US3769006A - Bright cast alloy, and composition - Google Patents

Bright cast alloy, and composition Download PDF

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Publication number
US3769006A
US3769006A US00221432A US3769006DA US3769006A US 3769006 A US3769006 A US 3769006A US 00221432 A US00221432 A US 00221432A US 3769006D A US3769006D A US 3769006DA US 3769006 A US3769006 A US 3769006A
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United States
Prior art keywords
percent
gold
lustrous
casting
alloy
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Expired - Lifetime
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US00221432A
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English (en)
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C Ingersoll
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GOLD REFINING W CO
GOLD REFINING W CO US
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GOLD REFINING W CO
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    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/84—Preparations for artificial teeth, for filling teeth or for capping teeth comprising metals or alloys
    • A61K6/844—Noble metals

Definitions

  • the present invention is directed to the prevention-of the forming of oxide coatingsduring casting of goldalloys. More particularly the presentlinventionis directed to the use of aluminum and/or silicon in'dental and jewelry gold alloys wherein copper, iron, tin, indium or tinlindium mixtures are utilized as-the hardening metal. Even further, in the present invention, a minor amount of silicon and/or aluminum is incorporated in the casting composition to provide for a glass-like coating on the surface of the cast product adjacent themold.
  • the usual hardening element is copper.
  • in'some casesiron, tin, indium, or tin/indium mixtures are used as the hardening element.
  • some of the alloy is partially oxidized during meltingaand casting procedures.
  • at leastsome of the hardening component is oxidized. .
  • the formation of e.q. copper oxide. produces a black deposit on the surface of the resulting casting which must be removed by e.g., pickling acid, grinding or sandblasting. After removal of the oxide coating, the dull finish-must then be polished in order to obtain a metallic luster on the product.
  • U.S. Pat. No. 3,613,209 utilizes an oxidationinhibitingametal, inert' gas, and injection molding to produce a gold alloy which doesnot have an oxide coating after molding.
  • the above process requires complexand expensive operations such as injection molding under high pressure and the use of inert gas around the melted alloy.
  • One standard method :of minimizingoxide content in cast metal is to add to the melt, an element which has an higher oxidation potential than the element to be protected from oxidation. This is called de-oxidation of the melt and the oxide primarily ends in slag on the surface of the melt. This slag is made-up of deliberately oxidized metals, accidentally oxidized metals and slagforming fluxes.
  • dex-oxidation is utilized by the inclusion of, for example zinc and/or indium in noble metal alloys, there. isadecrease in the oxide content of the cast alloy but the surface oxide is .still present unless the amount of additive utilized is so great as to alter the propertiesof the alloys drastically. Thus, the surface oxidemust still be removed prior to polishing.
  • the present invention has as one of its objects the protection of the cast piece from surface oxidation during the important period of solidification'and cooling of the alloy in the investment mold.
  • Another object of the present invention is to minimize still further the inclusion and and/or solution of copper oxide in the melt.
  • a still further object is to minimize the loss of copper or other hardening elements during. the melting and casting of the product.
  • the present invention has a further object the provision of a simple process which allows for the substantial, if not complete, elimination of the oxide coating on the surface of the cast product.
  • the present invention has as its object the production of an alloy which, as cast, has a lustrous gold finish which may be utilized without polishing.
  • a gold alloy containing for example, up to 50 percent copper or other hardening elements is, in'the'melt form, provided with an amount of silicon and/or aluminum to provide for a surface coating on the finally cast product.
  • Casting is done for example, by the lost wax process and an investment mold and then the product is cooled and removed.
  • the resulting product has a glass-like surface coating which is lustrous in character.
  • an alloy containing a hardening element preferably an element such as up to 50 percent by weight copper, most preferably more than about 5 percent copper, as well as other known additivessuch' as silver, zinc, etc. and has provided additionally, silicon and/or aluminum in an' amount sufficient to produce the lustrous cast product of the present invention.
  • the amount of aluminum and/or silicon required varies with the surface area of the mold. For example, when a spherical type mold or a tooth is molded, a smaller surface area is present than for example, when a grid structure is molded. Thus, more of the additive of the present invention is required to produce the lustrous finish of the present invention on a grid structure. However, generally from about 0.01 to about 2 percent by weight based on the total alloy content of aluminum, silicon or both'should be provided, preferably from about 0.04 to about 0.5 percent by weight is provided.
  • the preferred group includes copper, iron,
  • tin, indium, and mixtures of tin and indium When copper is utilized it may be present in amounts up to 50 percent by weight of the alloy, preferably above about 5 percent by weight. When iron is utilized it should be present in amounts up' toabo'ut'l percent by weight, preferably from about-0.25 percent to 0.75 percent by weight. When tin and/or indium are utilized the total amount of hardener," either-separately if one is used or combined if both are used, should be up to 7 percent by weight, preferably about 3 percent to 6 percent by weight.
  • Silber is the most common in alloys and is often present in amounts of up to about 30 percent by weight, preferably about 5 percent to 25 percent by weight when present.
  • the aluminum or silicon may be added to the melt or to a mixture of the metals as they are being melted in either the pure form, or as master alloys, e.g., alloyed with silver.
  • the alloy of the present invention may also be provided in e.g., bar form, having been previously cast and if needed rolled. In this case the original casting provides the coating, and the subsequent casting also provides a coating. In any case when a master alloy is utilized, the time of addition of the master alloy is not important. All of the components for the desired product alloy can be placed in e.g., a crucible or other heating means and melted, they may be melted singularly and mixed or melted in one crucible in any serial order. However, when aluminum and/or silicon is added in its unalloyed form, it is preferred that the silicon and/or aluminum be added last.
  • the alloy melt is then cast by normal procedures, e.g., pouring into a wax investment mold and cooling by standard procdures.
