Ocean Engng. Vol. 1, pp. 105-120. Pergamon Press 1968.

Printed in Great Britain

A SUMMARY OF RECENT RESEARCH ON THE NITINOL*

ALLOYS AND THEIR POTENTIAL APPLICATION IN
OCEAN ENGINEERING

WILLIAM J. BUmbLeR and P'hJ~mUCK E, W A N G

U.S. Naval Ordnance Laboratory,White Oak, SilverSpring,Maryland
(Received 21 July 1967)

Abstract--The Nitinol alloys are based on the i n ~ compound TiNi. Alloys on the
nickel-richside of stoichiometry contain a certain portion of the compound TiNi, in equilibrium
with TiNi and are hardenable. In other alloying variations some of the nickel is replaced with
coMt.
When a near stoich/ometric specimen is mechanically deformed Mow its martemitic transi-
tion temperature it retains this deformed shape indefinitely.Upon heating above its martemitic
transition temperature, however, it rapidly r e v ~ to the shape it had More deformation.
Thus the material exhibits a "mechanical memory" effect. The martmsitic transition tempera-
ture may be varied within wide limits by changing the composition of the alloy. Cobalt, in the
formula TiNi,CoI_,, is an effectivesubstitution element for loweringthe transition temperature.
The resistance of some of the Nitinol alloys to corrosion in sea water has been evaluated by
conducting high velocityimpingement,cavitation-erosion,stress corrosion and crevicecorrosion
measurements. The results of these tests have shown these alloys to be quite resistant to marine
corrosion.
Combination of the unusual mechanical and cortes/on properties exhibited by these alloys
make them especially suitable for applications in ocean engineering.

INTRODUCTION
EARLY investigations (Buehler and Wiley, 1961, 1962; Buehler et al., 1963; Buehler, 1963) at
the U.S. Naval Ordnance Laboratory revealed a new class of novel non-magnetic nickel-
titanium alloys based upon the ductile intermetallic compound TiNi. These near equiatomic
titanium-nickel alloys display two distinctly different sets of properties as a function of
composition and heat treatment. Early quantitative evidence of this significant distinction
was obtained through the use of hardness measurements. Hardness measurements over the
composition range from 50 to 64 weight per cent nickel, remainder titanium, are shown in
Fig. 1. Here it can be seen graphically that stoiciffometric TiNi (nominal 55-Nitinol) has a
minimum hardness and is relatively unaffected by rate of cooling from temperatures around
950°C. Contrasted with tiffs minimum hardness is the sharply increasing hardness exhibited
by those alloys containing in excess of 65 wt. per cent nickel when tested in the quenched
condition.
Further evidence of a constitutional difference between 55-Nitinol and the nickel-rich
alloys containing in excess of 56weight per cent nickel was revealed in the metallography.
The 55-Nitinol was found to be a single phase alloy containing only TiNi phase (with minor
oxide and nitride impurities), while nickel-rich TiNi alloys showed a TiNis phase that co-
e x i t e d in varying quantity with the TiNi phase.
Nominal 55-Nitinol, in addition to being single phase and ductile, exhibits a very unusual
*Name derived from Ni-Ti-NOL. Prefix numeral value (e.g., 55-Nitinol) indicat~ the nominal nkkel
content in weight per cent, balance titanium.
105
106 WILLIAMJ. BUEHLERa.nd FREDERJCKE. WANG

4.9 Ti Ni
;o I / I

.... I,<,o

50 52 54 56 58 60 62 64
NICKEL (wt "/.)

FiG. l. Hardness curves for various compositionNi-Ti alloys in the furnace cooled and
quenched conditions,followingheatinga suitabletime at about 950°C.

"mechanical memory" as a function of deformation and temperature. This "mechanical

memory" plus other overt properties, for example, high acoustic damping, direct conversion
of heat energy into mechanical energy, unusual fatigue properties and low temperature
ductility, are all attributed to a unique "martensitic" transition in near TiNi alloys. A brief
qualitative description of this highly important martensitic transition is given in the text
of this paper.
Deviation from 55-Nitinol (near stoichiometric TiNi) in the nickel-rich direction yields a
second group of alloys which are also completely non-magnetic but differ from 55-Nitinol in
their capability of being thermally hardened to high hardness levels. This latter group of
alloys, where TiNis phase coexists with T.N. phase, are generically referred to as 60-Nitinol.*
These nickel-rich alloys possess an unusual combination of properties: high hardness,
stably non-magnetic and marine corrosion resistant. This combination of properties is not
commonly found in other materials. Thus 55-Nitinol and 60-Nitinol must be considered as
separate and distinct alloy types. Each of the composition ranges possesses certain inherent
properties and engineering advantages. Many of these properties and their engineering
advantages are described in detail in the remainder of this paper.

ALLOY PROPERTIES
General properties of 55-Nitinol
The engineering potential of the 55-Nitinol is founded on its general as well as unique
properties. The general properties as summarized in Table 1 lead to the following brief
conclusions:
1. The moderate density of 6.45 g/cma provides a definite design advantage.
2. Despite its high nickel content, the material has a magnetic permeability of unity and
therefore is a non-magnetic alloy.
3. The relatively low yield strength cart be utilized to advantage in conjunction with its
drastic change at and around the "martensitic" transition temperature. This aspect
will be treated in more detail later in this section.
*Designation givento alloyscoveringthe compositionrange from 56 to 62 wt. per cent nickel,remainder
essentiallytitanium.
 Nitinol atio~ and tktr t~*m~i am~attion in ocean en~ae~ins 107

TABLE 1. SOJdB lPlIYlICAg,~ ~ 1)ItOl~ItTIIB OF NOMINAL

55-Nmm~ ~ W-Nn'mog, ALLOYS*
t i i

Property 55-Nitino¿ 60-Nitinol

Density, g/cm' 6"45 6"71

Melting point, °C 1310 1,1~ (4-25)
Magnetic pem'meability < 1.002 < 1.002
Electrical resistivity, microhm,cm see Fig. 6(a)
Mean Coef. of Thermal Expan~on
(24°C-9000C), per °C x 10"-* 10"4
Hardnesst (See Fig. I)
950°C-Furnace Cooled 89 Re 20-30 Re
950°C-Quenched (R.T. water) 89 Re 60-62 Re
Tensilet$
Ult. Tensile Str., ksi 125 154 (quenched)
137 (furn. cool.)
Yield Str., ksi 15-20 S
see Fig. I0
Elongation, per cent 60 7 (furn. cool.)
Young's Mod., psi x 10' 10.2 16.5 (quenched)
Shear Mod., psi x 10' 3"6
Poisson's ratio 0-33 --
Impactf (Charpy)
Unnotched (R.T.), ft-lbs 155 40 (quenched)
Unnotched (-- 80°C), ft-lbs 160
Notched (R.T.), ft-lbs 24 2 (quenched)
Notched (-- 80°C), fi-lbs 17 --
Fatigue*t (Std. R. R. Moore Test)
Stress (107cycles-runout), ksi 70 80 (furn.cool.)
50 (quenched)
*Tests were performed at room temperature, except where noted. Room
temperature, in case of 55-Nitinol, was below the A, transition temperature.
tData obtained on hot wrought alloys.
~.2-0in. gauge length.
SYield strength not precisely measured, but approached the value for ultimate
tensile strength.

4. The high ductility (up to 60 per cent elongation in tension) is extremely unusual for
an intermetallic compound alloy.
5. The dynamic impact strength at room and lower temperatures indicates both good
ductility and superior cryogenic behaviour.
6. Although the notched impact strengths are still at a useful level, it suffers from lowered
notched toughness. For this reason, the best design practices for notch-sensitive
materials will have to be used.
7. The unusual fatigue properties are undoubtedly related to its unique "martensitic"
transition. For example, it is possible to load a specimen up to approximately four
times its yield strength, accompanied by considerable specimen deflection during
testing, and yet have it run 10~ cycles without failure.
With these general properties briefly summarized, a more detailed description of the unique
properties of 55-Nitinol is in order.
108 Wiiaama J. Bumtta~ and FP.m3ERICKE. W ~ G

Uniqueproperties of 55-Nitinol
One of the unique properties of 55-Nitinol across its "martensitic" transition temperature
is the "mechanical memory". This is the material's capability to recover its original shape
or configuration after mechanical distortion, by simply heating it above the transition
temperature. Discovery of this unique phenomena was made at the U.S. Naval Ordnance
Laboratory in the early phases of research on the near 55-Nitinol alloys. Potential engineer-
ing application of this property has increased steadily in recent years. A typical example is
pictorially illustrated in Fig. 2, through the self-erectile action of a model disc-on-rod
antenna. The left panel of Fig. 2 shows the structure before folding. The upper middle panel
shows this same component after folding into an unrecognizable consolidated ball below
the transition temperature. By heating the disc-on-rod structure to above the transition
temperature (150°-200°F) it recovers its pre-folded shape. The rate of this recovery process is
primarily determined by the rate at which the critical temperature (A,) is reached. While not
precisely determined, the limiting rate for the atomic movements causing the phenomenon
is of the order of 10-4 sec. In practice, the limiting rate is moderated considerably by the
thermal conductivity and actual mass of the material involved.
Still another unique feature of 55-Nitinol is its ability to be highly damping and vibration
attenuating below the transition temperature (As). Yet, the same body when heated above
this critical temperature (A,) changes drastically to an essentially zero attenuation condition.
The internal friction study by Hasiguti Iwasaki (1967) at and around the transition tempera-
ture as given in Fig. 3 is enlightening. Disregarding the grain orientation effects which are
probably responsible for abrupt variation in Q-1 between 60°C (As) to about -- 100°C,
it can be seen that within this temperature range, mechanical vibration damping is high.
Hasiguti's data on 55-Nitinol are compared with the Damping Index compiled by Birchon
(1962, 1966) in Fig. 3.
The "mechanical memory" and the anomalous damping capacity changes occurring
in 55-Nitinol are directly related with the "martensitic" (diffusionless) transition. These
conclusions are based upon the overt mechanical properties and the results of single crystal

xlO 2
D/~vIPIN G
klASIC~ITI & IWAS

60 Cast Mg

40 Mn-Cu

Q4 "*,,~,
~-NfflklOb

2~

Gray Cast
Irofl

A i {o.3)
t :- . . . . . . . • * , | 0 ~ S t e e l (0.1)
o 200 400 600 800
T I[ M P E R A T U R E : (*C)

FIG. 3. Internal friction of nominal 55-Nitinol (where A, is about O0°C) as a function of

temperature. Comparative Damping Index for 55-Nitinol and other metallic materials is given
at right of figure.
FIG. 2. Demonstration of the self-erectile feature of 55-Nitinol when employed in a model
disc-on-rod antenna. The criffcal temperature for shape recovery was between 150°F and 200°F

FIG. 9. Illustrates the "mechanical memory" characteristic in a TiNi-base alloy having a

transition temperature well below room temperature. This alloy rod was bent after chilling in
liquid nitrogen and then made to straighten rapidly by immersion in room temperature water.
FlG. 11. Illustrating the change in solubility of the TiN a phase with temperature. This
retrograde solubility combined with rapid cooling promotes hardening in the 60-Nitinol alloys.

F[o. 13. Comparative results of cavitation-erosion testing (magnetostriction method) on

60-Nitinol and HY-100 steel. Photographs courtesy of the Naval Applied Science Laboratory.
(Bard, 1966)
FIG. 14. Comparative microstructures of induction melted, arc melted and hot wrought
55-Nitinol alloy.

FIG, 16. Exampl¢s of non-magnetic tools and cutlery fabricated from 60-Nitinol.
 Nitinol alloys and their potential applicaticm in ocean engineering 109

~~
13~o'c M.P.

jNi(]) --bcc (A2)

650~700C Transition with ~-"--'

f'corr~ex structure. ~'~
~TiNi(R) ~-A-B-B-A-B-B-.
JCsCl-type diffroction-J
t,Pattern. .J

..160---17(
~=~A; Shearmowrnent begins(-H )
~~]~i" mar tetSnsitic"
1 1 ........ transition bond
T i N i (111)-- - - complex
undefined

•" - 3 5 " K ..'Mf" shear- movement ends

r,-
T i N i (10")- complex
defined
Fxo. 4. Schematic diagram of the structural variations of stoichiomatric TiNi (nominal 55-
Nitinol) as a function of t©mpcrature. Mechanical memory and damping transition of these
alloys are related primarily to the A0 temlm'atur¢ and "dotted" area.

X-ray diffraction studies at and around the unique "martensitic" transition temperature.
The growth of single crystals and the results of the diffraction studies have been previously
described in detail (Wang et al., 1964; Buehler et al., 1965; Wang et al., 1965). Through this
study it was shown that the crystal structure of TiNi is rather complex and as a function of
temperature can be subdivided into: TiNi(1), (IT), (III) and (IV) as shown schematically in
Fig. 4.
The "martensitic" transition is a second-or~r phase transformation which involves
atomic shear movements as a function of temperature below A, temperature. A proposed
effect of temperature and plastic deformation below A, on the atomic shear movements
are shown schematically in Fig. 5. In this figure the directions of the atomic movements
initiated at A, are indicated by arrows. The maximum shear movement of the atoms
correspond to that when Ni and Ti atoms fall on the broken fine.
At the risk of over-simplification, it can be seen how a wire or sheet of 55-Nitinol alloy
can change its physical configuration through changes in the relative atomic positions,
below the transition temperature, A,. In heating the ~ f o r m e d structure above the A,
temperature, the atoms reverse to their original position and therefore restore the physical
configuration. It should be recognized that a deformation beyond the limiting atomic
positions (broken lines in Fig. 5). will result in classical plastic deformation which is ir-
recoverable and therefore has no "memory effect".
Similarly, the drastic change in damping capacity at and around the critical temperature,
A,, may in part be explained based upon the models given in Figs. 4 and 5. Above the A,
temperature the lattice vibration is higlgy restricted and results in the mechanical observable
low acoustic damping. Conversely, the relaxation of the bonding below ,4, temperature
enables atoms to assume arbitrary positions along the schematic paths shown by the arrows
 110 WILLIAM J. BUEHLER a n d FREDERICK E. WANG

4,--~;Ti-Ti distance(in metal) = 2.89~,

0--0; Ni-Ni d i s t a n c e ( i n m e t a l ) = 2 . 4 9 ~ .
o

l
,~,f"T\
*--- 4.2 4 A----*

v \
0.8

"~ . I ",.1v
• . 41 '\ "\ ,~ \
~a

\tr \@ ~ '\
•~ \ .2~, "\ \ A,,r,

0 • \
o \.a .()'~ "\ ,\() \, "\

[ J "\ ,,.,,,"
'\ ~#\ '~'",& \ -"

xl \ , \

,[11oJ
FIG. 5. Schematic representation o f martensitic displacement shear occurring in TiNi below
.4, as a function o f lowered temperature or plastic deformation. The model shown is the ( l i 0 )
plane o f the 9 A unit cell shown in Fig. 4 (between 170 ° and 650°C).

in Fig. 5. This latter situation restricts lattice vibration much less and results in a mechani-
cally observable high acoustic damping.
The internal friction data of Hasiguti and Iwasaki (1967) (Fig. 3) may be interpreted to
indicate that completion of the overall atomic shear movements has occurred at about
-- 100°C (M/) for the particular alloy in question.
Subsequent studies by Wang et al. (1967) and others employing varied experimental
approaches, have confirmed that near stoichiometric TiNi does not behave nearly as simply
as described above. For example, while investigating the transport properties it was dis-
covered that a 60°C irreversible range was associated with the structure transition. This
critical range is shown as the dotted area in Fig. 4 and has its upper limit coinciding with
the A, temperature. Figure 6 is presented further to amplify on this 60°C range and show the
effects on electrical resistivity of thermal cycling within this range.* Figure 6(a) shows the
"normal" electrical resistivity curve as a function of temperature. The descriptive term
"normal" refers to a TiNi alloy (nominal 55-Nitinol) which is completely ordered at about
650°C followed by a slow cooling to a temperature below point M ' of curve (a). If the
electrical resistivity is measured as a function of temperature, the curve shown in Fig. 6(a)
will be repeatedly obtained under certain temperature cycling conditions. That is, the
temperature extremities of the triangle (M~ and A,) must be exceeded, in cooling and heating
respectively, in order to retain the curve, Fig. 6(a). The well-defined sides of the triangle,
and their relation to temperature, imply that three distinct shear vectors are operable--one
on heating (M~ -- A,) and two on cooling (As -- Ms, Ms -- M's). It can be stated therefore
that the atomic movement associated with the unique martensitic transition, schematically
described in Fig. 5, is but one of the possible shear mechanisms.
Figures 6(b) and (c) graphically show the direct effect on electrical resistivity of thermal
cycling within the triangular area (between M~ and As). Figure 6(b) shows the result after
*"Off stoichiometry" o f the particular TiNi alloy shown in Fig. 6 was the reason for the A, tm'nlmrature
in this figure being at 62°C rather than in the 160°C-170°C range.
 Nitinol alloys and their potential application in ocean enoneering 111

61

oo

59

#
5S #

>_ ,

"
<
/ //!!if/>" ill
o_

I
,°,
i I I i i i
!ili( i I I
| I
-50 -40 -30 -20 -10 0 10 20 30 40 50 60 70 60

TEMPERATURE: (" C )

FIG. 6. Effect of "incomplete" cycles on the electrical resistivity of TiNi ( ~ 51 At per cent Ni)
at and around the "unique" martensitic transition; cycling direction is indicated by arrows,
(a) without "incomplete" cycling, Co) after six " i ~ o m p l e t e " cycles, and (c) after several
hundred "incomplete" cycles.

six such cycles, while Fig. 6(c) shows the result of several hundred such cycles. Undoubtedly
a relationship exists between these resistivity curves and the shear movements of atoms.
These results, therefore, directly shed some light on the variable memory performance of
treated and stored specimens.
The above description of the very complex and unique transition occurring in 55-Nitinol
now provides some base upon which to look at some key design and engineering variations as
related to the structure transition. One question that invariably arises is whether the.critical
temperature (As) of the "mechanical memory" and drastic damping change (Fig. 3 at
=60°C) can be controlled accurately and varied. Investigations by Wang eta/. (1965, 1967)
have shown it is possible to vary the critical transition temperature (,4,) either by minor
variation of the Ti :Ni composition ratio near stoichiometric TiNi or by substituting metallic
cobalt for nickel in TiNi on an atom-for-atom basis (e.g. TiNi=Co~_x). Figure 7 shows the
effect upon the As temperature by merely varying the Ti : Ni ratio. From this figure it can be
112 WILLIAM J. BUEHLER and FREDERICK E. WANG

53.5 54 54.5 55 55.5 56 51~.5

NICKEL ( w t . * l o )

FIG. 7. Martensitic transition temperature (A,) change with minor variations in the Ti : Ni
ratio. Note the maximum occurs close to 55-Nitinol composition (stoichiometric TiNi).

seen that the maximum As occurs near stoichiometric TiNi and significant lowerirtg of A,
is possible by making nickel-rich alloys. Caution must be exercised in adding nickel above
about 55.6 wt. per cent because the excess nickel tends to form the stable second phase
TiNiv This latter phase increasingly dilutes the TiNi phase and interferes with the normal
performance of TiNi. To avoid this problem, and yet progressively lower the A, temperature,
cobalt has been substituted for nickel in the ternary formulation TiNixCot_x. With TiCo
(x -~ 0) having a transition temperature (As) of approximately -- 238°C, any transition
temperature between -- 238°C and 166°C is therefore possible. The effect of various cobalt
additions on transition temperature is shown in Fig. 8. The sequence in Fig. 9 is given to show
graphically the "mechanical memory" in a lower transition temperature (A,) rod. In this
case chilling in liquid nitrogen was necessary to bend the rod below its As temperature.
Following this, immersion in room temperature water caused the reversion back to the
straight configuration.
It has been suggested that a partial transformation of "metallic" to "covalent" bonding
is involved in the "marteusitic" transition in TiNi (Wang et al., 1967). While this concept
has not been conclusively proven or quantitatively described, its effect as a function of
temperature change upon Young's modulus and yield strength has been observed. Using the
shaded area to represent the "below A," condition (as in Figs. 7 and 8) it can be seen clearly
in Fig. 10 that both elastic modulus and yield strength increase sharply above the As
temperature. Changes of this type should be reflected in a gross change in "modulus of
resilience", where this property changes directly with the square of the yield strength and
inversely with twice the elastic modulus. A simple experiment performed on a 55-Nitinol
ball when allowed to bounce on a hardened steel surface indicated clearly the temperature-
sensitive nature of modulus of resilience. The 55-Nitinol ball, when dropped from a constant
height at room temperature (below the As), bounced only slightly over half the height that
was reached by the same ball dropped above the A, temperature.
 Nitinol alloys and their potential application in ocean engineering 113

AC

5.(
Ln A s
(*K)

4~

3~
6.5 ?.0
Free Electron ConCCLmtrm.ion
TiFe TiCo TiNi

Fro. 8. Showsthe wide variation in the martensitic transition temperature (A0)possibleby

substituting cobalt for nickel.

60-Nitinol
As described earlier, 60-Nitinol is the generic name given to nickel-rich TiNi alloys con-
raining a small portion of second phase "FiNis. Figure 1 clearly shows the effect upon the
hardness property of these alloys when they are heated to 950°C* followed by extremes in
cooling rate. Very early in the research on 60-Nitinol it was recoanized (Buehler and WHey,
1962) that these alloys near 60 wt. per cent nickel provided a desirable combination of
properties. That is, they were non-magnetic, hardenable by simple thermal treatment alone
and were resistant to marine corrosion. Further, the divergence that exists between the
"quenched" and "furnace cooled" curves of Fig. 1 indicated clearly the possibility for
readily attsining any desired intermediate hardness. This could be accomplished either by
employing intermediate cooling rates or by inducing some form of "overaging" or "pseudo-
tempering" to occur by employing a post-quench heat treatment.
While the precise mechanism for thermal hardening 60-Nitinol is still unknown, it is
clear that it is related to the coexistence of the TiNis phase in TiNi, and the change in
solubility of the TiNis phase as a function of temperature. Figure 11 illustrates the TiNis
solubility change with temperature on a partial section of the Ti-Ni constitution diagram.
The marked change in solubility of the TiNis phase is clearly shown microscopically in the
photomicrographs of Fig. 11. In the quenched specimen much of the excess nickel (probably
as TiNi,) is held in solution in the TiNi matrix. If it is not in solution it is sub-microscopic
and not readily observed at 1,000 mar~,nifications.
What then is the hardening mechanism ? Based upon existing evidence it would*appear
that some form of precipitation hardening mechanism involving submicroscopic TiNi~
• Temperatures from about 800°C to 1,000°C will produce a similar herdemng response.
114 WILLIAMJ. BUEHLERand FREDERICKE. WANG

6 ~ 0.2"1* O f f s e t

(klli)

-200 0 200 400 600

TEMP~'RATURE (*C)

FIG. 10. Showingthe considerablevariationof yieldstrength and Young's modulus of nominal

55-Nitinol (A, ~ 70°C) as a function of temperature. Note the strengthening and stiffening
possible at temperatures above and below the A, temperature.

phase is responsible. However, unlike most precipitation hardening systems the hardening
occurs as a one-step process. This is in contrast to the normal two-steps of "solution
treating" followed by "aging". Low temperature "aging" treatment when applied to hardened
60-Nitinol only serves to soften or possibly "overage" the material. Overaging, or less
drastic quenching rates, have both been employed to produce lower hardness, tougher and
pseudo-tempered material. This latter product variability points up an important design
flexibility available in 60-Nitinol alloys for engineering applications.
A further consideration in any thermally hardenable material is its "hardenability".
Alternatively, how deep into the core of a given part will the hardness extend when quenched.
Employing the standard Jominy end-quench hardenability test the data shown in Fig. 12
was obtained. Comparison of 60-Nitinol (quenched from about 950°C) with S.A.E. 4340
and 1080 steels is also shown in Fig. 12. Based upon this comparison it can be seen that the
60-Nitinol alloy possesses a high hardenability.
In addition to the thermal hardening of 60-Nitinol some other key properties are listed
in Table 1. The most noteworthy engineering weakness of this material is its "notch sensi-
tive" nature. Engineering application of 60-Nitinol, therefore, requires the best design
practice for notch sensitive materials.

CORROSION RESISTANCE
Prolonged and effective corrosion resistance is a prime consideration in materials to be
exposed to a marine environment. Qualitatively it would be anticipated that the titanium-
nickel alloys should exhibit sea water corrosion resis~nce. Some quantitative testing to
establish the level of resistance to sea water has been performed in three U.S. Navy labora-
 Nitinol alloys and their potential application in ocean engineering 115

70

eO-NITINOL
%
g~
v 5(
in
tu
z
(3
er
<

4(

1080

30 ~ . .6 . . 10. . .14 . . 18 2'2 ' 26 ' 3 '0 ' 3'a ' 3'6 ' ,*'2 ' 4• ' 50
DISTANCE FROM QUENCHED END (1116 i n c h )

I~G. 12. Jominy end-quench hardenability curves for 60-Nitinol compared with SAE 4340
and 1080 steels.

tories.* The evaluations were made on commercial and laboratory prepared Nitinol alloys
varying in composition from 55 to 60 wt. per cent nickel. The tests were divided into four
somewhat distinct categories:
(1) High velocity impingement. Commercial 55- and 56-Nitinol in the form of rotating
disks and rectangular jet impingement specimens were employed. Sea water velocities
varying from 15 to 26 ft/sec were applied over a period of 60 days. The loss in Nitinol
specimen weight varied from nil to a few milligrams. All Nitinol specimens retained their
pre-testing appearance.
(2) Cavitation-erosion. Commercial 55- and 56-Nitinol speimens in the form of rectangular
radius-nosed bars with transverse holes down-stream were used. These specimens were
subjected for 30 days to a sea water velocity of 117 ft/sec. At the conclusion of testing the
55-Nitinol sustained a loss of 0.092 g (about the same as MST 821 titanium alloy under
similar test conditions), while the 56-Nitinol lost 0"050 g.
Commercial 60-Nitinol was evaluated at the U.S. Naval Applied Science Laboratory
(Bard, 1966). Both the rotating disk (velocities up to 150 fl/sec) and magnetostriction
(13 kc/sec, 0.002 in. amplitude) tests were conducted.
In the rotating disk test the erosion rate was negligible after 8 hr at 125 ft/sec. Only when
the velocity was increased to 150 ft/sec did the specimens of 60-Nitinol show the measurable
erosion of 0.12 g l./hr over an 8-hr test span.
Further confirming evidence of cavitation erosion resistance was obtained from mag-
netostriction test data. Here after 4 hr of exposure at a frequency of near 13 kc/s the weight
*(1) Naval Ship Research and Development Centre, Annapolis, Maryland, (formerly: U.S. Navy Marine
Engineering Laboratory).
(2) U.S. Naval Applied Science Laboratory, Brooklyn, New York.
(3) Naval Ship Research and Development Centre, Carderock, Maryland (formerly: David Taylor
Model Basin).
! 16 WILL~MJ. BUEHLERand FREDERICKE. WANG

loss for 60-Nitinol was 0.9 nag compared with 35.9 mg for HY-100 steel. Actual "after test"
photographs comparing magnetostriction test specimens of 60-Nitinol with HY-100 steel
are shown in Fig. 13.
It was concluded by the evaluation laboratory (Bard, 1966) that 60-Nitinol is highly
resistant to cavitation erosion at velocities up to 125 ft/sec. At a velocity of 150 ft/sec
(90 knots) its resistance begins to approach that of Stellite 6B and several titanium alloys
(Ti-8Mn, Ti-13V-11Cr-3AI, and Ti-7 AI-4 Mo).
(3) Stress corrosion. Specimens of 55- and 60-Nitinol were evaluated using current test
procedures. This evaluation employed a V-notched bar that was cyclically loaded until a
fatigue crack was introduced at the root of the notch. The cracked specimens were then
subjected to a constant load while immersed in sea water. 55-Nitinol specimens stressed
up to 100 per cent of the yield strength showed no crack propagation tendency. 60-Nitinol,
while somewhat lower in fracture toughness than 55-Nitinol, still did not appear to be
adversely affected by exposure to sea water at room temperature. Based upon the existing
evidence it can be concluded that the Nitinol alloys are not susceptible to stress corrosion
failure.
(4) Crevice corrosion. Both commercial and laboratory prepared specimens were tested.
Commercially prepared 55- and 56-Nitinol material exposed one year in stagnant sea water
showed definite pitting attack. Metallographic examination of these corrosion-susceptible
specimens revealed some inhomogeneitics and segregation in the material near the pitted
areas. Following this negative result crevice corrosion tests were performed on laboratory
prepared 55-Nitinol material and have shown no evidence of the pitting attack. The pitting
attack initially observed was probably directly related to improper alloying. Additional
testing in stagnant sea water will bea,equired to establish conclusively the corrosion resistance
of TiNi-base alloys in this environment.
While only limited data are currently available on marine corrosion resistance, it does
appear from the existing results that the Nitinol alloys will perform quite suitably in a marine
environment. Further, it seems reasonable, based upon the above experience, that marine
corrosion should not interfere with the full utilization of the unique properties in hydro-
space.

FABRICATION AND MACHINABILITY

Since the beginning phases of research on the TiNi-base alloys there has been a constant
buildup of metallurgical knowledge. Some of the existing knowledge on alloy melting
practice, mechanical working, joining, machining, etc. has already appeared elsewhere
(Buehler and Wiley, 1961; Buehler, 1965; Buehler and Wang, 1966; Gould, 1964), or is
informally known (Slaney, 1967). As a result, the following summary will only touch upon
the highlights.

Alloy melting
Near stoichiometric TiNi alloys have been satisfactorily produced by both arc and
induction melting methods. Arc melting, while introducing minimum contamination, has
the disadvantage of requiring multiple remelts to ensure chemical homogeneity. Vacuum
induction melting, if performed properly in a graphite crucible, ensures alloy mixing while
suffering only slight contamination from crucible-melt interaction. This contamination
occurs in the form of carbon pickup (0-03--0.08 wt. per cent) in the melt. Generally the
carbon is combined with titanium as TiC.
 Nitinol alloys and their potential application in ocean engineering 117

Figure 14 shows microstructures of both arc and induction cast material. There is a
general similarity between the products of these alloying techniques. The lamellar or eutectic-
like network in the TiNi matrix (shown in the left and centre photomicrographs of Fig. 14)
has been tentatively identified (R.ozner et al., 1965) as alternate layers of Ti4NisO and a
TiNi-base alloy. The stoichiometry of the oxide is such that a relatively small quantity of
oxygen will form a large weight of oxide. The ratio of oxide weight to oxygen weight is of
the order of twenty-to-one. Further, the formation of the Ti4NisO results in the dispropor-
tionate removal of titanium from the alloy matrix.This oxide contamination tends to leave
the alloy matrix richer in nickel. Our experience shows that the eutectic-like network has
been virtually eliminated by forming the alloy from high purity crystal bar titanium and
high purity nickel.
Hot working has the tendency of equilibrating the microstructure. The right photo-
micrograph of Fig. 14 illustrates how the oxide particles are evenly dispersed in the TiNi
matrix. Experimentation has shown that fairly large quantities of oxide present does not
seem to impair the unique properties of 55-Nitinol, e.g., mechanical memory, acoustic
damping, etc.

Mechanical working
Hot working and cold working (below the crystallization temperature) have both been
performed successfully on the Nitinol alloys. 55-Nitinol ingots, if chemically homogeneous,
are readily processed by all forms of hot working. About 20 per cent area reduction is
possible on 55-Nitinol at room temperature before intermediate annealing is required. The
effects of cryogenic deformation on strengthening have been studied and reported in the
literature (Rozner and Buehler, 1966). It was found that marked strengthening through low

x,iO3
3O6

Strengtl~
~100
_=

70
8o
A
20~ (a2et'Of14It)
40 z
o
O
Z
o

Elong(Ition .
15
1( , ~ ,"
lo 20 30
AREAREDUCTION( pet )
FIG, 15. Summarizes the resultant effects of cold working (below the critical A, temperature)
on the mechanical properties of nominal 33-Nitinol.
l 18 WILLIAM J. BUEHLERand FREDERICK E. WANG

temperature deformation was possible in 55-Nitinol while maintaining a minimum of about

12 per cent tensile elongation. These results are shown in Fig. 15.
60-Nitinol has been found to be more difficult to hot work directly from the cast ingot.
Whether this is associated with the coexistence of the second phase TiNi3 or composition
heterogeneity introduced during solidification is at present unknown, However, it has been
discovered that a long time high temperature soaking treatment leaves the ingot much more
amenable to the initial stages of hot working. Once the cast structure of a 60-Nitinol ingot
has been "'broken down" little if any further cracking (hot tearing) is encountered.

Jo/ning
Fusion welding, spot welding and brazing have all been successfully performed on the
Nitinol alloys. The joining of TiNi-base alloys requires about the same care and technique
applied to titanium-base alloys. If oxygen, nitrogen, and other interstitial contaminants
can be eliminated (or minimized) from the vicinity of the fusion or heat affected zone,
successful joining is assured. The U.S. Naval Applied Science Laboratory has made sound
welds in 60-Nitinol (Crisci, 1967) by employing trailing shield techniques designed for
titanium-base alloys.
Brazing of Nitinol to itself has been accomplished by using either pure silver or 85
Ag-15 Mn braze material. Maximum bond strengths (about 38,000 psi) were attained in
joints where braze melting was followed by immediate cooling. Prolonged heating at braze
melting temperature to effect diffusion only served to depreciate the bond strength. Brazing
was performed in vacuum to ensure clean TiNi surfaces and complete wetting.

Machining
The machinability of the Nitinol alloys was thoroughly investigated (Gould, 1964).
Based upon this investigation it was shown that sharp carbide tooling, light feeds and slow
speeds were required. Because of these restrictions and general abrasiveness, it must be
concluded the Nitinol alloys are difficult but not impossible to machine when using existing
tools and techniques.

APPLICATION IN HYDROSPACE
In the previous portion of this paper an effort has been made to point out many of the
unique properties of the Nitinol alloys. Some of these properties, or combinations of proper-
ties, are so unique in fact that they are not presently found in any other known system of
alloys. As a result, in considering the Nitinol alloys for hydrospace application one must
project his thoughts in two directions. Firstly, in the direction of how these materials may
be utilized in existing design concepts. Secondly, how the unique properties, or combinations
of properties, could be used as a basis for entirely new design concepts.
The first application area is quite well defined. Here the Nitinol alloys would be initially
selected, or substituted for existing materials, to provide optimum performance in existing
structures or components. The possible applications in this area are too numerous to list
when one considers the coupling of good corrosion resistance with other available properties
of lower density, hardening capability, non-magnetic character and high strength.
The second application area, or the one dealing with new design concepts, is far less well
defined. However, it is in this area that the design engineer has the greatest opportunity
to utilize the natural physical phenomena of the "mechanical memory" to his advantage.
To amplify on this point, reconsider two facts: (1) that the structural transition temperature
 Nitinol alloys and their potential application in ocean engineering 119

(A,) can be placed at any level f r o m about 160°C to well below 0°C through alloying (see
Figs. 7 and 8), (2) the mechanical memory response, which occurs as a result of deformation
and temperature increase above d,, can be made to effectively operate in water (see Fig. 9).
By coupling these properties with the marked increase in yield strength and elastic modulus
above the transition temperature A, (see Fig. 10) one has the basis for a rigid corrosion
resistant "self-erectile" structure for deployment in hydrospace. Further, if the structural
transition temperature, As, is designed to be below the lowest possible ambient temperature
to which the structure is exposed, the structure will remain rigid.
Hydrospace applications such as the deployment of air-dropped self-erectile structures,
potential energy tools for doing useful work, self-deploying magnetometer booms and high
damping structures are but a few general examples of how 55-Nitinol type alloys might be
spectfically employed.
The 60-Nitinol type alloys with their combined properties of marine corrosion resistance,
high hardness and strength and being stably non-magnetic suggest still another set of possible
hydrospace applicattons. Such things as non-magnetic hand tools, bearings for water-
flooded rotating components and inserts for critical cavitation-erosion surfaces on high-speed
hydrofoils are but a few possible applications. Figure 16 shows a few examples of prototype
non-magnetic tcols and cutlery fabricated from 60-Nitinol.
In conclusion, it would appear that the unique property capabilities of the Nitinol alloys
should provide the hydrospace design engineer with a completely new class of materials
to improve existing structures and components while stimulating many new design concepts.

Acknowledgements--The authors wish to acknowledge the assistance of the U.S. Naval Applied Science
Laboratory and the Naval Ship Research and Development Centre (formerly the U.S. Marine Engineering
Laboratory and David Taylor Model Basin) in the evaluation of the marine corrosion resistance. Further,
the authors wish to express their appreciation for the fusion welding feasibility studies performed out-of-
chamber by the Titanium Alloy Group of the Naval Applied Science Laboratory.

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