WO2009009877A1 - Brasages composites à matrice métallique - Google Patents

Brasages composites à matrice métallique Download PDF

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Publication number
WO2009009877A1
WO2009009877A1 PCT/CA2008/001282 CA2008001282W WO2009009877A1 WO 2009009877 A1 WO2009009877 A1 WO 2009009877A1 CA 2008001282 W CA2008001282 W CA 2008001282W WO 2009009877 A1 WO2009009877 A1 WO 2009009877A1
Authority
WO
WIPO (PCT)
Prior art keywords
solder
particles
partially wetted
composite
partially
Prior art date
Application number
PCT/CA2008/001282
Other languages
English (en)
Inventor
Scott E. Nichol
Lionel W. Nichol
Original Assignee
Nichol Scott E
Nichol Lionel W
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nichol Scott E, Nichol Lionel W filed Critical Nichol Scott E
Publication of WO2009009877A1 publication Critical patent/WO2009009877A1/fr

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Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
    • H05K3/3489—Composition of fluxes; Methods of application thereof; Other methods of activating the contact surfaces
    • 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
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
    • H05K3/3457—Solder materials or compositions; Methods of application thereof
    • H05K3/3485—Applying solder paste, slurry or powder
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0209—Inorganic, non-metallic particles

Definitions

  • Soldering involves melting a solder material between two metal objects to join the two objects without causing them to melt. Solder is useful for plumbing, electronic circuit boards, solar cells, radiators, tin coating and other known soldering applications.
  • a solder which comprises a composite solder combined with particles to form a metal matrix solder composite, wherein the particles are partially wetted particles having an average diameter sufficiently large to perform functionally as partially wetted particles when mixed with the solder.
  • the partially wetted particles have an average diameter of between about six (6) and 300 microns.
  • the partially wetted particles may be selected from aluminum oxide
  • the aluminum oxide (Al 2 O 3 ) particles have a size of about 150 to about 240 grit
  • the silicon dioxide (SiO 2 ) particles have a size of about 30 to 300 grit or 60 to 240 grit, such as about 60 grit.
  • the stainless steel particles have a size of about 60 to about 240 grit.
  • the partially wetted particles comprise 0.1 to five (5) wt% of the solder, 0.5 to five (5) wt% of the solder, or one (1) to four (4) wt% of the solder.
  • the solder comprises about 90 to about 99 wt% Sn and up to about six (6) wt% Cu. Such solder may further comprise about eight (8) to about 12 wt% Zn and about 83 to about 95 wt% Sn. In one embodiment, such solder further comprises about one (1) to about five (5) wt% aluminum oxide having a size of 150 grit.
  • a solder which comprises a lead-free solder combined with partially wetted particles to form a lead-free metal matrix solder composite, wherein the partially wetted particles have an average diameter greater than about 60 microns up to about 300 microns.
  • a method comprising providing molten solder; and adding partially wetted particles to the molten solder to produce a metal matrix composite solder.
  • the adding step comprises mechanically mixing the partially wetted particles into the molten solder between the liquidus and solidus temperatures of the solder (which includes any type of solder alloy), i.e., in the slushy phase, although the invention is not so limited.
  • the partially wetted particles are added at or above the solidus temperature of the solder.
  • the method may further comprise adding an inert gas blanket to minimize dross formation in the solder; and removing floating dross from the solder after mixing.
  • the method comprises mixing partially wetted particles into flux, the partially wetted particles having an average diameter of a size sufficient to function as partially wetted particles when mixed with solder; and soldering a component with the flux and the solder.
  • the partially wetted particles may additionally be mixed into the solder as described above.
  • novel MMC solders described herein provide improved wetting properties, increase the rate at which solder flows upon melting, and create higher strength in the joint as compared with traditional solder formulas. As a result, previously unacceptable formulations known in the art are now possible.
  • MMC solders are provided. In one embodiment, less solder is used to produce an acceptable soldered joint. It is also possible that metals which are known to be difficult to solder (e.g., aluminum) may be soldered with the novel MMC solders disclosed herein.
  • FIG. 1 shows a block flow diagram in one embodiment of the present invention.
  • wettability refers to the ability of liquids to spread on a surface, e.g., of a particle. Increased wettability is associated with a lower contact angle. Incomplete wettability occurs on surfaces with a contact angle less than 90 degrees.
  • completely wetted particle or “completely wetting particle,” as used herein, refers to a particle which dissolves into a molten mass, changing the composition of the molten mass. Copper is one example of a "completely wetted particle.” Copper slowly dissolves into a molten mass, and does not remain as a discrete particle.
  • partial wetting refers to incomplete wetting.
  • partially wetted particle refers to a particle with a surface which does not become completely wet when placed in a liquid or molten mass, i.e., the liquid does not spread completely onto the particle surface.
  • a “partially wetted particle” therefore does not dissolve in a molten mass (e.g., solder), but remains chemically inert.
  • a shearing force is required to mix a "partially wetted particle” into a molten mass.
  • the smaller the particle the larger the overall surface area. Therefore, smaller particles require a greater shearing force in order to wet the surface and mix the particle into the molten mass. If the particle size becomes too small, a "partially wetted particle” may functionally behave instead as a non-wetted particle (described below).
  • partially wetted powder refers to a plurality of partially wetted particles, as defined herein.
  • non-wetting refers to a surface property which does not allow a liquid to spread when the measured contact angle is equal to or greater than 90 degrees.
  • non-wetted particle or “non-wetting particle,” as used herein refers to a particle which is completely immiscible in a molten mass, even when a shearing force is applied. Once the shearing force (i.e., any type of mixing) stops, a non- wetted particle floats back to the surface of the molten mass.
  • a metal matrix composite (MMC) solder is disclosed.
  • the metal matrix composite solder comprises a lead-free solder or lead-free solder alloy together with partially- wetted particles of a sufficient average diameter or size.
  • the novel MMC solder may be a lead-based solder, as demonstrated in Example 7.
  • the composite comprises about 90 to about 99 wt% tin (Sn), and up to about six (6) wt% copper (Cu), with partially wetted particles having an average diameter of at least six (6) microns up to about 300 microns, although the invention is not so limited.
  • the average diameter may be about 14 to about 60 microns. In one embodiment, the average diameter is greater about 60 microns up to about 300 microns.
  • the concentration of the partially wetted particles in the composite is at a level to provide the requisite physical properties for a particular application. If the concentration of the partially wetted particles is too high, the ductility of the solder is decreased. Furthermore, particles unable to become wetted would remain floating on the surface after mixing is completed. If the concentration of the partially wetted particles is too low, the improved strength, wetting and flow characteristics are not achieved. In one embodiment, the concentration of the partially wetted particles in the solder is about 0.1 to five (5) wt%. In one embodiment, the concentration is about 0.5 to five (5) wt%. In one embodiment, the concentration of the partially wetted particles is about one (1) to about four (4) wt%.
  • the partially- wetted particles are selected from aluminum oxide (Al 2 O 3 ) particles, silicon carbide (SiC) particles, silicon dioxide (SiO 2 ) particles, stainless steel particles, silicon nitride (Si 3 N 4 ) particles, boron nitride (BN) particles, graphite particles and combinations thereof, with an average diameter of a size sufficient to function as partially wetted particles.
  • the requisite average diameter for a particle to function as a partially wetted particle depends on a number of variables, including, but not limited to, the type of particle, type of molten mass, particular type of joint desired, and so forth.
  • the partially wetted particles include, but are not limited to, aluminum oxide (Al 2 O 3 ) particles having a size of about 150 to about 240 grit, silicon dioxide (SiO 2 ) particles having a size of about 30 to 300 grit or 30 to 240 grit, such as about 50 to 70 grit, stainless steel particles having a size of about 60 to about 240 grit, and silicon carbide (SiC,) particles having an average particle diameter of about 12 to about 300 microns.
  • Al 2 O 3 aluminum oxide
  • SiO 2 silicon dioxide
  • SiC silicon carbide
  • the invention comprises a low cost Zn-Sn solder with partially wetted particles having improved physical properties and containing about eight (8) to about 12 wt% Zn, about 83 to about 95 wt% Sn, and about one (1) to about five (5) wt % aluminum oxide having a size of about 150 grit.
  • the novel MMC composite solders do not contain copper.
  • the solder may comprise up to 100% Sn.
  • the copper level is greater than zero (0) wt% up to at least one (1) wt%.
  • the copper level is greater than one (1) wt% up to at least two (2) wt%.
  • the copper level is greater than two (2) wt% up to at least three (3) wt%.
  • the copper level is greater than three (3) wt %, up to about 4 wt%, about 5 wt% or about 6 wt% or higher. If the concentration of copper is too high, the solder would not function properly.
  • the novel MMC solders described herein allow higher levels of copper to be used as compared with conventional solders, thus extending the useable range of copper.
  • a method for making MMC solders includes providing 102 a molten solder and adding 104 partially wetted particles to the molten solder to produce a metal matrix composite solder.
  • the solder is a solder alloy.
  • the adding step 104 includes mechanically mixing a plurality of partially wetted particles (i.e., a partially wetted powder) into molten solder between the liquidus and solidus temperatures of the solder
  • the partially wetted particles are added at or above the solidus temperature of the solder, which includes a solder alloy.
  • Minimization of dross creation during mixing can be achieved with an inert gas blanket of nitrogen or argon. Floating dross on the surface of the molten bath can be removed after mixing. Wettability of the solder is controllable with adjustments to the concentration, type, shape and size of particles used to make the MMC solder.
  • novel partially wetted particles may be added into the flux instead of or in addition to being added into the solder.
  • MMC solders are easier to use than standard lead free solders due to the visual flowing of the material into the joint.
  • MMC solders work well with brass, which is more difficult to solder than ordinary copper plumbing.
  • MMC solder can be used to improve the current silver-based lead free plumbing solders, thus making them more reliable and lower in cost, due to the addition of lower cost components.
  • MMC composite solders produce improved toughness and stronger solders due to better wetting and strength, resulting in less cyclical fatigue failure in the boards.
  • the lower temperature helps to reduce the temperature for wave soldering techniques preventing damage to delicate circuit board parts.
  • improved wetting allows less solder and higher densities of contacts on circuit boards.
  • copper dissolution from the printed circuit board components increases copper content in the melt.
  • the melt is eventually disposed of or diluted with fresh solder due to reduction in physical properties of the joint.
  • the improved wetting and strength of the novel MMC composite solders described herein may increase the tolerance of the bath to copper content before physical properties of the joint decrease to below acceptable levels.
  • Sn 97/Cu 3 solder commonly used for radiator core tubes is limited by contamination of copper into the solder during soldering, hi one embodiment, the use of MMC additives reduces this problem because the solder can be used with a higher copper concentration due to improved properties. The cost is lowered due to the reduced cost of the novel additives as compared with the base tin. Use of a lower temperature also results in energy savings. In one embodiment, improved wetting and bond strength allows the soldering process to proceed faster, thus resulting in further savings.
  • each individual solder alloy was added to a stainless steel cup and heated to approximately 240 °C using a hotplate until it melted to produce a molten solder alloy.
  • the desired amount of partially wetted powders were mixed into the molten solder alloy using simple stir casting mechanical mixing as is well known in the art, using a stainless steel spoon or rotating stainless steel drill bit. Dross was skimmed from the surface after the powder was mixed into the molten solder.
  • Table 1 shows the various combinations tested.
  • Example 2 Three cold samples of different solder compositions produced in Example 1 were placed on a 2.54 cm x 1.9 cm x 0.3 cm (one (1) in x 0.75 in x 0.125 in) copper plate on top of a steel plate to spread the heat evenly. The samples were then slowly heated up on a hot plate to compare the melting points. The temperature at which they flowed was measured with a laser pointer infrared pyrometer. The temperature was raised slowly and heat applied on and off, so that the temperature of each piece of solder remained within 15 0 C (five (5) 0 F) degrees of each other. The MMC solders with particles in then flowed sooner than comparable solders and flowed sooner and easier on the copper plate as shown in Table 2.
  • Example 1 The MMC solders made in Example 1 were poured off into small diameter rods for testing on standard copper plumbing joints. Standard Kester brand resin flux (Ag 1%/ Cu 3%/ Sn 96%) manufactured by Kester, having offices in Itasca, Illinois, was used as flux for all of the copper joints.
  • the MMC solders were drawn into the joint and thoroughly distributed inside the copper joint.
  • the SiO 2 MMC solders ran through the entire joint.
  • solder compositions were tested for use in wave soldering.
  • a solder composition of about 97% Sn and three (3)% copper with aluminum oxide particles of about 60 microns in a concentration of about three (3) wt% flowed at 222 0 C as compared with 227 0 C for a 100% Sn solder.
  • compositions tested had concentrations of copper up to about six (6) wt%. Good wetting properties were observed, even at copper levels of about six (6) wt%, which occurred due to contamination from the standard industrial processes.
  • a composition containing about three (3) % Alumina and about 97% Sn was also tested with good wettablity and bonding strength.
  • EXAMPLE 5 A 9% Zinc/91% Sn solder was compared to a solder containing about one (1) to about five (5) wt% aluminium oxide 150 added grit.
  • the zinc-tin solder did not solder well when attempting to solder a simple copper tube to a copper straight through plumbing fixture, i.e., the solder did not flow well and there were obvious holes in the joint.
  • this solder soldered extremely well, i.e., the solder flowed easily into the joint and flowed completely through the joint. In each case the melting point was below 200 0 C.
  • EXAMPLE 6 Standard solder paste (Masters soldering Paste imported by G.F. Thompson, New Market, Ontario, Canada and purchased locally, had three (3) to ten (10)% by weight of 240 grit aluminum oxide powder mechanically mixed into it using a spoon. This mixed paste was used under the same conditions as in Example 1 to melt 3% Cu-97% Sn solder obtained from Canada Metals in Toronto, onto a copper plate. A second identical plate was made using the plain paste (Masters) and the same 3% Cu-97% Sn solder. The two samples melted at approximately the same time and temperature. However, the one with the aluminum oxide powder wetted the surface better, i.e., it spread out much more.
  • the paste with aluminum oxide powder and without was used with the 3% Cu -97% Sn alloy to solder two sets of copper plates end to end.
  • the one with the aluminum oxide in it produced the stronger bond, as evidenced by simple bend until the joint broke, i.e., much more force was needed to break the joint.
  • EXAMPLE 7 A three (3) mm Kester solid wire solder obtained from a local retailer.
  • the solid wire solder was comprised of 60% Pb/40% Sn alloy composition had three (3)% by weight of 240 grit aluminum oxide melted into it and mechanically mixed as in Example 1. This mixed solder was compared to the simple three (3) mm Kester solid wire solder (60%Pb/40% Sn) by using a copper plate and using Masters solder paste for the plate and slowly increasing the temperature on a hot plate. The solder with the aluminum oxide in it appeared to flow at a temperature of about two (2)°C lower than the simple Pb/Sn solder. The wetting of the plate was greater as well. A simple break test using small copper plates was used for both of the above samples. The plates jointed by the solder containing aluminum oxide were more difficult to break by hand than the sample without the aluminum oxide added.
  • Embodiments of the present invention include a variety of metal matrix composite solders containing partially wetted particles dispersed throughout the matrix.
  • the novel MMC composite solders described herein have improved wetting properties, a lower flow temperature, improved ease of use, and improved bonding strength as compared with conventional solders.
  • standard tin solder alloys are converted to metal matrix composites (MMC) with addition of partially wetted particles.
  • MMC metal matrix composites
  • Such composites can be used as a solder or tinning material.
  • MMC solders can be used for any number of applications, including, but not limited to, plumbing, electronic circuit boards, manufacturing solar modules, radiators, tin coating, brazing and other traditional soldering applications.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Mechanical Engineering (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)

Abstract

L'invention porte sur un brasage composite qui comprend un brasage combiné avec des particules afin de former un brasage composite à matrice métallique (MMC), dans lequel les particules sont des particules partiellement humidifiées ayant un diamètre moyen suffisamment important pour agir fonctionnellement comme particules partiellement humidifiées lorsqu'elles sont mélangées avec le brasage. Dans un mode de réalisation, le brasage est un alliage de brasage. Le brasage MMC a une mouillabilité améliorée, une vitesse accrue d'écoulement lors de la fusion, et une résistance supérieure, par comparaison avec des formules de brasage traditionnelles. Dans un mode de réalisation, les particules partiellement humidifiées sont choisies parmi l'oxyde d'aluminium (Al2O3), le carbure de silicium (SiC), le dioxyde de silicium (SiO2), l'acier inoxydable, le nitrure de silicium ((Si3N4), le nitrure de bore (BN), le graphite et leurs combinaisons. Des modes de réalisation comprennent des procédés pour fabriquer et utiliser le brasage MMC.
PCT/CA2008/001282 2007-07-13 2008-07-11 Brasages composites à matrice métallique WO2009009877A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US94966107P 2007-07-13 2007-07-13
US60/949,661 2007-07-13

Publications (1)

Publication Number Publication Date
WO2009009877A1 true WO2009009877A1 (fr) 2009-01-22

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PCT/CA2008/001282 WO2009009877A1 (fr) 2007-07-13 2008-07-11 Brasages composites à matrice métallique

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140030140A1 (en) * 2011-04-08 2014-01-30 The University Of Queensland Solder alloy
CN107790915A (zh) * 2017-11-15 2018-03-13 广西塔锡科技有限公司 一种铝焊粉及其制备方法
CN114559180A (zh) * 2022-03-21 2022-05-31 太原理工大学 碳化硅颗粒增强型镁合金钎焊钎料及其制备方法和应用

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US5405577A (en) * 1993-04-29 1995-04-11 Seelig; Karl F. Lead-free and bismuth-free tin alloy solder composition
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140030140A1 (en) * 2011-04-08 2014-01-30 The University Of Queensland Solder alloy
EP2695701A1 (fr) * 2011-04-08 2014-02-12 Nihon Superior Co., Ltd. Alliage de brasure
EP2695701A4 (fr) * 2011-04-08 2014-09-24 Nihon Superior Co Ltd Alliage de brasure
JP5973992B2 (ja) * 2011-04-08 2016-08-23 株式会社日本スペリア社 はんだ合金
US9999945B2 (en) * 2011-04-08 2018-06-19 Nihon Superior Co., Ltd. Solder alloy
CN107790915A (zh) * 2017-11-15 2018-03-13 广西塔锡科技有限公司 一种铝焊粉及其制备方法
CN114559180A (zh) * 2022-03-21 2022-05-31 太原理工大学 碳化硅颗粒增强型镁合金钎焊钎料及其制备方法和应用
CN114559180B (zh) * 2022-03-21 2024-04-09 太原理工大学 碳化硅颗粒增强型镁合金钎焊钎料及其制备方法和应用

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