EP0182182A1 - Method and apparatus for making silver base two-layer contacts for electrical switches - Google Patents
Method and apparatus for making silver base two-layer contacts for electrical switches Download PDFInfo
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- EP0182182A1 EP0182182A1 EP85113995A EP85113995A EP0182182A1 EP 0182182 A1 EP0182182 A1 EP 0182182A1 EP 85113995 A EP85113995 A EP 85113995A EP 85113995 A EP85113995 A EP 85113995A EP 0182182 A1 EP0182182 A1 EP 0182182A1
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- silver
- substrate
- contact piece
- layer
- alloy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H1/00—Contacts
- H01H1/02—Contacts characterised by the material thereof
- H01H1/021—Composite material
- H01H1/023—Composite material having a noble metal as the basic material
- H01H1/0237—Composite material having a noble metal as the basic material and containing oxides
- H01H1/02372—Composite material having a noble metal as the basic material and containing oxides containing as major components one or more oxides of the following elements only: Cd, Sn, Zn, In, Bi, Sb or Te
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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
- C22C1/10—Alloys containing non-metals
- C22C1/1078—Alloys containing non-metals by internal oxidation of material in solid state
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
- C23C26/02—Coating not provided for in groups C23C2/00 - C23C24/00 applying molten material to the substrate
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/10—Oxidising
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H1/00—Contacts
- H01H1/02—Contacts characterised by the material thereof
- H01H1/021—Composite material
- H01H1/023—Composite material having a noble metal as the basic material
- H01H1/0231—Composite material having a noble metal as the basic material provided with a solder layer
Definitions
- the invention relates to a method for producing silver-metal oxide materials.
- the invention also relates to a device for carrying out the method with a generator for energy radiation and an associated transmission device, and to contact pieces for electrical switching devices produced therewith.
- Metal-metal oxide materials are often used for contacts in low-voltage switchgear, especially relays and contactors. They are characterized by high burn-off resistance and low tendency to sweat.
- AgCdO materials AgSnO,; ms and AgZnO materials with further additions of oxides of less noble metals than silver have recently become particularly important.
- the metals bismuth (Bi), copper (Cu), indium (In), tantalum (Ta) and / or tungsten can be used, the latter also being able to exist in non-oxidized form.
- such materials can be produced, for example, by powder metallurgy, specifically by sintering and compacting either mixtures of silver and metal oxide powders or else previously internally oxidized silver alloy powders (IOLP). However, it can also be produced by internal oxidation of silver alloys in compact form.
- powder metallurgy specifically by sintering and compacting either mixtures of silver and metal oxide powders or else previously internally oxidized silver alloy powders (IOLP).
- IOLP internally oxidized silver alloy powders
- Silver-metal oxide materials produced by powder metallurgy are known, for example, from EP-OS 0024349 and from DE-OS 2260559.
- the internal oxidation of alloy powders to the so-called IOLP occupies an excellent position, with the IOLP being able to produce semi-finished products for contact pieces either by extrusion or contact pieces by pressing to form molded parts.
- both methods are also possible using two-layer technology, the second layer on the underside of the contact having to be open.
- GB-OS 2055398 proposes a silver metal oxide material which is produced by internal oxidation of a silver alloy substrate by diffusion of oxygen. It is known from DE-PS 2063649 to increase the concentration of atomic oxygen on the substrate surface compared to the oxygen concentration in thermal equilibrium and to ionize the oxygen by additional energy radiation in order to shorten the diffusion time.
- the internal oxidation in the alloy substrate has the disadvantage that comparatively long glow times are required in an oxygen atmosphere in order to achieve oxidation by solid-state diffusion of oxygen into the alloy substrate to depths of one or more millimeters.
- solid diffusion inevitably creates an inhomogeneous distribution with regard to oxide content and oxide size.
- the back of the alloy substrate must be protected against oxidation in the manufacture of contact pieces in order to retain a solderable layer.
- the object of the invention is to provide new process technologies and devices for the production of silver-metal oxide materials with which, in particular, contact pieces for switching devices in power engineering can be manufactured.
- the object is achieved in that an alloy substrate made of silver and other base metals is locally supplied with oxygen and that the oxygen is dissolved by locally melting the substrate by means of energy radiation in the melt formed in each case (so-called gas alloying) and in the oxide of the less noble Component is transferred ..
- the oxides of the base metal can be directly formed quantitatively.
- further heat treatment of the substrate may also be necessary for this, it being possible for the heat treatment to take place simultaneously with gas alloying or subsequently.
- further temperature treatments of the finished material can be carried out to optimize the structure.
- the supplied oxygen can be supplied using increased pressure.
- the oxygen can also be diluted by carrier gases, for example helium, so that an external plasma for controllable absorption of the energy is generated by the energy radiation.
- the energy radiation can advantageously be pulsed.
- the energy radiation is preferably generated by a high-power laser, which can be handled comparatively easily in terms of apparatus.
- the transmission device for the energy beam is assigned a gas supply nozzle whose angle and distance from the substrate can be changed.
- the flow rate and / or composition of the supplied Oxygen can be adjusted including any carrier gas that may be present.
- the so-called "gas alloy” is used for the first time for the internal oxidation of a silver alloy.
- the necessary energy radiation can also be generated by an electron or ion beam, by an arc or by an HF plasma.
- a blank can advantageously be processed as an alloy substrate first to a flat profile, sheet metal and / or strip of suitable thickness as a semi-finished product for the contact pieces and then gas alloyed from the surface to a predetermined depth .
- a band-shaped sheet of 2 mm thickness is rolled from an alloy blank with a diameter of 20 mm and a length of 100 mm. This sheet serves as a semi-finished product, from which the contact pieces can later be removed by cutting or punching.
- FIG. 1 shows a silver alloy substrate 1 rolled into a strip as a semi-finished product for contact pieces, which is scanned on the surface in two directions point by point by an energy beam transmission device 2.
- the energy beam transmission device 2 specifically transmits a laser beam 3 from an external high-power laser (not shown), for example a CO or argon laser, to the substrate 1 and is focused on the surface of the alloy substrate 1 and the energy radiation transmission device 2 hermetically sealed against the environment by means of suitable sealants 4.
- suitable sealants 4 There can be pressure, vacuum or inert gas systems, which may also allow foreign gases to be extracted.
- the substrate is expediently moved by means of an x, y feed table (not shown in FIG. 1) relative to the stationary laser beam 3.
- the associated tools are not described in detail.
- the laser beam can also be moved via mirror systems.
- a cannula 5 with a nozzle 6 is guided laterally in the energy beam transmission device 2, the angle a and the distance h thereof from the surface of the substrate 1 can be changed. In this way, the impingement area of the laser beam 3 on the surface of the substrate 1 can be specifically washed around with oxygen.
- the azimuth angle ⁇ (not shown in FIG. 1), i.e. the direction of the nozzle 6 in the xy plane can be changed. It is expediently chosen (in deviation from FIG 1) so that the gas flow takes place in the direction of the unmelted workpiece 1
- the oxygen can also be mixed with a carrier gas, for example helium.
- a carrier gas for example helium.
- the composition or flow rate of carrier gas and / or oxygen and the pressure in the reaction space can be specified by means of external dosing agents.
- the high-power laser works in pulse mode. With a suitable focusing, there is a focal spot on the surface of the substrate 1 of approximately 100 ⁇ m in diameter. If the energy density is sufficient, the oxygen supplied by means of the nozzle 6 is ionized and is already in atomic form. Due to the high-energy laser radiation, when the ignition point is reached, oxygen and any carrier gas present form a plasma, which is concentrated above the point of impact of the laser beam and is used for energy transfer into the alloy substrate 1. As a result, melting zones 8 form around the point of incidence of the laser beam on the substrate 1, metal atoms being able to pass into the plasma.
- a locally targeted melting of the material to a sufficient depth, for example up to 1.5 mm, can be achieved in less than a millisecond.
- the supplied oxygen is introduced into the melted area of the substrate and evenly distributed in the metallic melt by means of convection.
- the mass transfer via convection results in a homogeneous oxygen distribution in the melted area.
- a more or less large proportion of the oxygen is already present as an oxide.
- the amount of gas can be regulated by mixing it with a carrier gas and adjusting the feed nozzle 6 to the substrate 1. If a simultaneous or subsequent heat treatment is necessary for a complete oxidation of the base metal part or for a structure optimization of these oxides, the parameters for this must be selected depending on the thermodynamic behavior of the alloy system.
- a two-layer contact piece 10 can be produced from the layer material thus produced by punching out.
- This consists of a silver metal oxide layer 12 in the upper region and a silver alloy layer 11 in the lower region, which are clearly separated from one another. Due to the manufacturing process described, the local melting in melting lobes 8 results in a typical wave structure of the interface, which does not change fundamentally even during subsequent temperature treatments.
- Such a profiled interface is of no importance for the intended use as a contact piece; it is important that the two-layer contact piece with its silver alloy layer 1 1 can be easily soldered onto a contact carrier.
- an AgSn alloy with 8% by mass of tin was assumed.
- other AgSn or AgZn alloys can be used.
- these alloys in particular require additional additions of less noble metals than silver to ensure adequate switching behavior of the contact materials produced therefrom.
- Bismuth (Bi), copper (Cu), indium (In), tantalum (Ta) and / or tungsten (W), for example, have proven suitable. These metals are easily oxidized, and tungsten can also be present in non-oxidized form.
- AgC ⁇ -L alloys can be used to produce AgC ⁇ 0 contact materials with possibly further metal oxide additives.
- Gas alloying using laser radiation enables local melting areas with depths of up to 4 mm.
- laser radiation other energy transmission methods with which a beam of sufficient energy density can be generated, for example electron or ion beam, arc or HF plasma, energy density can also be generated, for example, are possible.
- contact pieces for electrical shading devices can be manufactured with a comparatively small number of process steps.
- the internal oxidation can now be achieved quickly, although the desired homogeneity of the metal oxide distribution and concentration is given
- the surface can be prepared by mechanical or chemical roughening in such a way as is required for the subsequent contact surface.
- this also results in increased energy absorption.
- special reworking of the surfaces is generally no longer necessary.
- the back of the alloy substrate is solderable even after laser gas alloying without the inclusion of metal oxides on the contact carrier.
- the alloy substrate 1 as a semi-finished product to the contact carrier and then to subject it to the laser treatment described above for internal oxidation.
- the latter is advantageous for automated production since, for example in the case of robot handling, the semi-finished product can be soldered on any side and a separate ordering process of the two-layer contact pieces according to the contact side and solder side is therefore unnecessary.
- the contact carriers can also be soldered onto the entire semi-finished strand, the internal oxidation can be carried out by laser gas alloying and the finished contacts can then be punched or cut.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Composite Materials (AREA)
- Contacts (AREA)
- Laser Beam Processing (AREA)
- Manufacture Of Switches (AREA)
- Coupling Device And Connection With Printed Circuit (AREA)
Abstract
Description
Die Erfindung bezieht sich auf ein Verfahren zum Herstellen von Silber-Metalloxid-Werkstoffen. Daneben bezieht sich die Erfindung auch auf eine Vorrichtung zur Durchführung des Verfahrens mit einem Erzeuger für Energiestrahlung und einer zugehörigen Übertragungseinrichtung sowie auf damit hergestellte Kontaktstücke für elektrische Schaltgeräte.The invention relates to a method for producing silver-metal oxide materials. In addition, the invention also relates to a device for carrying out the method with a generator for energy radiation and an associated transmission device, and to contact pieces for electrical switching devices produced therewith.
Metall-Metalloxid-Werkstoffe werden häufig für Kontaktstücke bei Niederspannungsschaltgeräten, insbesondere bei Relais und Schützen, eingesetzt. Sie zeichnen sich durch hohe Abbrandfestigkeit und geringe Schweißneigung aus. Neben den seit langem bekannten AgCdO-Materialien sind neuerdings insbesondere AgSnO,;ms und AgZnO-Materialien mit weiteren Zusätzen von Oxiden unedlerer Metalle als Silber von Bedeutung. Beispielsweise kommen die Metalle Wismut (Bi), Kupfer (Cu), Indium (In), Tantal (Ta) und/oder Wotfram in Frage, wobei letzteres auch in nichtoxidierter Form vorliegen kann.Metal-metal oxide materials are often used for contacts in low-voltage switchgear, especially relays and contactors. They are characterized by high burn-off resistance and low tendency to sweat. In addition to the long-known AgCdO materials, AgSnO,; ms and AgZnO materials with further additions of oxides of less noble metals than silver have recently become particularly important. For example, the metals bismuth (Bi), copper (Cu), indium (In), tantalum (Ta) and / or tungsten can be used, the latter also being able to exist in non-oxidized form.
Die Herstellung solcher Werkstoffe kann nach dem Stand der Technik beispielsweise pulvermetallurgisch erfolgen, und zwar durch Sintem und Verdichten von entweder Gemischen aus Silber- und Metalloxid-Puivem oder auch von vorher inneroxidierten Silber-Legierungspulvem (IOLP). Die Herstellung kann aber auch durch Inneroxidation von Silber-Legierungen in Kompaktform erfolgen.According to the state of the art, such materials can be produced, for example, by powder metallurgy, specifically by sintering and compacting either mixtures of silver and metal oxide powders or else previously internally oxidized silver alloy powders (IOLP). However, it can also be produced by internal oxidation of silver alloys in compact form.
Pulvermetallurgisch erzeugte Silber-Metalloxid-Werkstoffe sind beispielsweise aus der EP-OS 0024349 sowie aus der DE-OS 2260559 bekannt. Speziell die innere Oxidation von Legierungspulvem zum sogenannten IOLP nimmt dabei eine hervorragende Stellung ein, wobei aus dem IOLP entweder durch Strangpressen ein Halbzeug für Kontaktstücke oder durch Pressen zu Formteilen direkt Kontaktstücke gefertigt werden können. Beide Methoden sind prinzipiell auch in Zweischicht-Technik möglich, wobei die zweite Schicht auf der Kontaktunterseite löffähig sein muß.Silver-metal oxide materials produced by powder metallurgy are known, for example, from EP-OS 0024349 and from DE-OS 2260559. In particular, the internal oxidation of alloy powders to the so-called IOLP occupies an excellent position, with the IOLP being able to produce semi-finished products for contact pieces either by extrusion or contact pieces by pressing to form molded parts. In principle, both methods are also possible using two-layer technology, the second layer on the underside of the contact having to be open.
Nachteilig ist, daß bei den pulvermetallurgischen Verfahren mit relativ eng tolerierten Oxidations-, Reduktions-und Sinterschritten gearbeitet werden muß. Außerdem ist der Preßdruck so hoch zu wählen, daß die Restporosität des Werkstoffes die geforderte Größenordnung erreicht.It is disadvantageous that the powder metallurgical processes have to be operated with relatively narrowly tolerated oxidation, reduction and sintering steps. In addition, the pressure must be chosen so high that the residual porosity of the material reaches the required magnitude.
Mit der GB-OS 2055398 wird dagegen ein Silber-Metalloxid-Werkstoff vorgeschlagen, der durch Inneroxidation eines Silber-Legierungs-Substrats durch Eindiffusion von Sauerstoff erzeugt wird. Bekannt ist aus der DE-PS 2063649, die Konzentration von atomarem Sauerstoff an der Substratoberfläche gegenüber der SauerstoffKonzentration im thermischen Gleichgewicht zu erhöhen und durch zusätzliche Energiestrahlung den Sauerstoff zu ionisieren, um die Diffusionszeit zu verkürzen.GB-OS 2055398, on the other hand, proposes a silver metal oxide material which is produced by internal oxidation of a silver alloy substrate by diffusion of oxygen. It is known from DE-PS 2063649 to increase the concentration of atomic oxygen on the substrate surface compared to the oxygen concentration in thermal equilibrium and to ionize the oxygen by additional energy radiation in order to shorten the diffusion time.
Insgesamt ist aber bei der inneren Oxidation im Legierungssubstrat nachteilig, daß vergleichsweise lange Glühzeiten in einer Sauerstoffatmosphäre benötigt werden, um eine Oxidation durch Festkörperdiffusion von Sauerstoff in das Legierungs-Substrat bis in Tiefen von einem oder mehreren Millimetern zu erreichen. Daneben entsteht aufgrund der Festkörperdiffusion zwangsläufig eine inhomogene Verteilung hinsichtlich Oxidgehalt und Oxidgröße. Außerdem muß bei der Herstellung von Kontaktstücken die Rückseite des Legierungs-Substrals gegen die Oxidation geschützt werden, um eine lötfahige Schicht zurückzubehalten.Overall, however, the internal oxidation in the alloy substrate has the disadvantage that comparatively long glow times are required in an oxygen atmosphere in order to achieve oxidation by solid-state diffusion of oxygen into the alloy substrate to depths of one or more millimeters. In addition, solid diffusion inevitably creates an inhomogeneous distribution with regard to oxide content and oxide size. In addition, the back of the alloy substrate must be protected against oxidation in the manufacture of contact pieces in order to retain a solderable layer.
Aufgabe der Erfindung ist es demgegenüber, neue Verfahrenstechnologien und Vorrichtungen zur Herstellung von Silber-Metalloxid-Werkstoffen anzugeben, mit denen insbesondere Kontaktstücke für Schaltgeräte der Energietechnik gefertigt werden können.In contrast, the object of the invention is to provide new process technologies and devices for the production of silver-metal oxide materials with which, in particular, contact pieces for switching devices in power engineering can be manufactured.
Die Aufgabe ist erfindungsgemäß dadurch gelöst, daß einem Legierungs-Substrat aus Silber und weiteren unedlen Metallen Sauerstoff Örtlich gezielt zugefürt wird und daß der Sauerstoff durch Örtliches Aufschmelzen des Substrates mittels Energiestrahlung in der jeweils gebildeten Schmelze gelöst (sogenanntes Gaslegieren) und in das Oxid der unedleren Komponente überführt wird..The object is achieved in that an alloy substrate made of silver and other base metals is locally supplied with oxygen and that the oxygen is dissolved by locally melting the substrate by means of energy radiation in the melt formed in each case (so-called gas alloying) and in the oxide of the less noble Component is transferred ..
Bei der Erfindung können die Oxide der unedlen Metalle unmittelbar quantitativ gebildet werden. Es kann dazu aber auch eine weitere Wärmebehandlung des Substrats notwendig sein, wobei die Wärmebehandlung gleichzeitig beim Gaslegieren oder anschließend erfolgen kann. Darüber hinaus können weitere Temperaturbehandlungen des fertigen Werkstoffes zur Gefügeoptimierung erfolgen.In the invention, the oxides of the base metal can be directly formed quantitatively. However, further heat treatment of the substrate may also be necessary for this, it being possible for the heat treatment to take place simultaneously with gas alloying or subsequently. In addition, further temperature treatments of the finished material can be carried out to optimize the structure.
Bei der Erfindung kann der zugeführte Sauerstoff unter Anwendung erhöhten Druckes zugeführt werden. Der Sauerstoff kann auch durch Trägergase, beispielsweise Helium, verdünnt werden, so daß durch die Energiestrahlung ein Fremdplama zur steuerbaren Absorption der Energie erzeugt wird. Dabei kann die Energiestrahlung vorteilhafterweise gepulst sein.In the invention, the supplied oxygen can be supplied using increased pressure. The oxygen can also be diluted by carrier gases, for example helium, so that an external plasma for controllable absorption of the energy is generated by the energy radiation. The energy radiation can advantageously be pulsed.
Die Energiestrahlung wird im Rahmen der Erfindung vorzugsweise durch einen Hochleistungs-Laser erzeugt, der sich apparativ vergleichsweise einfach handhaben läßt Dabei ist der Übertragungseinrichtung für den Energiestrahl eine Gaszuführungsdüse zugeordnet, deren Winkel und Abstand gegenüber dem Substrat veränderbar ist Die Durchflußmenge und/oder Zusammensetzung des zugeführten Sauerstoffes-läßt sich einschließlich des gegebenenfalls vorhandenen Trägergases einstellen.In the context of the invention, the energy radiation is preferably generated by a high-power laser, which can be handled comparatively easily in terms of apparatus. The transmission device for the energy beam is assigned a gas supply nozzle whose angle and distance from the substrate can be changed. The flow rate and / or composition of the supplied Oxygen can be adjusted including any carrier gas that may be present.
Mit der Erfindung wird erstmalig das sogenannte "Gaslegieren" zur inneren Oxidation einer Silber-Legierung verwendet. Statt durch einen Laser kann die notwendige Energiestrahlung auch durch einen Elektronen- oder Ionenstrahl, durch einen Lichtbogen oder durch ein HF-Plasma erzeugt werden.With the invention, the so-called "gas alloy" is used for the first time for the internal oxidation of a silver alloy. Instead of using a laser, the necessary energy radiation can also be generated by an electron or ion beam, by an arc or by an HF plasma.
Insbesondere das Verfahren des Gaslegierens wurde bereits für das Aufkohlen oder Nitrieren von Stählen vorgeschlagen. Daneben ist das Umschmelzen von Werkstoffen mittels eines Lasers bekannt (Bergmann et al., Zeitschrift für Werkstofftechnik 14, 228 bis 237 (1983)). Der Erfindung lag nun die Erkenntnis zugrunde, daß das Gaslegieren bei Beherrschung der Systemparameter gezielt zur Oxidation von Silber-Legierungen mit Metallkomponenten, die unedler als Silber sind, und damit zur Herstellung von Silber-Metalloxid-Werkstoffen verwendet werden kann. Insbesondere für die Verwendung solcher Werkstoffe als Kontaktstücke für elektrische Schaftgeräte läßt sich vorteilhaft als Legierungs-Substrat ein Rohling zunächst zu einem Flachprofil, Blech und/ oder Band geeigneter Dicke als Halbzeug für die Kontaktstücke verarbeiten und anschließend von der Oberfläche her bis zu einer vorgegebenen Tiefe gaslegieren. Damit lassen sich unmittelbar ZweiSchichten-Kontaktstücke mit einer Silber-Metalloxid-Schicht auf der Kontaktseite und einer lötfähigen Silber-Legierungsschicht auf der Rückseite fertigen.In particular, the method of gas alloying has already been proposed for the carburizing or nitriding of steels. In addition, remelting of materials by means of a laser is known (Bergmann et al., Zeitschrift für Werkstofftechnik 14, 228 to 237 (1983)). The invention was based on the knowledge that gas alloys with control of the system parameters can be used specifically for the oxidation of silver alloys with metal components that are less noble than silver, and thus for the production of silver-metal oxide materials. Particularly for the use of such materials as contact pieces for electrical shaft devices, a blank can advantageously be processed as an alloy substrate first to a flat profile, sheet metal and / or strip of suitable thickness as a semi-finished product for the contact pieces and then gas alloyed from the surface to a predetermined depth . This means that two-layer contact pieces with a silver-metal oxide layer on the contact side and a solderable silver alloy layer on the back can be produced immediately.
Weitere Einzelheiten und Vorteile der Erfindung ergeben sich aus der nachfolgenden Beschreibung von Ausführungsbeispielen, wobei teilweise auf die Zeichnung Bezug genommen wird.Further details and advantages of the invention result from the following description of exemplary embodiments, reference being made in part to the drawing.
Es zeigen
- die Figur 1 schematisch eine Vorrichtung zum Oxidieren einer Silber-Legierung durch Laser-Gaslegieren und
Figur 2 ein damit gefertigtes Zweischichten-Kontaktstück.
- 1 shows schematically a device for oxidizing a silver alloy by laser gas alloying and
- Figure 2 is a two-layer contact piece made with it.
Es wird von einer AgSn-Legierung mit einer Zusammensetzung in Massenanteilen von 8 % Zinn ausgegangen. Aus einem Legierungsrohling mit 20 mm Durchmesser und 100 mm Länge wird ein bandförmiges Blech von 2 mm Stärke gewalzt Dieses Blech dient als Halbzeug, aus dem später durch Abschneiden oder Ausstanzen die Kontaktstücke heraustrennbar sind.An AgSn alloy with a composition in mass fractions of 8% tin is assumed. A band-shaped sheet of 2 mm thickness is rolled from an alloy blank with a diameter of 20 mm and a length of 100 mm. This sheet serves as a semi-finished product, from which the contact pieces can later be removed by cutting or punching.
In Figur 1 ist ein zu einem Band gewalztes Silber-Legierungs-Substrat 1 als Halbzeug für Kontaktstücke dargestellt, das auf der Oberfläche in zwei Richtungen punktweise von einer Energiestrahl-Übertragungseinrichtung 2 abgerastert wird. Dabei kann zweckmäßigerweise fortlaufend in parallelen Streifen abgerastert werden, wobei bei Wiederholungen Überlappungen oder eine Abrasterung in senkrechter Streifenrichtung möglich ist.FIG. 1 shows a silver alloy substrate 1 rolled into a strip as a semi-finished product for contact pieces, which is scanned on the surface in two directions point by point by an energy
Die Energiestrahl-Übertragungseinrichtung 2 überträgt speziell einen Laserstrahl 3 von einem (nicht dargestellten) externen Hochleistungs-Laser, beispielsweise einem CO,-oder Argon-Laser, zum Substrat 1 und ist auf dessen Oberfläche fokusiert Legierungs-Substrat 1 und Energiestrahlungs-Übertragungseinrichtung 2 sind mittels geeigneter Dichtmittel 4 hermetisch gegen die Umgebung abgeschlossen. Es können Druck-, Vakuum- oder Schutzgassysteme vorhanden sein, die gegebenenfalls auch das Absaugen von Fremdgasen ermöglichen. Zweckmäßigerweise wird das Substrat mittels eines in der Figur 1 nicht dargestellten x, y-Vorschubtisches gegenüber dem ortsfest angeordneten Laserstrahl 3 bewegt. Die zugehörigen Hilfsmittel werden nicht im einzelnen beschrieben. Alternativ ist auch eine Bewegung des Laserstrahls über Spiegelsysteme möglich.The energy
In der Energiestrahl-Übertragungseinrichtung 2 ist seitlich eine Kanüle 5 mit Düse 6 geführt, deren Winkel a sowie deren Abstand h gegenüber der Oberfläche des Substrates 1 veränderbar ist. Damit kann der Auftreffbereich des Laserstrahls 3 an der Oberfläche des Substrates 1 örtlich gezielt mit Sauerstoff umspült werden. Neben dem Einfallswinkel a kann auch der Azimutwinkel φ (in FIG 1 nicht dargestellt), d.h. die Richtung der Düse 6 in der xy-Ebene, verändert werden. Sie wird zweckmäßigerweise (in Abweichung zu FIG 1) so gewählt, daß der Gasstrom in Richtung des nicht ungeschmolzenen Werkstückes 1 erfolgtA
Der Sauerstoff kann auch mit einem Trägergas, beispielsweise Helium, vermischt sein. Zusammensetzung bzw. Durchflußmenge von Trägergas und/oder Sauerstoff sowie Druck im Reaktionsraum können mittels externer Dosierungsmittel vorgegeben werden.The oxygen can also be mixed with a carrier gas, for example helium. The composition or flow rate of carrier gas and / or oxygen and the pressure in the reaction space can be specified by means of external dosing agents.
Der Hochleistungslaser arbeitet im Pulsbetrieb. Bei geeigneter Fokussierung ergibt sich ein Brennfleck auf der Oberfläche des Substrates 1 von etwa 100 pm Durchmesser. Bei genügender Energiedichte wird der mittels der Düse 6 zugeführte Sauerstoff ionisiert und liegt bereits in atomarer Form vor. Durch die energiereiche Laserstrahlung bildet sich bei Erreichen des Zündpunktes aus Sauerstoff und gegebenenfalls vorhandenem Trägergas ein Plasma, das oberhalb der Auftreffstelle des Laserstrahls konzentriert ist und zur Energieübertragung in das Legierungs-Substrat 1 ausgenutzt wird. Dadurch bilden sich um den Auftreffpunkt des Laserstrahls auf dem Substrat 1 Schmelzzonen 8 aus, wobei Metallatome in das Plasma übertreten können.The high-power laser works in pulse mode. With a suitable focusing, there is a focal spot on the surface of the substrate 1 of approximately 100 μm in diameter. If the energy density is sufficient, the oxygen supplied by means of the nozzle 6 is ionized and is already in atomic form. Due to the high-energy laser radiation, when the ignition point is reached, oxygen and any carrier gas present form a plasma, which is concentrated above the point of impact of the laser beam and is used for energy transfer into the alloy substrate 1. As a result, melting zones 8 form around the point of incidence of the laser beam on the substrate 1, metal atoms being able to pass into the plasma.
Aufgrund des sogenannten "keyhole"-Effektes läßt sich in weniger als einer Millisekunde ein örtlich gezieltes.Aufschmelzen des Materials in hinreichender Tiefe, beispielsweise bis 1,5 mm, erreichen. Mit dem Aufschmelzen wird der zugeführte Sauerstoff in den aufgeschmolzenen Bereich des Substrates eingebracht und mittels Konvektion in der metallischen Schmelze gleichmäßig verteilt Durch den Stofftransport über Konvektion ergibt sich im aufgeschmolzenen Bereich eine resultierende homogene Sauerstoffverteilung. Je nach Prozeßführung liegt ein mehr oder weniger großer Anteil des Sauerstoffs bereits als Oxid vor.Due to the so-called "keyhole" effect, a locally targeted melting of the material to a sufficient depth, for example up to 1.5 mm, can be achieved in less than a millisecond. With the melting, the supplied oxygen is introduced into the melted area of the substrate and evenly distributed in the metallic melt by means of convection. The mass transfer via convection results in a homogeneous oxygen distribution in the melted area. Depending on the process control, a more or less large proportion of the oxygen is already present as an oxide.
Geht man von Laserstrahlung mit vorgegebener Wellenlänge und Energiedichte aus, bleiben als Prozeßparameter Art, Menge und Druck der zugeführten Gase einerseits sowie Temperatur des Substrates andererseits. Wie bereits erwähnt, läßt sich die Gasmenge durch Mischung mit einem Trägergas und Einstellung der ZuführungsdÜse 6 zum Substrat 1 regulieren. Wird für eine vollständige Oxidation des Unedelmetalianteiis oder für eine Gefügeoptimierung dieser Oxide eine gleichzeitige oder nachträgliche Wärmebehandlung notwendig, so sind die Parameter hierfür in Abhängigkeit vom thermodynamischen Verhalten des Legierungssystems zu wählen.If one assumes laser radiation with a predetermined wavelength and energy density, the type, quantity and pressure of the gases supplied, on the one hand, and the temperature of the substrate, on the other, remain as process parameters. As already mentioned, the amount of gas can be regulated by mixing it with a carrier gas and adjusting the feed nozzle 6 to the substrate 1. If a simultaneous or subsequent heat treatment is necessary for a complete oxidation of the base metal part or for a structure optimization of these oxides, the parameters for this must be selected depending on the thermodynamic behavior of the alloy system.
Nachdem die gesamte Oberfläche des Substrates 1 überlappend abgerastert ist, läßt sich aus dem so entstandenem Schichtmaterial durch Ausstanzen ein Zweischichten-Kontaktstück 10 gemäß Figur 2 fertigen. Dieses besteht aus einer Silber-Metalloxid-Schicht 12 im oberen Bereich und einer Silber-Legierungs-Schicht 11 im unteren Bereich, die voneinander deutlich getrennt sind. Aufgrund des beschriebenen Herstellungsverfahrens ergibt sich durch das örtliche Aufschmelzen in Schmelzkeulen 8 eine typische Wellenstruktur der Grenzfläche, die sich auch bei anschließenden Temperaturbehandlungen nicht grundsätzlich ändert. Eine derartig profilierte Grenzfläche ist für den bestimmungsgemäßen Gebrauch als Kontaktstück ohne Bedeutung; es kommt darauf an, daß sich das gefertigte Zweischichten-Kontaktstück mit seiner Silber-Legierungsschicht 11 ohne weiteres auf einen Kontaktträger anlöten läßt.After the entire surface of the substrate 1 has been scanned with an overlap, a two-
Im obigen Beispiel wurde von einer AgSn-Legierung mit.8 % Massenanteilen an Zinn ausgegangen. In weiteren Ausführungsformen kann von anderen AgSn- oder aber auch von AgZn-Legierungen ausgegangen werden. Insbesondere bei diesen Legierungen sind erfahrungsgemäß zur Gewährleistung eines hinreichenden Schaltverhaltens der daraus erzeugten Kontaktwerkstoffe weitere Zusätze von unedleren Metallen als Silber notwendig. Als geeignet haben sich beispielsweise Wismut (Bi), Kupfer (Cu), Indium (In), Tantal (Ta) und/oder Wolfram (W) erwiesen. Diese Metalle sind leicht oxidierbar, wobei Wolfram auch in nichtoxidierter Form vorliegen kann.In the example above, an AgSn alloy with 8% by mass of tin was assumed. In other embodiments, other AgSn or AgZn alloys can be used. Experience has shown that these alloys in particular require additional additions of less noble metals than silver to ensure adequate switching behavior of the contact materials produced therefrom. Bismuth (Bi), copper (Cu), indium (In), tantalum (Ta) and / or tungsten (W), for example, have proven suitable. These metals are easily oxidized, and tungsten can also be present in non-oxidized form.
Entsprechend dem oben im einzelnen beschriebenen Verfahren lassen sich aus AgCd-L-gierungen AgCα0 Kontaktwerkstoffe mit gegebenenfalls weiteren Metalloxidzusätzen erzeugen.In accordance with the method described in detail above, AgCα-L alloys can be used to produce AgCα0 contact materials with possibly further metal oxide additives.
Durch das Gaslegieren mittels Laserstrahlung sind örtliche Aufschmelzbereiche mit Tiefen bis zu 4 mm möglich. Statt Laserstrahlung sind auch andere Energieübertragungsmethoden, mit denen ein Strahl hinreichender Energiedichte erzeugt werden kann, beispielsweise Elektronen- oder lonenstrahl, Lichtbogen oder HF-Plasma, Energiedichte erzeugt werden kann, beispielsweise möglich.Gas alloying using laser radiation enables local melting areas with depths of up to 4 mm. Instead of laser radiation, other energy transmission methods with which a beam of sufficient energy density can be generated, for example electron or ion beam, arc or HF plasma, energy density can also be generated, for example, are possible.
Mit dem neuen Herstellungsverfahren und der zugehörigen Vorrichtung können insbesondere Kontaktstücke für elektrische Schattgeräte mit einer vergleichsweisen geringen Anzahl von Verfahrensschritten gefertigt werden. Bei kompaktem Legierungs-Substrat läßt sich nunmehr die Inneroxidation schnell erreichen, wobei trotzdem die angestrebte Homogenität der Metalloxid-Verteilung und Konzentration gegeben istWith the new manufacturing process and the associated device, in particular contact pieces for electrical shading devices can be manufactured with a comparatively small number of process steps. In the case of a compact alloy substrate, the internal oxidation can now be achieved quickly, although the desired homogeneity of the metal oxide distribution and concentration is given
Beim Halbzeug für die Zweischichten-Kontaktstücke kann die Oberfläche durch mechanisches oder chemisches Aufrauhen derart vorbereitet werden, wie sie für die spätere Kontaktfläche erforderlich ist Insbesondere für das Laser-Gaslegieren läßt sich dadurch gleichermaßen eine erhöhte Energieabsorption erreichen. Anschließend ist eine besondere Nachbearbeitung der Oberflächen im allgemeinen nicht mehr notwendig. In jedem Fall ist die Rückseite des Legierungs-Substrates auch nach dem Laser-Gaslegieren ohne Einschluß von Metalloxiden auf den Kontaktträger lötfähig.In the semifinished product for the two-layer contact pieces, the surface can be prepared by mechanical or chemical roughening in such a way as is required for the subsequent contact surface. In particular for laser gas alloying, this also results in increased energy absorption. Subsequently, special reworking of the surfaces is generally no longer necessary. In any case, the back of the alloy substrate is solderable even after laser gas alloying without the inclusion of metal oxides on the contact carrier.
Im Rahmen der Erfindung ist es auch möglich, das Legierungs-Substrat 1 bereits als Halbzeug auf dem Kontaktträger zu befestigen und anschließend der oben beschriebenen Laserbehandlung zur inneren Oxidation zu unterziehen. Letzteres ist für eine automatisierte Fertigung vorteilhaft, da beispielsweise bei einer Roboterhandhabung das Verlöten des Halbzeuges auf beliebiger Seite erfolgen kann und somit ein separater Ordnungsvorgang der Zweischicht-Kontaktstücke nach Kontaktseite und Lötseite überflüssig wird. Es können auch die Kontaktträger auf den gesamten Halbzeugstrang gelötet, die innere Oxidation durch Laser-Gaslegieren durchgeführt und anschließend die fertigen Kontakte gestanzt oder geschnitten werden.In the context of the invention, it is also possible to attach the alloy substrate 1 as a semi-finished product to the contact carrier and then to subject it to the laser treatment described above for internal oxidation. The latter is advantageous for automated production since, for example in the case of robot handling, the semi-finished product can be soldered on any side and a separate ordering process of the two-layer contact pieces according to the contact side and solder side is therefore unnecessary. The contact carriers can also be soldered onto the entire semi-finished strand, the internal oxidation can be carried out by laser gas alloying and the finished contacts can then be punched or cut.
Claims (24)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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AT85113995T ATE40903T1 (en) | 1984-11-05 | 1985-11-04 | METHOD AND DEVICE FOR MANUFACTURING SILVER-BASED TWO-LAYER CONTACT PIECES FOR ELECTRICAL SWITCHGEAR. |
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DE3440335 | 1984-11-05 | ||
DE3440335 | 1984-11-05 |
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EP0182182A1 true EP0182182A1 (en) | 1986-05-28 |
EP0182182B1 EP0182182B1 (en) | 1989-02-22 |
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EP85113995A Expired EP0182182B1 (en) | 1984-11-05 | 1985-11-04 | Method and apparatus for making silver base two-layer contacts for electrical switches |
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AT (1) | ATE40903T1 (en) |
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Cited By (6)
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DE3541584A1 (en) * | 1985-11-25 | 1987-05-27 | Siemens Ag | Process and appliance for preparing metal-composite materials, and contact pieces produced therewith for electrical switchgear |
EP0288585A1 (en) * | 1987-03-24 | 1988-11-02 | INOVAN GmbH & Co. KG Metalle und Bauelemente | Method for producing a solderable or weldable underside of a silver-metaloxide contact piece |
WO1988010011A1 (en) * | 1987-06-12 | 1988-12-15 | Siemens Aktiengesellschaft | Process for manufacturing conductive regions from an oxide-ceramic superconducting material having a high conductivity-change temperature |
WO1997039855A1 (en) * | 1996-04-25 | 1997-10-30 | Strix Limited | Electrical contacts |
GB2327300A (en) * | 1996-04-25 | 1999-01-20 | Strix Ltd | Electrical contacts |
US9667015B2 (en) | 2011-04-06 | 2017-05-30 | Te Connectivity Germany Gmbh | Method for manufacturing at least one functional area on an electric contact element such as a switching contact or a plug contact |
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- 1985-11-04 EP EP85113995A patent/EP0182182B1/en not_active Expired
- 1985-11-04 AT AT85113995T patent/ATE40903T1/en not_active IP Right Cessation
- 1985-11-04 DE DE8585113995T patent/DE3568353D1/en not_active Expired
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FR1364152A (en) * | 1963-05-10 | 1964-06-19 | L Air Liquide Sa Pour L Expl D | Surface treatment of metals |
DE1533235B1 (en) * | 1966-12-15 | 1970-01-29 | E Duerrwaechter Doduco Kg Dr | Process for the production of solderable internally oxidized metal / metal oxide contact materials, in particular of the silver / cadmium oxide type |
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3541584A1 (en) * | 1985-11-25 | 1987-05-27 | Siemens Ag | Process and appliance for preparing metal-composite materials, and contact pieces produced therewith for electrical switchgear |
EP0288585A1 (en) * | 1987-03-24 | 1988-11-02 | INOVAN GmbH & Co. KG Metalle und Bauelemente | Method for producing a solderable or weldable underside of a silver-metaloxide contact piece |
WO1988010011A1 (en) * | 1987-06-12 | 1988-12-15 | Siemens Aktiengesellschaft | Process for manufacturing conductive regions from an oxide-ceramic superconducting material having a high conductivity-change temperature |
WO1997039855A1 (en) * | 1996-04-25 | 1997-10-30 | Strix Limited | Electrical contacts |
GB2327300A (en) * | 1996-04-25 | 1999-01-20 | Strix Ltd | Electrical contacts |
US9667015B2 (en) | 2011-04-06 | 2017-05-30 | Te Connectivity Germany Gmbh | Method for manufacturing at least one functional area on an electric contact element such as a switching contact or a plug contact |
US10862259B2 (en) | 2011-04-06 | 2020-12-08 | Te Connectivity Germany Gmbh | Method for manufacturing at least one functional area on an electric contact element such as a switching contact or a plug contact |
Also Published As
Publication number | Publication date |
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DE3568353D1 (en) | 1989-03-30 |
EP0182182B1 (en) | 1989-02-22 |
ATE40903T1 (en) | 1989-03-15 |
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