US20020170633A1 - Brazing filler metal - Google Patents

Brazing filler metal Download PDF

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US20020170633A1
US20020170633A1 US10/069,955 US6995502A US2002170633A1 US 20020170633 A1 US20020170633 A1 US 20020170633A1 US 6995502 A US6995502 A US 6995502A US 2002170633 A1 US2002170633 A1 US 2002170633A1
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brazing filler
filler metal
composition ratio
range
metal
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Hitoshi Uchida
Yoshitsugu Shibuya
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Citizen Watch Co Ltd
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Citizen Watch Co Ltd
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Assigned to CITIZEN WATCH CO., LTD. reassignment CITIZEN WATCH CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SHIBUYA, YOSHITSUGU, UCHIDA, HITOSHI
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C14/00—Alloys based on titanium
    • 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
    • B23K35/32—Selection of soldering or welding materials proper with the principal constituent melting at more than 1550 degrees C
    • B23K35/322—Selection of soldering or welding materials proper with the principal constituent melting at more than 1550 degrees C a Pt-group metal as principal constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/02—Alloys based on gold
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/04—Alloys based on a platinum group metal
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/06—Alloys based on silver
    • C22C5/08—Alloys based on silver with copper as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper

Definitions

  • the invention relates to a brazing filler metal with which brazing having excellent corrosion resistance and sufficient joining strength can be implemented, and in particular, to a brazing filler metal which is suitable for use in brazing of metals of which decorativeness in external appearance is required, such as titanium metal, and stainless steel, and with which brazing can be implemented at a temperature not higher than the transformation temperature of pure titanium.
  • brazing has been known for ages as one of metalworking techniques whereby mating metals can be joined with each other with relative ease. Since brazing is among important metalworking techniques of even today, it is applied to a wide variety of industrial sectors, and kinds of brazing filler metal for use in the brazing cover a broad spectrum.
  • Titanium metal pure titanium metal and titanium alloy included
  • titanium (Ti) metal has excellent properties such as light weight, high strength, and high corrosion resistance, it is in widespread use in various industrial sectors, and, as with stainless steel, is used even for metallic articles (for example, a wrist watch, the frame of eyeglasses) of which decorativeness in external appearance is required.
  • Crystals of pure titanium have a hexagonal close-packed structure at room temperature, however, they will have a body-centered cubic structure at a temperature not lower than 882° C. which is the transformation temperature (the temperature at which a phase change occurs) of pure titanium.
  • 5 Ti metal has a property of causing poor wettability of a brazing filler metal because the Ti metal has a thin oxide film, called a passivity film, formed on the surface thereof due to the effect of air, moisture, and so forth, and the passivity film is solid and difficult to remove, so that sufficient joining strength has not been obtained upon brazing. Accordingly, it is a normal practice adopted when brazing the Ti metals to use a flux (an organic solvent) for removal of the passivity film. The trouble, however, is that there has arisen a possibility that the interior of a furnace is polluted by organic substance when brazing is carried out in the furnace because the flux contains the organic substance such as resin, and so froth.
  • Silver solder as a brazing filler metal has its own melting point in a range of from about 800 to 1000° C.
  • a brazing filler metal include a brazing filler metal with which brazing can be executed at a temperature not higher than the transformation temperature of pure titanium, for example, BVAg-8 (melting point: 780° C.) according to the JIS specification, which is at times put to use in brazing of the Ti members.
  • BVAg-8 melting point: 780° C.
  • such a brazing filler metal as described is not in much use for brazing in fabrication of metallic articles such as a wrist watch, and the frame of eyeglasses, of which decorativeness in external appearance is required, because the brazing filler metal has poor corrosion resistance and is prone to initiation of corrosion after brazing.
  • titanium solder examples include a Ti—Cu—Ni based brazing filler metal.
  • the Ti—Cu—Ni based brazing filler metal has a melting point not lower than 900° C.
  • brazing has to be executed inevitably at a temperature higher than the transformation temperature of pure titanium, and consequently, it has a drawback in that the Ti members as brazed undergo a phase change after brazing, thereby causing the crystal structure thereof to be coarsened. Accordingly, in the case of brazing the Ti members with the titanium solder, there is the need for taking steps of removing coarsened portions of the crystal structure thereof by grinding, and so forth, and subsequently applying thereto mirror finish, and the like.
  • brazing filler metal capable of implementing joining of pure titanium metal or titanium alloy with pure gold or gold alloy without causing erosion of parts of the pure gold and the gold alloy is disclosed in JP 9-85485, A.
  • This brazing filler metal is composed of silver (Ag), as the base constituent, mixed with indium (In) and copper (Cu), so that the same has a drawback in that joining has to be executed at 1023° C. not lower than the transformation temperature of pure titanium.
  • a The invention has been developed to solve the problems as described above, and it is an object of the invention to provide a brazing filler metal for use in brazing of metals such as Ti metal and stainless steel, used in members of which decorativeness in external appearance is required, wherein brazing can be implemented at a temperature not higher than the transformation temperature of pure titanium while securing excellent corrosion resistance and sufficient joining strength.
