GB2428046A - A silver-copper-zinc-germanium brazing alloy - Google Patents

A silver-copper-zinc-germanium brazing alloy Download PDF

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Publication number
GB2428046A
GB2428046A GB0513985A GB0513985A GB2428046A GB 2428046 A GB2428046 A GB 2428046A GB 0513985 A GB0513985 A GB 0513985A GB 0513985 A GB0513985 A GB 0513985A GB 2428046 A GB2428046 A GB 2428046A
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GB
United Kingdom
Prior art keywords
alloy
silver
solder
alloys
copper
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
GB0513985A
Other versions
GB0513985D0 (en
Inventor
Peter Gamon Johns
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Middlesex Silver Co Ltd
Original Assignee
Middlesex Silver Co Ltd
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 Middlesex Silver Co Ltd filed Critical Middlesex Silver Co Ltd
Priority to GB0513985A priority Critical patent/GB2428046A/en
Publication of GB0513985D0 publication Critical patent/GB0513985D0/en
Priority to EP06744350A priority patent/EP1904263A1/en
Priority to PCT/GB2006/050149 priority patent/WO2007007120A1/en
Priority to CNA2006800246467A priority patent/CN101223003A/en
Publication of GB2428046A publication Critical patent/GB2428046A/en
Withdrawn legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C5/00Alloys based on noble metals
    • C22C5/06Alloys based on silver
    • C22C5/08Alloys based on silver with copper as the next major constituent
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/02Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0222Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
    • B23K35/0227Rods, wires
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24Selection of soldering or welding materials proper
    • B23K35/30Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24Selection of soldering or welding materials proper
    • B23K35/30Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/3006Ag as the principal constituent

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Adornments (AREA)

Abstract

A silver solder or brazing alloy of the Ag-Cu-Zn family comprises (by weight): more than 70 % silver and 0.5-3 % germanium. The alloy preferably contains 3 to less than 8 % zinc. The alloy may also contain 1-3 % tin and/or 0.05-0.4 % silicon. The alloy may be formed into rod, strip, wire or paste and be used to braze silver alloys.

