CN114395711A - Anti-tarnishing and anti-corrosion copper alloy material with rapid bacteriostasis effect and preparation method thereof - Google Patents
Anti-tarnishing and anti-corrosion copper alloy material with rapid bacteriostasis effect and preparation method thereof Download PDFInfo
- Publication number
- CN114395711A CN114395711A CN202111628280.7A CN202111628280A CN114395711A CN 114395711 A CN114395711 A CN 114395711A CN 202111628280 A CN202111628280 A CN 202111628280A CN 114395711 A CN114395711 A CN 114395711A
- Authority
- CN
- China
- Prior art keywords
- copper alloy
- alloy material
- corrosion
- rapid
- alloy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/04—Alloys based on copper with zinc as the next major constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23P—METAL-WORKING NOT OTHERWISE PROVIDED FOR; COMBINED OPERATIONS; UNIVERSAL MACHINE TOOLS
- B23P15/00—Making specific metal objects by operations not covered by a single other subclass or a group in this subclass
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention discloses an anti-tarnishing and anti-corrosion copper alloy material with a rapid antibacterial effect and a preparation method thereof. The copper alloy material comprises the following components in percentage by weight: zn: 5% -16%, Ni: 4% -6%, Sn: 1% -2%, La: 0-0.5%, Ce: 0-0.5%, Nd: 0 to 0.5 percent, and the balance of Cu. The preparation method of the copper alloy material comprises the following steps: (1) smelting and casting a copper alloy to obtain an alloy ingot; (2) milling the alloy cast ingot; (3) hot rolling; (4) heat treatment; (5) and cold rolling to obtain the copper alloy material. The final product contact concentration value is 1 × 108The antibacterial rate of cfu/mL escherichia coli after 15min is more than or equal to 99 percent; adding under neutral artificial sweat environmentThe corrosion rate after the rapid atmospheric corrosion for 14 days is less than 0.020mm/a, and the color difference value delta E is less than 15; the contact angle of the liquid on the surface is more than 90 degrees. The alloy material has excellent antibacterial property and corrosion resistance, and can be used for preparing coins frequently contacted with microorganisms and contact surfaces in public environments with gathered population.
Description
Technical Field
The invention relates to an anti-tarnishing and anti-corrosion copper alloy material with a quick bacteriostatic effect and a preparation method thereof, belonging to the technical field of copper alloy materials.
Background
Copper and copper alloy have natural bacteriostasis and have quick and wide inhibition effect on some bacteria, fungi and viruses with high toxicity. Laboratory and clinical research finds that copper and copper alloy have the effects of obviously reducing the biological load of the environmental surface, killing common pathogens of environmental infection and reducing the environmental infection rate. Scientific tests of related organizations show that pure copper and copper alloy with copper content more than 60% have good bacteriostatic function, and more than 350 copper and copper alloy products and materials registered by the Environmental Protection Agency (EPA) are defined as bacteriostatic copper. The composition of bacteriostatic copper is observed, the material covers almost all red copper with the copper content of more than 60 percent, the infectivity of human coronavirus HuCoV-229E on the surface of a common contact material is researched by UK Pudu university, and the bacteriostatic ability of different types of copper alloys is different, and the bacteriostatic ability of the material is influenced by the different addition of alloy elements. Microorganisms are ubiquitous in our lives, and toxic and harmful microorganisms can cause harm to human bodies. Recent outbreaks of new coronaviruses seriously affect the normal life and economic activities of human beings and even threaten human survival.
The environment is a storage bank of various microorganisms, such as the surfaces of objects contacted by patients can be vectors of virus infection, and the copper alloy is used as a surface contact antibacterial material, and the discoloration resistance and the corrosion resistance of the copper alloy are important concerns, so that research and development of the copper alloy material which has a rapid inhibition effect on harmful microorganisms and has excellent discoloration resistance and corrosion resistance are urgently needed, and the copper alloy material can be applied to hospital wards, currency coins, commemorative coins, indoor decoration, household high-grade utensils, art collection, various souvenirs and the like.
Disclosure of Invention
The invention aims to provide a discoloration-resistant corrosion-resistant copper alloy material with a rapid bacteriostasis effect, which has excellent antibacterial property and corrosion resistance and can be used for preparing contact surfaces in public environments with currency and population gathering frequently contacting microorganisms.
The invention also aims to provide a preparation method of the copper alloy material.
At present, the exact mechanism of copper for killing bacteria is still studied, and the existing research finds that the antibacterial activity of copper alloy is related to the release of copper ions by corrosion and dissolution of the surface of the copper alloy, the copper alloy has different components and different copper ion release capabilities after oxidation and corrosion, and the copper ions have two different valence states, and the copper ions with the valence states play the antibacterial role are unknown. Thus, the inventors aimed at the modification of copperThe oxide with the same valence state is tested by adopting GB/T20944.3-2008 standard suitable for porous powder materials, and the experimental result is shown in Table 1. Through experiments, the CuO and the Cu are found to be in short time2O has certain bacteriostatic effect, but Cu2The O antibacterial effect is more excellent, which shows that univalent Cu ions mainly play a role in the antibacterial effect in copper.
TABLE 1Cu2Results of O and CuO bacteriostatic experiments
The Zn element is used as a bacteriostatic element and has high solid solubility with copper, and the experimental result of the inventor in the early stage of the subject group finds that the Zn-added copper alloy can form Cu on the surface of a sample after being in short-time contact with bacterial liquid2Corrosion product films of O and ZnO, and the two oxides can play a synergistic bacteriostatic role; cu2O is a highly defective p-type semiconductor, and Ni may be added as Ni2+Form of (2) occupies Cu2Cation vacancies in O increase the ionic resistance of the film, thereby improving the corrosion resistance of the alloy. Research of subject groups finds that after rare earth La, Ce and Nd are added, the corrosion rate of the alloy is reduced, the corrosion current density is reduced to different degrees, and the corrosion resistance of the alloy is improved.
Based on the research and discovery, in order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides an anti-tarnishing and anti-corrosion copper alloy material with a rapid bacteriostasis effect, which comprises the following components in percentage by weight: zn: 5% -16%, Ni: 4% -6%, Sn: 1% -2%, La: 0-0.5%, Ce: 0-0.5%, Nd: 0 to 0.5 percent, and the balance of Cu.
As a preferred scheme of the invention, the copper alloy material comprises the following components in percentage by weight: zn: 5% -16%, Ni: 4% -6%, Sn: 1% -2%, La: 0.3% -0.5%, Ce: 0-0.5%, Nd: 0 to 0.5 percent, and the balance of Cu.
As a preferred scheme of the invention, the copper alloy material comprises the following components in percentage by weight: zn: 5% -16%, Ni: 4% -6%, Sn: 1% -2%, La: 0-05%, Ce: 0.1% -05%, Nd: 0-05% and the balance of Cu.
As a preferred scheme of the invention, the copper alloy material comprises the following components in percentage by weight: zn: 5% -16%, Ni: 4% -6%, Sn: 1% -2%, La: 0-0.5%, Ce: 0-0.5%, Nd: 0.1-0.5 percent, and the balance of Cu.
The invention also provides a preparation method of the copper alloy material, which comprises the following steps:
(1) smelting a copper alloy: firstly adding electrolytic copper, and preserving heat for 30-40 min after Cu is completely melted; adding metal Ni with higher melting point, and adding metal Zn and metal Sn after the melt is completely melted; finally, adding rare earth element intermediate alloys Cu-La, Cu-Ce and metal neodymium which are easy to burn out, wherein the addition amount of the metal or the intermediate alloy is subject to the requirement of meeting the final alloy component; fully degassing and removing impurities, preserving heat for 10min, fully stirring, standing for 5-10 min, and taking out of the furnace for casting to obtain an alloy ingot;
(2) milling the alloy cast ingot;
(3) hot rolling;
(4) heat treatment;
(5) and cold rolling to obtain the copper alloy material.
In the step (1), a non-vacuum induction furnace is adopted for smelting, the smelting temperature is 1300-1450 ℃, and the casting temperature is controlled to be 1200-1300 ℃.
In the step (3), the initial rolling temperature is controlled to be more than 700 ℃, the final rolling temperature is kept to be more than 600 ℃, and the hot rolling deformation is 80-98%.
In the step (4), the heat treatment temperature is 650-800 ℃, the time is 1-2 h, and the cooling mode is water cooling.
Wherein in the step (5), the cold rolling deformation is 50-98%.
The invention has the beneficial technical effects that:
the copper alloy material has excellent antibacterial property and corrosion resistance, and the contact concentration value is 1 multiplied by 108cfu/mL large intestine rodThe antibacterial rate after 15min is more than or equal to 99 percent; the corrosion rate is less than 0.020mm/a after the atmospheric corrosion is accelerated for 14 days under the neutral artificial sweat environment, and the color difference value delta E is less than 15; the contact angle of the liquid on the surface is more than 90 degrees.
