materials

Article
Influence of Anodizing Parameters on Tribological Properties
and Wettability of Al2O3 Layers Produced on the EN AW-5251
Aluminum Alloy
Mateusz Niedźwiedź * , Marek Bara , Władysław Skoneczny , Sławomir Kaptacz and Grzegorz Dercz

Institute of Materials Engineering, Faculty of Science and Technology, University of Silesia in Katowice,
41-500 Chorzów, Poland
* Correspondence: [email protected]; Tel.: +48-32-2691820

Abstract: The article presents the effect of anodizing parameters of the EN AW-5251 aluminum alloy
on the thickness and roughness of Al2 O3 layers as well as their wettability and tribological properties
in a sliding combination with the T7W material. The input variables were the current density of 1, 2,
3 A/dm2 and the electrolyte temperature of 283, 293, 303 K. The tribological tests were performed on
the T-17 tester in reciprocating motion, in conditions of technically dry friction. The tests were carried
out on a 15 km road with a constant average slip speed of 0.2 m/s and a constant unit pressure
of 1 MPa. The measurement of the wettability of the layers was performed using the sitting drop
method, determining the contact angles on the basis of which the surface free energy was calculated.
The profilographometric measurements were made. The analysis of the test results showed that the
anodizing parameters significantly affect the thickness of the Al2 O3 layers. The performed correlation
analysis also showed a significant relationship between the roughness parameters and the wettability
of the surface of the layers, which affects the ability to create and maintain a sliding film, which
in turn translates into sliding resistance and wear of the T7W material. The analysis of friction
Citation: Niedźwiedź, M.; Bara, M.; and wear tests showed that the layer with hydrophobic properties produced at a current density of
Skoneczny, W.; Kaptacz, S.; Dercz, G. 1 A/dm2 in an electrolyte at a temperature of 283 K is the most favorable for sliding associations with
Influence of Anodizing Parameters
T7W material.
on Tribological Properties and
Wettability of Al2 O3 Layers Produced
Keywords: aluminum alloys; oxide layer; contact angles; surface free energy; tribology
on the EN AW-5251 Aluminum Alloy.
Materials 2022, 15, 7732. https://
doi.org/10.3390/ma15217732

Academic Editor: Chang-Hwan Choi 1. Introduction

Received: 20 October 2022

Aluminum, after iron, is one of the most widely used metals in industry and the most
Accepted: 27 October 2022
abundant metal in the Earth’s crust. Its use is increasing, which makes it the metal of
Published: 3 November 2022
the future [1,2]. Pure aluminum is a material with low strength properties (including low
hardness); therefore, in order to improve its final properties, chemical elements are added,
Publisher’s Note: MDPI stays neutral
depending on the purpose of application, to form aluminum alloys [3]. The production
with regard to jurisdictional claims in
of aluminum alloys is carried out mainly by adding such elements as: iron, copper, mag-
published maps and institutional affil-
nesium, silicon, zinc, or manganese. Additions of alloying elements affect the strength of
iations.
aluminum—especially in combination with cold or hot deformation hardening. Aluminum
alloys with a high magnesium content and small admixtures of other elements (5xxx series)
are very well suited for anodizing. They are characterized by high plasticity and corrosion
Copyright: © 2022 by the authors.
resistance [4–7].
Licensee MDPI, Basel, Switzerland. The oxide layers produced using the anodic oxidation (anodization) method allowed to
This article is an open access article improve both the physical and surface properties of aluminum alloys (hardness, corrosion,
distributed under the terms and and abrasion resistance) [8]. The improvement of surface properties of aluminum alloys has
conditions of the Creative Commons resulted in their much wider application in various industries, such as machinery, aviation,
Attribution (CC BY) license (https:// automotive, electronics, and even in nanotechnology (production of nanowires and mem-
creativecommons.org/licenses/by/ branes for sensors) [9–11]. The oxide layers used in kinematic sliding nodes are suitable for
4.0/). cooperation with metals and ceramics (limited lubrication) and with plastics (technically

Materials 2022, 15, 7732. https://doi.org/10.3390/ma15217732 https://www.mdpi.com/journal/materials

Materials 2022, 15, 7732 2 of 21

dry friction). A very important element determining the tribological cooperation in the case
of technically dry friction is the formation of a lubricating layer between the cooperating
elements. It contributes to a significant reduction of friction, which results in lower wear
of cooperating elements [12]. During technically dry friction, the cooperation of Al2 O3
layers is carried out with plastics showing film-forming properties, which include graphite,
PTFE, and MoS2 . Currently, the materials containing PTFE (polytetrafluoroethylene), which
are characterized by a very low coefficient of friction, have the greatest application in the
sliding elements of industrial devices and machines. Examples include T5W and T7W [13].
Currently, great importance is attached to the energy state of materials. The hydropho-
bic properties of materials (repelling water molecules), and therefore with low surface
wettability, allow them to be used very often in surface engineering, most often as anti-icing
or self-cleaning materials [14,15]. The opposite of hydrophobic materials are hydrophilic
materials (attracting water molecules) with high surface wettability. They can be used
in biomaterials and photovoltaic panels [16–18]. The energy state of the surface also has
a significant influence on the mechanical and tribological properties. The contact angle of
the material, and thus the surface free energy, significantly contributes to the improvement
of material lubrication and reduction of friction [19–21]. More and more attention has been
paid in recent times to the tribology of surface layers in relation to the energy state of the
surface. This is due to the influence of surface free energy on the course of tribological
processes and on such phenomena as abrasive wear and the formation of a sliding film [22].
A hydrophobic surface is a surface with a contact angle greater than 90◦ , measured with
water. A surface with a contact angle for water greater than 150◦ is conventionally called
a super-hydrophobic surface. When the contact angle of the surface with water is less than
90◦ , we speak of hydrophilicity, i.e., the opposite of hydrophobicity [23]. The analysis of
world literature shows that the vast majority of scientific research on the wettability and
energy state of Al2 O3 layers mainly concerns the studies of Al2 O3 layers after modification.
No publications regarding the influence of anodizing parameters have been noticed (elec-
trolyte temperature, current density) on the wettability, and hence the energy state of the
oxide layers, which was the aim of the presented research. Then, the impact of the layers’
wettability on their tribological parameters (friction coefficient, mass loss) was investigated.

2. Materials and Methods

2.1. Research Material
As a substrate for the production of Al2 O3 layers, samples made of aluminum sheet
of the EN AW-5251 alloy were used. The process of preparing samples for anodizing
consisted of leveling the edges of the samples and removing any unevenness that appeared
when cutting the material with a stream of water from the rolled sheet. The samples were
sequentially cleaned of any contamination caused by processing using an ultrasonic washer.
Distilled water was used as the bath liquid. The next step was to glue the samples with
a two-component epoxy adhesive that does not react with the acid of the electrolyte and the
chemicals for etching and neutralization. Sample sticking is used to reduce the anodizing
surface only to the necessary (needed for testing). The last step before the actual process
was to subject the samples to etching, immediately before anodizing, in a 5% KOH solution
for 20 min and neutralization in a 10% HNO3 solution for 5 min. The processes were carried
out at room temperature.
In order to produce Al2 O3 layers, samples from the EN AW-5251 aluminum alloy were
electrolytically anodized with the direct current method using a stabilized GPR-25H30D
power supply. The surface of the aluminum alloy on which the layer was produced was
the anode, the cathode was a lead plate with dimensions corresponding to the dimensions
of the aluminum samples. In anodized oxidation processes, electrolyte-resistant metals
(usually stainless steel or lead) are used as the cathode. As a result of many years of
experience of our research team, we use lead sheet for the production of Al2 O3 in order to
compare the test results with previous tests. The diagram of the anodizing system used is
shown in Figure 1.
 dimensions of the aluminum samples. In anodized oxidation processes, electrolyte-re-
sistant metals (usually stainless steel or lead) are used as the cathode. As a result of many
years of experience of our research team, we use lead sheet for the production of Al2O3 in
Materials 2022, 15, 7732 3 of 21
order to compare the test results with previous tests. The diagram of the anodizing system
used is shown in Figure 1.

Figure1. 1.
Figure Diagram
Diagram of anodizing
of the the anodizing
systemsystem used during
used during the production
the production of the
of the oxide oxide
layer: layer:
1—alu-
1—aluminum
minum alloy EN alloy EN (anode),
AW-5251 AW-52512—lead
(anode),
plate2—lead plate
(cathode), (cathode), stirrer,
3—mechanical 3—mechanical stirrer,
4—electrolyte,
5—power supply.
4—electrolyte, 5—power supply.

TheTheanodizing
anodizingprocess
processwas
wascarried
carriedout
outinina athree-component
three-componentelectrolyte
electrolyteconsisting
consistingofof
ananaqueous
aqueous solution
solution of of
18%18% H24SO
H2SO (33 mL/L),
(334 mL/L), C2H2C O24 H 2O
(30 4 (30and
g/L), g/L),
C8Hand
6O4 C 8 Hg/L).
(76 6 O4 (76 g/L).
During
During the anodizing process, the solution was mixed with a mechanical
the anodizing process, the solution was mixed with a mechanical stirrer at a speed of 100 stirrer at a speed
of 100
rpm, rpm, changing
changing the direction
the direction of rotation
of rotation after10
after every every
min.10 min.
The The anodizing
anodizing parameters
parameters were
were selected on the basis of the experimental
selected on the basis of the experimental plan (Table 1). plan (Table 1).
Table
Table 1 presents
1. Total the plan.
experiment total experimental plan for two input variables with three varia-
ble values. Based on the matrix of the total experiment design, the parameters for anodiz-
ing the aluminum alloy were selected. The input Controlled Factors
variables were current density of 1, 2, 3
A/dm and electrolyte temperature
2 of 283,Scale
On a Natural 293, 303 K. The anodizing Ontime for all Scale
a Standard samples
Sample
was 20 min. After the completion
Current Density of the anodizing
Electrolyte Temperatureprocess, the samples were rinsed in
distilled water for 60 min. 2 ×1 ×2
j (A/dm ) T (K)
A 1 283 −1 −1
Table 1. Total experiment plan.
B 3 283 1 −1
C 1 303
Controlled Factors −1 1
D 3 303 1 1
E 1 On a Natural Scale
293 On
−1a Standard Scale
0
Sample
F Current 3Density Electrolyte
293Temperature 1 0
G 2
j (A/dm )
2 283
T (K) 0
×1 ×2−1
AH 12 303
283 0
−1 −1 1
I 2 293 0 0
B 3 283 1 −1
C 1 303 −1 1
DTable 1 presents 3the total experimental plan
303for two input variables
1 with three1 variable
values.
E Based on the
1 matrix of the total experiment
293 design, the parameters
−1 for
0 anodiz-
ing the aluminum alloy were selected. The input variables were current density of 1, 2,
F 3 293 1 0
3 A/dm2 and electrolyte temperature of 283, 293, 303 K. The anodizing time for all samples
G 2 283 0 −1
was 20 min. After the completion of the anodizing process, the samples were rinsed in
H 2
distilled water for 60 min.
303 0 1
IThe T7W material2 was used as a tribo partner
293 in tribological tests.
0 The T7W material
0 is
a composite made on the basis of PTFE with the dispersion phase in the form of powdered
The T7W
technical material
carbon. was usedisaswidely
The material a triboused
partner in tribological
in hydraulic tests. The piston-cylinder
and pneumatic T7W material
issystems,
a composite made on
as a material forthe basisrings
sealing of PTFE
used, with the dispersion
for example, phasecylinders.
in pneumatic in the form of

2.2. Research Methodology

Microscopic examinations were carried out using a Hitachi S-4700 scanning electron
microscope (Hitachi, Tokyo, Japan). Surface morphology images were taken at 50,000×
magnification to observe the nanopores. The anodic oxide layers are poorly conductive,
so they charge electrically during operation of the electron beam, which contributes to
incorrect observation. For proper observation, the layers were sprayed with carbon using
 2.2. Research Methodology
Microscopic examinations were carried out using a Hitachi S-4700 scanning electron
microscope (Hitachi, Tokyo, Japan). Surface morphology images were taken at 50,000×
magnification to observe the nanopores. The anodic oxide layers are poorly conductive,
Materials 2022, 15, 7732 so they charge electrically during operation of the electron beam, which contributes 4 of 21
to
incorrect observation. For proper observation, the layers were sprayed with carbon using
a turbomolecular carbon sputtering machine. The carbon layer enables the bouncing elec-
atrons to be discharged
turbomolecular carbonandsputtering
carried away during The
machine. the research.
carbon layer enables the bouncing
Chemical
electrons composition
to be discharged andtests wereaway
carried carried out for
during the both cross-sections. The chemical
research.
composition
Chemical ofcomposition
the layers was investigated
tests were carriedusing
outtheforNoranVantage
both cross-sections.EDS (Energy Disper-
The chemical
sive X-ray Spectroscopy)
composition of the layers was system connected
investigated usingto the
theNoranVantage
Hitachi S-4700EDS scanning
(Energymicroscope.
Dispersive
The EDS
X-ray tests for cross-sections
Spectroscopy) system connected were carried out onS-4700
to the Hitachi metallographic specimens. The EDS
scanning microscope.
In order
tests for to obtain were
cross-sections the phase
carried composition, diffraction tests
out on metallographic (XRD) were carried out on
specimens.
In order
the X-Pert to obtain
Philips the phase composition,
diffractometer. diffraction
The device operated testsparameters
at the (XRD) were ofcarried
30 mA out andon 40
the X-Pert PhilipsAlmelo,
kV (PANalytical, diffractometer. The deviceDuring
The Netherlands). operated theatresearch,
the parameters
a verticalof goniometer,
30 mA and
40 kV cradle,
Euler (PANalytical, Almelo,X-ray
and a copper The Netherlands).
source (λCuKα) During
were the
used research, a vertical goniometer,
with a wavelength of 1.54178
Euler
Å. X-raycradle, and a copper
diffraction X-ray
patterns weresource (λCuKα)
recorded werefrom
(GIXD) used anwith a wavelength
angle of 1.54178
of 2θ 10–100° in steps Å.
X-ray diffraction ◦ in steps of
of 0.05° for anglespatterns were recorded
of incidence α = 0.20°; (GIXD) from1.00°;
0.30°; 0.50°; an angle of 2.50°;
1.50°; 2θ 10–100
5.0°. Finally, the
0.05 ◦ = 0.20◦ ; 0.30◦ ; 0.50◦ ; 1.00◦ ; 1.50◦ ; 2.50◦ ; 5.0◦ . Finally, the
anglefor α =angles
0.20° wasof incidence
chosen to αillustrate.
angleThe α =thickness◦
0.20 wasofchosen to illustrate.
the oxide layers was measured by the contact method using a Fischer
The thickness
Dualscope of the oxide
MP40 instrument layers was
(Helmut measured
Fischer GmbHby the KG,
+ Co. contact method using
Shin-delfingen, a Fischer
Germany).
Dualscope
The deviceMP40 instrument
measures using the(Helmut
eddy Fischer
currentGmbHmethod. + Co.
On KG, Shin-delfingen,
the surface Germany).
of each sample, 10
The device measures
measurements using which
were made, the eddy current
were method.
then used On the the
to calculate surface of each
average valuesample,
of the
10 measurements
thickness werelayer
of the oxide made, which
with were then used to calculate the average value of the
deviations.
thickness of the oxide layer with deviations.
The tribological tests were carried out for the friction pair of the pin-plate type on the
T-17 The tribological
tester (Figure 2)tests
in a were carried out
reciprocating for the
motion friction
[24]. pair of slip
A constant the pin-plate
speed of 0.2typem/s
on and
the
T-17 tester (Figure 2) in a reciprocating motion [24]. A constant slip
a constant unit pressure of 1 MPa were used. The tests were carried out in dry technical speed of 0.2 m/s and
afriction
constant unit pressure
conditions, of 1 MPaambient
at a constant were used. The testsof
temperature were298carried
± 1 K and outainrelative
dry technical
air hu-
friction conditions, at a constant ambient temperature of 298 ±
midity of 40 ± 10%. The friction path during the tribological test was 15 km. The friction 1 K and a relative air
humidity of 40 ± 10%. The friction path during the tribological test
force was measured with the Spider 8 transducer, which allows the data to be exported to was 15 km. The friction
force was measured
a computer and saved with theCatman
using Spider 84.5transducer,
software. which allowscoefficients
The friction the data towere
be exported
calculated to
a computer and saved using Catman 4.5 software. The friction coefficients were calculated
from the stabilized range of friction force values. The mass loss of the pin was determined
from the stabilized range of friction force values. The mass loss of the pin was determined
by the weight method.
by the weight method.

Figure
Figure 2.2. Diagram
Diagram ofof the
the friction
friction junction
junction of
of the
the T-17
T-17 tester:
tester: (a)
(a) Force
Force sensor,
sensor, (b)
(b) collet,
collet, (c)
(c) clamping
clamping
nut,
nut, (d)
(d) upper
upper pin,
pin, (e)
(e) reservoir,
reservoir,(f)
(f)plate.
plate.

The profilographometric measurements were carried out in order to determine the

roughness parameters before and after the tribological test. Measurements were made using
a Form TalySurf Series 2.50i contact profilegraphometer (Taylor Hobson Ltd., Leicester, UK).
The wettability of the layers was measured using the sitting drop method at a constant
ambient temperature of 298 K. Four liquids were used, two polar (water and glycerine) and
two non-polar (α-bromonaphthalene and diiodomethane). On each of the Al2 O3 layers
using a 0.5 µL micropipette, 10 drops of each liquid were applied along the entire length
of the sample. After each drop was applied, it was photographed with a camera and
exported to a computer. The software used enables the automatic measurement of the
drop’s contact angle by marking the three extreme points of the drop in the picture. The
 Materials 2022, 15, 7732 5 of 21

smallest and largest values of the angles were rejected, the remaining eight were used to
calculate the average value of the contact angle for a given surface. The surface free energy
was calculated using the Owens–Wendt method using the contact angles for polar (distilled
water) and non-polar (α-bromonaphthalene) liquids using the following Equation (1):

γs = γs d + γs p , (1)

where γs responsible for the free surface energy of a solid, γs d is the component of surface
free energy dispersion, γs p is the component of surface free energy dispersion of materials.

