Journal Pre-proof

Effect of Nb additive on wear resistance and tensile properties of the

hypereutectic Fe-Cr-C hardfacing alloy

Sha Liu (Conceptualization) (Methodology) (Software), Zhijun Shi

(Data curation) (Writing - original draft), Xiaolei Xing (Visualization)
(Investigation), Xuejun Ren, Yefei Zhou (Supervision), Qingxiang
Yang (Writing - review and editing)

PII: S2352-4928(19)31039-6
DOI: https://doi.org/10.1016/j.mtcomm.2020.101232
Reference: MTCOMM 101232

To appear in: Materials Today Communications

Received Date: 8 October 2019

Revised Date: 1 April 2020
Accepted Date: 6 May 2020

Please cite this article as: Liu S, Shi Z, Xing X, Ren X, Zhou Y, Yang Q, Effect of Nb additive
on wear resistance and tensile properties of the hypereutectic Fe-Cr-C hardfacing alloy,
Materials Today Communications (2020), doi: https://doi.org/10.1016/j.mtcomm.2020.101232

This is a PDF file of an article that has undergone enhancements after acceptance, such as
the addition of a cover page and metadata, and formatting for readability, but it is not yet the
definitive version of record. This version will undergo additional copyediting, typesetting and
review before it is published in its final form, but we are providing this version to give early
visibility of the article. Please note that, during the production process, errors may be
discovered which could affect the content, and all legal disclaimers that apply to the journal
pertain.

© 2020 Published by Elsevier.

Effect of Nb additive on wear resistance and tensile properties of the hypereutectic

Fe-Cr-C hardfacing alloy

Sha Liu a*, Zhijun Shi a, Xiaolei Xing b, Xuejun Ren c, Yefei Zhou b, Qingxiang Yang a*
a State Key Laboratory of Metastable Materials Science & Technology, Hebei Key Laboratory for Optimizing Metal
Product Technology and Performance, College of Materials Science & Engineering, Yanshan University,
Qinhuangdao 066004, P. R. China
b College of Mechanical Engineering, Yanshan University, Qinhuangdao 066004, P. R. China
c School of Engineering, Liverpool John Moores University, Liverpool L3 3AF, UK
* Corresponding author: Tel. +86-335-838-7471
Fax. +86-335-807-4545
E-mail address: qxyang@ysu.edu.cn

of
Graphical abstract

ro
-p
re
lP
na

Highlights

 The microstructures and phase structures of hypereutectic Fe-Cr-C hardfacing alloy with
ur

and without Nb additive were observed and determined.

Jo

 The wear resistance was improved by the refinement effect of Nb.

 The tensile strength parallel to the primary (Fe,Cr)7C3 was improved by the refinement

effect of Nb, while that vertical to the primary (Fe,Cr)7C3 was lowered.

1
Abstract

The effects of Nb additive on wear resistance and tensile properties of the hypereutectic

Fe-Cr-C hardfacing (harden-surface-welding) alloys were investigated. The

microstructures and phase structures of the alloys with and without Nb additive were

of
compared by means of optical microscopy (OM) and X-ray diffractometer (XRD). The

ro
wear behaviors were measured by reciprocating wear tests via CSM Tribometer. The

tensile properties were measured by universal testing machine. In order to investigate

-p
the (Fe,Cr)7C3 carbides refinement by Nb additive, the formation thermodynamics of
re
NbC and the misfit between NbC and (Fe,Cr)7C3 were calculated. The results show that

the alloy with Nb additive contains NbC as well as (Fe,Cr)7C3 and γ-Fe. The size of the
lP

primary (Fe,Cr)7C3 carbides in the alloy with Nb additive is obviously smaller than that
na

without Nb additive. The mass loss of the alloy with Nb additive is less than that without

Nb additive. The worn surfaces also indicate that the amount of the cracks on the alloy
ur

surface with Nb additive is less than that without Nb additive. The tensile strength

parallel to the rod-like primary (Fe,Cr)7C3 carbides is larger than that vertical to the
Jo

primary (Fe,Cr)7C3 carbides. The tensile strength parallel to the primary (Fe,Cr)7C3

carbides of the alloy with Nb additive is larger than that without Nb additive, while the

tensile strength vertical to the primary (Fe,Cr)7C3 carbides of the alloy is lower than

that without Nb additive. The phase fraction vs. temperature curves of the alloy shows

2
that the alloy with Nb additive preferentially forms NbC and then primary (Fe,Cr)7C3

carbides. The lattice misfit between NbC and (Fe,Cr)7C3 is 2.16%, which proves NbC

can be as the heterogeneous nucleus to refine primary (Fe,Cr)7C3 carbides in the Fe-Cr-

C hardfacing (harden-surface-welding) alloy.

