EP0086013A2 - Material at least partly consisting of a component showing a one-way memory effect, and process for the manufacture thereof - Google Patents

Material at least partly consisting of a component showing a one-way memory effect, and process for the manufacture thereof Download PDF

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Publication number
EP0086013A2
EP0086013A2 EP83200129A EP83200129A EP0086013A2 EP 0086013 A2 EP0086013 A2 EP 0086013A2 EP 83200129 A EP83200129 A EP 83200129A EP 83200129 A EP83200129 A EP 83200129A EP 0086013 A2 EP0086013 A2 EP 0086013A2
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Prior art keywords
memory effect
way
component
way memory
produced
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EP83200129A
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German (de)
French (fr)
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EP0086013A3 (en
EP0086013B1 (en
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Joachim Dr. Albrecht
Thomas Dr. Duerig
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BBC Brown Boveri AG Switzerland
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BBC Brown Boveri AG Switzerland
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Priority to AT83200129T priority Critical patent/ATE23569T1/en
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    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/125—Deflectable by temperature change [e.g., thermostat element]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/125—Deflectable by temperature change [e.g., thermostat element]
    • Y10T428/12507—More than two components
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/125—Deflectable by temperature change [e.g., thermostat element]
    • Y10T428/12514—One component Cu-based
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12556—Organic component
    • Y10T428/12562—Elastomer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12556—Organic component
    • Y10T428/12569—Synthetic resin

Definitions

  • the invention relates to a material according to the preamble of claim 1 and a method according to the preamble of claim 5.
  • the invention has for its object to provide a new material based on Cu / Al / Ni and Cu / Al alloys and a corresponding method for its production, which has a considerable reversible two-way memory effect and is both for the production of semi-finished products in the form of bars, profiles and sheets, as well as components that can be used in practice.
  • Fig. 1 the longitudinal section through an embodiment of the material as a semi-finished product in bar form is shown.
  • Fig. La refers to the state after the first process step, Fig. Lb to the finished product.
  • 1 is the component showing the one-way memory effect (core material)
  • 2 is a metallic coating.
  • diffusion annealing creates the further component 3 as an edge zone (inactive zone) of the material in the form of a rod.
  • Fig. 2 shows the process flow and the means in the manufacture of the material in rod or strip form as a tri-metal.
  • 4 is the press cylinder of an extrusion press, 5 the corresponding press plunger (punch), 6 the die.
  • the latter advantageously has a relatively narrow tightening angle (corresponding to a cone angle in the case of round cross sections) in the tapered part.
  • 7 are the outer layers of a component of the compact which shows the one-way memory effect.
  • 8 represents the inner layer of the further (no memory 9) are the outer layers of the component of the finished material showing the one-way memory effect in cross-section (flat bar).
  • 10 is the inner layer consisting of the further (inactive) component of the finished material in cross section.
  • a powder-metallurgically produced alloy of the following composition belonging to the ⁇ -brass type was selected:
  • the memory alloy was transferred to a band 2.5 mm thick by hot rolling. Then a test rod with a square cross section 2.5 x 2.5 mm and a length of 35 mm was cut out of this tape.
  • This component corresponding to 1, which shows the one-way effect (core material) was provided on two opposite sides (preferably rolling sides) with a metallic coating 2 - in the present case nickel.
  • the nickel plating was carried out according to the electroless chemical method by immersing in a bath heated to 80 ° C. for 6 hours. The bath had the trade name "Electroless Nickel" (manufacturer: Oxy Metal Industries Congress SA, Avenches).
  • the coated rod was then subjected to an annealing treatment at a temperature of 900 ° C. for 30 minutes and quenched in water.
  • the nickel diffused into the Cu / Al / Ni core material and formed the edge zone representing the further component 3 (inactive zone). This measure changed the metallurgical composition of the latter compared to the core and thus also the physical properties.
  • the edge zone lost the properties of the classic memory alloy or, if it still existed, it was not used, at least in the temperature range of interest. What remained, however, was the highly elastic behavior of the edge zone. Well-known reversible two-way memory effects could be achieved with this material.
  • Example II The same alloy as in Example I was used as the starting material for the component showing the one-way effect.
  • Prismatic bodies were cut out of this material and assembled with a flat rod made of corrosion-resistant steel (18 Cr / 8 Ni) in such a way that a laminated body (sandwich) according to 7 and 8 of FIG. 2 was formed.
  • This pressing body of rectangular cross section was inserted into an extrusion press and pressed at a temperature of 800 ° C. to form a composite material in the form of a flat bar.
  • This type of tri-metal can be produced in practically any cross-section and commercially available lengths. A well-known two-way memory effect was measured on him.
  • the starting materials for the two components had the same alloy composition as in Example II (Cu / Al / Ni and Cr / Ni steel).
  • a round rod made of Cr / Ni steel was coaxially placed in the middle of a capsule made of soft, low-carbon steel (St 35) with a height of 200 mm, an outer diameter of 80 mm and a wall thickness of 2 mm of 5 mm in diameter.
  • the free space of the capsule was then filled with Cu / Al / Ni powder and the capsule was evacuated, welded and hot-isostatically pressed at 950 ° C. for 3 hours under a pressure of 140 MPa.
  • the casing made of soft steel was removed by mechanical processing and the pressed body made of composite material was hammered in several steps to the desired finished size (rod shape) at a temperature of 850 ° C.
  • the following alloy was selected as the starting material for a composite material for the first component (one-way memory effect):
  • a sintered round rod of 20 mm diameter was first produced from the first component using powder metallurgical methods by pre-compressing and sintering the powder mixture.
  • a tube with an inner diameter of 20 mm and a wall thickness of 2 mm was made from the Ti / Ni / Cu / Fe alloy manufactured, in which the round bar just fit. The latter was inserted into the pipe in such a way that it was just stuck.
  • the composite material prepared in this way was then heated to a temperature of 850 ° C. and, at this temperature, reduced to a diameter of 10 mm in several passes by rotary hammering.
  • the cross-sectional decrease per stitch was approx. 20%.
  • the round hammering produced a solid, compact composite material that had a significant two-way memory effect.
  • the second, inactive component forming the edge zone only exploited its highly elastic properties, but not its memory effects, which are also inherently present (they are not in the temperature range of interest).
  • the material is basically made up of several layers (at least two), with at least one component showing a one-way memory effect and at least one further component which inhibits the one-way effect of the former by internal tension. This condition can already be in the normal state, but must be fulfilled at the latest in the operating state, ie taking temperature and external loads into account.
  • the material can be in the form of a bar, wire, tube, profile, sheet or strip in the form of a semi-finished product, so that it can be further processed into individual components at least when cold.
  • All materials exhibiting this property come as the starting material for the first component which shows the one-way memory effect.
  • Another way of building materials consists in the fact that the layers, based on the first (active) and the second (inactive) components, essentially belong to the same type of alloy (eg Cu / Al / Ni), whereby the transitions can be fluid.
  • their compositions must differ chemically and their physical properties, particularly with regard to memory effects, must also be qualitatively different.
  • soldering, welding, roll cladding, extrusion or other metallurgical processes and gluing can be used as the manufacturing process for connecting the components with different physical properties.
  • two-layer (bimetal) or three-layer (trimetal) materials can be produced.
  • the material can be produced from the individual components using powder metallurgy and further processed into semi-finished bimetallic or trimetal products. This can be done by cold compression, sintering and extrusion, or by hot isostatic pressing with possibly round hammers.
  • an additional corrosion protection layer of, for example, 5 to 100 .mu.m thick can be applied or produced in the edge zone. The latter of course also applies to all other manufacturing processes.
  • the composite material does not necessarily have to consist only of metallic components.
  • the inactive second component can be a high-strength, highly elastic, heat-resistant plastic, which in turn is made of various components (including reinforcement materials) can be constructed. The condition is that the plastic can withstand the elastic movements without damage and tolerates the temperatures that occur during operation.
  • the new material and the corresponding manufacturing process give the person skilled in the art a means of considerably expanding the area of application of the two-way memory effect, in particular in the temperature range between approximately 100 ° C. and 200 ° C. This applies above all to the construction of switches, relays and temperature triggers.

