International Journal of Heat and Mass Transfer 192 (2022) 122937

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International Journal of Heat and Mass Transfer

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

Spontaneously grown boehmite structures improve pool boiling heat

transfer on aluminium surfaces
Xin Cheng, Guang Yang∗, Jingyi Wu
Institute of Refrigeration and Cryogenics, Shanghai Jiao Tong University, Shanghai 200240, China

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

Article history: Superhydrophilic nanostructures that function to improve wettability have been proven to enhance boil-
Received 16 March 2022 ing heat transfer. Herein, the mechanism for enhancing pool boiling heat transfer on aluminium surfaces
Revised 9 April 2022
by spontaneous growth of boehmite layers in boiling water was comprehensively explored. The mor-
Accepted 12 April 2022
phology and chemical composition of the nanolayers formed on boiling water-treated (BWT) aluminium
Available online 22 April 2022
surfaces were characterized. The surfaces were covered with abundant cross-linked nanosheets and dis-
Keywords: persed microclusters after BWT, which were verified to be boehmite. In addition, the effect of BWT time
Aluminium on the thickness and wettability of the boehmite layer was quantitatively studied. The results showed
Boiling water treatment that the aluminium surfaces became superhydrophilic after BWT for 30 minutes, and the thickness and
Boehmite nanostructures morphology of the boehmite layer achieved near stable after processing beyond 3 hours. Further, BWT
Superhydrophilic samples exhibited excellent thermal performance and reproducibility during pool boiling tests. Compared
Nucleate boiling enhancement
to the plain copper surface, a 49% higher critical heat flux and a 79.6% higher heat transfer coefficient
Thermal management
were demonstrated on BWT aluminium alloy surfaces. The stable and dense boehmite layer was proven
to significantly enhance the boiling heat transfer of the substrate by increasing the effective nucleation
sites, specific surface area, wettability, and capillary rewetting ability.
© 2022 Elsevier Ltd. All rights reserved.

1. Introduction hance capillary rewetting have received extensive attention in re-

Nucleate boiling is one of the most efficient heat transfer mech-
anisms utilizing the enormous latent heat of a working fluid, and it
plays a vitally important role in many industrial applications, such
as thermal and energy systems, chemical engineering, and thermal
management [1–5]. Critical heat flux (CHF) and heat transfer coef-
ficient (HTC) are key parameters to characterize boiling heat trans-
fer performance and are closely related to surface morphology and
wettability. Previous studies have shown that the onset of nucleate
boiling (ONB), bubble growth and departure, as well as critical heat
flux, are closely related to surface wettability [6–8]. Low wettabil-
ity surfaces have an early ONB and large nucleation density due
to the lower energy barrier for nucleation [9]. At high heat fluxes,
due to the merging of dense bubbles, a vapor film forms and ex-
pands to hinder the further improvement of CHF. On the contrary,
high wettability surfaces have a small diameter and a rapid fre-
quency of bubble departure, and are conducive to effective rewet-
ting, especially on the surface of texture structures, enabling them
to achieve high CHF values [10]. Hence, hydrophilic surfaces with
microcavities to increase nucleation sites or nanostructures to en-
∗
Corresponding author.
E-mail address: y_g@sjtu.edu.cn (G. Yang).
spect to high heat flux applications [11].
With the prosperous development of micro/nano-
manufacturing technology, researchers have expressed enormous
interest in synergistically enhancing the CHF and HTC of boiling
surfaces, and have made a great number of efforts to achieve that
via carbon nanotubes [12], nanowires [13], reentrant cavities [14],
micro meshes [15], micropillars [16], oxide coatings [17], etc. It is
known from boiling mechanisms that most of the heat is dissi-
pated through thin film evaporation and bubble dynamics near the
boiling surface. To improve the heat dissipation efficiency of boil-
ing surfaces, the nucleation density, heat transfer area and bubble
behavior can all be taken into account in surface modification. At
present, most micro/nano fabricating and coating methods (such
as thermal spraying, ultra-fast laser, electrochemical deposition,
chemical vapor deposition and chemical etching) lack scalability
and durability, which hinders their effective applications [18–20].
Recently, the method of hot water treatment was proposed as
a promising solution for fabricating nanostructures on metal
surfaces, due to its advantages in simplicity, scalability, low cost
and eco-friendliness [21]. Similarly, due to its excellent thermal
conductivity, lightweight and easy availability, aluminium has
always been favored by the thermal management industry, espe-
cially in the fields of aerospace and portable devices. Aluminium

https://doi.org/10.1016/j.ijheatmasstransfer.2022.122937
0017-9310/© 2022 Elsevier Ltd. All rights reserved.
X. Cheng, G. Yang and J. Wu
is relatively active and can react with water to generate hydrogen
and different oxides or hydroxides [22]. This phenomenon of
aluminium-water reaction has been widely studied and applied in
hydrogen energy industries [23–24], but they consider the stub-
born attachment of oxides or hydroxides to aluminium surfaces
as obstacles to efficient hydrogen production, and do their best to
eliminate these byproducts.
Recently, with the rapid development of functional nanostruc-
tured surfaces, the growth of boehmite structures on aluminium
surfaces through hot water treatment has attracted the inter-
est of researchers. Min et al. [25] studied the effect of hot wa-
ter treatment on aluminium fin stock’s long-term wetting and
corrosion characteristics. Their results showed that the wettabil-
ity of the treated aluminium fins was significantly improved and
it had durability under dry/wet cycling without causing conven-
tional corrosion. Zuo et al. [26] fabricated boehmite nanostruc-
tures on an aluminium surface with microcavities by hot wa-
ter treatment, and obtained a superhydrophobic anti-icing surface
after modification with hexadecyl-trimethoxy-silane. Ivvala et al.
[27] and Mandal et al. [28,29] developed a superhydrophobic sur-
face on1100 aluminium alloy via hot water treatment combined
with 1H,1H,2H,2H-perfluorooctyl-triethoxy-silane (FOTES) modifi-
cation. This surface had excellent self-cleaning properties, as well
as good chemical stability and durability under various extreme
conditions. Kim et al. [30] also fabricated some superhydrophilic
aluminium surfaces by boiling water treatment, and explored the
effects of roughness on the pool boiling heat transfer of these su-
perhydrophilic aluminium surfaces. Their results showed that CHF
was positively correlated with roughness within a certain range,
but when it exceeded a certain value, CHF maintained stability af-
fected by the hydrodynamic limit. Saadi et al. [31] obtained a su-
perhydrophilic nanostructured surface after immersing aluminium
foil in hot water at 75°C for 10 min. The antibacterial activity assay
showed that the antibacterial efficacy of aluminium foil was en-
hanced. Underhill et al. [32] explored the morphology and chem-
ical properties of the products generated by the reaction of 2024
bare and 7075 clad aluminium alloys with deionized (DI) wa-
ter at 40°C and 50°C, respectively. The results showed that the
products were mostly pseudo-boehmite and had a coarser pat-
tern at 50°C. In addition, the bare alloy had a faster reaction
rate. Using nanosecond laser ablation combined with boiling water
treatment, Ngo and Chun [33] fabricated a superhydrophilic alu-
minium surface with a combination of micro-burr structures and
nanostructures of boehmite. Building on this research, Tran and
Chun [34] fabricated complex superhydrophilic patterns on super-
hydrophobic aluminium surfaces via the organic combination of
laser ablation, boiling water treatment and silicone oil heat treat-
ment. Godinez et al. [35] realized that boehmite nanostructures
have significant advantages in improving surface wettability and
enhancing boiling CHF. Therefore, repeated tests were carried out
to explore the stability of the boiling performance of an aluminium
plate with sufficient boiling water treatment. The results showed
that the boehmite layer granted the aluminium surface stable su-
perhydrophilic properties and enhanced CHF, as well as high ther-
mal stability. However, although the previous studies have pro-
vided some essential understanding of the influence mechanism of
boehmite structures on improving surface wettability and boiling
heat transfer, many problems still need to be solved. As BWT time
is a critical parameter for surface modification, its effect on struc-
tural parameters, as well as on the wettability and thermal per-
formance of the surface has still not been systematically explored.
Meanwhile, the reproducibility and stability of the BWT surface
should also be studied, which are essential for its practical appli-
cations.
In this work, aluminium alloy surfaces were modified with
boehmite nanostructures through a cost-efficient and eco-friendly
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International Journal of Heat and Mass Transfer 192 (2022) 122937
method of boiling water treatment. The wettability and the thick-
ness of the boehmite layer were adjusted by changing the BWT
time to obtain highly repeatable aluminium surfaces with en-
hanced boiling heat transfer. Based on a fundamental understand-
ing of boehmite crystal structure and the formation mechanisms
of metal oxide nanostructures in water, the formation process of
spontaneous growth of boehmite structures on aluminium surfaces
was revealed. In addition, their morphology and chemical proper-
ties were characterized, and the effect of the BWT time on the
surface wettability and the thickness of the boehmite layer were
revealed. The reproducibility and reliability of growing boehmite
nanostructures as a method to enhance boiling heat transfer were
verified by pool boiling tests. This work further deepens the essen-
tial understanding of enhancing boiling heat transfer on aluminium
surfaces by the spontaneous growth of boehmite structures.
2. Characterization and experiments
2.1. Principle of aluminium-water reaction
Aluminium-water reactions can generate hydrogen and differ-
ent oxides or hydroxides [22], as shown in Table 1.
The products of an aluminium-water reaction under different
pressures and temperatures were predicted and the interval distri-
bution was plotted [36], as shown in Fig. 1. It could be revealed
that AlOOH (boehmite) was the solid product of an aluminium-
water reaction in the range of 0.1 MPa and 21°C∼305°C.
2.2. Sample preparation and characterization methods
Due to the low hardness of pure aluminium, a commercially
available 6061-T651 aluminium alloy (> 96% Al) plate was used
as the initial material. The chemical composition of this alloy is
shown in Table 2. It needs to be noted that the content of trace
elements in the alloy that can react with boiling water does not
exceed 2.3%, thus having a negligible effect on the experimental
results related to the aluminium-water reaction. After polishing to
remove scratches, the plate was laser-cut into multiple samples
with the same size of ϕ 10 mm × 1 mm. Prior to boiling water
treatment, the organic contaminants and oxides on the samples
needs to be remove. Next, the cleaned samples were placed in dif-
ferent watch glasses, which were immersed in boiling DI water.
The samples were immersed in boiling water for different precisely
controlled times and then were gently blown dry with nitrogen
gas.
To clearly identify the surface morphology characteristics of
the BWT and untreated samples, as well as explore the growth
thickness of the reaction products, Raman imaging combined with
emission scanning electron microscopy (SEM, RISE-MAGNA, TES-
CAN) and atomic force microscopy (AFM, MFP-3D, Asylum Re-
search) were applied. Meanwhile, the quantitative analysis results
of the elements (Al, O, C, Mg) of the reaction products on the sur-
face were obtained with the help of energy-dispersive X-ray spec-
troscopy (EDS, RISE-MAGNA, TESCAN). Further, the XPS spectra of
the untreated sample and the samples treated with boiling wa-
ter for 3 h were obtained via an X-ray photoelectron spectrometer
(XPS, AXIS Ultra DLD, Kratos). The Casa XPS program was used for
XPS spectra processing. The static contact angles for water droplets
on sample surfaces were also measured by a contact angle me-
ter (DSA100, Kruss) with controlled droplet volumes of 5 μL. The
measurement was performed at an ambient temperature (≈20°C)
and a relative humidity of approximately 50%. The instrument had
an advanced automatic control system, which ensured that accu-
rate volumes of water droplets were gently settled on the sample
surface and that the droplet contact angle was fitted and recorded
in real-time. Each sample was individually tested no less than five
X. Cheng, G. Yang and J. Wu International Journal of Heat and Mass Transfer 192 (2022) 122937

Table 1
aluminium oxide and hydroxide [22].

Chemical structure name Crystallographic designation Reaction formula

Gibbsite γ -Al(OH)3 /
Bayerite α -Al(OH)3 2Al+6H2 O→2Al(OH)3 +3H2
Boehmite γ -AlOOH 2Al+4H2 O→2AlOOH+3H2
Diaspore α -AlOOH
Corundum γ -Al2 O3 2Al+3H2 O→Al2 O3 +3H2

Fig. 1. Interval distribution of aluminium-water reactions under different pressures and temperatures [36].

Table 2
Chemical composition of 6061 aluminium alloy (ASTM-B-209M), %

Alloy Si Fe Cu Mn Mg Cr Zn Ti Al

6061 0.4-0.8 0.7 0.15-0.4 0.15 0.8-1.2 0.04-0.35 0.25 0.15 remainder

times, and the average value and standard error of the results were ple and the heat source were mechanically pressed together by a
calculated. customized sample retaining ring with reduced aperture, and the
contact surface was covered with a thin thermal grease to reduce
the thermal contact resistance. As shown in Fig. 2(b), a copper
2.3. Pool boiling experiments
block with an upper cross-sectional diameter of 10 mm was uti-
lized as the heat source. Four K-type thermocouples were arranged
The thermal performance tests were conducted through a self-
at equal intervals on the axis of the copper block near the upper
built pool boiling testing system, as shown in Fig. 2. The system
surface. The measured values of these thermocouples were used to
was composed of a heat source module, a temperature control
determine the actual input power of the sample by Fourier’s law
module, a DI water supply module, a data acquisition module, and
of heat conduction. The bottom of the copper block was embed-
a visualization module. Based on this system, the boiling curve and
ded with five cartridge heaters with a power of 80 W, and the
heat transfer coefficient curve of each sample were characterized,
gap was filled with thermal grease for better heat conduction. The
as well as the process of bubble dynamics evolution (nucleation,
total input power was controlled by an adjustable regulated DC
growth, merging and departure) was revealed. DI water was used
power supply. The entire copper heater was tightly wrapped by
as the working fluid for nucleate boiling experiments. The sam-

3
X. Cheng, G. Yang and J. Wu International Journal of Heat and Mass Transfer 192 (2022) 122937

Fig. 2. Experimental system for heat transfer performance: (a) schematic diagram of a self-built pool boiling testing system; (b) partial assembly drawing of heat source and
sample; (c) photo of the test setup.

rigid polyurethane foam to minimize heat leakage. The tempera-

 2  2  2 
ture control module consisted of a ring heater, a K-type thermo- 2 δ1 δAl δ2
UT = 2UT2 + Uq2 + +
couple and a PID controller. The temperature control point was se- λCu λAl λg
lected to be about 30 mm away from the sample surface, and the  q 2  q 2  2
temperature of this point was set to 98 °C to avoid violent boiling q
+UL2 + Uδ2 + Uδ2 (6)
near the ring heater affecting the testing of the sample. This was λCu λAl λg
due to the large distance between the control point and the ring
heater, which could cause a temperature difference. If the temper- Here, the accuracy of the K-type thermocouple was ± 1.5 °C,
ature at this point was set to 100 °C, intermittent violent boiling and the measurement errors of distance and thickness was ± 0.02
occurred near the ring heater, causing the water in the container to mm as measured by a vernier caliper. Therefore, the uncertainties
roll. Except for the critical heat flux condition, each testing condi- of heat flux, and superheat were within ± 1.8 W/cm2 , and ± 2.4
tion was maintained for about 8 minutes to ensure stable state, fol- °C, respectively. Also, the uncertainties of HTC were < 5% of the
lowed by recording the relevant data. Based on our previous work computed value.
[37], the heat flux (q"), the superheat (T) of the upper surface and
the heat transfer coefficient (h) were obtained using the following 3. Results and discussion
expressions:
1

T −T T −T
 There are enormous prospects in fabricating functional surfaces
q = λCu 3 1 + 4 2 (1) (such as self-cleaning, enhanced heat transfer) by adjusting the
2 L13 L24
wettability and nanostructure of aluminium surfaces based on the
Where, T1 , T2 , T3 and T4 are the measured values of thermo- aluminium-water reaction. Therefore, to comprehensively explore
couples arranged from top to bottom inside the copper block, K; the effect of a simple aluminium-water reaction on the boiling
and L13 and L24 represent the distances of corresponding thermo- heat transfer of aluminium materials, studies such as morphology
couples. characterization, wettability testing, analysis of hydrate formation
  process, and repeatability testing of the BWT method in enhancing
δ1 δ δ2
T = Tw − Tv = T1 − q + Al + − Tv (2) boiling heat transfer were conducted.
λCu λAl λg Fig. 3 shows the surface roughness of untreated and BWT sam-
ples measured by the AFM method. The untreated sample had a
Where λg is the thermal conductivity of the thermal grease; δ Al
smooth surface due to the previous polishing process [Fig. 3(a)].
is the thickness of the sample; and δ 1 and δ 2 are the distances
With the BWT process, it was obvious that the nano-scale rough
from the top thermocouple inside the copper block to the heater
structures gradually formed and enlarged on the surface [Fig. 3(b)
surface and the thickness of the thermal grease layer, respectively.
and (c)].
q Furthermore, the nanostructure morphologies of the differ-
h= (3)
T ent BWT samples were distinctly described utilizing the SEM
method combined with the EDS method (Figs. 4 and 5). The dense
The uncertainties of heat flux, heat transfer coefficient, and su- nanosheets were found to have grown cross-linked on the surface
perheat were determined using standard procedures as follows: of BWT samples [Fig. 4(b) and (c)]. The thickness and length of
  2  2   2 each nanosheet were about 20∼30 nm and 10 0∼20 0 nm respec-
λCu λCu (T4 − T2 )λCu
Uq2 = UT2 2 +2 + UL2 tively. There were abundant micron-scale clusters irregularly dis-
2L24 2L13 2L24 2 tributed above the nanosheet layer [Fig. 4(a) and (d)]. These clus-
 2  ters were formed by the accumulation of many small particles with
(T3 − T1 )λCu nanostructures on the surface [Fig. 4(e)]. Fig. 5 shows the effect of
+ (4)
2L13 2 different BWT times on the growth of surface nanostructures. Af-
ter boiling water treatment for 30 min, lots of tiny nanosheets and
Uq2 U 2 q2 clusters began to grow on the surface, but the interstitial cavities
Uh2 = + T 4 (5) of the nanosheets had not yet formed. After BWT for 10 h or 3 h,
 T2 T
4
X. Cheng, G. Yang and J. Wu
Fig 3. AFM images showing the topography of (a) untreated, (b) 30min-BWT, (c) 3h-BWT samples. The height profiles below the images showed the formation of nanos-
tructures.
Fig. 4. SEM images and EDS analysis of the 3h-BWT sample: (a) 1.00 kx image of surface, (b) 50.0 kx image of dense nanolayers, (c) 200 kx image of dense nanolayers, (d)
10.0 kx image of microcluster, (e) 50.0 kx image of microcluster, (f) Analysis of Al and O element content on the sample surface.
there were abundant interstitial cavities and clusters found on the
surface, and there was no obvious difference in the nanostructures
of these two sample types.
The EDS analysis [Fig. 4(f)] showed that the ratio of Al and O in
the nanostructured layer was close to 1:2, which met the boehmite
condition (Fig. 1). Furthermore, XPS spectra analysis was conducted
to verify the elemental composition of the surface structure of un-
treated and BWT samples [Fig. 6]. Fig. 6(a) and (c) show that the
surface of the BWT sample was completely covered by the prod-
ucts of the aluminium-water reaction, which caused the disappear-
ance of Mg in the spectrum. The most intensive peaks appearing
in both spectra were: O 1s, Al 2p, Al 2s, and C 1s. Carbon-based
molecules or functional groups in the air were adsorbed to the sur-
face of samples.
The high-resolution spectra of Al 2p peak [Fig. 6(b) and (d)]
revealed the contribution of aluminium oxide (binding energy ∼
75.4 eV), metallic aluminium (binding energy ∼72.1 eV) and alu-
minium hydroxide or oxyhydroxide (binding energy ∼74.2 eV)
[38,39]. Therefore, it was demonstrated that the surface structure
of BWT samples was boehmite (AlOOH) by combining the evidence
in Figs. 4(f) and 6(d). This conclusion was consistent with that of
Fig. 1.
The crystal structure of boehmite (γ -AlOOH) consists of
double-layers of edge-sharing Al-O octahedrals formed by dou-
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International Journal of Heat and Mass Transfer 192 (2022) 122937
ble molecules of AlOOH [40–42]. The hydroxyl groups are dis-
tributed on the outside of these layers, and adjacent layers are con-
nected by hydrogen bonds, which are conducive to the growth of
boehmite in a certain direction, forming a sheet-like structure.
Based on the crystal structure characteristics of boehmite and
the information of SEM images (Fig.4, and Refs. [26,34]), as well
as a fundamental understanding of the formation mechanism of
metal passivation films in water [21,43], we analyzed a reasonable
growth process of boehmite layer on aluminium surfaces in boiling
water. Initially, the aluminium plate with the oxide layer removed
is immersed in boiling water. On the one hand, the high tempera-
ture promotes the formation of active sites on the aluminium sur-
face. The activated aluminium cations are adsorbed near the ac-
tive sites due to the negative surface potential. Then, free hydroxyl
groups in water diffuse to the metal interface and react with alu-
minium cations to produce Al-O molecules and hydrogen. On the
other hand, oxygen dissolved in water also directly reacts with alu-
X. Cheng, G. Yang and J. Wu International Journal of Heat and Mass Transfer 192 (2022) 122937

Fig. 5. SEM images of (a-c) 30min-BWT, (d-f) 3h-BWT, (g-i) 10h-BWT samples.

Fig. 6. XPS spectra and high-resolution Al 2p peak of (a-b) untreated and (c-d) 3h-BWT samples.

6
X. Cheng, G. Yang and J. Wu
Fig. 7. The pivotal formation process of boehmite structure on the aluminium surface: migration-polymerization-hydrogen bonding.
minium atoms on the interface to produce Al-O molecules. The
dense aluminium atoms near the interface have enough attraction
to the Al-O molecules to adsorb them and for Al-O molecules to
gradually develop a thin porous layer on the aluminium surface.
As the reaction progresses, the porous layer serves as an abun-
dant substrate for the growth of boehmite crystals. The above pro-
cess can be called the in-situ growth stage (i.e., the first stage).
This explains why nanostructures can be formed even on an alu-
minium surface with complex microstructures (especially in anti-
gravity arrangements) through the method of hot water treatment
[26,34], rather than simply having a large number of nanostruc-
tures deposited at the defect and slit location. In addition, the even
thickness of the boehmite layer observed in this work similarly
proves this point. As the reaction proceeds, the hydrogen ions in
the water combine with the surplus electrons on the metal in-
terface to weaken the interface electronegativity. Meanwhile, the
thin porous layer on the interface hinders the migration of newly
generated aluminium cations on the metal interface. These fac-
tors cause the newly generated aluminium cations to easily depart
from the metal interface to form free aluminium cations. Many free
aluminium cations react with hydroxyl groups near the interface.
These newly generated Al-O molecules migrate from in-plane or
out-of-plane of the initial porous layer, colliding with each other
to form double-stranded molecules and then continue to develop
into double-layer octahedral structures. Larger molecular structures
are more likely to be captured by the surrounding porous sub-
strates. Eventually, the captured molecules develop on the porous
substrates along the crystal orientation with the minimum energy
via hydrogen bonding, forming nanosheet structures [Fig. 4(c)]. Si-
multaneously, when the uncaptured oxide molecules develop to a
certain extent, they will spontaneously deposit on the nanostruc-
ture surface and continue to agglomerate and develop into mi-
croclusters [Fig. 4(d)]. These processes are collectively called the
migration-polymerization-hydrogen bonding process (i.e., the sec-
ond stage), which is of great significance. The formation process of
this pivotal stage is illustrated in Fig. 7. Finally, the deposited crys-
tal structures completely block the contact channel between the
aluminium surface and water, resulting in the termination of the
aluminium-water reaction. It is worth mentioning that the above
formation process is also applicable to other metal surfaces with
similar characteristics (such as iron, nickel, etc.). The mechanism
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International Journal of Heat and Mass Transfer 192 (2022) 122937
thus explains convincingly the reasons for the formation of even
nanostructures (linear, spherical, flake and 3D polygonal) of differ-
ent metal oxides on structured surfaces.
The above mechanism not only explains the reasons for the
formation of dense nanosheet structures and abundant microclus-
ters in Figs. 4 and 5, but also reveals that the boehmite layer has
a limit to thickness, which occurs when the aluminium surface
is completely covered without aluminium cations. The thickness
of the boehmite layer under different BWT times was measured
through the process of grinding and polishing and the method of
SEM (Fig. 8). The results showed that with the increase of the BWT
time, the thickness of the boehmite layer increased rapidly at first
and then gradually stabilized at about 1 μm. When treated for 3
h, the layer thickness was 981 nm, which was only 11.6% less than
the maximum value. Here, stable nanostructures had been formed
on the sample surface, which were almost the same as in the sam-
ple treated for 24 h according to the SEM image. In addition, the
rate of aluminium-water reaction in boiling water decreases mono-
tonically with time, which is due to the adsorption and deposition
of reaction products on the surface resulting in a gradual decrease
in both the reaction areas and the density of activated aluminium
cations.
As mentioned above, the boehmite crystal has a double-layer
octahedral structure with abundant hydroxyl groups distributed on
the outside, which will combine with water molecules to make
the boehmite structure hydrophilic. To clarify the influence of the
forming process of the boehmite layer on surface wettability, we
explored the water contact angle of the samples under different
BWT times using the contact angle meter (Fig. 9). The results in-
dicated that the surface wettability was a very sensitive to the
presence and development of boehmite nanostructures. After BWT
for 30 min, surfaces quickly transformed from hydrophobic (∼94°)
to superhydrophilic (<10°) surfaces, which could maintain stability
after repeated wetting and drying operations. With increased BWT
time, boehmite structures on the sample surface gradually devel-
oped. The interlaced nanosheets combined with abundant micro-
clusters made the surface not only superhydrophilic, but also had
a certain wicking capacity. These characteristics were beneficial to
the boiling heat transfer on aluminium surfaces.
For clarifying the effect of boehmite structures on aluminium
surfaces on the enhancement of pool boiling heat transfer, we con-
X. Cheng, G. Yang and J. Wu
Fig. 8. The thickness of boehmite layers: (a) the relationship between the layer thickness and the BWT time; (b) the SEM image and EDS result of the layer thickness of
BWT for 3 h.
ducted boiling heat transfer tests on fully BWT samples and a pol-
ished plain copper sample. Initially, for the CHF of plain copper
surface, the difference between our results and those from Wen
et al. [6] is only less than 8%, which verifies the reliability of the
experimental system. The testing results are as displayed (Fig. 10),
with heat flux and HTC representing heat dissipation capacity and
efficiency, respectively. The thermal performance of the aluminium
samples treated with the same process exhibited satisfactory con-
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International Journal of Heat and Mass Transfer 192 (2022) 122937
sistency. Simultaneously, boiling heat transfer performance was
significantly improved in them. Compared with the plain copper
surfaces, their CHF and HTC were increased by 49% and 79.6%, re-
spectively. Fig. 11 depicts the bubble dynamics on plain copper sur-
faces and fully BWT aluminium surfaces at different heat fluxes.
The bubble departure diameter of the hydrophilic aluminium sur-
face was much smaller than that of the copper surface at low heat
fluxes [Fig. 11(a) and (d)]. The bubbles near the aluminium sur-
X. Cheng, G. Yang and J. Wu International Journal of Heat and Mass Transfer 192 (2022) 122937

Fig. 9. The effect of BWT time on the surface wettability of aluminium samples.

Fig. 10. Heat transfer performance of pool boiling. (a) boiling curve; (b) the relationship between HTC and heat flux.

face were more dispersed at high heat fluxes [Fig. 11(c) and (f)],
thereby delaying the merging of bubbles to form a gas film. There-
fore, this indicates that BWT is a promising potential strategy for
nucleate boiling enhancement of aluminium surfaces. In addition,
when the samples treated with boiling water for 3 h were im-
mersed in unsealed DI water at room temperature for many days
and boiling tests were performed after, the thermal performance
of these samples exhibited good consistency, as shown in Fig. 12.
The maximum deviations for CHF and HTC were 2.1% and 11.7%,
respectively, which illustrates the favorable reproducibility of the
BWT method.
Further, we analyzed the potential mechanism of the boehmite
layer enhancement of nucleate boiling heat transfer on aluminium
surfaces, as shown in Fig. 13. After sufficient BWT time (≥3 h),
a dense and stable boehmite structure was formed on the alu-
minium surface. The interlaced nanosheets on the surface provided
a larger specific surface area for heat transfer, and the tiny cav-
ities between the nanosheets supplied a high density of nucle-
ation sites, which were beneficial for improving HTC and reducing
ONB. Meanwhile, there were abundant microclusters unevenly dis-
tributed on the upper surface. These microclusters could effectively
prevent the merging and expansion of bubbles on the surface, as
well as accelerate the departure of bubbles. In addition, the clus-
ter structures possessed favorable capillarity, subtly constituting a
hierarchical structure among the nanosheets. The rewetting per-
formance of the surface was enhanced, and the CHF was further
improved.

9
X. Cheng, G. Yang and J. Wu International Journal of Heat and Mass Transfer 192 (2022) 122937

Fig. 11. Bubble dynamics on polished copper and fully BWT aluminium surfaces at different heat fluxes. (a-c) aluminium alloy surface; (d-f) plain copper surface.

Fig. 12. Thermal performance of the fully BWT samples after immersing in DI water for different times (0, 15, 32 and 46 days). (a) Boiling curve; (b) The relationship
between HTC and heat flux.

Fig. 13. Enhancement mechanism of the boehmite structure on boiling heat transfer.

10
X. Cheng, G. Yang and J. Wu
4. Conclusions
In summary, we comprehensively explored the improvement of
boiling heat transfer through the spontaneous growth of boehmite
structures on aluminium surfaces in boiling water. The morphol-
ogy characterization and chemical composition analysis of these
spontaneously-grown boehmite structures were conducted using
the AFM, SEM/EDS and XPS methods. Based on the achieved un-
derstanding of the relevant mechanism and the visualized ob-
servation of the microstructures, we proposed a reasonable for-
mation process for the boehmite layer, which consisted of three
steps: in-situ growth, migration-polymerization-hydrogen bonding
and deposition-blocking. The influence of BWT time on the thick-
ness and surface wettability of the boehmite layer was also quan-
titatively analyzed. The results showed that the thickness and sur-
face wettability of the boehmite layer exhibited prominent sensi-
tivity to the BWT time at the initial stage. A superhydrophilic sur-
face was obtained after only 30 min of boiling water treatment,
and it did not weaken after repeated wetting and drying opera-
tions. Moreover, the thickness of the boehmite layer was almost
stable after BWT for 3 h. Such surfaces not only achieved superhy-
drophilic characteristics but also exhibited a certain wicking ability.
Further, the mechanism of the boiling heat transfer enhancement
on the aluminium surface by spontaneously generated boehmite
was explicitly analyzed. With sufficient BWT time, the interlaced
nanosheets and abundant microclusters on the aluminium surface
significantly increased the specific surface area and effective nucle-
ation sites, as well as improved the wettability and rewetting abil-
ity. The aluminium surface after sufficient boiling water treatment
showed excellent superiority in the boiling heat transfer enhance-
ment proved by pool boiling tests. Compared with plain copper
surfaces, the CHF and HTC were increased by 49% and 79.6%, re-
spectively. Moreover, the fully BWT samples still maintained excel-
lent thermal performance after prolonged underwater immersion.
Therefore, the BWT method exhibited well reproducibility in the
boiling heat transfer tests, and it has tremendous potential and
prospects for application to aluminium surfaces in thermal man-
agement. This work established a fundamental understanding of
boiling heat transfer enhancement by the spontaneously growing
boehmite on aluminium surfaces. However, more work remains for
further exploration, including the surface properties under the re-
action conditions with higher pressure or temperature, durability
of the deposited films under continuous flow conditions, and ap-
plication of this spontaneous growth method on non-smooth sur-
faces.
Declaration of Competing Interest
None.
CRediT authorship contribution statement
Xin Cheng: Conceptualization, Methodology, Investigation,
Writing – original draft. Guang Yang: Conceptualization, Method-
ology, Writing – review & editing, Supervision. Jingyi Wu: Project
administration, Writing – review & editing.
Acknowledgments
This work was supported by the National Natural Science Foun-
dation of China (51906142 and 51936006) and Natural Science
Foundation of Shanghai (22ZR1434300).
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