US20090308102A1 - Tungsten ring composition - Google Patents

Tungsten ring composition Download PDF

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Publication number
US20090308102A1
US20090308102A1 US12/141,791 US14179108A US2009308102A1 US 20090308102 A1 US20090308102 A1 US 20090308102A1 US 14179108 A US14179108 A US 14179108A US 2009308102 A1 US2009308102 A1 US 2009308102A1
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powder mixture
article
weight
carbide
jewelry
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US12/141,791
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Glenn Miller
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Stuller Inc
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C32/00Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/001Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
    • C22C32/0015Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
    • C22C32/0031Matrix based on refractory metals, W, Mo, Nb, Hf, Ta, Zr, Ti, V or alloys thereof
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/04Making non-ferrous alloys by powder metallurgy
    • C22C1/05Mixtures of metal powder with non-metallic powder
    • C22C1/051Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00Supplementary information concerning processes or compositions relating to powder metallurgy
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10Processes characterised by the sequence of their steps
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00Aspects linked to processes or compositions used in powder metallurgy

Definitions

  • the present invention generally relates to the field of jewelry articles and specifically jewelry articles comprising tungsten.
  • a method of forming a jewelry article comprises (a) providing a powder mixture comprising tungsten and one or more of: titanium carbide, chromium carbide, nickel, molybdenum, vanadium carbide and iron, (b) placing the powder mixture in a mold and (c) applying sufficient pressure and temperature to the powder mixture to form a solid jewelry article.
  • a jewelry article comprises less than 50% by weight tungsten and balance titanium carbide, chromium carbide, nickel, molybdenum, vanadium carbide and iron.
  • FIG. 1 is a flow diagram illustrating the steps in the manufacture of a jewelry article, in accordance with one embodiment.
  • FIG. 2-3 are images of jewelry article manufacture equipments, a powder mixture and raw jewelry articles.
  • a method of forming a jewelry article comprises (a) providing a powder mixture comprising tungsten and one or more metallic and/or ceramic component(s), (b) placing the powder mixture in a mold and (c) applying sufficient pressure and temperature to the powder mixture to form a solid jewelry article.
  • the jewelry article formed according to the present embodiments comprises tungsten and one or more metallic and/or ceramic components.
  • the powder mixture comprises tungsten and one or more of: titanium carbide (TiC), chromium carbide (Cr 3 C 2 ), nickel, molybdenum, vanadium carbide (VC) and iron.
  • the powder mixture comprises tungsten, titanium carbide, chromium carbide, nickel, molybdenum, vanadium carbide and iron.
  • the weight percentage range of each component in the mixture may vary depending on the desired physical properties and/or aesthetic appearance of the jewelry article.
  • the weight percent of tungsten in the mixture is less than about 50%.
  • the tungsten weight percent is about 20-50%, and most preferably about 40-50%.
  • the powder mixture may comprise about 15-25%, preferably about 21-22% titanium carbide.
  • the chromium carbide content may be about 15-25%, preferably about 19-21%.
  • the nickel content may be about 15-25%, preferably about 22-23%.
  • molybdenum and vanadium carbide combined amount may be about 5-10%, preferably between 7-8%.
  • the iron content may be about 1-5%, preferably about 2-3%. All percent ranges described herein are by weight and include every individual value within each range.
  • the mixture comprises about 21-22% titanium carbide, about 20% chromium carbide, about 45% tungsten, about 22-23% nickel, about 7-8% molybdenum and vanadium carbide combined, and about 2-3% iron.
  • the powder mixture is prepared by milling a particle mixture of the components for a sufficient period of time to reduce the size of the mixture particles.
  • the powder mixture is prepared by combining components that are already in powder form (fine particles).
  • the mixture in addition to milling, is also subject to one or more steps of sedimentation/separation, drying and sifting.
  • a mixture comprising tungsten and one or more of titanium carbide, chromium carbide, nickel, molybdenum, vanadium carbide and iron is milled, followed by sedimentation/separation, drying and sifting steps to form a powder mixture.
  • a mixture of tungsten and one or more of titanium carbide, chromium carbide, nickel, molybdenum, vanadium carbide and iron is subjected to (a) milling (b) sedimentation/separation, (c) drying, (d) sifting and again (e) drying to form a powder mixture.
