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W. JACKSON

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O N T H E MECHANISM O F EMULSIFICATION BY ULTRASONIC WAVES.

BY C. BONDY AND K. SOLLNER.

Received 12th March, 1935.

It has been known since the work of Wood and Loomis,l that ultrasonic waves readily bring about the formation of emulsions in twoliquid systems such as water/oil (the term oil is used for organic liquids not miscible with water) or waterlmercury. The mechanism of this emulsification has been investigated more than once and theoretical explanations have been advanced to account for it.2 But since there is apparently as yet no really satisfactory theory, it seemed worth while to attack the problem again.3 Experimental results, which will be discussed later, led us to the conclusion that there is a fundamental difference in the mechanism leading to the formation of emulsions in water/oil and waterlmercury systems. This paper deals only with the former type of emulsions, mercury emulsions being discussed in the following paper. We further came to the conclusion that a so-called cavitation a t the interface causes emulsification. In the literature on ultrasonics the term cavitation has been used by several writers when merely referring specially to the expulsion of dissolved gases.4 We found it necessary to revert to its original meaning as known in hydrodynamics. Since cavitation and the phenomena correlated with it are not generally known, an introductory note will deal with them.
R. W. Wood and A. L. Loomis, Phil. Mug. (7), 1927. 4, 417. Soc., 1929, 51,1724. E. N. Harvey, Biol. Bull., 1930, 59, 306. N. Marinesco, Compt. rend., 1933, 196, 346: F. Rogowski and K. Sollner, 2. fjhysik. Chem. (A.), 1933, 166, 428. 3 The apparatus used for this work was described by H. Freundlich, F. Rogowski and K. Sollner, Kollch. Beih., 1933, 37, 223 ; see also the same authors, 2. fihysik. Chem. (A.), 1932, 160, 469. W. T. Richards and A. L. Loomis, J . A m . Chem. Soc., 1927,49,3086. F. 0. Schmitt, C. H. Johnson, and A. R. Olson, ibid., 1929, 51, 370. C. H. Johnson, J . Physiol., 1929, 67, 356. E. N. Harvey, loc. cit.2.
1

2W. T. Richards, J . A m . Chem.

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The Formation of Cavities in Liquids.

The word cavitation was introduced (in 1894)when engineers first 5 became acquainted with high speed propellers and steam turbines and. were, thus, obliged to take into account cavitations produced by the rapid rotation. Cavitation can occur as soon as the hydrodynamical pressure in a liquid is reduced t o the vapour pressure. Where this is the case the liquid may disrupt and so be transformed into a two-phase system, containing a fluid and a gaseous phase. This disruption is somewhat analogous t o the disruption of stretched liquids in the experiments of M. Berthelot, Worthington and J. Meyer.8 These will always be referred to as the experiment of Berthelot. Now in these cases the liquid does not disrupt under well-defined conditions ; the phenomenon is largely dependent upon fortuitous circumstances. It is commonly known, for instance, that stretched fluids are very sensitive to feeble shocks and furthermore that it is absolutely essential t o remove all nuclei of gases. Impurities likewise have a marked influence on the tensile strength of liquids. The theoretical values, as calculated from van der Waals equation, have never been realised, the maximum stretches found experimentally amounting only to a few per cent. of those theoretically possible. From this fact it is to be concluded t h a t there are always loose-spaces ( Lockerstellen ) present in a liquid. It is probable t h a t dissolved gases are instrumental in the formation of such loose-spaces. If a liquid, saturated with gas, is stretched, a gas nucleus may be formed which can act as a loose-space and so lead to the disruption of the fluid, provided that it is stretched t o a sufficient extent. Osborne Reynolds described a very impressive experiment demonstrating the formation of cavities in a streaming liquid. Water, allowed to stream through a convergent-divergent tube (see Fig. I), turns opaque at the narrowest constriction (of the FIG.I. tube), if the rate of flow exceeds a certain minimum value. The zone of opacity extends for some millimetres down stream. At the same time a loud hissing noise is heard ; Osborne Reynolds calls this phenomenon t h e boiling of water in an open tube a t ordinary temperature and points out that the hissing sound arises from the same cause (i.e., the collapse of cavities) as the singing of a kettle shortly before the water boils. In both cases, the hissing is caused by the condensation of steam bubbles passing into regions of higher pressure or lower temperature respectively. This experiment of Reynolds can readily be repeated by connecting to the water mains a not too narrow glass tube drawn down in the middle to about I mm. inside diameter.
The possibility of the formation of cavities was discussed by L. Euler as far back as 1754in his Theorie plus compl2te des machines, qui sont mises e n mouvement 9ar la daction de leau. A general account of cavitation is given in H y drpulische Probleme, V. D. I. Verlag, Berlin, 1926,and H. Mueller, Naturwissenschaften, 1928, 16, 423. It is not known, as yet, whether this is also true for absolutely pure and gasfree liquids. M. Berthelot, Ann. Physique et C h i m . ( 3 ) , 1850,30, 232. 8A. M. Worthington, Phil. Trans., 1892, 183A, 355 : Proc. Roy. SOC.,1892, n Fliissigkeiten, A b 50, 423. J. Meyer, Zur Kenntnis des negativen Drucks a handlungen d . Deutsch. Bunsengesellschajt, Nr. 6 (191 I). Osborne Reynolds, Papers on Mechanical and Physical Subjects, Cambridge, 1901, 2, 578.

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C. BONDY AND K. SOLLNER

The cavitation in such a tube is easily understood.

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According to

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( P being the hydrodynamical pressure, p the density and 3 the velocity), the sum of pressure and kinetic energy in a flowing liquid is a constant. Thus the velocity of a liquid passing through a restriction may become so high that the hydrodynamical pressure is reduced to the vapour tension. According to Reynolds the presence of dissolved air exerts a distinct influence. In liquids which, like tap water, contain a sufficient amount of dissolved air, cavitation is always accompanied by partial de-gassing.l @ This may be explained by the fact that minute gas bubbles are formed where the liquid disrupts. These bubbles quickly unite to larger ones, which are not so readily redissolved in regions of higher pressure.

The Collapse of Cavities.

One effect brought about by the collapse of cavities has already been mentioned, viz. the singing of a kettle. Cavities collapse, as soon as the conditions which have led t o their formation cease to exist. In most cases decavitation, so to speak, is due to rising pressure or decreasing temperature in the surrounding liquid. The investigations of Reynolds inspired the late Lord Rayleigh to calculate the pressure developed during the collapse of a spherical cavity." The result of his derivation is given by the equation : P'2 P RoS -I).

-=-(
2B

( P being the pressure at infinity external atmospheric pressure ; Ro the initial radius of the cavity ; / I the coefficient of compressibility ; P ' and I2 being the correlated pressure and radius of the cavity during the collapse .) Calculation shows that pressures of thousands of atmospheres may be developed at the moment when the cavity collapses to a small fraction of its original diameter. Obviously such collapses may cause enormous mechanical effects, high kinetic energies being concentrated a t very small spots. In fact, mechanical engineering and, specially, naval construction are quite familiar with effects of this kind. The mechanical impact due to decavitation produces extremely heavy erosion, which can be distinguished from ordinary corrosion by its different appearances and by the places where it occurs. These places moreover may be predicted from hydrodynamical reasoning. Fottinger,12 who advanced this theory of erosion by cavitation, was able to prove his views by showing that glass, which is chemically inert, is also attacked under corresponding conditions. To give some impression of the amazing effects of cavitation, it may be mentioned that after a destroyer had rushed for several hours a t maximum speed, the armour plates above the propeller were pierced by a hole of the dimensionsof about one square foot. Likewise turbines may be strongly attacked during short runs.13
l o 0. Reynolds describes this phenomenon as follows : " When the hiss is on, the water in,the tube will be somewhat opaque-rather foggy-which fog disappears after the hiss is stopped. This fog is caused by the separation of the air occluded in the water and corresponds exactly to the separation of the air, as when the temperature of the water in the kettle is above 174" F. In the case of the tube the bubbles of air, which separate out, are very much smaller than those in the kettle on account of the greater violence of the action." l1 Lord Rayleigh, Phil. Mag. (6), 19x7, 34, 94. l 2H. Fottinger, Hydraulische Probleme, Zoc. p. 14. l3 Apart from these mechanical effects, chemical effects of cavitation must also be assumed according to H. Fottinger, loc. it.,^ who points out, that owing

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It will be apparent therefore t h a t strong mechanical action may arise from cavitation. Now, we hope to show t h a t intense ultrasonic waves are able t o produce this phenomenon, and furthermore t h a t emulsification under their influence only takes place when there is a chance for the formation, as well as for the collapse, of cavities in the radiated system.

