J. Coat. Technol. Res.

, 8 (2) 153160, 2011

DOI 10.1007/s11998-010-9293-y

REVIEW ARTICLE

Anti-fingerprints fluorinated coating for anodized titanium

avoiding color alteration
Walter Navarrini, Tommaso Brivio, Dmitrij Capobianco,
Maria Vittoria Diamanti, Mariapia Pedeferri,
Luca Magagnin, Giuseppe Resnati

ACA and OCCA 2010

Abstract In this study amorphous fluorinated
coatings applied to anodized titanium surface have
been investigated. A copolymer between tetrafluoroethylene and perfluoro-4-trifluoromethoxy-1,3-dioxole
(AD60) and two perfluoropolyether containing ammonium phosphate (F10) or triethoxysilane (S10) functionalities have been tested. To estimate the color
alteration of the anodized titanium surfaces due to the
application of the coatings, spectrophotometric analyses have been made. Water and n-dodecane contact
angles as well as apparent surface energy have been
evaluated. Ellipsometry and atomic force microscopy
data have been used to measure the thickness of the
fluorinated coatings. A tailored mechanical preliminary test has also been explored to evaluate the
adhesion of the coatings on the anodized titanium
surface. The resistance to surface soiling with castor oil
was also preliminarily investigated. The fluorinated
coating tested on anodized titanium showed a low
apparent surface energy and high chromatic aspect
conservation, this is particularly evident for the titanium anodized coated with triethoxysilane functionalities fluoropolymers S10.
Keywords Anodized titanium, Fluorinated coatings,
Color alteration, Anti-fingerprint

W. Navarrini (&), D. Capobianco,

M. V. Diamanti, M. Pedeferri, L. Magagnin,
G. Resnati
Dipartimento di Chimica, Materiali e Ingegneria Chimica
G. Natta, Politecnico di Milano, via Mancinelli 7, 20131
Milan, Italy
e-mail: walter.navarrini@polimi.it
T. Brivio
Praxair S.r.l., 23804 Monte Marenzo, LC, Italy

Introduction
In the recent years, titanium has inspired and caught
the interest of engineers, architects, artists, and
scientists, thanks to its peculiar properties. Among
the most interesting characteristics of titanium, it is
worth mentioning the variety of surface coloration
that this metal can acquire when coated with different
thicknesses of its oxide, as well as the photocatalytic
activity of the latter, whenever in the appropriate
crystal phase.
Variable thicknesses and compositions of titanium
dioxide films can be obtained by titanium anodizing.1,2
Thanks to this technology, it is possible to achieve
superficial oxide films characterized by various colors,
which are due to interference phenomena and therefore depend on the oxide thickness,3,4 as well as
different crystal structures, e.g., oxide films rich in
anatase and rutile.
Therefore, through the titanium anodizing process it
is possible to produce articles characterized by lightness, unique corrosion resistance, appealing esthetics
as well as photoactive surface.57
One of the major drawbacks to the applications of
anodized titanium with esthetical value is the chromatic alteration that greasy traces of oily substances
cause on its surface, which therefore presents issues of
easy soiling.
To solve this inconvenience, anodized titanium
substrates have been coated with amorphous perfluorinated polymers, in particular with one high Tg
copolymer of tetrafluoroethylene and perfluoro4-trifluoromethoxy-1,3-dioxole in the ratio 40/60
(AD60),8,9 and with two different low Tg amorphous
perfluoropolyethers containing ammonium phosphate
(PFPE-F10) or silane groups (PFPE-S10) at the chainending positions.
Perfluoropolymers are characterized by very low
surface energies and low wettability.1012 These

153

J. Coat. Technol. Res., 8 (2) 153160, 2011

properties are useful to improve both the dirt

resistance and the washability of the anodized
surface, since the fluoropolymer coating lowers the
adhesion of staining agents to the coated surface.12
Moreover, amorphous perfluoropolymers are perfectly transparent to light in a very broad wavelength
region and are characterized by a very low refractive
index10,1315; therefore, these polymers should not
significantly modify the color of the substrate after
their application.

ratio 40/60, respectively,8,9 with polymeric structure

below reported:
CF3
CF

CF2

CF2

O
6

Fluoropolymer F10 is a ax ammonium phosphate

terminated perfluoropolyether with an average molecular weight (Mn) of 2200 g/mol16 with polymeric structure:

(NH4)2PO4 C2H4O CH2 RF CH2 OC2H4 PO4(NH4)2

m
m

RF = OCF2

OCF2CF2
n

m=12; n+p=915; p/n=12

In this study surface contact angle values have

been collected and analyzed to estimate how hydrorepellence, oleo-repellence, and apparent surface
energy of the coated titanium oxide samples influence
the wettability and the adhesion of dirt on the
substrate. It has also been evaluated how the application of the fluoropolymer coating alters the surface
coloration through spectrophotometric analyses. The
thickness of the deposited films has been investigated

(EtO)3SiO(CH2)3NHC(O)CF2

RF

where the unit OCF2 and OCF2CF2 are randomly distributed along the perfluorinated polymeric backbone RF.
The phosphate functionality at the chain-ending
position develops a specific polar interaction with the
anodized titanium surface increasing the adhesion of
the coating.
Fluoropolymer S10 is a ax-terminated triethoxysilane perfluoropolyether derivative with an Mn of
1800 g/mol.17

OCF2C(O)NH(CH2)3Si(OEt)3

RF =

OCF2

OCF2CF2
n

n+p=913; p/n=12

by means of ellipsometric and atomic force microscopy

(AFM) analyses.
Finally, selected preliminary tests have been used in
order to estimate the coating resistance to both: soiling
and mild mechanical stress.

Experimental

The triethoxysilane functionality at the chain-ending

positions has the purpose of reacting with the OH
groups present on the anodized titanium surface, thus
developing chemical bonds between coating and substrate. In addition, as described in the specialized
literature this polymer crosslinks at 150C.18
The GALDEN HT110 is perfluoropolyether solvent with boiling point of 110C and formula as follow: CF3O(CF2CF(CF3)O)p(CF2O)n CF3 p + n = 23;
p/n = 2050.

Materials
Materials used and investigated in the course of the
experimental sets include an anodized titanium substrate and three fluoropolymer coatings. Commercial
purity titanium, grade 2 in ASTM classification, was
used as metallic substrate, while the tested coatings
were commercial amorphous perfluoropolymers.
The tested fluoropolymers AD60, PFPE-F10, and
PFPE-S10 are produced and commercialized by
Solvay-Solexis S.A. under the following trade marks:
HYFLON AD60, FLUOROLINK F10, and
FLUOROLINK S10, respectively.
Fluoropolymer AD60 is a high-molecular-weight
(Mn 500.000 g/mol) random copolymer between TFE
and perfluoro-4-trifluoromethoxy-1,3-dioxole in the

154

General methodology for the preparation

of titanium anodized substrates
Titanium plates (sizes: 15 mm width, 270 mm height,
1.5 mm thick) were anodized in 0.5 M H2SO4 by
imposing a current density of 40 mA/cm2 and cell
voltage of 100 V, as reported in previous work.19 These
process parameters generate a TiO2 film rich in anatase
on the anodized surface, which is the most photoactive
crystal phase of TiO2. Moreover, a thin oxide layer
confers to the titanium surface an interference color,
whose hue is strictly dependent on the layer thickness.
After anodizing titanium plates by applying the chosen
parameters, the oxide appears violet.

J. Coat. Technol. Res., 8 (2) 153160, 2011

General methodology for the coating of anodized

titanium plates
Three anodized plates were separately coated by
brushing with one of the following fluoropolymers
solutions: AD60 at the concentration of 1 wt% in a
low-molecular-weight PFPE (GALDEN HT110) as a
solvent (Plate 1), F10 at the concentration of 1 wt% in
isopropyl alcohol (20 wt%) and water (77 wt%)
(Plate 2), and S10 at the concentration of 1 wt% in
isopropyl alcohol (94 wt%), water (4 wt%), and acetic
acid (1 wt%) (Plate 3).
After coating, the plates underwent the following
thermal treatment: holding in ambient atmosphere at
25C for 15 min, heating in oven to 100C for 30 min,
heating to 150C for 15 min, and cooling back to 25C
in ambient atmosphere.
The thermal treatment at 150C is applied to unwind
the deposed polymers layer at a temperature above Tg
and is also particularly necessary for the samples
coated with fluoropolymer S10, since this polymer also
crosslinks at this temperature.
Contact angle measurements
Static contact angle measurements were implemented
in order to determine the apparent surface energy,
hydrophobic, and oleophobic properties of the perfluoropolymeric coatings, as well as to qualitatively
evaluate the adhesion of staining agents on the coated
surface. Contact angle measurements were performed
with a Dataphysics OCA contact angle instrument
and elaborated with SCA20 software.
The static contact angle measurements reported in
Table 1 were calculated as average of four different
lecture points taken on the titanium anodized sample
and on the coated samples. In Table 1 we report the
experimental average values and related standard
variations for the treated samples and for the simple
anodized titanium sample as internal reference.

Table 1: Water and n-dodecane contact angle and

apparent surface energy of uncoated and coated substrates
Sample

Plate
Plate
Plate
Plate

Water

n-C12H14

0 49.12
5
1 119.53 0.22 64.84 3.32
2 90.53 3.69 66.67 4.56
3 121.78 1.32 65.33 4.27

Apparent surface
energy (mN/m)
46.16
24.77
25.89
24.80

Plate 0: uncoated anodized titanium; Plate 1: anodized titanium coated with fluoropolymer AD60; Plate 2: anodized
titanium coated with fluoropolymer F10; Plate 3: anodized
titanium coated with fluoropolymer S10

Spectrophotometry
Spectrophotometry allows the objective color determination of a sample surface by measuring the extent of
reflected light as a wavelength function of an incident
light beam. The color surface charts were standardized
by the CIE (Commission Internationale de lEclairage)
by creating the Lab color space (CIELab).20 In this
space, each color is defined by using three independent
coordinates: L*, a*, and b*, which define a point in the
CIELab sphere. L* represents the brightness, whereas
a* and b* are the chromatic coordinates which range
from green to red and from blue to yellow, respectively. In the CIELab system, differences between two
colors are measured as three-dimensional distances
between the points in the sphere that identify the
colors; such difference, indicated as DE, is then
calculated by the following equation:
h
i1=2
DE DL 2 Da 2 Db 2
wherein DL*, Da*, Db* are the differences between the
values of L*, a*, and b* of the analyzed colors. The
experimental evaluation of the CIELab coordinates
L*, a*, and b* was made by using a Minolta CM-2600d
spectrophotometer, with illuminating source D65 standard (xenon lamp that produces the closest spectrum to
that of solar light). The irradiated area is a circular spot
of 1 cm diameter. The experimental spectrophotometric values reported in Table 2 were calculated as
average of four different lecture points taken on the
titanium anodized samples and on the coated samples.
In Table 2 we report the experimental average values
and the standard variations for each treated sample
and for the simple anodized titanium samples as
internal reference.

Ellipsometry and AFM

In order to evaluate the thickness of the deposed films,
ellipsometry analyses have been made. Ellipsometric
analyses were done by using a Gaertner ellipsometer
L116S, equipped with an HeNe laser (k = 632.8 nm);
the size of the light beam being a microspot of about
15 lm, with a GlanThompson calcite polarizer and a
StokeMeter analyzer. That is a four-detector-photopolarimeter consisting of four specularly reflecting
photo-detectors. The incidence angle of the light was
70. The optical constants of the surface layers were
calculated through a MaxwellGarnett Effective Medium Approximation.2124 Surface layer before fluoropolymer coating can be assumed to be composed of a
mixture of Ti + TiO2 with 140230 nm thickness with a
complete absorption and reflection of the 632.8 nm
incident light due to its extinction coefficient of 1.97.
Optical constants were introduced into Fresnel equations to calculate W and D and the thickness of the
fluoropolymer layer, searching the best fitting between

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J. Coat. Technol. Res., 8 (2) 153160, 2011

Table 2: CIELab colorimetric data

Sample
Plate
Plate
Plate
Plate
Plate
Plate

0
1
0
2
0
3

L*
49.2
46.8
49.5
47.0
49.5
49.3

a*
0.09
0.70
0.06
0.57
0.07
0.05

15.0
7.1
15.9
8.0
13.3
11.0

b*
0.60
0.98
0.57
0.79
0.64
0.45

17.4
12.9
19.5
13.1
18.8
17.1

0.31
1.51
0.34
1.79
0.16
0.19

DL*

Da*

Db*

DE

2.4 0.79

7.9 1.58

4.5 1.82

9.5

2.5 0.63

7.9 1.36

6.4 2.13

10.4

0.3 0.12

2.4 1.09

1.7 0.35

2.9

Plate 0: uncoated anodized titanium plates; Plate 1: anodized titanium coated with fluoropolymer AD60; Plate 2: anodized
titanium coated with fluoropolymer F10; Plate 3: anodized titanium coated with fluoropolymer S10

experimental and calculated values with a trial-anderror procedure.21,24 The roughness value, before
treatment with fluoropolymers, was measured by
AFM, using a Veeco Digital Instruments Dimension
3100 scanning probe microscope. Scans of 10 lm 9
10 lm were acquired for each coupon in amplitude
modulation tapping mode, using silicon tips. Surface
roughness was evaluated by flattening the images (firstorder) using Nanoscope software.

With the data collected it was possible to evaluate

the apparent surface energy of the samples. The results
are noticeably lowered by the presence of the organic
coating, with respect to the anodized substrate. This
low apparent surface energy value may suggest a high
roughness of coated titanium oxide surface; indeed it
is well known that the roughness of a hydrophobic
solid enhances its hydrophobicity. The supposed high
roughness of coated titanium oxide surface is also
observed by preliminary AFM analysis as pointed out
in Fluoropolymer thickness evaluation section.

Results and discussion

Contact angle

Spectrophotometry

As mentioned above, perfluoropolymeric coatings

confer to the surfaces of a low surface energy and a
low wettability; materials treated with these products
become hydrophobic and assume water contact angle
values higher than 90. On the contrary, uncoated
anodized titanium (Plate 0) has a hydrophilic surface
with contact angle of about 49.
In Table 1 the obtained contact angle data are
summarized. It is possible to notice that fluoropolymers S10 and fluoropolymer AD60 give to the treated
surface (Plate 3 and Plate 1) an extremely high hydrophobicity, with average values of water contact angle,
respectively, of 122 and 120. Samples treated with
fluoropolymer F10 (Plate 2) are also characterized by a
hydrophobic surface, although hydrophobicity is less
pronounced in comparison to the other two coatings
with an average value of 91.
N-dodecane contact angle analyses were also performed. The obtained values confirm the ability of
coatings to lower the wettability of the treated surface
also when the surface interacts with low paraffin
compounds, thus giving to the TiO2 surface layer
oleophobic properties. N-dodecane contact angle values are about 65 in the case of the coated samples,
whereas on the uncoated TiO2 film the value is lower
than 5.
As it can be seen by the contact angles evaluated
in water and in N-dodecane the treated samples are at
the same time characterized by hydrophobic and
oleophobic properties.

The L* average value of the samples coated with

fluoropolymer AD60 (Plate 1) decreases from 49.2 for
the uncoated surface to 46.8 measured after the
coating, as shown by the data in Table 2. It is also
possible to notice the variations of the coordinates a*
and b* of the CIELab color space. The first one
decreases from 15 to 7.1, whereas the second one
increases from 17.4 to 12.9. The DE value obtained
for the sample coated with AD60 is 9.5.
In the sample coated with fluoropolymer F10
(Plate 2) the brightness L* decreases only by 2.5,
whereas a more intense variation of the colorimetric
coordinates a* and b* can be observed: the first one
decreasing from 15.9 to 8, the second decreasing
from 19.5 to 13.1, respectively. The total chromatic variation DE obtained for the samples coated
with fluoropolymer F10 is 10.4, and it is higher than
the DE of the sample coated with fluoropolymer
AD60.
The brightness of the sample coated with fluoropolymer S10 (Plate 3) (L* = 49.5) is very close to that
of the uncoated sample (L* = 46.3). The colorimetric
coordinates a* and b* follow the same trend of the
other samples, but variations are clearly smaller. The
coordinate a* decreases from 13.3 to 11.0, the coordinate b* increases from 18.9 to 17.1.
It is assumed that a variation of DE higher than 3 is
perceptible by the human eye: the DE obtained with
the average data collected from the sample coated with
fluoropolymer S10 is 2.9 (Fig. 1 and Table 2).

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J. Coat. Technol. Res., 8 (2) 153160, 2011

Fluoropolymer thickness evaluation

Variation

Thickness of the fluoropolymer layers was estimated

through ellipsometric measurements and compared to
Ponderal analysis estimated by weight differences.
Data obtained throughout ellipsometry characterization of the samples are shown in Table 3, in comparison with the Ponderal analysis reported in Table 4.
Calculated ellipsometric optical constants are in
good agreement with experimental ones. The thickness
values of the fluoropolymer layers calculated through
the ellipsometric model are slightly higher than those
estimated by weight differences, even if in the same
range. This could be related to the rough morphology
of the substrate, as shown by the preliminary AFM

12
10
8
6
4
2
0
2
4
6
8

Plate 1
Plate 2
Plate 3

L*

a*

b*

Fig. 1: Chart of colorimetric analysis: variation of (DL*),

(Da*), (Db*) and (DE) of anodized titanium plates coated with
fluoropolymer compared to uncoated anodized titanium
(Plate 1: anodized titanium coated with fluoropolymer
AD60, Plate2: anodized titanium coated with fluoropolymer
F10, and Plate 3: anodized titanium coated with fluoropolymer S10)

Table 3: Ellipsometry data and thickness of coated

substrates
Sample

Wsp

Dsp

Wcalc

Dcalc

Thickness (nm)

Plate 1
Plate 2
Plate 3

29.46
33.38
23.35

80.32
74.64
96

30.07
32.35
23.51

82.35
74.22
95.81

200
200
170

results in Fig. 2, with high value of the average heights

of the peaks (average heights Sh = 129 nm; average
roughness Ra = 22.5 nm; root mean square roughness
Rq = 25.3 nm). This value suggests a roughness of
titanium oxide coating which should affect the
observed high hydrophobicity.25,26 Moreover, coated
titanium anodized samples have been weighed after
and before polymers deposition. As the geometry of
the plates is known, it is possible to calculate an
average coating thickness. Data collected are reported
in Table 4 and appear to be comparable to the
thicknesses obtained by ellipsometric analyses.

Discussion
The high ionization potential of fluorine and its low
polarizability lead to the extremely low surface energy
of perfluoropolymers10; therefore, the surfaces coated
with the chosen fluorinated polymers are characterized
by low wettability and low friction coefficients. These
properties are sought and exploited to boost staining
agents resistance and washability of anodized titanium
surfaces.
Experimental data point out how each one of the
tested fluorine coatings sensibly improves anodized
titanium resistance to dirt, as well as boosts the ease to
clean these surfaces. However, the fluorinated coating
behaviors are not equivalent: in fact, while samples

nm
150
0
m
10

m
9

9
8
7

6
5

Plate 1: anodized titanium coated with fluoropolymer AD60;

Plate 2: anodized titanium coated with fluoropolymer F10;
Plate 3: anodized titanium coated with fluoropolymer S10

6
5

2
1

2
1

Fig. 2: AFM analysis of the uncoated anodized titanium

surface (average heights Sh = 129 nm, average roughness
Ra = 22.5 nm; root mean square roughness Rq = 25.3 nm.)

Table 4: Computation of samples coating thickness estimated by weight differences and by ellipsometry
Sample

Coating weight (g)

Coating density (g/cm3)

Volume (cm3)

Thickness (nm)

Ellipsometry thickness (nm)

Plate 1
Plate 2
Plate 3

0.0008
0.0009
0.0007

1.68
1.73
1.51

0.000476
0.000520
0.000464

176.37
192.68
171.69

200
200
170

Plate 1: anodized titanium coated with fluoropolymer AD60; Plate 2: anodized titanium coated with fluoropolymer F10;
Plate 3: anodized titanium coated with fluoropolymer S10

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J. Coat. Technol. Res., 8 (2) 153160, 2011

h arctanb =a
The decrease in chroma, i.e., the intensity of hue for a
precise brightness, is higher. Chroma is calculated by
the following equation:

1=2
C a2 b2
For Plate 1 the value of chroma is 36.1% lower than
the value calculated for the uncoated sample, for the

158

100

b* (D65)

50

50

100
100

50

50

100

a* (D65)
Plate 0

Plate 1

Plate 2

Plate 3

Fig. 3: Variation of the chromatic coordinates a* and b* in

the CIELab color space at constant L. Plate 0: uncoated
anodized titanium, Plate 1: anodized titanium coated with
fluoropolymer AD60, Plate 2: anodized titanium coated with
fluoropolymer F10, and Plate 3: anodized titanium coated
with fluoropolymer S10

0
5
10

Variation

coated with S10 and AD60 have water contact angle

values close to 120, fluoropolymer F10 confers to the
surface a definitely lower contact angle value (about
90). The less accentuated hydrophobic character of
coatings constituted by F10 is due to the terminal
hydrophilic ammonium phosphate functional group
present in the polymer.
Its presence causes the decrease in the hydrophobic
behavior of perfluoropolyether, as demonstrated by the
water contact angle measurements. Apparently, the
presence of this hydrophilic functional group does not
modify the oleophobicity, which is almost the same for
all of the used coatings.
By using the contact angle values obtained with
water and N-dodecane it was possible to evaluate the
apparent surface energy of the coated samples. As
expected, in agreement with the obtained values, the
apparent surface energy of the coated samples is
very low.
The low apparent surface energy is certainly due
to a combination of effect: fluoropolymer-coated surface and roughness of the coated surface as shown by
the Cassie and Wenzel models.21,25 In point of fact the
thickness of polymeric materials is adequate to completely fill up the roughness of the anodized titanium
surface, in addition the thermal post-treatments of the
coated surfaces should be adequate to relax and loosen
the deposed polymers. Therefore, the low apparent
surface energy should mainly be due to fluoropolymer
low surface energy rather than to Cassie effects.
Chemically inert and highly transparent amorphous
perfluoropolymers with low refractive index are successfully used to produce polymeric waveguides and
transparent thin films,15,27 thus they are the best choice
if durable maintaining of the chromatic properties of
the substrate is required after their application.
The colorimetric analysis pointed out that, after
AD60 and F10 fluoropolymer applications, a slight
chromatic alteration of anodized titanium occurs. With
fluoropolymer S10 as coating, these chromatic alterations are undetectable by human eye (Fig. 3).
It is remarkable that the variation of hue, the
perceptible attribute of color normally defined with
the words red, yellow, and blue, subsequent to
the application of all the tested coatings is low (less
than 4% for AD60, 3.4% for F10, and 0.8% for S10).
The evaluation of hue is obtained with the following
equation:

15
20
25

Plate 1

30

Plate 2

35

Plate 3

40

Fig. 4: Variation of chroma (DC) and hue (Dh) of anodized

titanium plates coated with fluoropolymer compared to
uncoated anodized titanium Plate 0. Plate 0: uncoated
anodized titanium, Plate 1: anodized titanium coated with
fluoropolymer AD60, Plate 2: anodized titanium coated with
fluoropolymer F10, and Plate 3: anodized titanium coated
with fluoropolymer S10

Plate 2 the variation is 38.9%, and for the Plate 3 the

variation is 10.2%. This variation mainly consists in a
loss of color intensity, as demonstrated by the decrease
in brightness and chroma, whereas the violet hue of the
samples is almost unchanged (Fig. 4).
In addition, ellipsometry and Ponderal analyses
estimated by weight differences also showed that
coating thicknesses are quite similar in all cases,
thus the coating performances obtained are directly

120

16

100

12
8

80

Variation

Contact angle ()

J. Coat. Technol. Res., 8 (2) 153160, 2011

60
Plate 1

40

0
4

Plate 2
20

Plate 3

12

30

60

90

120

150

180

210

240

270

Plate 0
Plate 1
Plate 2
Plate 3

300

L*

a*

b*

Number of rubbing cycles

Fig. 5: Results of preliminary mechanical resistance test

(Plate 1: anodized titanium coated with fluoropolymer
AD60, Plate 2: anodized titanium coated with fluoropolymer
F10, and Plate 3: anodized titanium coated with fluoropolymer S10)

comparable. Due to the low superficial energy, which

improves the washability of coated surfaces, perfluoropolymers often present a lack of adhesion to the
substrate. Therefore, some preliminary tests were
made in order to estimate coating resistance to a mild
mechanical stress, drawn out over time. After anodizing and application of the organic coating, the treated
titanium substrate was rubbed a counted number of
times by means of blotting paper with a contact surface
of 2 cm2, under a pressure of 63 kPa. The decrease in
contact angle as a function of the number of rubbing
cycles was measured. The obtained results, displayed in
Fig. 5, show that after 300 rubbing cycles there is a
1214 decrease for all the samples. In particular for
AD60 and S10-coated samples, the contact angle tends
to reach a plateau value at around 150 rubbing cycles.
Moreover, the surface of the substrate is rough, thus
allowing a better physical adhesive anchorage of all the
fluorinated coating on the titanium oxide rough surface
compared to a flat substrate surface.
We observed a fairly good adhesion of fluoropolymer AD60 on the uncoated substrate. The interaction
between this polymeric matrix and the titanium oxide
substrate is supposed to be low due to the perfluorinated nature of the coating; therefore, the observed
good adhesion of this coating should be ascribed to
the polymeric cohesive interaction due to the highmolecular-weight and the high Tg of the polymer
coating. These peculiar cohesive interaction properties
confer to the fluoropolymer AD60 coating a mechanical resistance to withstand the mechanical stress
imposed during the test at ambient temperature. Also
fluoropolymer S10 exhibits a good adhesion. Indeed,
this polymer crosslinks at 150C thanks to the hydrolysis/condensation reactions among polymer terminal
groups and the superficial substrate OH groups. This
allows the formation of bonds among silane functional
groups and the substrate surface, permitting both
polymeric cohesive and surface adhesive interactions.
Fluoropolymer F10 adheres to the surface of anodized titanium, thanks to the adhesive interaction

Fig. 6: Variation of chromatic coordinates L*, a*, b* and

total variation DE after soiling with castor oil and cleaning
with blotting paper. (Plate 0: uncoated anodized titanium,
Plate 1: anodized titanium coated with fluoropolymer AD60,
Plate 2: anodized titanium coated with fluoropolymer F10,
and Plate 3: anodized titanium coated with fluoropolymer
S10)

between the phosphate group and the OH groups

present on the substrate surface. Surprisingly, fluoropolymer F10 is constantly removed by increasing the
number of rubs as shown in Fig. 5, despite the specific
interaction between the phosphate group and the OH
groups on the substrate. The results of the preliminary
mechanical resistance test shows that this adhesive
interaction ensures less adhesion and lower mechanical
properties with respect to the other tested coatings.
This behavior can be ascribed to a very low Tg and lowmolecular-weight of the perfluoropolyether moiety,
therefore, to a very low polymeric cohesive interaction.
Moreover, the surface of the substrate is rough, thus
allowing a better physical adhesive anchorage of all the
fluorinated coatings on the titanium oxide rough
surface compared to a flat substrate surface.
The resistance to surface soiling with castor oil was
also investigated. After an initial spectrophotometric
measurement, specimens underwent the soiling (one
drop of castor oil) and cleaning procedure (30 rubbing
cycles by means of blotting paper under a pressure of
63 kPa) then spectrophotometric measurements were
repeated. On non-coated anodized titanium the chromatic variation was evident, with a DE of 15.6; in fact, a
dark spot was clearly visible on the surface after partial
oil removal. Fluoropolymers ensured a drastic
improvement of resistance to soiling: the total color
variation dropped down to 1 for AD60 and F10 and
low to 0.1 for S10. As shown in Fig. 6, in presence of
any of the fluorinated coating the chromatic alteration
was too low to be perceived by eye.

Conclusions
Fluoropolymer S10 coating ensures the best results
both in wettability properties and in the chromatic
aspect conservation. Fluoropolymer AD60 coating
showed a satisfying behavior as it both decreases
surface wettability and allows a satisfying maintenance

159

J. Coat. Technol. Res., 8 (2) 153160, 2011

of the original substrate color. Finally, fluoropolymer

F10 does not evidently modify the color of the sample;
however, it decreases the wettability of the surface in a
less effective way in comparison to the other coatings.
In addition, preliminary mechanical resistance tests
pointed out that fluoropolymers AD60 and S10 coatings have a better adhesion resistance compared to
fluoropolymer F10.
Acknowledgments The authors wish to thank SovaySolexis for the valuable research interactions and for
the generous endowment of FLUOROLINK and
HYFLON samples.

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