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Received 13 December 2002; received in revised form 13 December 2002; accepted 9 May 2003
Abstract
The effect of direct current upon interfacial reactions in the Ni–Ti system was investigated. Isothermal diffusion
couple experiments were conducted under varying current densities to de-couple Joule heating from intrinsic effects
of the current flux. Current densities of up to 2546 A cm⫺2 were used in the temperature range of 625–850 °C. All
of the intermetallic compounds (NiTi, Ni3Ti and NiTi2) present in the equilibrium phase diagram were identified in
the product layer. In addition, β-Ti solid solutions formed in samples annealed above the α→β temperature, 765 °C.
The growth of all product layers was found to be parabolic and the applied current was found to significantly increase
the growth rate of the intermetallic layers. Using Wagner’s analysis the present results were compared to published
results on current-free diffusion couples. The intrinsic growth rate constant of the NiTi2 intermetallic was found to be
43 times higher under the influence of 2546 A cm⫺2 than that obtained without a current at 650 °C. The effective
activation energy for the formation of all phases was found to decrease with increasing current density. The effect was
strong for all phases but the decrease was most marked for Ni3Ti. In this case, the activation energy decreased from
292 kJ mol⫺1 under the influence of a current density of 1527 A cm⫺2 to 86 kJ mol⫺1 when the current density was
2036 A cm⫺2. The results are explained in terms of current induced changes in the growth mechanism arising from
changes in the concentration of point defects or their mobility.
2003 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
Keywords: Electric current effects; Intermetallics; Growth rates; Titanium–nickel; Reactive diffusion
1359-6454/03/$30.00 2003 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/S1359-6454(03)00284-2
4488 J.E. Garay et al. / Acta Materialia 51 (2003) 4487–4495
have a significant role in activating the process, but in the Ni–Ti system (Fig. 1) Ni3Ti, NiTi and NiTi2.
also in influencing the nature of the product. In an Ni3Ti is a hexagonal close-packed superlattice and
investigation on the synthesis of Ti3Al, it was NiTi2 has a complex face-centered cubic structure
found that the rate of the reaction increased with with 96 atoms per unit cell (space group Fd3m)
an increase in the applied field and that the nature [15,16]. The structure of the third equilibrium
of the product changed with this increase. Ulti- phase NiTi is interesting in that it has a high and
mately at a relatively high field, only the desired low temperature crystal structures due to a mar-
Ti3Al phase was present [3]. Similar results were tensitic-type transformation. This transformation
obtained in the case of another intermetallic, leads to a shape memory effect. The high tempera-
FeAl [4]. ture “austenitic” phase has a B2 (CsCl) structure
In these and other similar observations, the role (space group Pm3m), while the low temperature
of the current was initially assumed to be thermal, “martensite” has a more complex monoclinic
providing Joule heat to the reactants and product. B19⬘-type structure (space group P21/m) [17].
Modeling studies based on this assumption have
been made and the results show qualitative agree-
ments with the experimental observations [5–7]. 2. Experimental procedure
However, non-thermal current effects on mass
transport through electromigration have been A schematic of the apparatus we used in our
known for decades and experimental observations experimental investigation is shown in Fig. 2. It
demonstrating such effects have been provided consists of a vertical cylindrical vacuum chamber
[8,9]. In a recent investigation, we have shown that housing two electrodes surrounded by a furnace.
the imposition of a DC current across interfaces The electrodes carry current to the sample and pro-
between Al and Au metal layers has a significant vide a small mechanical load to ensure good con-
effect on the growth rate of the intermetallic layers tact between the reactants. The electrodes are mol-
and on the incubation time for the nucleation of ybdenum rods 28 mm in diameter with a terminal
these product phases [10,11]. In these results, no part reduced to 5 mm diameter, allowing the exter-
effect of the direction of the DC current on the nal DC power supply to produce a current density
growth of the products was observed, implying that up to 3310 A cm⫺2 through the sample. The fur-
electromigration is not the dominant effect of the nace consists of a cylindrical tungsten mesh 16.5
current. cm in diameter and 6.5 cm long powered by an
In this paper, we investigate the effect of the AC power supply. A 0.5-mm diameter type K
current on the phase formation kinetics of products
resulting from the interaction of Ti and Ni and we
compare our results with those reported earlier on
diffusion couples without a current [12].
The Ni–Ti system has received much attention
primarily for its commercially important intermet-
allic phase, NiTi. This material has relatively high
ductility and corrosion resistance in addition to dis-
playing the shape memory effect. Other alloys in
the system have received attention, including a
quasi-crystalline phase which can be formed near
the NiTi2 compound, and also because Ti-rich Ni–
Ti alloys can form metallic glasses [13]. Also of
interest is replacing Al with Ti in Ni-based superal-
loys, because Ti is believed to enhance the high
temperature strength [14].
There are three equilibrium intermetallic phases Fig. 1. Ni–Ti phase diagram.
