The effect of ultrasonic vibrations crystallization processes

Stanley L. Hem*

on

Ultrasound has long been used during a phase transition to produce small, uniform crystals. Many theories have been suggested to explain the action of ultrasound in this application. This paper reviews the proposed mechanisms of ultrasonic crystallization.

Ultrasound applied during a phase transition is effective in reducing the particle size of a large number of substances, and has been widely used for producing small, uniform crystals. The insonation of solidifying metals produces ingots that are fine-grained, dense, and homogeneous.l The use of ultrasonic energy during the crystallization of supercooled melts results in an increased rate of crystallization, smaller crystals,2 and an increased number of nuclei.3 The ultrasonic treatment of supersaturated solutions produces crystals that have several advantages over particles produced by other methods of size reduction: they are smaller, more uniform, and do not carry an electrostatic charge.4 Unfortunately, the mechanism by which ultrasonic waves effect a phase transition is not understood. Optimum results would be possible if a clear understanding were available of their action during crystallization. The object of this paper is to review the proposed mechanisms. PROPOSED MECHANISMS Cavitation Virtually all theories agree that the effect of ultrasonic waves during crystallization is not due to the sound waves directly but to the effects caused by cavitation. The gas bubble formed in the rarefaction phase of the wave is known to collapse under the action of the next compression phase.596 Thus a cavitation bubble would experience a life of 50~s at a frequency of 2OkHz. Earlier work had concluded that cavitation bubbles grew by diffusion during several hundred cycles and would therefore have been present for a longer period.7 The presence of a cavitation bubble is important, since several workers believe that these sites act as nucleation centres. The violent collapse of the cavitation bubble causes localized high pressure areas (103atm) in the liquid. These high pressures are effective only for a distance equal to the radius of the collapsing bubble,8 but may be strong enough to increase the melting point of a liquid and thus initiate nucleation. Agitation The simplest mechanism suggested to explain the reduction in particle size is that of agitation. Abramovg studied the effect of ultrasound on supercooled molten metals in an attempt to understand the increased formation of crystallization centres. He found that antimony, supercooled by 15C, stayed liquid for 2Omin unless ultrasound was applied, * Senior Research Pharmacist, Wyeth Laboratories, Pennsylvania. 202 ULTRASONICS October 1967 Radnor,

when crystallization occurred in 1-2s. Since ordinary shaking or stirring with a prewarmed porcelain rod did not induce crystallization, he concluded that ultrasound did not act simply through agitation. Ultrasound applied during the precipitation of thorium oxalate reduced the particle size and increased the uniformity of the crystals.1 The results were superior to those obtained with various forms of agitation. The crystallization of aluminum hydroxide that occurs during the decomposition of aluminate solutions was accelerated by ultrasound, but was little affected by agitation alone.11 Cooling effect Several authors have hypothesized that ultrasonic crystalization occurs because of cooling effects. After observing that the crystallization velocity of benzophenone is increased by ultrasonic treatment, Guntheri concluded that the localized removal of heat at phase boundaries results in slight supercooling, which, together with sonophoretic movement of small crystals ahead of the crystallization front, causes an accelerated crystallization rate. During the growth of a cavitation bubble, evaporation from the surface of the cavity occurs, filling the cavity with vapour and cooling the surface. It has been suggested that this cooling is sufficient to cause nucleation. The surface temperature of a bubble depends on the rate and duration of evaporation. Hunt and Jacksonr3 calculated the cooling effect for cavitation bubbles that expand rapidly. Figure 1 is a plot of the calculated temperature change for cavitation bubbles of varying size. The calculated cooling is less than 1C for bubbles up to 0. lmm in diameter - a temperature change too small to produce nucleati.on. Also, as Hickling14 has pointed out, the total possible cooling is limited by the increasing vapour pressure within the bubble. Increased melting point Hunt and Jackson,ia by studying isolated cavitation events in a pure liquid sealed in a glass U-tube, were able to slow the formation and collapse of cavitation bubbles and thereby to observe that, in a supercooled liquid, nucleation occurs during the collapse of the bubble and not during its expansion. They found that both benzene, which expands on melting, and water, which contracts, exhibited this characteristic, but were not able to explain satisfactorily why these unlike materials behaved similarly. Using a pressure change of 103atm and the Clapeyron equation, dP _=dt AHv TAV