Abstract

Material, in the form of bars, tubes, profiles, wires, sheets, or bands, which is, at least partially, composed of a constituent showing a one-way shape memory effect, and a further inactive constituent hindering the one-way effect of the first, and which collectively exhibits a significant two-way effect. The one-way shape memory constituent can be a Cu-Al-Ni, Cu-Al, TiV, Ti-Nb, Ni-Ti, or Ni-Ti-Cu alloy. Production of bi- or multi-constituent components by brazing, welding, roll bonding, extruding, powder metallurgical methods, hot isostatic pressing, or gluing, or by the application of metallic coatings (2) onto a core material (1) and subsequent diffusion treatment to produce an inactive surface layer (3).

Description

Die Erfindung geht aus von einem Werkstoff nach der Gattung des Oberbegriffs des Anspruchs 1 sowie einem Verfahren nach der Gattung des Oberbegriffs des Anspruchs 5.The invention relates to a material according to the preamble of claim 1 and a method according to the preamble of claim 5.

Bei den Gedächtnislegierungen kann man im allgemeinen einen sog. Zweiwegeffekt von einem Einwegeffekt unterscheiden. Während letzterer in der Regel ausgeprägter und bekannter ist (Ni/Ti-Legierungen, β-Messinge) und auch zu zahlreichen Anwendungen geführt hat, ist der Zweiwegeffekt problematischer und schwieriger zu beherrschen. Doch besteht in der Technik ein allgemeines Bedürfnis nach Bauelementen aus Werkstoffen, welche einen quantitativ genügend grossen Zweiwegeffekt zeigen, um ein weiteres interessantes Anwendungsgebiet zu erschliessen. Meist liegt nun jedoch der Punkt der martensitischen Umwandlung der klassischen Zweiwegeffekt-Legierungen in einem ungünstigen Temperaturbereich. Es gibt jedoch eine Anzahl von Gedächtnislegierungen, vorab die dem /9-Messingtyp angehörenden klassischen Cu/Al/Ni- und Cu/Al-Legierungen, deren Umwandlungspunkt günstig liegt, die zwar wohl einen deutlichen Einweg- aber kaum einen namhaften Zweiwegeffekt zeigen.In the case of memory alloys, a so-called two-way effect can generally be distinguished from a one-way effect. While the latter is generally more pronounced and well-known (Ni / Ti alloys, β-brasses) and has also led to numerous applications, the two-way effect is more problematic and difficult to master. However, there is a general need in technology for components made of materials which have a quantitatively large enough two-way effect to open up another interesting area of application. Most of the time, however, the point of the martensitic transformation of the classic two-way effect alloys lies in an unfavorable temperature range. However, there are a number of memory alloys, in particular the classic Cu / Al / Ni and Cu / Al alloys belonging to the / 9 brass type, whose transformation point is favorable, which may have a clear one-way but hardly a well-known two-way effect.