  • a brazing filler metal according to the invention has a composition comprising palladium, metal having homogeneous solubility with the palladium, and phosphorus as main constituents thereof, wherein a composition ratio of the phosphorus falls within a range of 2 wt. % to less than 20 wt. %.
  • the brazing filler metal described above is preferably added with platinum and nickel, as the metal having homogeneous solubility with the palladium.
  • a composition ratio of the platinum falls within a range of 4 to less than 86 wt. %, and a composition ratio of the nickel falls within a range of 4 to less than 36 wt. %.
  • the composition ratio of the phosphorus preferably falls within a range of about 3 to about 17 wt. %, and the composition ratio of the platinum more preferably falls within a range of about 5 to about 85 wt. %.
  • the composition ratio of the nickel preferably falls within a range of about 5 to about 32 wt. %.
  • the invention further provides a brazing filler metal having a a composition comprising palladium, metal having homogeneous solubility with the palladium, and phosphorus as main constituents thereof, and added with copper and nickel, as the metal having homogeneous solubility with the palladium, wherein a composition ratio of the phosphorus falls within a range of about 4 to about 18 wt. %.
  • a composition ratio of the copper preferably falls within a range of about 2 to about 64 wt. %, and a composition ratio of the nickel more preferably falls within a range of about 7 to about 36 wt. %.
  • the invention still further provides a brazing filler metal having a composition comprising palladium, metal having homogeneous solubility with the palladium, and phosphorus as main constituents thereof, and added with gold and nickel, as the metal having homogeneous solubility with the palladium.
  • a composition ratio of the gold preferably falls within a range of 2 to less than 60 wt. %, and a composition ratio of the nickel more preferably falls within a range of 4 to 5 less than 32 wt. %.
  • a composition ratio of the phosphorus preferably falls within a range of about 3 to about 19 wt. %, and the composition ratio of the gold may fall within a range of about 3 to about 59 wt. %.
  • the composition ratio of the nickel preferably falls within a range of about 5 to about 31 wt. %.
  • the invention yet further provides a brazing filler metal having a composition comprising platinum, metal having homogeneous solubility with the platinum, and phosphorus, as main constituents thereof, wherein a composition ratio of the phosphorus falls within a range of about 4 to about 21 wt. %.
  • the brazing filler metal described above is preferably a brazing filler metal having a composition comprising platinum, metal having homogeneous solubility with the platinum, and phosphorus as main constituents thereof, and added with copper and nickel, as the metal having homogeneous solubility with the platinum.
  • a composition ratio of the phosphorus falls within a range of about 4 to about 19 wt. %
  • a composition ratio of the copper falls within a range of about 2 to about 66 wt. %.
  • a composition ratio of the nickel falls within a range of about 7 to about 36 wt. %.
  • the brazing filler metal described above may be a brazing filler metal having a composition comprising platinum, metal having homogeneous solubility with the platinum, and phosphorus as main constituents thereof, and added with gold and nickel, as the metal having homogeneous solubility with the platinum.
  • a composition ratio of the gold falls within a range of about 5 to about 62 wt. %
  • a composition ratio of the nickel falls within a range of about 5 to about 22 wt. %.
  • FIG. 1 is a phase diagram of a binary system of Pd—P, the horizontal axis thereof showing a composition ratio of P to Pd while the vertical axis thereof showing a melting point;
  • FIG. 2 a phase diagram of a binary system of Pt—P, the horizontal axis thereof showing a composition ratio of P to Pt while the vertical axis thereof showing a melting point;
  • FIG. 3 is a phase diagram of a binary system of Cu—P, the horizontal axis thereof showing a composition ratio of P to Cu while the vertical axis thereof showing a melting point;
  • FIG. 4 is a plan view showing a metallic member consisting of two pure titanium metal sheets, overlapped so as to cross each other;
  • FIG. 5 is a sectional view taken on line 5 - 5 in FIG. 4;
  • FIG. 6 is a sectional view of one of watch appearance portions shown in FIG. 7, cut along a plane containing a end-piece hole;
  • FIG. 7 is a perspective view showing a case fabricated by joining four pieces of the watch appearance portions to a case body.
  • FIG. 8 is an assembly view showing the case body and the four pieces of the watch appearance portions before joining the four pieces of the watch appearance portions to the case body.
  • the Pd—P based brazing filler metal is composed of palladium (Pd) and phosphorus (P) with addition of metals having homogeneous solubility with the Pd, and examples thereof include a Pd—Pt—Ni—P based brazing filler metal obtained by addition of platinum (Pt) and nickel (Ni) to the Pd—P based brazing filler metal.
  • the Pd—Pt—Ni—P based brazing filler metal is produced by a process comprising the steps of weighing respective quantities of palladium (Pd), platinum (Pt), nickel (Ni), and phosphorus (P) such that composition ratios as desired are obtained, respectively, producing an alloy by melting the respective metals by means of the high frequency melting process, and subsequently working the alloy into a slender foil-like shape (ribbon-like shape) about 60 gm thick in an argon (Ar) atmosphere.
