EP2145028A1 - Amalgam spheres for energy-saving lamps and the manufacture thereof - Google Patents

Amalgam spheres for energy-saving lamps and the manufacture thereof

Info

Publication number
EP2145028A1
EP2145028A1 EP08736446A EP08736446A EP2145028A1 EP 2145028 A1 EP2145028 A1 EP 2145028A1 EP 08736446 A EP08736446 A EP 08736446A EP 08736446 A EP08736446 A EP 08736446A EP 2145028 A1 EP2145028 A1 EP 2145028A1
Authority
EP
European Patent Office
Prior art keywords
amalgam
tin
powder
balls
spheres
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP08736446A
Other languages
German (de)
French (fr)
Other versions
EP2145028B1 (en
Inventor
Georg Ptaschek
Calogero Di Vincenzo
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Umicore AG and Co KG
Original Assignee
Umicore AG and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Umicore AG and Co KG filed Critical Umicore AG and Co KG
Priority to EP08736446A priority Critical patent/EP2145028B1/en
Priority to PL08736446T priority patent/PL2145028T3/en
Publication of EP2145028A1 publication Critical patent/EP2145028A1/en
Application granted granted Critical
Publication of EP2145028B1 publication Critical patent/EP2145028B1/en
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J61/00—Gas-discharge or vapour-discharge lamps
    • H01J61/02—Details
    • H01J61/12—Selection of substances for gas fillings; Specified operating pressure or temperature
    • H01J61/18—Selection of substances for gas fillings; Specified operating pressure or temperature having a metallic vapour as the principal constituent
    • H01J61/20—Selection of substances for gas fillings; Specified operating pressure or temperature having a metallic vapour as the principal constituent mercury vapour
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C13/00—Alloys based on tin
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C7/00—Alloys based on mercury
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J61/00—Gas-discharge or vapour-discharge lamps
    • H01J61/02—Details
    • H01J61/24—Means for obtaining or maintaining the desired pressure within the vessel
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J61/00—Gas-discharge or vapour-discharge lamps
    • H01J61/02—Details
    • H01J61/24—Means for obtaining or maintaining the desired pressure within the vessel
    • H01J61/28—Means for producing, introducing, or replenishing gas or vapour during operation of the lamp
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]