Als Stand der Technik können u.a. folgende Dokumente angeführt werden:

  • R.Haynes, Some Observations on Isothermal Transformations of Eutectoid Aluminium Bronzes Below Their MS Temperatures, Journal of the Institute of Metals 1954-55, Vol. 83, Seiten 357-358; W.A.Rachinger, A "super-elastic" single Crystal calibration bar, British Journal of Applied Physics, Vol.9, Juni 1958, Seiten 250-252; R.P.Jewett, D.J.Mack.Further Investigation of Copper-Aluminium Alloys in the Temperature Range below the
    Figure imgb0001
    Eutectoid, Journal of the Institute of Metals 1963-64, Vol. 92, Seiten 59-61; K.Otsuka and K.Shimizu, Memory Effect and Thermoelastic Martensite Transformation in Cu-Al-Ni Alloy, Scripta Metallurgia, Vol. 4, 1970 Pergamon Press Inc., Seiten 469-472; Kazuhiro Otsuka, Origin of Memory Effect in Cu-Al-Ni Alloy, Japanese Journal of Applied Physics, Vol. 10, No. 5, May 1971, Seiten 571-579; US-PS 3 783 037.
The following documents can be cited as state of the art:
  • R. Haynes, Some Observations on Isothermal Transformations of Eutectoid Aluminum Bronzes Below Their MS Temperatures, Journal of the Institute of Metals 1954-55, Vol. 83, pp. 357-358; WARachinger, A "super-elastic" single crystal calibration bar, British Journal of Applied Physics, Vol.9, June 1958, pages 250-252; RPJewett, DJMack.Further Investigation of Copper-Aluminum Alloys in the Temperature Range below the
    Figure imgb0001
     Eutectoid, Journal of the Institute of Metals 1963-64, Vol. 92, pages 59-61; K.Otsuka and K. Shimizu, Memory Effect and Thermoelastic Martensite Transformation in Cu-Al-Ni Alloy, Scripta Metallurgia, Vol. 4, 1970 Pergamon Press Inc., pages 469-472; Kazuhiro Otsuka, Origin of Memory Effect in Cu-Al-Ni Alloy, Japanese Journal of Applied Physics, Vol. 10, No. 5, May 1971, pages 571-579; U.S. Patent 3,783,037.

Es besteht daher ein Bedürfnis nach Bauelementen aus Gedächtnislegierungen des β-Messingtyps, welche bei für gewisse Anwendungen günstig liegender Umwandlungstemperatur einen namhaften Zweiwegeffekt aufweisen.There is therefore a need for components made of memory alloys of the β-brass type which have a well-known two-way effect at a transformation temperature which is favorable for certain applications.

Der Erfindung liegt die Aufgabe zugrunde, einen neuen Werkstoff auf der Basis von Cu/Al/Ni- und Cu/Al-Legierungen sowie ein entsprechendes Verfahren zu dessen Herstellung anzugeben, welcher einen beträchtlichen reversiblen Zweiweg-Gedächtniseffekt aufweist und sich sowohl zur Fabrikation von Halbzeug in Stangen-, Profil- und Blechform wie von für die Praxis brauchbaren Bauelementen eignet.The invention has for its object to provide a new material based on Cu / Al / Ni and Cu / Al alloys and a corresponding method for its production, which has a considerable reversible two-way memory effect and is both for the production of semi-finished products in the form of bars, profiles and sheets, as well as components that can be used in practice.

Diese Aufgabe wird durch die im kennzeichnenden Teil des Anspruchs 1 sowie des Anspruchs 5 angegebenen Merkmale gelöst.This object is achieved by the features specified in the characterizing part of claim 1 and claim 5 solved.

Die Erfindung wird anhand der nachfolgenden, durch Figuren näher erläuterten Ausführungsbeispiele beschrieben.The invention is described on the basis of the following exemplary embodiments which are explained in more detail by means of figures.

Dabei zeigen:

  • Fig. 1 eine Ausbildung des Werkstoffs in Form von Halbzeug (Stab),
  • Fig. 2 den Verfahrensablauf beim Strangpressen als Methode der Herstellung des Werkstoffs in Form von Trimetall.
Show:
  • 1 shows an embodiment of the material in the form of a semi-finished product (rod),
  • Fig. 2 shows the process flow during extrusion as a method of manufacturing the material in the form of trimetal.

In Fig. 1 ist der Längsschnitt durch eine Ausbildung des Werkstoffs als Halbzeug in Stabform dargestellt. Fig. la bezieht sich auf den Zustand nach dem ersten Verfahrensschritt, Fig. lb auf das Fertigerzeugnis. 1 ist die den Einweg-Gedächtniseffekt zeigende Komponente (Kernwerkstoff), 2 stellt einen metallischen Ueberzug dar. Durch Diffusionsglühung wird als Endergebnis die weitere Komponente 3 als Randzone (inaktive Zone) des Werkstoffs in Stabform gebildet.In Fig. 1 the longitudinal section through an embodiment of the material as a semi-finished product in bar form is shown. Fig. La refers to the state after the first process step, Fig. Lb to the finished product. 1 is the component showing the one-way memory effect (core material), 2 is a metallic coating. As a result, diffusion annealing creates the further component 3 as an edge zone (inactive zone) of the material in the form of a rod.

