WO2012031391A1 - Tarnish resistant silver alloy and producing method thereof - Google Patents

Tarnish resistant silver alloy and producing method thereof Download PDF

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Publication number
WO2012031391A1
WO2012031391A1 PCT/CN2010/076734 CN2010076734W WO2012031391A1 WO 2012031391 A1 WO2012031391 A1 WO 2012031391A1 CN 2010076734 W CN2010076734 W CN 2010076734W WO 2012031391 A1 WO2012031391 A1 WO 2012031391A1
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Prior art keywords
silver alloy
silver
tarnish
nickel
cobalt
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PCT/CN2010/076734
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French (fr)
Chinese (zh)
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吴峰华
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深圳市大凡珠宝首饰有限公司
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Priority to CN201080004808.7A priority Critical patent/CN102232121B/en
Priority to PCT/CN2010/076734 priority patent/WO2012031391A1/en
Publication of WO2012031391A1 publication Critical patent/WO2012031391A1/en

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • 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
    • C22C5/06—Alloys based on silver
    • 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
    • C22C5/06—Alloys based on silver
    • C22C5/08—Alloys based on silver with copper as the next major constituent

Definitions

  • the invention relates to the technical field of metal materials, and more particularly to an anti-tarnish silver alloy suitable for jewelry, decorations and the like and a preparation method thereof.
  • Silver is located between gold and copper in the periodic table and its chemical properties are stable. It is not easily oxidized even in the air even when heated. However, silver alloys are prone to discoloration. This seriously affected the appearance of the jewelry.
  • the discoloration of silver alloys is mainly due to the reaction of silver with sulfur to form black silver sulfide.
  • the surface of the silver jewelry is sulfate, chloride, oxide, organic carbon and carbonate. Both affect the apparent quality of silver alloys.
  • the discoloration of silver is a common phenomenon, and the irradiation of corrosive media and water, sulfur and sulfide, oxygen, and light can cause and exacerbate the surface discoloration of the silver alloy. Therefore, jewelry made of silver alloy should be treated with surface protection such as plating or passivation or coating. Solving the discoloration of silver alloy is a major problem in the jewelry production industry.
  • Alloying is an important means for metal materials to improve oxidation resistance.
  • nickel, chromium, titanium, etc. are added to iron to form stainless steel, but there is no good method for anti-vulcanization of silver.
  • the National Bureau of Standards believes that there is no other way to completely prevent the formation of silver sulfides unless alloyed with other precious metals.
  • silver must be at least 40% Pd, 70% Au or 60% Pt form an alloy, but this will result in a very high cost of the silver alloy.
  • the technical problem to be solved by the present invention is to provide a discoloration-resistant silver alloy which is simple in composition, good in anti-discoloration performance and low in cost, and a preparation method thereof, in view of the deficiencies of the existing anti-tarnishing silver alloy.
  • the anti-tarnish silver alloy according to the present invention wherein the weight percentage of the cobalt to nickel is 2.5 to 3.5:1.
  • the anti-tarnish silver alloy according to the present invention wherein the component weight percentage is: silver 87.5 to 92.5%, cobalt 4.5 to 5.5 %, nickel 1.5 to 2%, copper 1.5% to 5.5%.
  • the anti-tarnish silver alloy of the present invention wherein the weight percentage of the component is: silver 92.5%, cobalt 4.5 %, nickel 1.5%, copper 1.5%.
  • the anti-tarnish silver alloy of the present invention wherein the component weight percentage is: silver 92.5%, cobalt 1.5 %, nickel 0.5%, copper 5.5%.
  • the invention also provides a preparation method of an anti-tarnish silver alloy, comprising the steps of:
  • the raw materials are weighed and mixed according to the ratio, wherein silver is 82.5 to 92.5%, cobalt is 1.5 to 7.5%, and nickel is used. 0.5 to 2.5%, copper 0.5% to 15%;
  • the mixed raw materials are placed in a vacuum induction melting furnace for melting, and taken out and cooled to room temperature to form an ingot.
  • the ingot was repeatedly melted 1-10 times, and then taken out and cooled.
  • the weight percentage of the weighed cobalt and nickel is controlled to be 2.5 to 3.5:1.
  • composition is simple, and does not contain precious metals and rare metal components, and the cost is low;
  • a thin and dense CoNiO intercalation oxide can be formed on the surface, which has strong anti-tarnishing ability and can still ensure the luster of the silver alloy;
  • the hardness is similar to the commonly used 925 silver alloy, with good machinability, suitable for jewelry industry applications;
  • Example 1a is a photomicrograph of a discoloration test result of a sample of an anti-tarnish silver alloy according to Example 1 of the present invention in a 3.5% NaCl solution medium;
  • Figure 1b is a photomicrograph of the discoloration test results of a common 925 silver alloy sample in a 3.5% NaCl solution medium;
  • Example 2a is a photomicrograph of the discoloration test result of the anti-tarnish silver alloy sample of Example 1 of the present invention in a 0.2 ⁇ 10-3 MNa 2 S aqueous solution;
  • Figure 2b is a photomicrograph of the discoloration test results of a conventional 925 silver alloy sample in a 0.2 x 10-3 M Na2S aqueous solution;
  • FIG. 3 is a photomicrograph of a discoloration test result of a sample of an anti-tarnish silver alloy according to Example 2 of the present invention in a 3.5% NaCl solution medium;
  • Example 4 is a photomicrograph showing the results of discoloration experiments of the anti-tarnish silver alloy sample of Example 2 of the present invention in a 0.2 ⁇ 10-3 MNa 2 S aqueous solution.
  • the weight percentage of each component is 82.5 to 92.5% of silver (Ag), and 1.5 to 7.5 of cobalt (Co). %, nickel (Ni) 0.5 to 2.5%, copper (Cu) 0.5% to 15%.
  • the cobalt and nickel in the anti-tarnish silver alloy of the invention can form a thin and dense intercalation oxide (CoNiO) on the surface of the silver alloy in the atmosphere, blocking the erosion of S, Cl and O ions in the atmosphere and improving The anti-tarnishing ability of silver alloy.
  • CoNiO thin and dense intercalation oxide
  • the weight percentage of cobalt (Co) and nickel (Ni) is preferably controlled to 2.5 to 3.5:1 to facilitate formation of intercalation oxide (CoNiO) between cobalt (Co) and nickel (Ni).
  • the thickness of the formed CoNiO intercalation oxide can be ensured to be extremely thin, so that the surface gloss of the silver alloy can be ensured, so that the formed silver alloy does not need to be surface plated again.
  • the production and processing method of the anti-tarnish silver alloy of the invention is as follows: the raw materials are weighed and mixed according to the above ratio, and then placed in a vacuum arc melting furnace or a vacuum induction melting furnace to be melted and formed into ingots, in order to ensure uniform composition of the ingots, The ingot was subjected to repeated smelting 1-10 times.
  • the anti-tarnish silver alloy of the present invention will be specifically described below by way of specific examples.
  • the weight percentage of the anti-tarnish silver alloy component of the present embodiment is: silver 92.5%, cobalt 4.5%, nickel 1.5%, copper 1.5%.
  • the raw materials were weighed and mixed according to the above ratio, and then placed in a vacuum arc melting furnace for repeated smelting four times, and taken out and cooled to room temperature to form an ingot.
  • the prepared anti-tarnish silver alloy has a microhardness (HV) of 82, which is similar to the currently used 925 silver alloy.
  • the anti-tarnish silver alloy sample prepared in this example was placed in a 3.5% NaCl solution medium for color change test, and a common 925 silver alloy sample was used as a control test group.
  • the photomicrograph of the test result is shown in FIG. 1a and FIG. 1b. Show.
  • the anti-tarnish silver alloy sample prepared in this example was placed in a 0.2 ⁇ 10-3MNa2S aqueous solution for color change test, and a common 925 silver alloy sample was used as a control test group.
  • the photomicrograph of the test result is shown in Fig. 2a and Fig. 2b. Shown.
  • the silver alloy sample of the present embodiment is significantly more resistant to discoloration than the conventional 925 silver alloy.