Description

SILVER SOLDER OR BRAZING ALLOYS AND THEIR USE
FIELD OF THE IIVENTION
The present invention relates to silver solder or brazing alloys and to their use in making soldered joints in various grades of silver, particularly silversmithing grades. Silver brazing alloys are also known in the silversmithing trade as silver solders or solders and these tenns are used interchangeably herein.
BACKGROUND TO THE INVENTION
Various silver-based alloys of the silver-copper-zinc type are useful as solders (brazing materials). Brazing has been defined as a joining process in which a filler metal is used which has a melting point of above 450 C, but below that of the parent metal and which is distributed in the joint by capillary attraction.
Silver, copper and zinc form a ternary eutectic with a silver content of 56% and melting at 665 C, see a ternary phase diagram which is given in Fig. 2 of Jacobson et al, Development of new silver-free brazing alloys for steel tubular assembly, supplement to the Welding Journal (sponsored by the American welding Society/Welding Research Council), August 2002, pages 149-S to 155-S downloadable from http://www.aws.org/wj/supplement/08-2002-JACOBSON- p4f,. A commercially supplied silver alloy recommended by the AWS for brazing mild steel or copper has the composition of 44 wt % Ag, 30 wt % Cu and 26 wt % Zn. Such an alloy has too low silver content for use in silversinithing, where solder alloys of at least 55 wt % Ag are the norm.
Depending on their melting temperatures, brazing alloys for use in silversmithing are classified as Easy, Medium and Hard, and the major UK suppliers quote the values below: Thessco Solidus Liquidus Easy 705 C 725 C Medium 720 C 765 C Hard 745 C 778 C Johnson Matthey Solidus Liquidus Easy 705 C 723 C Medium 720 C 765 C Hard 745 C 778 C An alloy containing 75 wt % Ag, 22 wt % Cu and 3 wt % Zn is known and provides a good colour match for silver, but is high melting. An alloy with 70 wt % Ag, 20 wt % Cu and 10 wt % Zn is also of good colour and is lower melting, and a further alloy containing 65 wt % Ag, 20 wt % Cu and 15 wt % Zn is still lower melting, see http:/fwww.wlv.com/joining/silvabrazrefchart.xls. This is, of course, only one web page from one of the various suppliers of solder alloys for silversmiths.
A corrosion-resistant silver solder for use in the electronics industry is disclosed in JP 61078592 (Kyocera) and is based on Ag, 0.05-19 wI %, Ge, 0.01-1.0 wt % Pd, and 0.0 1-2 wt % Li. An exemplified composition contains Ag 94 wt %, Ge 4 wt %, Pd 0.5 wt %, Li 0.5 wt %, Fe 0.5 wt % and Ni 0.5 wt %, and another exemplified composition has Ag 80%, Ge 11.95%, Pd 8% and Li 0.05%.
Recommended amounts of germanium are relatively high. For silversmithing, the use of palladium is to be avoided, as is the use of lithium even in trace amounts.
Although spreadability and wettability are said to be desirable properties, colour match to the material being soldered is not necessary.
Patent GB-B-2255348 (Rateau, Albert and Johns; Metaleurop Recherche) discloses a novel silver alloy that maintains the properties of hardness and lustre inherent in Ag-Cu alloys while reducing problems resulting from the tendency of the copper content to oxidise. The alloys are ternary Ag-Cu-Ge alloys containing at least 92.5 wt% Ag, 0.5-3 wt % Ge and the balance, apart from impurities, copper. Patents US-A-616807l and EP-B-0729398 (Johns) disclose a silver/germanium alloy which comprises a silver content of at least 77 wt % and a germanium content of between 0.4 and 7%, the remainder principally being copper apart from any impurities, which alloy contains elemental boron as a grain refiner at a concentration of greater than 0 ppm. and less than 2Oppm. Silver alloys according to the teaching of GB-B-2255348 and EP-B-0729398 are now commercially available in Europe and in the USA under the trade name Argentium (Ag 92.5 wt%, Cu 6.3 wt%, Ge 1.2 wt %), and the word "Argentium" as used herein refers to these alloys.
WO 2005/051953 (the contents of which are incorporated herein by reference) discloses a silver solder alloy of the Ag-Cu-Zn family containing at least wt % Ag and from 0.5 to 3 wt % Ge. The Ag-Cu-Zn alloy typically contains 55- 77 wt % Ag, 10-30 wt% Cu (preferably 56-75 wt %) and 8-15 wt % Zn. The above alloys can exhibit an advantageous combination of relatively low melting point, high flowability and good colour. In particular, such alloys may have a solidus temperature in the range of about 700 to about 750 C and a liquidus temperature in the range of about 725 C to about 780 C. They can be used for soldering or brazing jewellery metals including grades of silver such as Sterling. They are particularly advantageous for soldering Argentium silver.
SUMMARY OF THE INVENTION
We have now found that solders of the "hard" category can be provided that have unusually high silver contents and correspondingly low zinc contents, and that these exhobit good colour and other properties.
The invention provides silver solders or brazing alloys of the Ag-Cu-Zn family containing more than 7Owt % Ag and from 0.5 to 3 wt% Ge.
DESCRIPTION OF PREFERRED FEATURES
Preferred solders contain 1.0-2.5 wt % Ge especially about 1.5 wt % Ge and optionally may further comprise 1-3 wt % Sn, especially about 1 wt % Sn. They may contain 3 - less than 8 wt% Zn, typically 4 - 5 wt% Zn, and they may further comprise 0.05-0.4 wt % Si e.g. about 0.1 wt% Si. Too large a proportion of Si gives rise to brittleness. It may further comprise an amount of boron of e.g. 1 ppm-0.3 wt % boron, and more typically 0.1-0.3 wt % of boron which reduces grain size and helps in rolling or drawing the composition. An embodiment of the solder contains about 75 wt% Ag, about 18 wt% Cu and about 4.5 wt% Zn, about 1.5 wt% Ge and about 1 wt% Sn.
The alloys of the invention may be provided any form that is convenient for silversmithing, e.g. rod, strip, wire, fine particles or a paste in which powdered metal is suspended in a vehicle, and may be used with conventional fluxes. In the case of pastes, US-A-5443658 (Hermanek) discloses a vehicle which is an aqueous gel containing 78 weight percent water, 10 weight percent mineral oil, 10 weight percent glycerin with the balance sodium carboxymethyl-cellulose. US-A-5 120374 (Mizuhara) discloses gels containing 1-4 wt. % hydroxypropylcellulose, 40- 80 vt.
% 1,2-propanediol, 18-58 wt. % 2-propanol or 1-4 wt. % hydroxypropylcellulose, 20-70 wt. % 1,2-propanediol, 26-76 wt. % water. US-A-4475959 discloses an organic vehicle system based on resins dispersed in hydroxylic solvents. Low- melting hydrocarbon vehicles may also be used. Useful materials include those melting below room temperature to normally solid materials, e.g. Ci- Cico petroleum hydrocarbon waxes melting from 28 C. to 100 C. Such materials should have a low ash or solid residue content and either melt and flow, sublime and/or thermally decompose below 500 C. Useful hydrocarbons may be paraffinic, aromatic, or mixed aromatic paraffinic or mixtures of compounds of such characteristics, and include various mixtures of hydrocarbons, e.g., octadecane, mineral spirits, paraffin wax, and petrolatum (a colloidal system of non-straight-chain solid paraffinic hydrocarbons and high boiling liquid paraffinic hydrocarbons, in which most of the liquid hydrocarbons are held inside the micelles), e. g., Vaseline.
The alloys can be used in any conventional soldering or brazing method e. g. using a hand torch, a fixed burner, induction or resistance heating or using a brazing furnace, preferably such a furnace which provides a protective atmosphere.
The invention is further illustrated in the following examples
Example 1
A brazing composition is prepared by melting together the following materials: Ag - 75% Ge 1.5% Sn - 1.0% Zn - 4.5% Cu - 18%.
The resulting composition is expected to roll well from cast ingot (satisfactory to 40% work hardened, then required annealing) and is a good solder when tested initially on gilding metal samples. The solder composition runs well along a T' join. The observed colour is good. On tarnish testing the present solder appears bright. Its melting point is within the range of "hard" solders for germanium-containing silver alloys.

