CN110951986A - Antioxidant silver alloy and preparation method and application thereof - Google Patents
Antioxidant silver alloy and preparation method and application thereof Download PDFInfo
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- CN110951986A CN110951986A CN201911092779.3A CN201911092779A CN110951986A CN 110951986 A CN110951986 A CN 110951986A CN 201911092779 A CN201911092779 A CN 201911092779A CN 110951986 A CN110951986 A CN 110951986A
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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
- C22C5/06—Alloys based on silver
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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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/14—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of noble metals or alloys based thereon
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- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention discloses an antioxidant silver alloy and a preparation method and application thereof, wherein the preparation method comprises the following steps: uniformly mixing silver, titanium, niobium and tantalum, carrying out vacuum melting, cooling to room temperature after the melting is finished, and then carrying out sequential heating treatment to reform the crystal form of the alloy. After alloy metal and silver are subjected to vacuum melting, the internal structure of the alloy metal and the silver is guaranteed to be compact and bubble-free, and crystal form transformation of the alloy metal and the silver is carried out through temperature programming heat treatment, so that the oxidation resistance and the machining performance of the alloy metal are optimized; the method utilizes an alloying process, greatly improves the oxidation resistance and the corrosion resistance of the silver while not influencing the appearance and the hand feeling of the silver, avoids the problems of non-neglect of weather resistance, high temperature resistance and the like of an organic film, and also avoids the problems of poor mechanical property and the like of an inorganic glass body; in addition, the processing process is safe and environment-friendly, so that the problems of environmental pollution and the like caused by an electroplating process are avoided, and the method has a good industrial application prospect.
Description
Technical Field
The invention relates to the technical field of silver oxidation resistance, and particularly relates to an oxidation-resistant silver alloy and a preparation method and application thereof.
Background
Pure silver is a beautiful silvery metal, has attractive metallic luster and collection and appreciation values, is popular with people, has the beauty name of female metal, and is widely used as jewelry, ornaments, silverware, tableware, worship gifts, medals and commemorative coins. Traditional silver ornaments mainly have 3 brands: pure silver, 958 silver and 925 silver, wherein 958 silver and 925 silver are binary alloys composed of copper as an alloying element. However, no matter which grade of silver is, the color of the silver is easy to change, and the surface of the ornament loses white luster and turns yellow and black after being placed in the atmospheric atmosphere for a period of time, so that the ornamental effect of the ornament is seriously influenced.
In order to improve the oxidation and discoloration resistance of silver, more researches have been carried out at home and abroad for many years, and the silver can be divided into two types according to the improvement approaches: 1. surface modification; 2. and (4) alloying treatment. The surface modification comprises surface coating and electroplating treatment, and the surface coating has the defects of poor weather resistance and short service life, so that the electroplating belongs to the high-pollution industry and faces increasingly severe environmental protection pressure. Various modes of silver discoloration resistance, including alloying treatment and surface treatment, are described in a text of silver discoloration resistance process research progress, published by Yangtze river, et al, Kunming theory university, electroplating and painting, 2009, volume 28, 6. Regarding surface treatment, the article introduces 10 approaches: 1) other metals, such as noble metals (which are costly) or metal coatings of Ta, Nb, Ti and Al, are plated onto the silver surface using electroplating or ion sputtering techniques, but the resistance to discoloration is limited due to the plating. 2) Chemical passivation, such as chromate passivation; 3) electrochemical passivation; 4) carrying out galvanic couple passivation; 5) depositing an oxide film, and depositing metal Al, Be, Zr, Mg, Nb and Ti in the 3 rd to 5 th periods of the periodic table of elements on the surface of Ag by a sputtering technology or electrophoresis in an aqueous solution to obtain an oxide film; 6) coating an organic adsorption passivation layer; 7) coating a resin coating; 8) coating a self-assembled film; 9) plasma polymerization; 10) spraying composite organic antitarnish agent. However, the surface treatment process for silver takes the following requirements into consideration: the original appearance of the silver and the silver alloy is kept, the surface treatment process is non-toxic and harmless, and the process is stable; the process has good operability; the thickness of the plating layer needs to be thin; the repair and the removal of the coating are simple; the coating is durable, including the ability to withstand abrasion; low treatment cost, etc., and the above 10 methods are difficult to meet the requirements by the same workers, so that the oxidation resistant silver prepared by surface treatment in the prior art has various defects.
