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Brown Boveri Reseach Center. CH-5405 Baden. Switzerland

(Received 2 Ju/!, 1980)

Abstract-A detailed study has been made of the mechanical properties of NiTi based alloys. Three
binary alloys. one ternary and one quaternary alloy were studied. and tensile. sharp notch tensile and
Charpy impact data were obtained as a function of temperature around the martensitit phase transform-
ation tem~rature. The factors governing the tensile behaviour are discussed. A toughness minimum is
observed in a certain temperature range and it is argued that this is a consequence of an interaction
between deformation by stress-induced martensite and conventional plastic flow when these mechanisms
operate simultaneously.

RkuumCNous avons elTectuCune etude detaillee des proprittes micaniques d’alliages a base de TiNi.
Nous avons itudie trois alliages binaires. un a&age ternaire et un alliage quaternaire. et nous avons
effectue des essais de rupture en traction sur eprouvette entaillee et des essais Charpy en fonction de la
temperature. au voisinage de la temperature de transition martensitique. Nous discutons les facteurs qui
gouvernent le ~mportement en traction. Nous observons un minimum de rksistance dans un certain
domaine de temperatures, et nous pensons que ctst une consequence de Iinteraction entre la deforma-
tion par martensite induite sous contrainte et ltcoulement plastique classique. lorsque ces deux meca-
nismes operent simultantment.

Zuommmfassang-Die mechanischen Eigenschaften von Legierungen auf Nifi-Basis wurden ausfiihr-

lich untersucht. An drei bin&en. einer tern&en und einer quaterdren Legierung wurde das Verhalten
beim Zugversuch mit und ohne scharfer Kerbe und beim Charpy-Einschlagversuch in Abhiingigkeit von
der Temperatur im Bereich der martensitischen Umwandlungstemperatur studiert. Die das Zugverhal-
ten bestimmenden Faktoren werden diskutiert. In einem gewissen Temperaturbereich wird ein ZShig-
kei~mj~murn beobachtet. Dieses ist. wit dargelegt wird. eine Folge der Wech~lwirkung zweier Verfor-
mungsmoden. der V~formung durch den sp~nun~induzierten Martensit und des iiblichen plastischen

1. INTRODUCTION Charpy tests made at different temperatures relative

to M,. where M, itself is also controlled by alloying.
There has been considerable recent interest in the
mecfiankal behaviour of alloys based on near qui- 2. EXPERIMENTAL
atomic NiTi compositions, this interest deriving pri- The alloys whose nominal compositions are shown
marily from their shape memory behaviour in which in Table 1 were prepared by vacuum induction
apparent plastic deformation of the low temperature melting in a graphite crucible argon arc premelted
marten&k phase is recovered on heating and revert- material, and casting in a water cooled copper mould.
ing to the high temperature (austcnitic) phase. Some Alloy 3 was however made by triple argon arc
tensile data has been reported as a function of test melting. After hot working all alloys were annealed
temperature [l-6] and the yield stress found to for I h at 950°C and air cooled. The tran~o~atjon
change rapidly in the vicinity of M,, the tem~rature tem~ratures also shown in Table 1 were determined
at which martensite first forms on cooling with no by dilatometry. Specimens for testing were machined
stress applied. The M, temperature is composition from the annealed material. Tensile specimens 5 mm
dependent, M, decreasing with decreasing titanium in diameter with a gage length of 25 mm were used,
content going away from the stoichiometric compo and for sharp notch testing a V-notch (described
sition [2,7,8] but no detailed mechanical property below) was machined in the centre. Impact testing
observation has been reported for a range of alloys was done with standard V-notch Charpy specimens.
where M, is controlled by compositional changes. Tensile testing as a function of temperature was done
Furthermore, little info~tion is available on the either in a cryostat containing alcohol, cooled with
effect of the martensite tr~~o~ation on the tough- liquid nitrogen (COT) in a water bath (O-100°C) or
ness of the material. it is the purpose of the present an oil bath (> 100°C). Throughout this paper, the
paper to analyse in detail the deformation behaviour values of stress and strain quoted are nominal, i.e.
of a series of NiTi baaed alloys and results are uncorrected for changes in specimen dimensions dur-
reported for tensile, sharp notch tensile and notched ing deformation.

