WO2015193659A2 - Compositions d'alliage - Google Patents

Compositions d'alliage Download PDF

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Publication number
WO2015193659A2
WO2015193659A2 PCT/GB2015/051765 GB2015051765W WO2015193659A2 WO 2015193659 A2 WO2015193659 A2 WO 2015193659A2 GB 2015051765 W GB2015051765 W GB 2015051765W WO 2015193659 A2 WO2015193659 A2 WO 2015193659A2
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WO
WIPO (PCT)
Prior art keywords
alloy
alloy composition
components
weight
gold
Prior art date
Application number
PCT/GB2015/051765
Other languages
English (en)
Other versions
WO2015193659A3 (fr
Inventor
Christopher Quayle
Original Assignee
Allied Gold Limited
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
Priority claimed from GB201410727A external-priority patent/GB201410727D0/en
Priority claimed from GB201503439A external-priority patent/GB201503439D0/en
Application filed by Allied Gold Limited filed Critical Allied Gold Limited
Publication of WO2015193659A2 publication Critical patent/WO2015193659A2/fr
Publication of WO2015193659A3 publication Critical patent/WO2015193659A3/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • 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
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
    • 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

Definitions

  • This invention relates to alloy compositions, especially alloy compositions based on one or more precious metals. More particularly, though not exclusively, the invention relates to precious metal-containing alloy compositions which include certain adjunct components which impart particular desirable physical properties thereto. BACKGROUND
  • Items of jewellery manufactured principally in either silver, gold, platinum or palladium typically comprise individual components which are joined together by soldering (more correctly termed "brazing") or occasionally by welding.
  • soldering more correctly termed "brazing”
  • such techniques are frequently disadvantageous, in that either the one or more filler metals used in the soldering/brazing joining process is/are typically of a different colour from the main jewellery components, or the actual welding of the parent metal(s) themselves creates distortions or melting of the pieces being joined.
  • Soldering and brazing typically employ a filler metal which melts below the melting- point of the parent metal(s) being joined. This filler metal "wets" onto both parent metal surfaces and is drawn into the joint gap therebetween by capillary attraction, where it solidifies to give a strong, ductile bond.
  • Different filler metal alloys melt at different temperatures, making it possible, if desired or necessary, to "step" joints that are close together, e.g. starting with a higher melting-point filler metal or alloy and then progressively using a lower melting-point filler metal or alloy.
  • some filler metals flow better than others: more free-flowing filler metals are better for very tight or narrow joint gaps, whereas less flowable (i.e. more "stodgy”) filler metals are better at filling wider joint gaps.
  • Brazing operations are generally defined as taking place at about 450 °C (-840 °F) or above, and soldering generally takes place below about 450 °C, but otherwise the two processes are in general terms the same.
  • silversmiths and goldsmiths frequently refer to the higher temperature brazing process as “soldering” and this can be a cause of some confusion. Therefore, as used herein the higher temperature joining process will be referred to as “soldering (brazing)" to differentiate it from the lower temperature “soldering” process and also to maintain the silversmith/goldsmith convention of nomenclature.
  • this is also a process for joining same or similar metals, although in this case the parent metals being joined are heated to above their melting point and a filler metal may also be applied.
  • this is typically a higher temperature process than either soldering or brazing and typically takes place in the temperature range of about 800-1635 °C (1500-3000 °F).
  • Solders and brazing alloys that are used for the joining of jewellery items have a different colour to the parent metals they are used to join, owing to the necessity of the lower melting-point ranges and the requirement for the alloy to flow during the soldering/brazing procedure.
  • the resulting soldered/brazed seams or joints are then conventionally disguised by one or more subsequent plating operations, e.g.
  • an alloy composition comprising:
  • balance being one or more optional adjunct components and/or impurities.
