EP2975143B1 - Procédé de préparation de sphères d'amalgame - Google Patents

Procédé de préparation de sphères d'amalgame Download PDF

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Publication number
EP2975143B1
EP2975143B1 EP15179281.9A EP15179281A EP2975143B1 EP 2975143 B1 EP2975143 B1 EP 2975143B1 EP 15179281 A EP15179281 A EP 15179281A EP 2975143 B1 EP2975143 B1 EP 2975143B1
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EP
European Patent Office
Prior art keywords
weight
amalgam
balls
process according
alloy powder
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EP15179281.9A
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German (de)
English (en)
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EP2975143A1 (fr
Inventor
Olivier Hutin
Hans Martin Ringelstein
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Saxonia Technical Materials GmbH
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Saxonia Technical Materials GmbH
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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
    • H01J61/24—Means for obtaining or maintaining the desired pressure within the vessel
    • H01J61/26—Means for absorbing or adsorbing gas, e.g. by gettering; Means for preventing blackening of the envelope
    • 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
    • C22C5/00—Alloys based on noble metals
    • C22C5/06—Alloys based on silver
    • 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
    • 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
    • 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
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J61/00—Gas-discharge or vapour-discharge lamps
    • H01J61/02—Details
    • H01J61/38—Devices for influencing the colour or wavelength of the light
    • H01J61/42—Devices for influencing the colour or wavelength of the light by transforming the wavelength of the light by luminescence
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J61/00—Gas-discharge or vapour-discharge lamps
    • H01J61/70—Lamps with low-pressure unconstricted discharge having a cold pressure < 400 Torr
    • H01J61/72—Lamps with low-pressure unconstricted discharge having a cold pressure < 400 Torr having a main light-emitting filling of easily vaporisable metal vapour, e.g. mercury
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
    • H01J9/38—Exhausting, degassing, filling, or cleaning vessels
    • H01J9/395—Filling vessels
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
    • H01J9/40—Closing vessels
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y10T428/12049—Nonmetal component
    • Y10T428/12056—Entirely inorganic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y10T428/12063—Nonparticulate metal component
    • Y10T428/1209—Plural particulate metal components