Chinese patent application CN104593795A published in 2015 at 5/6 discloses a silverware brightness maintaining agent, which is prepared by compounding the following components in parts by weight: 5-10 parts of sodium hypophosphite or sodium phosphite, 1-5 parts of coconut oil fatty acid diethanolamide, 1-3 parts of deionized water, 201-2 parts of tween-201, 1-3 parts of monopotassium phosphate, 1-3 parts of sodium dihydrogen phosphate, 3-5 parts of sodium carbonate, 1-3 parts of methyl propyl triazole, 1-3 parts of 2-mercaptobenzothiadiazole, 1-2 parts of sodium dodecyl sulfate and 0.5-1 part of sodium stearate. The brightener is convenient to use and operate, can effectively prevent the silver piece surface from discoloring within a certain time range, and has certain protective performance, however, a protective layer formed by the brightener can lose effectiveness gradually under the combined action of illumination, water vapor and air, and further loses the protective effect.
The Chinese patent application document CN106282984A published in 2017, 1 month and 4 days discloses a silver discoloration prevention agent, which is prepared by compounding the following substances in parts by weight: 4.2-5.4 parts of alkyl mercaptan with 12-18 carbon atoms, 0.51-0.64 part of N-sulfathiazole thioglycolic acid, 1.5-1.8 parts of benzotriazole, 0.2-0.4 part of morpholine, 3.6-4.2 parts of wetting agent, 0.36-0.51 part of ultraviolet absorbent and 48-57 parts of ethylene glycol are coated on the surface of a silver piece. The silver discoloration inhibitor compounded by the components can form a good protective film on the surface of silver, can effectively prevent the surface discoloration phenomenon of pure silver and silver-plated workpieces or products within a certain time range, and has good protective performance. However, the weather resistance of the silver discoloration inhibitor is still unsatisfactory, and the formed protective film still has aging degradation behavior under the combined action of illumination, water vapor and air, so that the protective effect on silver pieces is lost.
Chinese patent application CN109338340A published in 2019, 2 and 15 discloses an intermediate for preventing silver discoloration, a composition, a silver for preventing discoloration and a preparation method thereof, wherein silica, diboron trioxide and bismuth trioxide are used for treatment, and an antioxidant glass layer is formed on the silver surface. Chinese patent application CN11058064A published in 2019, 8, 23 and discloses an antioxidant silver and a preparation method thereof, wherein silver is treated by silicon dioxide, boron oxide, zinc oxide and potassium oxide to cover a layer of nanoscale dense antioxidant thin film on the surface of the silver, so that the problem of easy oxidation and discoloration of pure silver is effectively solved, however, the method also prepares an inorganic thin film, and the problems of falling resistance and scratch resistance of the inorganic thin film cannot be solved.
In conclusion, the surfacing treatment process is difficult to solve the silver oxidation discoloration problem, and alloying is an important way for improving the silver anti-discoloration capability. However, in the alloying treatment process in the prior art, a noble metal such as Au is generally used as an alloy element, which greatly increases the manufacturing cost of the silver product, and the obtained high silver-containing alloy has poor discoloration resistance (the higher the content is, the poorer the discoloration resistance is), and in addition, no mature product is available at present because of the immature process.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a preparation method of the antioxidant silver alloy, the antioxidant silver alloy can effectively solve the problem that pure silver is easy to oxidize and discolor, and meanwhile, the prepared silver alloy has good mechanical property and better anti-falling performance and scraping resistance.
The invention also provides the silver alloy prepared by the method.
The invention also provides application of the silver alloy.
The preparation method according to the embodiment of the first aspect of the invention comprises the following steps:
uniformly mixing silver, titanium, niobium and tantalum, carrying out vacuum melting, cooling to room temperature after the melting is finished, reforming the alloy crystal form through heat treatment, and cooling to obtain the alloy.
According to some embodiments of the invention, the temperature of the smelting operation is (960-1050) DEG C.
