The International Journal of Advanced Manufacturing Technology (2019) 105:1745–1756

https://doi.org/10.1007/s00170-019-04381-y

ORIGINAL ARTICLE

Tribological behavior of electroless Ni–P/Ni–P–TiO2 coatings

obtained on AZ91D magnesium alloy by a chromium-free process
Diego F. Carrillo 1 & Ana C. Santa 1 & Andrés Valencia-Escobar 2 & Alejandro Zapata 2 & Félix Echeverría 1 &
Maryory A. Gómez 1 & Alejandro A. Zuleta 2 & Juan G. Castaño 1

Received: 3 May 2019 / Accepted: 30 August 2019 / Published online: 24 October 2019
# Springer-Verlag London Ltd., part of Springer Nature 2019

Abstract
Studies about the tribological behavior of Ni–P–TiO2 coatings on magnesium alloys are very scarce and the wear mechanisms
involved are not analyzed. In this work, Ni–P and Ni–P/Ni–P–TiO2 nanocomposite coatings have been formed on AZ91D
magnesium alloy by direct electroless technique with multiple steps, avoiding both the use of Cr(VI) compounds and the HF
activation procedure. This work focused on two main aspects: (i) the formation of the composite coatings with different sizes and
concentrations of TiO2 nanoparticles, studying their morphology and chemical composition, and (ii) the study of the tribological
properties of the coatings under dry sliding conditions. For tribological and mechanical evaluation, dry sliding friction and wear
testing and nanoindentation measurements were performed. Scanning electron microscopy equipped with energy-dispersive X-
ray (SEM/EDX) and X-ray diffraction (XRD) was used for the characterization of the coatings. Wear tracks and debris were
analyzed by means micro-Raman spectroscopy and SEM/EDX. The addition of TiO2 nanoparticles decreases the wear rate and
improves the tribological behavior of the coatings. The wear mechanisms involve flattening of the nodules and abrasive wear to
three bodies, accompanied by tribo-oxidation.

Keywords Magnesium alloys . Electroless coatings . Ni–P . Surface morphology, tribology . TiO2 nanoparticles

1 Introduction application of Ni–P electroless coatings has proved to be an

Magnesium alloys are light materials with suitable physical
and mechanical properties for their use in industries like trans-
portation, aerospace, and electronics, including good electrical
and thermal conductivities, high strength to weight ratio, and
high anti-shock resistance and vibrations absorption.
However, due to their high reactivity and low wear resistance,
their application has been very limited [1–3]. In order to im-
prove these properties, different protection methods have been
developed, including anodizing, conversion coatings, thermal
spraying, and electroless coatings [1, 2, 4]. Particularly,
* Juan G. Castaño
juan.castano@udea.edu.co
1
Centro de Investigación, Innovación y Desarrollo de Materiales –
CIDEMAT, Universidad de Antioquia, Carrera 53 No. 61-30,
Medellín, Colombia
2
Grupo de Investigación de Estudios en Diseño - GED, Facultad de
Diseño Industrial, Universidad Pontificia Bolivariana, Sede
Medellín, Circular 1 No. 70-01, Medellín, Colombia
outstanding and effective technique for protection of magne-
sium alloys due to low energy consumption, formation of
uniform thicknesses (even in pieces with complex geome-
tries), and excellent resistance to corrosion [5–7].
Magnesium and its alloys easily dissolve in electroless
baths. For this reason, the substrates are usually subjected to
pretreatment in a solution of chromates and nitric acid follow-
ed by activation by immersion in hydrofluoric acid. This pro-
cess is potentially toxic and dangerous, and different alterna-
tives have been investigated to allow the deposition of Ni–P
electroless coatings on magnesium and its alloys without the
use of Cr(VI) compounds or HF [8–11]. In addition, some of
them use palladium for the pretreatment process, which makes
the process more expensive [8]. In previous works, alternative
methods have been developed to coat magnesium and its al-
loys with electroless coatings using NH4HF2 (a salt of easy
handling and less hazardous), in replacement of compounds
with chromium and hydrofluoric acid [12–14].
On the other hand, the development of composite electro-
less coatings, where particulate material is incorporated into
the electroless bath, allows increasing properties as hardness,
1746
wear, and corrosion resistance. The phosphorus content, the
amount of co-deposited particles and the heat treatment deter-
mine these properties in Ni–P coatings [11]. In the literature, Ni–
P electroless coatings on magnesium and its alloys with the co-
deposition of particles as SiC [15, 16], ZrO2 [17, 18], SiO2 [19,
20], TiN [21], and TiO2 [16, 18, 22] have been reported.
However, information related to the tribological behavior of
Ni–P–TiO2 coatings on magnesium alloys is very scarce. In gen-
eral, electroless Ni–P coatings are smooth and lubricious as a
result of their nodular microstructure, and the addition of hard
particles tends to increase the friction coefficient due to the loss of
their natural lubricity [23]. Chen et al. [22] developed a combi-
nation of sol-gel and electroless plating techniques to prepare
highly dispersive Ni–P–TiO2 composite coatings with a concen-
tration of particles of 5 g/L and an average diameter of less than
25 nm, finding that the wear resistance of the composite coating
has been enhanced significantly. However, the wear mechanisms
involved are not analyzed.
In this work, the tribological behavior of Ni–P/Ni–P–TiO2
composite electroless coatings obtained on AZ91D magne-
sium alloys was analyzed. The coatings were obtained by
direct electroless technique with multiple steps. All proce-
dures were chromium-free and no activation procedure was
needed. The coating properties were studied by SEM/EDX,
XRD, and nanoindentation. In addition, wear rates and friction
coefficients were obtained by pin-on-disk tribological tests,
and wear mechanisms were established based on SEM,
EDX, and micro-Raman characterization.
2 Experimental
2.1 Sample preparation
Rectangular specimens of 10 × 10 × 2 mm were cut from
AZ91D alloy (Al 9.5%, Zn 0.5%, Mn 0.3%, bal. Mg
(wt%)), mechanically polished with # 100 grit SiC paper,
and then grit blasted using a micro-sandblasting apparatus,
RENFERT-basic classic 2945-4025, containing alumina
grains of 150 μm and at pressure of 0.4 MPa. The substrates
were cleaned ultrasonically for 900 s in ethanol, rinsed with
deionized water, and dried in a warm airstream. They were
then immersed in an alkaline cleaning solution (37.0 g/L
NaOH and 10.0 g/L Na3PO4) for 600 s at 65 °C. Finally, the
cleaned substrates were transferred to a series of fresh electro-
less solutions according to the operation conditions described
in Table 1.
The deposition process was carried out in four consecutive
steps according to previous works developed in our laboratory
[12, 13, 16], where the steps (i) and (ii) constituted an alter-
native pretreatment that avoided the use of Cr and HF com-
pounds and allowed the formation of electroless coatings of
acid nature on magnesium alloys. The steps were the
Int J Adv Manuf Technol (2019) 105:1745–1756
following: (i) immersion in an alkaline bath for the fast growing
of the first layer of Ni–P, avoiding the excessive dissolution of the
magnesium alloy substrate. This layer is highly porous and its
thickness generally is close to 11 μm; (ii) immersion in a slightly
acidic bath, which allowed the formation of a Ni–P coating with
approx. 7 μm and high phosphorus content (12% approx.). This
layer covers the porous formed on previous step and improves the
isolation on the substrate; (iii) immersion in a slightly acidic bath
with higher concentration of nickel salt and reducing agent, which
allowed the formation of a deposit with high phosphorus content
(13% approx.) and improved the corrosion resistance; (iv) immer-
sion in a bath with the same composition of the third solution but
containing TiO2 (anatase) nanoparticles and adjusting pH to 4.5.
The pH variation for the last bath was carried out in order to
decrease the kinetics of the reaction and provide greater stability
due to the presence of TiO2 nanoparticles. Figure 1a shows a
scheme of the multilayer system Ni–P/Ni–P–TiO2.
TiO2 nanoparticles were added to the electroless bath iv in
two levels of size (5 and 100 nm) and two levels of concen-
tration (0.5 and 2.0 g/L). Before the deposition, the nanopar-
ticles were ultrasonically dispersed for 60 s using a SONICS-
VIBRA-CELL VCX130 high power ultrasonic probe appara-
tus at 70% of amplitude. For the co-deposition of nanoparti-
cles, it was necessary to keep the bath with constant agitation
in order to avoid the sedimentation of the nanoparticles. Due
to the low density of the magnesium, the samples were placed
in the device as shown in the Fig. 1b. The specimens were
rinsed with deionized water and dried in a warm airstream
after the deposition process.
2.2 Coating characterization
The morphology and thickness of the coatings, as well as the
features of wear tracks, were determined by SEM/EDX using
JEOL JSM 6490-LV scanning electron microscope coupled
with energy-dispersive X-ray spectroscopy (Oxford
IncaPentaFETx-3) for elemental compositional microanalysis.
The coating structure was studied by XRD using X’Pert
PANalytical Empyrean Series II diffractometer with detector
PIXcel 3D in the configuration θ = 2θ with Co Kα 1 =
0.178901 nm and Kα2 = 0.179290 nm 2012 model. Data for
the XRD measurements were recorded over the 2θ range of
20–80°, with a step size of 0.026° and time per step of 50 s.
These data were analyzed through the HighScore Plus soft-
ware. The crystallite size of Ni was calculated from Scherrer’s
equation based on Eq. (1):
Kλ
D¼ ð1Þ
βcosθ
where, K is Scherrer’s constant (K = 0.94), λ = 0.17890 nm is
the X-ray wavelength, β is the broadening at half the maxi-
mum intensity (FWHM), and θ is the Bragg angle.
Int J Adv Manuf Technol (2019) 105:1745–1756 1747

Table 1 Chemical composition of electroless nickel-plating bath and operating conditions

Chemical composition
Name Formula Concentration
Baths i and ii Baths iii and iv
Nickel sulfate hexahydrate NiSO4·6H2O 21.2 g/L 30.0 g/L
Sodium hypophosphite monohydrate NaH2PO2·H2O 24.2 g/L 51.0 g/L
Lactic acid C3H6O3 26.5 mL/L 9.0 mL/L
Propionic acid C3H6O2 2.2 mL/L –
Succinic acid C4H6O4 12.0 g/L –
Ammonium hydrogen bifluoride NH4HF2 13.3 g/L –
Operating conditions
Variable Bath
i ii iii iv
pH* 10.5 ± 0.1 6.5 ± 0.1 6.5 ± 0.1 4.5 ± 0.1
Time (min) 30 30 150 30
Magnetic stirring – – – 250 RPM
Temperature (°C) 80 °C ± 1 °C

*Adjusted with ammonium hydroxide

The roughness (Ra) of the surfaces was assessed using an
Interferometer KEYENCE 3D Laser Scanning Confocal
Microscope VK-X200; measurements were conducted in trip-
licate in different sections. Nanohardness tests were carried out
in an IBIS Authority nanoindentator from Fischer–Cripps
Laboratories. To determine the hardness, several indentations
were made superficially to each coating at a load range of 0–
400 mN. The analyzed depth was about 10% of the top layer
(Ni–P–TiO2) thickness of the coatings, in order to eliminate the
effect of the Ni–P layer.
2.3 Tribological properties
The friction and wear behavior in dry sliding tests were eval-
uated using a homemade ball-on-disk tribometer. Wear behav-
iors of the coatings were evaluated according to ASTM G99:
“Standard Test Method for Wear Testing with a Pin-on-Disk
Apparatus” [24]. Alumina balls of 6-mm diameter were used
as the sliding counterfaces. The testing conditions used for the
tribological performance of the Ni–P/Ni–P–TiO2 coatings are
given in Table 2.
The samples and counter bodies were ultrasonically
cleaned using acetone bath and weighed before and after each
tribological test using a Mettler Toledo MX5 micro-weighing
scale with a sensitivity of 0.1 μg. Tribological tests were per-
formed in triplicate for each concentration and size condition.
The friction coefficient and wear rate measurements were cal-
culated for each replica. The wear rate was determined by
Eq. (2):
ΔP
k¼ ð2Þ
FL
where k is the wear rate (kg/Nm), ΔP is the mass loss (kg), F is
the normal applied load (N), and L is the total sliding distance
(m).

Fig. 1 a Scheme of the multilayer system Ni–P/Ni–P–TiO2. b Device used with the electroless bath for the co-deposition of TiO2 nanoparticles
1748 Int J Adv Manuf Technol (2019) 105:1745–1756

Table 2 Conditions of
the wear test Parameter

Rotation speed (rpm) 100

Sliding velocity (mm/s) 10.5
Applied force (N) 10
Wear track radius (m) 0.002
Sliding distance (m) 56.6
Temperature (°C) 20 ± 2
Relative humidity (%) 50 ± 5
Motion Unidirectional
Moving element Sample

3 Results and discussion

3.1 Surface morphology and microstructure
of coatings
The thickness, roughness, and deposition rate of different
coatings are reported in Table 3. Ni–P coatings have the
highest deposition rate, near 4.62 μm/h, while Ni–P/Ni–P–
TiO2 coatings have lower deposition rate, between 1.64 and
3.97 μm/h, which is directly related to the thickness reached.
The reported values show that the higher the size and concen-
tration of the nanoparticles, the lower the thickness of the
coating, being higher the effect of the concentration.
Decreases of 43.6% and 51.2% in the deposition rate are ob-
served when going from the lower (0.5 g/L) to the higher level
(2.0 g/L) in the concentration of the TiO2 nanoparticles for 5
and 100 nm, respectively. This effect has already been evi-
denced by other authors and is attributed to the fact that some
particles can be physically adsorbed on the catalytic surface,
suppressing available active sites for the processes of oxide
reduction, which affects the general deposition rate [25]. On
the other hand, there is no significant change in roughness in
almost all samples (1.95 to 2.14 μm). However, for the Ni–P–
TiO2 sample with the smallest particle size and the highest
concentration, an increase in roughness of approximately
14.6% is evidenced. This may be due to the increase in the
porosity of the surface and the amount of agglomerates on it.
Figure 2 shows the diffraction pattern corresponding to the
Ni–P electroless coating obtained on the AZ91D alloy. It is
Fig. 2 XRD pattern of Ni–P electroless coating on the AZ91 alloy
possible to observe a wide peak centered at an angle 2θ = 52°
characteristic of crystalline nickel (ICSD 98-005-3807) and
corresponding to the plane (1 1 1). The width of the peak is
associated with the short-range ordering of nanocrystallinity
of this type of coatings [26], which is corroborated with the
determination of the crystallite size, close to 1.32 nm.
Additional species are not detected in the diffractogram.
Scanning electron microscopy showed considerable differ-
ences between the surface of Ni–P and Ni–P/Ni–P–TiO2 coat-
ings at different concentrations of TiO2 (Fig. 3). The micro-
graphs reveal the presence of nanoparticles agglomerates,
which is an effect that commonly occurs with the co-
deposition of nanoparticles [22]. The incorporation of nano-
particles does not occur individually although there are dis-
persion processes in previous stages. They tend to agglomer-
ate easily due to their size, high surface energy, and activity, as
well as pH conditions [20, 27]. During the deposition process,
the TiO2 agglomerated nanoparticles are solvated in water
molecules and surrounded by Ni2+ ions that are attracted by
the autocatalytic surface, thus achieving the incorporation of
the agglomerates in the coating [16]. It is evident that the
presence of agglomerates on the surface coatings is strongly
influenced by the amount of nanoparticles present in the bath.
At high concentration, there is a greater presence of ag-
glomerates on the surface (Fig. 3e) compared with the quantity

Table 3 Characteristics of Ni–P and Ni–P/Ni–P–TiO2 coatings

Type of coating Top layer thickness (μm) Coating total thickness (μm) Deposition rate of top layer Top layer roughness
(μm/h) Ra (μm)

Ni–P (until step iii) 11.56 ± 1.93 30.20 ± 2.82 4.62 ± 0.77 2.14 ± 0.21
Ni–P–TiO2/5 nm–0.5 g/L 1.98 ± 0.13 32.18 ± 2.95 3.97 ± 0.27 2.12 ± 0.06
Ni–P–TiO2/5 nm–2.0 g/L 1.12 ± 0.17 31.32 ± 2.99 2.24 ± 0.25 2.45 ± 0.17
Ni–P–TiO2/100 nm–0.5 g/L 1.70 ± 0.10 31.90 ± 2.92 3.40 ± 0.20 1.95 ± 0.28
Ni–P–TiO2/100 nm–2.0 g/L 0.82 ± 0.11 31.02 ± 2.93 1.64 ± 0.21 2.09 ± 0.26
Int J Adv Manuf Technol (2019) 105:1745–1756 1749

Fig. 3 Scanning electron micrographs (secondary electrons) and EDX spectra of the surface of Ni–P (a, b) and Ni–P/Ni–P–TiO2: 5 nm–0.5 g/L (c, d) and
5 nm–2.0 g/L (e, f)

and size of the agglomerates present at low concentration
(Fig. 3c). On the other hand, the formation of porosities is also
observed with the increase in the concentration of TiO2. This
behavior is observed in superficial (Fig. 4 a and b) and cross-
section images (Fig. 4 c and d). The total thickness of the
coatings is between 27 and 35 μm. The pores (indicated by
black arrows) have diameters between 0.5 to 2.0 μm and are
caused by the high catalytic activity of the nanoparticles, caus-
ing greater production of hydrogen. With the growth of the
coating, the hydrogen bubbles are trapped and when they
break or are released from the surface, pores are generated
[28, 29].
1750 Int J Adv Manuf Technol (2019) 105:1745–1756

Fig. 4 Scanning electron micrographs (secondary electrons) of the surface of the Ni–P–TiO2 coatings and cross-sections (backscattered electrons) of the
specimens with 5 nm–2.0 g/L (a, c) and 100 nm–2.0 g/L (b, d). Pores are indicated by black arrows

3.2 Hardness and elastic modulus
Figure 5 shows the values of hardness and elastic modulus for
AZ91D magnesium alloy [30]: Ni–P and Ni–P/Ni–P–TiO2 coat-
ings. The hardness values (Fig. 5a) for the coating with a particle
size of 5 nm, in both concentrations, are similar to the hardness
presented by the Ni–P coating without nanoparticles, indicating
that addition of TiO2 with a size of 5 nm does not represent a
significant increase in these properties. In the case of coatings co-
deposited with nanoparticles of 100 nm, for both concentrations,
hardness increases if compared with that of Ni–P coatings.
However, a decrease in hardness is observed with the increase
in the concentration of nanoparticles, from 19.68 GPa for the
higher concentration to 16.87 GPa for the lower concentration.
This decrease in hardness could be due to defects such as poros-
ities, as evidenced previously in Fig. 4, where it is possible to

Fig. 5 Nanoindentation results in coated samples and reference values for AZ91D alloy [30]: (a) nanoindentation hardness and (b) elastic modulus
Int J Adv Manuf Technol (2019) 105:1745–1756 1751

Fig. 6 Friction coefficient register vs. time for Ni–P (a) and Ni–P/Ni–P–TiO2 coatings with different sizes of nanoparticles: 5 nm (b) and 100 nm (c)

determine that the presence of porosities increases with the in- values closed to 820 HV (8 GPa approx.), while Chen et al. [22]
crease in the concentration of nanoparticles. Hardness values found values closed to 720 HV (7 GPa approx.) and 1025
obtained here are higher than those reported for Ni–P–TiO2 coat- (10 GPa approx.) for two different techniques for obtaining
ings on magnesium alloys. Georgiza et al. [18] found hardness coatings.

Fig. 7 Variation of a friction coefficient and b wear rate with concentration and size of TiO2 nanoparticles
1752
Fig. 8 SEM images (secondary
electrons) of wear tracks and
worn surfaces observed after dry
sliding wear test of Ni–P (a, b),
Ni–P–TiO2: 100 nm–0.5 g/L (c,
d), and Ni–P–TiO2: 100 nm–
2.0 g/L (e, f). White arrows
indicate the sliding direction
Regarding the behavior of the elastic modulus (Fig. 5b), a
decrease in the values obtained for Ni–P/Ni–P–TiO2 coatings
is observed if compared with those obtained for Ni–P coatings
without TiO2. The co-deposition of TiO2 nanoparticles could
reduce the percentage of phosphorus incorporated in the coat-
ing. In Ni–P coatings without TiO2 co-deposition, the higher
the phosphorus content, the greater the size of nickel
nanocrystals, which increases Young’s modulus [31].
However, it is known that the growth of nickel nanocrystals
is affected by the co-deposition of nanoparticles, achieving a
more refined matrix, with smaller nanocrystals, and producing
a decrease in the elastic modulus [32].
3.3 Friction coefficient
Figure 6 shows some typical records selected for the evolution
of the friction coefficient regarding time during dry sliding
wear tests for AZ91D magnesium alloy, Ni–P and Ni–P/Ni–
Int J Adv Manuf Technol (2019) 105:1745–1756
P–TiO2 coatings. The friction coefficient registers for the sub-
strate show a high fluctuation between 0.47 and 0.19 (Fig. 6a),
indicating constant and progressive wear of the material; how-
ever, these fluctuations occur around a stable friction coeffi-
cient value. At the beginning of the test, a remarkable change
in the friction coefficient is observed, because at this stage, the
roughness is reduced and some oxide layers or contamination
on the surface are removed. The friction coefficients reach
stable values after the accommodation of the tribological sur-
faces, which is observed around 20 s after the start of the test
for AZ91D, Ni–P, and Ni–P–TiO2 (5 nm), and around 600 s
for Ni–P–TiO2 (100 nm). On the other hand, for Ni–P and Ni–
P/Ni–P–TiO2 coatings, constant and stable records over time
are observed. The behavior of coatings co-deposited with
nanoparticles of titanium dioxide is similar for both sizes (5
and 100 nm). According to friction records (Fig. 6 b and c),
the higher the concentration of nanoparticles, the higher the
friction coefficient. The above can be related to the roughness
Int J Adv Manuf Technol (2019) 105:1745–1756
Fig. 9 SEM image (backscattered electrons) and EDX analyses of the wear track on electroless coatings Ni–P–TiO2 with 100 nm–2.0 g/L
of the coatings (Table 3), whose higher values can be associ-
ated with the high agglomeration of nanoparticles, as evidence
in Fig. 3. In conditions as those evaluated here, without lubri-
cation, roughness is an undesirable property because it allows
the increase of friction and wear [18, 33].
Figure 7 shows the average value of the friction coefficient
in steady state (Fig. 7a) and the wear rate (Fig. 7b), with their
respective standard deviation of the measurements obtained in
1753
triplicate of the electroless Ni–P and Ni–P/Ni–P–TiO2 coat-
ings, for the two concentration levels (0.5 and 2.0 g/L) and
sizes (5 and 100 nm) of nanoparticles. Additional tribological
test was carried out on Ni–P/Ni–P–TiO2 coatings including a
third concentration level (1.25 g/L) and 40-nm size in order to
observe the tribological behavior for an intermediate value. It
is observed that the intermediate levels in size and concentra-
tion of nanoparticles follow a linear behavior and this
1754
Fig. 10 Raman spectrum of debris on the wear track
behavior is represented by the trend lines and their respective
equation.
In the case of the magnesium alloy AZ91D, the wear rate is
6.37 × 10−9 kg/Nm and the friction coefficient is 0.33. In con-
trast, the Ni–P coatings exhibit values on the scale of 10−11 kg/
Nm which means a reduction of three orders of magnitude in
the rate of wear, with a friction coefficient of 0.29. However,
better behavior is observed at the lower level of concentration
of nanoparticles (0.5 g/L) and with the increase in concentra-
tion, an increase in the wear rate is observed. This behavior
may be due to the fact that nanoparticles are not co-deposited
as individual particles but as agglomerates are deposited.
These agglomerates, in contact with the alumina sphere, are
released in small quantities and, progressively, changing the
wear regime.
Regarding the variation in the wear rate and the friction coef-
ficient with respect to the size of nanoparticles, the same effect is
observed: increasing the size of the nanoparticles produces an
increase in both response variables. For higher sizes of nanopar-
ticles, the third bodies generated in dry sliding tests are larger,
which produces more severe wear conditions on the surfaces and
the friction coefficient increases. The best tribological behavior in
terms of the studied variables occurs with the combination of the
lower levels in size and concentration (5 nm and 0.5 g/L), where
the wear rate and the friction coefficient is 0.92 × 10−11 kg/Nm
and 0.21, respectively. For the higher levels of size and concen-
tration (100 nm and 2.0 g/L), values of 5.1 × 10−11 kg/Nm in the
wear rate and 0.42 in the friction coefficient are obtained, which
indicates that the wear rate is five times greater than that regis-
tered in the coating with smaller size and lower concentration of
particles, while the friction coefficient is twice as high. Therefore,
the addition of particles does not always provide a better tribo-
logical behavior of the system, since the mechanism of wear
between the surfaces can change into three bodies, which in-
creases the wear rate and the friction coefficient.
Int J Adv Manuf Technol (2019) 105:1745–1756
Figure 8 shows the wear tracks obtained after the tribolog-
ical tests. The first column of images shows the inside of the
tracks (Fig. 8a–e), while the second column (Fig. 8b–f) shows
the edge of the tracks. White arrows indicate the sliding
direction.
For the Ni–P electroless coating without nanoparticles (Fig. 8 a
and b), it is possible to observe a high plastic deformation of the
nodules, manifested in a severe flattening, while at the edge of the
track (Fig. 8b), a high accumulation of debris is observed, as a
product of the contact between the coating and the alumina sphere.
This behavior is also evidenced in the other coatings. However, in
the coating obtained with a nanoparticle size of 100 nm and a
concentration of 0.5 g/L (Fig. 8c and d), a less severe plastic
deformation is observed. This can be explained because the coat-
ing obtained under these conditions has a higher hardness, close to
19.68 GPa, which would hinder the plastic deformation of the
nodules. On the other hand, with the increase in the size and
concentration of the nanoparticles, the appearance of grooves
and micro-cuts in the wear track is observed (Fig. 8e). The above
would be related to the presence of agglomerates of TiO2 nano-
particles and the formation of hard particles, going from a two-
body regime to abrasive wear with three bodies, which is more
aggressive and generates an increase in both the wear rate and the
friction coefficient. Makkar et al. [34] identified adhesive mecha-
nisms in Ni–P–TiO2 coatings obtained at basic pH and with co-
deposition of irregular nanoparticles between 33 and 45 nm,
achieving a reduction of wear rates and friction coefficients in
comparison with Ni–P coatings without nanoparticles.
SEM image (backscattered electrons) and EDX analyses of the
wear track on the different conditions of size and concentration of
TiO2 nanoparticles showed similar behavior. The elemental map-
ping analysis of the wear track (Fig. 9), corresponding of the higher
condition (100 nm–2.0 g/L) is representative and indicates the
presence of oxygen in the places occupied by the debris (dark
areas), which would suggest the formation of oxides, coming from
processes of tribo-oxidation [35]. On the wear track, agglomerates
of titanium dioxide nanoparticles (indicated by black arrows), re-
sponsible for abrasion grooves, were also identified.
When analyzing by micro-Raman spectroscopy, the debris
of the wear track located in the dark areas, where a greater
concentration of oxygen was identified, the formation of nick-
el oxides on the surface of the tribological traces is evidenced.
The Raman spectrum is shown in Fig. 10 presents two vibra-
tional bands centered on the displacements of 550 and
1095 cm−1, characteristics of the nickel oxides, which would
confirm the existence of tribo-oxidation phenomena [36].
4 Conclusions
The incorporation of TiO2 nanoparticles improves the tribo-
logical properties of Ni–P coatings obtained on AZ91D alloy
by a chromium-free process. Better performance occurs in low
Int J Adv Manuf Technol (2019) 105:1745–1756
levels of concentration and size of nanoparticles (0.5 g/L and
5 nm). These conditions allow obtaining homogenous coat-
ings with low presence of agglomerates and porosities.
Regarding the high levels of size and concentration, an in-
crease in the friction coefficient and the wear rate is observed,
due to the increase in the number of defects and agglomerates
of TiO2 nanoparticles. Finally, the tribological tracks show
different wear phenomena ranging from the flattening of the
nodules to abrasive wear to three bodies, accompanied by
tribo-oxidation, evidenced by the formation of nickel oxides
on the surface of the tribological tracks.
Acknowledgments The authors are grateful to “Departamento
Administrativo de Ciencia, Tecnología e Innovación–COLCIENCIAS
(project 1115-715-51447, contract No. 284-2016),” “Centro de
Investigación para el Desarrollo y la Innovación (CIDI)” from the
Universidad Pontificia Bolivariana through UPB-Innova Rad: 742B-03/
17-35, and Universidad de Antioquia (2015-4964).
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