The copper alloy material disclosed by the invention not only has rapid and wide antibacterial ability, but also has excellent corrosion resistance and anti-tarnishing ability, and the product can be used for copper alloys such as coin making materials and public decorative materials which frequently contact with microorganisms, and can be used for preparing contact surfaces in public environments such as coins and population aggregations which frequently contact with microorganisms.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the present invention.
The reason for the copper alloy with the rapid antibacterial effect is that bacteria which are easy to cause infection can survive on the surface of the material for days or even months, and the shorter the survival time of the bacteria on the surface of the material is, the more effective the bacteria can prevent secondary pollution caused by close contact of the bacteria and a human body, thereby reducing the infection. In the previous experiments, the inventor discovers that when the antibacterial property test of the copper alloy is carried out by adopting JIS/Z2801-2000 standard, the antibacterial property of the copper alloy with different components is more than 99.9% after the copper alloy contacts with bacteria for 24h, and the antibacterial property of the copper alloy with different types can not be judged by the traditional test method. Therefore, according to the needs of practical application, the rapid sterilization capability of copper and copper alloy in a short time needs to be evaluated for screening copper alloy materials with rapid antibacterial effect.
The copper alloy material disclosed by the invention not only has rapid and wide bacteriostatic ability, but also has excellent corrosion resistance and discoloration resistance.
Example 1
The alloy of the embodiment is smelted by adopting the following raw materials: electrolytic copper, pure zinc, pure nickel, pure tin, copper lanthanum intermediate alloy, copper cerium intermediate alloy and metal neodymium. The composition of the alloy is shown in table 1, example 1. The preparation steps of the alloy are as follows:
1. smelting: smelting by adopting a non-vacuum induction furnace. The adding sequence of the alloy is as follows: firstly adding electrolytic copper, and preserving heat for 40min after Cu is completely melted; adding metal Ni with higher melting point, and adding metal Zn and metal Sn after the melt is completely melted; finally, adding rare earth element intermediate alloys Cu-La, Cu-Ce and metal neodymium which are easy to burn; degassing, removing impurities, keeping the temperature for 10min, stirring, standing for 10min, and taking out of the furnace for casting.
2. Milling a surface: and milling the alloy, wherein the upper surface and the lower surface are respectively milled by 1 mm.
3. Hot rolling: the initial rolling temperature is controlled to be higher than 860 ℃, the final rolling temperature is kept to be higher than 760 ℃, and the total hot rolling processing rate is 92%.
4. And (3) heat treatment: a heating furnace is adopted, the heating temperature is 800 ℃, the time is 0.5h, and the cooling mode is water cooling.
5. Cold rolling: and (3) cold rolling the alloy plate subjected to heat treatment at room temperature, wherein the cold rolling deformation is 80%.
After the processing treatments such as smelting, surface milling, hot rolling, heat treatment, cold rolling and the like, the contact concentration value of a tested product is 1 multiplied by 108Antibacterial rate of cfu/mL Escherichia coli after 15 min; accelerating the corrosion rate and the color difference value delta E after atmospheric corrosion for 14 days in a neutral artificial sweat environment; contact angle of liquid on surface. The properties are shown in Table 2.
The testing method of the bacteriostatic activity adopted by the invention is as follows:
(1) activation of bacteria
The colibacillus frozen at-20 deg.c is streaked on LB solid culture medium to separate single colony, and cultured at 37 deg.c. And (3) taking a single colony to be inoculated into 3mL of LB liquid medium, and carrying out constant temperature shaking table at 37 ℃ for overnight culture for 15-20 h until saturation. Mixing the raw materials in a ratio of 1: 100 were inoculated into 100mL of fresh LB liquid medium and cultured overnight on a shaker at 37 ℃.
(2) Bacterial suspension preparation
1mL of the overnight bacterial culture was taken, the OD at 600nm was measured with a spectrophotometer, and the overnight culture was diluted with Phosphate Buffered Saline (PBS) until OD was 0.1(OD 0.1 in general, Escherichia coli solution was 1X 108cfu/mL). Then, the OD-0.1 dilution was diluted with PBS in a gradient (dilutions 10, 10)2、103、104、105、106) Gradient dilution of OD 0.1 to 106cfu/mL/105cfu/mL, and the bacterial suspension was used as a bacterial liquid for experiments.
(3) The test method comprises the following steps: film coating method
Before the antibacterial performance test, all the experimental instruments were placed in a sterilization pot for sterilization at 121 ℃. + -. 2 ℃ for 20 min. All experimental samples are prepared into square slices of 10mm multiplied by 1mm, two sides of the samples are polished to be flat and then placed in absolute ethyl alcohol solution, ultrasonic cleaning is carried out for 5min, the samples are placed in ultraviolet irradiation for 1h for standby after being dried, the size of the samples is 50mm multiplied by 50mm, and the thickness of the samples is not more than 1 cm.
