Chemical Engineering Science 63 (2008) 874 880 www.elsevier.

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Effects of surface topography of material on nucleation site density of dropwise condensation

Chunfeng Mu, Jingjing Pang, Qiaoyu Lu, Tianqing Liu
School of Chemical Engineering, Dalian University of Technology, Dalian 116012, China Received 21 March 2007; received in revised form 25 August 2007; accepted 16 October 2007 Available online 18 October 2007

Abstract Heterogeneous nucleation is very important for the initial droplet formation of dropwise condensation, and it is directly related with the surface properties of materials. In this paper, the relationship of nucleation site density with surface topography in nanometer scale for dropwise condensation was experimentally studied on surfaces of magnesium in view of that magnesium can react with hot water (condensate) and make the chemical compositions of the surface changed, and thus leave the nucleation sites in nanometer on the surface. The differential box-counting was used to calculate the fractal dimension of these magnesium surfaces. And condensation experiments were carried out on the magnesium surfaces with different topography under same subcoolings and condensation time. The results showed that surface topography has a great inuence on nucleation site density. The larger the fractal dimensions the more the nucleation sites. A new formula to calculate the nucleation site density was proposed based on the modication of Roses formula with the experimental data. And this new formula can reect the effect of surface fractal dimension on the nucleation sites. 2007 Elsevier Ltd. All rights reserved.
Keywords: Nucleation sites; Dropwise condensation; Surface topography; Fractal dimension

1. Introduction Heterogeneous nucleation is an important process for phase transitions including the initial droplet formation of dropwise condensation. The initial droplets form only at the natural nucleation sites on the condenser surfaces, and the number of nucleation sites inuences dropwise condensation heat transfer signicantly (Rose, 2002). On the other hand, the number of nucleation sites is directly related with the surface properties of materials, thus it is important to study the relationship between surface topography and nucleation number. Lots of scientists and researchers have investigated the problem of nucleation site density of dropwise condensation. Glicksman and Hunt (1972) numerically simulated nucleation, growth, coalescence and renucleation of drops ranging in size from the smallest nucleating drops to departing drops. And their simulated results agreed well with the data of Krischer and Grigull (1971). Wu and Maa (1976) used the population
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E-mail address: liutq@dlut.edu.cn (T. Liu). 0009-2509/$ - see front matter 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.ces.2007.10.016

balance model to derive the size distributions for small pre-coalescence drops, and their calculation showed that the nucleation site density was around 2 107 cm2 . Grifth and Graham (Graham and Grifth, 1973; Graham, 1969) studied the nucleation site density with optical microscope photographs. Their results indicated that the site density was 2 108 cm2 . Tanasawa and co-workers (Tanasawa et al., 1974; Tanasawa, 1974) also investigated the nucleation site density with electron microscope photographs, they found, however, the density exceeded 1010 cm2 . Rose (1976) deduced an equation of nucle2 , with which his calculation ation site density, Ns = 0.037/rmin results illustrated that the nucleation densities were 5.9 109 and 2.9 1011 cm2 , respectively, for the minimum nucleation radius rmin being 0.07 and 0.01 m. All these different gures for nucleation site density from different researchers imply that the density may not be determined only by rmin . It should also be affected by the topography of a surface. And the difference may also result from the different methods applied by researchers to evaluate the nucleation site density from images. There are quite few studies related to the droplet nucleation of dropwise condensation inuenced by surface characteristics.

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McCormick and Westwater (1965) applied optical microscope and showed that the drops nucleated not only at natural cavities on the condenser surface but also at those produced by needles and by erosion and scratches on the surface. Therefore, surface properties of material affect the nucleation site density obviously. However, the work was only limited to a qualitative description and a quantitative investigation of the relationship between surface characteristics and nucleation site densities is necessary. Fractal dimension can be used to describe the irregularity and complexity of a rough surface. Wu et al. (2001) and Yang et al. (1998) studied the fractal character of dropwise condensation. They indicated that the droplet distribution of dropwise condensation appeared with self-similarity, one of the most important features of fractal. However, they only studied the fractal character of droplets themselves without considering the fractal of condensation surface. And there are no publications to date about the fractal investigation of condensation surface topography with its effect on the nucleation site density. In this paper therefore, we tried to nd the relation between the topography of a condensation surface and its nucleation site density quantitatively. Magnesium was applied as condensation surface since it can record the initial nucleation sites where chemical reaction took place when condensate drops formed on the surface (Liu et al., 2007). Meanwhile fractal dimension was used to characterize the topography and complex degree of condensation surface. And the differential box-counting was applied to calculate the fractal dimension of the surface.