Definitions

  • the invention relates to amalgam beads for the introduction of mercury in modern energy-saving lamps.
  • Modern energy-saving lamps of the TFL (Tube Fluorescent Lamp) or CFL (Compact Fluorescent Lamp) type belong to the low-pressure gas discharge lamps. They consist of a gas discharge flask filled with a mixture of mercury vapor and argon and internally coated with a fluorescent phosphor. The ultraviolet radiation of mercury emitted during operation is converted from fluorescence coating to visible light by the phosphor coating. The lamps are therefore also referred to as fluorescent lamps.
  • the mercury required for the operation of the lamps was formerly metered as liquid metal into the gas discharge flask.
  • US Pat. No. 4,145,634 describes the use of amalgam pellets with 36 atomic percent indium which, because of the high mercury content, already contain high liquid fractions at room temperature. The pellets tend to stick together when they get in contact with each other. By coating the pellets with suitable materials in powder form, this can be prevented. Stable metal oxides (titanium oxide, zirconium oxide, silica, magnesia and alumina), graphite, glass powder, phosphors, borax, antimony oxide and metal powders that do not form an amalgam with mercury (aluminum, iron and chromium) are suggested.
  • WO 94/18692 describes the use of pellets of zinc amalgam with 5 to 60, preferably 40 to 60 wt .-%, mercury.
  • the method described in US 4,216,178 is used, in which the molten amalgam is formed by a nozzle excited to vibration outlet into small Drop is divided and cooled in a cooling medium below the solidification temperature.
  • the pellets are not coated according to WO 94/18692.
  • amalgam balls from the melt the amalgam must be heated to a temperature at which the amalgam is completely melted. This is guaranteed with a zinc amalgam only at a temperature above 420 0 C with certainty. These high processing temperatures necessitate corresponding safety precautions because of the high mercury vapor pressure due to the toxicity of the mercury.
  • JP 2000251836 describes the use of amalgam cells of tin amalgam for the production of fluorescent lamps.
  • the tin amalgam preferably has only a low mercury content with a tin / mercury atomic ratio of between 90-80: 10-20. This corresponds to a mercury content of 15.8 to 29.7 wt .-%.
  • JP 2000251836 gives no information about how spherical pellets are produced from the amalgam.
  • a disadvantage of the Zinnamalgam described in JP 2000251836 is the low mercury content. This makes relatively large amalgam balls necessary if a certain amount of mercury is to be introduced into the discharge lamps. Because of the increasing miniaturization even in energy-saving lamps, this can lead to problems in the design and manufacture of the lamps.
  • amalgam balls of a Zinnamalgam which has a mercury content between 30 and 70 wt .-%.
  • the amalgam spheres preferably have a mercury content of from 30 to 60 and in particular from 40 to 55% by weight.
  • the balls can be produced from a melt of the amalgam according to a method described in EP 1381485 B1. For this purpose, this will be fully molten amalgam dripped into a cooling medium at a temperature below the solidification temperature of the amalgam. Preferably, the temperature of the cooling medium is 10 to 20 0 C below the liquidus temperature of the amalgam. It is advantageous here that Zinnamalgame completely melt already at temperatures below 230 0 C. The expense of ensuring job security in the production of Zinnamalgam balls is therefore significantly lower than in the case of zinc amalgam balls.
  • the cooling medium used is preferably a mineral, an organic or a synthetic oil.
  • Well proven has a silicone oil. After formation of the amalgam balls in the cooling medium, they are separated from the cooling medium and degreased.
  • amalgam spheres with diameters between 50 and 2000, preferably between 500 and 1500 microns are suitable.
  • the tendency of the amalgam beads to adhere can be largely suppressed if the defatted beads are coated with a metal or alloy powder which forms an amalgam with mercury. Due to the amalgamation of the metal powder, a surface layer with a low mercury content is formed on the spheres, which no longer contains any liquid phases at the usual processing temperatures of the amalgam spheres and thus prevents the tendency to stick to the untreated spheres.
  • the metal or alloy powder used for the coating should not contain particles with a grain diameter greater than 100 ⁇ m. Particles with larger grain diameters amalgamate only incomplete and lead to a rough surface of the balls, which makes it difficult to meter the balls.
  • a meter used tall- or alloy powder whose powder particles have a particle diameter of less than 80 microns. Particular preference is given to metal or alloy powders having an average particle diameter d 50 between 5 and 15 ⁇ m.
  • Suitable metals have been found to be tin and zinc or an alloy of tin or zinc. Tin or a tin alloy are preferred. Good results have been obtained with alloys of tin with silver and copper, especially with the alloy SnAg3CuO, 5.
  • the balls can be presented for example in a rotating vessel and sprinkled with continuous circulation with the metal or alloy powder until no sticking of the balls is more detectable.
  • the amount of metal or alloy powder applied here to the amalgam beads is between 1 and 10, preferably between 2 and 4,% by weight, based on the weight of the amalgam beads.
  • the amalgam balls additionally contain a powder of a metal oxide in an amount of 0.001 to 1, preferably 0.01 to 0.5 and in particular in an amount of 0.1 wt .-%, based on the weight of the amalgam balls are coated.
  • a powder of a metal oxide in an amount of 0.001 to 1, preferably 0.01 to 0.5 and in particular in an amount of 0.1 wt .-%, based on the weight of the amalgam balls are coated.
  • Suitable metal oxides for this coating are, for example, titanium oxide, zirconium oxide, silicon oxide and aluminum oxide. Preference is given to using an aluminum oxide produced by flame pyrolysis with an average particle size of less than 5, preferably less than 1 micron.
  • the applied powder layers improve the handling of the amalgam balls with dosing machines.
  • the amalgam spheres can be on average for up to three hours at room temperature before they are filled in a fluorescent lamp. It has been shown that the coated with metal or alloy powder and metal oxide powder amalgam balls survive the mean residence time of 3 hours at temperatures of up to 40 0 C in dosing without complaint. If only one of the two layers applied, it comes even before the average duration of residence of 3 hours to isolated separation of the applied layers.
  • the following table shows calculated values for the total mass (Sn + Hg) and the mercury mass (Hg) of tin amalgam spheres as a function of the diameter of the spheres and for tin amalgams with mercury contents between 20 and 50 wt%.
  • the table also shows the densities p of the different amalgams used in the calculations.
  • amalgam spheres made from a SnHg50 containing 50% by weight of mercury contain about three times the mass of mercury, such as amalgam spheres made of SnHg20 with only 20% by weight of mercury.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Discharge Lamp (AREA)
  • Powder Metallurgy (AREA)
  • Manufacture Of Electron Tubes, Discharge Lamp Vessels, Lead-In Wires, And The Like (AREA)
  • Luminescent Compositions (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)

Abstract

The spheres are made from tin amalgam with a mercury content in the range 30-70%. They are coated with a metal- or alloy powder, which forms an amalgam with mercury. The powder particle diameter is less than 100 mu m. The powder is tin, zinc or an alloy of tin or zinc. The spheres are coated with 10 wt% of the powder, based on their weight. In addition they are coated with 0.001 - 1 wt% of powdered metal oxide. The powder is tin or a tin alloy. It is alternatively an alloy of tin, silver and copper. The diameter of the spheres is 50-2000 mu m. To make them, the amalgam is completely melted and dripped into coolant, e.g. a silicon oil, at a temperature below the setting temperature of the amalgam. The spheres are then separated-out. The coolant is a mineral-, organic- or synthetic oil. Residual oil is removed from the spheres by de-greasing. At room temperature, under constant circulation, the spheres are coated with the powder, until they no longer stick together. In a further stage, they are similarly-coated with the metal oxide powder. An independent claim is included for the method of manufacturing the amalgam spheres.

Description

Amalgamkugeln für Energiesparlampen und ihre Herstellung Amalgam balls for energy-saving lamps and their manufacture
Beschreibungdescription
Die Erfindung betrifft Amalgamkugeln für die Einbringung von Quecksilber in moderne Energiesparlampen.The invention relates to amalgam beads for the introduction of mercury in modern energy-saving lamps.
Moderne Energiesparlampen vom TFL- (Tube Fluorescent Lamp) oder CFL-Typ (Compact Fluorescent Lamp) gehören zu den Niederdruck-Gasentladungslampen. Sie bestehen aus einem Gasentladungskolben, der mit einer Mischung aus Quecksilberdampfund Argon befüllt und innen mit einem fluoreszierenden Leuchtstoff beschichtet ist. Die im Betrieb emittierte Ultraviolettstrahlung des Quecksilbers wird von der Leuchtstoff-Beschichtung durch Fluoreszenz in sichtbares Licht umgewandelt. Die Lampen werden daher auch als Fluoreszenzlampen bezeichnet.Modern energy-saving lamps of the TFL (Tube Fluorescent Lamp) or CFL (Compact Fluorescent Lamp) type belong to the low-pressure gas discharge lamps. They consist of a gas discharge flask filled with a mixture of mercury vapor and argon and internally coated with a fluorescent phosphor. The ultraviolet radiation of mercury emitted during operation is converted from fluorescence coating to visible light by the phosphor coating. The lamps are therefore also referred to as fluorescent lamps.
Das für den Betrieb der Lampen benötigte Quecksilber wurde früher als flüssiges Metall in die Gasentladungskolben dosiert. Seit langem ist es jedoch bekannt, das Quecksilber in Form von Amalgamkugeln in die Gasentladungskolben einzubringen. Dies erleichtert die Handhabung des toxischen Quecksilbers und erhöht die Genauigkeit der Dosierung.The mercury required for the operation of the lamps was formerly metered as liquid metal into the gas discharge flask. For a long time, however, it has been known to introduce the mercury in the form of amalgam balls into the gas discharge pistons. This facilitates the handling of the toxic mercury and increases the accuracy of the dosage.
Die US 4,145,634 beschreibt die Verwendung von Amalgampellets mit 36 Atom-% Indium, die wegen des hohen Quecksilbergehalts schon bei Raumtemperatur hohe flüssige Anteile enthalten. Die Pellets neigen daher zum Verkleben, wenn sie untereinander Kontakt bekommen. Durch Beschichten der Pellets mit geeigneten Materialien in Pulverform kann das verhindert werden. Vorgeschlagen werden stabile Metalloxide (Titanoxid, Zirkonoxid, Siliziumdioxid, Magnesiumoxid und Aluminiumoxid), Graphit, Glaspulver, Phosphore, Borax, Antimonoxid und Metallpulver, die kein Amalgam mit Quecksilber bilden (Aluminium, Eisen und Chrom).US Pat. No. 4,145,634 describes the use of amalgam pellets with 36 atomic percent indium which, because of the high mercury content, already contain high liquid fractions at room temperature. The pellets tend to stick together when they get in contact with each other. By coating the pellets with suitable materials in powder form, this can be prevented. Stable metal oxides (titanium oxide, zirconium oxide, silica, magnesia and alumina), graphite, glass powder, phosphors, borax, antimony oxide and metal powders that do not form an amalgam with mercury (aluminum, iron and chromium) are suggested.
Die WO 94/18692 beschreibt die Verwendung von Pellets aus Zinkamalgam mit 5 bis 60, bevorzugt 40 bis 60 Gew.-%, Quecksilber. Zur Fertigung von sphäroidalen Amalgampellets wird das in der US 4,216,178 beschriebene Verfahren verwendet, bei dem das geschmolzene Amalgam durch eine zu Vibrationen angeregte Auslaufdüse in kleine Tropfen zerteilt und in einem Kühlmedium unter die Erstarrungstemperatur abgekühlt wird. Die Pellets werden gemäß der WO 94/18692 nicht beschichtet.WO 94/18692 describes the use of pellets of zinc amalgam with 5 to 60, preferably 40 to 60 wt .-%, mercury. For the production of spheroidal Amalgampellets the method described in US 4,216,178 is used, in which the molten amalgam is formed by a nozzle excited to vibration outlet into small Drop is divided and cooled in a cooling medium below the solidification temperature. The pellets are not coated according to WO 94/18692.
Zur Herstellung von Amalgamkugeln aus der Schmelze muß das Amalgam auf eine Temperatur erwärmt werden, bei der das Amalgam vollständig aufgeschmolzen ist. Das ist bei einem Zinkamalgam erst bei einer Temperatur oberhalb von 420 0C mit Sicherheit gewährleistet. Diese hohen Verarbeitungstemperaturen machen wegen des damit verbundenen hohen Dampfdrucks von Quecksilber entsprechende Sicherheitsvorkehrungen wegen der Toxizität des Quecksilbers notwendig.For the production of amalgam balls from the melt, the amalgam must be heated to a temperature at which the amalgam is completely melted. This is guaranteed with a zinc amalgam only at a temperature above 420 0 C with certainty. These high processing temperatures necessitate corresponding safety precautions because of the high mercury vapor pressure due to the toxicity of the mercury.
Die JP 2000251836 beschreibt für die Herstellung von Fluoreszenzlampen die Verwen- düng von Amalgampellets aus Zinnamalgam. Das Zinnamalgam weist bevorzugt nur einen geringen Quecksilbergehalt auf mit einem Zinn/Quecksilber-Atomverhältnis zwischen 90-80 : 10-20. Dies entspricht einem Quecksilbergehalt von 15,8 bis 29,7 Gew.-%. Die JP 2000251836 macht keine Angaben darüber, wie aus dem Amalgam kugelförmige Pellets hergestellt werden.JP 2000251836 describes the use of amalgam cells of tin amalgam for the production of fluorescent lamps. The tin amalgam preferably has only a low mercury content with a tin / mercury atomic ratio of between 90-80: 10-20. This corresponds to a mercury content of 15.8 to 29.7 wt .-%. JP 2000251836 gives no information about how spherical pellets are produced from the amalgam.
Nachteilig bei dem in der JP 2000251836 beschriebenen Zinnamalgam ist der geringe Quecksilbergehalt. Das macht relativ große Amalgamkugeln notwendig, wenn eine bestimmte Menge von Quecksilber in die Entladungslampen eingebracht werden soll. Wegen der auch bei Energiesparlampen zunehmenden Miniaturisierung kann dies zu Problemen bei der Konstruktion und Fertigung der Lampen führen.A disadvantage of the Zinnamalgam described in JP 2000251836 is the low mercury content. This makes relatively large amalgam balls necessary if a certain amount of mercury is to be introduced into the discharge lamps. Because of the increasing miniaturization even in energy-saving lamps, this can lead to problems in the design and manufacture of the lamps.
Es ist daher eine Aufgabe der Erfindung, Amalgamkugeln aus Zinnamalgam zur Verfügung zu stellen, die einen hohen Quecksilbergehalt aufweisen und ohne Gefährdung der menschlichen Gesundheit sicher gelagert und bei der Herstellung von Energiesparlampen eingesetzt werden können.It is therefore an object of the invention to provide amalgam balls of Zinnamalgam available, which have a high mercury content and can be safely stored without risk to human health and used in the production of energy-saving lamps.
Diese Aufgabe wird gelöst durch Amalgamkugeln aus einem Zinnamalgam, welches einen Quecksilbergehalt zwischen 30 und 70 Gew.-% aufweist. Bevorzugt weisen die Amalgamkugeln einen Quecksilbergehalt von 30 bis 60 und insbesondere von 40 bis 55 Gew.-% auf.This object is achieved by amalgam balls of a Zinnamalgam, which has a mercury content between 30 and 70 wt .-%. The amalgam spheres preferably have a mercury content of from 30 to 60 and in particular from 40 to 55% by weight.
Die Kugeln können nach einem in der EP 1381485 Bl beschriebenen Verfahren aus einer Schmelze des Amalgams hergestellt werden. Hierzu wird das vollständig aufge- schmolzene Amalgam in ein Kühlmedium mit einer Temperatur unterhalb der Erstarrungstemperatur des Amalgams eingetropft. Bevorzugt liegt die Temperatur des Kühlmediums 10 bis 20 0C unterhalb der Liquidustemperatur des Amalgams. Vorteilhaft ist hierbei, daß Zinnamalgame schon bei Temperaturen unterhalb von 230 0C vollständig aufschmelzen. Der Aufwand für die Gewährleistung der Arbeitsplatzsicherheit bei der Herstellung der Zinnamalgam-Kugeln ist daher deutlich geringer als im Falle der Zink- amalgam- Kugeln.The balls can be produced from a melt of the amalgam according to a method described in EP 1381485 B1. For this purpose, this will be fully molten amalgam dripped into a cooling medium at a temperature below the solidification temperature of the amalgam. Preferably, the temperature of the cooling medium is 10 to 20 0 C below the liquidus temperature of the amalgam. It is advantageous here that Zinnamalgame completely melt already at temperatures below 230 0 C. The expense of ensuring job security in the production of Zinnamalgam balls is therefore significantly lower than in the case of zinc amalgam balls.
Als Kühlmedium wird bevorzugt ein mineralisches, ein organisches oder ein synthetisches Öl verwendet. Gut bewährt hat sich ein Silikonöl. Nach Bildung der Amalgamku- geln im Kühlmedium werden sie vom Kühlmedium abgetrennt und entfettet.The cooling medium used is preferably a mineral, an organic or a synthetic oil. Well proven has a silicone oil. After formation of the amalgam balls in the cooling medium, they are separated from the cooling medium and degreased.
