CA1176488A - Nickel/titanium copper shape memory alloys - Google Patents
Nickel/titanium copper shape memory alloysInfo
- Publication number
- CA1176488A CA1176488A CA000385277A CA385277A CA1176488A CA 1176488 A CA1176488 A CA 1176488A CA 000385277 A CA000385277 A CA 000385277A CA 385277 A CA385277 A CA 385277A CA 1176488 A CA1176488 A CA 1176488A
- Authority
- CA
- Canada
- Prior art keywords
- atomic percent
- nickel
- titanium
- copper
- alloys
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/006—Resulting in heat recoverable alloys with a memory effect
Abstract
Nickel/Titanium/Copper Shape Memory Alloys ABSTRACT
The invention relates to shape memory alloys consisting essentially of nickel, titanium, and copper.
The alloys of this invention, which contain less than a stoichiometric amount of titanium, are capable of possessing shape memory with a temperature of mid-recovery greater than -196°C. The presence of from 1.5 to 9 atomic percent copper stabilizes the alloys to tempering, and also improves their workability and machinability.
Alloys according to this invention are useful in pipe couplings, electrical connectors, actuators, and similar applications involving shape memory.
The invention relates to shape memory alloys consisting essentially of nickel, titanium, and copper.
The alloys of this invention, which contain less than a stoichiometric amount of titanium, are capable of possessing shape memory with a temperature of mid-recovery greater than -196°C. The presence of from 1.5 to 9 atomic percent copper stabilizes the alloys to tempering, and also improves their workability and machinability.
Alloys according to this invention are useful in pipe couplings, electrical connectors, actuators, and similar applications involving shape memory.
Description
- " ~
Nickel/Titanium/Copper Shape Memory Alloys DESCRIPTION
This invention relates to shape memory alloys consisting essentially of nickel, titaniumr and copper.
i Alloys which exhibit the shape memory effect are now well~known, and include a number of alloys comprising nickel and titanium. See, e.gO, U.S. Pat. Nos. 3,174,851;
3,351,463; and 3,753,700. A wide variety of use~ul articles, such as electrical connectors, actuators~ and pipe couplings can be made from such alloys. See e.cl.
U~S. Pat. NosO 3,740,839; 4,035,077; and 4l198,081. 'I
It has been generally accepted that such alloys are unstable in the range of 100C to 500C if the titanium content i5 below 4g.9 atomic percent (See Wasilewski et al., Met. Trans., v. 2~ ppa 22~-38 (1971)~
The instability (temper instability) manifests itself as a change (generally an increase) in Ms, the temperature at which the austenite to martensite transition begins, between the annealed alloy and the same alloy which has been urther tempered. Annealing here means heating to a sufficiently high temperature and holding at that temperature lon~ enough to give a uniformr stress-ree condition, followed by sufi.ciently rapid cooling to maintain that condition. Temperatures around 900C for about 10 minutes are generally sufficient for annealing, and air cooling is generally sufficiently rapid, though ,~ .
quenching in water is necessary for some of the low Ti compositions. Tempering here means holding at an intermediate temperature for a suitably long period (such as a few hours at 200 - 400C). The instability thus makes the low titanium alloys disadvantageous for shape memory applications, where a combination of high yield strength and low~ reproducible Ms is desired.
~wo further requirements for these shape memory alloys should be noted. These are workability and machinabilityO
Workability is the ability of an alloy to be plastically deformed without crumbling or crackingl and is essential for the m~nufacture of articles (including even test samples) from the alloy. Machinability refers to the ability of the alloy to be shaped, such as by turning or drilling, economically. Although machinability is not solely a property of the alloy, Ni/Ti alloys are known to be difficult to machine (see, e.g., Machining Data Handbook, 2 ed. (1972) for comparati~e machining conditions for various alloys), i.e. they are expensive to shape, and a free-machining nickel/titanium shape memory alloy would be extremely economically attractive.
We have discovered that it is possible to produce a new class of nickel/titanium alloys which contain less than a stoichiometric amount of titanium but which surprisingly have good stability. Furthermore, this novel class of alloys has the generally desired combination of high yeild strength and low Ms, Yet more surprisingly, these alloys also possess sjgnificantly improved machinability, and workability.
