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WO2002099146A1 - Nouvelles brasures a haute temperature sans plomb - Google Patents

Nouvelles brasures a haute temperature sans plomb Download PDF

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Publication number
WO2002099146A1
WO2002099146A1 PCT/US2001/028387 US0128387W WO02099146A1 WO 2002099146 A1 WO2002099146 A1 WO 2002099146A1 US 0128387 W US0128387 W US 0128387W WO 02099146 A1 WO02099146 A1 WO 02099146A1
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WO
WIPO (PCT)
Prior art keywords
lead
solder alloy
melting point
amount
free
Prior art date
Application number
PCT/US2001/028387
Other languages
English (en)
Inventor
Randall M. German
Ronald G. Iacocca
Louis G. Campbell
Ravi Bollina
Original Assignee
The Penn State Research Foundation
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Filing date
Publication date
Application filed by The Penn State Research Foundation filed Critical The Penn State Research Foundation
Publication of WO2002099146A1 publication Critical patent/WO2002099146A1/fr

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Classifications

    • 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
    • C22C13/02—Alloys based on tin with antimony or bismuth as the next major constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • B23K35/262—Sn as the principal constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/047—Making non-ferrous alloys by powder metallurgy comprising intermetallic compounds
    • 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
    • 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
    • H01J9/24—Manufacture or joining of vessels, leading-in conductors or bases
    • H01J9/245—Manufacture or joining of vessels, leading-in conductors or bases specially adapted for gas discharge tubes or lamps
    • H01J9/247—Manufacture or joining of vessels, leading-in conductors or bases specially adapted for gas discharge tubes or lamps specially adapted for gas-discharge lamps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
    • B22F2009/0848—Melting process before atomisation

Definitions

  • the present invention relates to lead-free solder alloys and solder alloy compositions which are particularly useful in lighting applications.
  • Pb-Sn alloy solders have been used routinely to join materials. There are many historical reasons for the widespread use of Pb-Sn alloy solders. These reasons include the low solidus temperature of Pb solder alloys, the workability of Pb alloy solders over a wide temperature range, ready availability of process equipment, as well as the low cost of adjuncts such as resins, fluxes, and solder masks.
  • lead is a toxic, heavy metal with a relatively high vapor pressure. Its use is disfavored, and a need exists for a replacement .
  • U.S. Pat. Nos . 4,643,875 and 4,667,871 describe high temperature brazing alloys containing from 35% to 95% Sn, from 0.5 to 70% Ag, from 0.5 to 20% Cu, effective amounts of one or more of Ti, V, and Zr, and optionally with Ni , and Cr.
  • the disclosed brazing alloys require temperatures of at least 550 °C for good bonding.
  • U.S. Pat. No. 4,778,733 describes an article of manufacture containing from 92 to 99% Sn, from 0.7 to 6% Cu, and from 0.05-3% Ag.
  • U.S. Pat. No. 4,797,328 describes soft-solder alloys for bonding ceramic parts without premetallization.
  • the alloys which are disclosed to be useful for bonding alumina parts to Cu parts, contain from 86 to 99% Sn, from 0 to 13% Ag and/or Cu, from 0 to 10% In, and from 1 to 10% Ti .
  • U.S. Pat. No. 4,806,309 describes solder alloys containing from 90 to 95% Sn, from 3 to 5% Sb, from 1 to 4.5% Bi, and from 0.1 to 0.5% Ag.
  • Pb-Sn alloy solder A primary application for Pb-Sn alloy solder is in electronic assembly. Accordingly, most Pb-free solder alloys considered for use as a replacement for Pb-Sn alloy solders seek to have physical properties similar to Pb-Sn solder alloys. Pb-Sn solder alloys, however, are undesirable due to environmental concerns . Materials of ruse in lighting applications must be able to withstand temperatures in excess of about 200°C for time periods in excess of about 20,000 hours. Pb-Sn alloys, in addition to environmental concerns, suffer remelting and creep when exposed to the high operating temperatures of high intensity discharge lamps for extended time periods. High intensity discharge lamps require solders which survive high operating temperatures of more than 200 °C for extended time periods of approximately 2000 hours.
  • solder melting temperatures In manufacture of devices such as high intensity discharge lamps, it is desirable to use low solder melting temperatures to reduce heating time and to facilitate rapid assembly.
  • the solder alloys should not remelt and creep at the operating temperatures of the lamp.
  • FIG. 1 is a front view of an improved high intensity discharge lamp.
  • FIG. 1A is an enlarged, partial cross-sectional view taken along section line A-A of FIG. 1.
  • FIG. 2 represents a side view of an alternative embodiment of the high intensity discharge lamps shown in FIG. 1 where the base is at a right angle to the light source.
  • FIG. 2A is a side view of FIG. 2 showing lead wires.
  • FIG. 2B is a cross sectional view taken on line BB of FIG. 2.
  • FIG. 2C is an end view taken in the direction of Arrow A.
  • FIG. 3 is a side view in partial cutaway cross section of an improved sealed beam lamp.
  • FIG. 3A is a cross sectional view of FIG. 3 taken on line AA.
  • FIG. 4 is a side view of an improved composite lamp.
  • FIG. 4A is a cross sectional view of FIG. 6 taken on line AA.
  • FIG. 4B is a bottom view of the base section of the lamp of FIG. 4 taken in direction of arrow B.
  • FIG. 5 is a side view of an improved flourescent lamp.
  • FIG. 5A is an enlarged view of the plug section of the flourescent lamp of FIG. 5.
  • the invention relates to lead-free solder alloy compositions and lead-free solder alloys formed from those compositions.
  • the solder alloys have melting characteristics favorable for use in lighting applications such as high intensity discharge lamps, sealed beam lamps, and composite lamps. More particularly, the invention relates to a lead- free solder alloy of Sn, Bi and Sb wherein Sn is present in an amount of about 45 wt.%, Bi is present in an amount of about 20 wt.%, and Sb is present in an amount of about 33 wt.%, all amounts based on the total weight of the alloy.
  • the invention in another aspect, relates to a lead-free solder alloy of Sn, Sb, and Cu wherein Sn is present in an amount of about 71 wt.%, Sb is present in an amount of about 24 wt.%, and Cu is present in an amount of about 5 wt.%, all amounts based on the total weight of the alloy.