Table 1. The nominal composition and transformation temperatures, determined by dilatometry of the alloys used.

Transformation temperatures (“C)

Alloy Nominal composition (wt%) MS Mf A, AJ Hysteresis (‘C) $a)

: 54.5 Ni 45.5
54.8 45.2 Ti 57 -20 5 63
39 17
106 51
55 115
3 55.5 Ni 44.5 Ti -; -53 -12 0 32 75
4 51.4Ni 44.8 Ti 3.8 Cu -88 -50 -10 +30 39 75
5 49Ni44Ti5Cu2Fe -106 -58 -31 39 (75)

The values of hvsteresis shown were obtained from the dilatometer curves and are defined as the temperature width of
the loop at half i& height. u0 is the 0.2 yield stress at M,.

3. RESULTS AND DlSCUSlON However, in some cases the points lie on a common
curve (Figs 3 and 6) whereas in others they do not
3. I Tensile data (Figs 2, 4 and 5), the values of uo.2 above M,, being
Figure 1 shows a schematic stress-strain diagram different than expected from extrapolating the curve
for an alloy tested near M,, and it can be seen that of up to the same temperatures. Reasons for this are
after an initial plateau, where a large strain is pro- not clear.
duced at low stress levels as a result of martensite One additional observation apparent from the up
deformation processes, there is a second almost linear curve is that a sharp increase is observed at tempera-
part followed by a second apparent yielding. This tures just below Md, i.e. where up and uo.2 start to
second yield point we denote as bP and there seems to merge. This effect was found for all alloys, Figs 2-6.
be general agreement [S, 9-l l] that it corresponds to As this temperature regime is one where both stress
the stress at which significant normal plastic flow induced martensite and conventional plastic flow
occurs, although some dislocations are active in the occur at similar stress levels, this observation points
second linear part [l I]. On increasing the test tem- to some interaction between these deformation mech-
perature above M,, u,,~ increases until finally no pla- anisms. We can rule out the possibility that a concur-
teau is observed, o,, becoming synonymous with u~.~. rent phase transformation (R-phase) observed in some
The temperature variation of u~.~, up and uuTs are NiTi alloys [15-181 is responsible for this change in
shown in Figs 2-6, where it can be seen that the gen- u,,, since the increase is observed for all NiTi alloys,
eral features of the uo.2-Temperature curves are simi- including compositions where no R-phase was
lar to those reported previously [14]. At tempera- reported [ 17,181 and also for ternary NiTiCu alloys
tures immediately above M,, martensite is stress where no electrical resistivity anomaly prior to M,
induced and the higher the temperature the greater is (indicative of a premartensite phase [ 19-231) was
the stress required until above M,+ the maximum found [24.25]. The interaction between deformation
temperature at which martensite can be stress mechanisms is discussed further in section 3.2.
induced, the mechanism of yielding becomes plastic Considerable scatter in the values of elongation to
flow and a decrease in uo.2 with temperature is then fracture was obtained, and no trend as a function of
observed. Below M,, uo.2 increases slightly with de- temperature was apparent for all alloys. However,
creasing temperature, the slope corresponding fairly alloys 1 and 5 (Table 1) showed a weak ductility mini-
well for each alloy to the slope of the up curve in the mum at temperatures near Md.
same temperature range. The mechanism of yielding Early work on the effect of stress on martensite
in fully martensitic shape memory alloys is martensite formation predicted that the stress to form martensite
reorientation by twinning [ 10,12-141 or the stress should be zero at the M, temperature[26]. A later
assisted growth of one martensite orientation at the
expense of an adjacent, unfavourably oriented one
[14]. Although there is no direct evidence for the re-
orientation mechanism, the similar temperature
dependencies of uo.2 and up in this temperature range
are consistent with the martensite reorientation being
accomplished by twinning dislocations whose critical
stress for motion is related to u~.~. We thus interpret
both uo.2 and u, as stresses at which dislocation pro-
cesses occur on a large scale, the former correspond-
ing to glide in the twin plane itself, the latter to
general slip. Stmln -
As far as the experimental points permit a compari- Fig. 1. A schematic drawing of the stress-strain curve of a
son to be made, the slope of the uo.2-temperature NiTi-base alloy tested close to M., showing how CJ~.~ ’ =P
curve above M, is similar to that of up below M,. and cufs are determined.