The free energy of heterogeneous nucleation, AGhet, can be related to the free energy of homogeneous nucleation, AGhom. An equation15 has been derived for the nucleation of vapour drops on surfaces in terms of the contact angle 0: *et = AGhom(2 + CO6@(l - cos 612 4

It can be seen from this equation that &het will alWayS be smaller than AGhom: therefore, if heterogeneous nucleation is possible, it should induce crystallization more readily than would homogeneous nucleation.

lolo6

1cP

1e 1cP 1tP 16 Cavity radiuskm]

10

Bates and Weinstein consider that the size of the critical nuoleus may be decreased by ultrasound because of increased pressure at certain points in the liquid. The smaller critical nucleus, in addition to the disruption of the solid-liquid interface, would result in grain refinement. Van Hook,ls in his work on the ultrasonic crystallization of sucrose, proposed both a heterogeneous and a homogeneous mechanism. He statedthat ultrasoundactedin a homogeneous way to generate crystal nuclei within the small volume of cavitation loci. The crystal nuclei were then dispersed and grew to visible size. Insonated sucrose solutions produced 10s nuclei/ml, control solutions only 105 nuclei/ml. Van Hook also reported that insonation of a sterile, isolated solution gave a poor or no improvement in grain. This observation suggests that he may have been dealing with a solution that had no particles present to act as nuclei. The behaviour is in accord with a heterogeneous mechanism rather than the spontaneous generation of nuclei by the ultrasonic field. The author,lg while investigating the crystallization of hydrocortisone from ethanol, found that ultrasound acts on nuclei which form normally. In this work, the number of heterogeneous particles in unisonated samples was controlled by filtering saturated solutions through either a 0.45~ membrane filter or Whatman No 42 filter paper. The particle size distribution of each solution was then determined by Coulter counter analysis. Table 1 summarizes the particle analysis of saturated solutions prior to insonation. After saturation at 65C, the crystallization temperature was found to depend on the number of heterogeneous particles present. The decrease in crystallization temperature as the number of particles in the saturated solution was reduced is in agreement with the heterogeneous nucleation theory. Table 2 shows that ultrasonic treatment

Fig

1 The loss of temperature which occurs for different sizes of cavity

they calculated that the melting temperature of benzene should increase by 28C in the vicinity of a collapsing cavity. The sign of dP/dt would be positive for benzene, as for all materials that expand on melting. Hunt and Jackson believe that a sufficient change in melting point occurs to initiate nucleation in any supercooled pure liquid. They hypothesize that the difference in melting characteristics of benzene and water does not affect nucleation because benzene may nucleate in the positive pressure period immediately after the collapse of the cavity, while water does so during the subsequent negative pressure period. But if this negative pressure (which must follow any period of high pressure) has such an effect on water, why do the benzene nuclei not melt during this phase? The increased melting point theory, which is supported by Hickling, l4 applies only to pure liquids and does not adequately explain the ultrasonic crystallization of materials such as water and bismuth,9 in which the freezing points are depressed with increased pressure. Heterogeneous nucleation Several authors have concluded that ultrasonic crystallization results from homogeneous nucleation, while others have postulated heterogeneous mechanisms. In supersaturated solutions there is continual formation and dissolution of molecular clusters of solute. The Becker-Doring theory and the Christiansen-Nielsen theory view this as due to a series of bimolecular collisions.l5* 1s The clusters may continue to grow by collision or may shrink due to the loss of individual molecules. At the point where the tendency to dissociate is balanced by the tendency to grow (in order to decrease the surface-free energy), the cluster is termed a critical nucleus. The size of the critical nucleus is unknown, but it is thought to be several hundred mplecules for most solids. 1% 17 The tendency to grow is dominant once a cluster has become larger than the critical nucleus. Nucleation, followed by crystal growth, then proceeds. The basis of most homogeneous nucleation theories may be represented as follows:15 A A, +A-=A, +A=A, A= A, Critical Cluster Nucleation Crystal Growth

Table 1 Coulter counter analysis of saturated solutions after filtration Number of particles larger than D in 0.5ml of saturated solution after indicated treatment D (diameter) Unfiltered supernatant 78,000 28,000 12,000 3,700 2,000 800 300 140 100 40 21 8 Whatman No. 42 filter paper 31,000 7,500 2,500 700 350 150 100 35 30 22 14 4 0.45~ membrane filter 250 62 18 5 203

[WI
1.25 2.00 3.00 5.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00

Ax-1+

Ax + A +A,+, A x+1 + A -+ A,+,

The activation energy barrier to nucleation may be reduced by the catalytic effect of foreign particles in the solution. The presence of these particles, which act as substrates for the critical nucleus, permits nucleation to occur more readily. Nucleation which occurs on particles present in the solution is termed heterogeneous nucleation.