Fig. 2 zeigt den Verfahrensablauf und das Mittel bei der Herstellung des Werkstoffs in Stab- oder Bandform als Trimetall. 4 ist der Presszylinder einer Strangpresse, 5 der entsprechende Pressplunger (Stempel), 6 die Matrize. Letztere weist vorteilhafterweise einen verhältnismässig schlanken Anzugswinkel (entsprechend Konuswinkel im Fall von Rundquerschnitten) im sich verjüngenden Teil auf. 7 sind die äusseren Schichten aus einer den Einweg-Gedächtniseffekt zeigenden Komponente des Presskörpers. 8 stellt die innere Schicht der weiteren (keinen Gedächtniseffekt aufweisenden) Komponente des Presskörpers dar. 9 sind die äusseren Schichten der den Einweg-Gedächtniseffekt zeigenden Komponente des fertigen Werkstoffs im Querschnitt (Flachstab). 10 ist die innere Schicht bestehend aus der weiteren (inaktiven) Komponente des fertigen Werkstoffs im Querschnitt.Fig. 2 shows the process flow and the means in the manufacture of the material in rod or strip form as a tri-metal. 4 is the press cylinder of an extrusion press, 5 the corresponding press plunger (punch), 6 the die. The latter advantageously has a relatively narrow tightening angle (corresponding to a cone angle in the case of round cross sections) in the tapered part. 7 are the outer layers of a component of the compact which shows the one-way memory effect. 8 represents the inner layer of the further (no memory 9) are the outer layers of the component of the finished material showing the one-way memory effect in cross-section (flat bar). 10 is the inner layer consisting of the further (inactive) component of the finished material in cross section.

Ausführungsbeispiel I:Embodiment I: Siehe Fig. 1.See Figure 1.

Als Ausgangsmaterial für die den Einweg-Gedächtniseffekt zeigende Komponente wurde eine dem β-Messingtyp angehörende, pulvermetallurgisch hergestellte Legierung der nachfolgenden Zusammensetzung gewählt:

Figure imgb0002
As the starting material for the component showing the one-way memory effect, a powder-metallurgically produced alloy of the following composition belonging to the β-brass type was selected:
Figure imgb0002

Die Gedächtnislegierung wurde durch Warmwalzen in ein Band von 2,5 mm Dicke übergeführt. Daraufhin wurde aus diesem Band ein Probestab von quadratischem Querschnitt 2,5 x 2,5 mm und 35 mm Länge herausgeschnitten. Diese, den Einwegeffekt zeigende Komponente entsprechend 1 (Kernwerkstoff) wurde auf zwei gegenüberliegenden Seiten (vorzugsweise Walzseiten) mit einem metallischen Ueberzug 2 - im vorliegenden Fall Nickel - versehen. Die Vernickelung erfolgte nach dem stromlosen chemischen Verfahren durch Eintauchen in ein auf 80°C erwärmtes Bad während 6 h. Das Bad führte den Handelsnamen "Electroless Nickel" (Hersteller: Oxy Metal Industries Suisse SA, Avenches). Der beschichtete Stab wurde anschliessend bei einer Temperatur von 900°C während 30 min einer Glühbehandlung unterworfen und in Wasser abgeschreckt. Dabei diffundierte das Nickel in den Cu/Al/Ni-Kernwerkstoff hinein und bildete die die weitere Komponente 3 darstellende Randzone (inaktive Zone). Durch diese Massnahme wurde die metallurgische Zusammensetzung der letzteren gegenüber dem Kern und somit auch die physikalischen Eigenschaften verändert. Die Randzone verlor die Eigenschaften der klassischen Gedächtnislegierung oder, falls noch vorhanden, wurden diese zumindest im interessierenden Temperaturbereich nicht ausgenutzt. Was jedoch blieb, war das hochelastische Verhalten der Randzone. Mit diesem Werkstoff konnten namhafte reversible Zweiweg-Gedächtniseffekte erzielt werden.The memory alloy was transferred to a band 2.5 mm thick by hot rolling. Then a test rod with a square cross section 2.5 x 2.5 mm and a length of 35 mm was cut out of this tape. This component corresponding to 1, which shows the one-way effect (core material), was provided on two opposite sides (preferably rolling sides) with a metallic coating 2 - in the present case nickel. The nickel plating was carried out according to the electroless chemical method by immersing in a bath heated to 80 ° C. for 6 hours. The bath had the trade name "Electroless Nickel" (manufacturer: Oxy Metal Industries Suisse SA, Avenches). The coated rod was then subjected to an annealing treatment at a temperature of 900 ° C. for 30 minutes and quenched in water. The nickel diffused into the Cu / Al / Ni core material and formed the edge zone representing the further component 3 (inactive zone). This measure changed the metallurgical composition of the latter compared to the core and thus also the physical properties. The edge zone lost the properties of the classic memory alloy or, if it still existed, it was not used, at least in the temperature range of interest. What remained, however, was the highly elastic behavior of the edge zone. Well-known reversible two-way memory effects could be achieved with this material.

Ausführungsbeispiel II:Working example II: Siehe Fig. 2.See Figure 2.