According to some embodiments of the invention, the time of the smelting operation is (0.5-1.5) h.
According to some embodiments of the present invention, the heat treatment process is performed by first raising the temperature to (100-; preferably, the heat treatment is performed by heating to (100-.
According to some embodiments of the invention, the heat treatment is preferably performed in a protective gas atmosphere; the shielding gas comprises at least one of an inert gas or nitrogen.
According to some embodiments of the invention, the silver is present in an amount of (92.5 to 97)% by mass of the silver, the titanium, the niobium and the tantalum during the mixing process.
According to some embodiments of the invention, the silver, titanium, niobium and tantalum are mixed such that the percentage by mass of titanium is less than 7.5%.
According to some embodiments of the invention, the niobium is present in an amount less than 2% by weight of the silver, titanium, niobium and tantalum mixture.
According to some embodiments of the invention, the tantalum is present in an amount less than 2% by weight of the silver, titanium, niobium and tantalum mixture.
The preparation method provided by the embodiment of the invention has at least the following beneficial effects: after alloy metal and silver are subjected to vacuum melting, the internal structure of the alloy metal and the silver is guaranteed to be compact and bubble-free, and crystal form transformation of the alloy metal and the silver is carried out through temperature programming heat treatment, so that the oxidation resistance and the machining performance of the alloy metal are optimized; the method utilizes an alloying process, greatly improves the oxidation resistance and the corrosion resistance of the silver while not influencing the appearance and the hand feeling of the silver, avoids the problems of non-neglect of weather resistance, high temperature resistance and the like of an organic film, and also avoids the problems of poor mechanical property and the like of an inorganic glass body; in addition, the processing process is safe and environment-friendly, so that the problems of environmental pollution and the like caused by an electroplating process are avoided, and the method has a good industrial application prospect.
According to the oxidation-resistant silver alloy of the second aspect embodiment of the invention, the oxidation-resistant silver alloy is prepared by the method.
According to some embodiments of the invention, the silver alloy consists of the following components in weight percent: 92.5%, titanium 4.5%, niobium 1.5% and tantalum 1.5%.
According to some embodiments of the invention, the silver alloy consists of the following components in weight percent: 95.8% silver, 2% titanium, 1.1% niobium and 1.1% tantalum.
According to some embodiments of the invention, the silver alloy consists of the following components in weight percent: 97% of silver, 1% of titanium, 1% of niobium and 1% of tantalum.
The oxidation-resistant silver alloy provided by the embodiment of the invention has at least the following beneficial effects: the scheme of the invention solves the problem that silver is easy to oxidize and discolor by alloying, and reduces the maintenance treatment of the silver product in the later use process; the alloy takes titanium, niobium and tantalum as alloy elements, the metal elements have strong oxidation resistance, and a compact internal structure can be formed in the process of alloying with silver, so that the alloy has good oxidation resistance and machining performance.
According to the application of the embodiment of the third aspect of the invention, the silver-containing product is prepared by adopting the oxidation-resistant silver alloy.
According to some embodiments of the invention, the silver-containing article is a silver jewelry or silver ware.
The application of the embodiment of the invention has at least the following beneficial effects: the silver alloy of the scheme of the invention has high silver content, and the alloy elements do not contain noble metals, so that the production and manufacturing cost is saved, and the silver product prepared by the silver alloy has good commercial prospect.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
In order to explain the technical content, the objects and the effects of the present invention in detail, the following description will be given with reference to the embodiments.
The first embodiment of the invention is as follows: an antioxidizing Ag alloy contains Ag (92.5%), Ti (4.5%), Nb (1.5%) and Ta (1.5%).
The specific preparation process comprises the following steps:
1) 92.5g of silver, 4.5g of titanium, 1.5g of niobium and 1.5g of tantalum are accurately weighed, uniformly mixed, put into a vacuum smelting furnace, smelted at 960 ℃ for 1.5 hours, and cooled to room temperature after smelting is finished.
2) The heat treatment is carried out according to the following temperature rising program: heating from room temperature to 200 deg.C at a speed of 3 deg.C/min, heating to 400 deg.C at a speed of 1 deg.C/min, and naturally cooling to room temperature.
The anti-oxidation silver alloy prepared by the operation can not be corroded to change color when being placed in corrosive environments such as atmosphere, sweat, hydrogen sulfide atmosphere and the like, and can keep the original luster of metal for a long time.
The second embodiment of the invention is as follows: an antioxidizing Ag alloy contains Ag (95.8%), Ti (2%), Nb (1.1%) and Ta (1.1%).
The specific preparation process comprises the following steps:
1) accurately weighing 95.8g of silver, 2g of titanium, 1.1g of niobium and 1.1g of tantalum, uniformly mixing the silver, the titanium, the niobium and the tantalum, putting the mixture into a vacuum smelting furnace, smelting at 1000 ℃ for 1 hour, and cooling to room temperature after the smelting is finished.
2) The heat treatment is carried out according to the following temperature rising program: the temperature is raised from room temperature to 200 ℃ at the speed of 6 ℃/min, then raised to 400 ℃ at the speed of 1.5 ℃/min, and then naturally cooled to room temperature.
And (3) obtaining the oxidation-resistant silver alloy after heat treatment, wherein the oxidation-resistant silver alloy prepared by the operation can not be corroded and discolored when placed in corrosive environments such as atmosphere, sweat, hydrogen sulfide atmosphere and the like, and can keep the original luster of the metal for a long time.
The third embodiment of the invention is as follows: an anti-oxidation silver alloy comprises 97% of silver, 1% of titanium, 1% of niobium and 1% of tantalum.
The specific preparation process comprises the following steps:
1) 97g of silver, 1g of titanium, 1g of niobium and 1g of tantalum are accurately weighed, uniformly mixed, put into a vacuum smelting furnace, smelted at 1050 ℃ for 0.5 hour, and cooled to room temperature after smelting is finished.
2) The heat treatment is carried out according to the following temperature rising program:
heating from room temperature to 200 deg.C at 10 deg.C/min, heating to 400 deg.C at 1.5 deg.C/min, and naturally cooling to room temperature.
The oxidation resistant silver alloy can be obtained after heat treatment, and the prepared oxidation resistant silver alloy can not generate corrosion discoloration when being placed in the corrosion environment such as atmosphere, sweat, hydrogen sulfide atmosphere and the like, and can keep the original luster of the metal for a long time.
The first comparative example of the invention is an oxidation resistant silver, and the preparation scheme adopts the scheme of example 1 in the Chinese patent application document CN 110158064A.
The second comparative example of the invention is oxidation resistant silver, containing 92% silver, 7.5% titanium, 0.5% niobium and 0.5% tantalum. The preparation process is exactly the same as in the first example.
The third comparative example of the invention is antioxidant silver, containing 92.5% silver, 4.5% titanium, 2% niobium and 1% tantalum. The preparation process is exactly the same as in the first example.
The fourth comparative example of the invention is an oxidation resistant silver, which is different from the first example only in that: the temperature rising procedure is as follows: the temperature is raised from room temperature to 200 ℃ at a speed of 1.5 ℃/min, and then to 400 ℃ at a speed of 6 ℃/min.
Comparative example five of the present invention is pure silver.
The silver products prepared in the above examples 1 to 3 and comparative examples 1 to 5 were subjected to corrosion resistance test in hydrogen sulfide atmosphere:
a10% sodium sulfide solution was prepared and placed in a transparent sealed box at room temperature of 35 ℃ and comparative example 1 was placed in the sealed box together with the examples and observed for discoloration every half hour, the results of which are shown in Table 1 below.
TABLE 1 Oxidation resistance of different materials
As can be seen from Table 1, although the silver products prepared by the comparative examples 1-4 also have better corrosion resistance, the silver products prepared by the comparative example 1 cannot be processed, the practicability is extremely poor, the oxidation resistance in the comparative examples 2 and 3 is slightly poor, the situations of crystallization, bubbles and the like are easy to occur during casting, and the practical processing application limitation is larger. The silver material prepared by the scheme of the embodiment of the invention has excellent processing performance and good oxidation resistance, can effectively solve the problem that pure silver is easy to oxidize and discolor in the prior art, and simultaneously avoids the problems of poor mechanical performance and the like of the oxidation resistant silver prepared by the traditional method. The data of comparative examples 2-3 and example 1 show that when the content of titanium or niobium is too high, the oxidation resistance and the processability are reduced. Combining the data of comparative example 4 and example 1, it can be seen that the temperature rising mode has a great influence on the processing performance of the silver alloy.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent modifications made by the present invention in the specification or directly or indirectly applied to the related technical field are included in the scope of the present invention.
Claims (10)
1. The preparation method of the oxidation-resistant silver alloy is characterized by comprising the following steps: the method comprises the following steps:
uniformly mixing silver, titanium, niobium and tantalum, carrying out vacuum melting, cooling to room temperature after the melting is finished, reforming the alloy crystal form through heat treatment, and cooling to obtain the alloy.
2. The method for preparing the oxidation-resistant silver alloy according to claim 1, wherein: the temperature of the smelting operation is (960-1050) DEG C.
3. The method for preparing the oxidation-resistant silver alloy according to claim 1, wherein: the time of the smelting operation is (0.5-1.5) h.
4. The method for preparing the oxidation-resistant silver alloy according to claim 1, wherein: the heat treatment is carried out by heating to 100-.
5. The method for preparing the oxidation-resistant silver alloy according to claim 1, wherein: in the process of mixing the silver, the titanium, the niobium and the tantalum, the mass percent of the silver is (92.5-97)%.
6. The method for preparing the oxidation-resistant silver alloy according to claim 1, wherein: in the process of mixing the silver, the titanium, the niobium and the tantalum, the mass percent of the titanium is less than 7.5%.
7. The method for preparing the oxidation-resistant silver alloy according to claim 1, wherein: in the process of mixing the silver, the titanium, the niobium and the tantalum, the mass percent of the niobium is less than 2%.
8. The method for preparing the oxidation-resistant silver alloy according to claim 1, wherein: in the process of mixing the silver, the titanium, the niobium and the tantalum, the mass percent of the tantalum is less than 2%.
9. An oxidation resistant silver alloy made by the method of any one of claims 1 to 8.
10. An article containing silver, comprising the oxidation-resistant silver alloy of claim 9 as a starting material for its preparation.
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| CN201911092779.3A CN110951986B (en) | 2019-11-11 | 2019-11-11 | Antioxidant silver alloy and preparation method and application thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS637346A (en) * | 1986-06-27 | 1988-01-13 | Sumitomo Electric Ind Ltd | Electrical contact material and its production |
| CN1397655A (en) * | 2001-07-17 | 2003-02-19 | 华中科技大学 | Anti-colouring Ag-alloy material and its preparing process |
| WO2011065922A1 (en) * | 2009-11-24 | 2011-06-03 | Autium Pte Ltd | Tarnish-resistant silver alloy |
| CN108179304A (en) * | 2018-03-23 | 2018-06-19 | 依波精品（深圳）有限公司 | Silver alloy and its manufacturing process and application |
| CN109943745A (en) * | 2019-04-29 | 2019-06-28 | 邵明战 | A kind of anti-tarnishing silver alloy and preparation method thereof |
-
2019
- 2019-11-11 CN CN201911092779.3A patent/CN110951986B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS637346A (en) * | 1986-06-27 | 1988-01-13 | Sumitomo Electric Ind Ltd | Electrical contact material and its production |
| CN1397655A (en) * | 2001-07-17 | 2003-02-19 | 华中科技大学 | Anti-colouring Ag-alloy material and its preparing process |
| WO2011065922A1 (en) * | 2009-11-24 | 2011-06-03 | Autium Pte Ltd | Tarnish-resistant silver alloy |
| CN108179304A (en) * | 2018-03-23 | 2018-06-19 | 依波精品（深圳）有限公司 | Silver alloy and its manufacturing process and application |
| CN109943745A (en) * | 2019-04-29 | 2019-06-28 | 邵明战 | A kind of anti-tarnishing silver alloy and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 李永涛等: "首饰用抗变色银合金研究进展", 《材料导报》 * |
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