  • the powder mixture also comprises at least one rubber material.
  • the rubber assists in binding the powder particles together.
  • the rubber assist in processing and shaping the powder mixture.
  • the amount of rubber added may vary depending on the processing and shaping requirements. Examples of suitable rubbers include, but are not limited to, latex rubbers, butadiene rubbers, styrene butadiene rubbers, thermoplastic elastomers and melt processible rubbers. Of course, a combination of different types of rubbers may also be used.
  • the rubber material comprises styrene-butadiene-styrne (SBS). However, other similar polymeric materials such as styrene-isoprene-styrene may be equally useful.
  • the mixture processing step includes milling
  • the rubber material is preferably added after the milling step.
  • the weight percent of tungsten and other components in the powder mixture may differ from that in the raw jewelry article. For instance, addition of other components, such as SBS rubber, may lower the weight percent of the powder mixture components. Still, in some embodiments, the weight percent of the components in the powder mixture and jewelry article maybe about the same.
  • the particle size range is preferably small enough to allow effective sintering of said powder mixture. If needed, particle size may be reduced by running a particle mixture through a sieve, to obtain smaller particle sizes. For instance in a non-limiting example, a mixture is run through one or more sieves with mish hole diameter(s) less than 0.40 mm to obtain a powder mixture with an average particle size of about 1-2 ⁇ m.
  • the density and hardness of the formed article may vary depending on the type and amount of the components.
  • the formed jewelry article has a density between about 8-9 g/cm 3 and a HRC hardness of about 74.0 or higher.
  • the powder mixture also comprises components which impart color to the jewelry article. For instance an amount of a nitride may be added to change the color of the article.
  • the powder mixture is placed in the cavity of a mold and subjected to elevated pressures to form the raw jewelry article.
  • the mold cavity may be shaped according to any basic jewelry article design. In the preferred embodiments, the mold cavity produces an annular shaped jewelry article.
  • the formed raw jewelry article may comprise one or more facets, grooves, or notches.
  • the powder mixture is sintered (or melted) in the mold at a temperature of about 1440-1450° C.
  • the powder mixture is first heated to about 550° C. before sintering to remove the rubber contents (wax).
  • the raw jewelry article may be then subject to further processing steps, such as attaching precious metals pieces or gems to the article.
  • step 100 a mixture comprising 21.35% TiC, 20% chromium carbide, 45.87% W, 22.68% Ni, 7.54% Mo+VC and 2.18% Fe, is milled in ethanol for 72 hours.
  • step 102 the milled mixture undergoes sedimentation/separation followed by a drying step 104 at 90-100° C., 1 atm for 2.5 hours.
  • step 106 an amount of SBS rubber is then added to the powder mixture in step 108 .
  • This mixture is again sifted resulting in a powder mixture having particles sizes in the range of about 1-2 ⁇ m.
  • the first and second sifting steps are carried out using a mesh with 0.19 mm and 0.38 mm diameter holes, respectively.
  • the powder mixture is then dried in step 112 for about 1-1.5 hours and shaped in consecutive molding 114 and melting (sintering) 116 steps.
  • the melting step is carried out in a vacuum furnace by first heating the raw article (to remove the rubber) at 550° C. for 4-5 hours, then heating at 1440-1450° C. for 8-10 hours, followed by cooling for 10-12 hours.
  • the raw jewelry article is then obtained in step 118 for additional processing, as required.
  • FIGS. 2A-B depict manufacturing equipments connected with the steps shown in FIG. 1 .
  • FIG. 2A shows a milling machine 202 , sedimentation/separation equipment 204 , drying equipment 206 and 212 and adding/sifting apparatus 208 and 210 .
  • FIG. 2B shows a molding unit 216 , a vacuum furnace 218 , a powder mixture 214 as well as raw jewelry articles 220 .
  • the density of the jewelry article formed is about 8.81 g/cm 3 with an HRC hardness of about 74.0.
  • the manufacturing process described shows a 100 kg/day production capacity for powder mixture production. Also, the molding process has the capacity to handle 2500 pieces/mold in one day. Finally, the production of the raw jewelry article is about 5000 pcs/day.

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

Abstract

A method of forming a jewelry article comprises the steps of (a) providing a powder mixture comprising tungsten and one or more of: titanium carbide, chromium carbide, nickel, molybdenum, vanadium carbide and iron, (b) placing the powder mixture in a mold and (c) applying sufficient pressure and temperature to the powder mixture to form a solid jewelry article.