  • the temperature of the melt depends upon the alloy composition and is the same as standard conditions. Generally, however, temperatures from about l500 to about 2500F., preferably about 1650F to about 2200F are used.
  • the mold is held at standard temperatures during the period prior to casting, usually about 900F. to about l600F., preferably about 1 lOF to l500F. However, it should be noted that more of the additive of the present invention is required as the mold temperature is increased.
  • normal procedures are again followed.
  • the mold may be air cooled, quenched or even air cooled to some extent and then quenched.
  • exemplary alloys for dental uses in accord with the present invention are those containing from about 9 to 18 percent copper, as is standard in the art.
  • the wide variations standard in casting gold alloys for jewelry are possible. That is, normal jewelery alloys will contain from about 92 percent down to about 60 percent gold or lower, although other variations may be possible.
  • 18K gold contains about 75 percent gold and 10 to 20 percent silver in combination with to 15 percent copper, while a 14K dental gold contains normally 63 percent gold, 30 percent silver and 12 percent copper.
  • the process of the present invention is not dependent upon the various alloy compositions in order to obtain the product of the present invention, but the criticality of the present invention is the provision of sufficient silicon and/or aluminum to produce the glass-like coating on the surface of the molded product and thus produce the lustrous product.
  • the deoxidants such as zinc, magnesium, barium, may be used.
  • the glass-like surface coating is produced. Microscopic studies, utilizing a scanning electron microscope, have shown that there is a glassy coating on the surface of the cast product in the area in contact with the mold. Further, the surface is not oxidized, but if it is ground or otherwise abraded to remove the surface coat and then subjected to oxidizing conditions,
  • the glass-like nature of the coating appears to be the best way of describing it, although at the present time its actual character is not known. However, it appears that it may be some form of a silicon or aluminum containing material. If the silicon or aluminum is oxidized as the oxidation potential would indicate, silica or alumina would be produced. However, these compounds melt at above 2675F. and 3650F. respectively depending upon their structure and thus it would appear that no liquid form of the silica or alumina would be produced. However, a glasslike coating could be formed at the time of the oxidation reaction. Further, some form of Eutectic may be formed. Therefore, the exact nature of the coating is not clear but it is clear from the experimental results hereinafter disclosed that significant improvements occur by the addition of the present additives in the amounts discussed and that a coating of some nature which is not subject to oxidation is produced.
  • Example II A dental alloy containing 9 percent by weight copper, 12 percent by weight silver and 4 percent by weight palladium was cast after adding 0.02 percent lithium to the melt by pouring it into an investment mold wherein the mold temperature was llO0F. The resulting cast piece had no black copper oxide on its surface; but had no metallic luster.
  • EXAMPLE III A dental alloy alloy containing 9.5 percent by weight copper (as the alloy of'Example I) and 0.64 percent by weight titanium was melted and cast as in Example 11. The surface in contact with air during the solidification and cooling was blue-black, whilethe' surface'in contact with the investment during the solidification and cooling was gold in color but has no metallic luster.
  • EXAMPLE IV An alloy of the same composition as in Example III, except that 0.16 percent tantalum was substituted for the titanium, was cast in the same manner as Example III and the results were the same;
  • EXAMPLE V Three casting melts with the 9.5 percent copper alloy as in Example I, but with 0.04, 0.08, and 0.228 percent by weight, barium were prepared and cast. In all three cases the resulting alloy product had a gold color in the area in contact with the investment, but no luster.
  • EXAMPLE VII Numerous castings, as set forth'in the table below, were prepared with the results as listed; the castings containing 9 percent and 9.5 percent copper are the same as above except for the aluminum or silicon content, while 18 percent copper casting also contains, 13 percent silver and percent palladium, the remainder being gold.
  • the resulting casting was lustrous in the area in contact with the mold as well as the area in contact with air. Further, it appears that in addition to being lustrous the castings of the present inventionare more easily recovered from the investment mold. That is, there, appears to be no adhesion between the mold and the metal and thus the recovery is quite simple. This is possibly due to the lack of wetting of the investment by the molten alloy, although the reasons are not clear'at the present time.
  • EXAMPLE VlII An 18 percent copper containing metal alloy, as in Example VII, was cast with five different aluminumsilicon contents. Thecontents of the five different examples are set forth below.
  • EXAMPLE IX In gold basedental alloys containing, in addition to thegold, 3 percent palladium, 8 percent platinum, less than 1 percent indium and tin, and 0.25 percent by weight iron as the hardening agent, normally a dark oxide coating is formed when the lost wax process is utilized for casting. ,In accord with the present invention, however, varying amounts of aluminum were added to the casting melts with other results. When 0.01, 0.02, and 0.04 percent by weight of aluminum were'addedto three different casting compositions the resulting product was somewhat'lustrous butthe investment stuck to the surface of the cast product. However, when. 0.08, 0.16 and 0.32 percent aluminum were added the product was lustrous and was easily recovered from the investment.
  • Example XI Further dental casting alloys were prepared in accord with Example IX utilizing tin and/or indium as the hardening agent. The casting composition was moditied with aluminum in amounts of from 0.04 to 0.32 percent by weight. The resulting castings were lustrous but the investment tended to stick.
  • a gold alloy investment mold casting composition consisting essentially of from about 0.07 percent to about 0.32 percent by weight of silicon and aluminum,
  • said silicon being present in an amount of at least 0.05
  • a hardening element selected from the group consisting of copper, iron, tin, indium, and mixtures of tin and indium, said copper, when present, in amounts of 5 percent to 50 percent by weight of said alloy; iron, when present, in an amount of up to 1 percent by weight of said alloy; tin, when present, in amounts of up to 7 percent by weight of the alloy; indium, when present, in amounts of up to 7 percent by weight of the alloy; and both tin and indium combined, when present, in a total amount of up to 7 percent by weight of the alloy, the balance essentially gold.
  • composition of claim 1 wherein there is additionally present about 0.04 percent by weight, based on the composition, of chromium.
  • composition of claim 1 wherein said hardening element is copper.
  • composition of claim 1 wherein said harden- 5.
  • composition of claim '1 further including a deoxidant selected from the group consisting of zinc, magnesium, and barium.

