EP0328065B1 - Getter für Glühlampen - Google Patents

Getter für Glühlampen Download PDF

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Publication number
EP0328065B1
EP0328065B1 EP19890102142 EP89102142A EP0328065B1 EP 0328065 B1 EP0328065 B1 EP 0328065B1 EP 19890102142 EP19890102142 EP 19890102142 EP 89102142 A EP89102142 A EP 89102142A EP 0328065 B1 EP0328065 B1 EP 0328065B1
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EP
European Patent Office
Prior art keywords
lamp
getter
lamps
formula
oxygen
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Expired - Lifetime
Application number
EP19890102142
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English (en)
French (fr)
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EP0328065A2 (de
EP0328065A3 (de
Inventor
John W.. Shaffer
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Osram Sylvania Inc
Original Assignee
GTE Products Corp
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Publication date
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Publication of EP0328065A2 publication Critical patent/EP0328065A2/de
Publication of EP0328065A3 publication Critical patent/EP0328065A3/de
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01K—ELECTRIC INCANDESCENT LAMPS
    • H01K1/00—Details
    • H01K1/52—Means for obtaining or maintaining the desired pressure within the vessel
    • H01K1/54—Means for absorbing or absorbing gas, or for preventing or removing efflorescence, e.g. by gettering
    • H01K1/56—Means for absorbing or absorbing gas, or for preventing or removing efflorescence, e.g. by gettering characterised by the material of the getter

Definitions

  • This invention relates to incandescent lamps and more particularly to the gettering of such lamps.
  • the temperature at the tungsten coil is thermally sufficient to decompose water vapor into hydrogen and oxygen.
  • the resulting oxygen reacts with the tungsten in the coil to form volatile oxides which migrate to cooler parts of the lamp and condense. These oxide deposits are reduced by the gaseous hydrogen to yield black metallic tungsten and reformed water, which causes the cycle to repeat.
  • a commonly utilized solution to the oxygen problem in tungsten-halogen lamps is the introduction of one or more compounds into the lamp which will remove the excess oxygen and prevent its participation in the tungsten-halogen cycle. Such compounds are commonly referred to as oxygen getters.
  • oxygen getters and/or gettering systems have been used previously.
  • metallic getters such as tantalum, zirconium, niobium, copper, hafnium, titanium, aluminum, or various combinations thereof, have been employed as oxygen getters.
  • Metallic getters may be attached to a portion of the filament mount within the lamp, e.g., in the form of a crimped piece of metal. These metal getters may also be incorporated as an alloy in the molybdenum leads which support the filament within the lamp.
  • U.S. Patent No. 4,305,017 describes the use of the above-identified metals together with precious metals such as palladium, platinum and gold as oxygen getters.
  • Metal flags such as those described in the '017 patent, tend to be difficult and expensive to attach to the internal structure of a tungsten-halogen lamp.
  • some metallic getters that are used in incandescent lamps are not applicable for use in tungsten halogen lamps because they will react with the halogen and terminate the desired halogen cycle.
  • the fabrication of specialized getter alloys can also add considerably to the cost of manufacturing a tungsten-halogen lamp.
  • it is desirable for the getter to be present across the entire range of locations within the lamp. Such positioning is impossible with metallic flag getters, and/or metal alloy gettering systems, which are generally limited to specific discrete locations.
  • Phosphorus oxides which are formed by the gettering of oxygen are volatile, even at the cold spot temperatures found in hot operating incandescent lamps, including tungsten-halogen lamps.
  • Phosphorus can be deposited in a lamp, for example, on either the filament mount and/or the coil itself, e.g., by dipping a suspension of red phosphorus or P3N5 in a suitable solvent.
  • phosphorus can be deposited on the filament by evaporative coating of red phosphorus.
  • Phosphorus can also be introduced into incandescent lamps as phosphine gas (PH3), which is thermally decomposed into phosphorus and hydrogen by the heat of the coil at light-up.
  • phosphine gas PH3
  • Carbon getters may be introduced to the lamp as part of a hydrogenated hydrocarbon gas or as carbon monoxide. However, in addition to deleteriously affecting filament life in certain lamp types, carbon has failed to perform as expected as an oxygen getter.
  • a gettering system such as the gettering system of the present invention, wherein gettered oxygen is bound in a permanent, nonvolatile form, so that the getter is effective in even the hottest operating lamps, clearly represents an advance in this art.
  • a method of gettering an incandescent lamp comprises introducing a fill gas and a getter comprising a silane compound, or a partially halogenated derivative thereof and mixtures thereof, into an unsealed lamp envelope; sealing the lamp envelope; and heating the sealed envelope before light up of the lamp, for a sufficient period of time, and at a temperature sufficient to activate the getter before the decomposition of the getter.
  • the terms "partially halogenated derivatives” refer to those compounds of Formula I, wherein from 1, and up to (2a + 1), of the hydrogens have been replaced by a halogen, i.e., F, Cl, Br, and/or I. Preferably the replacement is accomplished by bromine. It must be noted that in the method of the present invention, one hydrogen atom must always be present in the "partially halogenated derivatives" of the compounds of Formula I.
  • the getter of Formula I is heated sufficiently to be "activated." It has been discovered that, for the compounds of Formula I, and the partially halogenated derivatives thereof, that the temperature and time required to "activate" the getter must be below the temperature and time which would otherwise cause decomposition of the getter prior to its performing the desired gettering function. In fact, when temperatures and/or heating times sufficient to cause premature decomposition of the getter compound are employed, the getter compositions recited above fail to function.
  • the Formula I getter reacts with residual impurities such as oxygen, water, etc., present in the sealed envelope, forming by-products including nonvolatile silicon dioxide and hydrogen.
  • by-products further include halogen compounds, e.g., Br2, I2, and the like.
  • the getter removes any oxygen impurity from the envelop by binding the oxygen in a stable, nonvolatile form, e.g., as silicon dioxide (SiO2), which does not decompose (and liberate oxygen) under the high operating temperatures of the lamp.
  • a stable, nonvolatile form e.g., as silicon dioxide (SiO2)
  • Figures 1 and 2 compare lamp test data for lamps fabricated using a phosphine getter against lamps fabricated in accordance with the method of the present invention.
  • the present invention is directed to an improved method of gettering incandescent lamps.
  • Incandescent lamps are well known in the lighting art. Such lamps typically include an hermetically sealed light pervious envelope such as quartz or hard glass, containing a fill gas. Typical fill gases include a halogen and an inert gas. Such fill gases may further include hydrogen. The principal function of the fill gas in incandescent lamps is to retard evaporation of the coil. In some lamps the fill gas may perform the additional secondary function of suppressing the arc.
  • the envelope also includes a filament wire, such as tungsten wire, which is in connection with lead-in wires sealed into and extending internally and externally of the lamp envelope. Such lead-in wires may extend from opposite ends of the envelope (double-ended lamp) or from the same end of the envelope (single-ended lamp). Such lamps may further be enclosed within an outer envelope or a parabolic reflector and a lens.
  • the present method removes residual impurities from the lamp after introducing the fill gas into the lamp envelope and sealing the lamp.
  • Such sealing step commonly referred to in the art as “tipping off,” is a routine step in the fabrication or manufacture of incandescent lamps.
  • the method of the present invention includes introducing a fill gas and a getter comprising a compound of Formula I: Si a H (2a + 2) wherein "a" is an integer greater than zero, or a partially halogenated derivative thereof, into an unsealed lamp envelope comprising a light pervious envelope having a filament wire therein, the filament wire being in electrical connection with lead-in wires which are sealed into and extend internally and externally from the lamp envelope.
  • the gaseous getter is introduced into the lamp envelope as a minor component of the fill gas.
  • the fill gas and gaseous getter are separately introduced into the lamp.
  • the lamp After the fill gas and getter have been introduced into the lamp envelope, the lamp is sealed by conventional lamp sealing techniques.
  • the lamp After the lamp has been sealed, the lamp is heated at a temperature, and for a period of time, sufficient to activate the getter, so as to convert residual impurities in the lamp into materials which are inert or nondetrimental to the chemical cycle of the lamp.
  • One preferred method for using a silane getter of Formula I is to introduce it as a minor component of the fill gas.
  • the lamp After the lamp has been tipped off, i.e., sealed, it is subjected to a bake cycle of five (5) minutes at 350°C. During this bake cycle, the silane reacts, essentially quantitatively, with any oxygen in the lamp to form nonvolatile silicon dioxide and hydrogen.
  • any oxygen liberated from the coil is consumed and the residual excess silane is thermally cracked to form elemental silicon and hydrogen.
  • the silicon forms a faint brown smoky deposit in the bottom of the lamp or capsule (assuming an inverted light-up position).
  • silane can react with halogen in the fill gas to form volatile halosilanes, which are as effective for gettering oxygen as silane itself.
  • halogen in the fill gas For example, in a lamp containing HBr as a fill component, monobromosilane is formed, assuming silane is introduced into the lamp in stoichiometric excess.
  • silanes for use in the present method include disilane (Si2H6), trisilane (Si3H8) and tetrasilane (Si4H10), as well as their various respective partially halogenated derivatives.
  • Appropriate getter activation temperatures are preferably from about 100°C to about 1000°C, and most preferably in the area of from 300°C to 500°C. Lower temperatures promote more gradual release of adsorbed water and significantly lower gettering reaction rates. With silane, a bake duration of five minutes at 350°C has been successfully used, as shown below. In order to facilitate automated lamp processing, a shorter time at higher temperatures is favored; e.g., one minute at 500°C. The optimum activation time and temperature will vary with the specific chemical getter used, from among those listed herein, and on the particular lamp construction being made. Some lamps contain internal structures that heat slowly by external heating and would therefore require a longer time at a given temperature for optimum gettering action to occur.
  • the optimum quantity of gettering additive will depend on the lamp internal volume, fill pressure, internal surface area, and the specific getter used. Depending upon lamp internal volume, fill pressure, and other variables, effective gettering action in accordance with the teachings of this invention can be attained over a concentration range of from about 0.001 percent to five percent getter additive by volume. At lower levels there may not be sufficient additive present to react with all the contaminants present. High excesses will promote undesired light loss due to the formation of elemental silicon within the lamp. As lamp surface area increases, as for example in an inside frosted or smoked bulb, more getter will be needed because of the relatively higher quantity of adsorbed moisture present. From the examples given, those skilled in the art of lampmaking can quickly arrive at appropriate getter additive levels for specific lamps of interest.
  • boron hydride compounds Elemental boron and silicon are analogous and they both form volatile hydrides that are pyrophoric; that is, they ignite spontaneously upon contact with air.
  • Materials such as diborane (B2H6) dihydrotetraborane (B4H10), pentaborane (B5H9), hexaborane (B6H10), as well as halogen derivatives such as, for example, monobromodiboropentahydide (B2H5Br) are expected to fully perform the inventive principles taught herein. In fact, these boron chemicals are expected to perform functionally superior to the silanes based upon their comparative thermochemistry.
  • silane compounds and partially halogenated derivatives thereof may be preferred, however, because they are less hazardous to work with, particularly in a non-laboratory, production oriented lamp manufacturing plant.
  • the boranes have positive heats of formation (in contrast to silane) and are accordingly unstable chemicals that can violently decompose, especially in concentrated or pure forms. In addition to this instability, the boranes are significantly more toxic than are the silanes.
  • TLV's published in 1984-5 by the American Conference of Governmental Industrial Hygienists, lists time-weights average (TWA) exposures of 0.1 for diborane and 5.0 for silane.
  • getters taught herein can, of course, be used together with other known getters such as, for example, phosphorus, if so desired.
  • 52 watt, 84 volt tungsten halogen capsules were fabricated from 10 mm o.d. aluminosilicate tubing and had a nominal internal volume of 1.1 cubic centimeters.
  • the fill gas was introduced to a pressure of 5.1 x 125 N/m2 (five atmospheres) and comprised 0.1 percent hydrogen bromide, 2.0 percent nitrogen, and the balance xenon.
  • the coils were of straight coiled coil design wound from no-sag tungsten wire having a wire weight of 9.28 mg/200 mm, and wound so as to produce an efficacy of 16.6 lumens per watt.
  • the finished capsules were mounted in outer bulbs with a diode in electrical series with the coil for life testing at 120 volts AC. These lamps were similar in construction to the Sylvania Capsylite A-Line lamp.
  • a second group contained phosphorus, formed in the capsule before final evacuation by the thermal cracking (with electrical heating of the coil) of a one percent mixture of phosphine in nitrogen at a pressure of approximately 925 x 133 Nm ⁇ 2 (925 millimeters of mercury).
  • the third group used no phosphine, but instead included a fill gas containing 0.083 volume percent silane in addition to the other gases.
  • curve a illustrates the data for the control lamps fabricated with a phosphine getter
  • curve b illustrates the data for lamps fabricated in accordance with the present invention.
  • silane showed a life improvement of 54 percent over no getter, and 20 percent over the commonly used phosphorus getter.
  • tungsten halogen capsules were fabricated from 12.5 mm o.d. aluminosilicate tubing and had a nominal internal volume of 2.0 cubic centimeters.
  • the fill gas was introduced to a pressure of 5.1 x 105 N/m2 (five atmospheres) and comprised 0.1 percent hydrogen bromide, 2.0 percent nitrogen, and the balance xenon.
  • the coils were of straight coiled coil design wound from no-sag tungsten wire having a wire weight of 7.47 mg/200 mm, and wound so as to produce an efficacy of 16.5 lumens per watt.
  • the finished capsules were mounted in PAR-38 lamps with a diode in electrical series with the coil. The lamps were life tested at 120 volts AC.
  • One group of capsules contained phosphorus, formed in the capsule before final evacuation by the thermal cracking of a one percent mixture of phosphine in nitrogen at 925 x 133 Nm ⁇ 2 (925 millimeters of mercury) pressure by electrically heating the coil.
  • a second group of capsules used 0.083 volume percent silane in the fill gas instead of phosphorus.
  • curve c illustrates the lamp test results for the control lamps including a phosphine getter.
  • Curve d represents the test data for lamps fabricated in accordance with the present invention.
  • silane as the oxygen getter resulted in a substantial life improvement of 45 percent.
  • the method of the present invention represents a major advance in the state of the art of incandescent lamp technology by providing a significantly extended lamp life thereof.
  • silane compound getters in incandescent lamps without the method of the present invention results in decomposition of the silane compound by the filament coil upon light-up of the lamp before gettering the contaminants in the lamp. Also, by not heating the capsules prior to coil light-up, adsorbed water on surfaces internal to the capsule is not released to be gettered by the additive prior to destruction of the additive by the coil. Furthermore, elevated temperatures are known to be needed to promote the rapid and complete reaction of even the highly active diborane in an excess of air. ("Fate of Pollutants in the Air and Water Environments," Part 2, pp. 167-192, 1977, by Edward I. Sowinski and Irwin H. Suffet.)

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  • Discharge Lamp (AREA)

Claims (9)

  1. Verfahren zum Gettern einer Glühlampe mit den folgenden Schritten:
    Einbringung eines Füllgases und einer Getterverbindung, die aus der Gruppe von Silanverbindungen gemäß folgender Formel ausgewählt wird:



            SiaH (2a + 2)



    worin "a" eine ganze Zahl größer als Null ist, oder eines teilweise halogenisierten Derivats derselben, sowie Mischungen derselben, in eine nicht versiegelte Lampenhülle; Versiegeln der Lampenhülle, und Aufheizen der abgedichteten Hülle vor dem Zünden der Lampe für eine ausreichende Zeitspanne bei einer ausreichenden Temperatur, um den Getter vor seinem Zerfall zu aktivieren.
  2. Verfahren nach Anspruch 1, bei welchem "a" gleich 1 ist.
  3. Verfahren nach Anspruch 1, bei welchem "a" gleich 2 ist.
  4. Verfahren nach Anspruch 1, bei welchem "a" gleich 3 ist.
  5. Verfahren nach Anspruch 1, bei welchem "a" gleich 4 ist.
  6. Verfahren nach Anspruch 1, bei welchem das teilweise halogenisierte Derivat der Silanverbindung die Formel besitzt:



            SiaH[(2a + 2)-b]Xb



    wobei "b" eine ganze Zahl ist, die einen Wert kleiner als oder gleich (2a + 1) aufweist, wobei X Brom bedeutet.
  7. Verfahren nach Anspruch 1, bei welchem das teilweise halogenisierte Derivat der Silanverbindung die Formel besitzt:



            SiaH[(2a + 2)-b]Xb



    wobei "b" eine ganze Zahl ist, die einen Wert kleiner als oder gleich (2a + 1) aufweist, wobei X Chlor bedeutet.
  8. Verfahren nach Anspruch 1, bei welchem das teilweise halogenisierte Derivat der Silanverbindung die Formel besitzt:



            SiaH[(2a + 2)-b]Xb



    wobei "b" eine ganze Zahl ist, die einen Wert kleiner als oder gleich (2a + 1) aufweist wobei X Jod bedeutet.
  9. Verfahren nach Anspruch 1, bei welchem das teilweise halogenisierte Derivat der Silanverbindung die Formel besitzt:



            SiaH[(2a + 2)-b]Xb



    wobei "b" eine ganze Zahl ist, die einen Wert kleiner als oder gleich (2a + 2) aufweist, wobei X Fluor bedeutet.
EP19890102142 1988-02-09 1989-02-08 Getter für Glühlampen Expired - Lifetime EP0328065B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US15386388A 1988-02-09 1988-02-09
US153863 2002-05-24

Publications (3)

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EP0328065A2 EP0328065A2 (de) 1989-08-16
EP0328065A3 EP0328065A3 (de) 1991-04-17
EP0328065B1 true EP0328065B1 (de) 1994-08-17

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EP19890102142 Expired - Lifetime EP0328065B1 (de) 1988-02-09 1989-02-08 Getter für Glühlampen

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EP (1) EP0328065B1 (de)
JP (1) JPH027354A (de)
CA (1) CA1325036C (de)
DE (2) DE68917492T2 (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0374345B1 (de) * 1988-12-21 1995-05-03 Gte Products Corporation Glühlampen mit einem kombinierten Getter
US6956328B1 (en) * 2000-11-22 2005-10-18 General Electric Company Tungsten halogen lamp with halogen-containing compound and silicon-containing compound
DE102024001888A1 (de) * 2024-06-11 2025-12-11 Maximilian Cornelius Barmeyer Beleuchtung von Modellen

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL27400C (de) * 1928-12-18
NL6808844A (de) * 1968-06-22 1969-12-24

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Publication number Publication date
DE68917492D1 (de) 1994-09-22
EP0328065A2 (de) 1989-08-16
DE68917492T4 (de) 1995-10-12
DE68917492T2 (de) 1995-04-06
CA1325036C (en) 1993-12-07
JPH027354A (ja) 1990-01-11
EP0328065A3 (de) 1991-04-17

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