ULTRASONICS October 1967

at two cavitation intensities did not change the crystallization temperature of the solutions. Insonation time of 5s to lmin gave similar size distributions. Ultrasound effects crystallization during the early nucleation step rather than during the later growth phase, and is believed to act by eroding, shattering, or in some way disrupting nuclei that form in a normal manner. This effect increases the number of crystal nuclei and results in reduced crystal size. Table 2 Occurrence of crystallization in filtered solutions 0.45~ membrane filter

crystallization centres as a result of ultrasonic scattering of the microcrystals forming in the melt. Polotskiiao presented photographic evidence to support the belief that ultrasound acts by dispersing nuclei. He observed that cavitation at the crystal-melt interface of supercooled, chemically pure salol caused strong dispersion of the newly formed crystals. In a later work,31 he photographed the shattering of acicular crystallites of salol and a naphthalenecamphor eutectic shortly after their formation. This did not occur in the absence of ultrasound. Van Hook32 found that the number of crystallization centres increases with the duration of insonation in an autocatalytic way. He suggested that, because of the limiting effect of prolonged treatment, ultrasound must act chiefly on newly formed crystallites. There is some confusion regarding the size of the crystallites that are dispersed by ultrasound. The effect on an aluminium-manganese alloy has been observed to vary depending on the stage during which the ultrasound is applied.33 Best results are obtained with insonation during the primary crystallization: treatment in the later phase has little effect on grain size. Kapustin,34 however, believed that ultrasonics can bring about the formation of new crystallization centres only when a crystal reaches a certain size: if it acts on critical clusters or nuclei and reduces them to subcritical clusters, ultrasonic crystallization can not occur. In a study of supersaturated aluminium fluoride solutions, it was concluded that only the rate and not the crystallization process is altered by the action of ultrasound.35 Teuminas explained that the action of ultrasound is due to the formation of cavitation processes, which disintegrate the growing crystals, to radiation pressure, which transports the crystal fragments to the body of the melt where they form fresh crystallization centres, and to agitation, which results in temperature equalization throughout the entire volume, thereby assisting bulk crystallization. Babikovs7 in general concurred with Teumin, but also pointed out the possible effect of ultrasound on the origination of primary crystallization centres. Mechanical vibrations Kavalyunaitea* stated that the effect of ultrasound is due to the acoustic wind and to the mechanical vibrations of the crystal. This hypothesis is based on the observation that the growth rate of a crystal in an ultrasonic field increases with the intensity of the ultrasound. Homogeneous nucleation Several workers feel that ultrasound acts in a homogeneous manner by generating crystal nuclei. Chormonov, 3g upon investigating the effect of an ultrasonic field on supersaturated solutions of thymol, Rochelle salt, salol, and hyposulphite, concluded that ultrasound significantly accelerates the process of spontaneous crystallization and plays an essential role during the formation of nuclei. Danilov40 claimed that insonation accelerated the production of the first crystallization centre in o -chloronitrobenzene when the melt was near the boundary of metastability. Because the compound was purified by repeated recrystallization and showed no signs of impurity activation effects it was concluded that the nuclei arose spontaneously. Kapustin4r also stated that ultrasound initiates the production of the first crystallization centre. This was based on the action of ultrasound on o -chloronitrobenzene. The compound was heated to lOOC, slowly cooled, and insonated. Ultrasound did not affect the production of the first crystallization centre above 20C but caused spontaneous crystallization to occur at 18-20C. Kapustin explained that a system which is macroscopically homogeneous has a certain micro-inhomogeneity which varies little with time. Thus ultrasound could bring about a redistribution of the micronuclei and alter the probability of spontaneous production of crystals. A triple mechanism has been proposed by Murza-Mucha for the insonation of solidifying metals. In this theory, the increase in the number of crystal nuclei is due to the

