coatings

Article
Microstructure Evolution and Failure Behavior of
Stellite 6 Coating on Steel after Long-Time Service
Jiankun Xiong 1,2,3 , Fuheng Nie 3 , Haiyan Zhao 1, *, Liangliang Zheng 3 , Jun Luo 3 , Lin Yang 2,3
and Zhongbo Wen 3
1 Department of Mechanical Engineering, Tsinghua University, Beijing 100084, China
2 State Key Laboratory of Long-life High Temperature Materials, Dongfang Turbine Co., Ltd.,
Deyang 618000, China
3 Manufacturing Technology Department, Dongfang Turbine Co., Ltd., Deyang 618000, China
* Correspondence: [email protected]; Tel.: +86-838-268-7424




Received: 30 July 2019; Accepted: 20 August 2019; Published: 22 August 2019


Abstract: The microstructure evolution, elements diffusion and fracture behavior of the Stellite 6
weld overlay, deposited on 10Cr9Mo1VNbN (F91) steel by the tungsten inert gas (TIG) cladding
process, were investigated after long-time service. Obvious diffusion of Fe occurred from the steel
and fusion zone to the Stellite overlay, resulting in the microstructure evolution and hardness increase
in the coating, where hard Co–Fe phases, σ phases (Fe–Cr metallic compounds) and Cr-rich carbides
(Cr18.93 Fe4.07 C6 ) were formed. Besides, the width of the light zone, combined with the fusion zone
and diffusion zone, increased significantly to a maximum value of 2.5 mm. The fracture of the Stellite
coating samples mainly occurred in the light zone, which was caused by the formation and growth of
circumferential crack and radial crack under high temperature and pressure conditions. Moreover,
the micro-hardness values in the light zone increased to the maximum (470–680 HV) due to the
formation and growth of brittle Co–Fe phases. The formation of these cracks might be caused by
formed brittle phases and changes of micro-hardness during service.

Keywords: Stellite 6 alloy; 10Cr9Mo1VNbN steel; TIG cladding; cracking; microstructure evolution

1. Introduction
10Cr9Mo1VNbN (F91) steel, as a martensitic, heat-resistant steel, has outstanding high-temperature
performance and corrosion resistance, and is massively applied in manufacture of steam boiler,
valve body, tube and turbine components [1]. The valve discs and seats mainly made of F91 steels are
easily subjected to the severe erosion and wear of solid particles under high temperature and pressure
in the service process. To enhance the service life of the valve discs and seats, protective coatings
with adequate mechanical properties, wear and spalling resistance, are usually required. Stellite alloy
(Co-based alloy), especially Stellite 6 alloy, is often used as a coating material in valve disc manufacturing,
due to its excellent wear resistance, corrosion resistance and high temperature properties [2–4].
In previous work, different overlaying methods have been performed to investigate the properties
of the wearing coating, including laser cladding, arc welding, plasma transferred arc (PTA) welding
and gas dynamic cold spray [5–14]. Kusmokoet et al. [15] deposited the Stellite 6 alloy on P22 steel
and P91steel plates by laser cladding and investigated the sliding wear characteristics of the coating.
The worn surface of the coating on P91 steel was much rougher compared to that on P22 steel plate,
and fewer strong carbide-forming elements resulted in the reduction of the amount of carbon loss in
the coating on P22 steel. Cincaet et al. [16] investigated the properties of Stellite 6 deposition on low
alloy carbon steel made by cold gas spraying and found that the increase of gas pressure and distance
could led to the reduction of deposition efficiencies.

Coatings 2019, 9, 532; doi:10.3390/coatings9090532 www.mdpi.com/journal/coatings

Coatings 2019, 9, 532 2 of 11

Ferozhkhanet et al. [17] investigated the microstructure, hardness and wear mechanism of Stellite
6alloy coating deposited on 9Cr–1Mo steel by plasma transferred arc welding process, and 309-16L was
used as the interlayer between the coating and 9Cr–1Mo steel. It was found that the amount of alloying
elements (Cr, W and Co) in the Stellite 6 coating was higher than that in the nominal composition,
and the dilution of Fe in Stellite coating was below 2%. Besides, the wear mechanism of the coating
was the combination of delamination and abrasive wear.
Tungsten inert gas (TIG) welding has the advantages of convenience operations, excellent arc
stability and welding quality. Wear-resistant layer surfacing in the valve body is often performed by TIG
cladding in the production of power generation assembly. Mirshekariet et al. [18] and Molleda et al. [19]
both characterized the microstructure and phase features of Stellite 6 surfacing layers deposited on
steel substrates. However, the Stellite coating deposited on the steel components by TIG cladding
could fracture after a long period of service process in power plants, due to the effect of the high
temperature and pressure environment.
The fracture and spalling of the Stellite layer is one of the key problems for the manufacturing of the
power generation assembly, especially a valve body; however, there are no systematic researches to be
reported about the fracture mechanism and alloying elements diffusion of Stellite alloy-deposited steel
parts after long-time service in power plants. In this paper, the TIG cladding method is used to deposit
the surfacing resistance coating (Stellite 6 alloy) onto the F91 steel, and the microstructure evolution,
alloying the elements diffusion and failure behavior of Stellite coating samples after long-time service
process, were investigated.

