CN115652131A - Cupronickel alloy for green environmental-protection decoration and preparation method thereof - Google Patents
Cupronickel alloy for green environmental-protection decoration and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a white copper alloy for green environmental protection decoration and a preparation method thereof, wherein the white copper alloy comprises 15-25 wt% of zinc, 15-25 wt% of silver, 0.5-1.5 wt% of tin, 1-2 wt% of germanium, 0.01-0.1 wt% of neodymium, 0.002-0.01 wt% of boron and the balance of copper. The cupronickel alloy is suitable for being used as a jewelry decorative material, and the cupronickel alloy obtains good comprehensive performance through the optimized matching of alloy elements, is friendly to human body, does not have sensitization risk, is green and environment-friendly, and has excellent antibacterial function; the alloy presents soft and comfortable color and has excellent decorative effect; the alloy does not contain elements which react with the gypsum mold, can be formed by adopting the gypsum mold precision casting process widely applied in the jewelry industry, and has good casting performance; the alloy can well meet the requirement of inlaying gems, has better corrosion resistance and excellent tarnish and tarnish resistance.
Description
Technical Field
The invention relates to the technical field of cupronickel alloys, in particular to a cupronickel alloy for green environmental protection decorations and a preparation method thereof.
Background
The cupronickel is widely used for products such as zippers, eye frames, coins, ornaments and the like, and is one of important ornament materials. The existing cupronickel material for ornaments uses nickel as bleaching element, the release rate of nickel exceeds the international and domestic standards by more than 35 times, and the serious risk of nickel sensitization exists. Patients with mild symptoms only show the parts of the jewelry in contact with the skin, such as ears, necks, wrists and fingers, have allergic symptoms; patients with severe symptoms may develop systemic anaphylaxis, which is a red swelling of the skin followed by small papules and blisters. Once a person develops a nickel allergy, he (she) will have a lifelong allergic response.
The european technical commission specifically established a working group to study the problem of nickel allergy in 1991. The working group tested the dissolution of nickel in sweat and finally presented a nickel directive to the european parliament and was finally accepted at month 6 of 1994, namely the "94/27/EC nickel directive". The instruction clearly specifies the nickel release rate threshold of the ornaments which are contacted with the human skin for a long time and the nickel content threshold of the punctured ornaments, and the overproof ornaments cannot be put on the market. The threshold for nickel release rate was also tightened in 2011. Similar standards are adopted in many countries except Europe, and China also adopts the national standard GB11887-2002 established in 2002, and the requirements of the European nickel instruction on the nickel content and the nickel release rate of jewelry are also followed by the regulations of China.
In addition, jewelry often carries a large number of bacteria that can cause skin disease and infection, and the microbial environment can also accelerate the corrosion of materials. Especially, the finger ring has more sweating in summer, is not usually taken down when being sleeved on a hand, is easy to store dirt and dirt, and is easy to cause mass propagation of bacteria due to local moisture to cause skin diseases. The world health organization WHO comprehensively researches the influence of hand hygiene on hospital care infection, makes corresponding specifications, lists a large number of cases to explain the bacteria carrying condition of fingers after wearing the ring, and finds that gram-negative bacteria (such as enterobacter cloacae, gram Lei Bashi bacteria, acinetobacter and the like), staphylococcus aureus, candida and the like carried by the skin at the bottom of the ring are increased obviously, and especially, a large number of bacteria can be inhabited by dirty rings and jewelry which are not clean. Moreover, many nursing staff are not clear about the relationship between wearing jewelry and carrying bacteria, and the ring is not believed to increase the risk of infection, and a considerable proportion of staff often work with the ring, resulting in infection accidents in multiple hospitals. To this end, the WHO recommends that conventional care with a wedding ring may be acceptable without a ring or other jewelry at the time of care, but that all jewelry be removed in high-risk situations such as operating theatres. The great britain publishes a ban that doctors are prohibited from wearing long-sleeve clothes, wearing jewelry and tying ties in hospitals to prevent the bacteria such as 'drug-resistant staphylococcus aureus' (MRSA) which are difficult to kill by the current antibacterial drugs from being transmitted to patients.