  • the weight percentage of the anti-tarnish silver alloy component of the present embodiment is: silver 92.5%, cobalt 1.5%, nickel 0.5%, copper 5.5%.
  • the production and processing method is as follows: the raw materials are weighed and mixed according to the above ratio, and then placed in a vacuum induction melting furnace for melting, taken out and cooled to room temperature to form an ingot, and the ingot can be repeatedly smelted 1-10 times.
  • the prepared anti-tarnish silver alloy was tested to have a microhardness (HV) of 85, which is similar to the currently used 925 silver alloy.
  • the anti-tarnish silver alloy sample prepared in this example was placed in a 3.5% NaCl solution medium for color change test, and a common 925 silver alloy sample was used as a control test group.
  • the photomicrograph of the test result is shown in Fig. 3a.
  • the anti-tarnish silver alloy sample prepared in this example was placed in a 0.2 ⁇ 10-3MNa2S aqueous solution for color change test, and a common 925 silver alloy sample was used as a control test group, and the micrograph of the test result is shown in Fig. 4a.
  • the silver alloy sample of the present embodiment is significantly more resistant to discoloration than the conventional 925 silver alloy.
  • the weight percentage of the anti-tarnish silver alloy component of this example was: silver 82.5%, cobalt 1.8%, nickel 0.7%, copper 15%.
  • the production and processing method is as follows: the raw materials are weighed and mixed according to the above ratio, and then placed in a vacuum induction melting furnace for melting, taken out and cooled to room temperature to form an ingot, and the ingot can be repeatedly smelted 1-10 times.
  • the prepared anti-tarnish silver alloy has a microhardness (HV) of 83, which is similar to the currently used 925 silver alloy.
  • the anti-tarnish silver alloy sample prepared in this example was placed in a 3.5% NaCl solution medium for color change test, and a common 925 silver alloy sample was used as a control test group; and the anti-tarnish silver alloy prepared in the present example was simultaneously prepared.
  • the sample was placed in a 0.2 ⁇ 10-3 M Na 2 S aqueous solution for color change test, and a common 925 silver alloy sample was used as a control test group.
  • test results show that the anti-tarnishing ability of the silver alloy sample of the present embodiment is significantly stronger than that of the ordinary 925 silver alloy.
  • the weight percentage of the anti-tarnish silver alloy component of this example was: silver 90.5%, cobalt 5.5%, nickel 1.8%, copper 2.2%.
  • the production and processing method is as follows: the raw materials are weighed and mixed according to the above ratio, and then placed in a vacuum induction melting furnace for melting, taken out and cooled to room temperature to form an ingot, and the ingot can be repeatedly smelted 1-10 times.
  • the prepared anti-tarnish silver alloy has a microhardness (HV) of 82, which is similar to the currently used 925 silver alloy.
  • the anti-tarnish silver alloy sample prepared in this example was placed in a 3.5% NaCl solution medium for color change test, and a common 925 silver alloy sample was used as a control test group; and the anti-tarnish silver alloy prepared in the present example was simultaneously prepared.
  • the sample was placed in a 0.2 ⁇ 10-3 M Na 2 S aqueous solution for color change test, and a common 925 silver alloy sample was used as a control test group.
  • test results show that the anti-tarnishing ability of the silver alloy sample of the present embodiment is significantly stronger than that of the ordinary 925 silver alloy.
  • the weight percentage of the anti-tarnish silver alloy component of this example was: silver 82.5%, cobalt 2.5%, nickel 1%, copper 14%.
  • the production and processing method is as follows: the raw materials are weighed and mixed according to the above ratio, and then placed in a vacuum induction melting furnace for melting, taken out and cooled to room temperature to form an ingot, and the ingot can be repeatedly smelted 1-10 times.
  • the prepared anti-tarnish silver alloy has a microhardness (HV) of 82, which is similar to the currently used 925 silver alloy.
  • the anti-tarnish silver alloy sample prepared in this example was placed in a 3.5% NaCl solution medium for color change test, and a common 925 silver alloy sample was used as a control test group; and the anti-tarnish silver alloy prepared in the present example was simultaneously prepared.
  • the sample was placed in a 0.2 ⁇ 10-3 M Na 2 S aqueous solution for color change test, and a common 925 silver alloy sample was used as a control test group.
  • test results show that the anti-tarnishing ability of the silver alloy sample of the present embodiment is significantly stronger than that of the ordinary 925 silver alloy.
  • the weight percentage of the anti-tarnish silver alloy component of this example was: silver 87.5%, cobalt 5%, nickel 1.43%, copper 6.07%.
  • the production and processing method is as follows: the raw materials are weighed and mixed according to the above ratio, and then placed in a vacuum induction melting furnace for melting, taken out and cooled to room temperature to form an ingot, and the ingot can be repeatedly smelted 1-10 times.
  • the prepared anti-tarnish silver alloy has a microhardness (HV) of 82, which is similar to the currently used 925 silver alloy.
  • the anti-tarnish silver alloy sample prepared in this example was placed in a 3.5% NaCl solution medium for color change test, and a common 925 silver alloy sample was used as a control test group; and the anti-tarnish silver alloy prepared in the present example was simultaneously prepared.
  • the sample was placed in a 0.2 ⁇ 10-3 M Na 2 S aqueous solution for color change test, and a common 925 silver alloy sample was used as a control test group.
  • test results show that the anti-tarnishing ability of the silver alloy sample of the present embodiment is significantly stronger than that of the ordinary 925 silver alloy.
  • the weight percentage of the anti-tarnish silver alloy component of this example is: silver 85%, cobalt 5%, nickel 2%, and copper 8%.
  • the production and processing method is as follows: the raw materials are weighed and mixed according to the above ratio, and then placed in a vacuum induction melting furnace for melting, taken out and cooled to room temperature to form an ingot, and the ingot can be repeatedly smelted 1-10 times.
  • the prepared anti-tarnish silver alloy has a microhardness (HV) of 82, which is similar to the currently used 925 silver alloy.
  • the anti-tarnish silver alloy sample prepared in this example was placed in a 3.5% NaCl solution medium for color change test, and a common 925 silver alloy sample was used as a control test group; and the anti-tarnish silver alloy prepared in the present example was simultaneously prepared.
  • the sample was placed in a 0.2 ⁇ 10-3 M Na 2 S aqueous solution for color change test, and a common 925 silver alloy sample was used as a control test group.
  • test results show that the anti-tarnishing ability of the silver alloy sample of the present embodiment is significantly stronger than that of the ordinary 925 silver alloy.
  • the weight percentage of the anti-tarnish silver alloy component of this example was: silver 91.5%, cobalt 6%, nickel 2%, copper 0.5%.
  • the production and processing method is as follows: the raw materials are weighed and mixed according to the above ratio, and then placed in a vacuum induction melting furnace for melting, taken out and cooled to room temperature to form an ingot, and the ingot can be repeatedly smelted 1-10 times.
  • the prepared anti-tarnish silver alloy has a microhardness (HV) of 82, which is similar to the currently used 925 silver alloy.
  • the anti-tarnish silver alloy sample prepared in this example was placed in a 3.5% NaCl solution medium for color change test, and a common 925 silver alloy sample was used as a control test group; and the anti-tarnish silver alloy prepared in the present example was simultaneously prepared.
  • the sample was placed in a 0.2 ⁇ 10-3 M Na 2 S aqueous solution for color change test, and a common 925 silver alloy sample was used as a control test group.
  • test results show that the anti-tarnishing ability of the silver alloy sample of the present embodiment is significantly stronger than that of the ordinary 925 silver alloy.
  • composition is simple, and does not contain precious metals and rare metal components, and the cost is low;
  • a thin and dense CoNiO intercalation oxide can be formed on the surface, which has strong anti-tarnishing ability and can still ensure the luster of the silver alloy;
  • the hardness is similar to the commonly used 925 silver alloy, with good machinability, suitable for jewelry industry applications;

