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Mat.-wiss. u. Werkstofftech. 2017, 48, 785–791 DOI 10.1002/mawe.

201700017 785

Abrasion and erosion wear of electrodeposited nickel -


silicon carbide nanocomposite coatings
Abrasiv- und Erosionsverschleiß von galvanisch Nickel -
Siliciumkarbid Nanokomposit-Beschichtungen

V. Alar1, I. Žmak1, I. Stojanović1, V. Šimunović1, Z. Čeralinac2

A nickel matrix with silicon carbide nanoparticles composite coating is prepared by


electrodeposition on non-alloyed steel, assisted with an ultrasonic treatment of the
galvanic bath. The abrasion and erosion wear resistance of the coating is de-
termined, as well as its micro-hardness. The structure and the composition of the
nickel nanocomposite coating is defined using scanning electron microscopy and
energy-dispersive X-ray spectroscopy. The corrosion behavior is investigated by
the potentiodynamic polarization methods in the 3.5 wt% sodium chloride solution.
The results show improved mechanical properties, wear and corrosion resistance
as compared to the nickel metallic coating.

Keywords: Nickel nanocomposite coating / silicon carbide nanoparticles /


electrodeposition / wear resistance / ultrasound treatment

Eine Nickelmatrix mit Siliciumkarbid-Nanopartikel Komposit-Beschichtung wurde


durch galvanische Abscheidung auf unlegiertem Stahl hergestellt. Die galvanische
Abscheidung ist durch eine Ultraschallbehandlung des galvanischen Bades unter-
stützt. Abrasiv- und Erosionsverschleißfestigkeit sowie Mikrohärte der Beschich-
tung wurden bestimmt. Struktur und Zusammensetzung der Nickel-Nanokomposit-
Beschichtung wurden unter Verwendung von Rasterelektronenmikroskopie und
energiedispersiver Röntgenspektroskopie untersucht. Das Korrosionsverhalten
wurde durch potenziodynamische Polarisationsverfahren in 3,5 Gew% Natrium-
chlorid-Lösung untersucht. Die Ergebnisse zeigen verbesserte mechanische Ei-
genschaften, Verschleiß- und Korrosionsbeständigkeit im Vergleich zur Nickel-Me-
tallbeschichtung.

Schlüsselwörter: Nickel-Nanokomposit-Beschichtung / Siliciumkarbid-Nanopartikel /


elektrochemische Abscheidung / Verschleißfestigkeit / Ultraschall-Behandlung

1 Introduction One of the most dangerous consequences of such


impacts is the corrosion, which initially causes the
Steel constructions and products are exposed to var- deterioration on the outer surfaces, subsequently
ious impacts from the surrounding environment. reaches the interior and can permanently damage a

1 University of Zagreb, Faculty of Mechanical Engi-


neering and Naval Architecture, I. Lučića 5, HR- Corresponding author: I. Žmak, University of Zagreb,
10000 Zagreb, Croatia Faculty of Mechanical Engineering and Naval Architec-
2 Končar Electrical Engineering Institute, Fallerovo ture, I. Lučića 5, HR-10000 Zagreb, Croatia,
šetalište 22, HR-10000 Zagreb, Croatia E-Mail: irena.zmak@fsb.hr

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certain product or a construction. The abrasion and (45 g L-1), boric acid (30 g L-1) and sodium dodecyl
erosion wear from the mechanical interaction be- sulphate (2 g L-1) [4]. The process parameters for
tween the components or fluids also contributes to the application of the nanocomposite coating were
the deterioration of various steel products. The need as follows: current density (j = 2 A dm-2), temper-
for the corrosion protection systems with an in- ature (T = 45 8C), pH value (pH = 4.5) and deposi-
creased wear resistance is therefore very important tion time (t = 30 min).
from the aspect of prolonging the durability of Nanoparticles of the silicon carbide, provided by
many steel applications. NaBond Technologies, Shenzhen, China were used
The development of the nanotechnology has during the nickel electrodeposition process. Three
opened new possibilities to produce coatings which different samples were prepared with 20 g L-1,
offer much better surface protection and increase 30 g L-1 and 40 g L-1 concentrations of the nano-
the durability of the steel products. One of the mate- particles in the electrolyte solution. The silicon car-
rials with improved properties is the nanocomposite bide particles had a spherical shape with the average
coating based on the metal matrix with embedded particle size of 50 nm, according to the manu-
nanoparticles of various dimensions and forms. The facturer’s specifications. Before the nanocomposite
embedded nanoparticles change the microstructure electrodeposition process was started, the silicon
of the metallic coating through the electrodeposition carbide nanoparticles were dissolved in the electro-
process, which results in nanostructured coatings. lyte solution with an ultrasonic probe. The ultra-
Such nanostructured coatings are more compact, sound was used in order to prevent the agglomer-
and thus more resistant to negative environmental ation and improve the dispersion of the silicon
impacts. The most prevailing metal coating in the carbide nanoparticles, which as a result should lead
industry is certainly the nickel coating. Nickel coat- to improved mechanical and protective properties of
ing was also used in this paper as the metal matrix the nanocomposite coating. It is expected that the
for the embedding of the silicon carbide nano- ultrasonic treatment should eliminate the pores and
particles, as well as in other recently published re- voids produced on the substrate surface by the hy-
search work [1-3]. This paper investigates the im- drogen evolution during the electrodeposition proc-
pact of the various concentrations of the silicon ess.
carbide nanoparticles onto the wear and corrosion During the electrodeposition process the silicon
resistance. As a novelty, the ultrasonic treatment of carbide nanoparticles are deposited on the cathode
the galvanic bath was applied during both the sus- together with the nickel ions. Thus, silicon carbide
pension preparation and the deposition process. nanoparticles are embedded in the crystal structure
of the nickel coating which results in a nano-
composite coating [5].
2 Preparation of the nickel nanocomposite
coating
3 Methods for determining the nickel
The nickel nanocomposite coating was prepared by nanocomposite coating properties
the electrodeposition process or electroplating. A
non-alloyed cold-bent steel plate was used as a base The structural analysis of the prepared nano-
for the coating. The dimensions of the steel plate composite coating was conducted with the surface
were 60 mm length, 20 mm width and 8 mm thick- analysis techniques, such as the scanning electron
ness, with a total surface area of 1200 mm2 to be microscopy and the energy-dispersive X-ray spec-
coated. Before the application of the nanocomposite troscopy on the electronic microscope VEGA TES-
coating, the sample surface was sanded with 600-, CAN TS 5136 MM equipped with the INCA soft-
800- and 1000-grit sandpaper and polished with the ware from Oxford Instruments.
suspension of 1 mm aluminium oxide particles. The The mechanical properties of the nickel nano-
sample surface was degreased in an ultrasonic bath composite coating were determined with the Knoop
of ethyl alcohol for five minutes. The electrolyte micro-hardness test and by measuring the abrasion
solution was defined according to Watts bath type, and erosion resistance. The Knoop micro-hardness
as: nickel sulphate (240 g L-1), nickel chloride test was conducted according to the EN ISO

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4516:2003 international standard with the micro- 4 Results and discussion


hardness tester TUKON TESTER Model FB WIL-
SON. The structural classification of the nickel nano-
The abrasion resistance was measured by the composite coating, conducted with the physical-sur-
standard dry sand/rubber wheel method, according face instrumental methods (the scanning electron
to the ASTM G65-94 international standard. The microscopy and the energy-dispersive X-ray spec-
OTAWA AFS 50/70 quartz sand of 300 mm and troscopy), provided the information on the quantity
1200 HV0.03 was used as the abrasive. The sam- and the allocation of the nanoparticles, as well as on
ples were loaded with 45 N force, and 500 wheel the structure and composition of the nanocomposite
turns in 100-turn steps were applied. The nano- coating. Scanning electron microscopy images of
composite coating mass loss due to the abrasive the nickel coating and nanocomposite coatings
wear was determined by weighing the sample be- show that the embedding of solid silicon carbide
fore and after the testing using the METTLER B5C nanoparticles in the nickel metal matrix has caused
1000 balance. The mass loss of the nanocomposite a change in the microstructure of the nanocomposite
coating was used as a measure of the abrasion wear coating in comparison to the nickel coating, Figure
resistance. 1. With the increase of the weight content of the sil-
The particle erosion resistance was tested by icon carbide particles, the microstructure of the
high speed rotation of the samples, which collide nanocomposite coating becomes more granular. The
with the abrasive particles of dry sand. Dry 300 mm silicon carbide particles act as the nucleation sites
OTAWA AFS 50/70 quartz sand of 1200 HV0.03 for the nickel deposition which results in a sig-
flowed freely from a tank through the nozzle. The nificant change in the size of the nickel crystal de-
sand entry angle was 908, which exposed the coat- posited on the nanocomposite coating [6].
ings to the highest erosion level. The erosion resist-
ance was determined with 20,000 pivot turns. The
impact of the sand onto the specimens leads to the
erosion wear on the surface hit by the sand par-
ticles. The nanocomposite coating mass loss was
determined by weighing the sample before and after
the testing, i. e. the mass loss of the nanocomposite
coating was used as a measure for the erosion wear
resistance.
The electrochemical measurements were also
performed. The polarization measurements were
conducted using the EG&G Model 273 Potentiostat/
Galvanostat with the SoftCorr III application, ac-
cording to the ASTM G61 standard test method.
Three electrode cells contained 600 mL of 3.5 wt%
sodium chloride solutions at room temperature. The
coated specimens were used as the working elec-
trode. Two graphite electrodes and one saturated
calomel electrode (SCE) were used as the counter
and the reference electrodes, respectively. The cor-
rosion potential (Ecorr), corrosion current density
(jcorr) and polarization resistance (Rp) were de- Figure 1. Scanning electron microscopy images of the nickel
termined from the polarization curves. coating (a); nickel nanocomposite coatings with 20 g L-1 (b);
30 g L-1 (c); and 40 g L-1 (d) silicon carbide particles in the elec-
trolyte solution.
Bild 1. Rasterelektronenmikroskopie-Bilder der Nickel-
schicht (a); Nickel Nanokomposit-Beschichtungen mit
20 g L-1 (b); 30 g L-1 (c); und 40 g L-1 (d) Siliciumkarbid-Teil-
chen in der Elektrolytlösung.

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The energy-dispersive X-ray spectroscopy mi- of the silicon carbide nanoparticles had a maximum
cro-images of the nickel nanocomposite coatings value of 1 wt% in the nanocomposite coating pre-
were taken by mapping 20 mm 3 20 mm sample sur- pared from the electrolyte solution with a 40 g L-1
face, in order to determine the composition of the concentration of the silicon carbide nanoparticles. In
nanocomposite coatings, Figure 2. Based on these addition, the energy-dispersive X-ray spectroscopy
results, it can be concluded that the increase in the micro-images clearly show that the silicon carbide
concentration of the silicon carbide nanoparticles in nanoparticles are well distributed over the entire
the electrolyte solution leads to an increase in the surface of the nanocomposite coating, and there
weight content of the silicon carbide nanoparticles isn’t any agglomeration of the nanoparticles.
in the nanocomposite coating. The weight content The Knoop micro-hardness test of the nickel
coating and silicon carbide nanocomposite coatings
was conducted under the load of 0.1 3 9.81 N for 15
seconds, Table 1. The results show that the nano-
composite coatings have higher micro-hardness val-
ues than the nickel coatings. The nanocomposite
coating prepared from the electrolyte solution with
the 40 g L-1 concentration of the silicon carbide
nanoparticles had the highest micro-hardness value
(HK0.1 = 832). The increase in the micro-hardness
of the nanocomposite coating can be ascribed to the
presence of the intrinsic hardness of the co-de-
posited ceramic phase, i.e. nano-sized silicon car-
bide, and to the fact that the ceramic phase is well
dissolved in the nickel metal matrix, which leads to
the enhancement of the nanocomposite coating mi-
crostructure [7]. Therefore, the increase in the con-
tent of the extremely hard silicon carbide nano-
particles contributes to the increase of the
nanocomposite coating hardness.
The increase of the silicon carbide nanoparticles
concentration in the electrolyte solution resulted
also in an increase of the nanocomposite coating
abrasion resistance, Figure 3. The greatest weight
loss (Dm = 60.6 mg) was observed on the nickel
coating, and the smallest (Dm = 29.7 mg) on the
nanocomposite coating prepared from the electro-
lyte solution with 40 g L-1 silicon carbide.
The increase of the silicon carbide nanoparticles
concentration in the electrolyte solution resulted in
an increase of the nanocomposite coating erosion
resistance as well, Figure 4. The worst erosion re-
Figure 2. Energy-dispersive X-ray spectroscopy analysis sistance (Dm = 17.3 mg) was observed on the nickel
and mapping of micro-images of the nickel nanocomposite coating and the best erosion resistance (Dm = 5.6
coating with: 20 g L-1 (a), 30 g L-1 (b) and 40 g L-1 (c) concen- mg) on the nanocomposite coating prepared from
trations of the silicon carbide particles in the electrolyte solu- the electrolyte solution with 40 g L-1 silicon carbide.
tion.
Homogenously allocated nano-sized silicon carbide
Bild 2. Energiedispersive Röntgenspektroskopie-Analyse
und Kartierung von Mikrobildern der Nickel Nanokomposit-
in the nickel matrix, with the microstructural mod-
Beschichtung mit: 20 g L-1 (a), 30 g L-1 (b) und 40 g L-1 (c) ifications of the nanocomposite coating formed dur-
Konzentrationen der Siliciumkarbid-Partikel in die Elektrolyt- ing the co-deposition of the silicon carbide nano-
lösung. particles with the nickel ions contribute to an

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Table 1. Knoop micro-hardness of the nickel- and nanocomposite coatings.


Tabelle 1. Knoop-Mikrohärte von Nickel- und Nanokomposit-Beschichtungen.

Coating type Concentration of the silicon carbide nanoparticles in the elec- Knoop micro-hard-
trolyte solution [g L-1] ness, HK0.1
Nickel coating - 562
Nanocomposite 20 649
coating
Nanocomposite 30 721
coating
Nanocomposite 40 832
coating

The pure presence of the silicon carbide nano-


particles is not enough to improve the corrosion re-
sistance, but a uniform particle dispersion is also es-
sential. The potentiodynamic polarization curves
were recorded for pure nickel and the nickel – sili-
con carbide nanocomposite coatings in 3.5 wt% so-
dium chloride solution, Figure 5. For each speci-
men following corrosion parameters were
determined: corrosion potential (Ecorr), polarization
resistance (Rp) and corrosion current density (jcorr),
Table 2. The increase in the amount of the co-de-
posited silicon carbide nanoparticles in the nickel
Figure 3. Abrasion resistance of the nickel- and nano-
composite coatings.
matrix improves the steel corrosion resistance in salt
solutions. The silicon carbide nanoparticles play a
Bild 3. Abriebbeständigkeit der Nickel- und Nanokomposit-
Beschichtungen. major role in improving the corrosion protection by
two mechanisms. Firstly, the silicon carbide nano-
particles act as an inert physical barrier to the ini-
tiation and development of the defects, modifying
the microstructure of the nickel layer, and hence im-

Figure 4. Erosion resistance of the nickel- and nanocompo-


site coatings.
Bild 4. Erosionbeständigkeit der Nickel- und Nanokomposit-
Beschichtungen.
Figure 5. Potentiodynamic polarization curves of nickel- and
nanocomposite coatings.
increase in the abrasion and erosion resistance of Bild 5. Potenziodynamische Polarisationskurven von Nickel-
the nickel nanocomposite coating [8]. und Nanokomposit-Beschichtungen.

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Table 2. Potentiodynamic polarization corrosion parameters for nickel coating and nickel - silicon carbide nanocompo-
site coatings in 3.5 wt% sodium chloride solution.
Tabelle 2. Potenziodynamische Polarisationsmessungen von Nickel-Beschichtung und Ni-SiC-Nanokomposit-Be-
schichtungen in 3,5 Gew.% Natriumchlorid-Lösung.

Coating type Corrosion potential, Ecorr Polarization resistance, Corrosion current density,
[mV (SCE)] Rp [kW cm2] jcorr [mA cm-2]
Pure nickel -459 1.53 65.19
Nickel + 20 g L-1 sili- -375 15.07 45.29
concarbide
Nickel + 30 g L-1 sili- -372 45.73 8.67
concarbide
Nickel + 40 g L-1 sili- -312 50.51 1.38
concarbide

proving the corrosion resistance of the coating. Sec- ution with 40 g L-1 silicon carbide. Also, by increas-
ondly, the dispersion of the silicon carbide nano- ing silicon carbide content in the coating, the
particles in the nickel layer results in the formation corrosion current density decreased and the corro-
of many corrosion microcells in which the silicon sion potential shifted towards more positive poten-
carbide nanoparticles act as a cathode and the nickel tials, which was determined through the potentiody-
as an anode, since the standard potential of the sili- namic polarization method in 3.5 wt% sodium
con carbide is more positive than that of the nickel. chloride solutions.
Such corrosion microcells could facilitate the anodic The increase in hardness and wear resistance
polarization [9, 10]. Therefore, the presence of the of the nanocomposite coating with reference to
silicon carbide inhibits the localized corrosion, and the nickel coating can be ascribed firstly to the
mainly the homogeneous uniform corrosion occurs. presence of the co-deposited ceramic phase, i.e.
hard silicon carbide nanoparticles. Secondly,
nano-sized silicon carbide is well dissolved in the
5 Conclusion nickel metal matrix, which leads to the enhance-
ment of the microstructure through the formation
The use of the physical-surface methods (the scan- of the nanocrystalline nickel, and thus a more
ning electron microscopy and the energy-dispersive compact coating structure. The refined micro-
X-ray spectroscopy) and tribological methods (mi- structure of the composite coatings correspond-
cro-hardness, abrasion and erosion resistance) de- ingly increased the wear resistance. In order to
termined the composition, structure, mechanical and enhance wear and corrosion resistance of a nano-
tribological properties of the electrodeposited nickel composite coating it is very important to deposit
– silicon carbide nanocomposite coatings. The re- it pore-free. This paper has demonstrated that the
sults indicate enhanced wear resistance of the nickel ultrasound treatment allows a successful applica-
nanocomposite coatings with reference to the nickel tion of high-quality and highly protective nano-
metallic coating. The use of the ultrasound during composite coatings.
electroplating of the nanocomposite nickel coating
improved the film properties by refining the micro-
structure and thus leading to a harder and more
compact coating layer. Ultrasonic treatment im- 6 References
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