Appl. Phys.
A (2017) 123:471
DOI 10.1007/s00339-017-1072-5
Simulation of Zr content in TiZrCuNi brazing filler metal
for Ti6Al4V alloy
Xishan Yue1,2 • Zonghong Xie1 • Yongjuan Jing2
Received: 18 February 2017 / Accepted: 30 May 2017 / Published online: 17 June 2017
 Springer-Verlag Berlin Heidelberg 2017
Abstract To optimize the Zr content in Ti-based filler
metal, the covalent electron on the nearest atoms bond in
unit cell (nu–v
A ) with Ti-based BCC structure was calcu-
lated, in which the brazing temperature was considered due
to its influence on the lattice parameter. Based on EET
theory (The Empirical Electron Theory for solid and
molecules), nuv
A represents the strength of the unit cell
with defined element composition and structure, which
reflects the effect from solid solution strengthening on the
strength of the unit cell. For Ti–Zr–15Cu–10Ni wt% filler
metal, it kept constant as 0.3476 with Zr as 37.5*45 wt%
and decreased to 0.333 with Zr decreasing from 37.5 to
25 wt%. Finally, it increased up to 0.3406 with Zr as
2*10 wt%. Thus, Ti-based filler metal with Zr content
being 2*10 wt% is suggested based on the simulation
results. Moreover, the calculated covalent electron of nu–v
A Based on the examination of the element distribution
showed good agreement with the hardness of the joint by
filler 37.5Zr and 10Zr. The composition of Ti–10Zr–15Cu–
10Ni wt% was verified in this study with higher tensile
strength of the brazing joint and uniform microstructure of
the interface.
& Xishan Yue
yuexs_0@163.com
1
School of Astronautics, Northwestern Polytechnical
University, Xi’an 710072, People’s Republic of China
2
Aeronautical Key Laboratory for Welding and Joining
Technology, AVIC Beijing Aeronautical Manufacturing
Technology Research Institute, Beijing 100024, People’s
Republic of China
1 Introduction
Brazing technology has found extensive use for production
of components in biomedical and aerospace applications
[1, 2]. In the brazing technology, BFMs (brazing filler
metals) have been recognized as the most important factor
for the excellent mechanical properties of the joint
[3–5].For Ti-based alloys which has widely been used in
aerospace industry, many Ti-based BFMs have been
designed for providing better strength and corrosion
resistance compared with Al-based and Ag-based BFM
[6–9]. Most of the research has focused on optimization of
the Ti-based BFMs and the brazing process (as brazing
temperature and holding time); however, it costs much
expense on experiments.
near the joint, the solid strengthening effect from the
filler elements on the joint has been proposed [10]. In
addition, the element distribution was influenced not
only by the brazing process, but also by the filler com-
position. Hence, the simulation of the strength of the
filler alloy can be one of the methods to predict the
strength of the joint. Besides, the mechanism for the
higher strength of the joint has been a big concern, even
though some reports published the joint strength as much
as that of the matrix [9, 11, 12].
Moreover, reduction of Zr content within the Ti-based
filler material at a certain extent was found to remain the
melting point of the brazing filler material [10]. It remains
in the lower brazing temperature below the b phase tran-
sition temperature. Meanwhile, based on the Ti-Zr phase
diagram, Ti and Zr elements are infinite mutual soluble
with each other. Due to the size difference between Zr and
Ti, the increase of Zr will increase the solid solution
hardening.
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471 Page 2 of 7
In this study, the covalent electron on the nearest atoms
bond in unit cell (nu–vA ) with Ti-based BCC structure was
calculated, in which the brazing temperature was consid-
ered due to its influence on the lattice parameter. The
model expressed the influence from the composition of the
filler on the strength of the filler metal. In addition, it
showed good agreement with the hardness results of the
joint. In addition, the suitable Zr content for brazing Ti-
based alloy was discussed based on the simulation results.
2 Model description on Ti-based brazing filler
design
2.1 Basic theory
The Empirical Electron Theory for solid and molecules
(EET) is used to calculate the bonding energy [13–15].
Based on EET, the bond energy of a unit cell can be cal-
culated by applying a mean-field model, assuming that the
nearest-neighbor interactions are so predominant that
higher neighbor interactions can be neglected. This implies
that only pair interactions between the nearest-neighbor
atoms are taken into account. Under the above assumption,
Becker developed his model for calculating the energy of a
disordered alloy where the regular solution model can be
used to describe the strength of the alloy, and this method
has been used for the prediction of the segregation solution
area in Al–Cu and Al–Ag alloy [16].
According to EET, in a crystalline structure, there
always exist kinds of generalized covalence electrons
between two neighbor atoms u and v. The number of these
covalence electrons may or may not be an integer. The
covalence electrons of an atom are on its nearest-neighbor
bond, its next nearest-neighbor bond, and on the second
nearest-neighbor bond.
The relationship between the bond distance Du–v na (or
Duv ) and the numbers of the covalence electrons n u–v
a for
na
each u–v bond are expressed as follows:
Duv u v uv
na ¼ R þ R  b lg na ð1Þ
u v
Duv
na ¼ R þ R  b lg nuv
a ð2Þ
X
ku nuc þ kv nvc ¼ Ia nuv ð3Þ
a
a þ RCu  15% þ RNi  10
 
DDuv
na ¼ Duv uv 
na  Dna : ð4Þ
To calculate nu–v
a , an important factor r for each atom is
predefined. Since a structure unit should be electronically
neutral, the covalent electrons of all the atoms in the unit
should be distributed on all the covalent bonds. In other
words, the numbers of the total covalent electrons of all the
atoms (kunuc ? kvnvc ) should be equal to the sum of the
123
X. Yue et al.
numbers of the electrons on all the covalent bonds in the
P
unit ( Ia nuv
a , a = A, B, C,…), as shown in Eq. (3).
a
Combining Eqs. (1) and (3), all the nu–v
a (a = A, B, C,…
represent all kinds of u–v bonds that cannot be neglected in
a structure) can be calculated according to the experimental
covalent bond lengths, defined hybrid state r of each atom
for Ri and nic(i = u or v), and the preselected value for b.
Finally, Duv
na can be calculated according to nu–v
a and
 uv 
Eq. (2), and DDna ¼ Dna  Duv
uv
na
 can be calculated.
The criterion (Eq. 4) for determining the number of
coherent electrons of each type of bond is the relative
difference between the experimental bond distance and the
theoretical one.
2.2 Model on TiZrXCu15Ni10 brazing filler
1. The mixed atom in the structure of lattice.
The parameters used in the model were listed in Table 2.
Due to the earlier experimental results [10], there are two
kinds of phases in the joint. Phase with HCP structure
was rich in Zr, Cu, and Ni elements, but it was identified
as the intermetallic compound—(Ti, Zr)(Ni, Cu)3 and
resulted in the crack initiation. The other phase with
BCC structure—(Ti, Zr)(Ni, Cu)—was the Ti-solid
solution, which is taken as the structure lattice in this
model (as shown in Fig. 1), because it is ductile and
benefit for the mechanical properties of the joint.
Besides, the HCP phase can be avoided by relative
higher brazing temperature and longer holding time.
The BCC structure lattice model was shown in Fig. 1a.
The BCC structure lattice model was shown in Fig. 1a.
Mixed atom was assumed in this study for calculation on
the bond energy with different Zr contents in the filler
metal. On the basis of the average atom model in EET
theory, atoms in mixed element fraction were named
with a kind of structure. Hence, u and v atom mentioned
in 2.1 is the same atom here (as shown in Fig. 1b). Thus,
Ru = Rv = R; nvC = nvC = nC, ku = kv = k = 2,
IA = 8; IB = 12; IC = 12, Du–v na = Dna(a = A; B; C).
Moreover, for calculation of Eqs. (1)–(3), the following
should be considered.
R ¼ RTi  ð100  X  15  10Þ% þ RZr  X%
ð5Þ
nC ¼ nTi Zr
C  ð100  X  15  10Þ% þ nC  X%
Cu Ni
þ nC  15% þ nC  10%
ð6Þ
pffiffiffi 1 pffiffiffi
DnA ¼ 2ai ; DnB ¼ ai ; Dnc ¼ 2ai ð7Þ
2
Simulation of Zr content in TiZrCuNi brazing filler metal for Ti6Al4V alloy Page 3 of 7 471

Fig. 1 BCC structure model and the schematic of the mixed atom

X is the fraction of Zr element in the filler alloy, as 3 Simulation and experimental results
shown in Fig. 1b. ai is the lattice constant.
2. The influence from brazing temperature on lattice 3.1 Simulation results
constant ai.
Temperature affects lattice constant and the elements The number of covalent electrons—nu–v a for each u–v bond
diffusion. The filler metal was used under the situation (a = A, B, C) with the corresponding 4Du–v na was calculated
of high temperature. In this study, it is 930 C (as and listed in Table 3. All the data of 4Du–v na satisfied the
shown in Table 1). The lattice constant ai can be criterion (Eq. 4). Due to A-bond is the nearest bond between
expressed as a function of temperature as: atoms in the BCC structure, the number of covalent elec-
ai ¼ ai0  ½1 þ bi  ðT  298:15Þ; ð8Þ trons—nu–v A is much higher than that of B- and C-bond.
Based on the theory of EET, nu–v A represents the strength of
where ai0 (as shown in Table 2) is the lattice constant the BCC structure with the defined fraction of Zr content in
of the element Ti at 298.15 K and bi is the linear the filler metal. Hence, the influence from the Zr content on
coefficient of temperature. the strength of unit cell of BCC structure can be analyzed.
bi ¼ bTi Zr As shown in Fig. 2, with the decreasing of Zr content,
i  ð100  X  15  10Þ% þ bi  X%
Cu Ni
þ bi  15% þ bi  10% ð9Þ first, nu–v
A kept constant as 0.3476 with Zr from 45 to
37.5 wt%. Then, it decreased to 0.333 with Zr from 37.5 to
with Eqs. (7), (8), and (9), the Du–v
na can be calculated. 25 wt%. After that, it increased up to 0.3406 with
With Dna and Eqs. (1) and (3), nu–v
u–v
a can be calculated. Zr = 2 wt%. With higher Zr content, the strength of the
With nu–v
a and Eq. (2), Duv can be calculated. Flow- filler metal is the most highest. And with relatively lower
 na 
ingly, the 4 Duv ¼ Duv  Duv  can be calculated.
na na na
Zr content, it is better. Therefore, based on the calculated
If the DDuv results, the Zr = 18*25 wt% is not suggested. Thus, the
na  0:005 nm, the hybrid state r for each
element is considered reasonable. If not, the hybrid strength of the unit cell for the filler metal was much
state r for each element should be changed until the affected by the Zr content, following the effect of the solid
DDuv strengthening by the elements of the filler alloy on the
na  0:005 nm:
brazing joint.

3.2 Experimental results

The Zr content of Ti-based filler metal is from 25*45 wt%

in the published report. Here, based on the above simulated
results (part 3.1), the Ti-based filler metal with
Zr = 2*18 wt% is suggested because of the higher
covalent electrons on bond A—which is the strongest bond
of the unit cell.
The brazing joints were fabricated by filler metal with
composition Ti–37.5Zr–15Cu–10Ni wt% and Ti–10Zr–
15Cu–10Ni wt%. The filler with Ti–37.5Zr–15Cu–
Fig. 2 Covalent electrons—nu–v
a (a = A) with different Zr content in 10Ni wt% is the commercial filler. The Ti–10Zr–15Cu-
filler metal 10Ni wt% has been studied in the earlier study [10]. The

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471 Page 4 of 7 X. Yue et al.

Table 1 Parameter and its definition in Eqs. (1)–(8)

Parameter Definition

i Atom in the unit cell, i = u and v

u and v A kind of atom, u and v may be the same or not the same kinds of atoms
nu–v
a Number of covalent electrons for each u–v bond of the a type, a = A, B, C,… represent all kinds of u–v bonds that cannot be
neglected in a structure. The bond with the A type is defined as the nearest bond
Du–v
na Actual distance between u and v atoms. It is called the experimental covalent bond length in the EET, which is equal to metallic
bond length in value and can be calculated with the practical lattice constant and the crystal structure
uv
Dna The theory distance between u and v atoms. It is used to represent the calculated distance between u and v atoms based on the
calculated nu–v
a

ki Number of i atoms in the unit cell

nic Number of covalence electrons of the i atom
Rri Single-bond radius of the atom i, the single-bond radius of the atom i at a particular hybrid state r. r can be obtained from the
tables of [13]
b A parameter depends on the largest nu–v
a in the structure
It equals 0.071 nm when {nu–v u–v
a }max \ 0.25 or {na }max [ 0.75
u–v
It equals 0.06 nm when 0:300 \ {na }max \ 0.700
It equals {0.071–0.22Xe} when {nu–v u–v
a }max = 0.25 ? e or {na }max = 0.75-e with 0 B e B 0.05

The value of{nu–v

a } max represents the largest nu–v
a in the structure. The choice of b is determined by the trial and error method
Ia Number of equivalent bonds for the bond u–v of the type a in the unit cell. Ia = IMIsIk, a = A, B, C,…
IM Number of the reference atoms in the unit cell
Is Number of equivalent bonds for a reference atom forming a type A-bond u–v
Ik A parameter equals 1 when the two atoms that form the bond u–v are of the same type occupying equivalent positions and 2 when
they are not the same
r Hybrid state. It can be defined from the tables of [13]