Abstract

Disclosed is a tarnish resistant silver alloy with the composition of (by wt%): silver 82.5-92.5%, cobalt 1.5-7.5%, nickel 0.5-2.5%, and copper 0.5-15%, wherein the weight ratio of cobalt and nickel is controlled within 2.5~3.5:1. The method for producing the silver alloy comprises the following steps: mixing raw materials according to the ratio, melting in a vacuum induction melting furnace, and then cooling to room-temperature to form cast ingot. The silver alloy comprises no noble metal and rare metal; has simple composition and low cost. The alloy can form a thin and dense intercalation oxide CoNiO on surface in atmosphere, has high tarnish resistance and can maintain the gloss of silver. The alloy has a hardness similar to that of sterling silver usually used at present and good machinability, and adapts to jewellry industry. The process of electric plating to the alloy is unnecessary.

Description

一种抗变色银合金及其制备方法 Anti-tarnish silver alloy and preparation method thereof 技术领域  Technical field
本发明涉及金属材料技术领域，更具体的说涉及一种适用于珠宝、装饰品等的抗变色银合金及其制备方法。The invention relates to the technical field of metal materials, and more particularly to an anti-tarnish silver alloy suitable for jewelry, decorations and the like and a preparation method thereof.
背景技术Background technique
银位于元素周期表中金和铜之间，其化学性能稳定。在空气中即使加热也不易氧化。但是，银合金容易变色。这严重影响了饰品的外观。银合金的变色主要是由于银易与硫反应形成黑色的硫化银。此外，银饰品表面的硫酸盐、氯化物、氧化物、有机碳和碳酸盐等。都影响银合金的表观质量。总之，银的变色是普遍的现象，而且在腐蚀介质和水、硫及硫化物、氧气、光线的照射都会导致和加剧银合金的表面变色。因此用银合金生产的首饰都要做电镀或钝化或涂覆等表面保护处理。解决银合金不变色是首饰生产行业的一大难题。Silver is located between gold and copper in the periodic table and its chemical properties are stable. It is not easily oxidized even in the air even when heated. However, silver alloys are prone to discoloration. This seriously affected the appearance of the jewelry. The discoloration of silver alloys is mainly due to the reaction of silver with sulfur to form black silver sulfide. In addition, the surface of the silver jewelry is sulfate, chloride, oxide, organic carbon and carbonate. Both affect the apparent quality of silver alloys. In short, the discoloration of silver is a common phenomenon, and the irradiation of corrosive media and water, sulfur and sulfide, oxygen, and light can cause and exacerbate the surface discoloration of the silver alloy. Therefore, jewelry made of silver alloy should be treated with surface protection such as plating or passivation or coating. Solving the discoloration of silver alloy is a major problem in the jewelry production industry.
合金化是金属材料提高抗氧化能力的一种重要手段，如在铁中加入镍、铬、钛等形成不锈钢，但对银的抗硫化则一直缺乏好的方法。美国国家标准局通过系统研究认为：除非与其他贵金属合金化外，没有别的方法可以完全防止形成银的硫化物。要完全防止形成硫化物，银必须与至少40% Pd、70% Au或60% Pt形成合金，但这样会导致银合金成本极高。Alloying is an important means for metal materials to improve oxidation resistance. For example, nickel, chromium, titanium, etc. are added to iron to form stainless steel, but there is no good method for anti-vulcanization of silver. According to systematic research, the National Bureau of Standards believes that there is no other way to completely prevent the formation of silver sulfides unless alloyed with other precious metals. To completely prevent the formation of sulfides, silver must be at least 40% Pd, 70% Au or 60% Pt form an alloy, but this will result in a very high cost of the silver alloy.
近年来，人们先后研发了了多种抗变色银合金，但这些银合金大都成分复杂，例如专利CN01114354.1中所公开的银合金元素达到10种之多，对制备工艺要求较为苛刻。此外，这些银合金在低温加工性能、表面光泽度方面也往往存在一些不足。In recent years, a variety of anti-tarnish silver alloys have been developed, but most of these silver alloys are complex. For example, as many as 10 kinds of silver alloy elements are disclosed in the patent CN01114354.1, the preparation process is more demanding. In addition, these silver alloys often have some disadvantages in terms of low-temperature processing properties and surface gloss.
发明内容Summary of the invention
本发明要解决的技术问题在于，针对现有抗变色银合金存在的不足，提供一种成分简单、抗变色性能好、成本低廉的抗变色银合金及其制备方法。The technical problem to be solved by the present invention is to provide a discoloration-resistant silver alloy which is simple in composition, good in anti-discoloration performance and low in cost, and a preparation method thereof, in view of the deficiencies of the existing anti-tarnishing silver alloy.
本发明解决其技术问题所采用的技术方案是：The technical solution adopted by the present invention to solve the technical problem thereof is:
构造一种抗变色银合金，其成分重量百分比为：银 82.5～92.5%，钴 1.5～7.5 %，镍 0.5～2.5%，铜 0.5%～15%。Constructing an anti-tarnish silver alloy with a composition weight percentage of: silver 82.5 to 92.5%, cobalt 1.5 to 7.5%, nickel 0.5 to 2.5%, copper 0.5% to 15%.
本发明所述的抗变色银合金，其中，所述钴与镍的重量百分比为2.5～3.5：1。The anti-tarnish silver alloy according to the present invention, wherein the weight percentage of the cobalt to nickel is 2.5 to 3.5:1.
本发明所述的抗变色银合金，其中，成分重量百分比为：银87.5～92.5%，钴4.5～5.5 %，镍1.5～2%，铜1.5%～5.5%。The anti-tarnish silver alloy according to the present invention, wherein the component weight percentage is: silver 87.5 to 92.5%, cobalt 4.5 to 5.5 %, nickel 1.5 to 2%, copper 1.5% to 5.5%.
本发明所述的抗变色银合金，其中，成分重量百分比为：银 92.5%，钴4.5 %，镍1.5%，铜1.5%。The anti-tarnish silver alloy of the present invention, wherein the weight percentage of the component is: silver 92.5%, cobalt 4.5 %, nickel 1.5%, copper 1.5%.
本发明所述的抗变色银合金，其中，成分重量百分比为：银92.5%，钴1.5 %，镍0.5%，铜5.5%。The anti-tarnish silver alloy of the present invention, wherein the component weight percentage is: silver 92.5%, cobalt 1.5 %, nickel 0.5%, copper 5.5%.
本发明还提供了一种抗变色银合金的制备方法，其包括步骤：The invention also provides a preparation method of an anti-tarnish silver alloy, comprising the steps of:
A、将原料按配比称重并混合，其中银 82.5～92.5%，钴 1.5～7.5 %，镍 0.5～2.5%，铜0.5%～15%；A. The raw materials are weighed and mixed according to the ratio, wherein silver is 82.5 to 92.5%, cobalt is 1.5 to 7.5%, and nickel is used. 0.5 to 2.5%, copper 0.5% to 15%;
B、将混合原料放置于真空感应熔炼炉内熔炼，取出冷却至室温，形成铸锭。B. The mixed raw materials are placed in a vacuum induction melting furnace for melting, and taken out and cooled to room temperature to form an ingot.
本发明所述的制备方法，其中，所述步骤B中：The preparation method of the present invention, wherein in the step B:
