International Journal of Heat and Mass Transfer 53 (2010) 58–67

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International Journal of Heat and Mass Transfer

journal homepage: www.elsevier.com/locate/ijhmt

Augmentation of nucleate boiling heat transfer and critical heat flux using
nanoparticle thin-film coatings
Eric Forrest a, Erik Williamson b, Jacopo Buongiorno a, Lin-Wen Hu c,*, Michael Rubner b, Robert Cohen d
a
Department of Nuclear Science and Engineering, Massachusetts Institute of Technology, USA
b
Department of Materials Science and Engineering, Massachusetts Institute of Technology, USA
c
Nuclear Reactor Laboratory, Massachusetts Institute of Technology, USA
d
Department of Chemical Engineering, Massachusetts Institute of Technology, USA

a r t i c l e i n f o a b s t r a c t

Article history: Nanoparticle thin-film coatings applied to boiling surfaces using a layer-by-layer (LbL) assembly method
Received 4 October 2009 demonstrated significant enhancement in the pool boiling critical heat flux (CHF) and nucleate boiling
Available online 31 October 2009 heat transfer coefficient. Up to 100% enhancement of the critical heat flux and over 100% enhancement
of the heat transfer coefficient were observed for pool boiling of nickel wires coated with different
Keywords: thin-films of silica nanoparticles. Surface characterization revealed that the surface wettability changed
Heat transfer enhancement drastically with the application of these coatings, while causing virtually no change in the surface rough-
Critical heat flux
ness. It is concluded that the nanoporous structure coupled with the chemical constituency of these coat-
Pool boiling
Thin-film coatings
ings leads to the enhanced boiling behavior.
Ó 2009 Elsevier Ltd. All rights reserved.

1. Introduction other boiling parameters such as nucleation site density, bubble

diameter, bubble departure frequency. These nanoparticle disper-
Heat transfer systems that operate in the nucleate boiling re- sions, or ‘‘nanofluids” as they are often referred to in the litera-
gime are limited by a critical heat flux (CHF), at which a vapor film ture, consist of particles such as metal oxides, metals, or
envelopes the heated surface and severely deteriorates heat trans- allotropes of carbon added to base fluids [3]. Various nanofluid
fer. It is crucial that systems such as nuclear reactors operate below boiling studies have reported up to 200% enhancement in pool
the critical heat flux to prevent a temperature excursion and sub- boiling CHF, with CHF enhancement being realized at very low
sequent failure of the heat transfer surface. Therefore, raising the nanoparticle loadings (60.1% by volume) [4]. For the heat transfer
upper limit of nucleate boiling could allow for higher safety mar- coefficient, some studies report enhancement, some deterioration,
gins, higher rates of heat transfer in existing systems, or a reduc- and others no change for boiling in dilute nanofluids [4]. Charac-
tion in the size of new systems while maintaining the same heat terization of these dilute nanofluids shows insignificant changes
transfer capability. As an example, it has been demonstrated that in fluid properties such as thermal conductivity, viscosity, etc.
a 32% increase in CHF would allow for a 20% power density uprate After boiling in nanofluids, a porous coating of nanoparticles is
in pressurized water reactors, thereby improving the economics for typically observed on heater surfaces, explaining increases in sur-
electricity generation [1]. face wettability and the resulting CHF enhancement [5]. Changes
The nucleate boiling heat transfer coefficient dictates the opera- in the boiling behavior for dilute nanofluids can therefore be
tional temperature of a boiling surface at a given heat flux. Devices attributed to surface modification resulting from nanoparticle
such as power electronics are highly sensitive to temperature in- deposition on the heater surface.
creases. It is therefore desirable to increase the nucleate boiling heat Modifying surfaces to augment boiling heat transfer and CHF is
transfer coefficient in two-phase cooling systems to optimize the not a new concept. Berenson observed that increasing surface
performance and operating lifetime of such devices. An overreach- roughness can affect the heat transfer coefficient by 500–600%
ing goal of thermal-fluid design has been to find a cost-effective [6]. Webb summarizes a number of surface treatment techniques,
means of enhancing CHF and boiling heat transfer [2]. including mechanical treatments to increase surface roughness
Studies in two-phase heat transfer over the past several years along with microparticle coatings to alter surface morphology
have demonstrated that the addition of nano-sized (1–100 nm) [7]. Hwang and Kaviany have demonstrated increases in CHF up
particles to base fluids can significantly increase CHF and alter to 96% for pool boiling of n-pentane using thin, uniform micropar-
ticle coatings on heater surfaces [8]. Kim et al. have reported
* Corresponding author. Tel.: +1 617 258 5860; fax: +1 617 253 7300. enhancement for both nucleate boiling heat transfer and CHF in
E-mail address: [email protected] (L.-W. Hu). FC-72 using microparticle coatings on wires [9].

