CN109943745A - A kind of anti-tarnishing silver alloy and preparation method thereof - Google Patents
A kind of anti-tarnishing silver alloy and preparation method thereof Download PDFInfo
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- CN109943745A CN109943745A CN201910356357.6A CN201910356357A CN109943745A CN 109943745 A CN109943745 A CN 109943745A CN 201910356357 A CN201910356357 A CN 201910356357A CN 109943745 A CN109943745 A CN 109943745A
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Abstract
The invention discloses a kind of anti-tarnishing silver alloys, according to percent by weight, including following components: silver 89.0~99.0%, aluminium 0.01~10%, iron 0.01~11%, copper 0.01~6%, titanium 0.01~10%, zirconium 0.01~11%, indium 0.01~6%, Al-Ti-B alloy 0~8%, cobalt 0.01~5%；It also discloses for said components to be put into electric arc furnaces and carries out melting, ingot casting is made, ingot casting is put into the resistance furnace of protective atmosphere, carries out homogenization heat treatment, the method that quenching heat treatment obtains silver alloy later.The alloying element that the present invention passes through addition, refine silver alloy crystallite dimension, it is anti-oxidant to improve silver alloy, sulfuration resistant, corrosion resistance, and the preparation process of silver alloy is simple, and alloying element is at low cost, it solves the problems, such as that silver alloy jewellery and vessel are easy to change in use, has broad application prospects.
Description
Technical field
The present invention relates to technical field of metal material, more particularly to a kind of anti-tarnishing silver alloy and its preparation side
Method.
Background technique
Silver and silver alloy are as a kind of noble metal, since it is with good chemical stability and thermal conductivity,
It is widely used in manufacturing bullion, the fields such as vessel and electronic device, pure metallic silver hardness is low, and it is easy to wear, it is difficult
To form manufacture.Sterling silver alloy (referred to as 925 silver medals) are prepared by adding 7.5wt% copper in fine silver, are significantly improved
The hardness and mechanical property of silver alloy, make it be widely used in bullion industry.But silver and silver alloy are easy to sulphide discoloration,
During silver jewellery is worn, it is easy to react discoloration, main reaction with sulfide present in atmosphere (hydrogen sulfide etc.) and sweat
Mechanism is: Ag+H2S→Ag2S+H2, due to leading to silver and silver alloy discoloration, generating blackspot in Silver Jewelry Surface Creation silver sulfide.
Silver-colored sulphide discoloration in order to prevent, in recent years, people plate one layer of protection in silver surface by completely cutting off the method for air
Film, Protective coatings can be metal oxide or transparent organic, however by plating layer protecting film in silver surface
Method its shortcoming is that, if during wearing jewellery scratch and damage, will result directly in protective film broken invalid, and then cause
Silver vulcanizes and changes colour；Simultaneously in silver surface protective film coating, the production process of silver and silver alloy product is increased, life is considerably increased
Produce cost.
In addition, improving also by silver metal alloying, its anti-discoloration can solve silver and silver alloy is easy to sulphide discoloration
Technology.By addition noble metal (gold, palladium, platinum etc.), base metal (zinc, germanium, indium, tin, gallium etc.) and rare earth element (rhenium, yttrium etc.) come
Prevent silver and silver alloy sulphide discoloration.The wherein addition of noble metal and rare earth element considerably increases the production of silver and silver alloy
Cost, it is difficult to it is widely used, and the addition of base metal can effectively improve the mechanical property and anti-discoloration of silver and silver alloy
Can, but since base metal is in the limitation of silver metal room temperature solubility, a small amount of addition cannot significantly improve the power of silver alloy
Learn the ability of performance and sulfuration resistant discoloration.
Therefore, how a kind of significant silver alloy of discoloration-resisting is provided and the low silver of simple process, production cost closes
The problem of preparation method of gold is those skilled in the art's urgent need to resolve.
Summary of the invention
In view of this, increasing base metal in silver metal the present invention provides a kind of anti-tarnishing silver alloy and its preparation process
Room temperature solubility significantly improves anti-oxidant silver alloy, sulfuration resistant, corrosion-resistant, fastness performance.
In order to achieve the above object, the present invention adopts the following technical scheme:
A kind of anti-tarnishing silver alloy, according to percent by weight, including 89.0~99.0% silver and surplus aluminium,
Any one in iron, copper, titanium, zirconium, indium, Al-Ti-B alloy or cobalt or several mixtures.