Keywords: hypereutectic Fe-Cr-C hardfacing alloy; wear; tensile strength; primary

(Fe,Cr)7C3 carbide; grain refinement

1. Introduction

of
In recent years, the metal based additive manufacture (AM) is one

ro
of the research focuses currently [1]. With excellent wear-resistance, the Fe-Cr-C

hardfacing (harden-surface-welding) alloy has been applied in AM field [2~4]. The

-p
microstructures of the Fe-Cr-C hardfacing alloys vary with carbon content, which can
re
be divided into hypoeutectic, eutectic and hypereutectic ones [5]. The hardness and

wear-resistance of the hypereutectic Fe-Cr-C hardfacing alloys (e.g. 2.5~5.5wt.%

lP

carbon, 10~30wt.% chromium) are higher than those of the eutectic and hypoeutectic
na

ones, which is ascribed to the large amount of primary (Fe,Cr)7C3 carbides [6]. The

primary (Fe,Cr)7C3 carbides in hypereutectic Fe-Cr-C hardfacing alloy can grow into
ur

rods along the cooling direction [7], namely the primary (Fe,Cr)7C3 carbides are vertical

to the hardfacing surface. The anisotropic primary (Fe,Cr)7C3 carbides shows more
Jo

excellent wear-resistance in the direction perpendicular to the hardfacing surface.

Combined with the eutectic carbides and the ductile eutectic austenite [8, 9], the

hypereutectic Fe-Cr-C hardfacing alloy has been applied in surface modification to

prolong the service life of the work-pieces [10~13].

3
 However, the impact-wear property of the hypereutectic Fe-Cr-C hardfacing alloy

may be decreased when the primary (Fe,Cr)7C3 carbides are coarse [14-16]. The refined

primary (Fe,Cr)7C3 carbides can dramatically improve the strength and toughness of

the hypereutectic Fe-Cr-C hardfacing alloy [17, 18]. So it is attractive to research the

refinement of primary (Fe,Cr)7C3 carbides in recent years. Rapid solidification

treatment [19, 20], lowering superheat [21], semi-solid process [22] and alloying

treatment [23~27] can effectively refine the primary (Fe,Cr)7C3 carbides in

of
hypereutectic Fe-Cr-C hardfacing alloy, in which, alloying treatment is one of the most

ro
economical and effective methods. X.H. Zhi et al. [23] studied the effect of Ti additive

on hypereutectic Fe-Cr-C hardfacing alloy and found that the primary (Fe,Cr)7C3
-p
carbides are effectively refined. They also found that Ce additive can refine the primary
re
(Fe,Cr)7C3 carbides and the impact toughness of the Fe-Cr-C hardfacing alloy can be

improved too [24]. X.W. Qi et al. [25] investigated the changes in microstructure and
lP

properties of the hypereutectic Fe-Cr-C hardfacing alloy by V additive, which indicates

na

that the primary (Fe,Cr)7C3 carbides are refined and the wear resistance of the

hypereutectic Fe-Cr-C hardfacing alloy is improved. Other alloying elements such as

ur

La and Y can refine the primary (Fe,Cr)7C3 carbides as well [26, 27].

Cracks often occur on the surface of the hypereutectic Fe-Cr-C hardfacing alloy
Jo

during solidification, which is always related to the tensile stress, so it is significant to

research the tensile properties of the hypereutectic Fe-Cr-C hardfacing alloy for

improvement of its cracking resistance. However, there are few reports about the

research on the tensile properties of the hypereutectic Fe-Cr-C hardfacing alloy.

4
 In this paper, the effects of Nb additive on wear resistance and tensile properties

of the hypereutectic Fe-Cr-C hardfacing alloy were investigated. The microstructures

and phase structures of the alloys with and without Nb additive were compared. The

wear behaviors and tensile properties were measured. The formation thermodynamics

of NbC and the misfit between NbC and (Fe,Cr)7C3 were calculated. The refinement

mechanism of (Fe,Cr)7C3 carbides by NbC was discussed, and the reason that the wear

and tensile properties of the hypereutectic Fe-Cr-C hardfacing alloys can be improved

of
by Nb additive was analyzed.

ro
2. Materials and experiments

2.1 Materials
-p
Two hypereutectic Fe-Cr-C hardfacing alloys with and without Nb additive were
re
prepared by cladding self-made flux cored wires on low-carbon steel. During cladding,

the open arc welding method was used, which is schematically illustrated in Fig.1.
lP

The optimized parameters of the hardfacing process are listed in Table 1. The
na

substrates were preheated before hardfacing, and welding zone was hammered during

hardfacing in order to relief stress. After hardfacing, the compositions of the

ur

hypereutectic Fe-Cr-C hardfacing alloys with and without Nb additive were determined

by CS-8800 infrared carbon-sulfur analyzer and Advant/p-381 x-ray fluorescence

Jo

spectrometer.

