materials
Article
Study of Microstructure and Performance Evaluation of
Zr-Sn-Nb Joints by Electron Beam Welding
Yanli Zhao 1 , Anrui Zhang 1 , Huifang Yue 1 , Houqin Wang 2 , Yong Xin 1 and Yi Zhou 1, *
Citation: Zhao, Y.; Zhang, A.; Yue, H.;
Wang, H.; Xin, Y.; Zhou, Y. Study of
Microstructure and Performance
Evaluation of Zr-Sn-Nb Joints by
Electron Beam Welding. Materials
2024, 17, 980. https://doi.org/
10.3390/ma17050980
Academic Editor: Carmine Maletta
Received: 3 January 2024
Revised: 8 February 2024
Accepted: 12 February 2024
Published: 20 February 2024
Copyright: © 2024 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Materials 2024, 17, 980. https://doi.org/10.3390/ma17050980
1 Science and Technology on Reactor System Design Technology Laboratory, Nuclear Power Institute of China,
Chengdu 610213, China; zyl695662724@163.com (Y.Z.)
2 National Key Laboratory of Precision Welding & Joining of Materials and Structures,
Harbin Institute of Technology, Harbin 150001, China
* Correspondence: zy214121048@163.com
Abstract: In this work, Zr-Sn-Nb alloy was joined by electron beam welding (EBW). A defect-free
Zr-Sn-Nb joint with sound appearance was obtained. The grains in the weld zone (WZ) and
heat-affected zone (HAZ) are significantly coarsened. The columnar grains with a maximum grain
size of 0.5 mm are distributed in the upper region of the WZ, while the equiaxed grains are almost
located in the bottom region of the WZ. The WZ is mainly composed of the dominant α-Zr, α′ -Zr
and a few β phases. The grain orientation of WZ and HAZ is uniform, indicating that no obvious
preferred orientation existed. Coarse grains and fine acicular α′ phases increase the strength of
the joint, but reduce the plasticity and toughness of the joint. The tensile strengths of the joints
at room temperature (RT) and 375 ◦ C were 438 MPa and 313 MPa, respectively. The RT impact
energy of the joint is 18.5 J, which is only 58.3% of the BM. The high purity of the EBW process
and unsignificant grain orientation minimizes damage to the corrosion resistance of Zr-Sn-Nb alloy
joints. The corrosion weight gain of the joint specimen and the BM specimen were 12.91 mg/dm2 and
12.64 mg/dm2 , respectively, and the thicknesses of the cross-section corrosion layer were 12–15 µm
and 9–12 µm, respectively.
Keywords: Zr-Sn-Nb alloy; electron beam welding; microstructure; joint properties
1. Introduction
Zirconium alloys have been widely used in nuclear reactors due to their resistance
to alkaline water corrosion containing boron and lithium, excellent high-temperature
mechanical properties, and low neutron absorption cross-sections [1,2]. The development
of nuclear reactors has put forward higher requirements on the service life and availability
of zirconium alloy components. Under the premise of ensuring the safety, high efficiency
and economy of the reactor, the fuel assembly burnup should be more than 50 GWd/tU.
Traditional Zr-4 alloys and improved Zr-4 alloys can no longer meet the current high
burnup requirements [3,4]. Consequently, the development of new zirconium alloys is
imperative. The production of Zr-Sn-Nb alloys by adding a variety of alloying elements
to improve the corrosion resistance, mechanics and other properties of zirconium alloys
has become a major trend in the research and development of new zirconium alloys, such
as Westinghouse’s Zirlo alloy in the U.S., Russia’s E635 alloy, as well as China’s N18
and N36 alloys [5–7].
Welding technology of zirconium alloy is of great significance to improve the man-
ufacturing quality and productivity of zirconium alloy fuel assemblies [8,9]. Zirconium
is a chemically active metal, and its welded joints are susceptible to contamination by
airborne gases such as oxygen, nitrogen and hydrogen, as well as grain coarsening and the
deterioration of joint properties due to the low thermal conductivity of the weld molten
pool heat accumulation [9]. For this reason, additional protective measures are required
during the zirconium alloy welding process.
https://www.mdpi.com/journal/materials
Materials 2024, 17, 980 2 of 14

When zirconium alloys are welded by gas-shielded arc welding, measures such as
the addition of trailing shields and backing shields, i.e., the extension of the shielding gas
supply, are required to avoid joint contamination [8,10–12]. The N and O in the atmosphere
will inevitably enter the weld during TIG welding of Zr-4 alloys, resulting in a signifi-
cantly higher weld hardness than the base metal (BM) [12]. Coating is another effective
protection method for the laser welding of zirconium alloys. A Cr coating with a thickness
of 8–10 microns is prepared on the surface of zirconium alloy, and a Cr2 O3 protective
layer is generated during the welding process to avoid high-temperature oxidation of the
zirconium alloy [13–15], but this inevitably reduces the purity of the zirconium alloy weld.
Electron beam welding (EBW) has the advantages of high purity of vacuum-protected
weld, high energy density, small heat input and small thermal impact on the BM, which
helps to ensure the performance of zirconium alloy welded joints [16,17]. The current
research on EBW of zirconium alloys focuses on traditional zirconium alloy, and scholars
are more concerned about the corrosion resistance of joints under service conditions. The
study by Jha et al. [18] showed that the hardness of Zr-4 alloy electron beam welded joints is
higher than that of the BM. The tensile properties of Zr-4 alloy electron beam welded joints
are not inferior to those of the parent material [19], but the presence of pores in the weld may
affect the corrosion performance of the joint [20]. Bandi et al. [21] demonstrated through
Raman spectroscopy that the pores in the Zr-4 electron beam welded joint are mainly
hydrogen pores. Zhang et al. [22] found that the EBW joint of Zr-702 alloy is composed of
α-Zr and β-Zr, and β-Zr small blocks are distributed along the edges of layered α-Zr, which
indicates that the joint has better corrosion resistance than the BM. Yao et al. [23] found
that the precipitation of Zr(Fe,Cr)2 s phase particles in the weld seam is the main reason for
the increase in hydrogen absorption of the joint after steam corrosion in a high-pressure
reactor, and the higher the Cr content in the joint, the greater the hydrogen absorption.
As a new type of zirconium alloy, research on the Zr-Sn-Nb system alloy in relation to
welding is still scarce. Scholars have carried out research on dissimilar materials joined by
partial transient liquid phase bonding of Zr-Sn-Nb alloy with stainless steel [24] and resis-
tance welding of Zr-Sn-Nb with Zr-Nb alloys [25]. For the welding of a single Zr-Sn-Nb al-
loy, Wei et al. tested the low-cycle fatigue properties of an electron beam welded Zr-Sn-Nb
alloy [26], but research on the microstructure analysis and the performance evaluation of
the new Zr-Sn-Nb alloy EBW joints is still insufficient. This article focuses on the evaluation
requirements of the service performance of Zr-Sn-Nb alloy welded joints in fuel compo-
nents. The optimization of Zr-Sn-Nb alloy EBW process parameters was carried out; the
formation and microstructure of Zr-Sn-Nb alloy welded joints under optimized parameters
were analyzed. The mechanical properties of the joints are tested and evaluated.

2. Experimental Section
Zr-Sn-Nb alloy plates with a thickness of 4 mm used in this work were cold rolled
and then annealed to a fully recrystallized state. The EBM-30H electron beam welder from
Kunta was used for the EBW test. Vacuum was drawn to 1.0 × 10−3 Pa before welding to
prevent the Zr-Sn-Nb alloy from reacting with O and N at high temperature. Two flat plates
with dimensions of 118 mm × 106 mm × 4 mm were butt-welded along the length direction
(perpendicular to the rolling direction) as shown in Figure 1. After welding and cooling
for 10 min, the vacuum chamber was opened to avoid oxidation of the workpiece at high
temperatures. Welding process parameters were optimized according to the guidelines of
excellent surface formation, backside penetration and low heat input, and the optimized
welding process parameters are shown in Table 1. The welding beam current varied from
26 to 28 mA, with 27 mA preferred for weld shaping. After welding, the welded specimens
were subjected to vacuum stress relieving and annealing (550 ◦ C, holding time 2 h).
Materials 2024, 17, x FOR PEER REVIEW 3 of 15

Materials 2024, 17, 980

specimens were subjected to vacuum stress relieving and annealing (550 °C, holding3 time
of 14
2 h).

Figure 1.
Figure 1. Schematic
Schematic diagram
diagram of
of EBW
EBW assembly
assembly of
of Zr-Sn-Nb
Zr-Sn-Nbplate.
plate.

Table 1. EBW parameters of Zr-Sn-Nb alloy.

Table 1. EBW parameters of Zr-Sn-Nb alloy.
Acceleration Focus Welding Beam Welding Working
Acceleration Welding Beam Working
Voltage Focus Current
Current Current Welding Speed
Speed Distance
Voltage Current Distance
/mA /(mm·min−1 )−1
/kV
/kV /mA /mA
/mA /(mm·min ) /mm
/mm
6060 714 * *
714 26–28
26–28 480
480 190.5
190.5
**The
Thefocused
focused electron
electron beam
beam spot spot is about
is about 8 mm 8higher
mm higher
than thethan theofsurface
surface of the workpiece.
the workpiece.

After
After welding,
welding,wire
wirecutting
cu ingisisused
usedtoto
cutcut
thethe
cross-section
cross-sectionof the weld
of the seam
weld to prepare
seam to pre-
metallographic specimens. After mechanical grounding and polishing,
pare metallographic specimens. After mechanical grounding and polishing, corrosive corrosive agents
(HF:HNO 3 :H2 O =
agents (HF:HNO 2:9:9)
3:H are used
2O = 2:9:9) are for
usedcorrosion. X-ray
for corrosion. diffractometer
X-ray diffractometer(XRD,(XRD,Panalytical,
Panalyt-
Empyrean,
ical, Empyrean,8◦ /min, 20 kV,
8°/min, Cu Cu
20 kV, Kα K) was used
α) was used totoanalyze
analyzethethephase
phasecomposition
composition of of the
the
joint.
joint. Olympus-SZX12
Olympus-SZX12metallographic
metallographic microscope
microscope and and
scanning electron
scanning microscope
electron (SEM,
microscope
Quanta-200
(SEM, Quanta-200FEG, ThermoFisher,
FEG) equipped Hillsboro, OR, USA)
with energy equipped
dispersive with energy
spectrometer dispersive
(EDS, Xplore)
spectrometer
were applied to characterize the microstructure of the joint. Electron back-sca erthe
(EDS, Xplore) were applied to characterize the microstructure of joint.
diffrac-
Electron back-scatter diffraction (EBSD) was carried out to analyze the grain
tion (EBSD) was carried out to analyze the grain orientation and texture of the joints. The orientation
and
EBSD texture
camera ofathe joints.
ached TheQuanta
to FEI EBSD scanning
camera attached
electron to FEI Quanta
microscope (FEIscanning
Company, electron
Hills-
microscope (FEI Company, Hillsboro, OR, USA) and HKL Channel
boro, OR, USA) and HKL Channel 5 software (Version: 5.11.20405) were used to collect 5 software (Version:
5.11.20405)
and processwere the used to collect
orientation and processThe
information. thetest
orientation
specimens information.
of weldedThe testand
joints specimens
BM are
of
prepared and tested under the same conditions to analyze the mechanical propertiesthe
welded joints and BM are prepared and tested under the same conditions to analyze of
mechanical
welded joints properties
relative of
to welded
the BM.joints relative was
HVS-1000A to the BM.toHVS-1000A
used was used to test
test the micro-hardness the
of dif-
micro-hardness of different areas of the joint, with a loading load of 200 g and a continuous
ferent areas of the joint, with a loading load of 200 g and a continuous loading time of 10
loading time of 10 s. The mechanical properties of the joint were tested on the Shimadzu
s. The mechanical properties of the joint were tested on the Shimadzu AG series electronic
AG series electronic universal testing machine equipment at room temperature (RT) and
universal testing machine equipment at room temperature (RT) and 375 °C. The strain rate
375 ◦ C. The strain rate value for the tensile test was 0.007 (mm/mm)/min. In order to test
value for the tensile test was 0.007 (mm/mm)/min. In order to test the tensile properties of
the tensile properties of the weld zone (WZ) and heat-affected zone (HAZ), the tiny tensile
the weld zone (WZ) and heat-affected zone (HAZ), the tiny tensile specimen shown in
specimen shown in Figure 2 was cut along the welding direction. The width of the parallel
Figure 2 was cut along the welding direction. The width of the parallel section at the center
section at the center of the specimen was 1.5 mm and the thickness was 2 mm. JBS-300B
of the specimen was 1.5 mm and the thickness was 2 mm. JBS-300B pendulum impact
pendulum impact tester (Shanghai Laiyang Electric Technology Co., Ltd, Shanghai, China)
tester was used to carry out Charpy impact test on V-notched welded joints.
was used to carry out Charpy impact test on V-notched welded joints.
Corrosion test specimens were prepared by intercepting test plates with dimensions
of 30 mm × 20 mm × 4 mm, including welds, and the length of the specimen was in the
welding direction. The comparison test specimens of BM with the same size were also
prepared. The corrosion test conditions were the following: 72 h of corrosion test at 400 ◦ C
and 10.3 MPa water vapor.
Materials 2024,
Materials 2024, 17,
17, 980
x FOR PEER REVIEW 4 of 15
4 of 14

Figure 2. Micro-tensile specimens and dimensions in different areas of the joint.

Corrosion test specimens were prepared by intercepting test plates with dimensions
of 30 mm × 20 mm × 4 mm, including welds, and the length of the specimen was in the
welding direction. The comparison test specimens of BM with the same size were also
prepared. The corrosion test conditions were the following: 72 h of corrosion test at 400
°C and 10.3 MPa water vapor.
Figure 2. Micro-tensile
Figure 2. Micro-tensile specimens and dimensions
specimens and dimensions in
in different
different areas
areas of
of the
the joint.
joint.

3.3.Results
Results andDiscussion
and
Corrosion Discussion
test specimens were prepared by intercepting test plates with dimensions
3.1.
3.1.
of Weld
30Weld Forming
mmForming
× 20 mm × 4 mm, including welds, and the length of the specimen was in the
welding Thedirection.
The morphology
morphology Theof
ofcomparison
theWZ
the WZin test
inthe
the specimens
Zr-Sn-Nb
Zr-Sn-Nb ofisis
joint
joint BM within
shown
shown the
in same
Figure
Figure 3.3.size
Thewere
The also
surface
surface of
of
prepared.
theweld
the weldseam The corrosion
seamisisflat,
flat,and test
andthe conditions
thefish
fishscale were
scalepattern the following:
pa ernisisrelatively 72 h
relativelyuniform. of corrosion
uniform.No Nodefects test
defectssuchat 400
suchas as
°C
spaand
spatter er10.3
and MPa watering
andundercutting
undercu vapor.
are
arefound,
found,as asshown
shownin inFigure
Figure3a. 3a.From
Fromthethecross-section
cross-sectionof ofthe
the
weld
weldin inFigure
Figure3b,3b,ititcan
canbe beseen
seenthat
thatthe
thetest
testplate
plateisiscompletely
completelypenetrated
penetratedand andslightly
slightly
3. Results
adhered
adhered toand
to the Discussion
thebottom
bo ompad.pad.The Thewidths
widthsof ofthe
theupper
upperpart,
part,middle
middlepart
partand
androot
rootpart
partof
ofthe
the
weld
weld are
are about
about
3.1. Weld Forming 4.3
4.3mm,
mm, 3.0
3.0 mm
mm and
and 1.5
1.5 mm,
mm, respectively.
respectively. And
And the
the width
width of
of the
the HAZ
HAZ on
on
one side
one The of the weld
side morphology is about
of the weld isofabout 1.7 mm.
1.7in
mm.
the WZ the Zr-Sn-Nb joint is shown in Figure 3. The surface of
the weld seam is flat, and the fish scale pa ern is relatively uniform. No defects such as
spa er and undercu ing are found, as shown in Figure 3a. From the cross-section of the
weld in Figure 3b, it can be seen that the test plate is completely penetrated and slightly
adhered to the bo om pad. The widths of the upper part, middle part and root part of the
weld are about 4.3 mm, 3.0 mm and 1.5 mm, respectively. And the width of the HAZ on
one side of the weld is about 1.7 mm.

Figure3.
Figure 3. Appearance
Appearance and
and cross-section
cross-sectionmorphologies
morphologiesofofZr-Sn-Nb
Zr-Sn-Nbjoint: (a)(a)
joint: surface appearance;
surface (b)
appearance;
cross-sectional morphology.
(b) cross-sectional morphology.

3.2. Microstructure Analysis

Figure 4 shows the metallographic microstructure of different regions of the joint. The
grains in the upper region of the weld grow in opposite directions from the fusion line
on both
Figure 3. sides to theand
Appearance center. The primary
cross-section β phaseofgenerated
morphologies by solidification
Zr-Sn-Nb joint: transforms
(a) surface appearance; (b)
′ phase during continuous cooling [27]. The coarse primary β-crystal grain
into acicular αmorphology.
cross-sectional
boundaries are significant, with the maximum size exceeding 0.5 mm. At the root of the
weld, there are coarse equiaxial crystals with a grain size of about 130 µm. The equiaxial
crystals are blocky α phase without acicular features. The HAZ is equiaxed in which the
grain size is about 80~100 µm near the weld, and the grain size is about 30~40 µm near the
 The grains in the upper region of the weld grow in opposite directions from the fusion
line on both sides to the center. The primary β phase generated by solidification trans-
forms into acicular α′ phase during continuous cooling [27]. The coarse primary β-crystal
grain boundaries are significant, with the maximum size exceeding 0.5 mm. At the root of
Materials 2024, 17, 980 5 of 14
the weld, there are coarse equiaxial crystals with a grain size of about 130 µm. The equi-
axial crystals are blocky α phase without acicular features. The HAZ is equiaxed in which
the grain size is about 80⁓100 µm near the weld, and the grain size is about 30⁓40 µm near
BM.BM.
the During EBW,
During the molten
EBW, poolpool
the molten solidified grains
solidified grow
grains along
grow the temperature
along the temperature gradient
gra-
towards the center of the molten pool, resulting in the formation of columnar
dient towards the center of the molten pool, resulting in the formation of columnar crys- crystals [28].
The bottom part of the weld is heated relatively less than the top part, the
tals [28]. The bo om part of the weld is heated relatively less than the top part, the tem- temperature
gradient gradient
perature is not significant, and equiaxed
is not significant, crystals are
and equiaxed formed
crystals areunder
formed theunder
effectthe
of welding
effect of
heat. The temperature in HAZ exceeds the recrystallization annealing temperature
welding heat. The temperature in HAZ exceeds the recrystallization annealing tempera- of the
BM, and significant grain growth also occurs in this region. The HAZ close
ture of the BM, and significant grain growth also occurs in this region. The HAZ close to to the weld is
severely
the weld affected by affected
is severely the welding
by theheat, and the
welding grains
heat, andinthe
this region
grains in are
thisrelatively
region arecoarse,
rela-
while the HAZ away from the weld is of fine crystalline.
tively coarse, while the HAZ away from the weld is of fine crystalline.