Taking the concentration as 105400 mu L of cfu/mL of experimental bacteria liquid is dripped on the surface of the test piece and covered by a sterile polypropylene film with the thickness of 40mm multiplied by 40mm, so that the film and the sample are uniformly covered without overflow. After incubation of the samples at 36 ℃ and 90% relative humidity for 15min, the samples were eluted thoroughly with PBS phosphate buffer. Using plate counting method, 100. mu.L of the eluted dilution was applied to LB solid agar. Culturing at constant temperature until the colony morphology is complete, calculating the number of viable bacteria, see formula 1, and performing each experiment at least three times.
N ═ C × D × V/a (formula 1)
In the formula: n: each test piece per cm2The number of viable bacteria of (c); c: number of colonies in the plate; d: dilution times; v: volume of eluate (mL); a: the film covers the area.
The bacterial kill rate (K/%) of the different concentrations of the material was calculated from the plate colony count results, see (formula 2).
K (%) - (number of blank sample colonies-number of antibacterial sample colonies)/number of blank sample colonies ] × 100% (formula 2)
The corrosion resistance test method adopted by the invention is as follows:
the salt spray test is carried out by referring to the condition of GB/T2423.17-93 salt spray test method when the simulated material is used as a surface contact material. The method is carried out by adopting an FT-YW160A composite salt spray corrosion test box, the temperature of the salt spray test box is adjusted to be (35 +/-2) DEG C, the corrosion mother liquor is neutral artificial sweat, the pH value is 6.5, and the components are shown in the following table.After the test condition in the test box is ensured to be stable operation, the test is carried out for 240 h. To ensure that the sedimentation rate of the salt solution is 1-3 mL (80 cm) during the test2And/h), the salt spray settling rate and the settled solution pH value are measured every 12h in the whole experimental period.
And after the experiment is finished, observing and analyzing the sample subjected to salt spray corrosion by adopting a visual and weighing method. In order to obtain the corrosion rate of the alloy, a hydrochloric acid aqueous solution with the volume ratio of 1: 1 is used for removing corrosion products, the alloy is soaked in the hydrochloric acid aqueous solution for about 3min and is subjected to ultrasonic oscillation, a sample is placed into a drying oven for drying after being cleaned by alcohol, and the mass loss before and after corrosion is calculated through a calculation formula (3).
R ═ K × W)/(a × T × D) (formula 3)
In the formula: r: corrosion speed mm/year; k: constant 8.76X 104(ii) a W: g, sample weight loss; a: cm of original surface area of the sample before soaking2(ii) a T: soaking time h; d: density of sample g/cm3. Each time point 3 replicates were soaked and the average was taken as the experimental result.
Artificial sweat ingredient table
The discoloration resistance test method adopted by the invention is as follows:
the samples were each processed into a rectangle of dimensions 50mm × 25mm, and polished sequentially on a water-abrasive paper until the surface was bright and mirror-finished. In order to simulate the using conditions, a sample is placed in a salt spray corrosion experiment box to carry out an atmospheric accelerated corrosion test, the environment medium is neutral artificial sweat, and the aerosol sedimentation rate is 1-2 mL/(80 cm)2H), at a constant temperature of 35 +/-1 ℃. The experimental time was 14 d. A CIELAB colorimetric reference system is selected as a measurement standard of alloy color, CIELAB (L, a and b) coordinate values are directly measured, a test device is an X-riteMA-5QC multi-angle color difference meter, and a standard illuminator (A, C, D65), a 45-degree view field and 0/d observation conditions are selected. The samples before and after the salt spray test are mutually contrasted, and the distance between two points in the chromaticity coordinate can be used for representing the two pointsThe difference of species color was calculated as shown in (equation 3), and the experiment was repeated three times.
In the formula: Δ E: color difference before and after sample experiment; subscripts 0 and 1: l, a and b values for the samples before and after the experiment, respectively.
Example 2
The alloy of the embodiment is smelted by adopting the following raw materials: electrolytic copper, pure zinc, pure nickel, pure tin and copper lanthanum intermediate alloy. The composition of the alloy is shown in table 1, example 2. The preparation steps of the alloy are as follows:
1. smelting: smelting by adopting a non-vacuum induction furnace. The adding sequence of the alloy is as follows: firstly adding electrolytic copper, and preserving heat for 35min after Cu is completely melted; adding metal Ni with higher melting point, and adding metal Zn and metal Sn after the melt is completely melted; finally, adding rare earth element intermediate alloy Cu-La which is easy to burn and lose; degassing, removing impurities, keeping the temperature for 10min, stirring, standing for 10min, and taking out of the furnace for casting.