Unfiltered Treatment tempera- No ture [Cl US 55 50 45 40 35 30 + + + + + +

Whatman No. 42 filter paper

RCI 1 + + + + + +

10 + + + + + +

No US

RCI 1

10

No US

RCI 1

10

+ + +

+ + +

+ + + + + + + + +

US = ultrasound + = occurrence

RCI = relative cavitation intensity of crystallization

Kapustinzp 21 reported that ultrasound affects crystallization in a heterogeneous manner by producing many fresh nuclei from any seed. A small crystal of thymol fixed in a wooden holder was immersed in water in a tube. Liquid thymol was carefully layered on the water. No crystals arose on standing but crystallization began when ultrasound was applied at the bottom of the tube. He observed the field to break off minute particles from the seed, which were carried to the interface. Identical tests without seed did not initiate crystallization. Sokolova2 also found that insonation produced more rapid crystallization when solutions of beet sugar and zinc sulphate were seeded prior to insonation. Kapustinzs studied the process of relieving supersaturation in an aqueous solution of potassium alum by ultrasonic action. In this case, similar results were obtained with and without a primer in the solution. Friction An experiment24t2s testing the effects of frequency and intensity on supercooled Woods metal led to the conclusion that friction between the solid and the melt is responsible for the reduction in grain size. Ultrasonic frequencies of 9kHz and 285kHz were used. It was found that the two frequencies gave the same result at any given intensity. In a study26 comparing the effect of stirring and insonation on an aluminate solution, it was concluded that the results observed from insonation were due to friction forces at the solution-crystal boundary. Dispersion of crystals Berlagaa7~as reported that ultrasound increased the number of nuclei in betol and consequently caused a great increase in the crystallization rate. He explained that acceleration by assuming that the field separates fresh nuclei from ones formed previously. This dispersion theory was used to explain the effect of ultrasound on the crystallization of salol, naphthalene, and camphor.2 It is believed, however, that the nuclei that Berlaga referred to are not nuclei in the sense of critical nuclei but rather are small crystals or crystallites, such as have been described by several other authors.2g-32 Kudryavtsev, 2 g who supported the dispersion theory, stated that the increased crystallization rate in the ultrasonic crystallization of metals is due to an increased number of 204 ULTRASONICS October 1967

coalescence of phase fluctuations (sub nuclei). At the same time, the resultant mechanical forces tend to disintegrate the growing crystals. Thirdly, the ultrasonic waves cause grain refinement. Brown43 stated that the effect of ultrasonic irradiation on the crystallization process is similar to its effect on precipitation, that is the cavitation produced offers nucleation centres for the crystals to initially form around, and it also breaks up any large crystals. Mazhul,44 who studied the electric fields associated with the boundaries of cavitation, concluded that they cannot explain nucleation in the melt and that, instead, the sites of cavitation themselves act directly as nuclei. He added that cavitation cannot be taken as the sole cause of the effects, for weak fields which do not cause cavitation still increase the nucleation rate. Later, after experiments on betol under varying external pressures, Mazhu14s stated that cavitational ruptures may themselves become crystallization centres. Fincher4s noted that ultrasound aided the crystallization of sulphisoxazole by supplying cavitation bubbles, which acted as the site of nucleation. The proponents of the homogeneous nucleation theory have not been able to advance the mechanism past the ill defined spontaneous crystallization or explain how a cavitation bubble acts as a site of nucleation. It is extremely difficult to separate homogeneous nucleation from heterogeneous nucleation. Techniques such as recrystallization, as used by Danilov,40 do not usually produce nuclei-free solutions. The droplet technique described by Melia and Moffittdr allows the preparation of portions of solutions which are completely free of foreign bodies. The solution to be studied is dispersed into a large number of small, isolated droplets which are suspended in oil or paraffin. The number of droplets is made to greatly exceed the number of foreign nuclei. By the statistical analysis of many drops it is possible to isolate homogeneous nucleation. Before the claim that ultrasonic crystallization is a homogeneous process can be accepted, it will be necessary to eliminate the possibility of heterogeneous nucleation. ULTRASONIC APPARATUS FOR CRYSTALLIZATION Many types of ultrasonic generators are useful for crystallization experiments. The author has found the Sonifier, Model S-125, to be suitable for laboratory scale experiments. It is a high-intensity piezoelectric type source with a frequency of 20kHz. For large scale processes, a jet-edge generator operating at 22kHz (such as the Rapisonic MarkV) has given good results. Virtually any generator that produces cavitation in the solvent can be used. Since all theories relate reduced crystal size to cavitation, the frequency should be chosen to give maximum cavitation effects. Kapustind8 studied the ultrasonic crystallization of thymol at a fixed intensity of 0.25W/cma and at frequencies of SOkHz,717, 5 760, and 9 6OOkHz. The maximum grain refinement occurred at a frequency of 3OkHz. Above a frequency of 717kHz grain refinement decreased until no refinement was observed at 9 6OOkHz. Badasarovas reported that frequencies greater than 3OkHz had little effect on the grain size of metals. Cavitation in liquids becomes less severe at increased frequencies, and the frequency selected should give the strongest possible cavitation effects. Sufficient power should be available to induce cavitation. Van Hook32 observed that at 8kHz a great reduction in crystal size occurred when the power level reached the cavitation threshold of 2W/cm2. Further increase in power level to 4W/cm2 gave little improvement in crystal size. Insonation below the cavitation threshold had little effect. The authorI obtained similar particle size distributions in the ultrasonic crystallization of hydrocortisone using a frequency of 2OkHz at several cavitation intensities. Weisslers method, 50 based on the sonochemical liberation of chlorine from carbon tetrachloride was used to measure the relative cavitation intensity. Ortho-tolidine was reacted with the liberated chlorine and yielded a yellow colour suitable for calorimetry. Various cavitation intensities were defined by plotting the absorbance of 436~ against time. The slopes of the straight lines given in Fig 2 are in the ratio of 1:2:10 and were used to designate a particular intensity.

The line voltage and the power level setting were used to vary the cavitation intensity. Table 3 lists the geometric mean, Mg, and the geometric standard deviation, og, for samples insonated for 6Os, 15s and 5s at relative cavitation intensities of 1, 2, and 10. As can be seen, increased cavitation intensities and increased insonation time did not further reduce the crystal size distribution. The prime requirement for ultrasonic crystallization is a generator that can produce cavitation in the system.

Table 3 Particle size distributions obtained at 25C Relative cavitation intensity Insonation time [s] 60 15 5 E, 4.7 4.4 4.6 gg 2.5 2.4 2.3 2 Mg 4.6 4.5 4.6 ug 2.3 2.4 2.3 10 Mg 4.6 4.3 4.3 Dg 2.3 2.4 2.4

Control Mg = 9.2, ug = 2.7; Mg and ug in rnp

3.0r

22 20
1.8 1.6
t

0 1.4 E x 1.2 P 2 1.0 i 0.8 t A

Insonation time [sets]

Fig 2 Calibration curves for measuring relative cavitation intensity

CONCLUSIONS The literature on ultrasonic crystallization contains a great deal of conflicting data, which is undoubtedly, in part, because of the lack of understanding of the crystallization process itself. In the study of homogeneous crystallization, methods must be used that will eliminate any possibility of heterogeneous nucleaction, which, if present, will cause crystallization to occur more readily than will homogeneous nucleation. In most instances, heterogeneous nucleation induced crystallization will be complete before homogeneous mechanisms have begun. ULTRASONICS October 1967 205

In examining the effects of cavitation, techniques must be developed that monitor the cavitation intensity at the reaction site. The sonochemical measurement of relative cavitation intensity51 makes it possible to calibrate an instrument and evaluate its day-to-day operation. These factors must be controlled to produce meaningful results. At present, the evidence in support of a heterogeneous mechanism seems strongest. This theory can be applied to metals, melts, and supersaturated solutions. Cavitation pressures could not alter the melting point in supersaturated solutions, but experimental data are available suggesting that cavitation sites act as nuclei in supercooled liquids and that cavitation pressures are important in initiating crystallization. A lack of understanding of ultrasonic crystallization has undoubtedly reduced the efficiency and therefore the industrial applications of this technique. It is hoped that the present review will help to stimulate further interest in the field.

