CN115652131B - Environment-friendly white copper alloy for decorations and preparation method thereof - Google Patents
Environment-friendly white copper alloy for decorations and preparation method thereof Download PDFInfo
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- CN115652131B CN115652131B CN202211404284.1A CN202211404284A CN115652131B CN 115652131 B CN115652131 B CN 115652131B CN 202211404284 A CN202211404284 A CN 202211404284A CN 115652131 B CN115652131 B CN 115652131B
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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 white copper alloy is suitable for being used as jewelry decoration materials, and good comprehensive performance is obtained by optimizing and matching alloy elements, so that the white copper alloy is friendly to the human body, has no sensitization risk, is green and environment-friendly, and has excellent antibacterial function; the alloy presents soft and comfortable colors and has excellent decorative effect; the alloy does not have elements which react with the gypsum mold, can be formed by adopting a gypsum mold precision casting process widely applied to jewelry industry, and has good casting performance; the alloy can well meet the requirements of stone inlaying, and has better corrosion resistance and excellent tarnish and color change resistance.
Description
Technical Field
The invention relates to the technical field of white copper alloy, in particular to a green environment-friendly white copper alloy for decoration and a preparation method thereof.
Background
White copper is widely used for products such as zippers, eye frames, coins, ornaments and the like, and is one of important ornament materials. The existing white copper material for ornaments uses nickel as bleaching element, the nickel release rate exceeds international and domestic standards by more than 35 times, and serious nickel sensitization risks exist. Patients with lighter symptoms only show allergic symptoms at the contact parts of jewelry and skin, such as ears, necks, wrists and fingers; patients with heavy symptoms can develop systemic allergic reactions, namely red and swollen skin, and then start to form small pimples and blisters. Once a person has developed a nickel allergy, he (she) will have an allergic reaction for life.
The European technical Committee of 1991 was specialized in the work group's study of nickel allergy problems. The working group tested the dissolution of nickel in sweat and finally developed a nickel instruction to the european meeting and was finally accepted in month 6 of 1994, namely "94/27/EC nickel instruction". The instruction clearly defines the nickel release rate threshold of ornaments contacted with human skin for a long time and the nickel content threshold of piercing ornaments, and exceeding ornaments cannot be put on the market. The threshold of nickel release rate was tightened again in 2011. Similar standards are adopted in a plurality of countries except europe, china also adopts the requirements of European nickel instruction in the national standard GB11887-2002 formulated in 2002 and regulations on the nickel content and the nickel release rate of jewelry.
In addition, jewelry often carries large amounts of bacteria that can cause skin diseases and infections, and the microbial environment can also accelerate corrosion of materials. Particularly, the sweat is more in summer, the ring is not very taken down when being sleeved on the hand, dirt is easy to be absorbed, and a large amount of bacteria are easy to multiply due to local dampness, so that skin diseases are caused. The WHO of the world health organization comprehensively researches the influence of hand hygiene on hospital nursing infection and makes corresponding specifications, enumerates a large number of cases to explain the bacteria carrying condition of fingers after wearing rings, and finds that gram-negative bacteria (such as enterobacter cloacae, gram Lei Bashi bacteria, acinetobacter and the like) carried by the skin at the bottom of the rings, staphylococcus aureus, candida and the like are obviously increased, and particularly, the dirty rings and jewelry which are not noticed to be clean can be lodged with a large number of bacteria. Moreover, many caregivers do not clearly wear the jewelry and carry bacteria, and it is not believed that the ring increases the risk of infection, and a considerable percentage of people often carry the ring to work, resulting in multiple hospital infection accidents. For this reason, WHO recommends that no ring or other jewelry is carried out during nursing, conventional nursing carries wedding ring or permission, but that all jewelry should be removed in high risk situations such as operating rooms. The uk promulgates bans to prohibit doctors from wearing long-sleeved clothes, jewelry and ties in hospitals to prevent bacteria such as "drug-resistant staphylococcus aureus" (MRSA) which are difficult to kill by current antibacterial agents from being transmitted to patients.
