International Journal of Refrigeration 29 (2006) 1218e1224 www.elsevier.

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Inuence of surface roughness on the supercooling degree: Case of selected water/ethanol solutions frozen on aluminium surfaces
Matthieu Faucheux, Guillaume Muller, Michel Havet, Alain LeBail*
UMR GEPEA (UA CNRS 6144), ENITIAA, Rue de la Geraudiere BP 82225, 44322 Nantes Cedex 03, France ` Received 10 October 2005; received in revised form 28 November 2005; accepted 12 January 2006 Available online 5 June 2006

Abstract This paper presents a study on the impact of the roughness of a metallic surface on the magnitude of the supercooling during freezing of an aqueous solution. Aqueous solutions of ethanol (5%, 10% and 15% w/w) were used as model solutions. Five tubes of aluminium (internal diameter 8 mm) were machined to obtain a roughness between 0.63 and 13.3 mm. These tubes were immersed in a refrigerated bath with a programmable temperature scan. Thermocouples located at the inner surface of the tubes and in the solution were used to measure the magnitude of supercooling. Crystallisations were monitored and supercooling released calculated for each experiments. Our experimental results reveal that roughness is the inuencing parameter of the supercooling released: larger the roughness, lower the supercooling. Moreover, a power law correlation between the roughness and supercooling was deduced. 2006 Elsevier Ltd and IIR. All rights reserved.
Keywords: Ice slurry; Binary mixture; Water; Ethanol; Two-phase ow; Roughness; Wall; Aluminium

Inuence de la rugosite de la paroi sur le degre de surfusion: etude de differentes solutions eau/ethanol congelees sur des surfaces en aluminium
Mots cles : Coulis de glace ; Melange binaire ; Eau ; Ethanol ; Ecoulement ; Diphasique ; Rugosite ; Paroi ; Aluminium

1. Introduction Intense research effort is carried out in many laboratories and industries to develop environmental friendly secondary refrigerant, with the objective of reducing the mass of refrigeration uids. Among these secondary refrigerant uids, ice slurry offers many advantages, among which a high specic

* Corresponding author. Tel.: 33 251 785 473; fax: 33 251 785 467. E-mail address: lebail@enitiaa-nantes.fr (A. LeBail). 0140-7007/$35.00 2006 Elsevier Ltd and IIR. All rights reserved. doi:10.1016/j.ijrefrig.2006.01.002

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Nomenclature free energy (J) latent heat of fusion for pure water at 273.15 K (333.3 103 J kg1) n number of experiments r(x) local roughness at location x (mm) Ra roughness (mm) SC or DT supercooling value (SC TIFPTRSC) (K) T temperature (K) TIFP temperature of initial freezing point (K) G L TRSC t X, x temperature at rupture of supercooling (K) time (s) length (m)

Greek symbols q, a angle (rd) g surface tension (N m1) s error (K)

energy and a reduced temperature shift over the melting domain. One of the major bottlenecks of the ice slurry technology lies in the development of reliable ice slurry generator. The complexity and cost of the existing devices still represents a main drawback of this technology. Researchers are now investigating different type of ice slurry generators such as generator using supercooled water with nucleation initialisation [1]. In this kind of generator, the mother solution is rst refrigerated until a supercooling state. Then nucleation is initialized with different methods such as momentum decrease, ultrasonic eld or bubble nucleation . The control of ice crystallisation and therefore of the supercooling remains a key aspect of this kind of generator. Research effort is thus needed to better understand the impact of roughness on the supercooling release in order to have a total control in this kind of generator. Nucleation occurs spontaneously if and only if the associated change in free energy G for the system is negative (DG < 0). Likewise, a system reaches equilibrium when the associated change in G for the system is zero (DG 0), and no spontaneous process will occur if the change in G is positive (DG > 0). The creation of a nucleus implies the formation of an interface at the boundaries of the new phase. Some energy is expended to form this interface, based on the surface energy of each phase. If a hypothetical nucleus is too small, the energy that would be released by forming its volume is not enough to create its surface, and nucleation does not proceed (DG > 0). As the phase transformation becomes more and more favorable, the formation

of a given volume of nucleus frees enough energy to form an increasingly large surface, allowing progressively smaller nuclei to become viable. Heterogeneous crystallisation is characterised by the fact that a crystal is initiated from impurities or from specic surface conditions. The associate free energy variation needed to this phase transition is called DG (Eq. (1)). Above this threshold, ice crystals are unstan ble; they appear and disappear but cannot grow [2]. In this case, the DG threshold is function of the wetting angle q n (Fig. 1 and Eq. (1)). This angle is linked to the roughness of the surface and to other specic characteristics such as surface tension. DG n
2 16pg3 TIFP f q 2 DT 2 3L 1 f q 2 cos q1 cos q2 4

1 2

It has been demonstrated for a long time that the roughness of a surface is supposed to interact with the level of supercooling. Besides, a limited amount of literature is available on this subject. Saito et al. [3] showed that the surface characteristics such as roughness inuenced the freezing temperature of supercooled water. Copper surfaces were considered with different surface roughnesses; nevertheless, no values of the roughness of the surfaces were

Fig. 1. Wetting angle q of a droplet of water of radius r being frozen onto a surface.

Fig. 2. Schematic view of a droplet of water undergoing crystallisation on notch.

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M. Faucheux et al. / International Journal of Refrigeration 29 (2006) 1218e1224 Table 1 TIFP obtained by extrapolation of the freezing plateau; number of experiments for each concentration % of ethanol 5 10 15 TIFP (  C) 2.3 4.5 7.5 Number of experiments 9 20 15

Fig. 3. Experimental cell used to measure and assess supercooling and crystallisation.

None of these studies specically proposed explicit relationships between the roughness as such and the supercooling degree. These authors were more comparing selected surfaces without measuring their effective roughness. The objective of this work is to study the impact of the roughness on supercooling using aluminium as a surface and an aqueous solution of ethanol (5%, 10% and 15% w/w). The nal objective is to provide relationship between supercooling degree and roughness. 2. Materials and methods An original set up has been designed for this study. Five experimental cells made of aluminium alloy have been designed. A scheme of a cell is presented in Fig. 3. The internal surface of these cells (8 mm inner diameter and 8 mm high) has been previously machined to obtain the desired roughness. Three K-type thermocouples (100 mm wire diameter) were installed at selected locations, namely at mid radius (T1) of the aluminium cell, at the inner surface of the cell (T2), and at centre of the uid domain (T3). A LED (Everlight 5 mm round T13/4 colorless) was installed at the bottom of each cell to light the uid volume. Each LED has got a low power dissipation (about 20 mW) and was not supposed to inuence the sample temperature. A PMMA disk was used as a separator between the sample and the LED.

provided. Mean degree of supercooling was between 7.4 and 13.8  C for porous surface and a buffed surface, respectively, using water. Okawa [4e6] compared ice crystallisation of pure water on a gold platted surface and on an electrolytically polished copper surface. He observed a higher supercooling for the gold platted surface (between 15 and 20 K depending on the cooling rate) whereas a lower supercooling was observed for the copper surface. Moreover, the larger the level of oxidation of the copper surface, the lower the supercooling, indicating a relationship between roughness and supercooling. Wakamoto [7] studied the stability of supercooled water in an ice generator. In this study they used a different form of the expression of the free energy DG (Eq. (3) and Fig. 2). In this case, q is assumed to n be equal to p/2 and a is the angle of the notch where the crystallisation occured. They supposed that the supercooling increases as the roughness of the surface decreases. DG n
2 8pg3 TIFP  a 1 cos 2 DT 2 3L 2

3
15 10

Temperature (C)

cell cell holder

5 0 -5 -10 -15 0 50 100 150 200 250

TIFP SC TRSC

Time (s)
Fig. 4. Picture (top view) showing the ve experimental cells installed in the cells holder. Fig. 5. Timeetemperature plot of a water/ethanol mixture (5% w/w); denition of the supercooling degree.

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Fig. 6. Typical roughness prole used to evaluate the mean value of the roughness from Eq. (4).

The ve cells were installed in a cell holder (Fig. 4) immersed in a programmable refrigerated bath. A ow of gaseous nitrogen was poured on the cells holder to avoid condensation on top of the cells. A video camera (Sony mini DV) was placed on top of the cells holder to visualize the freezing of the solution installed in the cells. The three thermocouples installed in each cell were previously calibrated against a platinum reference probe (Pt100). Temperatures were collected every second with a Datalog acquisition system. Temperature accuracy was 0.1 K. Aqueous solutions were done using distilled water and absolute ethanol. Concentrations of 5%, 10% and 15% (w/w) were used for these experiments. The cells were lled up with a new solution for each experiment. The initial freezing temperature (TIFP) of the aqueous solution was previously measured by logging the temperature evolution of a solution placed in a refrigerated reaction tube. The solution was stirred with a thermocouple, which helped in initiating the

freezing of the solution with a negligible supercooling. The initial freezing temperature was obtained by extrapolation of the freezing plateau (Table 1). Equilibrating the glycol bath and the sample holder at 10  C started the experimental runs. Then a timeetemperature program was run with the glycol bath to obtain a temperature scan at a scanning rate of 5 K/min. Previous experiments showed that a good temperature uniformity was observed between the ve cells installed in the glycol bath which was stirred with a built in circulating pump. Experiments have been completed until total freezing of the solutions contained in the cells. The supercooling (SC) was evaluated using the temperature difference between the temperature of the solution at supercooling breakdown (TRSC) and the initial freezing temperature (TIFP) that was previously determined. The total number of experiments was of 44. These comprised nine experiments for the 5% concentration, 20 experiments for the 10% concentration and 15 experiments for the 15% concentration. A typical timeetemperature plot is shown in Fig. 5 indicating how the supercooling was experimentally determined. For all experiments, the degree of supercooling (SC) was determined from the temperature logged with the thermocouple placed in the centre of the uid domain (T1 in Fig. 3). The roughness (Ra) of the surface of each cell was evaluated with a destructive analysis after completion of the experimental runs using an optical prolometer (UBM Corporation). The measurements were made on a window of 2 0.5 mm2 with a sampling of 200 points/mm. In a section perpendicular to the surface, the peaks and hollows are

t=t0

t=1/6 t1

t=2/6 t1

t=3/6 t1

t=4/6 t1

t=5/6 t1

t=t1

Fig. 7. Images showing the travelling of the freezing front during the release of the supercooling state. The time elapsed between initial (time t 0 s) and nal image (time t1) was between 1 and 5 s depending mainly on the supercooling degree and to a minor extend on the ethanol concentration.

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t=1/2 t2

t=t2

Fig. 8. Images taken during the secondary freezing following the release of the supercooling state. Images shown have been taken with a 5% solution at t t2 37 s and t t2 74 s (t2 total time to complete full freezing of the sample).

divided equally on either side of a central line (algebraic mean) also called average line (Fig. 6). Ra is the average deviation and dened as the arithmetic mean of the deviations absolute values between the peaks and the hollows (Eq. (4)). Ra measures the distance between this mean and the central line (r(x) 0). It is generally admitted that this notion summarizes approximately the different parameters involved in roughness. 1 Ra L L
0

Fig. 9. Typical crystallisation timeetemperature plot; phase 1: supercooling; phase 2: release of supercooling with dendrites front; phase 3: nal freezing (crystal growth).

