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WO2015183990A2 - Alliages à base de titane et articles formés à partir de ces alliages - Google Patents

Alliages à base de titane et articles formés à partir de ces alliages Download PDF

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Publication number
WO2015183990A2
WO2015183990A2 PCT/US2015/032723 US2015032723W WO2015183990A2 WO 2015183990 A2 WO2015183990 A2 WO 2015183990A2 US 2015032723 W US2015032723 W US 2015032723W WO 2015183990 A2 WO2015183990 A2 WO 2015183990A2
Authority
WO
WIPO (PCT)
Prior art keywords
article
alloy
jewelry
titanium
articles
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.)
Ceased
Application number
PCT/US2015/032723
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English (en)
Other versions
WO2015183990A3 (fr
Inventor
Andrew Derrig
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.)
FREDERICK GOLDMAN Inc
Original Assignee
FREDERICK GOLDMAN Inc
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 FREDERICK GOLDMAN Inc filed Critical FREDERICK GOLDMAN Inc
Publication of WO2015183990A2 publication Critical patent/WO2015183990A2/fr
Publication of WO2015183990A3 publication Critical patent/WO2015183990A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • A—HUMAN NECESSITIES
    • A44—HABERDASHERY; JEWELLERY
    • A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
    • A44C27/00—Making jewellery or other personal adornments
    • A44C27/001—Materials for manufacturing jewellery
    • A44C27/002—Metallic materials
    • A44C27/003—Metallic alloys
    • A—HUMAN NECESSITIES
    • A44—HABERDASHERY; JEWELLERY
    • A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
    • A44C9/00—Finger-rings
    • 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
    • G—PHYSICS
    • G04—HOROLOGY
    • G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
    • G04B37/00—Cases
    • G04B37/22—Materials or processes of manufacturing pocket watch or wrist watch cases
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/04—Alloys based on tungsten or molybdenum

