WO1998041847A1 - Chemical analyzer with free space communication link - Google Patents

Chemical analyzer with free space communication link Download PDF

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Publication number
WO1998041847A1
WO1998041847A1 PCT/US1998/004455 US9804455W WO9841847A1 WO 1998041847 A1 WO1998041847 A1 WO 1998041847A1 US 9804455 W US9804455 W US 9804455W WO 9841847 A1 WO9841847 A1 WO 9841847A1
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WO
WIPO (PCT)
Prior art keywords
analyzer
fiber
fibers
probe
output
Prior art date
Application number
PCT/US1998/004455
Other languages
French (fr)
Inventor
John M. Jarvis
John J. O'donnell
Eamon O'connor
Original Assignee
Rosemount Analytical Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rosemount Analytical Inc. filed Critical Rosemount Analytical Inc.
Publication of WO1998041847A1 publication Critical patent/WO1998041847A1/en

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Classifications

    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65Raman scattering

Definitions

  • the present invention relates generally to chemical analyzers, and has
  • the invention relates to the use of a wireless transceiver in a chemical
  • analyzer receives commands from an external control unit over the transceiver
  • the invention is a first and broadcasts an analyzer output over the transceiver.
  • the invention is a first and broadcasts an analyzer output over the transceiver.
  • the transceiver can comprise an antenna, an antenna, and an antenna
  • infrared transmitter/receiver or like wireless communication components.
  • FIG. 1 shows a system diagram of a preferred chemical analyzer in
  • FIG. 2 depicts chief components of a preferred optical filter used in the
  • FIG. 3 is an enlarged end view of optical fibers in the probe shown in
  • FIGS. 1 and 5; FIG. 4 is a perspective end view of a male fiber connector showing an
  • FIG. 1 A first figure.
  • FIG. 5 is a partially sectional view of a preferred optical probe useable
  • FIG. 6 is a sectional view of a distal end of the probe of FIG. 5 during probe fabrication
  • FIG. 7 is a block schematic of a preferred signal conditioning circuit
  • FIG. 8 is a schematic of a comparator/asymmetric discriminator circuit depicted as a block in FIG. 7;
  • FIG. 9 is a timeline showing signals at different points in the signal
  • optical refers to electromagnetic radiation, whether or not visible to the human eye.
  • FIG. 1 shows a preferred analyzer 10 that evaluates a specimen of
  • the analyzer 10 illuminates the specimen 12 with narrow-band light, collects backscattered light from the specimen,
  • the analyzer optically isolates a Raman scattering component from the backscattered light, and evaluates the Raman scattering component to calculate the analyzer output. Simultaneously, the analyzer isolates a Rayleigh scattering component from
  • the narrow-band light which may result for example from disconnecting a fiber connector or withdrawing the probe from the specimen
  • a diode laser 16 launches essentially monochromatic, narrow-band
  • nanometers (nm) for the narrow-band light has been found satisfactory.
  • a diode laser having a wavelength between about 750 and 850 nm is preferred.
  • the selected wavelength should not however coincide with an
  • the laser can have a multimode output and be capable of emitting
  • Laser 16 also serves as
  • the control input of laser 16 includes a driver circuit with a control input at line 24, and a temperature control circuit if the laser source is a diode laser.
  • the control input of laser 16 includes a driver circuit with a control input at line 24, and a temperature control circuit if the laser source is a diode laser.
  • Beamsplitter 20 divides the laser light launched into fiber 18a between fibers 18b, 22a, preferably in equal amounts although other ratios are also
  • the narrow band light passes from fiber 18b to a fiber 18c via a connector pair 26.
  • Connector pair 26 includes a male connector end holding
  • Fiber 18c connects to a bandpass filter 28 in a fiber
  • Fibers 18c, 18d are preferably part of armored cable assemblies 34,36 respectively.
  • the analyzer 10 is preferably arranged as a main analyzer unit 38
  • control room or other suitable location that can provide the
  • Main analyzer unit 38 is
  • Armored fiber cable assemblies 34,36 connect unit 38 to module 30, and module 30 to probe 32, respectively.
  • Cable assembly 34 can be tens or hundreds of meters long.
  • Optical fiber can itself generate Raman scattering and/or fluorescence
  • purious light signals from laser light passing through it
  • the spurious light signals are a function of the fiber properties (most
  • buffer layer material and generally have wavelengths longer than the laser
  • bandpass filter 28 is provided in the termination/filter module 30, and module 30 is located as close to the probe as possible to
  • module 30 mounted away from
  • probe 30 provides a more stable temperature environment for the filters 28,74.
  • Bandpass filter 28 blocks the spurious light signals originating in fibers
  • Spurious light signals can be further reduced by using silica-based fiber having an inert metal buffer layer such as gold. Such fibers have significantly lower spurious light signals than similar fibers having a polymer-based buffer
  • connectors 39a,39b hold the ends of fibers 18c, 18d against 0.25-pitch gradient
  • GRIN GRIN index
  • fiber 18d releasably connects to probe 32 by a
  • connector pair 44 located at a proximal end 32a of probe 32 and passes narrow band light to a fiber 18e that extends from connector pair 44 to a distal end
  • probe 32b of probe 32. Also housed in probe 32 are a fiber 46a and a group of five
  • fibers 48a The line representing fibers 48a, and some other lines in FIG. 1 , are shown thickened to indicate multiple optical fibers in the preferred
  • Fiber 46a connects to a connector pair 50 at proximal end 32a
  • analyzer 10 uses the multiple fibers 48a to boost the detected Raman
  • Backscattered light traveling down fiber 46a is directed to a detector 56
  • filter 62 The purpose of filter 62 is to prevent sunlight
  • Filter 62 also has the effect of preventing the weaker Raman component, if present, from reaching detector
  • An amplifier 64 couples to detector 56 to provide an amplified detector output on line 66.
  • the detector 56 output representative of the Rayleigh
  • Circuit 68 compares the detector output on
  • circuit 68 provides an output on line 24 that maintains laser 16 at its normal, relatively
  • circuit 68 provides an output on line 24 that shuts off laser
  • This lower intensity level 16 or at least controls it to a lower intensity level. This lower intensity level
  • BSI/EN 60825-1 class 1 operation i.e. ,
  • analyzer 10 can operate with high
  • One enhancement is the ability to
  • the circuit 68 continues driving laser 16 at its high operational intensity level in the presence of the truly transient losses, but shuts the laser down to the lower intensity level for the longer-lived losses.
  • probe 32 except at distal end 32b, where they are arranged around the emitting fiber as shown in FIG. 3, and at the proximal end 32a, where they are bundled
  • 70 holds the five fibers 48a as shown in the perspective end view of FIG. 4.
  • the other male connector end of pair 70 holds a single fiber 48b in alignment
  • fiber 48b can be about 300 ⁇ m (core dia.).
  • Fiber 48b Backscattered light is carried by fiber 48b to the entrance slit of an optical spectrograph 72 via a long pass filter 74, fibers 48c-e, and connector pairs
  • Long pass filter 74 has the same construction as the bandpass filter
  • the filter element 42 is fabricated to block the narrow band light of laser 16 and pass longer wavelengths.
  • the spectral transmission of filter 74 is less than 10 "6 at the laser wavelength 810
  • fiber termination/filter module 30 is mounted close to probe 32 to keep fiber 48b short (generally no more than a few, and preferably ⁇ 1 meter), so that no spurious light signals can be produced by Rayleigh