11

Tikhonov, V. N. and Kuenetsov, S. I., Tsvetnye Metally 38, 52 (1965) in Chemical Abstracts, 63,12386f (1965) Gunther, P., Zeil, W., Goring, W. and Bornhardt, J. F., Zeitschrift fiir anorganische und allgemeine Chemie, 285,191 (1956) in Chemical Abstracts, 50,15157c (1956) Hunt, J. D. and Jackson, K. A., Nucleation of solid in an undercooled liquid by cavitation, Journal of Applied Physics, 37, 254 (1966) Hickling, R., Nature, 206,915 (1965) Walton, A. G.,Science, 148, 601 (1965) Laitinen, H. A., Chemical analysis, McGraw-Hill, New York, 127-33 (1960) Van Hook, A., Crystallization theory and practice, Reinhold, New York, 113 (1961) Van Hook, A., Radle, W. F., Bujake, J. E. and Casazza, J. J., Journal of the American Society of Sugar Beet Technologists, 9,590 (1957) Hem, S. L., Skauen, D. M. and Beal, H. M., Journal of Pharmaceutical Sciences, 58,229 (1967) Kapustin, A. P., The effects of ultrasound on the kinetics of crystallization, Consultants Bureau, New York, 41 (1963) Ibid, 23 Sokolov, S. Ya., Technical Physics of the USSR, 3,176 (1936) in Kapustin, A. P., The effects of ultrasound on the kinetics of crystallization, Consultants Bureau, New York, 14 (1963) Kapustin, A. P. and Kovalynuaite, V. E., Kristallografiya, 7, 613 (1962) in Ultrasonics 1, Abstract 21 (1963) Schmid, G. and Roll, A., Zeitschrift fur Elektrochemie, 45, 769 (1939) in Kapustin, A. P., The effects of ultrasound on the kinetics of crystallization, Consultants Bureau, New York, 16 (1963) Ibid, 46, 653 (1940) Derevyankin, V. A., Tikhonov, V.N. and Kusnetsov, S. I. Mekhanizm i Kinetika Kristallizatsii, Nauchnyi Soviet Akademii Nauk Belorusskoi SRR pe Fizika Tverdogo Tela, 274 (1964) in Chemical Abstracts, 62,4896a (1965) Berlaga, R. Ya., Zhurnal Eksperimentalnoi i Teoreticheskoi Fiziki 9, 11 (1939) in Kapustin, A. P., The effects of ultrasound on the kinetics of crystallization,Consultants Bureau, New York, 14 (1963) Ibid, 16, 7 (1946) Kudryavtsev, B. B., Ultrasonic applications in industry, 34 in Ultrasound in industrial processing and control, (edited by V. F. Nozdreva), Consultants Burea. New York (1964) Polotskii, I. G. and Levin, G. I., Sbornik Nauchnykh Rabot Institut Metallofiziki Akademiya Nauk Ukrainskoi SSR, 13,176 (1961) in Chemical Abstracts 57,1579b (1962) Polotskii, I. G. and Levin, G. I., Kristallizatsiya i Fazovye Perekhody, Gtdel Fiziki Tverdogo, Tela i Poluprovodnikov, Akademii Nauk Belorusskoi, SSR, 372 (1962) in Chemical Abstracts, 58,9684a (1963) Van Hook, A., Crystallization theory and practice, Reinhold, New York, 208 (1961) Eskin, G. I., Fridlyander, I. N., and Rubleva, M. K., Izvestiya Akademii Nauk SSR, Otdelenie Tekhnicheskikh Nauk, Metallurgiya i Gornoe Delo, 1, 109 (1963) in Chemical Abstracts, 58, 1105Og (1963) Kapustin, A. P., Primenenie Ultraakustiki k Issledovaniya Veshchestva, 4,65 (1957) in Chemical Abstracts, 54,23568e (1960) Tyurin, Yu.N., Zhurnal Prikladnoi Khimii, 38,1126 (1965) in Chemical Abstracts 83, 639311(1965)

12

13

14 15 16 17 18

ACKNOWLEDGMENTS Figure 1 was supplied by courtesy of K. A. Jackson, Bell Telephone Laboratories, Murray Hill, New Jersey and is reproduced from reference 13. Tables 1,2, and 3 and Figure 2 were supplied by courtesy of the Journal of Pharmaceutical Sciences. Tables 1,2 and 3 are reproduced from reference 9.

19 20

21 22

EQUIPMENT The Sonifier Model S-125 is made by Branson Instruments, Danbury, Conneticut and the Rapisonic Mark V by Sonic Engineering, Stamford, Connecticut.

23 24

REFERENCES
1

Bates, H. E. and Weinstein, M., Journal of the Electrochemical Society, 112,693 (1965) Levin, G. I. and Polotskii, I. G., Izvestiya Akademii Nauk SSSR, Otdelenie Tekhnicheskikh Nauk, 3, 167 (1961) in Chemical Abstracts, 55,22982e (1961) Danilov, V. I., Pluzhnik, E. and Teverovskii, B., Zhurnal Eksperimentalnoi Teoreticheskoi Fiziki, 9,66 (1939) in Kapustin, A. P., The effects of ultrasound on the kinetics of crystallization, Consultants Bureau, New York, 113 (1963) Nash, R. A., Drug and Cosmetic Industry, 97,843 (1965) Elpiner, I.E., Ultrasound physical, chemical and bioiogical effects, Consultants Bureau, New York, 15 (1964) Saneyoshi, J. and Okushima, M., Proceedings 3rd International Congress on Acoustics, Elsevier, (1961) in Brown, B. and Goodman, J. E., High intensity ultrasonics, D. Van Nostrand, Princeton, New Jersey, 42 (1965) Willard, G. W., Journal of the Acoustical Society of America 25, 669 (1953) Brekhovskikh, L. M., Krasilnikov, V. A. and Rozenberg, L. D., The physical basis for the application of ultrasound in industry, 15 in Ultrasound in industrial processing and control, (edited by V. F. Nozdreva), Consultants Bureau, New York (1964) Abramov, 0. V., Neimark, V. E. and Teumin, I.I., Fizika Metallov i Metallovedeniya 13,875 (1962) in Chemical Abstracts, 57, 14831 (1962) 14832f (1962) Straughn, J. L. and Tarpley, W. B., US Atomic Energy Commission, NYO-7935 (1959) in Chemical Abstracts 54, 19025f (1960) 206 ULTRASONICS October 1967

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36

Teumin, I. I., Influence of elastic vibrations on the crystallization and technical properties of alloys, 83 in Ultrasound in industrial processing and control, (edited by V. F. Nozdreva) Consultants Bureau, New York (1964)

44

Mazhul, M. M., Cavitation phenomena and the formation of crystal nuclei, Dissertation (1954) in Kapustin, A. P., The effects of uItrasound on the kinetics of crystallization, Consultants Burau, New York, 14 (1963) Mazhul, M. M., Uchenye Zapiski, Belorusskii Gosudarstvennyi Universitet, 32,211 (1957) Referativnyi Zhurnal, Metallurgiya Abstract 24786 (1957) in Chemical Abstracts, 53,17619c (1959) Fincher, 3, H. Ph.D. Dissertation, The Graduate School, University of Connecticut, 48 (1964) Melia, T. P., and Moffitt, W. P., Journal of Colloid Science,

37 Babikov, 0. I., *Ultrasound and its industrial applications, Consultants Bureau,New York, 213 (1960) 38 Kavalyunaite, V., Primenenie Ultraakustiki k Issledovaniya Veshchestva, lS, 171 (1961) in Chemical Abstracts, 60,752Of (1964) Chormonov, T. Kh., Sbornik Nauchnykh Trudov Kazakhskoi Politechniko Institut, 21,271 (1960) From Referatiynyi Zhwti Khimiya, Abstract 16B 184 (1963) in Chemical Abstracts, 88,12727b (1964) Danilov, T. I. and Teverovskii, B., Zhurnal eksperirmentalnoi i teoreticheskoi Fiziki, 10,ll (1940) in Kasputin, A. P., The effects of ultrasound on the kinetics of crystallization, Consultants Bureau, New York, 39, (1963) Kapustin, A. P., The effects of ultrasound on the kinetics of crystallization, Consultants Bureau, New York, 39, (1963) Murza-Mucha, P.; Przeglad Gdlewnictwa, 15,173 (1965) in Chemical Abstracts, t&9362@ (1966) Brown, B. and Goodman, I. E., High intensity ultrasonics, D. Van Nostrand, Princeton, New Jersey, 209 (1965)

45

39

46

47 48

40

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Kapustin, A. P., The effects of ultrasound on the kinetics of crystallization, Consultants Bureau, New York, 31 (1963) Badasarov, Kh. S., Primenenie Ultrazvuka v Promy: shlennost Moskovoskii Dom Nauch. Tekh. Propagandy im F. E. Dzerzhinskogo, Sbornik State, 175 (1967) in Chemical Abstracts, 54,23571b (1960) Weissler, A., IRE International Convention Record, Part 6, 24 (1962) Neppiras, E. A., Ultrasonics, 3,9 (1965)

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49

42 43

50 51

ULTRASONICS October 1967

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