GB2355990A - A silver/copper/germanium alloy composition - Google Patents
A silver/copper/germanium alloy composition Download PDFInfo
- Publication number
- GB2355990A GB2355990A GB0003097A GB0003097A GB2355990A GB 2355990 A GB2355990 A GB 2355990A GB 0003097 A GB0003097 A GB 0003097A GB 0003097 A GB0003097 A GB 0003097A GB 2355990 A GB2355990 A GB 2355990A
- Authority
- GB
- United Kingdom
- Prior art keywords
- content
- copper
- silver
- germanium
- alloy
- 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- Withdrawn
Links
- 239000004332 silver Substances 0.000 title claims abstract description 53
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 52
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000010949 copper Substances 0.000 title claims abstract description 49
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 25
- 229910000927 Ge alloy Inorganic materials 0.000 title claims abstract description 24
- 239000000203 mixture Substances 0.000 title description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 34
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052802 copper Inorganic materials 0.000 claims abstract description 25
- 239000000654 additive Substances 0.000 claims abstract description 23
- 230000000996 additive effect Effects 0.000 claims abstract description 22
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052796 boron Inorganic materials 0.000 claims abstract description 21
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 19
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 17
- 239000010703 silicon Substances 0.000 claims abstract description 17
- 229910052718 tin Inorganic materials 0.000 claims abstract description 17
- 229910052738 indium Inorganic materials 0.000 claims abstract description 16
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910045601 alloy Inorganic materials 0.000 claims description 48
- 239000000956 alloy Substances 0.000 claims description 48
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 2
- 238000000137 annealing Methods 0.000 description 5
- 238000005476 soldering Methods 0.000 description 5
- 238000005096 rolling process Methods 0.000 description 4
- 238000007665 sagging Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 238000005494 tarnishing Methods 0.000 description 2
- 229910002058 ternary alloy Inorganic materials 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- PGWMQVQLSMAHHO-UHFFFAOYSA-N sulfanylidenesilver Chemical compound [Ag]=S PGWMQVQLSMAHHO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
-
- 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
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/3006—Ag as the principal constituent
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Adornments (AREA)
- Conductive Materials (AREA)
- Contacts (AREA)
Abstract
A silver/copper/germanium alloy comprising a silver content of at least 50% by weight, a germanium content of between 0.10 and 3% by weight, an elemental boron content of 100ppm or less and an additive content of 2% or less by weight, the remainder principally being copper, the additive content comprising one of, or a combination of, tin, antimony, silicon and indium.
Description
I 1 2355990 16A silver/copper/germanium alloy composition" THE PRESENT
INVENTION relates to a silver/copper/germanium alloy composition.
GB 2 255 348 discloses a silver based ternary alloy and more particularly, a silver/copper/germanium alloy having a germanium content of between 0. 5 to 3% by weight. Silver/copper/germanium alloys such as those disclosed in GB 2 255 348 provide improved mechanical and fire stain resistant properties over silver/copper alloys without a germanium content. However, these silver/copper/germanium alloys can still be improved upon over the complete range of germanium content.
For example, when such silver/copper/germanium alloys with a high germanium content (1% by weight or greater) are subjected to soldering or annealing operations, at temperatures over 700'C, heat distortion such as sagging can occur. It is thought that the heat distortion is due to an excess of or high concentrations of low melting phases. Another disadvantageous property is that at high soldering temperatures and during annealing when temperatures exceed 700'C, alloys with a low germanium content (1% by weight or less) have a reduced fire stain resistance.
It has also been noted that whilst reduction rates when rolling a cast alloy having a germanium content in the region of 1.5% and a silver content in the region of 80 to 83% are in the region of 90%, the reduction rate drops to in 2 the region of 40% before edge cracking begins when the germanium content is greater than 1% and the silver content is greater than 90%.
It is an object of the present invention to provide an improved silver/copper/germanium alloy. More particularly, it is an object of the present invention to seek to provide a silver/copper/germanium alloy which does not suffer from one, some or all of the above mentioned disadvantageous properties.
Accordingly, one aspect of the present invention provides a silver/copper/germanium alloy comprising a silver content of at least 50% by weight, a germanium content of between 0. 10 and 3% by weight, an elemental boron content of 100ppm or less and an additive content of 2% or less by weight, the remainder principally being copper, the additive content comprising one of, or a combination of, fin, antimony, silicon and indium.
Advantageously, the additive content is between 0.01 and 1%.
Preferably, the additive content is in the region of 0.2%.