  • the alloy compositions of the above first aspect of the invention may further comprise one or more secondary alloying elements or adjunct components conventionally included in gold or other precious metal alloy compositions for imparting thereto or enhancing one or more particularly desirable end properties, such as one or more of the following: whiteness, specific desired colour, hardness, workability, ductility, flowability, precious metal content.
  • Suitable components (a) for enhancing castability of the resulting alloy compositions may be selected from any suitable elements (or compounds) known in the art for that purpose. Examples may include one or more of indium (In), gallium (Ga) and tin (Sn). Suitable components (b) for acting as grain refiners may be selected from any suitable elements (or compounds) known in the art for that purpose. Examples may include one or more of silicon (Si), iridium (Ir), boron (B) and ruthenium (Ru).
  • Suitable components (c) for acting as flow- or ductility-enhancing components may be selected from any suitable elements (or compounds) known in the art for that purpose, e.g. one or more adjunct metals known for that purpose, e.g. silver, zinc.
  • one or more flow- or ductility-enhancing components may be included in the alloy composition in any suitable amount that imparts to the alloy a sufficient or desired degree of ductility or flow characteristics, e.g. depending on the alloy's composition of other components, its intended use or its treatment in any subsequent processing stage.
  • Suitable such amounts of this flow- or ductility-enhancing component (c) (or collectively such components (c), if more than one such component (c) is used) included in the composition for this purpose may be for example in the range of from about 0.0 or 0.1 or 0.5 up to about 5.0 or 10 or 15 or 20 or 30 or 40 or 50 or 60 or 65 % by weight of the composition.
  • Such amounts may include any amount of the same flow- or ductility- enhancing component (c) when it is optionally present in the composition for one or more other purposes, e.g. under optional components (d) and/or (e) below.
  • Suitable components (d) for acting as workability-enhancing components may be selected from any suitable elements (or compounds) known in the art for that purpose, e.g. one or more adjunct metals known for that purpose, e.g. silver, zinc.
  • one or more workability-enhancing components may be included in the alloy composition in any suitable amount that imparts to the alloy a sufficient or desired degree of workability or balance of workability properties, e.g. depending on the alloy's composition of other components, its intended use or its treatment in any subsequent processing stage.
  • Suitable such amounts of this workability-enhancing component (d) (or collectively such components (d), if more than one such component (d) is used) included in the composition for this purpose may be for example in the range of from about 0.0 or 0.1 or 0.5 up to about 5.0 or 10 or 15 or 20 or 30 or 40 or 50 or 60 or 65 % by weight of the composition. Such amounts may include any amount of the same workability-enhancing component (d) when it is optionally present in the composition for one or more other purposes, e.g. under optional components (c) above and/or (e) below.
  • adjunct precious metal components (e) may optionally be included in the alloy compositions of the invention, one example of which is silver or a silver-containing alloy, which silver may thus be present in its own right as an adjunct precious metal in addition to or alternatively from its optional presence (under optional components (c) and/or (d)) as a ductility-enhancing and/or workability-enhancing component.
  • Suitable such amounts of this adjunct precious metal component (e) (or collectively such components (e), if more than one such component (e) is used), included in the composition for this purpose may be for example in the range of from about 0.0 or 0.1 or 0.5 up to about 5.0 or 10 or 15 or 20 or 30 or 40 or 50 or 60 or 65 % by weight of the composition.
  • Such amounts may include any amount of the same adjunct precious metal component (e) when it is optionally present in the composition for one or more other purposes, e.g. under optional components (c) and/or (d) above.
  • the alloy compositions of the invention may further include one or more other elements or compounds of the nature of impurities (f), e.g. derived from any of the starting materials used for forming the alloys or from any of the processing steps used for their production.
  • impurity components(s) may for example be present in no more than about 0.0001 , 0.0005, 0.001 , 0.005, 0.01 , 0.05, 0.1 , 0.5, 1 .0, 1 .5 or even 2.0 % by weight of the total composition.
  • the alloy composition may be a gold-based alloy composition, in which case the alloy composition preferably comprises:
  • balance being one or more optional adjunct components and/or impurities.