  • the melting point is at 910° C. while in the case of the composition ratio of P being at 3 wt. % as with Sample 10), the melting point is lowered to 642° C., thereby enabling joining by brazing to be effected at a low temperature not higher than the transformation temperature of pure titanium, (referred to hereinafter as low temperature joining), which is an object of the invention, the composition ratio of P needs to be in excess of 2 wt. %, and is preferably not less than about 3 wt. %. Further, in view of findings that in the case of the composition ratio of P being at 20 wt.
  • the melting point is at 932° C. while in the case of the composition ratio of P being at 17 wt. % as with Samples 4), and 5), respectively, the melting point is lowered to 870° C., and 721° C., respectively, thereby enabling low temperature joining to be effected, the composition ratio of P needs to be less than 20 wt. %, and is preferably not more than about 17 wt. %. Accordingly, the composition ratio of P has a range necessary for the Pd—Pt—Ni—P based brazing filler metal to conform to the brazing filler metal as the object of the invention, and the range is from 2 wt. % to less than 20 wt. %, and is preferably from about 3 wt. % to about 17 wt. %.
  • the composition ratio of Pt is as follows.
  • the melting point is at 915° C. while in the case of the composition ratio of Pt being at 5 wt. % as with Samples 4), the melting point is lowered to 870° C., thereby enabling low temperature joining to be effected, the composition ratio of Pt needs to be in excess of 4 wt. %, and is preferably not less than about 5 wt. %.
  • the melting point is at 910° C.
  • the composition ratio of Pt while in the case of the composition ratio of Pt being at 85 wt. % as with Sample 15), the melting point is lowered to 860° C., thereby enabling low temperature joining to be effected, the composition ratio of Pt needs to be less than 86 wt. %, and is preferably not more than about 85 wt. %. Accordingly, the composition ratio of Pt has a range necessary for the Pd—Pt—Ni—P based brazing filler metal to conform to the brazing filler metal as the object of the invention, and the range is from 4 wt. % to less than 86 wt. %, and is preferably from about 5 wt. % to about 85 wt. %.
  • the composition ratio of Ni is as follows. In the case of the composition ratio of Ni being at 4 wt. % as with Sample 9), the melting point becomes lower than the transformation temperature of pure titanium, however, there is observed a tendency that wettability against titanium metal becomes insufficient. In the case of the composition ratio of Ni being at 5 wt. % as with Sample 8), however, the melting point becomes lower than the transformation temperature of pure titanium, and the wettability against titanium metal becomes sufficient. Then, in the case of the composition ratio of Ni being at 36 wt. % as with Sample 7), the melting point comes to exceed the transformation temperature of pure titanium although the wettability against titanium metal is excellent. However, if the composition ratio of Ni becomes 32 wt.
  • the composition ratio of Ni has a range necessary for the Pd—Pt—Ni—P based brazing filler metal to conform to the brazing filler metal as the object of the invention, and the range is from 4 wt. % to less than 36 wt. %, and is preferably from about 5 wt. % to about 32 wt. %.
  • the Pd—Pt—Ni—P based brazing filler metal is suited for low temperature joining provided that the composition ratio of P falls within the abovementioned range, and further, provided that the composition ratio of Pt as well falls within the abovementioned range, the Pd—Pt—Ni—P based brazing filler metal becomes a brazing filler metal satisfying all of three requirements, that is, securing of excellent corrosion resistance, and securing of sufficient joining strength in addition to the low temperature joining, and having improved wettability against titanium metal as well.
  • the Pd—Pt—Ni—P based brazing filler metal no longer has brittleness, and becomes a more preferable brazing filler metal having further improved wettability against titanium metal.
  • FIG. 1 is a phase diagram of a binary system of Pd—P, the horizontal axis thereof showing a composition ratio of P to Pd while the vertical axis thereof showing a melting point
  • FIG. 2 a phase diagram of a binary system of Pt—P, the horizontal axis thereof showing a composition ratio of P to Pt while the vertical axis thereof showing a melting point.
  • Literature 1 Detailed description on either of both is stated in detail, respectively, in Literature 1 given below.
  • Literature 1 “Binary Alloy Phase Diagrams”, Vol. 1, Vol. 2, American Society for Metals, Metals Park, Ohio 44073
  • the case where the Pd—Pt—Ni—P based brazing filler metal is able to conform to the brazing filler metal as the object of the invention represents also a case of the same having a specific composition wherein the eutectic composition of Pt—P can be utilized. It is further reasoned that if the Pd—Pt—Ni—P based brazing filler metal has a composition wherein both the first or second eutectic of Pd—P and the eutectic composition of Pt—P can be utilized, the melting point can be sharply lowered.
  • the Pd—P alloy will no longer has the first eutectic of Pd—P upon the composition ratio of P exceeding 6 wt. %, and will have the second eutectic of Pd—P upon the composition ratio of P reaching 12 wt. %
  • the first eutectic of Pd—P is utilized with a composition of the Pd—Pt—Ni—P based brazing filler metal, containing P at a composition ratio in a range of 3 to 10 wt. %
  • the second eutectic of Pd—P is utilized with a composition thereof, containing P at a composition ratio in a range of 10 to 17 wt. %.
  • the Pd—Pt—Ni—P based brazing filler metal may be considered to be an alloy composed of Pd, P and Pt at the specific composition ratios described above, respectively, with addition of Ni which is a metal having homogeneous solubility with the Pd. With addition of Ni, there is obtaining an advantageous effect in that wettability of the Pd—Pt—Ni—P based brazing filler metal, against metallic members to be joined together therewith, is improved, and quality thereof in respect of brittleness is improved.
  • Ni added is in effect substituted for Pd together with Pt, however, addition of Ni in an improper amount results in deviation of the composition ratios of Pd and P, respectively, from those required for the eutectic composition, thereby raising a possibility that a preferable brazing filler metal as the object of the invention is no longer obtainable due to a rise in a melting point and lack of occurrence of uniform solid solution. Accordingly, it is reasoned that the composition ratio of Ni has a range necessary for the Pd—Pt—Ni—P based brazing filler metal to conform to the brazing filler metal as the object of the invention.
  • the respective composition ratios of P, Pt, and Ni, composing the Pd—Pt—Ni—P based brazing filler metal have respective ranges required for obtaining the brazing filler metal as the object of the invention, and the respective ranges found from the results of the tests, shown with reference to Samples 1) to 16) described above, are preferable ranges of the respective composition ratios.
  • the Pd—Pt—Ni—P based brazing filler metal according to the invention is turned into a brazing filler metal with which low temperature joining can be executed by utilizing the first or second eutectic of Pd—P provided that the same has a composition wherein the composition ratio of P falls within a range of 2 to less than 20 wt. %, preferably within a range of about 3 to about 10 wt. %, and a range of about 10 to about 17wt. %.
  • the Pd—Pt—Ni—P based brazing filler metal according to the invention has a composition wherein the composition ratio of Pt falls within a range of 4 to less than 86 wt. %, preferably within a range of about 5 to about 85 wt.
  • a brazing filler metal with which brazing can be implemented at a still lower melting point by utilizing the eutectic of Pt—P as well, such a brazing filler metal being a brazing filler metal satisfying all of the three requirements, that is, securing of excellent corrosion resistance and securing of sufficient joining strength in addition to the low temperature joining, and having improved wettability against titanium metal as well.
  • the composition ratio of Ni exceeds 4 wt. %, and is less than 36 wt. %, preferably falling within a range of 5 to 32 wt. %, there results an alloy having homogeneity at a low melting point, so that a brazing filler metal having no brittleness and having more excellent wettability can be obtained.
  • This brazing filler metal is a Pd—Cu—Ni—P based brazing filler metal composed of palladium (Pd) and phosphorus (P) with addition of copper (Cu) and nickel (Ni) as metals having homogeneous solubility with the Pd.
  • the Pd—Cu—Ni—P based brazing filler metal is produced by the same method as that for the Pd—Pt—Ni—P based brazing filler metal described hereinbefore, omitting therefore detailed description of a method of producing the same.
  • the Pd—Cu—Ni—P based brazing filler metal conforms to the brazing filler metal as the object of the invention provided that the same is composed of metal elements at respective specified composition ratios, which is presumed to represent the case where the first or second eutectic of Pd—P as described above is utilized, or a case where a eutectic of Cu—P as described later is utilized.
  • FIG. 3 is a phase diagram of a binary system of Cu—P, the horizontal axis thereof showing a composition ratio of P to Cu while the vertical axis thereof showing a melting point, which is referred to in Literature 1 described hereinbefore.
  • a composition ratio of P is increased, and upon the composition ratio of P reaching about 8 wt. % with a composition ratio of Cu at about 92 wt. %, there occurs a eutectic composition, thereby a melting point thereof being lowered to about 714° C.
  • a state of such a eutectic composition is designated as a eutectic of Cu—P.
  • the composition ratio of P, necessary for the Pd—Cu—Ni—P based brazing filler metal to conform to the brazing filler metal as the object of the invention, is in a range of about 4 to about 18 wt. %. Further, it is reasoned that if the Pd—Cu—Ni—P based brazing filler metal comes to have a composition wherein the eutectic of Cu—P can be utilized, the same is turned into a brazing filler metal with which brazing can be implemented at a still lower melting point, and a composition ratio of Cu, required in such a case, is in a range of about 2 to about 64 wt. %.
  • a brazing filler metal having excellent corrosion resistance, sufficient joining strength, and improved wettability against titanium metal can be obtained. Further, there exists an optimum range for a composition ratio of Ni as well, and if the composition ratio of Ni falls within a range of about 7 to about 36 wt. %, there results an alloy not only capable of implementing low temperature joining but also having homogeneity at a low melting point, so that it is possible to obtain a brazing filler metal which has quality improved in respect of brittleness, and has more improved wettability.
