-diameter metal electrodes 96 and 97 of about 300 to 500 microns (0.3 to 0.5 mm) in diameter. Both electrodes 96 and 97 may be anchored within the same ceramic block 69 as shown in
a and 19b represent two versions 101 and 102 of the sensor system related to
The arrangements 112 and 102 shown in
Although the invention has been described with respect to at least one illustrative embodiment, many variations and modifications will become apparent to those skilled in the art upon reading the present specification. It is therefore the intention that the appended claims be interpreted as broadly as possible in view of the prior art to include all such variations and modifications.
The present application claims priority as a continuation-in-part to co-pending U.S. Nonprovisional application No. 10/749,863, filed Dec. 31, 2003, by Ulrich et al., and entitled “MICRO-PLASMA SENSOR SYSTEM”, which is incorporated herein by reference.
Number | Date | Country | |
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Parent | 10749863 | Dec 2003 | US |
Child | 10915577 | Aug 2004 | US |