Therefore, if the ornament material has good allergy preventing and antibacterial properties, the ornament material has definitely important significance for reducing or eliminating the problems of ornament sensitization and bacteria.
In the conventional technology, around the nickel sensitization problem of nickel-white copper and the antibacterial problem of copper alloy, some researchers have conducted researches on nickel-free white copper and antibacterial copper, and have achieved a certain result. However, these studies have not been developed for the material of ornaments, and the results thereof are not basically suitable for the manufacture of ornaments. For example, patent CN201210109779.1 discloses a nickel-free white copper alloy for coinage and a preparation method thereof, wherein the white copper comprises the following elements in percentage by mass: 16.0 to 19.0 percent of Zn, 3.0 to 4.0 percent of Mn, 2.3 to 3.5 percent of Ti, 0.3 to 0.6 percent of Fe, 0.3 to 0.6 percent of Al, 0.2 to 0.4 percent of Sb, 0.05 to 0.2 percent of Ce, the total amount of impurities is not more than 0.9 percent, and the balance of copper. The alloy contains harmful element antimony, 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, 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 copper, and the alloy contains a large amount of manganese, alkaline oxides are easy to form in the smelting process, and the alkaline oxides react with the surface of a gypsum casting mold to form serious 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 white copper alloy and a preparation method thereof, the components and the contents thereof are as follows: 19 to 21 percent of manganese, 8 to 10 percent of zinc, 8 to 9 percent of titanium, 5 to 6 percent of aluminum, 0.8 to 1.0 percent of iron, 0.05 to 0.08 percent of silver, 0.010 to 0.015 percent of rare earth RE, 0.6 to 0.7 percent of phosphorus, 0.1 to 0.2 percent of boron and the balance of copper, and the alloy contains a large amount of manganese and titanium and is not suitable for a 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 iron, aluminum, titanium, phosphorus and zinc, and the balance copper and impurities, but the alloy contains a large amount of tin, and forms a reticular brittle phase in a tissue, so that the toughness and plasticity of the material are obviously reduced, and the alloy has no practical application value. Patent CN02151489.5 discloses a nickel-free white copper alloy and a method for producing the nickel-free white copper alloy, the composition of which 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 percent are respectively 0.5-30, 1-7 and 0.1, and the alloy contains 1-7% of titanium, which is difficult to meet the molding requirement of jewelry. Patent cn201480066716.X discloses a white antibacterial copper alloy whose alloy composition is more than 60% of copper, and various alloy elements of nickel, zinc, manganese, antimony, tin, aluminum, sulfur, iron, lead, etc., which finally makes the copper alloy appear white gloss and have antibacterial property, but since the composition contains 8-10% of ni, 0.1-1% of sb, 0-0.09% of pb, these harmful elements make the material unsuitable for jewelry, and at the same time it also contains 8-12% of mn, 0-0.6% of fe, making it unsuitable for gypsum-type precision casting molding 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 silver-containing antibacterial copper alloy is basically consistent with that of pure copper.
Disclosure of Invention
Aiming at the problems of the prior art, the invention aims to provide a green environment-friendly white copper alloy for decoration, which is friendly to the human body, has no sensitization risk, is green and environment-friendly and has excellent antibacterial function; the alloy presents soft and comfortable color, has excellent decorative effect, better corrosion resistance and excellent tarnish and color resistance.
The second purpose of the invention is to provide a preparation method of the environment-friendly white copper alloy for decoration, which has simple preparation process and easy popularization.
One of the purposes of the invention is realized by adopting the following technical scheme:
the environment-friendly white copper alloy for 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 unavoidable impurity elements.
Namely, the environment-friendly white copper alloy for decoration of the invention is prepared by matching copper with zinc, silver, tin, neodymium, boron, germanium and other elements, and by optimizing and matching alloy elements, the white copper alloy has good comprehensive performance, is friendly to human body, does not have sensitization risk, is environment-friendly, and has excellent antibacterial function; the alloy presents soft and comfortable colors and has excellent decorative effect; the alloy does not contain elements which react with carbon, and can adopt the liquidus line of graphite crucible smelting commonly used in jewelry industry; the liquidus of the alloy is not more than 860 ℃, no element which reacts with gypsum mold reaction chemistry exists, the alloy can be molded by adopting a gypsum mold precision casting process widely applied to jewelry industry, and the alloy has good casting performance; the hardness of the alloy is between HV110 and 150, the requirement of stone inlaying can be well met, the alloy has better corrosion resistance and excellent tarnish and color resistance.
The specific technical principle is as follows:
as the ornament material contacting with the human body surface for a long time, the ornament material is required to be friendly to the human body, besides no nickel or nickel release amount is in the required threshold range, other harmful elements such as lead, antimony, cadmium and the like can not be contained, meanwhile, the structure of the ornament is slim and complex, most of the ornaments are formed by precision casting, and most of the ornaments need to be inlaid with precious stones, so that the ornament material is required to have proper hardness and elasticity, the precious stones are not inlaid firmly when the hardness is too low, the inlaying difficulty is high when the hardness is too high, and the tool loss is serious.
Since copper itself exhibits a purplish red color, it is necessary to add a considerable amount of bleaching elements, nickel and palladium being elements having a high bleaching ability, but the former being typical sensitization elements, and the latter being too expensive to be suitable for use. Therefore, the invention comprehensively designs alloy components from the aspects of decoration, corrosion resistance, processing performance, safety performance and the like, adopts a plurality of elements to carry out multi-element alloying, and respectively plays roles of bleaching, improving brightness, reducing red index and the like through different alloy elements, improves corrosion resistance, material hardness, processing performance, casting performance and the like, and has inertia to graphite crucible and gypsum casting materials and does not react with the graphite crucible and the gypsum casting materials. Through the optimized matching among alloy elements, the alloy has excellent effects in the aspects of color, casting performance, hardness, corrosion resistance, antibacterial performance and the like.
Wherein, (1) zinc. Zinc has a certain bleaching effect on copper and contributes to 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 reduces the aspiration oxidation tendency of the molten metal. However, when zinc is too high, the corrosion resistance of the alloy is not good, and dezincification corrosion is easily caused; and is also unfavorable for the toughness and plasticity of the alloy, and has adverse effects on the setting operation and the stability of the precious stone.
(2) Silver. Has excellent antibacterial property, has a bleaching effect on copper, and has poor bleaching effect when the copper is too low and increases the material cost when the copper is too high. Silver can reduce the oxidation tendency of metal liquid, improve the fluidity and improve the casting performance of alloy. Silver can improve the corrosion resistance, especially oxidation resistance, of the alloy.
(3) Tin. Has bleaching effect on copper and obviously improves the corrosion resistance of the alloy. Tin reduces the melting point of the alloy, but increases the solidification temperature range and the shrinkage tendency of the casting.
(4) Germanium. The alloy has a 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 and forms a hard and brittle mesophase in the alloy structure. The applicant has found through several experiments that when the germanium content exceeds 1%, the toughness and plasticity of the alloy will be affected.
(5) Boron. Can improve metallurgical quality, purify molten metal, reduce surface tension, improve metal fluidity, improve casting performance, and has grain refinement effect. However, when the content is too high, molten metal is caused to produce slag, 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.
In addition, (7) silicon. The copper-based alloy has a bleaching effect on copper, and has poor effect when the copper-based alloy is too low and affects the plasticity of the material when the copper-based alloy is too high. Silicon can reduce the surface quality of molten metal and improve the fluidity and casting performance. 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 can be reduced, and even the requirement of inlaying cannot be met.
(8) Indium. The bleaching effect on copper can reduce the melting point of alloy and the surface tension of molten metal, so that the bleaching agent is beneficial to the fluidity and casting performance of molten metal. Indium is also beneficial to improve 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 shrinkage porosity of the casting is increased.
(9) Ruthenium. Belongs to noble metal elements, has high melting point, plays an obvious role in refining grains of the alloy, and is beneficial to improving the surface quality and mechanical property of castings. However, ruthenium is expensive, and when the content is too high, hard particles are easily formed in the structure, deteriorating the polishing performance of the alloy.
In conclusion, by combining the performances of the materials, the composition of the materials is designed according to the action characteristics of alloy elements in copper alloy.
Further, the total content of the unavoidable impurity elements is not more than 0.1wt%.
Further, the environment-friendly white copper alloy for decoration comprises the following components in percentage by weight:
20% by weight of zinc, 15% by weight of silver, 0.5% by weight of tin, 2% by weight of germanium, 0.01% by weight of neodymium, 0.002% by weight of boron, and the balance copper and unavoidable impurity elements.
Further, the environment-friendly white copper alloy for decoration comprises the following components in percentage by weight:
24.4% wt of zinc, 20% wt of silver, 1% wt of tin, 1.5% wt of germanium, 0.05% wt of neodymium, 0.005% wt of boron, and the balance copper and unavoidable impurity elements.
Further, the environment-friendly white copper alloy for decoration comprises the following components in percentage by weight:
15% by weight of zinc, 25% by weight of silver, 1.5% by weight of tin, 1% by weight of germanium, 0.1% by weight of neodymium, 0.01% by weight of boron, and the balance copper and unavoidable impurity elements.
Further, the environment-friendly white copper alloy for decoration adopts a vacuum induction smelting mode to prepare the alloy.
The second purpose of the invention is realized by adopting the following technical scheme:
the preparation method of the white copper alloy for the green environment-friendly decoration 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 unavoidable impurity elements;
s2: pre-melting of master alloys
Preparing zinc, silver, tin, germanium, neodymium and boron of each material into intermediate alloy;
s3: smelting of cast alloys
And (3) proportioning copper and intermediate alloy according to a certain proportion, vacuum induction smelting, and casting the materials into ingots or granulating to obtain the environment-friendly white copper alloy for decoration.
Further, in step S1, copper is oxygen-free copper having a purity of 99.95% or more; zinc, silver, tin, germanium, neodymium and boron are all materials with the purity of more than 99.5 percent.
Further, in step S2, the master alloy is prepared by vacuum induction melting.
Further, in step S3, the specification of the particles is particles having a particle diameter of 2 to 6 mm.
Further, the vacuum induction melting mode comprises the following operation steps: vacuumizing to 5 Pa-20 Pa, then filling argon to 1.0 atm-1.02 atm, and after the metal materials are completely melted, using the action of mechanical stirring to promote the uniformity of the components and the temperature of the metal liquid, and casting into ingots or granulating according to the requirements.
Compared with the prior art, the invention has the beneficial effects that:
the environment-friendly white copper alloy for decorations is suitable for being used as jewelry decoration materials, copper is matched with elements such as zinc, silver, tin, neodymium, boron and germanium, and the alloy elements are optimally matched, so that the white copper alloy has good comprehensive performance, is friendly to the human body, does not have sensitization risk, is environment-friendly, and has excellent antibacterial function; the alloy presents soft and comfortable colors and has excellent decorative effect; the alloy does not contain elements which react with carbon, and can adopt the liquidus line of graphite crucible smelting commonly used in jewelry industry; the liquidus of the alloy is not more than 860 ℃, no element which reacts with gypsum mold reaction chemistry exists, the alloy can be molded by adopting a gypsum mold precision casting process widely applied to jewelry industry, and the alloy has good casting performance; the hardness of the alloy is between HV110 and 150, the requirement of stone inlaying can be well met, the alloy has better corrosion resistance and excellent tarnish and color resistance.
Drawings
FIG. 1 is a graph of the impedance of the alloy material of comparative example 1 in artificial sweat;
FIG. 2 is a graph of the 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 surface polishing effect of the alloy material of example 1;
FIG. 5 is an as-cast surface roughness map of comparative example 1;
FIG. 6 is a graph of bacterial colony on the surface of a blank glass plate;
FIG. 7 is a graph showing the antibacterial effect of the surface of the sample of comparative example 1;
FIG. 8 is a graph showing the antibacterial effect on the surface of the sample of example 2.
Detailed Description
The present invention will be further described with reference to the following specific embodiments, and it should be noted that, on the premise of no conflict, new embodiments may be formed by any combination of the embodiments or technical features described below. In the following examples, copper is oxygen-free copper having a purity of 99.95% or more; sn, zn, ag, ge, ga, B, ru, gd, nb all are materials with purity of more than 99.5%. The operation steps of the vacuum induction smelting mode are as follows: vacuumizing to 5 Pa-20 Pa, then filling argon to 1.0 atm-1.02 atm, and after the metal materials are completely melted, using the action of mechanical stirring to promote the uniformity of the components and the temperature of the metal liquid, and casting into ingots or granulating according to the requirements.
Example 1
The environment-friendly white copper alloy for decoration comprises the following preparation steps:
s1: weighing the following components in percentage by weight:
20% by weight of zinc, 15% by weight of silver, 0.5% by weight of tin, 2% by weight of germanium, 0.01% by weight of neodymium, 0.002% by weight of boron, and the balance of copper and unavoidable impurity elements; wherein the total content of unavoidable impurity elements is not more than 0.1wt%.
S2: pre-melting of master alloys
Preparing zinc, silver, tin, germanium, neodymium and boron of each material into intermediate alloy;
s3: smelting of cast alloys
Copper and intermediate alloy are proportioned according to a certain proportion, and after vacuum induction smelting, the materials are poured into ingots, thus obtaining the alloy.
Example 2
The environment-friendly white copper alloy for decoration comprises the following preparation steps:
s1: weighing the following components in percentage by weight:
24.4% wt of zinc, 20% wt of silver, 1% wt of tin, 1.5% wt of germanium, 0.05% wt of neodymium, 0.005% wt of boron, and the balance of copper and unavoidable impurity elements; wherein the total content of unavoidable impurity elements is not more than 0.1wt%.
S2: pre-melting of master alloys
Preparing zinc, silver, tin, germanium, neodymium and boron of each material into intermediate alloy;
s3: smelting of cast alloys
Copper and intermediate alloy are proportioned according to a certain proportion, and after vacuum induction smelting, the material is made into particles with the particle size of 2-6 mm, thus obtaining the alloy.
Example 3
The environment-friendly white copper alloy for decoration comprises the following preparation steps:
s1: weighing the following components in percentage by weight:
15% by weight of zinc, 25% by weight of silver, 1.5% by weight of tin, 1% by weight of germanium, 0.1% by weight of neodymium, 0.01% by weight of boron, and the balance of copper and unavoidable impurity elements; wherein the total content of unavoidable impurity elements is not more than 0.1wt%.
S2: pre-melting of master alloys
Preparing zinc, silver, tin, germanium, neodymium and boron of each material into intermediate alloy;
s3: smelting of cast alloys
Copper and intermediate alloy are proportioned according to a certain proportion, and after vacuum induction smelting, the materials are poured into ingots, thus obtaining the alloy.
Comparative example 1
The alloy of comparative document 1 is a Cu76Mn14Zn10Sn nickel-free white copper alloy.
Performance test:
1. the samples tested were: examples 1 to 3 and comparative example 1, the indexes such as physical properties, chemical properties, mechanical properties and technological properties were examined under the same conditions.
2. The testing method comprises the following steps: the melting temperature and crystallization interval of the material are detected by adopting a differential thermal analyzer, the hardness of the material is detected by adopting a gypsum type precision casting process, the casting compactness 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 property 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 intervals of example 1 and comparative example 1 after they were measured by a differential thermal analyzer are shown in Table 1.