3. Results and Discussion

3.1. Structure of the Oxide Layer
DC anodizing begins with a rapid increase in voltage, which is necessary to break
through the natural barrier layer, after reaching the maximum value (critical voltage) it
begins to decrease [25]. Reaching the minimum value results in the reconstruction of
the barrier layer at the oxide-electrolyte interface. In the next stage of the process, pores
are formed and deepened, leading to the growth of the oxide layer. This is caused by
an increase in tension over time, but much slower than at the beginning of the process.
The value of the critical voltage decreases with increasing electrolyte temperature, and it
increases with increasing current density [26,27]. The formation of the oxide layer during
the DC anodizing process proceeds according to the following processes: barrier layer
formation, propagation of disturbances in the oxide layer (microcracks), pore formation
Materials 2022, 15, x FOR PEER REVIEW process, growth of the oxide layer along with the deepening of the pores. 6 of 23
The graphical interpretation of the processes during DC anodizing, depending on the
voltage changes is shown in Figure 3 [27,28].

(a) (b)

(c) (d)
Figure 3. The
Figure 3. steps in theinformation
The steps of an of
the formation oxide layer layer
an oxide during DC anodizing:
during (a) barrier
DC anodizing: layerlayer
(a) barrier for-
mation, (b) propagation of disturbances in the oxide layer (microcracks), (c) pore formation
formation, (b) propagation of disturbances in the oxide layer (microcracks), (c) pore formation process,
(d) growth
process,of(d)
thegrowth
oxide layer
of thealong
oxide with
layer the deepening
along of the pores.
with the deepening of the pores.

Figure 4 shows the surface images of the oxide layer for four samples with different
properties. In order to observe nanopores characteristic of the oxide layers, a magnifica-
tion of 50,000× was used.
Materials 2022, 15, x FOR PEER REVIEW 7 of 2
Materials 2022, 15, 7732 6 of 21

Materials 2022, 15, x FOR PEER REVIEW

Figure 4 shows the surface images of the oxide layer for four samples with 7different
of 23
properties. In order to observe nanopores characteristic of the oxide layers, a magnification
of 50,000× was used.

(a) (b)

(a) (b)

(c) (d)
(c) (d)
Figure 4. Images of surface morphology of oxide layer: (a) sample A, (b) sample C, (c) sample E, (d
sample
Figure
Figure 4. G.
4. Images of surface
Images morphology
of surface of oxide
morphology layer:layer:
of oxide (a) sample A, (b)A,
(a) sample sample C, (c) sample
(b) sample E, (d) E,
C, (c) sample
sample G.
(d) sample G.
The porosity of the oxide layers is a characteristic feature of the oxide layers resultin
TheThe
porosity of the
porosity oxide
of the layers
oxide is aischaracteristic
layers feature
a characteristic of the
feature oxide
of the layers
oxide resulting
layers resulting
from the manufacturing parameters [29].
from
from thethe manufacturing
manufacturing parameters
parameters [29].
[29].
Figure 5 shows a cross-section of the oxide layer of sample A at 1000× magnification
Figure
Figure 5 shows
5 shows a cross-section
a cross-section of of
thethe oxide
oxide layer
layer of of sample
sample A 1000×
A at × magnification.
at 1000magnification.
In
In addition,
addition, thethe photo
photo shows
shows the the
oxide oxide
layer layer
and and
EDS EDS analysis
In addition, the photo shows the oxide layer and EDS analysis site for sample A.A.
analysis site for site for sample A.
sample

Figure 5. Cross-section of the oxide layer at a magnification of 1000× of sample A.

Figure
Figure 5. 5. Cross-section
Cross-section of oxide
of the the oxide
layerlayer at a magnification
at a magnification ofof
of 1000× 1000× of A.
sample sample A.
The chemical composition tests carried out with an EDS spectrometer on the cross-
sections of
Thethechemical
layers showed the aluminum
composition content at
tests carried thewith
out levelan
of EDS
55.9%spectrometer
and the oxygenon the cross
content
sections of the layers showed the aluminum content at the level of of
at the level of 44.1% for all tested layers. The chemical composition the oxide
55.9% and the oxyge
layers should be 52.9% Al and 47.1% O. However, only the EDS analysis carried out in the
content at the level of 44.1% for all tested layers. The chemical composition of the oxid
Materials 2022, 15, 7732 7 of 21

The chemical composition tests carried out with an EDS spectrometer on the cross-
sections of the layers showed the aluminum content at the level of 55.9% and the oxygen
Materials 2022, 15, x FOR PEER REVIEW 8 of 23
content at the level of 44.1% for all tested layers. The chemical composition of the oxide
layers should be 52.9% Al and 47.1% O. However, only the EDS analysis carried out in
the very center of the layer will show a chemical composition similar to the stoichiometric
very center of the layer will show a chemical composition similar to the stoichiometric
calculation. The decrease in the aluminum content and the increase in the oxygen content
calculation. The decrease in the aluminum content and the increase in the oxygen content
along the thickness of the
along thethickness
Al2 O3 layer
of theis
Aldue to the change in the stoichiometry of the
2O3 layer is due to the change in the stoichiometry of the re-
resulting layer. sulting layer.
Figure 6 shows the GIXD pattern 2 , at 283 2K.
Figure 6 shows thefor
GIXDsample Afor
pattern produced
sample Aatproduced
1 A/dmat 1 A/dm , at 283 K.

Figure 6. GIXD pattern for the angle of incidence α= 0.20 obtained.

Figure 6. GIXD pattern for the angle of incidence α = 0.20 obtained.
Aluminum oxide exists in an amorphous form and in several crystalline forms. Only
Aluminum oxide exists in an amorphous form and in several crystalline forms. Only
the α-Al2O3 form is a stable crystalline form. GIXD tests carried out for layers produced
the α-Al2 O3 form byis athe
stable crystallinemethod
electrochemical form. GIXD tests carried
in the ternary out showed
electrolyte for layers
thatproduced by coating
the obtained
the electrochemical method in regardless
is amorphous, the ternary electrolyte
of the productionshowed thatand
conditions thecan
obtained coating
be considered asis
an amor-
amorphous, regardless
phousof the production
x-ray pattern. The conditions
phase analysisandofcan
thebe considered
examined as an
layers amorphous
showed in all cases the
X-ray pattern. Thepresence
phase analysis of the
in the angular examined
range of 20–45layers
degreesshowed
2θ of thein all cases the
amorphous presence
“halo”, which is char-
acteristic
in the angular range for the
of 20–45 oxide 2θ
degrees layers produced
of the by the “halo”,
amorphous electrochemical
which ismethod (Figure 5). In no
characteristic
caseproduced
for the oxide layers were thereby any reflections
the belongingmethod
electrochemical to the elements
(Figurewith
5).aIn
crystalline
no case structure.
were
there any reflections belonging to the elements with a crystalline structure.
3.2. The Thickness of the Oxide Layer
3.2. The Thickness of theTable
Oxide2 shows
Layer the average measurement results of the thickness of the oxide layers
produced in accordance with the total plan with standard deviations.
Table 2 shows the average measurement results of the thickness of the oxide layers
produced in accordance with
Table 2. List of the
Al2Ototal plan with standard deviations.
3 layers thicknesses produced in anodizing process.

Table 2. List of Al2 O3 layers

Samplethicknesses produced
Oxidein anodizing
Layers process.
Thickness d (μm) Deviation (μm)
A 5.8 0.5
Sample Oxide Layers Thickness d (µm) Deviation (µm)
B 19.0 0.7
A C 5.8 5.1 0.5 0.2
B D 19.0 17.6 0.7 0.4
C E 5.1 5.2 0.2 0.3
D F 17.6 17.7 0.4 0.5
E G 5.2 11.9 0.3 0.5
F 17.7 0.5
H 11.3 0.1
G 11.9 0.5
I 11.4 0.3
H 11.3 0.1
I 11.4 0.3
The anodizing parameters affect the thickness of the oxide layer. The highest thick-
ness of the Al2O3 layer was measured for sample B produced at a current density of 3
The anodizing parameters affect the thickness of the oxide layer. The highest thickness
of the Al2 O3 layer was measured for sample B produced at a current density of 3 A/dm2
Materials 2022, 15, x FOR PEER REVIEW

Materials 2022, 15, 7732 8 of 21

A/dm2 and an electrolyte temperature of 283 K, and the lowest for sample C prod
Materials 2022, 15, x FOR PEER REVIEW 9 of 23
aand
current density
an electrolyte of 1 A/dm
temperature 2 and
of 283 an electrolyte
K, and the lowest fortemperature of 303
sample C produced at K.
a current
density of 1 A/dm 2 and an electrolyte temperature of 303 K.
Figure 7 shows the effect of anodizing parameters (current density and ele
Figure 7 shows the effect of anodizing parameters (current density and electrolyte
temperature) on oxidetemperature
A/dm2 and an electrolyte layer thickness.
of 283 K, and the lowest for sample C produced at
temperature) on oxide layer thickness.
a current density of 1 A/dm2 and an electrolyte temperature of 303 K.
Figure 7 shows the effect of anodizing parameters (current density and electrolyte
temperature) on oxide layer thickness.

Figure7.7.Dependence
Figure Dependence of
of the
the oxide
oxide layers
layers thickness
thickness of
of oxide
oxidelayers
layerson
onthe
thecurrent
currentdensity
densityand
andelec-
elec-
Figure 7. Dependence of the oxide layers thickness of oxide layers on the current density a
trolytetemperature.
trolyte temperature.
trolyte temperature.
Takinginto
Taking intoaccount
account the
the thickness
thickness measurements
measurements carried
carried out,
out, ititcan
canbebeconcluded
concludedthat that
the anodizing
the anodizing parameters
parameters (current
(current density
density andand electrolyte temperature)
electrolyte temperature) in the
in the constant
Taking into account the thickness measurements carried out, it constant
can be conclud
processtime
process timehave
haveaasignificant
significant impact
impact on on the
the thickness
thickness of of the
the Al
Al22OO33layers.
layers.As Asthe
thecurrent
current
the anodizing
densityincreased
density
parameters
increasedatataaconstant (current
constantelectrolyte density
electrolytetemperature,
temperature, and electrolyte
a significant
a significant
temperature)
increase
increase in in
thethe thick- in the c
thickness
process
ness
of time
theoflayer
the layer
was have
was a significant
observed.
observed. TheThe impact
increase
increase in inon the thickness
thethickness
the thickness theof
ofofthe the layer
oxide
oxide Al2Oisis
layer 3 layers.
caused As the
caused
by the
by the increasing
density increasing
increased value
at of
value the
theelectric
aofconstant charge.
electrolyte
electric charge.TheThe
increase in the
temperature,
increase intemperature
a significant
the temperatureof theincrease
elec-
of the in th
trolyte, at
electrolyte, a constant
at a current
constant density,
current reduces
density, the
reduces thickness
the thicknessof the
of
ness of the layer was observed. The increase in the thickness of the oxide layer islayer,
the which
layer, can
which be
can ex-
be
plained bybythe
explained theincreasing
increasingsecondary solubility ofof
the 2O3O
AlAl layer by bythethe
electrolyte with a
by the increasing valuesecondary solubility
of the electric the
charge. The layer
2 3increase in electrolyte
the temperature with
of t
ahigher
highertemperature.
temperature.
trolyte, at a constant current density, reduces the thickness of the layer, which ca
plained
3.3. by the
3.3.Tribological
Tribological increasing secondary solubility of the Al2O3 layer by the electrolyt
Tests
Tests
higherAsatemperature.
As aresult
result of
of tribological
tribological cooperation, a sliding
sliding film
film made
madeof
ofplastic
plasticwas
wasobtained
obtainedon
on
thesurfaces
the surfacesofofthe
thetested
testedsamples.
samples.Examples
Examplesofofsamples
sampleswith
withthe
theapplied
appliedfilm
filmare
areshown
shownin
in the
the Figure
Figure 8. 8.
3.3. Tribological Tests
As a result of tribological cooperation, a sliding film made of plastic was obta
the surfaces of the tested samples. Examples of samples with the applied film are
in the Figure 8.
(a) (b)
Figure8.8.The
Figure Thesurfaces
surfacesof
ofsamples
sampleswith
withaasliding
slidingfoil
foilapplied
appliedasasaaresult
resultofoftribological
tribologicaltests:
tests:(a)
(a)Sample
Sam-
ple B, (b) sample
B, (b) sample Al. Al.

Table33shows
Table showsthe
thevalues
valuesofofthe
thefriction
frictioncoefficient
coefficientµµduring
duringthethesliding
slidingcooperation
cooperationof
of Al O layers and the surface of the EN AW-5251 aluminum
Al2 O3 layers and the surface of the EN AW-5251 aluminum alloy with the
2 3 alloy with the T7W mandrel.
mandrel.
(a) (b)
The anodizing parameters influence the values of the friction coefficient µ. The
highest 8.
Figure friction coefficient
The surfaces among Alwith
of samples 2 O3 layers wasfoil
a sliding determined
applied as fora sample C tribological
result of produced tests:
ple B, (b) sample Al.

Table 3 shows the values of the friction coefficient µ during the sliding coop
of Al2O3 layers and the surface of the EN AW-5251 aluminum alloy with the T7W m
 Sample Coefficient of Friction μ
A 0.1425
B 0.1443
Materials 2022, 15, 7732 9 of 21
C 0.1661
D 0.1438
E
at a current density of 1 A/dm2 and an electrolyte temperature of 0.1463
303 K, while the lowest
2
for sample GFproduced at a current density of 2 A/dm and an electrolyte temperature
0.1615
of 283 K. The highest coefficient of friction µ, among the tested surfaces, was determined
G 0.1419
for the EN AW-5251 aluminum alloy without anodizing modification. Therefore, it can be
H the anodizing process contributes to the improvement
concluded that 0.1513 of the tribological
cooperation inI the reciprocating motion between the aluminum0.1564alloy (EN AW-5251) and
the T7W material.
Al 0.1932
Table 3. The values of the coefficient of friction µ of the Al2 O3 layers and of the aluminum alloy
when working with the T7W
The anodizing material.
parameters influence the values of the friction coefficient µ. Th
est friction coefficient
Sample among Al2O3 layers was determined
Coefficient forµsample C produ
of Friction
current density ofA1 A/dm and an electrolyte temperature
2
0.1425 of 303 K, while the low
sample G produced at a current density of 2 A/dm and an electrolyte temperatur
B 2 0.1443
C 0.1661
K. The highest coefficient
D
of friction µ, among the tested surfaces, was determined
0.1438
EN AW-5251 aluminum E alloy without anodizing modification.
0.1463 Therefore, it can
F
cluded that the anodizing 0.1615
process contributes to the improvement of the tribolog
G 0.1419
operation in the reciprocating
H motion between the aluminum 0.1513 alloy (EN AW-5251)
T7W material. I 0.1564
Al 0.1932
Figure 9 shows the effect of anodizing parameters (current density and ele
temperature) on the friction coefficient µ of the Al2O3 layer cooperation with T7W
Figure 9 shows the effect of anodizing parameters (current density and electrolyte
rial.
temperature) on the friction coefficient µ of the Al O layer cooperation with T7W material.
2 3

Figure 9. Dependence of the friction coefficient µ of oxide layers on the current density and
Figure 9. Dependence of the friction coefficient µ of oxide layers on the current density and
electrolyte temperature.
lyte temperature.
Based on the graph of the dependence of the friction coefficient µ on the production
Based(current
parameters on thedensity
graphandof electrolyte
the dependence of the
temperature), friction
it was foundcoefficient µ onofthe pro
that high values
the friction coefficient occur for the layers produced at an electrolyte
parameters (current density and electrolyte temperature), it was found temperature of 293 K,
that high
increasing gradually with increasing current density. The lowest values were observed
of the friction coefficient occur for the layers produced at an electrolyte temper
for the lowest electrolyte temperature of 283 K, where the values of the friction coefficient
293 increase
also K, increasing gradually
with increasing with
current increasing
density. current
The highest density.
value of The lowest
the coefficient values w
of friction
served
µ with the forT7W
thematerial
lowestwaselectrolyte
observed temperature of 283 K,atwhere
for the sample produced a currentthe values
density of of the
A/dm2 andalso
1coefficient an electrolyte
increasetemperature of 303 K current
with increasing (characteristic elevation
density. Theinhighest
the diagram).
value of th
cient of friction µ with the T7W material was observed for the sample produc
 Table 4. Mass loss of the T7W mandrel in association with the samples.

Mass Loss
Sample
Materials 2022, 15, 7732 (mg) 10 of 21
A 0.20
B current density during anodizing at an electrolyte temperature
The increase in the 0.60of 303 K
causes a gradual Cdecrease in the coefficient of friction. Summing up, it can be stated that
0.20
the best sliding cooperation (due to frictional forces) of T7W material occurs with Al2 O3
layers producedDat the lowest electrolyte temperature (283 K) gradually from 0.34
the current
density of 1 A/dm 2 (the lowest value). Table 4 shows the mass loss of T7W material during
E 0.86
sliding cooperation with the Al2 O3 layer and the EN AW-5251 aluminum alloy.
F 0.56
Table 4. Mass lossGof the T7W mandrel in association with the samples. 0.60
H
Sample
Mass Loss 0.16
(mg)
IA 0.20
0.84
AlB 0.60 0.60
C 0.20
D 0.34
E 0.86
The anodizing
F
parameters also significantly
0.56
affect the mass loss
ing the tribological
G run. The highest mass loss
0.60 was measured for sam
H 0.16
current density
I of 1 A/dm2 in an electrolyte0.84
with a temperature of 293
Al 0.60
loss was determined for sample H anodized at a current density of 2
lyteTheatanodizing
a temperature
parameters ofalso303 K. During
significantly tribological
affect the cooperation
mass loss of the material duringof the
the tribological
AW-5251 with run. The highest mass loss was measured for sample
T7W material, there is a significant wear of E produced at athe
current
material
2
density of 1 A/dm in an electrolyte with a temperature of 293 K. The lowest mass loss
almost
was fourfortimes
determined samplehigher than
H anodized at a for thedensity
current H sampleof 2 A/dmwith the
2 in an Al2O3atlayer w
electrolyte
a(0.16 mg).of 303 K. During tribological cooperation of the alloy aluminum EN AW-5251
temperature
with T7W material, there is a significant wear of the material mandrel (0.6 mg)—almost four
Figure 10 shows the effect of anodizing parameters (current den
times higher than for the H sample with the Al2 O3 layer with the lowest wear (0.16 mg).
temperature)
Figure 10 shows onthethe mass
effect loss ofparameters
of anodizing the T7W pin. density and electrolyte
(current
temperature) on the mass loss of the T7W pin.

Figure 10. Dependence of mass loss of T7W material on the current density and electrolyte tempera-
Figure
ture during10. Dependence of mass loss of T7W material on the current density
anodizing. a
ature during anodizing.
Materials 2022, 15, 7732 11 of 21

The analysis of the T7W pin mass loss relationship presented in three-dimensional
diagrams shows that high wear values occur for layers produced in the electrolyte at
a temperature of 293 K (>0.5 mg). The lowest wear of T7W material (<0.4 mg) was
measured for Al2 O3 layers produced in the electrolyte at a temperature of 303 K (the
lowest value among all samples for 2 A/dm2 , 0.16 mg). Low value of mass loss (<0.2 mg)
was also observed for sample A produced in 1 A/dm2 at 283 K (characteristic decrease in
the diagram). Taking into account the friction and wear tests, it can therefore be concluded
that these are the best parameters for the production of Al2 O3 layers for sliding associations
with the T7W material.

3.4. Surface Roughness Tests

Table 5 presents selected amplitude parameters (Rq—mean amplitude profile devia-
tion from the mean line along the measuring or elemental section, Rsk—profile asymmetry
coefficient, Rku—flattening coefficient) having the greatest impact on tribological coopera-
tion and parameters of the load curve (Abotta Fireston) Rk—reduced roughness height,
Rpk—reduced roughness profile elevation, Rvk—reduced roughness profile cavity height
before and after tribological tests.
Table 5. Amplitude parameters and parameters of the load capacity curve of layers before and
after friction.

Parameters of the Load Curve

Amplitude Parameters
Sample (Abott Fireston)
Rq (µm) Rsk Rku Rk (µm) Rpk (µm) Rvk (µm)
Before test
A 0.4625 −1.6561 8.1086 0.8090 0.2937 0.9324
B 0.5513 −1.3622 6.2085 1.0764 0.3112 0.9693
C 0.4815 −1.0896 12.1512 0.7486 0.9222 0.9337
D 0.5452 −1.9966 14.2198 0.8502 0.5683 1.2482
E 0.3381 −0.3301 11.8179 0.4928 0.6135 0.6071
F 0.5467 −1.0133 8.6509 0.9570 0.6454 0.9341
G 0.5392 −1.7443 5.4716 1.0826 0.3195 0.9328
H 0.5573 −1.9644 16.1986 0.7969 0.6299 1.1172
I 0.2970 −0.5330 7.3632 0.5634 0.4120 0.4280
Al 0.0765 −0.2227 9.8823 0.1415 0.0911 0.1162
After test
A 0.4068 −1.6021 8.7518 0.6347 0.3303 0.9389
B 0.3700 −1.4232 6.9293 0.6591 0.2449 0.6995
C 0.4385 −2.3079 12.9483 0.5856 0.3199 0.8947
D 0.4178 −2.7333 14.1218 0.6194 0.2655 1.0170
E 0.1946 −0.4623 5.2914 0.3416 0.2375 0.2871
F 0.2332 −0.5208 4.7619 0.4419 0.2375 0.3654
G 0.4182 −1.9585 10.4411 0.7215 0.2762 0.7879
H 0.3809 −2.6221 14.4178 0.5178 0.2793 0.8692
I 0.1735 0.1649 4.2484 0.3442 0.2384 0.1948
Al 0.8276 −0.7317 6.2506 1.7494 0.9724 1.6857

By analyzing both the amplitude parameters and the load capacity curve (Abott
Fireston) before the tribological test, one can notice large differences resulting from the
parameters of anodizing of the aluminum alloy. There is a significant relationship between
the increase in electrolyte temperature and the increase in the parameters of the load-
bearing curve Rku and Rpk. The Pearson correlation coefficient between the electrolyte
temperature and these parameters is above 0.82, so we can speak of a high co-relation and
significant dependence. The extreme amplitude parameters (the highest Rq, Rku, and the
lowest Rsk) were observed for sample H, which was characterized by the lowest material
wear during the tribological test. This sample is also characterized by high parameters of
the load capacity curve, in particular the Rvk parameter, which is responsible for keeping
the sliding film on the friction surface. Sample E, which is characterized by the highest
Materials 2022, 15, 7732 12 of 21

material wear among the oxide layers, has high amplitude parameters Rsk and Rku and low
parameters of the load capacity curve (Rk and Rvk). Such a difference in the dependence
of the above parameters resulted in a different nature of the overlap of the sliding film on
the surfaces of samples H and E, which in turn translated into differences in the wear of
T7W material during tribological tests with these samples. The aluminum alloy sample
showed a low roughness surface, it was characterized by very low amplitude parameters
Rq and Rku, high Rsk parameter, and the lowest values of the load-bearing capacity curve
parameters (Abott Fireston) among the tested samples, even several times lower compared
to the oxide layers, which resulted in difficulties in creating a sliding film.
The parameters after the tribological test underwent significant changes. Taking into
account the amplitude parameters, the Rq values for all Al2 O3 layers decreased, in the
case of aluminum alloy it increased almost 10 times. The profile asymmetry coefficient
(Rsk) increased only for three samples (A, F, I), for the others there was a decrease (over
3 times for aluminum alloy). The Rku parameter after the tribological test increased for
samples: A, B, C and G, for all other samples there was a decrease in this parameter. While
analyzing the parameters of the load curve, very interesting conclusions were noticed:
the Rk parameter decreased significantly for all oxide layers, but for the aluminum alloy,
it increased more than 10 times. The situation is similar for the Rpk parameter, its significant
decrease was also observed for almost all layers (except for sample A) where the increase
was insignificant and over 10-fold increase for the aluminum alloy. The reduced height
of the roughness profile cavity (Rvk) after the tribological test decreased for almost all
oxide layers (it increased slightly for sample A), and also increased over 15 times for the
aluminum alloy. Sample H, which showed the lowest material wear during the tribological
test, was characterized by a high Rq parameter, the highest Rku and one of the lowest Rsk
parameters among the tested. The layer also has high parameters of the load capacity curve
(Rk, Rpk, and Rvk) influencing the sliding cooperation and referring to the bearing nature
of the layer. The parameters are completely different for the oxide layer marked with the
symbol E, which is characterized by high material wear during friction. It has very low
amplitude parameters (Rq and Rku) and high Rsk. Taking into account the parameters of
the load curve, the sample has the lowest parameters Rk and Rpk and one of the lowest
Rvk. On the basis of these values, it can be concluded that the conducted friction tests
contributed to the formation of a sliding film on the sample surface, which will translate
into very good tribological cooperation of the above layer, high abrasion resistance, and
high load capacity of the layer.
Figure 11 shows the graphs of the relationship (correlation) between the mass loss
of T7W material during the tribological test and the amplitude parameters and the load
capacity curve with the highest correlations. The matching characteristics (middle line)
and the regression stripes (side lines) defining the confidence intervals are marked in the
figures showing the relationships.
Taking into account the correlation diagrams between the mass loss of the material
during the tribological test and the amplitude parameters and the load capacity curve,
a very high correlation (very large relationship) between the mass loss and the parameters
Rsk, Rpk and Rvk (after friction) can be noticed. A high correlation (significant dependence)
between the mass loss and the parameters Rsk and Rvk (before friction) as well as Rq (after
friction), Rsk (before) Rvk (before) was also noticed. In the case of the Rsk parameters before
and after friction, it can be stated that the increase in mass loss occurs with an increase in
the above-mentioned parameters. Taking into account the parameter Rvk before friction
and the parameters Rq, Rpk, Rvk after friction, it can be stated inverse proportionality to
the mass loss, in other words, an increase in parameters results in a decrease in material
wear. This indicates a strong relationship between the surface roughness and the wear of
the material during friction.
OR PEER REVIEW 14 of 23

Materials 2022, 15, 7732 13 of 21

(a) (b)

(c) (d)

(e) (f)
Figure 11. Relationships between
Figure the massbetween
11. Relationships loss of the
T7W material
mass and:material
loss of T7W (a) theand:
Rq parameter after the
(a) the Rq parameter after the
test, (b) the Rsk parameter before
test, (b) the Rsk the test, (c)before
parameter the Rsk
the parameter
test, (c) the Rskafter the test,
parameter (d)the
after the Rpk
test, (d) parameter
the Rpk parameter
after the test, (e) the Rvk
afterparameter before
the test, (e) the the test, (f)
Rvk parameter with
before thethe
test,Rvk parameter
(f) with after the after
the Rvk parameter test.the test.

Figure 12 shows the graphs of the relationship (correlation) between the friction coefficient
Taking into account theamplitude
µ and the correlation diagrams
parameters between
and the thecurve
load-bearing masswith
losstheof the material
highest correlations.
during the tribological test and the amplitude parameters and the load capacity curve, a
very high correlation (very large relationship) between the mass loss and the parameters
Rsk, Rpk and Rvk (after friction) can be noticed. A high correlation (significant depend-
ence) between the mass loss and the parameters Rsk and Rvk (before friction) as well as
Rq (after friction), Rsk (before) Rvk (before) was also noticed. In the case of the Rsk pa-
rameters before and after friction, it can be stated that the increase in mass loss occurs with
an increase in the above-mentioned parameters. Taking into account the parameter Rvk
 Materials 2022, 15, x FOR PEER REVIEW 15 of 23

Materials 2022, 15, 7732 Figure 12 shows the graphs of the relationship (correlation) between the friction co- 14 of 21
efficient µ and the amplitude parameters and the load-bearing curve with the highest cor-
relations.

