EP0245734B1 - Electric lamp - Google Patents

Electric lamp Download PDF

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Publication number
EP0245734B1
EP0245734B1 EP87106402A EP87106402A EP0245734B1 EP 0245734 B1 EP0245734 B1 EP 0245734B1 EP 87106402 A EP87106402 A EP 87106402A EP 87106402 A EP87106402 A EP 87106402A EP 0245734 B1 EP0245734 B1 EP 0245734B1
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EP
European Patent Office
Prior art keywords
mol
pbo
glass
molybdenum
electric lamp
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Expired - Lifetime
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EP87106402A
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German (de)
French (fr)
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EP0245734A3 (en
EP0245734A2 (en
Inventor
Werner Dr. Weiss
Ewald Pösl
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Osram GmbH
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Patent Treuhand Gesellschaft fuer Elektrische Gluehlampen mbH
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Priority to AT87106402T priority Critical patent/ATE74465T1/en
Publication of EP0245734A2 publication Critical patent/EP0245734A2/en
Publication of EP0245734A3 publication Critical patent/EP0245734A3/en
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Publication of EP0245734B1 publication Critical patent/EP0245734B1/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01K—ELECTRIC INCANDESCENT LAMPS
    • H01K1/00—Details
    • H01K1/38—Seals for leading-in conductors

Definitions

  • the invention relates to an electric lamp according to the preamble of claim 1.
  • a vacuum-tight electrical supply line is usually achieved by means of the film melting technique.
  • thermally highly stressed lamp types temperatures of more than 350 ° C occur in the area of the film melting.
  • the foils would be exposed to increased corrosion at these temperatures, which is why these cavities are sealed by a low-melting solder glass.
  • lead borate glasses to which ZnO and SiO2 are often added (eg US Pat. No. 2,889,952).
  • solder glasses based on antimony borate glass have been developed (for example US Pat. No. 3,588,315) which have no corrosive effect on molybdenum wire.
  • a use of these solder glasses is now however, no longer desirable due to the associated great health risk.
  • the object of the invention is to provide a solder glass which does not have a corrosive effect on molybdenum wire, has satisfactory flow properties in the temperature range from 350 ° C. to 500 ° C. and does not lead to any serious health risks associated with the processing of antimony.
  • solder glass contains lead borate and bismuth oxide in the following composition: 3-10 mol% Bi2O3, 25-40 mol% B2O3, the rest consisting essentially of PbO and possibly other additives.
  • BaO with a proportion of up to 15 mol% is possible as an additive.
  • a bismuth-lead borate solder glass with the composition 4-6 mol% Bi2O3, 33-37 mol% B2O3, the rest PbO is particularly advantageous.
  • the bismuth lead borate solder glasses according to the invention combine the advantages of the lead borate glasses (eg low melting and softening temperature, good wetting ability in the quartz glass-molybdenum system) with those of the antimony borate glasses (no corrosive effect on molybdenum).
  • the bismuth lead borate solder glasses are particularly difficult to reduce than the known lead borate glasses and therefore allow the use of the usual molybdenum wires.
  • the composition according to the invention in particular ensures good flow properties which enable the solder glass to penetrate into the capillary cavities.
  • the viscosity can be regulated by adding BaO.
  • the low tendency to crystallize should also be emphasized.
  • the figure shows a halogen lamp 1, pinched on one side, with high power (250 W).
  • the piston 2 is made of quartz glass; however, it would also be possible to use doped quartz glass or quartz-like glass (Vycor) with a high content (> 96%) of silica (SiO2).
  • the filling 3 contains inert gases (eg Kr or Xe) and halogen-containing additives (eg hydrogen halides, halogenated hydrocarbons).
  • a filament 4 made of tungsten is held in the bulb 2 by a pair of internal power leads 5 made of molybdenum.
  • the inner power supply lines 5 are each attached to the ends of thin, rectangular molybdenum foils 6, which are melted into the pinch seal 7.
  • the pinch seal 7 is heated to approximately 800 ° C., generally during lamp manufacture.
  • the point at which the external power leads 8 emerge from the pinch seal 7 is now dabbed with the solder glass drawn into a thin rod. Due to the high temperature, the solder glass melts and penetrates into the capillary cavities 9, as a result of which the foils 6 are sealed off from the outside.
  • a first embodiment of the solder glass (I) according to the invention can be melted from lead oxide, boron oxide and bismuth oxide in a hard porcelain crucible at temperatures of approximately 900 ° C. in a Simon-Müller furnace.
  • composition of the solder glass I is (in mol%) 35% B2O3, 5% Bi2O3, 60% PbO.
  • solder glass II has the composition 30% B2O3, 8% Bi2O3, 10% BaO, 52% PbO.
  • the composition of the solder glass III is similar: 35% B2O3, 5% Bi2O3, 10% BaO, 50% PbO. (The data are in mol%).
  • the solder glasses I - III show small differences in the crystallization behavior and in the temperature dependence of the viscosity. Their melting temperatures (corresponding to a viscosity of 102 dPas) are approx. 575 ° C, their softening temperatures (corresponding to a viscosity of 107 dPas) approx. 430 ° C.
  • the coefficient of thermal expansion is about 10 x 10 ⁇ 6 K ⁇ 1 (0-300 ° C), the transformation temperature about 320 ° C, the density about 6.29 g / cm3.
  • the field of application of the individual solder glass depends on the parameters of the respective lamp type.
  • the invention is not restricted to use with incandescent halogen lamps.
  • incandescent halogen lamps in which the technology of film melting is also used, temperatures can occur in the area of the pinch seal which make it necessary to use the solder glasses according to the invention.

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  • Glass Compositions (AREA)
  • Circuit Arrangements For Discharge Lamps (AREA)
  • Liquid Developers In Electrophotography (AREA)
  • Vessels And Coating Films For Discharge Lamps (AREA)

Abstract

To provide a melt glass (10) to seal capillary spaces (9) surrounding external current supply leads (8) of molybdenum passing to molybdenum foils (6) in a pinch or press seal (7) of a high temperature, for example incandescent halogen lamp, the melt glass (10) is made of 3-10% Bi2O3, 25%-40% B2O3, remainder PbO. The melt glass has low toxicity and is molybdenum-compatible. An additive of barium oxide, in up to 15% and preferably up to only about 10%, may be added to the PbO. All quantities in mol-percent.

Description

Die Erfindung geht aus von einer elektrischen Lampe nach dem Oberbegriff des Anspruchs 1.The invention relates to an electric lamp according to the preamble of claim 1.

Bei elektrischen Lampen mit Halogenfüllung, z.B. Halogenglühlampen und Metallhalogenidentladungslampen, wird üblicherweise eine vakuumdichte elektrische Zuleitung durch die Technik der Folieneinschmelzung erreicht. Bei thermisch hochbelasteten Lampentypen treten im Bereich der Folieneinschmelzung Temperaturen von mehr als 350 °C auf. Infolge des Eindringens von atmosphärischem Sauerstoff durch kapillare Hohlräume in der Umgebung der äußeren Stromzuführungen wären bei diesen Temperaturen die Folien einer erhöhten Korrosion ausgesetzt, weshalb diese Hohlräume durch ein niedrigschmelzendes Lotglas abgedichtet werden. Üblicherweise handelt es sich dabei um Bleiboratgläser, denen häufig ZnO und SiO₂ beigefügt ist (z.B. US-PS 2 889 952). Nachteilig bei diesen bekannten Bleiboratgläsern ist, daß sie zu einer erhöhten Korrosion der üblichen Stromzuführungen aus Molybdändraht führen und daß sie unbefriedigende Fließeigenschaften im Bereich von 350 °C bis 500 °C aufweisen. Deshalb wurden Lotgläser auf der Basis von Antimonboratglas entwickelt (z.B. US-PS 3 588 315), die keine korrodierende Wirkung auf Molybdändraht haben. Eine Verwendung dieser Lotgläser ist mittlerweile jedoch wegen des damit verbundenen großen gesundheitlichen Risikos nicht mehr erwünscht.In the case of electric lamps with halogen filling, for example halogen incandescent lamps and metal halide discharge lamps, a vacuum-tight electrical supply line is usually achieved by means of the film melting technique. With thermally highly stressed lamp types, temperatures of more than 350 ° C occur in the area of the film melting. As a result of the penetration of atmospheric oxygen through capillary cavities in the vicinity of the external power supply lines, the foils would be exposed to increased corrosion at these temperatures, which is why these cavities are sealed by a low-melting solder glass. Usually these are lead borate glasses, to which ZnO and SiO₂ are often added (eg US Pat. No. 2,889,952). A disadvantage of these known lead borate glasses is that they lead to increased corrosion of the usual power supply lines made from molybdenum wire and that they have unsatisfactory flow properties in the range from 350 ° C. to 500 ° C. For this reason, solder glasses based on antimony borate glass have been developed (for example US Pat. No. 3,588,315) which have no corrosive effect on molybdenum wire. A use of these solder glasses is now however, no longer desirable due to the associated great health risk.

Aufgabe der Erfindung ist es, ein Lotglas zu schaffen, das nicht korrodierend auf Molybdändraht wirkt, befriedigende Fließeigenschaftem im Temperaturbereich 350 °C - 500 °C aufweist und zu keiner starken gesundheitlichen Gefährdung führt, wie sie mit der Verarbeitung von Antimon verbunden ist.The object of the invention is to provide a solder glass which does not have a corrosive effect on molybdenum wire, has satisfactory flow properties in the temperature range from 350 ° C. to 500 ° C. and does not lead to any serious health risks associated with the processing of antimony.

Diese Aufgabe wird erfindungsgemäß dadurch gelöst, daß das Lotglas Bleiborat sowie Wismutoxid in folgender Zusammensetzung enthält: 3-10 Mol-% Bi₂O₃, 25-40 Mol-% B₂O₃, wobei der Rest im wesentlichen aus PbO und ggf. weiteren Zusätzen besteht. Insbesondere ist als Zusatz BaO mit einem Anteil bis zu 15 Mol-% möglich. Besonders vorteilhaft ist ein Wismut-Bleiborat-Lotglas mit der Zusammensetzung 4-6 Mol-% Bi₂O₃, 33-37 Mol-% B₂O₃, Rest PbO.This object is achieved in that the solder glass contains lead borate and bismuth oxide in the following composition: 3-10 mol% Bi₂O₃, 25-40 mol% B₂O₃, the rest consisting essentially of PbO and possibly other additives. In particular, BaO with a proportion of up to 15 mol% is possible as an additive. A bismuth-lead borate solder glass with the composition 4-6 mol% Bi₂O₃, 33-37 mol% B₂O₃, the rest PbO is particularly advantageous.

Die erfindungsgemäßen Wismut-Bleiborat-Lotgläser kombinieren die Vorteile der Bleiboratgläser (z.B. niedrige Schmelz- und Erweichungstemperatur, gutes Benetzungsvermögen im System Quarzglas-Molybdän) mit denen der Antimonboratgläser (keine korrodierende Wirkung auf Molybdän). Die Wismut-Bleiborat-Lotgläser lassen sich insbesondere schwieriger reduzieren als die bekannten Bleiboratgläser und erlauben deshalb die Verwendung der üblichen Molybdändrähte. Die erfindungsgemäße Zusammensetzung sichert insbesondere gute Fließeigenschaften, die das Lotglas befähigen, in die kapillaren Hohlräume einzudringen. Die Viskosität läßt sich durch den BaO-Zusatz regeln. Hervorzuheben ist weiterhin die geringe Neigung zur Kristallisation.The bismuth lead borate solder glasses according to the invention combine the advantages of the lead borate glasses (eg low melting and softening temperature, good wetting ability in the quartz glass-molybdenum system) with those of the antimony borate glasses (no corrosive effect on molybdenum). The bismuth lead borate solder glasses are particularly difficult to reduce than the known lead borate glasses and therefore allow the use of the usual molybdenum wires. The composition according to the invention in particular ensures good flow properties which enable the solder glass to penetrate into the capillary cavities. The viscosity can be regulated by adding BaO. The low tendency to crystallize should also be emphasized.

Ausführungsbeispiele der Erfindung sollen im folgenden näher erläutert werden. Ein Ausführungsbeispiel der Erfindung ist in der Figur dargestellt.Embodiments of the invention will be explained in more detail below. An embodiment of the invention is shown in the figure.

Die Figur zeigt eine einseitig gequetschte Halogenglühlampe 1 mit hoher Leistung (250 W). Der Kolben 2 besteht aus Quarzglas; es wäre jedoch auch die Verwendung von dotiertem Quarzglas oder quarzähnlichem Glas (Vycor) mit einem hohen Gehalt (>96 %) an Kieselsäure (SiO₂) möglich. Die Füllung 3 enthält Inertgase (z.B. Kr oder Xe) und halogenhaltige Zusätze (z.B. Halogenwasserstoffe, halogenierte Kohlenwasserstoffe). Ein Leuchtkörper 4 aus Wolfram wird im Kolben 2 von einem Paar innerer Stromzuführungen 5 aus Molybdän gehaltert. Die inneren Stromzuführungen 5 sind jeweils an den Enden von dünnen, rechteckigen Molybdänfolien 6 befestigt, die in die Quetschdichtung 7 eingeschmolzen sind. An den entgegengesetzten Enden der Molybdänfolien 6 sind jeweils äußere Stromzuführungen 8, ebenfalls aus Molybdän, befestigt, die aus der Quetschdichtung 7 heraus nach außen geführt sind. Durch den Prozeß der Quetschung bedingt und wegen der nicht angepaßten thermischen Ausdehnungskoeffizienten von Molybdän und Quarz bilden sich in der Umgebung der Stromzuführungen 5, 8 im Kolbenglas kapillare Hohlräume 9 aus, die im Fall der äußeren Stromzuführungen 8 das Eindringen von Luftsauerstoff bis hin zu den Folien 6 ermöglichen. Bei Lampen, die im Bereich der Quetschdichtung 7 hohe Betriebstemperaturen (ca. 400 °C) aufgrund einer hohen Lampenleistung aufweisen, würde die Oxidation der Folien 6 wesentlich schneller (entsprechend einer exponentiellen Abhängigkeit) fortschreiten als bei Lampen, die im Bereich der Quetschdichtung eine relativ niedrige Betriebstemperatur aufweisen. Diese schnellere Oxidation läßt sich dadurch vermeiden, daß die kapillaren Hohlräume 9, die die äußeren Stromzuführungen 8 umgeben, mit einem Lotglas 10 gefüllt werden.The figure shows a halogen lamp 1, pinched on one side, with high power (250 W). The piston 2 is made of quartz glass; however, it would also be possible to use doped quartz glass or quartz-like glass (Vycor) with a high content (> 96%) of silica (SiO₂). The filling 3 contains inert gases (eg Kr or Xe) and halogen-containing additives (eg hydrogen halides, halogenated hydrocarbons). A filament 4 made of tungsten is held in the bulb 2 by a pair of internal power leads 5 made of molybdenum. The inner power supply lines 5 are each attached to the ends of thin, rectangular molybdenum foils 6, which are melted into the pinch seal 7. At the opposite ends of the molybdenum foils 6, external power supply lines 8, also made of molybdenum, are fastened, which lead out of the pinch seal 7 to the outside. Due to the process of crushing and due to the unmatched thermal expansion coefficients of molybdenum and quartz, capillary cavities 9 form in the vicinity of the power supply lines 5, 8 in the bulb glass, which in the case of the external power supply lines 8 prevent the penetration of atmospheric oxygen through to the foils 6 enable. With lamps that have high operating temperatures (approx. 400 ° C) in the area of the pinch seal 7 due to a high lamp power, the oxidation of the foils 6 would proceed much faster (corresponding to an exponential dependency) than with lamps that in the area of the pinch seal have relatively low operating temperature. This faster oxidation can be avoided by filling the capillary cavities 9, which surround the external power leads 8, with a solder glass 10.

Zu diesem Zweck wird die Quetschdichtung 7 - im allgemeinen während der Lampen-Herstellung - auf etwa 800 °C erwärmt. Die Stelle, an der die äußeren Stromzuführungen 8 aus der Quetschdichtung 7 austreten, wird nun mit dem zu einem dünnen Stäbchen gezogenen Lotglas betupft. Aufgrund der hohen Temperatur schmilzt das Lotglas und dringt in die kapillaren Hohlräume 9 ein, wodurch eine Abdichtung der Folien 6 nach außen hin erfolgt.For this purpose, the pinch seal 7 is heated to approximately 800 ° C., generally during lamp manufacture. The point at which the external power leads 8 emerge from the pinch seal 7 is now dabbed with the solder glass drawn into a thin rod. Due to the high temperature, the solder glass melts and penetrates into the capillary cavities 9, as a result of which the foils 6 are sealed off from the outside.

Im normalen Betrieb der Lampe treten dagegen nur mehr Temperaturen von 400 °C an der Quetschdichtung auf; dabei erweicht das Lotglas und bildet eine zähe Schmelze. Eine kristalline Struktur des Lotglases unter Betriebsbedingungen wäre dagegen unerwünscht, da an den Kristallgrenzen sich unvermeidlich Diffusionsspalte für den Luftsauerstoff bilden könnten. Dagegen ist die Bildung von Rissen im Lotglas nach dem Abschalten der Lampe unkritisch, da aufgrund der dann vorliegenden niedrigen Temperaturen dann auch das Oxidationsvermögen des Sauerstoffs herabgesetzt ist.In normal operation of the lamp, however, only temperatures of 400 ° C occur at the pinch seal; the solder glass softens and forms a tough melt. In contrast, a crystalline structure of the solder glass under operating conditions would be undesirable since diffusion gaps for the atmospheric oxygen could inevitably form at the crystal boundaries. In contrast, the formation of cracks in the solder glass after the lamp is switched off is not critical, since the oxidizing ability of the oxygen is then also reduced due to the then low temperatures.

Ein erstes Ausführungsbeispiel des erfindungsgemäßen Lotglases (I) läßt sich aus Bleioxid, Boroxid und Wismutoxid in einem Hartporzellantiegel bei Temperaturen von ca. 900 °C im Simon-Müller-Ofen erschmelzen.A first embodiment of the solder glass (I) according to the invention can be melted from lead oxide, boron oxide and bismuth oxide in a hard porcelain crucible at temperatures of approximately 900 ° C. in a Simon-Müller furnace.

Die Zusammensetzung des Lotglases I beträgt (in Mol-%) 35 % B₂O₃, 5 % Bi₂O₃, 60 % PbO.The composition of the solder glass I is (in mol%) 35% B₂O₃, 5% Bi₂O₃, 60% PbO.

Mit der gleichen Technik und ähnlichen Grundsubstanzen - außer den Oxiden des ersten Ausführungsbeispiels wird zusätzlich Bariumcarbonat verwendet - lassen sich zwei weitere Ausführungsbeispiele des erfindungsgemäßen Lotglases (II und III) herstellen. Lotglas II hat die Zusammensetzung 30 % B₂O₃, 8 % Bi₂O₃, 10 % BaO, 52 % PbO. Ähnlich ist die Zusammensetzung des Lotglases III: 35 % B₂O₃, 5 % Bi₂O₃, 10 % BaO, 50 % PbO. (Die Angaben verstehen sich in Mol-%).With the same technology and similar basic substances - in addition to the oxides of the first exemplary embodiment, barium carbonate is additionally used - two further exemplary embodiments of the solder glass (II and III) according to the invention can be produced. Solder glass II has the composition 30% B₂O₃, 8% Bi₂O₃, 10% BaO, 52% PbO. The composition of the solder glass III is similar: 35% B₂O₃, 5% Bi₂O₃, 10% BaO, 50% PbO. (The data are in mol%).

