Materials Science and Technology

ISSN: 0267-0836 (Print) 1743-2847 (Online) Journal homepage: http://www.tandfonline.com/loi/ymst20

Growth kinetics of reaction layers formed during

diffusion bonding of SiC ceramic to TiAl alloy

H.J. Liu, J.C. Feng, H. Fujii & K. Nogi

To cite this article: H.J. Liu, J.C. Feng, H. Fujii & K. Nogi (2004) Growth kinetics of reaction layers
formed during diffusion bonding of SiC ceramic to TiAl alloy, Materials Science and Technology,
20:8, 1069-1072, DOI: 10.1179/026708304225017274

To link to this article: http://dx.doi.org/10.1179/026708304225017274

Published online: 19 Jul 2013.

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 Growth kinetics of reaction layers formed during
diffusion bonding of SiC ceramic to TiAl alloy
H. J. Liu, J. C. Feng, H. Fujii, and K. Nogi

In order to comprehend and simulate the interfacial reactions between SiC ceramic and TiAl alloy, a mathematical
model for describing the growth behaviour of reaction layers is established according to the synthetic effects of
chemical reaction and physical diffusion, and the method and formulae for calculating the kinetic parameters from
the experimental data are given. Two reaction layers, TiC and (Ti5Si3CxzTiC), are formed during the diffusion
bonding, and their kinetic parameters are determined. The calculation indicates that the two reaction layers have
essentially the same critical growth time, but the chemical reaction constant and physical diffusion constant of the
TiC layer are smaller than those of the (Ti5Si3CxzTiC) layer. Therefore, the two reaction layers always grow in
the same control regime, but the growth rate of the TiC layer is slower than that of the (Ti5Si3CxzTiC) layer. In
addition, the kinetic equations of the two reaction layers are presented, and the simulated results are quite consistent
with the experimental data. MST/5920
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Keywords: Diffusion bonding, Silicon carbide, Titanium aluminides, Interfacial reactions, Reaction layers, Growth kinetics

Dr Liu (liuhj@hope.hit.edu.cn or lhj@jwri.osaka-u.ac.jp) and Professor Feng are in the National Key Laboratory of Advanced
Welding Production Technology, Harbin Institute of Technology, Harbin 150001, China and Dr Fujii and Professor Nogi are in
the Joining and Welding Research Institute, Osaka University, Osaka 567 – 0047, Japan. Manuscript received 28 July 2003;
accepted 24 February 2004.
# 2004 IoM Communications Ltd. Published by Maney for the Institute of Materials, Minerals and Mining.

composed of lamellar (cza2) phases, and this alloy is

Introduction
Both SiC ceramic and TiAl alloy are important structural
materials for advanced applications in the space and military
industries, owing to their promising properties such as low
density, high elevated temperature strength and excellent
oxidation resistance. However, it is necessary to join SiC
ceramic or TiAl alloy to metals to expand their practical
applications, and some joining processes in this context have
been developed in previous decades. In particular, the
diffusion bonding process has been studied in detail, and is
considered to be an optimum joining process. There are many
reports of the diffusion bonding or interfacial reactions
between SiC ceramic and refractory metals such as Nb
(Ref. 1), Ti (Ref. 2), Ta (Ref. 3), V (Ref. 4), Mo (Ref. 5), Zr
(Ref. 6), Cr (Ref. 7) and Ni (Ref. 8), and between TiAl alloy
and metals such as titanium alloys9 – 11 and carbon steel.12,13
Some studies have involved the direct diffusion bonding of
SiC ceramic to TiAl alloy.14 – 16
In practice, a joint composed of SiC ceramic and TiAl
alloy has great potential to become an important candidate
for special application in armour systems.17 The concept of
utilising ceramic and intermetallic materials to attain a
complete, functionally graded armour system by means of a
joining process is a recent approach for protection of
armour against projectiles.9,17 Therefore, the feasibility of
diffusion bonding of SiC ceramic to TiAl alloy has been
studied.14 – 16 Based on this, the present study focuses on the
interfacial reaction kinetics of SiC ceramic – TiAl alloy in
order to comprehend, simulate and control their interfacial
reactions and thus improve the joint performance.
Experimental procedure
The materials used in the experiments were SiC rods
(diameter 6 mm, height 4 mm) with a small amount of
Al2O3 as sintering additive, and TiAl alloy foils (thickness
0.2 mm) with an average composition of Ti – 43Al – 1.7Cr –
1.7Nb (at.-%). The microstructure of the TiAl alloy was
referred to as TAD in the present study. The stacked
SiC/TAD/SiC assemblies were diffusion bonded at
1473 – 1573 K for 15 – 240 min under a load of 35 MPa.
Cross-sections of the SiC/TAD joints were prepared for
metallographic analysis using standard polishing techni-
ques. The reaction products and the interfacial structures of
the joints were examined by scanning electron microscopy
(SEM, S-570), electron probe X-ray microanalysis (EPMA,
JXA-8600) and X-ray diffraction (XRD, JDX-3530M). The
thickness of each reaction layer was directly measured by
SEM and expressed as an average of 10 values obtained
from different locations of the same cross-section.
Kinetic model and parameters
KINETIC MODEL
In order to establish a mathematical model for describing
the growth behaviour of a reaction layer, two important
concepts must be introduced here, i.e. critical growth
thickness yc and critical growth time tc. With respect to any
reaction layer whose thickness varies with bonding time,
when the quantity of atoms able to diffuse to the reaction
interface through the reaction layer is just equal to that of
atoms required by a continuous chemical reaction at the
interface, the thickness of the reaction layer at this very
moment is the critical growth thickness, and the time
expended for the reaction layer to grow to the critical
thickness is the critical growth time.
When the thickness of the reaction layer is much smaller
than yc, the quantity of atoms able to diffuse to the reaction
interface through the reaction layer is more than that of
atoms required by the continuous chemical reaction at the
interface. In this case, the growth of the reaction layer is
essentially controlled by a chemical reaction regime, and the
growth rate of the reaction layer is a constant, i.e.
 