  • a preferred amount of germanium may for example be in the range of from about 2 or 3 % by weight up to about 5 or 6 % by weight.
  • the alloy composition may be a platinum-based alloy composition, in which case the alloy composition preferably comprises:
  • the alloy composition may be a palladium-based alloy composition, in which case the alloy composition preferably comprises:
  • balance being one or more optional adjunct components and/or impurities.
  • the alloy composition may comprise gold in combination with one or more alloying elements that are typical of and/or are consistent with generally established definitions or physical appearances of gold-based alloys commonly termed any of the following: yellow gold, white gold, rose gold, crown gold, red gold, pink gold, spangold, green gold, grey gold.
  • gold-alloying elements may include for example silver and/or copper (e.g. as defined in the embodiments above), and/or any other alloying elements known for use in such coloured gold-based alloys.
  • Gold-based alloy compositions of the invention that are of the "white gold” type, may be particularly useful, as they may be designed to have high whiteness properties, yet without the deleterious effects and health risks (especially because of allergic reactions) often associated with such alloys based conventionally on nickel (Ni) as a major alloying element in addition to the gold.
  • the alloy composition in which the alloy composition is a gold-based alloy composition, the alloy composition may comprise gold in a total amount (by weight of the total composition) appropriate for satisfying a particular selected or predefined carat (or karat) rating for the gold alloy in question.
  • carat or karat
  • Such overall gold contents for particular carat gold alloys are well known in the art and examples will be given hereinbelow in the context of preferred embodiments and working examples illustrating same.
  • the article may comprise a plurality of component parts, at least one of which is joined, preferably by means of a fusion or diffusion process, to at least one other component part thereof, wherein at least one of, preferably each of, said component parts is, or is formed from, an alloy composition according to the first aspect of the invention or any embodiment thereof.
  • the article may comprise a plurality of component parts, at least one of which is joined, preferably by means of a fusion or diffusion process, to at least one other component part thereof, wherein at least one first component part thereof is, or is formed from, an alloy composition according to the first aspect of the invention or any embodiment thereof, and at least one second component part thereof is, or is formed from, a metal or alloy other than an alloy composition according to the first aspect of the invention or any embodiment thereof.
  • the at least one second component part may be, or may be formed from, another precious metal or precious metal alloy, i.e. a precious metal or alloy other than gold, platinum or palladium or gold-based, platinum-based or palladium- based, e.g. silver or a silver-based alloy, e.g. an Argentium (RTM) silver composition.
  • the Argentium (RTM) silver composition may comprise at least 92.5% by weight silver, the balance being substantially copper and germanium. In many cases the amount of germanium present may be such as to replace a minor proportion of the customary 7.5% by weight of copper normally present in a standard Sterling silver composition.
  • the Argentium (RTM) silver may be substantially 92.5% silver, with the balance provided substantially by copper and germanium.
  • the amount of germanium may for example be present in the range from about 0.05 to about 1 or 2 or 3 or 4 or possibly even up to about 7% by weight, optionally from about 0.4% to about 1 or 2 or 3 or 4% by weight.
  • Boron may optionally be present as a grain refiner in the silver composition, e.g. in an amount of up to about 20ppm in some embodiments.
  • a method of making an article according to the third aspect or any embodiment thereof comprising joining the said component parts using a fusion or diffusion process.
  • the method may comprise fusing together the said component parts by placing the said component parts together so as to define at least one area or region of each in mutual contact with the other, and heating at least the said area or region so that the said alloy composition of each component undergoes incipient melting and a solid metal bond is formed between the two component parts upon cooling of the said areas or region.