2. Milling a surface: and milling the alloy, wherein the upper surface and the lower surface are respectively milled by 1 mm.
3. Hot rolling: the initial rolling temperature is controlled to be above 850 ℃, the final rolling temperature is kept to be above 750 ℃, and the total hot rolling processing rate is 90%.
4. And (3) heat treatment: a heating furnace is adopted, the heating temperature is 750 ℃, the time is 1h, and the cooling mode is water cooling.
5. Cold rolling: and (3) cold rolling the alloy plate subjected to heat treatment at room temperature, wherein the cold rolling deformation is 50%.
After the above processing treatments such as melting, face milling, hot rolling, heat treatment, cold rolling and the like, the performance of the product was tested, and the test method and the calculation method of each performance parameter were the same as those in example 1. The properties are shown in Table 2.
Example 3
The alloy of the embodiment is smelted by adopting the following raw materials: electrolytic copper, pure zinc, pure nickel, pure tin, copper lanthanum intermediate alloy and metal neodymium. The composition of the alloy is shown in table 1, example 3. The preparation steps of the alloy are as follows:
1. smelting: smelting by adopting a non-vacuum induction furnace. The adding sequence of the alloy is as follows: firstly adding electrolytic copper, and preserving heat for 30min after Cu is completely melted; adding metal Ni with higher melting point, and adding metal Zn and metal Sn after the melt is completely melted; finally, adding rare earth element intermediate alloy Cu-La and metal neodymium which are easy to burn and lose; degassing, removing impurities, keeping the temperature for 10min, stirring, standing for 10min, and taking out of the furnace for casting.
2. Milling a surface: and milling the alloy, wherein the upper surface and the lower surface are respectively milled by 1 mm.
3. Hot rolling: the initial rolling temperature is controlled to be more than 820 ℃, the final rolling temperature is kept to be more than 720 ℃, and the total hot rolling processing rate is 80 percent.
4. And (3) heat treatment: a heating furnace is adopted, the heating temperature is 700 ℃, the time is 2 hours, and the cooling mode is water cooling.
5. Cold rolling: and (3) cold rolling the alloy plate subjected to heat treatment at room temperature, wherein the cold rolling deformation is 60%.
After the above processing treatments such as melting, face milling, hot rolling, heat treatment, cold rolling and the like, the performance of the product was tested, and the test method and the calculation method of each performance parameter were the same as those in example 1. The properties are shown in Table 2.
Example 4
The alloy of the embodiment is smelted by adopting the following raw materials: electrolytic copper, pure zinc, pure nickel, pure tin, copper cerium intermediate alloy and metal neodymium. The composition of the alloy is shown in table 1, example 4. The preparation steps of the alloy are as follows:
1. smelting: smelting by adopting a non-vacuum induction furnace. The adding sequence of the alloy is as follows: firstly adding electrolytic copper, and preserving heat for 35min after Cu is completely melted; adding metal Ni with higher melting point, and adding metal Zn and metal Sn after the melt is completely melted; finally, adding rare earth element intermediate alloy Cu-Ce and metal neodymium which are easy to burn and lose; degassing, removing impurities, keeping the temperature for 10min, stirring, standing for 10min, and taking out of the furnace for casting.
2. Milling a surface: and milling the alloy, wherein the upper surface and the lower surface are respectively milled by 1 mm.
3. Hot rolling: the initial rolling temperature is controlled to be above 800 ℃, the final rolling temperature is kept above 700 ℃, and the total hot rolling processing rate is 98%.
4. And (3) heat treatment: a heating furnace is adopted, the heating temperature is 750 ℃, the time is 1h, and the cooling mode is water cooling.
5. Cold rolling: and (3) cold rolling the alloy plate subjected to heat treatment at room temperature, wherein the cold rolling deformation is 50%.
After the above processing treatments such as melting, face milling, hot rolling, heat treatment, cold rolling and the like, the performance of the product was tested, and the test method and the calculation method of each performance parameter were the same as those in example 1. The properties are shown in Table 2.
