US3529958A - Method for the formation of an alloy composed of metals reactive in their elemental form with a melting container - Google Patents

Method for the formation of an alloy composed of metals reactive in their elemental form with a melting container Download PDF

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US3529958A
US3529958A US592069A US3529958DA US3529958A US 3529958 A US3529958 A US 3529958A US 592069 A US592069 A US 592069A US 3529958D A US3529958D A US 3529958DA US 3529958 A US3529958 A US 3529958A
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tini
alloy
crucible
alloys
melting
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William James Buehler
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C22C1/023—Alloys based on nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting

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  • the present invention relates to a method and apparatus for forming alloys, and more particularly for forming alloys composed of component metals that are reactive in their elemental form with the melting container such as a crucible.
  • Some of these alternate prior art methods include arcmelting, both of the consumable and non-consumable type, utilizing an inert water-cooled copper crucible to contain the melt; another known technique, the so-called levitation melting which utilizes electrical induction to both melt and suspend the molten alloy in the induced field, is not an economical or commercially feasible technique though producing excellent high purity alloys.
  • TiNi base-type alloys refers to the TiNi alloys as described in U.S. Pat. 3,174,851 as well as to those ternary, intermediate alloys, such as TiNi Co TiNi Fe etc., as described in the co-pending application Ser. No. 579,185, filed on Sept. 9, 1966, in the name of Fred Wang and William J. Buehler, which discloses the addition of Co, Fe, etc.
  • the present invention is therefore concerned with a method of and apparatus for forming, within a suitable container or crucible, relatively unreactive alloys, from highly reactive component metals without undue contamination during the fusion and alloy formation as well as with a method of and apparatus for realizing solid cast ingots from the melt characterized by great ingot efficiency.
  • the present invention makes use of this particular discovery and phenomenon of slow rate and limited solubility of the near equi-atomic TiNi alloys for carbon, and essentially consists in so charging a graphite crucible as to prevent direct contact between the elemental Ti and Ni with the walls of the graphite crucible.
  • the longer period of time to handle the molten alloys as allowed by the use of the present invention has obvious advantages in commercial production, for example, as regards the mixing, composition adjustment, purification, etc.
  • the minute limited quantity of TiC particles in the TiNi matrix which may form in the course of the method according to the present invention, are widely and uniformly dispersed and are insignificant and can be completely neglected for all practical purposes.
  • the present invention is concerned with ingot solidification techniques and suitable mold design therefor to promote greatest ingot efiiciency, i.e., to produce a solid cast ingot free of liquid-to-solid shrinkage porosity.
  • Another object of the present invention resides in a method and apparatus for forming, within a suitable container or crucible, relatively unreactive alloys from highly reactive component metals without undue contamination during the fusion and alloy formation.
  • a further object of the present invention resides in a method and apparatus for induction melting titanium and nickel to form TiNi base alloys and related alloys containing reactive elements in a graphite or other suitable carbonaceous crucible without the danger of contamination and resulting non-homogeneity.
  • a still further object of the present invention resides in a method and apparatus for induction melting alloys containing highly reactive component metals in containers normally reacting with these component metals which not only benefit from the associated mixing, composition control and adjustment, purification and temperature control features attendant to induction melting methods but completely and effectively avoid the danger of a rapid reaction of these reactive component metals with the crucible or container used for the melt.
  • Still another object of the present invention resides in a method and apparatus for forming alloys that are reactive in their elemental form with the melting container which can be carried out on a commercial scale in a highly economic manner.
  • Still a further object of the present invention resides in a method for producing TiNi base alloys which are chemically homogeneous without the need for repeated melting and cycling.
  • Another object of the present invention resides in a method for forming TiNi-base alloys which does not require rapid handling, yet assures completely reproducible compositions of chemically homogeneous nature.
  • a further object of the present invention resides in a method and apparatus for improving the ingot solidification by properly accommodating the liquid-to-solid shrinkage and thus minimizing the shrinkage pipe, porosity, etc.
  • FIGS. 1a and 1b are schematic views showing two extremes possible in random distribution of Ti and Ni metals created by indiscriminately charging elements to the graphite crucible.
  • FIGS. 2a, 2b and 2c are schematic views illustrating three different modifications of charging schemes for carrying out the method in accordance with the present invention in order to minimize the actual contact between elemental Ti and Ni with the graphite crucible during induction melting.
  • FIGS. 3a and 3b are schematic views illustrating two possible faults in charging to be avoided by the present invention.