Advantageously, the boron content is 20ppm or less.
In order that the present invention may be more readily understood, it will now be described, by way of examples.
As previously mentioned, silver/copper/germanium alloys can suffer from a number of disadvantageous properties such as: sagging during soldering or annealing, a reduction in fire stain resistance at high temperatures (e.g. during annealing) and reduced reduction rates when rolling cast alloys.
3 The addition of a minor amount of tin, antimony, silicon or indium. to a silver/copper/gertnanimn alloy having an elemental boron content has been found to ameliorate one, some or all of these problems.
Over the germanium content range of 0. 1% to 3%, it has been found that the addition of tin, antimony, silicon or indium in small quantities, less than 2% by weight, brings advantages in that the mechanical properties of the resultant silver/copper/germanium. alloy are improved. For example, heat distortion such as sagging of the silver/copper/germanium. alloy at high solder temperatures is reduced, the alloy can be more readily rolled further from the as cast state and the alloy does not work harden so quickly during other cold work processes.
In one example, a silver/copper/germanium. alloy having a germanium content of 1% includes a fin content of between 0.01 and 1%. The silver/copper/germanium alloy also has an elemental boron content of 100ppm. or less. The addition of the tin positively influences the distribution of the low inelfing point eutectics. The low tin content causes a reduction in coarse dendrific formations and secondary dendritic arms. Thus, excessively high concentrations of low melting point phases which predispose the alloy to heat distortion are avoided and the resultant alloy is therefore less susceptible to heat distortion at high soldering temperatures (typically >700'C) than the same silver/copper/germanium alloy would be without the tin content. The effects of using antimony, silicon or indium in place of tin as an additive are comparable. Additionally, beneficial effects are achievable with an additive comprising a combination of any or all of tin, antimony, silicon or indium.
Another example provides a cast silver/copper/germanium alloy having a germanium content of 1%, a fin content of 0.2% and an elemental boron 4 content. Boron is present in the alloy at less than 100ppm. The resultant cast silver/copper/germanium alloy is suitable for rolling and will reduce by 90% before edge cracking occurs. This is at least twice that of the comparable silver/copper/germanium alloy with a germanium content of 1% or greater and without a tin, antimony, silicon or indium content which would have a maximum reduction of between 40 to 50%.
A further example provides a silver/copper/germanium alloy having a germanium content of between 0.3 and 1.1%, a tin content of 0.2% and an elemental boron content. Boron is present in the alloy at less than 100ppm. The resultant silver/copper/germanium alloy is fire stain resistant even at high soldering and annealing temperatures (>700'C) at which comparable silver/copper/germanium alloys without a tin, antimony or indium content would exhibit reduced fire stain resistance.
In the above mentioned examples, the silver content can be as low as 50% by weight with the remainder content principally being copper. Preferably, the silver content is as low as 50% by weight with the remainder content being copper apart from any impurities. Elemental boron is required to be present in accordance with the present invention. A boron content of 20ppm is preferred but the boron content should be constrained at 100ppm or less.
For cast silver/copper/germanium alloys with germanium contents of 1.5% to 3%, it is preferable that the silver content is greater than 90% and most preferably, greater than 92.51/o, which ranges have been found to be particularly advantageous for good reduction rates when rolling the cast alloy.
For silver/copper/germanium alloys with germanium contents of 1. 1% or less, it has been found that the addition of a tin, antimony or indium content of 2% or less preserves the fire stain resistance of the resultant silver/copper/germanium. alloy. As such the germanium content can be reduced to between 0.3 to 1%.
The addition of tin, antimony, silicon or indium. further improves (most notably with the antimony and silicon additives) the tarnish resistance of silver/copper/germanium. alloys. The addition appears to be protecting the copper in the alloy. Earlier tarnishing tests on binary silver/germanium. alloys showed that the silver in binary silver/germaniurn alloys was protected almost completely from tarnishing by the germanium. However, ternary alloys with copper such as those proposed by the present invention (but without a tin, antimony, silicon or indium. addition) showed a discolouning of the alloy from copper oxide and sulphide even though no silver sulphide was formed.
Due to a reduction in the amount of copper present in the alloys embodying the present invention (as a result of the presence of the additive content), it is desirable to improve the hardness of the silver/copper/gerTnanium alloys embodying the present invention. This can be achieved by adding a small amount of nickel to the alloy, preferably from 0. 0 1 to 2% by weight.