Example 5
The alloy of the embodiment is smelted by adopting the following raw materials: electrolytic copper, pure zinc, pure nickel, pure tin and copper cerium intermediate alloy. The composition of the alloy is shown in table 1, example 5. The preparation steps of the alloy are as follows:
1. smelting: smelting by adopting a non-vacuum induction furnace. The adding sequence of the alloy is as follows: firstly adding electrolytic copper, and preserving heat for 35min after Cu is completely melted; adding metal Ni with higher melting point, and adding metal Zn and metal Sn after the melt is completely melted; finally, adding rare earth element intermediate alloy Cu-Ce which is easy to burn and lose; degassing, removing impurities, keeping the temperature for 10min, stirring, standing for 10min, and taking out of the furnace for casting.
2. Milling a surface: and milling the alloy, wherein the upper surface and the lower surface are respectively milled by 1 mm.
3. Hot rolling: the initial rolling temperature is controlled to be above 700 ℃, the final rolling temperature is kept to be above 600 ℃, and the total hot rolling processing rate is 80%.
4. And (3) heat treatment: a heating furnace is adopted, the heating temperature is 650 ℃, the time is 2 hours, and the cooling mode is water cooling.
5. Cold rolling: and (3) cold rolling the alloy plate subjected to heat treatment at room temperature, wherein the cold rolling deformation is 90%.
After the above processing treatments such as melting, face milling, hot rolling, heat treatment, cold rolling and the like, the performance of the product was tested, and the test method and the calculation method of each performance parameter were the same as those in example 1. The properties are shown in Table 2.
Example 6
The alloy of the embodiment is smelted by adopting the following raw materials: electrolytic copper, pure zinc, pure nickel, pure tin, copper lanthanum intermediate alloy, copper cerium intermediate alloy and metal neodymium. The composition of the alloy is shown in table 1, example 6. The preparation steps of the alloy are as follows:
1. smelting: smelting by adopting a non-vacuum induction furnace. The adding sequence of the alloy is as follows: firstly adding electrolytic copper, and preserving heat for 35min after Cu is completely melted; adding metal Ni with higher melting point, and adding metal Zn and metal Sn after the melt is completely melted; finally, adding rare earth element intermediate alloys Cu-La, Cu-Ce and metal neodymium which are easy to burn; degassing, removing impurities, keeping the temperature for 10min, stirring, standing for 10min, and taking out of the furnace for casting.
2. Milling a surface: and milling the alloy, wherein the upper surface and the lower surface are respectively milled by 1 mm.
3. Hot rolling: the initial rolling temperature is controlled to be more than 750 ℃, the final rolling temperature is kept to be more than 650 ℃, and the total hot rolling processing rate is 85%.
4. And (3) heat treatment: a heating furnace is adopted, the heating temperature is 700 ℃, the time is 1h, and the cooling mode is water cooling.
5. Cold rolling: and (3) cold rolling the alloy plate subjected to heat treatment at room temperature, wherein the cold rolling deformation is 90%.
After the above processing treatments such as melting, face milling, hot rolling, heat treatment, cold rolling and the like, the performance of the product was tested, and the test method and the calculation method of each performance parameter were the same as those in example 1. The properties are shown in Table 2.
Example 7
The alloy of the embodiment is smelted by adopting the following raw materials: electrolytic copper, pure zinc, pure nickel and pure tin. The composition of the alloy is shown in table 1, example 7. The preparation steps of the alloy are as follows:
1. smelting: smelting by adopting a non-vacuum induction furnace. The adding sequence of the alloy is as follows: firstly adding electrolytic copper, and preserving heat for 35min after Cu is completely melted; adding metal Ni with higher melting point, and adding metal Zn and metal Sn after the melt is completely melted; (ii) a Degassing, removing impurities, keeping the temperature for 10min, stirring, standing for 10min, and taking out of the furnace for casting.
2. Milling a surface: and milling the alloy, wherein the upper surface and the lower surface are respectively milled by 1 mm.
3. Hot rolling: the initial rolling temperature is controlled to be above 850 ℃, the final rolling temperature is kept to be above 750 ℃, and the total hot rolling processing rate is 90%.
4. And (3) heat treatment: a heating furnace is adopted, the heating temperature is 750 ℃, the time is 1h, and the cooling mode is water cooling.
5. Cold rolling: and (3) cold rolling the alloy plate subjected to heat treatment at room temperature, wherein the cold rolling deformation is 50%.
After the above processing treatments such as melting, face milling, hot rolling, heat treatment, cold rolling and the like, the performance of the product was tested, and the test method and the calculation method of each performance parameter were the same as those in example 1. The properties are shown in Table 2.
TABLE 1 alloy composition recipes for examples 1-7
TABLE 2 alloy properties of examples 1-7
Claims (9)
1. The anti-tarnishing and anti-corrosion copper alloy material with the rapid bacteriostasis effect is characterized by comprising the following components in percentage by weight: zn: 5% -16%, Ni: 4% -6%, Sn: 1% -2%, La: 0-0.5%, Ce: 0-0.5%, Nd: 0 to 0.5 percent, and the balance of Cu.
2. The anti-tarnishing and anti-corrosion copper alloy material with rapid bacteriostasis effect according to claim 1, which is characterized in that the components and contents of the copper alloy material are as follows by weight percentage: zn: 5% -16%, Ni: 4% -6%, Sn: 1% -2%, La: 0.3% -0.5%, Ce: 0-0.5%, Nd: 0 to 0.5 percent, and the balance of Cu.
3. The anti-tarnishing and anti-corrosion copper alloy material with rapid bacteriostasis effect according to claim 1, which is characterized in that the components and contents of the copper alloy material are as follows by weight percentage: zn: 5% -16%, Ni: 4% -6%, Sn: 1% -2%, La: 0-0.5%, Ce: 0.1% -0.5%, Nd: 0 to 0.5 percent, and the balance of Cu.
4. The anti-tarnishing and anti-corrosion copper alloy material with rapid bacteriostasis effect according to claim 1, which is characterized in that the components and contents of the copper alloy material are as follows by weight percentage: zn: 5% -16%, Ni: 4% -6%, Sn: 1% -2%, La: 0-0.5%, Ce: 0-0.5%, Nd: 0.1-0.5 percent, and the balance of Cu.
5. The preparation method of the anti-tarnish and corrosion-resistant copper alloy material with the rapid bacteriostasis effect, which is characterized by comprising the following steps of:
(1) smelting a copper alloy: firstly adding electrolytic copper, and preserving heat for 30-40 min after Cu is completely melted; adding metal Ni with higher melting point, and adding metal Zn and metal Sn after the melt is completely melted; finally, adding rare earth element intermediate alloys Cu-La, Cu-Ce and metal neodymium which are easy to burn out, wherein the addition amount of the metal or the intermediate alloy is subject to the requirement of meeting the final alloy component; fully degassing and removing impurities, preserving heat for 10min, fully stirring, standing for 5-10 min, and taking out of the furnace for casting to obtain an alloy ingot;
(2) milling the alloy cast ingot;
(3) hot rolling;
(4) heat treatment;
(5) and cold rolling to obtain the copper alloy material.
6. The preparation method of the anti-tarnishing and anti-corrosion copper alloy material with the rapid bacteriostasis effect according to the claim 5, wherein in the step (1), a non-vacuum induction furnace is adopted for smelting, the smelting temperature is 1300-1450 ℃, and the casting temperature is controlled at 1200-1300 ℃.
7. The method for preparing the tarnish and corrosion resistant copper alloy material with the rapid bacteriostasis effect according to the claim 5, wherein in the step (3), the initial rolling temperature is controlled to be more than 700 ℃, the final rolling temperature is kept to be more than 600 ℃, and the hot rolling deformation is 80-98%.
8. The method for preparing the anti-tarnishing and anti-corrosion copper alloy material with the rapid bacteriostasis effect according to the claim 5, wherein in the step (4), the heat treatment temperature is 650-800 ℃, the time is 1-2 h, and the cooling mode is water cooling.