(a) (b)

(c)
Figure
Figure 12. 12.
Relationships between
Relationships the coefficient
between of friction
the coefficient of µ and: (a)µthe
friction Rpk
and: (a)parameter before the before the
the Rpk parameter
test, (b) the Rsk parameter before the test, (c) the Rk parameter after the test.
test, (b) the Rsk parameter before the test, (c) the Rk parameter after the test.
The analysis of the correlation of the friction coefficient µ showed that the Rpk pa-
The analysis of the correlation of the friction coefficient µ showed that the Rpk pa-
rameter before the tribological test shows a high correlation (significant relationship) with
rameter before the tribological test shows a high correlation (significant relationship) with
the friction coefficient µ. On the other hand, the parameters Rsk before the tribological
the friction coefficient
test and the parameter µ. On
Rk after thethe other hand,
tribological the parameters
test show Rsk before
a moderate correlation the tribological
(signifi-
test and the parameter Rk after the tribological test show a moderate
cant relationship) with the friction coefficient µ. The Rpk and Rsk parameters before the correlation (signifi-
cant relationship) with the friction coefficient µ. The Rpk and Rsk parameters
tribological test are characterized by a positive correlation, in other words, the change in before the
tribological test are characterized by a positive correlation, in other words,
the friction coefficient µ is proportional to the change in parameters. The values of the Rk the change in
the friction coefficient µ is proportional to the change in parameters. The values of the Rk
parameter after the tribological test are inversely proportional to the friction coefficient µ.
Figure 13 shows
parameter
Materials 2022, 15, x FOR
thethe
after
PEER REVIEW
roughness profiletest
tribological for are
the aluminum
inversely alloy EN AW-5251
proportional andfriction
to the the Al2Ocoefficient
3 µ. 16 o
layer (sample F).
Figure 13 shows the roughness profile for the aluminum alloy EN AW-5251 and the Al2 O3
layer (sample F).

(a)

(b)
Figure 13.
Figure 13. Roughness Roughness
profiles: profiles: (a)
(a) aluminum aluminum
alloy alloy EN
EN AW-5251, AW-5251,
(b) Al (b) Al2O3 layer.
2 O3 layer.

Based on the analysis of the roughness profiles for the aluminum alloy EN AW-5
without modification and the Al2O3 layer, significant differences are noticeable. Tribop
ner (T7W material) with a diameter of ϕ9 mm coincides with the width of the sliding
marked in Figure 6. Before the tribological test, aluminum alloy is characterized by
 (a)

Materials 2022, 15, 7732 15 of 21

(b)
Based on theFigure
analysis of the roughness
13. Roughness profilesalloy
profiles: (a) aluminum for EN
theAW-5251,
aluminum (b) Alalloy EN AW-5251
2O3 layer.

without modification and the Al2 O3 layer, significant differences are noticeable. Tribopart-
ner (T7W material) with Basedaon the analysis
diameter of ofφ9 themm roughness profiles
coincides for the
with thealuminum
width of alloy
theEN AW-5251
sliding
without modification and the Al2O3 layer, significant differences are noticeable. Tribopart-
film marked in Figure 6. Before the tribological test, aluminum alloy is characterized by
ner (T7W material) with a diameter of ϕ9 mm coincides with the width of the sliding film
low roughness, but marked in Figure with
cooperation thethe
6. Before material contributed
tribological to a significant
test, aluminum increasebyinlow
alloy is characterized
roughness and theroughness,
appearance of a significant number of peaks on the surface,
but cooperation with the material contributed to a significant increase which results in
in a higher coefficient of friction and uneven overlapping of the sliding film on the friction
roughness and the appearance of a significant number of peaks on the surface, which re-
sults in a higher coefficient of friction and uneven overlapping
surface. The sample with the oxide layer before friction had a much greater roughness than of the sliding film on the
friction surface. The sample with the oxide layer before friction had a much greater rough-
the aluminum alloy, but the tribological test influenced the smoothing of the sample and
ness than the aluminum alloy, but the tribological test influenced the smoothing of the
filling the cavitiessample
in the and
profile through
filling anin
the cavities evenly superimposed
the profile through an evenly sliding film.
superimposed sliding film.
Figure 14 shows Figure
the roughness profiles before and after the tribological
14 shows the roughness profiles before and after the tribological test for
test the
for the
oxide layers with oxide
the highest material
layers with mass
the highest loss (sample
material mass lossE) and the
(sample E) andlowest material
the lowest mass
material mass
loss (sample H). loss (sample H).

(a1) (a2)

(b1) (b2)

Figure 14. Figure

Roughness 14. Roughness
profiles: profiles:
(a) sample (a) sample
E, (b) sampleE,H,
(b) 1—before
sample H, 1—before the tribological
the tribological test, 2—after
test, 2—after
the tribological test.
the tribological test.
By analyzing the roughness profiles for the oxide layers with the highest (sample E)
By analyzingand thethe
roughness profiles
lowest material wearfor the oxide
(sample layers with
H), interesting the highest
relationships can be(sample E) At
observed.
and the lowest material wearyou
first glance, (sample
can seeH), interesting
a much greater relationships can beH,observed.
roughness for sample At first
it has a much greater
glance, you can see number
a muchof recesses
greaterinroughness
the profile. The
for tribological
sample H,test contributed
it has a muchtogreater
the smoothing
number of the
vertices for
of recesses in the profile. Theboth the first andtest
tribological the second layer. However,
contributed sample H, whose
to the smoothing of thematerial
verticeswear
as a result of the tribological test was over 5 times lower than that of sample E, is still
for both the first and the second layer. However, sample H, whose material wear as17a result
Materials 2022, 15, x FOR PEER REVIEW characterized by a significant number of cavities in the profile, which proves thatofthey 23 are
of the tribological not
testcompletely
was over filled
5 timeswithlower than film.
the sliding that The
of sample E, iscan
lower wear stillbecharacterized
explained by a bymuch
a significant number of cavities in the profile, which proves that they are not completely
filled with the sliding film. The lower wear can be explained by a much better retention of
better retention of the sliding film in the cavities, thanks to which a self-lubricated layer is
the sliding film in the cavities, thanks to which a self-lubricated layer is formed. A much
formed. A much larger number of cavities after the tribological test for sample H may
larger number of cavities after the tribological test for sample H may indicate a much
indicate a much longer time to fill them with a sliding film. In turn, the higher coefficient
longer time to fill them with a sliding film. In turn, the higher coefficient of friction can
of friction can be attributed to the higher surface roughness.
be attributed to the higher surface roughness.
Figure
Figure1515shows
showsthe theroughness
roughnessprofiles
profilesbefore
beforeand andafter
afterthe
thetribological
tribologicaltest testfor
forthe
the
oxide
oxidelayers
layerswith
withthe
thehighest
highestcoefficient
coefficientofoffriction
frictionµµamong
amongthe theoxide
oxidelayers
layers(sample
(sampleC) C)
and
andwith
withthe
thelowest
lowestcoefficient
coefficientof offriction
friction(sample
(sampleG). G).

(a1) (a2)

(b1) (b2)
Figure
Figure15.
15.Roughness
Roughnessprofiles:
profiles:(a)
(a)sample
sampleC,C,(b)
(b)sample
sampleG,
G,1—before
1—beforethe
thetribological
tribologicaltest,
test,2—after
2—after
the
thetribological
tribologicaltest.
test.

When analyzing the roughness profiles of Al2O3 layers with the highest (sample C)
and the lowest (sample G) friction coefficient µ, a significant influence of the roughness
on this value was observed. The roughness profile of sample C, which was characterized
by the highest coefficient of friction µ, has significantly higher peaks and a greater number
of peaks than sample G. As a result of the tribological test, these peaks were smoothed,
Materials 2022, 15, 7732 16 of 21

When analyzing the roughness profiles of Al2 O3 layers with the highest (sample C)
and the lowest (sample G) friction coefficient µ, a significant influence of the roughness on
this value was observed. The roughness profile of sample C, which was characterized by
the highest coefficient of friction µ, has significantly higher peaks and a greater number
Materials 2022, 15, x FOR PEER REVIEW 17 of 23
of peaks than sample G. As a result of the tribological test, these peaks were smoothed,
but their abrasion increased the friction coefficient. The profile of sample C after friction
also has a smaller number of cavities, most probably as a result of sealing them with T7W
better retention
material with theofproducts
the sliding
of film in thewhich
tip wear, cavities, thanks toinfluenced
negatively which a self-lubricated layer is
the friction process.
formed.
In the caseAofmuch
sample larger number
G, larger of cavities
cavities after the
after friction aretribological testhas
visible, which fora sample
positiveHeffect
may
indicate a much longer time to fill them with a sliding film. In
on maintaining the sliding film and reducing the coefficient of friction µ. turn, the higher coefficient
of friction can be attributed to the higher surface roughness.
Figure 15 shows
3.5. Measurements the roughness
of Wettability profiles before
and Calculation and
of Surface after
Free the tribological test for the
Energy
oxideTable 6 shows the contact angle values measured withoxide
layers with the highest coefficient of friction µ among the layerswater
distilled (sampleandC)
and with the lowest coefficient
α-bromonaphthalene. of friction
Table 7 lists (sample
the contact G). measurements with glycerin and
angle
diiodomethane. Examples of drops on the surface of layer G (with the greatest contact
angle) are shown in Figure 16.
Table 6. Contact angles of oxide layers and aluminum alloy measured by distilled water and
α-bromonaphthalene.
(a1) (a2)
Contact Angle Contact Angle
Sample Deviation (◦ ) Deviation (◦ )
(Distilled Water) (◦ ) (α-Bromonaphthalene) (◦ )
A 90.80 2.70 39.88 4.44
B 82.16 5.70 29.34 2.54
C 82.25 5.14 37.68 3.23
D 85.06(b1) 3.67 30.12 (b2) 2.43
E 15. Roughness
Figure 65.49profiles: (a) sample
5.98C, (b) sample G, 1—before
33.05 the tribological test,
2.802—after
F 82.46 6.29 27.18 2.24
the tribological test.
G 95.33 3.86 31.54 3.75
H 83.81 2.25 29.83 3.75
I When analyzing85.83 the roughness4.11 profiles of Al2O3 layers
32.54with the highest (sample
2.45 C)
andAlthe lowest (sample
71.59 G) friction coefficient
4.14 µ, a significant
36.12 influence of the roughness
2.36
on this value was observed. The roughness profile of sample C, which was characterized
by the
Table 7. highest coefficient
Contact angles of oxideof layers
friction µ,aluminum
and has significantly higherbypeaks
alloy measured andand
glycerin a greater number
diiodomethane.
of peaks than sample G. As a result of the tribological test, these peaks were smoothed,
but their abrasion
Sample
Contactincreased
Angle the friction coefficient. The
Deviation (◦ )
profile
Contact of sample Deviation
Angle C after friction
(◦ )
(Glycerin)
also has a smaller number (◦ ) of cavities, most probably (Diiodomethane) (◦ )
as a result of sealing them with T7W
material
A with the84.25
products of tip wear, which negatively 59.05
7.69 influenced the friction2.26process.
InBthe case of sample
69.59G, larger cavities3.01 41.38 which has a positive
after friction are visible, 3.19 effect
onCmaintaining the 80.22 5.24
sliding film and reducing 44.74
the coefficient of friction µ. 6.38
D 78.80 1.36 45.76 7.09
E 73.80 2.55 47.74 7.75
3.5.
F
Measurements69.27
of Wettability and Calculation
2.89
of Surface Free Energy
46.51 3.65
G Table 6 shows the contact angle values
87.03 4.10 measured with distilled water and4.98
50.52 α-bromo-
H
naphthalene. 72.60
Table 7 lists the contact 4.04
angle measurements 46.09
with glycerin and 5.93
diiodome-
I
thane. Examples88.54
of drops on the surface 2.76 of layer G (with47.77
the greatest contact3.02
angle) are
Al 80.67 3.67 52.19 2.14
shown in Figure 16.

Figure 16. Sample photo of a drop on the surface of the G sample layer.
Figure 16. Sample photo of a drop on the surface of the G sample layer.
 F 82.46 6.29 27.18 2.24
G 95.33 3.86 31.54 3.75
H 83.81 2.25 29.83 3.75
I 85.83 4.11 32.54 2.45
Materials 2022, 15, 7732 Al 71.59 4.14 36.12 2.3617 of 21

Figure 17 shows graphs of the relationship (correlation) between the contact angle
measured by 17
Figure water
showsandgraphs
the amplitude parameters(correlation)
of the relationship and the load-bearing curve
between the with angle
contact the
highest correlations.
measured by water and the amplitude parameters and the load-bearing curve with the
highest correlations.

Materials 2022, 15, x FOR PEER REVIEW 19 of 23

Table 7. Contact angles of oxide layers and aluminum alloy measured by glycerin and diiodome-
thane.

Contact Angle Deviation Contact Angle Deviation

Sample (a) (b) (°)
(Glycerin) (°) (°) (Diiodomethane) (°)
FigureA 17.17.
Figure TheThe 84.25 between
relationship
relationship betweenthe 7.69 angle
thecontact
contact anglemeasured
measuredby 59.05
by water
water and:
and: (a)(a) the Rsk2.26
the Rsk parame-
parameter,
ter, B
(b) the Rpk 69.59
parameter.
(b) the Rpk parameter. 3.01 41.38 3.19
C 80.22 5.24 44.74 6.38
DBy Byanalyzing
analyzing the correlation
the
78.80 correlation between
between
1.36 the contact
the angles
contact measured
angles
45.76 measuredby water,
by the am-
water,
7.09 the
plitude
amplitude
E parameters
parameters and
73.80 the
and load-bearing
the load-bearing
2.55curve, it
curve, can
it be
can concluded
be concluded
47.74 that the
that roughness
the roughness
7.75 of of
the surface has a significant
theFsurface has a significant69.27 impact on
impact on2.89 its wettability. There
its wettability. There46.51 is a high correlation
is a high correlation (significant(signifi-
3.65
cant Grelationship)
relationship) between
between87.03 the the
Rsk Rsk parameter
parameter
4.10 and and
the the contact
contact angle
angle
50.52 for for water,
water, andanda a mod-
moderate
4.98
correlation
erate correlation (significant
(significantrelationship)
relationship) for for
thethe
Rpk Rpkparameter.
parameter. The Thecorrelation
correlation between
between the
H 72.60 4.04 46.09 5.93
contact
the contact angle
angle and thethe
and parameters
parameters RskRskandand RpkRpkis negative,
is negative,in other
in otherwords, an increase
words, in the
an increase
I 88.54 2.76 47.77 3.02
inroughness
the roughness parameters causes
parameters a decrease
causes in thein
a decrease contact angle angle
the contact (increase in wettability).
(increase in wettabil- This
Al 80.67 3.67 52.19 2.14
is consistent
ity). with thewith
This is consistent Wenzelthe equation, which claims
Wenzel equation, whichthat an increase
claims that an in surfaceinroughness
increase surface
causes ancauses
roughness increase anin surfacein
increase wettability (a decrease
surface wettability (ain the contact
decrease in the angle)
contactfor hydrophilic
angle) for
Considering
surfaces, for distilled water
hydrophobic surfacesas the
the measuring
relationship liquid,
is the greatest contact angle was
inversely.
hydrophilic surfaces, for hydrophobic surfaces the relationship is inversely.
measured for sample
Considering G produced
distilled waterduring
as the anodizing
measuringatliquid, a current density of
the greatest 2 A/dm
contact
2, in an
angle was
electrolyte
measuredatfor a temperature
sample G produced of 283 K, and was
during 95.33 ±at3.86°.
anodizing The second
a current densitysampleof 2 A/dm with2 ,ain
contact angle exceeding
an electrolyte 90° is sample
at a temperature of 283A,K,theandlayer
was of95.33
which ±was
3.86formed duringsample
◦ . The second anodizing with
ataacontact
currentangledensity of 1 A/dm ◦2 and an electrolyte temperature of 283 K, and the angle was
exceeding 90 is sample A, the layer of which was formed during anodizing
90.8
at a± current
2.7°. Both sample
density of 1GA/dm
and A2 and are layers with hydrophobic
an electrolyte temperatureproperties.
of 283 K, and It follows
the angle from
was
the above
90.8 ± 2.7that
◦ low current
. Both sample G density
and Avalues combined
are layers with a shortproperties.
with hydrophobic anodizing time (20 min)
It follows from
allow the production
the above of a layer
that low current with high
density values contact
combined angles (low
with wettability).
a short anodizing time (20 min)
allow the production of a layer with high contact angles (low wettability).the contact an-
Figure 18 shows the graphs of the relationship (correlation) between
gles measured
Figure 18with glycerin
shows and diiodomethan,
the graphs of the relationship and the(correlation)
amplitude parameters
between the and the
contact
load-bearing curve with the highest correlations.
angles measured with glycerin and diiodomethan, and the amplitude parameters and the
load-bearing curve with the highest correlations.

(a) (b)
Figure
Figure18.18.
The relationship
The relationshipbetween
betweenthe
thecontact
contactangle:
angle: (a)
(a)measured
measured by glycerin and
by glycerin and the
theRq
Rqparameter
param-
eter before the test, (b) measured by diiodomethane and the Rpk parameter before
before the test, (b) measured by diiodomethane and the Rpk parameter before the test. the test.

The contact angle measured by glycerin and diiodomethane was found to be related
to the amplitude parameters and the load capacity curve. There is a moderate correlation
(significant relationship) between the contact angles for glycerin and diiodomethane and
the Rq and Rpk parameters. The correlation is negative, which means an increase in con-
Materials 2022, 15, 7732 18 of 21

The contact angle measured by glycerin and diiodomethane was found to be related
to the amplitude parameters and the load capacity curve. There is a moderate correlation
Materials 2022, 15, x FOR PEER REVIEW 20 of 23
(significant relationship) between the contact angles for glycerin and diiodomethane and
the Rq and Rpk parameters. The correlation is negative, which means an increase in contact
angles with a decrease in Rq and Rpk parameters, similar to the measurements by water.
Table
Table 8. Free8surface
showsenergy
the of
values of surface
Al2O3 layers free and
for glycerin energy (SFE) calculated using the
diiodomethane.
Owens–Wendt method using the contact angles for distilled water and α-bromonaphthalene.
Sample SFE Owens–Wendt (mJ/m2)
A 36.68
Table 8. Free surface energy of Al2 O3 layers for glycerin and diiodomethane.
B 42.49
C Sample SFE Owens–Wendt (mJ/m2 )
39.75
D A 41.46 36.68
E B 48.31 42.49
F C 43.04 39.75
D 41.46
G 35.61
E 48.31
H F 41.87 43.04
I G 40.48 35.61
Al H 49.81 41.87
I 40.48
Al 49.81
When analyzing the values of surface free energy (Table 8), the highest SFE value
was observed for sample E anodized at a current density of 1 A/dm2 at an electrolyte tem-
When analyzing the values of surface free energy (Table 8), the highest SFE value
perature
was of 293for
observed K sample
(the highest value ofatmass
E anodized loss ofdensity
a current T7W material was2 demonstrated
of 1 A/dm at an electrolytefor
this sample). The lowest SFE value was calculated for sample G produced
temperature of 293 K (the highest value of mass loss of T7W material was demonstrated at a current
density
for of 2 A/dm
this sample).
2, at an electrolyte temperature of 283 K (the lowest coefficient of friction
The lowest SFE value was calculated for sample G produced at a current
was demonstrated
density of 2 A/dm2 ,for thiselectrolyte
at an sample). Sample G hasofthe
temperature 283highest contactcoefficient
K (the lowest angle for water and
of friction
one of the highest for glycerin. The inverse proportionality of the surface
was demonstrated for this sample). Sample G has the highest contact angle for water andfree energy value
to the
one value
of the of contact
highest angles was
for glycerin. The also noted.
inverse proportionality of the surface free energy value
Figure 19 shows the dependence
to the value of contact angles was also noted. of the SFE on electrolyte temperature and current
density.
Figure 19 shows the dependence of the SFE on electrolyte temperature and current density.

Figure 19. Dependence

Figure19. Dependenceof
ofSFE
SFEon
onelectrolyte
electrolytetemperature
temperatureand
andcurrent
currentdensity.
density.

Based
Basedononthe
theanalysis
analysisofofthe
theinfluence
influence ofofthe
theelectrolyte temperature
electrolyte temperature andand
current density
current den-
on the surface free energy (Figure 11), it was found that high values (over 42 mJ/m 2 ) were
sity on the surface free energy (Figure 11), it was found that high values (over 42 mJ/m 2)
recorded for layers produced by anodizing at a current density of 3 A/dm 2 , in the full
were recorded for layers produced by anodizing at a current density of 3 A/dm2, in the
temperature range.range.
full temperature The highest value was
The highest valueachieved for the lowest
was achieved for thecurrent
lowest2values A/dm2(1)
current(1values
and
A/dm electrolyte temperature
2) and electrolyte of 293 K.of
temperature The293lowest
K. The SFE values
lowest < 38
SFE mJ/m
values < 38occur
mJ/mat2 occur
middle at
current density values and low electrolyte temperatures.
middle current density values and low electrolyte temperatures.
Figure 20 shows the graphs of the dependence (correlation) between the SFE calcu-
lated using the Owens–Wendt method and the Rsk parameter and the mass loss with the
highest correlation.
 Materials 2022, 15, 7732 19 of 21

Materials 2022, 15, x FOR PEER REVIEW 21 of 23

Figure 20 shows the graphs of the dependence (correlation) between the SFE calcu-
lated using the Owens–Wendt method and the Rsk parameter and the mass loss with the
highest correlation.

(a) (b)
Figure 20.20.Relationship
Figure Relationshipbetween SFE and:
between SFE and:(a)
(a)Rsk
Rsk parameter
parameter before
before the test,
the test, (b) mass
(b) mass loss ofloss of the
the material.
material.
When analyzing the correlation between the surface free energy, roughness parameters,
andWhenmass analyzing
loss, a moderate correlation
the correlation (significant
between relationship)
the surface with the
free energy, Rsk parameter
roughness parame-was
found.
ters, and The
masscorrelation is positive,
loss, a moderate which indicates
correlation therelationship)
(significant proportionality
withofthe
theRskSFEparam-
value to
thewas
eter Rskfound.
parameter, it is analogous
The correlation to the values
is positive, which of the contact
indicates angles, the values
the proportionality of which
of the SFE
are inversely proportional to the free surface energy. The increase in SFE
value to the Rsk parameter, it is analogous to the values of the contact angles, the values also affects the
ofmass
which loss
areofinversely
the material during friction.
proportional to theThe
freeanalysis
surfaceshowed
energy. aThe
moderate
increasecorrelation,
in SFE alsoand
thus the
affects a significant
mass lossrelationship
of the material between
duringthe surface
friction. Thefree energyshowed
analysis and material
a moderatewear.cor-
The
correlation
relation, and is positive,
thus which indicates
a significant the proportionality
relationship of thefree
between the surface SFEenergy
value toandthematerial
mass loss
of the material.
wear. The correlation is positive, which indicates the proportionality of the SFE value to
the mass loss of the material.
4. Conclusions
4. •Conclusions
The research results and their analysis presented in the article confirm the legitimacy of
anodizing the EN AW-5251 aluminum alloy in order to improve its sliding properties.
• The research results and their analysis presented in the article confirm the legitimacy
• The anodizing parameters used during the experiment significantly affect the thickness
of anodizing the EN AW-5251 aluminum alloy in order to improve its sliding prop-
of the Al2 O3 layers. Increasing the current density causes a significant increase in the
erties.
thick-ness of the layer, as a result of increasing the electric charge, while the increase in
• The anodizing parameters used during the experiment significantly affect the thick-
temperature causes a decrease in the thickness of the layer, as a result of the increased
ness of the Al2O3 layers. Increasing the current density causes a significant increase
secondary solubility of the Al O layer by the electrolyte with a higher temperature.
in the thick-ness of the layer, as2 a3result of increasing the electric charge, while the
• The correlation analysis also showed a significant relationship between the anodizing
increase in temperature causes a decrease in the thickness of the layer, as a result of
parameters and the surface roughness of the samples, which in turn affects the wear of
the increased secondary solubility of the Al2O3 layer by the electrolyte with a higher
the material and the resistance to motion. An increase in the Rsk parameter and a de-
temperature.
crease in Rvk causes an increase in the consumption of T7W material, while a decrease
• The correlation analysis also showed a significant relationship between the anodiz-
in Rsk and an increase in Rvk contribute to a reduction in material consumption. An
ing parameters
increase in theand
Rskthe surface
value roughness
also increases theoffriction
the samples, whichThe
coefficient. in differences
turn affectsin the
the
wear of the material and the resistance to motion. An increase in the
roughness parameters result in a different character of the overlapping of the sliding Rsk parameter
and a decrease
film in Rvkofcauses
on the surface an increase
the layers, which inin the
turnconsumption
translates into of differences
T7W material, while
in material
a wear
decrease
andin Rsk and an
movement increase in Rvk contribute to a reduction in material con-
resistance.
• sumption.
The anodizing parameters Rsk
An increase in the andvalue alsoroughness
surface increases also
the friction coefficient.
affect the Theof
wettability dif-
the
ferences in the roughness parameters result in a different character
surface of the layers, which also affects the ability to form and maintain a slidingof the overlapping
offilm.
the sliding film ondensity
Low current the surface of (1
values theand
layers, which
2 A/dm in combination
2 ) in turn translates intolow
with differences
electrolyte
intemperature
material wear and movement resistance.
(283 K) allow for the production of a layer with high contact angles
• The
(lowanodizing parameters
wettability). and surface
The correlation roughness
between also affect
the contact anglethe
and wettability
the Rsk and of the
Rpk
surface of theis
parameters layers, which
negative; also affects
in other words,theanability to in
increase formtheand maintain
roughness a sliding film.
parameters causes
Low current in
a decrease density valuesangle
the contact (1 and 2 A/dm2in
(increase ) in combination with low electrolyte tem-
wettability).
• perature (283 K) allow for the production
The analysis of friction and wear tests showed that of a layer with
the high
layer withcontact angles proper-
hydrophobic (low
wettability). The correlation between the contact 2 angle and the Rsk
ties, produced at a current density of 1 A/dm in an electrolyte at a temperature of and Rpk param-
eters
283 is
K,negative;
is the most in favorable
other words, an increase
for sliding in the roughness
associations parameters causes a
with T7W material.
decrease in the contact angle (increase in wettability).
Materials 2022, 15, 7732 20 of 21

Author Contributions: Methodology, M.N. and M.B.; conducting research, M.N., S.K., and G.D.;
formal analysis, M.N., M.B., W.S., and G.D.; writing—preparation of the original project and editing,
M.N. and M.B.; writing—review, M.N., M.B., W.S., S.K., and G.D. All authors have read and agreed
to the published version of the manuscript.
Funding: This research received no external funding.
Institutional Review Board Statement: Not applicable.
Data Availability Statement: The data presented in this study are available on request from the
corresponding author. The data are not publicly available due to insufficient space to insert data.
Conflicts of Interest: The authors declare no conflict of interest.

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