S c r i p t a METALLURGICA V o l . 24, p p .

2 2 1 - 2 2 6 , 1990 Pergamon Press plc

e t MATERIALIA Printed in the U.S.A. All rights reserved

THE STUDY OF NIOBIUM-RICH PRECIPITATES IN A Ni-Ti-Nb

SHAPE MEMORY ALLOY

L.C.ZHAO*, T.W.DUERIG t , S.JUSTI t , K.N.MELTON t, J.L.PROFT t, W. yIjt AND C.M.WAYMAN°

*Harbin Institute of Technology, Harbin, China;
tRaychem Corporation, Menlo Park, CA. USA;
°University of Illinois, 1304 W.Green St., Urbana, IL.61801, USA.
( R e c e i v e d F e b r u a r y 3, 1989)
{ R e v i s e d November 21, 1989)

Introduction

Recently, ternary additions of niobium to Ni-Ti have been reported to significantly widen the thermal hysteresis
of the martensitic gansformation (1,2). These expanded hysteresis alloys have important practical utility for the
shape memory field: if the transformation temperatures can be adjusted so that room temperature is located
ncar the middle of the hysteresis loop, and if the hysteresis is sufficiently wide, devices can bc fabricated and
conveniently stored at ambient temperature and still retain the austenitic structure to very low temperatures once
recovered.

It was previously found (2) that the microstructure of Ni47Ti44Nb 9 is remarkably different from the TiNi binary
alloy. An insoluble dispersed phase is found which exhibits globular or elliptical morphology. The matrix is
identified as a TiNi phase which exhibits transformation behavior similar to that of nearly stoichiometric TiNi
alloys (3). In previous studies (2,3) it was speculated that the niobium-rich precipitates increase the hysteresis of
deformed NiTi by partitioningthe totalstrainintoreversibleand irreversiblecomponents: the reversibleportion
being accommodated by martensite twinning, and the irreversibleportion being accommodated by particle
deformation. In such a scenario the irreversibleportion would resistthe reversion to austenite and thus resist
the shape recovery process. The success of this hypothesis, however, depends upon the relativeflow stresses
for thc two processes being similar.

The purpose of the present work is to clarify the compositional and structural aspects of the niobium-rich
precipitateand the deformation behavior of the precipitatedparticlesaftera tensilestrain.

Exoerimental

The composition used for the present study was 47 at% Ni, 44 at% Ti and 9 at% Nb. This alloy was melted in
an electron beam furnace and the resulting ingots were hot swaged at approximately 850"C. Tensile bars
(6.35mm in diameter) were machined from the hot swaged ingot, while other samples were cut from the hot-
rolled strips of approximately 0.50mm thickness using a diamond saw. All the samples were furnace cooled
after heat treatment. The transformation temperatures were measured by an electrical resistance method, and
M s, Mr, A s, Af were found to be -90, -175, -85 and -35"C respectively.

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Copyright (c) 1990 Pergamon Press plc
222 Ni-Ti-Nb ALLOY Vol. 24, No. 2

TEM/EDX analysis was carried out in a Philips EM400, operating at 120kV, equipped with an energy
dispersive X-ray analysis system. Quantitative x-ray microanalysis was carried out on TEM foils by using k-
ratios and a thin-f'dm correction method. 13-Nb was electrolydcally extracted from the matrix in a solution of
25% HNO 3 in methanol, and sieved via US Standard Sieve No. 325 (size 0.044 mm). X-ray diffraction
measurements were carried out on a Siemens D500 powder diffractometer using Cu-ka radiation at 50 kV and
36 mA. Intensities were measured by a scintLllation counter at 0.02 degree 20 steps. Dcbye-Scherrer powder
photographs were obtained using filtered CuKa radiation.

Results and Discussion

3.1 Composition and structure of niobium-rich phase.

The extensive SEM observations indicate the pressure of three phases as shown in Figure l(a): a dark, coarse,
blocky phase, a bright, finely dispersed precipitate, and the matrix itself. The dark phase was shown by
SEM/EDX to be a compound of approximate composition Ti3(Ni,Nb) 2 Figure 1(c) shows the EDX spectrum
taken from the dark phase labeled D in Figure l(a). Both the coarse dark phase and the fine bright precipitates
are insoluble when heated to 1100"C, as shown in Figurel(b). As the heating dine was extended, the fine
particles were found to grow, while the dark retained their original shape; this indicates that the latter are
formed at a higher temperature. It is likely that the Ti3(Ni,Nb) 2 phase was precipitated from the liquid while
the bright insoluble phase was precipitated from the matrix.

The chemical composition of the precipitate was examined by TEM/EDX analysis. Figure 2(a) is a TEM
micrograph of the same specimen shown in Figure l(a). The precipitates which exhibited bright globular or
elliptical morphology in Figure 1 now appear dark due to preferential polishing of the matrix. Figure 2(b) shows
an EDX spectrum taken from a precipitate labeled P in Figure 2(a). In order to avoid overlapping absorption
from the matrix, all EDX spectra of the precipitate were taken from the edge of the hole as shown in Figure2(a).
The compositions from three different precipitates arc presented in Table I, which shows that the precipitate is
a niobium-rich phase. The results of X-ray powder diffraction (Debye-Scherrer method) for the precipitate are
listed in Table II, and indicate that both the structure and lattice parameter of the precipitate lie close to the 13
phase of a l~o-Ti solid solution containing 80 at% Nb, which has a body-centered-cubic structure with a lattice
parameter of 0.329nm (4). The lattice parameter of the niobium-rich precipitates was determined by X-ray to be
0.32963nm. Thus we conclude that the niobium-rich precipitates arc body-centered-cubic ~-Nb containing
some amount of Ni and Ti.

TABLEI
TEM/EDXAnalysisofThmeDiffemntPointsforthePrecipit~einFig. l(a).
Observadon Ni(at%) Ti(at%) Nb(at%)
I 7.685 11.592 80.723
2 6.693 11.637 81.667
3 6.359 11.949 81.691
Vol. 24, No. 2 N f - T i - N b ALLOY 223

'I'AIILE 11
Spacings of the Niobium-rich Precipitate from X-ray diffraction.
a o = 0 , 3 2 9 6 3 nm

Spacin 5 d (nm) hkl Observed related intensity

0.22773 110 vs
0.16435 200 ms
0.13449 211 s
O.11646 220 m
0.10409 310 ms
0.09508 222 mw
0.08805 321 ms
0.08242 400 w
0.07769 411,330 ms

Order of intensities v s > s > m s > m w > w .

3.2 Mechanical behavior of niobium-rich phase

In order to more quantitatively determine how much the Niobium-rich precipitates are deformed, a series of
bulk specimens were strained different amounts (0, 3, 6, 9,1 2, 25, 40, and 60%) at -60°Cand the precipitates
extracted to determine the extent of X-ray line-broadening via powder diffraction experiments. The relation
between line broadening and non-uniform strain is obtained by differentiation of Bragg's Law (5):

b = A20 = 2(Ad/d)tan0

Here b is the extra broadening, over and above the instrumental breadth of the line, due to a fractional variation
Acl/d in the line spacing d. This fractional variation is caused by elastic strain due to residual stress associated
with plastic flow. Figures 3(a) and (b) show the (110) and (220) Bragg reflections of the ~-Nb powders which
were extracted from the stretched specimens. As the deformation of the specimens is increased the peaks
broaden significantly, but their positions are not shifted. This broadening indicates that the ~-Nb particles
themselves were deformed when the bulk specimen was plastically strained.

Figure 4(a) shows the relation between the line broadening and the microscopic elasticstrainof the specimens.
Figure 4(b) shows the relation between the lattice strain of ~-Nb which is extracted from the deformed
specimens and the microscopical strainof the specimens. The latticestrain,ad/d in equation l includes both
tensile and compressive strains. In the present experiment the m a x i m u m tensile and compressive strains are
assumed to be equal.

Conclusions

Ternary niobium additions to the NiTi intermetalliccompound form an insoluble dispersed phase of essentially
pure bcc niobium. The niobium is very soft,with a flow stressapparently very similar to that of the martensitic
224 Ni-Ti-Nb ALLOY Vol. 24, No. 2

phase of NiTi (a flow stress of about 150-200 MPa). During even small deformations of the martensitic
structure, substantial plastic deformation was found to occur in the niobium particles. This "partitioning" of
strain into a reversible component (the NiTi matrix) and an irreversible component (the niobium phase) is
thought to be responsible for the abnormally large thermal hysteresis exhibited by these alloys. A more detailed
discussion of the mechanism of hysteresis expansion will be published in a subsequent paper.

References

1. K.N.Melton, J.A.Simpson and T.W.Duerig, Proc. Int. Conf.Martensite, Jap. Inst.

Met., 1053 (I 986).
2. K.N.Mehon, J.L.Proft and T.W.Duerig, "Wide Hysteresis Shape Memory Alloys based on
the Ni-Ti-Nb System", Inst. MRS meeting (1988).
3. L.C.Zhao, T.W.Duerig and C.M.Wayman, "Transformation and Mechanical Behavior of a
Ni47Ti44Nb9 Shape Memory Alloy", Inst. MRS meeting (1988).
4. Bulletin of Alloy Phase Diagrams, 2,No. 1, p. 55 (1981).
5. B.D.Cullity, Elements of X-ray Diffraction, second edition, Addison-Wesley Publishing
Company (1978).

FIG.I: Scanning electron

micrographs showing two kinds of
insoluble dispersed phases (a) after
annealed at 850"C for 30 minutes
and (b) after heating to 1100"C for
12 hours and furnace cooling; and (c)
an EDX spectrum taken from the
dark blocky phase labeled D in (a).

FIG. 2: Transmission electronmicrograph (a) afterannealing at 850"C for 30 min. and (b) an E D X spectrum
taken from precipitate labeled P in (a).
Vol. 24, No. 2 Ni-Ti-Nb ALLOY 225

I , , I I [ I I

8 b 220

~J
o

~ 12 %

: I"" 0%

¢ N ~14o %

~?.3
I
3"1.I 37.t 311.2 31LS 3I.I 3S.I 39-4
I
3!11.7
_J I
31.•
I
83-1
I
83.4
I
S3.7
1
83-0
•
II 3.3
I
33.11
r
113.9

2 9 Cdeg.) 2e C deg.)

FIG. 3: X-ray diffraction spectra of the (I I 0) and (2 2 0) peaks of the Nb precipitates after electrochemically
extracting from specimens deformed in tension various amounts.
0.8

0.7

i 0.6

O.S

0.4
1
~ 0.3

0.2

0°I

b
1.0

~ 0.8

'~ O.a FIG. 4: The relationship between

.£ the macroscopic tensile strains to
t 0.4 0 Peak at 38,6
which tensile specimens were
IJ exposed and (a) the observed X-ray
0.2 line broadening and (b) the lattice
strain.
I I I I I
10 20 30 40 SO IO

Strain ( ~o )