  • Filter 74 blocks any Rayleigh backscattered
  • Fiber 48b preferably has a metal (gold)- buffer layer.
  • Fibers 18a-e, 46a, 48a, 48e, and 22a-d are preferably relatively small
  • fibers 48b-d are preferably relatively
  • Fibers 46b-e can be either small or
  • connector pair 78 are held at connector pair 78 in a substantially circular pattern (similar to FIG. 4) for optimal coupling to fiber 48d, while at the entrance slit to spectrograph
  • Fibers 18d, 18e, 46a, 48a, and 48b all have
  • a diamond reference 80 is provided in main analyzer unit 38. Fibers
  • Bandpass filter 82 substantially identical to filters 28 and 62, blocks
  • Fiber-generated Raman scattering Six fibers 22c surround fiber 22b at the diamond surface (similar to FIG. 3) to capture backscattered light from diamond 80.
  • a longpass filter 84 substantially identical to filter 74, blocks
  • Fibers 22d six in number, are
  • the linear arrays of fibers 22d and 48e are arranged colinearly, one
  • Spectrograph 72 is
  • detector array 77 preferably 750 pixels wide by 240 pixels high, intercepts
  • recognition software also residing in computer 14 calculates the chemical
  • Such pattern recognition software is
  • main analyzer unit 38 is preferably intrinsically safe. Although computers having intrinsically safe keyboards and
  • computer 14 is preferably equipped with a transceiver 86 such as
  • a user can send instructions to
  • laptop computer 88 equipped with a similar transceiver 90.
  • Such communication preferably occurs over a wireless, fiberless free space path 91, allowing the user to freely move from place to place with computer 88 and
  • Preferred transceivers 86,90 are commercially available
  • radio LAN cards for desktop or laptop computers, for example the
  • Transceiver 86 is depicted in FIG. 1 as such an antenna device, that
  • the transceiver can also be an infrared emitter/receiver
  • Computer 88 has a
  • keyboard and a mouse that are used to send queries and commands to
  • Computer 88 also has a display to graph or otherwise show the
  • computer 14 is preferably equipped with neither a display screen, a keyboard, nor a mouse, to satisfy intrinsic safety requirements as well as to reduce the
  • main analyzer unit 38 size, weight, and electrical requirements of main analyzer unit 38.
  • Probe 32 is described in more detail in connection with FIGS. 5 and 6, together with previously discussed FIGS. 1, 3, and 4. Probe 32 preferably has
  • a probe body with three main components: a terminus 32c, a shank 32d, and
  • a connector housing 32e all made of 316 stainless steel or other suitable inert
  • Terminus 32c, shank 32d, and housing 32e are rotationally
  • terminus 32c, braze joint 92, and shank 32d is polished to a smooth finish (0.25 in. dia.) to permit sealing with a ferrule
  • Fibers 18e, 46a, and 48a (only one of which is shown in its entirety in
  • FIGS. 5 and 6 for simplicity) extend from their respective male connector ends
  • fibers are step-index, with silica or doped silica core/cladding, and have a thin
  • Temperature sensor 98 is preferably disposed proximate distal end 32b for
  • the output of sensor 98 can be used as a rough indication of the specimen temperature, whereupon probe 32 takes on a dual role as a fiber optic chemical analysis probe and a specimen thermometer.
  • electrical sensors are preferable for their simplicity, and most preferable is a
  • thermocouple e.g. type K
  • the output of thermocouple e.g. type K
  • sensor 98 can be monitored with a portable, hand-held device coupled directly
  • such as a twisted wire pair can be included in cable assemblies 36,34.
  • terminus 32c is
  • the gold plating extends inside a bore 104 and in the vicinity thereof,
  • An anti-wicking agent or stop-flow substance preferably a suspension of
  • magnesium hydroxide in water is applied to each of the fibers in a zone
  • Zone 106 approaches but does not touch the distal portion of the fibers that extend into bore 104.
  • wicking agent inhibits the flow of molten braze material along the fibers
  • the assembly is positioned in a vacuum oven 108 as shown in FIG. 6, with a
  • braze materials for platings 100 made of gold are gold
  • braze type BAg-8 a binary alloy composed of about 72% silver and 28% copper, is most preferable.
  • vacuum oven 108 is then heated to a temperature sufficient to melt braze
  • molten braze material does not run out of but rather tends to stay in and
  • braze material forms a solid hermetic
  • a sleeve 112 of terminus 32c is brazed to
  • shank 32d using localized heating, and shank 32d is then brazed to connector
  • the sleeve 112 partially isolates the brazed fibers in bore 104 from heat generated during brazing of terminus 32c
  • Braze material BAg-8 is used for all braze joints.
  • FIG. 7 depicts in block schematic form a preferred signal conditioning
  • Circuit 68 receives on line 66 the amplified detector output, representative of the Rayleigh scattering component from specimen 12, and
  • comparator/asymmetric discriminator circuit 114 compares the amplified
  • detector output to an adjustable internal threshold.
  • the threshold is adjusted
  • OR gate 116 and a latch 118 as shown. OR gate 116 in turn drives a FET
  • transistor 120 which connects directly or through one or more buffer
  • Circuit 114 also preferably performs a discrimination function against transient losses of the detected Rayleigh scattering component. This function
  • the latch 118 is provided so that computer 14 can monitor the activity
  • An output line 118a conveys the status of the latch to the
  • a reset line 118b permits the computer to reset the latch.
  • circuit 68 also includes a low duty cycle pulse generator 122 that also feeds into OR gate 116.
  • a pulse having a 5 millisecond (ms) duration is generated at a 1 Hz repetition
  • OR gate 116 Another input to OR gate 116 is a manual override pushbutton 124.
  • pushbutton 124 When activated, pushbutton 124 forces laser 16 to the high output intensity.
  • amplifier 64 is shown in more detail as a first stage transimpedance amplifier
  • circuit 114 is shown as three circuits 114a, 114b, 114c connected in series. Circuit 114a, configured as shown, performs the comparator function described previously. Adjustment of
  • potentiometer 126 adjusts the electric potential at the noninverting input of
  • operational amplifier 128 is wired as a comparator, it has
  • circuit 114a was directly connected to circuit 114c, the circuit 114 output on line 130 would respond equally as rapidly to positive-going and negative-going
  • Circuit 114b discriminates between positive-going and negative-going transitions.
  • the output of op amp 128 is LO
  • the potential at node 134 is LO
  • capacitor Cl is not charged
  • transistor 132 is off. If the Rayleigh scattering component suddenly drops
  • Diode Dl is reverse biased (nonconducting), and the combination of resistors
  • Rl , R2, and capacitor Cl delay the turn-on of transistor 132.
  • the delay ( ⁇ )
  • transistor 132 will turn
  • op amp 128 output will immediately go LO, diode Dl will be
  • resistor R2 Preferably, the value of Rl is much greater than R2.
  • Rl 200 k ⁇
  • R2 10 k ⁇
  • Cl 10 picofarads.
  • Preferred delay times ⁇ are in the range of about 0 to 44 ms, and are
  • circuit 114b discriminates between a transitory loss in
  • FIG. 9 depicts the output of pulse generator 122, the amplified detector output on line 66, and the output of circuit 114 as waveforms 136, 138, 140
  • broken line 142 represents the threshold level set in circuit 114.
  • Waveform 140 therefore
  • waveform 140 rapidly responds. Between time t 4 and t s , small bubbles passing through detection zone 54 cause transitory dips in waveform 142
  • a transitory increase in waveform 138 between t 6 and t 7 has no effect on waveform 140, since waveform 138 stays above threshold 142 during that
  • Waveform 138 responds immediately to the interruption, while waveform 140 responds after the delay
  • embodiment can be replaced with equivalent digital circuits, e.g., DSP filters.