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Plastic & Reconstructive Surgery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Epidemiology (AREA)
  • Metallurgy (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Dental Prosthetics (AREA)
  • Dental Preparations (AREA)
US00221432A 1972-01-27 1972-01-27 Bright cast alloy, and composition Expired - Lifetime US3769006A (en)

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US22143272A 1972-01-27 1972-01-27

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US (1) US3769006A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
JP (1) JPS4884031A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
DE (1) DE2303519A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
FR (1) FR2169328B3 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
IT (1) IT978421B (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3958322A (en) * 1974-06-10 1976-05-25 Rhodes William A Method of casting an alloy having the appearance of gold
US4066819A (en) * 1971-10-21 1978-01-03 The United States Of America As Represented By The Secretary Of The Navy Method of bonding gold films to non-electrically conducting oxides and product thereby obtained
US4214904A (en) * 1978-12-12 1980-07-29 The United States Of America As Represented By The Secretary Of The Air Force Gold-tin-silicon alloy for brazing silicon to metal
US4466940A (en) * 1981-10-27 1984-08-21 Demetron Gesellschaftfur Electronik-Werstoffe mbh Multicomponent alloy for sputtering targets
DE3631830A1 (de) * 1986-09-19 1988-03-31 Demetron Mehrstofflegierung fuer targets von kathodenzerstaeubungsanlagen und deren verwendung
US5340529A (en) * 1993-07-01 1994-08-23 Dewitt Troy C Gold jewelry alloy
CN110314001A (zh) * 2018-03-30 2019-10-11 株式会社松风 氧化锆用不透明性赋予液
US10514661B2 (en) 2013-02-06 2019-12-24 Rolex Sa Timepiece made from rose gold alloy