  • the Pd—P based brazing filler metals described in the foregoing there have so far been described the Pd—Pt—Ni—P based brazing filler metal obtained by adding Pt and Ni thereto as metals having homogeneous solubility with Pd, and the Pd—Cu—Ni—P based brazing filler metal obtained by adding Cu and Ni thereto as metals having homogeneous solubility with Pd, however, the Pd—P based brazing filler metals are not limited thereto, and include a Pd—Au—Ni—P based brazing filler metal as well.
  • the Pd—Au—Ni—P based brazing filler metal is composed of palladium (Pd) and phosphorus (P) with addition of gold (Au) and nickel (Ni) as metals having homogeneous solubility with the Pd.
  • the Pd—Au—Ni—P based brazing filler metal is produced by the same method as that for the Pd—Pt—Ni—P based brazing filler metal, omitting therefore detailed description of a method of producing the same.
  • the melting point is at 902° C., and accordingly, the composition ratio of P needs to be in excess of 2 wt. % in order to enable low temperature joining to be executed, however, in the case of the composition ratio of P being at 20 wt. % as with Sample 19), the melting point is at 927° C., and accordingly, the composition ratio of P needs to be less than 20 wt. %.
  • the composition ratio of P is preferably in a range of about 3 to less than 19 wt. %.
  • the melting point is at 889° C. while in the case of the composition ratio of Au reaching 6 wt. % as with Sample 24), the melting point is lowered to 619° C., the composition ratio of Au needs to be in excess of 2 wt. %, and is preferably not less than about 3 wt. %.
  • the melting point is at 933° C. while in the case of the composition ratio of Au becoming 38 wt. % as with Sample 21), the melting X point is lowered to 774° C., the composition ratio of Au needs to be less than 60 wt. %, and is preferably less than 59 wt. %.
  • the melting point becomes lower than the transformation m temperature of pure titanium, however, there is observed a tendency that wettability against titanium metal becomes insufficient.
  • the composition ratio of Ni at not less than about 5 wt. % is preferable for obtaining sufficient wettability against titanium metal.
  • the melting point exceeds the transformation temperature of pure titanium although the wettability against titanium metal is excellent.
  • the composition ratio of Ni at not more than about 31 wt. % is preferable to render the melting point lower than the transformation temperature of pure titanium.
  • the composition ratio of Ni, necessary for the Pd—Au—Ni—P based brazing filler metal to conform to the brazing filler metal as the object of the invention is in a range of 4 to less than 32 wt. %, and is preferably in a range of about 5 to about 31 wt. %.
  • the Pd—Au—Ni—P based brazing filler metal is turned into a brazing filler metal capable of effecting low temperature joining provided that the composition ratio of P falls within the abovementioned range, and is further turned into a brazing filler metal having satisfactory corrosion resistance, and joining strength provided that the composition ratio of Au as well falls within the abovementioned range.
  • the composition ratio of Ni falling within the abovementioned range there results an alloy having homogeneity at a low melting point, thereby forming a more preferable brazing filler metal which has quality improved in respect of brittleness, and, in addition, has improved wettability against titanium metal.
  • Au has homogeneous solubility with Pd in common with Pt and Cu, but does not form a eutectic composition with P, so that, unlike the other Pd—P based brazing filler metals (the Pd—Pt—Ni—P based, and Pd—Cu—Ni—P based), the Pd—Au—Ni—P based brazing filler metal is not turned into a brazing filler metal utilizing a eutectic of Au—P.
  • the Pt—P based brazing filler metal is composed of platinum (Pt) and phosphorus (P) with addition of metals having homogeneous solubility with the Pt, and examples thereof include a Pt—Cu—Ni—P based brazing filler metal obtained by addition of copper (Cu) and nickel (Ni) to the Pt—P based brazing filler metal.
  • the Pt—Cu—Ni—P based brazing filler metal as well is produced by the same method as that for the Pd—Pt—Ni—P based brazing filler metal described hereinbefore, omitting therefore detailed description of a method of producing the same.
  • the Pt—Cu—Ni—P based brazing filler metal as well is able to conform to the brazing filler metal as the object of the invention provided that the same is composed of metal elements at respective specified composition ratios, which is presumed to represent the case where the eutectic of Pt—P shown in FIG. 2 is utilized, or a case where the eutectic of Cu—P shown in FIG. 3 is utilized.
  • the Pt—Cu—Ni—P based brazing filler metal is able to conform to a brazing filler metal capable of low temperature joining, which is the object of the invention, provided that the same has a composition wherein the eutectic of Pt—P can be utilized, and to that end, a composition ratio of P is to be in a range of about 4 to about 19 wt. %. With the composition ratio of P falling in that range, there results an alloy having homogeneity at a low melting point, thereby forming a brazing filler metal capable of effecting low temperature joining.
  • brazing filler metal with which brazing can be implemented at a still lower melting point if the alloy comes to have a composition wherein the eutectic of Cu—P can be utilized, and a composition ratio of Cu, required for that purpose, is in a range of about 2 to about 66 wt. %. With the composition ratio of Cu falling in that range, there can be obtained a brazing filler metal not only capable of implementing brazing at a still lower melting point below the transformation temperature of pure titanium, but also having excellent corrosion resistance, and sufficient joining strength, thereby satisfying all of the three requirements, and improved wettability against titanium metal as well.