jrxjdx

3. Results The video monitoring of experiments showed that the release of supercooling was occuring at different times depending on the cell roughness. Ice crystallisation was always starting from the metallic surface and not from the bottom disk of the cells. Indeed, this bottom surface was made of PMMA, which was showing a glassy surface aspect. In addition, no homogenous nucleation was observed (nucleation in the uid volume), neither nucleation starting from the thermocouple T1 located in the uid domain. Figs. 7 and 8 show selected images taken during the video monitoring of a typical crystallisation experiment. Fig. 9 shows a schematic timeetemperature plot. The supercooling release starts at time t t0 and ends at time t t1. It corresponds to a temperature rise from TRSC until a temperature very close to TIFP. The release of supercooling lasted between 1 and 5 s depending on the experimental conditions. This supercooling release phase (2) is followed by freezing phase (3) in Fig. 9 during which the temperature of the sample will decrease until the nal temperature. The freezing front has reached the centre of the sample at time t2. This third phase lasted around 75 s for most experiments Fig. 7 shows pictures of a cell taken between the release of the supercooling (between time t0 and time t1), whereas Fig. 8 shows pictures of a cell during the second phase (between time t1 and time t2).

The roughness measurements were made after experiments. Figs. 10 and 11 showed a visual aspect of the inner surface of the cells A and E. Among the ve cells, only four gave consistent results. Indeed, the cell E was machined with a thread exhibiting a very rough surface. As the roughness of cell E is out of the range of the optical prolometer and lead in non-consistent SC, it is no more considered in this study. The roughness and SC obtained with cells AeD are shown in Table 2. Comparison between results was carried out by variance analysis at a 95% condence level (Fishers least signicant difference (LSD)) against the roughness and against the concentration. For all concentrations of ethanol, all cells give results that are statistically different against the roughness variable. In other words, the roughness has a signicant effect on supercooling whatever the concentration was. As cells differ only by their surface

Fig. 10. Picture of the inner surface of the cell A; Ra 0.63 mm.

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12 10 8 6 4 2 0

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SC mean (K)

10

15

Ra (m)
Fig. 11. Picture of the inner surface of the cell E; Ra > 500 mm. Fig. 12. Graph of the mean SC vs. roughness Ra. Points show the experimental results with error and bold line shows the regression obtained by least square regression (Eq. (6)).

characteristics, we can say that roughness inuences the degree of supercooling. Concerning the impact of the concentration, it can be seen from Table 2 that no strong inuence of the concentration on the supercooling degree was observed. A signicant difference was observed twice for cells A and C between concentrations 5% and 10%. No signicant differences were observed for cell B. For cell D, a signicant difference was observed between the 10% and the 5% and 15%. Therefore, in our experimental conditions the ethanol concentration did not inuence signicantly the supercooling in comparison to the roughness parameter. Results clearly demonstrated that the lower the roughness, the higher the supercooling. This conclusion is consistent with existing data from the literature. A t between the experimental results was then researched. Since no real interaction between ethanol concentration and supercooling was observed, supercooling values obtained for each of the three concentrations were pooled, making a set of 44 values for each roughness. A t between the mean supercooling value obtained for each roughness and the roughness value was researched and yield in a power law relationship. The power law trend was chosen due to Eq. (3), which can be rewritten in a different form (Eq. (5)). In this equation we can assume that the tension surface g and the angle of the notch a are linked to the roughness Ra. For example a represents the

angle of a notch; one can easily understand that the higher the roughness the lower will be angle a. In our conditions, the same material and the same solution were used. Therefore, no specic interaction between the surface tension and the supercooling degree is expected. An interaction between the concentration and the supercooling degree can also be suspected; indeed, it is known that solute concentration is linked to the surface tension, the lower the concentration, the higher the surface tension. Nevertheless, the variance analysis done with the results and presented in Table 2 showed that considering our experimental conditions, no real link was clearly demonstrated. The two coefcients of Eq. (6) were found by a least square optimization method. This relationship is plotted in Fig. 12. Due to the relatively low number of experimental points, a standard deviation of 2s (Eq. (7)) was considered. Direct comparison with existing works was not possible. Nevertheless, the results are in agreement with the theory of ice crystallisation. s 2 8pg3 TIFP  a 5 1 cos f Ra aRb DT a 2 DG 2 3L n SC mean 7:15R0:196 a 6

Table 2 Roughness Ra mean supercooling SC obtained for the four cells AeD and standard deviation SD Cell Ra (mm) 5% SC mean (K) A B C D 0.63 1.04 2.43 13.33 8.49 7.51(b,1) 4.99(c,1) 4.20(d,1e2)
(a,1)

10% SD 0.60 0.25 0.48 0.22 SC mean (K) 7.14 8.04(b,1) 6.05(c,2) 4.05(d,1)
(a,2)

15% SD 1.16 1.50 0.90 0.19 SC mean (K) 6.78 8.11(b,1) 5.80(c,2) 3.97(d,2)
(a,2)

SD 0.97 1.68 0.77 0.86

For each column, the letters (a, b, c and d) represent the group that has signicant (P < 0.05) difference of the mean values between each other. For each line, the numbers (1 and 2) represent the group that has signicant (P < 0.05) difference of the mean values between each other.

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q P SC SC2 =n 1 SD p s p n n 4. Conclusion

(ENITIAA) who developed the experimental set up and to Nicole LANGLOIS (POLYTECH-University of Nantes) for providing the roughness analysis.

References
This study aimed at studying the impact of the roughness of a surface on the degree of supercooling during freezing of an aqueous solution (watereethanol mixture in our case) onto a refrigerated surface. Aluminium surfaces were considered with roughness between 0.63 and 13.33 mm. A signicant inuence of the roughness on the degree of supercooling was observed, whereas no signicant impact of the ethanol concentration was observed. We showed that roughness has a strong inuence on the supercooling phenomena, conrming the fact previously seen in the literature that the lower the roughness, the higher the supercooling. A power law relationship was experimentally obtained in our conditions using three aqueous solutions of absolute ethanol of 5%, 10% and 15% w/w concentrations. Such data could be of interest for any ice slurry set up based on supercooling of the mother solution. Acknowledgements This is supported by a co-funding of ADEME (Agence De lEnvironnement et de la Matrise de lEnergie e France) and of the Region Pays-de-la-Loire. Special thanks are addressed to Luc GUIHARD and Christophe COUEDEL
[1] P.W. Egolf, M. Kauffeld, From physical properties of ice slurries to industrial ice slurry applications, Int. J. Refrigeration 28 (1) (2005) 4e12. [2] P. Papon, J. Leblond, P.H.E. Meyer, Physique des transitions de phases. Concepts et applications, Dunod, 1999. [3] A. Saito, Y. Utaka, S. Okawa, K. Matsuzawa, A. Tamaki, Fundamental research on the supercooling phenomenon on heat transfer surfaces-investigation of an effect of characteristics of surface and cooling rate on a freezing temperature of supercooled water, Int. J. Heat Mass Transf. 33 (8) (1990) 1697e1709. [4] A. Saito, S. Okawa, Fundamental research on initiation of freezing of supercooled water on heat transfer surface, Proceedings of the 10th International Heat Transfer Conference, 1994. [5] A. Saito, S. Okawa, A. Tamaki, Fundamental research on supercooling phenomenon on heat transfer surfaces, Proceedings of the International Symposium on Cold Regions Heat Transfer, 1989. [6] S. Okawa, A. Saito, H. Suto, The experimental study on freezing of supercooled water using metallic surface, Int. J. Refrigeration 25 (5) (2002) 514e520. [7] S. Wakamoto, et al., Study of the stability of supercooled water in an ice generator, ASHRAE Trans. 102 (2) (1996) 142e150.