Emulsification Caused by the Collapse of Steam Bubbles.

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We will first prove that the collapse of cavities does indeed represent a most efficient method for dispersing systems of water and oil. Probably the simplest way of producing cavities is to let steam condense in its own liquid phase, as in the case of the singing kettle. If for instance steam from boiling water-or even better, superheated steam -is brought through a nozzle of about I mm. diameter into the interface of water and oil, it condenses with the well-known rattling noise, a highly dispersed emulsion of the O/W type being formed at the same time. When using a soap solution instead of pure water, concentrated emulsions may be produced, provided the experiment is continued long enough. It is evident that this experiment is fundamentally different from all those where an emulsion is obtained when the steam of the disperse phase is introduced into the cool medium of dispersion. The fact that emulsification ceases as soon as the water becomes too warm to allow of sufficiently rapid condensation proves that in our case the collapse of cavities is essential. If air, instead of steam, was blown' into the system, there was no effect whatsoever, in agreement with what was t o be expected. On the contrary the addition of air to the steam reduces its efficiency, since the gas buffers the impact of the collapsing steam bubbles. The method of dispersing organic liquids in water by means of steam turned out to be of quite general value when producing all sorts of emulsions.

Cavitation Caused by Acoustic Waves.

How far may ultrasonic and also acoustic waves give rise to similar effects ? Since sound waves consist of periodical compressions and expansions, it seems quite legitimate to suppose that, provided the energy is sufficiently high, cavities may be formed in a liquid during the expansion phase. Some sixty years ago it was shown that acoustic waves are able to disrupt a fluid. Kundt and Lehmann l4 in their wellknown paper on dust figures and velocities of sound in liquids describe an interesting experiment as follows : " If a tube was completely filled with water which had not been de-gassed, but from which all-even the smallest-bubbles had been removed, and was set into vibration by strongly rubbing the glass rod, air bubbles were formed which grew markedly when the vibration continued. This is able to drive the dissolved air out of the water. The air bubbles disappear again, i.e., the air is absorbed, if the experiments are stopped for 'some time." Even more conclusive is the following observation of Kundt and Lehmann, which was made with a carefully de-gassed fluid : " While the whole system was vibrating vehemently we several times noticed
to locally developed high pressures and temperatures and to the possibility of ballo-electric phenomena the occurrence of oxidations, dissociations, etc., is to be expected. 1 * 4 Kundt-and . 0. Lehmann, Ann. Physik, (Pogg.), 1874, 153, I.

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that the water close to the end of the vibrating rod turned turbid. Since it was entirely free from air, these small bubbles causing the turbidity could only be due to the disruption of the water (Zerreissen in kleine Partien) under the influence of these intense vibrations. This is evidently the same phenomenon as the formation of cavities in Reynolds experiment mentioned above. Kundt and Lehmanns experiments definitely show that acoustic waves may cause cavitation in de-gassed liquids and the expulsion of dissolved gas in gas-containing liquids.

Cavitation Caused by Ultrasonic Waves.