Figure 4. Metallographic microstructure of Zr-Sn-Nb joint: (a) upper part of weld; (b) lower part of
Figure 4. Metallographic microstructure of Zr-Sn-Nb joint: (a) upper part of weld; (b) lower part of
weld; (c) HAZ.
weld; (c) HAZ.

In
In order
order toto further
further confirm
confirm the the microstructure
microstructure morphology
morphology and and its
its compositional
compositional
characteristics
characteristics within the weld, SEM-EDS analysis was performed. As shown in
within the weld, SEM-EDS analysis was performed. As shown in Figure
Figure 5,
5,
WZ contains two main phases, namely the lath-like matrix phase and
WZ contains two main phases, namely the lath-like matrix phase and the second phase the second phase
precipitated
precipitated along
along the
the grain
grain boundaries.
boundaries. The The EDS
EDS results
results of
of the
the two
two phases
phases areare shown
shown inin
Table 2. The
Table 2. The precipitated
precipitatedphase
phase(point
(pointA)
A)with
witha asize
size
ofof about
about 5 µm
5 µm is dominated
is dominated by the
by the Nb
Nb element.
element. TheThe formation
formation of β-Nb
of β-Nb phase
phase is induced
is induced whenwhen
the the local
local Nb/Fe
Nb/Fe ratio
ratio of Zr-Sn-
of Zr-Sn-Nb
Nb alloy is relatively large. It is assumed that the precipitated phase is
alloy is relatively large. It is assumed that the precipitated phase is the β-Nb phase the β-Nb phase
[29].
The matrix phase is mainly composed of the Zr element, and identified as an α-Zr phase
based on the Zr-Nb binary phase diagram [30,31].

Table 2. EDS results of WZ in Figure 5 (at.%).

Point Position Sn Cr Fe Zr Nb Possible Phases

A 0.89 1.22 1.29 18.12 78.48 β-Nb
B 0.8 0 0 99.2 0 α-Zr
Materials 2024, 17, x FOR PEER REVIEW 6 of 15

Materials 2024, 17, x FOR PEER REVIEW 6 of 15

Materials 2024, 17, 980

[29]. The matrix phase is mainly composed of the Zr element, and identified as an 6α-Zr of 14

phase based
[29]. The matrixon the isZr-Nb
phase mainlybinary phase
composed of thediagram [30,31].
Zr element, and identified as an α-Zr
phase based on the Zr-Nb binary phase diagram [30,31].

Figure 5. SEM microstructure of WZ: (a) white precipitate; (b) matrix.

Table 2. EDS results of WZ in Figure 5 (at.%).

Figure
Point5. SEM microstructure of WZ:Fe
(a) white precipitate; (b) Possible
matrix.
Figure 5.Position Sn
SEM microstructureCr Zrprecipitate;
of WZ: (a) white Nb (b) matrix. Phases
A 0.89 1.22 1.29 18.12 78.48 β-Nb
Table 2. EDS
3.3. XRD results of
B Analysis 0.8WZ in 0Figure 5
0 (at.%).
99.2 0 α-Zr

In order
3.3.Point
to determine
Position
XRD Analysis Sn the phasesCr inFethe BM andZr WZ, XRD Nb diffractionPossibleanalysis
Phaseswas
performed
In order
and the results
A to determine the
0.89 are shown
phases 1.22
in
in the BM1.29
Figure 6. From the
18.12diffraction
and WZ, XRD
diffraction
78.48
analysis was
pattern,
β-Nb it can be
seen that
performed B the α-Zr diffraction
and the results are peak is mainly
0.8shown in0Figure 6. From 0 present in
the diffraction
99.2 both the BM and
pa 0ern, it can be WZ, which is
α-Zr
consistent
seen that thewith the EDS peak
α-Zr diffraction results in Table
is mainly 2. The
present shift
in both the in
BMthe
anddiffraction
WZ, which ispeaks of the weld
consistentto
relative with
thethe
BM EDS results the
proves in Table 2. The shift
distortion in the lattice
of α-Zr diffractionin peaks of the which
the weld, weld coincides with
3.3. XRD
relative Analysis
to the BM proves the distortion
′ of α-Zr la ice in the weld, which coincides with
the observation of acicular α -Zr in Figure 4.
the observation
In order oftoacicular α′-Zr inthe
determine Figure 4.
phases in the BM and WZ, XRD diffraction analysis was
performed and the results are shown in Figure 6. From the diffraction pa ern, it can be
seen that the α-Zr diffraction peak is mainly present in both the BM and WZ, which is
consistent with the EDS results in Table 2. The shift in the diffraction peaks of the weld
relative to the BM proves the distortion of α-Zr la ice in the weld, which coincides with
the observation of acicular α′-Zr in Figure 4.

Figure 6. XRD diffraction pa erns of BM and WZ.

Figure 6. XRD diffraction patterns of BM and WZ.

3.4. EBSD Analysis

In order to analyze the texture characteristics of different areas in the welded joint,
EBSD analysis was conducted. Figure 7 shows the inverse pole figures (IPF) of the mi-
crostructure of the BM, WZ and HAZ. Different colors reflect different grain orientations,
and blocks with larger color contrasts represent larger grain orientation differences, with
red indicating <0001> orientation, green indicating <−12–10> orientation and blue indicat-
ing <01–10> orientation. The BM area consists of irregular equiaxed grains, with <−12–10>,
<01–10>
Figure 6. XRD <−13–20>pagrains
and diffraction erns ofparallel
BM andto the X0 direction being dominant. The grain
WZ.
orientation and microstructure in the HAZ and WZ changed. The grain orientation in the
HAZ was relatively uniform, but the orientation of coarse grains <−13–20> and <01–10>
were oriented parallel to the X0 direction. The grain orientation in the WZ showed <02–21>,
<01–10> and <−12–12> grain direction indices parallel to the X0 direction.
 <01–10> orientation. The BM area consists of irregular equiaxed grains, with <−12–10>,
<01–10> and <−13–20> grains parallel to the X0 direction being dominant. The grain orien-
tation and microstructure in the HAZ and WZ changed. The grain orientation in the HAZ
was relatively uniform, but the orientation of coarse grains <−13–20> and <01–10> were
Materials 2024, 17, 980 7 of 14
oriented parallel to the X0 direction. The grain orientation in the WZ showed <02–21>,
<01–10> and <−12–12> grain direction indices parallel to the X0 direction.

Figure 7. IPF of different regions in the welded joint: (a) BM; (b) WZ; (c) HAZ.
Figure 7. IPF of different regions in the welded joint: (a) BM; (b) WZ; (c) HAZ.

Figure 88 shows
Figure shows the the pole
pole figure
figure ofof the
the microstructure
microstructure in in different
different areas
areas ofof the
the joint,
joint,
where X0 is the rolling direction of the Zr-Sn-Nb alloy flat plate and
where X0 is the rolling direction of the Zr-Sn-Nb alloy flat plate and Y0 is perpendicu- Y0 is perpendicular
to the
lar rolling
to the direction.
rolling Contoured
direction. Contouredpole figures were realized
pole figures using using
were realized 10° half10width
◦ half and
width5°
cluster◦ size. From the pole diagram, it can be seen that BM exhibits
and 5 cluster size. From the pole diagram, it can be seen that BM exhibits a bimodal a bimodal basal tex-
ture, but
basal therebut
texture, is a there
certainis difference in the strength
a certain difference in theofstrength
the texture on both
of the sides.
texture The upper
on both sides.
The upper peak is around 6.0 mud in the {0001} pole figure, while the lower 9.39
peak is around 6.0 mud in the {0001} pole figure, while the lower peak can reach peakmud,can
indicating
reach 9.39 amud,
relatively uniform
indicating texture orientation
a relatively withinorientation
uniform texture the BM. The extremely
within the BM. strong
The
points generated
extremely strong in the HAZ
points and WZ
generated correspond
in the HAZ and to WZthe BM, but the to
correspond texture
the BM,strength of
but the
the extremely
texture strengthstrong
of the points significantly
extremely increases,
strong points reaching around
significantly increases,60 mud in strength.
reaching around
Compared
60 with BM,
mud in strength. the pole in
Compared theBM,
with HAZ theand
poleWZ is more
in the HAZ andconcentrated,
WZ is more indicating that
concentrated,
the grain orientation inside the WZ and HAZ is uniform and there
indicating that the grain orientation inside the WZ and HAZ is uniform and there is no is no obvious preferred
orientation.
obvious preferred orientation.
The Kernel Average Misalignment (KAM) analysis results corresponding to different
regions within the joint are shown in Figure 9. KAM represents the Kernel-averaged
mismatch of the grains, which is the average orientation difference (less than 5◦ ) between a
point within the same grain and its nearest neighbor, corresponding to the local orientation
gradient induced by deformation within the grain [32,33]. The blue color represents the
region with the smallest lattice distortion, with a KAM of 0~1◦ . The red color represents
the region with the highest lattice distortion, with a KAM of 4~5◦ . From Figure 9, it can be
seen that there is a higher content of green areas in the BM, while the green areas in the WZ
and HAZ are relatively lower, which is mainly related to their grain size. As the grain size
increases, the KAM values of the grains gradually decrease, while the grains in the WZ and
HAZ show remarkable coarsening compared to the BM, resulting in a relative decrease
in KAM values in the WZ and HAZ. In addition, from the statistics of KAM in different
regions in Figure 9d, it can be seen that there is a KAM between 1 and 2◦ in the WZ and
HAZ, which is consistent with the above analysis.
Materials 2024, 17, 980
Materials 2024, 17, x FOR PEER REVIEW 8 of 158 of 14

Figure
Materials 2024, 17, x FOR PEER REVIEW 8. Polar figure of different regions of welded joint: (a) BM; (b) WZ; (c) HAZ.
9 of 15
Figure 8. Polar figure of different regions of welded joint: (a) BM; (b) WZ; (c) HAZ.
The Kernel Average Misalignment (KAM) analysis results corresponding to different
regions within the joint are shown in Figure 9. KAM represents the Kernel-averaged mis-
match of the grains, which is the average orientation difference (less than 5°) between a
point within the same grain and its nearest neighbor, corresponding to the local orienta-
tion gradient induced by deformation within the grain [32,33]. The blue color represents
the region with the smallest la ice distortion, with a KAM of 0⁓1°. The red color repre-
sents the region with the highest la ice distortion, with a KAM of 4⁓5°. From Figure 9, it
can be seen that there is a higher content of green areas in the BM, while the green areas
in the WZ and HAZ are relatively lower, which is mainly related to their grain size. As the
grain size increases, the KAM values of the grains gradually decrease, while the grains in
the WZ and HAZ show remarkable coarsening compared to the BM, resulting in a relative
decrease in KAM values in the WZ and HAZ. In addition, from the statistics of KAM in
different regions in Figure 9d, it can be seen that there is a KAM between 1 and 2° in the
WZ and HAZ, which is consistent with the above analysis.

Figure 9. KAM results of different regional microstructures in welded joints: (a) BM; (b) WZ; (c)
Figure KAM results
9. Statistics
HAZ; (d) of different regional microstructures in welded joints: (a) BM; (b) WZ; (c) HAZ;
of KAM.
(d) Statistics of KAM.
3.5. Mechanical Properties Evaluation of Zr-Sn-Nb Joint
3.5.1. Micro-Hardness
Figure 10 shows the micro-hardness distribution curve of the weld cross-section
along the vertical weld direction. The micro-hardness of the WZ fluctuates greatly be-
tween 160 HV and 194 HV, which is the region with the highest micro-hardness of the
joint. The micro-hardness of the HAZ is between 150 HV and 175 HV, and the micro-
Materials 2024, 17, 980 Figure 9. KAM results of different regional microstructures in welded joints: (a) BM; (b) WZ; (c)
9 of 14
HAZ; (d) Statistics of KAM.

3.5. Mechanical
3.5. Mechanical Properties
Properties Evaluation
Evaluation of
of Zr-Sn-Nb
Zr-Sn-Nb Joint
Joint
3.5.1. Micro-Hardness
3.5.1. Micro-Hardness
Figure10
Figure 10shows
showsthethe micro-hardness
micro-hardness distribution
distribution curve
curve of theofweld
the cross-section
weld cross-section
along
along
the the vertical
vertical weld direction.
weld direction. The micro-hardness
The micro-hardness of theof
WZthefluctuates
WZ fluctuates
greatlygreatly
between be-
160 HV160
tween andHV194and
HV, 194
whichHV,is which
the region with
is the the highest
region with themicro-hardness of the joint.ofThe
highest micro-hardness the
micro-hardness of the HAZ of
joint. The micro-hardness is between
the HAZ150 HV and 175
is between 150HV,
HVandandthe175micro-hardness of the
HV, and the micro-
BM is between
hardness of the141
BMHV and 159141
is between HV.HVWelded
and 159joints
HV.show a trend
Welded jointsofshow
gradually decreasing
a trend of gradu-
micro-hardness
ally decreasing from the WZ to the
micro-hardness BM.
from the WZ to the BM.

220
BM HAZ FZ HAZ BM
200

180
Hardness(HV)

160

140

120

100
-6 -4 -2 0 2 4 6
Position(mm)

Figure10.
Figure 10. The
The micro-hardness
micro-hardnessdistribution
distributionof
ofZr-Sn-Nb
Zr-Sn-Nbjoint.
joint.

3.5.2.
3.5.2. Tensile
Materials 2024, 17, x FOR PEER REVIEW Tensile Properties
Properties of
of the
theWhole
WholeJoint
Joint 10 of 15
The ◦C
The Zr-Sn-Nb
Zr-Sn-Nb joints
joints were
were subjected
subjected toto RT
RT and
and 375
375 °C tensile
tensile tests
tests and
and analyzed
analyzed in in
comparison
comparison with the BM. The specimens after the tensile test of the welded joint are
with the BM. The specimens after the tensile test of the welded joint are shown
shown
in Figure 11. All the specimens
specimens fractured
fractured in BM. The tensile test results of the joints and
BM
BM are
are shown
shown in Figure 12.
in Figure The tensile
12. The tensile strength,
strength, yield
yield strength
strength and
and elongation
elongation of the joint
of the joint
tested at RM
tested at RM were
were 438438 MPa,
MPa, 313
313 MPa
MPa and
andabout
about30.1%,
30.1%,respectively,
respectively, which
which reached
reached 97.5%,
97.5%,
90.4%
90.4% and
and 91.2%
91.2% of of the
the BM.
BM. OnOn the
the other
other hand,
hand, the
the tensile
tensile strength,
strength, yield
yield strength
strength andand
elongation of the joint at 375 ◦ C were 195 MPa, 121 MPa and 34.6%, reaching 92.4%, 82.8%
elongation of the joint at 375 °C were 195 MPa, 121 MPa and 34.6%, reaching 92.4%, 82.8%
and 83.1% of the BM,
BM, respectively.
respectively. After ◦ C necking
and 83.1% of the After tensile
tensile testing,
testing, the
the joints
joints at
at RT
RT and
and 375
375 °C necking
occurs
occurs on
on both
both sides
sides ofof the
the weld, and fracture
weld, and fracture occurs
occurs on
on the
the side
side of
of the
the BM
BM away from the
away from the
HAZ. This indicates
HAZ. This indicates thatthat the
the strengths
strengths of
of the
the WZ
WZ and
and HAZ
HAZ are are higher
higher than
than that
that of
of the
the BM,
BM,
and the joint is as strong as the BM. However, the tensile results of the Zr-Sn-Nb
and the joint is as strong as the BM. However, the tensile results of the Zr-Sn-Nb joint are joint are
slightly lower than the BM, which is related to the fluctuations in the properties
slightly lower than the BM, which is related to the fluctuations in the properties of the BM of the BM
and ◦C
and the
the error
error of
of the
the test. The yield
test. The yield strength
strength and
and elongation
elongation of of the
the joints
joints at
at RM
RM andand 375375 °C
are
are lower
lower than
than that
that of
of the
the BM,
BM, reflecting
reflecting the
the decline
decline in
in the
the plasticity
plasticity ofof the
the joints.
joints.

Figure 11. Electron beam welded joints after tensile test: (a) RM; (b) 375 °C.
Figure 11. Electron beam welded joints after tensile test: (a) RM; (b) 375 ◦ C.
Materials 2024, 17, 980 10 of 14

Figure 11. Electron beam welded joints after tensile test: (a) RM; (b) 375 °C.

Figure12.
Figure 12.Tensile
Tensiletest
testresults
resultsofofthe
thejoint
jointand
andBM.
BM.

Figure1313shows
Figure showsthe thefractured
fractured surface
surface ofof
thethe tensile
tensile specimen.
specimen. There
There areare obvious
obvious plas-
plastic
tic deformation
deformation and and dimples
dimples on fracture
on the the fracture surface,
surface, as well
as well as some
as some residual
residual micropores,
micropores, as
as shown
shown in Figure
in Figure 13b.13b. It could
It could be be determined
determined that
that the
the specimenundergoes
specimen undergoesthetheinitiation,
initiation,
growthand
growth andaggregation
aggregationofofthe themicropore
microporeduring
duringthethedeformation
deformationprocess,
process,ultimately
ultimately
leadingtotothe
leading
Materials 2024, 17, x FOR PEER REVIEW theductile
ductilefracture,
fracture,which
whichisisconsistent
consistentwith
withthethecharacteristics
characteristicsofofmicropore
micropore
11 of 15
aggregation
aggregationfracture
fracture[34].
[34].

Figure 13. The fracture morphology of Zr-Sn-Nb joint: (a) 33×; (b) 500×.
Figure 13. The fracture morphology of Zr-Sn-Nb joint: (a) 33×; (b) 500×.

3.5.3. Tensile Properties of Different

Different Regions of Whole Joint
Due to tothe
theextremely
extremely narrow
narrow weld seam
weld of EBW,
seam of EBW,the standard tensiletensile
the standard test in Section
test in
3.5.2 cannot
Section 3.5.2characterize the performance
cannot characterize of the weldof
the performance seamthe and
weld HAZ.
seam Therefore,
and HAZ. theThere-
small
tensile
fore, thespecimen shown
small tensile in Figure
specimen 3 is used.
shown The tensile
in Figure 3 is used.testThe
results of small
tensile specimens
test results are
of small
shown in Table
specimens 3. Compared
are shown in Tableto3.tensile tests in
Compared to Section 3.5.2, in
tensile tests theSection
results3.5.2,
of small tensile
the results
tests
of on WZ
small metal
tensile show
tests on WZthatmetal
the average
show thattensile
the strength
average of the weld
tensile is 499
strength of MPa, 11.6%
the weld is
higher
499 MPa,than the BM,
11.6% and than
higher the yield strength
the BM, and is 9%yield
the higher than the
strength is BM. The average
9% higher elonga-
than the BM.
The
tion average elongation
after fracture of theafter
weldfracture
and HAZ of the weld and
is 12.5%, onlyHAZ69.4% is of
12.5%, onlyThe
the BM. 69.4% of the
results ofBM.
the
The
smallresults
tensileofspecimen
the small testing
tensile confirm
specimenthat testing confirm that
the strengths theWZ
of the strengths
and HAZof the
areWZ and
higher
HAZ are higher
than that thanwhich
of the BM, that ofwell
theexplains
BM, which the well
jointexplains
tensile testthefracture
joint tensile
at thetest
BMfracture at
in Figure
the BM in Figure 11. Coarse grains and fine acicular α ′ phases increase the strength of the
11. Coarse grains and fine acicular α′ phases increase the strength of the joint, but reduce
joint, but reduce
the plasticity thejoint
of the plasticity of the joint [35,36].
[35,36].

Table 3. Tensile test results of different regions of Zr-Sn-Nb alloy welded joints.

WZ HAZ BM
Tensile strength (MPa) 499 496 447
Yield strength (MPa) 368 386 337
Elongation (%) 12.5 12.5 18.0
Materials 2024, 17, 980 11 of 14

Table 3. Tensile test results of different regions of Zr-Sn-Nb alloy welded joints.

WZ HAZ BM
Tensile strength (MPa) 499 496 447
Yield strength (MPa) 368 386 337
Elongation (%) 12.5 12.5 18.0

3.5.4. Impact Property

Impact property of Zr-Sn-Nb joint and BM were conducted. The fracture morphologies
of the specimens are shown in Figure 14. The Zr-Sn-Nb joints were subjected to brittle
fracture after impact loading without significantly plastic deformation, two of the specimens
were not completely fractured at the root, and the other specimen was completely fractured.
The results of impact energy testing are shown in Table 4. The impact performance of the
BM is good and has high consistency. The average value of the RM impact energy of
welded joints is 18.5 J, which is only 58.3% of that of the BM, indicating that the toughness
Materials 2024, 17, x FOR PEER REVIEW
of the joints decreases significantly relative to that of the BM. This is related to the12high
of 15
hardness of the WZ and HAZ [27].

Figure14.
Figure 14.Fracture
Fracturemorphology
morphologyofofspecimens:
specimens:(a)
(a)joint;
joint;(b)
(b)BM.
BM.

Table 4. Impact energy of Zr-Sn-Nb joints (J).

Table 4. Impact energy of Zr-Sn-Nb joints (J).
Sample 1 Sample 2 Sample 3 Average Value
Sample 1 Sample 2 Sample 3 Average Value
WZ 20.5 17 18 18.5
WZ 20.5 17 18 18.5
BM 31.3 31.5 32.3 31.7
BM 31.3 31.5 32.3 31.7
3.5.5. Corrosion Resistance
3.5.5. The
Corrosion Resistance
specimens of three joints and three specimens of BM after corrosion test are
shownTheinspecimens
Figure 15.ofThethree jointsof
surface and
sixthree specimens
specimens of BM
changed afterthe
from corrosion
originaltest are gloss
white shownto
in Figure
black 15. and
gloss, The the
surface
surfaceof six specimens
formed a black,changed from the
dense, glossy andoriginal
uniform white gloss film.
oxidized to black
The
gloss,
weld and thecan
traces surface formed
be seen a black,
in the centerdense,
of theglossy
joint and uniformthe
specimens; oxidized film. specimens
three joint The weld
traces
weightcan be seen
gains werein the center
12.35, 12.91 and of the joint
13.49 mg/dmspecimens; theaverage
2, with an three joint specimens
value weight2.
of 12.91 mg/dm
gains were 12.35, 12.91 and 13.49 mg/dm 2 , with an average value of 12.91 mg/dm 2 . Three
Three BM specimens’ weight gains were 12.63, 12.63 and 12.66 mg/dm , with an average 2

BM specimens’ weight 2gains were 12.63,that

12.63 2 , with an average value of
value of 12.64 mg/dm . It can be seen theand 12.66 mg/dm
corrosion of the joints’ weight gain average
12.64 2
valuemg/dm
is higher. Itthan
can that
be seen
of thethatBM.theThe
corrosion of the of
consistency joints’ weight
the test gainofaverage
results the BM value is
is good,
higher thantest
while the that of theofBM.
values theThejointconsistency
specimens of arethe test results
relatively sca ofered.
the BM is good, while the
test values of the joint specimens are relatively scattered.
 weld traces can be seen in the center of the joint specimens; the three joint specimens
weight gains were 12.35, 12.91 and 13.49 mg/dm2, with an average value of 12.91 mg/dm2.
Three BM specimens’ weight gains were 12.63, 12.63 and 12.66 mg/dm2, with an average
value of 12.64 mg/dm2. It can be seen that the corrosion of the joints’ weight gain average
Materials 2024, 17, 980
value is higher than that of the BM. The consistency of the test results of the BM is12good,
of 14

while the test values of the joint specimens are relatively sca ered.

Figure15.
Figure 15.Surface
Surfacemorphology
morphologyofofcorroded
corrodedspecimens:
specimens:(a)
(a)BM;
BM;(b)
(b)joint.
joint.

Materials 2024, 17, x FOR PEER REVIEW Thejoint

The jointcorrosion
corrosionspecimen
specimenin inthe
theweld
weldisisdominated
dominatedby bythe
theBM,BM,and
andaccording
according to
13 ofto
15
thesize
the sizeofofthe
thecorrosion
corrosionspecimen
specimenand andthethesize
sizeofofthe
theweld
weldin inFigure
Figure3,3,thethelength
lengthofofthe
the
weldon
weld onthe
thecross-section
cross-sectionofofthe
thecorrosion
corrosionspecimen
specimenaccounts
accountsfor for12%
12%of ofthe
thecircumference
circumference
ofofthe
the cross-section. Assuming that the corrosion rate of the HAZ and the BMisisthe
cross-section. Assuming that the corrosion rate of the HAZ and the BM thesame,
same,
ititcan 2
canbebededuced
deducedthat
thatthe
thecorrosion
corrosionweight
weightgain
gainvalue
valueatatthe
theweld
weldisis14.89 mg/dm
14.89 mg/dm,2,which
which
isis17.8%
17.8%higher
higher than
than that
that of
of the
the BM.
BM. IfIf the
the decrease
decrease inin corrosion
corrosionresistance
resistanceininthetheHAZ
HAZis
istaken
takeninto
intoaccount,
account,thethedecrease
decrease in in corrosion
corrosion resistance
resistance of of the weld relative to theBM
the weld relative to the BM
would
would be even lower. Figure 16 shows the cross-sectionalmorphology
be even lower. Figure 16 shows the cross-sectional morphologyofofthe thecorroded
corroded
specimen.
specimen.The Thethickness
thicknessofofthe
thecorrosion
corrosionlayer
layeratatthe
theBM
BMand andWZWZvaried
variedfrom
from99toto12
12µm
µm
and 12 to 15 µm, respectively.
and 12 to 15 µm, respectively.

Figure16.
Figure 16.Cross-section
Cross-sectionmorphology
morphologyofofcorroded
corrodedspecimens:
specimens:(a)
(a)BM;
BM;(b)
(b)joint.
joint.

TheWZ
The WZand and HAZHAZ of of zirconium
zirconium havehave a worse
a worse corrosion
corrosion resistance
resistance than
than the BM the
in BM
mostin
most[8].
cases cases
EBW[8].isEBW is carried
carried out in aout in a vacuum
vacuum environment
environment withoutwithout the addition
the addition of filler of filler
metal,
metal,effectively
which which effectively controls
controls the the gas contamination
gas contamination from the environment
from the environment and the variationand theof
variation
weld of weldcaused
composition composition caused by
by the welding the welding
material. On thematerial. On there
other hand, the other
is no hand, there
significant
is no orientation
grain significant grainin theorientation in theinjoint
joint as shown as shown
Figure in Figure
8, which 8, which
is favorable foristhe
favorable
corrosion for
performance
the corrosionofperformance
the joint [37].ofZirconium alloyZirconium
the joint [37]. welded joints have
alloy residual
welded stresses,
joints which
have residual
isstresses,
an important
whichfactor in the reduction
is an important factorinincorrosion resistance
the reduction of the joint
in corrosion [38,39].of the joint
resistance
[38,39].
4. Conclusions
This paper investigated the microstructure and properties of Zr-Sn-Nb alloy EBW
4. Conclusions
joints.This
The paper
main conclusions
investigatedare asmicrostructure
the follows: and properties of Zr-Sn-Nb alloy EBW
(1) EBW
joints. Theofmain
Zr-Sn-Nb alloy can
conclusions are obtain a weld with a flat surface and relatively uniform
as follows:
(1) fish
EBW scale pattern. The
of Zr-Sn-Nb interior
alloy of theaweld
can obtain weldiswith
free aofflat
defects.
surface and relatively uniform
(2) Thefish WZ and
scale pa HAZ
ern. grains
The were
interior significantly
of the weld coarsened,
is free of with the formation of acicular
defects.
α ′ -Zr in the upper part of the weld and the maximum size of the primary β grains
(2) The WZ and HAZ grains were significantly coarsened, with the formation of acicular
exceeding
α′-Zr in the0.5upper
mm. part
The blocky α phase
of the weld andformed
the maximumin the root
sizeof
ofthe
theweld. Theβ EBSD
primary grains
exceeding 0.5 mm. The blocky α phase formed in the root of the weld. The EBSD
results indicate that the grain orientation inside the WZ and HAZ is uniform and
there is no obvious preferred orientation.
(3) Coarse grains and fine acicular α′ phases increase the strength of the joint, but reduce
the plasticity of the joint. The tensile strengths of the joints at RT and 375 °C were 438
Materials 2024, 17, 980 13 of 14

results indicate that the grain orientation inside the WZ and HAZ is uniform and
there is no obvious preferred orientation.
(3) Coarse grains and fine acicular α′ phases increase the strength of the joint, but reduce
the plasticity of the joint. The tensile strengths of the joints at RT and 375 ◦ C were
438 MPa and 313 MPa, respectively, and fracture occurred in the BM. The strength of
the WZ and HAZ were higher than that of the BM, but the elongation was significantly
lower than that of the BM.
(4) Hardening of the joint significantly reduces the toughness of the joint. The RM impact
energy of the joint is 18.5 J, which is only 58.3% of the BM.
(5) The high purity of the EBW process and unsignificant grain orientation minimizes
damage to the corrosion resistance of Zr-Sn-Nb alloy joints. The corrosion weight gains
of the joint specimen and the BM specimen were 12.91 mg/dm2 and 12.64 mg/dm2 ,
respectively, and the thicknesses of the cross-section corrosion layer were 12–15 µm
and 9–12 µm, respectively.
The significant decrease in joint plasticity and toughness as well as the loss of joint
corrosion properties need to be further studied and improved. Post-weld heat treatment is
expected to improve the welded joint properties of Zr-Sn-Nb alloys. This will be carried
out in subsequent work.

Author Contributions: Y.Z. (Yanli Zhao): writing—original draft and funding acquisition; A.Z.:
validation, conceptualization and formal analysis; H.Y.: conceptualization and supervision; H.W.:
data curation and formal analysis; Y.X.: data curation, methodology and validation; Y.Z. (Yi Zhou):
investigation, resources and methodology. All authors have read and agreed to the published version
of the manuscript.
Funding: This research received no external funding.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The raw data generated during the present study are available from
the corresponding author on reasonable request.
Conflicts of Interest: 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.

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