Surface & Coatings Technology 294 (2016) 115–121

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Surface & Coatings Technology

journal homepage: www.elsevier.com/locate/surfcoat

The effect of nitrogen alloying to the microstructure and mechanical

properties of martensitic stainless steel hardfacing
J.B. Wang a, Y.F. Zhou a,b,⁎, X.L. Xing a, S. Liu a, C.C. Zhao a, Y.L. Yang b, Q.X. Yang a,⁎⁎
a
State Key Laboratory of Metastable Materials Science & Technology, Yanshan University, Qinhuangdao 066004, PR China
b
College of Mechanical Engineering, Yanshan University, Qinhuangdao 066004, PR China

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

Article history: The effect of nitrogen additive on the microstructure and mechanical properties of martensitic stainless steel
Received 19 December 2015 hardfacing was investigated in this work. The phase structure of the hardfacing was analyzed by X-ray diffraction
Revised 25 March 2016 (XRD). The microstructures with and without nitrogen additive were observed by field emission scanning elec-
Accepted in revised form 25 March 2016
tron microscope (FESEM) and transmission electron microscope (TEM). The mechanical properties of the
Available online 31 March 2016
hardfacing were measured, and the fracture surfaces were observed by FESEM. The equilibrium phase diagram
Keywords:
and phase precipitation rule were calculated by ThermoCalc software. The results show that, by replacing carbon
Hardfacing with nitrogen in hardfacing, the martensitic lath is refined, and the segregation and precipitation on prior austen-
Martensitic stainless steel ite grain boundary cannot be found. In addition, the mechanical properties of the hardfacing can be improved
Nitrogen additive obviously after composition optimization, in which, the yield strength and tensile strength are increased from
Mechanical properties 884 MPa and 996 MPa to 1078 MPa and 1554 MPa respectively. Meanwhile, the ductile of the hardfacing is sig-
Microstructure nificantly increased. The fracture surface is transformed from brittle intergranular fracture into ductile
transgranular one.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction
Continuous casting roller is a key component in continuous casting
and rolling production. With high heat resistance, abrasive resistance,
corrosion resistance and mechanical properties, the martensitic stain-
less steel was usually chosen to manufacture the continuous casting
roller [1–3]. During continuous casting and rolling production, the con-
tinuous casting roller always failed because of its lower mechanical
properties. The failed roller could be remanufactured by hardfacing
method to restore its initial shape and size, and obtain higher mechan-
ical properties.
It is recognized that nitrogen as an alloy element can reinforce
Fe-based alloy [1,4]. With the development of high-pressure melting
and higher nitrogen content in steel, the effect of microstructure and
properties caused by nitrogen additive in Fe-based alloy have been
investigated deeply [5–10].
Nitrogen additive in austenite stainless steel has been abundantly
studied [11–13]. Because the radius of nitrogen atom is smaller than
that of carbon atom, researchers found that nitrogen atoms could solute
in austenite instead of carbon atoms, especially the strength [11] and
corrosion resistance [14,15] of austenite stainless steel can be improved
⁎ Correspondence to: Y.F. Zhou, State Key Laboratory of Metastable Materials Science &
Technology, Yanshan University, Qinhuangdao 066004, PR China.
⁎⁎ Corresponding author.
E-mail addresses: yfzhou@ysu.edu.cn (Y.F. Zhou), qxyang@ysu.edu.cn (Q.X. Yang).
obviously by nitrogen additive. J.W. Simmons [6] reviewed that the me-
chanical, corrosion and fatigue properties of the high nitrogen stainless
steel can be improved by nitrogen additive. Werner [16] believed that
nitrogen as an element in austenite stainless steel is more effective on
solid-solution strengthening and grain refinement strengthening than
carbon. Balachandran et al. [17,18] found that with increasing nitrogen
content, the austenite stability can be improved significantly. Soussan
[19] also found that by nitrogen additive, the strain hardening rate of
the austenite alloy is improved greatly. Lo et al. [20,21] discovered
that the strength of Fe-based alloys can be improved significantly by
nitrogen additive. Meanwhile, the ductility is not decreased.
In recent years, researchers have begun to focus on the effect
of nitrogen additive in martensitic stainless steel. X.P. Ma [22]
investigated the properties of the martensitic stainless steel of
13Cr5Ni1Mo0.025Nb0.09V0.06N, and found that the formation tenden-
cy of ferrite and deformation induced martensite transformation can be
reduced. Lee et al. [23] found that it is beneficial to improve creep resis-
tance and fatigue abrasive resistance by N additive.
At present, researchers are just beginning to study the effect of
nitrogen additive on hardfacing. Yang [24] studied carbonitrides precip-
itations in martensitic hardfacing, which could improve abrasion resis-
tance and fatigue flake resistance. Moon [25,26] made a systematic
study on the mechanical properties and microstructure of heat affect
zone in high nitrogen stainless steel. However, up to now, the effect of
nitrogen additive on the microstructure and mechanical properties of
martensitic hardfacing has not been found.