  • a method of increasing or enhancing the fusibility of a precious metal-containing alloy composition wherein the alloy composition comprises at least one precious metal selected from gold (Au), platinum (Pt) and palladium (Pd), together with one or more optional components and/or impurities, wherein the method comprises incorporating in the alloy composition a fusibility- promoting or enhancing amount of an alloying component comprising:
  • alloy compositions in accordance with many embodiments of the present invention may exist in the form of discrete articles, bodies, masses, coatings or other volumes of any desired shape which consist of or comprise the said alloy composition.
  • alloy compositions in accordance with certain embodiments of the present invention may exist in the form of one or more portions or regions or phases within or forming a part of a larger article, body, mass, coating or other volume of any desired shape, which portion(s), region(s) or phase(s) consists of or comprises the said alloy composition.
  • such an alloy composition may be formed for example in situ in such a portion, region or phase, e.g.
  • an example of such an in s/fu-formed alloy composition within the scope of some embodiments of the invention may be that formed in an interfacial region or portion upon diffusion-bonding an article of gold (or e.g. white or other species of gold) with an article of Argentium silver, whereby in the interfacial diffusion region an alloy composition comprising at least gold (from the gold-based article), and copper and germanium (from the silver-based article) is formed in situ.
  • the advantageous properties of the gold-based alloy composition of the invention may be realised at the in situ site, region or portion of formation of the alloy composition itself.
  • FIGURE 1 is a graphical illustration of the CIELab system of colour measurement showing orthogonal axes L * , a * and b * .
  • the Yellowness Index (Yl) is calculated from the CIE tri-stimulus values, X, Y and Z, thus:
  • Yl [100 (1 .28X-1 .06Z) / Y ]
  • the Yl scale is linear: as the number decreases, so the alloy is whiter.
  • Table 1 gives the typical Yellowness Index and CIELab values for various known "white” precious metal alloys, the rhodium plating used to make white gold alloys “white” and the initial colour measurements of the 9 carat and 18 carat germanium- containing white gold alloys according to embodiments of the present invention.
  • Table 1 Surface Colour Measurement of various "white” precious metals/alloys
  • Example alloys according to the present invention as exemplified in the Examples below.
  • Table 1 clearly demonstrates how much whiter these white gold alloys were that contain germanium, in accordance with embodiments of the present invention, as compared with the traditional "white gold" alloys. It is also important to note that this improvement in whiteness is based on relatively small additions of germanium compared with the levels of nickel and/or palladium which would conventionally be present as traditional whitening elements. In other words, germanium is 3 or 4 times a more effective whitening addition component compared with the conventional metal(s) it replaces.
  • the copper : germanium ratio required to achieve a workable alloy increases with the amount of the germanium addition. Therefore, for example, for an alloy with a 1 % germanium addition a workable alloy is achievable with a 1 % copper addition (i.e. a 1 :1 ratio). However, to achieve a workable alloy with a 5% germanium addition, the amount of copper needed increases to a 2.5:1 copper : germanium ratio.
  • Examples of 14 carat white and 14 carat red gold alloys according to the invention had compositions as shown in Table 4 below (all amounts being given as % by weight of the total composition): Table 4 - 14 carat white and red gold alloys according the invention
  • the 4% germanium addition showed good colour but poor workability, as shown in the test results presented further below. It is believed that the workability may be improved by reducing the germanium addition to the 3% level whilst maintaining the exceptional whiteness of this alloy. For the white gold alloys the limit of improved whiteness visually appears to be at around the 4% germanium level.
  • the constituent metals were place in a controlled atmosphere melting machine to prevent oxygen being absorbed by the molten metal.
  • the gold and silver were initially alloyed together, followed by the copper and germanium, and then finally the metal temperature was reduced prior to adding the zinc (to reduce metal fuming) if this metal was required.
  • Pd and Pt-based alloys were made up likewise.
  • the parts to be fused had to be clean, free from oils, greases and surface oxides. They needed to be assembled so that they fitted tightly together and they were then heated to a temperature below the melting point of the parent metals, held at that temperature for a period then removed and cooled.

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

Abstract

Des compositions d'alliage contenant un métal précieux présentant une bonne fusibilité ainsi que des propriétés d'aptitude au façonnage et de couleur satisfaisantes comprennent : (i) au moins un métal précieux sélectionné parmi l'or (au), le platine (Pt) et le palladium (Pd) ; et (ii) une quantité favorisant la fusibilité d'un composant d'alliage de cuivre comprenant: (iia) du cuivre et (iib) du germanium, le solde étant composé d'un ou plusieurs composants adjuvants facultatifs et/ou d'impuretés.
PCT/GB2015/051765 2014-06-16 2015-06-16 Compositions d'alliage WO2015193659A2 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB201410727A GB201410727D0 (en) 2014-06-16 2014-06-16 Alloy compositions
GB1410727.0 2014-06-16
GB201503439A GB201503439D0 (en) 2015-02-27 2015-02-27 Alloy compositions
GB1503439.0 2015-02-27

Publications (2)

Publication Number Publication Date
WO2015193659A2 true WO2015193659A2 (fr) 2015-12-23
WO2015193659A3 WO2015193659A3 (fr) 2016-02-25

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2697142C1 (ru) * 2018-12-05 2019-08-12 Федеральное государственное автономное образовательное учреждение высшего образования "Сибирский федеральный университет" Сплав белого цвета на основе золота 585 пробы
EP3783124A1 (fr) * 2019-08-23 2021-02-24 Omega SA Piece d'horlogerie, de bijouterie ou de joaillerie en or
RU2751061C1 (ru) * 2020-11-26 2021-07-07 Федеральное государственное автономное образовательное учреждение высшего образования "Сибирский федеральный университет" Сплав на основе платины 585 пробы
EP4198157A1 (fr) * 2021-12-14 2023-06-21 Nivarox-FAR S.A. Alliage de platine

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GB2283934A (en) 1993-11-18 1995-05-24 Univ Middlesex Serv Ltd Diffusion bonding process using silver/germanium alloys and a silver germanium alloy for use in the method

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GB2283934A (en) 1993-11-18 1995-05-24 Univ Middlesex Serv Ltd Diffusion bonding process using silver/germanium alloys and a silver germanium alloy for use in the method
GB2283934B (en) 1993-11-18 1996-04-24 Univ Middlesex Serv Ltd A silver/germanium alloy

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CORTI, CHRISTPHER W.: "The Santa Fe Symposium on Jewelry Manufacturing Technology", PROCEEDINGS OF THE SANTA FE SYMPOSIUM IN ALBUQUERQUE, May 2005 (2005-05-01), pages 103 - 119
MACCORMACK, I BRUCE; BOWERS, JOHN E.: "New White Gold Alloys", GOLD BULL., vol. 14, no. 1, 1981, pages 19 - 24, XP009017359
NORMANDEAU; GREG: "White Golds: A Review of Commercial Material Characteristics & Alloy Design Alternatives", GOLD BULL., vol. 25, no. 3, 1992, pages 94 103

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2697142C1 (ru) * 2018-12-05 2019-08-12 Федеральное государственное автономное образовательное учреждение высшего образования "Сибирский федеральный университет" Сплав белого цвета на основе золота 585 пробы
EP3783124A1 (fr) * 2019-08-23 2021-02-24 Omega SA Piece d'horlogerie, de bijouterie ou de joaillerie en or
US11441210B2 (en) 2019-08-23 2022-09-13 Omega Sa Timepiece or piece of jewellery or gemstone jewellery made of gold
RU2751061C1 (ru) * 2020-11-26 2021-07-07 Федеральное государственное автономное образовательное учреждение высшего образования "Сибирский федеральный университет" Сплав на основе платины 585 пробы
EP4198157A1 (fr) * 2021-12-14 2023-06-21 Nivarox-FAR S.A. Alliage de platine
US11702722B2 (en) 2021-12-14 2023-07-18 Nivarox-Far S.A. Platinum alloy
JP7429757B2 (ja) 2021-12-14 2024-02-08 ニヴァロックス－ファー ソシエテ アノニム 白金合金

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