In one aspect, this invention provides a shape memory alloy consistiTI~ essentially of nickel, titanium, and copper within an area defined on a nickel, titanium, and copper ternary composition diagram by a triangle ABC with vertex A
at 49/7 atomic percent nickel, 48.8 atomic percent titanium, and 1.5 atomic percent copper; vertex B at 47.5 atomic percent nickel, 47.5 atomic percent titanium, and 5.0 atomic percent copper; and vertex C at 47.5 atomic percent nickel, 43.5 atomic percent titanium, and 9.0 atomic percent copper~
Preferablyl the composition lies within an area defined on a nickel, titanium, and copper ternary composition diagram by a quadrilateral ABDE with vertex A at 49.7 atomic percent nickel, 48.8 atomic percent titanium, and loS atomic percent copper; vertex B at 47.5 atomic percent nickel, 47.5 atomic percent titanium, and 5.0 atomic percent copper; vertex D at 47.5 atomic percent nickel, 46.0 atomic percent titanium, and 6.5 atomic percent copper;
and vertex E at 48.9 atomic percent nickel, 46.8 atomic percent titanium, and 4.3 atomic percent copper~
These alloys advantageously display high strength and low transformation temperature, which as mentioned above is desirable for shape memory applications, and furthermore, the alloys display unexpectedly good stability,workability and machinability.
In a second aspect, this invention provides articles having shape memory made from the alloys defined above, which articles may be produced at an economically attractive cost.
Shape meTnory alloys according to the invention may conveniently be produced by the methods described in, for example, U.S.
Pats. No. 3,753,700 and 4,144,057. The following example illustrates the method of preparation and testing of samples of memory alloys.
~'7~
EXAMPLE
Commercially pure titanium, carbonyl nickel, and OFHC
copper were weighed in proportions to give the atomic percentage compositions listed in Table 1 (the total mass for test ingots was about 330 g). 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 elec~ron beam.
The resulting ingots were hot swaged and hot rolled in air at approximately 850C to produce strip o~ approximately 0.5 mm thickness. After de-scaling, samples were cut from the strip and vacuum annealed at 900C.
The annealed samples were cooled and re-heated while the change in resistance was measured. From the resistance-temperature plot, the temperature at which the martensitic transformation was complete, Mf, was determined. ~he samples were then cooled below Mf and deformed. The deforming force was then released, and the recovery under no load monitored as the temperature was increased.
The transformation temperature of each alloy was determined as the temperature at which 50% of the total recovery had occurred, referred to as Aso. A50 is a particularly suitable measure of tranformation temperature, since the temperature of transformation is known to be stress~dependent.
~ter tempering each sample for two hours at 400C, the tests were repeated. The average of the temperature shift of the resistivity change and of A50 for the annealed versus the tempered samples was used as an index oE instability: the greater the absolute value of the index, the greater the instability. The yield 7 ~ MP0748 . -5-strength of annealed samples was measured at temperatures high enough to avoid the formation of stress-induced martensite. Values for A50, the instability index, and the yield strength are listed in Table 1. On the basis of these data, the preferred composition limits for this invention have been defined.
Table I. Propertles of Nickel/Titanium/Copper Allo~s ~ Composition, Atomic Percent Temperature of . Mid-RecoveryInstability Yield Ni Ti Cu (As0),C Index Strength, MPa __ _ _ _ 9, 00.00 _57 ~3 820 50.50~9O000.50 -37 38 634 50.0049.001.00 -9 14 531 50.5048.5~1.00 -106 68 738 50.7048.301.00 -170 94 896 50.0048.S01.50 -113 -2 724 49.0049.002.00 . 6 -4 427 49.5048.502.00 -62 1 634 49.904~.102.00 ~168 11 807 ~8.0049.003.00 22 -3 393 48.5048.503.00 -42 -3 552 49.1047.903.00 -153 -5 793 48.5047~504~00 -87 6 710 45.5048.506.00 8 ~ 621 ~7.0047.006.00 -34 -2 820 . ' .
~ 7~
.
The composition oE the alloy of this invention can be described by reference to an area on a nickel, titaniumS
and copper ternary composition diagram. The general area of the alloy on the composition diagram is shown by the small triangle in Figure 1. This area of the composition diagram is enlarge~ and shown in Figure 2.