Die Lotgläser I - III zeigen kleine Unterschiede im Kristallisationsverhalten und in der Temperaturabhängigkeit der Viskosität. Ihre Schmelztemperaturen (entsprechend einer Viskosität von 10² dPas) liegen bei ca. 575 °C, ihre Erweichungstemperaturen (entsprechend einer Viskosität von 10⁷ dPas) bei ca. 430 °C. Der thermische Ausdehnungskoeffizient beträgt etwa 10 x 10⁻⁶ K⁻¹ (0-300 °C), die Transformationstemperatur etwa 320 °C, die Dichte etwa 6,29 g/cm³. Der Anwendungsbereich des einzelnen Lotglases hängt von den Parametern des jeweiligen Lampentyps ab.The solder glasses I - III show small differences in the crystallization behavior and in the temperature dependence of the viscosity. Their melting temperatures (corresponding to a viscosity of 10² dPas) are approx. 575 ° C, their softening temperatures (corresponding to a viscosity of 10⁷ dPas) approx. 430 ° C. The coefficient of thermal expansion is about 10 x 10⁻⁶ K⁻¹ (0-300 ° C), the transformation temperature about 320 ° C, the density about 6.29 g / cm³. The field of application of the individual solder glass depends on the parameters of the respective lamp type.

Die Erfindung ist nicht auf die Anwendung bei Halogenglühlampen beschränkt. Insbesondere bei kompakten Hochdruckentladungslampen mit Metallhalogenidfüllung, bei denen ebenfalls die Technik der Folieneinschmelzung verwendet wird, können im Bereich der Quetschdichtung Temperaturen auftreten, die den Einsatz der erfindungsgemäßen Lotgläser notwendig machen.The invention is not restricted to use with incandescent halogen lamps. In particular in the case of compact high-pressure discharge lamps with metal halide filling, in which the technology of film melting is also used, temperatures can occur in the area of the pinch seal which make it necessary to use the solder glasses according to the invention.

Claims (3)

  1. An electric lamp having a bulb (2) of high-silica glass which contains a luminous body (4) or electrodes and also a filling with a halogen-containing additive and into which electrical supply conductors are introduced in vacuum-tight fashion through at least one pinch seal (7), which supply conductors consist of a pair of internal and external supply leads connected to each other by means of a sealed-in foil, the pinch seal (7) having, in the surroundings of the external supply leads (8), capillary cavities (9) which are filled with a low-melting lead borate sealing glass (10), characterised in that said sealing glass (10) additionally contains bismuth oxide and, moreover, has the following composition (in mol-%):
    3 - 10 % Bi₂O₃
    25 - 40 % B₂O₃
    remainder PbO and, optionally, further additives.
  2. Electric lamp according to Claim 1, characterised in that the sealing glass (10) has the following composition (in mol-%):
    4 - 6 % Bi₂O₃
    33 - 37 % B₂O₃
    remainder PbO.
  3. Electric lamp according to Claim 1, characterised in that the sealing glass contains up to 15 mol-% of barium oxide (BaO) as further additive.
EP87106402A 1986-05-12 1987-05-04 Electric lamp Expired - Lifetime EP0245734B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87106402T ATE74465T1 (en) 1986-05-12 1987-05-04 ELECTRIC LAMP.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19863615944 DE3615944A1 (en) 1986-05-12 1986-05-12 ELECTRIC LAMP
DE3615944 1986-05-12

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EP0245734A2 EP0245734A2 (en) 1987-11-19
EP0245734A3 EP0245734A3 (en) 1989-11-02
EP0245734B1 true EP0245734B1 (en) 1992-04-01

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US (1) US4766346A (en)
EP (1) EP0245734B1 (en)
JP (1) JPH0719582B2 (en)
AT (1) ATE74465T1 (en)
CA (1) CA1270038A (en)
DE (2) DE3615944A1 (en)

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US4522925A (en) * 1983-09-01 1985-06-11 Owens-Illinois, Inc. Sealing glass and method of making a Willemite filler therefor
US4493944A (en) * 1984-01-04 1985-01-15 Gte Products Corporation Solder glass and electrical device employing same
US4492814A (en) * 1984-01-04 1985-01-08 Gte Products Corporation Solder glass and electrical device employing same

Also Published As

Publication number Publication date
ATE74465T1 (en) 1992-04-15
DE3615944A1 (en) 1987-11-19
JPH0719582B2 (en) 1995-03-06
DE3777873D1 (en) 1992-05-07
JPS62272454A (en) 1987-11-26
EP0245734A3 (en) 1989-11-02
CA1270038A (en) 1990-06-05
US4766346A (en) 1988-08-23
EP0245734A2 (en) 1987-11-19

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