  • FIG. 4 is a diagram showing the transistion temperature as a function of composition of a TiNi-base alloy.
  • FIG. 5 is a diagram illustrating the solidification range of various TiNi-base alloy compositions.
  • FIG. 6 is a partial schematic cross-sectional view illustrating the solidification shrinkage of the molten base alloy in a prior art mold and the resulting low pressure zone created between the solidification ingot and the mold walls.
  • FIG. 7a illustrates schematically an ingot obtained by the use of prior art molds.
  • FIG. 7b illustrates schematically a desirable ingot as obtained by the use of a mold in accordance with the present invention.
  • FIGS. 8a and 8b are schematic, cross-sectional views through mold designs in accordance with the present invention.
  • FIGS. 9a and 9b illustrate schematically the solidification in a prior art mold and in a mold according to the present invention.
  • FIGS. la and 1b which illustrate two statistical extremes, are given to describe the importance of charging as related to the present invention.
  • a predominance of Ti is in contact with graphite forming a large amount of TiC before the remaining Ti and Ni can alloy to form the relatively unreactive TiNi.
  • a predominance of Ni is in contact with the graphite; the Ni+C reaction can occur with its associated reaction rate to form a nickel carbide.
  • the present invention as a refinement to melting in a graphite crucible, only the relatively unre active T iNi alloy is permitted to come in contact with the graphite at all times during the alloying. This minimizes carbon pick-up in the melt, maintains a more constant Ti-to-Ni ratio based upon the initial charge, [and produlces consistent and predictable composition melts based upon experience, charge element purity, and empirical melting data.
  • FIG. 2a illustrates one charging scheme in accordance with the present invention; in this embodiment, a TiNi starter plate or scrap pieces of TiNi alloy (of known composition) are placed at the bottom of the graphite crucible, and mechanically mixed and compacted titanium plus nickel blocks of proper mixture ratio are placed over the TiNi starter plate. The induction field then first melts the TiNi plate, having the lowest melting point of about 1,300 C. on the bottom of the graphite crucible.
  • this TiNi plate or scrap pieces are also melted first by virtue of the location thereof in the normally hottest section of the crucible. Following the initial melting of the pre-alloyed TiNi plate, the stacked blocks of mixed Ti-l-Ni would melt into the molten alloy pool forming additional molten alloy before any elemental Ti and/or Ni could come in contact with the graphite crucible walls. This process is continued until the entire charge is molten and alloyed.
  • FIG. 2b illustrates an alternative arrangement for charging the graphite crucible to achieve the objects of the present invention.
  • a starter plate of TiNi-base alloy or scraps of TiNi-base alloy are placed at the bottom of the graphite crucible.
  • the crucible is thereupon induction heated in a conventional manner and the elemental Ti and Ni metals are then simultaneously metered into the molten pool of the TiNi-base alloy with the rate controlled in any conventional known manner to prevent Ti and/or Ni coming in direct contact with the graphite. Since numerous devices for simultaneously charging the elemental metals as well as for controlling the charging rate thereof are known in the art and are commercially available, a detailed description is dispensed with herein.
  • FIGS. 3a and 3b illustrate the only possible contact between the hote graphite crucible and elemental Ti or Ni as might occur in following the method illustrated in FIG. 2a.
  • Tilting can be arrested by having the stack of compacted blocks guided through holes in their centers by a pre-alloyed rod that is fastened in a proper vertical position above the crucible.
  • the stacked blocks can similarly be centered and fed vertically through a suitable alloy tube (matching the melt) positioned concentrically in the graphite crucible.
  • the problem of excessive column weight causing the stacked blocks to contact the graphite crucible bottom as shown in FIG. 3b can be avoided by releasing the blocks to the molten alloy pool, from above, one or more at a time to allow the buoyancy or viscosity of the molten alloy pool to float the block or blocks until the elements thereof are dissolved into the molten alloy.
  • FIG. illustrates still another alternative for lowering a Ti+Ni mixture to avoid the shortcomings mentioned in connection with FIGS. 3a and 3b.
  • the graphite crucible again contains a starter plate or scrap pieces forming a molten TiNi base alloy at the bottom thereof.
  • the Ti+Ni mixture itself is lowered in this embodiment into the molten pool of the T iNi base alloy within a can of Ni.
  • the can is constituted by a cylindrical sheet of Ni in the form of a tubular member spot welded into the proper shape with a Ni sheet bottom spot welded to the tubular member.
  • a guide rod is secured to the cylindrical tubular Ni casing by means of TiNi-base alloy straps or wires.
  • the rate of lowering the T iNi mixture within the Ni can is carefully chosen in accordance with the principles set forth above; when the TiNi straps or wires connecting the Ni can to the guide rod get into the melt and fuse, the guide rod can then be withdrawn.
  • melts of the TiNi type base alloy are possible with very definite homogeneity and composition control.
  • the actual process of induction melting may be accomplished in a chamber where the pressure can vary from a few microns to more than one atmosphere. However, Where the chamber pressure exceeds a few microns, it is preferable to utilize an atmosphere of dry, inert gas such as argon, helium, etc.
  • the induction melting itself only requires sufficient power and proper frequency such as, for example, 3,000 cycles, to rapidly melt the charge and, following melting, to promote suitable melt stirring.
  • the latter which is inherently produced when utilizing induction melting is necessary to maintain proper alloy mixing and chemical homogeneity.
  • EXAMPLE The following is an illustrative step-by-step melting operation used to prepare a composition-controlled TiNi base alloy in accordance with the present invention though it is understood that the various steps thereof can be modified and changed within the scope of a person skilled in the art.
  • the equipment utilized for carrying out the present invention includes a conventional vacuum-melting furnace having a chamber, an induction coil, temperature monitoring devices, an induction power supply, gas inlet ports, a vacuum pumping system etc. Since such vacuum melting furnaces are known, per se, in the prior art, and form no part of the present invention, a detailed description is dispensed with herein.
  • a source of purified inert gases such as helium or argon is desirable.
  • a conventional high-purity and dense graphite crucible of any suitable capacity is used. The latter should preferably be thoroughly dried by pre-firing in a vacuum.
  • a suitable mold is used for casting the ingot from the melt as will be described more fully hereinafter.
  • High purity component metals such as Ti sponge, Ni shot, and elemental additions for instance Co, Fe, etc. are used for charging the graphite crucible.
  • the melting chamber is closed tightly and pumped to a reasonably low vacuum, for example, to a vacuum of less than 10 microns.
  • the chamber is thereupon refilled partially to a predetermined pressure with dry argon or helium.
  • the pressure is chosen in relation to the temperature and charge element purity (particularly entrapped gases, e.g., 0 N H H O, etc.) to prevent violent boiling as will also be described more fully hereinafter.
  • the crucible will get hot from the bottom to the top. It is preferred according to the present invention that the crucible get hottest in the zone near the TiNi alloy piece. This can be assured by positioning the crucible in such a manner to assure most efiicient heating (coupling) at the crucible bottom.
  • melt temperature is adjusted to a level between 100 and 200 C. above the melting point of the alloy in question, and the melt is poured in the vacuum.
  • the amount of partially refilling the chamber to a predetermined pressure should be such that no violent boiling would occur, yet not excessive so as to waste argon or helium. Again, a balance would normally be struck between the requirements and the economic factors.
  • TiNi and alloys based on TiNi have rather limited ranges of solidification.
  • the fact that TiNi and its alloys solidify over a narrow range presents both an advantage as well as a disadvantage.
  • the advantage lies in the chemical homogeneity of the solidified melt.
  • the disadvantage lies in the area of producing a solid cast ingot free of liquid-to-solid shrinkage porosity.
  • the TiNi base melt is poured into a mold of conventional construction in a vacuum and at a temperature only slightly above the melting point, the melt solidifies in the mold and forms initially a shell that separates from the mold wall as illustrated in FIG. 6. As a result thereof, a continuous gap forms around the solidified alloy shell. Since the gap is at the chamber pressure, it is essentially a vacuum. Owing to the presence of the gap, the heat transfer from the ingot to the mold and from the mold to the furnace wall will be mostly by radiation. This poses a serious problem in producing an ingot that is efficient in terms of limited piping and porosity without altering the chemical homogeneity of the solidified material.
  • FIG. 7a illustrates an ingot obtained with a conventional mold. This ingot not only shows a large shrinkage pipe but also shows other objectionable porosity due to the aforementioned problems in the solidification.
  • FIG. 7b represents an ingot obtained in accordance with the present invention which is devoid of porosity and large piping.
  • the mold which may be of any suitable material such as graphite is generally designated in FIG. 8a by reference numeral 10 and includes a base portion 11 and a cylindrical neck portion 12.
  • the cylindrical neck portion 12 is of substantially constant thickness and passes over into the reinforced, wider base portion 11 by way of a transition portion 13 having downwardly outwardly flaring external walls 13 connecting the cylindrical external walls 12' of the neck portion 12 with the cylindrical external walls 11' of the base portion.
  • the neck portion 12, the transition portion 13, as well as the base portion 11 have surfaces so constructed and arranged as to offer an interior mold design of cylindrical shape.
  • the mold may also have any other desired shape.
  • a cylindrical rim portion 14 which adjoins the upper end of the neck portion 12 projects radially outwardly substatnially at right angle with respect to neck portion 12.
  • a heater element generally designated by reference numeral 15 and of any conventional construction such as a resistance heater, an induction heater, and the like surrounds the neck portion 12 of the mold and may even extend over a part of the transition portion 13.
  • the heater element may be such as to produce a uniform amount of heat per length or may also be so arranged and constructed, for example, by appropriate spacing of the windings of the resistance or induction coil as to produce a properly proportioned amount of heat in the various parts of the mold.
  • FIG. 8b which is a modified embodiment of a mold in accordance with the present invention, differs from FIG. 8a by the use of a water-cooled copper container.
  • FIG. 8b again consists of a graphite mold generally designated by reference numeral 10 which includes a base portion 11, a neck portion 12, and a transition portion 13.
  • the base portion 11 is placed into a copper container 16 of appropriate shape so that the outer wall surfaces of the base portion 11 are in contact with the inner wall portions of the copper container 16.
  • the copper container 16 may be water-cooled by any conventional means.
  • a suitable heater element such as heater 15 of FIG. 8a and a rim portion 14 may also be provided with the mold of FIG. 81).
  • FIG. 9a illustrates what takes place in a conventional mold in which liquid TiNi pockets are formed causing problems in porosity and producing an internal and disconnected piping in the final ingot.
  • FIG. 9b illustrates what takes place when utilizing the mold of FIG. 8b in which the solidified TiNi has a temperature T about equal to the heated wall 12, 13 of the mold having a temperature of T This latter design causes the heat of the alloy to be extracted downward and outward and provides continued solidification from bottom to top. However, a delicate heat transfer balance must be maintained, too slow cooling may produce some degradation of alloy homogeneity.
  • composition control from melt to melt.
  • the TiNi base alloys are essentially a matrix with the above non-metallic inclusions dispersed in this matrix. Since the unique proper-ties of the TiNi base alloys are dependent principally upon the matrix composition (e.g., martensitic transition temperature, acoustic damping, mechanical memory, hardening capability, etc. as described in 'U.S. Pat. 3,174,851) it is of prime importance in alloying to produce the desired and consistent matrix compositions and be able to conclusively determine the matrix composition.
  • the teachings of this application provide an economical and desirable method of preparing quality and controlled alloys. To determine the matrix composition of near stoichiometric TiNi alloys on the other hand requires a unique approach.
  • the transition temperature for the four alloys given in Table I are very similar, yet experimental errors in chemical analysis and for the above stated reasons, the Ni composition is shown to vary plus or minus 0.4 percent by weight. This is indicative of the usefulness of acoustic damping (internal friction) as an analytical tool in connection with near stoichiometric TiNi binary alloys and Co and Fe substituted ternary combinations thereof.
  • the amount of pick-up of C from the graphite crucible when using the present invention, is consistently nominal and of a value completely insignificant to the properties of the alloys as shown by the small increase in the amount of C in the alloy, when starting with a constant amount of C in the charge composition. Yet this insignificant increase is a substantially consistent amount which allows a consistent empirical variation in the charge to yield a final alloy with a predetermined matrix composition.
  • the method of determining the matrix composition by measuring the internal friction is also particularly suitable for use during the production of the alloy.
  • Small amounts of a sample of the molten alloy may be removed from the crucible, for example, by way of a vacuum-lock system, may then be cooled and thereupon subjected to a test for determining the internal friction of the sample, e.g., by measuring the acoustic damping thereof. All of this can be done while the alloy is still in molten condition in the crucible so that the matrix composition in the crucible can be adjusted by the selective addition of either nickel or tita nium as may be required from the results of this test to produce the desired matrix composition in the final alloy product.
  • internal friction refers to the amount of acoustic energy absorbed in a given material and converted into some other form of energyas determined, for example, by measuring the acoustic damping characteristics of a given material.
  • the present invention is not limited thereto but is susceptible of numerous changes and modifications as known to a person skilled in the art; for example, the methods and apparatus of the present invention may also be used for forming alloys and casting ingots of other metals which possess the same characteristics to the crucible material in their elemental and alloyed condition and which exhibit the same solidification characteristics.
  • the mold according to the present invention may be used in lieu of the so-called Hot-Top type mold or in conjunction therewith; in the latter case the Hot Top is placed on top of the ingot mold in the usual manner.
  • the auxiliary heating means 15 may also be extended to the Hot Top selecting a suitable number and distribution of turns to achieve the desired temperature gradients.
  • any conventional graphite crucible may be used, such as conventional high-density, high-purity graphite crucibles, pyrolytic graphite crucibles, etc.
  • the mold may be made of any known appropriate material, though graphite molds are also suitable for the present invention.
  • a method for forming carefully controlled compositions of TiNi-base alloys composed of metals reactive in their elemental form with a graphite crucible comprising the steps of placing into the graphite crucible a prealloyed material of the alloy type to be obtained, heating by external application of power the contents in the crucible to a predetermined temperature above the melting point of the pre-alloyed material, and thereupon charging and melting the component metals in the molten alloy within the crucible in such a manner as to substantially prevent direct contact between the component metals and the crucible walls and in such proportion that the molten alloy stays within such range as will not pick up substantial amounts of graphite from the crucible.
  • a method according to claim 13 characterized in that an inert atmosphere is provided during the melting of the component metals within the crucible.
  • TiNi-base alloy is a near equi-atomic TiNi-base alloy.
  • a method for forming carefully controlled compositions of TiNi-base alloys reactive in their elemental form with a graphite crucible comprising the steps of drying the crucible, placing on the bottom of the crucible at least one piece of a TiNi base alloy of predetermined composition, evacuating the melting chamber within the crucible to a predetermined vacuum, refilling the chamber partially to some predetermined pressure with an inert gas, heating the crucible to a temperature above the melting temperature of the piece of TiNi-base alloy, charging and melting the component metals of the alloy in the molten TiNi-base alloy in such a manner as to prevent direct contact between the component metals and the crucible walls and in such proportion that the molten alloy stays within such range as will not pick up substan tial amounts of graphite from the crucible, maintaining the temperature in said chamber at a predetermined temperature above the melting point of the alloy, gradually reducing the pressure in said chamber, and thereafter pouring the molten alloy for subsequent processing.

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3598168A (en) * 1968-10-14 1971-08-10 Trw Inc Titanium casting process
US3985177A (en) * 1968-12-31 1976-10-12 Buehler William J Method for continuously casting wire or the like
US4007770A (en) * 1975-03-05 1977-02-15 Amax Inc. Semi-consumable electrode vacuum arc melting process for producing binary alloys
US4079523A (en) * 1976-11-08 1978-03-21 The International Nickel Company, Inc. Iron-titanium-mischmetal alloys for hydrogen storage
US4168182A (en) * 1975-11-11 1979-09-18 Motoren- Und Turbinen-Union Munchen Gmbh Method of producing shaped metallic parts
US4282033A (en) * 1980-06-16 1981-08-04 The United States Of America As Represented By The Secretary Of The Navy Melting method for high-homogeneity precise-composition nickel-titanium alloys
US4304613A (en) * 1980-05-12 1981-12-08 The United States Of America As Represented By The Secretary Of The Navy TiNi Base alloy shape memory enhancement through thermal and mechanical processing
US4310354A (en) * 1980-01-10 1982-01-12 Special Metals Corporation Process for producing a shape memory effect alloy having a desired transition temperature
EP0409794A1 (en) 1989-07-21 1991-01-23 Energy Conversion Devices, Inc. Alloy preparation of hydrogen storage material
WO1991001480A1 (en) * 1989-07-20 1991-02-07 Harold Brandt Adhesive template tape
US6548013B2 (en) 2001-01-24 2003-04-15 Scimed Life Systems, Inc. Processing of particulate Ni-Ti alloy to achieve desired shape and properties

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113358591B (zh) * 2021-07-09 2023-01-31 王春莲 一种食品质量安全检测用食用菌探测金属探测装置

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US841178A (en) * 1904-04-16 1907-01-15 John D Prince Process of mixing metals.
US1003806A (en) * 1911-01-06 1911-09-19 Titanium Alloy Mfg Co Article composed of titanium and nickel alloyed together and method of producing the same.
US2159169A (en) * 1936-12-24 1939-05-23 Mautsch Robert Electric furnace for melting metals
US2291865A (en) * 1939-05-17 1942-08-04 Chemical Marketing Company Inc Process for the production of metal alloys
US2822269A (en) * 1953-06-22 1958-02-04 Roger A Long Alloys for bonding titanium base metals to metals
US2854333A (en) * 1957-04-29 1958-09-30 Ethyl Corp Method and apparatus for forming liquid alloys of alkali metals
US3008821A (en) * 1959-06-17 1961-11-14 Union Carbide Corp Method of melting and alloying metals
US3075263A (en) * 1958-05-21 1963-01-29 Dow Chemical Co Apparatus for melting metals
US3130045A (en) * 1959-10-13 1964-04-21 Owens Illinois Glass Co Method of effecting exothermic reactions
US3174851A (en) * 1961-12-01 1965-03-23 William J Buehler Nickel-base alloys

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US841178A (en) * 1904-04-16 1907-01-15 John D Prince Process of mixing metals.
US1003806A (en) * 1911-01-06 1911-09-19 Titanium Alloy Mfg Co Article composed of titanium and nickel alloyed together and method of producing the same.
US2159169A (en) * 1936-12-24 1939-05-23 Mautsch Robert Electric furnace for melting metals
US2291865A (en) * 1939-05-17 1942-08-04 Chemical Marketing Company Inc Process for the production of metal alloys
US2822269A (en) * 1953-06-22 1958-02-04 Roger A Long Alloys for bonding titanium base metals to metals
US2854333A (en) * 1957-04-29 1958-09-30 Ethyl Corp Method and apparatus for forming liquid alloys of alkali metals
US3075263A (en) * 1958-05-21 1963-01-29 Dow Chemical Co Apparatus for melting metals
US3008821A (en) * 1959-06-17 1961-11-14 Union Carbide Corp Method of melting and alloying metals
US3130045A (en) * 1959-10-13 1964-04-21 Owens Illinois Glass Co Method of effecting exothermic reactions
US3174851A (en) * 1961-12-01 1965-03-23 William J Buehler Nickel-base alloys

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3598168A (en) * 1968-10-14 1971-08-10 Trw Inc Titanium casting process
US3985177A (en) * 1968-12-31 1976-10-12 Buehler William J Method for continuously casting wire or the like
US4007770A (en) * 1975-03-05 1977-02-15 Amax Inc. Semi-consumable electrode vacuum arc melting process for producing binary alloys
US4168182A (en) * 1975-11-11 1979-09-18 Motoren- Und Turbinen-Union Munchen Gmbh Method of producing shaped metallic parts
US4079523A (en) * 1976-11-08 1978-03-21 The International Nickel Company, Inc. Iron-titanium-mischmetal alloys for hydrogen storage
US4310354A (en) * 1980-01-10 1982-01-12 Special Metals Corporation Process for producing a shape memory effect alloy having a desired transition temperature
EP0033421B1 (en) * 1980-01-10 1985-08-28 Special Metals Corporation Process for producing a shape memory effect alloy having a desired transition temperature
US4304613A (en) * 1980-05-12 1981-12-08 The United States Of America As Represented By The Secretary Of The Navy TiNi Base alloy shape memory enhancement through thermal and mechanical processing
US4282033A (en) * 1980-06-16 1981-08-04 The United States Of America As Represented By The Secretary Of The Navy Melting method for high-homogeneity precise-composition nickel-titanium alloys
WO1991001480A1 (en) * 1989-07-20 1991-02-07 Harold Brandt Adhesive template tape
EP0409794A1 (en) 1989-07-21 1991-01-23 Energy Conversion Devices, Inc. Alloy preparation of hydrogen storage material
US6548013B2 (en) 2001-01-24 2003-04-15 Scimed Life Systems, Inc. Processing of particulate Ni-Ti alloy to achieve desired shape and properties

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DE1608113A1 (de) 1972-03-02
SE351682B (da) 1972-12-04
GB1213611A (en) 1970-11-25
AT288042B (de) 1971-02-25
ES346783A1 (es) 1969-03-01
DK135593B (da) 1977-05-23
NL6714971A (da) 1968-05-06
DE1608113B2 (de) 1973-01-18
AT301224B (de) 1972-08-25
DK135593C (da) 1977-11-07
BE706024A (da) 1968-03-18
CH519025A (de) 1972-02-15
NO123761B (da) 1972-01-10

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