The compositions at the pointst A, B~ C, D, and E are shown in Table 2 below.
Table 2 Atomic Percent Composition Point Nickel Titanium Copper ~ 49.7 48~8 1.5 B 47.5 47.5 5.0 C 47.5 43.5 g.0 D 47~5 46.0 6.5 E 48.9 46.8 4.3 The lines AB and BC correspond approximately to an A50 o -50C, while the line AC corresponds to the stability -limit of these alloys; alloys to the right of khe line, or ~ith a lower copper concentration than at point A, are generally un~table with respect to manufacturing conditions.
As the extent of thermally recoverable plastic deformation (shape memory) that can be induced in these alloys decreases with decreasing titanium content, the particularly preferred alloys of this invention will lie nearer vertex A (the high titanium vertex) of the triangle ABC
of Figure 2, within the quadrilateral ABDE.
..
..
L~ ~ 8 It has been found that the alloys of this invention possess machinability which is unexpectedly considerably better than would be predicted from similar Ni/Ti alloys. While not wishing to be held to any particular theory, it is considered that this free-machining property of the alloys is related to the presence of a second phase, possibly Ti2(Ni,Cu)3, in the TiNi matrix. It is therefore considered that this improved machinability will manifest itself only when the titanium content is below the stoichiometric value and the Ti:Ni:Cu ratio is such as to favor the formation of the second phase.
In addition to the method described in the Example, alloys according to the invention may be manufactured from their components (or appropriate master alloys) 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 melting in an inert atmosphere or in vacuum, are well Xnown to those skilled in the art and are not repeated here.
Alloys obtained by these methods and using the materials described will contain small quanities oE 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 transform-ation temperature of the alloys.
7~
: . . .: .
The alloys of this invention possess good temper stability, are hot-workable, and are free-machining;
- in contrast to prior art alloys. They are also capable of possessing shape memory, and have an A50 below -50C and above the boil.ing point of liquid nitrogen
Nickel/Titanium/Copper Shape Memory Alloys DESCRIPTION
This invention relates to shape memory alloys consisting essentially of nickel, titaniumr and copper.
i Alloys which exhibit the shape memory effect are now well~known, and include a number of alloys comprising nickel and titanium. See, e.gO, U.S. Pat. Nos. 3,174,851;
3,351,463; and 3,753,700. A wide variety of use~ul articles, such as electrical connectors, actuators~ and pipe couplings can be made from such alloys. See e.cl.
U~S. Pat. NosO 3,740,839; 4,035,077; and 4l198,081. 'I
It has been generally accepted that such alloys are unstable in the range of 100C to 500C if the titanium content i5 below 4g.9 atomic percent (See Wasilewski et al., Met. Trans., v. 2~ ppa 22~-38 (1971)~
The instability (temper instability) manifests itself as a change (generally an increase) in Ms, the temperature at which the austenite to martensite transition begins, between the annealed alloy and the same alloy which has been urther tempered. Annealing here means heating to a sufficiently high temperature and holding at that temperature lon~ enough to give a uniformr stress-ree condition, followed by sufi.ciently rapid cooling to maintain that condition. Temperatures around 900C for about 10 minutes are generally sufficient for annealing, and air cooling is generally sufficiently rapid, though ,~ .
quenching in water is necessary for some of the low Ti compositions. Tempering here means holding at an intermediate temperature for a suitably long period (such as a few hours at 200 - 400C). The instability thus makes the low titanium alloys disadvantageous for shape memory applications, where a combination of high yield strength and low~ reproducible Ms is desired.
~wo further requirements for these shape memory alloys should be noted. These are workability and machinabilityO
Workability is the ability of an alloy to be plastically deformed without crumbling or crackingl and is essential for the m~nufacture of articles (including even test samples) from the alloy. Machinability refers to the ability of the alloy to be shaped, such as by turning or drilling, economically. Although machinability is not solely a property of the alloy, Ni/Ti alloys are known to be difficult to machine (see, e.g., Machining Data Handbook, 2 ed. (1972) for comparati~e machining conditions for various alloys), i.e. they are expensive to shape, and a free-machining nickel/titanium shape memory alloy would be extremely economically attractive.
We have discovered that it is possible to produce a new class of nickel/titanium alloys which contain less than a stoichiometric amount of titanium but which surprisingly have good stability. Furthermore, this novel class of alloys has the generally desired combination of high yeild strength and low Ms, Yet more surprisingly, these alloys also possess sjgnificantly improved machinability, and workability.
In one aspect, this invention provides a shape memory alloy consistiTI~ essentially of nickel, titanium, and copper within an area defined on a nickel, titanium, and copper ternary composition diagram by a triangle ABC with vertex A
at 49/7 atomic percent nickel, 48.8 atomic percent titanium, and 1.5 atomic percent copper; vertex B at 47.5 atomic percent nickel, 47.5 atomic percent titanium, and 5.0 atomic percent copper; and vertex C at 47.5 atomic percent nickel, 43.5 atomic percent titanium, and 9.0 atomic percent copper~
Preferablyl the composition lies within an area defined on a nickel, titanium, and copper ternary composition diagram by a quadrilateral ABDE with vertex A at 49.7 atomic percent nickel, 48.8 atomic percent titanium, and loS atomic percent copper; vertex B at 47.5 atomic percent nickel, 47.5 atomic percent titanium, and 5.0 atomic percent copper; vertex D at 47.5 atomic percent nickel, 46.0 atomic percent titanium, and 6.5 atomic percent copper;
and vertex E at 48.9 atomic percent nickel, 46.8 atomic percent titanium, and 4.3 atomic percent copper~
These alloys advantageously display high strength and low transformation temperature, which as mentioned above is desirable for shape memory applications, and furthermore, the alloys display unexpectedly good stability,workability and machinability.
In a second aspect, this invention provides articles having shape memory made from the alloys defined above, which articles may be produced at an economically attractive cost.
Shape meTnory alloys according to the invention may conveniently be produced by the methods described in, for example, U.S.
Pats. No. 3,753,700 and 4,144,057. The following example illustrates the method of preparation and testing of samples of memory alloys.
~'7~
EXAMPLE
Commercially pure titanium, carbonyl nickel, and OFHC
copper were weighed in proportions to give the atomic percentage compositions listed in Table 1 (the total mass for test ingots was about 330 g). 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 elec~ron beam.
The resulting ingots were hot swaged and hot rolled in air at approximately 850C to produce strip o~ approximately 0.5 mm thickness. After de-scaling, samples were cut from the strip and vacuum annealed at 900C.
The annealed samples were cooled and re-heated while the change in resistance was measured. From the resistance-temperature plot, the temperature at which the martensitic transformation was complete, Mf, was determined. ~he samples were then cooled below Mf and deformed. The deforming force was then released, and the recovery under no load monitored as the temperature was increased.
The transformation temperature of each alloy was determined as the temperature at which 50% of the total recovery had occurred, referred to as Aso. A50 is a particularly suitable measure of tranformation temperature, since the temperature of transformation is known to be stress~dependent.
~ter tempering each sample for two hours at 400C, the tests were repeated. The average of the temperature shift of the resistivity change and of A50 for the annealed versus the tempered samples was used as an index oE instability: the greater the absolute value of the index, the greater the instability. The yield 7 ~ MP0748 . -5-strength of annealed samples was measured at temperatures high enough to avoid the formation of stress-induced martensite. Values for A50, the instability index, and the yield strength are listed in Table 1. On the basis of these data, the preferred composition limits for this invention have been defined.
Table I. Propertles of Nickel/Titanium/Copper Allo~s ~ Composition, Atomic Percent Temperature of . Mid-RecoveryInstability Yield Ni Ti Cu (As0),C Index Strength, MPa __ _ _ _ 9, 00.00 _57 ~3 820 50.50~9O000.50 -37 38 634 50.0049.001.00 -9 14 531 50.5048.5~1.00 -106 68 738 50.7048.301.00 -170 94 896 50.0048.S01.50 -113 -2 724 49.0049.002.00 . 6 -4 427 49.5048.502.00 -62 1 634 49.904~.102.00 ~168 11 807 ~8.0049.003.00 22 -3 393 48.5048.503.00 -42 -3 552 49.1047.903.00 -153 -5 793 48.5047~504~00 -87 6 710 45.5048.506.00 8 ~ 621 ~7.0047.006.00 -34 -2 820 . ' .
~ 7~
.
The composition oE the alloy of this invention can be described by reference to an area on a nickel, titaniumS
and copper ternary composition diagram. The general area of the alloy on the composition diagram is shown by the small triangle in Figure 1. This area of the composition diagram is enlarge~ and shown in Figure 2.
The compositions at the pointst A, B~ C, D, and E are shown in Table 2 below.
Table 2 Atomic Percent Composition Point Nickel Titanium Copper ~ 49.7 48~8 1.5 B 47.5 47.5 5.0 C 47.5 43.5 g.0 D 47~5 46.0 6.5 E 48.9 46.8 4.3 The lines AB and BC correspond approximately to an A50 o -50C, while the line AC corresponds to the stability -limit of these alloys; alloys to the right of khe line, or ~ith a lower copper concentration than at point A, are generally un~table with respect to manufacturing conditions.
As the extent of thermally recoverable plastic deformation (shape memory) that can be induced in these alloys decreases with decreasing titanium content, the particularly preferred alloys of this invention will lie nearer vertex A (the high titanium vertex) of the triangle ABC
of Figure 2, within the quadrilateral ABDE.
..
..
L~ ~ 8 It has been found that the alloys of this invention possess machinability which is unexpectedly considerably better than would be predicted from similar Ni/Ti alloys. While not wishing to be held to any particular theory, it is considered that this free-machining property of the alloys is related to the presence of a second phase, possibly Ti2(Ni,Cu)3, in the TiNi matrix. It is therefore considered that this improved machinability will manifest itself only when the titanium content is below the stoichiometric value and the Ti:Ni:Cu ratio is such as to favor the formation of the second phase.
In addition to the method described in the Example, alloys according to the invention may be manufactured from their components (or appropriate master alloys) 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 melting in an inert atmosphere or in vacuum, are well Xnown to those skilled in the art and are not repeated here.
Alloys obtained by these methods and using the materials described will contain small quanities oE 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 transform-ation temperature of the alloys.
7~
: . . .: .
The alloys of this invention possess good temper stability, are hot-workable, and are free-machining;
- in contrast to prior art alloys. They are also capable of possessing shape memory, and have an A50 below -50C and above the boil.ing point of liquid nitrogen
Claims (3)
1. A shape memory alloy consisting essentially of nickel, titanium, and copper within an area defined on a nickel, titanium, and copper ternary composition diagram by a triangle ABC with vertex A at 49.7 atomic percent nickel, 48.8 atomic percent titanium, and 1.5 atomic percent copper; vertex B at 47.5 atomic percent nickel, 47.5 atomic percent titanium, and 5.0 atomic percent copper; and vertex C at 47.5 atomic percent nickel, 43.5 atomic percent titanium, and 9.0 atomic percent copper.
2. A shape memory alloy according to Claim 1 wherein the composition lies within an area defined on a nickel, titanium, and copper ternary composition diagram by a quadrilateral ABDE with vertex A at 49.7 atomic percent nickel, 48.8 atomic percent titanium, and 1.5 atomic percent copper; vertex B at 47.5 atomic percent nickel, 47.5 atomic percent titanium, and 5.0 atomic percent copper; vertex D at 47.5 atomic percent nickel, 46.0 atomic percent titanium, and 6.5 atomic percent copper;
and vertex E at 48.9 atomic percent nickel, 46.8 atomic percent titanium, and 4.3 atomic percent copper.
and vertex E at 48.9 atomic percent nickel, 46.8 atomic percent titanium, and 4.3 atomic percent copper.
3. A article possessing the property of shape memory which is made from an alloy as defined in Claims 1 or 2.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US184,602 | 1980-09-05 | ||
| US06/184,602 US4337090A (en) | 1980-09-05 | 1980-09-05 | Heat recoverable nickel/titanium alloy with improved stability and machinability |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1176488A true CA1176488A (en) | 1984-10-23 |
Family
ID=22677580
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000385277A Expired CA1176488A (en) | 1980-09-05 | 1981-09-04 | Nickel/titanium copper shape memory alloys |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4337090A (en) |
| EP (1) | EP0047639B1 (en) |
| JP (1) | JPS5779138A (en) |
| AT (1) | ATE12525T1 (en) |
| CA (1) | CA1176488A (en) |
| DE (1) | DE3169690D1 (en) |
| GB (1) | GB2083501B (en) |
| SG (1) | SG58287G (en) |
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| ITMI20141346A1 (en) | 2014-07-24 | 2016-01-24 | Getters Spa | SAILS FOR BOATS INCLUDING SHAPE MEMORY MATERIAL ELEMENTS, APPARATUS AND METHOD FOR THEIR OPERATION |
| US20180140321A1 (en) | 2016-11-23 | 2018-05-24 | C. R. Bard, Inc. | Catheter With Retractable Sheath And Methods Thereof |
| US11596726B2 (en) | 2016-12-17 | 2023-03-07 | C.R. Bard, Inc. | Ultrasound devices for removing clots from catheters and related methods |
| US10758256B2 (en) | 2016-12-22 | 2020-09-01 | C. R. Bard, Inc. | Ultrasonic endovascular catheter |
| US10582983B2 (en) | 2017-02-06 | 2020-03-10 | C. R. Bard, Inc. | Ultrasonic endovascular catheter with a controllable sheath |
| CN107008905B (en) * | 2017-02-25 | 2018-08-17 | 河北工业大学 | The preparation method of TiNiCu marmem based damping composite materials |
| CN107523719B (en) * | 2017-09-22 | 2019-09-20 | 北京航空航天大学 | A kind of novel high rigidity NiTi based alloy |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3174851A (en) * | 1961-12-01 | 1965-03-23 | William J Buehler | Nickel-base alloys |
| US3351463A (en) * | 1965-08-20 | 1967-11-07 | Alexander G Rozner | High strength nickel-base alloys |
| US3558369A (en) * | 1969-06-12 | 1971-01-26 | Us Navy | Method of treating variable transition temperature alloys |
| NL7002632A (en) * | 1970-02-25 | 1971-08-27 | ||
| US3753700A (en) * | 1970-07-02 | 1973-08-21 | Raychem Corp | Heat recoverable alloy |
| DE2111372A1 (en) * | 1971-03-10 | 1972-09-28 | Siemens Ag | Brittle, oxidn resisting titanium nickelide - for use as powder in batteries |
| US3740839A (en) * | 1971-06-29 | 1973-06-26 | Raychem Corp | Cryogenic connection method and means |
| US4198081A (en) * | 1973-10-29 | 1980-04-15 | Raychem Corporation | Heat recoverable metallic coupling |
| NL171933C (en) * | 1975-03-03 | 1983-06-01 | Oce Van Der Grinten Nv | COPIER. |
| CH606456A5 (en) * | 1976-08-26 | 1978-10-31 | Bbc Brown Boveri & Cie | |
| CH616270A5 (en) * | 1977-05-06 | 1980-03-14 | Bbc Brown Boveri & Cie |
-
1980
- 1980-09-05 US US06/184,602 patent/US4337090A/en not_active Expired - Lifetime
-
1981
- 1981-09-04 EP EP81304038A patent/EP0047639B1/en not_active Expired
- 1981-09-04 AT AT81304038T patent/ATE12525T1/en not_active IP Right Cessation
- 1981-09-04 DE DE8181304038T patent/DE3169690D1/en not_active Expired
- 1981-09-04 GB GB8126903A patent/GB2083501B/en not_active Expired
- 1981-09-04 CA CA000385277A patent/CA1176488A/en not_active Expired
- 1981-09-04 JP JP56140225A patent/JPS5779138A/en active Granted
-
1987
- 1987-07-14 SG SG582/87A patent/SG58287G/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP0047639B1 (en) | 1985-04-03 |
| SG58287G (en) | 1987-10-23 |
| ATE12525T1 (en) | 1985-04-15 |
| GB2083501B (en) | 1984-08-15 |
| EP0047639A2 (en) | 1982-03-17 |
| EP0047639A3 (en) | 1982-03-24 |
| US4337090A (en) | 1982-06-29 |
| GB2083501A (en) | 1982-03-24 |
| JPH0335371B2 (en) | 1991-05-28 |
| DE3169690D1 (en) | 1985-05-09 |
| JPS5779138A (en) | 1982-05-18 |
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