Delayed freezing of water droplet on silver nanocolumnar thin film

Dhruv P. Singh and Jitendra P. Singh Citation: Appl. Phys. Lett. 102, 243112 (2013); doi: 10.1063/1.4811751 View online: http://dx.doi.org/10.1063/1.4811751 View Table of Contents: http://apl.aip.org/resource/1/APPLAB/v102/i24 Published by the American Institute of Physics.

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APPLIED PHYSICS LETTERS 102, 243112 (2013)

Delayed freezing of water droplet on silver nanocolumnar thin film

Dhruv P. Singh and Jitendra P. Singha)
Department of Physics, Indian Institute of Technology Delhi, Hauz Khas, New Delhi 110016, India

(Received 7 May 2013; accepted 6 June 2013; published online 21 June 2013) Silver nanocolumns were grown on Si substrate using glancing angle deposition method. Interestingly, the cold nanocolumnar surface was observed to make a delay of more than 62 s in freezing compared to the conventional silver thin lm. The observed delay in freezing on silver nanocolumns is explainable in terms of reduction in effective liquid-solid interface area within the framework of Cassie-Baxter model. This study shows the possibility of using silver nanocolumnar C 2013 AIP Publishing LLC. lms in ice free coatings and surfaces with tunable freezing properties. V [http://dx.doi.org/10.1063/1.4811751] Understanding freezing mechanisms of water droplet on solid surface is a problem of fundamental importance. Particularly, it attracts a special interest due to the serious effects of water droplets freezing on surface in a wide range of applications such as power transmission lines, aircrafts, cooling equipments, boats, and wind turbines.15 The Effect of ambient conditions and cold surface temperature on freezing of a water droplet is well understood and has been discussed in several studies.68 Recently, effect of surface modication, particularly the formation of hydrophobic surface on the freezing process of static water droplets, has also been observed.911 Tourkine et al. observed the freezing process of static water drop to be delayed by a factor of about 3 when deposited on the pre-cooled hydrophobic copper surface at 7  C.9 It was noticed that, if the copper substrate is slightly tilted, the drop can be removed without freezing and without accumulating on the substrate.9 In another study, Huang et al. studied the freezing of water droplet on cooling copper surface from normal temperature to 8.5  C. They observed that the contact angle of surface has a strong inuence on the water droplet freezing time.10 The observed variation in freezing process with hydrophobicity was attributed to the reduction in contact area of water drop on cold solid surface. In both of these studies, the contact angle was increased by chemical etching of surface followed by the coating with low surface energy materials. The etching simply increases surface roughness without formation of any specic regular patterns or textures on the surface, which might affect the droplet freezing process as well. The study of freezing process of the impacting or colliding water droplets on cold superhydrophobic surface has also been performed by Mishchenko et al.12 They observed that the cold hydrophobic surface repel the impacting water droplets before ice nucleation occurs and considering this effect, they suggested a possibility to use the hydrophobic surface as ice-free coatings. Although these studies disclose the ability of a hydrophobic surface to facilitate the removal of ice or retard its formation on cold surface, further research and experiments are still required to understand the mechanism as well as the effect of underlying surface features of nanostructured hydrophobic surface on the freezing process of water droplets.
a)

Author to whom correspondence should be addressed. Electronic mail: jpsingh@physics.iitd.ac.in

In the present study, we have investigated the effect of Ag nanocolumnar thin lm on the freezing process of static sessile water droplets. The freezing experiment was performed by cooling the Ag samples before and after the droplet deposition. In both the conditions, the nanocolumnar lm leads to a signicant delay in the freezing process of water droplets compared to the conventional Ag thin lm. The observed delay in freezing of water droplet is explained in terms of increase in hydrophobicity and therefore the resulting reduction in effective liquid-solid interface area on the Ag nanocolumnar lm. The study provides an understanding of freezing mechanism of water droplet on nanostructured hydrophobic surface as well as shows the possibility to manipulate freezing process of water droplet by the growth of nanocolumns on solid surface. The Ag nanocolumnar thin lms were grown over Si(100) substrates by thermal evaporation of Ag powder (99.95%) using glancing angle deposition (GLAD) method.1318 For the growth of nanocolumnar lm, the substrates were inclined in polar direction such that the substrate normal made a very high angle (a 85 ) with direction of incident vapor ux. During deposition, vacuum in the GLAD chamber was better than 2 106 Torr. For reference, a sample of conventional Ag thin lm was also grown with the normal incidence (a 0 ) of vapor ux on the Si substrate. Analysis of lm morphology was done using scanning electron microscope (SEM, ZEISS EVO 50). Figure 1 illustrates the schematic of apparatus used for the freezing experiment of water droplets. The experimental setup mainly consists of a digital camera, cooling sample stage, and a light source. The cooling sample stage is basically a xyz stage equipped with a hollow copper block on top, over which the samples are being placed. A thermoelectric cooler (Thermo Cube, SS Cooling Systems, USA) was used to reduce the temperature of copper block with precision of 60.1  C. The temperature of block was measured using a PT100 temperature sensor placed close to the sample position. The presence of impurities in liquid or on the surface is essential to start the ice nucleation in water.19,20 In the absence of any such impurities or the ice nucleation centers, pure water may remain in super cooled state even at temperatures well below the freezing point.19,20 Therefore to avoid this situation, normal tap water was used for this study. During experiment, water droplets of 3 ll volume were
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Appl. Phys. Lett. 102, 243112 (2013)