http://dx.doi.org/10.1016/j.surfcoat.2016.03.076
0257-8972/© 2015 Elsevier B.V. All rights reserved.
116 J.B. Wang et al. / Surface & Coatings Technology 294 (2016) 115–121

Fig. 1. Diagrammatic view of flux-cored wire manufacturing.

analyzer. In this paper, substrate steel for the welding surface was pre-
Table 1 pared from steel plate of Q235, whose chemical composition is listed in
Chemical composition of H08A. Table 3. With the method of submerged-arc hardfacing, five layers were
Element C Si Mn Cr Ni Cu S P welded onto the surface of each substrate steel. The parameters of
Content ≤0.10 ≤0.03 0.35–0.60 ≤0.20 ≤0.30 ≤0.20 ≤0.03 ≤0.03
hardfacing process are listed in Table 4.
(wt.%) Firstly, specimens with size 10 × 10 × 10 mm3 were cut off from the
middle of the hardfacing by electrical discharge wire-cutting. The spec-
imens were ground on SiC waterproof paper with grit from 150 to 1200,
Table 2 and were polished with diamond compound polishing paste. The phase
Chemical composition of the hardfacings (wt.%).
structure of the hardfacing was analyzed by X-ray diffraction (XRD)
Element C N Si Mn Cr Mo Ni V Nb using a D/max-2500/PC diffractometer equipped with Cu-Kα radiation,
No. 1 0.19 – 0.36 1.18 12.8 0.5 1.3 – – with the scanning range 40° ≤ 2θ ≤ 100° and a step size of 0.02°and the
No. 2 0.095 0.07 0.328 1.24 13.22 2.21 2.63 0.155 0.049 dwell time was 2 s. After etched with aqua regia, the microstructure and
elements segregation of the hardfacing were analyzed by using a Hitachi
S4800-IIfield emission scanning electron microscope (FESEM) and
Table 3 energy dispersive X-ray spectrometry (EDS). The crystal structure was
Chemical composition of Q235. determined by transmission electron microscope (TEM) JOEL 2010.
Element C Si Mn S P Three tensile specimens parallel and perpendicular to the welded
Content (wt.%) ≤0.20 ≤0.35 ≤1.40 ≤0.03 ≤0.03
trace were taken from the welded layer to examine the yield and tensile
strength by using Inspekt Table 100 type electromechanical universal
testing machine. The size and shape of the specimens have been
inserted in Fig. 2. Then the fractographies were analyzed by using
In our previous research, the high-alloyed martensite in hardfacing FESEM.
with different carbon contents has been investigated [27,28]. Based At last, ThermoCalc software was employed to calculate the phase
on the effect of carbide precipitation on the hardfacing abrasive resis- diagram and the variation of different phase fractions as a function of
tance, such as nitrided ferrochrome, ferromolybdenum, ferronickel, temperature of the hardfacing.
ferrovanadium, ferroniobium and so on were added in the flux core to
optimize flux-cored wire. The optimized flux-core wire could obtain a 3. Experimental results
better microstructure and mechanical property of the hardfacing,
which may provide guidance for hardfacing remanufacturing of the 3.1. Microstructure
continuous casting roller.
3.1.1. Phase structure
2. Experimental materials and methods The XRD diffraction pattern for No. 1 hardfacing in comparison with
that for No. 2 hardfacing is shown in Fig. 3. The main phase of both No. 1
As shown in Fig. 1, the flux-core wire was manufactured with rolling and No. 2 hardfacing is α-Fe, which may be martensite. Moreover, a lit-
and drafting process. The outer shell of the flux-cored wire was the tle part of γ-Fe phase was found in No. 1 hardfacing, which might be
low-carbon steel strip of H08A, whose chemical composition is listed retained austenite. One can immediately realize that the (110) diffrac-
in Table 1. The core powders mainly consist of ferrochrome, ferroman- tion peak in both No. 1 and No. 2 hardfacing is extremely strong. In ad-
ganese, ferrosilicon, molybdenum powder, and nickel powder and dition, the (211) diffraction peak is stronger than the (200) diffraction
so on. No. 1 wire was the traditional martensitic stainless steel flux- peak in No.1 hardfacing. On the contrary, in No. 2 hardfacing, the
cored wire, which has been widely used in actual application for (200) diffraction peak is stronger.
hardfacing continuous casting roller. No. 2 wire was the added nitrided The structure was refined on the XRD diffraction patterns with
ferrochrome flux-cored one, as is listed in Table 2, the composition of Rietveld method. It can be found that 5.5 ± 0.5% γ-Fe phase exists
No. 2 welded hardfacing was optimized. The chemical compositions of in No.1 hardfacing. No γ-Fe phase diffraction peak is found in No. 2
the hardfacing were determined by using Advant/p-381 X-ray fluores- hardfacing. Moreover, no diffraction peaks of carbides, nitrides and
cence spectrometer and CS-8800 high frequency infrared carbon sulfur carbonitrides can be found in the hardfacing.