Table 2 Parameters used in the model The simulation results showed good agreement of the
Composition of Structure Lattice Brazing hardness results (as shown in Fig. 4). The ultimate tensile
TiZrXCu15Ni10 wt% of lattice constant ai0 temperature strength of the sample with brazing joint was 881,880,846
(nm) (C) MPa with average 869 MPa by filler 10Zr. All the samples
fractured in the matrix, which meant that the strength of the
X = 45 Cu = 15; BCC-Ti ai0 = 0.332 930
joint was as strong as that of the matrix. Hence, the larger
X = 40 Ni = 10;
the covalent electron number of the A-bond is, the stronger
X = 37.5 The rest is Ti.
the hardness of the joint. Thus, the model for investigation
X = 25
on the covalent electron number in the unit cell with filler
X = 18
composition and defined structure can be used to predict
X = 10
the composition for the Ti-based filler metal.

data of the fillers and the brazing process were listed in

Table 4. All the interface microstructure was examined by
SEM (scanning electron microscope). The hardness and the
tensile strength of the joint were tested and the elements
distribution across the joint was mapped by EBSD (electron
back scatter diffraction). As shown in Fig. 3, Widmanstätten
microstructure was found throughout the entire joint section
due to eutectoid reaction. No voids or cracks along the joint
were found. Furthermore, no intermetallic compounds were
observed in the joint, which have been commonly observed
in the brazed joint for Ti-based alloys, as shown in Table 4.
Compared with the microstructure by filler 37.5Zr, the grain
size of the joint by filler 10Zr was finer.
4 Discussion
For joining a ? b Titanium alloys such as Ti-6Al-4 V with
b-transus temperature (Tb) of 1268 K (995 C), the brazing
temperature should usually be about 38–66 K (responding
to 929–957 C) below the Tb to avoid the mechanical
property impairment of the base materials caused by the
phase transformation and grain coarsening. In general, the
brazing temperature is more than 50 C higher than the
liquid temperature of the filler metal. Thus, the liquid
temperature of the filler metal should be less than 900 C at
least.

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Simulation of Zr content in TiZrCuNi brazing filler metal for Ti6Al4V alloy Page 5 of 7 471

Table 3 Number of covalent

Fraction of Zr wt% Bond name nu–v
a Du–v
na nm Duv
na nm
4 Duv
na nm
electrons—nu–v
a for each u–v
bond (a = A, B, C)
45 A 0.3476 0.2863 0.2911 0.0047
B 0.0635 0.3307 0.3354 0.0047
C 3.3198 9 10-4 0.4675 0.4723 0.0004
40 A 0.3476 0.2863 0.2894 0.0030
B 0.0635 0.3307 0.3337 0.0030
C 3.3198 9 10-4 0.4675 0.4706 0.0003
37.5 A 0.3476 0.2863 0.2886 0.0022
B 0.0635 0.3307 0.3329 0.0022
C 3.3201 9 10-4 0.4675 0.4697 0.0002
25 A 0.3330 0.2863 0.2891 0.0028
B 0.0608 0.3307 0.3334 0.0028
C 3.1805 9 10-4 0.4675 0.4703 0.0002
18 A 0.3388 0.2863 0.2838 0.0025
B 0.0619 0.3307 0.3282 0.0025
-4
C 3.2363 9 10 0.4675 0.4650 0.0002
10 A 0.3406 0.2863 0.2820 0.0043
B 0.0622 0.3307 0.3263 0.0043
C 3.2531 9 10-4 0.4675 0.4632 0.0004
2 A 0.3406 0.2863 0.2820 0.0043
B 0.0621 0.3307 0.3263 0.0043
-4
C 3.2531 9 10 0.4675 0.4632 0.0004

Table 4 Chemical composition of the filler metal and the brazing shown in Fig. 5b. The arrows showed the 900 C line. The
process liquid temperature is suggested not higher than 900 C.
Composition/wt% Melting point/ C Brazing process Based on the simulated results, the filler with Zr content
being 37.5*45 (highlighted in the black box in Fig. 5b)
Ti–37.5Zr–15Cu–10Ni 830–840 930 C/30 min and 2*18 wt% are suggested. However, the more the Zr
Ti–10Zr–15Cu–10Ni 880–890 930 C/30 min content present in the filler metal, the more likely is the
segregation of elements as Ti, Zr, Cu, and Ni occurs. This
was prone to form the intermetallic compounds, which is
The liquid temperature of the filler metal was influenced the main reason for the propagation of the crack in the
by its composition. It affects the brazing temperature. As joint. Lots of studies reported that the intermetallic com-
shown in Fig. 5a, there is a list of most of the published Ti- pound occurred in the joint with the higher Zr content in
based filler metals (No. 1–No. 22) with increscent of the the filler, as shown in Table 5 with Zr from 20*60 wt%.
liquid temperature of the filler metal. And the corre- In addition, the lower the Zr content (2*18 wt%) in the
sponding composition of the filler (No. 1–No. 22) was filler resulted in the increase of the liquid temperature of

