index difference and d = 12.5pm the separation of the fibre axes.

The fibre modal parameters are U = p(kZn,: - /3, W = p(Bz - k2n~)t2,V 2 = ( U z+ W*) where nc, is the , IS the index of the surrounding index of the cladding, n lthe propagation constant and k the free-space medium, / wavenumber. The slight difference betwen the core and cladding indices is ignored in this calculation. From the plots of zb in Fig. 2 it can be seen that a typical tapered cladding radius of 4,um with A > 0.5% the beatlength (twice the coupling length) will be effectively infinite (>25cm) compared to the length over which the cores are closely spaced (-mm) (see loss Section below). It should be noted that this coupling reduces further as d increases.

maximum reflected power of -40dB provided the cores are aligned.

Conclusions: We have outlined the practical basis and theo-

retical justification for a fibre connector for low-loss coupling from single-core to multicore fibres. The device should have a low insertion loss, with negligible crosstalk and backreflection. Similar low-loss connectors for multicore fibres with a larger number of cores should also be feasible. Work is in progress to demonstrate this device experimentally.
A c k n o w l e d g m e n t s : This work was funded by the Department of Industry, Technology and Commerce of the Australian

Government through Generic Industrial Research and Development Grant number 17011. The sponsorship of the OFTC by OTC limited is acknowledged.
S. B. POOLE Optical Fibre Technology Centre f Sydney University o Sydney NSW 2006, Australia

11th June 1991

J. D. LOVE Optical Sciences Centre Australian National University Canberra ACT 2601, Australia

References
1 2

3
2

3
cladding radius, pm

:oo3/i

4
5
6

Fig. 2 Plots o f beatlength in centimetres against tapered single-core fibre cladding radius in micrometres for various values of relative index diffmence between the cladding and surrounding medium in Fig. I

Fibre cladding index of 1.447 is for silica at 1.3flm

Splicing: We assume that the tapered connector is butted against the twin cores so that the respective axes are aligned. If we ignore offset and tilt losses, then losses arise from the mismatch between the indices and core sizes, and reflection from the splice. The former is negligible if the spot size of the singlemode fibre matches that of one of the cores of the twincore fibre. Given the refractive-indices and core size of the twin-core fibre, the appropriate choice of relative index difference and core size for the singlemode fibres can be accurately quantified within the Gaussian a p p r ~ x i m a t i o n . The ~ splice loss may then be simply expressed as

c., S C H ~ I D E R H., , and SCHONER, G.:Double-coresinglemode optical fibre as directional coupler, Appl. Phys., 1980, 23, pp. 4145 DUNPHY, 1. R., MELTZ, G., ABOU EL LEIL, U. M., and SNITZER, E.: Twin-core fiber-optic sensor for simultaneous temperature and strain measurement. Proc. 3rd Conf. on Optical Fiber Communications, New Orleans, 1984, pp. 5840 FRIBERG, S. R . , SILBERBERG, Y., OLIVER, M. K., ANDREJCO, M. J., SAIFI, M. A., and SMITH, P. w.: Ultrafast all-optical switching in a dualcore fiber non-linear coupler,Appl. Phys. Lett., 1987,51, p. 1135 LUI, F., and cm, P. L.: A twin-core to twin fibre connector. Proc. 13th Australian Conf. on Optical Fibre Technology, Surfers Paradise, 1987, pp. 185-188 SNYDER, A. w., and UIVE, I. D.: Optical waveguide theory (Chapmanand Hall, London, 1983), Chaps. 15 and 18 STEWART, w. J., and WVE,J. U , : Design limitations on tapers and couplers in single mode fibres and devices. Proc. Int. Conf. on Integrated Optica and Optical Communications, Venice, 1985, pp. 559-562
SCHIFFNER,

FIBRE OPTIC p H SENSORS PREPARED BY SOL-GEL IMMOBILISATION TECHNIQUE

Indexing terms: Glass, Opticalfibre

where S , = p1/(2 In and S, = pJ(2 In V2)lizand where @,, Vi), @, V,) apply to the tapered single-core and twin-core fibres, respectively. It can be shown that the splice loss (excluding reflection losses, see below) to a core of any given twin-core fibre may be made arbitrarily small simply by matching the mode field diameters of the connector and twin-core fibre. Similarly, by using different diameter input fibres, low-loss splices can be made to twin-core fibres with nonidentical cores.