2. Materials and Methods

Stellite6 alloy coating was deposited onto a F91martensitic heat-resistant steel valve disc
(240 mm × 107 mm) by a multi-pass tungsten inert gas (TIG) cladding process with AWS ERCoCr-A
(Shanghai, China) consumable (4.0 mm). The TIG welding machine is theTSP-300 (Panasonic, Kadoma,
Japan) equipped a positioner and an automatic wire feeder. The nominal composition of F91 steel and
ERCoCr-A wire were shown in Table 1. In addition, the micro-hardness of the Stellite 6 alloy and F91
steel are about 380–450 HV and 200 HV, respectively. Before cladding welding, the F91 steel should
undergo a preheating treatment (200 ◦ C for 1 h) in the electric furnace. During the cladding process,
the welding current (200–290 A), arc voltage (22–30 V), wire feed speed (50–70 mm/min) and travel
speed (80–180 mm/min) were kept constant. The shielding gas is argon, with a flow rate of 15–20 L/min.
There were three layers in the multi-pass surfacing, and the thickness of the surfacing is about 4 mm.
The extension length and diameter of the tungsten electrode was around 8 and 4.0 mm, respectively.
After cladding welding, the weldments were subject to post-welding heat treatment, which was
performed at 400 ◦ C for 1 h. Two components with Stellite 6/F91 TIG cladding structure were obtained.
The component#1 is on the pre-service condition, while the component #2 has been used in the main
stop valve of the steam turbine for about 26,280 h, operating at 566 ◦ C and 9.94 MPa. The weldments
before and after long-time service in a power plant were marked as #1 and #2, respectively.

Table 1. The nominal composition of F91 steel and consumable.

Element (wt %)
Material
C Cr Mo Ni W Nb V
F91 0.091 9.01 0.90 0.010 – 0.083 0.17
Stellite 6 0.93 27.3 0.26 1.81 3.36 – –
Element (wt %)
Material
N Si Mn P S Co Fe
F91 0.040 0.33 0.42 0.014 0.0011 – Bal.
Stellite 6 – 1.08 0.13 0.014 0.0063 Bal. 2.17
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2019, 9, FOR PEER REVIEW 33of
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The main microstructures of F91 steel are tempered martensite (Figure 1a), and the Stellite 6
The main microstructures of F91 steel are tempered martensite (Figure 1a), and the Stellite 6 alloy
alloy consists of Co-rich dendrites matrix and eutectic carbides within grain boundaries (GBs)
consists of Co-rich dendrites matrix and eutectic carbides within grain boundaries (GBs) (Figure 1b).
(Figure 1b). The samples were cut from weldment #1 and #2 for microstructure analysis, and then
The samples were cut from weldment #1 and #2 for microstructure analysis, and then they were etched
they were etched for 20 s with FeCl3 solution after sectioning, grinding and polishing. The
for 20 s with FeCl3 solution after sectioning, grinding and polishing. The microstructure features
microstructure features were studied using an optical microscope (OM, Leica, DM2700M, Wetzlar,
were studied using an optical microscope (OM, Leica, DM2700M, Wetzlar, Germany). In order to
Germany). In order to observe the microstructure evolution, the samples were examined by
observe the
scanning microstructure
electron microscopyevolution,
(SEM, the samples
VEGA3 were
SBH, examinedBrno,
TESCAN, by scanning
Czech electron
Republic), microscopy
and the
micro-hardness profile across the sample was measured. Moreover, the composition inthe
(SEM, VEGA3 SBH, TESCAN, Brno, Czech Republic), and the micro-hardness profile across sample
different
was measured.
regions Moreover,
of samples the composition
was measured in different
with energy regions
dispersive of samples
spectrum (EDS,was measured
VEGA3 SBH,with energy
TESCAN),
dispersive spectrum (EDS, VEGA3 SBH, TESCAN), and the phase identification
and the phase identification of the coating layer was performed by X-ray diffraction (XRD, of the coating layer
was performed by X-ray diffraction (XRD, D/MAX-1200, Rigaku Industrial Corporation,
D/MAX-1200, Rigaku Industrial Corporation, Osaka, Japan). In addition, the microstructure of Osaka, Japan).
In addition, the microstructure
Stellite-deposited steel samples of Stellite-deposited
was investigated by steel samples electron
transmission was investigated
microscopy by (TEM,
transmission
Tecnai
electron microscopy (TEM, Tecnai G2 20 S-TWIN, FEI, Hillsboro, OR, USA), and the
G2 20 S-TWIN, FEI, Hillsboro, OR, USA), and the TEM samples were prepared by focused ion beam TEM samples were
(FIB, AURIGA, Zeiss, Oberkochen, Germany). Figure 1c,d illustrates the schematic of the Stellitethe
prepared by focused ion beam (FIB, AURIGA, Zeiss, Oberkochen, Germany). Figure 1c,d illustrates 6
schematic
alloy weldof the Stellite
overlay on F916 alloy
steelweld
by theoverlay on F91 steel
TIG cladding by the
process andTIG
thecladding
samples process and the samples
for microstructural and
for microstructural
micro-hardness and micro-hardness analyses.
analyses.

(a)Microstructure
1. (a)
Figure 1. MicrostructureofofF91F91steel;
steel;(b)(b)Microstructure
Microstructure of of Stellite
Stellite 6 alloy;
6 alloy; (c) (c)
TheThe schematic
schematic of
of the
the overlay
overlay weldment
weldment of of Stellite
Stellite 6 6alloy
alloyononF91 F91steel;
steel;(d)
(d) the
the sample
sample forfor microstructural
microstructural and
micro-hardness analysis.