Als Ausgangsmaterial für die den Einwegeffekt zeigende Komponente wurde die gleiche Legierung wie in Beispiel I verwendet. Aus diesem Material wurden prismatische Körper herausgeschnitten und derart mit einem Flachstab aus korrosionsbeständigem Stahl (18 Cr/8 Ni) zusammengestellt, dass ein Schichtkörper (Sandwich) gemäss 7 und 8 der Fig.2 gebildet wurde. Dieser Presskörper rechteckigen Querschnitts wurde in eine Strangpresse eingeführt und bei einer Temperatur von 800°C zu einem Verbundwerkstoff in Form eines Flachstabes verpresst. Diese Art Trimetall kann in praktisch beliebigen Querschnitten und kommerziell gängigen Längen hergestellt werden. Es wurde an ihm ein namhafter Zweiweg-Gedächtniseffekt gemessen.The same alloy as in Example I was used as the starting material for the component showing the one-way effect. Prismatic bodies were cut out of this material and assembled with a flat rod made of corrosion-resistant steel (18 Cr / 8 Ni) in such a way that a laminated body (sandwich) according to 7 and 8 of FIG. 2 was formed. This pressing body of rectangular cross section was inserted into an extrusion press and pressed at a temperature of 800 ° C. to form a composite material in the form of a flat bar. This type of tri-metal can be produced in practically any cross-section and commercially available lengths. A well-known two-way memory effect was measured on him.

Ausführungsbeispiel III:Working example III:

Die Ausgangsmaterialien für die beiden Komponenten hatten die gleiche Legierungszusammensetzung wie im Beispiel II (Cu/Al/Ni und Cr/Ni-Stahl). In eine als Umhüllung dienende Kapsel aus weichem, niedriggekohlten Stahl (St 35) von 200 mm Höhe, 80 mm Aussendurchmesser und 2 mm Wandstärke wurde in die Mitte koaxial ein Rundstab aus Cr/Ni-Stahl von 5 mm Durchmesser gestellt. Dann wurde der freie Raum der Kapsel mit Cu/Al/Ni-Pulver ausgefüllt und die Kapsel evakuiert, verschweisst und bei 950°C während 3 h unter einem Druck von 140 MPa heiss-isostatisch gepresst. Nach dem heiss-isostatischen Pressen wurde die Umhüllung aus weichem Stahl durch mechanische Bearbeitung entfernt und der gepresste Körper aus Verbundwerkstoff durch Rundhämmern bei einer Temperatur von 850°C in mehreren Schritten auf das gewünschte Fertigmass (Stabform) gebracht.The starting materials for the two components had the same alloy composition as in Example II (Cu / Al / Ni and Cr / Ni steel). A round rod made of Cr / Ni steel was coaxially placed in the middle of a capsule made of soft, low-carbon steel (St 35) with a height of 200 mm, an outer diameter of 80 mm and a wall thickness of 2 mm of 5 mm in diameter. The free space of the capsule was then filled with Cu / Al / Ni powder and the capsule was evacuated, welded and hot-isostatically pressed at 950 ° C. for 3 hours under a pressure of 140 MPa. After the hot-isostatic pressing, the casing made of soft steel was removed by mechanical processing and the pressed body made of composite material was hammered in several steps to the desired finished size (rod shape) at a temperature of 850 ° C.

Ausführungsbeispiel IV:Working example IV:

Als Ausgangsmaterialien für einen Verbundwerkstoff wurde für die erste Komponente (Einweg-Gedächtniseffekt) die folgende Legierung gewählt:

Figure imgb0003
The following alloy was selected as the starting material for a composite material for the first component (one-way memory effect):
Figure imgb0003

Als zweite Komponente (inaktives, superelastisches Material) diente eine Legierung der nachfolgenden Zusammensetzung:

Figure imgb0004
An alloy of the following composition was used as the second component (inactive, superelastic material):
Figure imgb0004

Aus der ersten Komponente wurde zunächst nach pulvermetallurgischen Methoden durch Vorverdichten und Sintern der Pulvermischung ein gesinterter Rundstab von 20 mm Durchmesser hergestellt. Aus der Ti/Ni/Cu/Fe-Legierung wurde ein Rohr von 20 mm Innendurchmesser und 2 mm Wandstärke gefertigt, in welches der Rundstab gerade hineinpasste. Letzterer wurde derart in das Rohr eingeschoben, dass er gerade festsass. Dann wurde das auf diese Weise vorbereitete Verbundmaterial auf eine Temperatur von 850°C erhitzt und bei dieser Temperatur in mehreren Stichen durch Rundhämmern auf einen Durchmesser von 10 mm reduziert. Die Querschnittsabnahme pro Stich betrug ca. 20 %. Durch das Rundhämmern wurde ein fester, kompakter Verbundwerkstoff erzeugt, der einen bedeutenden Zweiweg-Gedächtniseffekt aufwies. Dabei ist zu betonen, dass bei der zweiten, inaktiven, die Randzone bildenden Komponente lediglich ihre hochelastischen Eigenschaften, nicht aber deren von Natur aus ebenfalls vorliegenden Gedächtniseffekte (sie liegen nicht im interessierenden Temperaturgebiet) ausgenutzt wurden.A sintered round rod of 20 mm diameter was first produced from the first component using powder metallurgical methods by pre-compressing and sintering the powder mixture. A tube with an inner diameter of 20 mm and a wall thickness of 2 mm was made from the Ti / Ni / Cu / Fe alloy manufactured, in which the round bar just fit. The latter was inserted into the pipe in such a way that it was just stuck. The composite material prepared in this way was then heated to a temperature of 850 ° C. and, at this temperature, reduced to a diameter of 10 mm in several passes by rotary hammering. The cross-sectional decrease per stitch was approx. 20%. The round hammering produced a solid, compact composite material that had a significant two-way memory effect. It should be emphasized that the second, inactive component forming the edge zone only exploited its highly elastic properties, but not its memory effects, which are also inherently present (they are not in the temperature range of interest).