3. Determination of surface fractal dimensions Fractal dimension can be used to scale the irregularity and complexity of a rough surface quantitatively. And the boxcounting is one of the well established methods to measure the fractal dimension (D) for materials. It is applied often because it needs less test time and brings about less error than other methods. When a box with side length r is used to cover a certain geometric gure, the gure is said to be a fractal with selfsimilarity if the box number Nr can satisfy the formula Nr = r D . (1)

Then the fractal dimension D is dened by taking the logarithm of both sides of Eq. (1) and letting r 0: D = lim
r 0

log(Nr ) . log(r)

(2)

2. Preparation of magnesium surfaces with different topography Magnetic-control sputtering (MCS), a novel plating lm technology with high speed and low temperature, was used to prepare the magnesium surfaces. The multifunction and ultra high vacuum system (Shenyang Instrument Plant, China) was applied to deposit the magnesium lm on the monocrystalline silicon substrate. The substrate and the magnesium target with purity of 99.999% were completely cleaned before plating the lm. The diameter of the magnesium target was 60 mm. The working pressure, sputtering power and sputtering time were altered to prepare six kinds of magnesium surfaces with different topographies. The corresponding manufacturing parameters are shown in Table 1.
Table 1 Main controlled parameters of the magnetic-controlled sputtering method
Coupon number 1# 2# 3# 4# 5# 6# Sputtering power (W) 90 60 80 65 60 70 Pressure (Pa) Sputtering time (min) 150 120 100 90 60 30 Fractal dimensions (D) 2.628 2.691 2.755 2.778 2.799 2.812

From the geometric sense of fractal, the dimension intuitively can be used to describe the roughness of a surface (Mandelbrot, 1982). An irregular line or a surface with bore can be expressed with D = 1.2, while a rough surface or a hexahedron with bore can be expressed with D = 2.3. The rougher a surface the larger the fractal dimension. In this paper, the differential box-counting method introduced by Sarkar and Chaudhuri (1992) was used to calculate the fractal dimensions of the magnesium surfaces. For an image with area M M , suppose it has been divided into r r blocks, where r is an integer between 1 and M/2. Then the scale factor s now is r/M . Usually an image can be viewed as a three dimension space (x, y, z), where (x, y) is the planar position of a pixel and z is the gray level of this pixel. If plane (x, y) is divided into r r grids, there will be a series of r r s boxes on each grid in the direction of z with s as their height. To ensure the same compressibility factor in the direction of x, y and z, the size of boxes should be restricted as follows: g M 1 = = , s r s (3)

where g is the gray-level index, s is the scale factor. If the minimum and the maximum of gray in (i, j )-grid are located in the boxes p and q, respectively, then the number of the boxes in (i, j )-grid is nr (i, j ) = q p + 1. And the nr (i, j ). total number of the boxes in the image is Nr = Therefore different Nr can be obtained from different r, and the tting of the straight line from log(Nr ) and log(r) can be achieved by means of the least square linear regression method. Then according to Eq. (2), the slope of the line is the fractal dimension (D). 4. Dropwise condensation experiments for nucleation sites The initial dropwise condensation of steam on the magnesium surfaces was realized with the designed apparatus as described in our previous work (Liu et al., 2007).

0.5 0.7 0.6 0.8 0.8 0.7

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Fig. 2. Structural diagram of condensation chamber: 1, condensate drainage; 2, steam inlet; 3, thermocouples in the chamber; 4, coupons; 5, vent of steam or nitrogen; 6, back cover; 7, front cover; 8, hole for thermocouple wires; 9, air outlet; 10, thermocouples in coupons; 11, air inlet; 12, nitrogen inlet.

Fig. 1. Schematic diagram of experiment: 1, steam generator; 2, vaporliquid segregator; 3, nitrogen gas; 4, condensation chamber; 5, air pump; 6, air heater; 7, computer.