dy
~kR : : : : : : : : : : : : : (1)
dt R
where y is the thickness of the reaction layer, t is the

DOI 10.1179/026708304225017274 Materials Science and Technology August 2004 Vol. 20 1069
 1070 Liu et al. Growth of reaction layers in diffusion bonding of SiC to TiAl

bonding time, kR is the chemical reaction constant, and (dy/ where kR0 and kD0 are the chemical reaction constant and
dt)R denotes the growth rate controlled by the chemical physical diffusion constant independent of T, respectively;
reaction regime. QR and QD are the reaction activation energy and diffusion
On the other hand, when the thickness y of the reaction activation energy, respectively; and R is the gas constant.
layer is much greater than yc, the quantity of atoms able to The terms kR0, kD0, QR and QD are known as standard
diffuse to the reaction interface through the reaction layer is kinetic parameters. They can be calculated from the
less than that of atoms required by the continuous chemical experimental results according to equations (13) – (20)
reaction at the interface. In this case, the growth of the below
reaction layer is essentially controlled by a physical T1 T2

diffusion regime, and the growth rate of the reaction kR0 ~kR (T1 )T1 {T2 |kR (T2 )T2 {T1 : : : : : : : (13)
layer is inversely proportional to y, i.e. T1 T2
  kD0 ~kD (T1 ) T1 {T2
|kD (T2 ) T2 {T1
: : : : : : : (14)
dy kD
~ : : : : : : : : : : : : : (2) RT1 T2 ln ½kR (T2 )=kR (T1 )

dt D y QR ~ : : : : : : (15)
where kD is the physical diffusion constant, and (dy/dt)D T2 {T1
denotes the growth rate controlled by the physical diffusion RT1 T2 ln ½kD (T2 )=kD (T1 )

QD ~ : : : : : : (16)
regime. T2 {T1
In fact, the growth of any reaction layer is generally y(T1 ,t1 ):y(T1 ,t2 )½y(T1 ,t2 ){y(T1 ,t1 )

controlled not only by the chemical reaction regime but also kR (T1 )~ (17)
t1 y2 (T1 ,t2 ){t2 y2 (T1 ,t1 )
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by the physical diffusion regime. Only in the extreme can

either regime play a dominant role. To reflect the synthetic y(T1 ,t1 ):y(T1 ,t2 )½y(T1 ,t2 ){y(T1 ,t1 )

kD (T1 )~ (18)
effects of the chemical reaction regime and physical 2½t2 y(T1 ,t1 ){t1 y(T1 ,t2 )

diffusion regime, equations (1) and (2) should be merged y(T2 ,t1 ):y(T2 ,t2 )½y(T2 ,t2 ){y(T2 ,t1 )

into a general equation, i.e. kR (T2 )~ (19)
 {1  {1  {1 t1 y2 (T2 ,t2 ){t2 y2 (T2 ,t1 )
dy
~
dy
z
dy
: : : : : : : (3) y(T2 ,t1 ):y(T2 ,t2 )½y(T2 ,t2 ){y(T2 ,t1 )

kD (T2 )~ (20)
dt dt R dt D 2½t2 y(T2 ,t1 ){t1 y(T2 ,t2 )

dy kR kD where kR(T1), kR(T2), kD(T1) and kD(T2) are the chemical
~ : : : : : : : : : : : : (4)
dt kR yzkD reaction constants and physical diffusion constants at
Provided that t~0, y~0, the solution of equation (4) is T~T1 and T2, respectively; and y(T1,t1), y(T1,t2), y(T2,t1)
and y(T2,t2) are the thickness of the reaction layer at T~T1
y2 y and T2 for t~t1 and t2, respectively.
z ~t : : : : : : : : : : : : : (5)
2kD kR
Therefore, equation (5) becomes a general mathematical
model or kinetic expression for describing the growth Results and discussion
behaviour of the reaction layer.
In addition, according to the definitions of critical growth INTERFACIAL STRUCTURE OF JOINTS
thickness and critical growth time, their expressions can be
derived from equation (5) and are given by Figure 1 shows backscattered electron images of the cross-
sections of SiC/TAD joints diffusion bonded under different
yc ~kD =kR : : : : : : : : : : : : : : (6) bonding conditions. It can be seen from Fig. 1 that both
3 kD SiC/TAD joints exhibit similar interfacial structures
tc ~ 2
: : : : : : : : : : : : : : (7) although their bonding conditions are not the same. Two
2 kR
kinds of reaction layers have developed between SiC and
TAD. For the sake of convenience, the reaction layer
KINETIC PARAMETERS adjacent to SiC is referred to as the A layer, and the reaction
In order to utilise equations (5) – (7) to analyse and simulate layer dotted with a small amount of grey phase, adjacent to
the growth behaviour of the reaction layer, kR and kD must TAD, is referred to as the B layer. Therefore, the interfacial
be known in advance. In practice, kR and kD are both structure of the SiC/TAD joints can be expressed by SiC/A/
functions of bonding temperature T, and therefore B/TAD.
equations (5) – (7) can be expressed by Table 1 gives detailed results for the reaction layers
examined by EPMA and XRD. According to Table 1, it can
y2 (T,t) y(T,t)
z ~t : : : : : : : : : : (8) be determined that two kinds of reaction product, i.e. TiC
2kD (T) kR (T) and Ti5Si3Cx, have formed during the diffusion bonding of
yc (T)~kD (T)=kR (T) : : : : : : : : : : (9) SiC to TAD. The A layer is composed of continuous TiC,
3 kD (T) and the B layer is composed of Ti5Si3Cx matrix and TiC
tc (T)~ 2 (T)
: : : : : : : : : : : : (10) particles. Therefore, the interfacial structure of the SiC/
2 kR TAD joints is SiC/TiC/(Ti5Si3CxzTiC)/TAD, and this
where y(T,t) denotes the instantaneous thickness of the structure will not change with bonding time once it
reaction layer corresponding to T; yc(T) and tc(T) are forms, but the thickness of each reaction layer will increase
the critical growth thickness and critical growth time of the with increases in bonding temperature and bonding time.
reaction layer corresponding to T, respectively; and kR(T)
and kD(T) are the chemical reaction constant and physical
diffusion constant corresponding to T, respectively.
GROWTH KINETICS OF REACTION LAYERS
According to the physical – chemical theory, kR(T) and Table 2 indicates the practical thickness of the TiC and
kD(T) can be expressed by the Arrhenius equations18,19 (Ti5Si3CxzTiC) layers formed under the different bonding
  conditions. First, substituting the thickness of the TiC layer
{QR
kR (T)~kR0 exp : : : : : : : : : (11) into equations (17) – (20) can provide the chemical reaction
RT constants kR(T1) and kR(T2) and physical diffusion con-
  stants kD(T1) and kD(T2) of the TiC layer at T1~1523 K
{QD
kD (T)~kD0 exp : : : : : : : : : (12) and T2~1573 K, and the specific results are listed in
RT Table 3. Second, utilising the abovementioned results can

Materials Science and Technology August 2004 Vol. 20

 Liu et al. Growth of reaction layers in diffusion bonding of SiC to TiAl 1071

a at 1573 K for 30 min; b at 1473 K for 120 min

1 Backscattered electron images of SiC/TiAl (TAD) joints diffusion bonded under given bonding conditions
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give the chemical reaction constant kR0, physical diffusion
constant kD0, reaction activation energy QR and diffusion
activation energy QD of the TiC layer according to
equations (13) – (16), and these kinetic parameters are
listed in Table 4. Finally, substituting kR0, kD0, QR and
QD of the TiC layer into equations (8) – (10) can provide the
kinetic expression y(T,t), critical growth thickness yc(T) and
critical growth time tc(T) of the TiC layer, as indicated in
equation (21) and Table 3
   
