Proceedings of the ASME 2012 International Mechanical Engineering Congress & Exposition IMECE2012 November 9-15, 2012, Houston,

Texas, USA

IMECE2012-87147
UNUSUAL FAST EVAPORATION FROM NANOHOLES
ZHI HUANG School of Power and Mechanical Engineering, Wuhan University Wuhan, Hubei,430072, China zhuangwhu@gmail.com YUANCHEN HU School of Power and Mechanical Engineering, Wuhan University Wuhan, Hubei, 430072,China huyc@whu.edu.cn

KANG LIU School of Power and Mechanical Engineering, Wuhan University Wuhan, Hubei,430072, China liukang@whu.edu.cn

XUEJIAO HU School of Power and Mechanical Engineering, Wuhan University Wuhan, Hubei,430072, China xjhu@whu.edu.cn

ABSTRACT

Water evaporation is an important physical phenomenon that occurs in nature and several industrial applications such as food drying processes, cooling in air-conditioning systems and desalination. In all these systems, it is necessary to have a good prediction and control of evaporation rate as a function of various system parameters. Attempts to understand the affecting factors have mostly focus on the flow rates of gas or water streams, relative humidity of the air, presence of dissolved or suspended material in the water, temperatures of the air and water streams. However, as water surface partially covered (less surface area) is generally thought to have lower evaporation rate, little notice has ever put on it. Here we consider the evaporation case of water surface covered with nano-through-hole lid (NHL) of which the radius size is nearly equal to the average free path of the vapor. Using a gravimetric method, we experimentally measured the evaporation rate of water at the orifice of the nano-holes. The results indicate that the evaporation rate is 1-6 times faster than the nonsheltered water surface with the same liquid area.

Moreover, with the porosity of the lid decreasing, the evaporation rate per unit area increases. A theoretical model is developed for this novel phenomenon from the view of molecular dynamics during evaporation and vapor diffusion. We envision that this finding may have new inspirations on phase change phenomenon in nano- confined space and put forward one new way for promoting evaporation of liquid.
INTRODUCTION

Evaporation in nanoscale is a rather complex, difficult-controlling, usually non-equilibrium and still far-from-clear question [1-5]. Along with the capillary induced liquid transportation such as film flow and corner flow [1], the absolute pressure of the water in nano-confined space is often negative [2,3] and the liquid is thermodynamically metastable with respect to the vapor pressure [4]. Previous works on the question have thus far focused on capillary flow, the negative pressure and the evaporation-induced cavitation [5], which mainly occurred inside the nanospace. However, as a controlled process during evaporation, vapor diffusion through the nano-hole or
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nano-channel is often weakened due to the gas adsorption on the inner surface of the pore or channel [6], further limiting the evaporation rate. Intrigued by this, we explored the evaporation rate of water surface at the orifice of the nano-holes, where vapor diffuse from nano-holes to bulk space.
EXPERIMENTAL

Evaporation rate is usually measured by direct observation of the water surface receding [5] or the gravimetric method [7]. Here we also utilize the latter method by using the electronic balance to weigh the evaporation specimen every 30 seconds. The process is conducted in an open air passage where air with constant controlled temperature (293 K) and humidity (from 0.2 to 1) flows through the specimen at a fixed speed of 0.45m/s (Figure 1b). The NHL is placed on top of an open water vessel filled with

water of which the height is about 100 m (Figure 1a). Water is sucked into the nano-holes by the capillary force and reach to the orifice of the holes. As evaporation proceeds, water surface stays at the orifice while receding water surface form between the surrounding ring supporting the NHL and the bottom surface of the collecting vessel (Figure 1c). The supporting ring is wide enough avoiding the water surface recedes to contact with the lid during the evaporation. We first test the evaporation rate of water surface covered by nano-porous Al2O3 film [8] (NAF, Figure 1d) with distributed nano-holes (the pore radius is 100 nm, the film thickness is 60 m and the surface porosity is 0.58) under different relative humidity (RH) as compared to that with no lid. The results are presented by the mass loss deviding the lid area and the actual evaporation area m as a function

a
Water

Surpporting Ring Nano-holes Plate

b
Air Flow

Vessel

Receding Water surface

To Balance

Figure 1 Experimental setup. a, Water surface with a nano-through-holes lid. The supporting ring and the nano-holes plate constitute the lid, water can only evaporates from the holes. b, Experimental measurement device. The air with controlled humidity and temperature flows through the passage uniformly at a fixed rate of 0.45 m/s, and the passage is thermally insulated. The specimen is placed on a stent whose base is on a electronic balance out of the passage to gain timely mass loss. c, Details of the specimen during evaporation. Meniscus forms between the ring and the bottom surface as evaporation occurs. The picture below gives the model of the nano-holes plate. d, The scanning microscopy image of nano-porous alumina film. The scale bar is 500 nm. e, The scanning microscopy image of nano-porous gold flake. The scale bar in the picture is 50 nm.

