EP2497841A1 - Sn-Ag-Cu-Alliages - Google Patents

Sn-Ag-Cu-Alliages Download PDF

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Publication number
EP2497841A1
EP2497841A1 EP20110157478 EP11157478A EP2497841A1 EP 2497841 A1 EP2497841 A1 EP 2497841A1 EP 20110157478 EP20110157478 EP 20110157478 EP 11157478 A EP11157478 A EP 11157478A EP 2497841 A1 EP2497841 A1 EP 2497841A1
Authority
EP
European Patent Office
Prior art keywords
amalgam
balls
alloy powder
weight
tin
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
EP20110157478
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German (de)
English (en)
Other versions
EP2497841B1 (fr
Inventor
Olivier Hutin
Hans-Martin Ringestein
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
Priority to EP11157478.6A priority Critical patent/EP2497841B1/fr
Application filed by Umicore AG and Co KG filed Critical Umicore AG and Co KG
Priority to EP15179281.9A priority patent/EP2975143B1/fr
Priority to PCT/EP2012/053730 priority patent/WO2012119977A1/fr
Priority to CA2829140A priority patent/CA2829140A1/fr
Priority to KR1020137026456A priority patent/KR20140018275A/ko
Priority to BR112013022454A priority patent/BR112013022454A2/pt
Priority to RU2013144956/02A priority patent/RU2013144956A/ru
Priority to CN201280011467.5A priority patent/CN103403200B/zh
Priority to US14/003,697 priority patent/US9263245B2/en
Priority to JP2013557061A priority patent/JP2014513205A/ja
Publication of EP2497841A1 publication Critical patent/EP2497841A1/fr
Priority to ZA2013/06115A priority patent/ZA201306115B/en
Application granted granted Critical
Publication of EP2497841B1 publication Critical patent/EP2497841B1/fr
Priority to US15/000,752 priority patent/US9659762B2/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J61/00Gas-discharge or vapour-discharge lamps
    • H01J61/02Details
    • H01J61/24Means for obtaining or maintaining the desired pressure within the vessel
    • H01J61/26Means for absorbing or adsorbing gas, e.g. by gettering; Means for preventing blackening of the envelope
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C13/00Alloys based on tin
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C5/00Alloys based on noble metals
    • C22C5/06Alloys based on silver
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C7/00Alloys based on mercury
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C26/00Coating not provided for in groups C23C2/00 - C23C24/00
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C30/00Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J61/00Gas-discharge or vapour-discharge lamps
    • H01J61/02Details
    • H01J61/12Selection of substances for gas fillings; Specified operating pressure or temperature
    • H01J61/18Selection of substances for gas fillings; Specified operating pressure or temperature having a metallic vapour as the principal constituent
    • H01J61/20Selection of substances for gas fillings; Specified operating pressure or temperature having a metallic vapour as the principal constituent mercury vapour
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J61/00Gas-discharge or vapour-discharge lamps
    • H01J61/02Details
    • H01J61/38Devices for influencing the colour or wavelength of the light
    • H01J61/42Devices for influencing the colour or wavelength of the light by transforming the wavelength of the light by luminescence
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J61/00Gas-discharge or vapour-discharge lamps
    • H01J61/70Lamps with low-pressure unconstricted discharge having a cold pressure < 400 Torr
    • H01J61/72Lamps 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J9/00Apparatus 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
    • H01J9/38Exhausting, degassing, filling, or cleaning vessels
    • H01J9/395Filling vessels
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J9/00Apparatus 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
    • H01J9/40Closing vessels
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12014All metal or with adjacent metals having metal particles
    • Y10T428/12028Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y10T428/12049Nonmetal component
    • Y10T428/12056Entirely inorganic
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12014All metal or with adjacent metals having metal particles
    • Y10T428/12028Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y10T428/12063Nonparticulate metal component
    • Y10T428/1209Plural 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.
  • For the production of spheroid Amalgampellets is in the US 4,216,178 described method used in which the molten amalgam by a vibrated spout nozzle into small Drop is divided 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.
  • amalgam balls wherein the balls are coated with an alloy powder, wherein the alloy powder has the composition Ag 3 - 80, Cu 0.5 - 43, Sn 0 - 96.5, Zn 0 - 5, In 0-10 and Au / Pd / Pt 0-5.
  • alloy powders which contain more than 3% by weight of 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 powders usually form an amalgam with the mercury. Due to the amalgamation of the alloy 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 adhesion tendency in comparison to untreated spheres.
  • the alloy powder used for the coating should contain less or no particles with a grain diameter larger than 100 ⁇ m. Particles with larger diameter diameter only partially amalgamate 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 Kom bemesser 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 Wt%, tin (Sn) 10 wt% to 48 wt%, zinc (Zn) 0.1 wt% to 3 wt%, indium (In) 0.1 wt% to 5% by weight and gold, palladium and platinum (Au / Pd / Pt), singly 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) 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 % By weight to 35% by weight, zinc (Zn) 0% by weight to 3% by weight, 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 .-% to , 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 the following Table 1.
  • 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 are shown in Table 1, respectively, and the contents of tin (Sn) are 0 Wt .-% to 35 wt .-% and copper (Cu) 12.5 Wt .-% to 28 wt .-% and the proportions of the metals add up to 100 wt .-%.
  • 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 are given in Table 1, respectively, and the contents of tin (Sn) are 0 Wt .-% to 96.5 wt .-% and of copper (Cu) Copper (Cu) 12.5 wt .-% to 28 wt .-% amount 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 are given in Table 1, respectively, and the contents of tin (Sn) are 10 Wt .-% to 48 wt .-% and copper (Cu) 12.5 Wt .-% to 28 wt .-% and the proportions of the metals add up to 100 wt .-%.
  • 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 of 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 are given in Table 1, respectively, and the contents of tin (Sn) are 20 Wt .-% to 35 wt .-% and copper (Cu) 12.5 Wt .-% to 28 wt .-% and the proportions of the metals add up to 100 wt .-%.
  • 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) 0 wt .-% to 96.5 wt .-% and copper (Cu) copper (Cu) 0.5 wt .-% to 43 wt .-% amount and the proportions the metals to 100 wt .-% complete, wherein the silver content is greater than 3 wt .-%, when the content of tin 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 can after a 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 to ensure 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 achieved by additionally coating the amalgam balls with a powder of a metal oxide in a further step.
  • a further reduction in the tendency to sticking can be achieved by subjecting the amalgam balls to a heat treatment after being sprinkled with alloy powder be subjected. This heat treatment can be carried out by tempering the amalgam beads 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 balls with alloy powder, coating with a metal oxide, or heat treating the amalgam balls 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 be applied in several steps.
  • the alloy powders or metal oxides which are applied in the various steps may be identical or different, so that multilayer coatings, if appropriate also alternating alloy powder and metal oxide layers are obtainable, whereby the alloy powder and metal oxide may each differ from each other.
  • a coating with two different alloy powder 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 recording 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.
  • the glass body of the lamp is then closed and optionally reworked.
  • the 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 present invention also relates to amalgam spheres, which according to the invention with an alloy powder are coated, even if these amalgam balls without coating do not tend to stick together.
  • the invention therefore also relates to a method of controlling the reabsorption of mercury in amalgam spheres by coating the amalgam spheres with an alloy powder having a composition as described above.
  • 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 a break for cleaning of the dosing machine and the loading of new amalgam balls is required.
EP11157478.6A 2011-03-09 2011-03-09 Sn-Ag-Cu-Alliages Active EP2497841B1 (fr)