Table 4
Hardfacing processing parameters.

Wire diameter (mm) Voltage (V) Current (A) Travel speed (mm/s) Substrate steel thickness (mm) Layer thickness (mm)

2.8 28–30 280–300 5 20 15

 J.B. Wang et al. / Surface & Coatings Technology 294 (2016) 115–121
Fig. 2. Diagrammatic view of tensile specimen.
Fig. 3. XRD diffraction patterns of the hardfacings.
3.1.2. Metallographic structure
Fig. 4 illustrates FESEM of the hardfacing, which shows that the mi-
crostructure is similar and the prior austenite grain boundary can be ob-
served obviously. No defects such as pores and cracks were found in the
obtained hardfacing. However, the prior austenite grain is refined in
hardfacing with nitrogen additive. It has been found that microstructure
of the hardfacings is mostly martensitic according to Figs. 3 and 4. The
precipitation distributions of the hardfacing are given in Fig. 5, in
which some precipitations are identified on grain boundary of No. 1
hardfacing. Moreover, concentration of chromium and manganese,
and reduction of iron are also discovered. On the contrary, grain bound-
ary of No. 2 hardfacing is clear and smooth, on which has no precipita-
tions existed. The elements distribute homogeneously.
Fig. 4. Microstructures of the hardfacings: (a) No. 1 (b) No. 2.
117
3.1.3. TEM patterns
Fig. 6 illustrates lath martensite of the hardfacing. The average mar-
tensitic lath width of No. 1 hardfacing is 0.35 μm, while that of No. 2
hardfacing is 0.2 μm and also the grain size distribution is more even.
With zone axis of [ 1 11], the electron diffraction was carried out
for the hardfacings, and then the interplanar distances from the plane
(011) were measured. The interplanar distances of the hardfacing are
dNo. 1 = 0.208 nm and dNo. 2 = 0.212 nm respectively. In addition, the
lattice parameter of the hardfacing is calculated, and the results are
aNo. 1 = 2.94 Å and aNo. 2 = 3.00 Å respectively.
3.2. Mechanical properties and fractography
3.2.1. Mechanical properties
Table 5 lists the mechanical properties of the hardfacing. For No. 1
hardfacing, the tensile strength is 996 MPa, the yield strength is
884 MPa and the percentage elongation is 10.7 ± 0.3%. The reduction
of cross-sectional area is small, and brittle fracture occurs. There is no
difference about the mechanical properties in the parallel and perpen-
dicular to the welded trace. However, the mechanical properties of No.
2 hardfacing are improved significantly, in which, the tensile strength
is 1554 MPa, the yield strength is 1078 MPa, the percentage elongation
is 17.7 ± 0.5% and the reduction of cross-sectional area is 17.3 ± 0.8%. It
is clear that the ductile fracture occurs. Compared with No. 1 hardfacing,
the tensile strength of No. 2 hardfacing is increased by 56% and the yield
strength by 22%.
3.2.2. Fracture surface morphology
The macro fracture surfaces of the hardfacing are presented in
Fig. 7(a) and (b). In No. 1 hardfacing, the cracks initiate and propagate
along grain boundary during the tensile process, and brittle fracture
occurs. Fracture surface of No. 2 hardfacing is presented in Fig. 7(b),
in which, shear lip exists on the fracture surface and typical ductile
fracture can be found. Fig. 7(c) and (d) show the micro fracture surface
of the hardfacing. The precipitations and cleavage plane can be
identified in Fig. 7(c), which is correspondent with Fig. 5, where many
118 J.B. Wang et al. / Surface & Coatings Technology 294 (2016) 115–121