将铸锭反复熔炼1-10次后，取出冷却。The ingot was repeatedly melted 1-10 times, and then taken out and cooled.
本发明所述的制备方法，其中，所述步骤A中，所称取的钴与镍的重量百分比控制在2.5～3.5：1。In the preparation method of the present invention, in the step A, the weight percentage of the weighed cobalt and nickel is controlled to be 2.5 to 3.5:1.
本发明的抗变色银合金有益效果是：The beneficial effects of the anti-tarnish silver alloy of the present invention are:
1、成分简单，且不含有贵金属及稀有金属成分，成本较低；1. The composition is simple, and does not contain precious metals and rare metal components, and the cost is low;
2、在大气环境下，可在表面生成一层薄且致密的CoNiO插层氧化物，抗变色能力强，且仍能保证银合金的光泽；2. In the atmosphere, a thin and dense CoNiO intercalation oxide can be formed on the surface, which has strong anti-tarnishing ability and can still ensure the luster of the silver alloy;
3、硬度与现在常用的925银合金相近，具有良好的可加工性能，适合首饰行业应用；3, the hardness is similar to the commonly used 925 silver alloy, with good machinability, suitable for jewelry industry applications;
4、采用本发明的抗变色银合金生产的首饰可以免电镀，节省电镀费用并降低污染。4. Jewelry produced by using the anti-tarnish silver alloy of the invention can be electroplated, saving plating costs and reducing pollution.
附图说明DRAWINGS
下面将结合附图及实施例对本发明作进一步说明，附图中：The present invention will be further described below in conjunction with the accompanying drawings and embodiments, in which:
图1a为本发明实施例1的抗变色银合金样品在3.5%的NaCl溶液介质中变色试验结果显微照片；1a is a photomicrograph of a discoloration test result of a sample of an anti-tarnish silver alloy according to Example 1 of the present invention in a 3.5% NaCl solution medium;
图1b为普通的925银合金样品在3.5%的NaCl溶液介质中变色试验结果显微照片；Figure 1b is a photomicrograph of the discoloration test results of a common 925 silver alloy sample in a 3.5% NaCl solution medium;
图2a为本发明实施例1的抗变色银合金样品在0.2×10-3MNa2S水溶液中的变色实验结果显微照片；2a is a photomicrograph of the discoloration test result of the anti-tarnish silver alloy sample of Example 1 of the present invention in a 0.2×10-3 MNa 2 S aqueous solution;
图2b为普通的925银合金样品在0.2×10-3MNa2S水溶液中的变色实验结果显微照片；Figure 2b is a photomicrograph of the discoloration test results of a conventional 925 silver alloy sample in a 0.2 x 10-3 M Na2S aqueous solution;
图3为本发明实施例2的抗变色银合金样品在3.5%的NaCl溶液介质中变色试验结果显微照片；3 is a photomicrograph of a discoloration test result of a sample of an anti-tarnish silver alloy according to Example 2 of the present invention in a 3.5% NaCl solution medium;
图4为本发明实施例2的抗变色银合金样品在0.2×10-3MNa2S水溶液中的变色实验结果显微照片。4 is a photomicrograph showing the results of discoloration experiments of the anti-tarnish silver alloy sample of Example 2 of the present invention in a 0.2×10-3 MNa 2 S aqueous solution.
具体实施方式detailed description
下面结合图示，对本发明的优选实施例作详细介绍。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail in conjunction with the drawings.
本发明的抗变色银合金中，各成分重量百分比为银（Ag）82.5～92.5%，钴（Co） 1.5～7.5 %，镍（Ni）0.5～2.5%，铜（Cu）0.5%～15%。In the anti-tarnish silver alloy of the present invention, the weight percentage of each component is 82.5 to 92.5% of silver (Ag), and 1.5 to 7.5 of cobalt (Co). %, nickel (Ni) 0.5 to 2.5%, copper (Cu) 0.5% to 15%.
本发明的抗变色银合金中的钴与镍，在大气环境下可在银合金表面生成一层薄且致密的插层氧化物（CoNiO），阻挡大气中S、Cl、O离子的侵蚀，提高银合金的抗变色能力。The cobalt and nickel in the anti-tarnish silver alloy of the invention can form a thin and dense intercalation oxide (CoNiO) on the surface of the silver alloy in the atmosphere, blocking the erosion of S, Cl and O ions in the atmosphere and improving The anti-tarnishing ability of silver alloy.
本发明的抗变色银合金中，优选将钴（Co）与镍（Ni）的重量百分比控制在2.5～3.5：1，以利于钴（Co）与镍（Ni）形成插层氧化物（CoNiO），且能保证所形成的CoNiO插层氧化物的厚度极薄，因此仍能保证银合金的表面光泽，使得生成的银合金不需再次进行表面电镀。In the anti-tarnish silver alloy of the present invention, the weight percentage of cobalt (Co) and nickel (Ni) is preferably controlled to 2.5 to 3.5:1 to facilitate formation of intercalation oxide (CoNiO) between cobalt (Co) and nickel (Ni). Moreover, the thickness of the formed CoNiO intercalation oxide can be ensured to be extremely thin, so that the surface gloss of the silver alloy can be ensured, so that the formed silver alloy does not need to be surface plated again.
本发明抗变色银合金的生产加工方法为：将原料按上述配比称重并混合，然后放置于真空电弧熔炼炉或真空感应熔炼炉内熔炼并形成铸锭，为保证铸锭成分均匀，可对铸锭进行1-10次的反复熔炼。The production and processing method of the anti-tarnish silver alloy of the invention is as follows: the raw materials are weighed and mixed according to the above ratio, and then placed in a vacuum arc melting furnace or a vacuum induction melting furnace to be melted and formed into ingots, in order to ensure uniform composition of the ingots, The ingot was subjected to repeated smelting 1-10 times.
下面通过具体实施例对本发明的抗变色银合金进行具体的说明。The anti-tarnish silver alloy of the present invention will be specifically described below by way of specific examples.
实施例1： Example 1:
本实施例的抗变色银合金成分重量百分比为：银 92.5%，钴 4.5 %，镍 1.5%，铜 1.5%。The weight percentage of the anti-tarnish silver alloy component of the present embodiment is: silver 92.5%, cobalt 4.5%, nickel 1.5%, copper 1.5%.
将原料按上述配比称重并混合，然后放置于真空电弧熔炼炉内反复熔炼4次，取出冷却至室温，形成铸锭。The raw materials were weighed and mixed according to the above ratio, and then placed in a vacuum arc melting furnace for repeated smelting four times, and taken out and cooled to room temperature to form an ingot.
经测试，所制备的抗变色银合金的显微硬度（HV）为82，与现在常用的925银合金相近。The prepared anti-tarnish silver alloy has a microhardness (HV) of 82, which is similar to the currently used 925 silver alloy.
将本实施例所制备的抗变色银合金样品置于3.5%的NaCl溶液介质中进行变色试验，并以普通的925银合金样品作为对照试验组，试验结果显微照片如图1a和图1b所示。同时将本实施例所制备的抗变色银合金样品置于0.2×10-3MNa2S水溶液中进行变色试验，并以普通的925银合金样品作为对照试验组，试验结果显微照片如图2a和图2b所示。 The anti-tarnish silver alloy sample prepared in this example was placed in a 3.5% NaCl solution medium for color change test, and a common 925 silver alloy sample was used as a control test group. The photomicrograph of the test result is shown in FIG. 1a and FIG. 1b. Show. At the same time, the anti-tarnish silver alloy sample prepared in this example was placed in a 0.2×10-3MNa2S aqueous solution for color change test, and a common 925 silver alloy sample was used as a control test group. The photomicrograph of the test result is shown in Fig. 2a and Fig. 2b. Shown.
