U.S. patent number 3,753,700 [Application Number 05/052,112] was granted by the patent office on 1973-08-21 for heat recoverable alloy.
This patent grant is currently assigned to Raychem Corporation. Invention is credited to Jei Y. Choi, John D. Harrison, Peter R. Marchant.
United States Patent |
3,753,700 |
Harrison , et al. |
August 21, 1973 |
HEAT RECOVERABLE ALLOY
Abstract
An alloy capable of having the property of heat recoverability
imparted thereto comprising 49.1 to 50.2 atomic percent of
titanium, 2.1 to 4.7 atomic percent of iron and the remainder
nickel.
Inventors: |
Harrison; John D. (Palo Alto,
CA), Choi; Jei Y. (Palo Alto, CA), Marchant; Peter R.
(San Francisco, CA) |
Assignee: |
Raychem Corporation (Menlo
Park, CA)
|
Family
ID: |
21975547 |
Appl.
No.: |
05/052,112 |
Filed: |
July 2, 1970 |
Current U.S.
Class: |
148/402;
420/459 |
Current CPC
Class: |
C22C
19/007 (20130101); C22F 1/006 (20130101) |
Current International
Class: |
C22F
1/00 (20060101); C22C 19/00 (20060101); C22c
015/00 () |
Field of
Search: |
;75/170,175.5,134F,122
;148/32,32.5 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Dean; Richard O.
Claims
What is claimed is:
1. An alloy consisting essentially of 49.1 to 50.2 atomic percent
titanium, 3.2 to 3.6 atomic percent of iron and the remainder
nickel, the martensitic transformation temperature of said alloy
being such as to permit impartation of heat recoverability to an
object formed thereof at a temperature above the boiling point of
liquid nitrogen.
2. A titanium, nickel and iron alloy within an area defined on a
titanium, nickel and iron ternary phase diagram by a quadrilateral
with its first corner at 49.1 atomic percent titanium, 47.3 atomic
percent nickel and 3.6 atomic percent iron; its second corner at
49.1 atomic percent titanium, 48.8 atomic percent nickel and 2.1
atomic percent iron; its third corner at 50.2 atomic percent
titanium, 46.8 atomic percent nickel and 3.0 atomic percent iron;
and its fourth corner at 50.2 atomic percent titanium, 45.1 atomic
percent nickel and 4.7 atomic percent iron, the martensitic
transformation temperature of said alloy being such as to permit
impartation of heat recoverability to an object formed thereof at a
temperature above the boiling point of liquid nitrogen.
Description
BACKGROUND OF THE INVENTION
In U.S. Patent application Ser. No. 852,722 filed Aug. 25, 1969 now
abandoned by John D. Harrison and James E. Jervis, the disclosure
of which is incorporated by reference herein, there is disclosed a
heat recoverable metallic coupling, especially suitable for use on
hydraulic lines in aircraft. The requirements of such a coupling
are many. First, it must be heat recoverable, that is, it must
recover from a heat unstable configuration to a heat stable
configuration upon the application of heat alone. It has been found
that certain alloys are capable of having this property of heat
recoverability imparted to them if they are formed in the heat
stable condition while in the austenitic state, then cooled until
they undergo a martensitic transition, and then deformed while
maintained in the martensitic state. When heated to a temperature
where the alloy is again transformed into the austenitic state, the
formed object will revert to its original configuration.
Inasmuch as an alloy is considerable stronger in its austenitic
state than in its martensitic, a second requirement of an alloy
suitable for use in a coupling is that its transition temperature,
that is, the temperature (more precisely, the temperature range)
where it changes from its austenitic state to its martensitic
state, must be below any expected operating temperature of the
coupling. In addition, of course, the material from which the
coupling is made must inherently have a yield strength sufficient
to endure the operating conditions to which it is to be subjected.
Conflicting, however, with the requirement for strength is the
requirement for light weight. This is particularly true in
couplings to be used in aircraft. What is desired is an alloy that
can be fabricated into a coupling having the highest possible
strength and the lowest possible weight. The alloy must also be
sufficiently workable so that it can be formed into the parts and
must not be overly brittle.
Various alloys of titanium and nickel have in the past been
disclosed as being capable of having the property of heat
recoverability imparted thereto. Examples of such alloys may be
found in U.S. Pat. Nos. 3,174,851 and 3,351,463. The alloys
disclosed in these patents are binary alloys but ternary alloys
have also been suggested. For example, see the article by
Goldstein, Buehler and Wiley entitled "Effects of alloying upon
certain properties of 55.1 Nitinol" (Published Aug. 1965 by U.S.
Naval Ordnance Laboratory, White Oak, Maryland as NOLTR 64-235).
None of the alloys disclosed in these patents and publications,
however, are satisfactory for use in couplings or other devices for
use on aircraft because they do not have the required combination
of attributes discussed above, and are particularly deficient with
respect to their transition temperatures which in all cases are
above the temperature generally considered the maximum for safety
-- minus 65.degree.F, and in most cases are substantially above
this temperature. In those few cases where the alloys have a
transition temperature fairly close to that desired, they had a
relatively low yield strength and thus require the use of a
substantial volume of metal with the result that the parts are
heavier than desired.
SUMMARY OF THE INVENTION
According to the present invention a heat recoverable metal alloy
has been provided which has a transition temperature below any
temperatures expected during aircraft operations. In addition, the
alloy can be worked within the bounds of reasonable manufacturing
processes, is not brittle, is not susceptible to embrittlement, and
has a high strength to weight ratio. The alloy is thus acceptable
for use in aircraft and is particularly useful in constructing
hydraulic couplings for such use. It has been found that in order
that the alloy have the necessary properties it must contain very
close to 50 atomic percent titanium with a small percentage of iron
substituted for nickel. Specifically, the alloy must contain from
49.1 to 50.2 atomic percent of titanium and 2.1 to 4.7 atomic
percent of iron, the remainder being nickel. The most desirable
alloy is obtained when the iron content is between 3.2 and 3.6
atomic percent. The latter alloy will have the maximum strength to
weight ratio consistent with the required transition temperature
and will still allow practical treatment to permit the impartation
of heat recovery to the alloy. From a practical standpoint, the
alloy must have a transition temperature which is above that of
liquid nitrogen. If it is lower, it becomes commercially
impractical if not impossible to maintain the alloy in its
martensitic state during deformation and installation of the part
fabricated from it.
Alloys may be prepared in accordance with the present invention as
follows:
EXAMPLE 1
Equal width and length strips were cut from sheet stock of nickel
(International Nickel 270) titanium (Titanium Metals Corporation
35A) and iron (99.9 percent pure). The strips were cleaned to
remove any dirt or grease, weighed and assembled in bundles such
that the elements were in the ratio of 50 atomic percent titanium,
3 atomic percent iron and 47 atomic percent nickel at each cross
section through the longitudinal axis of the bundle. The bundle was
then hung in the chamber of a Lepel HCP-F floating zone unit. The
chamber was evacuated, then filled with high purity argon to a
pressure of 1 atmosphere; this procedure was repeated twice; after
the third filling a pressure of + 3 p.s.i. gauge was established
and maintained during the melting to minimize air influx.
The lower end of the sample was heated by a single turn induction
coil attached to the secondary winding of a 12:1 load matching step
down transformer, the primary being powered by a Lepel high
frequency induction heating unit (Model T-10-3-DF-E-H) operating in
the Kilo Hertz range. Rapid melting resulted from the combination
of induction heating and the heat of formation of the intermetallic
compound TiNi 0.94 Fe 0.06. The falling droplets of alloy were
collected in a cold copper mold, the bundle being fed into the
induction coil until it had all been melted and collected in the
mold. After cooling, the copper mold and dripcast ingot were
removed from the chamber, and the mold was stripped.
The dripped ingot, which was a semi-compact cylinder, was returned
to the chamber and an argon atmosphere established as before. A
molten zone was passed along the ingot from bottom to top at a rate
of about 0.5 cm/minute using the floating zone technique to avoid
possible contamination by a crucible. The product was a
homogeneous, void-free bar of alloy about 2 cm. diameter, 12 cm.
long.
The composition of the alloy of this invention can be described by
reference to an area on the titanium nickel and iron phase diagram.
The general area of the alloy on the phase diagram is shown by the
circled portion of Diagram 1 below. This area of the phase diagram
is enlarged and shown in Diagram 2. The compositions at the corners
of the quadrilateral are shown in Table 1 below.
ATOMIC PERCENT
Titanium Nickel Iron A 49.1 47.3 3.6 B 49.1 48.8 2.1 C 50.2 46.8
3.0 D 50.2 45.1 4.7
TABLE I ##SPC1##
EXAMPLE 2
In addition to the method described in Example 1, alloys according
to the invention may be manufactured from their components by other
methods suitable for dealing with high-titanium alloys. The details
of these methods, and the precautions necessary to exclude oxygen
and nitrogen either by working in an inert atmosphere or in a
vacuum, are well known to those skilled in the art and are not
repeated here.
It appears however that alloys obtained by the methods and using
the materials described will contain small quantities of other
elements, including oxygen and nitrogen in total amounts from about
0.05 to 0.2 percent. The effect of these materials is generally to
reduce the martensitic transformation temperature of the
alloys.
In a Temescal 900 kW electron-beam furnace, bundles of bars, as
described in Example 1, containing Titanium (49.6 atomic percent),
Nickel (47.2 atomic percent) and Iron (3.2 atomic percent) were
melted. On analysis, the resulting ingot was found to contain the
same relative proportions.
The properties of the resulting alloy are as follows:
Ms -88.degree.C to -118.degree.C Yield point at room temperature
66,000 psi to 79,000 psi Elongation 20% Hardness Rockwell A 60 to
64
Samples of the composition were hot-workable, could be machined,
and displayed no propensity for embrittlement.
The alloy was also capable of at least 5 percent recovery. For
example, a hydraulic coupling made of the alloy was provided with a
heat unstable diameter of 8% greater than the heat stable
diameter.
* * * * *