Die Erfindung ist nicht auf die vorstehenden Ausführungsbeispiele beschränkt. Grundsätzlich ist der Werkstoff aus mehreren Schichten (mindestens zwei) aufgebaut, wobei mindestens eine, einen Einweg-Gedächtniseffekt zeigende Komponente und mindestens eine weitere Komponente vorhanden sein muss, die den Einwegeffekt der ersteren durch innere Verspannung hemmt. Diese Bedingung kann schon im Normalzustand, muss aber spätestens im Betriebszustand, d.h. unter Berücksichtigung von Temperatur und von aussen wirkender Belastung erfüllt sein. Der Werkstoff kann als Halbzeug in Stangen-, Draht-, Rohr-, Profil-, Blech- oder Bandform vorliegen, so dass er mindestens im kalten Zustand zu einzelnen Bauteilen weiterverarbeitet werden kann. Als Ausgangsmaterial für die erste, den Einweg-Gedächtniseffekt zeigenden Komponente kommen alle,diese Eigenschaft aufweisenden Materialien, besonders Cu/Al/Ni-, Cu/Al-, Cu/Zn/Al-, Ti/V-, Ti/Nb-, Ni/Ti- und Ni/Ti/Cu-Legierungen in Frage. Eine weitere Möglichkeit des Werkstoffaufbaus besteht darin, dass die Schichten, bezogen auf die erste (aktive) und die zweite (inaktive) Komponente im wesentlichen dem gleichen Legierungstyp (z.B. Cu/Al/Ni) angehören, wobei die Uebergänge fliessend sein können. Ihre Zusammensetzungen müssen sich-jedoch chemisch unterscheiden und ihre physikalischen Eigenschaften, insbesondere bezüglich Gedächtniseffekt müssen ebenfalls qualitativ unterschiedlich sein. Dies kann z.B. durch Erhöhung des Nickelgehalts in der Randzone geschehen, wobei das Plateau der superelastischen Dehnung nach anderen Spannungswerten verschoben wird. Dadurch wird die Kernzone an der freien Entfaltung des Einwegeffekts gehemmt und es stellt sich ein Zweiwegeffekt ein.The invention is not restricted to the above exemplary embodiments. The material is basically made up of several layers (at least two), with at least one component showing a one-way memory effect and at least one further component which inhibits the one-way effect of the former by internal tension. This condition can already be in the normal state, but must be fulfilled at the latest in the operating state, ie taking temperature and external loads into account. The material can be in the form of a bar, wire, tube, profile, sheet or strip in the form of a semi-finished product, so that it can be further processed into individual components at least when cold. All materials exhibiting this property, in particular Cu / Al / Ni, Cu / Al, Cu / Zn / Al, Ti / V, Ti / Nb, come as the starting material for the first component which shows the one-way memory effect. Ni / Ti and Ni / Ti / Cu alloys in question. Another way of building materials consists in the fact that the layers, based on the first (active) and the second (inactive) components, essentially belong to the same type of alloy (eg Cu / Al / Ni), whereby the transitions can be fluid. However, their compositions must differ chemically and their physical properties, particularly with regard to memory effects, must also be qualitatively different. This can be done, for example, by increasing the nickel content in the peripheral zone, whereby the plateau of the superelastic elongation is shifted to other stress values. As a result, the core zone is inhibited from free development of the one-way effect and a two-way effect occurs.

Als Herstellungsverfahren zur Verbindung der Komponenten mit unterschiedlichen physikalischen Eigenschaften können grundsätzlich Löten, Schweissen, Walzplattieren, Strangpressen oder andere metallurgische Verfahren sowie Kleben herangezogen werden. Es können auf diese Weise u.a. Zwei- schicht-(Bimetall) cder auch Dreischicht-(Trimetall) Werkstoffe hergestellt werden. Der Werkstoff kann pulvermetallurgisch aus den einzelnen Komponenten hergestellt und zu Bimetall- oder Trimetall-Halbzeug weiterverarbeitet werden. Dies kann durch Kaltverdichten, Sintern und Strangpressen oder durch heiss-isostatisches Pressen mit ev. nachgeschaltetem Rundhämmern erfolgen. Dabei kann gleichzeitig oder anschliessend noch zusätzlich eine Korrosionsschutzschicht von z.B. 5 bis 100 µ Dicke aufgebracht oder in der Randzone erzeugt werden. Dies letztere gilt selbstverständlich auch für alle anderen Herstellungsverfahren. Der Verbundwerkstoff braucht nicht notwendigerweise nur aus metallischen Komponenten zu bestehen. Die inaktive zweite Komponente kann ein hochfester, hochelastischer, wärmebeständiger Kunststoff sein, der seinerseits wieder aus verschiedenen Komponenten (inklusive Bewehrungsmaterialien) aufgebaut sein kann. Bedingung ist, dass der Kunststoff die elastischen Bewegungen ohne Schaden mitmacht und die im Betrieb auftretenden Temperaturen verträgt.Basically, soldering, welding, roll cladding, extrusion or other metallurgical processes and gluing can be used as the manufacturing process for connecting the components with different physical properties. In this way, two-layer (bimetal) or three-layer (trimetal) materials can be produced. The material can be produced from the individual components using powder metallurgy and further processed into semi-finished bimetallic or trimetal products. This can be done by cold compression, sintering and extrusion, or by hot isostatic pressing with possibly round hammers. At the same time or subsequently, an additional corrosion protection layer of, for example, 5 to 100 .mu.m thick can be applied or produced in the edge zone. The latter of course also applies to all other manufacturing processes. The composite material does not necessarily have to consist only of metallic components. The inactive second component can be a high-strength, highly elastic, heat-resistant plastic, which in turn is made of various components (including reinforcement materials) can be constructed. The condition is that the plastic can withstand the elastic movements without damage and tolerates the temperatures that occur during operation.

Durch den neuen Werkstoff und das entsprechende Herstellungsverfahren wird dem Fachmann ein Mittel in die Hand gegeben, den Anwendungsbereich des Zweiweg-Gedächtniseffekts insbesondere im Temperaturbereich zwischen etwa 100°C und 200°C beträchtlich zu erweitern. Dies betrifft vor allem den Schalter-, Relais- und Temperaturauslöserbau.The new material and the corresponding manufacturing process give the person skilled in the art a means of considerably expanding the area of application of the two-way memory effect, in particular in the temperature range between approximately 100 ° C. and 200 ° C. This applies above all to the construction of switches, relays and temperature triggers.

Claims (15)

1. Werkstoff, welcher mindestens teilweise aus einer einen Einweg-Gedächtniseffekt zeigenden sowie mindestens aus einer weiteren Komponente aufgebaut ist, dadurch gekennzeichnet, dass er aus mehreren Schichten unterschiedlicher Zusammensetzung und unterschiedlicher physikalischer Eigenschaften besteht, die entweder bereits im Normalzustand, spätestens aber im Zustand bei Betriebstemperatur derart gegeneinander verspannt sind, dass die aus der den Einweg-Gedächtniseffekt zeigenden Komponente aufgebaute Schicht mindestens teilweise an der freien Entfaltung dieses Einwegeffekts gehemmt wird und dass der Werkstoff als Ganzes mindestens-in einer bevorzugten Richtung einen Zweiweg-Gedächtniseffekt aufweist.1.Material which is at least partially composed of a one-way memory effect and at least one further component, characterized in that it consists of several layers of different composition and different physical properties, which are either already in the normal state, but at the latest in the state Operating temperature are braced against each other in such a way that the layer built up from the component showing the one-way memory effect is at least partially inhibited from free development of this one-way effect and that the material as a whole has a two-way memory effect at least in a preferred direction. 2. Werkstoff nach Anspruch 1, dadurch gekennzeichnet, dass er in Stangen-, Draht-, Rohr-, Profil-, Blech- oder Bandform vorliegt und mindestens im kalten Zustand zu einzelnen Bauteilen weiterverarbeitet werden kann.2. Material according to claim 1, characterized in that it is in rod, wire, tube, profile, sheet metal or strip form and can be processed at least in the cold state to individual components. 3. Werkstoff nach Anspruch 1, dadurch gekennzeichnet, dass seine den Einweg-Gedächtniseffekt zeigende Komponente eine Cu/Al/Ni-, Cu/Al-, Cu/Zn/Al-, Ti/V-, Ti/Nb-, Ni/Ti- oder Ni/Ti/Cu-Legierung ist.3. Material according to claim 1, characterized in that its component showing the one-way memory effect is a Cu / Al / Ni, Cu / Al, Cu / Zn / Al, Ti / V, Ti / Nb, Ni / Ti or Ni / Ti / Cu alloy. 4. Werkstoff nach Anspruch 1, dadurch gekennzeichnet, dass die Schichten im wesentlichen dem gleichen Legierungstyp angehören, sich jedoch chemisch voneinander unterscheiden und qualitativ unterschiedliche Gedächtniseigenschaften aufweisen, dergestalt, dass mindestens eine Schicht die andere oder die anderen Schichten an der Entfaltung des Einweg-Gedächtniseffektes hemmt.4. Material according to claim 1, characterized in that the layers essentially belong to the same alloy type, but differ chemically from one another and have qualitatively different memory properties, in such a way that at least one layer the other or the other layers at the unfolding of the one-way memory effect inhibits. 5. Verfahren zur Herstellung eines einen Zweiweg-Gedächtniseffekt aufweisenden Werkstoffs, dadurch gekennzeichnet, dass eine einen Einweg-Gedächtniseffekt zeigende Komponente mindestens einer weiteren Komponente mit hoher elastischer Dehnbarkeit derart zugeordnet wird, dass eine feste mechanische Verbindung der Komponenten vorliegt.5. A method for producing a material having a two-way memory effect, characterized in that a component showing a one-way memory effect is assigned to at least one other component with high elastic extensibility such that a firm mechanical connection of the components is present. 6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, dass die den Einweg-Gedächtniseffekt zeigende Komponente mit einer oder mehreren Schichten der weiteren Komponente durch Löten, S:hweissen, Walzplattieren, Strangpressen oder ein anderes metallurgisches Verbindungsverfahren oder durch Kleben zu einem festen hochelastischen Verbundwerkstoff zusammengefügt wird.6. The method according to claim 5, characterized in that the component showing the one-way memory effect is joined to one or more layers of the further component by soldering, welding: welding, roll cladding, extrusion or another metallurgical joining process or by gluing to form a solid, highly elastic composite material becomes. 