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Journal of Food Engineering 50 (2001) 117120

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Research Note

Droplet size determination in food emulsions: comparison of ultrasonic and light scattering methods
John N. Coupland *, D. Julian McClements
Department of Food Science, Food Colloids and Biopolymers Laboratory, University of Massachusetts, Amherst, MA 01003, USA Received 26 November 1996; received in revised form 18 September 2000; accepted 4 November 2000

Abstract Ultrasonic velocity and attenuation spectra (15 MHz) were measured for a series of corn-oil-in-water emulsions (20 wt% oil in 2 wt% polyoxyethylene sorbitan monolaurate) with a range of dierent mean droplet diameters (0.51.5 lm). Multiple scattering theory was used to calculate mean diameters for each emulsion from both spectra. Droplet size was also determined using two commercial light scattering instruments. All techniques showed the same general trend of decreased size with increased degree of homogenization but there was only limited quantitative agreement between the various measurement techniques. 2001 Elsevier Science Ltd. All rights reserved.
Keywords: Emulsion; Ultrasound; Particle-sizing; Light-scattering

1. Introduction The colloidal properties of a food are important in determining bulk qualities such as mouthfeel, appearance and rheology (Dickinson & McClements, 1995); this is particularly true for food emulsions. A food emulsion consists of a suspension of small oil droplets in an aqueous continuum (e.g., milk, salad dressings, ice cream mix) or vice versa (e.g., butter, margarine, chocolate). It is therefore important to develop methods to accurately characterize the colloidal properties of food emulsions. The properties of a food emulsion that most contribute to its perceived characteristics are particle size distribution and oil concentration. Direct determination of these parameters is dicult because droplets are often too small to be resolved by conventional light microscopy. Electron microscopy provides adequate resolution, but sample preparation is more disruptive and may generate artifacts. The most commonly used technique for the characterization of food emulsions is laser light scattering, but this is only suitable for very dilute systems / < 0:05 wt% and

* Corresponding author. Present address: Department of Food Science, 103 Borland Laboratory, The Pennsylvania State University, University Park, PA 16802, USA. Tel.: +1-814-865-2636; fax: +1-814863-6132.

dilution of more concentrated emulsions may disrupt delicate aggregates. Nuclear magnetic resonance has been used to characterize concentrated food emulsions but the apparatus is expensive and dicult to operate (Dickinson & McClements, 1995). Measurements of the electrical properties of an emulsion can also be related to its particle size distribution (e.g., Coulter Counter, electroacoustic techniques), but these techniques are often limited to charged particles in a conducting medium. Techniques to extend the ease-of-use and versatility of laser scattering particle sizing instruments to the more concentrated emulsions commonly found in foods would therefore be valuable. An ideal technique would be reliable, rapid, and applicable to real food emulsions under a range of process conditions. It would also be advantageous to make on-line, non-invasive measurements for process control. Ultrasonic sensors have the potential to meet many of these needs. It has been shown that the scattering of ultrasound by an emulsion is related to the size and concentration of the droplets as well as the physicochemical properties of the component phases (McClements, 1996). Various theories exist to predict the ultrasonic properties of an emulsion (Allegra & Hawley, 1971; Harker & Temple, 1988) as a function of droplet size and concentration. By calculating the particle size distribution that generates the best theoretical t to experimental measurements it is possible to characterize an unknown emulsion.

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2. Materials and methods 2.1. Materials Polyoxyethylene sorbitan monolaurate (Tween 20) was obtained from the Sigma Chemical Company (St. Louis, MO). Corn oil was purchased from a local supermarket. 2.2. Sample preparation Surfactant solution was prepared by dissolving 2 wt% Tween 20 in distilled, deionized water. An emulsion was prepared by homogenizing 20 wt% corn oil in surfactant solution using a high speed blender (High Shear Homogenizing Container, Waring Laboratory, New Hartford, CT, 0.55 min), followed by sonication (Braun Sonic-U, 060 s, maximum power) and high pressure valve homogenization (Rannie 8.30R, Wilmington, MA, 0-3 passes, 1001000 bar). Samples were withdrawn at dierent stages of the process to prepare a series of emulsions of dierent size but similar composition. The emulsions were coded 16 corresponding to increased degrees of homogenization. 2.3. Light scattering Two commercial static light scattering instruments (Horiba LA-900, Horiba Instruments Incorporated, Irvine, CA and Malvern Mastersizer Model 3.01, Malvern Instruments, Worcs., UK) were employed to measure the droplet size distributions. A relative refractive index of 1.08 (the ratio of the refractive index of the oil to that of the surrounding aqueous phase) and an absorbance index of 0.01 were used by the Horiba instrument to calculate the droplet size distribution from the measured light intensities; corresponding values were used by the Malvern instrument (presentation code 0405). To prevent multiple scattering eects the emulsions were diluted with distilled water prior to analysis so the droplet concentration was less than 0.02 wt%. All the emulsion size distributions were approximately lognormal and fairly monodisperse; representative examples areP shown P in Fig. 1. The mean diameters (d32 ni di3 = ni di2 , where ni is the number of particles of diameter di ) are reported in Fig. 3. 2.4. Ultrasonic measurements The ultrasonic properties of the emulsions were measured using a frequency scanning pulse echo reectometer (McClements & Fairley, 1992). All measurements were conducted at 19:0 0:1C using a pulsed (10 kHz) electrical spike signal (5900PR, Panametrics, MA), and a 5 MHz broadband ultrasonic transducer (Panametrics, MA). No dilution was required in the ultrasonic

Fig. 1. Particle size distributions of representative emulsions determined by light scattering (Horiba LA-900). Emulsions 2, 4, and 6 (not shown) had similar but slightly smaller distributions to those of 1, 3, and 5, respectively.

method; samples were merely poured into the cell, allowed to thermally equilibrate (ca. 10 min) and measured (<1 s). Repeated measurements of the same emulsion were very reproducible (velocity 0:1 m s1 , attenuation 3%). Stirring the emulsions and repeating the measurements on subsequent days caused no change in the readings.