Preferably, in a kind of above-mentioned anti-tarnishing silver alloy, according to percent by weight, including 89.0~99.0%
Silver and 0.01~10% aluminium, 0.01~11% iron, 0.01~6% copper, 0.01~10% titanium, 0.01~11%
Zirconium, 0.01~6% indium, in 0~8% Al-Ti-B alloy or 0.01~5% cobalt any one or it is several mixed
Close object.
Preferably, in a kind of above-mentioned anti-tarnishing silver alloy, the Al-Ti-B alloy is AlTi5B1、AlTi5B0.6、
AlTi5B0.2、AlTi3B1In any one.
The present invention makes an addition in the alloying element of silver, and aluminium and ferro element need at least to add one kind, and other elements can be any
Ratio addition, aluminium improve the tensile strength and inoxidizability of silver alloy；Iron has refined silver alloy crystallite dimension, improves silver-colored conjunction
The sulfuration resistant of gold；Copper improves the hardness and strength of silver alloy；Titanium and zirconium improve the corrosion resistance of silver alloy；Indium improves
The hardness and wearability of silver alloy；Al-Ti-B alloy has refined silver alloy crystallite dimension, improves the intensity of silver alloy and resists
Cure.Alloy on the basis of adding copper, add aluminium, titanium, zirconium arbitrary element, can improve simultaneously silver alloy intensity and
Inoxidizability；Alloy is on the basis of adding copper, addition iron, indium, cobalt, and Al-Ti-B alloy can improve silver alloy simultaneously
Intensity and sulfuration resistant.
The invention also discloses a kind of preparation methods of anti-tarnishing silver alloy, comprising the following steps:
(1) it weighs above-mentioned each elemental constituent and is put into non-consumable electrode electric arc furnace and carry out melting, ingot casting is made；
(2) ingot casting by step (1) melting is put into the resistance furnace of protective atmosphere, carries out homogenization heat treatment；
(3) ingot casting by step (2) heat treatment carries out quenching heat treatment.
Preferably, in a kind of above-mentioned anti-tarnishing silver alloy, the temperature of step (2) the homogenization heat treatment is 600-
800 DEG C, soaking time 1-24h.
Preferably, in a kind of above-mentioned anti-tarnishing silver alloy, step (2) protective atmosphere is high-purity argon gas or vacuum.
Preferably, in a kind of above-mentioned anti-tarnishing silver alloy, step (3) the quenching heat treatment condition is: will be heat-treated
Ingot casting be furnace-cooled to 100-300 DEG C of temperature, water cooling to room temperature remains solid solubility of the alloying element in silver at high temperature, disappears
Except the formation of precipitated phase in cooling procedure, and then room temperature solid solubility of the alloying element in silver is improved, is a kind of to prepare high conjunction
The effective way of gold dollar cellulose content silver alloy.
It can be seen via above technical scheme that compared with prior art, the present disclosure provides a kind of conjunctions of fastness silver
Gold and preparation method thereof has the advantage that
(1) present invention makes an addition to the alloying element in silver, can refine the crystallite dimension of silver alloy, be obviously improved silver alloy
Mechanical property, solve the problems, such as silver alloy it is oxidizable vulcanization and it is easy to change；
(2) silver alloy that the present invention prepares, element without precious metal, production cost is low, simple process, is easy to industry
Metaplasia produces；
(3) silver alloy that the present invention prepares can significantly improve the anti-of silver alloy containing high alloying element content
Oxidation, sulfuration resistant is corrosion-resistant, the performance of fastness.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 attached drawing is the vulcanization experimental result of silver alloy and fine silver made from embodiment 1；
Fig. 2 attached drawing is the vulcanization experimental result of silver alloy and fine silver made from embodiment 2；
Fig. 3 attached drawing is that silver alloy made from embodiment 3 is exposed to the experimental result in air；
Fig. 4 attached drawing is that silver alloy made from embodiment 4 is soaked in the experimental result in human sweat；
Fig. 5 attached drawing is that silver alloy made from embodiment 5 is soaked in the experimental result in human sweat.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, the described embodiment is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the reality in the present invention
Example is applied, every other embodiment obtained by those of ordinary skill in the art without making creative efforts all belongs to
In the scope of protection of the invention.
