Engineering Science and Technology, an International Journal 24 (2021) 533–542

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Engineering Science and Technology,

an International Journal
journal homepage: www.elsevier.com/locate/jestch

Full Length Article

The influence of chromium content on wear and corrosion behavior

of surface alloyed steel with Fe(16
x)Crx(B,C)4 electrode
Engin Kocaman a,⇑, Bülent Kılınç b, Mustafa Durmaz c, Sß aduman Sß en c, Uğur Sß en c
a
Zonguldak Bulent Ecevit University, Faculty of Engineering, Department of Metallurgical and Materials Engineering, Zonguldak 67100, Turkey
b
Sakarya University of Applied Sciences, Vocational School of Arifiye, Machine and Metal Program, Sakarya 54800, Turkey
c
Sakarya University, Faculty of Engineering, Department of Metallurgical and Materials Engineering, Sakarya 54100, Turkey

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

Article history: In this study, the electrodes containing Fe(16
X)CrX(B,C)4 (X = 3,4,5) were used for surface alloying on an
Received 4 May 2020 AISI 1010 steel substrate. The alloy structure of the coating exhibits in-situ composite structure with a
Revised 1 August 2020 large amount of reinforcing carbides and borides phases as to be hypoeutectic and hypereutectic struc-
Accepted 6 August 2020
ture in the surface alloyed layer. The obtained composition of the alloy shows that it contains much more
Available online 29 August 2020
interstitial hard phases in the alloyed layer than the conventional hardfacing alloys used in the industrial
applications for the hardfacing of the steels. The morphological and microstructural properties showed
Keywords:
that layer microstructure changed from hypoeutectic to hypereutectic structure with an increase in chro-
Hardfacing
Surface alloying
mium content. The results of these studies revealed that the microstructure of hardfacing layers consists
Hardness of interstitial phases of a(Fe-Cr) and (Fe,Cr)23(C,B)6 as major phases, (Fe,Cr)2(C,B) and (Fe,Cr)7(C,B)3 as
Wear minor phases in the in-situ composite structure. The composite hardness’ in the alloyed surface layers
Corrosion of the Fe(16
X)CrX(B,C)4 alloys ranged from 711 HV to 1164.3 HV. Wear test against alumina ball shows
that the friction coefficients of the surface alloyed layers decreased with increase in applied loads and
decrease in chromium content in the Fe(16
X)CrX(B,C)4 alloy composition. Coefficient of friction ranged
from 0.55 to 0.79 in the present study. Wear rates of the surface alloyed steels caused to increase with
decrease in chromium content and increase in applied loads. The wear rates of the alloyed layer changed
between 3.07  10 and 5 mm3/m and 6.95  10
5 mm3/m. The corrosion resistance of the alloyed layers
was measured by a potentiostatic polarization test. Icorr and Ecorr of the coated layers changed from 1.813
to 9.965 mA/cm2 and
704.786 to
745.792 mV, depending on alloyed layer compositions. With increas-
ing chromium content, the corrosion resistance of the coating layer has changed in a nobler side.
Ó 2020 Karabuk University. Publishing services by Elsevier B.V. This is an open access article under the CC
BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction technology due to its economically and higher deposition rate

compared with the others. Many welding methods such as
The need for machine parts used in aggressive working condi- shielded manual arc welding (SMAW) [3], submerged arc welding
tions is increasing day by day in the modern world. Parts working (SAW) [4], gas tungsten arc welding (GTAW) [5], plasma trans-
under these conditions are exposed to surface losses with wear and ferred arc welding (PTA) [6], flux cored arc welding (FCAW) [7].
corrosion. Since the replacement of these parts will cause high Laser metal deposition (LMD) [8] processes are mostly used for
operating costs, service times can be extended with a suitable coat- surface alloying treatment. However, among all these methods
ing process on the part surface. Today, many methods, such as SMAW is come forward from the others because of its higher
thermal spray, cladding, and welding, are used in the surface coat- mobility and deposition rate along with economical benefits. Also,
ing processes of machine parts. Various surface alloys can be an increasing number of hardfacing alloys can be applied using the
coated on to an appropriate substrate using thermal spraying, SMAW method in the industry.
cladding, and welding techniques [1,2]. However, welding is key In many industrial applications, iron-chromium-carbon based
electrodes are used to increase the surface hardness, wear, and cor-
rosion resistance of the steels. On the surfaces covered with elec-
⇑ Corresponding author at: Zonguldak Bulent Ecevit University, Faculty of
Engineering, Department of Metallurgical and Materials Engineering, Zonguldak
trodes with this composition, structures such as hypoeutectic,
67100, Turkey (E. Kocaman). eutectic, and hypereutectic are obtained according to the electrode
E-mail address: [email protected] (E. Kocaman). composition [9,10]. The properties of coating vary depending on
Peer review under responsibility of Karabuk University. factors such as the amount, distribution, and morphology of the

https://doi.org/10.1016/j.jestch.2020.08.003
2215-0986/Ó 2020 Karabuk University. Publishing services by Elsevier B.V.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
534 E. Kocaman et al. / Engineering Science and Technology, an International Journal 24 (2021) 533–542

hard carbides of the transition metals such as MC, M2C, M3C, M7C3, the surface alloying treatment were 70 mm in length, 30 mm in
and M23C6 formed in-situ in the structure [11–13]. It is also known width, and 8 mm in thickness. The deposition was carried out in
that chromium is a strong boride forming element. Additionally, a the flat position; the current and travel speed was fixed in all tests.
small amount of boron in the Fe-Cr system causes the stabile bor- In order to reduce the effect of dilution, the hardfacing bead was
ides of transition metals such as MB, M2B, M5B3, MB4 can form [14– deposited as two layers; the total thickness of the hardfacing layer
16]. In the case of carbon and boron in the hard surface alloy com- was about 4–6 mm. The welding parameters were as follows: the
position at the same time, the alloy structure shows the in-situ welding current is 120–130 A, arc voltage is 20–25 V, and the tra-
composite structure, including the ductile a-phase and the hard vel speed is 25–30 cm/min.
phases of carbides and borides of transition metals. The Microstructures were observed with scanning electron micro-
microstructure can exhibit hypoeutectic (a-eutectic(a + Mx(C,B)), scopy (SEM) (JEOL-JSM-6060). The phase analysis of the hardfacing
eutectic (a-Mx(C,B)) and hypereutectic (eutectic(a + Mx(C, layer formed on the steel substrate was determined by X-ray
B) + Mx(C,B) blocky phase) microstructures. The alloyed layer, diffraction analysis with Cu-Ka radiation; the compositions of the
including these microstructures, plays a crucial role in the wear formed phases in the alloyed layers were investigated using elec-
and corrosion resistance of the alloyed layers [17,18]. tron dispersive spectroscopy (EDS). The hardness of the seam sec-
Both manufacturers and researchers have been developing spe- tion was measured with Vickers-Hardness (Future-Tech FM 700) at
cialized welding electrodes for industrial applications. Fe-Cr-C 0.5 mm intervals from the substrate material to the top of coating.
alloys are very popular with the use of other welding methods. All the samples were cut from cross-section and grinded with
However, there are limited researches on Fe(16-X)CrX(B, emery papers up to 1200 grid and polished with 0.3 mm Alumina
C)4(X = 3,4,5) coatings produced by shielded manual arc welding paste. Ultrasonically cleaned samples with ethyl alcohol was
(SMAW). In this paper, Fe-Cr-B-C based hardfacing electrodes con- etched with 3%Nital solution before the microstructural
taining various amounts of chromium and boron along with carbon examinations.
were developed by SMAW, and their microstructural observation Ball-on-disk reciprocal wear test was carried out in dry sliding
and corrosion behaviors were investigated. conditions at room temperature using a friction and wear tester
_
(TRIBOtechnic-TRIBOtester). The ball material of the wear couple
2. Experimental was Al2O3 (1850 HV0.1). The diameter of the alumina ball was
10 mm. The tested specimens were machined to block with the
Three types of electrodes were prepared and used as hardfacing size of 50 mm  30 mm  10 mm. The wear conditions were a nor-
alloys in the SMAW process. The electrodes were coated with dif- mal loads of 2 N, 5 N and 8 N with a sliding speed of 30 mm.s
1 and
ferent compositions of the powder mixtures of ferrous chromium a sliding distance of 200 m.
containing high carbon (Fe–Cr (HC)), ferrous boron (Fe–B), and The wear volume was calculated using Eq. (1)
Armco iron powders together with fluxes. Rutile (TiO2), calcium
V ¼ A:l ð1Þ
carbonate (CaCO3), calcium fluoride (CaF2), silica (SiO2), alumina
(Al2O3), and some additives like K-alginate and potassium silicate where l is the track line formed on the worn surface (mm) and A is
(K2O.SiO2) binder were used as flux materials together with ferrous the crosscut track area of the worn path (mm2) measured with 3D
alloys. Composition of the hardfacing electrodes cover Fe(16- optical (Huvitz) profilometer. The wear volume loss was calculated
X)CrX(B,C)4 (X = 3,4,5), see Table 1. The core wire of the electrode after a certain time interval. The coefficient of friction (COF) was
was H08A stick with a diameter of 2.5 mm. The diameter of the calculated with the formulas of Eq. (2);
coated electrode is about 5.5 mm. The compositions of H08A, Fe–
Fs
Cr(HC), and Fe–B alloys are given in Table 2. COF ¼ ð2Þ
The hardfacing was carried out on AISI 1010 plain carbon steel FN
substrate (see Table 3) by means of the SMAW process with direct where COF represents the friction coefficient, Fs is the lateral
current reverse polarity. The dimensions of the substrate used for force (N) recorded during the sliding time and FN is the applied
normal load (N). A real time by a computerized data acquisition
system was used recorded the friction coefficient of the hardfacing
layer. Wear rate (WR) of the hardfacing layer via alumina ball was
Table 1
Atomic percentages of chromium, boron in the prepared electrodes cover (%at.)
calculated using the formula;

Compound Cr %B %C Fe WR ¼ V=S ð3Þ

Fe13Cr3(B,C)4 15 10 10 Bal. where V is the wear volume and S is the sliding distance (m). Cor-
Fe12Cr4(B,C)4 20 10 10 Bal.
rosion test was carried out using the potentiodynamic polarization
Fe11Cr5(B,C)4 25 10 10 Bal.
method according to ASTM G59-97. All electrochemical

Table 2
Composition of the powders used in electrode coer (%at.)

C Cr B Mn Si Fe
H08A <0.1 0.064 – 0.35–0.40 0.10 Bal.
Ferro-Cr 6.81 68.21 – 0.51 24.468
Ferro -B 0.312 – 18.58 0.39 80.602

Table 3
The chemical composition of AISI 1010 Steel substrate.

C Si Cr S P Mn Fe
0.09 0.001 0.064 0.022 0.026 0.4 Bal.
 E. Kocaman et al. / Engineering Science and Technology, an International Journal 24 (2021) 533–542 535

measurements were performed using Gamry 300 electrochemical cathodic and anodic corrosion current (Icorr) and corrosion poten-
analyzer system (Warminster, PA, USA) equipped with a paraCell tial (Ecorr) values. Accordingly, the following relation was used to
electrochemical cell for corrosion with a waterproof gasket, leaving determination of the corrosion rate:
an exposed area of 1 cm2 on the hardfaced surface for corrosion and
the data were analyzed in the Gamry EChem Analyst software pack- IcorKEW
age (Gamry Instruments, PA, USA). The potentiodynamic polariza-
CR ¼ ð4Þ
dA
tion tests were carried out at a scanning rate of 1 mV/s in a
In the Eq. (4), K is a constant, EW is the equivalent weight in
3.5 wt% NaCl solution from
500 to +1.500 mV via standard calomel
grams/equivalent, d is density in grams/cm3, A is sample area in
reference electrode (SCE) and graphite as the counter electrode. The
cm2. Subsequently, the corrosion current was calculated according
tests were carried out at atmospheric conditions (25 °C) and humid-
to the following relation:
ity level of 31% (+/
1). To optimizing the results each corrosion
tests were repeated three times using the constant conditions such
babc
as solution weight, solution temperature and the solution pH = 6. icor ¼ ð5Þ
Polarization curves were obtained and Icorr (corrosion current), Ecorr
2:3Rpðba þ bcÞ
(corrosion potential), and Rp (polarization resistance) values were where: ba and bc are the anodic and cathodic Tafel Constant,
determined. Tafel plots were obtained by the intersection of respectively on volts/decade.

Fig. 1. SEM micrographs of the surface alloyed layers with a) Fe11Cr5(B,C)4b) Fe13Cr4(B,C)4 and c) Fe12Cr3(B,C)4 alloys.

Fig. 2. SEM micrographs and EDS analysis of the surface alloyed steel samples a) Fe11Cr5(B,C)4.
536 E. Kocaman et al. / Engineering Science and Technology, an International Journal 24 (2021) 533–542

Fig. 3. SEM micrographs and EDS analysis of the surface alloyed steel samples a) Fe12Cr4(B,C)4 and b) Fe13Cr3(B,C)4 alloys.

3. Results the matrix. Dark color boride phases were surrounded by a white
color a-(Fe-Cr) phase. Fig. 1(b) and (c) show the microstructures
3.1. Microstructure and phases of Fe13Cr3(B,C)4 and Fe12Cr4(B,C)4 compositions, which have a
relatively low Cr ratio compared to the composition of the
Hardfacing electrodes including the different atomic percent- Fe11Cr5(B,C)4 alloy. According to the microstructures, the pres-
ages of chromium, boron, and carbon and fluxes coated on the ence of pre-eutectic primary ferrite (a-(Fe-Cr)) phase + eutectic
steel substrate by SMAW process, and then quenched in air. (a-(Fe-Cr) + M23C6) structures were revealed. Also, the eutectic
The average coating layer thickness ranged from 4 to 5 mm regions decreased with the decrease of Cr ratio, as shown in
and has a smooth surface and porosity free topography. SEM the microstructures. The white regions took place in the
images of the coating layers are illustrated in Fig. 1. As shown microstructure considered as a primary ferrite, that increased
in Fig. 1(a), the electrode of Fe11Cr5(B,C)4 alloy caused the forma- with the decrease of chromium.
tion of hypereutectic microstructure. It was shown that the sur- Figs. 2 and 3 show the cross-sectional SEM images and EDS
face alloyed layer has a well distributed composite structure, analysis of the surface alloyed layers with the composition of Fe11-
including the eutectic matrix and primary blocky carbo-boride Cr5(B,C)4, Fe12Cr4(B,C)4 and Fe13Cr3(B,C)4. It is seen that Fe and Cr
phase with dark color. Blocky carbo-borides formed in the coated peaks are present in the region indicated as primary ferrite, and
layers have a sharp corner structure and were well-distributed in Fe and B peaks, as well as B and Cr peaks, are found in the EDS
 E. Kocaman et al. / Engineering Science and Technology, an International Journal 24 (2021) 533–542 537

analysis taken from eutectic structure. It can be understood from 3.2. Hardness and wear behavior
here that it supported the idea of the white block phases are
primary ferrite, and the eutectic structure consists of (a-(Fe-Cr) + Hardness of the coated surface was measured at 0.3 mm inter-
M23(C,B)6) phases. vals from the substrate to the end of the coating layer. The hard-
XRD analysis of the surface alloyed layer showed that the major ness of the hardfacing coatings is strongly dependent on the
phases formed in are a-(Fe-Cr) and M23(C,B)6 phases (M = Fe,Cr), fraction of hard phases like carbides and borides in the microstruc-
see Fig. 4. XRD analysis shows that, all compositions of the surface ture [22,23]. The hardness values are given in Fig. 5 with line-scan.
alloyed layers has similar phases. However, SEM images, EDS anal- Therefore, the hard phase contents affect the composite hardness
ysis, and elemental maps showed that the Fe11Cr5(B,C)4 composi- of the produced surface layer.
tion presents the hypereutectic microstructure which has blocky Fe11Cr5(B,C)4 composition yields highest hardness, because it
hard carbo-boride primary phase of ((Fe,Cr)23(C,B)6) together with has much more carbo-boride phases than that of the Fe13Cr3(B,
eutectic (a-(Fe-Cr)+(Fe,Cr)23(C,B)6) along with minor (Fe,Cr)2(C,B) C)4 and Fe12Cr4(B,C)4 compositions. Whereas, Fe13Cr3(B,C)4 has
and (Cr,Fe)7(C,B)3 phases. J.X. Gong et al. explained that the the fewest carbo-boride phase among all compositions. The com-
microstructure of the Fe-Cr-B-C hardfacing alloys consists of fer- posite hardness values of the surface alloyed layers increased with
rite, austenite, martensite and borides of (Fe, Cr)2B, (Fe, Cr)23(C, increase Cr, B, and C content, so it caused to form the higher carbo-
B)6, (Fe,Cr)B and (Fe,Cr)3(B,C) [19]. In the present study, a-(Fe-Cr) boride phases in the alloyed layer. Hardness value increases with
solute solution and major (Fe,Cr)23(C,B)6 carbo-boride phase exist increasing Cr content in the compositions of Fe13Cr3(B,C)4 to Fe11-
together with minor (Fe,Cr)2(C,B) and (Cr,Fe)7(C,B)3 phases. (Fe, Cr5(B,C)4, respectively. The hardnesses of the surface alloyed layers
Cr)B and (Fe,Cr)3(B,C) phases were not detected for any alloy changed from between 711 and 1164.3 HV, depending on the alloy
compositions. composition. Özel et all. obtained hardness values changing
Cr-C binary phase diagram shows that hypereutectic composi-
tions initially lead to the formation of Cr7C3 minor phase under
the liquidus line. Then Cr7C3 phase transforms into Cr23C6 phase
with peritectic reactions. A peritectic is known as a reaction where
a solid phase and a liquid phase will together form a second solid
phase at the particular temperature and composition. In this case,
(Cr,Fe)7(C,B)3 may remain untransformed in the system under
rapid solidification conditions.
It is also known that Fe and B form a boride phase primarily in
the Fe2B structure. In the alloy systems, interstitial elements like
C and B can take place with each other like substitution elements
like Fe and Cr [20]. However, the pre-eutectic microstructure is
observed in Fe13Cr3(B,C)4 and Fe12Cr4(B,C)4 compositions. Cr-C
binary diagram shows that pre-eutectic compositions initially
form a-phase under the liquidus. As the temperature decreased
below the eutectic line, Cr23C6 phase took place in the microstruc-
ture in the a + eutectic form. As seen from Figs. 2 and 3 and
Fig. 4, a-(Fe,Cr) + eutectic (a-(Fe-Cr)+(Fe,Cr)23(C,B)6) microstruc-
ture formed. However, decreasing the chromium and carbon con-
tent leads to increased a-(Fe-Cr) content and decreased the
eutectic (a-(Fe-Cr) + (Fe,Cr)23(C,B)6) content in the microstructure.
R. Shara et al. showed that (Fe,Cr)23(C,B)6) phase can be thermo-
Fig. 5. Hardness distributions of the alloyed layers.
dynamically formed in all composition of Fe-Cr-C-B system with
different C-B content [21]. Similarly, M.J. Duarte et al. explained
that (Fe,Cr)23(C,B)6 major phases can be formed in the unstable
metallic glass of the alloys, including Fe, Cr, Mo, B and C
elements.

Fig. 6. Plots of friction soeffcient, depending on the sliding distance under

Fig. 4. XRD patterns of Fe(16-X)CrX(B,C)4 (X = 3,4,5) hardfacing coating. 30 mm.s
1 speed and 2 N-5 N and 8 N load.
538 E. Kocaman et al. / Engineering Science and Technology, an International Journal 24 (2021) 533–542

results measured from the entire surface with 0.5 mm interval

shows that the coating is performed homogeneously.
Fig. 6 shows the friction coefficient values obtained from the
wear tests of the Fe(16
X)CrX(B, C)4 (X = 3,4,5) based electrodes
coating layers on the steel surfaces against alumina (Al2O3) ball.
It is seen in Fig. 6 that the coefficient of frictions of the alloys
was changing between 0.55 and 0.79, depending on applied loads.
C. Ozel et al. studied on the Fe-Cr-B-C surface alloyed steel, and
they obtained friction coefficients between 0.5 and 0.75, which
agrees with the present study [24]. G. Cui et al. studied on Fe-Cr-
B alloys that the coefficient of friction against the SiC ball was
about 0.45. It_ is lower than that of the present study and Ozel
et al. studies [24,25].
_ is possible that carbon addition leads to increases coefficient
It
of friction along with SiC lubricant effects. As shown from the Fig. 6
that increase in load and decreasing Cr content in the alloys lead to
the decreased coefficient of friction. It is possible that the increase
in applied load caused the adhesion according to the softer a-
Fig. 7. Wear rate of coatings depending on the different loads. phase increase in the microstructure and caused a little increase
of friction coefficient of Fe13Cr3(B,C)4 composition at highest load
value (8 N). Fig. 7 shows that increase in applied load and decrease
between 580 Hv and 1200 Hv from the hardfacing study of Fe-Cr- in Cr content in the alloyed layer caused to increase in wear rate.
B-C alloy carried out by PTA welding method. The results seem to As shown from the results that the highest the hardness value,
be consistent with this study. However, methods that measure the highest the interstitial carbo-boride phases content and the
from a small point such as micro hardness in composite materials highest the Cr, B, and C content caused to decrease the wear rates
may not reflect the overall result. For this reason, it is important to of the surface alloyed layers. Gibbs free energies of the chromium
measure macro hardness. In this study, macro hardness results carbides and borides together with iron carbides and borides are
were measured as 61.9 HRC (+/
0.5), 65.3 HRC (+/
0.4) and 68.3 much lower than that of the matrix. Also, covalent bonding of
HRC (+/
0.3), respectively, according to the increasing chromium the interstitial atoms like boron and carbon make strong bonding
ratio. In addition, the low standard deviation in the hardness force according to metallic bond of the iron and chromium atoms,

Fig. 8. Wear trace of Fe12Cr4(B,C)4 composition under 5 N load (a) SEM microstructure (b)–(d) EDS analyses.
 E. Kocaman et al. / Engineering Science and Technology, an International Journal 24 (2021) 533–542 539

Fig. 9. Wear trace of surface alloyed layers under 5 N a-b) Fe11Cr5(B,C)4c-d) Fe13Cr4(B,C)4 and e-f) Fe12Cr3(B,C)4 alloys.

so elastic modulus and hardness of these phases are much higher with iron and eutectic grains of the pearlite-like microstructure
than that of the matrix [26,27]. In the metal matrix composite caused to withstand of the in-situ composite structure in aggres-
structures, increase in reinforced hard phases in the matrix caused sive wear conditions.
to increase of the composite hardness and wear resistance accord- In the present study, wear rates of the Fe11Cr5(B,C)4, Fe12Cr4(B,
ing to well-known Archard’s rules [28,29]. As known, a decrease in C)4 and Fe13Cr3(B,C)4 surface alloyed steels ranged from
dimensions of dispersed reinforced hard phases for the same volu- 3.07  10
5 mm3/m to 4.23  10
5 mm3/m, 3.89  10
5 mm3/m
metric scales caused to increase of the hardness and so wear resis- to 5.8  10
5 mm3/m and 4.2  10
5 mm3/m to
tance [30]. Here, dislocations movements restrict with dispersed 6.95  10
5 mm3/m, respectively.
hard phases and thus increase to the hardness of the composite The study agrees with G. Hu et al. study that increases in the
structure. Eutectics of the steel matrix and carbo-boride phases load value caused an increase in wear rates [31]. G. Cui et al.’s
caused to toughened and hardened structure formation, so hard study showed that the Fe-Cr-B surface alloyed layers showed on
phase in aggressive conditions can be broken with applied high the order of ~10
4 mm3/m wear rates [25]. Whereas, in the present
load values. However, eutectic microstructure supports the hard study, wear rates ten times lower than that of the G. Cui et al.
carbo-boride phase with tough steel matrix with pearlite like study. The carbon may exist in the alloy composition caused an
structures. Primer carbo-boride phases of the chromium together increase in wear resistance of the alloyed layer. A 150% increase
540 E. Kocaman et al. / Engineering Science and Technology, an International Journal 24 (2021) 533–542

in load value (from 2 N to 5 N) leads to an increase of 22.2% wear that Cr content has a considerable effect on the corrosion behavior
rate for Fe11Cr5(B,C)4 alloy; When the increase in load value is a of the surface alloyed layers. It is observed from the curves that the
300% (from 2 N to 8 N), the increase in wear rate is 37.7%. This current decreases with the increase of the potential of the cathodic
value for Fe12Cr4(B,C)4 and Fe13Cr3(B,C)4 alloys respectively; 19– region. This behavior states that corrosion occurs with an
49.1% and 23.8–65.5%, respectively. Wear rates of all alloys are activation-controlled mechanism. It has been reported that nega-
generally close to each other. As can be seen from the graph, the tive potentials in Tafel curves increase the cathodic reaction rate
increase in chromium content (for 8 N load) caused a decreased required for metal dissolution. It is seen that the corrosion poten-
wear rate of 65.54%. tial increases with the increase of the amount of chromium in the
In Fig. 8, the result of EDS analysis taken from the surface after electrode cover composition. Corrosion potential of the coating
wearing under 5 N load of the coated with Fe12Cr4(B,C)4 composi- made with an electrode with 15 %at. chromium content increased
tion is given. The SEM picture shows that wear products accumu- by 10% compared to the substrate material. It is seen that the
late along the wear track. In EDS analysis, it is seen that there is increase is approximately 16% in the surface coated with the elec-
oxygen in addition to elements such as carbon, boron, chromium trode with 25% (at.). chromium content.
and iron in its composition. Therefore, oxidative, micro-abrasive Table 4 shows the data obtained from the potentiodynamic
with the polishing process has developed as a general wear mech- polarization curves. While the corrosion potential increases with
anism in all samples. However, in the SEM pictures taken after the the increasing amount of chromium, the current density decreases.
wear test with 5 N load given in Fig. 9, it is understood that differ- According to Galvele, current density values are directly related to
ent wear mechanisms have developed in the samples. It is seen in the electrode potentials and can give more accurate results about
Fig. 9b that the hard phases formed along the grain boundary cause the electrochemical behavior of the material [33]. It is known that
fatigue cracks. These phases in the eutectic composition ((a-(Fe-Cr) there will be an increase in corrosion resistance with decreasing
+(Fe,Cr)23(C,B)6)) withstand damage during wear, but the matrix current density. According to these results, it can be said that the
was pitted under the adhesive wear effect. Therefore, fatigue wear coating has turned into a nobler character with increasing chro-
mechanism is also observed in this composition. A similar mecha- mium ratio.
nism is observed in the study conducted by Torabinejad et al. [32]. The coatings contain a-matrix (Fe-Cr) as well as other carbo-
In Fig. 9d, it is seen that the hill parts, which are hard phases, are boride phases depending on the chromium ratio of the structure,
not affected by abrasion, but, soft phases are worn. In addition, as stated in microstructural studies. The main electrochemical
micro-abrasive lines can be clearly distinguished on the worn sur- reaction expected to be in the A-matrix structure is an oxidation
face. Therefore, adhesive abrasive and polishing type wear mecha- reaction, and the corrosion reactions of iron-based alloys in a con-
nisms have developed during the wear of this composition. taining dissolved oxygen near-neutral pH may be generally written
Similarly, it is seen that the coating with Fe11Cr5(B,C)4 composition as following [34,35];
given in Fig. 9f does not have any cracks in the SEM picture and
block phases are resistant to abrasion, but the matrix phase is pit- Anodic reaction : Fe ! Feþ2 þ 2e
ð6Þ
ting. This shows that the coating contains polishing type wear. It is
known that the chromium added to the steel increases its tough- Cathodic reaction : 1=2O2 þ H2 O þ 2e
! 2OH
ð7Þ
ness. In addition, the increasing chromium ratio contributes to Cathodic reaction can be with oxygen reduction.
both the hardness of the matrix and hardness with blocky hard Overall reaction;
carbo-boride phases. In the wear tests carried out in the study, it
is observed that the fatigue wear mechanism develops in the coat- 2Fe þ 2H2 O þ O2 ! 2Feþ2 þ 4OH
! 2FeðOHÞ2 ð8Þ
ing with the decrease of the chromium ratio. Therefore, increasing
chromium ratio contributes to the wear resistance of the coating. On the other hand, another factor that determines the chemical
stability of a-matrix is chromium dispersed in the structure.
3.3. Corrosion behavior Anodic reaction : Cr ! Cr þþþ3 þ 3
ð9Þ

Fig. 10 shows the Tafel plots derived from the potentiodynamic As known, chromium content in the steels caused the formation
polarization curves of alloyed surface layers. The curves indicate of Cr2O3 adhesive layer on the surface and, the increase in the Cr
content caused the increase of corrosion resistance because of
the formation of more Cr2O3 layer. General Cr2O3 reaction in 3.5%
NaCl aqueous solution for the Fe–Cr alloys is shown following [36];