The compositions of the hypereutectic Fe-Cr-C hardfacing alloys are listed in

Table 2, in which, the alloy without Nb additive is named as No.1 alloy, and that with

Nb additive is named as No.2 alloy.

5
 Table 1 Parameters of hardfacing process.

Cladding
Wire diameter Welding voltage Welding current Welding speed
thickness
(mm) (V) (A) (mm•min-1.)
(mm)
3.2 24~26 200~224 300 4.6~5.0

Table 2 Chemical compositions of the hypereutectic Fe-Cr-C hardfacing alloys (wt.%).

No. C Cr Si Mn V Nb Mo Fe
No.1 3.69 26.30 0.93 1.42 0.11 0 0.16 Bal.
No.2 3.70 26.29 0.90 1.36 0.10 1.2 0.14 Bal.

2.2 Experiments

of
Specimens with dimension of 10mm×10mm×10mm were cut from the

hypereutectic Fe-Cr-C hardfacing alloys and then ground by SiC abrasive papers. The

ro
ground specimens were mechanical polished to improve the surface brightness. Then
-p
D/max-2500/PC X-ray diffractometer (XRD) was used to detect the phase structures of

the alloys with Cu Kα radiation (20-120°, 1°/s). The microstructures of the alloys were
re
observed by Axiovert 200 MAT optical microscopy (OM) after the polished specimens
lP

were dyed with 25%K3Fe(CN)6+7%NaOH+68%H20 solution. According to the

chemical compositions, the phase fraction vs. temperature curves of the hypereutectic
na

Fe-Cr-C alloys were calculated by Thermal-calc 4.0 software.

Reciprocating wear tests of the hypereutectic Fe-Cr-C hardfacing alloy specimens

ur

with size 20mm×10mm×10mm were carried out with the CSM Tribometer. In order to
Jo

simulate similar service conditions, the tungsten steel ball (diameter=3mm) was chosen

for the friction pair because its hardness is HRA92, which is dramatically higher than

that of the hypereutectic Fe-Cr-C hardfacing alloys (HRA75~80). The wear test is

schematic illustrated as follows. Firstly, the tungsten steel ball was installed on the ball

fixture and then the ball fixture was tightly fixed on the swing arm by the bolt. Secondly,
6
we adjusted balance of the swing arm till the tungsten steel ball just touched the

specimen while did not apply force to the specimen. Thirdly, 5N weight was applied

and then the reciprocating wear test was carried out by the advance and return

movement of the specimen along with the specimen fixture. The velocity of the

specimen fixture was 5cm/s and the length of the worn trace was 10mm. The duration

of wear test was 240min. Then the worn surfaces were observed by Hitachi S3400 field

emission scanning electron microscope (FESEM) and elementary surface scanned by

of
energy spectrum diffraction (EDS). The mass loss of the specimen after wear test was

ro
also weighted. Each group was weighted 5 times.

Tensile tests of the hypereutectic Fe-Cr-C hardfacing alloys at room temperature

-p
were conducted by the universal testing machine. The tensile specimens are shown in
re
Fig.2, in which, the geometry and dimensions of specimens for tensile tests are

schematically shown in Fig.2a. The thickness of the specimens is 2mm. Due to the
lP

primary (Fe,Cr)7C3 carbides in hypereutectic Fe-Cr-C hardfacing alloys are rod-like,

na

the tensile tests were divided into two sets. In one set, the direction of the tensile force

was parallel to the primary (Fe,Cr)7C3 carbides, which is shown in Fig.2b. In the other
ur

set, the direction of the tensile force was vertical to the primary (Fe,Cr)7C3 carbides,

which is shown in Fig.2c. Before the tensile tests, the specimens were ground by SiC
Jo

abrasive papers. The loading rate of the tensile tests was 0.84mm/min. The

fractographies were observed by Hitachi S3400N FESEM and elementary surface

scanned by EDS.

3. Experimental results

7
3.1 Phases and microstructures

The XRD patterns of the hypereutectic Fe-Cr-C hardfacing alloys are shown in

Fig.3, in which, No.1 alloy mainly consists of (Fe,Cr)7C3 and γ-Fe (austenite), while

No.2 alloy also contains NbC besides of (Fe,Cr)7C3 and γ-Fe.

The microstructures of the dyed hypereutectic Fe-Cr-C hardfacing alloys are

shown in Fig.4, in which the brown polygons are the cross-sections of the primary

(Fe,Cr)7C3 carbides. By comparing Fig.4a and Fig.4b, it can be found that primary

of
(Fe,Cr)7C3 carbides in No.2 alloy are effectively refined compared to No.1 alloy. The

ro
statistics data on the area of primary (Fe,Cr)7C3 carbides is displayed in Fig.4c. It is

obvious that the area span of the primary (Fe,Cr)7C3 carbides in No.1 alloy is much

larger than No.2 alloy .

-p
re
3.2 Wear properties

The mass loss of the hypereutectic Fe-Cr-C hardfacing alloys from the wear test
lP

is shown in Fig.5. The mass loss of the No.2 alloy is 60mg, which is less than that of
na

the No.1 alloy (82mg). It indicates the wear resistance is improved by adding Nb

additive in the alloy.

ur

The worn surfaces of the hypereutectic Fe-Cr-C hardfacing alloys and

corresponding element distribution maps are shown in Fig.6. From the worn surface of
Jo

the No.1 alloy in Fig.6a, several cracks up to tens of microns can be seen. With the help

of element distribution in Fig.6b, where green color represents Cr accumulation (i.e.

the primary (Fe,Cr)7C3 carbides) and blue color represents Fe accumulation (i.e.

austenite), the cracks mainly occur at the joint between primary (Fe,Cr)7C3 carbides

8
and austenite. The worn surface of the No.2 alloy is shown in Fig.6c. Compared with

Fig.6a, the amount of cracks is evidently reduced. The corresponding element

distribution map is shown in Fig.6d, where the pink color represents Nb accumulation

(i.e. NbC). The comparison of Fig.6b and Fig.6d also proves that (Fe,Cr)7C3 carbides

are effectively refined by Nb additive.

3.3 Tensile properties

Table 3 Tensile strengths of the hypereutectic Fe-Cr-C hardfacing alloys (MPa).

of
No. parallel to primary (Fe,Cr)7C3. vertical to primary (Fe,Cr)7C3.

No.1 150 120

ro
No.2 340 50

The tensile curves of the hypereutectic Fe-Cr-C hardfacing alloys parallel to and
-p
vertical to primary (Fe,Cr)7C3 carbides are shown in Fig.7, and the tensile strengths are
re
listed in Table 3. Because the hypereutectic Fe-Cr-C hardfacing alloys are typical brittle

materials, no yielding phenomenon appears in the tensile curves. When the tensile
lP

direction is parallel to the primary (Fe,Cr)7C3 carbides, it can be seen that the tensile

strength of the No,2 alloy is 340MPa, which is almost twice higher than that of No.1
na

alloy (150 MPa). When the tensile direction is vertical to the primary (Fe,Cr)7C3
ur

carbides. It is worth noting that the tensile strength of the No.2 alloy is 50MPa, which

much lower than that of the No.1 alloy (120 MPa). It indicates that the tensile strength
Jo

strongly depends on the orientation of the primary (Fe,Cr)7C3 carbides. The tensile

strength parallel to the primary (Fe,Cr)7C3 carbides is much higher than that vertical to

the primary (Fe,Cr)7C3 carbides.

The fractographies as well as the corresponding element distribution maps of the

9
hypereutectic Fe-Cr-C hardfacing alloys after tensing parallel to the primary (Fe,Cr)7C3

carbides are shown in Fig.8. It can be seen from Fig.8a and Fig.8c that the

fractographies of the hypereutectic Fe-Cr-C hardfacing alloys present cleavage

characteristics. Based on the element distribution maps in Fig.8b and Fig.8d, it can be

deduced that the cleavage surfaces are occurred on primary (Fe,Cr)7C3 carbides.

Together with the fact that the cleavage surfaces are vertical to the c-axis of the primary

(Fe,Cr)7C3 carbides, it can be known that the cleavage surfaces of the primary

of
(Fe,Cr)7C3 carbides are close-packed (0001) planes. The right lower corner in Fig.8c is

ro
the magnification of the dashed box. According to the element distribution map in

Fig.8d, the dark area in the dashed box is NbC. It can be observed that NbC also presents
-p
cleavage characteristics. In addition, NbC is tightly combined with primary (Fe,Cr)7C3
re
carbides during tensing, which means the cohesion between NbC and (Fe,Cr)7C3 is

strong.
lP

The fractographies as well as the corresponding element distribution maps of the

na

hypereutectic Fe-Cr-C hardfacing alloys after tensing vertical to the primary (Fe,Cr)7C3

carbides is shown in Fig.9. The cleavage surfaces of primary (Fe,Cr)7C3 carbides are
ur

close-packed (0001) planes, which are shown in Fig.8. While it can be seen in Fig.9

that even more smooth fractographies are emerged, which means the
Jo

(Fe,Cr)7C3/austenite interfaces are separated while tensing vertical to primary

(Fe,Cr)7C3 carbides. According to Fig.9d, the dark particles in Fig.9c are NbC. Due to

some NbC particles are enclosed within primary (Fe,Cr)7C3 carbides, there is

considerable difference in the size of them Fig.9c. The right lower corner in Fig.9c is

10
the magnification of the dashed box, which is the largest NbC particle in Fig.9c. It can

be seen that the NbC particle is tightly combined with primary (Fe,Cr)7C3 carbides

when the (Fe,Cr)7C3/austenite interface separates, rather than peeled off along with

austenite. It means the cohesion between primary (Fe,Cr)7C3 carbides and NbC is

stronger than that between austenite and NbC.

4. Discussion

It has been known from above results that, the primary (Fe,Cr)7C3 carbides in the

of
hypereutectic Fe-Cr-C hardfacing alloy with Nb additive are obviously refined

ro
compared to that without Nb additive. In addition, the refinement of the primary

(Fe,Cr)7C3 carbides also affect on the wear resistance and tensile properties of the
-p
hypereutectic Fe-Cr-C hardfacing alloys. Therefore, it is necessary to investigate the
re
refinement mechanism of the primary (Fe,Cr)7C3 carbides by Nb additive.

4.1 Phase fraction vs. temperature curves

lP

The phase fraction vs. temperature curves of the two hypereutectic Fe-Cr-C
na

hardfacing alloys are shown in Fig.10. From Fig.10a, it can be found that primary

(Fe,Cr)7C3 carbides in the No.1 alloy starts to precipitate at 1330℃, and then eutectic
ur

reaction occurs at 1300℃ (liquid → eutectic (Fe,Cr)7C3 + eutectic austenite). The

phase is consistent with the XRD pattern in Fig.3. From Fig.10b, it can be found that
Jo

MC in the No.2 alloy firstly starts to precipitate at 1350℃, and then primary (Fe,Cr)7C3

carbides starts to precipitate at 1330℃. The eutectic reaction occurs at 1300℃. Except

for the formation of MC in the No.2 alloy, the phase transitions and phase fractions of

the two alloys are almost the same. According to the XRD patterns in Fig.3, it can be

11
deduced that the MC precipitated at 1350℃ is NbC. It should be noted from Fig.5d,

Fig.8d and Fig.9d that NbC mainly distribute in the primary (Fe,Cr)7C3 carbides

boundaries or within the primary (Fe,Cr)7C3 carbides, which illustrates that primary

(Fe,Cr)7C3 carbides may be combined with the preferentially formed NbC during its

nucleation and growth. Therefore, the refinement of primary (Fe,Cr)7C3 carbides may

be attributed to that NbC acts as the heterogeneous nucleation of primary (Fe,Cr)7C3

carbides .

of
4.2 Misfit between NbC and (Fe,Cr)7C3

ro
By the two-dimensional lattice misfit theory proposed by B.L. Bramfitt [28], the

lattice misfit between the substrate and the nucleated solid smaller than 6% means that
-p
the substrate can be the heterogeneous nucleus of the nucleated solid, and so the
re
nucleated solid will be refined. The two-dimensional lattice misfit theory also declares

that the lattice misfit 6~12% is middle-effective in heterogeneous nucleation, and that
lP

larger than 12% is ineffective. The lattice misfit δ between NbC and (Fe,Cr)7C3 can be
na

expressed as the following equation:

(ℎ𝑘𝑙)
𝛿(ℎ𝑘𝑙)𝑛𝑠 = ∑3𝑖=1[(|𝑑[𝑢𝑣𝑤]𝑠 𝑖 cos 𝜃 − 𝑑[𝑢𝑣𝑤]𝑛 𝑖 |/𝑑[𝑢𝑣𝑤]𝑛 𝑖 )/3] × 100% (1)
ur

where (hkl)s is a low-index plane of NbC and [uvw]s is a low-index direction in (hkl)s;

(hkl)n is a low-index plane of (Fe,Cr)7C3 and [uvw]n is a low-index direction in (hkl)n;

Jo

d is the interatomic spacing along [uvw]; θ is the angle between [uvw]n and [uvw]s.

The low-index planes chosen in this paper are (110)NbC and (010) (Fe,Cr) C , whose
7 3

relationship is illustrated in Fig.11. The red circles represent the atoms in NbC, while

the green circles represent the atoms in (Fe,Cr)7C3. δ between NbC and (Fe,Cr)7C3 is

12
calculated based on Eq.(1) and the result is listed in Table 4. From Table 4, δ between

NbC and (Fe,Cr)7C3 is 2.16%, which is dramatically smaller than 6%. It means that the

preferentially formed NbC can be the heterogeneous nucleus of primary (Fe,Cr)7C3

carbides. Therefore, the primary (Fe,Cr)7C3 carbides in the hypereutectic Fe-Cr-C

hardfacing alloy with Nb additive are effectively refined compared to that without Nb

additive.
Table 4 Lattice misfit between (Fe,Cr)7C3 and NbC.
Matching interface (110)NbC//(010) (Fe,Cr)7C3

of
[uvw]s [200] [011] [211]
[uvw]n [001] [100] [101]