Therefore, if the ornament material has good allergy prevention and antibacterial performance, the ornament material has important significance for reducing or eliminating the problems of sensitization and bacteria carrying of the ornament.
In the traditional technology, partial researchers have conducted the research on nickel-free cupronickel and antibacterial copper around the nickel sensitization problem of the nickel cupronickel and the antibacterial problem of the copper alloy, and certain results are obtained. However, these studies have not been developed for a material for ornaments, and the results thereof are basically not suitable for the production of ornaments. For example, patent CN201210109779.1 discloses a nickel-free cupronickel alloy for coinage and a preparation method thereof, wherein the cupronickel comprises the following elements by mass percent: 16.0 to 19.0 percent of Zns, 3.0 to 4.0 percent of Mn3, 2.3 to 3.5 percent of Tis, 0.3 to 0.6 percent of Fes, 0.3 to 0.6 percent of Als, 0.2 to 0.4 percent of Sb0.05 to 0.2 percent of Ces, less than or equal to 0.9 percent of total impurities and the balance of copper. The alloy contains antimony which is a harmful element, and is not suitable for ornaments. Patent CN201010262393.5 discloses a nickel-free white copper alloy containing rare earth additive elements and a preparation method of a plate thereof, wherein the composition of the nickel-free white copper alloy comprises 0.02-0.1% of rare earth elements, 5-20% of zinc, 8-18% of manganese, 0.5-2.0% of aluminum, 0-0.5% of iron, 0-0.5% of titanium, 0-0.1% of zirconium and the balance of copper, the alloy contains a large amount of manganese, an alkaline oxide is easily formed in the smelting process, and the alloy and the surface of a gypsum casting mold are subjected to chemical reaction to form severe sand sticking, so the nickel-free white copper alloy is not suitable for being used as an ornament material. Patent CN201910575930.2 discloses a nickel-free cupronickel alloy and a preparation method thereof, and the components and contents of the nickel-free cupronickel alloy are as follows: 19-21% of manganese, 8-10% of zinc, 8-9% of titanium, 5-6% of aluminum, 0.8-1.0% of iron, 0.05-0.08% of silver, 0.010-0.015% of rare earth element RE, 0.6-0.7% of phosphorus, 0.1-0.2% of boron and the balance of copper, wherein the alloy contains a large amount of manganese and titanium and is not suitable for gypsum type precision casting process. Patent CN02112102.8 discloses a copper-based high-tin boron alloy, which contains 12-18% of tin, 0.01-2% of boron, at least one of five elements of iron, aluminum, titanium, phosphorus and zinc, and the balance of copper and impurities, but the alloy contains a large amount of tin, forms a network brittle phase in the structure, leads the toughness and plasticity of the material to be obviously reduced, and has no practical application value. Patent CN02151489.5 discloses a nickel-free cupronickel alloy and a production method thereof, the composition of the nickel-free cupronickel alloy is CuaZnbTiC or CuaZnbTiCXd, wherein X is at least one element selected from Al, sn, ag and Mn, b, c and d expressed by mass percentage are respectively 0.5-30 of b, 1-7 of c <7 and 0.1, the alloy contains 1-7% of titanium, and the requirement of jewelry molding is difficult to meet. Patent No. cn201480066716.X discloses a white antibacterial copper alloy whose alloy composition is more than 60% copper, and various alloy elements such as nickel, zinc, manganese, antimony, tin, aluminum, sulfur, iron, lead, etc., eventually rendering the copper alloy white gloss and having antibacterial properties, but since its composition contains 8 to 10% ni,0.1 to 1% sb,0 to 0.09% pb, these harmful elements make the material unsuitable for jewelry, and at the same time it also contains 8 to 12% mn,0 to 0.6% fe, making it unsuitable for the gypsum type precision casting process. Patent CN201810739567.9 discloses a silver-containing antibacterial copper alloy and a preparation method thereof, wherein the silver-containing antibacterial copper alloy comprises 0.07-0.15% of silver, 99.75-99.92% of copper and 0.01-0.1% of other impurities, but the color of the material is basically consistent with that of pure copper.