  • composition ratio of Ni there exists an optimum range for a composition ratio of Ni, and if the composition ratio of Ni falls within a range of about 7 to about 36 wt. %, there results an alloy not only capable of implementing low temperature joining but also having homogeneity at a low melting point, so that it is possible to obtain a preferable brazing filler metal which has improved quality in respect of brittleness, and has more improved wettability against titanium metal.
  • the Pt—P based brazing filler metal may be added with a metal other than Cu as a metal having homogeneous solubility with Pt, and even if, for example, Au is added thereto, there results a preferable brazing filler metal as the brazing filler metal according to the invention, and such a brazing filler metal is a Pt—Au—Ni—P based brazing filler metal.
  • the Pt—Au—Ni—P based brazing filler metal as well is able to conform to a brazing filler metal capable of low temperature joining, which is the object of the invention, provided that the same has a composition wherein the eutectic of Pt—P can be utilized, and to that end, a composition ratio of P is to be in a range of about 4 to about 21 wt. %. With the composition ratio of P falling in that range, there results an alloy having homogeneity at a low melting point, thereby forming a brazing filler metal capable of effecting low temperature joining.
  • composition ratio of Au there exists an optimum range for a composition ratio of Au, and if the composition ratio of Au falls within a range of about 5 to about 62 wt. %, it is possible to obtain a brazing filler metal not only satisfying all of the three requirements, that is, ability to enable low temperature joining to be implemented, excellent corrosion resistance, and sufficient joining strength, but also having improved wettability against titanium metal. Further, there exists an optimum range for a composition ratio of Ni as well, and if the composition ratio of Ni falls within a range of about 5 to about 22 wt.
  • a metallic member 17 as shown in FIG. 4 were prepared to conduct the following tests thereon.
  • the metallic member 17 consist of two pure titanium metal sheets, 15 , 16 , each about 25 mm in length ⁇ about 5 mm in width ⁇ about 1 mm in thickness, overlapped so as to cross each other, and the first brazing filler metal described above (the Pd—Pt—Ni—P based, the Pd—Cu—Ni—P based, and Pd—Au—Ni—P based) or the second brazing filler metal described above (the Pt—Cu—Ni—P based, and Pt—Au—Ni—P based) 19 is sandwiched between the two pure titanium metal sheets 15 , 16 at an intersection 18 where the two pure titanium metal sheets 15 , 16 are in contact with each other, thereby preparing 14 samples including Examples 1 to 8 shown in Table 3, and Examples 9 to 14 shown in Table 4.
  • a corrosion resistance test was conducted on the respective Samples of the metallic member 17 in accordance with the CASS test specified by ISO3370, and joining strength was measured by conducting a tensile test on the respective Samples whereby the pure titanium metal sheets 15 , 16 were pulled in the direction of thickness, a and b, respectively, by use of a tool(not shown).
  • the composition ratio of Pd is 34 wt. %, that of Pt 53 wt. %, that of Ni 8 wt. %, and that of P 5 wt. %.
  • TABLE 5 Comp Exp a b c d e 1) Ti 60 Cu 25 Ni 15 ⁇ 820 MPa 1000° C. exist 2) Ag 58 Cu 32 Pd 10 x 530 MPa 780° C. no
  • Examples 1 to 4 shown in Table 3 indicate the results of tests conducted on the Pd—Pt—Ni—P based brazing filler metals, and Examples 1 to 3, among these Examples, indicate the results of the tests conducted on the Pd—Pt—Ni—P based brazing filler metals wherein the composition ratio of the respective metal elements is within the respective ranges as described hereinbefore.
  • Examples 5 and 6, shown in Table 3, indicate the results of tests conducted on the Pd—Cu—Ni—P based brazing filler metals, and Example 5, among these Examples, indicates the results of the tests conducted on the Pd—Cu—Ni—P based brazing filler metal wherein the composition ratio of the respective metal elements is within the respective ranges as described hereinbefore.
  • Examples 7 and 8 shown in Table 3, indicate the results of tests conducted on the Pt—Cu—Ni—P based brazing filler metals, and Example 7, among these Examples, indicates the results of the tests conducted on the Pt—Cu—Ni—P based brazing filler metal wherein the composition ratio of the respective metal elements is within the respective ranges as described hereinbefore.
  • Examples 9 to 12 shown in Table 4 indicate the results of tests conducted on the Pd—Au—Ni—P based brazing filler metals obtained by adding Ni and Au to the Pd—P based brazing filler metal, and Examples 9 to 11, among these Examples, indicate the results of the tests conducted on the Pd—Au—Ni—P based brazing filler metals wherein the composition ratio of the respective metal elements is within the respective ranges as described hereinbefore.
  • Examples 13 and 14 shown in Table 4 indicate the results of tests conducted on the Pt—Au—Ni—P based brazing filler metals obtained by adding Au and Ni to the Pt—P based brazing filler metal, and Examples 13, among these Examples, indicates the results of the tests conducted on the Pt—Au—Ni—P based brazing filler metal wherein the composition ratio of the respective metal elements is within the respective ranges as described hereinbefore.
  • any of the brazing filler metals according to the invention exhibits excellent corrosion resistance. Further, the joining strength of Example 7 at 790 MPa and that of Example 11 at 800 MPa are slightly lower than that of Comparative Example 1, however, the joining strength of any of other Examples indicates better values than those for Comparative Examples 1 and 2.
  • the brazing temperature for Comparative Example 1 is at 1000° C. which is in excess of the transformation temperature of pure titanium.
  • the brazing filler metals according to the invention are found to satisfy all of the three requirements, that is, securing of excellent corrosion resistance and sufficient joining strength, along with capability of implementing brazing at a temperature not higher than the transformation temperature of pure titanium. Accordingly, it can be said that the brazing filler metals according to the invention are superior to a conventional Ti—Cu—Ni based brazing filler metal (Comparative Example 1) because even if the former are used in joining together metallic articles made of Ti, the surface condition of the respective metallic articles, prior to joining, can be maintained without causing the crystal structure of the metallic articles to be coarsened. It can also be said that the brazing filler metals according to the invention are significantly superior to silver solder (Comparative Example 2) in respect of corrosion resistance and joining strength in comparison with the latter.
  • FIG. 7 is a perspective view showing a case 2 fabricated by joining 4 pieces of the watch appearance portions 3 , 5 , 7 , and 9 to a case body 1 with the Pd—Pt—Ni—P based brazing filler metal which is the first brazing filler metal according to the invention.
  • the case body 1 comprises a sidewall made of Ti, formed in the shape of a cylinder thin in wall thickness, and a bottom made of Ti, and is polished so as to have a mirror-finished surface including contacting surfaces thereof, opposite to the watch appearance portions.
  • Each of the watch appearance portions 3 , 5 , 7 , and 9 made of titanium alloy, is formed by applying grinding and polishing thereto, and the outside surface thereof except a contacting surface with the case body 1 , is polished so as to have a hairline finished surface. Further, each of the watch appearance portions 3 , 5 , 7 , and 9 is worked on beforehand for drilling a end-piece hole 11 therein.
  • the case body 1 and the watch appearance portions 3 , 5 , 7 , and 9 are formed by forging, respectively.
  • a Pd—Pt—Ni—P based brazing filler metal 19 (Pd at 34 wt. %, Pt at 53 wt. %, Ni at 8 wt. %, and P at 5 wt. %) according to the invention was sandwiched between the faying surface of the case body 1 and that of the respective watch appearance portions 3 , 5 , 7 , and 9 , and was pressed into contact with the respective contacting surfaces before secured by tools (not shown). Thereafter, the case body 1 and respective watch appearance portions 3 , 5 , 7 , and 9 were heated to a temperature at 700° C.
  • Pd—Pt—Ni—P based brazing filler metal 19 instead of the Pd—Pt—Ni—P based brazing filler metal 19 , however, use may be made of a Pd—Au—Ni—P based brazing filler metal (Pd at 72 wt. %, Au at 11 wt. %, Ni at 10 wt. %, and P at 7 wt. %).
  • both the metallic articles can be joined together in a preferable condition.
  • case body and respective watch appearance portions are to be fabricated separately, and finished in a different surface condition, respectively.
  • the case body is to be finished so as to have a mirror-finished surface while the respective watch appearance portions are to be finished so as to have a hairline finished surface.
  • a conventional case has been fabricated as an integrally formed component comprising the respective watch appearance portions to be linked with a bracelet, and the interface between case and watch appearance portion is continuous surface, it has been difficult to definitely identify the interfaces between the case body to be finished to have the mirror-finished surface, and the respective watch appearance portions to be finished to have the hairline finished surface.
  • the shape of the respective watch appearance portions is subject to considerable constraints in terms of designing.
  • the respective watch appearance portions is provided with a end-piece hole for inserting a spring bar with which the bracelet is secured thereto, formed in a post-working process using a drill, and there has been no choice but to drill the end-piece hole from the inside of the respective watch appearance portions on the ground that the end-piece hole opened in the respective watch appearance portions, if it can be seen from the outside, is undesirable from the external appearance point of view.
  • a kind of metal suitable for satisfactory joining to the other of the same by use of the brazing filler metal according to the invention is titanium metal. Since a typical titanium alloy, for example, Ti-6Al-4V, has its transformation temperature at 995° C., the brazing filler metal according to the invention is adequate for application to a titanium alloy. Furthermore, the scope of application of the brazing filler metal according to the invention is not limited to titanium metal, but include other metals, for example, stainless steel, so that the brazing filler metal according to the invention is applicable to various metals of which decorativeness in external appearance is required.
  • the brazing filler metal according to the invention has no limitation in its shape. Considering convenience in executing a joining work, the same is preferably produced in the shape of a sheet, foil, wire, and so forth, however, there can be cases where its shape is accompanied by brittleness to some extent, depending on the chemical composition thereof, in which case the brazing filler metal according to the invention may be used after reducing the same to powders, and pressing the powders for molding.
