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CRYSTAL GROWTH OF WATER ETHANOL MIXTURE

Keiichi Kuwahara, Consulting Manager, Aero-Engine & Space Operations, IHI Corporation
Koto-ku, Tokyo, 135-8710, Japan
Hirotoshi Ohkubo, Professor, College of Engineering, Tamagawa University
Machida-shi, Tokyo, 194-8610 Japan
ABSTRACT
Water and ethanol exist together as a mixture in both liquid and solid phases. From this
characteristic, along with recent advances in low-temperature technologies, water ethanol mixture has
become important as environment-friendly coolants or thermal storage materials. In this study, in
order to investigate the mechanisms of crystal formation and crystal growth in a water-ethanol mixture,
we observe by microscope the crystal behaviors in a hemispherical minute droplet used for cooling a
thin rod. It is found that equiaxed crystals form and then grow to hexagonal plane crystals, and these
migrate toward the top of the droplet and arrange themselves in a honeycomb structure. Marangoni
convection induced by the difference in concentration is considered as a way to move the equiaxed
crystals.
1

INTRODUCTION
Ethanol (or ethyl alcohol) is a common substance familiar to many people, but its water solution

is somewhat mysterious in that it shows complex changes in many of its properties, depending on the
ethanol concentration.
A water ethanol mixture has a liquidus line (or crystal1izing line) and a solidus line (or melting
line) that are separated, and thus it can exist together both liquid and solid phases. As a result, with the
advances in low-temperature technology in recent times, water ethanol mixture becomes important
as environment-friendly coolant or thermal storage material.
In this study, we examined the crystal-formation process in a water ethanol mixture as well as
the formation process of a mushy layer on a refrigerated surface. Even though there seems to have
been a large number of research studies on crystal formations, in fact it is difficult to find any
systematic study on them.
We reported in a previous study [1] that crystal growth of a water ethanol mixture occurs in two
ways: the first is equiaxed crystal growth and the second is crystal growth within the mushy layer
(consisting of liquid and solid phases) formed on a refrigerated surface. lf we could understand these
crystallizing processes, it would be possible for us to arrive at better methods for making use of water
ethanol mixture either as a secondary coolant, a thermal storage substance having fluidity, or as a
substance suitable for thermal storage by ice. Of these crystallizing processes, crystal growth in a
mushy layer has been widely studied in multi-component liquids, including water ethanol mixture.
On the other hand, equiaxed crystals are known to be one form of crystals used in the
2010 International Symposium on Next-generation Air Conditioning and Refrigeration Technology,
17 19 February 2010, Tokyo, Japan

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solidification of metals and have been widely researched in that field. A few studies have focused on
equiaxed crystals in the solidification of water solutions: this author's study on water ethanol mixture
[1], visual observations on magnesium chloride by Fukusako [2], and a series of research works on
ammonium-chloride-water solution by Ohno [3].
2

PHASE DIAGRAM OF WATER-ETHANOL MIXTURE

Ohkubo [4] proposed and mapped melting-point diagrams for water ethanol mixture, such as

that shown in Figure 1. As shown in the figure, solids and liquids coexist in three regions: L+S0, L+Sl
and L+S2. Among these regions, solidified water or ice is in the L+ S0 region, hydrate of ethanol is in
the L+Sl region, and ethanol itself is in the L+S2 region. In the figure, the Sl region has a structure
whose ratio of ethanol to water is 1:2.

Figure 1. Phase diagram (melting-point diagram) of water ethanol mixture [4]

EXPERIMENTAL APPARATUS AND METHOD

In this study, we attempted to understand by experiment the crystal growth in water ethanol

mixture, including the mechanism of equiaxed crystal formation.

Figure 2 shows a schematic diagram of the experimental apparatus. We observed crystal growth
in a droplet of the mixture placed on a refrigerated surface. The refrigerated surface is one end of a
copper cylinder with a diameter of 4 mm. The surface was cooled to a pre-determined temperature by
using liquid nitrogen in a vessel, and its temperature was controlled by stopping the liquid nitrogen
supply and letting the temperature rise gradually in a natural manner. The sampling droplet of the
2010 International Symposium on Next-generation Air Conditioning and Refrigeration Technology,
17 19 February 2010, Tokyo, Japan

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mixture was placed on the refrigerated surface by using a hypodermic syringe after removing the mist

Figure 2. Experimental apparatus

on the surface. The state of crystal growth was video recorded from the top and sides, using a CCD
camera and a microscopic photography apparatus. The temperature of the refrigerated surface was
measured at a point l mm below the surface with a CA thermocouple of 0.1 mm wire diameter.
The water ethanol mixture was prepared by measuring quantities of water and ethanol with a
precision balance and mixing them, followed by thoroughly stirring the mixture. Therefore, we
expressed the concentration of the water ethanol mixture as a mass percent. In preparing the solution,
we used ionized water, and the ethanol had a purity over 99.8.
4

EXPERIMENTAL RESULTS AND DISCUSSIONS

4.1

Visual observational results on equiaxed crystal

Figure 3 shows the crystallizing process occurring within a minute droplet with regard to the

solid-liquid region; these results were obtained from the video recording apparatus. Figure 4 shows a
sketch based on these observational results. We can identify two types of crystals among the crystals
formed or grown in the water ethanol mixture droplet: crystals called equiaxed crystals that grow
within the liquid phase and those in a mushy layer grown from the refrigerated surface. For
comparison, we also carried out an experiment on the freezing of water, but in the obtained results we
did not see equiaxed crystals.
Equiaxed crystals originated from the entire refrigerated surface beneath the droplet.
Simultaneously, a mushy layer also formed, but the minute equiaxed crystals grew as they kept rising
within the droplet. However, depending on the conditions, the growth of a mushy layer was so rapid
that minute equiaxed crystals were observed to be trapped inside the mushy layer close to its boundary.
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17 19 February 2010, Tokyo, Japan

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From the top view, we observed that the equiaxed crystals were hexagonal plane crystals that arranged
themselves in a honeycomb structure.

C=30mass%

t=-42.7

tli=20.3

Figure 3. Crystallizing process occurring within a minute droplet of water ethanol mixture

Figure 4. Sketch based on observation results

4.2

Growth of equiaxed crystal

We measured the crystal growth of an equiaxed crystal by photographing it from the side of the

droplet, and Figure 5 shows the characteristic length, la, of the crystal as a function of time. The
characteristic length of the crystal is considered the diagonal length la of the hexagon. In the figure,
time on the x-axis and crystal size on the y-axis have each been non-dimensionalized, respectively, by
time e, which is the finishing time or the time needed for the equiaxed crystals to arrange themselves
in a honeycomb structure, and by the crystal dimension lac for that period of time. We can see from
Figure 5 that the crystal size increases in proportion to time.
4.3

Flow generated in droplet

Horibe [5] investigated the supercooling phenomenon of ethylene glycol water solutions and

NaCl water solutions. Rising flow was observed on the surface of the droplet placed on the
refrigerated surface, and this is considered to be mainly caused by the difference in the surface tension
of the solution based on the difference in temperature. However, no equiaxed crystals were formed in
their experiment.
2010 International Symposium on Next-generation Air Conditioning and Refrigeration Technology,
17 19 February 2010, Tokyo, Japan

Figure 5 Characteristic length la of the crystal as a function of time

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In this study, a rising flow also occurred on the droplet surface, judging from the migration
direction of the equiaxed crystal. The migration velocity was approximately 0.7 mm/s under the
conditions shown in Figure 5. Here, we examine the cause of this rising flow, limited to the areas of
the L+S0 region. Although the density of the equiaxed crystal (ice) is smaller than that of the
neighboring water ethanol mixture and rises in the droplet while disregarding other driving forces, our
examination results show that the buoyancy effect is small and does not generate such a migration
velocity.
Next, we consider the concentration of the mixture along the equiaxed crystal. Because the
droplet is cooled from its bottom but makes contact with the atmosphere from above, the temperature
at the bottom side of the crystal is lower than at its upper side. The ethanol concentration distribution
beneath the equiaxed crystal is determined according to the liquidus line, corresponding to the
temperature distribution. Along the liquidus line, the concentration of ethanol increases with
decreasing temperature. Although temperature decreases along the liquidus line, surface tension
decreases because the dominant effect on it is the decrease in concentration. Since the crystal grows as
it rises within the droplet as mentioned in 4.2, the concentration difference is maintained along the
ethanol near the crystal as the crystal grows. Therefore, qualitative investigation led us to conclude
that this rising flow is mainly caused by the difference in the mixtures surface tension due to the
concentration difference.

CONCLUSIONS
An experimental study was conducted to better understand the solid phases of a water ethanol

mixture, with particular attention given to equiaxed crystals. The results obtained led us to the
2010 International Symposium on Next-generation Air Conditioning and Refrigeration Technology,
17 19 February 2010, Tokyo, Japan

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following conclusions.
1) Equiaxed crystals were formed and grew to hexagonal plane crystals within a droplet, and a mushy
layer formed and grew on a refrigerated surface.
2) Equiaxed crystals departed from the refrigerated surface by a flow that is considered Marangoni
convection induced by differences in concentration. These were hexagonal plane crystals that arranged
themselves in a honeycomb structure.
REFFERNCES
[1] H. Ohkubo, N. Matsumoto, J. Ochiai and M. Nakajima, Crystal growth of water and ethanol,
Trans. of the JSRE 18, 1, 435-442 (2001).
[2] S. Fukusako and H. Inaba, Heat Transfer Phenomena at Low Temperature, (Yokendoh, Tokyo,
1996).
[3] A. Ohno, Solidification of Metal (Chijin-Tosho, Tokyo, 1997).
[4] H. Ohkubo, I. Tanasawa, R. Shirakashi, J. Ochiai and Y. Kitaka, Study on phase diagram of water
ethanol solution, Proc. of 18th Japan Symp. on Thermophysical Properties, 361-363 (1997).
[5] A. Horibe, S. Fukusako and M. Yamada, Freezing characteristics of droplet on a cooled wall,
Trans. of the JAR 12, 1, 63-71 (2001).

2010 International Symposium on Next-generation Air Conditioning and Refrigeration Technology,

17 19 February 2010, Tokyo, Japan