In these circumstances one need not hesitate to assume that intense ultrasonic vibrations may also cause cavitation. The following facts confirm this assumption : I . Hopwood showed that liquids having a low boiling-point may be made to distil a t room temperature when radiated by ultrasonics.15 This agrees with the fact described by Richards and Loomis l6 that ultrasonics lower the boiling-point. 2 . The ability of ultrasonics to evolve gas from gas-containing liquids.l7 3. The fact l8 that liquids stretched according to Berthelots method (ie., liquids cooled down slowly after having been sealed into a tube a t higher temperatures) are disrupted a t a higher temperature, i.e., a t a feebler static stress, when exposed to ultrasonics. The formation of cavities seems to be favoured a t interfaces. This may be correlated to the fact, already emphasised by Wood and Loomis, that ultrasonics are specially active a t interfaces (heat effects, etc.). It can be seen from an experiment of Freundlich and Lindau that cavities tend to appear a t the interface of two liquids. If water, in a Berthelot experiment, is stretched in a tube which also contains mercury, bubbles appear notably a t the interface water/mercury, when the liquid disrupts. When an oil-wetted tube is used, many small bubbles are formed a t the wall on disrupting, whereas only one bubble appears, when the walls of the tube have been wetted with water. The most direct evidence is that, when radiating a two-phase system with ultrasonics the formation of gas bubbles is seen to be most pronounced a t the interface.

Emulsification by Ultrasonics.
When applying these results to the question of emulsification the following assertion has to be proved : emuIsions are only obtained when the conditions are such that cavities are not only produced but also collapse. Their formation alone does nok give rise to any remarkable
15F. L. Hopwood, Nature, 1931, 128, 748. This reminds of the remark of 0. Reynolds quoted above : The boiling of water in an open tube a t ordinary temperature. l6 Richards and Loomis, Zoc. it.^ l 7 It is important to remark that de-gassing does not implicitly require cavitation. Expansions, many times smaller than those necessary for cavitation, are sufficient to cause bubbling in gas-containing fluids. This was first emphasised by R. W. Boyle and G. B. Taylor, Physic. Rev. (z), 1926, 27, 518. This typical la Unpublished experiments of H. Freundlich and G. Lindau. example may be mentioned: de-gassed water, sealed into a tube a t 43 C. disrupts a t 31 c., if cooled down in the usual way, i t already disrupts at 36 c. if radiated by ultrasonics.

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Pressure in

Hg,
00

~ispene Phase (after 3O sec-) in Per Cent.

0'0

60
I00

Od

0.3
1 ' 0

150
200

2-6

300 600

760
II 0 0 I 500
2 300

3 ' 2 4'1 4'4

5'0
4'1
1'2

5'7

4000

studied a t different air pressures, the liquids being always in equilibrium with the gas. The experiments with pressures smaller than atmospheric were done in sealed tubes, the others in open tubes of exactly the same shape, the latter being connected to a compressed air cylinder. When comparing the resulting emulsions of toluene in water, it was evident that a high concentration was not reached until the pressure exceeded a value of about 100 mm. H g ; then, there is a broad range where the Concentration increases with increasing pressure. At still higher pressures, above about 2 atmospheres, e-mulsification de-

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C. BONDY AND K. SdLLNER acts again as a buffer, as was the case in the experiments done with steam.21 There is yet another most important similarity to the dispersing action of steam : emulsification by ultrasonics is much feebler when hot liquids are used. This is quite contrary to the usual experience in the technique of emulsification. It is hard to imagine any other mechanism in which emulsification would be decreased by a rise in temperature. All kinds of stirring effects, as assumed by some previous authors, should be improved a t higher temperatures. Some details as to the formation of cavities by ultrasonic waves also deserve further consideration. When discussing the experiments of Berthelot and Osborne Reynolds, i t was emphasised that the disruption of liquids largely depends upon a ready production of nuclei from dissolved gases. As was to be expected, a similar influence is found with ultrasonics : pairs of liquids such as waterlbenzene or water/nitrobenzene-saturated with gas a t atmospheric pressure-were radiated a t higher hydrostatic pressures.22 The liquids were contained in long tubes (about 25 cm.) of 10 mm. diameter. The amount of the heavier liquid was so small that its height was not more than 2.5 cm., while the lighter liquid practically filled the rest of the tube. Pressure was provided by a compressed-air cylinder. As the pressure increased emulsification rapidly decreased, and no emulsion was obtained when the pressure exceeded a certain value. This value depends on the ultrasonic energy, the temperature and the liquids used. A hydrostatic pressure of several hundred mm. Hg exerted a decisive influence.23 This behaviour was not changed by stabilisers such as soaps or gelatin. Control experiments a t normal pressure always showed strong emulsification. This result may be explained as follows : when hydrostatic pressure is applied, the system is no longer saturated as to the gas, the high column of liquid preventing saturation. Nuclei, which might have been present, are dissolved and conditions are unfavourable for the production of new ones. Consequently no cavities are formed and emulsification is prevented. It is evident that for this reason also, the liquids are not de-gassed under these conditions. Another point needs discussion. The stretching of a liquid in the experiments of Berthelot is different from that caused by ultrasonic waves, in so far as, in the former case, the liquid only undergoes a static stress, whereas ultrasonic cause a stress varying with the period of the vibration, thus' causing strong movement. The latter circumstance evidently favours disruption. This is also borne out by the fact that in Berthelot's experiment the stretched liquid is sensitive towards gentle shocks. We leave undecided the exact mechanism of this process, there being involved the extremely difficult problem of the formation of primary nuclei and their size.
21 This buffering action is perhaps also the reason why a certain time of initiation must elapse before strong emulsification begins. 22 Experiments, mainly biological, with pressures both lower and higher than atmospheric have already been carried out by several authors : F. 0. Schmitt, C . H. Johnson and A. R. Olson, C. H. Johnson, E. N. Harvey, Zoc. ciL4 23 It is well known that cavitation can be prevented by an external pressure. Engineers make use of this fact by applying hydrostatic pressures to pumps and turbines and by designing propellers of ships to operate a t the lowest possible position below the water level.