ro
θ (°) 0 0 1.6
ds (Å) 4.469 3.160 5.473
dn (Å) 4.540 3.021 5.453
δ (%) 2.16%

4.3 Explanation on the wear resistance

-p
re
The cracks amount reduction of the No.2 alloy during wear test mainly comes from
lP

the refinement of primary (Fe,Cr)7C3 carbides. Because the hardness of the rod-like

primary (Fe,Cr)7C3 carbides in hypereutectic Fe-Cr-C hardfacing alloy is high [7],

na

which plays a supporting role by directly contacting with the friction pair during wear

test compared with soft austenite. Under the condition of the same friction pair, large-
ur

sized primary (Fe,Cr)7C3 carbides contact with the friction pair for a longer time than

small-sized (Fe,Cr)7C3 carbides. As a result, the oscillating amplitude of the large-sized

Jo

primary (Fe,Cr)7C3 carbides along with the sliding friction pair is larger than that of the

small-sized primary (Fe,Cr)7C3 carbides. After a period of time of reciprocating wear

test, the cracks are appeared at the joint between primary (Fe,Cr)7C3 carbides and

austenite because their interface is seperated. The oscillating amplitude of the refined

13
primary (Fe,Cr)7C3 carbides is small, so the amount of the cracks in Fig.5c is

dramatically smaller than that in Fig.5a. The cracks can directly cause primary

(Fe,Cr)7C3 carbides to fall off, so the mass loss of the hypereutectic Fe-Cr-C hardfacing

alloy with Nb additive is less than that without Nb additive.

4.4 Explanation on the tensile strength

It has been mentioned in Fig.10 that, the phase fractions of the two hypereutectic

Fe-Cr-C hardfacing alloys are almost the same except for some NbC in the No.2 alloy,

of
so the doubled tensile strength in Table 3 is due to the refinement of the primary

ro
(Fe,Cr)7C3 carbides. The strength of the primary (Fe,Cr)7C3 carbides is higher than that

of austenite, so it can act as tensile “fiber” while tensing parallel to the primary
-p
(Fe,Cr)7C3 carbides. When the fractions of primary (Fe,Cr)7C3 carbides are almost the
re
same, the reduction in size means the number of primary (Fe,Cr)7C3 carbides is

increased. Therefore, the tensile strength parallel to the primary (Fe,Cr)7C3 carbides of
lP

the No.2 alloy is increased significantly. Tensile tests of the hypereutectic Fe-Cr-C
na

hardfacing alloys vertical to the primary (Fe,Cr)7C3 carbides mainly depends on the

cohesion the (Fe,Cr)7C3/austenite interface. Due to the fact the (Fe,Cr)7C3/austenite

ur

interface is easily separated during tensing, when the size of the primary (Fe,Cr)7C3

carbides are decreased (namely area of the (Fe,Cr)7C3/austenite interface is increased),

Jo

the tensile strength vertical to the primary (Fe,Cr)7C3 carbides is reduced. It is the reason

why the tensile strength vertical to the primary (Fe,Cr)7C3 carbides of the hypereutectic

Fe-Cr-C hardfacing alloy with Nb additive is much lower than that without Nb additive.

5. Conclusion

14
 (1) The hypereutectic Fe-Cr-C hardfacing alloy without Nb additive consists of

(Fe,Cr)7C3 and austenite, while that with Nb additive contains NbC, (Fe,Cr)7C3 and

austenite. The size of the primary (Fe,Cr)7C3 carbides in the hypereutectic Fe-Cr-C

hardfacing alloy with Nb additive is much smaller than that without Nb additive.

(2) The refined primary (Fe,Cr)7C3 carbides reduce the amount of the cracks on

the hypereutectic Fe-Cr-C hardfacing alloy during wear test. The mass loss comparison

also shows that the refined primary (Fe,Cr)7C3 carbides promote the wear resistance of

of
the hypereutectic Fe-Cr-C hardfacing alloy.

ro
(3) Primary (Fe,Cr)7C3 carbides and NbC both displays cleavage fracture

characteristic during tensing, but the cohesion between them is strong so they are tightly
-p
combined with each other. The refined primary (Fe,Cr)7C3 carbides improve the tensile
re
strength parallel to the primary (Fe,Cr)7C3 carbides, while reduce the tensile strength

vertical to the primary (Fe,Cr)7C3 carbides.

lP

(4) The hypereutectic Fe-Cr-C hardfacing alloy with Nb additive forms NbC firstly,
na

after then the phase transition is the same as that without Nb additive. The δ between

NbC and (Fe,Cr)7C3 is 2.16%, which means the preferentially formed NbC refine the
ur

primary (Fe,Cr)7C3 carbides by acting as heterogeneous nucleus.

Jo

CRediT author statement

Sha Liu: Conceptualization, Methodology, Software.

Zhijun Shi: Data curation, Writing- Original draft preparation.

Xiaolei Xing: Visualization, Investigation.