Table 1 comparison table of characteristic temperatures
| Material | Liquidus temperature, DEG C | Crystallization temperature interval, 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 was substantially close to that of comparative example 1, both of which had a lower crystallization interval, which was advantageous for densification and uniformity of composition of the coagulated structure. Whereas example 1 has a liquidus significantly lower than that of comparative example 1 and is free of alloying elements that react with the gypsum mold, and thus can be melted by conventional melting means and is suitable for molding by a gypsum mold precision casting process. In contrast, comparative example 1 contains a large amount of manganese, cannot be melted by using a graphite crucible, must be melted by using a crucible such as zirconia or magnesia, has poor thermal shock property, does not allow rapid temperature rise and temperature drop, and cannot use a gypsum mold which is most commonly used in jewelry production, because even if vacuum protection melting is used, impurities such as manganese oxide are inevitably generated, and manganese oxide easily reacts chemically with a mold material, resulting in a very rough surface.
(2) Hardness of
As jewelry is mostly molded by casting, as-cast hardness is a very interesting index in production, especially for inlaid jewelry, when the blank hardness is too high, the jewelry is difficult to inlay, when the hardness is too low, the jewelry is at risk of falling, and the hardness range is usually preferably 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 state | Solid solution aging state | State of processing (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 meet the damascene requirement. However, the work hardening effect of comparative example 1 is strong, and when the working ratio reaches 30%, the hardness exceeds HV200, so it is difficult to meet the requirements of the inlay process such as forced inlay. In example 3, the hardness of the alloy after 30% working ratio was not more than HV180, and therefore, the alloy was suitable for various damascene methods.
(3) Density of cast ingot
The initial density of the ingot is detected by adopting an Archimedes method, and then the ingot is rolled, so that possible looseness, pores and the like in the ingot are compacted, and the density condition of the ingot is reflected by the initial density of the ingot and the density change rate after rolling treatment. Taking example 1 and example 3 as examples, the test results of the test with comparative example 1 are shown in table 3.
Table 3 comparative table of density
| Material | Density of cast ingot, g/cm3 | Density increase 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 densities of example 1 and example 3 were slightly higher than those of comparative example, and the increase in density after rolling was lower than that of comparative example 1, indicating that the compactibility was superior to that of comparative example 1, and that the polishing performance and the surface effect were improved.
(4) Color of
The color index values of each of example 1 and comparative example 1 are shown in table 4.
Table 4 color comparison table
| 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, the brightness value L of example 1 is higher than that of the comparative example, and the values a and b are lower than those of the comparative example, which shows that the brightness is better, and the surface of the ornament is better. The yellow hue in the red-green color pair is lower and thus more prone to white than the yellow hue in the yellow-blue color pair is closer to no hue.
(5) Corrosion resistance
The impedance and polarization behavior in artificial sweat of example 3 and comparative example 1 were tested using an electrochemical workstation and the test results are shown in fig. 1 and 2, respectively. Wherein, FIG. 1 is an impedance spectrum of the alloy material of comparative example 1 in artificial sweat; fig. 2 is a graph of the impedance spectrum of the alloy material of example 3 in artificial sweat.
As can be seen from fig. 1 and 2, the impedance value of example 3 is higher than that of comparative example 1, indicating that the corrosion resistance of example 3 is superior to that of comparative example 1.
(6) Casting performance
The screen and jewelry blanks of example 1 and comparative example 1 were cast using a gypsum type precision casting process, and their casting properties were tested, and the test 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 surface polishing effect 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 comparative example 1, the filling rate of the screen mesh of example 1 reaches 100%, the surface of the jewelry blank is smooth, no obvious casting defects such as sand holes and shrinkage porosity are generated, and excellent surface effect is obtained after polishing. Whereas the casting surface of the comparative example was rough as shown in fig. 5.
(7) Antibacterial property
The test strain adopts freshly cultured staphylococcus aureus, bacterial liquid is uniformly coated on the surfaces of comparative example 1 and example 2, and then a sterile film is covered, and the bacteria are cultured for 24 hours at 37 ℃ and RH > 90%. And (3) eluting with PBS buffer solution fully, serial dilution, sampling, performing viable count culture, and calculating the 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.
As can be seen from the graph, the blank glass plate has no antibacterial effect, the antibacterial rate of example 2 reaches more than 99%, while the antibacterial rate of comparative example 1 is only about 92%, i.e. the antibacterial performance of example 1 is obviously better than that of comparative example 1.
The above embodiments are only preferred embodiments of the present invention, and the scope of the present invention is not limited thereto, but any insubstantial changes and substitutions made by those skilled in the art on the basis of the present invention are intended to be within the scope of the present invention as claimed.
Claims (9)
1. The environment-friendly white copper alloy for decoration is characterized by comprising the following components in percentage by weight:
15-25% by weight of zinc, 15-25% by weight of silver, 0.5-1.5% by weight of tin, 1-2% by weight of germanium, 0.01-0.1% by weight of neodymium, 0.002-0.01% by weight of boron, and the balance of copper and unavoidable impurity elements; the liquidus of the environment-friendly white copper alloy for decoration is not more than 860 ℃, the green environment-friendly white copper alloy is molded by adopting a gypsum type precision casting process in the jewelry industry, and the hardness is between HV110 and 150;
the preparation method of the environment-friendly white copper alloy for decoration comprises the following preparation steps:
s1: weighing the following components in percentage by weight:
15-25% by weight of zinc, 15-25% by weight of silver, 0.5-1.5% by weight of tin, 1-2% by weight of germanium, 0.01-0.1% by weight of neodymium, 0.002-0.01% by weight of boron, and the balance of copper and unavoidable impurity elements;
s2: pre-melting of master alloys
Preparing zinc, silver, tin, germanium, neodymium and boron of each material into intermediate alloy;
s3: smelting of cast alloys
And (3) proportioning copper and intermediate alloy according to a certain proportion, vacuum induction smelting, and casting the materials into ingots or granulating to obtain the environment-friendly white copper alloy for decoration.
2. The green-decorative white copper alloy according to claim 1, wherein the total content of the unavoidable impurity elements is not more than 0.1wt%.
3. The environment-friendly white copper alloy for decoration according to claim 1, which is characterized by comprising the following components in percentage by weight:
20% by weight of zinc, 15% by weight of silver, 0.5% by weight of tin, 2% by weight of germanium, 0.01% by weight of neodymium, 0.002% by weight of boron, and the balance copper and unavoidable impurity elements.
4. The environment-friendly white copper alloy for decoration according to claim 1, which is characterized by comprising the following components in percentage by weight:
24.4% wt of zinc, 20% wt of silver, 1% wt of tin, 1.5% wt of germanium, 0.05% wt of neodymium, 0.005% wt% of boron, and the balance of copper and unavoidable impurity elements.
5. The environment-friendly white copper alloy for decoration according to claim 1, which is characterized by comprising the following components in percentage by weight:
15% by weight of zinc, 25% by weight of silver, 1.5% by weight of tin, 1% by weight of germanium, 0.1% by weight of neodymium, 0.01% wt% by weight of boron, and the balance of copper and unavoidable impurity elements.
6. A method for preparing the white copper alloy for green environmental protection decoration according to claim 1, which is characterized by comprising the following preparation steps:
s1: weighing the following components in percentage by weight:
15-25% by weight of zinc, 15-25% by weight of silver, 0.5-1.5% by weight of tin, 1-2% by weight of germanium, 0.01-0.1% by weight of neodymium, 0.002-0.01% by weight of boron, and the balance of copper and unavoidable impurity elements;
s2: pre-melting of master alloys
Preparing zinc, silver, tin, germanium, neodymium and boron of each material into intermediate alloy;
s3: smelting of cast alloys
And (3) proportioning copper and intermediate alloy according to a certain proportion, vacuum induction smelting, and casting the materials into ingots or granulating to obtain the environment-friendly white copper alloy for decoration.
7. The method for producing a white copper alloy for green environmental protection according to claim 6, wherein in step S1, copper is oxygen-free copper having a purity of 99.95% or more; zinc, silver, tin, germanium, neodymium and boron are all materials with the purity of more than 99.5 percent.
8. The method of producing a white copper alloy for green house keeping according to claim 6, wherein in step S2, the intermediate alloy is produced by vacuum induction melting.
9. The method of producing a white copper alloy for green house keeping according to claim 6, wherein in step S3, the size of the particles is 2 to 6 mm.
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