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of

time

(Figure

2a),

60 m and the surface porosity is 0.25, Figure 1e) was experimentally examined [9]. Identical results are found (Figure 2b), to be noticed, the enhanced rate can be 6 to 7 times considering the actual evaporation area. From the above, at least two conclusions can be gained: firstly, evaporation can be enhanced by just adding a NHL onto the water surface, as means decreasing the evaporation area can enhance evaporation ; secondly, the enhanced rate has relation with the porosity of the lid, strangely, the rate increases when the porosity reduces.
THEORETICAL ANALYSIS

To understand the mechanism behind the phenomenon, we established a theoretical model including the two main processes during evaporation - phase change from liquid to vapor and vapor diffusion from nano-holes to the bulk space by assuming that there is no temperature difference between vapor and liquid. As the two processes are in series connection, the evaporation rate is controlled by the lower rate of the two. The phase change rate is determined by [10] M Jp = (1) 2RT C1 Piv (Tiv ) C2 Pv iv , where Jp is the phase change rate, positive for the interfacial evaporation rate, and negative for the interfacial condensation rate; M is the molecular weight, R the general gas constant, Piv(Tiv) the saturated vapor pressure with respect to the interfacial temperature Tiv and Pv is the bulk vapor pressure adjacent to the liquid-vapor interface. C1 and C2 (in order of 1) are the accommodation coefficients of vaporization and condensation, respectively . In order to explore the relationship between C1 and C2 in the case of evaporation with and without NHL, the vaporization and condensation resistance are analyzed from the molecular point in detail. During water surface evaporation without lid, part of liquid molecules overcome the phase change energy barrier to escape from the liquid to vapor (Figure 3a), as is called vaporization; a section of vapor molecules are bounced back to the water surface by other
1/ 2

Figure 2 Experimental results. a, The evaporation rate of the water surface with or without nano-porous alumina film (NAF) lid, J, plotted as function of the relative humidity (RH) of the flowing air. The solid diamond points represent the results of water surface with NAF lid considering the actual evaporation area. Inset in top right is the evaporation mass loss per unit area m as a function of time t when the RH is 50%. b, The evaporation mass loss per unit area m of water surface with or without nano-porous gold flake (NGF) lid, plotted for time t.

respectively. Interestingly, with a NAF, evaporation occurred 0-0.5 times faster than the water surface. If the actual evaporation area is taken account into the results, the rate can be 1 to 2. To further understand the mechanism behind the phenomenon, another kind of NHL nano-porous gold flake (NGF, the average pore radius is about 20nm, the film thickness is also

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molecules including vapor and the air (Figure 3a), as is called condensation. The two processes are nearly in dynamic equilibrium during water evaporation, thus C1 and C2 are approximately equal, as means that the phase change is nearly thermodynamic equilibrium. The resistance for the molecules escaping out or bouncing back is equivalent to the resistance of mass transfer Rm between the vapor adjacent to the interface and the liquid surface, which can be expressed by the average free path length and the diffusion coefficient D of the vapor molecules, Rm =/D. However, when there is a NHL covering and the evaporation occurs at the orifice of the nano-holes, the radius r of the evaporation surface is nearly equal to the average free path length of the vapor molecules, the situation is quite different. The vaporization process is still diffusion limited, while the condensation process is more complex. Vapor molecules are not only bounced back to the water

surface in the nano-holes, but also bounced back to the wall between the holes and reflex (Figure 3a). Thus, transfer of vapor molecules from bulk space to nano-holes is more difficult than that from bulk to bulk space. Similar to the phonon resistance of an orifice at large Knudsen number [11], considering that there are many holes in parallel connection per unit area, the additional geometry resistance of nanoholes Rg can be expressed as Rg = 4K/3Drn (2) where K is the Knudsen number, K = /r, n is the number of the holes, n = /r2, where is the surface porosity of the NHL. From the above analysis, the vaporization resistance (Figure 3a) can be expressed as Rv = Rm, and the condensation resistance Rc = Rm + Rg. The relation between C1 and C2 can be determined by C1/C2 = Rc/Rg (3) As can be seen from Equation (3), the unbalance of the vaporization and condensation can cause the
A Rm

A C Rg Wall Water Surface B Water Surface

Rm B C

Clusters

Figure 3 a, Molecular dynamics to illustrate the resistance of the vaporization and condensation. There are three kinds of vapor molecules escaping out of the water surface near the nano-holes: A escaping to the bulk vapor region, B being bounced by other molecules back to the water surface and C being bounced back to the wall and reflexing. As for water, C is bounced back to the water as there is no wall. Vapor molecules have additional resistance Rg back to the water surface at the orifice of nanoholes. b, Larger resistance back cause accumulation of the vapor molecules near the nano-holes. Condensation into liquid or nano-clusters may occur, as enhance the diffusion from the liquid-vapor interface to the bulk space as compared with the water surface in the right picture.