4NaCl þ Cr 2 O3 þ 2H2 O þ 3=2O2 ! Na2 CrO4 þ HCl ð10Þ

Also, the contribution of other phases in the structure to the
corrosion resistance affects the total corrosion resistance of the
coating. As the chromium ratio increases, the amount of free chro-
mium in the matrix phase will increase. This case will contribute to
the corrosion resistance of the coating. However, corrosion poten-
tial of carbide and boride phases may be nobler than that of the
matrix due to their low free energy. For instance, the corrosion
potential of (a-(Fe-Cr)+(Fe,Cr)23(C,B)6) is believed to be nobler than
that of a-(Fe-Cr) matrix. The chromium content of (Fe,Cr)23(C,B)6 is
higher than that of the eutectic matrix (a-(Fe-Cr)+ (Fe,Cr)23(C,B)6).
Also, the minor phases such as (Fe,Cr)2(C,B) and (Fe,Cr)7C3 con-
tribute to the corrosion resistance of the surface coating. As a
result, the coating containing mainly M23(C,B)6 and minor M7(C,
B)3 phases may change the corrosion potential [9,37–39].
In Fig. 11, the SEM image of the corroded surfaces after polariza-
Fig. 10. Potentiodynamic polarization curves of coating layers. tion test is given. Some residues have appeared on the surfaces of
 E. Kocaman et al. / Engineering Science and Technology, an International Journal 24 (2021) 533–542 541

Table 4
Potentiodynamic polarization test results of corroded layers

Electrode Ecorr Icorr ba Βc Corrosion Rate

mV mA/cm2 V/decade V/decade mpy
Fe11Cr5(B,C)4
704.786 1.813 490 473.2 1.197
Fe12Cr4(B,C)4
727.256 6.069 196 146 4.309
Fe13Cr3(B,C)4
745.792 9.965 218.3 144.3 6.088
AISI 1010
849.68 50.341 1227.1 159 30.757

Fig. 11. Corroded surfaces of hardfaced with various Cr contents a)Substrate (AISI 1010) b)Fe11Cr5(B,C)4c)Fe12Cr4(B,C)4 d)Fe13Cr3(B,C)4.

Fig. 11(a) and (b). This can be explained that the fluctuations in the seen that the corrosion rate decreases with increasing chromium
anodic parts of the Tafel curves occur due to the separation of the content. This is an expected result due to the high corrosion resis-
protective layer from the surface [40]. It may indicate that the fluc- tance of the phases formed by chromium and the chromium being
tuations in the Tafel curve of the substrate given in Fig. 9 and the galvanically nobler than iron. Therefore the Fe11Cr5(B,C)4 coating
Fe11Cr5(B,C)4 coating layer are associated with this surface layer exhibit superior corrosion resistance as compared to the others.
that forms on the surface and then breaks and accumulates.
There are partial gaps between the matrix phase and the struc- 4. Conclusions
tured eutectic phases in Fig. 11(c) and (d). Grabke et al. indicated
that molecular chlorine penetrating the grain boundaries could In the present work, three different chemical compositions of
react with M23C6 type carbides. Chlorine can react with M23C6 type Fe(16
X)CrX(B,C)4 (X = 3,4,5) surface alloying electrodes were pro-
carbide in the presence of oxygen via grain boundaries according to duced successfully. SMAW techniques were used for surface alloy-
the reaction below. The chlorine required for the reaction is ing treatment. The following results have been obtained.
obtained by reacting HCl in Reaction (6) with dissolved oxygen
in solution. Such a situation harms the corrosion resistance of 1. All the compositions of the surface alloyed layers include simi-
the coating [36,41]. lar phases. However, SEM, EDX and elemental mapping studies
shows that the Fe11Cr5(B,C)4 alloy composition presents the
Cr 23 C 6 þ 23Cl2 þ 3O2 ! 23CrCl2 þ 6CO ð11Þ
hypereutectic microstructure which has blocky hard carbo-
Another matter that affects the corrosion resistance is the sili- boride major phase (M23(C,B)6) together with eutectic (a-(Fe-
con that can come from ferroalloys. Silicium is not present in car- Cr) + M23(C,B)6) besides (Fe,Cr)2(C,B) and (Cr,Fe)7(C,B)3 minor
bide or boride phases and is dissolved in the matrix phase [42]. phases. However, the pre-eutectic microstructure is exhibited
Generally, silicon dissolved in the matrix is thought to contribute in Fe13Cr3(B,C)4 and Fe12Cr4(B,C)4 compositions. a-(Fe,Cr) + eu
to the corrosion resistance of the coating [9]. Consequently, it is tectic (a-(Fe-Cr) + M23(C,B)6) microstructure formed. However,
542 E. Kocaman et al. / Engineering Science and Technology, an International Journal 24 (2021) 533–542

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