0017-9310/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijheatmasstransfer.2009.10.008
 E. Forrest et al. / International Journal of Heat and Mass Transfer 53 (2010) 58–67 59

Nomenclature

D wire diameter, m Twall wall temperature, °C

Dc cavity diameter, m DT temperature difference, °C
g gravitational acceleration, m/s2 a temperature coefficient of resistance, K1
heff effective heat transfer coefficient, W/(m2 K) b receding contact angle, °
hfg heat of vaporization, J/kg csv solid–vapor interfacial tension, N/m
I current, A csl solid–liquid interfacial tension, N/m
K Zuber constant de equivalent macrolayer thickness, m
L wire length, m h contact angle, °
NA nucleation site density, #/m2 hA apparent contact angle, °
q00 heat flux, W/m2 hI intrinsic contact angle, °
q00CHF critical heat flux, W/m2 j hot/dry spot constant
R electrical resistance, X qf liquid density, kg/m3
rb bubble radius, m qg vapor density, kg/m3
T temperature, °C r surface tension, N/m
T0 nominal temperature, °C u Heater orientation, °
Tsat saturation temperature, °C

Although various methods have been tested for modifying boil- More recently, Lee et al. have demonstrated the ability to create
ing surfaces over the years, the predominant focus has been on nanoparticle thin-film coatings of controlled thickness and compo-
microscale modification of surface morphology. The recent work sition using different types of nanoparticles and deposition condi-
in the field of nanofluids has led to an interest in the nanoscale tions [15–17]. The use of nanoparticle thin-film coatings has been
modification of surfaces and its effect on nucleate boiling heat investigated for glass and other non-metallic substrates for use in a
transfer and CHF. The expected advantages of nanoscale modifica- variety of applications including anti-fog, anti-reflection, and self-
tions include finer control over porosity and surface roughness, cleaning coatings [18].
thinner coating layers to reduce thermal resistance and thermal This work investigates pool boiling characteristics of polymer/
stress and ultimately higher durability. Boiling deposition of nano- SiO2 nanoparticle multilayers applied to nickel wire using the
particles on surfaces has been proven to enhance CHF, but the layer-by-layer (LbL) deposition method. Various coating features
nanoparticle-surface adsorption phenomenon is not well under- were altered in this study to explore the effects of surface param-
stood. Additionally, this method has little to no control over sur- eters such as wettability and coating thickness on the nucleate
face characteristics such as coating thickness or porosity. boiling heat transfer coefficient and CHF. Additionally, stainless
Continuous immersion in dilute nanofluids offers the potential steel plates were coated with polymer/SiO2 thin-film coatings in
for a regenerative nanoparticle coating were parts to scale off. order to further explore the characteristics of such coatings on
However, this scenario may not be applicable to certain systems. metal substrates.
A carefully engineered approach to coating surfaces with nanopar-
ticles may resolve issues associated with boiling deposition of
nanoparticles. Control of coating thickness, chemical constituency, 2. Experimental procedure
and porosity not only provide the potential for optimal enhance-
ment of the nucleate boiling heat transfer coefficient and CHF, 2.1. Preparation of thin-film coatings
but also provide insight into the physical mechanism of CHF, which
is not well understood. Several recent studies on nano-structured Three types of thin-film coatings were prepared using the LbL
surfaces have found favorable boiling heat transfer properties of assembly method, following a procedure similar to that used by
nano-structured surfaces. Ahn et al. demonstrated that multi- Bravo et al. [19]. The prepared coatings will be described as hydro-
walled carbon nanotube forests, up to 25 lm in height, increased philic, superhydrophilic, or hydrophobic. The substrates were 0.0100
both pool boiling heat transfer and CHF using refrigerant PF-5060 (0.25 mm) nickel wires (99.98% pure, metals basis) and A286 stain-
[10]. Ujereh et al. reported that carbon nanotubes coating on sili- less steel plates. For the coating process, all polymer solutions were
con and copper substrates is highly effective in reducing the incip- prepared to 10 mM concentrations (repeat-unit basis). Solutions
ience boiling superheat, and enhancing both heat transfer were titrated to the required pH using either 1 M aqueous hydro-
coefficient and CHF using FC-72 with higher enhancement found chloric acid or 1 M aqueous sodium hydroxide. Ultra-pure de-ion-
on silicon than copper substrate [11]. Chen et al. obtained 100% in- ized water (>18.2 MX, Millipore Milli-Q) was used for all solutions
crease in heat transfer rate and CHF with copper and silicon nano- and rinse water.
wires about 200–300 nm in diameter and 50 lm long. They Multilayer assembly involved immersing the substrate in a
attributed the heat transfer enhancement to high nucleation site solution of a positively charged species for 10 min, followed by
density, superhydrophilicity, and capillary pumping effect [12]. immersion in three separate rinse baths for 2 min, 1 min, and
Layer-by-layer (LbL) deposition offers a means to easily apply 1 min, respectively. The substrate was then immersed in a solution
conformal thin-film coatings of nanoparticles while carefully con- of a negatively charged species for 10 min, followed by immersion
trolling surface characteristics. The LbL assembly method is an in three rinse baths. The assembly of one layer of positively
aqueous chemical method that achieves surface adhesion and the charged species and one layer of negatively charged species is re-
adsorption of subsequent layers onto the surface through alternat- ferred to as a bilayer. By repeating the assembly process, multiple
ing the charge of the deposited particles. This technique was first bilayers can be deposited onto a substrate. Fig. 1 depicts the bilayer
presented by Iler in 1966 for depositing nanoparticles of alternat- assembly process.
ing charge on a surface [13]. Decher and Hong later demonstrated Hydrophilic thin-film coatings were prepared using the follow-
the ability to construct multilayers using charged polymers [14]. ing procedure. Solutions of sodium poly(styrene sulfonate) (SPS,
60 E. Forrest et al. / International Journal of Heat and Mass Transfer 53 (2010) 58–67

Fig. 1. Illustration of the assembly process for constructing one bilayer on a nickel or stainless steel substrate.

nominal Mn = 70,000 g/mol) and poly(allylamine) hydrochloride

(PAH, nominal Mn = 70,000 g/mol) were each prepared and titrated
to pH 4.00. A second solution of PAH was prepared and titrated to
pH 7.50. A silica nanoparticle dispersion was prepared by first add-
ing 0.1 M NaCl to pH 9.00 buffer solution and then adding
0.03 wt.% of both 24 nm silica particles (Ludox TM-40) and
50 nm silica particles (Polysciences microspheres). Using a Zeiss
HMS programmable slide stainer, five bilayers of PAH (pH 4.00)/
SPS (pH 4.00) were applied to the substrates. The PAH/SPS bilayers
were applied to ensure adhesion of subsequent PAH/SiO2 nanopar-
ticle bilayers. After applying the PAH/SPS adhesion bilayers, be-
tween 10 and 40 bilayers of PAH (pH 7.50)/SiO2 (pH 9.00) were
applied, depending on the desired coating thickness. The samples
were then allowed to dry overnight.
Superhydrophilic thin-film coatings were prepared in the exact
manner described above for the hydrophilic coatings, with one
additional step at the end of the process, i.e., the samples were cal- Fig. 2. Schematic of the wire boiling facility.
cinated at 550 °C for 4 h in a furnace. The calcination removes the
polymeric components from the coating, leaving behind only a
pressure. For the boiling experiments, the wire was heated resis-
SiO2 nanoparticle matrix. The calcination serves to increase the
coating’s durability, effectively sintering the nanoparticles to each tively using a Sorensen SRL DC power supply. While an electric
pre-heater brought the isothermal bath and test fluid up to satura-
other and the substrate. What remains is a mechanically durable
tion temperature, the wire was maintained at low heat flux in or-
coating with good adhesion, which, according to Cebeci et al.
der to remove any non-condensable gas bubbles stuck to the
[18], survives aggressive rubbing and easily passes a standard
heater surface. An Agilent Technologies 34980A Data Acquisition
scotch tape peel test on glass substrates. It should be noted that
System measured the voltage drop across the wire, along with
superhydrophilicity has been defined as a water droplet having a
the voltage drop across a shunt resistor to determine the current
contact angle of 5° or less within 0.5 s of contacting the surface
passing through the wire. The heat flux through the wire was cal-
[18]. To simplify discussion of the results, the definition here will
culated by:
be loosened to include surfaces with water droplet contact angles
less than 15° after 0.5 s and virtually zero degree contact angle IV
after several seconds.
q00 ¼ ð1Þ
pDL
Hydrophobic thin-film coatings were prepared using the exact
A type K thermocouple measured the temperature of the test bath
procedure described for the superhydrophilic coatings, with one
to ensure it remained at saturation. The temperature of the nickel
additional step. After calcination, the samples were placed in a
wire was calculated using the temperature coefficient of resistance
polytetrafluoroethylene (PTFE) container with an open vial of
method, where the change in electrical resistance of the wire was
1H,1H,2H,2H-perfluorodecyltriethoxysilane (fluorosilane, Alfa-
correlated to the temperature change of the wire using:
Aesar). The sealed PTFE container was then placed in a 140 °C oven
for 30 min. After standing overnight, the resulting nickel and stain- RðTÞ ¼ RðT 0 Þ½1 þ aDT ð2Þ
less steel samples exhibited hydrophobic behavior due to the
Nickel was chosen due to its corrosion resistance and high sensitiv-
chemical vapor deposition of the fluorosilane on the SiO2 nanopar-
ity in electrical resistivity over the temperature range of interest
ticle matrix.
(i.e. large temperature coefficient of resistance), as is the case for
most pure metals when compared to metal alloys. The linearized
2.2. Pool boiling tests temperature coefficient of resistance, a, for the nickel was deter-
mined to be 0.0053 ± 0.0006 K1 over the temperature range of
The boiling heat transfer coefficient and critical heat flux were interest. The temperature coefficient of resistance was verified
measured for bare nickel wires and coated nickel wires in pure within the measurement uncertainty for bare and oxidized wires,
de-ionized water using the pool boiling apparatus depicted in and in power cycling tests. A Biot-type analysis reveals that one
Fig. 2. All boiling experiments were conducted at atmospheric may approximate the surface temperature of the wire as equal to
 E. Forrest et al. / International Journal of Heat and Mass Transfer 53 (2010) 58–67 61

the average radial temperature due to the small diameter and high Microscope measured the surface roughness of bare and coated
thermal conductivity of nickel. stainless steel plates. Table 2 summarizes the results of surface
Boiling tests were conducted by increasing the power in steps roughness measurements for the plates. The measurements indi-
until CHF was reached. At CHF, the nickel wire typically became cate that there is virtually no change in surface roughness with
red hot and subsequently failed. At each power step, the heat flux the application of the thin-films. This implies that the nanoparti-
and wire resistance were recorded for the purpose of plotting boil- cle-based coatings fill microscale deformities in the stainless steel
ing curves and calculating the effective heat transfer coefficient. surface conformally, which is expected with the LbL deposition
The effective heat transfer coefficient is given by Newton’s Law method.
of Cooling:
3.1.3. Thin-film coating thickness
q00 ¼ heff ðT w  T sat Þ ð3Þ
SEM images were taken for nickel wires coated with PAH/SiO2
Measurement uncertainty was typically 2.2% or less for the heat flux, thin-films. Images show qualitatively that the coatings are gener-
11% or less for the wall superheat, and 12% or less for the heat transfer ally smooth and homogenous on the microscale. Estimates of coat-
coefficient. Uncertainty in the wall superheat and heat transfer ing thickness can also be obtained from SEM images. SEM images
coefficient was primarily due to the uncertainty associated with the reveal that 10-bilayer PAH/SiO2 coatings are of the order of
linearized temperature coefficient of resistance for the nickel wire. 300 nm thick, 20-bilayer coatings are of the order of 600 nm thick,
and 40-bilayer coatings are of the order of 1 lm thick. Therefore,
3. Thin-film coating characterization and experimental results coating thickness is almost linearly proportional to the number
of bilayers. Fig. 4 shows a front-on view of a clipped 0.0100 nickel
3.1. Characterization of thin film coatings wire coated with 40-bilayers of PAH/SiO2. These data correspond
closely to data previously collected for multilayers of the same
3.1.1. Contact angle measurements composition deposited on glass substrates. On glass, the per-bi-
Contact angles for thin-film coatings on flat stainless steel layer thickness was 28 nm, constant up to at least 40 bilayers [19].
plates are listed in Table 1. A CAM 101 contact angle analyzer
and optical measurement software (KSV Instruments) measured 3.2. Pool boiling results
the static and dynamic contact angles of de-ionized water on bare
and coated stainless steel plates, providing insight into the wetta- Fig. 5 shows boiling curves obtained for nickel wires coated
bility change by applying the PAH/SiO2 thin-film coatings. All mea- with hydrophilic, superhydrophilic, and hydrophobic PAH/SiO2
surements were taken at room temperature. Contact angles are nanoparticle thin-films. Note that the boiling curve for the hydro-
reported after 0.480 s for the superhydrophilic cases, as the static philic test case closely resembles that of the bare wire, except that
contact angles were so small as to be immeasurable (less than CHF is enhanced considerably. For the hydrophobic wire, the shape
3°). Note that starting with the same calcinated PAH/SiO2 coating, of the boiling curve resembles that of the bare wire and hydrophilic
dramatically different contact angles can be achieved by altering wire, except that it is shifted to the left. The substantial reduction
the chemical constituency of the top surface. in the wall superheat for the hydrophobic wire signifies apprecia-
Typically, the static contact angle is expected to be between the ble enhancement in the nucleate boiling heat transfer coefficient.
static receding contact angle and static advancing contact angle Additionally, CHF is still enhanced for the nickel wire with hydro-
[20]. For the hydrophobic surface, an unusually large contact angle phobic treatment over the bare wire test case. As seen in Fig. 5, the
hysteresis was observed, with receding contact angles as low as most unusual behavior is exhibited by the wire with the superhy-
19°. Fig. 3 depicts the various contact angles, highlighting the stark drophilic coating, where the wire temperature increases dramati-
differences in wettability that can be achieved with the PAH/SiO2 cally until falling at high heat fluxes.
coatings. The images shown in Figs. 6 and 7 help explain the shapes of the
Since contact angle depends on the chemical constituency of boiling curves plotted in Fig. 5. Figs. 6 and 7 show boiling from the
the coating and not the substrate, one would expect similar wet- wire for the different test cases at different heat fluxes. As seen in
ting properties for coatings on other substrates. However, since Fig. 6, the hydrophobic wire has more bubble nucleation sites than
the coating is conformal, one should not neglect the roughness of the bare wire at low heat fluxes. This implies that the hydrophobic
the substrate, as it could have an effect on the contact angle. Since wire will have a higher heat transfer coefficient for a given heat
expected contact angles for smooth nickel are typically between flux, which is corroborated by the boiling curve. Conversely, even
60° and 80° [21,22], changes in contact angle for a smooth nickel at a relatively high heat flux of 500 kW/m2, the wire with the
surface coated with these thin-film coatings should be similar to superhydrophilic coating has a considerably lower number of
changes seen for stainless steel plates. nucleation sites than the bare wire, as shown in Fig. 7. This implies
that the wall superheat will be much greater than that for the bare
3.1.2. Surface roughness measurements wire, which is once again corroborated by the boiling curve in
Confocal microscopy provided measurements of the surface Fig. 5.
roughness value for stainless steel plates with PAH/SiO2 thin-film For the superhydrophilic PAH/SiO2 thin-film coating, 10-bilayer,
coatings. An Olympus LEXT OLS3000 Confocal Scanning Laser 20-bilayer, and 40-bilayer cases were examined to evaluate the ef-
fect of coating thickness on the heat transfer coefficient and CHF.
Table 1 Fig. 8 displays the nominal CHF values versus coating thickness.
Summary of measured contact angles for flat stainless steel plates. Typical measure- For the PAH/SiO2 coatings, thickness of the polymer adhesion lay-
ment uncertainty is ±5°. ers is negligible compared to SiO2 nanoparticle layers. Therefore, a
Surface Static (°) At t = 480 ms 20-bilayer coating may be considered twice as thick as a 10-bilayer
Clean surface 84 Not measured
coating, and a 40-bilayer coating twice as thick as a 20-bilayer
40 Bilayers PAH/SiO2 21 Not measured coating. Fig. 8 indicates that CHF increases with coating thickness
10 Bilayers PAH/SiO2, calcinated <3 11° between 10 and 40 bilayers.
20 Bilayers PAH/SiO2, calcinated <3 12° Table 3 summarizes average CHF values for all nickel wire boil-
40 Bilayers PAH/SiO2, calcinated <3 11°
ing test cases. Note that CHF enhancement was observed for all
20 Bilayers PAH/SiO2, calcinated fluorosilane 141 Not measured
nickel wires with thin-film coatings, regardless of the final treat-
62 E. Forrest et al. / International Journal of Heat and Mass Transfer 53 (2010) 58–67

Fig. 3. Static contact angles of water on stainless steel plates for. (a) clean surface, (b) surface coated with 40 bilayers of PAH/SiO2, and (c) surface coated with 20 bilayers of
PAH/SiO2, calcinated, and treated with fluorosilane. Contact angles after 480 ms on plates with calcinated PAH/SiO2 for (d) 10 bilayers, (e) 20 bilayers, and (f) 40 bilayers.
Advancing (g) and receding (h) contact angles for surface coated with 20 bilayers of PAH/SiO2, calcinated, and treated with fluorosilane.

Table 2 accounts for both the nucleate boiling heat transfer coefficient
Ra values for flat plates coated with PAH/SiO2. Typical measurement uncertainty is and CHF.
±0.1 lm.

Case Ra (lm) 4. Discussion

Bare plate 0.290
40 Bilayers PAH/SiO2 0.261 4.1. Effect of surface structure and chemical constituency on
20 Bilayers PAH/SiO2, calcinated, fluorosilane 0.225
wettability
10 Bilayers PAH/SiO2, calcinated 0.281
20 bilayers PAH/SiO2, calcinated 0.222
40 Bilayers PAH/SiO2, calcinated 0.268 Previous work on boiling heat transfer of nanofluids by Kim
et al. [5] has shown that porous deposits of nanoparticles on boil-
ing surfaces lead to a substantial increase in the surface wettabil-
ment. The maximum average CHF value of 101% was observed for ity, as measured by the contact angle of water on the surface.
the nickel wires that were coated with 40-bilayers of PAH/SiO2 and Fig. 3 shows that a wide range of contact angles can be achieved
calcinated. with the nanoparticle thin-film coatings tested in this study. For
Although the superhydrophilic wires displayed the greatest a perfectly flat surface, the intrinsic contact angle may be deter-
enhancement in CHF, they suffered substantial degradation in the mined using Young’s equation:
heat transfer coefficient. Fig. 9 shows the effective heat transfer csv  csl
cos hI ¼ ð4Þ
coefficient plotted against heat flux for nickel wire coated with r
the PAH/SiO2 thin-films. Nickel wires with the non-calcinated, Here csv  csl represents the adhesion tension for the liquid/solid
hydrophilic coating showed virtually no change in the heat transfer combination, and r is the surface tension of the liquid. However,
coefficient at a given heat flux when compared with the base case. if a surface is not perfectly flat, one must account for the surface
The wires with the hydrophobic treatment showed on average roughness, as described by Wenzel [23], in order to determine the
127% enhancement in heff over the untreated surfaces at their apparent contact angle:
respective critical heat fluxes. Clearly, the hydrophobic coating
demonstrates the optimum performance enhancement when one cos hA ¼ r cos hI ð5Þ
 E. Forrest et al. / International Journal of Heat and Mass Transfer 53 (2010) 58–67 63

Fig. 4. SEM image showing diametric view of 0.0100 nickel wire with 40 bilayers PAH/SiO2. The light gray portion is the nickel wire, whereas the darker profile surrounding it is
the PAH/SiO2 coating.

Fig. 5. Boiling curves for 0.0100 Diameter bare nickel wire (squares), wire coated with 40 bilayers of PAH/SiO2, (circles), wire coated with 40 bilayers PAH/SiO2 and calcinated
(inverted triangles), and wire coated with 20 bilayers PAH/SiO2 and calcinated with fluorosilane treatment (triangles). All wires were boiled in pure de-ionized water. The
highest heat flux of each boiling curve corresponds to CHF.

Fig. 6. (a) Bare nickel wire at q00 = 150 kW/m2 and (b) hydrophobic wire at q00 = 150 kW/m2.

Here r is the roughness factor, which Wenzel defined as the total of line tension, the local contact angle on a rough surface will be ex-
surface area divided by the projected area. Note that, in the absence actly equal to the intrinsic contact angle for that material.
64 E. Forrest et al. / International Journal of Heat and Mass Transfer 53 (2010) 58–67

Fig. 7. (a) Bare nickel wire at q00 = 500 kW/m2 and (b) superhydrophilic wire at q00 = 500 kW/m2.

with the calcinated coatings. This can be attributed to the presence

of PAH in the multilayers, which is slightly hydrophobic in nature.
Therefore, removal of the PAH during calcinations increases the
hydrophilicity of the coating. Nonetheless, significant improve-
ment in wettability is still observed due to the effect of the silica
particles (h = 84–21°) even if the PAH is not burned out. Following
calcination, a contact angle of about 10° is observed 480 ms after
droplet contact, with nearly perfect wetting after several seconds.
The hydrophobic surface is perhaps the most fascinating, as the
hydrophobic behavior is achieved from the superhydrophilic coat-
ing through only slight changes in surface chemistry. As discussed,
wettability is controlled by both the surface energy (the adhesion
tension) and the geometry or texture of the surface (the r term
in Eq. (5)). The hydrophobic coating, while maintaining the same
geometry and surface texture as the superhydrophilic coating,
experiences a substantial change in wettability by changing the
Fig. 8. Average CHF enhancement versus coating thickness for calcinated PAH/SiO2
surface adhesion tension through application of the fluorosilane.
coated nickel wires. Error bars indicate the standard deviation in CHF for three
nominally identical tests. The wetting behavior of the hydrophobic surface is also character-
ized by a large contact angle hysteresis, with an advancing angle
around 160° and a receding angle around 20°. For the hydrophobic
Table 3
coatings investigated in this study, the nanostructure, combined
Summary of CHF values for 0.0100 nickel wire boiling tests. Average enhancement for with the chemical vapor deposition of fluorosilane, leads to the
coated wire over untreated wire is also provided. high advancing contact angles and large contact angle hysteresis.
Test case Average CHF CHF Std. CHF
By isolating the parameters that effect surface energy, this study
(kW/m2) Dev.a (%) enhancement provides insight into the individual effects of surface energy and
Bare wire 862 7.4 –
surface geometry/texture on wettability and boiling heat transfer.
40 Bilayers PAH/SiO2 1583 4.5 84%
20 Bilayers PAH/SiO2, 1458 21 69% 4.2. Effect of thin-film coatings on boiling heat transfer
calcinated, fluorosilane
10 Blayers PAH/SiO2, 1241 6.4 44%
calcinated As seen in Fig. 9, for a given heat flux, the hydrophobic surface
20 Bilayers PAH/SiO2, 1402 9.5 63% has the greatest enhancement in the nucleate boiling heat transfer
calcinated coefficient, up to about 100%, whereas the hydrophilic surface suf-
40 Bilayers PAH/SiO2, 1735 1.6 101%
fers a slight degradation, 10%, compared to the base case. The
calcinated
superhydrophilic surface, however, shows substantial degradation
a
Standard deviation (% of average CHF) over three nominally identical tests. of about 50% in the heat transfer coefficient, only recovering at very
high heat fluxes.
Research in the field of boiling heat transfer indicates that en-
For very porous materials, the r term becomes very large, trapped gas in surface cavities leads to the initial nucleation pro-
implying that the surface will have an apparent contact angle of cess [25]. Therefore, cavities that are not completely flooded by
0° if the intrinsic contact angle is less than 90°, or 180° if the liquid water can promote bubble nucleation at lower wall super-
intrinsic contact angle is higher than 90° [24]. This happens to be heats. Young and Hummel obtained higher nucleate boiling heat
the case for the calcinated PAH/SiO2 coatings. Although the higher transfer by adding PTFE to localized regions of a boiling surface,
adhesion tension associated with silica certainly improves wetta- resulting in better nucleation [26]. Enhancement in boiling heat
bility over the bare metal substrates, it is the nanoporous nature transfer from the PAH/SiO2 multilayers with hydrophobizing treat-
of the coatings that leads to the superhydrophilicity and wettabil- ment can be explained in a similar manner. The surface structure
ity. Cebeci et al. [18] attribute the superhydrophilicity of the PAH/ and chemical constituency of the calcinated PAH/SiO2 multilayers
SiO2 multilayers to the 3D nanoporous network of controlled thick- with vapor-deposited fluorosilane result in a surface with a high
ness and the resulting nanowicking of water into that network. advancing and static contact angle This implies that cavities on
They also note that there is a minimum critical film thickness the surface will not be flooded, but rather, filled with air and vapor.
needed to obtain the super wetting behavior, likely due to a critical It is hypothesized that this in turn leads to preferential nucleation
volume capacity. from these cavities at lower wall superheats, explaining the con-
For the non-calcinated PAH/SiO2 coatings, the contact angle is siderable enhancement in the nucleate boiling heat transfer
reduced relative to the bare metal, but not to the same extent as coefficient.
 E. Forrest et al. / International Journal of Heat and Mass Transfer 53 (2010) 58–67 65

Fig. 9. Heat transfer coefficient versus heat flux for uncoated and coated nickel wires boiled in pure water.

For wires coated with the hydrophilic and superhydrophilic sur- for nucleation. However, upon nucleation, vapor becomes en-
faces, one may infer that cavities are more likely to be flooded trapped in the cavities, lowering the required superheat. To test
when compared to the wires with the hydrophobic coating. Addi- this hypothesis, additional boiling experiments with superhydro-
tionally, cavities that do become active will require higher super- philic wires were conducted where the heat flux was cycled up
heats to nucleate. For example, Wang and Dhir predicted that and down below the expected CHF. Since the test bath was kept
surfaces with higher wettability will display poorer nucleate boil- at saturation, one would expect a hysteresis in the boiling curve
ing heat transfer, whereas surfaces with reduced wettability will due to the creation of entrapped vapor in cavities that became acti-
exhibit better nucleate boiling heat transfer, and provided a corre- vated at high wall superheats. Fig. 10 shows the boiling curve for
lation to predict the nucleation site density as a function of contact one such test, clearly demonstrating a hysteresis of the boiling
angle at a fixed wall superheat [27]: curve. As expected, entrapped vapor lowers the required superheat
for nucleation, thereby shifting the boiling curve to the left for sub-
Na ðsites=cm2 Þ / ð1  cos hA ÞD6:0
c ð6Þ sequent cycles.
where N a is the active nucleation site density and Dc is the cavity
mouth diameter. 4.3. Critical heat flux enhancement
Eq. (6) predicts a higher nucleation site density and thus a high-
er heat transfer rate for higher contact angle, which is in agreement The exact mechanism and parameters affecting the boiling cri-
with observations, as depicted in Fig. 6. However, one cannot pre- sis, or CHF, remain to this day unclear. For many years, the hydro-
dict the boiling heat transfer coefficient solely from the knowledge dynamic instability theory, developed by Zuber, has been widely
of the nucleation site density because parameters such as bubble used to predict the departure from nucleate boiling or CHF [28]:
diameter and bubble departure frequency, which affect nucleate
boiling heat transfer, are also altered by application of the thin-film " #1=4
g rðqf  qg Þ
coatings but were not measured in our experiments. q00CHF ¼ K qg hfg ð7Þ
The boiling behavior of nickel wire with the calcinated PAH/ q2g
SiO2 multilayers, shown in Fig. 5, is particularly unusual due to
the reversal of the boiling curve at high heat fluxes. Fig. 7 shows where K is a constant that only depends on the geometry of the sys-
qualitatively that there are very few active nucleation sites at a tem. The hydrodynamic theory has been scrutinized in recent years
heat flux of 500 kW/m2. However, at even higher heat fluxes, a sig- because it does not account for surface characteristics such as wet-
nificant number of nucleation sites appear, cooling the wire sub- tability. Recent work at MIT by Kim et al. [5], among others, clearly
stantially, resulting in the reversing trend observed in the boiling revealed the effects of surface parameters on CHF. The hydrody-
curve. This late activation of nucleation sites results in high wall namic instability theory fails to predict the enhancement associated
superheats for the wire. The situation exhibited by the superhydro- with modified surfaces, such as those created by the boiling deposi-
philic wire is similar to that described by Carey for boiling experi- tion of nanoparticles. The CHF enhancement presented here for pool
ments seeking to eliminate trapped gas in surface cavities. Such boiling of nickel wires coated with nanoparticle thin-films also
experiments displayed very high superheats for the initiation of demonstrates the limitation of this theory.
nucleation, but after nucleation was initiated, the superheat re- Two popular theories, which do include dependence on surface
quired to sustain bubble formation dropped to a lower value characteristics such as wettability, are the macrolayer dryout the-
[25]. The superheat required for nucleation falls due to the refilling ory [29,30] and the hot/dry spot theory [31]. For the macrolayer
of cavities with vapor upon nucleation. dryout theory, the dependence of CHF on surface wettability is tied
For the superhydrophilic wires, one may presume that the high to the thickness of a liquid macrolayer covering the surface be-
wettability leads to the majority of cavities being flooded at the tween vapor bubbles. The equivalent thickness of the macrolayer
start of each test, which, in turn, requires higher wall superheats can be calculated by:
66 E. Forrest et al. / International Journal of Heat and Mass Transfer 53 (2010) 58–67

Fig. 10. Boiling test results for 0.0100 nickel wire coated with 20 bilayers PAH/SiO2 and calcinated (superhydrophilic). The heat flux was cycled three times, demonstrating a
hysteresis in the boiling curve likely resulting from vapor entrapment in initially fully-flooded cavities. Note that the heat flux was kept below CHF.

h p i
de ¼ r b cos h  ð3 cos h  cos3 hÞ ð8Þ model, as shown in Table 4. Varying the coating thickness yields
12 significant differences in CHF enhancement, while the measured
The equivalent thickness from Eq. (8) is directly proportional to the contact angles for these coatings were virtually identical. Both
dryout time of the liquid macrolayer. CHF occurs if the liquid mac- the macrolayer dryout theory and the hot/dry spot theory predict
rolayer vaporizes completely. As contact angle decreases, the equiv- a direct dependence based on surface contact angles.
alent liquid macrolayer thickness increases, so CHF will also For the calcinated, superhydrophilic coatings, the only variable
increase proportionally. The macrolayer dryout theory qualitatively of the 10-bilayer, 20-bilayer and 40-bilayer cases is coating thick-
captures the wettability effect on CHF for hydrophilic surfaces. ness. This implies that the total pore volume increases linearly
The hot/dry spot theory predicts that CHF will occur at a nucle- with increasing thickness. Although the pore volume is closely tied
ation site when rewetting is unable to occur at a growing hot spot. to the surface wettability, test results clearly indicate that the
Therefore, increasing the surface wettability would allow for easier thickness of the porous layer, in addition to the apparent contact
rewetting of hot spots, thereby delaying CHF. Theofanous and Dinh angle, should be accounted for when evaluating parameters that
[31] give the following expression for the critical heat flux based affect CHF.
off the hot/dry spot theory: Although the CHF enhancement associated with the hydropho-
" #1=4 bic coating seems counterintuitive, one must recognize that the
g rðqf  qg Þ hydrophobic coating is characterized by a large contact angle hys-
q00CHF ¼j 1=2
qg hfg ð9Þ teresis. The hydrophobic coating has static and advancing contact
q2g
angles of about 140° and 160°, respectively, but the static receding
Eq. (9) is almost identical to the Zuber equation, except that the contact angle is only about 20°. Kandlikar explains that the reced-
leading constant depends on surface characteristics such as wetta- ing contact angle is the parameter influencing the dryout phenom-
bility. Kim et al. [5] derived the following analytical expression for enon [32,33]. The static receding contact angle can be closely
j: correlated to the receding contact angle. Therefore, for low reced-
 1=2 ing contact angles, one would expect a higher CHF, which is exhib-
sin h p=2  h ited with the hydrophobic coating. Therefore, the hydrophobic
j¼ 1  ð10Þ
2 2 cos h thin-film coating appears to be the ideal surface treatment for aug-
menting heat transfer, i.e., offering a large advancing contact angle
Using Eqs. (9) and (10), one would also expect an increase in CHF
with a reduction in contact angle. However, Eq. (10) is only applica- Table 4
ble for h 6 90°. Comparison of measured and predicted CHF enhancements for various thin-film
coatings.
Another pool boiling CHF model, proposed by Kandlikar, can be
applied to both hydrophilic and hydrophobic surfaces [32]: Test case Measured CHF Predicted CHF Predicted CHF
  enhancement enhancement enhancement
1 þ cos b (%) Eq. (9) Eq. (11) (%)
q00CHF ¼ qg1=2 hfg
16 10 Bilayers PAH/ 44 225% 117
 1=2 SiO2, calcinated
2 p
 þ ð1 þ cos bÞ cos / ½rgðqf  qg Þ1=4 ð11Þ 20 Bilayers PAH/ 63 224% 116
p 4 SiO2, calcinated
40 Bilayers PAH/ 101 225% 117
where b is the receding contact angle for the surface-fluid SiO2, calcinated
combination. 40 Bilayers PAH/SiO2 84 114% 110
a
It is important to note that all wires coated with nanoparticle 20 Bilayers PAH/ 69 111
SiO2, calcinated,
thin-films demonstrated CHF enhancement. However, one incon-
fluorosilane
gruity arises from the results of this study when compared with
a
the CHF predictions of the hot/dry spot theory and Kandlikar’s Eq. (9) is applicable only to hydrophilic surface 6 90°.
 E. Forrest et al. / International Journal of Heat and Mass Transfer 53 (2010) 58–67 67

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