Für die Zwecke der Erfindung sind Amalgamkugeln mit Durchmessern zwischen 50 und 2000, bevorzugt zwischen 500 und 1500 μm geeignet.For the purposes of the invention amalgam spheres with diameters between 50 and 2000, preferably between 500 and 1500 microns are suitable.
Es hat sich gezeigt, daß auf der Oberfläche der so hergestellten Amalgamkugeln flüssige Phasen auftreten, so daß die Kugeln bei Lagerung und Handhabung miteinander verkleben, wenn keine Maßnahmen dagegen unternommen werden. Das Verkleben kann zum Beispiel verhindert werden, wenn die Amalgamkugeln bei Temperaturen unter 8 0C gelagert und verarbeitet werden. Für die Lagerung wird eine Temperatur von -18 0C bevorzugt.It has been found that liquid phases occur on the surface of the amalgam beads thus produced, so that the balls stick together during storage and handling, if no measures are taken against it. The bonding can be prevented, for example, if the amalgam balls are stored and processed at temperatures below 8 0 C. For storage, a temperature of -18 0 C is preferred.
Die Neigung der Amalgamkugeln zum Verkleben kann weitgehend unterbunden wer- den, wenn die entfetteten Kugeln mit einem Metall- oder einem Legierungspulver beschichtet werden, welches mit Quecksilber ein Amalgam bildet. Durch die Amalgamie- rung des Metallpulvers bildet sich auf den Kugeln eine Oberflächenschicht mit einem geringen Quecksilbergehalt aus, die bei den üblichen Verarbeitungstemperaturen der Amalgamkugeln keine flüssigen Phasen mehr enthält und somit die Klebeneigung gegenüber den unbehandelten Kugeln unterbindet.The tendency of the amalgam beads to adhere can be largely suppressed if the defatted beads are coated with a metal or alloy powder which forms an amalgam with mercury. Due to the amalgamation of the metal powder, a surface layer with a low mercury content is formed on the spheres, which no longer contains any liquid phases at the usual processing temperatures of the amalgam spheres and thus prevents the tendency to stick to the untreated spheres.
Das für die Beschichtung eingesetzte Metall- oder Legierungspulver sollte keine Teilchen mit einem Korndurchmesser größer als 100 μm enthalten. Teilchen mit größeren Korndurchmessern amalgamieren nur unvollständig und führen zu einer rauhen Oberfläche der Kugeln, die eine Dosierung der Kugeln erschwert. Bevorzugt wird ein Me- tall- oder Legierungspulver verwendet, dessen Pulverteilchen einen Korndurchmesser von kleiner als 80 μm aufweisen. Besonders bevorzugt sind Metall- oder Legierungspulver mit einem mittleren Teilchendurchmesser dso zwischen 5 und 15 μm. Als geeignete Metalle haben sich Zinn und Zink erwiesen oder eine Legierung des Zinns oder des Zinks. Zinn oder eine Zinnlegierung sind dabei bevorzugt. Gute Ergebnisse wurden mit Legierungen des Zinns mit Silber und Kupfer erhalten, besonders mit der Legierung SnAg3CuO,5.The metal or alloy powder used for the coating should not contain particles with a grain diameter greater than 100 μm. Particles with larger grain diameters amalgamate only incomplete and lead to a rough surface of the balls, which makes it difficult to meter the balls. Preferably, a meter used tall- or alloy powder whose powder particles have a particle diameter of less than 80 microns. Particular preference is given to metal or alloy powders having an average particle diameter d 50 between 5 and 15 μm. Suitable metals have been found to be tin and zinc or an alloy of tin or zinc. Tin or a tin alloy are preferred. Good results have been obtained with alloys of tin with silver and copper, especially with the alloy SnAg3CuO, 5.
Zur Beschichtung der Amalgamkugeln mit dem Metall- oder Legierungspulver können die Kugeln zum Beispiel in einem rotierenden Kessel vorgelegt und unter ständigem Umwälzen mit dem Metall- oder Legierungspulver bestreut werden, bis kein Verkleben der Kugeln mehr feststellbar ist. Die hierbei auf die Amalgamkugeln aufgebrachte Menge an Metall- oder Legierungspulver beträgt zwischen 1 und 10, bevorzugt zwischen 2 und 4 Gew.-%, bezogen auf das Gewicht der Amalgamkugeln.For coating the amalgam balls with the metal or alloy powder, the balls can be presented for example in a rotating vessel and sprinkled with continuous circulation with the metal or alloy powder until no sticking of the balls is more detectable. The amount of metal or alloy powder applied here to the amalgam beads is between 1 and 10, preferably between 2 and 4,% by weight, based on the weight of the amalgam beads.