Fig. 5. Distribution of chemical elements in the microstructure of the hardfacings: (a) No. 1, (b) No. 2.

precipitations exist and segregation of chromium and manganese on
grain boundary can be found. On the country, from Fig. 7(d), there is
no cleavage plane, while many dimples exist in No. 2 hardfacing.
4. Analysis and discussion
From the experimental results, by adding nitrogen additive in
the hardfacing, the retained austenite fraction can be reduced, the
prior austenite grain can be refined, and the martensitic lath is
decreased, so that the mechanical properties of the hardfacing can be
improved significantly.
4.1. Effect of nitrogen additive on austenite transformation
It is shown in Fig. 4 that the prior austenite grain of No. 2 hardfacing
was obviously refined. By calculating the equilibrium phase diagram, it
is found that peritectic reaction occurs in the hardfacing, as shown in
Figs. 8 and 9. During equilibrium solidification, δ-Fe firstly precipitates
from liquid phase, and the transformation Liquid → δ takes place.
When temperature is cooling down to peritectic line, peritectic reaction
Liquid + δ → γ occurs. With a lower carbon content, the rate of
peritectic reaction of No. 2 hardfacing is lower than that of No. 1
hardfacing. Fig. 9 illustrates the variation of different phase fractions
as a function of temperature. Ferrite (δ-Fe) firstly precipitates from the
liquid phase, and then the retained liquid reacts with the primary ferrite
precipitated at 1400 °C and austenite transformation occurs. When the
peritectic reaction is accomplished, the austenite fraction of No. 1 and
No. 2 hardfacing were 32% and 6% respectively. In addition, vanadium
and nitrogen additive in No. 2 hardfacing can increase martensite start
temperature [29,30]. So the transformation time of austenite in No. 2
hardfacing is shorter than that in No. 1 hardfacing, which causes grain
coarser in No. 1 hardfacing than that in No. 2 hardfacing.
Refined austenite grains can increase pressure at the grain boundary,
and decrease the critical half-thickness of the martensite crystal nucleus
[31]. By refining austenite grains, even the nanostructured lath mar-
tensite can be transformed from refined austenite [32]. Therefore, the
fine lath martensite of No. 2 hardfacing can be transformed from
grain-refined prior austenite. In addition, in order to increase nitrogen
solubility, vanadium and niobium were added in the No. 2 hardfacing,
and molybdenum content was increased at the same time. Because

Fig. 6. TEM patterns of the hardfacings: (a) No. 1, (b) No. 2.

 J.B. Wang et al. / Surface & Coatings Technology 294 (2016) 115–121
Table 5
Mechanical properties of the hardfacings.
Hardfacing σs (MPa) σb (MPa) A (%) Z (%)
No. 1 884 ± 48 996 ± 46 10.7 ± 0.3 –
No. 2 1078 ± 45 1554 ± 32 17.7 ± 0.5 17.3 ± 0.8
vanadium, niobium and molybdenum mentioned above are all substitu-
tional elements which lead to the change of lattice parameters of prior
austenite, the lattice parameters of obtained martensite were also
changed after transforming from austenite to martensite.
According to Fig. 5, segregation of chromium and manganese on
grain boundary exists in No. 1 hardfacing, which leads to the increase
of the chromium and manganese contents. So martensite finish temper-
ature decrease, what leads to incomplete transformation process from
austenite to martensite has not been completed. It is known that chro-
mium favours the formation of ferrite, and nitrogen and manganese
have the effect of stabilizing austenite [12]. But from Fig. 3 results,
there exists retained austenite. So it can be inferred that the effect of
manganese with stabilizing austenite is greater than that of chromium
with ferrite formation.
On the contrary, no segregation of chromium and manganese on
grain boundary in No. 2 hardfacing might be observed, the transforma-
tion from austenite to martensite is complete, so there is no retained
austenite at all.
4.2. Effect of nitrogen additive on the mechanical properties
Wang et al. [32] demonstrated that the smaller the austenite grain
size is, the larger was the transformation resistance from austenite to
martensite, and then martensitic lath is refined. As shown in Figs. 4
and 6, because the austenite grain size in No. 2 hardfacing is smaller
than that in No. 1 hardfacing, the martensitic lath is refined from
0.35 μm to 0.2 μm and the laths distribute homogenously in No. 2
hardfacing.
Fig. 7. Fracture surfaces of the hardfacings: (a), (c) No. 1; (b), (d) No. 2.
119
In order to explain the relationship between microstructure refine-
ment and mechanical properties, S. Degallaix et al. [1] modified Hall-
Petch relationship, which is given in Eq. (1). They calculated the yield
strength of high nitrogen austenite stainless steel with Eq. (1), which
is matched with experimental results very well.
pffiffiffiffiffiffi ½7 þ 78CN 
σ s ¼ 127:6 þ 309:9 CN þ pffiffiffiffi ð1Þ
D
where CN is the nitrogen content in wt.%; D is the grain diameter.
In this paper, the martensitic lath width is taken as D. The martens-
itic lath width of No. 1 and No. 2 hardfacing are 0.35 μm and 0.2 μm
respectively. The yield strength of the hardfacing are calculated with
Eq. (1), which are listed in Table 6.
From Table 6, the martensitic lath width of the hardfacing could be
effectively equal to grain diameter D in the modified Hall-Petch
Eq. (1). With nitrogen additive, martensitic lath in the No. 2 hardfacing
is refined, and the strength is improved effectively, which match very
well with the Hall-Petch Eq. (1). Therefore, the martensitic lath refine-
ment is the main reason for significantly improving the mechanical
properties of No. 2 hardfacing.
It has been known that brittle phase such as carbide and nitride
on grain boundary acts as preferential site for premature crack
initiation and propagation and causes fracture mode to be brittle
[13]. The distribution of carbides on prior austenite grain boundary of
No. 1 hardfacing has negative effect on mechanical properties, which
cause brittle fracture. On the contrary, carbides and nitrides on prior
austenite grain boundary of No. 2 hardfacing were not discovered, so
mechanical prosperities have not been affected, and ductile fracture
occurs.
5. Conclusion
(1) In hardfacing, by replacing carbon with nitrogen, the rate of
peritectic reaction reduced, and then prior austenite grain size
can be refined. Moreover the martensitic lath is also refined.
120 J.B. Wang et al. / Surface & Coatings Technology 294 (2016) 115–121

Fig. 8. Equilibrium phase diagrams of the hardfacings: (a) No. 1, (b) No. 2.

Fig. 9. Precipitate phases as a function of temperature in the hardfacings: (a) No. 1, (b) No. 2.

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