从图1a、图1b、图2a和图2b中可以看出，本实施例的银合金样品的抗变色能力明显强于普通的925银合金。As can be seen from Fig. 1a, Fig. 1b, Fig. 2a and Fig. 2b, the silver alloy sample of the present embodiment is significantly more resistant to discoloration than the conventional 925 silver alloy.
实施例2：Example 2:
本实施例的抗变色银合金成分重量百分比为：银 92.5%，钴 1.5 %，镍 0.5%，铜 5.5%。The weight percentage of the anti-tarnish silver alloy component of the present embodiment is: silver 92.5%, cobalt 1.5%, nickel 0.5%, copper 5.5%.
生产加工方法为：将原料按上述配比称重并混合，然后放置于真空感应熔炼炉内熔炼，取出冷却至室温，形成铸锭，并可将铸锭反复熔炼1-10次。The production and processing method is as follows: the raw materials are weighed and mixed according to the above ratio, and then placed in a vacuum induction melting furnace for melting, taken out and cooled to room temperature to form an ingot, and the ingot can be repeatedly smelted 1-10 times.
经测试，所制备的抗变色银合金的显微硬度（HV）为85，与现在常用的925银合金相近。The prepared anti-tarnish silver alloy was tested to have a microhardness (HV) of 85, which is similar to the currently used 925 silver alloy.
将本实施例所制备的抗变色银合金样品置于3.5%的NaCl溶液介质中进行变色试验，并以普通的925银合金样品作为对照试验组，试验结果显微照片如图3a。同时将本实施例所制备的抗变色银合金样品置于0.2×10-3MNa2S水溶液中进行变色试验，并以普通的925银合金样品作为对照试验组，试验结果显微照片如图4a所示。The anti-tarnish silver alloy sample prepared in this example was placed in a 3.5% NaCl solution medium for color change test, and a common 925 silver alloy sample was used as a control test group. The photomicrograph of the test result is shown in Fig. 3a. At the same time, the anti-tarnish silver alloy sample prepared in this example was placed in a 0.2×10-3MNa2S aqueous solution for color change test, and a common 925 silver alloy sample was used as a control test group, and the micrograph of the test result is shown in Fig. 4a.
从图1b、图2b、图3和图4中可以看出，本实施例的银合金样品的抗变色能力明显强于普通的925银合金。As can be seen from Fig. 1b, Fig. 2b, Fig. 3 and Fig. 4, the silver alloy sample of the present embodiment is significantly more resistant to discoloration than the conventional 925 silver alloy.
实施例3：Example 3:
本实施例的抗变色银合金成分重量百分比为：银 82.5%，钴 1.8 %，镍 0.7%，铜 15%。The weight percentage of the anti-tarnish silver alloy component of this example was: silver 82.5%, cobalt 1.8%, nickel 0.7%, copper 15%.
生产加工方法为：将原料按上述配比称重并混合，然后放置于真空感应熔炼炉内熔炼，取出冷却至室温，形成铸锭，并可将铸锭反复熔炼1-10次。The production and processing method is as follows: the raw materials are weighed and mixed according to the above ratio, and then placed in a vacuum induction melting furnace for melting, taken out and cooled to room temperature to form an ingot, and the ingot can be repeatedly smelted 1-10 times.
经测试，所制备的抗变色银合金的显微硬度（HV）为83，与现在常用的925银合金相近。The prepared anti-tarnish silver alloy has a microhardness (HV) of 83, which is similar to the currently used 925 silver alloy.
将本实施例所制备的抗变色银合金样品置于3.5%的NaCl溶液介质中进行变色试验，并以普通的925银合金样品作为对照试验组；同时将本实施例所制备的抗变色银合金样品置于0.2×10-3MNa2S水溶液中进行变色试验，并以普通的925银合金样品作为对照试验组。The anti-tarnish silver alloy sample prepared in this example was placed in a 3.5% NaCl solution medium for color change test, and a common 925 silver alloy sample was used as a control test group; and the anti-tarnish silver alloy prepared in the present example was simultaneously prepared. The sample was placed in a 0.2×10-3 M Na 2 S aqueous solution for color change test, and a common 925 silver alloy sample was used as a control test group.
试验结果表明，本实施例的银合金样品的抗变色能力明显强于普通的925银合金。The test results show that the anti-tarnishing ability of the silver alloy sample of the present embodiment is significantly stronger than that of the ordinary 925 silver alloy.
实施例4：Example 4:
本实施例的抗变色银合金成分重量百分比为：银 90.5%，钴 5.5 %，镍1.8%，铜 2.2%。The weight percentage of the anti-tarnish silver alloy component of this example was: silver 90.5%, cobalt 5.5%, nickel 1.8%, copper 2.2%.
生产加工方法为：将原料按上述配比称重并混合，然后放置于真空感应熔炼炉内熔炼，取出冷却至室温，形成铸锭，并可将铸锭反复熔炼1-10次。The production and processing method is as follows: the raw materials are weighed and mixed according to the above ratio, and then placed in a vacuum induction melting furnace for melting, taken out and cooled to room temperature to form an ingot, and the ingot can be repeatedly smelted 1-10 times.
经测试，所制备的抗变色银合金的显微硬度（HV）为82，与现在常用的925银合金相近。The prepared anti-tarnish silver alloy has a microhardness (HV) of 82, which is similar to the currently used 925 silver alloy.
将本实施例所制备的抗变色银合金样品置于3.5%的NaCl溶液介质中进行变色试验，并以普通的925银合金样品作为对照试验组；同时将本实施例所制备的抗变色银合金样品置于0.2×10-3MNa2S水溶液中进行变色试验，并以普通的925银合金样品作为对照试验组。The anti-tarnish silver alloy sample prepared in this example was placed in a 3.5% NaCl solution medium for color change test, and a common 925 silver alloy sample was used as a control test group; and the anti-tarnish silver alloy prepared in the present example was simultaneously prepared. The sample was placed in a 0.2×10-3 M Na 2 S aqueous solution for color change test, and a common 925 silver alloy sample was used as a control test group.
试验结果表明，本实施例的银合金样品的抗变色能力明显强于普通的925银合金。The test results show that the anti-tarnishing ability of the silver alloy sample of the present embodiment is significantly stronger than that of the ordinary 925 silver alloy.
实施例5：Example 5:
本实施例的抗变色银合金成分重量百分比为：银 82.5%，钴 2.5 %，镍 1%，铜 14%。The weight percentage of the anti-tarnish silver alloy component of this example was: silver 82.5%, cobalt 2.5%, nickel 1%, copper 14%.
生产加工方法为：将原料按上述配比称重并混合，然后放置于真空感应熔炼炉内熔炼，取出冷却至室温，形成铸锭，并可将铸锭反复熔炼1-10次。The production and processing method is as follows: the raw materials are weighed and mixed according to the above ratio, and then placed in a vacuum induction melting furnace for melting, taken out and cooled to room temperature to form an ingot, and the ingot can be repeatedly smelted 1-10 times.
经测试，所制备的抗变色银合金的显微硬度（HV）为82，与现在常用的925银合金相近。The prepared anti-tarnish silver alloy has a microhardness (HV) of 82, which is similar to the currently used 925 silver alloy.
将本实施例所制备的抗变色银合金样品置于3.5%的NaCl溶液介质中进行变色试验，并以普通的925银合金样品作为对照试验组；同时将本实施例所制备的抗变色银合金样品置于0.2×10-3MNa2S水溶液中进行变色试验，并以普通的925银合金样品作为对照试验组。The anti-tarnish silver alloy sample prepared in this example was placed in a 3.5% NaCl solution medium for color change test, and a common 925 silver alloy sample was used as a control test group; and the anti-tarnish silver alloy prepared in the present example was simultaneously prepared. The sample was placed in a 0.2×10-3 M Na 2 S aqueous solution for color change test, and a common 925 silver alloy sample was used as a control test group.
试验结果表明，本实施例的银合金样品的抗变色能力明显强于普通的925银合金。The test results show that the anti-tarnishing ability of the silver alloy sample of the present embodiment is significantly stronger than that of the ordinary 925 silver alloy.
实施例6：Example 6
本实施例的抗变色银合金成分重量百分比为：银 87.5%，钴 5%，镍 1.43%，铜 6.07%。The weight percentage of the anti-tarnish silver alloy component of this example was: silver 87.5%, cobalt 5%, nickel 1.43%, copper 6.07%.
生产加工方法为：将原料按上述配比称重并混合，然后放置于真空感应熔炼炉内熔炼，取出冷却至室温，形成铸锭，并可将铸锭反复熔炼1-10次。The production and processing method is as follows: the raw materials are weighed and mixed according to the above ratio, and then placed in a vacuum induction melting furnace for melting, taken out and cooled to room temperature to form an ingot, and the ingot can be repeatedly smelted 1-10 times.
经测试，所制备的抗变色银合金的显微硬度（HV）为82，与现在常用的925银合金相近。The prepared anti-tarnish silver alloy has a microhardness (HV) of 82, which is similar to the currently used 925 silver alloy.
将本实施例所制备的抗变色银合金样品置于3.5%的NaCl溶液介质中进行变色试验，并以普通的925银合金样品作为对照试验组；同时将本实施例所制备的抗变色银合金样品置于0.2×10-3MNa2S水溶液中进行变色试验，并以普通的925银合金样品作为对照试验组。The anti-tarnish silver alloy sample prepared in this example was placed in a 3.5% NaCl solution medium for color change test, and a common 925 silver alloy sample was used as a control test group; and the anti-tarnish silver alloy prepared in the present example was simultaneously prepared. The sample was placed in a 0.2×10-3 M Na 2 S aqueous solution for color change test, and a common 925 silver alloy sample was used as a control test group.
试验结果表明，本实施例的银合金样品的抗变色能力明显强于普通的925银合金。The test results show that the anti-tarnishing ability of the silver alloy sample of the present embodiment is significantly stronger than that of the ordinary 925 silver alloy.
实施例7：Example 7
本实施例的抗变色银合金成分重量百分比为：银 85%，钴 5%，镍 2 %，铜 8%。The weight percentage of the anti-tarnish silver alloy component of this example is: silver 85%, cobalt 5%, nickel 2%, and copper 8%.
生产加工方法为：将原料按上述配比称重并混合，然后放置于真空感应熔炼炉内熔炼，取出冷却至室温，形成铸锭，并可将铸锭反复熔炼1-10次。The production and processing method is as follows: the raw materials are weighed and mixed according to the above ratio, and then placed in a vacuum induction melting furnace for melting, taken out and cooled to room temperature to form an ingot, and the ingot can be repeatedly smelted 1-10 times.
经测试，所制备的抗变色银合金的显微硬度（HV）为82，与现在常用的925银合金相近。The prepared anti-tarnish silver alloy has a microhardness (HV) of 82, which is similar to the currently used 925 silver alloy.
将本实施例所制备的抗变色银合金样品置于3.5%的NaCl溶液介质中进行变色试验，并以普通的925银合金样品作为对照试验组；同时将本实施例所制备的抗变色银合金样品置于0.2×10-3MNa2S水溶液中进行变色试验，并以普通的925银合金样品作为对照试验组。The anti-tarnish silver alloy sample prepared in this example was placed in a 3.5% NaCl solution medium for color change test, and a common 925 silver alloy sample was used as a control test group; and the anti-tarnish silver alloy prepared in the present example was simultaneously prepared. The sample was placed in a 0.2×10-3 M Na 2 S aqueous solution for color change test, and a common 925 silver alloy sample was used as a control test group.
试验结果表明，本实施例的银合金样品的抗变色能力明显强于普通的925银合金。The test results show that the anti-tarnishing ability of the silver alloy sample of the present embodiment is significantly stronger than that of the ordinary 925 silver alloy.
实施例8：Example 8
本实施例的抗变色银合金成分重量百分比为：银 91.5%，钴 6%，镍 2%，铜 0.5%。The weight percentage of the anti-tarnish silver alloy component of this example was: silver 91.5%, cobalt 6%, nickel 2%, copper 0.5%.
生产加工方法为：将原料按上述配比称重并混合，然后放置于真空感应熔炼炉内熔炼，取出冷却至室温，形成铸锭，并可将铸锭反复熔炼1-10次。The production and processing method is as follows: the raw materials are weighed and mixed according to the above ratio, and then placed in a vacuum induction melting furnace for melting, taken out and cooled to room temperature to form an ingot, and the ingot can be repeatedly smelted 1-10 times.
经测试，所制备的抗变色银合金的显微硬度（HV）为82，与现在常用的925银合金相近。The prepared anti-tarnish silver alloy has a microhardness (HV) of 82, which is similar to the currently used 925 silver alloy.
将本实施例所制备的抗变色银合金样品置于3.5%的NaCl溶液介质中进行变色试验，并以普通的925银合金样品作为对照试验组；同时将本实施例所制备的抗变色银合金样品置于0.2×10-3MNa2S水溶液中进行变色试验，并以普通的925银合金样品作为对照试验组。The anti-tarnish silver alloy sample prepared in this example was placed in a 3.5% NaCl solution medium for color change test, and a common 925 silver alloy sample was used as a control test group; and the anti-tarnish silver alloy prepared in the present example was simultaneously prepared. The sample was placed in a 0.2×10-3 M Na 2 S aqueous solution for color change test, and a common 925 silver alloy sample was used as a control test group.
试验结果表明，本实施例的银合金样品的抗变色能力明显强于普通的925银合金。The test results show that the anti-tarnishing ability of the silver alloy sample of the present embodiment is significantly stronger than that of the ordinary 925 silver alloy.
本发明的抗变色银合金有益效果是：The beneficial effects of the anti-tarnish silver alloy of the present invention are:
1、成分简单，且不含有贵金属及稀有金属成分，成本较低；1. The composition is simple, and does not contain precious metals and rare metal components, and the cost is low;
2、在大气环境下，可在表面生成一层薄且致密的CoNiO插层氧化物，抗变色能力强，且仍能保证银合金的光泽；2. In the atmosphere, a thin and dense CoNiO intercalation oxide can be formed on the surface, which has strong anti-tarnishing ability and can still ensure the luster of the silver alloy;
3、硬度与现在常用的925银合金相近，具有良好的可加工性能，适合首饰行业应用；3, the hardness is similar to the commonly used 925 silver alloy, with good machinability, suitable for jewelry industry applications;
4、采用本发明的抗变色银合金生产的首饰可以免电镀，节省电镀费用并降低污染。4. Jewelry produced by using the anti-tarnish silver alloy of the invention can be electroplated, saving plating costs and reducing pollution.
应当理解的是，对本领域普通技术人员来说，可以根据上述说明加以改进或变换，而所有这些改进和变换都应属于本发明所附权利要求的保护范围。It is to be understood that those skilled in the art will be able to make modifications and changes in accordance with the above description, and all such modifications and variations are intended to be included within the scope of the appended claims.

Claims (8)

  1. 一种抗变色银合金，其特征在于，成分重量百分比为：银 82.5～92.5%，钴 1.5～7.5 %，镍 0.5～2.5%，铜 0.5%～15%。 An anti-tarnish silver alloy characterized in that the weight percentage of the component is: silver 82.5 to 92.5%, cobalt 1.5 to 7.5%, nickel 0.5 to 2.5%, copper 0.5% to 15%.
  2. 根据权利要求1所述的抗变色银合金，其特征在于，所述钴与镍的重量百分比为2.5～3.5：1。The anti-tarnish silver alloy according to claim 1, wherein the weight percentage of cobalt to nickel is from 2.5 to 3.5:1.
  3. 根据权利要求1所述的抗变色银合金，其特征在于，成分重量百分比为：银87.5～92.5%，钴4.5～5.5 %，镍1.5～2%，铜1.5%～5.5%。The anti-tarnish silver alloy according to claim 1, wherein the component weight percentage is: silver 87.5 to 92.5%, and cobalt 4.5 to 5.5. %, nickel 1.5 to 2%, copper 1.5% to 5.5%.
  4. 根据权利要求1所述的抗变色银合金，其特征在于，成分重量百分比为：银 92.5%，钴4.5 %，镍1.5%，铜1.5%。The anti-tarnish silver alloy according to claim 1, wherein the component weight percentage is: silver 92.5%, cobalt 4.5 %, nickel 1.5%, copper 1.5%.
  5. 根据权利要求1所述的抗变色银合金，其特征在于，成分重量百分比为：银92.5%，钴1.5 %，镍0.5%，铜5.5%。The anti-tarnish silver alloy according to claim 1, wherein the component weight percentage is: silver 92.5%, cobalt 1.5 %, nickel 0.5%, copper 5.5%.
  6. 一种抗变色银合金的制备方法，其特征在于，包括步骤：A method for preparing an anti-tarnish silver alloy, comprising the steps of:
    A、将原料按配比称重并混合，其中银 82.5～92.5%，钴 1.5～7.5 %，镍 0.5～2.5%，铜0.5%～15%；A. The raw materials are weighed and mixed according to the ratio, wherein silver is 82.5 to 92.5%, cobalt is 1.5 to 7.5%, and nickel is used. 0.5 to 2.5%, copper 0.5% to 15%;
    B、将混合原料放置于真空感应熔炼炉内熔炼，取出冷却至室温，形成铸锭 。B. The mixed raw materials are placed in a vacuum induction melting furnace for melting, and taken out and cooled to room temperature to form an ingot.
  7. 根据权利要求6所述的制备方法，其特征在于，所述步骤B中：The preparation method according to claim 6, wherein in the step B:
    将铸锭反复熔炼1-10次后，取出冷却 。The ingot was repeatedly melted 1-10 times, and then taken out and cooled.
  8. 根据权利要求6所述的制备方法，其特征在于，所述步骤A中，所称取的钴与镍的重量百分比控制在2.5～3.5：1。The preparation method according to claim 6, wherein in the step A, the weight percentage of the weighed cobalt and nickel is controlled to be 2.5 to 3.5:1.
PCT/CN2010/076734 2010-09-08 2010-09-08 Tarnish resistant silver alloy and producing method thereof WO2012031391A1 (en)

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CN102560179A (en) * 2012-03-10 2012-07-11 金保全 Silver ornament alloy taking silver as main component
JP5811157B2 (en) * 2013-10-24 2015-11-11 トヨタ自動車株式会社 Decorative coating
CN103740968B (en) * 2013-12-19 2015-08-26 北海鑫利坤金属材料科技开发有限公司 A kind of manufacture craft of anti-tarnishing silver alloy

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GB577714A (en) * 1943-04-10 1946-05-29 Mallory Metallurg Prod Ltd Improvements in or relating to thermostatic metals
US3929474A (en) * 1974-08-05 1975-12-30 Williams Gold Refining Co Tarnish resistant silver based dental casting alloy capable of bonding to porcelain
JPS58104139A (en) * 1981-12-17 1983-06-21 Tanaka Kikinzoku Kogyo Kk Sliding contact material
JP2004002929A (en) * 2001-08-03 2004-01-08 Furuya Kinzoku:Kk Silver alloy, sputtering target, reflector for reflection lcd, reflection wiring electrode, thin film, manufacturing method therefor, optical recording medium, electro magnetic wave shield, metal material for electronic part, wiring material, electronic part, electronic appliance, processing method of metal film, electron optical part, laminate, and glass of building material

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB102828A (en) * 1916-01-07 1917-01-04 Pascal Marino Improvements in the Electrolytic Deposition of a Cobalt-silver Alloy.
GB577714A (en) * 1943-04-10 1946-05-29 Mallory Metallurg Prod Ltd Improvements in or relating to thermostatic metals
US3929474A (en) * 1974-08-05 1975-12-30 Williams Gold Refining Co Tarnish resistant silver based dental casting alloy capable of bonding to porcelain
JPS58104139A (en) * 1981-12-17 1983-06-21 Tanaka Kikinzoku Kogyo Kk Sliding contact material
JP2004002929A (en) * 2001-08-03 2004-01-08 Furuya Kinzoku:Kk Silver alloy, sputtering target, reflector for reflection lcd, reflection wiring electrode, thin film, manufacturing method therefor, optical recording medium, electro magnetic wave shield, metal material for electronic part, wiring material, electronic part, electronic appliance, processing method of metal film, electron optical part, laminate, and glass of building material

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