Applied Surface Science 283 (2013) 10411050

Contents lists available at ScienceDirect

Applied Surface Science

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

Superhydrophobic aluminium-based surfaces: Wetting and wear

properties of different CVD-generated coating types
M. Thieme a, , F. Streller a,1 , F. Simon b,2 , R. Frenzel b,2 , A.J. White c,3
a
Technische Universitt Dresden, Institute of Materials Science, 01062 Dresden, Germany
b
Leibniz-Institut fr Polymerforschung Dresden, Postfach 120 411, 01005 Dresden, Germany
c
GVD Corporation, 45 Spinelli Place, Cambridge, MA 02138, USA4

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

Article history: In view of generating superhydrophobic aluminium-based surfaces, this work presents further results for
Received 15 April 2013 the combination of anodic oxidation as the primary pretreatment method and chemical vapour deposition
Received in revised form 12 July 2013 (CVD) variants for chemical modication producing coatings of 2501000 nm thickness. In detail, CVD
Accepted 13 July 2013
involved the utilisation of i hexauoropropylene oxide as precursor within the hot lament CVD process
Available online 22 July 2013
for the deposition of poly(tetrauoroethylene) coatings at alternative conditions (PTFE-AC) and ii 1,3,5-
trivinyltrimethylcyclotrisiloxane for the deposition of polysiloxane coatings (PSi) by initiated CVD. The
Keywords:
substrate material was Al Mg1 subjected to usual or intensied sulphuric acid anodisation pretreatments
Superhydrophobicity
Anodized aluminium
(SAAu, SAAi, respectively) affording various degrees of surface micro-roughness (SAAu < SAAi) to the oxidic
PTFE layers layers. Performance characteristics were evaluated in the original as-coated states and after standardised
Polysiloxane layers articial weathering and/or mild wear testing.
Wear testing Superhydrophobicity (SH) was observed with the system SAAi + PTFE-AC similarly to former ndings
Articial weathering with the standard hot lament CVD PTFE coating variant (SAAi + PTFE-SC). The results indicated that the
specic coating morphology made an important contribution to the water-repellency, because even some
of the SAAu-based samples tended to reveal SH. Subjecting samples to weathering treatment resulted in
a general worsening of the wetting behaviour, primarily limited to the receding contact angles. These
tendencies were correlated with the chemical composition of the sample surfaces as analysed by X-
ray photoelectron spectroscopy. The wear tests showed, as evaluated by scanning electron microscopy
and contact angle measurement, that the PTFE coatings were relatively sensitive to friction. This was
connected with a dramatic deterioration of the water-repelling properties.
PSi-coated surfaces generally showed rather poor water-repellency, but this coating type was sur-
prisingly resistant towards the applied friction test. From these ndings it may be concluded that the
combination of hydrophobic uorine containing structure elements and cross-linking of the polymeric
chains would likely afford highly durable SH.
2013 Elsevier B.V. All rights reserved.

1. Introduction

Superhydrophobic surfaces are characterised by advancing

and receding contact angles higher than 150 and the absence
Abbreviations: CVD, chemical vapour deposition; FT-IRRAS, Fourier-transform
of a distinct contact angle hysteresis, which is dened as the
reection-absorption infrared spectroscopy; HFCVD, hot lamentCVD; PSi,
polysiloxane; PTFE-AC, poly(tetrauoroethylene) alternative coating; PTFE-SC,
difference between the advancing and receding contact angles.
poly(tetrauoroethylene) standard coating; SAAi, intensied sulphuric acid anodis- The production of such surfaces requires a low surface energy
ation; SAAu, usual sulphuric acid anodisation; SEM, scanning electron microscopy; in combination with a micro-rough morphology. The publica-
SH, superhydrophobicity; WEA, wear testing; WTH, articial weathering; XPS, X-ray tions in the eld of superhydrophobicity (SH) reveal meanwhile
photoelectron spectroscopy.
Corresponding author. Tel.: +49 351 463 0; fax: +49 351 463 33207.
an overwhelming number of systems displaying such prop-
E-mail addresses: michael.thieme@tu-dresden.de (M. Thieme),
erties. A selection of recent reviews is compiled in [14].
streller@seas.upenn.edu (F. Streller), frsimon@ipfdd.de (F. Simon), Focusing on metals as solids with typically high-energy sur-
frenzelr@ipfdd.de (R. Frenzel). faces and, hence, a hydrophilic nature, the usual experimental
1
Present address: University of Pennsylvania, Department of Materials Science approach involves the sequence of micro-roughening plus chem-
and Engineering, 19104 Philadelphia, PA, USA.
2 ical modication using hydrophobic substances. In the case of
Tel.: +49 351 4658 0; fax: +49 351 4658 214.
3
Tel.: +1 617 661 0060. aluminium, a number of sub-variants have been described in the
4
info@gvdcorp.com. literature:

0169-4332/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.apsusc.2013.07.065
1042 M. Thieme et al. / Applied Surface Science 283 (2013) 10411050

i. Roughening is solely implemented by a suitable pretreatment invert their wetting behaviour the following polymer coatings were
of the metal, whereas the chemical modication gives no deposited on the sample surfaces:
contribution to the morphology. This principal route utilised
alkaline or acid etching [510], hot-water corrosion [11,12], (i) A poly(tetrauoroethylene)-like polymer (PTFE) was deposited
anodizing [1320], and a special sequence of etching and oxide by a HFCVD process, where hexauoropropylene oxide
formation, which eventually led to the transformation of the (DuPont, USA) was used as precursor. In comparison to GVDs
nanopore array to a nanowire array and super-repellency [21]. standard coating process (SC [28]), the coating conditions were
Moreover, appropriate roughening was also achieved by micro- characterised by elevated substrate temperatures (alternative
embossing followed by micro-blasting [16], and laser ablation conditions, AC). The former was taken as reference.
[16,22]. Remarkably, the Canadian group of Farzaneh investi- (ii) A uorine-free polysiloxane (PSi) was deposited by initiated
gated different methods of roughening and coating to produce CVD with 1,3,5-trivinyltrimethylcyclotrisiloxane (99% purity;
superhydrophobic aluminium surfaces [8,9,12,15], where the Gelest, USA) as precursor and di-tert-butyl peroxide as a free-
latter route consists of a combination of phosphoric acid anodi- radical-generating initiator (98% purity; Sigma-Aldrich, USA).
sation and rf-sputtering of PTFE. Subsequent annealing at 250 C/1 h is denoted by T.
Wet-chemical routes for the preparation of micro-rough lay-
ers of aluminium oxyhydroxides without referring to a metallic
The thicknesses of the applied polymer lms were 250, 500,
substrate are not considered here.
and 1000 nm. Additionally, thicknesses of 2 m were applied for
ii. Roughening is solely brought in by the substance that creates
special analytical measurements. The thickness of the coatings
also the water-repelling effect. This pathway was practiced very
was expressed as a number following the polymer type and the
seldom only [22,23] aside from approaches using nanoporous
conditions of deposition, such as PTFE-AC250 or PSi1000T. The
aluminium oxide as templates for generating suitable coating
coated thicknesses were estimated based on the thickness mea-
morphologies [25,26].
sured in situ and in real-time on a silicon witness wafer via laser
iii. Essential parts of the nal morphology are produced both by
interferometry.
pretreatment and modication. In this group our recent inves-
tigations [27,28] may be classied, where the well-established
hot lament CVD technique (HFCVD, [29,30]) was utilised to 2.2. Contact angle measurements
produce poly(tetrauoroethylene) (PTFE) coatings. The inherent
morphological characteristics of the coating are superimposed Contact angles were measured by sessile drop experiments as
to the 3-D surface features of the primarily anodised metal. advancing ( a ) and receding contact angles ( r ). The advancing con-
tact angle is the maximum contact angle which is determined upon
increasing the droplet volume, whereas the receding contact angle
These investigations have been expanded now to two types
is the minimum contact angle which can be measured by decreasing
of relatively thick CVD-generated coatings on aluminium-based
the droplet volume. The droplet volume was varied between 2 and
substrates. The coatings, having thicknesses up to 1000 nm, con-
8 L.
sist of i PTFE-AC, where the so-called alternative condition
The angles were measured using an OCA 15 instrument (Dat-
(AC) process was selected from the variety of possible coat-
aPhysics Instruments, Germany). Droplets of deionised water
ing deposition conditions, and ii of a special uorine-free
(surface tension 72.8 mN/m) were placed with a motor-driven
polysiloxane, PSi, which accesses recent technological develop-
syringe onto the sample surface. The syringe was kept in the droplet
ments based in turn on laboratory-scale developments [31]. As
during the contact angle measurement. The corresponding contact
previously [27,28], the performance of the coated systems was
angle was determined from the tangents appropriately positioned
studied by the implementation of certain stress tests, which reect
to the contour of the droplet.
their stability against the impacts of light and moisture, but also
The contact angle values given here are mean values of three
their wear stability. The wetting performance of the two coat-
individual measurements carried out on different locations on the
ing types differed considerably, with true SH generated only by
sample. In the case of the smaller wear-tested areas two mea-
PTFE-AC. On the contrary, the polysiloxane proved promising for an
surements were performed. In addition, the averaged values of the
enhanced mechanical performance due to the highly cross-linked
standard deviations of the individual measurements are stated (i.e.
structure.
154 1 ).

2. Experimental
2.3. Scanning electron microscopy (SEM)

2.1. Samples
Sheet pieces (26 38 1 mm3 ) of the commercially available
aluminium alloy (Al Mg1, EN AW-5005) were cleaned by pick-
ling in 1 mol/L NaOH for 10 min, followed by dipping in 1 mol/L
HNO3 for 1 min and rinsing with de-ionized water. Anodic oxi-
dation as a general pretreatment was carried out in a mixture
of sulfuric acid and aluminium sulfate (c(SO4 2 ) = 2.3 mol/L). In a
rst variant, the usual conditions were applied (bath temperature
T < 20 C, current density j = 15 mA/cm2 , treatment time t = 20 min;
abbreviated SAAu). Secondly, intensied conditions were utilised
(T = (40 1) C, j = 30 mA/cm2 , t = 20 min; denoted by SAAi). The
anodised samples were carefully rinsed with tap water and then
immersed in de-ionised water for 30 min. Details of these treatment
methods and the relationship between the process parameters and
the surface topography were published previously [9]. In order to
For the morphological characterisation of the surfaces, a DSM
982 Gemini microscope (Carl Zeiss, Germany) provided with a eld
emission cathode was used at an acceleration voltage of 2 keV and
detection of secondary electrons. Following a thin carbon coating,
the samples were inspected under 35 tilt to gain information on
the 3-D character of the surfaces.
2.4. Fourier-transform reection-absorption infrared
spectroscopy (FT-IRRAS)
Spectra were recorded using an FTS 2000 instrument (Perkin-
Elmer, Germany) over the wavenumber range 5504000 cm1 as
averages of 150 single individual reection spectra measured at
normal incidence at two positions on each sample. The analysed
spot had a diameter of ca. 100 m.
 M. Thieme et al. / Applied Surface Science 283 (2013) 10411050
2.5. X-ray photoelectron spectroscopy (XPS)
The studies were carried out using an AXIS ULTRA photoelectron
spectrometer (Kratos Analytical, UK) equipped with a monochro-
matic Al K (1486.6 eV) X-ray source of 300 W at 15 kV. The kinetic
energy of the photoelectrons was determined with a hemispheric
analyser set to pass energy of 160 eV for wide-scan spectra and
20 eV for high-resolution elemental spectra, respectively. During
all measurements electrostatic charging of the sample was com-
pensated by means of a low-energy electron source working in
combination with a magnetic immersion lens. The spectra recorded
for PTFE coatings were shifted by the amount which was necessary
to set the component peak showing the CF2 groups to 292.48 eV
[34]. Likewise, for the PSi coatings a shift was applied to set the
signal of saturated hydrocarbons to 285.00 eV. The maximum infor-
mation depth for the C 1 s region was less than 10 nm. Quantitative
elemental compositions were determined from peak areas using
experimentally determined sensitivity factors and the spectrom-
eter transmission function. Spectrum background was subtracted
according to Shirley.
2.6. Articial weathering (WTH)
Following the recommendations of DIN EN ISO 11341 articial
weathering was accomplished under continuous Xe-arc irradiation
and cyclic wetting-drying sequences over 360 h using a Xenotest
Alpha device (Atlas, USA).
2.7. Wear stability tests (WEA)
Wear stability was tested by applying soft friction using a pol-
ishing felt as counter-part (circular piece, diameter 10 mm) under
dened loads up to 1000 mN/0.8 cm2 (Fig. 1). The felt was mounted
on the front surface of a cylinder, which was rotated once in 1 s. The
conditions are coded in the form WEA1000 for a force of 1000 mN,
for instance. For further details regarding this in-house-constructed
test apparatus see Ref. [20].
Fig. 1. Wear stability testing; (a) in-house constructed test apparatus; location of the turnable felt-mounted cylinder and the sample xture is marked (arrow); (b) arrangement
of the circular wear test areas on the as-coated samples (forces referring to 0.8 cm2 each).
1043
3. Results and discussion
The substrate surfaces produced by SAAu and SAAi, respectively,
were thoroughly described earlier [16,18]. In short, the thicknesses
of the oxidic layers are typically 1015 m. SAAu surfaces have a
more or less at-rippled morphology, whereas the SAAi pretreat-
ment leads to a specic morphology of the oxide layer which is
characterised by an irregularly ordered mountain-like structure
with typical top-to-valley and lateral distances of about 2 m each.
Additionally, sub-m roughness components are present. Freshly
prepared, the surfaces show hydrophilic properties, where a water
droplet spreads spontaneously, especially in case of the SAAi sur-
faces.
In contrast to the situation with most of our thin-lm, wet-born
coatings, which do not signicantly alter the original morphology
[1620], the CVD-based coatings of this study bring about their own
contributions to the microscopic shape of the respective surfaces.
3.1. PTFE-AC coatings
As already stated for the PTFE-SC coatings [27,28], PTFE-AC lms,
deposited at thicknesses of up to 1 m, conform to the oxide surface
prole so that the different shapes of the substrates are still clearly
discernible. This is illustrated by the comparison of the Fig. 2a and
b for the more or less at SAAu substrate with Fig. 2c and d for the
micro-rough SAAi surface with the specic mountain features. The
inherent microscopic morphological features of the PTFE-AC coat-
ing are noticeably distinct not only from the oxidic substrates [16],
but also from those observed with PTFE-SC coatings [27,28]. While
SC conditions exhibit very small protrusions of about 0.1 m in
height (Fig. 2e and f), the AC deposition regime produces interpen-
etrating akes with dimensions in the sub-m range (Fig. 2ad).
Higher magnication reveals that increased coating thicknesses
generate a more complex structure of the PTFE akes (Fig. 2b) and
more effective roughness properties in the low-m range.
In view of the wetting behaviour, the desired SH status was
unequivocally achieved for all the coating thickness variants of
1044 M. Thieme et al. / Applied Surface Science 283 (2013) 10411050

Fig. 2. SEM images of PTFE-coated surfaces provided with corresponding contact angle data ( a // r given in ); (a) SAAu + PTFE-AC250; (b) SAAu + PTFE-AC1000; (c) SAAi + PTFE-
AC250; (d) SAAi + PTFE-AC1000; (e) SAAu + PTFE-SC1000; (f) SAAi + PTFE-SC1000. The image of (f) shows a low-temperature fractured specimen with its outermost surface
(upper part) and the fracture area (lower part), fractured PTFE-SC layer marked by arrows (specimens tilted by 35 ).

the treatment SAAi + PTFE-AC (insets of Figs. 2c and d and 3a, red
bar pairs). Astonishingly, SAAu + PTFE-AC samples also afforded
high advancing angles (insets of Figs. 2a and b and 3a, green
bar pairs), despite only minute roughness imparted by the
SAAu pretreatment. However, for lower coating thickness, the
receding angle,  r , is markedly lower than  a leading to a
signicant hysteresis ( a  r ). On the contrary, the enhanced
(sub)micro-roughness that comes in with the increased coating
thickness of 1000 nm obviously compensates for the poorer
roughness conditions of the SAAu substrate. Nevertheless,
the SAAu + PTFE-AC combination does not generally produce
SH.

Fig. 3. Water contact angles ( a // r pairs) determined for different pretreatment and coating procedures; (a) as-coated surfaces and (b) after additional WTH testing. (For
interpretation of the references to color in the text, the reader is referred to the web version of the article.)
 M. Thieme et al. / Applied Surface Science 283 (2013) 10411050 1045

Fig. 3a provides a comparison of the wetting results discussed H G D A H G D A

above with those for PTFE-SC coatings (right half of the diagram).
Slightly decreased water-repellence is exhibited for SAAu + PTFE-
SC (blue bar pairs), because the receding angles are generally lower
than 150 , i.e. below the generally accepted threshold for SH. These
ndings agree with the morphological appearance as indicated by
SEM. Clearly, the special branching of the ne akes of PTFE-AC
(Fig. 2b) has a stronger effect on the water-repelling properties a) b)
than the cauliower-like morphology of PTFE-SC (Fig. 2e). With
superior substrate roughness (SAAi), however, there is practically
no difference in the water-repelling performance of the two PTFE
variants.
The wetting behaviour of the differently pretreated and
coated aluminium surfaces after passing through the articial
weathering procedure, WTH, may be seen from Fig. 3b. The results
make it clear that the weathering test inuenced all sample c) d)
types. However, the receding angles were more affected than
the advancing angles, preferentially for those samples with SAAu
pretreatment. SAAi-based surfaces with their higher degree on
micro-roughness were considerably less affected. It may be noted
that it is well-known from various methods, which are applied to
make polyolen surfaces hydrophilic, such as plasma and corona
treatments or aming, that the receding contact angle reacts more e) f)
sensitively on endowing the surface with polar groups [32]. More-
over, PTFE-AC-coated samples tended to be more stable than with 295 290 285 280 295 290 285 280
PTFE-SC coatings Binding Energy (eV) Binding Energy (eV)
An examination of surface morphology and chemistry was
Fig. 4. C 1s high-resolution spectra recorded from differently pretreated and coated
carried out to identify differences in repellence between the SAAi- aluminium surfaces. Left column shows spectra recorded from as-coated samples,
based vs. SAAu-based samples. According to the SEM ndings, right column shows spectra of articially weathered samples. (a) SAAu + PTFE-AC250;
the respective morphology properties were not altered by the (b) SAAu + PTFE-AC250 + WTH; (c) SAAi + PTFE-AC500; (d) SAAi + PTFE-AC500 + WTH;
articial weathering. Therefore, the chemical properties of the (e) SAAi + PTFE-SC500; (f) SAAi + PTFE-SC500 + WTH. The meaning of the component
peaks A, D, G and H is described in the text.
weathered surfaces were examined by XPS and compared to the
as-coated states. As already mentioned, the XPS method is a very
surface-sensitive analytical method. Wide-scan spectra recorded

Fig. 5. SEM images of PTFE-AC-coated surfaces after local wear testing provided with the corresponding contact angle data ( a // r given in ); (a) SAAu + PTFE-AC250 + WEA200;
(b) SAAu + PTFE-AC250 + WEA1000; (c) SAAi + PTFE-AC250 + WEA200; (d) SAAi + PTFE-AC250 + WEA1000 (specimens tilted by 35 ).
1046 M. Thieme et al. / Applied Surface Science 283 (2013) 10411050

from PTFE-coated samples before and after the articial weathering

did not show any peaks arising from the aluminium substrate mate-
rial. The absence of Al 2p and Al 2s peaks in the XPS spectra makes
sure that the PTFE coating was completely closed and thicker than
the maximum information depth of the XPS method. However, as
can be seen in Fig. 4 (right column), the articial weathering affects
the surface chemistry of the PTFE coatings. Especially the C 1s high-
resolution spectrum recorded of SAAu + PTFE-AC250 + WTH (Fig. 4b)
shows a rather complex shape that indicates numerous different
binding states of the carbon atoms. Of course, computer programs
are able to deconvolute such complex spectra, but in many cases
the results of the deconvolution process cannot be interpreted with
a high degree of certainty. Hence, the C 1s spectra in Fig. 4 will
be discussed on the basis of the signicant component peaks A Fig. 6. Water contact angle data measured for PTFE-AC coated samples following
(285.0 eV), G (ca. 292 eV), and H (ca. 294 eV), which are ascribed to the WEA procedure with varied wear forces (advancing angles full symbols/solid
saturated hydrocarbons (also including contaminations due to air lines, receding angles open symbols/dashed lines).

storage), CF2 and CF3 groups, respectively [34]. The regions, which
were designated with letter D indicate the presence of carbon atoms
involved in different bonds to oxygen (such as alcoholic, ether, car-
bonic ester and carbonic acid groups) and/or uorine (such as CHF
groups) or hydrocarbons in the neighbourhood of strongly elec-
tronegative functional groups.
The C 1s high-resolution spectra show at rst glance that the CF2
binding state represents the dominant bond type for all the coat-
ing variants tested. Contrarily, terminal CF3 groups are indicated
in very low fractions only (position H). Likewise, other component
peaks (A, D) are also of very low intensity. This structure of the C 1s
spectrum exhibits a considerably higher clarity and unambiguous-
ness than that recorded for a sample type produced by rf-sputtering
of PTFE on anodised aluminium [15]. This is an indication that the
polymer substances produced by HFCVD and rf-sputtering, respec-
tively, represent markedly different purities and/or structures of
the generated polymer coatings.
In the case of weathered samples, the component peak D
points to unwanted decomposition effects due to the weathering
inuences, i.e. moisture and light, because uorine as the origi-
nal binding partner was substituted by oxygen and/or hydrogen.
Notably, PTFE-AC coatings appear to be slightly less sensitive to
such degradation than PTFE-SC (Fig. 4d and f). Further, some inu-
ence of the anodic pretreatment, i.e. of the morphology, appears
to be present, as well. Fig. 4b and d suggests that SAAu was more
affected than SAAi. This nding cannot be explained at present.
These ndings conrm the impact of the weathering test on
the wetting behaviour, as documented in Fig. 3b. Thus, the system
SAAi + PTFE-AC experienced the least weathering-related changes
with respect to its wetting behaviour and its chemical state.
Wear stresses proved to have signicant effects on coating mor-
phology, as documented in Fig. 5 for low-proled SAAu-pretreated
and PTFE-AC-coated surfaces (Fig. 5a and b) as well as for micro-
rough SAAi-based samples (Fig. 5c and d). The surfaces were more
or less levelled; only the deep regions left of the 3-D surfaces
retained the original morphological features. Damage is more pro-
nounced when the wear force is increased from 200 mN (left
column) to 1000 mN (right column). However, the friction did not
lay the underlying anodic oxide bare this also holds true for
the SAAi-based samples with its relatively vulnerable mountain-
ous morphology. In view of the effective mechanism, the relatively
soft coating substance may have been partially removed, but the
polymer coating was also smeared and redistributed over the
area where the friction was applied. It is clear that these effects
were even more pronounced with the highest coating thickness of
1000 nm (not shown).
It may be expected that these massive morphological changes
would strongly affect the water-repelling properties, i.e. the orig-
inally existing SH. The insets of Fig. 5 and the following diagram
(Fig. 6) display the water contact angles obtained for the individual
circular wear-stressed areas of PTFE-AC coated samples. Generally,
increasing load resulted in greater loss of hydrophobicity. How-
ever, the advancing angles are again less affected than the receding
angles, which decreased markedly even for the lowest force level of
50 mN, as the diagram documents. Furthermore, Fig. 6 shows that
for medium forces the advancing contact angles for SAAi-treated
samples are less reduced than for SAAu-based surfaces. The rea-
son is seen in the fact that, according to Fig. 5c, there are still
micro-rough, hydrophobic cavities on the surface, although the
summits are abraded away. This produces smaller steps of the
advancing contact line, when the droplet grows (stick-slip motion
[33]), and, hence, higher advancing angles compared to the more
or less smooth surface in the case SAAu + PTFE-AC + WEA.
For surfaces, which were treated with the maximum force of
1000 mN, the advancing contact angle values tend to 110120
(Fig. 6) corresponding to the characteristic data of smooth PTFE
surfaces [35].
Similar results have been found for wear-stressed samples that
underwent the weathering procedure, although two force levels
only (100 and 200 mN) could be applied due to limited space on
those samples.
3.2. PSi coatings
This coating type differs from PTFE coatings in several respects.
First, PSi-coated surfaces show a different morphology, because
there are practically no specic morphological features as in the
case of PTFE-AC or PTFE-SC coatings (Fig. 7a and b). With growing
coating thickness the low-roughness surface of SAAu is increasingly
levelled out. As the Fig. 7c and d illustrate, this tendency is observed
also for the SAAi substrates, where the summits of the oxidic layer
are increasingly rounded.
Secondly, the PSi polymer proved to have a considerably less
water-repelling performance. For the relatively at SAAu + PSi sur-
faces, even the recorded advancing angles remained below 100
(insets in Fig. 7a and b). These values are in a good agreement
with the static water contact angle of (92 2) as determined by
the manufacturer. The advancing angles for SAAi + PSi are consider-
ably higher. In case of the 250 nm coating the bre-like features are
still retained (Fig. 7c) so that the threshold of SH is reached by the
advancing angle. With the 1000 nm coating (Fig. 7d), the decrease
of the contact angles reects the increasing smoothness and the
loss of the sub-m roughness features. In each case there are sub-
stantial hystereses, which indicate that true SH is not achieved by
far.
Similar relations were obtained for the samples that had under-
gone an additional articial weathering, whereupon the absolute
water contact angles were reduced by 2030 .
 M. Thieme et al. / Applied Surface Science 283 (2013) 10411050 1047

Fig. 7. SEM images of PSi-coated surfaces provided with corresponding contact angle data ( a // r given in ); (a) SAAu + PSi250; (b) SAAu + PSi1000; (c) SAAi + PSi250; (d)
SAAi + PSi1000 (specimens tilted by 35 ).

FT-IRRAS and XPS measurements were accomplished to charac-
terise structural properties of PSi coatings and to pursue the effects
of articial weathering and the optionally inserted annealing
step.
The water-repelling properties of PSi are assumed to be pre-
dominantly caused by the methyl groups in the proposed structure
model [31] (cf. inset in Fig. 8). These groups are evidenced by the IR
absorption bands at wavenumbers of ca. 2965 cm1 (Fig. 8). Unfor-
tunately, the interference phenomena present in the upper curve
pair do not allow a reliable evaluation, whether or not the con-
centration of these groups has diminished due to the weathering
procedure. Such a tendency would be suggested by the worsened
water-repellency. The presence of methylene groups (a CH2
2920 cm1 , s CH2 2852 cm1 [36]), as they had been indicated
for the chemical modication by hexadecyltrimethoxysilane [17]
or poly(octadecene-alt-maleic anhydride) [28], for example, can-
not be determined unambiguously. Doubtless, the lack of longer
alkyl groups is associated with the poor water-repelling properties
of PSi. On the other hand, Jia et al. [24] derived from IR ndings
that the SH of their ame-made SiO2 nanoparticle coatings should
be caused by Si-CH3 moieties without the presence of longer alkyl
groups. Turning back to the spectra recorded for SAAu + PSi1000T

Fig. 8. FTIR spectra of PSi-coated samples with different post-treatments; uncoated SAAu as reference. Inset: structure model of the polymer [31].
1048 M. Thieme et al. / Applied Surface Science 283 (2013) 10411050
and SAAu + PSi1000T + WTH, respectively, the comparison in the
region of 800-1300 cm1 suggests that there are no principal alter-
ations in the structure of the deposited polymer due to the impacts
of light and moisture during the WTH treatment. However, compar-
ing these spectra with those published by the group of Gleason and
co-workers [31], a considerable disagreement is perceptible. From
this reason, some additional coatings were prepared omitting the
usual primary anodisation. With bare aluminium as substrate, the
typical triple band structure with peaks at 780, 1011 and 1271 cm1
is displayed, as the lower two spectra of Fig. 8 illustrate. The main
band of these features is ascribed to SiOSi stretch vibrations in
trisiloxane ring moieties [31] being typical for this special molec-
ular structure. Thus, it may be concluded that an unambiguous
identication of a polymer coating is not possible, when it has only a
low thickness and when the underlying substance strongly absorbs
in the same region. This is the case with the anodised oxidic lay-
ers in the low-wavenumbers region (Fig. 8, middle curve), where
OAlO stretch vibrations are located [37].
Moreover, there are two further ndings: i The PSi coating
(Al + PSi2000), which did not undergo the thermal post-treatment,
appears to indicate a lower fraction of linear siloxane sequences.
This may be recognised by the shoulder at about 1080 cm1 [31]
for the corresponding curve in Fig. 8. ii The fraction of a hydrated
oxide layer, as can be seen in the region of 3400 cm1 , is inuenced
by the technologic steps applied. The OH content of the sample
type SAAu + PSi is lower than for SAAu alone because of the par-
tial water removal due to the increased stage temperature [31].
Clearly, the lowest OH content is found for the samples without
anodisation.
Further information on the characteristics of PSi coatings and
the inuence of the thermal post-treatment as well as of arti-
cial weathering was gained from XPS. The Si 2p high-resolution
spectra showed one peak at about 102 eV. Independently of the
Fig. 10. SEM images of PSi-coated surfaces after local wear testing provided with corresponding DCA data ( a // r ); (a) SAAi + PSi250 + WEA200; (b) SAAu + PSi250 + WEA1000;
(c) SAAi + PSi1000 + WEA200; (d) SAAi + PSi1000 + WEA1000; images (b) and (d) showing mechanical decapitation of some summits (arrows) and broken-off debris (dashed
arrows); (specimens tilted by 35 ).
Si Si
DC E DC
A A
a) b) B
295 290 285 280 295 290 285 280
Binding Energy (eV) Binding Energy (eV)
Fig. 9. C 1s high-resolution spectra recorded from a PSi2000 (a) and a PSi2000T
coating (b), respectively.
fact that this peak consists of 2p1/2 and 2p3/2 contributions [38],
this nding points to the presence of one silicon species, which
corresponds to OSi[CHx ]2 moieties. On the contrary, the C 1s
HR spectra of Fig. 9 reveal differently bonded carbon atoms. As
Fig. 9a illustrates for PSi2000, there are two major constituents: The
component peak Si (284.4 eV) reects the SiC bonds of the siloxane
and component peak A (285.00 eV) indicates considerable amounts
of hydrocarbons. The small component peaks C and D at higher
binding energies indicate the presence of polar groups containing
oxygen. Peak C may be ascribed to COH and/or COC, whereas D
corresponds to C O. These ndings correlate with the hypothesised
coating structure (inset in Fig. 8 [31]), where the carbon-oxygen
bonds are assumed to stem from the initiator di-tert-butyl perox-
ide. This fact is also reected by the O/C atom ratio (0.34) and the
C/Si atom ratio (3.8). The latter exceeds the original atom ratio in
the siloxane molecule (3.0) and, at the same time, agrees very well
with the former nding of 3.9 by Gleasons group [31].
In the case of the annealed sample PSi2000T a changed C 1s
spectrum was observed. Apart from the increased intensities of
 M. Thieme et al. / Applied Surface Science 283 (2013) 10411050
the component peaks C and D mentioned above, an additional
component peak E appeared at 289.1 eV. Obviously, the coating
layer contains small amounts of carboxylic acid groups. This indi-
cates thermally initiated degradation reactions in the course of the
annealing, where the uppermost surface of the polymer layer is
slightly oxidised. The formation of polar surface groups increases
the surface free energy and, hence, the tendency to adsorb contam-
inations from the environment.
Subsequently performed articial weathering
(SAAu + PSi250 + WTH) caused further increase of the com-
ponent peaks with higher binding energies. Principally, this
conrms the changes as noticed by FT-IR and water contact angle
measurements.
Turning to the wear behaviour of PSi towards soft friction, this
coating type proved to be much more resistant than PTFE coatings,
as described above. With SAAu-based specimens no trace of wear
occurred within the force range up to 1000 mN. Correspondingly,
the contact angle data recorded on the wear-tested areas did not
change remarkably in comparison to the data stated in Fig. 7a and
b.
For SAAi-based specimens the situation changes slightly in that
a portion of the coated summits was decapitated for the load
of 1000 mN, as Fig. 10b and d illustrate (arrows). In some cases,
the broken material could be detected in cavities or attached to
anks near the sheared summits (dashed arrows). This behaviour
is caused by the considerably enhanced effective load exerted on
the tops of the characteristic micro-prole. Altogether, the wetting
behaviour is not signicantly affected by the wear treatment.
Doubtless, the unambiguously positive wear behaviour is based
on the structure of the applied polymer, which contains not
only cyclic siloxane moieties, but is also characterised by pro-
nounced cross-linkages [31]. On the contrary, the soft polymer
poly(tetrauoroethylene) has a non-cross-linked structure distin-
guished by comparatively weak intermolecular forces between the
individual chains. Although the water-repelling behaviour of PSi-
coated surfaces, especially the absolute level of the receding angles,
is not satisfactory in view of SH, the mechanical features can be con-
sidered as an encouraging sign for the development of a suitable
synthetic route: In order to produce durable superhydropho-
bic surfaces, it appears to be necessary to combine intrinsically
hydrophobic structure elements of the coating, preferably uorine-
containing groups, with cross-linkage of the polymeric chains. This
approach will be pursued in further research.
4. Conclusions
Continuing the investigations for generation and charac-
terisation of superhydrophobic aluminium-based surfaces, the
investigations have been expanded to two further types of CVD-
produced coatings with thicknesses from 250 to 2000 nm: i a
special poly(tetrauoroethylene) coating, PTFE-AC, as a variant to
the standard coating process (PTFE-SC) [2730] and ii a special
uorine-free polysiloxane, PSi [31]. In addition to evaluating the
wetting, morphological, and chemical properties, the performance
of the coated systems was assessed after subjection to stress tests,
designed to test their stability towards the impact of light and mois-
ture as well as wear.
Superhydrophobicity (SH) was primarily observed with systems
based on anodised, micro-rough aluminium (SAAi) subsequently
coated with PTFE-AC or PTFE-SC. High water contact angles of at
least 150 occurred also under conditions of a relatively at sub-
strate (SAAu), when the coating exhibited roughness features in
both the sub-micrometre and low-micrometre ranges. However,
the hystereses observed for SAAu-based PTFE-AC-coated surfaces
were not always consistent with the denition of superhydropho-
bicity.
1049
Coatings of PSi afforded relatively smooth surfaces without
specic morphological features. In combination with its inher-
ent incomplete water-repelling properties SAAu-based PSi-coated
surfaces showed contact angles of less than 100 , whereas for
micro-rough SAAi + PSi250 surfaces advancing contact angles of
150 were achieved. Additional annealing (250 C/1 h) led to partial
degradation and/or contamination effects.
Articial weathering resulted in a general worsening of the
wetting behaviour of PTFE-AC systems, with deleterious effects
conned primarily to the receding contact angles and occurred
preferentially with SAAu-pretreated samples. These tendencies
could be correlated to alterations in the surface chemistry as stated
by XPS. Similar effects of WTH were found also for PSi-coated sam-
ples.
The wear tests showed that the PTFE-AC coatings were consider-
ably sensitive to friction, which resulted in a dramatic deterioration
of the water-repelling properties. In contrast, PSi coatings were
surprisingly resistant towards friction. It can be concluded from
these results that the combination of uorine containing hydropho-
bic structure elements and cross-linkages between the polymeric
chains appears to be a crucial prerequisite for producing mechani-
cally stable superhydrophobic surfaces.
Acknowledgements
The authors are indebted to Ms. J. Jia (Technische Universitt
Dresden) for her careful wetting measurements on the PSi-coated
samples as well as to Mr. G. Wiemann (Technische Universitt
Dresden) and Mrs. M. Auf der Landwehr (IPF Dresden e.V.) for
experimental support.
References
[1] X. Liu, Y. Liang, F. Zhou, W. Liu, Extreme wettability and tunable adhesion:
biomimicking beyond nature, Soft Matter 8 (2012) 20702086.
[2] Y.Y. Yan, N. Gao, W. Barthlott, Mimicking natural superhydrophobic surfaces
and grasping the wetting process: A review on recent progress in prepar-
ing superhydrophobic surfaces, Advances in Colloid and Interface Science 169
(2011) 80105.
[3] K. Liu, L. Jiang, Metallic surfaces with special wettability, Nanoscale 3 (2011)
825838.
[4] C.-H. Xue, S.-T. Jia, J. Zhang, J.-Z. Ma, Large-area fabrication of superhydropho-
bic surfaces for practical applications: an overview, Science and Technology of
Advanced Materials 11 (2010) 033002.
[5] L. Yin, Y. Wang, J. Ding, Q. Wang, Q. Chen, Water condensation on super-
hydrophobic aluminium surfaces with different low-surface-energy coatings,
Applied Surface Science 258 (2012) 40634068.
[6] B. Qian, Z. Shen, Fabrication of super-hydrophobic surfaces by dislocation-
selective chemical etching on aluminium, copper, and zinc substrates,
Langmuir 21 (2005) 90079009.
[7] D. Xie, W. Li, A novel simple approach to preparation of superhydrophobic
surfaces of aluminium alloys, Applied Surface Science 258 (2011) 10041007.
[8] D.K. Sarkar, M. Farzaneh, Lotos effect on Al-surfaces, Vol. 3, Nano Science and
Technology Institute, 2006, pp. 166169, ISBN 976-79858-1.
[9] D.K. Sarkar, M. Farzaneh, R.W. Paynter, Superhydrophobic properties of ultra-
thin rf-sputtered Teon lms coated etched aluminium surfaces, Materials
Letters 62 (2008) 12261229.
[10] Q. Wang, B. Zhang, M. Qu, J. Zhang, D. He, Fabrication of superhydrophobic
surfaces on engineering material surfaces with stearic acid, Applied Surface
Science 254 (2008) 20092012.
[11] S. Ren, S. Yang, Y. Zhao, T. Yu, X. Xiao, Preparation and characterization of an
ultrahydrophobic surface based on a stearic acid self-assembled monolayer
over polyethyleneimine thin lms, Surface Science 546 (2003) 6474.
[12] R. Jafari, M. Farzaneh, Fabrication of superhydrophobic nanostructured surface
on aluminium alloy, Applied Physics A 102 (2011) 195199.
[13] K. Tsujii, T. Yamamoto, T. Onda, S. Shibuichi, Superlabstoende Oberchen,
Angewandte Chemie International Edition 109 (1997) 10421044.
[14] S. Shibuichi, T. Yamamoto, T. Onda, K. Tsujii, Super water- und oil-repellent
surfaces resulting from fractal structure, Journal of Colloid and Interface Science
208 (1998) 287294.
[15] R. Jafari, R. Menini, M. Farzaneh, Superhydrophobic and icephobic surfaces
prepared by RF-sputtered polytetrauoroethylene coatings, Applied Surface
Science 257 (2010) 15401543.
[16] M. Thieme, R. Frenzel, S. Schmidt, H. Worch, F. Simon, K. Lunkwitz, D. Scharn-
weber, Generation of ultrahydrophobic properties of aluminiuma rst step
1050 M. Thieme et al. / Applied Surface Science 283 (2013) 10411050
to self-cleaning transparently coated metal surfaces, Advanced Engineering
Materials 3 (2001) 691695.
[17] M. Thieme, R. Frenzel, V. Hein, H. Worch, Metal surfaces with ultrahydrophobic
properties: perspectives for corrosion protection and self-cleaning, Journal of
Corrosion Science and Engineering 6 (2003), Paper C113.
[18] M. Thieme, H. Worch, Ultrahydrophobic aluminium surfaces: properties and
EIS measurements of different oxidic and thin-lm coated states, Journal of
Solid State Electrochemistry 10 (2006) 737745.
[19] R. Frenzel, C. Blank, K. Grundke, V. Hein, B. Schmidt, F. Simon, M. Thieme, H.
Worch, Wettability of methacrylate copolymer lms deposited on anodically
oxidized and roughened aluminium surfaces, Journal of Adhesion Science and
Technology 23 (2009) 469482.
[20] C. Blank, V. Hein, M. Thieme, H. Worch, S. Hhne, F. Simon, Ultrahydrophobe
chitosanstabilisierte Kompositschichten auf Aluminiumwerkstoffen, in: G.
Petzow (Ed.), Praktische Metallographie, Sonderband 39, Werkstofnforma-
tionsges, Frankfurt, 2007, pp. 175182.
[21] W. Wu, X. Wang, D. Wang, M. Chen, F. Zhou, W. Liu, Q. Xue, Alumina nanowire
forests via unconventional anodization and super-repellency plus low adhesion
to diverse liquids, Chemical Communications 104 (2009) 10431045.
[22] H. Schulz, M. Leonhardt, H.-J. Scheibe, B. Schultrich, Ultra hydrophobic wetting
behaviour of amorphous carbon lms, Surface and Coatings Technology 200
(2005) 11231126.
[23] Y. Yin, T. Liu, Sh Chen, T. Liu, Sh Cheng, Structure stability and corrosion inhi-
bition of super-hydrophobic lm on aluminium in seawater, Applied Surface
Science 255 (2008) 29782984.
[24] Y. Jia, R. Yue, G. Liu, J. Yang, Y. Ni, X. Wu, Y. Chen, Facile fabrication of
nano-structured silica hybrid lm with superhydrophobicity by one-step VAFS
approach, Applied Surface Science 265 (2013) 405411.
[25] K. Honda, H. Yamaguchi, M. Kobayashi, M. Morita, A. Takahara, Surface
molecular aggregation structure and surface physicochemical properties of
poly(uoroalkyl acrylate) thin lms, Journal of Physics: Conference Series 100
(2008) 012035.
[26] S. Lee, W. Hwang, Ultralow contact angle hysteresis and no-aging effects in
superhydrophobic tangled nanober structures generated by controlling the
pore size of a 99.5% aluminium foil, Journal of Micromechanics and Microengi-
neering 19 (2009) 035019.
[27] C. Blank, M. Thieme, V. Hein, H. Worch, T. Burkhardt, R. Frenzel, S. Hhne,
H. Pryce Lewis, A.J. White, Superhydrophobic Aluminium Surfaces: Extended
Preparation Routes and Characterisation, in: J. Hirsch, B. Skrotzki, G. Gottstein
(Eds.), Aluminium Alloys Their Physical and Mechanical Properties, Wiley
VCH, Weinheim, 2008, ISBN 978-3-527-32367-8, pp. 21312138.
[28] M. Thieme, C. Blank, A. Pereira de Oliveira, H. Worch, R. Frenzel, S. Hhne,
F. Simon, H. Pryce Lewis, A.J. White, Superhydrophobic aluminium surfaces:
preparation routes, properties and articial weathering impact, in: K. Mittal
(Ed.), Contact Angle, Wettability and Adhesion, Vol. 6, Brill, Leiden, Boston,
2009, ISBN 978-9-00416-932-6, pp. 251267.
[29] K.K.S. Lau, J.A. Cauleld, K.K. Gleason, Structure and morphology of uoro-
carbon lms grown by hot lament chemical vapor deposition, Chemistry of
Materials 303 (2000) 30323037.
[30] K.K.S. Lau, ShK. Murthy, H.G. Pryce Lewis, J.A. Cauleld, K.K. Gleason, Fluorocar-
bon dielectrics via hot lament chemical vapor deposition, Journal of Fluorine
Chemistry 122 (2003) 9396.
[31] W.Sh. OShaughnessy, M. Gao, K.K. Gleason, Initiated chemical vapor deposi-
tion of trivinyltrimethylcyclotrisiloxane for biomaterial coatings, Langmuir 22
(2006) 70217026.
[32] K. Jhnichen, J. Frank, D. Pleul, F. Simon, A study of paint adhesion to poly-
meric substrates, Journal of Adhesion Science and Technology 17 (2003) 1635
1654.
[33] A. Marmur, Soft contact: measurement and interpretation of contact angles,
Soft Matter (2006) 1217.
[34] G. Beamson, D. Briggs, High resolution XPS of organic polymers, in:
The Scienta ESCA 300 Database, John Wiley & Sons, Chichester, 1992,
pp. 230239.
[35] Surface Energy Data for PTFE: Polytetrauoroethylene, CAS # 9002-84-
0; 2009 Diversied Enterprises; http://www.accudynetest.com/polymer
surface data/ptfe.pdf (120316).
[36] I.L. Liakos, R.C. Newman, E. McAlpine, M.R. Alexander, Comparative study
of self-assembly of a range of monofunctional aliphatic molecules on
magnetron-sputtered aluminium, Surface and Interface Analysis 36 (2004)
347354.
[37] S.W. Gaarenstroom, Growth and characterization of aluminum oxide thin lms
for evaluation as reference materials, Journal of Vacuum Science & Technology
A 15 (3) (1997) 470477.
[38] D. Pleul, R. Frenzel, M. Eschner, F. Simon, X-ray photoelectron spectroscopy
used to show different SiO binding states of silicon, Analytical and Bioanalyt-
ical Chemistry 375 (2003) 12761281.