Embodiment 1
By weight percentage, 92.5% silver medal is taken, 5% bronze medal is put into non-consumable electrode electric arc furnace after the mixing of 2.5% aluminium and carries out
Melting repeats melting and button shape ingot casting is made three times.By the ingot casting of melting, 750 DEG C are put into the resistance furnace of argon atmosphere,
Heat preservation 4 hours, furnace is cooled to 100 DEG C of temperature, water cooling to room temperature.Under 3kg load, alloy Vickers hardness is 80.According to
HB5051-93 is put into 30min in 1% sodium sulfide solution by manufactured dore bullion bar under the conditions of 23 DEG C, as shown in Figure 1,
The silver alloy surface on the left side does not change colour, and the obvious blackening of the fine silver on the right.
Embodiment 2
By weight percentage, 92.5% silver medal is taken, is put into non-consumable electrode electric arc furnace after the mixing of 7.5% aluminium and carries out melting,
It repeats melting and button shape ingot casting is made three times.By the ingot casting of melting, 800 DEG C are put into the resistance furnace of argon atmosphere, heat preservation 4
Hour, furnace is cooled to 300 DEG C of temperature, water cooling to room temperature.Under 3kg load, alloy Vickers hardness is 83.According to HB5051-93,
By manufactured dore bullion bar under the conditions of 23 DEG C, it is put into 30min in 1% sodium sulfide solution, as shown in Fig. 2, the silver on the left side closes
Gold surface does not change colour, and the obvious blackening of the fine silver on the right.
Embodiment 3
By weight percentage, 92.5% silver medal, 5% bronze medal, 2.5% Al-Ti-B alloy AlTi are taken5B1Non-consumable electricity is put into after mixing
Melting is carried out in pole electrical arc furnace, repeats melting and button shape ingot casting is made three times.By the ingot casting of melting, it is put into argon atmosphere
800 DEG C in resistance furnace, 4 hours are kept the temperature, furnace is cooled to 300 DEG C of temperature, water cooling to room temperature.Under 3kg load, alloy Vickers hardness
It is 85.By manufactured dore bullion bar under the conditions of 23~35 DEG C, it is placed in and is exposed to the sun in air and 3 months in gift box, such as Fig. 3
Shown, silver alloy surface does not change colour, better than [Wen Yongbo, Zeng Quanhui, Li Jiawei probe into fine silver ornaments in document (comparative example)
Antioxygenic property modern surveying and laboratory room managing .2016,5:10-13] report fine silver effect (be exposed to the sun 22 days, it is common to encapsulate
48 days), the results are shown in Table 1.
1 oxidation results contrast table of table
| Alloy | It is exposed to the sun | As a result | Common encapsulation | As a result |
| Embodiment 3 | 90 days | Do not change colour | 90 days | Do not change colour |
| Comparative example | 22 days | Discoloration | 48 days | Discoloration |
Embodiment 4
By weight percentage, 92.5% silver medal is taken, 5% bronze medal is put into non-consumable electrode electric arc furnace after the mixing of 2.5% iron and carries out
Melting repeats melting and button shape ingot casting is made three times.By the ingot casting of melting, 600 DEG C are put into the resistance furnace of argon atmosphere,
Heat preservation 4 hours, furnace is cooled to 100 DEG C of temperature, water cooling to room temperature.Under 3kg load, alloy Vickers hardness is 90.It will be manufactured
Dore bullion bar is placed in simulation human sweat 7 days under the conditions of 23~35 DEG C, as shown in figure 4, silver alloy does not change colour, better than text
Offer in (comparative example) [Wen Yongbo, Zeng Quanhui, Li Jiawei probe into fine silver ornaments antioxygenic property modern surveying and laboratory manage
Manage .2016,5:10-13] the fine silver result (3 days change colour) of report, the results are shown in Table 2.
Embodiment 5
By weight percentage, 92.5% silver medal is taken, is put into non-consumable electrode electric arc furnace after the mixing of 7.5% iron and carries out melting,
It repeats melting and button shape ingot casting is made three times.By the ingot casting of melting, 700 DEG C are put into the resistance furnace of argon atmosphere, heat preservation 4
Hour, furnace is cooled to 100 DEG C of temperature, water cooling to room temperature.Under 3kg load, alloy Vickers hardness is 89.By manufactured alloy pig
It under the conditions of 23~35 DEG C, is placed in simulation human sweat 7 days, silver alloy does not change colour, better than [Wen Yong in document (comparative example)
Wave, Zeng Quanhui, Li Jiawei probe into the antioxygenic property modern surveying and laboratory room managing .2016,5:10-13 of fine silver ornaments]
The fine silver result (changing colour for 3 days) of report, the results are shown in Table 2.
Human sweat's ingredient is simulated in embodiment 4-5 are as follows: sodium chloride (20 ± 0.01g), ammonium chloride (17.5 ± 0.1g), urine
Element (5 ± 0.05g), acetic acid (2.5 ± 0.05g), lactic acid (5 ± 0.1g), pH value 4.7.
2 human body fluid test comparison table of table
| Alloy | Impregnate number of days | As a result |
| Embodiment 4 | 7 days | Do not change colour |
| Embodiment 5 | 7 days | Do not change colour |
| Comparative example | 3 days | Discoloration |
Each embodiment in this specification is described in a progressive manner, the highlights of each of the examples are with other
The difference of embodiment, the same or similar parts in each embodiment may refer to each other.For device disclosed in embodiment
For, since it is corresponded to the methods disclosed in the examples, so being described relatively simple, related place is said referring to method part
It is bright.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.
Claims (7)
1. a kind of anti-tarnishing silver alloy, which is characterized in that according to percent by weight, including 89.0~99.0% silver, and
Any one in the aluminium of surplus, iron, copper, titanium, zirconium, indium, Al-Ti-B alloy or cobalt or several mixtures.
2. a kind of anti-tarnishing silver alloy according to claim 1, which is characterized in that according to percent by weight, including
89.0~99.0% silver and 0.01~10% aluminium, 0.01~11% iron, 0.01~6% copper, 0.01~10%
Any one in titanium, 0.01~11% zirconium, 0.01~6% indium, 0~8% Al-Ti-B alloy or 0.01~5% cobalt
Or several mixture.
3. a kind of anti-tarnishing silver alloy according to claim 1, which is characterized in that the Al-Ti-B alloy is AlTi5B1、
AlTi5B0.6、AlTi5B0.2、AlTi3B1In any one.
4. a kind of preparation method of anti-tarnishing silver alloy, which comprises the following steps:
(1) it the described in any item elemental constituents of claim 1-3 is weighed is put into non-consumable electrode electric arc furnace and carry out melting, be made
Alloy cast ingot；
(2) ingot casting by step (1) melting is put into the resistance furnace of protective atmosphere, carries out homogenization heat treatment；
(3) ingot casting by step (2) heat treatment carries out quenching heat treatment.
5. a kind of preparation method of anti-tarnishing silver alloy according to claim 3, which is characterized in that step (2) is described
The temperature for homogenizing heat treatment is 600-800 DEG C, soaking time 1-24h.
6. a kind of preparation method of anti-tarnishing silver alloy according to claim 3, which is characterized in that step (2) described guarantor
Protecting atmosphere is high-purity argon gas or vacuum.
7. a kind of preparation method of anti-tarnishing silver alloy according to claim 3, which is characterized in that step (3) is described to quench
Burning hot treatment conditions are: the ingot casting of heat treatment being furnace-cooled to 100-300 DEG C of temperature, water cooling to room temperature.
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Cited By (4)
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|---|---|---|---|---|
| CN110618126A (en) * | 2019-09-27 | 2019-12-27 | 武汉理工大学 | Method for detecting anti-discoloration performance of silver alloy |
| CN110951986A (en) * | 2019-11-11 | 2020-04-03 | 湘南学院 | Antioxidant silver alloy and preparation method and application thereof |
| CN114921679A (en) * | 2022-05-20 | 2022-08-19 | 浙江福达合金材料科技有限公司 | Silver sulfide-resistant electrical contact material and preparation method thereof |
| CN115074573A (en) * | 2022-07-21 | 2022-09-20 | 武汉范琦珠宝饰品有限公司 | High-oxidation-resistance color-changing silver-based alloy for jewelry and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110618126A (en) * | 2019-09-27 | 2019-12-27 | 武汉理工大学 | Method for detecting anti-discoloration performance of silver alloy |
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| CN115074573A (en) * | 2022-07-21 | 2022-09-20 | 武汉范琦珠宝饰品有限公司 | High-oxidation-resistance color-changing silver-based alloy for jewelry and preparation method thereof |
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