An improved fibre optic sensor with extended lifetime for pH measurements has been developed. The sensor is based on the absorbance change of organic indicators immobilised in a silica matrix coated as a thin film onto a porous glass optical fibre by the sol-gel technique. This approach has allowed the development of a highly stable, chemically durable and ruggedised fibre optic pH sensor. The sensor also has potential application in aqueous solutions at high temperatures and in those containing organic solvents.
l n t r o d u c t i o n : Continuous pH measurements remain impor-

Loss: Tapering of the two fibres in the connector introduces loss through coupling of the fundamental mode to higherorder modes propagating in the cladding and the lower-index surrounding medium. A simple criterion gives an approximate upper bound on the local taper angle at each point along the taper for negligible IOSS,~ and simple estimation suggests that a low-loss connector with a taper length a few millimetres should be achievable. Simple plane-wave analysis suggests a
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tant in a number of applications, such as the detection of environmental pollutants, chemical process control and the study of physiological systems. Fibre optic pH sensors can possess significant advantages over conventional, commercially available micro-pH electrodes because the optical signal is not subject to electromagnetic interference. In addition, the measurement can be performed by a single optrode without the secondary reference detector typically required by
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electronically-based devices.' Optical sensors also offer good mechanical flexibility, very small size, low cost, safety and more precise measurement of extreme values of pH.' Most present generation fibre optic chemical sensors use polymers as a substrate to immobilise optically active organic indicators.*~'However, these devices often exhibit significant degradation in the presence of organic solvents, strong acids or strong bases. Moreover, they also are less tolerant of the high temperatures or pressures typically encountered in many industrial and practical applications. The sol-gel technique for immobilising fluorescent chemical indicators in a highly durable matrix has been used as a successful approach by Badini e t a/.' and MacCraith e t aL9 The motivation of the current research was to develop a durable and environmentally ruggedised fibre optic pH sensor which relies on absorbance changes. This report describes the use of the sol-gel technique as a generic method for immobilising absorption type pH indicators in a glass matrix to yield a stable, reversible and highly sensitive pH sensor. T o achieve high resolution and sensitivity, a silica-gel immobilised with pH indicators was coated as thin Mm into a porous silica fibre substrate. A high surface area in the region of inline interaction between the analyte and the indicators causes a significant change in optical signal with p H level. In principle, this technique can be applied to any organic indicator having a molecular size larger than that of the glass former (silica in this case) where it is trapped in the 'cage' formed by the silica ring structure. In this work, bromocresol purple and bromocresol green were employed as pH indicators. The dynamic pH range of these indicators is 3.8-5.4 and 5.2-6.8, respectively."
E x p e r i m e n t : A porous glass fibre was prepared by chemically leaching a small section (Icm) of a phase-separated sodium borosilicate glass fibre prepared using methods previously described." Using a sol-gel technique outlined in Fig. 1, the porous section was coated by silica gel co-immobilised with the two selected indicators in a 1 : 1 molar ratio. The optical glass fibre with the porous sensor section was mounted in an environmental test chamber that allowed access to solutions of different pH values. Fig. 2 provides the schematic diagram of the experimental setup and the basic configuration of the porous fibre sensing element. The sensors were immersed in water prior to installation in the testing chamber for optical measurement, allowing the excess, unbound indicators to be removed.

R e s u l t s : Typical transmission spectra against pH level of the

fibre optic sensor prepared by immobilisation of bromocresol purple and bromocresol green using a sol-gel technique are

,
P O1 4

Fig. 2 Schematic diagram o f experimental setup for porous glass fibre f sensing element optic pH sensor and configuration o

shown In Fig. 3. The sensor was evaluated at pH levels of 3.0, 5.0, 7.0 and 9.0 by injection of buffer solutions (Fisher Scientific Co.) into the testing chamber. The results show good sensitivity a t all pH levels and represent the widest dynamic range that has been reported to date for fibre optic pH sensors. This range could in principle be extended further by combining different pH indicators, as long as the pH sensitive range of the indicators matches appropriately. The most sensitive measurement wavelength of the present sensor is 610nm, which lies between the optimum sensing wavelengths of the two indicators in their aqueous solutions: 616nm for bromocresol green and 588 nm for bromocresol purple, respectively. Fig. 4 illustrates the dynamic response and reversibility of the sensor when exposed to solutions of pH 3 and 8. An excel-

loo

I------

metal alkoxides hydrolysis

mixing w i t h indicators

coating with porous gloss fibre

500

drying organic indicators immobilised 8 n porous glass fibres

660 wavelength ,nm

bo

1210131

pq
Fig. 1 Schematic diagram o f immobilisation o f pH indicators onto porous glassfibres b y sol-gel technique

Fig. 3 Transmission spectra o f porous glass fibre co-immobilised with pH indicators of bromocresol purple and bromocresol green by sol-gel technique at different pH levels pH levels (i) 3-0 (ii) 5-0 (iii) 7.0 (iv) 9.0 Temperature = 25C

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lent response time of only a few seconds has been achieved for this particular sensor by controlling the pore size of the porous glass and optimizing the thickness of the silica gel coating. Exposing the sensor in water for up to several days did not impair the stability or calibration of the indicators during subsequent optical measurements. In addition, the porous fibre optic pH sensor treated by the sol-gel technique can be employed for pH measurement in solutions containing organic solvents, which usually degrade or destroy polymerbased sensors. For example, the pH-sensitive silica gel showed very good stability and sensitivity to pH changes in organic solvents such as benzene, methylene chloride and alcohol. Its potential usefulness and survivability in high-temperature p H measurements was also demonstrated by heating the sensor to 200C for 2 h without a resultant loss in the response of the sensor to p H changes.