Priority Applications (12)

Application Number Priority Date Filing Date Title
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
JP2013557061A JP2014513205A (ja) 2011-03-09 2012-03-05 合金被膜を有するアマルガム球
KR1020137026456A KR20140018275A (ko) 2011-03-09 2012-03-05 합금 코팅을 갖는 아말감 볼
BR112013022454A BR112013022454A2 (pt) 2011-03-09 2012-03-05 esferas de amálgama tendo um revestimento de liga
RU2013144956/02A RU2013144956A (ru) 2011-03-09 2012-03-05 Амальгамные шарики с покрытием из сплава
PCT/EP2012/053730 WO2012119977A1 (fr) 2011-03-09 2012-03-05 Sphères d'amalgame dotées d'un revêtement d'alliage
US14/003,697 US9263245B2 (en) 2011-03-09 2012-03-05 Amalgam balls having an alloy coating
CA2829140A CA2829140A1 (fr) 2011-03-09 2012-03-05 Spheres d'amalgame dotees d'un revetement d'alliage
CN201280011467.5A CN103403200B (zh) 2011-03-09 2012-03-05 具有合金涂层的汞齐球
ZA2013/06115A ZA201306115B (en) 2011-03-09 2013-08-14 Amalgam balls having an alloy coating
US15/000,752 US9659762B2 (en) 2011-03-09 2016-01-19 Amalgam balls having an alloy coating

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP11157478.6A EP2497841B1 (fr) 2011-03-09 2011-03-09 Sn-Ag-Cu-Alliages

Related Child Applications (1)

Application Number Title Priority Date Filing Date
EP15179281.9A Division EP2975143B1 (fr) 2011-03-09 2011-03-09 Procédé de préparation de sphères d'amalgame

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EP2497841A1 true EP2497841A1 (fr) 2012-09-12
EP2497841B1 EP2497841B1 (fr) 2015-09-02

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EP11157478.6A Active EP2497841B1 (fr) 2011-03-09 2011-03-09 Sn-Ag-Cu-Alliages
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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ATE514797T1 (de) 2007-04-28 2011-07-15 Umicore Ag & Co Kg Amalgamkugeln für energiesparlampen und ihre herstellung
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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JP2000251836A (ja) 1999-02-27 2000-09-14 Matsugaki Yakuhin Kogyo Kk 蛍光灯用のアマルガムペレット及びこれを用いた蛍光灯
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Also Published As

Publication number Publication date
EP2975143B1 (fr) 2018-12-19
KR20140018275A (ko) 2014-02-12
CA2829140A1 (fr) 2012-09-13
US9659762B2 (en) 2017-05-23
US9263245B2 (en) 2016-02-16
EP2975143A1 (fr) 2016-01-20
CN103403200A (zh) 2013-11-20
US20140055026A1 (en) 2014-02-27
WO2012119977A1 (fr) 2012-09-13
CN103403200B (zh) 2017-03-01
US20160133453A1 (en) 2016-05-12
RU2013144956A (ru) 2015-04-20
JP2014513205A (ja) 2014-05-29
ZA201306115B (en) 2014-04-30
EP2497841B1 (fr) 2015-09-02
BR112013022454A2 (pt) 2016-12-06

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