[0001] This invention relates to the field of processes suitable for producing a nickel/titanium-based
shape memory alloy and a shape memory alloy article. This invention further relates
to the field of methods and processes suitable for producing a nickel/titanium-based
shape memory alloy composite coupling.
[0002] Materials, both organic and metallic, capable of possessing shape memory are well
known. An article made of such materials can be deformed from an original, heat-stable
configuration to a second, heat-unstable configuration. The article is said to have
shape memory for the reason that, upon the application of the heat alone, it can be
caused to revert or attempt to revert from its heat-unstable configuration to its
original heat-stable configuration, i.e., it "remembers" its original shape.
[0003] Among metallic alloys the ability to possess shape memory is a result of the fact
that the alloy undergoes a reversible transformation from an austenitic state to a
martensitic state with a change of temperature. Also, the alloy is considerably stronger
in its austenitic state than in its martensitic state. This transformation is sometimes
referred to as a thermoelastic martensitic transformation. An article made from such
an alloy, for example, a hollow sleeve, is easily deformed from its original configuration
to a new configuration when cooled below the temperature at which the alloy is transformed
from the austenitic state to the martensitic state. The temperature at which this
transformation .begins is usually referred to as M
s and the temperature at which it finishes M
f. When an article thus deformed is warmed to the temperature at which the alloy starts
to revert back to austenite, referred to as As (A
f being the temperature at which the reversion is complete), the deformed object will
begin to return to its original configuration.
[0004] Commercially viable alloys of nickel and titanium have been demonstrated to have
shape-memory properties which render them highly useful in a variety of applications.
[0005] Shape-memory alloys have found use in recent years in, for example, pipe couplings
(such as are described in U.S.P. 4,035,007 and 4,198,081 to Harrison and Jervis),
electrical connectors (such as are described in U.S.P. 3,740,839 to Otte and Fischer),
switches (such as are described in U.S.P. 4,205,293 to Melton and Mercier), etc.,
the disclosures of which are incorporated herein by reference.
[0006] It is, of course, advantageous to have the alloy austenitic at the service temperature
which is often but not necessarily near room temperature, since the austenite phase
is stronger than the martensite phase. In fact, it would be desirable to have the
alloy remain austenitic over a wide range of service temperatures, for example from
substantially below room temperature to substantially above room temperature, so that
the alloy has practical utility.
[0007] As an illustration, Military Specification MIL-F-85421 requires a product that is
functional to about -55°C. If the product comprises a shape memory alloy, then for
convenience in shipping the product in the heat-unstable configuration, the product
should not recover prior to about 50°C. It is a matter of commercial reality, within
and without the military, that the product satisfy these requirements.
[0008] It is also desirable that the alloy be martensitic in the vicinity of room temperature
so that the article can be fabricated, stored, and shipped at or near room temperature.
The reason for this is that in the case of an article made from the alloy, a coupling,
for example, the article would not recover prematurely.
[0009] Conceptually, one way to achieve these desirable results, to wit, an alloy that is
martensitic near room temperature and which is also austenitic over a large range
of temperatures including room temperature, is to have an alloy which exhibits a sufficiently
wide tranformation hysteresis, say, greater than about 125°C. If the hysteresis were
sufficiently wide and room temperature could be located near the middle of the hysteresis,
then the alloy could be fabricated and conveniently stored while in the martensitic
condition. Since the hysteresis is sufficiently wide, the alloy would not transform
to austenite until heated substantially above room temperature. This heating would
not be applied until the alloy (in the form of a coupling, for example) was installed
in its intended environment. The alloy, which would then be in the austenitic condition,
would remain in the austenitic condition after cooling down since the service temperature
(which may be above or below room temperature) would be substantially above the martensite
transformation temperature. Thus, the above-noted desirable results could be achieved.
[0010] Unfortunately, there is believed to be no commercially viable nickel/titanium-based
alloy that has a hysteresis sufficiently wide to achieve these desirable results.
[0011] For example, the commercially viable near equiatomic binary nickel-titanium alloys
can have a hysteresis width of about 30°C. The location of the hysteresis for this
alloy is also extremely composition sensitive so that while the hysteresis can be
shifted from sub-zero temperatures to above-zero temperatures, the width of the hysteresis
does not appreciably change. Thus, if the alloy were martensitic at room temperature,
the service temperature must be above room temperature. Similarly, if the service
temperature was at room temperature, the alloy would be martensitic below room temperature
so that the alloy would require special cold-temperature equipment for fabrication,
shipping, and storage. Ideally, as discussed above, room temperature should be located
near the middle of the transformation hysteresis. However, since the width of the
hysteresis in the binary alloy is so narrow, the range of service temperatures for
any particular alloy is necessarily limited. As a practical matter, the alloy would
have to be changed to accommodate any change in service temperatures.
[0012] It can be appreciated that the relative lack of commercialization of shape memory
alloys must be due, at least in part, to their extreme sensitivity to temperatures
as discussed above. Alloying and processing have not solved the problem.
[0013] Nickel/titanium/iron alloys, e.g., those in Harrison et al., USP 3,753,700, while
having a wide hysteresis, up to about 70°C, are the typical cryogenic alloys which
always undergo the martensite/austenite transformation at sub-zero temperatures. It
should be noted that in general, the colder shape-memory alloys such as the cryogenic
alloys have a wider transformation hysteresis than the warmer shape memory alloys.
In the case of the cryogenic alloys, the alloys must be kept very cold, usually in
liquid nitrogen, to avoid the transformation from martensite to austenite. This makes
the use of shape memory alloys inconvenient, if not uneconomical.
[0014] The nickel/titanium/copper alloys of Harrison et al., U.S. Patent Application No.
537,316, filed September 28, 1983, and the nickel/titanium/vanadium alloys of Quin,
U.S. Patent Application Serial No. 541,844, filed October 14, 1983, are not cryogenic
but their hysteresis may be extremely narrow <10-20°C) such that their utility is
limited for couplings and similar articles.
[0015] The problems experienced with the nickel/titanium-based shape memory alloys have
been somewhat overcome by processing in the copper-based shape memory alloys. It is
now known that the hysteresis in copper-based shape memory alloys can be temporarily
expanded by mechanical preconditioning, austenitic aging and heat treating. In this
regard, see Brook et al., USP 4,036,669; 4,067,752; and 4,095,999.