Abstract

An analyzer unit (38) has a remote probe (32) coupled thereto and has a wireless transceiver (86) which receives commands from an external control (88). The analyzer unit (38) responds to the commands and broadcasts an analyzer output over the transceiver (86). The transceiver (86) includes an antenna and a wireless communication transmitter/receiver operable with the main analyzer unit (38) in an intrinsically safe housing.

Description

CHEMICAL ANALYZER WITH FREE SPACE COMMUNICATION
LINK
Background of the Invention
The present invention relates generally to chemical analyzers, and has
particular application to such analyzers designed for process control
environments.
Brief Summary of the Invention
The invention relates to the use of a wireless transceiver in a chemical
analyzer that has a remote probe coupled to a main analyzer unit. The
analyzer receives commands from an external control unit over the transceiver,
and broadcasts an analyzer output over the transceiver. The invention is
preferably implemented in an analyzer where the main analyzer unit is housed
in an intrinsically safe housing. The transceiver can comprise an antenna, an
infrared transmitter/receiver, or like wireless communication components.
Brief Description of the Drawings
FIG. 1 shows a system diagram of a preferred chemical analyzer in
accordance with an aspect of the invention;
FIG. 2 depicts chief components of a preferred optical filter used in the
analyzer of FIG. 1;
FIG. 3 is an enlarged end view of optical fibers in the probe shown in
FIGS. 1 and 5; FIG. 4 is a perspective end view of a male fiber connector showing an
arrangement of optical fibers at the connector end as used in the analyzer of
FIG. 1;
FIG. 5 is a partially sectional view of a preferred optical probe useable
with the analyzer of FIG. 1;
FIG. 6 is a sectional view of a distal end of the probe of FIG. 5 during probe fabrication;
FIG. 7 is a block schematic of a preferred signal conditioning circuit
useable with the analyzer of FIG. 1;
FIG. 8 is a schematic of a comparator/asymmetric discriminator circuit depicted as a block in FIG. 7; and
FIG. 9 is a timeline showing signals at different points in the signal
conditioning circuit of FIG. 7.
For convenience, items in the figures having the same reference symbol
are the same or serve the same or a similar function.
Detailed Description of the Preferred Embodiments
As used herein, "optic"(al) and "light" refer to electromagnetic radiation, whether or not visible to the human eye.
FIG. 1 shows a preferred analyzer 10 that evaluates a specimen of
interest 12 and provides on a computer 14 or other suitable output medium an
analyzer output indicative of the presence or amount of one or more chemical
constituents of the specimen. The analyzer 10 illuminates the specimen 12 with narrow-band light, collects backscattered light from the specimen,
optically isolates a Raman scattering component from the backscattered light, and evaluates the Raman scattering component to calculate the analyzer output. Simultaneously, the analyzer isolates a Rayleigh scattering component from
the backscattered light. If the Rayleigh scattering component falls below a
threshold level, which may result for example from disconnecting a fiber connector or withdrawing the probe from the specimen, the narrow-band light
illumination is shut off. This shut off technique is most effective in specimens such as liquids that have significantly higher Rayleigh scattering levels than
that of gasses such as air.
A diode laser 16 launches essentially monochromatic, narrow-band
light into a fiber 18a of a 2-by-2 beamsplitter 20. A wavelength of about 810
nanometers (nm) for the narrow-band light has been found satisfactory.
Shorter wavelengths increase the amount of Raman scattering, but may also
produce unwanted fluorescence in some specimens; longer wavelengths are
less likely to produce fluorescence but yield a lower Raman signal. In
practice, a diode laser having a wavelength between about 750 and 850 nm is preferred. The selected wavelength should not however coincide with an
absorption line of the specimen 12, if maximum Raman scattering levels are
desired. The laser can have a multimode output and be capable of emitting
700 mW to 1.2W of optical power during analyzer operation. Laser 16 also
includes a driver circuit with a control input at line 24, and a temperature control circuit if the laser source is a diode laser. The control input of laser 16
controls the amount or intensity of narrow band light injected into fiber 18a.
Beamsplitter 20 divides the laser light launched into fiber 18a between fibers 18b, 22a, preferably in equal amounts although other ratios are also
contemplated. The narrow band light passes from fiber 18b to a fiber 18c via a connector pair 26. Connector pair 26 includes a male connector end holding
each fiber end, the connector ends facing each other inside an alignment
bushing. SMA-type connector pairs are preferred for robustness and ease of
modification to nonstandard bore sizes, but other known styles such as ST or
FC are also contemplated. Fiber 18c connects to a bandpass filter 28 in a fiber
termination/filter module 30. Laser light passes through filter 28 to a fiber
18d, which carries the light to a probe 32 adapted to contact the specimen 12.
Fibers 18c, 18d are preferably part of armored cable assemblies 34,36 respectively.
The analyzer 10 is preferably arranged as a main analyzer unit 38
situated in a control room (or other suitable location that can provide the
necessary electrical power), a probe 32 located at the specimen, and the
termination/filter module 30 located near the probe. Main analyzer unit 38 is
preferably housed in an intrinsically safe enclosure, configured with an
industry standard Z-purge capability at a port 38a that maintains a positive air
pressure inside unit 38 relative to its surroundings.. Armored fiber cable assemblies 34,36 connect unit 38 to module 30, and module 30 to probe 32, respectively. Cable assembly 34 can be tens or hundreds of meters long.
Optical fiber can itself generate Raman scattering and/or fluorescence
(hereinafter, "spurious light signals") from laser light passing through it,
which if detected can be confused with Raman scattering from the specimen. The spurious light signals are a function of the fiber properties (most