Definitions

  • 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. Tanning and disinfection lamps work on the same principle, but are optimized for the emission of UV radiation and usually have no phosphor.
  • the US 4,145,634 describes the use of Amalgampellets with 36 at% indium, which contain high liquid content even at room temperature because of the high mercury content.
  • 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 phosphors
  • borax antimony oxide
  • metal powders that do not form an amalgam with mercury (aluminum, iron and chromium) are suggested.
  • the WO 94/18692 describes the use of pellets of zinc amalgam with 5 to 60, preferably 40 to 60 wt .-%, mercury.
  • pellets of zinc amalgam with 5 to 60, preferably 40 to 60 wt .-%, mercury.
  • For the production of spheroid Amalgampellets is in the US 4,216,178 described method in which the molten amalgam by a vibrationally excited outlet nozzle in split small drops and cooled in a cooling medium below the solidification temperature.
  • the pellets are in accordance with WO 94/18692 not coated.
  • 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 ° 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.
  • the 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 .-%.
  • the JP 2000251836 Does not give any information about how the amalgam spherical pellets are made.
  • EP 2145028 shows amalgam balls with higher mercury content, which, however, tend to stick. Although this problem is reduced by a proposed coating of the amalgam balls with an amalgam-forming metal powder, but not completely solved for all purposes.
  • Claim 9 defines a process for the preparation of low-pressure Gasentaldungslampen.
  • Amalgam spheres produced according to the invention are spheres coated with an alloy powder, the alloy powder having the composition Ag 3 - 80, Cu 0.5 - 43, Sn 0 - 96.5, Zn 0 - 5, In 0-10 and Au / Pd And wherein the amalgam spheres after the coating are subjected to a heat treatment at a temperature of 35 ° C to 100 ° C for a period of 2 hours to 20 hours.
  • Particularly suitable are alloy powders which contain more than 3 wt. -% silver or copper if the tin content exceeds 90% by weight. Such alloy powders are very suitable when they form an amalgam with mercury.
  • the amalgam spheres according to the invention are amalgams of the metals tin (Sn), zinc (Zn), bismuth (Bi), indium (In) and their alloys with one another.
  • these are amalgams with a mercury content between 30 and 70 wt .-%, in further embodiments of the invention have 40 to 60 and in particular from 40 to 55 wt .-% mercury content.
  • Amalgam spheres containing these mercury contents are in particular tin amalgam spheres, but also zinc amalgam spheres, ie SnHg30 to SnHg70, or SnHg40 to SnHg60, or SnHg45 to SnHg55 or SnHg50 or ZnHg30 to ZnHg70, or ZnHg40 to ZnHg60, or ZnHg45 to ZnHg55, or Bi ad 100% by weight, 10% by weight to 30% by weight, Sn 10% by weight to 40% by weight of mercury (BiSn10-30Hg10-40).
  • amalgam spheres which contain far smaller quantities of mercury, such as amalgams of bismuth, indium or mixtures thereof and mercury.
  • the proportions of the metals of the alloy complement each other to 100 wt .-%.
  • amalgam spheres with diameters between 50 ⁇ m and 3000 ⁇ m, in particular 100 ⁇ m to 2500 ⁇ m, or 200 ⁇ m to 2000 ⁇ m or between 500 ⁇ m and 1500 ⁇ m are particularly suitable.
  • the alloy powder used for the coating should contain less or no particles with a grain diameter larger 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. It is better in this aspect to use an alloy powder whose powder particles have a particle diameter of less than 80 microns. In addition, alloy powders having an average particle diameter d 50 of 2 ⁇ m to 20 ⁇ m or of 5 ⁇ m to 15 ⁇ m or of 2 ⁇ m to 15 ⁇ m or of 5 ⁇ m to 20 ⁇ m or of 2 ⁇ m to 5 ⁇ m are well suited. The shape of the powder particles is generally free from any special requirements, so that spherical, angular, platelet-shaped, flake-shaped, needle-shaped, granular alloy powders or combinations thereof can be used.
  • alloys of tin or silver have preferably been used together, optionally also with zinc. Good results were obtained with alloys of tin with silver and copper.
  • Suitable alloy powders have a composition of silver (Ag) 3 wt% to 80 wt%, copper (Cu) 0.5 wt% to 43 wt%, tin (Sn) 0 wt% to 96 , 5 wt .-%, zinc (Zn) 0 wt .-% to 5 wt .-%, indium (In) 0 wt .-% to 10 wt .-% and gold, palladium and platinum (Au / Pd / Pt ), individually or in combination with each other, from 0 wt .-% to 5 wt .-%, wherein the proportions of the metals add up to a total of 100 wt .-%.
  • alloy powders which contain more than 3% by weight of silver or copper if the tin content exceeds 90% by weight.
  • the alloy powders have the composition silver (Ag) 24 wt .-% to 75 wt .-%, copper (Cu) 5 wt .-% to 43 wt .-% or 20 wt .-% to 30 %
  • tin (Sn) 10% by weight to 48% by weight zinc (Zn) 0.1% by weight to 3% by weight, indium (In) 0.1% by weight to 5% by weight and gold, palladium and platinum (Au / Pd / Pt), individually or in combination, from 0.1% to 5% by weight, with the proportions of the metals totaling 100% by weight ,
  • the alloy powders have the composition silver (Ag) 56 wt .-% to 72 wt .-%, copper (Cu) 12.5 wt .-% to 28 wt .-%, tin (Sn) 20 Wt .-% to 35 wt .-%, zinc (Zn) 0 wt .-% to 3 wt .-%, indium (In) 0 wt .-% to 5 wt .-% and gold, palladium and platinum (Au / Pd / Pt), individually or in combination with each other, from 0 wt .-% to 5 wt .-%, wherein the proportions of the metals add up to a total of 100 wt .-%.