Eine weitere Verminderung der Verklebungsneigung erhält man, wenn die Amalgam- kugeln nach der Beschichtung mit dem Metall- oder Legierungspulver zusätzlich mit einem Pulver eines Metalloxids in einer Menge von 0,001 bis 1, bevorzugt 0,01 bis 0,5 und insbesondere in einer Menge von 0,1 Gew.-%, bezogen auf das Gewicht der Amalgamkugeln beschichtet werden. Zu diesem Zweck kann genauso vorgegangen werden wie bei der Aufbringung des Metall- oder Legierungspulvers. Geeignete Metalloxide für diese Beschichtung sind zum Beispiel Titanoxid, Zirkonoxid, Siliziumoxid und Aluminiumoxid. Bevorzugt wird ein durch Flammenpyrolyse hergestelltes Aluminiumoxid mit einer mittleren Korngröße von weniger als 5, bevorzugt von weniger als 1 μm verwendet.A further reduction in the tendency to sticking is obtained if, after the coating with the metal or alloy powder, the amalgam balls additionally contain a powder of a metal oxide in an amount of 0.001 to 1, preferably 0.01 to 0.5 and in particular in an amount of 0.1 wt .-%, based on the weight of the amalgam balls are coated. For this purpose, the same procedure can be used as in the application of the metal or alloy powder. Suitable metal oxides for this coating are, for example, titanium oxide, zirconium oxide, silicon oxide and aluminum oxide. Preference is given to using an aluminum oxide produced by flame pyrolysis with an average particle size of less than 5, preferably less than 1 micron.
Die aufgebrachten Pulverschichten verbessern die Handhabbarkeit der Amalgamkugeln mit Dosierautomaten. In solchen Dosierautomaten können sich die Amalgamkugeln im Mittel bis zu drei Stunden bei Raumtemperatur befinden, bevor sie in eine Fluoreszenzlampe eingefüllt werden. Dabei hat sich gezeigt, das die mit Metall- oder Legierungspulver und mit Metalloxidpulver beschichteten Amalgamkugeln die mittlere Aufenthaltsdauer von 3 Stunden bei Temperaturen von bis zu 40 0C im Dosierautomaten ohne Beanstandungen überstehen. Wird nur eine der beiden Schichten aufgebracht, kommt es schon vor Ablauf der mittleren Aufenthaltsdauer von 3 Stunden zu vereinzelten Ablösungen der aufgebrachten Schichten.The applied powder layers improve the handling of the amalgam balls with dosing machines. In such dosing machines, the amalgam spheres can be on average for up to three hours at room temperature before they are filled in a fluorescent lamp. It has been shown that the coated with metal or alloy powder and metal oxide powder amalgam balls survive the mean residence time of 3 hours at temperatures of up to 40 0 C in dosing without complaint. If only one of the two layers applied, it comes even before the average duration of residence of 3 hours to isolated separation of the applied layers.
Zur weiteren Erläuterung der Erfindung dient die folgende Tabelle. Sie zeigt berechnete Werte für die Gesamtmasse (Sn+Hg) und die Quecksilbermasse (Hg) von Zinnamal- gam-Kugeln in Abhängigkeit vom Durchmesser der Kugeln und für Zinnamalgame mit Quecksilbergehalten zwischen 20 und 50 Gew.-%. In der Tabelle sind außerdem die Dichten p der verschiedenen Amalgame angegeben, wie sie für die Berechnungen verwendet wurden.To further explain the invention, the following table is used. It shows calculated values for the total mass (Sn + Hg) and the mercury mass (Hg) of tin amalgam spheres as a function of the diameter of the spheres and for tin amalgams with mercury contents between 20 and 50 wt%. The table also shows the densities p of the different amalgams used in the calculations.
Durch Verwendung von Zinnamalgam mit hohen Quecksilbergehalten kann mit Kugeln gleichen Durchmessers deutlich mehr Quecksilber in die Gasentladungskolben eingebracht werden als mit einem Zinnamalgam mit geringem Quecksilbergehalt von nur 20 Gew.-%. So enthalten Amalgamkugeln aus einem SnHg50 mit 50 Gew.-% Quecksilber etwa die dreifache Masse an Quecksilber wie Amalgamkugeln aus SnHg20 mit nur 20 Gew.-% Quecksilber.By using tin amalgam with high mercury contents, significantly more mercury can be introduced into the gas discharge flask with balls of the same diameter than with a tin amalgam with a low mercury content of only 20% by weight. Thus, amalgam spheres made from a SnHg50 containing 50% by weight of mercury contain about three times the mass of mercury, such as amalgam spheres made of SnHg20 with only 20% by weight of mercury.
Tabelle: Gesamtmasse und Quecksilbermasse in Abhängigkeit vom Kugeldurchmes- ser für Zinnamalgam-Kugeln mit Quecksilbergehalten zwischen 20 und 50 Gew.-%Table: Total mass and mercury mass as a function of the ball diameter for tin amalgam spheres with mercury contents between 20 and 50% by weight

Claims

Patentansprüche claims
1. Amalgamkugeln für Fluoreszenzlampen, dadurch gekennzeichnet, daß die Amalgamkugeln ein Zinnamalgam mit einem Quecksilbergehalt zwischen 30 und 70 Gew.-% enthalten.1. amalgam beads for fluorescent lamps, characterized in that the amalgam contain a Zinnamalgam with a mercury content between 30 and 70 wt .-%.
2. Amalgamkugeln nach Anspruch 1 , dadurch gekennzeichnet, daß die Kugeln mit einem Metall- oder einem Legierungspulver beschichtet sind, welches mit Quecksilber ein Amalgam bildet.2. Amalgamkugeln according to claim 1, characterized in that the balls are coated with a metal or an alloy powder which forms an amalgam with mercury.
3. Amalgamkugeln nach Anspruch 2, dadurch gekennzeichnet, daß die Pulverteilchen einen Korndurchmesser kleiner als 100 μm aufweisen.3. amalgam beads according to claim 2, characterized in that the powder particles have a particle diameter smaller than 100 microns.
4. Amalgamkugeln nach Anspruch 3, dadurch gekennzeichnet, daß das Metall- oder Legierungspulver aus Zinn, Zink oder einer Legierung des4. Amalgamkugeln according to claim 3, characterized in that the metal or alloy powder of tin, zinc or an alloy of
Zinns oder des Zinks besteht.Tin or zinc.
5. Amalgamkugeln nach Anspruch 4, dadurch gekennzeichnet, daß die Amalgamkugeln in einer Menge von 1 bis 10 Gew.-%, bezogen auf ihr Gewicht, mit dem Metall- oder Legierungspulver beschichtet sind.5. amalgam beads according to claim 4, characterized in that the amalgam balls in an amount of 1 to 10 wt .-%, based on their weight, are coated with the metal or alloy powder.
6. Amalgamkugeln nach Anspruch 5, dadurch gekennzeichnet, daß die Amalgamkugeln zusätzlich mit einem Pulver eines Metalloxids in einer Menge von 0,001 bis 1 Gew.-% beschichtet sind.6. amalgam beads according to claim 5, characterized in that the amalgam balls are additionally coated with a powder of a metal oxide in an amount of 0.001 to 1 wt .-%.
7. Amalgamkugeln nach Anspruch 6, dadurch gekennzeichnet, daß das Metall- oder Legierungspulver aus Zinn oder einer Zinnlegierung besteht. 7. Amalgam balls according to claim 6, characterized in that the metal or alloy powder consists of tin or a tin alloy.
8. Amalgamkugeln nach Anspruch 7, dadurch gekennzeichnet, daß das Metall- oder Legierungspulver aus einer Legierung des Zinns mit Silber und Kupfer besteht.8. amalgam balls according to claim 7, characterized in that the metal or alloy powder consists of an alloy of tin with silver and copper.
9. Amalgamkugeln nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß die Kugeln einen Durchmesser zwischen 50 und 2000 μm aufweisen.9. amalgam balls according to any one of the preceding claims, characterized in that the balls have a diameter between 50 and 2000 microns.
10. Verfahren zur Herstellung der Amalgamkugeln nach einem der vorstehenden10. A process for the preparation of the amalgam beads according to one of the preceding
Ansprüche, dadurch gekennzeichnet, daß das Amalgam vollständig aufgeschmolzen wird und die Schmelze in ein Kühlmedium mit einer Temperatur unterhalb der Erstarrungstemperatur des Amalgams eingetropft wird und anschließend die gebildeten Amalgamkugeln vom Kühlmedium abgetrennt werden.Claims, characterized in that the amalgam is completely melted and the melt is dropped into a cooling medium having a temperature below the solidification temperature of the amalgam and then the amalgam spheres formed are separated from the cooling medium.
11. Verfahren nach Anspruch 10, dadurch gekennzeichnet, daß als Kühlmedium ein mineralisches, ein organisches oder ein synthetisches Öl verwendet wird.11. The method according to claim 10, characterized in that a mineral, an organic or a synthetic oil is used as the cooling medium.
12. Verfahren nach Anspruch 11 , dadurch gekennzeichnet, daß die Amalgamkugeln nach dem Abtrennen vom Kühlmedium entfettet und bei Raumtemperatur unter ständigem Umwälzen mit einem Metall- oder Legierungspulver bestreut werden, welches mit Quecksilber ein Amalgam bildet, bis kein Verkleben der Kugeln mehr feststellbar ist.12. The method according to claim 11, characterized in that the amalgam is degreased after separation from the cooling medium and sprinkled at room temperature with constant circulation with a metal or alloy powder which forms an amalgam with mercury until no sticking of the balls is more detectable.
13. Verfahrennach Anspruch 12, dadurch gekennzeichnet, daß die Amalgamkugeln in einem weiteren Schritt unter ständigem Umwälzen zusätzlich mit einem Pulver eines Metalloxids beschichtet werden. 13. The method according to claim 12, characterized in that the amalgam balls are additionally coated in a further step under constant circulation with a powder of a metal oxide.
14. Verwendung der Amalgamkugeln nach einem der Ansprüche 1 bis 9 für die Herstellung von Fluoreszenzlampen. 14. Use of the amalgam beads according to any one of claims 1 to 9 for the production of fluorescent lamps.
EP08736446A 2007-04-28 2008-04-22 Amalgam spheres for energy-saving lamps and the manufacture thereof Not-in-force EP2145028B1 (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2497841A1 (en) 2011-03-09 2012-09-12 Umicore AG & Co. KG Sn-Ag-Cu-Alloys
DE202011110608U1 (en) 2011-03-09 2015-02-23 Umicore Ag & Co. Kg alloys
US9324555B2 (en) 2007-04-28 2016-04-26 Umicore Ag & Co. Kg Amalgam spheres for energy-saving lamps and their production

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011127480A1 (en) * 2010-04-09 2011-10-13 Advanced Lighting Technologies, Inc. Mechanically plated pellets and method of manufacture
CN102329979A (en) * 2011-08-13 2012-01-25 何志明 Hg-rich type Sb-Sn-Hg alloy
CN102626781B (en) * 2012-03-26 2014-04-16 上海亚尔光源有限公司 Zinc tin amalgam granule and preparation method and application thereof
CN102626782B (en) * 2012-03-26 2014-07-16 上海亚尔光源有限公司 Zinc amalgam particle and preparing process and usage thereof
CN102626783B (en) * 2012-03-26 2014-02-12 上海亚尔光源有限公司 Tin amalgam particle and preparing method and application thereof
CN104148628B (en) * 2013-05-13 2017-02-08 上海亚尔光源有限公司 Amalgam powder coating process
WO2015021183A1 (en) * 2013-08-06 2015-02-12 Advanced Lighting Technologies, Inc. Intermetallic compounds for releasing mercury
CN103730307B (en) * 2013-12-17 2016-09-07 家雄灯饰（濮阳）有限公司 Electricity-saving lamp full-automatic injecting mercury seal device
CN108998691A (en) * 2017-12-25 2018-12-14 中国地质大学（北京） A kind of method of harmless treatment liquid mercury

Family Cites Families (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4015162A (en) 1975-07-07 1977-03-29 Westinghouse Electric Corporation Fluorescent lamp having implanted amalgamative metal for mercury vapor regulation
US4216178A (en) 1976-02-02 1980-08-05 Scott Anderson Process for producing sodium amalgam particles
US4145634A (en) * 1978-02-17 1979-03-20 Westinghouse Electric Corp. Fluorescent lamp having integral mercury-vapor pressure control means
JPS5595254A (en) * 1979-01-16 1980-07-19 Mitsubishi Electric Corp Manufacturing method of high-pressure metal vapor discharge lamp
AR223024A1 (en) 1980-01-31 1981-07-15 Macrodent Sa A PRODUCT TO BE USED IN COMPRESSED DENTAL AMALGAMAS OR DISINTEGRABLE PILLS OBTAINED BY AGGLOMERATION OF SUCH PRODUCT AND AMALGAMAS OBTAINED FROM THIS LAST
DE3485382D1 (en) * 1983-09-30 1992-02-06 Toshiba Kawasaki Kk METHOD FOR PRODUCING A LOW-MELTING ALLOY FOR SEALING FLUORESCENT LAMPS.
JPS6210838A (en) * 1986-03-14 1987-01-19 Toshiba Corp Fluorescent lamp
DE3717048C1 (en) 1987-05-21 1988-11-03 Degussa Process for the preparation of alloy powders for dental amalgams
BR9405796A (en) 1993-02-12 1995-12-12 Apl Engineered Mat Inc Fluorescent lamp that does not rely on an amalgamative metal to control the vapor pressure temperature-controlled fluorescent lamp having a predetermined amount of mercury sealed in it lamp filling material fluorescent lamp with mercury
JPH07192689A (en) * 1993-12-28 1995-07-28 Toshiba Lighting & Technol Corp Mercury vapor discharge lamp and its manufacturing method and lighting system
IT1273338B (en) * 1994-02-24 1997-07-08 Getters Spa COMBINATION OF MATERIALS FOR MERCURY DISPENSING DEVICES PREPARATION METHOD AND DEVICES SO OBTAINED
US5882237A (en) 1994-09-01 1999-03-16 Advanced Lighting Technologies, Inc. Fluorescent lamp containing a mercury zinc amalgam and a method of manufacture
CA2177108C (en) * 1996-05-22 2002-10-22 Minoru Myojo Low pressure mercury vapor filled discharge lamp
JP4228046B2 (en) * 1999-02-27 2009-02-25 松垣薬品工業株式会社 Amalgam pellets for fluorescent lamps and fluorescent lamps using the same
US6312499B1 (en) * 1999-05-07 2001-11-06 Institute Of Gas Technology Method for stabilization of liquid mercury
US6427492B1 (en) 2000-03-31 2002-08-06 Owens Corning Fiberglas Technology, Inc. Bushing including a terminal ear
DE10120612A1 (en) 2001-04-26 2002-11-21 Omg Ag & Co Kg Method and device for producing spherical metal particles
CN100543922C (en) * 2003-02-17 2009-09-23 东芝照明技术株式会社 Fluorescent lamp, ball type fluorescent lamp and lighting device
JP4235720B2 (en) * 2004-04-21 2009-03-11 松垣薬品工業株式会社 Amalgam for fluorescent lamp and fluorescent lamp using the same
CN1694221A (en) * 2004-05-07 2005-11-09 东芝照明技术株式会社 Compact fluorescent lamp and luminaire using the same
ITMI20041494A1 (en) * 2004-07-23 2004-10-23 Getters Spa COMPOSITIONS FOR THE RELEASE OF MERCURY AND PROCESS FOR THEIR PRODUCTION
JP4077448B2 (en) * 2004-07-30 2008-04-16 松下電器産業株式会社 Fluorescent lamp, illumination device, and method of manufacturing fluorescent lamp
CN100383909C (en) * 2005-07-05 2008-04-23 朱升和 Low temp amalgam
CN100434552C (en) * 2006-03-13 2008-11-19 高邮高和光电器材有限公司 Solid mercury with high content
US8668841B2 (en) 2006-06-09 2014-03-11 Advanced Lighting Technologies, Inc. Bismuth-zinc-mercury amalgam, fluorescent lamps, and related methods
PL1985717T3 (en) 2007-04-28 2011-11-30 Umicore Ag & Co Kg Amalgam globules for energy saving lamps and their manufacture
WO2011127480A1 (en) 2010-04-09 2011-10-13 Advanced Lighting Technologies, Inc. Mechanically plated pellets and method of manufacture
EP2497841B1 (en) 2011-03-09 2015-09-02 Umicore AG & Co. KG Sn-Ag-Cu-Alloys

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2008132089A1 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9324555B2 (en) 2007-04-28 2016-04-26 Umicore Ag & Co. Kg Amalgam spheres for energy-saving lamps and their production
EP2497841A1 (en) 2011-03-09 2012-09-12 Umicore AG & Co. KG Sn-Ag-Cu-Alloys
WO2012119977A1 (en) 2011-03-09 2012-09-13 Umicore Ag & Co. Kg Amalgam balls having an alloy coating
DE202011110608U1 (en) 2011-03-09 2015-02-23 Umicore Ag & Co. Kg alloys
EP2975143A1 (en) 2011-03-09 2016-01-20 Umicore AG & Co. KG Alloys
US9263245B2 (en) 2011-03-09 2016-02-16 Umicore Ag & Co. Kg Amalgam balls having an alloy coating
US9659762B2 (en) 2011-03-09 2017-05-23 Umicore Ag & Co. Kg Amalgam balls having an alloy coating

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CN101960027A (en) 2011-01-26
ATE514797T1 (en) 2011-07-15
WO2008132089A1 (en) 2008-11-06
PL2145028T3 (en) 2010-12-31
ATE473307T1 (en) 2010-07-15
US9324555B2 (en) 2016-04-26
JP5599449B2 (en) 2014-10-01
US20140009059A1 (en) 2014-01-09
EP2145028B1 (en) 2010-07-07
DE502008000912D1 (en) 2010-08-19
JP5193285B2 (en) 2013-05-08
CN101960027B (en) 2013-05-01
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JP2010527097A (en) 2010-08-05
US8497622B2 (en) 2013-07-30

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