  • the invention relates to a lead-free solder alloy of Sn, Sb and Cu wherein Sn is present in an amount of about 94 wt.%, Sb is present in an amount of about 5 wt.%, and Cu is present in an amount of about 1 wt.%, all amounts based on the total weight of the alloy.
  • the invention relates to a lead- free solder alloy of Sn, Cu and Ag wherein Sn is present in an amount of about 73 wt.%, Cu is present in an amount of about 2 wt.%, and Ag is present in an amount of about 25 wt.%, all amounts based on the total weight of the alloy.
  • the invention in a second embodiment, relates to novel compositions of a lead-free solder alloy component and a higher melting point additive component.
  • the additive component can be obtained from, for example, the substrate being soldered or by physical addition of various forms of the additive.
  • the additive component reacts with the molten lead- free solder alloy during soldering to produce a high melting point intermetallic compound which has characteristics favorable for use in lighting applications such as high intensity discharge lamps.
  • the invention relates to a high melting point intermetallic compound that includes a reaction product of 20Bi-33Sb-47Sn solder alloy and Ti in an amount of 0.5% based on weight of the solder alloy.
  • the invention relates to a high melting point intermetallic compound that includes a reaction product of 5Cu-24Sb-71Sn solder alloy and Ti in an amount of 0.5% based on weight of the solder alloy.
  • the invention relates to a high melting point intermetallic compound that includes a reaction product of 2Cu-25Ag-73Sn solder alloy and Ti in an amount of 0.5% based on weight of the solder alloy.
  • the invention relates to a high melting point intermetallic compound that includes high melting point intermetallic compound of a reaction product of lCu-5Sb-94Sn solder alloy and Ti in an amount of 0.5% based on weight of the solder alloy.
  • the invention relates to a high melting point intermetallic compound that is a reaction product of 20Bi-33Sb-47Sn solder alloy and Cu in an amount of 2.0% based on weight of the solder alloy. In an additional aspect, the invention relates to a high melting point intermetallic compound that includes a reaction product of 20Bi-33Sb-47Sn solder alloy and Cu in an amount of 5.0% based on weight of the solder alloy.
  • a method of manufacture of a high melting point intermetallic compounds also is disclosed.
  • the method entails reacting a lead-free, solder alloy which includes one or more low melting point component metals such as Sn, Ga and In with an additive which has a melting point greater than the melting point of the lead-free, solder alloy, wherein at least one of Sn, Ga and In is present. At least one of Sn, Ga and In is present in a sufficient amount whereby about 15 to about 50 at . % of the metal is free for reaction with a high melting point additive, based on the total at . % of the lead-free, solder alloy and high melting point additive.
  • the method of manufacture of a high melting point intermetallic compound entails reacting a lead-free, solder alloy which includes one or more low melting point metals such as Sn, Ga and In with a higher melting point additive such as Co, Ni, Pd, Fe, Cu, Ag, Ti, and Au. At least one of these higher melting point additive metals is present in a sufficient amount whereby about 15 to about 50 at . % of the metal based on the total at . % of the alloy and high melting point additive, is free for reaction with the high melting point additive.
  • a lead-free, solder alloy which includes one or more low melting point metals such as Sn, Ga and In with a higher melting point additive such as Co, Ni, Pd, Fe, Cu, Ag, Ti, and Au. At least one of these higher melting point additive metals is present in a sufficient amount whereby about 15 to about 50 at . % of the metal based on the total at . % of the alloy and high melting point additive, is free for reaction with the high melting point
  • the invention further relates to an improved high intensity discharge lamp which includes soldered joints such as soldered side joints, soldered eyelet joints and soldered mechanical interlocks which include a solder alloy of any of
  • the invention also relates to an improved high intensity discharge lamp which includes soldered joints such as soldered side joints, soldered eyelet joints and soldered mechanical interlocks which include an intermetallic reaction product of any of 20Bi-33Sb-47Sn, 5Cu-24Sb-71Sn, 2Cu-25Ag-73Sn and lCu- 5Sb-94Sn solder alloys, and intermetallic reaction products formed of any of 20Bi-33Sb-47Sn, 5Cu-24Sb-71Sn, 2Cu-25Ag-73Sn, and lCu-5Sb-94Sn with a high melting point additive such as Cu and Ti .
  • soldered joints such as soldered side joints, soldered eyelet joints and soldered mechanical interlocks which include an intermetallic reaction product of any of 20Bi-33Sb-47Sn, 5Cu-24Sb-71Sn, 2Cu-25Ag-73Sn and lCu- 5Sb-94Sn solder alloys, and intermetallic reaction products formed of any
  • the invention further relates to an improved sealed beam lamps which includes soldered joints such as soldered side joints, soldered eyelet joints and soldered mechanical interlocks which include an intermetallic reaction product of any of 20Bi-33Sb-47Sn, 5Cu-24Sb-71Sn, 2Cu-25Ag-73Sn, and lCu- 5Sb-94Sn with a high melting point additive such as Cu and Ti .
  • soldered joints such as soldered side joints, soldered eyelet joints and soldered mechanical interlocks which include an intermetallic reaction product of any of 20Bi-33Sb-47Sn, 5Cu-24Sb-71Sn, 2Cu-25Ag-73Sn, and lCu- 5Sb-94Sn with a high melting point additive such as Cu and Ti .
  • solder alloys of the first embodiment as well as the intermetallic compounds formed from reaction of lead-free, solder alloy and high melting point additive metal, have advantages such as electrical conductivity, resistance to long term failure by creep, oxidation, and thermal fatigue, are able to sustain modest stresses in use and during installation, and can be easily repaired.
  • compositions used in manufacture of the high melting point intermetallic compounds can be formulated to produce intermetallic products which readily bond to substrates such as Ni plated Fe, Ni alloys such as monel, brass (Cu-Zn) alloys such as 95 wt.% Cu-5 wt.% Zn, and Ni plated Cu-Zn alloys.
  • the high melting point intermetallic compounds have a solidus temperature of more than about 250 °C.
  • the invention relates to lead-free solder compositions for manufacture of lead-free solder alloys, and to the lead-free solder alloys produced from those compositions.
  • solder alloys are preferably completely free of Pb, it is to be understood that impurities such as Pb, Cd, and Hg may be present in the lead- free solder alloys in amounts of up to about 0.5% based on the weight of the solder alloy.