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU523626B2 (en) * 1979-01-18 1982-08-05 Murao Shoten K.K. (au + cu) base-ag-zn alloy
US5491034A (en) * 1988-05-02 1996-02-13 Nippon Steel Corporation Bonding wire for semiconductor element
JP2745065B2 (ja) * 1988-05-02 1998-04-28 新日本製鐵株式会社 半導体素子用ボンディングワイヤ
JPH02225655A (ja) * 1989-02-28 1990-09-07 Agency Of Ind Science & Technol 光沢のある黒色に着色する金合金とその着色法
DE9003308U1 (de) * 1990-03-21 1990-07-26 Beckmann, Wolfgang, 8264 Waldkraiburg Schlüssel, zum Öffnen von allen bekannten Schließvorrichtungen
JPH0625772A (ja) * 1992-07-08 1994-02-01 Masahiro Yamazoe 装飾用金合金の製造方法
JPH0764700B2 (ja) * 1992-09-29 1995-07-12 九州大学長 口腔内温度で時効硬化する歯科用金合金

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1339009A (en) * 1918-09-21 1920-05-04 Baker & Co Inc Alloy
US1557431A (en) * 1925-09-04 1925-10-13 Victor D Davignon Gold alloy and method of making the same
US1580443A (en) * 1924-05-15 1926-04-13 Shields & Moore Gold alloy
US2654146A (en) * 1949-04-02 1953-10-06 Wilson H A Co Gold base alloy
US2747971A (en) * 1953-07-20 1956-05-29 Westinghouse Electric Corp Preparation of pure crystalline silicon
US2840468A (en) * 1958-02-04 1958-06-24 Sigmund Cohn Corp Novel gold alloys and potentiometer wires produced from them
US2980998A (en) * 1957-02-04 1961-04-25 Ney Co J M Dental prosthesis and method of manufacture
US3613209A (en) * 1969-12-09 1971-10-19 Piquerez Sa Ervin Process for manufacturing gold alloy watch casings

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1339009A (en) * 1918-09-21 1920-05-04 Baker & Co Inc Alloy
US1580443A (en) * 1924-05-15 1926-04-13 Shields & Moore Gold alloy
US1557431A (en) * 1925-09-04 1925-10-13 Victor D Davignon Gold alloy and method of making the same
US2654146A (en) * 1949-04-02 1953-10-06 Wilson H A Co Gold base alloy
US2747971A (en) * 1953-07-20 1956-05-29 Westinghouse Electric Corp Preparation of pure crystalline silicon
US2980998A (en) * 1957-02-04 1961-04-25 Ney Co J M Dental prosthesis and method of manufacture
US2840468A (en) * 1958-02-04 1958-06-24 Sigmund Cohn Corp Novel gold alloys and potentiometer wires produced from them
US3613209A (en) * 1969-12-09 1971-10-19 Piquerez Sa Ervin Process for manufacturing gold alloy watch casings

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4066819A (en) * 1971-10-21 1978-01-03 The United States Of America As Represented By The Secretary Of The Navy Method of bonding gold films to non-electrically conducting oxides and product thereby obtained
US3958322A (en) * 1974-06-10 1976-05-25 Rhodes William A Method of casting an alloy having the appearance of gold
US4214904A (en) * 1978-12-12 1980-07-29 The United States Of America As Represented By The Secretary Of The Air Force Gold-tin-silicon alloy for brazing silicon to metal
US4466940A (en) * 1981-10-27 1984-08-21 Demetron Gesellschaftfur Electronik-Werstoffe mbh Multicomponent alloy for sputtering targets
DE3631830A1 (de) * 1986-09-19 1988-03-31 Demetron Mehrstofflegierung fuer targets von kathodenzerstaeubungsanlagen und deren verwendung
US4808373A (en) * 1986-09-19 1989-02-28 Leybold-Heraeus Gmbh Multiple-substance alloy for targets of cathode sputtering apparatus
US5340529A (en) * 1993-07-01 1994-08-23 Dewitt Troy C Gold jewelry alloy
US10514661B2 (en) 2013-02-06 2019-12-24 Rolex Sa Timepiece made from rose gold alloy
CN110314001A (zh) * 2018-03-30 2019-10-11 株式会社松风 氧化锆用不透明性赋予液
CN110314001B (zh) * 2018-03-30 2022-05-10 株式会社松风 氧化锆用不透明性赋予液

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Publication number Publication date
JPS4884031A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1973-11-08
FR2169328A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1973-09-07
IT978421B (it) 1974-09-20
DE2303519A1 (de) 1973-08-09
FR2169328B3 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1976-01-30

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