Description

    CROSS-REFERENCE TO RELATED APPLICATIONS
  • This application is a continuation of ______ filed on 14 Jun. 2008 in China, entitled “TUNGSTEN RING COMPOSITION”, the contents of which are incorporated by reference herein.
  • BACKGROUND
  • The present invention generally relates to the field of jewelry articles and specifically jewelry articles comprising tungsten.
  • There is a need in the jewelry industry for a durable jewelry article that comprises mainly of tungsten but is free of tungsten carbide. Furthermore, the currently available tungsten carbide articles, such as jewelry rings, typically exhibit a dark gray luster. For aesthetic purposes, it is advantageous to be able to offer jewelry articles based on tungsten with different color tints.
  • SUMMARY
  • In one embodiment, a method of forming a jewelry article comprises (a) providing a powder mixture comprising tungsten and one or more of: titanium carbide, chromium carbide, nickel, molybdenum, vanadium carbide and iron, (b) placing the powder mixture in a mold and (c) applying sufficient pressure and temperature to the powder mixture to form a solid jewelry article.
  • In another embodiment, a jewelry article comprises less than 50% by weight tungsten and balance titanium carbide, chromium carbide, nickel, molybdenum, vanadium carbide and iron.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • FIG. 1 is a flow diagram illustrating the steps in the manufacture of a jewelry article, in accordance with one embodiment.
  • FIG. 2-3 are images of jewelry article manufacture equipments, a powder mixture and raw jewelry articles.
  • DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
  • In the present embodiments, a method of forming a jewelry article comprises (a) providing a powder mixture comprising tungsten and one or more metallic and/or ceramic component(s), (b) placing the powder mixture in a mold and (c) applying sufficient pressure and temperature to the powder mixture to form a solid jewelry article. Thus, the jewelry article formed according to the present embodiments comprises tungsten and one or more metallic and/or ceramic components.
  • Powder Mixture
  • In one embodiment, the powder mixture comprises tungsten and one or more of: titanium carbide (TiC), chromium carbide (Cr3C2), nickel, molybdenum, vanadium carbide (VC) and iron. In the preferred embodiments, the powder mixture comprises tungsten, titanium carbide, chromium carbide, nickel, molybdenum, vanadium carbide and iron.
  • The weight percentage range of each component in the mixture may vary depending on the desired physical properties and/or aesthetic appearance of the jewelry article. In general, the weight percent of tungsten in the mixture is less than about 50%. Preferably, the tungsten weight percent is about 20-50%, and most preferably about 40-50%. The powder mixture may comprise about 15-25%, preferably about 21-22% titanium carbide. The chromium carbide content may be about 15-25%, preferably about 19-21%. Additionally, the nickel content may be about 15-25%, preferably about 22-23%. Further, molybdenum and vanadium carbide combined amount may be about 5-10%, preferably between 7-8%. Finally, the iron content may be about 1-5%, preferably about 2-3%. All percent ranges described herein are by weight and include every individual value within each range.
  • In a non-limiting example, the mixture comprises about 21-22% titanium carbide, about 20% chromium carbide, about 45% tungsten, about 22-23% nickel, about 7-8% molybdenum and vanadium carbide combined, and about 2-3% iron.
  • In one embodiment, the powder mixture is prepared by milling a particle mixture of the components for a sufficient period of time to reduce the size of the mixture particles. In another embodiment, the powder mixture is prepared by combining components that are already in powder form (fine particles). In a further embodiment, in addition to milling, the mixture is also subject to one or more steps of sedimentation/separation, drying and sifting.
  • In a non-limiting example, a mixture comprising tungsten and one or more of titanium carbide, chromium carbide, nickel, molybdenum, vanadium carbide and iron is milled, followed by sedimentation/separation, drying and sifting steps to form a powder mixture.
  • In another non-limiting example, a mixture of tungsten and one or more of titanium carbide, chromium carbide, nickel, molybdenum, vanadium carbide and iron, is subjected to (a) milling (b) sedimentation/separation, (c) drying, (d) sifting and again (e) drying to form a powder mixture.