15
Yefei Zhou: Supervision.

Qingxiang Yang: Writing- Reviewing and Editing,

Declaration of interests
The authors declare that they have no known competing financial interests or personal
relationships that could have appeared to influence the work reported in this paper.

Acknowledgements

of
The authors would like to express their gratitude for projects supported by the

ro
National Natural Science Foundation of China under the Contract no. 51771167 and

EU H2020 Marie Skłodowska-Curie project “i-Weld” (No 823786).

References
-p
re
[1] X. Chen, C. Su, Y. Wang, A.N. Siddiquee, S. Konovalov, S. Jayalakshmi, R.A. Singh, Cold

metal transfer (CMT) based wire and arc additive manufacture (WAAM) system, J. Surf.
lP

Investig. 12 (2018) 1278-1284.

[2] Y.H. Qu, J.D. Xing, X.H. Zhi, J.Y. Peng, H.G. Fu, Effect of cerium on the as-cast
na

microstructure of a hypereutectic high chromium cast iron, Mater. Lett. 62 (2008) 3024-3027.
ur

[3] C. Scandian, C. Boher, J.D.B. de Mello, F. Rézaï-Aria, Effect of molybdenum and chromium

contents in sliding wear of high-chromium white cast iron, Wear 267 (2009) 401-408.
Jo

[4] Y.L. Yuan, Z.G. Li, Eff ects of rod carbide size, content, loading and sliding distance on the

friction and wear behaviors of (Cr, Fe)7C3-reinforced α-Fe based composite coating produced

via PTA welding process, Surf. Coat. Technol. 248 (2014) 9-22.

[5] L. Lu, H. Soda, A. McLean, Microstructure and mechanical properties of Fe-Cr-C eutectic

16
 composites, Mater. Sci. Eng. A. 347 (2003) 214-222.

[6] N. Yüksel, S. Şahin, Wear behavior-hardness-microstructure relation of Fe-Cr-C and Fe-Cr-C-

B based hardfacing alloys, Mater. Des. 58 (2014) 491-498.

[7] N. Barnes, S. Borle, M. Dewar, J. Andreiuk, P.F. Mendez, 3D microstructure reconstruction of

chrome carbide weld overlays, Sci. Technol. Weld. Joi. 29, (2014) 696-702.

[8] A. Bedolla-Jacuinde, R. Correa, I. Mejia, J.G. Quedaza, W.M. Rainforth, The effect of titanium

on the wear behaviour of a 16%Cr white cast iron under pure sliding, Wear 263 (2007) 808-

of
820.

ro
[9] T.A. Adler, Ö.N. Dogan, Erosive wear and impact damage of high-chromium white cast irons,

Wear 225 (1999) 174-180.

-p
[10] C.M. Chang, C.M. Lin, C.C. Hsieh, J.H. Chen, C.M. Fan, W. Wu, Effect of carbon content on
re
microstructural characteristics of the hypereutectic Fe-Cr-C claddings, Mater. Chem. Phys. 117
lP

(2009) 257-261.

[11] C.M. Chang, L.H. Chen, C.M. Lin, J.H. Chen, C.M. Fan, W. Wu, Microstructure and wear
na

characteristics of hypereutectic Fe-Cr-C cladding with various carbon contents, Surf. Coat.

Technol. 205 (2010) 245-250.

ur

[12] C.M. Lin, C.M. Chang, J.H. Chen, W. Wu, Hardness, toughness and cracking systems of

primary (Cr, Fe)23C6 and (Cr, Fe)7C3 carbides in high-carbon Cr-based alloys by indentation,
Jo

Mater. Sci. Eng. A 527 (2010) 5038-5043.

[13] C.M. Lin, C.M. Chang, J.H. Chen, W. Wu, The effects of additive elements on the

microstructure characteristics and mechanical properties of Cr-Fe-C hard-facing alloys, J.

Alloy. Compd. 498 (2010) 30-36.

17
[14] H.S. Ding, S.Q. Liu, H.L. Zhang, J.J. Guo, Improving impact toughness of a high chromium

cast iron regarding joint additive of nitrogen and titanium, Mater. Des. 90 (2016) 958-968.

[15] M. Filipovic, Z. Kamberovic, M. Korac, M. Gavrilovski, Microstructure and mechanical

properties of Fe-Cr-C-Nb white cast irons, Mater. Des. 47 (2013), 41-48.

[16] X.J. Wu, J.D. Xing, H.G. Fu, X.H. Zhi, Effect of titanium on the morphology of primary M7C3

carbides in hypereutectic high chromium white iron, Mater. Sci. Eng. A 457 (2007) 180-185.

[17] S. Kou, Welding Metallurgy, 2nd ed., John Wiley, Hoboken, New Jersey, 2003.

of
[18] T. Yuan, S. Kou, Z. Luo, Grain refining by ultrasonic stirring of the weld pool, Acta. Mater.

ro
106 (2016) 144-154.