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The influence of gases is so important and so complicated that it seems advisable to summarise all effects discussed here.

I. Dissolved gases may favour emulsification, because they favour

the formation of nuclei and thus of cavities :

At higher concentrations they may be unfavourable to the production

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of emulsification, because they have a buffering effect upon the collapse of cavities.

11. An (external) hydrostatic pressure may be exerted by gases, and thus they may exert an influence.
Pressure may favour emulsification, because it is necessary for causing an efficient collapse. A higher pressure may be unfavourable to emulsification :I . If equilibrium is attained, because the energy of the ultrasonics applied can only overcome a certain pressure when forming cavities ; 2. If there is an over-pressure, not in equilibrium with the gas in solution :

(a) Because over-pressure disfavours the formation of nuclei a t the interface and therefore the production of cavities ; ( b ) for the same reason as mentioned under 11, I .
Ultrasonics do not reveal any peculiarities as to the ease of emulsification, apart from the fact that emulsification is favoured a t low temperature ; the properties of the emulsions formed are also the same as those of emulsions produced by the usual methods. Ultrasonics, nevertheless represent a very convenient, and efficient, method of preparing protected and unprotected emulsions under clean and reproducible conditions. We are inclined to believe that many of the destructive effects of ultrasonic vibrations upon living cells as described by biologists 24 are based on the same mechanism as emulsification, i.e., on the collapse of cavities.25

Summary.
I. The emulsifying action of ultrasonic waves in oil/water systems is due to cavitztion. Emulsification occurs when cavities collapse. 2. It is shown that cavitation can be caused by sound waves and ultrasonics. 3. The influence of gases upon cavitation is complex. Dissolved gases as nuclei favour the formation of cavities. The hydrostatic pressure exerted by gases is necessary for the collapse of cavities. 4. A new and general method for the preparation of emulsions based on the collapse of cavities was found : the sudden condensation of vapours, such as steam, at the interface of two immiscible liquids rapidly causes strong emulsification.
24 R. W. Wood and A. L. Loomis, Zoc. tit.', C. H. Johnson, doc. it.,^ E. K. Harvey, Zoc. cit.' (which see for further references). 25 It does not seem improbable that the chemical effects of ultrasonic waves can be explained in the same way, as was assumed by H. Fattinger, Zoc. cit.l*, for chemical effects o f cavitation in general.

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Our heartiest thanks are due to Professor H. Freundlich for his very helpful criticism and advice during this work. We are also greatly indebted to Professor F. G. Donnan, F.R.S., for his generous hospitality and his interest.

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F r o m the S i r W i l l i a m Ramsay Laboratories of Inorganic and Physical Chemistry, University College, London.