3. Results
3. Results
3.1. Microstructure
3.1. Microstructure
The typical microstructures at cross sections of sample #1 are shown in Figure 2. The boundary
The typical microstructures at cross sections of sample #1 are shown in Figure 2. The boundary
between the base material and coating was obvious, and a wide fusion zone was observed in Figure 2a.
between the base material and coating was obvious, and a wide fusion zone was observed in Figure
Moreover, the microstructure of the Stellite weld overlay zone (WOZ) was a typical hypoeutectic
2a. Moreover, the microstructure of the Stellite weld overlay zone (WOZ) was a typical
dendritic in Figure 2b, which consisted of Co solid solution and a network of small carbides particles.
hypoeutectic dendritic in Figure 2b, which consisted of Co solid solution and a network of small
The Co solid solution consisted of fcc γ and hcp ε phases, and the carbides particles were mainly
carbides particles. The Co solid solution consisted of fcc γ and hcp ε phases, and the carbides
M23 C6 , Cr7 C3 and Co3 W intermetallic phases, where M was (Cr, Co, W, Ni, Fe) [2,20].During the TIG
particles were mainly M23C6, Cr7C3 and Co3W intermetallic phases, where M was (Cr, Co, W, Ni, Fe)
cladding process, thermal cycle could result in the formation of microstructures with different features
[2,20].During the TIG cladding process, thermal cycle could result in the formation of
in the heat-affected zone (HAZ), which was divided into a coarse grain heat-affected zone (CG-HAZ),
microstructures with different features in the heat-affected zone (HAZ), which was divided into a
fine grain heat-affected zone (FG-HAZ) and partial normalized zone (PNZ), as shown in Figure 2c–e.
coarse grain heat-affected zone (CG-HAZ), fine grain heat-affected zone (FG-HAZ) and partial
Obviously, grain coarsening occurred in the CG-HAZ, where the austenitizing induced by the high
normalized zone (PNZ), as shown in Figure 2c–e. Obviously, grain coarsening occurred in the
peak temperature happened during TIG cladding, following a significant growth of austenite grains.
CG-HAZ, where the austenitizing induced by the high peak temperature happened during TIG
Finally, coarse original austenite grains remained after cooling. The fine austenite grains formed in
cladding, following a significant growth of austenite grains. Finally, coarse original austenite grains
FG-HAZ due to relatively low heat input compared with CG-HAZ, in which the pinning effect of
remained after cooling. The fine austenite grains formed in FG-HAZ due to relatively low heat
undissolved precipitated phases would restrain the grain boundary migration. Furthermore, a part of
input compared with CG-HAZ, in which the pinning effect of undissolved precipitated phases
would restrain the grain boundary migration. Furthermore, a part of the microstructure in PNZ
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Coatings 2019, 9, x FOR PEER REVIEW 4 of 11

the microstructure
underwent in PNZ underwent
an austenitizing an austenitizing
transformation, transformation,
while the while theofother
other part remained part remained
martensite of
structure,
martensite structure, which eventually generated a mixture structure which consisted of un-tempered
which eventually generated a mixture structure which consisted of un-tempered martensite and
martensite and over-tempered
over-tempered martensite. martensite.

Figure2.2.Microstructure
Figure Microstructureofofsample
sample#1: #1:(a)
(a)Stellite-steel
Stellite-steelinterface;
interface;(b)
(b)Stellite
Stellitecoating;
coating;(c)coarse
(c)coarsegrain
grain
heat-affectedzone
heat-affected zone (CG-HAZ);
(CG-HAZ); (d)(d)
finefine grain
grain heat-affected
heat-affected zone zone (FG-HAZ);
(FG-HAZ); (e) partial
(e) partial normalized
normalized zone.
zone.
The fusion zone had broadened in the Stellite 6 coating layer near F91 steel due to the diffusion
of elements fromzone
The fusion the steel to the Stellite
had broadened 6 coating
in the Stelliteafter the service
6 coating process.
layer near The due
F91 steel elements
to thediffusion
diffusion
eventually
of elementsmade fromathe wider
steellight
to thezone form,6 consisting
Stellite coating after of the
the service
originalprocess.
fusion zone and newdiffusion
The elements mutual
diffusion zone, as shown in Figure 3. The light zone still showed a dendritic
eventually made a wider light zone form, consisting of the original fusion zone and new mutual microstructure as same as
that in our zone,
diffusion Stelliteasweld
shown layer of sample
in Figure #2. light
3. The The width of the
zone still fusionazone
showed was measured
dendritic as 31, as
microstructure 28 same
and
49 µm at different locations of sample #1 in Figure 3a, indicating the width
as that in our Stellite weld layer of sample #2. The width of the fusion zone was measured as 31, 28 of the fusion zone was
non-uniform.
and 49 μm atAfter long-time
different locations service, the width
of sample #1 inofFigure
the fusion zone increased
3a, indicating significantly
the width to form
of the fusion a
zone
large
was diffusion
non-uniform. zoneAfter
as marked
long-time in Figure
service,3b (sample
the width #2),ofwhich couldzone
the fusion even increased
reach to around 2.5 mm,
significantly to
indicating that a high temperature environment could promote the extent
form a large diffusion zone as marked in Figure 3b (sample #2), which could even reach to around of the light zone through
influencing the diffusion
2.5 mm, indicating that aofhigh alloying elementsenvironment
temperature and the formation and growth
could promote of metallic
the extent of thecompound
light zone
phases
through and carbides. the
influencing Figure 3c,d shows
diffusion the XRD
of alloying results and
elements of phases in the light
the formation andzone of samples
growth of metallic#1
and #2. It can be seen from the XRD results in Figure 3c that the
compound phases and carbides. Figure 3c,d shows the XRD results of phases in the light zone ofphases in the light zone mainly
consist
samples of #1
Co–Feand substitution
#2. It can be solid solutions
seen from and σ
the XRD phases
results in(Fe–Cr
Figure metallic compounds),
3c that the phases in the andlight
the two
zone
elements, Co and Fe, have good solid solubility, thus they could dissolve
mainly consist of Co–Fe substitution solid solutions and σ phases (Fe–Cr metallic compounds), and with each other by almost
any
the proportion.
two elements, TheCocarbides
and Fe, were have not
good found
solidfrom the XRD
solubility, thusresults due todissolve
they could the smallerwithquantity
each other andby
small
almostsize.
any The type of phases
proportion. Theincarbides
the lightwere
zone ofnotsample
found#2from was similar
the XRD to that of sample
results due to#1; thehowever,
smaller
there existed
quantity andasmall
more size.
evident Thediffraction
type of phases peak ofin carbides
the light in Figure
zone 3d, which
of sample #2 waswere Cr18.93to
similar Fethat
4.07 Cof
6
carbides. It meant that the formation and growth of the precipitated
sample #1; however, there existed a more evident diffraction peak of carbides in Figure 3d, whichphases happened, and the Co
matrix
were Cr had evolved
18.93Fe4.07C6 to form Co–Fe
carbides. phases
It meant thatduring the service,and
the formation which couldofresult
growth the in the increasing
precipitated of
phases
the micro-hardness and brittleness of this light zone.
happened, and the Co matrix had evolved to form Co–Fe phases during the service, which could
result in the increasing of the micro-hardness and brittleness of this light zone.
3.2. Distribution of Alloying Elementsand Phases
The microstructure of the boundary between the Stellite alloy and F91 steel of sample #1 and #2
were shown in Figure 4, and the major composition of different positions in Figure 4 was measured by
EDS, as shown in Table 2. It can be seen that the microstructure evolution was obvious on the F91
steel side, where a mass of carbides within grains dissolved, precipitated and then grew along GBs,
forming coarse prior austenite grain boundaries (PAGBs). Comparing the composition in position A
with that in position C, it was found that the content of Fe elements increased obviously, while the
content of Co, Cr and W decreased. It indicated that the diffusion process of Fe from the fusion zone to
the Stellite layer predominated. The decrease of Cr content might be attributed to the diffusion of Fe,
the formation of a Co–Fe matrix and a composition fluctuation of alloying elements. Thus, the content of
 Coatings 2019, 9, x FOR PEER REVIEW 5 of 11