Claims (15)

1. A silver solder or brazing alloy of the Ag-Cu-Zn family containing more than 70 wt % Ag and from 0.5 to 3 wt% Ge.
2. The alloy of claim 1, containing 1.0-2.5 wt % Ge.
3. The alloy of claim 1, containing about 1.5 wt % Ge.
4. The alloy of any preceding claim, further comprising 1-3 wt % Sn.
5. The alloy of claim 4, comprising about 1 wt % Sn.
6. The alloy of any preceding claim containing 3 - less than 8 wt% Zn
7. The alloy of any preceding claim containing 4 - 5 wt% Zn
8. The alloy of any preceding claim, further comprising 0.05-0.4 wt % Si.
9. The alloy of claim 8, comprising about 0.1 wt% Si.
10. The alloy of any preceding claim, containing about 75 wt% Ag, about 18 wt% Cu and about 4.5 wt% Zn, about 1.5 wt% Ge and about 1 wt% Sn.
11. Use of the alloy of any preceding claim to solder or braze a joint in silver.
12. Use of the alloy of any of claims 1-10 to solder or braze ajoint in Sterling silver.
13, Use of the alloy of any of claims 1-10 to solder or braze a joint in silver alloy of silver content at least Ag 92.5 wt% and containing germanium in an amount effective to impart firestain and/or tarnish resistance.
14. An alloy according to any of claims 1-10, which is in the form of rod, strip or wire.
15. An alloy according to any of claims 1-0, which is in the form of paste.
GB0513985A 2005-07-07 2005-07-07 A silver-copper-zinc-germanium brazing alloy Withdrawn GB2428046A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
GB0513985A GB2428046A (en) 2005-07-07 2005-07-07 A silver-copper-zinc-germanium brazing alloy
EP06744350A EP1904263A1 (en) 2005-07-07 2006-06-12 Silver solder or brazing alloys and their use
PCT/GB2006/050149 WO2007007120A1 (en) 2005-07-07 2006-06-12 Silver solder or brazing alloys and their use
CNA2006800246467A CN101223003A (en) 2005-07-07 2006-06-12 Silver solder or brazing alloys and their use