J.E. Garay et al. / Acta Materialia 51 (2003) 4487–4495 4489
3. Results
Fig. 5. Product layer thickness squared (⌬x)2 vs. time for Fig. 6. NiTi layer thickness (⌬x) vs. current density for
samples reacted at 650 °C with current density of 2036 A cm⫺2. samples reacted at 650 °C for 4 h.
J.E. Garay et al. / Acta Materialia 51 (2003) 4487–4495 4491
assumptions that: the growth of all phases is para- where Ci = √kIi, Vi the molar volumes, and ni the
bolic, local equilibrium is established at each inter- stoichiometric coefficients of each phase nor-
face, the phases have narrow homogeneity ranges, malized to 1 mol of component B, AniB. Values of
and the extent of solubility in the terminal phases, kiII represent the intrinsic property of each phase,
i.e., Ti and Ni, in this case, is limited. These depending only on the interdiffusion coefficient
assumptions can be reasonably applied to the Ni– and the free energy of formation of that phase.
Ti system in the temperature range of this investi- The intrinsic rate constants obtained through this
gation. The homogeneity range of the phases NiTi method for all the experiments performed at tem-
and NiTi2 below 750 °C is relatively small and the peratures (650–750 °C) below the α→β transition
fairly large solubility of Ti in Ni can be ignored temperature for Ti are reported together with the
since the diffusivity of Ti in Ni is extremely slow first kind constants in Table 1. It should be noted
even at fairly high temperatures [18]. that no data are reported in this table for the highest
Using the nomenclature of Wagner, we calculate current density, 2456 A cm⫺2, at 750 °C. Under
the rate constant of the first kind, kI, from the these conditions, the growth rate is so high that the
slopes of lines such as those shown in Fig. 7 which middle, Ni, layer of the starting material will be
is for the growth of the NiTi layer at 750 °C under completely consumed after a relatively short time.
different current densities. Thus When this occurs, the equilibrium conditions will
be different. Table 2 reports the first kind rate con-
(⌬x)2 ⫽ kIi t (1)
stants for experiments performed at temperatures
where ⌬x is the thickness of the layer of the inter- (800–850 °C) above the α→β transition tempera-
metallic and t is time. When only one phase forms, ture for Ti. Intrinsic (second kind) rate constants
then the constant is the true rate constant and is cannot be calculated for the higher temperatures,
referred to as the rate constant of the second kind, since above 765 °C, the extensive solubility of Ni
kiII. The relationship between kiI and kiII has been in Ti to form β-Ti violates the assumption in the
provided by Buscaglia and Anselmi-Tamburini as derivation of this kinetic parameter, as indicated
冋冘
above.
(ni⫺1⫺ni+1)Vi
i⫺1
Cj ni
kIIi ⫽ C2 n ⫹ (2)
(ni⫺1⫺ni)(ni⫺ni+1) i ij ⫽ 1VjCi Vi
冘 册
n
4. Discussion
njCj
⫹ i ⫽ 1,…,n
V C From the calculations described above, we are
j ⫽ i⫹1 j i
able to compare our results with those of Bastin
and Rieck [12,18]. The rate constant, kII, determ-
ined by these authors for the growth of the NiTi
phase at 700 °C (grown from the couple Ni3Ti and
NiTi2) is reported as 1.5 × 10⫺11 cm·s⫺1. Under
the same conditions (i.e., at 700 °C and without
using a current) but starting with the couple Ni and
Ti, we calculate a value for the intrinsic constant
of 2.43 × 10⫺11 cm·s⫺1. The agreement between
the two values is reasonable.
However, the imposition of a current during the
reaction shows a significant change in this con-
stant. Table 3 shows the ratios of the kII values
calculated in this work under various current den-
sities to those calculated by Bastin and Rieck (with
Fig. 7. NiTi layer thickness squared (⌬x)2 vs. time for experi- no current) at the temperatures indicated for the
ments reacted at 650 °C for different current densities. phases NiTi and NiTi2. No comparison is made for
4492 J.E. Garay et al. / Acta Materialia 51 (2003) 4487–4495
Table 1
Calculated growth rate constants for intermetallic phases in the Ni–Ti system. T below α→β transition of Ti
T (°C) Current density (A cm⫺2) Phase kI × 1012 (cm2 s⫺1) kII × 1012 (cm2 s⫺1)
Table 2
Table 3
Calculated growth rate constants for intermetallic phases in the
Ratios of intrinsic rate constant of this work (kII) with current
system Ni–Ti. T above α→β transition of Ti; current density
to values calculated from Bastin and Rieck, kIIBR, without cur-
= 1527 A cm⫺2
rent [12]
experimental growth constant for the NiTi phase measurements and positron annihilation
from the results of Bastin and Rieck and from spectroscopy.
those obtained in this study when a current density
of 1527 A cm⫺2 was employed. In both cases, a
discontinuity is observed in a temperature range Acknowledgments
very close to the transformation temperature (1 / T
= 9.63 × 10⫺4). In addition to confirming the effect The financial support of this work by the
of phase transformation on the kinetics, this obser- National Science Foundation is gratefully
vation is also a validation of the temperature acknowledged.
measurements in our system.
References
5. Conclusion
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