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increase of the vapor pressure near the phase-change surface. From the experimental results and Equation (1), Jp/(M/2RTiv)1/2 <<C1Piv, it can be concluded that C1Piv C2Pv , yielding that the super-saturation rate Pv/Piv is about C1/C2. Nucleation into liquid or vapor molecules clusters may occur under the supera

saturation [12], as has a enhancement of vapor diffusion. Under the conditions, the diffusion rate can be written as P M J d = hm v ( Piv P ) Piv RT (4) where is a coefficient only as a function of the system temperature T, which is a constant parameter in this case (see supplementary), hm the mass transfer rate and P is the bulk vapor pressure. As for water surface without lid, =1, =1, Pv Piv. The enhancement rate is actually Pv/Piv. Modeling results of the case with NAF lid under different humidity compared with the experimental results are shown in Figure 4a. The model also gives a prediction for the evaporation rate as a function of the surface porosity under the humidity of 50% (Figure 4b).
CONCLUSION

In summary, a novel evaporation phenomenon has been investigated experimentally and theoretically in this paper. Faster evaporation was observed when the water surface was covered a nano-through-hole lid, as is different from the evaporation case occurred in macro-scale. The phenomenon can be explained by the breakthrough of the diffusion-limited evaporation rate happens near the orifice of the nano-holes. The finding may open a new avenue of phase change in Figure 4 Modeling and theoretical prediction. a, Modeling results nano-scale and put forward a new possible way to of the experimental evaporation rate J(Figure 2a) as a function of increase and control the evaporation rate.
the relative humidity RH. The diamond scatter points represent the evaporation rate per unit actual evaporation area, for which ACKNOWLEDGEMENTS the dashed line theoretically predicts. b, Theoretical prediction The authors gratefully acknowledge the financial for the evaporation rate J as a function of the porosity under the supports received from NSFC 50906064, DF of humidity of 50%. The triangle point represents the case of nanoporous alumina film (NAF, = 0.58), the diamond point MOE 20100141110022, SYG 201132 represents the case of nano-porous gold flake (NGF, = 0.25). REFERENCE

[1] Eijkel, J. C. T., Reemeijer, H. W., Hermes, D. C., Bomer, J. G., van den Berg, A., 2005, Strongly accelerated and humidity-independent drying of nanochannels induced by sharp corners, Physical Review Letters, 95, 256107. [2] Tas, N. R., Mela, P., Kramer, T., Berenschot, J.

W., van den Berg, A., 2003, Capillarity induced negative pressure of water plugs in nanochannels, Nano Letters, 3, 11, 1537-1540. [3] Kim, B. M., Sinha, S., Bau, H. H., 2004, Optical microscope study of liquid transport in carbon nanotubes, Nano Letters, 4, 11, 2203-2208. [4] Tobias, D. W., Abraham, D. S., 2008, The
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transpiration of water at negative pressure in a synthetic tree, Nature, 455, 208-212. [5] Duan, C. H., Karnik, R., 2012, Evaporationinduced cavitation in nanofluidic channels, Proceedings of the National Academy of Sciences, 109, 10, 3688-3693. [6] Malek, K., Coppens, M., 2001, Effects of surface roughness on self- and transport diffusion in porous media in the Knudsen regime, Physical Review Letters, 87, 122505. [7] Kate, J. B., John, H. C., Paul, D. I. F., Sarah, T., 1999, Evaporation rates of water contained within porous silica particles, Physical Chemistry Chemistry Physical, 1, 909-911. [8] Masuda, H., Fukuda, K., 1995, Ordered metal nanohole arrays made by a two-step replication of honeycomb structures of anodic alumina, Science,

268, 5216, 1466-1468. [9] Ding, Y., Kim, Y., Erlebacher, J., 2004, Nanoprous gold leaf: ancient technology / advanced material, Advanced Materials, 16, 21, 1897-1900. [10] Eames, I. W., Marr, N. J., Sabir, H., 1997, The evaporation coefficient of water: a review, International Journal of Heat and Mass Transfer, 40, 2963-2973. [11] Wexler, G., 1966, The size effect and the nonlocal Boltzmann transport equation in orifice and disk geometry, Proceedings of Physical Society, 89, 926942. [12] Daniel, E. R., 1967, Enhancement of diffusionlimited vaporization rates by condensation within the thermal boundary layer, International Journal of Heat and Mass Transfer, 10, 1267-1279.

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