4.1. Experimental fundamentals Magnesium can react with hot water, i.e. Mg + 2H2 O(hot water ) = Mg(OH)2 + H2 , while the reaction will be very slow if the reactant is steam and the later reaction can be neglected during short time. If we use metal magnesium as condensation surface, the hot condensate of steam will react with magnesium. Thus the chemical composition of the local surface where the condensate forms will change. Besides, the initial liquid droplet formation of dropwise condensation on the magnesium surfaces can be achieved by controlling the subcooling and the contacting time between the steam and the magnesium surface. In this case, the chemical reaction and thus the variation of the chemical composition will take place only at the places where the initial condensate nuclei form, while the chemical composition on the other places without liquid formation will not change. Therefore, we can nd these nucleation sites afterwards through identifying the oxygen distribution on the surface. It has been proved in our previous work (Liu et al., 2007) that the initial dropwise condensation process can be ensured with steam condensing on the magnesium surface we prepared. The dropwise condensation will not transform to lmwise condensation since the condensation time is only within 10 s in the experiment. Therefore, the nucleation site densities found in this investigation really refer to the dropwise condensation process. 4.2. Experimental apparatus The apparatus used for the initial dropwise condensation in the experiments is shown in Fig. 1, which consists of condensation chamber, air heating, steam generation, nitrogen protection and data collection and control. (1) Condensation chamber: its structural diagram is shown in Fig. 2. It mainly consists of the baseboard and front and back covers. The baseboard and the covers are made from polytetrauoroethylene and polycarbonate, respectively. The outer

size of the chamber is 15 cm in diameter and 5 cm in thickness. Four holes were opened on the baseboard with 1 cm in diameter. The test coupons made of magnesium with 3 mm in thickness were inlaid in these holes. On the back of each coupon a 0.3 mm small hole was drilled to insert a thermocouple for temperature measurement. There are inlets and outlets on the backside and frontside for air and steam or nitrogen gas, respectively. The air owed in the backside while steam or nitrogen owed in the front side. The condensation of steam on the test surfaces could be viewed through the front cover. (2) Air heating: the air in room temperature was pumped by an air compressor and ows through a rotameter and the electric heater. The temperature of exit air can be controlled with the input power of the heater. The hot air entered the back channel of the condensation chamber, contacted the back surfaces of the magnesium coupons which had been xed in the condensation chamber and made the temperature of the coupons rise to the set value. Since wire net packings were inserted in the back channel of the condensation chamber, the temperature in the coupons was uniform and was close to that of hot air because of the enhanced heat transfer with the packings. The set temperature of the coupons was lower than the temperature of steam, thus we could obtain the needed subcooling. The hot air entered the atmosphere when it left the back place of the chamber. (3) Steam generation: a 1 l ask lled with 80% water was put in an electric heating jacket. Steam can be generated by inputting proper power to the jacket. The steam entered the vaporliquid separator before it owed into the condensation chamber, where partial steam condensed on the coupon surfaces and rest steam exited the chamber into the atmosphere. (4) Nitrogen protection: nitrogen out from a nitrogen bottle owed through the condensation chamber with low ow rate so that the magnesium coupons xed in the chamber could be protected against oxidization before and after they contacted with steam. (5) Data collection and control: the thermocouples and the relative electromagnetic valves were linked to a computer with a data collecting and controlling board. And a visual basic program was used to collect temperature data and control the valves.

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Fig. 3. AFM photographs of surfaces in Table 1: (a) topography of 1#; (b) amplitude of 1#; (c) topography of 6# and (d) amplitude of 6#.

4.3. Test methods of initial condensation Nitrogen began to ow through the condensation chamber after the magnesium coupons were xed in the chamber. Then, the air pump and the heater were switched on to make the heated air ow through the back channel of the condensation chamber. When the temperature of the coupons reached the set value and the system arrived stable, nitrogen was shut off and steam began to ow into the chamber with the designed period. After that, steam was closed and replaced with nitrogen again. In this way, the initial condensation on the coupon surfaces with different subcoolings and different condensation time could be realized. 4.4. Measurement of chemical composition of the material surface The chemical compositions of magnesium, oxygen, etc., on the test surfaces as well as their variations before and after condensation were measured with the electron probe microanalyzer (EPMA-1600, Shimadzu, Japan) by randomly selecting the micro areas on the surfaces. Also, the distributions of these elements on the surfaces were scanned with the instrument. The measurement principle of an EPMA is that the characteristic X-ray of an element on the sample surface can be excited out with the incidence of a nely focused electron beam. Then the kinds and contents of elements on the sample surface can be identied by analyzing the wavelength and intensity of the X-ray, respectively. In this way we can determine where the condensate reacted with the magnesium. The minimum scanned analyzed area could be 1 m 1 m. 5. Results and discussion 5.1. Topography and roughness of the magnesium surfaces The topography of the prepared magnesium surfaces and their surface roughnesses were characterized with the atomic force microscope (AFM, PicoPlus, Molecular Imaging Company, US). The average value of three local measurements randomly selected on each surface was taken as the average roughness for the surface. Two different surfaces are shown in Fig. 3, which clearly indicates that different surface topographies and roughnesses can be obtained with different sputtering conditions. Additionally, the thickness of the magnesium lm plated with MCS method was measured with the

Fig. 4. SEM micrograph of 1# magnesium surface.

electron probe microanalyzer (EPMA-1600, Shimadzu, Japan). The thickness of the plated lm was 21 m, which meant that the substrate surface was completely covered by magnesium. 5.2. Fractal dimension of magnesium surfaces The photographs were taken from six groups of magnesium surfaces using scanning electron microscope (SEM) JSM5600LV. The typical gray-scale image of 1# surface is shown in Fig. 4. The noise signal was removed from the images with Image Pro-Plus5.0 image processing software, and the images were treated particularly to make them have the optimal contrast degree. Then the fractal images can be obtained. The higher the position on an image, the brighter the corresponding pixel on the image. Five districts with 400 400 pixel units for each were randomly selected from each SEM micrograph image. Then the box number Nr corresponding to the different size r on each district was calculated according to the differential box-counting method with the program developed by ourselves in MATLAB software And then the line of log(Nr ) vs. log(r) could be tted by the least square linear regression method as typically illustrated in Fig. 5. Since log(Nr ) has a good linear relationship with log(r), obvious fractal character exists on each of the magnesium surfaces. Besides, the fractal dimensions at different district of the same magnesium surface were almost the same, which indicated that each magnesium surface prepared with magnetron sputtering was uniform. The average of the fractal dimensions of the ve different districts was taken as the fractal dimension of the surface, which is shown in the column 5 of Table 1. 5.3. Nucleation site density of magnesium surfaces The distributions of oxygen and magnesium on all the six test surfaces were scanned with EPMA before and after the initial dropwise condensation. And the typical results of surface 1# as an example under nanometer scale are shown in Fig. 6a1 and b1.

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The oxygen element distribution images a1 and b1 in Fig. 6 were rstly transformed into gray images a2 and b2, from which the corresponding histograms a3 and b3 could be found. It can be seen that the locations with gray values higher than 100 show the reaction areas where condensate is generated. Then three districts with 128 128 pixel units for each were randomly selected from each gray image Furthermore the area ratio in each district with gray value higher than 100 was calculated with Image Pro-Plus5.0 software, and the average of all area ratios of theses three districts was expressed with AR , which was taken as the area ratio occupied by condensate for the surface. Therefore, the nucleation site density can be expressed

as follows:
Ns = AR
2 r 0

area ratio occupied by all condensate nuclei . area occupied by an averaged condensate nucleus

(4) In this equation, the denominator represents the area of a single condensate nucleus with nuclear average radius, whereas the numerator represents the area occupied by all nuclei on unit area. Thus, Eq. (4) can be used to calculate the nucleation site density based on the experimental measurement. r 0 in Eq. (4) is the average nuclear radius, which is dened as r 0 =
rmin rmax 1/2 2 r0 d(Ns )

Ns

(5)

The minimum nuclear radius rmin , maximum droplet radius rmax and the nucleation site density Ns can be calculated by the following formulas, respectively (Graham and Grifth, 1973; Le Fevre and Rose, 1965, 1966; Rose, 2002), rmin = 2 Ts , hfg T
1/2

(6)

rmax = 0.4 Ns = 0.037 . 2 rmin

(7) (8)

By substituting Eq. (8) to Eq. (5), r 0 becomes r 0 = 2 ln

Fig. 5. Linear relation between logarithmic box number and its size for 1# magnesium surface.

rmax rmin

1/2

rmin .

(9)

Thus, the nucleation site densities of all the six magnesium surfaces under different subcoolings can be found according to

Fig. 6. Distributions of oxygen and magnesium on 1# surface in nano-scale before and after condensation. EPMA scanned area 1 m 1 m. Green color: oxygen; blue color: magnesium. (a1), (b1): EPMA scanned pictures; (a2), (b2): gray images corresponding to (a1) and (b1); (a3), (b3): gray histograms corresponding to (a2) and (b2) to conrm image threshold value.