Definitions

  • the present application generally relates to compositions of matter and articles of manufacture, such as jewelry items.
  • Jewelry such as finger rings, pendants, bracelets, and necklaces have traditionally been made of soft metals such as gold, silver and platinum because those metals are malleable, and easily formed by casting, forging and molding.
  • jewelry items have been formed from harder materials such as alloys or composites such as "cermets.”
  • An alloy is a mixture or metallic solid solution composed of two or more elements.
  • a cermet is a composite material composed of a ceramic and metallic material.
  • a metal is used as a binder for an oxide, boride, nitride, or carbide.
  • Some specific attempts to form jewelry from these types of materials include alloys or composites having titanium, zirconium (U.S. Patent 3,669,695), titanium-niobium-zirconium (U.S. Patent 6,759,134) and tungsten carbide (U.S. Patents 6,553,667; 6,990,736; 6,993,842; 7,032,314; 7,076,972).
  • Such jewelry is much more resistant to scratching and other damage than traditional jewelry made of softer metals.
  • certain alloys containing these metals, prepared under certain conditions have an attractive dark grey or black color. See, e.g., U.S.
  • Patent 6,759,134 describing articles made from an alloy of 51 -70 weight-percent (wt%) titanium, 3-17% niobium, and the balance zirconium, tantalum, molybdenum, hafnium zirconium, chromium, or mixtures thereof, having a black surface layer of a niobium oxide.
  • articles made from certain titanium-based alloys such as, for example, alloys having about 35 % to about 55 % Ti, among other constituents, which will be described in further detail herein, advantageously, according to certain embodiments, possess a unique combination of desirable features.
  • alloys formed according to the principles of the present invention possess desirable coloration, hardness and density properties which makes them particularly attractive for use in forming certain articles, such as articles of jewelry.
  • an article comprising a titanium-based alloy having about 35 wt.% to about 55 wt.% titanium, the article having a hardness of about 1300 HV or greater, and a coloration characterized by an "L" value of about 56 to about 60, an "a” value of about 1 .0 to about 1 .5, and a "b" value of about 3.7 to about 3.8, wherein the L, a, and b values are color values according to the CIE L * a * b * color scale.
  • An article formed according to the principles of the present invention may further possess a density of about 6.0 to about 6.35 g/cm3.
  • the remainder of the alloy composition may have one or more of: Si, Ta, Al, Mn, Nb, Zr and O.
  • the article of can be in the form of an item of jewelry.
  • the article may be in the form of a ring, a pendant, a dog tag, a hairclip, a chain, a watchcase, a pin, a bracelet, a necklace, an earring or a charm.
  • the article may be in the form of a finger ring.
  • the article may include at least one of a precious metal, a stone, a gemstone, a crystal, or another material suitable for use in jewelry affixed to the article.
  • the article may be in the form of a finger ring, and my have at least one depression that extends into, and at least substantially around the circumference of, an outer surface of the finger ring, wherein the depression is substantially filled with a material, such as metal, or a precious metal.
  • the present invention may address one or more of the problems and deficiencies of the prior art discussed above. However, it is contemplated that the invention may prove useful in addressing other problems and deficiencies, or provide benefits and advantages, in a number of technical areas. Therefore the claimed invention should not necessarily be construed as being limited to addressing any of the particular problems or deficiencies discussed herein.
  • FIG. 1 is a perspective view of a plain band-like finger ring in accordance with an illustrative embodiment.
  • FIGS. 2A-2B are perspective views of finger rings that were machined in accordance with an alternate illustrative embodiments.
  • FIG. 3 is a view of a finger ring that has been decoratively machined in accordance with another alternate illustrative embodiment.
  • FIG. 4 is a view of a finger ring with a diamond inset. DETAILED DESCRIPTION
  • ICP-MS is a type of mass spectrometry capable of accurately measuring metals and non-metals at very low concentrations.
  • the sample is ionized by inductively coupled plasma and then the ions are separated and quantified by a mass spectrometer. This technique is familiar to those skilled in the art.
  • HV hardness number values described herein refer to the hardness value measured according to the Vickers hardness test, performed according to the ASTM:E384-1 1 81 standard (last revised March 2012).
  • L refers to the color values measured according to the CIE 1976 (L * , a * , b * ) color space (or CIELAB) scale. These values disclosed herein were measured by a Konica Minolta Spectrophotometer model CM- 600.
  • All of the stated compositions and methods disclosed herein are to be construed as “comprising,” “consisting essentially of,” and “consisting of” the stated constituents and method steps.
  • Articles formed according to the principles of the present invention are formed, at least in part, from a particular alloy composition.
  • the alloy composition is titanium-based. According to further embodiments, the alloy composition is titanium-based.
  • the alloy composition further includes, in addition to titanium, one or more of tungsten, nickel, chromium, carbon, molybdenum and/or copper.
  • the alloy composition is selected from a combination of one or more, or all, elements listed in the table below, in any of the amounts described in the Table.
  • the alloy composition may include about 35 - 55 wt.% of Ti. Amounts of Ti below this threshold are not preferred because depending on which materials are used to replace Ti, the weight of the composition could increase, the hardness of the composition could decrease, the coloration may be modified in an unfavorable manner, and less than optimal or unfavored optical properties such as reflectivity, and other undesired changes to the composition may result. Compositions that include Ti in amounts beyond the upper limit of this range are not preferred because , depending on which materials replace Ti in the composition, the alloy could exhibit increased brittleness, undesirable modification coloration, reduced machine ability, and unfavorable changes in optical properties such as reflectivity, and/or other undesired changes to the properties of composition.
  • the alloy composition may include no more than about 60 wt. % W. According to further embodiments, the alloy contains no more than about 20% wt.% W. According to further optional embodiments, the alloy composition includes at least about 10 wt. % W.
  • the alloy composition may include about 5 to about 20 wt.% Ni.
  • Compositions that include Ni in amounts below the minimum value of this range are not preferred because such compositions tend to exhibit increased hardness of the solid solution elements, and resulting increases in brittleness.
  • Compositions that include Ni in amounts above the maximum value of this range are not preferred because such compositions exhibit a decrease in hardness of the alloy which in turn will decrease the hardness, where resistance, corrosion resistance, as well as increase the risk of allergic reaction based on the EN181 1/201 1 standard.
  • the alloy composition may include no more than about 2 wt.% Cr. Amounts of Cr above this level are not preferred because such
  • the alloy composition includes about 0 to about 5 wt.% Cr. Compositions that include Cr in amounts below the lower limit of this range are not preferred because such
  • compositions exhibit undesirable changes in coloration, optical properties such as reflectivity, hardness, and ductility.
  • the alloy composition may include about 10 wt.% or greater C. Amounts of C below this threshold are not preferred because enough carbon should be present such that it can form carbides with W and Ti in solid solution.
  • the alloy composition includes about 8 to about 20 wt.% C. Compositions that include C in amounts beyond the upper limit of this range are not preferred because compositions having carbon in such amounts form excess carbides which in turn result in increased brittleness of sintered parts and cause unwanted binding or carbonization with other free elements.
  • the alloy composition may include about 6.5 wt.% or greater Mo. Amounts of Mo below this threshold are not preferred because unfavorable changes in ductility, coloration and reflectivity of the composition may result.
  • the alloy composition includes about 3 to about 10 wt.% Mo.
  • Compositions that include Mo in amounts beyond the upper limit of this range are not preferred because substantial changes in ductility, coloration, composition and reflectivity may occur.
  • a substantial increase in ductility will make the finished parts, such as parts in the form of a finger ring, difficult to remove by breaking in a vice in the event of an emergency, thus necessitating the use of more dangerous and less favorable means (e.g., wet cutting using a circular diamond grinding wheel) in order to break the ring and remove it from the finger if necessary.
  • the alloy composition may include about 0.5 to about 2.0 wt.% Cu.
  • Compositions that include Cu in amounts below the minimum value of this range are not preferred because property such as ductility, fusion temperature and coloration may be impacted in an adverse manner.
  • Compositions that include Cu in amounts above the maximum value of this range are not preferred because such compositions increase the potential peroxidation breakdown of the metal matrix, thereby decreasing the where resistance and lifespan of finished articles such as jewelry pieces.
  • Alloy compositions formed according to the principles of the present invention may include, in addition to the above-described elements, one or more of the following constituent elements, in relatively minor amounts: Si, Ta, Al, Mn, Nb, Zr, and/or O.
  • Alloy compositions formed according to further embodiments of the present invention preferably do not include cobalt (Co) or iron (Fe). More specifically, neither Co nor Fe are intentionally added as constituent components of the alloy composition. However, trace amounts of these elements may be found in compositions formed according to the present invention. For example, modern steelmaking
  • article formed from an alloy according to the principles of the present invention possesses the following:
  • the entire article is made from the alloy.
  • only a portion of the article is made from the alloy.
  • the decorative portion of a pin can be made from the alloy and the rest of the pin can be made from standard materials.
  • the alloy can comprise the majority of the ring, except for an inlaid gemstone, or an inlay in an annular groove formed in the alloy, e.g., as illustrated in relation to rings made from tungsten carbide in U.S. Patent 7,076,972.
  • Those rings have at least one depression that extends into, and at least substantially around the circumference of, an outer surface of the finger ring. In some embodiments, the depression in those rings is substantially filled with a precious metal.
  • the alloy can comprise a minority of the article, for example as a portion of a sculpture primarily made of other materials, or as a contrasting band in a ring made primarily from another metal such as gold or silver.
  • the article is a decorative or artistic item, for example, a sculpture, a portion of a picture frame, a paperweight, a portion of a piece of furniture ⁇ e.g., an inlay), or jewelry.
  • Nonlimiting examples of jewelry that can be made from the Ti-based alloy are rings ⁇ e.g., finger rings, toe rings, nose rings), pendants, tags, dog tags, hairclips, chains, watchcases, pins, bracelets, anklets, necklaces, earrings and charms.
  • the item of jewelry comprising the alloy can further comprise any other material used in jewelry affixed or integrated into the item.
  • examples include a precious metal ⁇ e.g., gold, silver, platinum) either as part of the alloy or affixed to the item, a stone, a gemstone, a crystal, or any other material suitable for use in jewelry affixed to the item.
  • the item of jewelry is a finger ring.
  • the ring can be made entirely of the alloy, or the ring can further comprise other materials, for example an inlaid gemstone, or an inlay in an annular groove formed in the alloy.
  • FIGS. 1 -4 Illustrative examples of finger rings are provided in FIGS. 1 -4.
  • FIG. 1 shows a plain band-like ring made from the Ti-based alloy described herein.