  • the lead-free solder alloy compositions relate to component metal compositions for manufacture of lead-free, Sn-Bi-Sb solder alloys, and to Sn-Bi-Sb solder alloys produced from those compositions.
  • Sn may be present in an amount of about 30 to about 70 wt.%, preferably about 30 wt.% up to about 40 wt.%, more preferably about 32 wt.%; Bi may be present in an amount of about 1 wt.% to about 45 wt.%, preferably about 20 wt.% to about 45 wt.%, more preferably about 43 wt.%; and Sb may be present in an amount of about 25 to about 35 wt.%, preferably about 25 wt.% to about 30 wt.%, more preferably about 25 wt.%, all amounts based on the total weight of the composition.
  • An especially preferred Sn-Bi-Sb component metal composition has about 32 wt.%Sn, about 43 wt.% Bi, and about 25 wt.% Sb.
  • the lead-free solder alloy produced from this composition is 47Sn-20Bi-33Sb.
  • the lead- free solder alloy compositions relate to component metal compositions for manufacture of lead-free Sn-Sb-Cu solder alloys.
  • Sn may be present in amounts of about 60 wt.% to about 94 wt.%, preferably about 60 to about 88 wt.%; more preferably, about 60 wt.%; Sb may be present in amounts of about 5 to about 30 wt.%, preferably about 10 wt.% to about 30 wt.%, more preferably about 28 wt.%; and Cu may be present in the amounts of about 1 wt.% to about 15 wt.%, preferably about 5 wt.% to about 12 wt.%, more preferably about 12 wt.%, all amounts based on the total weight of the
  • Sn-Sb-Cu component metal composition An especially preferred component metal composition includes about 60 wt.% Sn, about 28 wt.% Sb, and about 12 wt.% Cu. This composition yields a lead-free solder alloy of 71Sn-24Sb-5Cu.
  • Another especially preferred component metal composition includes about 88 wt.% Sn, about 10 wt.% Sb, and about 2 wt . % Cu. This composition yields a lead-free solder alloy of 94Sn-5Sb-lCu.
  • the lead-free solder alloy compositions relate to component metal compositions for manufacture of lead-free, Sn-Ag-Cu solder alloys.
  • Sn may be present in an amount of about 55 wt.% to 85 wt.%, preferably about 55 wt.% to about 70 wt.%, more preferably about 58 wt.%;
  • Ag may be present in amounts of about 20 wt.% to about 30 wt.%, preferably about 23 wt .
  • % to about 29 wt.%, more preferably about 26 wt.%, and Cu may be present in amounts of about 1 wt.% to about 18 wt.%, preferably about 10 wt.% to about 16 wt.%, more preferably about 16 wt.%, all amounts based on the total weight of the component metal composition.
  • An especially preferred component metal composition has about 58 wt.% Sn, about 26 wt.% Ag, and about 16 wt.% Cu. This composition yields a lead-free solder alloy of 73Sn-25Ag-2Cu.
  • solder alloys In manufacture of lead-free solder alloys, the metal components of the alloy are blended, and then furnace melted to form a molten blend. The molten blend then is gas atomized into powder.
  • the component metals employed are in the form of shot of about 99.5% purity. Shot of Sn, Zn, Sb and Cu are obtained from Nathan Trotter, Inc. Bi and Ag shot are obtained from Alpha-Fry Technologies, Altoona, PA.
  • Furnace melting is done at temperatures sufficient to achieve homogenization, preferably complete homogenization, of the alloy formed from the metals. Homogenization is performed at temperatures below that which would undesirably cause one or more of the component metals to vaporize so as to produce a solder alloy that deviates from the desired solder alloy.
  • homogenization is achieved when the melt is held at a sufficient temperature for a sufficient time to produce a homogenous molten alloy, that is, an alloy which is free of chemical gradients over a thickness of about 1 mm. If in the event that vaporization of a component metal such as Sb, Cu, Zn, Bi occurs so as to produce a solder alloy which deviates from the desired solder alloy, loss of the component metal can be compensated by including an additional amount of that component metal in the melt.
  • a component metal such as Sb, Cu, Zn, Bi
  • the component metals are mixed in a tapered cylindrical alumina crucible, and heated in a retort furnace equipped with an Inconel shell in dry hydrogen that has a dew point of -40°C or less to produce a homogenous alloy.
  • the heating program employed to produce a homogenous solder alloy entails heating the component metal compositions at about 5°C/min to the melt temperature, holding the resulting melt for about 3 hours to achieve homogenization, and then furnace cooling at about 10°C/min to room temperature to form a slug of homogenous, lead-free solder alloy.
  • This heating program may be varied according the specific component metal composition. Accordingly, the crucible material and shape, use of faster or slower heating rates, use of faster or slower cooling rates, use of differing soak temperatures and time periods may be varied.
  • slugs of the lead-free solder alloy produced above are cut by a 25 cm resin-bonded alumina abrasive cut off wheel into 12 mm x 12 mm x 25 mm pieces. These pieces are placed into the melt crucible of a model Atomatic Lab-scale gas atomizer from HJE Corp., Glen Falls, NY. Graphite is the preferred material for the melt crucible.
  • the crucible may, however, be formed from any material compatible with the heating system of the atomizer and which does not react with the molten alloy.
  • solder alloy pieces after having been placed into the atomizer, are induction heated under argon by using an Induetotherm VIP Power-Trak induction power supply connected to a water-cooled induction coil.
  • the solder alloy pieces are superheated to above their theoretical liquidus, preferably about 150 °C above their theoretical liquidus.
  • the molten, superheated solder alloys are then atomized by the atomizer at a nitrogen gas pressure of about 1.1 MPa.
  • molten solder alloy is drawn by the gas pressure through a graphite nozzle of 2.5 mm diameter.
  • the pressures and nozzle size conditions are sufficient to produce an atomized powder which has a particle size range of about lO ⁇ m to about 250 ⁇ m.
  • the atomized powder is sieved to remove particles and agglomerates larger than 90 ⁇ m.
  • the diameters of the nozzle, melting conditions, atomization temperatures, and atomization gas pressures can be varied to produce powders of a desired range of particle size and shape. Accordingly, inert gases other than argon such as nitrogen and helium may be used as the cover gas for the melt while in the melt crucible and as the atomization gas. Hydrogen or air also can be used as a cover gas for the melt depending on the composition of the solder alloy and process equipment.
  • the component metal compositions of examples 1-8 of Table 1 are melted, homogenized, and then atomized into powder of lead-free solder alloy.
  • the component metal compositions employed, the melt and homogenization temperatures used, as well as the atomization temperatures and pressures used are given in Table 1.
  • Table 1 the wt.% amounts of the component metals used in the component metal ⁇ composition are based on the total weight of the component metal composition.
  • the lead-free solder alloys produced from the component metal compositions also are shown in Table 1. Differences in composition between the solder alloy produced and the component metal composition is due to volatilization of one or more of the metal components used in the component metal composition.
  • solder alloys of Table 1 are analyzed by electron microprobe and inductively coupled plasma mass spectroscopy.
  • the wt.% amounts of the metals in the resulting lead-free solder alloy are based on the total weight of the solder alloy.
  • the solidus and liquidus temperatures of the lead-free solder alloys in Table I are measured using a Netzsch STA 409 Differential Scanning Calorimeter (DSC) under argon.
  • the thermal profile used entails heating atomized lead-free solder alloy powders at 10°C/min to either 500°C or to 600 °C, and then cooling at 10°C/min to a temperature of 50°C. This cycle is repeated twice to determine the solidus and liquidus on initial heating, and after full melting and re-solidification.
  • the first cycle simulates initial melting of the solder alloy during soldering.
  • the second cycle simulates the solder alloy properties after the solder joint has been formed.
  • mixtures which include one or more lead-free solder alloys and one or more high melting point additive metals which have a melting point higher than the lead-free solder alloy are reacted to produce a high melting intermetallic compound.
  • the intermetallic compound has a melting point higher than that of the lead-free solder alloy.
  • the lead-free solder alloy employed includes one or more component metals such as Sn, Ga and In which can form intermetallic compounds with the high melting point additive metals at the soldering temperature.
  • the amount of Sn in the lead-free solder alloy is more than about 45 wt.% based on the weight of the solder alloy, preferably more than about 60 wt.%, more preferably more than about 85 wt.% Sn.
  • the Sn content in the solder alloy is not so high as to cause corrosive attack of the substrate by the solder alloy over long-term exposure of the substrate to temperatures above about 200°C.
  • Examples of useful lead-free solder alloys which have Sn as the low melting point component metal have about 15 at . % to about 50 at . % free Sn. Free Sn is Sn which is not strongly bound within the lead-free solder alloy and which is able to react with the additive metals. Where the low melting point metal in the lead-free solder alloy is In or Ga, useful lead- free solder alloys typically have about 15 at . % to about 50 at . % free In or Ga. Especially preferred lead-free solder alloys include the alloys of examples 3,6,7 and 8 of Table 1. These lead-free solder alloys have high solubility for the high melting point additive metals.
  • the high melting point additive metals may be employed in various forms with the lead-free solder alloys.
  • These high melting point additive metals include but are not limited to transition metals such as Co, Ni, Pd, Fe, Cu, Ag, Ti, and Au; alloys of transition metals such as Cu-based alloys such as brass and bronze; Ni-Cu alloys such as monel; Ni-Fe alloys such as Invar; Pd alloys such as Paliney alloys; Ti alloys such as Ti-6A1-4V; Co alloys such as Vitalium and other Co-Cr alloys; precious metal alloys such as sterling silver, gold, gold-palladium alloys, and gold-silver alloys, ferrous alloys such as low-alloy steel, and alloys of other metals such as Kolar (Fe-29Ni-17Co) .
  • the high melting point additive metals may be obtained from various sources in forms such as powder, wire, and ribbon.
  • the high melting point additive metals also may be obtained by diffusion from the substrate when the substrate is heated during soldering. In this aspect, care must be taken that the solder alloy does not react so strongly with the substrate that it penetrates or otherwise adversely affects the substrate.
  • the amount of high melting point additive metal provided by diffusion from the substrate can be controlled by varying the time and/or temperatures employed during the soldering process.
  • the amount of high melting point additive metal diffused from the substrate also can be controlled by varying the surface area of the high melting point additive metal.
  • a lead-free solder alloy in the form of a thin wire which has a high surface area compared to the substrate is contacted with the substrate. By increasing the surface area of the solder alloy, the amount of high melting point additive metal diffused from the substrate during soldering increases; similarly, decreasing the surface area decreases the amount of high melting point additive metal diffused during soldering.
  • the presence of undesirable low melting point metals which may reduce solubility of the high melting point additive metal in the molten lead-free solder alloy is minimized.
  • undesirable metals include Zn, Bi, Cs, Cd, Hg, and Ga .
  • the atomic ratios of any of these undesirable metals to the intermetallic-forming component of the solder typically is less than about 0.3, based on the total atomic composition of the lead-free solder alloy.
  • the amounts of Zn and Bi in the solder alloy preferably is less than an amount which would produce a Bi:Sn atomic ratio of more than about 0.3 or Zn:Sn atomic ratio of more than about 0.3.
  • the Zn:In atomic ratio preferably is less than about 0.3 and the Bi : In atomic ratio preferably is less than about 0.3; in lead-free solder alloys where Ga is the predominant component metal, the Zn:Ga atomic ratio preferably is less than about 0.3 and the Bi:Ga atomic ratio preferably is less than about 0.3.
  • Various optional additives may be combined with the high melting point additive to form an additive package.
  • optional additives include but are not limited to antioxidants, metastable polymers, compounds which have affinity for oxygen, grain refiners which induce nucleation from the melt to give a finer scale microstructure with improved mechanical properties, dross control agents, inert fillers such as glass and minerals, and fluxes.
  • Antioxidants which may be employed include but are not limited to metals such as Si, Ti , Zr, Al , Nb, and Cr; metastable polymers which may be employed include but are not limited to those which have active carbon-oxygen-hydrogen groups such as carbonates and acetals; compounds which have affinity for oxygen which may be employed include but are not limited to boric acid and boron oxide, phosphates such as boron phosphide and phosphoric acid, and graphite; examples of useful grain refiners include but are not limited to transition metals such as Re, Ir, Cr, Mo, W, Ta, and Nb; and examples of dross control additives include but are not limited to strong oxide formers such as Si, Ca, Al , Ti , Zr, Nb, and Cr.
  • Fluxes also may be included in the additive package.
  • Useful fluxes include but are not limited to active, water soluble, and inert fluxes.
  • active fluxes include rosins, zinc chloride, ammonium chloride and other halide salts, boric acid, borates and any other material that chemically reduces oxides or removes surface contamination on the substance to be soldered.
  • Water soluble fluxes include fluxes which employ combinations of the above active flux ingredients chosen so that the flux is soluble in water and can be rinsed.
  • Inert fluxes are non-chemically active fluxes, usually in polymer form, which produce a coating that prevents oxidation or degradation of the solder alloy and the substrate during soldering.
  • the additive package may be in the form of multiple core wires, twisted strands of wires, mixed powders, and laminated sheet preforms produced by techniques such as extrusion which are well known in the art.
  • the amounts and particle sizes of the lead-free solder alloy and high melting point additive metal, as well as optional additives can be varied over a wide range.
  • the amounts and types of high melting point additives can be varied to control the rate of formation of a high melting point intermetallic compound based on the melting range of the lead-free solder alloy.
  • the amount and type of optional additives can be varied to protect the lead-free solder alloy from oxidation during melting.
  • the amounts and types of lead- free solder alloy and high melting point additive metal may be varied to produce an intermetallic compound which has a desired remelt temperature and creep resistance at high temperatures such as are experienced during operation of lamps such as high intensity discharge lamps.
  • the amounts and types of high melting point additive metals are selected to react with the lead-free solder alloy to produce an intermetallic compound which has a solidus temperature above about 225°C, more preferably above about 250 °C.
  • the amounts and types of high melting point additive metals and lead-free solder alloy are chosen to produce an intermetallic compound that is about 80% or more liquid at 350 °C upon first melting.
  • the liquidus of the intermetallic compound formed from the composition after soldering and cooling is about 300°C to about 450°C.
  • compositions of lead-free solder alloy and high melting point additive, as well as optional additives can be combined into various forms such as pastes, wires, strip, ribbon and rod.
  • a paste powders of the lead-free solder alloy and additives are combined with a viscous polymeric carrier, usually a flux.
  • a viscous polymeric carrier usually a flux.
  • the amounts and sizes of particles of the lead-free solder alloy, high melting point additive, as well as optional additives can be chosen to produce a paste which has a desired rheological behavior, and viscosity, as well as shape retention after application to the substrate.
  • Useful forms of wires include composite wires such as those which have a higher melting point additive in the form of a core such as a Cu core surrounded by a sheath of the lead-free solder alloy.
  • the high melting point intermetallic compounds are produced by reacting a mixture of lead-free solder alloy and a higher melting point additive metal.
  • the lead-free solder alloy when in its molten state, has solubility for the higher melting point additive metal.
  • the mixture of lead-free solder alloy and additive metal has a melting point between 140°C and 250°C when first melted.
  • a transient liquid phase reaction occurs.
  • a transient liquid phase reaction occurs during first melting to produce a high melting point intermetallic compound.
  • the transient liquid phase reaction occurs to produce an intermetallic compound which has a melting point of about 250 °C or more.
  • the transient liquid phase reaction enables formation of the intermetallic compound in-situ.
  • a free low melting point metal such as Sn, In and Ga in the lead-free solder alloy reacts with a high melting point additive metal such as Cu, Fe, Ti and Ni to consume the free low melting point metal and to form a high melting point intermetallic compound. This reaction is described by equation I:
  • This transient liquid phase reaction can be used with a wide range of amounts and types of lead-free solder alloys and high melting point additive metals to form a variety of intermetallic compounds.
  • the intermetallic compounds can be produced have solidus and liquidus temperatures of from about 250 °C to about 1490°C.
  • a molten lead-free solder alloy which has free Sn reacts with a higher melting point additive metal such as Cu
  • the free Sn is consumed to produce a high melting point, Cu-Sn intermetallic compound such as Cu 6 Sn 5 that is stable up to about 415°C. Formation of Cu 6 Sn 5 can continue until all of the free Sn is consumed.
  • the high melting point additive metal is Ti
  • the free Sn reacts with Ti to form Sn 5 Ti 6 that is stable up to about 1494°C
  • the high melting point additive metal is Ni
  • the free Sn reacts with Ni to form Ni 3 Sn 4 that has a remelt temperature greater than about 790 °C
  • the high melting point additive metal is Fe
  • the free Sn reacts with Fe to form FeSn 2 that has a remelt temperature of about 513 °C.
  • free Ga can react with Cu to form CuGa 2 that has a remelt temperature of about 254°C
  • Ni can react with free In to form Ni 28 In 72 that is stable to about 400°C.
  • the amount and type of high melting point additive metal employed can vary depending on the lead-free solder alloy.
  • the amount of high melting point additive metal added to the lead- free solder alloy is sufficient to reduce the amount of a low melting point free metal such as free Sn to about 2 at . % to about 10 at.%, preferably about 6 at . % to about 8 at.%, based on the total atomic weight of the solder alloy and additive metal.
  • a low melting point free Sn in the solder alloy reacts with the Cu additive to form a high melting point Cu 6 Sn 5 intermetallic compound. In doing so, the amount of free Sn is reduced by 2 at.% per each 1 wt.% of Cu added, according to the rule of mixtures.
  • Examples 9-14 of Table 3 show mixtures of lead-free solder alloy and high melting point additive metal for production of a high melting point intermetallic compound.
  • preferred compositions are represented by examples 9-12.
  • the amounts of the elemental metals in the mixtures used to make the intermetallic compounds of examples 9-14 are shown in Table 3A.
  • Table 3A all amounts are in wt.%. based on the total weight of the mixture. These amounts are calculated by taking the elemental metals shown in the alloys used in the mixtures of Table 3 and applying the rule of mixtures to calculate the amounts of elemental metals present after addition of the Cu or Ti additive.
  • Intermetallic compounds produced in examples 9-14 of Table 3 are analyzed by electron microprobe and inductively coupled plasma mass spectroscopy .
  • the wt.% amounts of elemental metals in the lead-free solder alloys of examples 3,6,7 and 8 and the wt.% amounts of metals in the intermetallic compounds produced in examples 9-14 are shown in Table 4.
  • the amounts of free tin in the lead-free solder alloys of examples 3,6,7 and 8 are shown.
  • the amounts of free tin in the lead- free solder alloys employed are expressed in at.% based on the total weight of the lead-free solder alloy and additive.
  • the amount of free tin in the lead-free solder alloy for alloys which contain tin, bismuth, copper, titanium, antimony and silver is the total at.% tin minus any tin bound in intermetallics such Cu 6 Sn 5 , SbSn, Ag 3 Sn and Ti 6 Sn 5 present in the solder, or in the intermetallic compound from reaction of the solder and additive.
  • the amount of free tin is calculated from Equation II
  • At.% Free Tin (Total At.% Sn - 5/6 (at.% Cu) - 5/6 (at.%
  • each of the at.% Sn, at.% Cu, at.% Ti, at.% Sb, and at.% Ag are based on the total atomic percents of Sn, Cu, Ti, Sb and Ag in the mixture of solder alloy and high melting point additive.
  • the amount of free In and Ga is calculated similarly by subtracting the atomic% of In and Ga bound into intermetallic phases such as CuGa and Ni 28 In 72 .
  • solder pastes include atomized powders of the lead-free solder alloys. Solder pastes also can include mixtures of these solder alloys and high melting point additives, together with optional additives such as antioxidants .
  • powders of lead-free solder alloy, optionally with high melting point additives are mixed with a flux, preferably in a 90/10 wt . ratio of powder to flux. This ratio may be varied to achieve desired rheological characteristics in the solder paste.
  • a high intensity discharge lamp 1 as shown in FIGS. 1 and 1A, includes outer envelope 3, base 5, eyelet 7, lead wires 9 and 11, and light source 13.
  • the lower section of outer envelope 3, shown in FIG.1A, is threaded to join with matching threads on the inside of base 5.
  • This lower section of outer envelope 3 includes dimple 12 into which lead wire 9 is placed. In dimple 12, wire 9 is joined to wall 4 of base 5 in a side solder joint.
  • Base 5 can be formed from a non-passivating transition metal such as Cu, brass, bronze, and Cu-based composite materials such as W-Cu, Ta-Cu, and Mo-Cu where the copper content is approximately 15 wt.% or more; Fe, mild steels, tool steels which have low chromium content; Ni, monel, and Ni-plated alloys; silver and sterling silver; Zn and high-Zn alloys such as Zn die-casting alloys; noble metals and alloys such as 10-24 karat gold, gold-plated alloys and platinum.
  • a non-passivating transition metal such as Cu, brass, bronze, and Cu-based composite materials such as W-Cu, Ta-Cu, and Mo-Cu where the copper content is approximately 15 wt.% or more; Fe, mild steels, tool steels which have low chromium content; Ni, monel, and Ni-plated alloys; silver and sterling silver; Zn and high-Zn alloys such as Zn die-casting alloys; noble metals and alloys such
  • Base 5 also can be formed from a passivating alloy such as stainless steel, titanium and its alloys, zirconium and its alloys, as well as aluminum and its alloys depending on the choice of flux.
  • a passivating alloy such as stainless steel, titanium and its alloys, zirconium and its alloys, as well as aluminum and its alloys depending on the choice of flux.
  • Useful fluxes which may be used with passivating alloys include, alone or in combination, zinc chloride, ammonium chloride, hydrochloric acid, hydrofluoric acid, sodium hydroxide and any other chemical that can break down the passive oxide layer on the surface of the alloy.
  • Outer envelope 3 can be formed from a broad range of glass compositions which can withstand the soldering temperatures.
  • Useful glass compositions include but are not limited to: 1. borosilicates which have about 73% Si0 2 , about 14.8% B 2 0 3 ⁇ about 5.45% PbO, about 3.6% Na 2 0, and about 3.15%A1 2 0 3 ;
  • Lead wires 9, 11 can be Ni-plated Fe, and eyelet 7 can be formed from, such as, Cu/Zn 37% alloy.
  • Ni-plated Fe and Cu/Zn37% alloys each are well known and commercially available .
  • Examples of a suitable light source 13 include but are not limited to an arc tube assembly, a sodium light assembly, a mercury vapor light assembly, a metal halide assembly, a ceramic metal halide assembly, and a tungsten filament.
  • First lead wire 9 is positioned in dimple 12 for contact with sidewall 4 of base 5. Lead wire 11 is threaded through a hole in eyelet 7. Base 5 then is placed onto envelope 3.
  • Solder paste which includes one of the afore described lead free solder alloys, or a mixture of one of these lead free solder alloys and high melting point additive, is applied to wire 9 at dimple 12.
  • the paste is heated to form a soldered side joint between sidewall 4 and wire 9.
  • Solder paste also is applied to wire 11 and eyelet 7 and heated to form a soldered eyelet joint with eyelet 7.
  • the solder paste is heated to burn out the flux in the paste and to fully melt the solder to form the joint .
  • a side joint between wire 9 and sidewall 4 of base 5 formed of brass is made by using a wire solder formed from a lead-free solder alloy such as that of example 6 of Table 4. Formation of the side joint is accomplished by preheating base 5. A flux is applied to dimple 12 that has lead wire 9 therein and to side wall 4. The wire solder is inserted into dimple 12. Dimple 12 and sidewall 4 areas are then heated until the solder is molten and flows to produce the side joint. Similarly, solder wire is applied to wire 11 and eyelet 7 and heated to form a soldered eyelet joint with eyelet 7.
  • Cast wire soldering likewise can be performed using composite wires formed of high melting point additives such as Cu, Cu alloy, Ti, Ni , Ni alloys, Pd, bronze, and brass encapsulated in a sheath of the lead-free solder alloy.
  • high melting point additives such as Cu, Cu alloy, Ti, Ni , Ni alloys, Pd, bronze, and brass encapsulated in a sheath of the lead-free solder alloy.
  • antioxidants such as antioxidants, wetting agents and flux also can be incorporated.
  • High intensity discharge lamps which employ solder joints from alloys 1 to 8 are evaluated in two tests. In the first test, the lamps are aged in aging racks with the base up for
  • base 5 can be attached to envelope 3 by an adhesive such as phenolic resin or methyl phenyl silicone resin applied to the threads on any of envelope 3 or base 5.
  • lead wire 9 can be extended over an edge of base 5 and soldered to the exterior of base 5.
  • base 5A may be a positioned at a right angle to light source 13A.
  • Base 5A includes base cap 35, lamp lead wire 37, and base lead wire 39.
  • lamp leads 37 are fed through base holes 41 as shown in FIG. 2B and soldered to base lead 39.
  • solders and intermetallic alloys of the invention include sealed beam lamps and composite lamps.
  • Sealed beam lamp 40 shown in FIGS. 3 and 3A can be used in vehicles such tractors, aircraft and automobiles.
  • Sealed beam lamp 40 includes lens 42 formed from materials such as glass, reflector 42A formed from materials such as glass, light source 46, lead wires 48, ferrule 50, ferrule cavity 52, and base contacts 54.
  • Sealed beam lamp 40 is made by placing any of the afore described lead free solder alloys and mixtures of those alloys with high melting point additives into ferrule cavity 52, and heating to their liquidus.
  • Lead wire 48 then is placed into the resulting liquid material and is cooled to form a solid solder joint.
  • Clear lens 56 of glass or heat resistant plastic then can be attached to reflector 58 by flame sealing or adhesive.
  • Base contacts 60 are then soldered to ferrule 50 with any of the aforedescribed lead free solder alloys and mixtures of those alloys with high melting point additives.
  • Composite lamp 90 as shown in FIGS. 4-4B, includes light source 80, base 82 formed of plastic or plastic-metal composite, metal lead wires 83, metal feed-throughs 85 molded into base 82, and metal base connections 84. Feed-throughs 85 and base connections 84 may be a single component. Lead wires 83 attached to light source 80, are guided through feed- throughs 85. Solder formed of any of the aforedescribed lead free solder alloys and mixtures of those alloys with high melting point additives is melted into feed-throughs 85 to make a soldered joint between lead wires 83 and base connections 84. This soldered joint can function to provide electrical connection between light source 80 as well as to retain alignment of light source 80 and lead wires 83.
  • the soldered joint may include a solder alloy such as 20Bi-33Sb-47Sn, 5Cu-24Sb-71Sn, 2Cu-25Ag-73Sn, and lCu-5Sb-94Sn.
  • the solder joint also may include the reaction products of a solder alloy such as 20Bi-33Sb-47Sn, 5Cu-24Sb- 71Sn, 2Cu-25Ag-73Sn and lCu-5Sb-94Sn with Ti in an amount of about 0.5% wherein the amount of Ti is based on the weight of the alloy; reaction products of 20Bi-33Sb-47Sn with Cu in an amount of about 2.0% wherein the amount of Cu is based on total weight of the solder alloy; the reaction product of a solder alloy of 20Bi-33Sb-47Sn with Cu in an amount of about 5.0% wherein the amount of Cu is based on total weight of the lead-free, solder alloy.
  • the solder joint may include a solder alloy such as 20Bi-33Sb-47Sn,5Cu-24Sb-71Sn, 2Cu-25Ag-73Sn, and lCu- 5Sb-94Sn.
  • the solder joint also may include the reaction products of a solder alloy such as 20Bi-33Sb-47Sn, 5Cu-24Sb- 71Sn, 2Cu-25Ag-73Sn and lCu-5Sb-94Sn with Ti in an amount of about 0.5% wherein the amount of Ti is based on the weight of the alloy; reaction products of 20Bi-33Sb-47Sn with Cu in an amount of about 2.0% wherein the amount of Cu is based on total weight of the solder alloy; the reaction product of a solder alloy of 20Bi-33Sb-47Sn with Cu in an amount of about 5.0% wherein the amount of Cu is based on total weight of the lead-free, solder alloy.
  • an improved fluorescent lamp such as linear flourescent lamp 100 as shown in FIGS. 5 and 5A.
  • Linear flourescent lamps as is well known in the art, includes hollow prongs 102 an lead wires 104 joined to prongs 102 and to coil 106. Lead wires 104 receive electrical energy from prongs 102 to energize coil 106 for activation of lamp 100.
  • a solder joint between lead wires 104 and prongs 102 is made by of any of the afore described lead free solder alloys and mixtures of those alloys with high melting point additives.
  • the solder joint may include a solder alloy such as 20Bi-33Sb-47Sn,5Cu-24Sb-71Sn, 2Cu-25Ag-73Sn, and lCu- 5Sb-94Sn.
  • the solder joint also may include the reaction products of a solder alloy such as 20Bi-33Sb-47Sn, 5Cu-24Sb- 71Sn, 2Cu-25Ag-73Sn and lCu-5Sb-94Sn with Ti in an amount of about 0.5% wherein the amount of Ti is based on the weight of the alloy; reaction products of 20Bi-33Sb-47Sn with Cu in an amount of about 2.0% wherein the amount of Cu is based on total weight of the solder alloy; the reaction product of a solder alloy of 20Bi-33Sb-47Sn with Cu in an amount of about 5.0% wherein the amount of Cu is based on total weight of the lead-free, solder alloy.
  • the lead-free solder alloys and the high melting point, intermetallic compounds of the invention form strong, heat resistant, electrically conductive bonds between base 5 and outer envelope 3, as well as between lead wires and each of base 5 and eyelet 7.
  • the lead-free solder alloys and the intermetallic compounds of the invention form solder joints which have mechanical integrity up to about 240 °C .
  • These solder joints have a liquidus temperature below about 1490 °C, preferably between 450 °C and a solidus above about 250°C.
  • Liquidus temperatures below about 450°C advantageously enable rework of the solder joints, if necessary.
  • Liquidus temperatures below about 450°C also advantageously avoid generating unacceptable thermal stresses in the glass envelope-metal base assembly of the high intensity discharge lamp.
  • the lead-free solder alloys and the high melting point intermetallic compounds formed from reaction of the lead-free solder alloy and high melting point additive of the invention, as discussed above, are especially suited for use in lighting applications such as high intensity discharge lamps.
  • Other lighting applications include sealed beam lamps and composite lamps.
  • alloys and intermetallic compounds of the invention may be used in, for example, automotive radiators, industrial assembly and any other application where it is important that the solder joint maintain integrity up to about 450°C.
  • the lead free solders and high melting point intermetallic compounds of the invention have a low initial melting point of about 140°C to about 225°C, and a higher remelt temperature of about 250 °C to about 450 °C.
  • the low initial melting point allows for simpler industrial assembly than a homogenous solder alloy which has a remelt temperature in the same range .
  • solder pastes and wire solders produced from the lead-free solder alloys, as well as from mixtures thereof with high melting point additives may be employed to solder a variety of substrates.
  • these substrates include Cu, brass, bronze, Cu-based composite materials such as Mo-Cu, Ta-Cu, and W-Cu, having Cu contents greater than about 15 wt.%; Fe, mild steels, tool steels with low chromium content; Ni, monel (Ni-Cu alloys), Ni-plated alloys; silver, sterling silver; Zn and high-Zn alloys such as Zn die-casting alloys; noble metals and alloys such as 10-24 karat gold, gold-plated alloys, and platinum, and palladium alloys (Paliney alloys) .
  • solders and intermetallic compounds inhibit long-term diffusion and attendant failure modes caused by solder penetration of the substrate, oxidation, formation of reactive products, and creep.
  • the intermetallic compounds are resistant to thermal fatigue.
  • the solders and intermetallic compounds of the invention when used in manufacture of high intensity discharge lamps, provide a strong mechanical/metallurgical bond between each of base 5, eyelet 7 and the outer envelope 3 components of the bulb, as well as an electrically conductive bond between the lead wires of the bulb and each of the side wall and eyelets of the base. The bond does not degrade due to high/low temperature cycling.
  • the invention enables use of lead free solder alloys as well as use of mixtures of lead free solders and high melting point additives to produce solders which have a desired remelt temperature.
  • the properties of the lead-free solder alloys and intermetallic compounds formed from the reaction of these alloys with high melting point additives can be tailored to achieve a heat resistant solder joint based on desired assembly times, flow behavior, as well as long-term creep and substrate penetration resistance.
  • the lead-free solder alloys can be employed with a wide variety of fluxes, including extremely aggressive fluxes.
  • aggressive fluxes are compositions which include acidic or basic compounds such as HF and highly aggressive salts. Since the flux removes oxides present on the substrate, the choice of flux is a function of the metal used in the substrate. For metals such as aluminum which oxidize easily to form strong oxide layers, aggressive compounds such as HF or chloride fluxes can be used with the solders of the invention.
  • the solder alloys of the invention do not require chloride compounds for wetting of non-passivating substrates. This avoids undesirable corrosive attack of the metal by chlorine.

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Abstract

L'invention concerne des nouveaux alliages de brasure sans plomb et des composés intermétalliques. Les brasures sont utilisées pour une lampe (1) à décharge de haute intensité. Les joints de brasure formés à partir de ces alliages sont résistants au fluage dans des environnements à haute température, tels que ceux auxquels sont exposés les lampes à décharge de haute intensité (1). Les alliages de brasure sans plomb peuvent être amenés à réagir avec des additifs à point de fusion plus élevé par réaction en phase liquide transitoire pour former des composés intermétalliques ayant un point de fusion plus élevé que celui de l'alliage de brasure sans plomb.
PCT/US2001/028387 2001-06-05 2001-09-11 Nouvelles brasures a haute temperature sans plomb WO2002099146A1 (fr)

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WO2005001882A3 (fr) * 2003-06-30 2006-08-03 Koninkl Philips Electronics Nv Lampe fluorescente compacte integree compatible avec le test de determination de la caracteristique de toxicite par lixiviation (tclp)
DE102005059544A1 (de) * 2005-12-13 2007-06-14 Ecka Granulate Gmbh & Co. Kg Sn-haltige hochbelastbare Materialzusammensetzung; Verfahren zur Herstellung einer hochbelastbaren Beschichtung und deren Verwendung
US20090301607A1 (en) * 2005-11-11 2009-12-10 Kosuke Nakano Solder Paste and Solder Joint
US7982377B2 (en) 2004-10-20 2011-07-19 Koninklijke Philips Electronics N.V. High-pressure gas discharge lamp
WO2012024795A1 (fr) * 2010-08-26 2012-03-01 Dynajoin Corporation Brasures à point de fusion variable
US8348139B2 (en) 2010-03-09 2013-01-08 Indium Corporation Composite solder alloy preform
WO2015105089A1 (fr) * 2014-01-07 2015-07-16 株式会社村田製作所 Procédé de réparation et matériau de réparation
US10195698B2 (en) 2015-09-03 2019-02-05 AIM Metals & Alloys Inc. Lead-free high reliability solder alloys
CN113789449A (zh) * 2021-09-28 2021-12-14 四川兰德高科技产业有限公司 一种细化剂及其制备方法和应用

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005001882A3 (fr) * 2003-06-30 2006-08-03 Koninkl Philips Electronics Nv Lampe fluorescente compacte integree compatible avec le test de determination de la caracteristique de toxicite par lixiviation (tclp)
US7982377B2 (en) 2004-10-20 2011-07-19 Koninklijke Philips Electronics N.V. High-pressure gas discharge lamp
US20090301607A1 (en) * 2005-11-11 2009-12-10 Kosuke Nakano Solder Paste and Solder Joint
US9162324B2 (en) * 2005-11-11 2015-10-20 Senju Metal Industry Co., Ltd. Solder paste and solder joint
DE102005059544A1 (de) * 2005-12-13 2007-06-14 Ecka Granulate Gmbh & Co. Kg Sn-haltige hochbelastbare Materialzusammensetzung; Verfahren zur Herstellung einer hochbelastbaren Beschichtung und deren Verwendung
WO2007068503A3 (fr) * 2005-12-13 2007-08-16 Ecka Granulate Gmbh & Co Kg Matiere a forte capacite de sollicitation contenant du sn, procede de fabrication d'un revetement a forte capacite de sollicitation et utilisation dudit revetement
US8348139B2 (en) 2010-03-09 2013-01-08 Indium Corporation Composite solder alloy preform
US20120055586A1 (en) * 2010-08-26 2012-03-08 Dynajoin Corporation Variable melting point solders
US9095936B2 (en) * 2010-08-26 2015-08-04 Dynajoin Corporation Variable melting point solders
WO2012024795A1 (fr) * 2010-08-26 2012-03-01 Dynajoin Corporation Brasures à point de fusion variable
WO2015105089A1 (fr) * 2014-01-07 2015-07-16 株式会社村田製作所 Procédé de réparation et matériau de réparation
US10994366B2 (en) 2014-01-07 2021-05-04 Murata Manufacturing Co., Ltd. Repair method and repair material
US10195698B2 (en) 2015-09-03 2019-02-05 AIM Metals & Alloys Inc. Lead-free high reliability solder alloys
CN113789449A (zh) * 2021-09-28 2021-12-14 四川兰德高科技产业有限公司 一种细化剂及其制备方法和应用

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