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WO 2012/125516 A2 20 September 2012 (20.09.2012) P O P C T

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WO 2012/125516 A2 20 September 2012 (20.09.2012) P O P C T (12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (10) International Publication Number (43) International Publication Date WO 2012/125516 A2 20 September 2012 (20.09.2012) P O P C T (51) International Patent Classification: (81) Designated States (unless otherwise indicated, for every C22C 5/06 (2006.01) kind of national protection available): AE, AG, AL, AM, AO, AT, AU, AZ, BA, BB, BG, BH, BR, BW, BY, BZ, (21) International Application Number: CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, DO, PCT/US20 12/028676 DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, HN, (22) International Filing Date: HR, HU, ID, IL, IN, IS, JP, KE, KG, KM, KN, KP, KR, 11 March 2012 ( 11.03.2012) KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD, ME, MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ, (25) Filing Language: English OM, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SC, SD, (26) Publication Language: English SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW. (30) Priority Data: 61/45 1,760 11 March 201 1 ( 11.03.201 1) US (84) Designated States (unless otherwise indicated, for every kind of regional protection available): ARIPO (BW, GH, (71) Applicant (for all designated States except US): KF LI¬ GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, SZ, TZ, CENSING, INC. [US/US]; 159 Myrtle Avenue, Millburn, UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, MD, RU, NJ 07041 (US). TJ, TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, DK, EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU, (72) Inventor; and LV, MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK, (75) Inventor/Applicant (for US only): FOGEL, Kenneth SM, TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, [—/US]; 159 Myrtle Avenue, Millburn, NJ 07041 (US). GW, ML, MR, NE, SN, TD, TG). (74) Agents: BUTCH, Peter, J. et al; Fox Rothschild LLP, Published: 997 Lenox Drive, Building 3, Lawrenceville, NJ 08648- 2311 (US). — without international search report and to be republished upon receipt of that report (Rule 48.2(g)) < o (54) Title: TARNISH-RESISTANT STERLING SILVER ALLOYS (57) Abstract: Titanium sterling silver alloy compositions that exhibit enhanced tarnish resistance while maintaining an acceptable hardness. Applications and manufacturing methods thereof are disclosed. TARNISH-RESISTANT STERLING SILVER ALLOYS CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority under 35 U.S.C. § 119(e) to U.S. Provisional Patent Application Serial No. 61/451,760, filed on March 11, 201 1, which is hereby incorporated by reference in its entirety. FIELD OF THE INVENTION The present invention relates to sterling silver alloy compositions demonstrating hardness in combination with tarnish resistance. More particularly the invention relates to alloy compositions alloying silver with titanium and optionally palladium or niobium, among other metals. BACKGROUND OF THE INVENTION Silver metal is very ductile and malleable (being only slightly harder than gold) and is the most lustrous metal on Earth. Silver's brilliant white metallic luster can take a high degree of polish making silver highly desirable in the production of jewelry and tableware. Silver's unique properties are important in the decorative arts, coinage, industry and photography, for example. Silver categorized as "fine silver" contains at least 99.5 percent pure silver. Fine silver is generally too soft for the production of large, functional objects. Although the malleability of fine silver permits it to be easily shaped into attractive forms, products made with pure soft silver are easily dented or bent out of shape. Fine silver has good tarnish resistance. In fact, the tarnish resistance of silver alloys increases as the percentage of fine silver increases, as pure silver is unreactive in clean air under normal conditions and unreactive with clean water. Because of its softness and malleability, however, fine silver is commonly combined with other metals to produce more durable products, thus increasing its susceptibility to tarnish. When fine silver is combined with other metals to form a new material, the new material is referred to as an alloy. Alloyed silver cannot be classified as sterling silver unless it consists of at least 92.5 percent fine silver, whereas the remaining 7.5 percent may be a combination of other elements in various proportions. Sterling silver alloy is the material of choice where appearance is paramount and strength is important, such as in the manufacture of jewelry, coinage, and silverware. Sterling silver sets the standard for high quality silver products. In addition to offering increased strength and durability, products made with sterling silver will not wear away, as silver plating can. The most common sterling silver alloy consists of at least 92.5 percent silver and up to 7.5 percent copper. Adding copper to silver improves hardness and durability while maintaining the beautiful color of the pure silver, and is a well-known practice in the art of silver manufacture. The difference between the softness of fine silver and the hardness of copper-sterling silver alloy is such that the practice is wide ly, if not nearly ubiquitously, used in the vast majority of sterling silver production because of the great need in the industry for material that is harder than fine silver. While the small amount of copper that is added to fine silver produces an alloy with increased hardness and durability, the presence of copper in the alloy introduces a susceptibility to color change in processing and during everyday wearing. Copper tarnishes much more readily than does silver as copper, unlike silver, has a great affinity for oxygen. When copper reacts with oxygen it may form cupric or cuprous oxide, or both. There have been some attempts at alleviating some of the aforementioned problems associated with conventional sterling silver alloys. Early attempts to provide silver alloys having tarnish resisting properties and improved workability were concerned with either silver alloys that did not contain enough silver to qualify as sterling silver or with fine silver alloys, i.e., nearly pure silver. Silver alloys contain ing less than 92.5 percent pure silver are not of interest to the jewelry making industry because this silver cannot be labeled as sterling. Conversely, fine silver is not of interest to the jewelry making industry because it is too soft and too expensive. There is an intermediate composition called Britannia Silver which is 95% silver. Granted, sterling silver is far more prolific. The jewelry industry would become interested in even finer grades of silver if it was hard enough. Thus, it is appreciated that there is still an unmet need for a sterling silver alloy that is tarnish-resistant while maintaining an acceptable hardness. SUMMARY OF THE INVENTION Accordingly, the present invention provides for a unique titanium-containing sterling silver alloy composition with a noteworthy combination of hardness and tarnish resistance. The present invention delivers these benefits and improvements by providing a sterling silver alloy containing the following parts by weight: about 92.5 to about 99.5% silver, about 0.5 to about 7.0% titanium, about 0 to about 6.5%> palladium, and about 0 to about 7.0% niobium. As is well known in the art, the percentage of silver may be varied depending upon the desired quality and/or desired properties of the alloy to be produced. That is, the proportions of the alloy components may be varied relative to each other and to the silver content depending upon the desired quality and/or desired properties of the alloy to be produced, keeping in mind that the maximum percent of non-silver elements cannot exceed 7.5 percent if the final composition is to maintain a sterling silver classification. Thus, in one aspect, the present invention provides a sterling silver alloy composition containing from about 92.5 wt% to about 99.5 wt% silver and from about 0.5 wt%> to about 7.0% wt%> titanium. Depending on desired properties, the composition of the silver alloy can be adjusted in order to have enhanced or balanced properties of hardness, color, firestain resistance and/or tarnish resistance in comparison with conventional sterling silver alloy having a composition of silver (92.5%) and copper (7.5%). Further, depending on desired properties, the titanium-containing sterling silver alloy can contain additional metal components selected from palladium, niobium, aluminum, germanium, boron, zinc, copper and zirconium. In another aspect, the present invention provides a method of making a titanium-containing sterling silver alloy, including melting a mixture of silver and titanium containing 92.5-99.5 wt% of silver and 0.5-7.5 wt% titanium until the mixture is uniformly mixed, and transferring the melt mixture into a cast or mold. Depending on the desired properties, the mixture can contain additional metal components selected from palladium, niobium, aluminum, germanium, boron, zinc, copper and zirconium. In another aspect, the present invention provides an article of manufacture made from a titanium-containing sterling silver alloy described according to any of the embodiments disclosed herein. The article of manufacture includes, but is not limited to, jewelry, silverware, tubing, electrical contacts and dental or body implants. The details of these and other aspects or embodiments of the invention are set forth in the accompanying drawings, description and claims below. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 illustrates work hardenability and heat treatability of a sterling silver containing 1.9 wt% titanium in silver.
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