  • In one embodiment, the powder mixture also comprises at least one rubber material. In one aspect, the rubber assists in binding the powder particles together. In a further aspect, the rubber assist in processing and shaping the powder mixture. Thus, the amount of rubber added may vary depending on the processing and shaping requirements. Examples of suitable rubbers include, but are not limited to, latex rubbers, butadiene rubbers, styrene butadiene rubbers, thermoplastic elastomers and melt processible rubbers. Of course, a combination of different types of rubbers may also be used. Preferably, the rubber material comprises styrene-butadiene-styrne (SBS). However, other similar polymeric materials such as styrene-isoprene-styrene may be equally useful. Where the mixture processing step includes milling, the rubber material is preferably added after the milling step.
  • In certain cases, the weight percent of tungsten and other components in the powder mixture may differ from that in the raw jewelry article. For instance, addition of other components, such as SBS rubber, may lower the weight percent of the powder mixture components. Still, in some embodiments, the weight percent of the components in the powder mixture and jewelry article maybe about the same.
  • In the powder mixture, the particle size range is preferably small enough to allow effective sintering of said powder mixture. If needed, particle size may be reduced by running a particle mixture through a sieve, to obtain smaller particle sizes. For instance in a non-limiting example, a mixture is run through one or more sieves with mish hole diameter(s) less than 0.40 mm to obtain a powder mixture with an average particle size of about 1-2 μm.
  • The density and hardness of the formed article may vary depending on the type and amount of the components. In some embodiments, the formed jewelry article has a density between about 8-9 g/cm3 and a HRC hardness of about 74.0 or higher.
  • In one embodiment, the powder mixture also comprises components which impart color to the jewelry article. For instance an amount of a nitride may be added to change the color of the article.
  • Molding/Melting (Sintering)
  • Once formed, the powder mixture is placed in the cavity of a mold and subjected to elevated pressures to form the raw jewelry article. The mold cavity may be shaped according to any basic jewelry article design. In the preferred embodiments, the mold cavity produces an annular shaped jewelry article. The formed raw jewelry article may comprise one or more facets, grooves, or notches.
  • In a non-limiting example, the powder mixture is sintered (or melted) in the mold at a temperature of about 1440-1450° C. In yet another non-limiting example, the powder mixture is first heated to about 550° C. before sintering to remove the rubber contents (wax).
  • After molding, the raw jewelry article may be then subject to further processing steps, such as attaching precious metals pieces or gems to the article.
  • The flow diagram of FIG. 1 provides a non-limiting example of manufacturing steps 100-118, for forming a jewelry article in accordance with one embodiment. Accordingly, in step 100, a mixture comprising 21.35% TiC, 20% chromium carbide, 45.87% W, 22.68% Ni, 7.54% Mo+VC and 2.18% Fe, is milled in ethanol for 72 hours. In step 102, the milled mixture undergoes sedimentation/separation followed by a drying step 104 at 90-100° C., 1 atm for 2.5 hours. Following a sifting step 106, an amount of SBS rubber is then added to the powder mixture in step 108. This mixture is again sifted resulting in a powder mixture having particles sizes in the range of about 1-2 μm. The first and second sifting steps are carried out using a mesh with 0.19 mm and 0.38 mm diameter holes, respectively. The powder mixture is then dried in step 112 for about 1-1.5 hours and shaped in consecutive molding 114 and melting (sintering) 116 steps. The melting step is carried out in a vacuum furnace by first heating the raw article (to remove the rubber) at 550° C. for 4-5 hours, then heating at 1440-1450° C. for 8-10 hours, followed by cooling for 10-12 hours. The raw jewelry article is then obtained in step 118 for additional processing, as required.
  • FIGS. 2A-B depict manufacturing equipments connected with the steps shown in FIG. 1. Specifically, FIG. 2A shows a milling machine 202, sedimentation/separation equipment 204, drying equipment 206 and 212 and adding/ sifting apparatus 208 and 210. FIG. 2B shows a molding unit 216, a vacuum furnace 218, a powder mixture 214 as well as raw jewelry articles 220. The density of the jewelry article formed is about 8.81 g/cm3 with an HRC hardness of about 74.0.
  • The manufacturing process described shows a 100 kg/day production capacity for powder mixture production. Also, the molding process has the capacity to handle 2500 pieces/mold in one day. Finally, the production of the raw jewelry article is about 5000 pcs/day.
  • Although the foregoing refers to particular preferred embodiments, it will be understood that the present invention is not so limited. It will occur to those of ordinary skill in the art that various modifications may be made to the disclosed embodiments and that such modifications are intended to be within the scope of the present invention.