For the sake of clarity, it should be noted that where the present specification refers to a boron content of less than 100pprn or an additive content of 2% or less, it is always essential that, in the silver/copper/germanium. alloy according to the present invention, there is both a boron content and an additive content of greater than zero. The boron is elemental boron.
A master alloy comprising copper, germanium, boron and the additive content of tin, antimony, silicon or indiurn is a convenient means of delivering the constituent parts of the alloy embodying the present invention in a form 6 which can simply be combined with silver to produce the resultant silver/copper/germaniurn alloy. If the resultant alloy also requires a nickel content, then the nickel content would be one of the constituents of the master alloy.
The benefits achieved by the present invention can be attributed to the addition of fin, antimony, silicon or indiurri contents to the silver/copper/germanium alloy. As well as achieving these benefits by adding fin, antimony, silicon or indium individually, the benefits can also be achieved by adding tin, antimony, silicon or indium contents in any combination with one another, the total additive content not exceeding 2% by weight.
The additive content of fin, antimony, silicon or indium is 2% by weight or less of the resultant silver/copper/germaniurn alloy. Conveniently, the additive content should be between 0.01 and 1% by weight. Preferably, the additive content is in the region of 0.2% by weight.
7
Claims (18)
1. A silver/copper/germanium alloy comprising a silver content of at least 50% by weight a germanium content of between 0. 10 and 3% by weight, an elemental boron content of 100ppm. or less and an additive content of 2% or less by weight the remainder principally being copper, the additive content comprising one of, or a combination of, fin, antimony, silicon and indium.
2. An alloy according to Claim 1, wherein the additive content is between 0.01 and 1% by weight.
3. An alloy according to Claim 2, wherein the additive content is in the region of 0.2% by weight.
4. An alloy according to any preceding claim, wherein the silver content is 80% or greater.
5. An alloy according to any preceding claim, wherein the silver content is 83% or greater.
6. An alloy according to any preceding claim, wherein the silver content is 92.5% or greater.
7. An alloy according to any preceding claim, wherein the germanium content is 1. 1% or less.
8. An alloy according to any preceding claim, wherein the germanium content is between 0.3 and 1. 1%.
8
9. An alloy according to any preceding claim, wherein the germanium content is between 0.9 and 1%.
10. An alloy according to any one of Claims I to 6, wherein the germanium content is between 1.5% and 3%.
11. An alloy according to any preceding claim, wherein the boron content is 20ppm or less.
12. An alloy according to any preceding claim, wherein the boron content is 20ppm.
13. An alloy according to any preceding claim, including a nickel content of from 0. 0 1 to 2% by weight.
14. An alloy according to any preceding claim, wherein the remainder is copper apart from any impurities.
15. A copper/germanium master alloy having a copper, germanium, boron and additive content for the production of a silver/copper/gennanium alloy according to any preceding claim, the additive content comprising one or a combination of tin, antimony, silicon and indium.
16. A copper/germanium master alloy according to Claim 15, wherein the master alloy also includes a nickel content.
17. An silver/copper/gerinanium alloy substantially as hereinbefore described.
9
18. Any novel feature or combination of features disclosed herein.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GBGB9926313.9A GB9926313D0 (en) | 1999-11-05 | 1999-11-05 | A silver/copper/germanium alloy composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB0003097D0 GB0003097D0 (en) | 2000-03-29 |
| GB2355990A true GB2355990A (en) | 2001-05-09 |
Family
ID=10864078
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GBGB9926313.9A Ceased GB9926313D0 (en) | 1999-11-05 | 1999-11-05 | A silver/copper/germanium alloy composition |
| GB0003097A Withdrawn GB2355990A (en) | 1999-11-05 | 2000-02-10 | A silver/copper/germanium alloy composition |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GBGB9926313.9A Ceased GB9926313D0 (en) | 1999-11-05 | 1999-11-05 | A silver/copper/germanium alloy composition |
Country Status (1)
| Country | Link |
|---|---|
| GB (2) | GB9926313D0 (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004106567A1 (en) * | 2003-06-03 | 2004-12-09 | Middlesex Silver Co. Limited | Silver ternary alloy |
| WO2005056213A1 (en) * | 2003-12-10 | 2005-06-23 | Middlesex Silver Co. Limited | Silver chain manufacture |
| GB2414739A (en) * | 2004-06-02 | 2005-12-07 | Middlesex Silver Co Ltd | Process for making finished or semi-finished articles of silver alloy |
| GB2418432A (en) * | 2004-09-23 | 2006-03-29 | Middlesex Silver Co Ltd | Silver alloy and its production using a master metal |
| WO2006032933A1 (en) * | 2004-09-23 | 2006-03-30 | Middlesex Silver Co. Limited | Copper-boron master alloy and its use in making silver-copper alloys |
| WO2007023308A1 (en) * | 2005-08-23 | 2007-03-01 | Middlesex Silver Co. Limited | Silver wire |
| RU2332477C1 (en) * | 2006-11-15 | 2008-08-27 | Юлия Алексеевна Щепочкина | Silver based alloy |
| RU2475552C1 (en) * | 2012-02-09 | 2013-02-20 | Юлия Алексеевна Щепочкина | Silver-based alloy |
| US9222150B2 (en) | 2004-06-02 | 2015-12-29 | Peter Gamon Johns | Process for making finished or semi-finished articles of silver alloy |
| CN109175784A (en) * | 2018-10-31 | 2019-01-11 | 无锡日月合金材料有限公司 | A kind of novel oxidation-resistant quaternary alloy solder |
| CN110238559A (en) * | 2019-06-17 | 2019-09-17 | 无锡日月合金材料有限公司 | A kind of novel quaternary alloy solder and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114393345A (en) * | 2021-12-30 | 2022-04-26 | 无锡日月合金材料有限公司 | Low-silver vacuum solder with small temperature difference of melting point and flow point |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995014112A1 (en) * | 1993-11-15 | 1995-05-26 | Apecs Investment Castings Pty. Ltd. | Silver alloy compositions |
| WO1996022400A1 (en) * | 1995-01-18 | 1996-07-25 | Apecs Investment Castings Pty. Ltd. | Silver alloy compositions |
-
1999
- 1999-11-05 GB GBGB9926313.9A patent/GB9926313D0/en not_active Ceased
-
2000
- 2000-02-10 GB GB0003097A patent/GB2355990A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995014112A1 (en) * | 1993-11-15 | 1995-05-26 | Apecs Investment Castings Pty. Ltd. | Silver alloy compositions |
| WO1996022400A1 (en) * | 1995-01-18 | 1996-07-25 | Apecs Investment Castings Pty. Ltd. | Silver alloy compositions |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004106567A1 (en) * | 2003-06-03 | 2004-12-09 | Middlesex Silver Co. Limited | Silver ternary alloy |
| EA011015B1 (en) * | 2003-06-03 | 2008-12-30 | Миддлсекс Силвер Ко. Лимитед | Silver ternary alloy |
| WO2005056213A1 (en) * | 2003-12-10 | 2005-06-23 | Middlesex Silver Co. Limited | Silver chain manufacture |
| GB2414739B (en) * | 2004-06-02 | 2008-03-19 | Middlesex Silver Co Ltd | Process for making finished or semi-finished articles of silver alloy |
| GB2414739A (en) * | 2004-06-02 | 2005-12-07 | Middlesex Silver Co Ltd | Process for making finished or semi-finished articles of silver alloy |
| US9222150B2 (en) | 2004-06-02 | 2015-12-29 | Peter Gamon Johns | Process for making finished or semi-finished articles of silver alloy |
| GB2418432A (en) * | 2004-09-23 | 2006-03-29 | Middlesex Silver Co Ltd | Silver alloy and its production using a master metal |
| CN100478469C (en) * | 2004-09-23 | 2009-04-15 | 米德尔塞克斯银有限公司 | Method of producing a copper-germanium-boron master alloy and its use in making silver-copper alloys |
| WO2006032933A1 (en) * | 2004-09-23 | 2006-03-30 | Middlesex Silver Co. Limited | Copper-boron master alloy and its use in making silver-copper alloys |
| WO2007023308A1 (en) * | 2005-08-23 | 2007-03-01 | Middlesex Silver Co. Limited | Silver wire |
| RU2332477C1 (en) * | 2006-11-15 | 2008-08-27 | Юлия Алексеевна Щепочкина | Silver based alloy |
| RU2475552C1 (en) * | 2012-02-09 | 2013-02-20 | Юлия Алексеевна Щепочкина | Silver-based alloy |
| CN109175784A (en) * | 2018-10-31 | 2019-01-11 | 无锡日月合金材料有限公司 | A kind of novel oxidation-resistant quaternary alloy solder |
| CN110238559A (en) * | 2019-06-17 | 2019-09-17 | 无锡日月合金材料有限公司 | A kind of novel quaternary alloy solder and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| GB9926313D0 (en) | 2000-01-12 |
| GB0003097D0 (en) | 2000-03-29 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |