METHOD AND APPARATUS FOR ANALYSING LIQUID PROPERTIES

Abstract: An apparatus for measuring a property of a liquid comprises at least one guide (10) for electromagnetic radiation, means (20) for directing electromagnetic radiation into the guide, means (16) for providing at least one drop of liquid (15) in contact with the guide at a position where radiation from the guide can enter the drop, and means (22) for deriving a signal which is a function of the interaction of the radiation with the liquid of the drop.

Description: This invention relates to an apparatus and method for measuring a property of a liquid according to the preamble of claims 1 and 12. An apparatus according to the preamble of claim 1 is described in EP-A-0 144 928. This shows a photometer head having two horizontal light guides whose free ends are fixed facing one another a small distance apart in a recess in a block of material, and a third horizontal light guide whose free end is likewise supported in the recess close to and at 90° to the first two. A dispenser needle located above the light guides is used to apply a drop of liquid to the light guides, which is retained by surface tension between and in contact with the free ends. The apparatus is used to measure the optical properties of the liquid drop, by transmitting light into the drop from one of the light guides and detecting it using one or both of the other light guides. In this apparatus, however, the results of the optical measurements are largely determined by the nature of the liquid and the fixed spacing and geometrical arrangement of the light guides, and the size of the drop is not a significant factor in the measurement. Analytical Chemistry, Vol. 56, No. 1, Jan 1984, pages 16A-34A, Am. chem. soc., Baltimore, US; W. R. SEITZ: "Chemical sensors based on fiber optics" discusses the use of optical fibres to detect the change in optical properties of a reagent phase after interaction with an analyte. However, in this article the reagent phase is either coated on a solid support medium which is confined to a region at the end of the optical fibre, or is contained in a vessel in which the fibre is dipped. The technique does not use drops of liquid suspended from the fibre. It is an object of the present invention to provide an apparatus and method of the aforesaid type which can investigate a wide variety of properties of a liquid. According to a first aspect of the present invention an apparatus for measuring a property of a liquid comprises first and second electromagnetic radiation guides, at least the first guide having a downwardly facing free end, first means for directing electromagnetic radiation into the first guide for guidance to the free end thereof, second means for forming at least one drop of liquid in contact with the free end of the first guide, so that the drop of liquid hangs downwardly from the free end, by supplying liquid to flow under gravity down the surface of the first guide or the second guide, and third means for deriving a signal which is a function of the interaction of the radiation with the liquid of the drop by detecting the amplitude of the radiation reflected internally of the drop into the first guide or the second guide. According to a second aspect of the present invention a method for measuring a property of a liquid comprises providing first and second electromagnetic radiation guides, at least the first guide having a downwardly facing free end, directing electromagnetic radiation into the first guide for guidance to the free end thereof, forming at least one drop of liquid in contact with the free end of the first guide, so that the drop of liquid hangs downwardly from the free end, by supplying liquid to flow under gravity down the surface of the first guide or the second guide, and deriving a signal which is a function of the interaction of the radiation with the liquid of the drop by detecting the amplitude of the radiation reflected internally of the drop into the first guide or the second guide. The liquid may be formed as a static drop suspended at the free end of the radiation guide, e.g. a light guide, or it may be a dynamic drop - one of a succession of drops allowed to drip from the end of the guide. Thus one can perform measurements on small volumes, or continuously monitor a liquid in a flow process by bleeding off sample droplets for measurement. The electromagnet radiation may be any such radiation which can be guided along a radiation guide to the drop, and may be continuous, pulsed or otherwise modulated to facilitate the particular analysis being performed. The electromagnetic radiation supplied to the drop along the guide may be combined with other electromagnetic energy or other forms of energy (for example acoustic energy) also supplied to the drop, either applied along the guide, by an external field or by any other method of energising the drop. Such other forms of energy may be used to pump a process in or outside the drop in order to change the conditions relating to the measurement being performed. The temperature or other ambient conditions may be changed in any desired manner to vary the physical conditions for the measurement or as experimental control variables. The signal which is a function of the interaction of the liquid with the radiation may be derived by any device appropriate to the particular analysis, and may comprise a dedicated instrument or system or an instrument or system with general applications. Although the invention is described herein using optical fibres as radiation guides, the latter could be formed by other radiation-guiding means such as capillary tubes or other radiation guides. The invention can be used inter alia to measure a wide range of physical, chemical, electrical, opto-acoustical and other properties of the liquid, either singly or in any combination. These include: 1. Refractive index. 