Coatings 2019, 9, 532 5 of 11

Cr decreased in the matrix and formed Cr-rich second phases in some positions. Moreover, the content
of Co in positions B and D were similar, demonstrating that the diffusion rate of Co elements from the
Stellite layer to the steel was relatively low under the high temperature and pressure condition.

Figure 3. The interface between Stellite 6 and F91 steel of samples (a) #1 and (b) #2; The X-ray
diffraction (XRD) results of phases in (c) fusion zone of sample #1 and (d) light zone of sample #2.

3.2. Distribution of Alloying Elementsand Phases

The microstructure of the boundary between the Stellite alloy and F91 steel of sample #1 and #2
were shown in Figure 4, and the major composition of different positions in Figure 4 was measured
by EDS, as shown in Table 2. It can be seen that the microstructure evolution was obvious on the F91
steel side, where a mass of carbides within grains dissolved, precipitated and then grew along GBs,
forming coarse prior austenite grain boundaries (PAGBs). Comparing the composition in position A
with that in position C, it was found that the content of Fe elements increased obviously, while the
content of Co, Cr and W decreased. It indicated that the diffusion process of Fe from the fusion
zone to the Stellite layer predominated. The decrease of Cr content might be attributed to the
diffusion of Fe, the formation of a Co–Fe matrix and a composition fluctuation of alloying elements.
Thus, the content of Cr decreased in the matrix and formed Cr-rich second phases in some positions.
Moreover, the
Figure 3.3.
Figure Thecontent
Theinterfaceof
interface Co inStellite
between
between positions
6 and
Stellite 6 BF91
and
and F91Dof
steel were ofsimilar,
samples
steel demonstrating
(a) #1 and
samples (a)(b)
#1#2;
andThe thatdiffraction
X-ray
(b) #2; theX-ray
The diffusion
rate(XRD)
of Co elements
results
diffraction from
of phases
(XRD) the Stellite
resultsinof(c)phases layer
fusioninzone to the
of sample
(c) fusion steel was
zone#1ofand relatively
(d) light
sample zone
#1 and low under
(d)oflight
sample the
zone#2. high temperature
of sample #2.
and pressure condition.

Figure4.4.Photos
Figure Photosofofthe
themicrostructure
microstructurearound
aroundthe
theboundary
boundarybetween
betweenStellite
Stellitealloy
alloyand
andF91
F91steel
steelofof
sample(a)
sample (a)#1#1and
and(b)
(b)#2.
#2.

Table 2. The major composition in different positions around the boundary between Stellite alloy and
Table 2. The major composition in different positions around the boundary between Stellite alloy
F91 steel.
and F91 steel.
Element (mol
Element (mol%)%)
Position
Position
Fe Fe Co Co Cr
Cr W W
A A 46.86 46.86 28.48
28.48 20.17
20.17 4.494.49
B B 89.13 89.13 1.321.32 9.55
9.55 – –
C 76.69 13.21 8.08 2.02
C 76.69 13.21 8.08 2.02
D 88.47 – 11.53 –
D 88.47 – 11.53 –

The
Themicrostructure
microstructurearound
aroundthe boundary
the boundarybetween
betweenthethe
Stellite andand
Stellite thethe
steel of samples
steel #1 and
of samples #2
#1 and
are
#2 shown in Figure
are shown 5a,e, and
in Figure 5a,e,the distributions
and of Co, Cr
the distributions of and
Co, Fe
Crinand
the rectangle
Fe in the area are displayed
rectangle area are
indisplayed
Figure 5b–d,f–h. It can be seen that Co mainly formed a Co matrix in the Stellite
in Figure 5b–d,f–h. It can be seen that Co mainly formed a Co matrix in the Stellite layer, and Fe
layer,
mainly distributed in the steel region to form Fe-base phases and Fe-rich carbides in
and Fe mainly distributed in the steel region to form Fe-base phases and Fe-rich carbides in FigureFigure 5b,d.
Besides, the distribution of Cr was uniform from the Stellite layer to the steel in Figure 5c. It was found
 Coatings 2019, 9, x FOR PEER REVIEW 6 of 11
Coatings 2019, 9, 532 6 of 11

5b,d. Besides, the distribution of Cr was uniform from the Stellite layer to the steel in Figure 5c. It
waschanging
that found that changing
of the Co andofCrthe Co and
content Cr content
around around the
the Stellite-steel Stellite-steel
interface was notinterface wasafter
significant not
significant
the after theinservice
service process Figure process in Figure
5f,h. However, as 5f,h.
shown However,
in Figureas5h,
shown in Figure
an apparent 5h, an of
increase apparent
the Fe
increasewas
content of happening
the Fe content
in thewas happening
Stellite in the interface,
layer near Stellite layer near the
indicating thatinterface,
a mass ofindicating that a
Fe had diffused
massthe
from of steel
Fe hadintodiffused from
the Stellite the steel
because intolarge
of the the diffusion
Stellite because
rate of of
Fe.the large diffusion
Obvious rate of Fe.
mutual diffusion of
Obvious
major mutual
elements diffusion
happened of the
near major elements
boundary happened
during nearprocess
the service the boundary
due to theduring the service
high temperature
process due
condition, to the
thereby high to
leading temperature
the formationcondition, thereby
of a mutual leading
diffusion zoneto in
thetheformation of anear
Stellite layer mutual
the
diffusion
fusion zone in the Stellite layer near the fusion zone.
zone.

Coatings 2019, 9, x FOR PEER REVIEW 6 of 11

5b,d. Besides, the distribution of Cr was uniform from the Stellite layer to the steel in Figure 5c. It
was found that changing of the Co and Cr content around the Stellite-steel interface was not
significant after the service process in Figure 5f,h. However, as shown in Figure 5h, an apparent
increase of the Fe content was happening in the Stellite layer near the interface, indicating that a
mass of Fe had diffused from the steel into the Stellite because of the large diffusion rate of Fe.
Obvious mutual diffusion of major elements happened near the boundary during the service
process due to the high temperature condition, thereby leading to the formation of a mutual
diffusion zone in the Stellite layer near the fusion zone.

Figure5.5.The
Figure Thealloying
alloyingelements
elements distribution
distribution around
around thethe Stellite-steel
Stellite-steel boundary
boundary of samples
of samples (a–d)(a–d) #1
#1 and
(e–h) #2. #2.
and (e–h)

The
Therapid
rapiddiffusion
diffusionof ofFeFecould
couldchange changethe thestructure
structureand andinduce
inducethe theformation
formation of of new
new phases,
phases,
resulting
resulting inin the property variation
the property variationofofthe theStellite
Stellitecoating
coating components
components afterafter
the the service
service process.
process. The
The distribution curve of Fe, Co and Cr content perpendicular
distribution curve of Fe, Co and Cr content perpendicular to the fusion line of sample #1 and #2 is
Figure 5. The alloying elements distribution around the Stellite-steel to
boundarythe of fusion
samples line
(a–d) #1 of sample #1 and
and (e–h) #2.
#2 is presented
presented usingusing
EDS,EDS, as shown
as shown in Figure
in Figure 6. It 6.
canIt becanseenbe seenthat that
the Co thecontent
Co content in the insteel
the steel
was wasvery
very
low. The amount of Fein the Stellite coating near the fusion line was around 30 mol %–60 mol %,
low. The amount The of
rapidFein the
diffusion Stellite
of Fe could coating
change the near the
structure fusion
and induce line
the was
formation around
of new 30 mol
phases, %–60 mol %,
resulting in the property variation of the Stellite coating components after the service process. The
indicating
indicatingthe thediffusion
diffusion process
process hadhad beenbeen occurred.
occurred. TheThe amount
amount of Fe
of Fereached
distribution curve of Fe, Co and Cr content perpendicular to the fusion line of sample #1 and #2 is reached 30 mol
30 mol%–35
%–35 mol %
mol at
%
the distance
at the distanceof presented
2.2 mm
of 2.2 mm from
using from
EDS,the Stellite-steel
asthe
shown in Figure 6.interface
Stellite-steel interface
It can be seeninthat
the
in theStellite
the Stellite
Co contentcoating.
the steelBesides,
coating.
in very the
Besides,
was thevariation
variation
of low.CrThe amount of Fein the Stellite Therefore,
coating near the fusion line was around 30 mol the
%–60 mol %, alloy elements
ofthe
theamount
amountof of Crwas wasnot notsignificant.
significant. Therefore, the thediffusion
diffusionof ofFe
indicating the diffusion process had been occurred. The amount of Fe reached 30 mol %–35 mol %
Fewas was themain main alloy elements
migration
migrationininthe atweld
the weld
the overlay,
overlay,
distance resulting
of 2.2 mm resulting in microstructure
in microstructure
from the Stellite-steel interface in theevolution
evolution
Stellite in the
coating. in light zone.zone.
thethelight
Besides, variation Comparing
Comparing the
of theCoamount
distribution
the distributionof Fe,of Fe, CoofCr
and Cr of
and wassample
Crnotofsignificant.
sample Therefore,
#2 with thattheof
#2 with diffusion
thatsample of Fe
of sample #1,wasthetheFe
#1, main alloy elements
theincreased
Fe increased obviously
obviouslyin thein
migration in the weld overlay, resulting in microstructure evolution in the light zone. Comparing
light zone near
the light zone the the
near fusion line
the fusion
distribution due
of Fe, Coline to
and Cr diffusion
due of
to diffusion
of sample Fe during
#2 with thatof the
Fe during
of sample service.
#1, the Fethe The
service.
increased difference of Fe content
Theindifference of Fe
obviously
between
content sample
between #1light
the and
sample #2near
zone decreased
#1 the
and #2gradually
fusion line when
due to diffusion
decreased ofaway
gradually from
Fe during the the
when fusion
service.
away linethe
Thefrom in of
difference theFe Stellite
fusion linecoating.
in the
content between sample #1 and #2 decreased gradually when away from the fusion line in the
In addition, the variation
Stellite coating.Stellite
In addition, tendency of
the variation
coating. In addition,
Cr and
the variation
Co
tendency was
tendency ofof
not
Cr Cr
very
and and
significant
Co was Co notwas
after the
not veryafter
very significant
service.
significant
the after the
service. service.

Figure 6. Element distribution perpendicular to fusion line of samples #1 and #2.

 Coatings 2019, 9, x FOR PEER REVIEW 7 of 11
Coatings 2019, 9, 532 7 of 11
Figure 6. Element distribution perpendicular to fusion line of samples #1 and #2.

TEM
TEMinvestigations
investigations were
wereperformed
performed to analyze
to analyze the phases in thein
the phases diffusion zone. Figure
the diffusion zone. 7Figure
shows7
the
shows the TEM images and diffraction patterns of the microstructure in the light zone betweenand
TEM images and diffraction patterns of the microstructure in the light zone between the Stellite the
the steel of sample #2. The TEM image of the matrix in the diffusion zone
Stellite and the steel of sample #2. The TEM image of the matrix in the diffusion zone was displayed was displayed in Figure 7a,
which
in Figurewas 7a,
cubic
which structure Co–Fe
was cubic phase, according
structure Co–Fe phase, to the diffraction
according pattern
to the in Figure
diffraction 7b, asinwell
pattern as
Figure
XRD results and EDS analysis. It meant that Fe gradually diffused from
7b, as well as XRD results and EDS analysis. It meant that Fe gradually diffused from the fusion the fusion zone and the steel to
the
zoneStellite
and layer in the
the steel highStellite
to the temperature
layer inenvironment,
the high temperatureand then the Fe and Co and
environment, werethen
mutually
the Fesoluble
and Co
with each other to form the Co–Fe matrix in the coating layer.
were mutually soluble with each other to form the Co–Fe matrix in the coating layer.
Furthermore,
Furthermore,there thereexisted
existedsome
someCr-rich
Cr-richphasesphasesininthe thediffusion
diffusionzone, zone,as asshown
shownininFigure
Figure7c, 7c,
which were black knife-like particles with a sharp edge. It can be determined
which were black knife-like particles with a sharp edge. It can be determined that these Cr-rich that these Cr-rich phases
were
phases(Cr,were
Fe)23 C 6 carbides
(Cr, Fe)23C6 (Cr 18.93 Fe4.07
carbides (CrC 6 )Fe
18.93
through indexing the corresponding diffraction pattern.
4.07C6) through indexing the corresponding diffraction
The black The
pattern. particles
blackinparticles
the lightinzone
the were
light σzonephases were(Fe–Cr phases)
σ phases withphases)
(Fe–Cr a size ofwith
abouta hundreds
size of aboutof
nanometers. According to the Fe–Cr phase diagram, these
hundreds of nanometers. According to the Fe–Cr phase diagram, these σ phases formedσ phases formed intemperatures ranging
from 450–830 ◦ C,ranging
intemperatures and werefromalso detected
450–830 °C, and in alloys
were alsowithdetected
23.4 wtin%–33.7 wt %23.4
alloys with Cr wt
during
%–33.7plastic
wt %
deformation followed by aging due to a composition fluctuation
Cr during plastic deformation followed by aging due to a composition fluctuation of alloyingof alloying elements [21,22]. Thus,
under the condition of in-service ◦ C) and a large stress load, the formation of multiple
elements [21,22]. Thus, under temperature
the condition (566of in-service temperature (566 °C) and a large stress
brittle
load, σthephases could beofpredicted,
formation multiplewhich could
brittle lead to deterioration
σ phases of both corrosion
could be predicted, which resistance
could lead andto
ductility of the coatings.
deterioration of both corrosion resistance and ductility of the coatings.
Figure
Figure7g,h7g,hshows
showsthe theTEM
TEMimages
imagesofofthe themicrostructure
microstructureininthe thelight
lightzone
zonebetween
betweenthe theStellite
Stellite
and
andthe thesteel.
steel. ItIt can
canbebeseen
seenthat
thatthere
therewere
weremany manysmall,small,black
blackprecipitate
precipitateparticles
particlesin inthe
thematrix.
matrix.
These
Thesenano-scaled
nano-scaled carbides
carbides M6 C carbides
werewere M6C carbidesaccording to their small
according size and
to their smalldispersive
size and distribution.
dispersive
Mdistribution.
6 C carbides could significantly
M6C carbides couldinhibit the dislocation
significantly inhibitmotion within the matrix,
the dislocation motion thereby
within inducing
the matrix, a
stronger strengthening effect than that of M C carbides. Therefore, the
thereby inducing a stronger strengthening effect than that of M23C6 carbides. Therefore, the strength
23 6 strength and hardness of the
matrix was improved.
and hardness of the matrix was improved.

Figure7.7.TEM
Figure TEMimages
images(a,c,e)
(a,c,e)and
anddiffraction
diffractionpatterns
patterns(b,d,f)
(b,d,f)ofofthe
themicrostructure
microstructureininlight
lightzone
zoneofof
sample#2;
sample #2;TEM
TEMbright
brightfield
fieldimages
imagesinin(g)
(g)the
thefusion
fusionzone
zoneand
and(h)
(h)diffusion
diffusionzone
zoneofof sample
sample #2.#2.

3.3.
3.3.Failure
FailureAnalysis
Analysis
Figure
Figure8a8ashows
showsthe micro-hardness
the micro-hardnessprofilesprofiles
perpendicular to the fusion
perpendicular line along
to the fusiontheline
cross-section
along the
ofcross-section
the samples.ofIt the
cansamples.
be seen that
It can be seen that the micro-hardness in the weld overlay was in
the micro-hardness in the weld overlay was higher than that the
higher
steel. Meanwhile, the micro-hardness in the HAZ was higher compared with F91
than that in the steel. Meanwhile, the micro-hardness in the HAZ was higher compared with F91 steel for the sample
#1. After
steel fora the
longsample
period #1.of service,
After athe micro-hardness
long valuesthe
period of service, of sample #2 increased
micro-hardness to the
values ofmaximum
sample #2
(470–680 HV) in the weld overlay near fusion zone due to the formation and growth
increased to the maximum (470–680 HV) in the weld overlay near fusion zone due to the formation of hard matrix
phases.
and growth of hard matrix phases. Moreover, as for sample #2, the micro-hardness values in as
Moreover, as for sample #2, the micro-hardness values in the HAZ dropped to be the same the
HAZ dropped to be the same as that in the base metal, and the micro-hardness values in the Stellite
Coatings 2019, 9, 532 8 of 11
Coatings 2019, 9, x FOR PEER REVIEW 8 of 11

that in thehad
overlay baseincreased
metal, and the micro-hardness
(450–500 HV). In the HAZvaluesofinF91
thesteel,
Stellite
theoverlay had increased
micro-hardness (450–500
decreased HV).
because
Inofthe HAZ of F91 steel, the
the coarsening of carbides. micro-hardness decreased because of the coarsening of carbides.
There
Therewere
weretwotwokinds
kindsofofcracks
cracksexisting
existingininthetheweld
weldoverlay
overlayofofsample
sample#2#2asasshown
shownininFigure
Figure8b.8b.
One
One kind of them is the circumferential crack paralleling to the fusion line, and the other aone
kind of them is the circumferential crack paralleling to the fusion line, and the other one is radial
is a
crack
radialperpendicular to the fusion
crack perpendicular to theline. When
fusion line.the two the
When kinds
twoof kinds
cracksofmerged
cracks gradually, the coating
merged gradually, the
could fracture and fall off. Figure 8c shows the failure locations of sample #2, and it
coating could fracture and fall off. Figure 8c shows the failure locations of sample #2, and it can becan be seen that
the fracture
seen mainly
that the occurred
fracture mainlyinoccurred
the lightinzone.
the light zone.

Figure8. 8.
Figure (a)(a) Transverse
Transverse micro-hardness
micro-hardness profiles
profiles of samples
of samples #1(b)
#1 and #2; and #2; of
Image (b)cracks
Image of cracks
distribution
ofdistribution of sample
sample #2; (c) #2;fracture
Image of (c) Image of fracture
paths paths
in partial in partial
region region
of sample #2. of sample #2.

4.4.Discussion
Discussion
After
Afterthe theservice
serviceprocess,
process, hard
hardCo–Fe
Co–Fe matrix
matrixand σ phases
and σ phases formed,
formed,caused by the
caused diffusion
by the of Feof
diffusion
from steelsteel
Fe from into the
intoStellite layer,layer,
the Stellite resulting in the in
resulting formation of a wide
the formation of alight
widezone,
lightwhich
zone, consisted of the
which consisted
original fusion zone and new mutual diffusion zone. The growth of the Co–Fe
of the original fusion zone and new mutual diffusion zone. The growth of the Co–Fe matrix phases matrix phases with high
hardness in the light zone led to formation of an interface between the
with high hardness in the light zone led to formation of an interface between the light zone and light zone and Stellite layer.
The micro-hardness
Stellite layer. The in the light zone in
micro-hardness wasthe higher
lightthanzonethat
was in the Stellite
higher than layer
thatsignificantly,
in the Stelliteandlayer
the
maximum difference in micro-hardness between the two zones was
significantly, and the maximum difference in micro-hardness between the two zones was even up even up to 230 HV. Moreover,
from theHV.
to 230 Stellite layer tofrom
Moreover, the light zone near
the Stellite layerthetointerface,
the lightthe zonemicro-hardness
near the interface,suddenly changed from
the micro-hardness
450 to 680 HV as displayed in Figure 8a. It indicated that the changes
suddenly changed from 450 to 680 HV as displayed in Figure 8a. It indicated that the of micro-hardness between
changes theof
light zone and Stellite layer happened after a long period of service process.
micro-hardness between the light zone and Stellite layer happened after a long period of service Large stress concentrations
could easily
process. occurstress
Large on this interface because
concentrations could of changes
easily occurin micro-hardness,
on this interface resulting
because in the
of formation
changes in
ofmicro-hardness,
a vast nucleation site of micro-cracks in the interface as shown in Figure 9a.
resulting in the formation of a vast nucleation site of micro-cracks in the interface In addition, the σ
phases,
as shown in Figure 9a. In addition, the σ phases, which are hard and brittle, harmfully affect by
which are hard and brittle, harmfully affect the mechanical properties of the coatings the
creating local embrittlement and by forming micro-cracks at the γ/σ phase
mechanical properties of the coatings by creating local embrittlement and by forming micro-cracks interfaces during loading.
After
at thenucleating
γ/σ phase at these interfaces,
interfaces the cracks
during aggregated
loading. After and grew gradually
nucleating at thesein interfaces,
Figure 9b. Finally the
the cracks
cracks propagated
aggregated into the
and grew light zone
gradually and became
in Figure largethe
9b. Finally cracks.
cracksThe large cracks
propagated gradually
into the lightincreased,
zone and
and thus led to the fracture and fall off of the coating.
became large cracks. The large cracks gradually increased, and thus led to the fracture and fall off of
the coating.
Coatings 2019, 9, 532 9 of 11
Coatings 2019, 9, x FOR PEER REVIEW 9 of 11

Figure9.9.Schematic
Figure Schematicdiagrams
diagramsofofinitiation
initiationand
andpropagation
propagationofofcracks:
cracks:(a)
(a)Initiation
Initiationofofmicro-cracks;
micro-cracks;
(b)Aggregation
(b) Aggregationand
andgrowth
growthofofmicro-cracks;
micro-cracks;(c)(c)Propagation
Propagationofofcracks.
cracks.

AsAsshown
shownininFigure
Figure8b,c,
8b,c,the
theformation
formationofofcircumferential
circumferentialcracks
cracksononthe
theinterface
interfacewaswasrelated
relatedtoto
the
thehardness
hardnesschanges
changesbetween
betweenthe thelight
lightzone
zoneandandStellite
Stellitelayer,
layer,which
whichcould
couldbe beseparated
separatedfromfromthe
the
Stellite weld layer and the light zone, and fracture under the combined effect of high
Stellite weld layer and the light zone, and fracture under the combined effect of high temperature temperature and
impact load under
and impact service
load under conditions.
service conditions.
Besides,
Besides, inter-dendritic regions were
inter-dendritic regions were weak
weakzones,
zones, where
whereimpurities,
impurities, coarse
coarse carbides
carbides and
and
micro-cracks
micro-crackscaused
causedby bythermal
thermalstress
stressand
andresidual
residualstress
stressexisted,
existed,which
whichcould
couldinduce
inducethe theformation
formation
ofofradial
radialcracks.
cracks.TheThehigh
highhardness
hardnessmade madeititeasier
easierfor
forthe
themicro
microcracks
crackstotoform
formandandpropagate
propagateininthethe
light zone. The cracks which initiated on the interface between the light zone and
light zone. The cracks which initiated on the interface between the light zone and Stellite layer Stellite layer could
propagate into the into
could propagate lightthe
zone gradually
light and formand
zone gradually a large
formmacro-crack. Thus, the Thus,
a large macro-crack. light zone becomes
the light zone
the weakest
becomes theregion
weakestandregion
fractureandfailure could
fracture happen
failure in happen
could this zone.in this zone.

5.5.Conclusions
Conclusions
Overlaying
Overlayingofof Stellite 6 alloy
Stellite on F91
6 alloy onsteel
F91 substrates was performed
steel substrates with multi-pass
was performed TIG cladding
with multi-pass TIG
method. The effect of in-service environment on the element diffusion, microstructure evolution
cladding method. The effect of in-service environment on the element diffusion, microstructure and
fracture behavior
evolution of the resultant
and fracture behavior weld overlay
of the were weld
resultant investigated.
overlayThe conclusions
were are listed
investigated. as follows:
The conclusions
•are The
listed as follows: of the Stellite weld overlay near the fusion zone had changed to form a light
microstructure
• zone,
The consisting
microstructure of Co–Fe
of the substitution
Stellite weld solidoverlay
solutions,
nearσ phases
the fusion(Fe–Crzonemetallic compounds)
had changed to formanda
Cr 18.93 Fe
light 4.07 C6 consisting
zone, carbides. The of high
Co–Fe temperature environment
substitution could promote
solid solutions, the extent
σ phases of the
(Fe–Cr light
metallic
zone. After service,
compounds) and Cr the
18.93width
Fe4.07Cof the light The
6 carbides. zone, combined
high with fusion
temperature zone and
environment diffusion
could promote zone,
the
increased significantly to form a large diffusion zone, which could even
extent of the light zone. After service, the width of the light zone, combined with fusion zonereach to around 2.5 mm.
• The
andobvious
diffusion diffusion of Fe occurred
zone, increased from the
significantly steelaand
to form largefusion zonezone,
diffusion to thewhich
Stellite overlay,
could even
resulting in the microstructure
reach to around 2.5 mm. evolution and hardness increase in the weld overlay. The content
• ofThe Fe increased intensively,
obvious diffusion of but the content
Fe occurred of Co
from thedecreased,
steel and which
fusion could
zone eventually
to the Stelliteleadoverlay,
to the
formation
resulting of inhard
the and brittle Co–Feevolution
microstructure phases. and hardness increase in the weld overlay. The
• content
The of Fe increased
micro-hardness in theintensively,
Stellite weldbut the content
overlay of Co
was higher decreased,
than which
that in the steel.could
After eventually
cladding,
lead
the to the formation
micro-hardness of hard
in the HAZand brittle Co–Fe
increased. phases.
After the service process, the micro-hardness values in
• the The micro-hardness
Stellite overlay slightlyin the Stellitetoweld
increased overlay
450–500 was those
HV, while higherin than that dropped
the HAZ in the steel.
whereAfter
the
cladding, had
precipitates the coarsened.
micro-hardnessMoreover, in the HAZ increased.
the micro-hardness After
values thelight
in the service process, the
zone increased to
micro-hardness
the maximum (470–680 valuesHV),
in the Stellite overlay
resulting in changesslightly increased to 450–500
of micro-hardness betweenHV, whilematerial
the base those in
thethe
and HAZ dropped
Stellite weldwhere
overlay. the precipitates had coarsened. Moreover, the micro-hardness values
• in the
The light zone
fracture of theincreased
Stellite to the maximum
coating samples (470–680 HV), resulting
mainly occurred in thein light
changes zoneof
(fusion zone + diffusion zone) after the service process. The formation of these cracks might
micro-hardness between the base material and the Stellite weld overlay.
• beThe fracture
caused of the brittle
by formed Stellitephases
coating samples
and changes mainly occurred in the
of micro-hardness light
during zone (fusion zone +
service.
diffusion zone) after the service process. The formation of these cracks might be caused by
formed brittle phases and changes of micro-hardness during service.
Author Contributions: Conceptualization, J.X. and F.N.; Methodology, L.Y.; Validation, J.X.; Formal Analysis, J.X.,
F.N. and J.L.;
Author Investigation,
Contributions: J.X., F.N., H.Z., J.L.J.X.
Conceptualization, and Z.W.;
and Resources,
F.N.; H.Z. and
Methodology, Z.W.;
L.Y.; Data Curation,
Validation, H.Z. and
J.X.; Formal L.Z.;
Analysis,
Writing—Original Draft Preparation, J.X. and F.N.; Writing—Review and Editing, J.X. and H.Z.; Visualization, L.Y.;
J.X., F.N. and J.L.; Investigation, J.X., F.N., H.Z., J.L. and Z.W.; Resources, H.Z. and Z.W.; Data Curation, H.Z.
Supervision, L.Z.; Project Administration, J.X.; Funding Acquisition, J.X. and L.Z.
and L.Z.; Writing—Original Draft Preparation, J.X. and F.N.; Writing—Review and Editing, J.X. and H.Z.;
Funding: This research
Visualization, received no
L.Y.; Supervision, external
L.Z.; Projectfunding.
Administration, J.X.; Funding Acquisition, J.X. and L.Z.

Funding: This research received no external funding.

Coatings 2019, 9, 532 10 of 11

Acknowledgments: This work was supported by State Key Laboratory of Long-life High Temperature Materials
of Dongfang Turbine Co., Ltd. in Deyang. This work was technically supported by College of Materials Science
and Engineering of Chongqing University in Chongqing.
Conflicts of Interest: The authors declare no conflict of interest.

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