Claims (20)

1. A method of forming a jewelry article comprising:
providing a powder mixture comprising tungsten and one or more of: titanium carbide,
chromium carbide, nickel, molybdenum, vanadium carbide and iron;
placing the powder mixture in a mold; and
applying sufficient pressure and temperature to the powder mixture to form a solid
jewelry article.
2. The method of claim 1, wherein powder composition comprises less than 50% tungsten by weight.
3. The method of claim 1, wherein the powder composition comprises about 21-22% titanium carbide by weight.
4. The method of claim 1, wherein the powder mixture comprises about 19-21% chromium carbide by weight.
5. The method of claim 1, wherein the powder mixture comprises about 22-23% nickel by weight.
6. The method of claim 1 wherein the powder mixture comprises about 7-8% molybdenum and vanadium carbide combined, by weight.
7. The method of claim 1, wherein the powder mixture comprises about 2-3% iron by weight.
8. The method of claim 1, wherein the mold comprises a cavity having an annular configuration.
9. The method of claim 1, further comprising the step of adding a rubber material to the powder mixture before placing said mixture in the mold.
10. The method of claim 9, wherein the rubber material comprises SBS.
11. The method of claim 10, further comprising sifting the powder mixture before adding the rubber material.
12. A jewelry article formed according to any one of claims 1 to 11.
13. A jewelry ring formed according to the method of claim 8.
14. A jewelry article comprising about 20-50% by weight tungsten and balance titanium carbide, chromium carbide, nickel, molybdenum, vanadium carbide and iron.
15. The jewelry article of claim 14, wherein said article comprises about 21-22% titanium carbide by weight.
16. The jewelry article of claim 14, wherein said article comprises about 19-21% chromium carbide by weight.
17. The jewelry article of claim 14, wherein said article comprises about 22-23% nickel by weight.
18. The jewelry article of claim 14, wherein said article comprises 7-8% molybdenum by weight.
19. The jewelry article of claim 14, wherein said article comprises 2-3% iron by weight.
20. The jewelry article of claim 14, wherein said article has a density of about 8-9 g/cm3.
US12/141,791 2008-06-13 2008-06-18 Tungsten ring composition Abandoned US20090308102A1 (en)

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CNA2008101737471A CN101602106A (en) 2008-06-13 2008-06-13 Finger ring product containing tungsten

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US20050154491A1 (en) * 2002-01-25 2005-07-14 Anderson Gregor J.M. Medicament dispenser
US8927107B2 (en) 2011-06-03 2015-01-06 Frederick Goldman, Inc. Multi-coated metallic products and methods of making the same
US8956510B2 (en) 2011-06-03 2015-02-17 Frederick Goldman, Inc. Coated metallic products and methods for making the same
WO2016186232A1 (en) * 2015-05-21 2016-11-24 최정남 Cermet alloy for jewelry and method for producing same
US9949539B2 (en) 2010-06-03 2018-04-24 Frederick Goldman, Inc. Method of making multi-coated metallic article

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CN102825250A (en) * 2011-06-15 2012-12-19 张乃文 Tungsten carbide ornament processing technique

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US4636252A (en) * 1983-05-20 1987-01-13 Mitsubishi Kinzoku Kabushiki Kaisha Method of manufacturing a high toughness cermet for use in cutting tools
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US4374900A (en) * 1978-07-04 1983-02-22 Sumitomo Electric Industry, Ltd. Composite diamond compact for a wire drawing die and a process for the production of the same
US4636252A (en) * 1983-05-20 1987-01-13 Mitsubishi Kinzoku Kabushiki Kaisha Method of manufacturing a high toughness cermet for use in cutting tools
US7076972B2 (en) * 1997-09-08 2006-07-18 Trent West Tungsten carbide-based annular jewelry article

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9636471B2 (en) 2002-01-25 2017-05-02 Glaxo Group Limited Medicament dispenser
US8511304B2 (en) * 2002-01-25 2013-08-20 Glaxo Group Limited Medicament dispenser
US20050154491A1 (en) * 2002-01-25 2005-07-14 Anderson Gregor J.M. Medicament dispenser
US11503886B2 (en) 2010-06-03 2022-11-22 Frederick Goldman, Inc. Multi-coated metallic articles
US9949539B2 (en) 2010-06-03 2018-04-24 Frederick Goldman, Inc. Method of making multi-coated metallic article
US9949538B2 (en) 2011-06-03 2018-04-24 Frederick Goldman, Inc. Multi-coated metallic products and methods of making the same
US9629425B2 (en) 2011-06-03 2017-04-25 Frederick Goldman, Inc. Coated metallic products and methods for making the same
US9034488B2 (en) 2011-06-03 2015-05-19 Frederick Goldman, Inc. Coated metallic products and methods for making the same
US8956510B2 (en) 2011-06-03 2015-02-17 Frederick Goldman, Inc. Coated metallic products and methods for making the same
US8932437B2 (en) 2011-06-03 2015-01-13 Frederick Goldman, Inc. Multi-coated metallic products and methods of making the same
US11234500B2 (en) 2011-06-03 2022-02-01 Frederick Goldman, Inc. Multi-coated metallic products and methods of making the same
US8927107B2 (en) 2011-06-03 2015-01-06 Frederick Goldman, Inc. Multi-coated metallic products and methods of making the same
WO2016186232A1 (en) * 2015-05-21 2016-11-24 최정남 Cermet alloy for jewelry and method for producing same

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CA2668794A1 (en) 2009-12-13

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