FIG. 1. Schematic of the experimental apparatus used for observing the freezing behavior of static sessile water droplets.

deposited on the Ag samples and images of the droplets were captured at 25 frames per second. The contact angles of Ag samples were measured by analyzing the images of water droplets with the ImageJ software (National Institute of Health, USA). It was observed during the freezing experiment that, without any precaution, the cold sample surface was covered with frost within few seconds. This phenomenon of the ice formation on cold sample surface simply wipes out the effect of nanostructured porous interface to the deposited water droplets. Therefore, it is very crucial to avoid frost during the experiment. To stop the frost formation, the sample stage was placed inside a close transparent box and before start the cooling, dry nitrogen gas was introduced in the box to reduce the humidity of inside air. SEM images of the conventional and nanocolumnar thin lm Ag samples are shown in Fig. 2. The average length and diameter of nanocolumns were found to be about 1.6 lm and 120 nm, respectively. To understand the effect of nanocolumnar thin lm on the freezing process of a water droplet, samples of conventional and nanocolumnar Ag thin lms were simultaneously put on the sample stage. Initially the temperature of sample stage was set to 10  C and after depositing the water droplets on both samples, cooling was started to reduce the surface temperature below the freezing point. The snapshots of water droplets sitting over the samples at different time instants are shown in Fig. 3. Readers should also refer to a supplementary video that shows the freezing of water droplets on nanocolumnar and conventional Ag thin lm samples as shown in Fig. 3 (the movie is played fast-forwarded at 4 times). Interestingly, it was observed that the droplets on both samples remain in liquid

FIG. 3. Two water droplets deposited on Ag nanocolumnar lm (droplet 1) and conventional Ag thin lm (droplet 2). (a) The droplets were just deposited on both the samples at temperature 10  C. After depositing the droplets, cooling of both the samples was started. On reaching to sub-zero temperature (4  C), (b) freezing of droplet 2 starts, time is set to 0 s (c) complete freezing of droplet 2 in 31.2 s (d) freezing of droplet 1 starts at 62.4 s (e) complete freezing of droplet 1 at 99.6 s (enhanced online) [URL: http:// dx.doi.org/10.1063/1.4811751.1].

FIG. 2. SEM images of Ag samples, (a) conventional thin lm (a 0 ) and (b) nanocolumnar thin lm (a 85 ).

state even when the temperature crossed the freezing point. In this stage, the water attains a super cooled state and remains unfreeze. When the temperature decreases to about 4  C the transparency of droplet on conventional lm appears to decrease gradually, indicating the start of ice nucleation. The counting of time was started from the instant when the water droplet begins to freeze. The droplet on conventional lm surface freezes completely with formation of a small sharp-pointed protrusion on the top in the next 31.2 s. This observed appearance of pointed protrusion on top can be considered as the combining effect of expansion of the ice and surface tension of water inside the droplet.10,21 Here it is interesting to notice that even up to this instant, the droplet on nanocolumnar sample remains unchanged. The ice formation in this droplet was started after the time interval of about 62.4 s and completed in the next 37.2 s. This observed time gap of 62.4 s between the start of ice formation in the droplets clearly indicates that the evolution of nanocolumns induce a signicant delay in the start of freezing of the water droplet on Ag surface. In this case, the water droplet was rst deposited on the Ag samples and then the cooling was started. In the next set of experiments, another possible condition of the freezing of water droplet on a solid surface was investigated. We observed the effect of nanocolumnar lm when water droplet was deposited on a pre-cooled Ag sample surface. In this experiment, both the conventional and nanocolumnar thin lm samples were kept on the cooling stage and temperature was set to 10  C. The water droplets were deposited only when the temperature of sample surface reached to 10  C.