: 481 000 : 2 120 000 :
0 102 exp y z27 248 exp y~t (21)
RT RT
Similarly, utilising the abovementioned calculation steps
can also determine the kinetic parameters of the
(Ti5Si3CxzTiC) layer (see Tables 3 and 4), and the kinetic
expression of the (Ti5Si3CxzTiC) layer is
   
: 415 000 : 2 80 000 :
5 87 exp y z390 625 exp y~t (22)
RT RT
It can be seen from Table 3 that the TiC layer and
(Ti5Si3CxzTiC) layer have essentially the same critical
growth time for the same bonding temperature, and the
critical growth time is relatively short although it increases
with bonding temperature. This result implies that both
reaction layers always grow in the same control regime, and
the growth process soon changes to a parabolic stage
controlled by the physical diffusion regime from a linear
stage controlled by the chemical reaction regime.
In addition, it can also be found from Tables 3 and 4 that
kR0 and kD0 of the (Ti5Si3CxzTiC) layer are much smaller

Table 1 Detailed results for reaction layers examined by electron probe microanalysis and X-ray diffraction
Major chemical constituents of phase, at.-%

Reaction layer Morphology of phase Formula of phase Ti Al Si C

A Continuous TiC 43.4 8. 9 3. 5 44.2

B Matrix Ti5Si3Cx 53.9 3. 3 30.7 12.1
B Particle TiC 41.3 9. 2 4. 4 45.1

Table 2 Thickness of reaction layers formed between SiC and TiAl for given reaction temperatures and times
Thickness of reaction layer, mm

Reaction layer 1523 K/7.2 ks 1523 K/14.4 ks 1573 K/7.2 ks 1573 K/14.4 ks

TiC 1.41 2.02 2.55 3.66

Ti5Si3CxzTiC 2.51 3.59 4.17 5.99

Table 3 Kinetic parameters of reaction layers formed at specific temperatures

1523 K 1573 K
2
Reaction layer kR, nm s 21
kD, nm s 21
yc, nm tc, s kR, nm s21 kD, nm2 s21 yc, nm tc, s

TiC 2.72 149 55 30 3.68 499 136 56

Ti5Si3CxzTiC 4.69 472 100 32 5.73 1340 234 61

Table 4 Standard kinetic parameters of reaction layers

Reaction layer kR0, 1026 m s21 kD0, 1022 m2 s21 QR, 103 J mol21 QD, 103 J mol21

TiC 36.7 486 120 481

Ti5Si3CxzTiC 2.56 8.52 80 415

Materials Science and Technology August 2004 Vol. 20

 1072 Liu et al. Growth of reaction layers in diffusion bonding of SiC to TiAl
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2 Simulated curves and measured results for thickness
of reaction layers
than those of the TiC layer, but kR and kD of the
(Ti5Si3CxzTiC) layer are still greater than those of the TiC
layer because QR and QD of the (Ti5Si3CxzTiC) layer are
smaller than those of the TiC layer. Therefore, compared
with the TiC layer, the (Ti5Si3CxzTiC) layer has a
relatively high growth rate, and its thickness must be
relatively wide. This inference is consistent with the
experimental results.
Figure 2 shows a comparison between the measured data
and simulated curves drawn using equations (21) and (22).
The simulated curves are in close agreement with the
measured results. This indicates that the kinetic model for
describing the growth of the reaction layer is quite
consistent with the practical results, and thus can be used
to simulate and analyse the growth behaviour of the
reaction layer.
Conclusions
1. A mathematical model for describing the growth
behaviour of reaction layers is established according to the
synthetic effects of chemical reaction and physical diffusion
during the interfacial reaction, and the related kinetic
parameters can be calculated from the experimental results.
2. Two reaction layers, i.e. TiC and (Ti5Si3CxzTiC),
have formed during the diffusion bonding of SiC ceramic to
Materials Science and Technology August 2004 Vol. 20
TiAl alloy, and the final interfacial structure is SiC/TiC/
(Ti5Si3CxzTiC)/TiAl.
3. The specific kinetic parameters and kinetic equations
of the TiC and (Ti5Si3CxzTiC) layers are given, and the
simulated results are quite consistent with the experimental
data.
4. The TiC layer and (Ti5Si3CxzTiC) layer have
essentially the same critical growth time, but the chemical
reaction constant and physical diffusion constant of the
former are smaller than those of the latter. Therefore, both
reaction layers always grow in the same control regime, but
the growth rate of the TiC layer is slower than that of the
(Ti5Si3CxzTiC) layer.
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