2. Surface tension. 3. Specific gravity. 4. Viscosity (absolute or Kinematic). 5. Turbidity. 6. Absorption or chemical composition. 7. Fluorescence. 8. pH. 9. Conductivity or ion type. 10. Opto-acoustical properties. 11. Adhesion or other mechanical properties. 12. Pressure head. 13. Liquid volume. 14. Any other properties, such as humidity, which may condition the drop and so be indirectly measured. Embodiments of the invention will now be described, by way of example, with reference to the accompanying drawings, in which: Figure 1 is a schematic diagram of an embodiment of an apparatus for performing the invention; Figure 2 is an enlarged view of the downwardly facing free ends of the optical fibres shown in Figure 1; Figure 3 illustrates how the fibres may be securely supported in the position shown in Figure 2 for handling and protection; Figure 4 is a voltage/time diagram of a typical signal produced by the detector circuit of Figure 1 for a transparent liquid with low absorption; Figure 5 is a similar voltage/time diagram for a liquid having significant absorption; Figure 6 shows a form of the apparatus for measuring pH; Figure 7 shows a form of the apparatus for measuring conductivity; and Figures 8 to 9 illustrate alternative light guide and detection arrangements. Referring to Figure 1, first and second radiation guides in the form of optical fibres 10 and 11 are brought close together at their downwardly facing free ends 12 and 13 respectively. The free end of a liquid feed pipe 14 is also brought into close proximity to the ends 12 and 13 of the optical fibres, so that liquid supplied by the latter can form a drop 15, or a succession of drops, at the ends of the fibres. The pipe 14 may be supplied by a syringe type plunger so that a single static drop 15 may be formed, or alternatively the pipe 14 may be fed by a constant head of liquid from a constant head apparatus so that a succession of reproducible drops 15 are fed under gravity to the ends 12 and 13 of the optical fibres and allowed to drip therefrom. These alternatives are schematically shown at 16, and are so well known that no detailed description is thought necessary. Referring to Figure 2, which shows the free ends of the fibes 10 and 11 and the pipe 14 to an enlarged scale, at their free ends 12 and 13 the axes of the fibres 10 and 11 are disposed symmetrically on either side of a vertical plane 17 at an angle of 18° to 22° with respect to one another, and preferably at an angle of 20° as shown. The fibres may be polymethyl methacrylate fibres with an actual fibre core diameter (i.e. excluding the outer casing) of 1mm. The centres of their lower ends are spaced apart by about 2.6 mm as shown. The fibres may be step index fibres. Graded index or monomode fibres may be used although it will be readily understood that in such cases other geometries must be used for optimum working. It will be noted that the pipe 14 is offset from the centre plane 17 between the fibres 10 and 11, so that the liquid flows down the fibre 11 to the ends 12 and 13. In order to securely support the fibres 10 and 11 and the pipe 14 in their relative positions shown in Figure 2, their lower free ends are fixed in epoxy resin 18 in a glass cylinder 19, Figure 3, the lower end of the cylinder extending slightly below the free ends 12 and 13 of the fibres for protection and handling. Referring again to Figure 1, infra-red (IR) or visible radiation in the range 0.3um to 1.3um is supplied by an LED, solid state laser or other radiation source 20 which directs radiation into the end of the optical fibre 10 remote from the drop 15, and such radiation travels along the fibre 10 to the drop 15. The radiation may be continuous, varied in a cyclic manner, or otherwise varied to facilitate a particular measurement. In the present case the radiation source 20 is a "Honeywell Sweet Spot" pulsed LED operated in the range 50Hz to 10KHz by a square wave signal generator 21. The generator 21 provides for stable operation of the LED 20, as well as providing advantages in measurement to be described. Radation from the source 20 travels along the fibre 10 to reach the drop 15 and is reflected internally of the drop 15 to travel up to the second optical fibre 11 to a detector circuit 22 (e.g. an IR detector or light-dependent resistor) where the level of the reflected radiation is measured. For example, the detector 22 may be an infra-red phototransistor configured in a simple potential divider circuit with approximately 9 volts supply. The detected output level is supplied to one or more of a digital voltmeter 23, a storage oscilloscope 24, a chart recorder 25 and a data logging computer 26 with associated printer 27. In the case of a liquid drop held suspended at the ends 12 and 13 of the optical fibres, i.e. a static drop, the level of radiation reflected up on the optical fibre 11, as measured by the digital voltmeter 23, is directly proportional so the refractive index of the liquid, assuming constant drop size and absorbance. It was found in the static mode by experiment that the most reproducible results were obtained by careful tilting of the apparatus out of the vertical plane (i.e. out of the plane of Figure 2) and adjusting the drop size, using the syringe, to obtain a maximum signal. It will be noted that the modulation of the IR source 20 by the generator 21 is not registered by the digital voltmeter 23. Thus, by taking voltmeter reading for liquids of known refractive index and plotting these as a straight line graph of refractive index against the voltmeter reading, the refractive index of any other liquid can be determined from the graph by its voltmeter reading. Other properties of the liquid can also be determined by the static method, for example, absorbance (concentration of dissolved chemicals in a given solvent). Conventionally, absorbance is measured using a cuvette. Light is passed through the cuvette, and the absorbance A is given by A = log(I o /I) where I o is the incident intensity and I is the intensity after passing through the cuvette. Since A = E.c.1 where E = extinction coefficient, c = concentration and l = distance travelled by the light through the cuvette, c (concentration) can be determined from A, since E can be obtained from reference books and 1 is known for the cuvette. However, cuvettes are subject to variations in tolerance, and since a drop 15 can be reproduced almost exactly on the present apparatus, it can therefore effectively constitute an almost ideal cuvette. Thus by plotting A against c for liquids of known concentration, where in this case I o = input level to the drop and I = output level as measured by the digital voltmeter 23, a calibration curve can be obtained. In the case of dynamic drops, Figure 4 showns (for a relatively transparent liquid with low absorption) the voltage/time diagram as each drop falls from the ends of the optical fibres 10 and 11 into the beaker 28. This diagram will be produced by the oscilloscope 24, the chart recorder 25, and the printer 27 of the computer 26. The broad peak 30 corresponds to the growth of the drop, and the final narrow peak 31 is from the ends of the optical fibres. It is to be understood that the diagram used in the present analysis is one where the height of the narrow peak 31 is as close to the height of the broad peak 30 as possible, and this is achieved by tilting the apparatus as previously described until the best results are achieved. From such a diagram, the time period T₂ can be used to determine the refractive index of the liquid using a calibration procedure. Thus, if n (refractive index) is plotted against T₂/V (where V = volume per second) for a number of liquids of known refractive index, a calibration curve is obtained which can be used to determine the refractive index of liquids whose refractive index is not known. Further, the overall cycle period T₁ of the diagram is a function of the surface tension of the liquid and the kinematic viscosity in a gravity feed constant head apparatus. The kinematic viscosity can be determined by a calibration technique from the slope 32, and the surface tension can then be determined from the kinematic viscosity and T₁. The width of the peak 31 at half its amplitude is a measure of the specific gravity of the liquid. Other properties can be determined by processing the data from the trace, either manually from the trace or by suitably programming the computer 26. In this connection, the square wave superimposed on the trace assists in ascertaining the various measuring points required. Differentiation and double differentiation will also help to identify points of interest, and if necessary, any modulation applied by the generator 21 (Figure 1) can be filtered out before this is done. Figure 5 shows how the trace of Figure 4 is modified by absorption. For chemical analysis, an analysis time T A is fixed and the height of the signal S 1 for an absorbing liquid can be measured for different concentrations at one measurement wavelength. A graph of absorbance A = log(S₀/S₁) can be plotted against concentration and from this calibration graph the concentration of an unknown solution can be determined. Alternatively, chemical analysis may be performed by integrating the detected signal, i.e. measuring the area under the trace during the cycle period T 1 . The area will decrease with increasing concentration. The analysis of turbidity can be done in a similar fashion by measuring the decrease in S o with increasingly turbid solutions. If the liquid is flourescent, then an excitation wavelength, such as UV or blue, can be used and the signal measured at the detector 22 which in this case has a monochromatic filter at a longer wavelength, such as orange, placed in front of it. The measurement would be done by the standard fluorescent methods of plotting this signal against the concentration of the fluorescent substance to obtain a calibration graph from which an unknown can be determined. Referring now to Figure 6, the apparatus is shown modified to measure pH. In this case, a pair of large area capacitor plates 40 and 41 are disposed respectively one above and one below the free ends 12 and 13 of the optical fibres, and are separated from the latter by 4 to 5 cm. Each drop 15 becomes charged as it detaches from the ends of the fibres, usually positively under normal atmospheric conditions, which charges up the lower plate 41 of the capacitor. Thus the drops are increasingly repelled, so that T₁ increases until a maximum is reached where the additional charge from each drop equals the leakage from the plate 41. This maximum value of T₁ gives a measure of the pH value of the liquid. An AC or DC voltage supply can be connected across the plates of the capacitor to vary T₁, and these variations can be related to the electrical properties of the liquid. Likewise, the liquid feed could be charged to vary T₁. The pH of the solution can be obtained by placing the drop in an electric field and the drop time, T₁, can be made to vary according to the voltage developed on the capacitor. A voltage will appear by self charging of the capacitor due to the rupture of the drop from the body of supporting liquid, and this will lead to an increase in the drop time, which itself will be a function of the electrical properties of the liquid. The electrical condition of the atmosphere can be monitored via the simple fibre drop analyser by connecting the liquid drop feed to a voltmeter and allowing the induced charge on the drop to continue to carry away charge until the equilibrium situation is obtained when the voltage of the feed equates with the voltage of the potential of the surrounding air. Referring to Figure 7, the conductivity of a liquid can be measured by providing respective electrodes 42 and 43 adjacent the fee ends of each fibre 10 and 11 respectively. Respective conductors 44 and 45 extending from each electrode along the exterior of each fibre in the direction away from the free ends permit connection of the electrodes 42 and 43 to an external electrical circuit comprising, in this case, a constant voltage supply 46 and an ammeter 47. The foregoing describes just some of the many uses of the apparatus described. For example, the apparatus can be used as a rain guage. If the syringe or constant head apparatus 16 is replaced by, for example, a funnel open at the top to rainfall and whose bottom is connected to the pipe 14, the rainfall may be measured by counting the total number and/or frequency of drops. This measurement may be effected, for example, by counting the broad peaks 30 of the trade in the computer 26 or in a separate counter. Also, the time T₁ could be used to monitor pressure head where this was important for control purposes. The dynamic properties of a liquid may be examined with the drop in situ . Thus the drop can be caused to oscillate, while remaining on the ends of the fibres, by the application of varying electromagnetic or electrostatic fields, or by mechanical vibration. In this case the trace would have symmetrical peaks 30, and no peaks 31. The period, amplitude and phase of the oscillations, as measured by the detector 22, would give information regarding the mechanical and/or electrical properties of the liquid depending on the circumstances of the procedure. While the above has shown an arrangement where there are two optical fibres, a source fibre and a receiving fibre, other geometries for the fibre optics or other light guides are possible. Thus, as shown in Figure 8, the source fibre 10 injects light into a drop which couples into two receiving optical fibres 11' and 11" which can detect individually the quantity of radiation coupled to a respective detector at the end of the fibre, or it may be used to compare the difference between the light coupled to produce a differential analyser. In Figure 9, a single bifurcated optical fibre is used, the left hand branch 10 constituting the source, and the right hand branch 11 the receiver. This design produces an increased coupling to the receiving fibre when the fibre is tilted, but one which is asymmetric having a preferential clockwise tilt. A multi-fibre system could also be used to carry many wavelengths into the drop to enable, for example, the chemical analysis of several components simultaneously. The commercial applications of the apparatus are many: 1. A system monitor and controller for an industrial flow process. 2. A water monitor for monitoring a selection of quantities for a reservoir or industrial process. 3. A household water quantity and quality meter. 4. A rain guage to measure the properties of rain water, e.g. acid rain. 5. A laboratory liquid analyser, either dedicated for a specific application or general purpose. 6. A medical or clinical drip analyser. 7. A saccharimeter.

Claims: An apparatus for measuring a property of a liquid, comprising first and second electromagnetic radiation guides (10,11), at least the first guide (10) having a downwardly facing free end (12), first means (20) for directing electromagnetic radiation into the first guide for guidance to the free end thereof, second means (14,16) for forming at least one drop of liquid (15) in contact with the free end of the first guide, so that the drop of liquid hangs downwardly from the free end, by supplying liquid to flow under gravity down the surface of the first guide or the second guide, and third means (22) for deriving a signal which is a function of the interaction of the radiation with the liquid of the drop by detecting the amplitude of the radiation reflected internally of the drop into the first guide (10, Figures 9 and 10) or the second guide (11, Figures 1 to 3). An apparatus according to claim 1, wherein the first and second electromagnetic radiation guides (10,11) have respective downwardly-facing free ends (12,13) closely adjacent to one another with the guides diverging upwards away from the free ends, and the second means (14,16) forms at least one drop of liquid suspended in common from the free ends of both the first and second guides. An apparatus according to Claim 2, wherein at their free ends (12, 13) the axes of the first and second radiation guides (10, 11) are disposed at an angle of between 18° and 22° with respect to one another. An apparatus according to Claim 1, 2 or 3, wherein the first means (20) comprises a light emitting diode. An apparatus according to Claim 1, 2 or 3, wherein the first means (20) comprises a laser. An apparatus according to any preceding claim, further including means (21) to modulate the radiation before it enters the drop. An apparatus according to any preceding claim, wherein the radiation is infra red or visible light in the range 0.3 µm to 1.3 µm. An apparatus according to any preceding claim, wherein the second means (14, 16) comprises means for providing a succession of drops which drip from the free end of the guide. An apparatus according to Claim 8, wherein the second means (16) comprises a constant head apparatus. An apparatus according to any one of Claims 1 to 7, wherein the second means (14, 16) comprises means for providing a single static drop at the free end of the guide. An apparatus according to any preceding claim, wherein the said first guide is an optical fibre. A method for measuring a property of a liquid, comprising providing first and second electromagnetic radiation guides (10,11), at least the first guide (10) having a downwardly facing free end (12), directing electromagnetic radiation into the first guide for guidance to the free end thereof, forming at least one drop of liquid (15) in contact with the free end of the first guide, so that the drop of liquid hangs downwardly from the free end, by supplying liquid to flow under gravity down the surface of the first guide or the second guide, and deriving a signal which is a function of the interaction of the radiation with the liquid of the drop by detecting the amplitude of the radiation reflected internally of the drop into the first guide (10, Figures 9 and 10) or the second guide (11, Figures 1 to 3).

Inventors: MCMILLAN, NORMAN
Applicants: MCMILLAN, NORMAN
Application year: 1988
Main classification: G01N21
IPC codes: G01N21, G01N13, B01L3, G01N35, G01N19, G01N11, G01N9