lions. Proc. OFS 89, Paris, Springer-Verlag Proceedings in Physics, 1989,44, pp. 4 3 W 2 B. D., RUDDY, v., POTTER, e., OKELLY, B . , and MCGILP, J. 9 MACCRAITH, F.: Optical waveguide sensor using evanescent wave excitation of fluorescent dye in sol-gel glass, Elerrron. Lerr., 1991, 27, (14L pp.
1247-1248 10

KING, E . J : Qualitative analysis and electrolytic solutions (Harcourt, Brace & World, Inc., New York, 1978), p. 285 1 1 ZHOU, Q., SHAHRIARI. M. R., KRITZ, U,, and SIGEL, G. H.: Porous fiber-optic sensor for high-sensitivity humidity measurements, Anal. Chem., 1988.60, pp. 2317-2320

TECHNIQUE OF MEASURING SOUND VELOCITY I N LIQUID A N D SOLID MATERIALS USING FREQUENCY MULTIPLICATION TYPE ULTRASONIC CORRELATION SYSTEM
Indexing term: Measurement A technique of measuring sound velocity using the frequency

multiplication type ultrasonic correlation system is described. Experiments with liquid and solid samples have been made at a frequency of 5MHz. The results obtained for the liquid samples are in good agreement with those in the literature within 0.02%, whereas for solid samples, an agreement within 0-1/, of the results by the PE0 method has been attained.
time,s

pc;
Introduction I The measurement of sound velocity provides a

Fig. 4 Response curve for porous glass fibre co-immobilised with pH indicators of bromocresol purple and bromocresol yreen by sol-gel thin film coating Temperature = 25C
Conclusion: We report the development of a new fibre optic pH sensor that uses a porous glass optical fibre and a sol-gel immobilisation technique. The sensor is stable and reversible, with a wide dynamic range (pH 3-9) and short response time. Advantages of this new type of sensor over existing polymerbased sensors include its potential application for p H measurement in solutions containing organic solvents and in high-temperature environments. J. Y. DING M. R. SHAHRIARI G. H. SIGEL, JUN. Fiber Optic Materials Research Program Rutgers-The State Uniuersity of New Jersey Piscataway, N J 08854, U S A 16th July 1991

clue to the physical properties of materials such as the mechanism of absorption, structure and relaxation. Recently, the reflection type ultrasonic correlation system for use in VjUHF ranges and at 5 MHz2 were developed for the accurate measurement of sound velocity. In this Letter a novel ultrasonic correlation system introducing a frequency multiplication method for velocity measurements at 5 MHz is described. The measurement principle and the equipment used are detailed and the effectiveness of the system is demonstrated through the experiments.
Principle and apparutus: Fig. 1 is a schematic diagram of the

system. Burst pulse, generated by the continuous wave generator (CW gen), frequency divider (f div) and gate circuit (gate),
micrometer

References
1 WANG, G.,
YU, D., and SUN, Y . . pH-ISFET used as a detector in a flow injection titration system, Sens. Actuators, 1989, 19, pp.

41-52 2

5
6
7

PETERSON, J. I., GOLDSTEIN, s. R., FITZGERALD, R. v., and BUCKHOLD, D K.: Fiber optic pH probe for physiological use, Anal. Chem., 1980,52, pp 866869 EDMONDS, I. E., FLATTERS, N. J., JONFS, c. F., and MILLER, J . N.: Determination of pH with acid-base indicators. implications for optical fiber probes, Talanta, 1988, 35, pp. 103-107 MUNKHOLM, c., WALT, 0.R., MILANOVICH, F. P., and KLAINER, s. M. Polymer modification of fiber optical chemical sensors as a method of enhancing fluorescence signal for pH measurement, Anal Chem., 1986.58, pp. 1427-1430 SERRA, G., SCHIRONE, A. , and BONIFORTI, : R Fiber-optic pH sensor for seawater monitoring using a single dye, Analytica Chimica Acta., 1990, 232, pp. 337-344 CRUZMORENO, M., JIMENEZ, M., CONDE, C . P., and C A M A R A , C . : Analytical performance of an optical pH sensor for acid-base titration, Analytica Chimica Acta., 1990, 230, pp. 35-40 ELAYLOCK, M. E : Method of producing fiber optic chemical sensors incorporating photocrosslinked polymer gels. US Patent
4842783, 1989

multi

trigger signal

SiH
digital

voltmeter

8 BADINI, G.E.,GRATTAN, K. I. v., PALMER, A. w., and TSEUNG, A C. c.: Development of pH sensitive substrates for optical sensor applica-

Fig. 1 Schematic diagram of reflemon type ultrasonic correlation system introducing frequency multiplication method

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