  • a heating temperature at the time of brazing is in a range of 620 to 850° C., preferably in a range of 650 to 750° C., brazing time is preferably in the order of from about 5 minutes to about 1 hour, and an atmosphere in a furnace at the time of brazing is preferably at a pressure not higher than 10 Torr.
  • brazing filler metal according to the invention joining of metallic articles by brazing can be implemented at a temperature not higher than the transformation temperature of pure titanium, and sufficient joining strength as well as excellent corrosion resistance of the metallic articles joined together can be secured. Accordingly, the brazing filler metal according to the invention is suitable for use in brazing of metals such as titanium metal, and stainless steel, of which decorativeness in external appearance is required. In addition, since the brazing filler metal according to the invention has improved wettability against titanium metal, flux is unnecessary in executing brazing, and there is no need for post-working after the brazing, so that the brazing filler metal according to the invention is suited for brazing of metallic articles complex in construction.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Products (AREA)
  • Die Bonding (AREA)
  • Pressure Welding/Diffusion-Bonding (AREA)
US10/069,955 2000-07-11 2001-07-11 Brazing filler metal Abandoned US20020170633A1 (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030085258A1 (en) * 2001-11-06 2003-05-08 Sumitomo Special Metals Company, Ltd. Phosphorus-copper brazing material, brazing sheet, methods of manufacturing the material and the sheet, and flow path structure for heat exchangers
US20040229069A1 (en) * 2003-05-16 2004-11-18 Sandin Thomas A. Method for brazing components using a Ni-Au-P ternary brazing alloy, the assembly so produced and the ternary alloy
WO2012153226A1 (fr) * 2011-05-06 2012-11-15 Koninklijke Philips Electronics N.V. Composé d'étanchéité et enceinte de décharge en céramique comprenant ledit composé d'étanchéité
US20140079881A1 (en) * 2012-09-20 2014-03-20 Pessach Seidel Corrosion resistant compositions for titanium brazing and coating applications and methods of application

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Publication number Priority date Publication date Assignee Title
CN110976748B (zh) * 2019-11-22 2021-08-13 广东长盈精密技术有限公司 不锈钢表壳的锻压方法、制作方法以及不锈钢表壳

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JPS5471748A (en) * 1977-11-21 1979-06-08 Seiko Epson Corp Brazing filler metal
JPS54109049A (en) * 1978-02-16 1979-08-27 Seiko Epson Corp Brazing metal
JPH0791610B2 (ja) * 1985-06-17 1995-10-04 日本電装株式会社 非酸化物セラミックヒータ用金属ロー材
JP2773909B2 (ja) * 1989-07-28 1998-07-09 田中貴金属工業株式会社 パラジウムろう合金
EP0638656A4 (fr) * 1993-02-03 1995-06-07 World Metal Co Ltd Alliage a plaquer, son procede de placage et solution de placage.

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030085258A1 (en) * 2001-11-06 2003-05-08 Sumitomo Special Metals Company, Ltd. Phosphorus-copper brazing material, brazing sheet, methods of manufacturing the material and the sheet, and flow path structure for heat exchangers
US6761306B2 (en) * 2001-11-06 2004-07-13 Sumitomo Special Metals Co, Ltd. Phosphorus-copper brazing material, brazing sheet, methods of manufacturing the material and the sheet, and flow path structure for heat exchangers
US20040229069A1 (en) * 2003-05-16 2004-11-18 Sandin Thomas A. Method for brazing components using a Ni-Au-P ternary brazing alloy, the assembly so produced and the ternary alloy
WO2004103696A1 (fr) * 2003-05-16 2004-12-02 Praxair S. T. Technology, Inc. Procede de brasage de composants metalliques
US6863995B2 (en) * 2003-05-16 2005-03-08 Praxair S.T. Technology, Inc. Method for brazing components using a Ni-Au-P ternary brazing alloy, the assembly so produced and the ternary alloy
WO2012153226A1 (fr) * 2011-05-06 2012-11-15 Koninklijke Philips Electronics N.V. Composé d'étanchéité et enceinte de décharge en céramique comprenant ledit composé d'étanchéité
US9093257B2 (en) 2011-05-06 2015-07-28 Koninklijke Philips N.V. Sealing compound and ceramic discharge vessel comprising such sealing compound
RU2608078C2 (ru) * 2011-05-06 2017-01-13 Филипс Лайтинг Холдинг Б.В. Уплотнительный компаунд и керамический разрядный баллон, содержащий такой уплотнительный компаунд
US20140079881A1 (en) * 2012-09-20 2014-03-20 Pessach Seidel Corrosion resistant compositions for titanium brazing and coating applications and methods of application

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CN1189286C (zh) 2005-02-16
EP1300214A4 (fr) 2004-10-06
EP1300214B1 (fr) 2006-06-07
CN1386082A (zh) 2002-12-18
DE60120408D1 (de) 2006-07-20
DE60120408T2 (de) 2007-05-24
EP1300214A1 (fr) 2003-04-09
JP3830891B2 (ja) 2006-10-11
WO2002004164A1 (fr) 2002-01-17

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