Disclosure of Invention
Aiming at overcoming the defects of the prior art and solving the problems of the prior art, the invention aims to provide the environment-friendly decorative cupronickel alloy, which solves the problems of the prior art, is friendly to human body, does not have sensitization risk, is environment-friendly and has excellent antibacterial function; the alloy has soft and comfortable color, good decorative effect, better corrosion resistance and good tarnish and tarnish resistance.
The invention also aims to provide a preparation method of the cupronickel alloy for green environmental protection decorations, which has simple preparation process and easy popularization.
One of the purposes of the invention is realized by adopting the following technical scheme:
the cupronickel alloy for the green environmental protection decoration comprises the following components in percentage by weight:
15 to 25 percent of zinc, 15 to 25 percent of silver, 0.5 to 1.5 percent of tin, 1 to 2 percent of germanium, 0.01 to 0.1 percent of neodymium, 0.002 to 0.01 percent of boron, and the balance of copper and inevitable impurity elements.
The environment-friendly decorative white copper alloy has the advantages that copper is matched with elements such as zinc, silver, tin, neodymium, boron, germanium and the like, and the white copper alloy obtains good comprehensive performance through the optimized matching of alloy elements, is environment-friendly to human bodies, does not have sensitization risk, is environment-friendly and has an excellent antibacterial function; the alloy presents soft and comfortable color and has excellent decorative effect; the alloy does not contain elements which react with carbon, and can adopt a liquidus line which is smelted by a graphite crucible commonly used in the jewelry industry; the liquidus of the alloy is not more than 860 ℃, elements which react with the gypsum mold do not exist, the alloy can be formed by adopting the gypsum type precision casting process widely applied in the jewelry industry, and the alloy has good casting performance; the hardness of the alloy is between HV 110-150, the alloy can well meet the requirements of inlaying gems, and the alloy has better corrosion resistance and excellent tarnish and tarnish discoloration resistance.
The specific technical principle is as follows:
as an ornament material which is in long-term contact with the body surface of a human body, the ornament material is firstly required to be friendly to the human body, except that the release amount of nickel is not contained or the release amount of nickel is within the required threshold range, the ornament material can not contain other harmful elements such as lead, antimony, cadmium and the like, meanwhile, the structure of the ornament is fine and complex, most of the ornament material is formed by precision casting, most of the ornament material needs to be embedded with gems, the material is required to have proper hardness and elasticity, when the hardness is too low, the gems are not firmly embedded, when the hardness is too high, the embedding difficulty is high, and the tool loss is serious.
Because copper is purple red, a considerable amount of bleaching elements are required to be added to obtain good white, and nickel and palladium are elements with strong bleaching capacity, but the former is a typical sensitizing element, and the latter is too expensive, so that the copper is not suitable for use. Therefore, the invention designs the alloy components comprehensively from the aspects of decoration, corrosion resistance, processability, safety performance and the like, adopts multiple elements to carry out multi-element alloying, and respectively plays the roles of bleaching, improving brightness, reducing red index and the like through different alloy elements, improves corrosion resistance, improves material hardness, improves processability, improves casting performance and the like, and the alloy elements are inert to the graphite crucible and the gypsum casting mold material and cannot generate chemical reaction with the graphite crucible and the gypsum casting mold material. Through the optimized matching among alloy elements, the alloy obtains excellent effects in the aspects of color, casting performance, hardness, corrosion resistance, antibacterial performance and the like.