[0016] The methods of the Brook et al. patents have been applied to nickel/titanium-based
alloys; however, it has been found that these methods have no beneficial effect on
nickel/titanium-based alloys.
[0017] It is known that under certain conditions the hysteresis of nickel/titanium-based
alloys can be shifted as opposed to expanded. It should be understood that shifting
of the hysteresis means that the M
S, M
f, As, and A
f temperatures have all been
' translated to M
s', M
f', A
s' and A
f' such that there is substantially no change in the width of the hysteresis. It should
be noted that the translated transformation temperatures may be higher or lower than
the normal transformation temperatures. On the other hand, expansion of the hysteresis
should generally be understood to mean that As and A
f have been elevated to A
s' and A
f' while at least M
s and usually also M
f remain essentially constant. Aging, heat treatment, composition, and cold work can
all effectively shift the hysteresis. For example, if the stress is applied to the
shape memory alloy at room temperature the hysteresis may be shifted so that the martensite
phase can exist at a temperature at which there would normally be austenite. Upon
removal of the stress, the alloy would isothermally (or nearly isothermally) transform
from martensite to austenite.
[0018] Miyazaki et al., ("Transfomation Pseudoelasticity and Deformation Behavior in a Ti-50.6
at % Ni Alloy", Scripta Metallurgica, vol. 15, no. 3, pp. 287-292, (1981) have studied
the deformation behavior of binary nickel-titanium alloys. As implied in Figure 3
of this reference, the austenite transformation temperatures can be elevated when
nonrecoverable strain is imparted to the alloy. That is, when the alloy was strained
to 8% or higher and the stress then removed, there was some component of the strain
which remained at the deformation temperature of 243°K (compared to an A
f of 221°K). This component recovered when heated to 373°K (see dotted lines on Figure
3) although the precise recovery temperature was never measured. It is not clear from
this reference whether the hysteresis was shifted or expanded since the binary nickel-rich
alloy tested is extremely unstable when rapidly quenched as was done in this reference.
In fact, one skilled in the art would have concluded that the hysteresis was shifted
and not expanded due to the unstable alloy tested. There is no illustration of the
transformation hysteresis to contradict this conclusion.
[0019] In the Melton et al. patent previously mentioned, a nickel/titanium/copper alloy
was deformed beyond a critical strain so as to impart nonrecoverable strain. However,
no expansion of the transformation hysteresis was observed.
[0020] While it can be appreciated that it would be desirable to have a nickel/titanium-based
shape memory alloy and article with a sufficiently wide transformation hysteresis,
the prior art has thus far remained silent on a way to achieve it.
[0021] As mentioned earlier, shape-memory alloys have found use in pipe couplings. The pipe
coupling may be a monolithic pipe coupling as described in the earlier-mentioned Harrison
and Jervis patents. Alternatively, the pipe coupling may be a composite coupling as
described in the earlier-mentioned Clabburn patent and in U.S. Patent Nos. 4,379,575;
4,455,041; and 4,469,357 to Martin, the disclosures of which are incorporated herein
by reference. As noted in Martin, the composite coupling comprises a driver member
and a sleeve member.
[0022] Composite couplings present the problem of how best to assemble them. In the Martin
patents, there are noted several ways to assemble the couplings. In one way, the sleeve
may be assembled with the driver just after the expansion of the driver so as to take
advantage of the elastic springback of the material. The driver and sleeve membres
are then stored in a cryogenic fluid until ready for installation.
[0023] Alternatively, the driver alone may be stored in a cryogenic fluid and then joined
with the sleeve a the time of installation. Once joined with the sleeve, the driver
is allowed to fully recover.
[0024] In practice, the driver may be expanded and, after springback has occurred, joined
with the sleeve while both are immersed in a cryogenic fluid. Since no recovery of
the driver has occurred, the sleeve is only loosely joined and would, in fact, become
separated from the driver if means were not provided to prevent this separation. The
means to prevent this separation is usually provded in the form of a flaring of one
end of the sleeve which makes for a slight interference fit between the sleeve and
the driver.
[0025] All of these methods suffer from the disadvantage that the driver must be stored
in a cryogenic or other cold fluid prior to installation. The second method suffers
from the additional disadvantage that the driver may recover prior to joining with
the sleeve, thus rendering useless the composite coupling. The last method disadvantageously
required the additional step of flaring the sleeve to prevent diengagement of the
driver and sleeve.
[0026] In Clabburn, a keeper is utilized to apply a stress sufficient to temporarily raise
the austenite transformation temperature. The shape-memory alloy remains in the martensitic
state while the stress is applied. This method is known as constrained storage.
[0027] It can be appreciated that it would be desirable to have the driver and sleeve preassembled
such that one could merely remove the preassembled coupling from a carton on a shelf
and then proceed to install the coupling without the need to worry about cold storage
of the coupling. Thus far, the prior art has remained silent on a way to achieve this
desirable result.
[0028] Thus, it is an object of the invention to have a nickel/titanium-based shape memory
alloy and article with a wide transformation hysteresis.
[0029] It is another object of the invention to process a nickel/titanium-based shape memory
alloy and article so as to temporarily enlarge the transformation hysteresis of the
alloy and article.
[0030] It is also an object of the invention to have a method of preassembling a composite
coupling without the need for a cryogenic or other cold fluid.
[0031] It is another object of the invention to have a method of preassembling a composite
coupling wherein the preassembled coupling may be stored without the need for a cryogenic
or othe cold fluid.
[0032] It is a further object of the invention to have a composite coupling preassembled
by the method of the invention so that cryogenic or other cold fluid is not necessary.
[0033] This invention relates to a method of processing a nickel/titanium-based shape memory
alloy. The purpose of the method is temporarily to raise the As and A
f temperatures to A
s' and A
f', respectively. This method has been found useful in fabricating shape memory alloy
articles such as couplings.
[0034] There is also disclosed a method of preassembling a composite coupling. The coupling
has at least one heat recoverable driver member and at least one metallic insert.
The driver member is made from a nickel/titanium-based shape memory alloy having a
transformation hysteresis defined by
Ms,
Mf, As, and Af temperatures. The method comprises overdeforming the driver member by
applying a stress sufficient to cause nonrecoverable strain in the driver member so
that the As and A
f temperatures are temporarily raised to A
S, and Af', respectively; removing the stress; engaging the driver member and insert;
and warming the driver and insert to a temperature less than A
s'.
[0035] We have found that by taking advantage of the expansion of the hysteresis caused
by overdeformation of the driver member the composite coupling may be preassembled
simply and efficiently.
[0036] Embodiments of the invention will now be described, by way of example, with reference
to the accompanying drawings, wherein:
Figure 1 is a schematical illustration of the shifting of the shape memory alloy transformation
hysteresis.
Figure 2 is a schematical illustration of the expansion of the shape memory alloy
transformation hysteresis according to the invention.
Figure 3 is a schematical stress/strain curve for a binary nickel/ titanium-based
shape memory alloy.
Figure 4 schematically illustrates the binary alloy strained as in Figure 3 in the
unrecovered and recovered state.
Figure 5 is a schematical transformation hysteresis curve for a nickel/titanium/vanadium
alloy after recovery of a 5% deformation and illustrating the presence of the R phase.
Figure 6 is a schematical transformation hysteresis curve for a nickel/titanium/vanadium
alloy after recovery of a 16% deformation and illustrating the absence of the R phase.
Figure 7 is a schematical stress/strain curve similar to Figure 3 but for a typical
nickel/titanium-based shape memry alloy.
Figure 8 schematically illustrates similar to Figure 3 the shape memory alloy strained
in Figure 7 in the unrecovered and recovered state.
[0037] Referring to the figures in more detail and particularly referring to Figures 1 and
2, there is graphically illustrated the transformation hysteresis for a shape memory
alloy. Figure 1 illustrates the shifting of the transformation hysteresis as would
occur if, for example, a stress was applied. The hysteresis has moved upwardly in
temperature from position 2 to position 4, shown in dotted lines. While the entire
hysteresis has moved upwardly in temperature it can be seen that the width of the
hysteresis, indicated generally by 6 has remained approximately constant. In other
words, M
s, M
f, As, and A
f have all been translated to higher temperatures and are now denoted as M
s', M
f', A
s', and A
f'. Of course, as stated earlier, there are circumstances where the transformation
temperatures may be translated to lower temperatures.
[0038] In contrast to the shifting of the hysteresis as illustrated in Figure 1, Figure
2 now illustrates in general the expansion of the hysteresis. It can be seen that
the martensite transformation temperatures remain constant but the austenite transition
temperatures have been translated upwardly so that the width of the hysteresis indicated
generally by 6 has now been expanded as indicated generally by 8. That is, M
s and M
f remain constant or nearly constant while As and A
f have been translated to higher temperatures and are now denoted as A
s' and A
f'.
[0039] The advantages of temporarily expanding the hysteresis versus shifting the hysteresis
can be explained as follows. Referring again to Figure 1, a coupling may be expanded
and held in the expanded condition so as temporarily to raise, i.e., temporarily shift,
the hysteresis. As long as the stress is applied, the hysteresis will be shifted.
If it is desired, for example, to use this coupling in ambient temperature, indicated
by T
A, the coupling will not transform to austenite as long as temperature T
A is below A
s'. Upon the removal of the stress, the coupling will isothermally (or nearly isothermally)
transform into austenite. In other words, the coupling will be at T
A when the stress is removed but the hysteresis will have shifted from position 4 back
to position 2. The coupling being martensitic before the shift from position 4 to
position 2 must necessarily be austenitic after the shift. This method may be used
for constrained storage (see, e.g., Clabburn, USP 4,149,911) wherein a coupling is
expanded and then held on a mandrel in the expanded condition until it is ready to
be used, at which time it is cooled to below the M
s temperature so that it may be released from the mandrel and then installed. The problem
with this method is that while the coupling is held (during shipping, for example)
in the expanded position which is necessary to shift the hysteresis, the coupling
may relax so that a certain, perhaps very substantial, amount of recovery motion will
be permanently lost.
[0040] Referring now to Figure 2 it can be seen that by temporarily widening the hysteresis,
as long as the coupling is held at a T
A less than A
s' there will be no transformation. Since no stress need be continually applied to
the coupling to widen the hysteresis, relaxation is not a problem. Upon use, the coupling
would simply be heated above A
s', transformation from the martensite to the austenite would occur, and the hysteresis
would then shrink back down to its former position.
[0041] According to the invention there is disclosed a method of processing a nickel/titanium-based
shape memory alloy having a transformation hysteresis defined by M
s, M
f, As, and A
f temperatures. In general, the method comprises temporarily expanding the transformation
hysteresis by elevating the As and A
f temperatures to A
s' and A
f', respectively, so that the temperature difference between A
s' and M
s is greater than the temperature difference between As and M
s. The-means for expanding the transformation hysteresis may be removed and then the
alloy is stored at a temperature less than A
s'.
[0042] Usually, according to the invention, both the M
s and M
f temperatures will remain essentially constant during the expansion of the hysteresis.
However, in certain alloys, as will become apparent hereafter, either or both of the
M
s and M
f temperatures may permanently change. This change may result from the varying of the
slope or even movement of the martensitic part of the transformation hysteresis curve
due to the interaction of certain metallurgical conditions. However, the important
point to emphasize here is that there will always be a net increase of the width of
the transformation hysteresis according to the method of the invention.
[0043] The means for expanding the transformation hysteresis comprises overdeforming the
alloy by applying a stress sufficient to cause nonrecoverable strain in the alloy.
It should be understood that nonrecoverable strain means strain which is not recovered
after deformation and subsequent no-load heating to at least the A
f' temperature.
[0044] It is important to understand and appreciate that the current practice in forming
shape memory alloys as is well known to one skilled in the art is to void any nonrecoverable
strain. The reason for avoiding any nonrecoverable strain is that the presence of
nonrecoverable strain'tends to reduce the amount of motion upon recovery. It has been
found, however, that the amount of lost motion is relatively small when compared to
the enhanced utility of shape memory alloys having an expanded transformation hysteresis
according to the present invention.
[0045] It is preferred that a stress is applied sufficient to cause at least 1% or more
of nonrecoverable strain in the alloy. Usually (but not necessarily) after the alloy
is overdeformed the stress will be removed.
[0046] It is necessary to the invention that the overdeforming takes place at a temperature
which is less than about the maximum temperature at which martensite can be stress-induced.
To those skilled in the art this temperature is commonly known as:M
d. It is preferred however that the overdeforming temperature be above M
s.
[0047] Once the hysteresis has been expanded at least partial recovery of the alloy article
can occur when the alloy is heated to a temperature greater than about A
s'. By heating to at least A
s' the transformation of the martensite to the austenite can effectively begin. It
is preferred however that the heating temperature be greater than A
f' so as to effect full recovery of the alloy.
[0048] It has been found that the nickel/titanium-based shape memory alloy may be a binary
or it can be at least a ternary. If it is a ternary nickel/titanium-based shape memory
alloy the ternary consists essentially of nickel, titanium and at least one other
element selected from the group consisting of iron, cobalt, vanadium, aluminum, and
niobium. The most preferred ternary, for reasons which will become apparent hereafter,
consists essentially of nickel, titanium, and niobium.
[0049] It has also been found that those shape memory alloys having an M
s less than about 0°C are preferred since these alloys have the most utility and best
performance.
[0050] The benefits of expansion of the shape memory alloy transformation hysteresis have
already been disclosed in our U.S. Patent Application Serial No. 668,771 filed November
6, 1984 entitled "A Method of Processing a Nickel/Titanium-Based Shape Memory Alloy
and Article Produced Therefrom" the disclosure of which is incorporated herein by
reference. We have found that if in conjunction with the expansion of the hysteresis
of the the driver member, the driver member is preassembled with the sleeve, then
the preassembly is greatly facilitated.
[0051] Referring again to the figures Figure 7 schematically illustrates a stress-strain
curve for a typical shape memory alloy which was overdeformed. The load was then removed.
With overdeformation there is by definition a substantial amount of non-recoverable
strain imparted to the alloy. Nonrecoverable strain will occur when the alloy, generally
speaking, is strained past its second yield point indicated approximately by reference
numerical 10. After removal of the stress, the alloy was heated.
[0052] In Figure 8 curve 12 illustrates the heating after the removal of the stress. When
the transformation was complete the alloy was cooled down as illustrated by curve
14. During the cooling down under a small load and M
s and M
f temperatures were measured. The alloy was then reheated (curve 16) to measure the
recovered austenitic transition temperatures As and Af.
[0053] As we stated in our patent application above there is more than one way to locate
on a transformation hysteresis curve the martensitic and austenitic transformation
temperatures. Referring again to figure 8 the literal starting and ending of the austenitic
transformation may be indicated for example by points 18 and 20 respectively on curve
12. However, the austenitic transformation effectively begins at about point 24 (denoted
as A
s') and the austenitic transformation effectively ends at about point 26 (denoted as
A
f'). Thus it can be said that the bulk of the transformation occurs between A
s' and A
f'. The same is true for the other transformations as illustrated by curves 14 and
16. The effective austenitic and martensitic transformation temperatures may be conveniently
determined by the intersection of tangents to the transformation hysteresis curves.
For example, tangents 22 on curve 12 locate A
s' and A
f'.
[0054] Whenever the austenitic and martensitic transformation temperatures are mentioned
in this specification it should be understood that these temperatures refer to the
austentic and martensitic transformation temperatures determined by the above noted
method of intersecting tangents. Whenever the literal starting and ending points of
the martensitic and austentic transformations are indicated these temperatures will
be referred to as the true martensitic and austenitic transformation temperatures.
Thus, the literal starting and ending points of the austenitic transformation after
expansion of the hysteresis are referred to as true A
s' and true A
f'.
[0055] Curves 14 and 16 represent the shape memory alloy transformation hysteresis in the
recovered state while curves 12 and 14 represent the shape memory alloy transformation
hysteresis in the unrecovered state. Thus it can be seen that the overdeformation
of the alloy according to the patent application above has substantially and temporarily
widened the hysteresis.
[0056] Now according to a second aspect of the invention there is disclosed a method of
preassembling a composite coupling having at least one heat recoverable driver member
and at least one metallic insert. The driver member is made from a nickel/titanium-based
shape memory alloy having a transformation hysteresis defined by M
s, M
f, As and A
f temperatures. The method comprises overdeforming the driver member by applying a
stress sufficient to cause nonrecoverable strain in the driver member so that the
As and A
f temperature are temporarily raised to A
s' and A
f', respectively. The method further comprises removing the stress; engaging the driver
member and insert; and then warming the driver and insert to a temperature less than
A
s'.
[0057] Usually, as stated earlier, both the M
s and M
f temperatures will remain essentially constant during the expansion of the hysteresis.
However, in certain alloys either or both of the M
s and M
f temperatures may permanently change. This change may result from the varying of the
slope or even movement of the martensitic part of the transformation hysteresis curve
due to the interaction of certain metallurgical conditions. However, the important
point to emphasize here is that there will always be a net increase of the width of
the transformation hysteresis according to the method of the invention. That is, the
temperature difference between A
s' and M
S will be greater than the temperature difference between As and M
s.
[0058] According to the invention, there must be at least one driver member; however, there
may be more than one such as when ring drivers are used. Similarly, there must be
at least one insert but there may be mroe than one such as when mult-piece inserts
were utilized.
[0059] It should be understood that while the driver and insert preferably need to be warmed
to a temperature which is less than A
s', they in any case need to be raised to a temperature above the true A
s'. The reason for this is that below true A
s' there will not be any recovery of the shape memory alloy. Referring again to figure
8 it can be seen that between true A
s' and A
s' there will be a small amount of recovery indicated by 28. After A
s' is passed the bulk of the recovery will effectively occur as indicated by 30. From
figure 8 then it is apparent that to get to any amount of recovery the material has
to be heated above true A
s'.
[0060] However, since the amount of recovery occurring between true A
s' and A
s' is much less than the recovery occurring between A
s' and true A
f' little shape memory recovery will actually be lost by allowing the driver member
to partially recover according to the invention. This partial recovery is not so great
as to crush the insert but only so great as to be able to hold the insert and driver
snugly engaged.
[0061] It should be understood that the metallic insert may take many forms. for example,
the insert may be tubular, tapered or slotted, all of which are disclosed in the above
Martin patents. Additionally, the insert may be single or multipiece. Finally, the
insert may have an irregular shape such as to be x-shaped, y-shaped or t-shaped.
[0062] The insert may also have sealing means as also disclosed in the above Martin patents.
The sealing means any comprise, for example, teeth or gall-prone materials.
[0063] It should also be understood that the driver member may take many forms. It is preferred,
however, that the driver member be a tubular driver or a ring driver.
[0064] In the step of overdeforming the driver member it is preferred that a stress is applied
sufficient to cause at least one percent of nonrecoverable strain in the driver member.
Of course the nonrecoverable strain may be much more than one percent which is usually
the case but it is preferred that there be at least one percent strain.
[0065] It is preferred that the overdeforming take place at a temperature which is less
than about the maximum temperature at which martensite can be stress-induced. The
temperature is also known as the M
d temperature. The reason for this is that when the material has been deformed at a
termperature greater than M
d the amound of strain recoverable upon subsequent heating is drastically and dramatically
reduced. Generally, the more the deformation temperature is raised above M
d, the greater will be the reduction in recoverable strain. It is most preferred that
the overdeforming temperature be between M
s and As.
[0066] It is desirable that the nickel/titanium-based shape memory alloy has an M
s temperature less than about 0°C. However, it is preferred that the nickel/titanium-based
shape memory alloy is stable, does not contain an R phase and has an M
s temperature less than about 0°C. To those skilled in the art the R phase is known
as a transitional phase between the austentite and martensite and has a structure
different than either. The effect of the R phase is to depress the austenitic and
martensitic transformation temperatures. Alloys that are stable (i.e. exhibit temper
stability) have an M
s that does not change more than about 20°C after annealing and water quenching and
subsequent aging between 300 and 500°C.
[0067] The nickel/titanium-based shape memory alloy may be a binary or at least a ternary.
In the case where the shape memory alloy is a ternary, the ternary may comprise nickel/titanium
and at least one other element selected from the group consisting of iron, cobalt,
vanadium, aluminum and niobium. It is most preferred that the ternary nickel/titanium-based
shape memory alloy comprise nickel, titanium and niobium.
[0068] It is believed that the teaching of this invention will have most application to
couplings processed by the method of the invention. However it should be understood
that the teaching of the invention applies to other articles and devices processed
by the method of the invention.
[0069] Embodiments of the invention are now described, by way of example, with reference
to the following examples.
Example 1
[0070] Commercially pure titanium and carbonyl nickel were weighed in proportions so as
to give a composition of 50.7 atomic percent nickel and 49.3 atomic percent titanium.
The total mass for test ingots was about 330 grams. These metals were placed in a
water-cooled, copper hearth in the chamber of an electron beam melting furnace. The
chamber was evacuated to 10-
5 Torr and the charges were melted and alloyed by use of the electron beam.
[0071] The resulting ingots were hot swaged and hot rolled in air at approximately 850°C
to produce a strip of approximately 0.025-in. thickness. Samples were cut from the
strip, descaled and vacuum annealed at 850°C for 30 minutes and furnace cooled. The
strip was then elongated. After elongation the stress was removed and the strip was
heated unrestrained so as to effect recovery of the shape memory alloy. The recovery
was monitored and plotted as a function of temperature. When the transformation was
complete, the sample was cooled and then reheated so as to complete the measurement
of the martensite and austenite transformation temperatures before recovery and after
recovery. The results are tabulated below in Table 1.
[0072] The measure
As' minus
Ms is very useful since M
s is directly indicative of the lower functional limit of the alloy and the A
s' is directly indicative of the highest temperature which may be encountered (e.g.
during storing and shipping) before the austenite transformation will effectively
begin. Thus,
Ag
' minus M
s defines the operating range of the alloy when processed according to the invention.
This measure should be compared to As minus M
s which defines the operating range of the alloy after the temporary expansion of the
hysteresis has been recovered. As minus M
s is also indicative of the operating range of the alloy if it were never processed
according to the invention. Thus, comparing
As' minus M
s to As minus Ms provides useful indicia of the expansion of the hysteresis as well
as the advantages of the invention.
[0073] Referring now to Table 1, A
s' minus M
s and As minus M
s are about the same at 5% elongation; however, at 16% elongation, the difference becomes
substantial. It is useful to note that A
s' after 16% elongation is above normal room temperature so that the alloy may now
be handled at room temperature so that the alloy may now be hadled at room temperature
without the necessity of providing a cold environment.
[0074] Another useful measurement for indicating the expansion of the hysteresis are the
M
50, A
50, and A
50' values. These are the martensite and austenite transformation temperatures at which
the transformation is 50% complete. Thus, referring to Table 1 it can be seen that
the the sample was cooled and then reheated so as to complete the measurement of the
martensite and austenite transformation temperatures before recovery and after recovery.
The results are tabulated below in Table 1.
[0075] The measure
As' minus M
s is very useful since M
s is directly indicative of the lower functional limit of the alloy and the A
s' is directly indicative of the highest temperature which may be encountered (e.g.
during storing and shipping) before the austenite transformation will effectively
begin. Thus,
As' minus M
s defines the operating range of the alloy when processed according to the invention.
This measure should be compared to As minus M
s which defines the operating range of the alloy after the temporary expansion of the
hysteresis has been recovered. As minus M
s is also indicative of the operating range of the alloy if it were never processed
according to the invention. Thus, comparing
As' minus M
s to As minus M provides useful indicia of the expansion of the hysteresis as well
as the advantages of the invention.
[0076] Referring now to Table 1, A
s' minus M
s and As minus M
s are about the same at 5% elongation; however, at 16% elongation, the difference becomes
substantial. It is useful to note that A
s' after 16% elongation is above normal room temperature so that the alloy may now
be handled at room temperature so that the alloy may now be hadled at room temperature
without the necessity of providing a cold environment.
[0077] Another useful measurement for indicating the expansion of the hysteresis are the
M
50, A
50, and A
50' values. These are the martensite and austenite transformation temperatures at which
the transformation is 50% complete.
[0078] In referring to Table 1 it can be seen that the difference between M
50 and A
50, the permanent width of the hysteresis, is about 60°C. However, the width of the
hysteresis may be temporarily enlarged, i.e., A
50' minus M
50, from 64°C at 5% elongation (at which there is no nonrecoverable strain) to 91°C
at 16% elongation (at which there is substantial nonrecoverable strain). The M
50, A
50, and A
50' values are also useful because they are the most easily determined as will become
apparent hereafter.
[0079] These results are graphically illustrated in Figures 3 and 4. Figure 3 illustrates
a stress/strain curve for the binary alloy which was strained to 16%. The load was
then removed. With 16% strain there is a substantial-amount of nonrecoverable strain
imparted to the alloy. Nonrecoverable strain will occur when the alloy, generally
speaking, is strained past its second yield point indicated approximately by reference
numeral 10. After removal of the stress, the alloy was heated.
[0080] In Figure 4, curve 12 illustrates the heating after the removal of the stress. When
the transformation was complete, the alloy was cooled down as illustrated by curve
14. During the cooling down under a small load the M
s and Mf temperatures were measured. The alloy was then reheated (curve 16) to measure
the recovered austenite transition temperatures As and A
f.
[0081] There is more than one way to locate on a transformation hysteresis curve the martensite
and austenite transformation temperatures. Referring again to Figure 4, the literal
starting and ending of the austenite transformation may be indicated, for example,
by points 18 and 20, formation effectively begins at about point 24 (denoted as A
s') and the austenite transformation effectively ends at about point 26 (denoted as
A
f'). Thus it can be said that the bulk of the transformation occurs between A
s' and A
f'. The same is true for the other transformations as illustrated by curves 14 and
16. The effective austenite and martensite transformation temperatures may be conveniently
determined by the intersection of tangents to the transformation hysteresis curves.
For example, tangents 22 on curve 12 locate A
s' and A
f'. The mid-point of the transformation, for example A
50' on curve 12, is simply vertically equidistant from the literal starting and ending
points, for example 18 and 20 on curve 12, of the transformation.
[0082] Whenever the austenite and martensite transformation temperatures are mentioned in
this specification, it should be understood that these temperatures refer to the austenite
and martensite transformation temperatures determined by the above-noted method of
intersecting tangents.
[0083] Curves 14 and 16 represent the shape memory alloy transformation hysteresis in the
recovered state while curves 12 and 14 represent the shape memory alloy transformation
hysteresis in the unrecovered state. Thus it can be seen that the elongation of the
alloy according to the invention has substantially and temporarily widened the hysteresis.
[0084] In sum, the expansion of the hysteresis will facilitate the convenient handling and
shipping of the alloy. This particular binary alloy would now be more suitable for
a variety of applications and temperatures where the service temperature is above
room temperature.
Example 2
[0085] Commercially pure titanium, carbonyl nickel and iron were weighed in proportions
so as to give a composition of 47 atomic percent nickel, 50 atomic percent titanium
and 3 atomic percent iron. The total mass for test ingots was about 330 grams. These
alloys were melted in an electron beam furnace in the same manner as the nickel-titanium
binary. The resulting ingots were hot swaged at approximately 850°C. Round, tensile
bars (1/4" in diameter) were then machined from the hot swaged ingot, vacuum annealed
at 850°C for 30 minutes, and then furnace cooled.
[0086] The tensile bars were then elongated. After elongation the stress was removed and
the bars were heated so as to effect recovery of the ternary shape memory alloy in
the same manner as the binary alloy. Due to the extreme low temperatures involved,
some of the values had to be extrapolated as noted. The results are tabulated below
in Table 2.
[0087] The discrepancy in the martensite and austenite transformation temperatures (between
5 and 16% elongation) can be explained in part by the interference of the R phase,
to be discussed in more detail later.
[0088] As it can be appreciated, the width of the hysteresis and the operating range have
been enlarged as a result of the 16% elongation of the alloy. The import of this is
that after elongation of the alloy, the alloy no longer has to be stored in liquid
nitrogen to prevent it from transforming into austenite. Since A
s' has been raised to -88°C other forms of cold storage may now be used to store and
ship the nickel/titanium/iron alloy prior to its final use. It is believed that this
will result in greater utility of the alloy.
Example 3
[0089] Commercially pure titanium, carbonyl nickel and niobium were weighed in proportions
so as to give a composition of 47 atomic percent nickel, 44 atomic percent titanium,
and 9 atomic percent niobium. The total mass for test ingots was about 330 grams.
The composition was melted in an electron beam furnace as was the case with the alloys
in Examples 1 and 2. The resulting ingots were hot swaged in air at approximately
850°C. The resulting bar was machined into rings which were vacuum annealed in 850°C
for 30 minutes and then furnace cooled. The rings were then enlarged, unstressed and
subsequently heated so as to measure the free recovery of the alloy. The results are
tabulated below in Table 3.
[0090] It can be seen from Table 3 that the hysteresis width (A
50 -M
50) in the fully recovered state is about 55°C with As being -56°C. With the austenite
temperature in this range it is still necessary for the alloy to be cold stored in
order to prevent transformation of the martensite into the austenite. However, if
the ring is now enlarged about 5%, the As temperature has been temporarily raised
to -14°C which would still require cold storage. By enlarging the ring 12.1% at which
point there is now substantial nonrecoverable strain, the As has been temporarily
increased to 27°C. Thus, at this temperature the alloy may be stored and shipped at
room temperature. No cold storage provisions are required. It also can be seen that
the width of the hysteresis has now been increased to 124°C from 55°C and the operating
range (A
s'-M
s> has been increased to 117°C. By enlarging the ring 16.2% As has now been temporarily
raised to 41°C with the width of the hysteresis now being 140° and the operating range
now being 131°C.
[0091] It is believed that to have the most commercially practical alloy it is necessary
to have an hysteresis width of greater than about 125°C with ambient or room temperature
somewhere in the middle of that hysteresis so as to allow a substantial leeway on
either side of room temperature for temperature excursions. Strictly speaking, it
would be most preferred if the A
s' could be raised to about 50°C.
[0092] The first three samples enlarged at 5.2, 12.1, and 16.2% were enlarged in liquid
nitrogen which is substantially below M
s. If the samples were now enlarged in -90°C alcohol, which is at the M
s temperature, it can be seen that the austenite transition temperatures have been
raised to higher values than when enlarged in liquid nitrogen. By comparison, the
A
s' temperatures have been raised from 41 to 50°C. While this increase is not of great
magnitude it is nevertheless important.
[0093] It is most preferred that the temperature of deformation be above M
s. The importance of this limitation is illustrated in the next sample which was deformed
at -70°C (compared to an Mg of -90°C). It can be seen that A
s', and A
50'-M
50 and A
s'-M
s have all been increased more than any of the previous samples.
[0094] The next sample was enlarged at 0°C. While it can be seen that the hysteresis has
been expanded, the effect of the expansion of the hysteresis has not been as great
as when it was enlarged in -90°C alcohol or -70°C alcohol since A
s' has only been raised to 34°C.
[0095] The previously stated results have been obtained by expanding the hysteresis through
overdeforming of the alloy so as to impart nonrecoverable strain, removing the stress
and then storing the alloy at a temperature less than A
s'.
[0096] The process may be varied somewhat so as to give equally dramatic results. Thus a
sample may be overdeformed at low temperatures such as -90°C in alcohol to stabilize
the martensite at or near room temperature. When the stress is removed there will
be an elastic springback of about 4%. Now if the alloy is redeformed at 20°C to the
same amount of overdeformation, 16.2%, and the stress removed, it can be seen in the
last column of Table 3 that the austenite transition temperatures have been raised
to even higher values when compared to a single expansion in -90°C alcohol. Thus,
A
s' has been moved from 50°C to 55°C. Again, while this increase in A
s' may appear to be a small amount of temperature increase it is nevertheless of great
importance. One easy way to accomplish this process is to deform the ring on a mandrel
and then let the ring and mandrel warm to room temperature.
[0097] The nickel/titanium/niobium ternary alloys are preferred alloys due to their ready
susceptibility to expansion of the transformation hysteresis as illustrated above.
Of all the ternary niobium alloys, those that are stable, have an M
s greater than 0°C and do not have an R phase are the most preferred. The R phase,
as further discussed below, is a transitional phase between austenite and martensite.
Since the R phase is not present, there is substantial uniformity in the martensite
and austenite transformation temperatures from sample to sample. Alloys that are stable
(i.e., exhibit temper stability) have an M
s that does not change more than about 20°C after annealing and water quenching and
subsequent aging between 300 and 500"C.
Examples 4, 5, and 6
[0098] Commercially pure titanium, carbonyl nickel and amounts of vanadium, cobalt, and
aluminum were weighed in proportions so as to give compositions of: 46 atomic percent
nickel, 49 atomic percent titanium, and 5 atomic percent vanadium; 49 atomic percent
nickel, 49 atomic percent titanium, and 2 atomic percent cobalt; and 50 atomic percent
nickel, 48.5 atomic percent titanium, and 1.5 atomic percent aluminum. Each of the
compositions was melted and 0.025-in.-thick strips prepared in the same way as that
previously stated with respect to the binary.
[0099] After elongation, the stress was removed and the strip was heated unrestrained so
as to effect recovery which was monitored and plotted as a function of temperature.
When the transformation was complete, the sample was cooled and then reheated so as
to complete the measurement of the martensite and austenite transformation temperatures
before recovery and after recovery. In the case of the cobalt alloy, the martensite
and austenite transformation temperatures were measured with a load of 20 ksi and
then extrapolated to 0 ksi. The results are tabulated below in Tables 4, 5, and 6.
[0100] Referring to Table 4, the large discrepancy between the martensite and austenite
transformation temperatures at 5 and 16%, respectively, is believed due to the interference
of the R-phase. Referring to Figure 5, the presence of the R phase 28 is most noticeable
on the austenite leg of the transformation hysteresis for the alloy deformed 5%. As
stated previously the R phase is a transitional phase between the austenite and martensite
and has a structure different than either. The effect of the R phase is to depress
the austenite and martensite transformation temperatures. Figure 6 illustrates the
transformation hysteresis curve for the same alloy, but after recovering from 16%
deformation. The R phase is noticeably absent. The austenite and martensite transformation
temperatures in Figure 6 are also noticeably higher.
[0101] Referring again to Table 4, it can be seen that a 5% deformation has little effect
on the expansion of the hysteresis. Thus, A
s' minus M
s and As minus M
s are substantially the same. This is not the case after 16% deformation wherein the
transformation hysteresis has been noticeably enlarged.
[0102] The results in Table 5 are similar to those in Table 4 in that a 5% deformation (no
nonrecoverable strain) had little effect on the expansion of the transformation hysteresis
whereas a 16% deformation (substantial nonrecoverable strain) had a marked effect
on the expansion of the transformation hysteresis.
[0103] The change in the recovered martensite and austenite transformation temperatures
between the 5% and 16% deformations is again believed due to the interference of the
R phase in the sample deformed 5%.
[0104] Referring now to Example 6 and Table 6, the sample deformed 16%, and thus having
substantial nonrecoverable strain, shows a marked expansion of the transformation
hysteresis (as in the previous two examples) whereas the sample deformed at 5% shows
essentially no expansion of the transformation hysteresis.
[0105] Again, the interference of the R phase has manifested itself by depressing the martensite
and austenite transformation temperatures in the sample deformed 5%.
[0106] It bears repeating here that the lack of utility of shape memory alloys has resulted
at least in substantial part from the fact that the alloys cannot be deformed and
then,stored at room temperature. The present invention has solved all the problems
of the prior art and has now resulted in an alloy and article which at least in the
case of the most preferred niobium ternary alloy can be deformed and stored at room
temperature or at least can be deformed in cold temperatures but can be stored and
shipped at room temperature without the provision of cold storage procedures.
[0107] It can be appreciated that while this invention is most advantageous with respect
to those alloys having an enlarged hysteresis with its middle near room temperature,
it is within the scope of the invention to apply the teachings of this invention to
other alloys as well, as illustrated in the above examples.
[0108] It can also be appreciated that the expansion of the transformation hysteresis will
be more dramatic in some alloys than in others. This conclusion becomes apparent when
comparing the transformation hysteresis expansion of the binary alloy with the transformation
hysteresis expansion of the most preferred niobium ternary alloy.
Example 7
[0109] A cylindrical driver member was made from an alloy having the composition of 47 atomic
percent nickel, 44 atomic percent itanium and 9 atomic percent niobium.
[0110] The nickel/titanium/niobium alloys, in general, are the most preferred alloys. These
alloys were described in our U.S. Patent Application Serial No. 668,777 filed November
6, 1984, entitled "Nickel/Titanium/Niobium Shape Memory Alloy and Article", the disclosure
of which is incorporated by reference herein.
[0111] The driver was melted and processed as noted in our patent application above except
that a coupling was machined instead of a ring. The driver was machined to have an
inside diameter of .847 inches, an outside diameter of 1.313 inches and a length of
2.12 inches.
[0112] A cylindrical insert was then made to be eventually joined with the driver so as
to form a composite coupling. The insert was machined from 316 stainless steel so
as to have an inside diameter of .850 inches, an outside diameter of .970 inches and
a length of 2.12 inches. It is not necessary to the invention that the insert be made
from stainless steel. It is only necessary that the insert be made from a material
that is sufficiently soft such that it may be crushed by the driver upon full recovery
thereof.
[0113] With the particular alloy utilized, the M
s temperature was -90°C, the As temperature was -56°C and the M
d temperature was -10°C. Although not actually measured, such an alloy expanded about
16% at -50°C would be expected to have a true A
s' of -52°C and an A
s' of +52°C. Thus, immediately after expansion, the driver was near the literal starting
temperature of the austenitic transformation of the temporarily expanded transformation
hysteresis.
[0114] After expansion, the driver was removed from the cold fluid and placed on a work
bench. The insert was then slipped into the driver. Thereafter, the driver and insert
were allowed to warm to room temperature, which it is noted is substantially below
A
s'. It was found that the driver and insert were snugly engaged and could only be moved
relative to each other with great difficulty.. It should be noted that while-the driver
and insert became snugly engaged, there was no crushing of the insert.
[0115] The driver, prepared as described above, would be expected to have about 8% recoverable
strain. About 1% of that recoverable strain was utilized in the preassembling of the
driver and insert. Thus, about 7% recoverable strain remains for the actual coupling
of the substrates.
[0116] The composite coupling is now preassembled and ready for storage or use.
Example 8
[0117] Commercially pure titanium, carbonyl nickel and niobium were weighed in proportions
so as to give a composition of 47 atomic percent nickel, 44 atomic percent titanium,
and 9 atomic percent niobium. The total mass for test ingots was about 330 grams.
These metals were placed in water-cooled, copper hearth in the chamber of an electron
beam melting furnace. The chamber was evacuated to 10-
s Torr and the charges were melted and alloyed by use of the electron beam. The resulting
ingots were hot swaged in air at approximately 850°C. The resulting bar was machined
into rings which were vacuum annealed in 850°C for 30 minutes and then furnace cooled.
The rings were then enlarged, unstressed and subsequently heated so as to measure
the free recovery of the alloy. The results are tabulated below in Table 7.
[0118] While the data relate to the expansion of rings, the date is nevertheless indicative
of how the material would perform as a driver. In each case, there is a substantial
difference between true A
s' and A
s' indicating that the material will achieve the objects of the invention. The true
A
s' for the sample expanded at -70°C is believed to be an anomaly in that the sample
may have inadvertently warmed to near room temperature prior to the actual measurement
of true A
s' and As' .
[0119] It is preferred that the material be expanded at temperatures no higher than M
d (-10°C in Table 1) since expansion at higher temperatures will cause a dramatic decrease
in the amount of recoverable strain obtainable. However, expansion at temperatures
higher than M
d does not appear to affect the difference between true A
s' and A
s'.
[0120] It is most preferred that expansion takes place between As and M
s. This is because at temperatures higher than As or lower than M
s, elastic springback of the material may be increased. Additionally, the material
has somewhat more ductility when expanded between As and Ms.
Examples 9 to 13
[0121] Commercially pure titanium and carbonyl nickel were weighed in proportions so as
to give a composition of 50.7 atomic percent nickel and 49.3 atomic percent titanium.
Additionally, commercially pure titanium, carbonyl nickel and amounts of vanadium,
cobalt, aluminum and iron were weighed in proportions so as to give compositions of:
46 atomic percent nickel, 49 atomic percent titanium and 5 atomic percent vanadium;
49 atomic percent nickel, 49 atomic percent titanium and 2 atomic percent cobalt;
50 atomic percent nickel, 48.5 atomic percent titanium and 1.5 atomic percent aluminum;
and 47 atomic percent nickel, 50 atomic percent titanium and 3 percent iron.
[0122] These metals were placed in a water-cooled, copper hearth in the chamber of an electron
beam melting furnace. The chamber was evacuated to 10-
5 Torr and the charges were melted and alloyed by use of the electron beam.
[0123] The resulting iron-containing ingots were hot swaged at approximately 850°C. Round,
tensile bars (1" in diameter) were then machined from the hot swaged ingot, vacuum
annealed at 850°C for 30 minutes, and then furnace cooled. The tensile bars were then
elongated. After elongation, the stress was removed and the bars were heated unrestrained
so as to effect recovery of the shape memory alloy. The recovery was monitored and
plotted as a function of temperature. When the transformation was complete, the sample
was cooled and then reheated so as to complete the measurement of the martensitic
and austenitic transformation temperatures before recovery and after recovery. The
results are tabulated in Table 8.
[0125] As stated earlier it is believed that the above data while not derived from drivers
per se is nevertheless indicative of how each of these materials will perform as a
driver. Thus, for each of these materials, in addition to having an expanded hysteresis,
there is a substantial difference between A
s' and A
s' so that these materials are suitable to achieve the objects of the invention.
[0126] Finally, it can be apprecated that while the samples in the above examples were deformed
by application of a tensile stress, the objects of the invention can be fully achieved
by application of a compressive stress.
[0127] The invention, as defined by the claims provides a number of methods. Articles by
any one, or any combination of those methods also form part of the present invention.
Particularly preferred articles include couplings.