-40 0 40 Ix) O-40 0 40 80 120

T -*c 1-V

Fig. 2. Fig. 3.




-80 -40 0 40 60 0 40 60
T--V f-T

Fig. 4 Fig. 5.





Fig. 6.

Figs 2-6 co+ rrc and cLm for the alloys 1-S respectively (fisted in Table 1) as a function of test
temperature. Also shown is the fracture energy for sharp notch specimens (Figs 3 and 4) and V-notch
Charpy specimens (Fig. 6).

Table 2. The measured parameters used for and the value pute as to how to define To for thermoelastic mar-
of AH calculated from equation (11. AH,,,, was obtained tensites[18.31-341. but for the present purposes we
by calorimetry for alloys of the same nominal composition shall use To = l/2 (MS + A,). The computed values of
da d7 70 AH,,,, AH,,,, AH are shown in Table 2 for the Nifi binary alloys
Alloy k (MPa K) (K) (J :kg) (J ‘kg) together with the measured parameters for equation
(1). A common value of 6.45 x IO3 kg/m2 [6] was
1 0.054 13.33 29.4 used as the density p. Calorimetry values of AH for
2 0.0465 14.0 20.16
alloys of identical nominal composition [353 are also
3 0.0515 7.568 15.70 -
shown. and it can be seen that the same trend is
present. i.e. AH decreases with decreasing Ti content.
The AH computed from the present study is some-
paper [273 retated the temperature dependence of the what higher than the calorimetric values. and this
stress to form martensite to the work done on the may be a result of more elastic energy being stored for
martensite plate. Thus although at the M, sufficient the stress induced as opposed to the thermally formed
undercooling is available so that the strain energy martensite. However it is unlikely that all the discrep
term is compensated by an increased driving force ancy can be thus accounted for. because the elastic
from the chemical free energy. the applied stress can strain energy contribution to thermoelastic martensite
only do work if it causes the martensite-austenite transformations is usually considered to be small.
interface to move. Further errors in using equation 1 can arise (i) from
Any friction stress resisting this interface movement measurements of Ae which was not always invariant
would then lead to a finite yield stress on nucleating with temperature. an average value being used (ii)
martensite and causing apparent plastic flow by pre- from uncertainties in 7e: defining 7e as (M, + A,),‘2
ferential growth of the martensite. In a study of the giving AH values approximately JO?,,,lower (iii) from
thermodynamics of the thermoelastic martensitic errors in measuring da/d?- from the slope. since the
transfo~ation in a Cu-Al-Ni alloy it was experimental curve is S-shaped with a relatively small
shown [283 that the main factor causing a tempera- straight portion. Nevertheless the results emphasise
ture hysteresis in the single interface transformation the fact that on changing the composition slightly. the
of single crystals was a friction force resisting motion details of the martensite transformation are changed.
of the austenite-martensite interface. If our suppo-
sition is correct that the yield stress at M, (called u,, in
3.2 Fracture toughrless data
the following) is also related to a friction force resist-
ing the phase interface movement under stress. then a There is no published information on the effect of
correlation between o0 and the thermal hysteresis of the thermoelastic martensite transformation in NiTi
the stress free transformation would be expected. The based alloys on their toughness behaviour. In this
results are included in Table I where the hysteresis section some preliminary results are shown. which
width was measured as the temperature width at half were obtained with the aim of investigating further
height of the dilatometer loops used to measure the the mechanical behaviour at t~~ratures near Mb
transfo~ation temperatures. In view of the fact that where from the previous section a sharp rise in up was
possible differences in stored elastic energy between observed. Because the material in the martensitic con-
the alloys {the present transformations are not single dition is soft and ductile, valid I<# specimens could
interface single crystal and thus elastic energy will be be large, and material is not commercially available in
stored [283) may additionally influence the hysteresis plate form. Consequently data is presented from test-
and furthermore the friction force could also vary ing methods using smaller specimens.
with changing interstitial content and small devi- 3.2.1 Sharp notch tensile data. The sharp notch ten-
ations from stoichiometry. the correlation is reason- sile test has been used to provide fracture toughness
able. data[37-393 and as a quality control method after
An approximation of the effect of stress on the an initial correlation between Ktc and sharp notch
martensite transformation can be obtained from the data was made [40]. AIthou~ valid fracture tough-
Clausius-~a~yron equation [29,30] ness data may be obtained directly from a correctly
performed sharp notch test, this testing procedure is
da paAH used in the present work to provide a method of esti-
dT &.T, mating the effect of stress induced marten&e trans-
where da/d7 is the temperature coefficient of the formations on the toughness of the material. For
critical stress for the transformation in the tempera- aluminium alloys, the notch yield ratio (notch tensile
ture range above M, but below M,+ & is the amount strength/unnotched yield strength) was used as a
of strain due to the transformation. measured from measure of toughness[40]. However, because of the
the length of the initial plateau on the stress strain very strong temperature dependence of the yield
curve, p is the density of the alloy, AH the heat of strength of the present alloys, the notch yield ratio
transformation at the temperature r, where the two provided data which were not readily interpretable.
phases are in chemical equilibrium. There is some dis- Instead the energy to fracture, defined as the area

under the load-extension curve of a sharp notched However, in the latter case. martensite formation pro-
specimen, was used. duces a high rate of work hardening, whereas ther-
The specimen geometry was chosen to be propor- moelastic transformatjons such as in NiTi provide
tionally scaled down from the ASTM recommended essentially no hardness increase. and the misfit across
specimens[41]. A 6O’V-notch with root radius the parent-martensite interface is small.
0.018 mm was machined into a 5 mm diameter speci- This interface is mobile under stress. in contrast to
men, the net diameter at the notch being 3.75 mm. steels, and small changes rn the lattice defect concen-
This configuration provides a static stress concen- tration resulting from pfastic deformation would be
tration factor K, of around 8.5 [42]. Although reason- expected to markedly reduce this mobility.
able precaution was taken to reduce the possibility of
bending stresses, no test for the amount of bending CONCLUStONS
was done [413.
In a study of the mechanical properties of NiTi
The results are shown in Figs 3 and 4 for the alloys
based alloys it was shown that:
2 and 3 (Table 1). The fracture energy is divided by
the net area at the notch, and it can be clearly seen 1. below M, the temperature sensitivity of the
that there is a sharp minimum in each case at tem- stress to cause martensite reorientation is similar to
peratures just below M,+ This minimum corresponds the plastic yield stress indicating similar dislocation
to the temperature at which the rapid increase in cr,,is processes.
found. 2. at M, the yield stress does not go to zero and it
3.2.2 Charp~ tests. To further study the effect of is concluded that this arises from a friction force
changing test temperature on the fracture behaviour, resisting martensite-parent interface movement
standard V-notch Charpy impact tests were per- 3. a toughness minimum exists at temperatures just
formed on alloy 5, Table 1, and the results are also below Md and it is argued that this arises from an
shown in Fig. 6. A minimum in fracture energy is interaction between stress induced martensite and dis-
found at temperatures just below Mh consistent with location motion when these processes occur simul-
the results of the sharp notch tensile data. However, taneously.
the Charpy data give higher fracture energies for the 4. disptacing the M, tem~rature by compositional
aust~ite phase in contrast to the sharp notch tensile adjustments changes the details of the transformation.
test results where the martensitic fracture energy is
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