Wherein, (1) zinc. The zinc has certain bleaching effect on the copper, and is helpful for improving the color of the alloy. The zinc can obviously reduce the melting point of the alloy, can reduce the surface tension of molten metal, improve the fluidity of the molten metal, can form zinc vapor in the smelting process and reduce the gas-suction oxidation tendency of the molten metal. However, when the zinc content is too high, the corrosion resistance of the alloy is not good, and dezincification corrosion is easily caused; but also the toughness and plasticity of the alloy are not favorable, and the inlaying operation and the stability of the jewel are adversely affected.
(2) Silver. Has excellent antibacterial property, has a bleaching effect on copper, has poor bleaching effect when the bleaching effect is too low, and increases material cost when the bleaching effect is too high. Silver can reduce the oxidation tendency of molten metal, improve the fluidity of the molten metal and improve the casting performance of the alloy. Silver improves the corrosion resistance, especially the oxidation resistance, of the alloy.
(3) And tin. Has bleaching effect on copper and obviously improves the corrosion resistance of the alloy. Tin can lower the melting point of the alloy, but can enlarge the solidification temperature range and increase the shrinkage porosity tendency of the casting.
(4) And (3) germanium. Has certain bleaching effect on copper, can reduce the surface tension of molten metal and improve the casting performance of the alloy. However, germanium reduces the thermoplasticity of the alloy, forming a hard and brittle interphase in the alloy structure. The applicant has found through several tests that the toughness and plasticity of the alloy are affected when the germanium content exceeds 1%.
(5) And boron. Can improve metallurgical quality, purify molten metal, reduce surface tension, improve metal fluidity, improve casting performance, and refine crystal grains. However, when the content is too high, slag is generated in the molten metal, resulting in casting defects.
(6) Neodymium. Can obviously refine the grain structure of the alloy and improve the metallurgical quality. However, when the content is too high, slag is easily generated and the toughness and plasticity of the alloy are affected.
Further, (7) silicon. Has bleaching effect on copper, has poor effect when the copper is too low, and influences the plasticity of the material when the copper is too high. Silicon can reduce the surface quality of molten metal and improve the fluidity and casting performance of the molten metal. Silicon can improve the strength of the material and improve the corrosion resistance, but when the content is too high, the plasticity of the material is reduced, and even the inlaying requirement cannot be met.
(8) And (4) indium. Has bleaching effect on copper, can reduce the melting point of the alloy, and can also reduce the surface tension of molten metal, thereby being beneficial to the fluidity and the casting performance of the molten metal. Indium is also beneficial for improving the corrosion resistance of the alloy. However, if the content is too high, the crystallization temperature range of the alloy is widened, and the tendency of the casting to be loosened is increased.
(9) Ruthenium. Belongs to noble metal elements, has high melting point, plays a role in obviously refining grains of the alloy and is beneficial to improving the surface quality and the mechanical property of a casting. However, ruthenium is expensive, and when the content is too high, hard particles are easily formed in the structure, and the polishing performance of the alloy is deteriorated.
In conclusion, by combining the properties of the materials, the material composition is designed according to the action characteristics of the alloy elements in the copper alloy.
Further, the total content of the inevitable impurity elements does not exceed 0.1wt%.
Further, the white copper alloy for green environmental decorations comprises the following components in percentage by weight:
zinc 20wt%, silver 15wt%, tin 0.5wt%, germanium 2wt%, neodymium 0.01wt%, boron 0.002wt%, and the balance copper and inevitable impurity elements.
Further, the cupronickel alloy for the green environmental-friendly decorations comprises the following components in percentage by weight:
24.4% by weight of zinc, 20% by weight of silver, 1% by weight of tin, 1.5% by weight of germanium, 0.05% by weight of neodymium, 0.005% by weight of boron, and the balance copper and inevitable impurity elements.
Further, the white copper alloy for green environmental decorations comprises the following components in percentage by weight:
zinc 15wt%, silver 25wt%, tin 1.5wt%, germanium 1wt%, neodymium 0.1wt%, boron 0.01wt%, and the balance copper and inevitable impurity elements.
Further, the white copper alloy for green environmental decorations is prepared by adopting a vacuum induction melting mode.