  • FIGS. 2A-2B show other examples of finger rings made from the Ti-based alloy. These rings were machined after preparation.
  • FIG. 3 shows an additional example of a finger ring made from the Ti- based alloy that has a decorative pattern machined therein.
  • FIG. 4 illustrates a ring having a diamond set therein as a further example of a finger ring made from the Ti- based alloy.
  • the articles provided here can be made by any method known. In some embodiments, an ingot, bar, sheet or other form of the alloy is provided, followed by cutting, shaping and polishing the ingot or bar to form a piece having a desired shape, then optionally polishing the piece with a finish polish.
  • a "blank" of the article can then be cut from the bar or sheet, for example using wire electric discharge machining (EDM). Any internal areas that need to be hollowed out of the blank ⁇ e.g., the center portion of a ring) can be removed, e.g., using a sink EDM.
  • EDM wire electric discharge machining
  • a CNC lathe can then be used to prepare the outer shape of the article, followed by polishing. At this point, any inlays, setting or engraving can be performed.
  • a CNC lathe, followed by an inner polish can be used at this point.
  • the article can be subjected to one or more heat treatment(s), followed by final polishing followed and any additional engraving desired, for example using a CNC lathe or CNC engraving.
  • articles having any of the compositions described herein can be formed by a powder metallurgy process, wherein the above-described constituent components are blended in powder form, then pressed or injected to form a blank.
  • the constituents described herein may be provided in their elemental powdered form.
  • the powders may themselves be combinations of different metals or constituent components.
  • the blank may approximate the final shape or form of the article. This is often referred to as "near-net-shape.” The blank can them be
  • the result of the sintering is a dense object possessing the desired coloration, etc.
  • One non-limiting example of a possible powder metallurgy based formation technique is Hot Isostatic Pressing (HIP).
  • An article, such as any of the articles of jewelry described herein, formed at least in part from cermet can be produced by any suitable technique that results in a dense object having the desired physical properties as well as the desired coloration.
  • suitable methods may comprise combining the constituent elements in powder form, pressing or injecting the powders to form a blank or near net-shape object, and sintering to consolidate the blank or object and provide a grey/dark grey/black appearance.
  • Examples of specific techniques for pressing, injecting, molding and sintering to form a final article, such as an article of jewelry have been previously described above in connection with powder metallurgical techniques. These techniques can also be used to form articles, such as articles of jewelry, and are incorporated herein by reference.
  • the methods or techniques described in the United States Patent Application Publication No. US 2012-0304694 may be used, the content of which is incorporated herein by reference in its entirety.
  • Articles formed according to the principles of the present invention, including the articles of jewelry described herein, may have one or more advantageous properties and/or characteristics.
  • articles formed according to the principles of the present invention possess a Vickers hardness number (HV) of about 900HV, 1200HV, 1300HV or greater, according to one specific, illustrative, and non- limiting example, an article formed according to the principles of the present invention possesses an HV value of about 1350HV, or greater than 1350HV.
  • HV Vickers hardness number
  • an article formed according to the principles of the present invention possesses a coloration characterized by a range of L, a, and b values. More specifically, articles formed according to the principles of the present invention possess a "L" value of about 57 to about 59. According to further embodiments, the articles further possess an "a" value of about 1 .0 to about 1 .5. According to additional embodiments, the articles further possess a "b" value of about 3.7 to about 3.8. According to one illustrative, non-limiting example, an article formed according to the principles of the present invention
  • articles can be formed which possess a favorable density property. More specifically, articles formed according to the principles of the present invention may possess density values of about 6.0 to about 6.35 g/cm 3 . According to one specific, illustrative, and non-limiting example, an article formed according to the principle the present invention possesses a density value of about 6.2 g/cm 3 .
  • compositions formed according to the principles of the present invention are utilized to produce articles of jewelry to be worn on the body, another important property is the ability of such articles formed thereby to be removed from the body in the event of an emergency.
  • the compositions formulated according to the principles of the present invention have been designed to serve the need of a lightweight scratch resistant product, yet still have the ability to be removed by conventional techniques involving applying pressure to the article jewelry in a vice-like handheld or stationary tool.
  • a welding laser can be used to weaken the structure of the article jewelry. When such a welding laser is used, cool and should be used in conjunction with a moderately applied laser contact. Once the surface of the ring has been compromised, it can be more easily fractured and removed.
  • Appropriate settings for such an industrial welding laser may include: voltage (220 V-240 V), cycle (5-5.5 Hz), and application time (3.25-3.5 milliseconds).
  • compositions formulated according to the principles of the present invention have been designed so as to facilitate laser engraving of decorative patterns thereon, and the like.
  • Appropriate laser settings can be determined by those skilled in the art. According to certain illustrative and nonlimiting examples, appropriate laser settings may include: power (19.8 W), cycle speed (7000 Hz), rotation speed (100 mm/s). A desirable depth of cut can be achieved to render an aesthetically pleasing design.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Adornments (AREA)

Abstract

La présente invention concerne un article ou des articles formés, au moins en partie, par un alliage à base de titane comportant environ 35 à environ 55 % en poids ou plus du titane. Le ou les articles présentent une dureté d'environ 1 350 HV ou plus, et une coloration caractérisée par une valeur L d'environ 56,00 à environ 60,00, une valeur a d'environ 1,0 à environ 1,5, et une valeur b d'environ 3,65 à environ 3,75, les valeurs L, a, et b étant des valeurs de couleurs en fonction de la gamme de couleurs CIE L*a*b*.
PCT/US2015/032723 2014-05-27 2015-05-27 Alliages à base de titane et articles formés à partir de ces alliages Ceased WO2015183990A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201462003514P 2014-05-27 2014-05-27
US62/003,514 2014-05-27

Publications (2)

Publication Number Publication Date
WO2015183990A2 true WO2015183990A2 (fr) 2015-12-03
WO2015183990A3 WO2015183990A3 (fr) 2016-03-31

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WO (1) WO2015183990A2 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105522137B (zh) * 2014-10-24 2018-09-11 比亚迪股份有限公司 一种金属陶瓷复合体及其制备方法
USD793896S1 (en) * 2014-12-21 2017-08-08 John William Reed, Jr. Jewelry ring
US20190150576A1 (en) * 2016-05-31 2019-05-23 Crown Ring Inc. Ring assembly, and corresponding kit and method for assembling the same
CN109789028B (zh) * 2016-09-30 2022-01-14 株式会社中目 矫正器具
US10653215B2 (en) 2017-04-05 2020-05-19 Tough Love Rings, LLC Ergonomic silicone wedding ring

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69216156T2 (de) * 1991-06-27 1997-07-03 Kyocera Corp Goldfarbige gesinterte Legierung
DE69419310T2 (de) * 1993-12-28 1999-12-16 Citizen Watch Co., Ltd. Weisses dekoratives teil und verfahren zu dessen herstellung
EP2338373B1 (fr) * 2001-12-28 2014-09-17 Citizen Holdings Co., Ltd. Article décoratif doté d'une couche blanche et son procédé de fabrication
US7140567B1 (en) * 2003-03-11 2006-11-28 Primet Precision Materials, Inc. Multi-carbide material manufacture and use as grinding media
DE10329552B4 (de) * 2003-06-30 2011-03-17 Meyer, Lothar W., Prof. Dr.-Ing. Verfahren zur Herstellung von Durchdringungs-Verbundwerkstoffen
TW201127248A (en) * 2010-01-19 2011-08-01 Hon Hai Prec Ind Co Ltd Casing having color and the related surface-treating method
TW201127253A (en) * 2010-01-19 2011-08-01 Hon Hai Prec Ind Co Ltd Casing having color and the related surface-treating method
EP2568055B1 (fr) * 2011-03-07 2016-11-02 Sumitomo Electric Hardmetal Corp. Matériau pour élément décoratif
US8932437B2 (en) * 2011-06-03 2015-01-13 Frederick Goldman, Inc. Multi-coated metallic products and methods of making the same

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Publication number Publication date
US20150344993A1 (en) 2015-12-03
WO2015183990A3 (fr) 2016-03-31

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