Fig. 3 Microstructure of the

joint. a Joint by filler Ti–
37.5Zr–15Cu–10Ni; b joint by
Ti–10Zr–15Cu–10Ni

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471 Page 6 of 7
Fig. 4 Hardness of the joints by different filler
the filler metal. The balance between the solid strength-
ening effect on the filler metal from the elements and the
liquid temperature of the filler metal is a big concern in the
further study. Especially better diffusion of the filler metal
in the brazing joint is much more important for the com-
plicated brazing structure, e.g., honeycomb structure.
Fig. 5 Liquid temperature of the brazing filler alloy with different composition. a Liquid temperature increment from filler No. 1–22;
b composition of filler No. 1–22
123
X. Yue et al.
5 Conclusion
The covalent electron on the nearest atoms bond in unit cell
(nu–v
A ) with Ti-based BCC structure was calculated, in
which the brazing temperature was considered due to its
influence on the lattice parameter. The suitable Zr content
was analyzed with the solid solution effect and the liquid
temperature of the filler, which affects the brazing tem-
perature. Conclusions are as follows.
1. With the decreasing of Zr content, first, nu–v A kept
constant as 0.3476 with Zr from 45 to 37.5 wt%. Then,
it decreased to 0.333 with Zr from 37.5 to 25 wt%.
After that, it increased up to 0.3406 with Zr = 2 wt%.
Ti-based filler metal with Zr content being 10-2 wt% is
suggested based on the simulation results.
2. The covalent electron on bond A showed good
agreement with the hardness of the joints by filler
Ti–37.5Zr–15Cu–10Ni and Ti–10Zr–15Cu–10Ni. The
tensile joint strength of Ti6Al4 V by Ti–10Zr–15Cu–
Simulation of Zr content in TiZrCuNi brazing filler metal for Ti6Al4V alloy Page 7 of 7 471

Table 5 Summary of published results for brazing Ti-based alloys

Interface microstructure Matrix Filler metal composition References

Acicular Widmanstätten microstructure with no intermetallics Ti-6Al-4 V Ti–10Zr–15Cu–10Ni, wt% (This study)
A continuously segregated phase regarded as a [Ti,(Zr)]2(Cu, Ni) intermetallic Ti-6Al-4 V 62.7Zr–11.0Ti–13.2Cu– [12]
phase; the acicular Ti-rich grains 9.8Ni–3.3Be, wt%
ZrO2/TiO ? TiO2 ? Cu2Ti4O ? Ni2Ti4O/a-Ti ? (Ti, Zr)2(Cu, Ni)eutectic/ Ti-6Al-4 V Ti–28Zr–14Cu–11Ni, at. % [8]
(Ti, Zr)2(Cu, Ni)/acicular Widmanstäten and Zirconia
Cu/Ni[Ti(Zr)]2 and Lave(Cu/Ni)2[Ti,(Zr)] Pure titanium Ti–27Zr–14Cu–13Ni, wt% [17]
(Ti–CP)
Cu/Ni[Ti(Zr)]2 and Lave(Cu/Ni)2[Ti,(Zr)] Ti-6Al-4 V Ti–27Zr–14Cu–13Ni, wt% [17]
Widmanstätten structure consisting mainly of a-Ti, b-Ti and Ti–Zr-rich phase Ti-6Al-4 V Ti50–Zr27–Cu8–Ni4–Co3– [18]
and a small amount of brittle intermetallics Fe2–Al3–Sn2–Si1, wt%
Zr2Cu, Ti2Cu, and (Ti, Zr)2Ni intermetallic compounds Ti-6Al-4 V Ti–26.8Zr–13Ni–13.9Cu, [6]
wt%
A fine lamellar eutectic joint microstructure consisting of a-Ti and c- Ti-6AI-4 V 25Ti–25Zr–50Cu, wt% [11]
[Ti(Zr)]zCu (tetragonal MoSie-type) phase
Three distinctive phases(a Ti-rich phase alloyed with low Cu, Ni, Zr contents, a Ti-6Al-4 V Ti–20Zr–20Cu–20Ni, wt% [19]
Cu–Ni-rich Ti phase and a Cu–Ni–Zr-rich Ti phase) and SP-700

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