importantly its length, but also including core material, cladding material, and
buffer layer material), and generally have wavelengths longer than the laser
wavelength. Therefore, bandpass filter 28 is provided in the termination/filter module 30, and module 30 is located as close to the probe as possible to
minimize fiber 18d length and thus minimize any spurious light signals
generated in fiber 18d. In a benign environment, the cable assembly 36
(including fiber 18d) can be eliminated and the filter 28 and the other filter
(74, discussed below) can be mounted directly on the proximal end of the
probe 32. However, in many practical applications the temperature or change in temperature encountered even at the proximal end of the probe can have
adverse effects on filter performance. Hence, module 30 mounted away from
probe 30 provides a more stable temperature environment for the filters 28,74.
Bandpass filter 28 blocks the spurious light signals originating in fibers
18a, 18b, 18c, from reaching fiber 18d, but passes narrow band light from laser
16. Spurious light signals can be further reduced by using silica-based fiber having an inert metal buffer layer such as gold. Such fibers have significantly lower spurious light signals than similar fibers having a polymer-based buffer
layer such as polyimide The relatively high cost of the metal-coated fibers
however can make it impractical to use them exclusively in analyzer 10,
depending on the distances involved. Instead, the use of filters 28,74 permits
lower cost, polymer-based fibers to be used between the main analyzer unit 38
and the filters, and the preferred gold-coated fibers to be used in probe 32 and
between probe 32 and the filters. A preferred embodiment of filter 28 is depicted in FIG. 2. Male fiber
connectors 39a,39b hold the ends of fibers 18c, 18d against 0.25-pitch gradient
index (GRIN) lenses 40a,40b respectively. A filter 42 sandwiched between lenses 40a,40b provides the desired spectral filtering characteristics. Filter 42
preferably comprises an interference-type filter.
Turning again to FIG. 1 , fiber 18d releasably connects to probe 32 by a
connector pair 44 located at a proximal end 32a of probe 32 and passes narrow band light to a fiber 18e that extends from connector pair 44 to a distal end
32b of probe 32. Also housed in probe 32 are a fiber 46a and a group of five
fibers 48a. The line representing fibers 48a, and some other lines in FIG. 1 , are shown thickened to indicate multiple optical fibers in the preferred
embodiment. Fiber 46a connects to a connector pair 50 at proximal end 32a,
and at distal end 32b is brazed or otherwise held in position together with fibers 18e and 48a. At end 32b, the fibers are polished to a mirror finish and arranged as shown in FIG. 3. A braze material 52 holds the fiber ends in place and hermetically seals the probe at end 32b. The probe design and construction is discussed further below.
Narrow band light exits fiber 18e and illuminates specimen 12 in a detection zone 54 defined by the numerical aperture of fiber 18e. The
surrounding six fibers (46a and 48a) collect some of the backscattered light,
which will include a relatively strong Rayleigh component (same wavelength
as the narrow band light) and a relatively weak Raman component (longer
wavelength than the narrow band light). As will be seen, the preferred
analyzer 10 uses the multiple fibers 48a to boost the detected Raman
component and the single fiber 46a to sense the Rayleigh component for
continuity.
Backscattered light traveling down fiber 46a is directed to a detector 56
via fibers 46b-e, connector pairs 58,60, and a bandpass filter 62. Filter 62
passes the narrow band light wavelength and is substantially identical to
previously described filter 28. The purpose of filter 62 is to prevent sunlight,
room light, or any other extraneous light collected by fiber 46a from being
mistaken for Rayleigh backscattered light. Filter 62 also has the effect of preventing the weaker Raman component, if present, from reaching detector
56. An amplifier 64 couples to detector 56 to provide an amplified detector output on line 66. Advantageously, the detector 56 output, representative of the Rayleigh
scattering component, is fed back through a signal conditioning circuit 68 to
the laser control input at line 24. Circuit 68 compares the detector output on
line 66 with a predefined threshold. If the detector output is above the
threshold, indicating that the analyzer optical system is intact, circuit 68 provides an output on line 24 that maintains laser 16 at its normal, relatively
high, output level. If on the other hand the detector output is below the
threshold, indicating a fiber disconnection or break, or removal of the probe
from the specimen, circuit 68 provides an output on line 24 that shuts off laser
16 or at least controls it to a lower intensity level. This lower intensity level
can be set such that the light intensity emitted from probe fiber 18e, and
preferably from fiber 18b, is within BSI/EN 60825-1 class 1 operation (i.e. ,
nonhazardous direct viewing). In this way, analyzer 10 can operate with high
laser light levels during normal operation and automatically shut down if a discontinuity is sensed by detector 56, thereby avoiding hazardous viewing by an operator.
Several enhancements to the basic shut-down technique are also
provided by signal conditioning circuit 68. One enhancement is the ability to
discriminate between transient losses in the Rayleigh scattering component,
such as may be caused by small bubbles 69 of air or other gas passing through
the detection zone 54, and longer lived losses in the signal which may result
from fiber disconnection or break, or a withdrawal of probe 32 from the specimen. The circuit 68 continues driving laser 16 at its high operational intensity level in the presence of the truly transient losses, but shuts the laser down to the lower intensity level for the longer-lived losses. This
discrimination function prevents unnecessary and annoying shutdowns during
operation of analyzer 10. Another enhancement involves periodically
interrogating the laser 16 after a shutdown has occurred, or at startup, so that
if system integrity is restored the analyzer 10 will automatically return to
normal operation (i.e. , high laser intensity level). These capabilities of circuit
68 are described in more detail below.
Turning again to probe 32 in FIG. 1, fibers 48a are unsupported in
probe 32 except at distal end 32b, where they are arranged around the emitting fiber as shown in FIG. 3, and at the proximal end 32a, where they are bundled
together at a connector pair 70. One of the male connector ends 70a of pair
70 holds the five fibers 48a as shown in the perspective end view of FIG. 4.
The other male connector end of pair 70 holds a single fiber 48b in alignment
with the fibers 48a, where fiber 48b has a diameter sufficiently large to
capture light emitted from all of the fibers 48a. For example, if fibers 48 are
lOOμm (core diameter), fiber 48b can be about 300μm (core dia.). This
arrangement greatly simplifies analyzer 10 interconnections: rather than five separate fibers, connector pairs, and filters connecting the Raman pickup fiber
channel from the probe 32 to the main analyzer unit 38, only one-fifth of those
components are required by using a large fiber to collect light from fibers 48. Backscattered light is carried by fiber 48b to the entrance slit of an optical spectrograph 72 via a long pass filter 74, fibers 48c-e, and connector pairs
76,78. Long pass filter 74 has the same construction as the bandpass filter
shown in FIG. 2 except that the filter element 42 is fabricated to block the narrow band light of laser 16 and pass longer wavelengths. Preferably the spectral transmission of filter 74 is less than 10"6 at the laser wavelength 810
nm and rises to half of its peak transmittance (70% typ. peak trans.) at about
833 nm. As discussed, fiber termination/filter module 30 is mounted close to probe 32 to keep fiber 48b short (generally no more than a few, and preferably < 1 meter), so that no spurious light signals can be produced by Rayleigh
backscattered light in fiber 48b. Filter 74 blocks any Rayleigh backscattered
light from reaching fibers 48c-e. Fiber 48b preferably has a metal (gold)- buffer layer.
Fibers 18a-e, 46a, 48a, 48e, and 22a-d are preferably relatively small
diameter (e.g. lOOμm core) fibers, while fibers 48b-d are preferably relatively
large diameter (e.g. 300μm core) fibers. Fibers 46b-e can be either small or
large diameter, but preferably are no smaller than fiber 46a. All can be
graded-index or, preferably, step-index for increased light levels. Fibers 48e
are held at connector pair 78 in a substantially circular pattern (similar to FIG. 4) for optimal coupling to fiber 48d, while at the entrance slit to spectrograph
72 they are held in a linear array. Fibers 18d, 18e, 46a, 48a, and 48b all have
inert metal buffer layers, preferably gold. A diamond reference 80 is provided in main analyzer unit 38. Fibers
18a, 22a,22b carry narrow band light from laser 16 to the surface of diamond
80. Bandpass filter 82, substantially identical to filters 28 and 62, blocks
fiber-generated Raman scattering. Six fibers 22c surround fiber 22b at the diamond surface (similar to FIG. 3) to capture backscattered light from diamond 80. A longpass filter 84, substantially identical to filter 74, blocks
Rayleigh scattered light from fibers 22d. Fibers 22d, six in number, are
arranged circularly at filter 84 and linearly at the spectrograph 72 entrance slit.
The linear arrays of fibers 22d and 48e are arranged colinearly, one
abutting the other, at the entrance slit to spectrograph 72. Spectrograph 72 is
preferably equivalent to model SP-150 available from Acton Research Corp. ,
and has a ruled grating with 400 grooves/mm and blazed at 750 nm. A
detector array 77, preferably 750 pixels wide by 240 pixels high, intercepts
and simultaneously monitors the spatially separated Raman scattered light
spectra from the specimen 12 and from the diamond reference 80. The output from detector array 77 is fed to computer 14 over a line 75. Signal processing
software residing in computer 14 is used to produce a standardized Raman
spectrum of the specimen using the diamond Raman spectrum. Pattern
recognition software also residing in computer 14 calculates the chemical
composition of specimen 12 from the standardized Raman spectrum of the
specimen and calibration training data. Such pattern recognition software is
available from Galactic Industries, Boston, MA. As previously mentioned, main analyzer unit 38 is preferably intrinsically safe. Although computers having intrinsically safe keyboards and
monitors are commercially available, there are significant difficulties in
providing a convenient and aesthetic user interface using these components.
Therefore, computer 14 is preferably equipped with a transceiver 86 such as
an antenna or an infrared transmitter/receiver. A user can send instructions to
and receive information from computer 14 using a second device such as a
laptop computer 88 equipped with a similar transceiver 90. Such communication preferably occurs over a wireless, fiberless free space path 91, allowing the user to freely move from place to place with computer 88 and
permitting greater flexibility and choice in a mounting location for main
analyzer unit 38. Preferred transceivers 86,90 are commercially available
radio LAN cards for desktop or laptop computers, for example the
WAVELAN card available from AT&T Lucent Technologies, designed to
interface to a standard PC/MCIA slot or Industry Standard Architecture (ISA)
bus slot. Transceiver 86 is depicted in FIG. 1 as such an antenna device, that
partially extends out of the housing of unit 38 and connects to computer 14 by a coax line 86a. The transceiver can also be an infrared emitter/receiver
disposed inside the housing of unit 38 behind a window. Computer 88 has a
keyboard and a mouse that are used to send queries and commands to
computer 14. Computer 88 also has a display to graph or otherwise show the
analyzer output data transmitted from computer 14. With this arrangement, computer 14 is preferably equipped with neither a display screen, a keyboard, nor a mouse, to satisfy intrinsic safety requirements as well as to reduce the
size, weight, and electrical requirements of main analyzer unit 38.
Probe 32 is described in more detail in connection with FIGS. 5 and 6, together with previously discussed FIGS. 1, 3, and 4. Probe 32 preferably has
a probe body with three main components: a terminus 32c, a shank 32d, and
a connector housing 32e, all made of 316 stainless steel or other suitable inert
materials capable of withstanding several hundred degree C temperatures, such
as Hastelloy C. Terminus 32c, shank 32d, and housing 32e are rotationally
symmetric about a probe axis 32f, and are connected by braze joints 92,94 as
shown. The outer diameter of terminus 32c, braze joint 92, and shank 32d is polished to a smooth finish (0.25 in. dia.) to permit sealing with a ferrule
inside the bore of a standard pipe fitting, such as those available from
Swagelok Corp., or the bore of some other container that holds specimen 12.
Fibers 18e, 46a, and 48a (only one of which is shown in its entirety in
FIGS. 5 and 6 for simplicity) extend from their respective male connector ends
44a, 50a, and 70a at proximal probe end 32a to distal end 32b. Each of the
fibers are step-index, with silica or doped silica core/cladding, and have a thin
outer buffer layer of gold, nickel, or other inert metal along their entire length. Male connector ends 50a, 44a, and 70a are fixed to connector housing
32e to permit probe 32 to be conveniently disconnected and reconnected to
cable assembly 36 for ease of installation and servicing. Also affixed to housing 32e is a connector 96 for a temperature sensor 98 included in probe 32. Temperature sensor 98 is preferably disposed proximate distal end 32b for
diagnostic purposes to ensure that probe 32 does not exceed its rated
temperature. Alternately, the output of sensor 98 can be used as a rough indication of the specimen temperature, whereupon probe 32 takes on a dual role as a fiber optic chemical analysis probe and a specimen thermometer.
Although known fiber optic temperature sensors can be used for sensor 98,
electrical sensors are preferable for their simplicity, and most preferable is a
thermocouple (e.g. type K) for its low-cost and reliability. The output of
sensor 98 can be monitored with a portable, hand-held device coupled directly
to connector 96, or with computer 14, in which case an additional channel
such as a twisted wire pair can be included in cable assemblies 36,34.
The procedure for brazing fibers 46a, 18e,48a into the stainless steel
terminus 32c will now be described. To enhance adhesion, terminus 32c is
plated with gold 100 or other metal matching the metal buffer layer of the fibers. The gold plating extends inside a bore 104 and in the vicinity thereof,
but preferably is removed from or not provided on the remaining surfaces of
terminus 32c. This is to keep molten braze material in the vicinity of bore 104
during fabrication, preventing it from spreading over the entire terminus 32c.
An anti-wicking agent or stop-flow substance, preferably a suspension of
magnesium hydroxide in water, is applied to each of the fibers in a zone
indicated generally at 106 prior to brazing. Zone 106 approaches but does not touch the distal portion of the fibers that extend into bore 104. The anti-
wicking agent inhibits the flow of molten braze material along the fibers
substantially beyond bore 104. With the fibers and terminus 32c so prepared,
the assembly is positioned in a vacuum oven 108 as shown in FIG. 6, with a
small ring or loop of solid braze material 110 resting on top of terminus 32c at
or near bore 104. Preferred braze materials for platings 100 made of gold are
cadmium-free varieties; widely available braze type (AWS) BAg-8, a binary alloy composed of about 72% silver and 28% copper, is most preferable. The
vacuum oven 108 is then heated to a temperature sufficient to melt braze
material 110. By preparing the fibers and terminus 32 as described, the
molten braze material does not run out of but rather tends to stay in and
around the vicinity of bore 104, wicking between the fibers and filling the
spaces between them. Upon cooling, the braze material forms a solid hermetic
seal within bore 104, uniformly filling the inter- fibral spaces inside bore 104 with few or no voids (see FIG. 3).
As final fabrication steps, a sleeve 112 of terminus 32c is brazed to
shank 32d using localized heating, and shank 32d is then brazed to connector
housing 32e also using localized heating. The sleeve 112 partially isolates the brazed fibers in bore 104 from heat generated during brazing of terminus 32c
to shank 32d. Braze material BAg-8 is used for all braze joints. The fiber
ends are polished to a flat, mirror-smooth finish at distal end 32b. Lastly, the other fiber ends are potted into the male connector ends, which connector ends are also brazed to connector housing 32e at proximal end 32a.
FIG. 7 depicts in block schematic form a preferred signal conditioning
circuit 68. Circuit 68 receives on line 66 the amplified detector output, representative of the Rayleigh scattering component from specimen 12, and
provides on line 24 an output that controls a light output level of laser 16. A
comparator/asymmetric discriminator circuit 114 compares the amplified
detector output to an adjustable internal threshold. The threshold is adjusted
according to the desired laser operational output level, fiber attenuation losses,
filter and connector pair losses, and specimen scattering characteristics, to a level less than an output level on line 66 for a fully intact system with the
probe contacting the specimen, and greater than a lower output level
corresponding to the amount of Rayleigh scattered light received when the
probe is withdrawn from the specimen and pointed into the air, or when one of
the fiber connector pairs is uncoupled. The output of circuit 114 feeds into an
OR gate 116 and a latch 118 as shown. OR gate 116 in turn drives a FET
transistor 120 which connects directly or through one or more buffer
amplifiers if desired to line 24. Thus, as long as analyzer 10 is intact and probe 32 is disposed in the specimen, the signal on line 66 will be higher than
the threshold level, the output of circuit 114 will be "HI" , the output of OR
gate 116 will be "HI", turning transistor 120 "ON" to couple the + 12V
voltage to line 24, thereby maintaining laser 16 at its high operational output intensity. If the probe 32 is withdrawn from the specimen, however, the output of circuit 114 will go "LO", as will OR gate 116, turning off transistor
120 and forcing laser 16 to a lower (preferably zero) intensity level.
Circuit 114 also preferably performs a discrimination function against transient losses of the detected Rayleigh scattering component. This function
is described in connection with FIG. 8.
The latch 118 is provided so that computer 14 can monitor the activity
of circuit 114. An output line 118a conveys the status of the latch to the
computer, and a reset line 118b permits the computer to reset the latch.
Advantageously, circuit 68 also includes a low duty cycle pulse generator 122 that also feeds into OR gate 116. In a preferred embodiment, a pulse having a 5 millisecond (ms) duration is generated at a 1 Hz repetition
rate. When the laser 16 is in its zero or low intensity state, as it would be on
power-up of analyzer 10 and as it would be after a drop in the detected Rayleigh scattering component below the threshold, each pulse from generator
122 causes the laser to momentarily (for the duration of the pulse) provide the
higher output intensity. The pulses are kept short enough, and the duty cycle
small enough, to keep the light emitted from probe 32 or even from connector
pair 22 below the safety limits for the human eye and for explosive atmosphere
environments. When system integrity returns to analyzer 10, the Rayleigh
backscatter signal will return to line 66 during one of the pulses, causing
circuit 114 to turn "ON", thereby establishing normal analyzer operation. Still another input to OR gate 116 is a manual override pushbutton 124.
When activated, pushbutton 124 forces laser 16 to the high output intensity.
This capability is provided for troubleshooting purposes.
Turning now to FIG. 8, the asymmetric transient discrimination feature of comparator/asymmetric discriminator circuit 114 will be described. The
amplifier 64 is shown in more detail as a first stage transimpedance amplifier
and a second stage amplifier with gain. The circuit 114 is shown as three circuits 114a, 114b, 114c connected in series. Circuit 114a, configured as shown, performs the comparator function described previously. Adjustment of
potentiometer 126 adjusts the electric potential at the noninverting input of
operational amplifier 128, which electric potential functions as the threshold
referred to previously, against which the amplified detector output on line 66
is compared. Since operational amplifier 128 is wired as a comparator, it has
essentially a digital output. This digital output changes state very rapidly every time the signal on line 66 crosses the threshold potential at the noninverting input of op amp 128. Ignoring circuit 114b for the moment, if
circuit 114a was directly connected to circuit 114c, the circuit 114 output on line 130 would respond equally as rapidly to positive-going and negative-going
changes in the line 66 signal as it crossed the threshold. However, as is
apparent from the wiring of FET transistor 132 in circuit 114c, the polarity of
the signal on line 130 is opposite that of the signal at the output of op amp 128. Circuit 114b, however, discriminates between positive-going and negative-going transitions. During normal analyzer operation, with a Rayleigh
scattering component above the threshold level, the output of op amp 128 is LO, the potential at node 134 is LO, capacitor Cl is not charged, and
transistor 132 is off. If the Rayleigh scattering component suddenly drops
below the threshold level, the output of op amp 128 immediately goes HI.
Diode Dl is reverse biased (nonconducting), and the combination of resistors
Rl , R2, and capacitor Cl delay the turn-on of transistor 132. The delay ("τ")
is proportional to (Rl +R2)*C1. If the Rayleigh scattering component stays
below the threshold level for at least the delay time τ, transistor 132 will turn
on, causing the laser 16 to shut down. If however the detected Rayleigh
component returns to a level above the threshold level before time τ has
elapsed, op amp 128 output will immediately go LO, diode Dl will be
forward biased (conducting), and capacitor Cl will discharge rapidly through
only resistor R2. Preferably, the value of Rl is much greater than R2. In a
preferred embodiment Rl =200 kΩ, R2 = 10 kΩ, and Cl = 10 picofarads.
Preferred delay times τ are in the range of about 0 to 44 ms, and are
preferably programmable by computer 14 (e.g. by a computer-controlled switch and one or more resistors in circuit 114b that changes the effective resistance in parallel with diode Dl). In this manner, circuit 114b discriminates between a transitory loss in
the detected Rayleigh scattering component and a transitory appearance of such
component.
FIG. 9 depicts the output of pulse generator 122, the amplified detector output on line 66, and the output of circuit 114 as waveforms 136, 138, 140
respectively. Broken line 142 represents the threshold level set in circuit 114.
At time t=0, the analyzer is powered up, the laser is off, and the probe is
withdrawn from the specimen. At times tj and t2, the pulse generator pulses
the laser on, but only a very low Rayleigh scattering component is detected
since the probe is not contacting the specimen. Waveform 140 therefore
remains off. Between times t2 and t3, the probe is inserted into the specimen, so that at the next pulse of waveform 136 at time t3, a Rayleigh scattering
component above the threshold is produced in waveform 138, and circuit 114
(waveform 140) rapidly responds. Between time t4 and ts, small bubbles passing through detection zone 54 cause transitory dips in waveform 142
below threshold 142. The duration of such dips is less than τ, so the
waveform 140 remains unchanged. Between time t5 and t6, a larger bubble
passes through detection zone 54, causing a dip in signal 138 with a duration
longer than τ, whereupon waveform 140 drops to zero. By the time t6, the
large bubble has passed zone 54 and the pulse of waveform 136 brings back
the Rayleigh scattering component in waveform 138 and the output of circuit
114. A transitory increase in waveform 138 between t6 and t7 has no effect on waveform 140, since waveform 138 stays above threshold 142 during that
time. Between time t7 and t8, an interruption such as a fiber break, fiber
disconnection, or probe withdrawal occurs. Waveform 138 responds immediately to the interruption, while waveform 140 responds after the delay
time τ.
Although the present invention has been described with reference to preferred embodiments, workers skilled in the art will recognize that changes may be made in form and detail without departing from the spirit and scope of
the invention. For example, analog circuits disclosed in the preferred
embodiment can be replaced with equivalent digital circuits, e.g., DSP filters.

Claims

WHAT IS CLAIMED IS:
1. An analyzer, comprising:
a main analyzer unit;
a remote probe coupled to the analyzer unit; and
a wireless transceiver carried by the analyzer unit, the analyzer responding to commands received by the transceiver and broadcasting an analyzer output over the transceiver.
2. The analyzer of claim 1, wherein the wireless transceiver comprises an antenna.
3. The analyzer of claim 1 , wherein the main analyzer unit includes an intrinsically safe housing.
4. The analyzer of claim 3, wherein the intrinsically safe housing has a Z-purge
port.
PCT/US1998/004455 1997-03-14 1998-03-06 Chemical analyzer with free space communication link WO1998041847A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US4109697P 1997-03-14 1997-03-14
US60/041,096 1997-03-14

Publications (1)

Publication Number Publication Date
WO1998041847A1 true WO1998041847A1 (en) 1998-09-24

Family

ID=21914721

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1998/004455 WO1998041847A1 (en) 1997-03-14 1998-03-06 Chemical analyzer with free space communication link

Country Status (1)

Country Link
WO (1) WO1998041847A1 (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01233353A (en) * 1988-03-14 1989-09-19 Chubu Electric Power Co Inc Remote monitor for inspection of transmission wire
US5112127A (en) * 1989-11-28 1992-05-12 Eic Laboratories, Inc. Apparatus for measuring Raman spectra over optical fibers
US5507288A (en) * 1994-05-05 1996-04-16 Boehringer Mannheim Gmbh Analytical system for monitoring a substance to be analyzed in patient-blood
US5673692A (en) * 1995-02-03 1997-10-07 Biosignals Ltd. Co. Single site, multi-variable patient monitor

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01233353A (en) * 1988-03-14 1989-09-19 Chubu Electric Power Co Inc Remote monitor for inspection of transmission wire
US5112127A (en) * 1989-11-28 1992-05-12 Eic Laboratories, Inc. Apparatus for measuring Raman spectra over optical fibers
US5507288A (en) * 1994-05-05 1996-04-16 Boehringer Mannheim Gmbh Analytical system for monitoring a substance to be analyzed in patient-blood
US5507288B1 (en) * 1994-05-05 1997-07-08 Boehringer Mannheim Gmbh Analytical system for monitoring a substance to be analyzed in patient-blood
US5673692A (en) * 1995-02-03 1997-10-07 Biosignals Ltd. Co. Single site, multi-variable patient monitor

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 013, no. 557 (P - 974) 12 December 1989 (1989-12-12) *

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