  • the alloy powders have the composition silver (Ag) 56 wt .-% to 72 wt .-%, copper (Cu) 12.5 wt .-% to 28 wt .-%, tin (Sn) 0 Wt .-% to 35 wt .-%, zinc (Zn) 0 wt .-% to 3 wt .-%, indium (In) 0 wt .-% to 5 wt .-% and gold, palladium and platinum (Au / Pd / Pt), individually or in combination with each other, from 0 wt .-% to 5 wt .-%, wherein the proportions of the metals add up to a total of 100 wt .-%.
  • the alloy powders have the composition silver (Ag) 56 wt .-% to 72 wt .-%, copper (Cu) 12.5 wt .-% to 28 wt .-%, tin (Sn) 0 Wt .-% to 35 wt .-%, zinc (Zn) 0.1 wt .-% to 3 wt .-%, indium (In) 0 wt .-% to 5 wt .-% and gold, palladium and platinum (Au / Pd / Pt), individually or in combination with each other, from 0 wt .-% to 5 wt .-%, wherein the proportions of the metals add up to a total of 100 wt .-%.
  • the alloy powders have the composition silver (Ag) 56 wt .-% to 72 wt .-%, copper (Cu) 12.5 wt .-% to 28 wt .-%, tin (Sn) 0 Wt .-% to 35 wt .-%, zinc (Zn) 0 wt .-% to 3 wt .-%, indium (In) 0.1 wt .-% to 5 wt .-% and gold, palladium and platinum (Au / Pd / Pt), individually or in combination with each other, from 0 wt .-% to 5 wt .-%, wherein the proportions of the metals add up to a total of 100 wt .-%.
  • the alloy powders have the composition silver (Ag) 56 wt .-% to 72 wt .-%, copper (Cu) 12.5 wt .-% to 28 wt .-%, tin (Sn) 0 Wt .-% to 35 wt .-%, zinc (Zn) 0 wt .-% to 3 wt .-%, indium (In) 0 wt .-% to 5 wt .-% and gold, palladium and platinum (Au / Pd / Pt), individually or in combination with each other, from 0.1 wt .-% to 5 wt .-%, wherein the proportions of the metals add up to a total of 100 wt .-%.
  • the alloy powders have the composition silver (Ag) 56 wt .-% to 72 wt .-%, copper (Cu) 12.5 wt .-% to 28 wt .-%, tin (Sn) 0 Wt .-% to 35 wt .-%, zinc (Zn) 0 wt .-% to 3 wt .-%, indium (In) 0 wt .-% to 5 wt .-% and gold, palladium and platinum (Au / Pd / Pt), individually or in combination with each other, from 1 wt .-% to 8 wt .-%, wherein the proportions of the metals add up to a total of 100 wt .-%.
  • Suitable combinations of the elements silver, zinc, indium and gold, palladium and platinum are described in Table 1 below.
  • Suitable compositions of the alloy powders are listed in the following Tables 2 to 17, where the copper and silver contents are given. Individual combinations are designated by the number of the table, followed by the number of the respective combination of the elements silver, zinc, indium and gold, palladium and platinum (individually or in combination) from Table 1.
  • the alloy composition 2.005 means the combination of Elements silver, zinc, indium and also gold, palladium and platinum as in Table 1, position No.
  • Table 2 consists of 81 alloy compositions 2.001 to 2.081, wherein the contents of the elements silver, zinc, indium and gold, palladium and platinum (individually or in combination with each other) in weight percent are given in Table 1, respectively, and the contents of tin (Sn) are 0 Wt .-% to 35 wt .-% and of copper (Cu) 0.5 wt .-% to 43 wt .-% amount and the proportions of the metals add up to 100 wt .-%.
  • Table 3 consists of 81 alloy compositions 3.001 to 3.081, wherein the contents of the elements silver, zinc, indium and gold, palladium and platinum (individually or in combination with each other) in weight percent in each case in Table 1 and the contents of tin (Sn) 0 wt .-% to 35 wt .-% and copper (Cu) 12.5 wt .-% to 28 wt. % and the proportions of the metals add up to 100% by weight.
  • Table 4 consists of 81 alloy compositions 4.001 to 4.081, wherein the contents of the elements silver, zinc, indium and gold, palladium and platinum (individually or in combination with each other) in weight percent are given in Table 1, respectively, and the contents of tin (Sn) are 0 Wt .-% to 35 wt .-% and copper (Cu) 5 wt .-% to 43 wt .-% amount and the proportions of the metals to 100 wt .-% complementary.
  • Table 5 consists of 81 alloy compositions 5,001 to 5,081, wherein the contents of the elements silver, zinc, indium and gold, palladium and platinum (individually or in combination with each other) in weight percent are given in Table 1, respectively, and the contents of tin (Sn) are 0 Wt .-% to 35 wt .-% and copper (Cu) 20 wt .-% to 30 wt .-% amount and the proportions of the metals to 100 wt .-% complement.
  • Table 6 consists of 81 alloy compositions 6,001 to 6,081, wherein the contents of the elements silver, zinc, indium and gold, palladium and platinum (individually or in combination with each other) are given by weight in Table 1, respectively, and the contents of tin (Sn) are 0 % By weight to 96.5% by weight and copper (Cu) copper (Cu) 0.5% by weight to 43% by weight and the proportions of the metals to 100% by weight.
  • Table 7 consists of 81 alloy compositions 7,001 to 7,081, wherein the contents of the elements silver, zinc, indium and gold, palladium and platinum (individually or in combination with each other) in weight percent in each case in Table 1 and the contents of tin (Sn) 0 wt .-% to 96.5 wt .-% and copper (Cu) copper (Cu) 12.5 wt. % to 28 wt .-% and the proportions of the metals add up to 100 wt .-%.
  • Table 8 consists of 81 alloy compositions 8,001 to 8,081, wherein the contents of the elements silver, zinc, indium and gold, palladium and platinum (individually or in combination with each other) in weight percent are given in Table 1, respectively, and the contents of tin (Sn) are 0 Wt .-% to 96.5 wt .-% and copper (Cu) 5 wt .-% to 43 wt .-% amount and the proportions of the metals to 100 wt .-% complement.
  • Table 9 consists of 81 alloy compositions 9.001 to 9.081, wherein the contents of the elements silver, zinc, indium and gold, palladium and platinum (individually or in combination with each other) in weight percent are given in Table 1, respectively, and the contents of tin (Sn) are 0 Wt .-% to 96.5 wt .-% and of copper (Cu) 20 wt .-% to 30 wt .-% amount and the proportions of the metals to 100 wt .-% complementary.
  • Table 10 consists of 81 alloy compositions 10,001 to 10,081, wherein the contents of the elements silver, zinc, indium and gold, palladium and platinum (individually or in combination with each other) in weight percent are given in Table 1, respectively, and the contents of tin (Sn) are 10 Wt .-% to 48 wt .-% and of copper (Cu) 0.5 wt .-% to 43 wt .-% amount and the proportions of the metals add up to 100 wt .-%.
  • Table 11 consists of 81 alloy compositions 11.001 to 11.081, wherein the contents of the elements silver, zinc, indium and gold, palladium and platinum (individually or in combination with each other) in weight percent in each case in Table 1 and the contents of tin (Sn) 10 wt .-% to 48 wt .-% and copper (Cu) 12.5 wt .-% to 28 wt. % and the proportions of the metals add up to 100% by weight.
  • Table 12 consists of 81 alloy compositions 12.001 to 12.081, wherein the contents of the elements silver, zinc, indium and gold, palladium and platinum (individually or in combination with each other) in weight percent are given in Table 1, respectively, and the contents of tin (Sn) are 10 Wt .-% to 48 wt .-% and of copper (Cu) 5 wt .-% to 43 wt .-% amount and the proportions of the metals to 100 wt .-% complementary.
  • Table 13 consists of 81 alloy compositions 13.001 to 13.081, wherein the contents of the elements silver, zinc, indium and gold, palladium and platinum (individually or in combination with each other) in weight percent are given in Table 1, respectively, and the contents of tin (Sn) are 10 Wt .-% to 48 wt .-% and copper (Cu) 20 wt .-% to 30 wt .-% amount and the proportions of the metals to 100 wt .-% complement.
  • Table 14 consists of 81 alloy compositions 14,001 to 14,081, wherein the contents of the elements silver, zinc, indium and gold, palladium and platinum (individually or in combination with each other) in weight percent are given in Table 1, respectively, and the contents of tin (Sn) are 20 Wt .-% to 35 wt .-% and copper (Cu) 0.5 wt .-% to 43 wt .-% amount and the proportions of the metals add up to 100 wt .-%.
  • Table 15 consists of 81 alloy compositions 15.001 to 15.081, wherein the contents of the elements silver, zinc, indium and gold, palladium and platinum (individually or in combination with each other) in weight percent in each case in Table 1 and the contents of tin (Sn) 20 wt .-% to 35 wt .-% and copper (Cu) 12.5 wt .-% to 28 wt. % and the proportions of the metals add up to 100% by weight.
  • Table 16 consists of 81 alloy compositions 16.001 to 16.081, wherein the contents of the elements silver, zinc, indium and gold, palladium and platinum (individually or in combination with each other) in weight percent are given in Table 1, respectively, and the contents of tin (Sn) are 20 Wt .-% to 35 wt .-% and copper (Cu) 5 wt .-% to 43 wt .-% amount and the proportions of the metals to 100 wt .-% complementary.
  • Table 17 consists of 81 alloy compositions 17,001 to 17,081, wherein the contents of the elements silver, zinc, indium and gold, palladium and platinum (individually or in combination with each other) in weight percent are given in Table 1, respectively, and the contents of tin (Sn) are 20 Wt .-% to 35 wt .-% and copper (Cu) 20 wt .-% to 30 wt .-% amount and the proportions of the metals to 100 wt .-% complement.
  • Table 18 consists of 81 alloy compositions 18,001 to 18,081, wherein the contents of the elements silver, zinc, indium and gold, palladium and platinum (individually or in combination with each other) in weight percent are given in Table 1, respectively, and the contents of tin (Sn) are 0 Wt .-% to 96.5 wt .-% and copper (Cu) copper (Cu) 0.5 wt .-% to 43 wt .-% amount and the proportions of the metals add up to 100 wt .-%, wherein the copper content is greater than 3 wt .-%, when the tin content exceeds 90 wt .-% and the silver content is less than 3 wt .-%.
  • Table 19 consists of 81 alloy compositions 19,001 to 19,081, wherein the contents of the elements silver, zinc, indium and gold, palladium and platinum (individually or in combination with each other) in weight percent are given in Table 1, respectively, and the contents of tin (Sn) are 0 Wt .-% to 96.5 wt .-% and copper (Cu) copper (Cu) 0.5 wt .-% to 43 wt .-% amount and the proportions of the metals add up to 100 wt .-%, wherein the silver content is greater than 3 wt .-%, when the tin content exceeds 90 wt .-% and the copper content is less than 3 wt .-%.
  • compositions of the alloy powders can be found in Tables 2 to 19, to which Table 20 refers.
  • Individual combinations are designated with the number of Table 20, followed by the number of the respective combination of amalgam, ball diameter and the coating table to be applied.
  • the combination 20.005 means the combination of a binary Zinnamalgams with 30 to 70 wt .-% mercury and a diameter of 50 to 2000 microns with the coatings of Table 4.
  • the amalgam balls are made according to one in the EP 1381485 B1 described method are prepared from a melt of the amalgam.
  • the completely melted amalgam is dropped into a cooling medium having a temperature below the solidification temperature of the amalgam.
  • the temperature of the cooling medium is 10 to 20 ° C below the liquidus temperature of the amalgam.
  • the melted amalgam is dripped into the cooling medium via a vibrating nozzle, wherein in a further embodiment of the invention the nozzle is immersed in the cooling medium.
  • the effort for the warranty The job security in the production of amalgam balls is therefore significantly reduced.
  • Another advantage is that Zinnamalgame completely melt at temperatures below 230 ° C.
  • 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.
  • the balls can be presented after degreasing, for example, in a rotating vessel and sprinkled with constant circulation with the metal or alloy powder until no sticking of the balls is more noticeable.
  • Well suitable devices for carrying out this method are e.g. V-Blender, Tubularmixer or Dragierkessel.
  • 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.
  • a further reduction in the tendency to sticking is obtained when the amalgam spheres are additionally coated, after coating with the metal or alloy powder, with 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 coating of the amalgam balls thus takes place in that the amalgam beads are degreased after separation from the cooling medium and sprinkled at room temperature with constant circulation with an alloy powder described above until no sticking of the balls is more detectable.
  • a further reduction in the tendency to sticking can be brought about by additionally coating the amalgam balls with a powder of a metal oxide in a further step with continuous circulation.
  • the reduction in adhesion is caused by the amalgam spheres after being sprinkled with alloy powder, be subjected to a heat treatment at a temperature of 35 ° C to 100 ° C for a period of 2 to 20 hours.
  • one of the steps selected from the group consisting of sprinkling the amalgam spheres with alloy powder, coating with a metal oxide, or heat treating the amalgam spheres may be repeated.
  • the desired coating with alloy powder or metal oxide is not achieved in one step, but it is applied in a first step, the alloy powder and (optionally after the separation of excess alloy powder) in a further step again coated with an alloy powder, as above described.
  • metal oxide can also be applied in several steps.
  • the alloy powders or metal oxides which are applied in the various steps may be the same or different, so that multilayer coatings, if appropriate also alternating alloy powder and metal oxide layers are obtainable, whereby the alloy powders and metal oxides may each differ from one another.
  • a coating with two different alloy powders according to the invention thus also exists if, for example, in a first step, a coating with an alloy powder having a mean particle diameter d 50 of 50 microns and in a subsequent step, a coating with an alloy powder of the same chemical composition and an average particle diameter d 50 of 15 microns are applied.
  • the amalgam spheres coated with alloy powder according to the invention are provided as described above.
  • the glass body of the gas discharge or fluorescent lamp is in the simplest case a glass tube, which can be bent one or more times and often has a diameter of about 4 mm to 80 mm, in particular from 6 mm to 40 mm.
  • a simple, straight glass tube can be used, for energy-saving lamps usually multi-curved glass tubes are used with a diameter of 4 to 10 mm.
  • the amalgam beads according to the invention are then introduced into the glass tube. These are usually placed at certain locations, which are provided with a receptacle for the amalgam balls or fixed at a designated location, so that the amalgam remain in this place. At this location, the amalgam balls can also be heated during the later use of the fluorescent lamp.
  • the introduction can also be done by fixing the amalgam ball or amalgam balls according to the invention in the receptacle and then introduced.
  • the receptacle can also be a part which is attached to or in the fluorescent lamp, such as a closure for the glass body.
  • the desired atmosphere is then produced in the glass body, if not already done, which can be effected, for example, by purging with a gas (such as argon), evacuating the glass body, or a combination thereof.
  • a gas such as argon
  • the glass body must be provided with a fluorescent phosphor.
  • phosphors calcium halophosphates are often used. The procedure in detail for this purpose is known to the person skilled in the art and is generally carried out in the case of fluorescent lamps.
  • Post-processing may include several subsequent steps, such as cleaning, providing electrical contacts or sockets, or mounting a protective container. These options for post-processing are known as such and include, for example, steps such as post-cleaning, attaching contacts or sockets or even attaching electrical and / or electronic components, such as the attachment of ballasts.
  • the powder layers applied to the amalgam balls 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 amalgam spheres according to the invention survive the average residence time of 24 hours at temperatures of up to 40 ° C in dosing without complaint.
  • Amalgam spheres of the compositions specified below are prepared with a diameter of about 1 mm ⁇ 0.1 mm, classified and coated after degreasing with an alloy powder indicated in the table by a one-minute circulation in a tubular mixer.
  • a quantity of about 4,000 amalgam balls is placed in a metering machine and introduced into fluorescent lamps at a rotation speed of one revolution per minute.
  • the service life is evaluated in accordance with the scheme given below, each determining the time at which production had to be interrupted either due to sticking of the balls or if such a large amount of dissolved alloy powder contamination is detected by visual inspection that there is an interruption to cleaning of the dosing machine and the loading of new amalgam balls is required.

Claims (9)

  1. Procédé de fabrication de billes d'amalgame revêtues d'une poudre d'alliage, dans lequel
    - on provoque la fusion complète de l'amalgame, et on introduit goutte à goutte la masse fondue dans un fluide réfrigérant à une température intérieure à la température de solidification de l'amalgame, puis on sépare du milieu réfrigérant les billes d'amalgame formées ;
    - on dégraisse les billes d'amalgame après la séparation, et on les saupoudre à la température ambiante, en les retournant en permanence, d'une poudre d'alliage qui présente la composition suivante : argent (Ag) 3 % en poids à 80 % en poids, cuivre (Cu) 0,5 % en poids à 43 % en poids, étain (Sn) 0 % en poids à 96,5 % en poids, zinc (Zn) 0 % en poids à 5 % en poids, indium (In) 0 % en poids à 10 % en poids, et or, palladium et platine (Au/Pd/Pt), à titre individuel ou en combinaison les uns avec les autres, de 0 % en poids à 5 % en poids, la somme des proportions en poids des métaux faisant en tout 100 % en poids, jusqu'à ce qu'on ne puisse plus détecter d'agglutination des billes ;
    caractérisé en ce que les billes d'amalgame, après avoir été saupoudrées de la poudre d'alliage, sont soumise à un traitement thermique à une température de 35 °C à 100 °C pendant une durée de 2 à 20 heures.
  2. Procédé selon la revendication 1, caractérisé en ce que les particules de la poudre présentent une granulométrie inférieure à 100 µm.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que la poudre d'alliage contient plus de 3 % en poids d'argent ou de cuivre, quand la teneur en étain est supérieure à 90 % en poids.
  4. Procédé selon l'une ou plusieurs des revendications 1 à 3, caractérisé en ce que les poudres d'amalgame sont revêtues de la poudre d'alliage en une quantité de 1 à 10 % en poids, exprimée en poids.
  5. Procédé selon l'une ou plusieurs des revendications 1 à 4, caractérisé en ce que les billes d'amalgame sont en outre revêtues d'une poudre d'un oxyde métallique en une quantité de 0,001 à 1 % en poids.
  6. Procédé selon l'une ou plusieurs des revendications 1 à 5, caractérisé en ce que l'amalgame est l'un des métaux étain (Sn), zinc (Zn), bismuth (Bi), indium (In), ou leurs alliages les uns avec les autres.
  7. Procédé selon l'une ou plusieurs des revendications 1 à 6, caractérisé en ce que les billes présentent un diamètre de 50 à 3000 µm.
  8. Procédé selon l'une ou plusieurs des revendications 1 à 7, dans lequel on répète au moins l'une des étapes choisies dans le groupe consistant en le saupoudrage des billes d'amalgame avec la poudre d'alliage, le revêtement avec un oxyde métallique ou le traitement thermique des billes d'amalgame.
  9. Procédé de fabrication de lampes à décharge de gaz basse pression, qui comprend au moins les étapes suivantes :
    - fourniture de billes d'amalgame obtenues par un procédé selon l'une des revendications 1 à 8 ;
    - fourniture d'un corps en verre pour la lampe à décharge de gaz basse pression ;
    - introduction d'une ou plusieurs billes d'amalgame dans le corps en verre ;
    - obturation du corps en verre.
EP15179281.9A 2011-03-09 2011-03-09 Procédé de préparation de sphères d'amalgame Not-in-force EP2975143B1 (fr)

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EP15179281.9A EP2975143B1 (fr) 2011-03-09 2011-03-09 Procédé de préparation de sphères d'amalgame
EP11157478.6A EP2497841B1 (fr) 2011-03-09 2011-03-09 Sn-Ag-Cu-Alliages

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EP2975143A1 EP2975143A1 (fr) 2016-01-20
EP2975143B1 true EP2975143B1 (fr) 2018-12-19

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EP15179281.9A Not-in-force EP2975143B1 (fr) 2011-03-09 2011-03-09 Procédé de préparation de sphères d'amalgame

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EP (2) EP2497841B1 (fr)
JP (1) JP2014513205A (fr)
KR (1) KR20140018275A (fr)
CN (1) CN103403200B (fr)
BR (1) BR112013022454A2 (fr)
CA (1) CA2829140A1 (fr)
RU (1) RU2013144956A (fr)
WO (1) WO2012119977A1 (fr)
ZA (1) ZA201306115B (fr)

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EP1985717B1 (fr) 2007-04-28 2011-06-29 Umicore AG & Co. KG Boules d'amalgame pour lampes à économie d'énergie et leur fabrication
EP2497841B1 (fr) * 2011-03-09 2015-09-02 Umicore AG & Co. KG Sn-Ag-Cu-Alliages
CN104148628B (zh) * 2013-05-13 2017-02-08 上海亚尔光源有限公司 一种汞齐涂粉工艺
ITUB20152876A1 (it) 2015-08-05 2017-02-05 Bluclad S R L Leghe stagno/rame contenenti palladio, metodo per la loro preparazione e loro uso.
PT3150744T (pt) * 2015-09-30 2020-05-12 Coventya S P A Banho de galvanoplastia para deposição eletroquímica de uma camada de liga de cu-sn-zn-pd, método para a deposição eletroquímica da referida camada de liga, substrato que compreende a referida camada de liga e utilizações do substrato revestido
CN110752376B (zh) * 2019-11-04 2021-12-03 天津理工大学 一种原位形成金属-汞齐活性集流体的制备方法与应用

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Also Published As

Publication number Publication date
US9263245B2 (en) 2016-02-16
EP2497841A1 (fr) 2012-09-12
JP2014513205A (ja) 2014-05-29
US20160133453A1 (en) 2016-05-12
EP2975143A1 (fr) 2016-01-20
CA2829140A1 (fr) 2012-09-13
WO2012119977A1 (fr) 2012-09-13
US9659762B2 (en) 2017-05-23
BR112013022454A2 (pt) 2016-12-06
EP2497841B1 (fr) 2015-09-02
ZA201306115B (en) 2014-04-30
RU2013144956A (ru) 2015-04-20
CN103403200A (zh) 2013-11-20
US20140055026A1 (en) 2014-02-27
CN103403200B (zh) 2017-03-01
KR20140018275A (ko) 2014-02-12

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