3. Results and discussion Ultrasonic velocity (c; m s1 ) and attenuation (a; Npm1 ) spectra were measured as a function of frequency (f, MHz) for the emulsions (Fig. 2). Velocity and attenuation both increased with frequency for all emulsions. The ultrasonic properties of 20 wt% monodisperse corn-oil-in-water emulsions were calculated as a function of frequency, and diameter as described by McClements and Coupland (1996) using physicochemical data was taken from the literature (Coupland & McClements, 1998). The mean particle size was estimated from the ultrasonic spectra by iteratively adjusting the diameter, d, to minimize the function P f jcTHEORYf ;d cEXPTf j; where f is the frequency, and cEXPT and cTHEORY are the experimentally measured and theoretically predicted velocity (or attenuation), respectively. The values from velocity and attenuation sizing are shown alongside the light scattering measurements in Fig. 3. All particle sizing methods showed the same expected trend, i.e., a larger degree of homogenization causing a decrease in size, however, there was poor numerical agreement between methods,

J.N. Coupland, D.J. McClements / Journal of Food Engineering 50 (2001) 117120

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Fig. 2. Ultrasonic velocity (a), and attenuation (b), spectra for corn-oil-in-water emulsions. Emulsions are numbered 16 (shown as j, , d, , x, and w, respectively) with increasing degrees of processing.

Fig. 3. Mean droplet diameters determined by various methods. Emulsions are numbered 16 with increasing degrees of processing.

particularly for large droplets. It is particularly surprising to see such poor agreement between the two commercial light scattering instruments. Adequate particle sizing depends on an ultrasonic theory that completely describes the system under investigation. The theory used here works well at low concentrations but above / $ 0:25 the quality of t progressively declines as the multiple scattering eects become more important (McClements, 1988). Although the emulsions used here (/ 0:2) are within the established limits of the theory, it is possible that marginal inaccuracy leads to imprecise sizing. The theory would not be expected to perform well for occulated emulsions where multiple scattering eects would be very

important but as there was no change in the readings on stirring the emulsions or repeating the measurements over several days there is no evidence of emulsion instability in the present case. Another reason for poor predictions from scattering theory would be inaccurate physicochemical data used as constants in the calculations. The data used here (Coupland & McClements, 1998) were generated by averaging multiple data sets from the literature but it is possible that the inherent variability in samples is sucient to make them unreliable. Importantly, all of these reasons could be equally applied to light scattering instruments with the important additional problems of sample disruption by dilution and the much more complex scattering theory used. The ultrasonic particle sizing approach used here can be used to generate a rapid mean diameter for an unknown emulsion, which would be valuable for process control technologies (e.g., an automated control system for a homogenizer). In other circumstances it may be important to calculate a full size distribution by replacing d in the scattering theory with an appropriate distribution function or the sum of several distribution functions. The solution achieved here was based on a single unknown, a full monodisperse distribution would require at least two, a bimodal distribution ve, etc., and it is expected that the additional precision of the t would be unjustied from such a narrow region of the spectrum. In conclusion, it should be noted that a light scattering instrument, whilst enjoying wide acceptance, does not necessarily measure the true particle size. Ultrasonic sizing is a new technique, but there is no reason the measurements should be seen as less reliable. Indeed, ultrasonic sensors may be more appropriate for the optically opaque, concentrated emulsions commonly found

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in foods. Commercial devices are already available to measure the speed of sound in a liquid owing down a pipe at a single frequency (e.g., Cygnus Instruments Dorset, UK or GRC Instruments, Santa Barbara, CA), which is typically related to solute concentration. Results presented here suggest it would be possible to use these sensors and a suitable calibration curve to estimate the mean diameter of an emulsied food without the need for additional hardware. Acknowledgements This material is based on the work supported by the Cooperative State Research, Education, and Extension Service, US Department of Agriculture, under Agreement No. 95-37500-2051. We are grateful to the laboratory of Prof. Stephanie Dungan for making some of the light scattering measurements.

References
Allegra, J. R., & Hawley, S. A. (1971). Attenuation of sound in suspensions and emulsions: theory and experiments. Journal of the Acoustical Society of America, 51, 15451564. Coupland, J. N., & McClements, D. J. (1998). Physical properties of liquid edible oils. Journal of the American Oil Chemists Society, 74, 15591564. Dickinson, E., & McClements, D. J. (1995). Advances in Food Colloids. Glasgow: Blackie & Academic Professional. Harker, A. H., & Temple, J. A. G. (1988). Velocity and attenuation of ultrasound by emulsions. Journal of Physics D, 21, 3847. McClements, D. J., (1988). The use of ultrasonics for characterizing fats and emulsions, Ph.D. dissertation, University of Leeds. McClements, D. J. (1996). Principles of ultrasonic droplet size determination in emulsions. Langmuir, 12, 34543461. McClements, D. J., & Coupland, J. N. (1996). Theory of droplet size distribution measurements in emulsions using ultrasonic spectroscopy. Colloids and Surfaces A, 117, 161170. McClements, D. J., & Fairley, P. (1992). Frequency scanning ultrasonic pulse echo reectometer. Ultrasonics, 30, 405.