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The snapshots of droplets at different time instants starting from the time when deposited on cooled sample surfaces to the complete freezing are shown in Fig. 4. In this case, the freezing of droplets begins immediately after depositing on the cooled sample surface. The ice formation starts near the liquid-solid interface, and a clear upward movement of the ice front with time was observed. The position of ice fronts within the water droplets on both the samples is indicated by the dotted red lines in Fig. 4. Comparing to the conventional thin lm, a clear lack in the progress of ice front with time can be observed for the nanocolumnar sample. This difference in the position of ice fronts at different time instants suggests for the variation in freezing process on the two samples. Here we consider the freezing time as the time taken by a water droplet after deposited on cooled sample surface to the complete freezing with pointed top. Then the freezing time on conventional and nanocolumnar lm samples comes out to be about 33.8 and 71.1 s, respectively. It suggests that the freezing of water droplet on the nanocolumnar surface takes more than double the time of conventional Ag thin lm. In case of a sessile droplet on cold surface, the thermal exchange occurs mainly at the liquid-solid interface.9,12,22 It suggests that the heat transfer or cooling rate in a droplet will be low on the sample offering a small interface area. The interface area on conventional Ag thin lm of at surface will be the circular contact area of droplet at the base, and it can be calculated simply by measuring the base radius (1.1 mm) of water droplet. The value of interface area on conventional Ag lm comes out to be about 3.8 mm2. On the other hand, the standing nanocolumnar growth makes the lm surface very rough and porous so actual interface area cannot be calculated directly without knowing the exact wetting behavior of Ag nanocolumnar lm. To understand the wetting behavior, the contact angles of both the conventional

as well as nanocolumnar Ag lm samples were measured at room temperature (25  C). The contact angle was found to increase from 92 for the conventional lm to 135 for nanocolumnar Ag sample. The observed increase in contact angle on nanocolumnar surface can be explained using the CassieBaxter model.2326 In the model, for a nanostructured porous surface, the water droplet is considered to be sitting upon a composite surface of the solid tops and the air gaps, alternating between a liquidsolid interface and a liquidair interface. So, the replacement of solid surface by air reduces the availability of effective surface energies resulting in the less force acting to drag the water to spread over the surface and nally leads to the increase in contact angle. For Ag nanocolumnar lm, air can exist in the vicinity of the columns to make it a composite (Ag-air) surface. The similar increments in contact angle on nanocolumnar thin lms have also been reported in previous studies.2628 Thus, in case of Ag nanocolumnar lm, instead of a continuous at surface, the water droplet sits on Ag-air composite surface. The thermal conductivity of air (0.024 W m1 K1) is almost negligible compared to Ag (406 W m1 K1). Therefore, only the solid surface area of Ag nanocolumns in contact with the water droplet can be considered as an effective interface area for the thermal exchange. Schematic of the water droplet on Ag nanocolumnar surface showing the effective interface (liquid-solid) area and the liquid-air interface area is given in Fig. 5. The area fraction of the liquid-solid interface is dened as solid fraction25,26,29,30 (f) that can be calculated using the Cassie-Baxter equation24,25 f 1 cos h0 =1 cos h; (1)

where, h0 is the contact angle on nanostructured surface and h is the contact angle on conventional surface. Taking h as the contact angle (92 ) measured on conventional Ag thin lm, the f for nanocolumnar sample of contact angle (h0 ) 135 comes out to be 0.3. Now, once the solid fraction f is known, the effective interface area can be calculated by simply multiplying f with the total interface (liquid-solid and liquid-air) area. If the water wets only the top of the silver nanocolumns, then the droplet base area can be considered as total interface area. Measuring the base radius (0.56 mm), the droplet base area on nanocolumnar sample was found to be 0.98 mm2. Considering the values of droplet base area and the calculated solid fraction, the effective interface area comes out to be 0.3 mm2 for the nanocolumnar surface which is about one tenth of the value obtained for the conventional thin lm sample (3.8 mm2). This large reduction in the effective interface area on nanocolumnar surface, which yields high thermal exchange, can be considered as a deciding factor for the observed variation in freezing process of a sessile water droplet.

FIG. 4. Water droplet freezing process on the two Ag samples kept at temperature of 10  C. The dotted red line indicates the position of ice front at different time instants.

FIG. 5. Schematic of a water droplet sitting on Ag nanocolumnar thin lm.

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In conclusion, the present work shows the effect of nanocolumnar morphology of Ag thin lm on the freezing process of a static sessile water droplet. A series of observations of the water droplet freezing processes were carried out under the two different possible surface temperature conditions: cooling of samples was started after depositing the droplets and second, the droplets were deposited on precooled samples (10  C). Taking the conventional Ag thin lm as reference surface, the experimental results showed that the nanocolumnar thin lm signicantly delays as well as slows down the freezing process of water droplet. The observed delay in freezing on silver nanocolumns is explained in terms of reduction in effective interface area within the framework of Cassie-Baxter model. D.P.S. kindly acknowledges CSIR, India, for the senior research fellowship. This research was supported by the nancial grant (Grant No. RP02444) from DST, India.
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