7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, dass durch Verbindung einer den Einweg-Gedächtniseffekt zeigenden Komponente mit einer weiteren Schicht ein Zweischicht-Werkstoff in Form eines Bimetalls hergestellt wird.7. The method according to claim 6, characterized in that a two-layer material in the form of a bimetal is produced by connecting a component showing the one-way memory effect to a further layer. 8. Verfahren nach Anspruch 6, dadurch gekennzeichnet, dass durch Verbindung einer den Einweg-Gedächtniseffekt zeigenden Komponente mit zwei weiteren Schichten ein Drei- schicht-Werkstoff in Form eines Trimetalls hergestellt wird.8. The method according to claim 6, characterized in that a three-layer material in the form of a tri-metal is produced by connecting a component showing the one-way memory effect to two further layers. 9. Verfahren nach Anspruch 6, dadurch gekennzeichnet, dass durch Verkleben einer den Einweg-Gedächtniseffekt zeigenden Komponente mit einer oder zwei weiteren Schichten einer hochelastischen und hochfesten Kunststoffkomponente, welche ihrerseits wieder aus verschiedenen Komponenten aufgebaut sein kann, ein Zwei- oder Dreischicht-Werkstoff hergestellt wird.9. The method according to claim 6, characterized in that by gluing a component showing the one-way memory effect with one or two further layers of a highly elastic and high-strength plastic component, which in turn can be composed of different components, a two or three layer material is produced. 10. Verfahren nach Anspruch 5, dadurch gekennzeichnet, dass die den Einweg-Gedächtniseffekt zeigende Komponente als Kernwerkstoff (1) benutzt wird, dessen Oberfläche metallurgisch derart verändert wird, dass eine die weitere Komponente darstellende Randzone (3) mit vom Kernwerkstoff (1) abweichenden physikalischen Eigenschaften erzeugt wird.10. The method according to claim 5, characterized in that the component showing the one-way memory effect is used as the core material (1), the surface of which is changed metallurgically in such a way that an edge zone (3) representing the further component with the core material (1) is different physical properties is generated. 11. Verfahren nach Anspruch 10, dadurch gekennzeichnet, dass die Randzone (3) durch Aufbringen eines metallischen Ueberzugs (2) mit nachfolgendem Diffusionsglühen erzeugt wird.11. The method according to claim 10, characterized in that the edge zone (3) is produced by applying a metallic coating (2) with subsequent diffusion annealing. 12. Verfahren nach Anspruch 11, dadurch gekennzeichnet, dass die den Einweg-Gedächtniseffekt zeigende, als Kernwerkstoff (1) benutzte Komponente eine Cu/Al/Ni-oder Cu/Al-Legierung ist und dass die Randzone .(3) durch Aufbringen eines galvanischen Ueberzugs (2) von Nickel mit nachfolgendem Diffusionsglühen bei einer Temperatur von 9000C während 30 min erzeugt wird.12. The method according to claim 11, characterized in that the component which shows the one-way memory effect and is used as the core material (1) is a Cu / Al / Ni or Cu / Al alloy and that the edge zone (3) by applying a galvanic coating (2) of nickel with subsequent diffusion annealing at a temperature of 900 0 C is generated for 30 min. 13. Verfahren nach Anspruch 5, dadurch gekennzeichnet, dass der Werkstoff pulvermetallurgisch aus den einzelnen Komponenten hergestellt und zu einem Bimetall-oder Trimetall-Halbzeug weiterverarbeitet wird.13. The method according to claim 5, characterized in that the material is produced by powder metallurgy from the individual components and is further processed into a bimetal or trimetal semi-finished product. 14. Verfahren nach Anspruch 13, dadurch gekennzeichnet, dass der Werkstoff durch Kaltverdichten der Pulvermischung, Sintern und Strangpressen oder durch heiss-isostatisches Pressen der Pulvermischung mit gegebenenfalls nachgeschaltetem Rundhämmern hergestellt wird.14. The method according to claim 13, characterized in that the material is produced by cold compressing the powder mixture, sintering and extrusion or by hot-isostatic pressing of the powder mixture with, if appropriate, downstream rotary hammering. 15. Verfahren nach Anspruch 5, dadurch gekennzeichnet, dass der Werkstoff während oder nach der Herstellung zusätzlich mit einer 5 bis 10 µ dicken Korrosionsschutzschicht versehen wird.15. The method according to claim 5, characterized in that the material is additionally provided with a 5 to 10 micron thick corrosion protection layer during or after manufacture.
EP83200129A 1982-02-05 1983-01-26 Material at least partly consisting of a component showing a one-way memory effect, and process for the manufacture thereof Expired EP0086013B1 (en)

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ATE23569T1 (en) 1986-11-15
JPS58151242A (en) 1983-09-08
US4518444A (en) 1985-05-21
CH660882A5 (en) 1987-05-29
EP0086013A3 (en) 1983-09-21
DE3367625D1 (en) 1987-01-02
JPH0129144B2 (en) 1989-06-08
EP0086013B1 (en) 1986-11-12

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