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Table 2 Nucleation site densities on different magnesium surfaces
Coupon number 1# 2# 3# 4# 5# 6# 1# 2# 3# 4# 5# 6# 1# 2# 3# 4# 5# 6# AR (%) 7.096 8.101 8.729 8.985 16.547 17.050 10.218 13.274 21.584 22.966 24.165 28.971 16.916 17.980 25.981 28.037 32.927 39.541 Subcooling 1.9 1.9 1.8 1.6 1.6 1.6 2.7 2.3 2.3 2.3 2.5 2.3 4.6 4.6 4.6 4.5 4.5 4.4 Ns (sites/ m2 ) 96 106 111 103 189 195 206 220 358 381 443 480 609 754 1089 1139 1338 1555 D 2.628 2.691 2.755 2.778 2.799 2.812 2.628 2.691 2.755 2.778 2.799 2.812 2.628 2.691 2.755 2.778 2.799 2.812 f (D) 0.011 0.014 0.018 0.029 0.031 0.032 0.012 0.017 0.023 0.030 0.029 0.038 0.014 0.015 0.022 0.024 0.028 0.034

879

Fig. 8. Relation between fractal dimension D and f (D).

nuclei without getting larger but leaving the reaction mark (the initial nucleation sites) on the magnesium surface. 5.4. Quantitative correlation between nucleation density and fractal dimensions Roses formula for nucleation site density calculation, formula (8), only includes the effect of the minimum nucleation radius, which in turn includes the subcooling T , on the nucleation site density, but without considering the inuence of surface topography. Quantitative relationship between nucleation site density and surface topography is necessary to be set up since our experiments have clearly indicated their obvious correlation. Here, we propose the following formula to modify Roses calculation: Ns = f (D) , 2 rmin (10)

Fig. 7. Relationship of fractal dimension (D) and nucleation site density under different subcoolings.

where f (D) is a function of D, an expression to be founded to reect the effect of fractal dimension on nucleation site density. If we replace Eq. (8) with Eq. (10) and then substitute it into Eq. (5) and then in Eq. (4), the following can be obtained: f (D) = AR . 2 ln(rmax /rmin ) (11)

Eq. (4) with the experimentally obtained AR . And the results are summarized in Table 2 and showed in Fig. 7, which clearly shows that the nucleation site densities change not only with subcoolings but also with surface fractal dimensions. Therefore, the surface topography has important effect on the nucleation site density of dropwise condensation. It should be pointed out the reason why the initial condensate nuclei can be preserved on the magnesium surface. The key point is that the initial droplets will react with magnesium and reduce the size of a droplet. According to the thermodynamics theory, only the initially formed droplets with the radius larger than the minimum nucleation radius can grow, while those with the radius less than the minimum nucleation radius will disappear. Therefore, the condensate nuclei formed on magnesium surface will reduce their size since the instantaneous chemical reaction consumes the condensate, which results in the formed

Hence the values of f (D) could be found under all the conditions and they are listed in the last column of Table 2. Furthermore, the relation between f (D) and D is plotted in Fig. 8 and the function format of f (D) could be determined by tting all these values with the function. Finally the new formula to calculate Ns is founded after substituting f (D) into Eq. (10): Ns = 0.01 + 2.019 1021 e15.62D . 2 rmin (12)

Eq. (12) indicates that the nucleation site density for dropwise condensation increases with surface fractal dimension within the range of 2.62752.812. As the higher fractal dimension of a condensation surface reveals more aws such as

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sidelines, angles and edges existed on the surface, the probability of producing more active positions increases with fractal dimensions. These active positions have higher priority of forming initial nuclei. That is, the higher the fractal dimensions of a surface, the more the nucleation sites on it. 6. Conclusions (1) The topography of condensation surface has a great inuence on nucleation site density. The larger the surface fractal dimension, the more the nucleation sites. (2) A new formula of nucleation site density for dropwise condensation is proposed based on the modication of Roses formula. It can reect the effect of surface topography on the nucleation site density. Notation AR D g hfg M Nr Ns Ns r r0 r0 rmax rmin s s Ts T reacted area ratio on magnesium surface fractal dimension the gray-levels of an image latent heat of vaporization, J kg1 the length of an images side, m the number of boxes used to cover a certain geometric gure nucleation site density with Roses formula, m2 nucleation site density with modied formula, m2 the length of a single boxs side, m nuclear radius, m average nuclear radius, m maximum droplet radius, m minimum nuclear radius, m scale factor the height of a single box, m saturated temperature, K surface subcooling, K density of the condensate, kg m3 surface tension, N m1

Acknowledgment This work was supported by the National Natural Science Foundation of China (50376006). References
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