The second purpose of the invention is realized by adopting the following technical scheme:
a preparation method of a cupronickel alloy for green environmental decorations comprises the following preparation steps:
s1: weighing the following components in percentage by weight:
15 to 25 percent of zinc, 15 to 25 percent of silver, 0.5 to 1.5 percent of tin, 1 to 2 percent of germanium, 0.01 to 0.1 percent of neodymium, 0.002 to 0.01 percent of boron, and the balance of copper and inevitable impurity elements;
s2: premelting of master alloys
Preparing zinc, silver, tin, germanium, neodymium and boron of each pure metal material into an intermediate alloy;
s3: melting of casting alloys
Proportioning copper and the intermediate alloy in proportion, and casting the material into ingots or preparing the material into particles after vacuum induction melting to obtain the environment-friendly decorative white copper alloy.
Further, in step S1, the copper is oxygen-free copper with a purity of 99.95% or more; zinc, silver, tin, germanium, neodymium and boron are all pure metal materials with the purity of more than 99.5 percent.
Further, in step S2, the intermediate alloy is prepared by vacuum induction melting.
Further, in step S3, the size of the pellets is 2 to 6 mm.
Further, the operation steps of the vacuum induction melting mode are as follows: vacuumizing to 5-20 Pa, filling argon to 1.0-1.02 atm, mechanically stirring to make molten metal homogeneous, and casting to form ingot or granule.
Compared with the prior art, the invention has the beneficial effects that:
the cupronickel alloy for green environmental protection decorations is suitable for being used as jewelry decoration materials, the cupronickel alloy obtains good comprehensive performance through the matching of copper and elements such as zinc, silver, tin, neodymium, boron, germanium and the like and the optimized matching of alloy elements, is friendly to human body, does not have sensitization risk, is green and environmental-friendly, and has excellent antibacterial function; the alloy presents soft and comfortable color and has excellent decorative effect; the alloy does not contain elements which react with carbon, and can adopt a liquidus line which is smelted by a graphite crucible commonly used in the jewelry industry; the liquidus of the alloy is not more than 860 ℃, elements which react with the gypsum mold and react chemically do not exist, the alloy can be formed by adopting the gypsum type precision casting process widely applied in the jewelry industry, and the alloy has good casting performance; the hardness of the alloy is between HV 110-150, the alloy can well meet the requirements of inlaying gems, and the alloy has better corrosion resistance and excellent tarnish and tarnish discoloration resistance.
Drawings
FIG. 1 is an impedance spectrum of the alloy material of comparative example 1 in artificial sweat;
FIG. 2 is an impedance spectrum of the alloy material of example 3 in artificial sweat;
FIG. 3 is an as-cast surface roughness map of example 1;
FIG. 4 is a graph showing the effect of surface polishing of the alloy material of example 1;
FIG. 5 is an as-cast surface roughness plot for comparative example 1;
FIG. 6 is a diagram showing bacterial colonies on the surface of a blank glass plate;
FIG. 7 is a graph showing the antibacterial effect on the surface of the sample of comparative example 1;
FIG. 8 is a graph showing the antibacterial effect of the surface of the sample in example 2.
Detailed Description
The present invention is further described below with reference to specific embodiments, and it should be noted that, without conflict, various embodiments or technical features described below may be arbitrarily combined to form a new embodiment. In the following examples, the copper is oxygen-free copper with a purity of 99.95% or more; sn, zn, ag, ge, ga, B, ru, gd, and Nb are all pure metal materials with a purity of 99.5% or more. The operation steps of the vacuum induction melting mode are as follows: vacuumizing to 5-20 Pa, filling argon to 1.0-1.02 atm, mechanically stirring to make molten metal homogeneous, and casting to form ingot or granule.
Example 1
The white copper alloy for green environmental protection decorations comprises the following preparation steps:
s1: weighing the following components in percentage by weight:
zinc 20wt%, silver 15wt%, tin 0.5wt%, germanium 2wt%, neodymium 0.01wt%, boron 0.002wt%, and the balance copper and inevitable impurity elements; wherein the total content of unavoidable impurity elements does not exceed 0.1wt%.
S2: premelting of master alloys
Preparing zinc, silver, tin, germanium, neodymium and boron of each pure metal material into an intermediate alloy;
s3: melting of casting alloys
Proportioning copper and intermediate alloy according to a proportion, carrying out vacuum induction melting, and then casting the material into ingots to obtain the copper-intermediate alloy.
Example 2
The white copper alloy for green environmental protection decorations comprises the following preparation steps:
s1: weighing the following components in percentage by weight:
24.4% by weight of zinc, 20% by weight of silver, 1% by weight of tin, 1.5% by weight of germanium, 0.05% by weight of neodymium, 0.005% by weight of boron, and the balance copper and inevitable impurity elements; wherein the total content of unavoidable impurity elements does not exceed 0.1wt%.
S2: premelting of master alloys
Preparing zinc, silver, tin, germanium, neodymium and boron of each pure metal material into an intermediate alloy;
s3: melting of casting alloys
Proportioning copper and intermediate alloy in proportion, and preparing the material into particles with the particle size of 2-6 mm after vacuum induction melting.
Example 3
The white copper alloy for green environmental protection decorations comprises the following preparation steps:
s1: weighing the following components in percentage by weight:
zinc 15wt%, silver 25wt%, tin 1.5wt%, germanium 1wt%, neodymium 0.1wt%, boron 0.01wt%, and the balance copper and inevitable impurity elements; wherein the total content of unavoidable impurity elements does not exceed 0.1wt%.
S2: premelting of master alloys
Preparing zinc, silver, tin, germanium, neodymium and boron of each pure metal material into an intermediate alloy;
s3: melting of casting alloys
Proportioning copper and intermediate alloy according to a proportion, carrying out vacuum induction melting, and then casting the material into ingots to obtain the copper-intermediate alloy.
Comparative example 1
The alloy of comparative document 1 is a Cu76Mn14Zn10Sn nickel-free cupronickel alloy.
And (3) performance testing:
1. the samples tested were: in examples 1 to 3 and comparative example 1, indexes such as physical properties, chemical properties, mechanical properties, process properties and the like are detected under the same conditions.
2. The test method comprises the following steps: the melting temperature and the crystallization interval of the material are detected by adopting a differential thermal analyzer, the hardness of the material is detected by adopting a microhardness meter by adopting a plaster type precision casting process, the casting density of the material is detected by adopting an Archimedes method, the color of the material is detected by adopting a spectrocolorimeter, the impedance and polarization curve of the material are detected by adopting an electrochemical workstation, and the antibacterial performance of the material is detected by adopting a contact method.
3. The test results are shown below.
(1) Melting temperature and crystallization Interval
The liquidus temperature and crystallization temperature interval of example 1 and comparative example 1 were measured by a differential thermal analyzer as shown in Table 1.
TABLE 1 comparison of characteristic temperatures
| Material | Liquidus temperature,. Degree.C | Interval of crystallization temperature,. Deg.C |
| Example 1 | 860 | 79 |
| Comparative example 1 | 1025 | 60 |
As can be seen from Table 1 above, the crystallization interval temperature of example 1 is substantially close to that of comparative example 1, and both have a low crystallization interval, which is advantageous for the densification and composition uniformity of the solidification structure. And the liquidus of the embodiment 1 is obviously lower than that of the comparative example 1, and the alloy elements which can react with the plaster casting mold are not contained, so the melting can be carried out by adopting the conventional melting means, and the plaster casting mold is suitable for being formed by adopting the plaster casting mold precision casting process. In contrast, comparative example 1 contains a large amount of manganese, cannot be smelted by a graphite crucible, but must be smelted by crucibles such as zirconia and magnesia, and the crucible materials have poor thermal shock performance, and are not allowed to be heated and cooled rapidly.
(2) Hardness of
As most ornaments are molded by casting, as-cast hardness is a very concerned index in production, particularly for inlaid ornaments, when the hardness of a blank is too high, the blank is difficult to be inlaid, when the hardness is too low, the gem has the risk of falling, and the hardness range which is more suitable under the common condition is HV 90-180.
The as-cast hardness of example 3 and comparative example 1 were measured, respectively, and the results are shown in table 2.
TABLE 2 comparison of as-cast hardness (HV 0.5)
| Material | As-cast condition | Solid solution aging state | Processing state (30%) |
| Example 3 | 113 | 140 | 161 |
| Comparative example 1 | 140 | 157 | 213 |
As can be seen from Table 2 above, both example 3 and comparative example 1 are within this range and can satisfy the damascene requirements. However, comparative example 1 has a strong work hardening effect, and when the working ratio reaches 30%, the hardness thereof exceeds HV200, and thus it is difficult to meet the requirements of the insert process such as forced setting. In contrast, in example 3, the hardness did not exceed HV180 even after 30% reduction, and thus it was suitable for various damascene processes.
(3) Compactness of cast ingot
And detecting the initial density of the cast ingot by an Archimedes method, then rolling the cast ingot to compact the possible looseness, pores and the like in the cast ingot, and reflecting the density condition of the cast ingot by using the initial density of the cast ingot and the density change rate after rolling treatment. The test results of example 1 and example 3 are shown in table 3 together with the test results of comparative example 1.
TABLE 3 comparison of densities
| Material | Ingot density, g/cm3 | Density improvement rate after rolling |
| Example 1 | 8.62 | 1.65％ |
| Example 3 | 8.83 | 1.47％ |
| Comparative example 1 | 8.1 | 3.48％ |
As can be seen from table 3 above, the density of examples 1 and 3 is slightly higher than that of comparative example, and the density increase after rolling is lower than that of comparative example 1, indicating that they have better compactness than comparative example 1, and have better polishing performance and surface effect.
(4) Colour(s)
The color index values of each of example 1 and comparative example 1 are shown in table 4.
TABLE 4 comparison of colors
| Material | L* | a* | b* |
| Example 1 | 87.06 | 0.69 | 22.32 |
| Comparative example 1 | 84.82 | 7.89 | 27.47 |
As can be seen from table 4 above, the brightness value L of example 1 is higher than that of the comparative example, and a and b are both lower than those of the comparative example, which shows that the brightness is better and is beneficial to the surface gloss of the ornament. Closer to no hue in the red-green color pair and lower yellow hue in the yellow-blue color pair, and thus more towards white.
(5) Corrosion resistance
The impedance and polarization behavior of example 3 and comparative example 1 in artificial sweat was tested using an electrochemical workstation and the results are shown in fig. 1 and fig. 2, respectively. Wherein, FIG. 1 is an impedance spectrum of the alloy material of comparative example 1 in artificial sweat; FIG. 2 is an impedance spectrum of the alloy material of example 3 in artificial sweat.
As can be seen from fig. 1 and 2, the resistance value of example 3 is higher than that of comparative example 1, indicating that the corrosion resistance of example 3 is better than that of comparative example 1.
(6) Castability
The screen mesh and jewelry blanks were cast by the gypsum type precision casting process in example 1 and comparative example 1, and the casting properties were measured, and the results are shown in fig. 3 to 5 below. FIG. 3 is an as-cast surface roughness map of example 1; FIG. 4 is a graph showing the effect of surface polishing of the alloy material of example 1; fig. 5 is an as-cast surface roughness map of comparative example 1.
As can be seen from the figure, compared with the comparative example 1, the filling rate of the screen in the example 1 reaches 100%, the surface of a jewelry blank is smooth, casting defects such as obvious sand holes, shrinkage porosity and the like do not exist, and after polishing, a good surface effect is obtained. While the casting surface of the comparative example was rough, as shown in fig. 5.
(7) Antibacterial property
The test strain adopts fresh cultured staphylococcus aureus, the bacteria liquid is evenly coated on the surfaces of the comparative example 1 and the example 2, and then a sterile film is covered on the surfaces of the staphylococcus aureus, and the staphylococcus aureus is cultured for 24 hours under the conditions of 37 ℃ and RH being more than 90 percent. Fully eluting with PBS buffer solution, performing serial dilution, sampling, performing viable bacteria counting culture, and calculating antibacterial rate. The antibacterial effects of example 2 and comparative example 1 are shown in fig. 6 to 8, using a glass plate as a blank.
It can be seen from the figure that the blank glass plate has no antibacterial effect, the antibacterial rate of the example 2 reaches more than 99%, and the antibacterial rate of the comparative example 1 is only about 92%, namely the antibacterial performance of the example 1 is obviously better than that of the comparative example 1.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.
Claims (10)
1. The cupronickel alloy for green environmental protection decorations is characterized by comprising the following components in percentage by weight:
15 to 25 percent of zinc, 15 to 25 percent of silver, 0.5 to 1.5 percent of tin, 1 to 2 percent of germanium, 0.01 to 0.1 percent of neodymium, 0.002 to 0.01 percent of boron, and the balance of copper and inevitable impurity elements.
2. The cupronickel alloy for green environmental decorations according to claim 1, characterized in that the total content of the inevitable impurity elements does not exceed 0.1 wt.%.
3. The cupronickel alloy for green environmental decorations according to claim 1, characterized by comprising the following components in percentage by weight:
zinc 20wt%, silver 15wt%, tin 0.5wt%, germanium 2wt%, neodymium 0.01wt%, boron 0.002wt%, and the balance copper and inevitable impurity elements.
4. The cupronickel alloy for green environmental decorations according to claim 1, characterized by comprising the following components in percentage by weight:
24.4% by weight of zinc, 20% by weight of silver, 1% by weight of tin, 1.5% by weight of germanium, 0.05% by weight of neodymium, 0.005% by weight of boron, and the balance copper and inevitable impurity elements.
5. The cupronickel alloy for green environmental decorations according to claim 1, which comprises the following components in percentage by weight:
zinc 15wt%, silver 25wt%, tin 1.5wt%, germanium 1wt%, neodymium 0.1wt%, boron 0.01wt%, and the balance copper and inevitable impurity elements.
6. The cupronickel alloy for green environmental protection decorations according to claim 1, wherein the cupronickel alloy for green environmental protection decorations is prepared by vacuum induction melting.
7. The preparation method of the cupronickel alloy for the green environmental protection decorations is characterized by comprising the following preparation steps:
s1: weighing the following components in percentage by weight:
15 to 25 percent of zinc, 15 to 25 percent of silver, 0.5 to 1.5 percent of tin, 1 to 2 percent of germanium, 0.01 to 0.1 percent of neodymium, 0.002 to 0.01 percent of boron, and the balance of copper and inevitable impurity elements;
s2: premelting of master alloys
Preparing zinc, silver, tin, germanium, neodymium and boron of each pure metal material into an intermediate alloy;
s3: melting of casting alloys
Proportioning copper and the intermediate alloy in proportion, and casting the materials into ingots or preparing the materials into particles after vacuum induction melting to obtain the green environment-friendly decorative cupronickel alloy.
8. The method for preparing a cupronickel alloy for green environmental decorations according to claim 7, wherein in step S1, the copper is oxygen-free copper with a purity of 99.95% or more; zinc, silver, tin, germanium, neodymium and boron are all pure metal materials with the purity of more than 99.5 percent.
9. The method for preparing the cupronickel alloy for green environmental decorations according to claim 7, wherein in the step S2, the master alloy is prepared by vacuum induction melting.
10. The method for preparing a cupronickel alloy for green environmental decorations, according to claim 7, wherein, in the step S3, the size of the particles is 2 to 6 mm.
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