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB0513985A GB2428046A (en) 2005-07-07 2005-07-07 A silver-copper-zinc-germanium brazing alloy

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GB0513985D0 GB0513985D0 (en) 2005-08-17
GB2428046A true GB2428046A (en) 2007-01-17

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EP (1) EP1904263A1 (en)
CN (1) CN101223003A (en)
GB (1) GB2428046A (en)
WO (1) WO2007007120A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102012100920A1 (en) * 2012-02-03 2013-08-08 Horwitz-Hamburg GmbH Silver alloy, useful for preparing jewelry, comprises silver, and alloying additive comprising copper, zinc and boron

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102513726B (en) * 2011-12-22 2014-11-12 佛山市益宏焊接有限公司 Silver-based flux-cored wire and manufacturing method thereof
CN114193026A (en) * 2021-12-30 2022-03-18 郑州机械研究所有限公司 High-silver brazing filler metal for welding pure silver jewelry and preparation method thereof
CN114473292A (en) * 2021-12-30 2022-05-13 郑州机械研究所有限公司 Low-silver brazing filler metal for welding pure-silver jewelry and preparation method thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3811876A (en) * 1969-02-05 1974-05-21 Suwa Seikosha Kk Silver alloys having high sulphuration resistance
JPS6134148A (en) * 1984-07-25 1986-02-18 Tanaka Kikinzoku Kogyo Kk Sliding contact material
JPH04339590A (en) * 1991-05-10 1992-11-26 Citizen Watch Co Ltd Silver brazing filler metal
WO1995014112A1 (en) * 1993-11-15 1995-05-26 Apecs Investment Castings Pty. Ltd. Silver alloy compositions
NZ506379A (en) * 1999-08-24 2001-12-21 Degussa Cadmium-free brazing alloys comprising 45-75 weight % Ag, 10-30 weight % Cu, 1-25% weight Zn, and other elements
WO2005051593A1 (en) * 2003-11-19 2005-06-09 Middlesex Silver Co. Limited Silver solder or brazing alloys and their use
GB2418432A (en) * 2004-09-23 2006-03-29 Middlesex Silver Co Ltd Silver alloy and its production using a master metal

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1029087A (en) * 1996-07-12 1998-02-03 Tanaka Kikinzoku Kogyo Kk Low melting brazing filler metal for platinum ornaments
GB0328603D0 (en) * 2003-12-10 2004-01-14 Cole Paul G Silver chain manufacture

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3811876A (en) * 1969-02-05 1974-05-21 Suwa Seikosha Kk Silver alloys having high sulphuration resistance
JPS6134148A (en) * 1984-07-25 1986-02-18 Tanaka Kikinzoku Kogyo Kk Sliding contact material
JPH04339590A (en) * 1991-05-10 1992-11-26 Citizen Watch Co Ltd Silver brazing filler metal
WO1995014112A1 (en) * 1993-11-15 1995-05-26 Apecs Investment Castings Pty. Ltd. Silver alloy compositions
NZ506379A (en) * 1999-08-24 2001-12-21 Degussa Cadmium-free brazing alloys comprising 45-75 weight % Ag, 10-30 weight % Cu, 1-25% weight Zn, and other elements
WO2005051593A1 (en) * 2003-11-19 2005-06-09 Middlesex Silver Co. Limited Silver solder or brazing alloys and their use
GB2418432A (en) * 2004-09-23 2006-03-29 Middlesex Silver Co Ltd Silver alloy and its production using a master metal

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102012100920A1 (en) * 2012-02-03 2013-08-08 Horwitz-Hamburg GmbH Silver alloy, useful for preparing jewelry, comprises silver, and alloying additive comprising copper, zinc and boron

Also Published As

Publication number Publication date
GB0513985D0 (en) 2005-08-17
CN101223003A (en) 2008-07-16
WO2007007120A1 (en) 2007-01-18
EP1904263A1 (en) 2008-04-02

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