9. The method for preparing the tarnish and corrosion resistant copper alloy material with the rapid bacteriostasis effect according to the claim 5, wherein the cold rolling deformation amount in the step (5) is 50-98%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111628280.7A CN114395711A (en) | 2021-12-28 | 2021-12-28 | Anti-tarnishing and anti-corrosion copper alloy material with rapid bacteriostasis effect and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111628280.7A CN114395711A (en) | 2021-12-28 | 2021-12-28 | Anti-tarnishing and anti-corrosion copper alloy material with rapid bacteriostasis effect and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114395711A true CN114395711A (en) | 2022-04-26 |
Family
ID=81229237
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111628280.7A Pending CN114395711A (en) | 2021-12-28 | 2021-12-28 | Anti-tarnishing and anti-corrosion copper alloy material with rapid bacteriostasis effect and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114395711A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115710655A (en) * | 2022-11-25 | 2023-02-24 | 有研工程技术研究院有限公司 | High-corrosion-resistance antibacterial copper alloy material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11328939A (en) * | 1998-05-14 | 1999-11-30 | Furukawa Electric Co Ltd:The | Copper alloy strip for hard disk drive case |
| CN101717878A (en) * | 2009-12-10 | 2010-06-02 | 北京有色金属研究总院 | Seawater scouring corrosion resistant nickel-copper alloy and tubular product and preparation method thereof |
| CN101899588A (en) * | 2010-08-25 | 2010-12-01 | 江西理工大学 | Nickel-free white copper alloy containing rare earth additional elements and method for manufacturing plates made of same |
| CN102061406A (en) * | 2010-11-30 | 2011-05-18 | 江西理工大学 | Novel high-elasticity Cu-Ni-Mn alloy and preparation method thereof |
-
2021
- 2021-12-28 CN CN202111628280.7A patent/CN114395711A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11328939A (en) * | 1998-05-14 | 1999-11-30 | Furukawa Electric Co Ltd:The | Copper alloy strip for hard disk drive case |
| CN101717878A (en) * | 2009-12-10 | 2010-06-02 | 北京有色金属研究总院 | Seawater scouring corrosion resistant nickel-copper alloy and tubular product and preparation method thereof |
| CN101899588A (en) * | 2010-08-25 | 2010-12-01 | 江西理工大学 | Nickel-free white copper alloy containing rare earth additional elements and method for manufacturing plates made of same |
| CN102061406A (en) * | 2010-11-30 | 2011-05-18 | 江西理工大学 | Novel high-elasticity Cu-Ni-Mn alloy and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115710655A (en) * | 2022-11-25 | 2023-02-24 | 有研工程技术研究院有限公司 | High-corrosion-resistance antibacterial copper alloy material and preparation method and application thereof |
| CN115710655B (en) * | 2022-11-25 | 2023-10-27 | 有研工程技术研究院有限公司 | High-corrosion-resistance antibacterial copper alloy material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Esteban-Tejeda et al. | Antibacterial and antifungal activity of a soda-lime glass containing copper nanoparticles | |
| Esteban-Tejeda et al. | The antibacterial and antifungal activity of a soda-lime glass containing silver nanoparticles | |
| Dobaradaran et al. | Heavy metals (Cd, Cu, Ni and Pb) content in two fish species of Persian gulf in Bushehr Port, Iran | |
| Zhang et al. | New strategy to delay food spoilage: Application of new food contact material with antibacterial function | |
| WO2011060034A1 (en) | Antitarnish, antimicrobial copper alloys and surfaces made from such alloys | |
| CN114395711A (en) | Anti-tarnishing and anti-corrosion copper alloy material with rapid bacteriostasis effect and preparation method thereof | |
| Al-Shabib et al. | Bio-inspired facile fabrication of silver nanoparticles from in vitro grown shoots of Tamarix nilotica: Explication of its potential in impeding growth and biofilms of Listeria monocytogenes and assessment of wound healing ability | |
| CN100581636C (en) | Cu-Ag antimicrobial filtering metal material and preparing method and application thereof | |
| RUSDARYANTI et al. | Antibacterial activity of CaO from blood cockle shells (Anadara granosa) calcination against Escherichia coli | |
| Yakubu et al. | Quality assessment of smoked-dried fish from five different markets in Lafia, Nigeria | |
| US7381686B2 (en) | Composite for inhibiting algae growth and use therof | |
| CN107267814B (en) | A kind of Antibacterial aluminum alloy and preparation method thereof | |
| CN108812678A (en) | A kind of compound corrosion-retarding germicide | |
| CN114540696B (en) | High-mechanical-property copper-silver-containing antibacterial antiviral high-entropy alloy and preparation method thereof | |
| CN100529144C (en) | Nano precipitated phase martensite antimicrobial stainless steel | |
| CN108728769B (en) | Strongly antibacterial austenitic stainless steel | |
| Moon et al. | The intrinsic antimicrobial activity of bamboo salt against Salmonella enteritidis | |
| US9420798B2 (en) | Preparation of silver ion | |
| KR20050029649A (en) | A matural antibacterial composite | |
| CN112030078A (en) | Austenitic stainless steel with strong antibacterial function | |
| JP2021123785A (en) | Phosphor bronze alloy and antibacterial member using the same | |
| Wong et al. | Hydrophobicity, cell adherence, cytotoxicity, and enterotoxigenicity of starved Vibrio parahaemolyticus | |
| CN108728766B (en) | High-antibacterial-performance austenitic stainless steel applied to building and decoration products | |
| Jabini et al. | Biosynthesis of silver nanoparticles from juniper tree extracts | |
| Ayuba et al. | Microbial load on the African catfish (Clarias gariepinus) sold in Markurdi metropolis: a case study of selected markets |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |