EP1730493A2 - Appareil et procedes de surveillance de fluides - Google Patents

Appareil et procedes de surveillance de fluides

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Publication number
EP1730493A2
EP1730493A2 EP05718127A EP05718127A EP1730493A2 EP 1730493 A2 EP1730493 A2 EP 1730493A2 EP 05718127 A EP05718127 A EP 05718127A EP 05718127 A EP05718127 A EP 05718127A EP 1730493 A2 EP1730493 A2 EP 1730493A2
Authority
EP
European Patent Office
Prior art keywords
fluid
cavity
fibre
light
sensor
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP05718127A
Other languages
German (de)
English (en)
Inventor
Andrew Mark Shaw
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evanesco Ltd
Original Assignee
Evanesco Ltd
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
Priority claimed from GBGB0405821.0A external-priority patent/GB0405821D0/en
Application filed by Evanesco Ltd filed Critical Evanesco Ltd
Publication of EP1730493A2 publication Critical patent/EP1730493A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/55—Specular reflectivity
    • G01N21/552—Attenuated total reflection
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/7703—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator using reagent-clad optical fibres or optical waveguides

Definitions

  • This invention is generally concerned with apparatus and methods for monitoring fluids, in particular critical fluids such as lubricants, based upon evanescent wave techniques- These will be described with particular reference to cavity ring-down spectroscopy although embodiments of the apparatus and methods do not rely upon multiple passes of a light pulse back and forth within a cavity.
  • Cavity Ring-Down Spectroscopy is known as a high sensitivity technique for analysis of molecules in the gas phase (see, for example, G. Berden, R. Peeters and G. Meijer, Int. Rev. Phys. Chem., 19, (2000) 565, P. Zalicki and R.N, Zare, J. Chem. Phys. 102 (1995) 2708, M.D. Levinson, B.A. Paldus. T.G. Spence, C.C. Harb, J.S. Harris and R.N. Zare, Chem. Phys. Lett. 290 (1998) 335, B.A. Paldus, C.C. Harb, T.G. Spence, B. Wilkie, J.
  • the CRDS technique can readily detect a change in molecular absorption coefficient of 10 " ⁇ cm"', with the additional advantage of not requiring calibration of the sensor at the point of measurement since the technique is able to determine an absolute molecular concentration based upon known molecular absorbance at the wavelength or wavelengths of interest.
  • the acronym CRDS makes reference to spectroscopy in many cases measurements are made at a single wavelength rather than over a range o avelengdis.
  • FIG. la which shows a cavity 10 of a CRDS device, illustrates the main principles of the technique.
  • the cavity 10 is formed by a pair of high reflectivity mirrors at 12, 14 positioned opposite one anodier (or in some otlier configuration) to form an optical cavity or resonator.
  • a pulse of laser light 1 enters lite cavity through the back of one mirror (mirror 12 in figure la) and makes many bounces between the mirrors, losing some intensity at each reflection. Light leaks out through the mirrors at each bounce and the intensity of light in the cavity decays exponentially to zero with a half-life decay time, ⁇ .
  • Curve 18 of Figure la illustrates the origin of the phrase "ring-down", the light ringing backwards and forwards between the two mi ⁇ Ors and gradually decreasing in amplitude.
  • the decay time ⁇ is a measure of all the losses in the cavity, and when molecules 11 which absorb the laser radiation are present in the cavity the losses are greater and the decay time is shorter, as illustratively shown by trace 20.
  • ⁇ ⁇ is a function of the strength of absorption of the molecule at the frequency, v, of interest ⁇ (v) (the molecular extinction coefficient) and of the concentration per unit length, / s , of the absorbing species and is given by equation 1 below. ⁇ t « / r / ⁇ 2 ( 1 - R ) + ⁇ (v) / , ⁇ (Equation 1)
  • the reflectivities of mirrors 12, 14 should be high (whilst still permitting a detectable level of light to leak out) and typically R equals 0.9999 to provide of the order of 10 A bounces. If the total losses in the cavity are around 1 % there will only be 3 or 4 bounces and consequently the sensitivity of the apparatus is very much reduced; in practical terms it is desirable to have total losses less than 0,25%, corresponding to around 200 bounces during decay time ⁇ , or approximately 1000 bounces during ring down of the entire cavity,
  • e-CRDS evanescent wave CRDS
  • FIG. lb in which like elements to those of Figure la are indicated by like reference numerals, shows the idea underlying evanescent wave CRDS.
  • a prism 22 (as shown, a pellin broca prism) is introduced into the cavity such that total internal reflection (TIR) occurs at surface 24 of the prism (in some arrangements a monolithic cavity resonator may be employed).
  • TIR total internal reflection
  • Total internal reflection will be familiar to the skilled person, and occurs when the angle of incidence (to a normal surface) is greater than a critical angle ⁇ e where sin ⁇ c is equal to n ni where n? is the refracted index of the medium outside the prism and K
  • e-wave evanescent wave
  • This e-wave penetrates into the medium above the prism but it's intensity decreases exponentially with distance from the surface, typically over a distance of the order of the a wavelength.
  • the penetration depth is approximately 175 nm and for a silica/water interface the depth is approximately 250 nm, which may be compared with the size of a molecule, typically in the range 0.1-1.0 nm.
  • a molecule adjacent surface 24 and within the e-wave field can absorb energy from the e-wave illustrated by peak 26, thus, in effect, absorbing energy from the cavity.
  • the "total internal reflection” is sometimes refe ⁇ 'ed to as attenuated total internal reflection (ATIR).
  • a loss in the cavity is detected as a change in cavity ring-down decay time, and in this way the technique can be extended to measurements on molecules in a liquid or solid phase as well as molecules in a gaseous phase.
  • molecules near the total internal reflection surface 24 are effectively in optical contact with the cavity, and are sampled by die e-wave resulting from the total internal reflection at the surface.
  • the inventors have recognised that techniques related to e-CRDS can be employed to determine the condition of a fluid, in particular a fluid having a high optical density, for which conventional optical techniques fail.
  • conventional optical techniques are difficult to apply to fluids having an absorbance of greater than unity as so little light is transmitted by such fluids.
  • the invention provides a sensor module for use with attenuated total internal reflection or oilier evanescent field sensing apparatus for optically determining the condition of a fluid, the module having an evanescent wave sensor, a module housing for the sensor, and an optical connector to connect the sensor to the apparatus.
  • the senor comprises a portion of fibre optic configured, preferably tapered.
  • the connector comprises another portion of the same fibre optic, in embodiments to avoid the need to splice two fibres together.
  • a high reflectivity mirror is formed, preferably directly, on either or both ends of the fibre to provide a two-pass system or, with two mirrors, an optical cavity.
  • the housing may be fabricated from a cera ic material for physical/chemical robustness; this may comprise a ferule at either end of the sensor portion of the fibre, optionally spaced apart for example by one or more posts, in order to provide a fluid-permeable region in the vicinity of the "exposed" portion of the fibre.
  • the sensor module is incorporated into a dipstick, for example with a metal housing and a cage around the evanescent wave sensing portion of the fibre.
  • the invention also provides ATIR or other evanescent field sensing apparatus incorporating the module/dipstick.
  • apparatus for optically determining the condition of a fluid
  • the apparatus comprising: a light source to provide light for interacting with said fluid; a detector for detecting a level of light from said light source; and an optical path between said light source and said detector, said optical path including a reflection from an evanescent wave interface, such as a substantially totally internally reflecting (TIR) interface; and wherein said apparatus is configured such that said fluid may be brought sufficiently close to said interface for an evanescent wave formed by total internal reflection of light at said interface to interact with said fluid; whereby a condition of said fluid is deter inable from said detected light level.
  • TIR total internal reflection
  • the optical path further includes a mirror (or other reflecting surface) reflection so that the light makes a double pass dirough a sample region comprising said TIR interface.
  • a mirror or other reflecting surface
  • a pair of mirrors can be employed to form an optical cavity for ring-down monitoring of a fluid characteristic or condition but it has been found experimental !y that in many cases such multiple reflections of light back and forth through the sample region (reflecting from the interface) are not necessary to obtain a useful sensitivity.
  • the optical path includes a fibre optic (FO).
  • FO fibre optic
  • the TTR interface may be formed by modifying the fibre, for example by removing a portion of the FO surface and/or tapering the FO, to provide access to the evanescent wave.
  • the degree of modification/taper the evanescent field in particular the extension of the evanescent field from the interface, may also be controlled and hence adapted to a particular sensing function or application.
  • a FO may be selected or fabricated such that an evanescent field extension from the interface (or taper diameter/length) is suitable for the absorbance or expected absorbance range of a fluid whose condition is to be de.enr.ined or monitored.
  • the FO is provided with a protective housing, which in embodiments may be configured as a dipstick.
  • the monitored fluid may comprise a lubricant, such as engine oil, for any of a range of engines, turbines, generators, transmissions and the like, or a hydraulic fluid, la other applications the monitored fluid may comprise oil, for example crude or pre-refined oil or oil at any stage in the refinement process including, but not limited to, feed stock and vistar/post-cracking oil.
  • a lubricant such as engine oil, for any of a range of engines, turbines, generators, transmissions and the like
  • the monitored fluid may comprise oil, for example crude or pre-refined oil or oil at any stage in the refinement process including, but not limited to, feed stock and vistar/post-cracking oil.
  • the interaction of the evanescent wave with the fluid will generally include some absorption of light by the fluid but other interactions may also be present.
  • the refractive index of the fluid which may change with temperature and or odier parameters such as age, use/treatment history and the like
  • the apparatus can be though of a monitoring the complex refractive index of a fluid, that is either or both of a real component of the refractive index and an imaginary component representing absorption.
  • the apparatus includes a signal processor coupled to the detector.
  • This may comprise a conventional computing device with a digitiser to digitise an output from the detector.
  • the signal processor may then be programmed to detect a change in the fluid condition, for example in substantially real-time, and to provide an output signal.
  • Such an output signal may comprise data or a data file, for example sent to a disk or over a network, and/or a signal lo drive an indicator such as a warning indicator.
  • the apparatus may be configured to detect/determine a degree of scatter of light by the fluid, for example by illuminating and detecting the attenuated TIR at two or more wavelengths or colours (either discrete or continuous). This can be used as a measure of degradation of the fluid, being responsive to a level or concentration of particulaies within the fluid.
  • Measuring at three (or two to four or more) colours facilitates distinguishing between a change in response due to scattering, which is wavelength dependent (as 1/ ⁇ 4 ), for example due to a change in particulate density or characteristics, and a change in response due to a change in temperature of the monitored fluid, which affects all die colours in a similar manner, for example the response at all three colours changing similarly.
  • a method of optically determining the condition of a fluid using attenuated total internal reflection comprising: measuring an attenuation of a total internal reflection at an interface due to an interaction of light with said fluid mediated by an evanescent wave formed at said interface; and determining a condition of said fluid from said attenuation.
  • the invention also provides a method, and corresponding apparatus, for determining a degree of degradation of a fluid, the method comprising measuring a level of particulate scattering by said fluid; and determining said degree of degradation of the fluid from said level of particulate scattering. Again measuring a response at two or more different colours can help distinguish between particulate scattering and temperature effects.
  • Such computer program (or processor control) code may be provided on a carrier such as a CD- or D ⁇ D-ROM or on read only memory (Firmware) or as a signal on an optical or electrical signal carrier.
  • Such computer program code may be written in any conventional programming language and may be distributed between a plurality of coupled components, for example over a network.
  • the invention also provides an optical cavity, in particular a fibre optic, including a TIR surface or interface as described above.
  • the optical cavity may be provided without one or both mirrors since these may be provided by the cavity sensing apparatus within which the TIR surface or interface is to operate.
  • the apparatus/methods need not operate in the TIR regime, depending upon the taper parameters and/or the fluid llie condition of which is to be determined.
  • the apparatus/methods need not operate in the TIR regime, depending upon the taper parameters and/or the fluid llie condition of which is to be determined.
  • the optical properties of a fluid depend on complex refractive index
  • CRI Crohn's disease
  • the TIR condition is maintained within the fibre-liquid/fluid and substantially only the radiation in the e-field interacts with the fluid, typically by both mechanisms of scatter and absorption.
  • the CRI of the fluid is above that of the effective refractive index (RI) of the taper the radiation may be at least partially coupled out of the fibre through the evanescent field, with losses characteristic of the CRI of the fluid and the taper.
  • Thin tapers of order ⁇ 5 ⁇ minimum diameter favour the guided regime and fatter tapers favour the coupled regime.
  • the above described aspect of the invention suitable for use with ATIP apparatus is aiso suitable for operation in a non-ATIR regime, and generally here (A)TIR should be understood as also including sensors/apparatus in which radiation is partially or wholly coupled out of an evanescent wave interface.
  • optical fluid sensing apparatus comprising, an illumination source to source illumination at an operating wavelength of the apparatus, and a tapered fibre optic configured to couple light at said operating wavelength out of said taper and into said fluid, whereby a real of complex refractive index of said fluid may be determined.
  • the sensitivity of an e-CRDS or a conventional CRDS-based device may be improved by taking a succession of measurements and averaging the results.
  • the frequency at which such a succession of measurements can be made is limited by the maximum pulse rate of the pulsed laser employed for injecting light into the cavity.
  • This limitation can be addressed by employing a continuous wave (CW) laser such as a laser diode, since such lasers can be switched on and off faster than a pulsed laser's maximum pulse repetition rate,
  • CW continuous wave
  • there are significant difficulties associated with coupling light from a CW laser into the cavity particularly where a so- called stable cavity is employed, typically comprising planar or concave mirrors.
  • a cavity ring-down sensor with a light source, such as a continuous wave laser, of a power and bandwidth sufficient to overcome losses within the cavity and couple energy into at least two modes of oscillation (either transverse or longitudinal) of the cavity.
  • a light source such as a continuous wave laser
  • the light source is operable as a substantially continuous source and has a bandwidth sufficient to provide at least a half maximum power output across a range of frequencies equal to at least a free spectral range of the cavity. This facilitates coupling of light into the cavity even when modes of the light source and cavity are not exactly aligned.
  • the light source may be shuttered or electronically controlled so that the excitation may be cut off to allow measurement of a ring-down decay curve.
  • the CW light source output is preferably cut off in less than 100ns, more preferably less than 50ns.
  • the cavity When driven with a CW laser the cavity preferably has a length of greater than 0.5m more preferably greater than 1.0m because a longer cavity results in closer spaced longitudinal modes.
  • An evanescent wave cavity-based optical sensor may comprise: an optical cavity formed by a pair of highly reflective surfaces such that light within the cavity makes a plurality of passes between the surfaces, an optical path between the surfaces including a reflection from a totally internally reflecting (TIR) surface, the reflection from the TIR surface generating an evanescent wave to provide a sensing function; a light source to inject light inlo the cavity; and a detector to detect a light level within the cavity.
  • TIR totally internally reflecting
  • a cavity ring-down sensor may comprise: a ring-down optical cavity for sensing a substance modifying a ring-down characteristic of the cavity; a light source for exciting the cavity; and a detector for monitoring the ring-down characteristic.
  • the cavity may comprise a fibre optic sensor including a fibre optic cable configured io provide access to an evanescent field of light guided within the cable for d e sensing.
  • the evanescent wave may either sense a substance directly or may mediate a sensing interaction through sensing a substance or a property of a material.
  • the detector detects a change in light level in the cavity resulting from absorption of the evanescent wave, and whilst in practice this is almost always performed by measuring a ring-down characteristic of the cavity, in principle a ring-up characteristic of a cavity could additionally or alternatively be monitored.
  • the reflecting surfaces of the cavity are optical surfaces generally characterized by a change in reflective index, and may physically comprise internal or external surfaces.
  • the number of passes light makes through the cavity depends upon the Q of the cavity which, for most (but not ail) applications, should be as high as possible.
  • the cavity ring-down is responsive to absorption in the cavity this absorption may either be direct absorption by a sensed material or may be a consequence of some other physical effect, for example surface plasr ⁇ o ⁇ resonance (SPR) or measured property.
  • SPR surface plasr ⁇ o ⁇ resonance
  • the cavity comprises a fibre optic cable with reflective ends.
  • this provides a number of advantages including physical and optical robustness, physically small size, durability, ease of manufacture, and flexibility, enabling use of such a sensor in a wide range of non lab-based applications.
  • a fibre optic cable a ⁇ ' be modified to provide access to an evanescent field of light guided within the cable.
  • the invention provides a fibre-optic sensor of this sort, for example for use in evanescent wave cavity ring-down device of the general type described above.
  • a fibre optic cable typically comprises a core configured to guide light down the fibre surrounded by an outer cladding of lower refractive index than the core.
  • a sensing portion of the fibre optic cable may be configured have a reduced thickness cladding over part or all of the circumference of the fibre such that an evanescent wave from said guided light is accessible for sensing.
  • the evanescent wave can interact directly with a sensed material or substance or attenuation of light within the cavity via absorption of the evanescent wave can be indirectly modified, for example in an SPR- based sensor by modifying the interaction of a surface plasmon excited in overlying conductive material with the evanescent wave (a shift or modification of a plasmon resonance changing the absorption).
  • One, or preferably both ends of the fibre optic cable may be provided with a highly reflecting surface such as a Bragg stack.
  • the fibre optic cable thus provides a stable cavity, that is guided light confined within the cable will retrace its path many times.
  • the fibre optic cable (and hence cavity) has a length of at least a length of 0.5m, and more preferably of at least 1.0m, to facilitate coupling of a continuous wave laser to the fibre optic sensor, as described above.
  • the sensor may be coupled to a fibre optic extension and, optionally, may include an optical fibre amplifier; such an amplifier may be incorporated within the cavity.
  • the fibre optic cable is preferably a step index fibre, although a graded index fibre may also be used, and may comprise a single mode or polarization-maintaining or high birefringence fibre.
  • the sensing portion of the cable has a loss of less than 1%, more preferably less than 0,5%, most preferably less than 0.25%, so that the cavity has a relatively high Q and consequently a high sensitivity.
  • the core of the fibre should have a greater refractive index titan that of the liquid in which it is to be immersed in order to restrict losses from the cavity.
  • the sensor may be attached to a Y-coupling device to facilitate single- ended use, for example inside a human or animal body.
  • references to optical components and to light includes components for and light of non-visible wavelengths such as infrared and other light.
  • Figures la - show, respectively, an operating principle of a CRDS-type system, an operating principle of an e- CRDS-typs system, a block diagram of a continuous wave e-CRDS system, and first, second and third total internal reflection devices for a CW e-CRDS system;
  • Figure 2 shows a flow diagram illustrating operation of the system of figure lc
  • Figures 3a- 3c show, respectively, cavity oscillation modes for the system of figure lc, a first spectrum of a CW laser for use with the system of figure lc, and a second CW laser spectrum for use with the system of figure lc;
  • Figures 4a - 4e show, respectively, a Fibre optic-based e-CRDS system, a fibre optic cable for the system of figure 4a, an illustration of the effect of polarization in a total internal reflection device, a fibre optic cavity- based sensor, and fibre optic cavity ring-down profiles;
  • Figures 5a and 5b show, respectively, a second fibre optic based e-CRDS device, and a variant of this device;
  • Figures 6a and 6b show, respectively, a cross sectional view and a view from above of a sensor portion of a fibre optic cavity
  • Figures 7a and 7b show, respectively, a procedure for forming the sensor portion of figure 6, and a detected light intensity-time graph associated with the procedure of figure 7a;
  • Figure 8 shows an example of an application of an e-Cr ⁇ S-based fibre optic sensor
  • Figure 9 shows synthesis of a Nile Blue derivative
  • Figure 10 shows a schematic diagram of a chrompohore attached to a sensor surface to provide a pH sensor
  • Figure 11 shows an example of a ring-down trace for a fibre optic cavity
  • Figure 12 shows fibre optic bend losses in a 2m fibre cavity
  • Figure 13 shows a graph of cavity loss against taper waist for a tapered fibre optic cavity with crystal violet deposited on a totally internally reflecting evanescent wave surface of the fibre taper;
  • Figure 14 shows a fibre optic cavity incorporating a taper
  • Figure 15 shows variation of cavity ring-down time ⁇ with cavity length for a fibre cavity
  • Figure 16 shows a wavelength division multiplexed fibre optic cavity sensor system
  • Figure 17 shows transmittance of an optical cavity illustrating the cavity free spectral range and finesse
  • Figure 18 shows UV/Visible spectra forEurolite I0W-30 during temperature degradation
  • Figure 19 shows variation of absorbance at 637 nm and 820 nm with thermal degradation
  • Figure 20 shows UV / visible spectra for vehicle oil degradation using Eurolite oil (flushed & changed) at 38 miles, I7S miles, 358 miles, 505 miles, 758 miles, 1011 miles, 1320 miles, and 1680 miles;
  • Figure 21 shows absorbance vs 1/ ⁇ 4 showing the evolution of scalter-do inated spectra al 38 miles, 178 miles,
  • Figure 22 shows a plot of straight-line gradient in Figure 21 vs vehicle mileage, showing oil performance degradation
  • Figure 23 shows variation of absorbance at 637 nm and 820 nm in vehicle test oil
  • Figure 25 shows a fibre optic dipstick (with a 10 pence piece for scale);
  • Figure 26 shows variation of a dipstick response for engine oil (Eurolite 10W-30) for clean oil and after 1680 miles;
  • Figure 27 shows dipstick responses in crude oil samples of feed and vistar for heating (to the left) and cooling (to the right);
  • Figure 2Sa shows the response (arbitrary units) of a fibre optic dipstick according to an embodiment of the present invention monitoring heating and cooling of Castrol R40 racing oil
  • Figure 28b shows detail of the transition of Figure 28a;
  • Figures 29a to 29c show a typical asphaltene particle and graphs of absorbance and extinction against complex refractive index
  • Figures 30a and 30b show, respectively, a further example of a fibre optic dipstick, and a fibre optic cavity for the dipstick of Figure 30a;
  • Figures 31a and 3 lb show, respectively, a fibre optic sensor module, and a dipstick incorporating the module.
  • this shows an example of an e-C/fjDS-based system 100, in which light is injected into the cavity using a continuous wave (CW) laser 102.
  • the ring-down cavity comprises high reflectivity mirrors 108, 110 and includes a total internal reflection device 112.
  • Mirrors 108 and 110 may be purchased from Layertec, Ernst-Abbe-Weg 1, D-99441, Mellingen, Germany, In practice the tunability of the system may be determined by the wavelength range over which the mirrors provide an adequately high reflectivity.
  • Light is provided to the cavity by laser 102 through die rear of mirror 108 via an acousto-optic (AO) modulator 104 to control the injection of light.
  • AO acousto-optic
  • the output of laser 102 is coupled into an optical fibre and then focused onto a AO modulator 104 with 100 micron spot, the output from
  • AOM 104 then can be collected by a further fibre optic before being introduced into the cavity resonator.
  • This arrangement facilitates chop times of the order of 50ns, such fast chop times being desirable because of the relatively low finesse of the cavity resonator.
  • Laser 102 may comprise, for example, a CW ring dye laser operating at a wavelength of approximately 630nm or some other CW light source, such as a light emitting diode may be employed.
  • the bandwidth of laser (or other light source) 102 should be greater than one free spectral range of the cavity formed by mirrors 108,110 and in one dye laser-based embodiment laser 102 has a bandwidth of approximately 5 GHz.
  • a suitable dye laser is the Coherent 899-01 ring-dye laser, available from Coherent Inc, California, USA.
  • a radio frequency source 120 drives AO modulator 104 to allow the CW optical drive to cavity 108, 110 to be abruptly switched off (in effect the AO modulator acts as a controllable diffraction grating to steer the beam from laser 102 into or away from cavity 108, 100).
  • a typical cavity ring-down time is of the order of a few hundred nanoseconds and therefore, in order to detect light from a significant number of bounces in the cavity, the CW laser light should be switched off in less than 100ns, and preferably in less than about 30ns. Data collected during this initial 100ns period, that is data from an initial portion of the ring-down before the laser has completely stopped injecting light into the cavity, is generally discarded.
  • an AO modulator such as the LM250 from Isle Optics, UK, maybe used in conjunction with a RF generator such as the MD250 from the same company.
  • the RF source 120 and, indirectly, the AO modulator 104, is controlled by a control computer 118 via an IEEE bus 122.
  • the RF source 120 also provides a timing pulse output 124 to the control computer to indicate when light from laser 102 is cut off from the cavity 108 - 110. It will be recognized that the timing edge of the timing pulse should have a rise or fall time comparable with or preferably faster than optical injection shut-off time.
  • a tunable light source such as a dye laser has advantages for some applications but in otlier applications a less tunable CW light source, such as a solid state diode laser may be employed, again in embodiments operating at approximately 630nm. It has been found that a diode laser maybe switched off in around 10ns by controlling the electrical supply to the laser, thus providing a simpler and cheaper alternative to a dye laser for many applications.
  • RF source 120 is replaced by a diode laser driver which drives laser 102 directly, and AO modulator 104 may be dispensed with.
  • An example of a suitable diode laser is the PPMT LD1338-F2, from Laser 2000 Ltd, UK, which includes a suitable driver, and a chop rate for the apparatus, and in particular for this laser, may be provided by a Techstar FG202 (2MHz) frequency generator.
  • PMT photo -multiplier tube
  • Suitable devices are the H7732 photosensor module from Hammatsu with a standard power supply of 15V and an (optional) Ortec 9326 fast pre-amplifier.
  • Detector 114 preferably has a rise time response of less than 100ns more preferably less than 50ns, most preferably less than 10ns.
  • Detector 114 drives a fast analogue-to-digital converter 1 16 which digitizes die output signal from detector 114 and provides a digital output to the control computer 118; in one embodiment an A to D on board a LeCroy waverunner LT 262 350 MHz digital oscilloscope was employed.
  • Control computer 118 may comprise a conventional general purpose computer such as a personal computer with an IEEE bus for communication with the scope or A/D 116 may comprise a card within this computer.
  • Computer 118 also includes input/output circuitiy for bus 122 and timing line 124 as Well as, in a conventional manner, a processor, memory, non-volatile storage, and a screen and keyboard user interface.
  • the non-volatile storage may comprise a hard or floppy disk or CD-ROM, or programmed memory such as ROM, storing program code as described below.
  • the code may comprise configuration code for Lab View (Trade Mark), from National Instruments Corp, USA, or code written in a programming language such as C.
  • FIG. 1d shows a fibre optic cable-based sensing device, as described in more detail later.
  • Figure le shows a first, Pellin Broca type prism, and figure If shows a second prism geometiy.
  • Prisms of a range of geometries, including Dove prisms, may be employed in the apparatus of figure lc, particularly where an anti-reflection coating has been applied to the prism.
  • the prisms of figures l e and If may be formed fro a range of materials including, but not limited to glass, quartz, mica, calcium fluoride, fused silica, and borosilicate glass such as BK7.
  • FIG 2 shows a flow diagram of one example of computer program code operating on control computer 118 to control the apparatus of figure l c.
  • control computer 118 sends a control signal to RF source 120 over bus 122 to control radio frequency source 120 to close AO shutter 104 to cut off the excitation of cavity 108 ⁇ 110, Then at step S202, the computer waits for a liming pulse on line 124 to accurately define the moment of cut-off, and once the timing pulse is received digitized light level readings from detector 114 are captured and stored in memory.
  • Data may be captured at rates up to, for example, 1G samples per second (lsample/ns at either 8 or 16 bit resolution) preferably over a period of at least five decay lifetimes, for example, over a period of approximately 5 ⁇ s, Computer 1 18 then controls RF generator to re-open the shutter and the procedure loops back to step S200 to repeat the measurement, thereby capturing a set of cavity ring-down decay curves in memory.
  • Computer 1 18 controls RF generator to re-open the shutter and the procedure loops back to step S200 to repeat the measurement, thereby capturing a set of cavity ring-down decay curves in memory.
  • decay curves When a continuous wave laser source is used to excite the cavity decay curves may be captured at a relatively high repetition rate, For example, in one embodiment decay curves were captured at a rate of approximately 20kH-- per curve, and in theory it should be possible to capture curves virtually back-to-back making measurements substantially continuously (with a small allowance for cavity ring-up time). Thus, for example, when capturing data over a period of approximately 5 ⁇ s it should be possible to repeat measurements at a rate of approximately 20kH2.
  • the data from the captured decay curves are then averaged al step S206, although in otlier embodiments otlier averaging techniques, such as a running average, may be employed.
  • the procedure fits an exponential curve to the averaged captured data and uses this to determine a decay time TQ for the cavity in an initial condition, for example when no material to be sensed is present.
  • the decay time ⁇ 0 is the time taken for the light intensity to fall to 1 /e of its initial value (e - 2.718).
  • Any conventional curve fitting metliod may be employed; one straight - forward method is to take a natural logarithm of the light intensity data and then to employ a least squares straight line fit.
  • data at the start and end of the decay curve is omitted when determining the decay time, to reduce inaccuracies arising from the finite switch-off time of the laser and from measurement noise.
  • data between 20 percent and 80 percent of an initial maximum may be employed in the curve fitting.
  • a baseline correction to the captured light intensity may be applied prior to fitting the curve; this correction may be obtained from an initial calibration measurement.
  • the apparatus controls the apparatus to apply a sample (gas, liquid or solid) to the total internal reflection device 112 within the ring-down cavity; alternatively the sample may be applied manually.
  • the procedure then, at slep S212, effectively repeats steps S200 ⁇ S208 for the cavity including the sample, capturing and averaging data for a plurality of ring-down curves and using this averaged data to determine a sample cavity ring-down decay time ⁇ j.
  • the procedure determines an absolute absorption value for the sample using the difference in decay times ( ⁇ 0 - ⁇ ) and, at step S216, the concentration of the sensed substance or species can be determined. This is described further below.
  • t r is the round trip time for the cavity, which can be determined from the speed of light and from the optical path length including the total internal reflection device. The molecular concentration can then be determined using equation 3;
  • this shows a graph of frequencies (or equivalently, wavenumber) on the horizontal axis against transmission into a high Q cavity such as cavity 108, 11 O of figure lc, on the vertical axis.
  • a high Q cavity such as cavity 108, 11 O of figure lc
  • FSR free spectral range
  • / is the length oi ' tlie cavity and c' is the effective speed of light within the cavity, that is the speed of light taking into account the effects of a non-unity refractive index for materials within the cavity.
  • the free spectral range is approximately 150MHz.
  • Lines 300 in figure 3a illustrate successive longitudinal cavity modes.
  • Figure 3a also shows (not to scale) a set of additional, transverse cavity modes 302a, b associated with each longitudinal mode, although these decay rapidiy away from the longitudinal modes.
  • transverse modes are much more closely spaced than the longitudinal modes since they are determined by the much shorter transverse cavity dimensions.
  • the light source with sufficient bandwidth to overlap at least too longitudinal cavity modes may be employed. This is shown in figure 3b.
  • Figure 3b shows figure 3a with an intensity (Watts per nf) or equivalently power spectrum 304a, b for a continuous wave laser superimposed. It can be seen that provided tire full width at half maximum 306 of the laser output spans at least one FSR laser radiation should continuously fill the cavity, even if the peak of the laser output moves, as shown by spectra 304a and b.
  • Hie laser output may not have the regular shape illustrated in figure 3b and figure 3c illustrates, diagrammatically an example of the spectral output 308 of a dye laser which, broadly speaking, comprises a super imposition of a plurality of broad resonances at the cavity modes of the laser.
  • transverse modes have not been shown in figure 3b or figure 3c but it will be appreciated light may be coupled into modes with a transverse component as well as a purely longitudinal modes, although to ensure continuous excitation of a cavity it is desirable to overlap at least two different longitudinal modes of the cavity
  • Figure 4a shows a fibre optic-based e-CRDS type sensing system 400 similar to that shown in figure lc, in which like elements are indicated by like reference numerals.
  • mirrors 108, 110, and total internal reflection device 112 are replaced by fibre optic cable 404, the ends of wliich have been treated to render them reflective to form a fibre optic cavity.
  • collimating optics 402 are employed to couple light into fibre optic cable 404 and collimating optics 406 are employed to couple light from fibre optic cable 404 into detector 414.
  • FIG 4b shows further details of fibre optic cable 404, whic , in a conventional manner comprises a central core 406 surrounded by cladding 408 of lower refractive index than the core.
  • Each end of the fibre optic cable 404 is, in the illustrated embodiment polished flal and provided with a ulti layer Bragg stack 410 to render it highly reflective at the wavelength of interest.
  • a Bragg stack is a stack of quarter wavelength tliick layers of materials of alternating refractive indices.
  • the ends of the fibre optic cable are first prepared by etching away the surface and then polishing the etched surface flat lo within, for example, a tenth of a wavelength (this polishing criteria is a coramonly adopted standard for high-precision optical surfaces), Bragg stacks may then be deposited by ion sputtering of metal oxides; such a service is offered by a range of companies including the above-mentioned Layertec, Gmb ⁇ i, Fibre optic cable 404 includes a sensor portion 405, as described further below.
  • optical fibre 404 is a single mode step index fibre, advantageously a single mode polarization preserving fibre to facilitate polarization-dependent measurements and to facilitate enhancement of the evanescent wave field.
  • Such enhancement can be understood with reference to figure 4c which shows total internal reflection of light 412 at a surface 414. It can be seen from inspection of figure 4c that p-polarized tight (within the plane containing light 412 and the normal to surface 414) generates an evanescent wave which penetrates further from surface 414 than does s-polarized light (perpendicular to the plane containing light 412 and the normal to surface 414).
  • the fibre optic cable is preferably selected for operation at a wavelength or wavelengths of laser 102.
  • a wavelength or wavelengths of laser 102 For example, where laser 102 operates in the region of 630nm so called short-wavelength fibre may be employed, such as fibre from INO at 2470 Einstein Street, Sainte-Foy, Quebec, Canada.
  • suitable fibre optic cables are available over a wide range of wavelengths from less than SOOnm to greater than 1500nm.
  • Preferably low loss fibre is employed.
  • the decay time is given by equation 5 below where the symbols have then- previous meanings, /is the loss in the fibre (units of m *1 i.e. percentage loss per metre) and / is the length of the fibre in metres.
  • Figure 4d illustrates a simple example of an alternative configuration of the apparatus of figure 4a, in which fibre optic cavity 404 is incorporated between two additional lengths of fibre optic cable 416, 418, light being injected at one end of fibre optic cable 416 and recovered from fibre optic cable 418, which provides an input to detector 114.
  • Fibre optic cables 414, 416 and 418 may be joined in any conventional manner, for example using a standard FC/PC - type connector.
  • Figure 4e shows two examples of cavity ring-down decay curves obtained with apparatus similar to that shown in figure 4a with a cavity of length approximately one meter and the above mentioned single mode fibre.
  • Figure 4 ⁇ shows two sampling oscilloscope faces captured at 500 mega samples per second with a horizontal (time) grid division of 0.2 ⁇ s and a vertical grid division of50 ⁇ V.
  • Curve 450 represents a single measurement and curve 452 and average of nine decay curve measurements (in figure 4e the curve has been displaced vertically for clarity) the decay time for the averaged decay curve 452 was determined to be approximately 1.7 ⁇ s.
  • the slight departure from an exponential shape (a slight kink in the curve) during the initial approximately 100ns is a consequence of coupling of radiation into the cladding of the fibre, which is rapidly attenuated by the fibre properties and losses to the surroundings.
  • FIG 5a shows a variant of the apparatus of figure 4a, again in which like elements are indicated by like reference numerals.
  • a single-ended connection is made to fibre cavity 404 although, as before, both ends of fibre 404 are provided with highly reflecting surfaces
  • a conventional Y-type fibre optic coupler 502 is attached to one end of fibre cavity 404, in the illustrated example by an FC/PC screw connector 504.
  • the Y connector 502 has one arm connected to collimating optics 402 and its second arm connecting to collimating optics 406, To allow laser light to be launched into fibre cavity 404 and light escaping from fibre cavity 404 to be detected from a single end of the cavity.
  • fibre cavity-based sensor such as is described in more detail below
  • Such applications include intravenous sensing within a human or animal body and sensing within an oil weli bore hole,
  • Figure 5b shows a variant in which fibre cavity 404 is coupled to Y-connector 502 via an intermediate length of fibre optic cable 506 (which again may be coupled to cable 504 via a FC/PC connector).
  • Figure 5b also illustrates the use of an optional optical fibre amplifier 508 such as an erbium-doped fibre amplifier.
  • fibre amplifier 508 is acting as a relay amplifier to boost the output of collimating optics 402 after a long run through a fibre optic cable loop 510. (For clarity in figure 5b the pump laser for fibre amplifier 508 is not shown).
  • the skilled person will appreciate that many other configurations are possible.
  • the fibre amplifier is relatively tinear it may be inserted between Y coupler 502 and collinaating optics 506 without great distortion of the decay curve.
  • detector 114 is relatively physically close to the output arm of Y coupler 512, that is preferably no more than a few centimeters from the output of this coupler to reduce losses where practically possible; alternatively a fibre amplifier may be incorporated within cavity 404.
  • multiple fibre optic sensors may be employed, for example by splitting the shuttered output of laser 102 and capturing data from a plurality of detectors, one for eacl sensor, Alternatively laser 102, shutter 104, and detector 1 14 may be multiplexed between a plurality of sensors in a rotation.
  • Figures 6a and 6b show one way in which such access may be provided. Broadly speaking a portion of cladding is removed from a short length of the fibre to expose the core or more particularly to allow access to die evanescent wave of light guided in the core by, for example, a substance to be sensed.
  • Figure 6a shows a longitudinal cross section tiirough a sensor portion 405 of the fibre optic cable 404 and figure 6b shows a view from above of a part of the length of fibre optic cable 404 again showing sensor portion 405.
  • the fibre optic cable comprises an inner core 406, typically around 5 ⁇ m in diameter for a single mode fibre, surrounded by a glass cladding 408 of lower refractive index around the core, the cable also generally being mechanically protected by a casing 409, for example comprising silicon rubber and optionally armour.
  • the total cable diameter is typically around 1mm and the sensor portion may be of the order of 1cm in length.
  • the cladding 408 is at least partially removed to expose the core and hence to permit access to the evanescent wave from guided light within- the core.
  • the thickness of the cladding is typically lOQ ⁇ m or more, but the cladding need not be entirely removed although preferably less than 1 O ⁇ m thickness cladding is left at the sensor portion of the cable. It will be appreciated dial there is no specific restriction on the length of the sensor portion although it should be short enough to ensure that losses are kept well under one percent. It will be recognized that, if desired, multiple sensor portions may be provided on a single cable.
  • the characteristic penetration depth, d p of an evanescent wave, at which the wave amplitude falls to 1/c of its value at the interface is determined by: ⁇ - ⁇
  • ⁇ is the wavelength of the
  • 0 is the angle of incidence at the interface with respect to the normal
  • « t2 is the ratio of the refractive index of the material (at ⁇ ) to the medium above the interface.
  • d p is less than 500nm; for a typical configuration d p is less than 200 ⁇ _m, often less than lOOnm,
  • a sensor portion 405 on a fibre optic cable may be created either by mechanical removal of the casing 409 and portion of the cladding 408 or by chemical etching.
  • Figures 7a and 7b demonstrate a mechanical removal process in which the fibre optic cable is passed over a rotating grinding wheel ⁇ with a relatively fine grain) which, over a period of some minutes, mechanically removes the casing 409 and cladding 408.
  • the point at which the core 406 is optically exposed may be monitored using a laser 702 injecting light into the cable which is guided to a detector 704 where the received intensity is monitored.
  • Refractive index matching fluid (not shown in figure 7a) is provided at the contact point between grinding wheel 700 and table 404, this fluid having a higher refractive index than die core 406 so that when the core is exposed light is coupled out of the core and the detected intensity fails to zero.
  • Figure 7b shows a graph of light intensity received by detector 704 against time, showing a rapid fall in received intensity at point 706 as the core begins to be optically exposed so that energy from the evanescent wave can couple into the index matching fluid and hence out of the table.
  • a chemical etching process a similar procedure may be employed to check when the evanescent wave is accessible, that is when the core is being exposed, by removing the fibre from the chemical etch ant at inteivals and checking light propagation tiirough the fibre when index matching fluid is applied at the sensor portion of the fibre.
  • An example of a suitable enchant is hydrofluoric acid (HF).
  • Figure 8 shows a simple example of an application of the apparatus of figure 4a
  • Fibre optic cable 404 and sensor 405 are immersed in a flow cell 802 tiirough which is passed an aqueous solution containing a chromophore whose absorbance is responsive to a property to be measured such as pH, Using die apparatus of figure 4a at a wavelength corresponding to an absorption band of the chromophore very small changes, in this example pH, may be measured.
  • Instruments of the type described may operate at any of a wide range of wavelengths or at multiple wavelengths.
  • optical high reflectivity are mirrors available over the range 200nm - 20 ⁇ m and suitable light sources include Ti.sapphire lasers for the region 600nm - lOOOnm and, at the extremes of the frequency range, synchrotron sources.
  • Instruments of the type shown in figure 4 a may also operate at any of a wide range of wavelengths provided that suitable fibre optic cable is available.
  • evanescent wave cavity ring-down spectroscopy in a rugged field instrument is facilitated by construction of the optical resonator within a fibre optic. This effectively makes alignment automatic and makes the cavity robust but highly flexible.
  • the choice of fibre optic and wavelength of operation is controlled by the optical loss budget with the cavity to enable the e-CRDS ring-down teclraique to be implemented and, for functional ised surfaces, the design of the absorption specific chemistry for the preparation of these surfaces.
  • the loss budget for die optical resonator determines the ultimate sensitivity of the technique together with the ability to determine the losses from each component in the fabrication of the cavity.
  • reflection from a totally internally reflecting (TIR) surface generates an evanescent wave to provide a sensing function
  • the TIR surface is provided with a functionalising material over at least part of its surface such that the evanescent wave is modified by the functionalising material so that an interaction between the functionalising material and a target to be sensed is detectable as a change in absorption of the evanescent wave and hence a change in the ring-down characteristics (time) of the cavity.
  • the ftmctionalising material may, for example, be a host for a guest species or ligand, and in preferred arrangements comprises a cliromophore (to provide absorption at a wavelength of operation of the apparatus).
  • the fimctionalismg material may be attached by means of a molecular tether or link; where the TIR surface comprises silica the tether may be attached by a Si-O-Si bond.
  • FIG. 10 shows a schematic diagram of the chrompohore attached to a sensor surface to provide a pH sensor.
  • the tether has a trielhoxysilane group that forms a Si-O-Si bond at the surface to bind the species to the surface.
  • the ethoxy group acts as a leaving group when the silicon undergoes nucleophilic attack by the surface silanol group.
  • the OEt leaving group can be replaced with a chloro group producing a chiorosilane derivative with different tethering properties.
  • the tethering process can be varied to provide 1, 2 or 3 -OEt or -CI on the tethered molecule to establish 1,2 or 3 anchoring points to the surface or the formation of a cross-linked surface polymer chain.
  • Fibre optic was purchased from Oz Optics (Ontario, Canada) with a minimum absorption at 633 nm specified at 7dB km "1 .
  • the losses at 633 nm are dominated by the absorption losses of the silica in the Fibre and a shift to longer wavelength can allow the operation of the cavity in a region of lower lo-sses in the absorption spectrum of the silica.
  • the minimum absorption occurs at 1.5 ⁇ m, the telecom wavelength.
  • Table 1 The specification for die fibre is shown in Table 1 below.
  • the fibres were fabricated in two batches, one supplied and prepared with hig-h-reflectivity mirror coalings by INO (Institute National d'Optique - National Optics Institute, Quebec, Canada), and one supplied by Oz optics with high-reflectivity mirror coatings provided by Research Electro Optics (RJEO), Inc, of Colorado, USA, Each fibre was polished flat as part of a standard INO pieparation procedure and then connectorised with a standard FC/PC patchchord connector. For the REO batch the mirror coatings were applied to the end of the poiished fibre with the FC PC connectors in place. The fabrication process may coat the mirrors before or after connectorisalion.
  • the batch from INO was supplied as patch-chords with a rugged plastic covering around the fibres (likely added after the mirrors were coated); the batch sent to REO had ano outer coating, except the silicone covering, around 1 mm in diameter to minimise out-gassing during the coating processes.
  • Fibie optic tapers were prepared under contract by Sifam Fibre Optics, Torquay, Devon, UK, tapering the fibre optic revealing some of the evanescent wave, as described above, allowing it to couple (o molecules in the outside medium. This was measured with a solution of ciystal violet (CV*), which has an absorbance al 633 nm - CV placed on die surface of the taper absorbs the radiation from the evanescent field and this is seen as a loss in the intensity of the radiation in the fibre, as shown in the graph of induced loss against taper waist (corresponding to extension) shown in Figure 13.
  • CV* ciystal violet
  • the fibre of Table i has a "W" index profile which leads to increased losses in the tapering process, and therefore tapers were drawn in the fibre specified in Table 2 below, which has a simple step index profile.
  • a tapered fibre was then spliced into a cavity t ⁇ provide an overall cavity length of 4.2m; more than one taper could be spliced into a cavity in a similar way,
  • the cavity length was chosen to be tin ' s length to increase the ring down time ⁇ (which has a linear dependence on t r the round trip time).
  • the mirrors maybe deposited onto a fibre with a desired index profile.
  • the CRDS technique facilitates measurements of fibre optic propagation and fabrication losses. Measurements of the effect of bending on a fibre cavity are summarised in Table 4 and shown in Figure 12.
  • the bend radius of a fibre is the minimum radius at which the fibre should be bent to avoid significant propagation losses; a typical radius is ⁇ 2cm.
  • Tapered fibre cavities may be made by pulling under heating to a known radius to produce t e taper, for example by Sifam, as mentioned above.
  • the taper may d en be spliced into a fibre cavity to form a complete sensor, as shown in Figure 14,
  • the observed losses for a taper prepared with INO fibre are large due to the "W" shaped refractive index profile of these fibres and instead a step index profile fibre is preferable; this may then be spliced into an INO fibre cavity,
  • the tapered region may be supported in a 'U 1 shaped gutter.
  • FIG. 13 shows results of experiments performed to investigate the evanescent wave coupling to crystal violet as a function of taper diameter.
  • the experiments were performed in the presence of crystal violet (CV ⁇ 122 ⁇ M at pH 8.6, chosen to maximise the binding of CV to the (charged) silica surface, The results show thac losses are tolerable for tapers of diameter 25-30 ⁇ m.
  • the losses in fibre optic are measured in decibels (dB) per kilometre, with the dB defined by the following equation: where Pj service and P 0 nieth, are the input and output powers respectively.
  • the losses in CRDS experiments are measured by the ring-down time, ⁇ , with contributions from:
  • R(v) is the frequency dependent reflectivity of the mirrors
  • 7 - is the transmission loss of the fibre and L,- are all other losses to include scatter and diffraction effects.
  • the abso ⁇ tion of any molecular species witliin the cavity is assumed to follow Beers Law with /being the length of the cavity and .? is the number of bounces. Absorption within the evanescent field will also be by Beers law but with an effective penetration depth for the radiation, _/ admir and a concentration profile. Equation 7 can be re-arranged to give:
  • the ring down time of the cavity, ⁇ is given by:
  • t r is the round-trip time and R is the mirror reflectivity.
  • a fibre optic cavity may be fabricated with a broadband mirror.
  • the ring down time and hence die sensitivity of fibre based e-CRDS is determined by the propagation losses in the fibre and the production of the taper.
  • the losses in d e fabrication of a single taper have yet to be determined but appears fljat the mirrors are not the limiting factor.
  • This enables the reflectivity specification to be lowered to values around 0.999.
  • Mirror production techniques allow the preparation of broadband very high reflectivity coatings over a wavelength region of at least 500 - 1000 nm. This enables radiation of different wavelengths to propagate along the same cavity, for example to interrogate different sensor regions.
  • Wavelength division multiplexing (WDM) in fibre optics is a well established technique in the telecoms industty and wdm coupler and switch technology can be employed to couple multiple wavelengths into a common cavity for parallel detection scenarios. For example switching of radiation of different colours, say red, green and blue, can be straightforwardly inco ⁇ orated into a fibre network design, as shown schematically in the fibre sensor network 1600 of Figure 16, Referring to Figure 16, a fibre cavity 1602 includes one or more tapered regions to provide one or more evanescent wave sensing surfaces and hence a network of sensors.
  • Console 1608 may comprise, for example, a wavelengtii division demultiplexer coupled to one or more PMTs (each) having a digitised output, tiiese signals being provided to a computer programmed to determine cavity ring-down time at each of the wavelengths and hence to determine a (change in) cavity loss at die relevant wavelength (as described above) to provide a combined sensed signal dala output or plurality of sensed signal/data outputs. Console 1608 may also provide centralised monitoring/ command/control of the sensor network.
  • Molecules absorbing at different wavelengths can be used to construct smart or functionalised surfaces either for monitoring the change of the same species or of different target species with the same cavity.
  • haemoglobin has abso ⁇ tions al 425nm (due to the iron) and at 830nm (due to the prophyrin ring) and can be used to functionalise a surface to sense oxygen, CO, and/or NO.
  • parallel detection of the same target using different functionalising molecules (absorbing at different wavelengths) allows measurements to be compared/combined, for example for increased confidence in detection or for a confidence limit assessment to be made.
  • a multiplexed fibre optic network of sensors working at different detection wavelengths is deployed in a public place or around (within) a building, vessel, or other structure,
  • a multiplexed sensor network may be used to monitor carbon dioxide level(s) in the air of a submarine.
  • a free-running cavity structure allows a broad bandwidth cw laser to overlap with many cavity modes so that radiation will always enter the cavity.
  • the observed ring down profile is then a convolution of the ring down of several modes each in principle with die own, slightly different ⁇ .
  • Each ⁇ wiil depend on how flat the mirror reflectivity curve is over the bandwidth of the laser and whether there are any frequency dependent losses (e.g. diffraction losses) that are significantly different over the bandwidth of the laser.
  • the free-running cavity allows the laser to be chopped at, for example, 10 kHz, which may be averaged to improve the noise statistics.
  • the ring-down time shows a deviation error, ⁇ / ⁇ ⁇ 1%, which determines the ultimate absorbance sensitivity of the fibre cavity technique.
  • the absorbance by a species in the cavity is related to the cavity l ⁇ ngdi (the round-trip time) and the minimum detectable change in x, the ring down time given by the formula:
  • the separation FSR becomes 2.1 kHz.
  • the power intensity within a free-running cavity depends on die overlap of the input radiation with the cavity modes.
  • the free-running cavity overlaps at least two modes, one FSR, and so light will always couple into the cavity.
  • the output profile of a laser is generally rather broad, of order 5 nm, and so generally only a fraction this will couple to the cavity.
  • Coupling light into die cavity depends both on the number of longitudinal modes overlapped by die input light som-ce and the width of the modes.
  • the full width half max (FWHM) of each mode is controlled by the cavity finesse as defined below.
  • the finesse of the cavity is 3140. If R is replaced by die general round trip loss for the fibre cavity, (0.9921) tiien the finesse of the fibre cavity is 396.
  • the Q-factor may be defined by equation 17 below, which for die fibre cavity takes die value 395.7 - in close agreement with the calculated cavity finesse,
  • multi-node fibres may be used as an alternative to single mode fibre, and a range of different index profiles may be employed to give a range of taper configurations
  • tapers may be prepared in situ with a mirrored fibre so the losses can be monitored as the taper is pulled; this may be used to optimise the ring down time with the taper present in the cavity
  • different taper thickness may be drawn to control the amount of evanescent field present outside the fibre and hence interaction with sensor molecules. Controlling the taper tiiickness can also be used to adjust die dynamic range of the sensor. Changing (increasing) the length of the taper changes (increases) the interaction length for the sensor surface and this can increase the sensitivity of a sensor.
  • the networking potential for the sensors has been established, with cavity lengths of up to 100m or more.
  • a longer wavelength than 639nm, say -SOOnm, may be used for example with a "dirty bomb" sensor surface as the molecule to which the target binds, isoamethyrin, (targets comprise aclinyls such as U0 2 2 ⁇ Pu0 2 1+ , Np0 2 ⁇ ') have an abso ⁇ tion maximum at approximately 830 nm.
  • a functionalising molecule may employ an extended po ⁇ hyrin structure to tune the molecular electronics into this region of the spectrum.
  • Liquid phase abso ⁇ tion spectra at 1.5 ⁇ m (6666 cm" 1 ) tend to be dominated by overtone abso ⁇ tions but gas phase abso ⁇ tion occurs at these wavelengths, in particular CH,, and C0 2 , which may be employed for monitoring submarine environments.
  • the target molecule is required to land on die silica surface before detection, but die collision with the surface is directly proportional to the gas phase concentration.
  • Longer wavelength radiation may also be employed with a suitable chromophore.
  • infrared chromophores tuned at 1 ,5 ⁇ m can be designed to allow the much Sower transmission losses of silica at tiiis wavelength to be exploited.
  • the above described fibre optic-based or more generally waveguide-based CRDS systems may be employed to provide a range of sensor systems. Broadly speaking such sensor systems fall into two classes, intrinsic sensors based ' on losses in a fibre or a change in fibre properties in response to the surrounding environment, and extrinsic sensors (e-CRDS) where something is added to the surface of the fibre that will interact with a target or demonstrate an interaction witii changing properties.
  • intrinsic sensors based ' on losses in a fibre or a change in fibre properties in response to the surrounding environment and extrinsic sensors (e-CRDS) where something is added to the surface of the fibre that will interact with a target or demonstrate an interaction witii changing properties.
  • e-CRDS extrinsic sensors
  • a ring-down detector such as a PMT responsive to a light level within die cavity
  • a signal processor such as a general pu ⁇ ose computer system, programmed in accordance widi the above equations to determine a cavity ring-down time and hence a cavity loss
  • This information may be output directly (either as an output signal from the computer or as data written to a file or provided by a network connection) or fiirther processing may be applied to determine a sensor signal representing, for example, a change in a sensed parameter such as a level of a target species present.
  • one or more intrinsic properties of a fibre used to form the cavity may be determined or, where a portion of a fibre included within the cavity is bent, changes in die cavity loss at the bend due to a change in say pressure, may be very sensitively monitored.
  • the losses in the fibre may be sensitive to an external variable such as temperature or electric or magnetic field; in such arrangements it is often preferable that the fibre is doped to increase die desired sensing response.
  • the light level detecting arrangement is able to resolve one or a group of individual light pulses bouncing to and fro within the cavity (for example using the
  • CRDS techniques include (but are not limited to) sensors to measure stress, strain, temperature, pressure, to act as hydrophone arrays, magnt ⁇ -optic sensors, electro-optic sensors, flow sensors and displacement sensors.
  • a "smart" or functionalised sensor surface may be employed to provide chemical/biological sensors benefiting from the above described CRDS techniques.
  • the preparation of a tapered fibre allows the evanescent wave to explore a region of the medium above the fibre substantially equal to the penetration depth.
  • the penetration depth is of order ⁇ where ⁇ is the wavelength of the radiation and hence for the wavelengths mentioned above the penetration depth will be of order 600-lOOOnm.
  • the techniques have applications for monitoring the condition of a fluid, in particular a fluid critical to the proper performance of a system, such as engine oil, turbine lubricant, gearbox lubrication, and hydraulic fluid, by monitoring the change in the complex refractive index detected by a tapered fibre or other evanescent-wave cavity.
  • a fluid critical to the proper performance of a system such as engine oil, turbine lubricant, gearbox lubrication, and hydraulic fluid
  • Measurements of temperature induced degradation of an engine oil show a clear variation of the visible spectrum with time that is diagnostic of die length of heating. Furthermore measurements of the spectrum of oil from an automotive engine as a function of general use mileage show a transition from abso ⁇ tion to particulate dominated scatter after 750 miles. The degree of scatter in the optical spectrum is diagnostic of the mileage of the car. Measurements using a fibre optic dipstick have shown a response to this change in sifit and in real-time at 110 °C, reporting the results to a control panel. The optical density of die fluid increases 5-fold in less than 100 miles. However control of the optical interaction with the fluid enables high-optical density fluids to be monitored and this is demonstrated for crude oil feed and vislar oil samples.
  • the Jet Oil 2 was not 'new" and worked for over 1000 hours within a small Ce ⁇ trax engine system. Some automotive fluids are dyed to identify their applications and die abso ⁇ tio ⁇ spectra of die dye is clearly visible.
  • the automatic gearbox fluid and synthetic gear oil have strong absorbance around 525 nm and thus are dyed red; specialist hydraulic fluid absorbs in the blue (453 - 476 nm) and die red (600 - 650 nm) and thus is dyed green.
  • IR spectroscopy of tliese fluids shows a characteristic but non-diagnostic absorbance associated with the -CH functionality of these compounds.
  • the visible spectrum evolves with die degradation of the fluid showing contributions from scatter of particulates within the fluid.
  • the extinction of the light by particles within the fluid should follow a 1/ ⁇ 4 law associated with Rayleigh scatter.
  • the evolution of the abso ⁇ tion spectrum of an engine oil with heating has been observed and is presented below. Al! measurements were performed using a 1 cm pathlength cuvette within a standard bench- top UV/Visible spectrometer, but can also be made using the CRDS apparatus described herein.
  • Themial degradation of an automotive lubricant was set up to give a control experiment where there would be no complication due to the production of 'soot' as a result of the exhaust gas bypass (which takes place around the piston rings in a conventional combustion engine),
  • the control experiment involved maintenance of the 'Eurolite' 10W-30 engine oil at a temperature above 100 °C for a long period of time (in excess of 1000 hours) with sampling at known intervals, A 1 litre round bottomed boiling flask was set up on a stirrer hot plate and sand bath with the temperature maintained above 105"C (a common engine sump temperature). As time proceeded, die oil became darker in colour due to oxidation but still maintained its clarity indicating very little particulate formation.
  • Tims Figure 18 shows UV/Visible spectra for Eurolite IOW-30 during temperature degradation; with spectra progression at the following times 30 h, 339.5 h, 533 h, 750 h, 871 h and 1102 h.
  • the variation with temperature can be characterised at two wavelengths which, for operational reasons, are chosen as 637 and 820 n
  • the variation is shown in Figure 19 and it is this output that preferably forms the basis of the optical output of the sensor.
  • Figure 19 shows variation of absorbance at (A) 637 nm and ( «) 820 nm widi thermal degradation.
  • a 1/ ⁇ 4 analysis of these data suggest that the spectra after 1000 hrs of heating are not dominated by scatter.
  • a program of lubricant degradation tests within an automotive engine was set up to assess the potential of die technology to detect real-time oil degradation.
  • the vehicle (a 1990 Mazda 323F, 1.61, 4 cylinder, petrol) engine was flushed with a proprietary flushing oil and a full oii and filter change using 'Eurolite' 10W-30 oil was performed.
  • the fluid was sampled directly from the dipstick port at intervals and UV/Visible spectra measured, The UV/Visible spectra as a function of mileage are shown in Figure 20.
  • Figure 20 shows UV / visible spectra for vehicle oil degradation using Eurolite oil (flushed & clianged) at 38 miles, 178 miles, 358 miles, 505 miles, 758 miles, 1011 miles, 1320 miles, and 1680 miles.
  • Figure 21 shows absorbance vs 1/ ⁇ 4 showing die evolution of scatter-dominated spectra at 38 miles, 178 miles, 308 miles, 505 miles, 758 miles, 1011 miles, 1320 miles and 1680 miles.
  • the slope of the straight line may be used as a measure of the particulate concentration within the fluid, Figure 22.
  • the slope varies rapidly once the particulate nuclealion processes start and this is likely to be the onset of oil performance degradation.
  • Figure 22 shows a plot of straight-line gradient in Figure 21 vs vehicle mileage, showing oil performance degradation.
  • Figure 23 shows variation of absorbance at ( ⁇ ) 637 nm and (B) 820 nm in vehicle test oil.
  • optical density of the oil clearly increases dramatically after only a few miles of travel and this presents a considerable problem for I cm patiilength optical analysis.
  • control of the pathlength sampled by a tapered fibre optic means die rapid increase in optical depth can be monitored directly even when the condition of die oil has become very poor.
  • Figure 24 shows UV / Visible spectra for crude oil and vistar.
  • the spectra are dominated by a strong absorbance below 400 nm associated with the aromatic ring structure of die hydrocarbon species widiir ⁇ the sample.
  • the vistar shows a clear red-shift in the absorbance spectrum (but tiiis may be affected by uniformity of the sample film thictaiess - each affects are substantially eliminated with a fibre-optic dipstick).
  • FIG. 25 shows a fibre optic dipstick (with a 10 pence piece for scale).
  • the optical patii length for the radiation is controlled by the diameter of the taper so that a thicker taper can be pulled for media with high optical density such as the crude oil samples.
  • the dipstick is encased in a stainless steel tube such as a hypodermic needle and placed directly into the oil sample.
  • the losses of the fibre are monitored in real-time, digitised and returned to a PC, for example via a US bus.
  • the output from the dipstick in die engine oils after 0 and 1680 miles is shown in Figure 26.
  • Figure 26 shows variation of-a dipstick response for engine oil (Eurolite IOW-30) for clean oil and after 1680. iles.
  • the samples were maintained at 11 'C, close to an engine sump temperature. There is a clear and diagnostic difference in the response of the dipstick between the two oil samples widi a number of transient features associated with moving between samples.
  • optical characteristics of oil are a diagnostic of its condition with a direct and obvious transition in the spectrum associated with the scatter of radiation due to particulates - Rayleigh scatter.
  • the teclmology we have described allows even highly optically dense liquids to be sampled at elevated temperatures, and is able to provide fluid monitoring on-line and in real time.
  • Figure 28a shows the response (arbitrary units) of a fibre optic dipstick according to an embodiment of the present invention monitoring heating and cooling of Castro! R40 racing oil.
  • Figure 28b shows detail of the transition of Figure 28a. It can be seen that on heating the refractive index of the oil changes and that at around 72°C there is a match to the fibre, coupling light out of the fibre.
  • apparatus which measures a response at between two and four different colours, for example using diode (or other) lasers or LEDs of different wavelengths. Since, as previously mentioned scattering is wavelength dependent (as 1/ ⁇ 4 ) whereas a change in temperature of the monitored fluid is not wavelength dependent in the same way, by measuring a response at, say, three colours particular scattering effects can be distinguished from temperature change effects.
  • the apparatus can be calibrated using a range of fluids with different particulate levels and at different temperatures to provide correction values based on a common (temperature change) response at the different colours.
  • Figure 29a shows a typical asphallene particle.
  • An asphaltene stability test used as a standard in the oil industry. Heptane is added to a toluene or dichloromethane oil dilution and the onset of asphaltene precipitation is observed - asphaltenes are the ⁇ nsoluable part of the oil in heptane,
  • the asphaltene destabilisation test (ADT) is a measure of the carbon content of an oil sample whether from a feed stock or a vistar.
  • the extended carbon- ring structure such as shown in Figure 29a forms a stable suspension in oil and organic solvents such as toluene with high refractive indices but the addition of heptane to the oil or oil dilution results in the destabilisation of the asphaltene suspension and precipitation begins. Adding heptane continuously to a mixture of oil in toluene or dichloromethane, results in a change in the refractive index of the binary mixture which is monitored as a complex refractive index by the ta ⁇ er(s).
  • Example results are shown in Figures 29b and 29c which show, respectively, absorbance (y-axis) against complex refractive index (x-axis) at 980nm (upper line) and 635nm (lower line), and extinction (y-axis) against complex refractive index (CRI) (x-axis) at 980am (right peak) and 635nm (left peak).
  • the CRI at which deslabilisation occurs is a measure of both the particle size and the local solution refractive index (RI) measured as both RI and scatter by the taper, hence giving.a measure of CRI.
  • the CRI is different at the two colours because of the RI properties of the taper - propagation at 980 and 635 nm in the fibre is at different speeds.
  • die 635 light responds to the ADT before the 980 nm,
  • the position and rate of change of the radiation extinction is diagnostic of the CRI of the medium and hence the quality of the oil.
  • the onset in the red is at a lower refractive index from the near infrared as the CRI and fibre refractive indices are different at the two wavelengths.
  • the separation may be employed to calibrate the scale.
  • the two-pass technique is able to detect CRI changes as small as 5 x 10 "4 based on a loss change of 0.1% with die smaller (apers.
  • the e-CRDS detection sensitivity should allow CRI changes as small as 10 " ° to be detected.
  • the exact relationship between loss change and CRI depends upon characteristics of the apparatus, in particular d e size, diameter, minimum length and profile of the taper dipping in the fluid and on whether we are in the guided or coupled propagation regimes. Thus for some applications calibration of an instrument prior to use may be needed.
  • a metal-cased dipstick 900 containing module 901 incorporating a tapered fibre optic sensor surface 902 The outer casing is permeable in the sensor region 904, for example by means of a cage, allowing the sample to enter freely without capillarity and to drain rapidly.
  • the fibre optical pigtailed cable 906 is strained relieved and preferably capable of withstanding significant strain.
  • the entire design is preferably chemically resistant (e.g. hardened) and capable of withstanding a range of operating temperatures.
  • Figure 30b shows a fibre optic cavity for die dipstick of figure 30a.
  • the fibre optic cavity preferably comprises a continuous piece of fibre 906 without splices tapered and mirrored on each end, Ml , M2.
  • the integrity of the fibre cavity, its losses in propagation and taper pulling losses can limit the sensitivity of the technology and should therefore be kept low.
  • the connection efficiency can affect the reproducibility of the results and although a simple FC/PC connector 908 may be sufficient, lower loss connectors are preferable.
  • the module 901 is preferably fabricated from ceramic material such as zirconia or macor. It may be dropped into and secured in the outer dipstick case. This confers flexibility on the design; the core taper module can then easily be incorporated into designs for other applications or markets.
  • the module includes a female 910 at each end of die sensor spaced apart by post(s) 912; it is loaded into a jig and sent for mirror coating, at Ml and M2 for a fibre optic cavity and al Ml only for a two-pass taper.
  • Figure 31b shows die module of figure 35a incorporated into a dipstick.
  • the mirrors are preferably specified to maximise the light content of the cavity but to have sufficient reflectivity to be greater than die propagation losses by 10 percent,
  • the ring-down time in die fibre is controlled by the losses of the cavity: 1) propagation loss at target wavelength; and 2) mirror reflectivities.
  • the reflectivity of the mirror also controls the light intensity within the cavity.
  • the fibre propagation loss specification and the miiTor reflectivity are preferably specified to be consistent.
  • the taper module has Ml and M2 coated and then the fibre may optionally be processed by dip-coating smart surfaces as described above onto the taper for target molecule sensing. The dipstick can then be assembled for testing.

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Abstract

Cette invention concerne, de façon générale, un appareil et des procédés pour surveiller des fluides, en particulier des fluides critiques tels que des lubrifiants, sur la base de techniques à ondes évanescentes. Un module de détection, à utiliser en particulier avec un appareil à réflexion totale interne atténuée (ATIR) pour la détermination optique de l'état d'un fluide, comprend un capteur à ondes évanescentes, un logement de module pour ledit capteur et un connecteur optique prévu pour connecter ce capteur à l'appareil à réflexion totale interne atténuée. De préférence, ledit capteur comporte une fibre optique effilée pourvue d'un miroir à haute réflexivité à une ou aux deux extrémités. Cette invention concerne également un appareil à réflexion totale interne atténuée pour ledit capteur.
EP05718127A 2004-03-15 2005-03-15 Appareil et procedes de surveillance de fluides Withdrawn EP1730493A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GBGB0405821.0A GB0405821D0 (en) 2004-03-15 2004-03-15 Fluid monitoring apparatus and methods
GBGB0415634.5A GB0415634D0 (en) 2004-03-15 2004-07-13 Fluid monitoring apparatus and methods
PCT/GB2005/050035 WO2005088270A2 (fr) 2004-03-15 2005-03-15 Appareil et procedes de surveillance de fluides

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CA2989931C (fr) 2011-01-04 2019-12-03 Exxonmobil Upstream Research Company Methode et appareil pour un systeme dans l'infrarouge moyen (ir moyen) pour la detection en temps reel de petrole dans des suspensions colloidales de sediments et des boues de forage lors des operations de forage, de diagraphie et de production

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GB2171796A (en) * 1985-03-01 1986-09-03 Coal Ind Liquid level sensor
US4945245A (en) * 1986-01-14 1990-07-31 Levin Herman W Evanescent wave background fluorescence/absorbance detection
GB2212261B (en) * 1987-11-06 1991-06-26 Stc Plc Liquid contamination meter
IL91614A (en) * 1989-09-12 1992-07-15 Israel Atomic Energy Comm Method of performing attenuated total reflection spectroscopy
US5239176A (en) * 1991-10-03 1993-08-24 Foster-Miller, Inc. Tapered optical fiber sensing attenuated total reflectance
JPH05172732A (ja) * 1991-12-25 1993-07-09 Hitachi Electron Eng Co Ltd 液体中微粒子検出装置およびその検出方法
EP1195582A1 (fr) * 2000-10-09 2002-04-10 Eidgenössische Technische Hochschule Zürich Capteur à fibres optiques avec un résonateur optique
US6515749B2 (en) * 2001-01-10 2003-02-04 The United States Of America As Represented By The Secretary Of Commerce Sensitive and selective chemical sensor with nanostructured surfaces

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