[19] L.E. Eiselstein, O.A. Ruano, O.D. Sherby, Structural characterization of rapidly solidified
-p
white cast iron powders, J. Mater. Sci., 18 (1983) 483-492.
re
[20] K.H.W. Seah, J. Hemanth, S.C. Sharma, Wear characteristics of sub-zero chilled cast iron,
lP

Wear, 192 (1996) 134-140.

[21] G. Laird II, Microstructures of Ni-hard I, Ni-hard IV and high-Cr white cast irons, AFS Trans.
na

99 (1991) 339-357.

[22] Z.F. Huang, W.D. Huang, A.F. Zhang, J.D. Xing, Impact and wear properties of semisolid
ur

hypereutectic high chromium cast iron, J. Xi’an Jiaotong Univ. 39 (2005) 775-778.

[23] X.H. Zhi, J.D. Xing, H.G. Fu, Y.M. Gao, Effect of titanium on the as-cast microstructure of
Jo

hypereutectic high chromium cast iron, Mater. Charact. 59 (2008) 1221-1226.

[24] X.H. Zhi, J.Z. Liu, J.D. Xing, S.Q. Ma, Effect of cerium modification on microstructure and

properties of hypereutectic high chromium cast iron, Mater. Sci. Eng. A 603 (2014) 98-103.

[25] X.W. Qi, Z.N. Jia, Q.X. Yang, Y.L. Yang, Effects of vanadium additive on structure property

18
 and tribological performance of high chromium cast iron hardfacing metal, Surf. Coat. Technol.

205 (2011) 5510-5514.

[26] J. Yang, J.J. Tian, F.F. Hao, T. Dan, X.J. Ren, Y.L. Yang, Q.X. Yang, Microstructure and wear

resistance of the hypereutectic Fe-Cr-C alloy hardfacing metals with different La2O3 additives,

Appl. Surf. Sci. 289 (2014) 437-444.

[27] X. Yun, Y.F. Zhou, J. Yang, X.L. Xing, X.J. Ren, Y.L. Yang, Q.X. Yang, Refinement of nano-

Y2O3 on microstructure of hypereutectic Fe-Cr-C hardfacing coatings, J. Rare. Earth. 33 (2015)

of
671-678.

ro
[28] B.L. Bramfitt, The effect of carbide and nitride additions on the heterogeneous nucleation

behavior of liquid iron. Metall. Trans. 1 (1970) 1987-1995.

-p
re
lP
na
ur

Fig.1 Schematic of the hardfacing process by open arc welding method.

Jo

19
Fig.2 Tensile specimens (a) Geometry and dimensions of specimens for tensile test (unit: mm); (b)
specimens tensed parallel to the primary (Fe,Cr)7C3; (c) specimens tensed vertical to the primary
(Fe,Cr)7C3.

of
ro
-p
re
lP

Fig.3 XRD patterns of hypereutectic Fe-Cr-C hardfacing alloys.

na
ur
Jo

Fig.4 Microstructures of hypereutectic Fe-Cr-C hardfacing alloys.

(a) No.1 alloy; (b) No.2 alloy; (c) area statistics of No.1 alloy (green dots) and No.2 alloy (blue
dots).

20
 Fig.5 Mass loss of hypereutectic Fe-Cr-C hardfacing alloy after wear test.

of
ro
-p
re
lP
na
ur
Jo

Fig.6 Worn surfaces of hypereutectic Fe-Cr-C hardfacing alloys and corresponding element
distribution maps.
(a) Worn surface and (b) element distribution map of No.1 alloy;
(c) worn surface and (d) element distribution map of No.2 alloy.

21
Fig.7 Tensile curves of hypereutectic Fe-Cr-C alloys parallel to (a) and vertical to (b)

of
primary (Fe,Cr)7C3.

ro
-p
re
lP
na
ur
Jo

Fig.8 Fractographies after tensing parallel to primary (Fe,Cr)7C3 and corresponding element
distribution maps.
(a) Fractography and (b) element distribution map of No.1 alloy;
(c) fractography and (d) element distribution map of No.2 alloy.

22
 of
ro
Fig.9 Fractographies after tensing vertical to primary (Fe,Cr)7C3 and corresponding element
distribution maps.
-p
(a) Fractography and (b) element distribution map of No.1 alloy;
(c) fractography and (d) element distribution map of No.2 alloy.
re
lP
na
ur
Jo

Fig.10 Phase fraction vs. temperature curves of hypereutectic Fe-Cr-C hardfacing alloys.
(a) No.1 alloy; (b) No.2 alloy.

23
 Fig.11 Relationship between (110)NbC and (010) (Fe,Cr)7C3.

of
ro
-p
re
lP
na
ur
Jo

24