A copper alloy for glass wine bottle molds and its preparation method

Abstract

The present invention discloses a copper alloy for glass wine bottle molds and a preparation method thereof. The copper alloy comprises 53-57% of Cu, 2.0-5.0% of Al, 1.0-3.0% of Si, 9.0-13.0% of Ni, 0.5-2.5% of Fe, with impurities ≤ 0.8%, and the balance being Zn. The copper alloy prepared by the present invention has better thermal conductivity. When mass-producing glass wine bottles under the same working conditions, the working temperature is only 470°C. The lower working temperature speeds up the solidification rate of the glass melt, and the production rhythm of glass wine bottles per minute is increased by 2-3 groups, improving the production efficiency. Moreover, the surface roughness of the glass wine bottle mold prepared from the copper alloy is lower, and the surface of the finally produced glass wine bottle is also smoother. In addition, the glass wine bottle mold prepared from the copper alloy has excellent high-temperature oxidation resistance. The excellent high-temperature oxidation resistance reduces the number of mold repairs, and the production efficiency is improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of alloys, and particularly relates to a copper alloy for glass wine bottle molds and a preparation method thereof. Background Art

[0002] Glass wine bottle molds are the main forming process equipment for glass wine bottles. During the forming process of glass wine bottles, the molds come into contact with molten glass at 900°C to 1000°C at high speed and frequently. The molds are subjected to the effects of oxidation, growth, thermal shock, friction, and thermal fatigue. Currently, vermicular graphite cast iron is mainly used for glass wine bottle molds. Vermicular graphite cast iron refers to a type of cast iron in which most of its graphite is in a vermicular shape and part is in a spherical shape. Its structure and properties are between those of nodular graphite cast iron and gray cast iron, and it has good comprehensive properties. The mechanical and physical properties of vermicular graphite cast iron depend on factors such as the vermicularization state of graphite and the matrix structure, among which the vermicularization state of graphite has the greatest influence. Generally, the vermicularization rate is required to be ≥50%. The main matrix structure of vermicular graphite cast iron used for glass wine bottle molds is ferrite + pearlite, and the chemical composition (mass fraction) / %: C 3.36%, Si 2.43%, Mn 0.6%, P 0.06%, S 0.028%, Re 0.024%, Mg 0.014%, Ti 0.13%. However, there are the following defects in using vermicular graphite cast iron to prepare glass wine bottle molds:

[0003] 1. The vermicular graphite cast iron glass wine bottle mold has poor thermal conductivity;

[0004] 2. The surface roughness of the wine bottles produced by the vermicular graphite cast iron glass wine bottle mold is poor;

[0005] 3. The vermicular graphite cast iron glass wine bottle mold has a high repair frequency;

[0006] 4. The production efficiency of the vermicular graphite cast iron glass wine bottle mold is not high;

[0007] 5. The vermicular graphite cast iron glass wine bottle mold has poor high-temperature oxidation resistance. Summary of the Invention

[0008] In view of the above-mentioned prior art, the present invention provides a copper alloy for glass wine bottle molds and a preparation method thereof to develop a brand-new copper alloy for glass wine bottle molds.

[0009] In order to achieve the above object, the technical solution adopted by the present invention is: to provide a copper alloy for glass wine bottle molds, including the following components in mass percentage:

[0010] Cu 53 - 57%, Al 2.0 - 5.0%, Si 1.0 - 3.0%, Ni 9.0 - 13.0%, Fe 0.5 - 2.5%, impurities ≤0.8%, and the balance is Zn.

[0011] On the basis of the above technical solutions, the present invention can also be improved as follows.

[0012] Further, the copper alloy for the glass wine bottle mold in the present invention comprises the following components in mass percentage:

[0013] Cu 55.73%, Al 3.57%, Si 2.15%, Ni 11.37%, Fe 0.76%, impurities ≤ 0.8%, and the balance is Zn.

[0014] The present invention also discloses a preparation method of the above copper alloy for the glass wine bottle mold, which comprises the following steps:

[0015] S1: Put electrolytic copper plates, remelted aluminum ingots, aluminum-iron master alloy, electrolytic nickel plates, silicon blocks and fluxes into a melting equipment, heat up to 1100 - 1160 °C, and completely melt the materials to obtain a metal liquid.

[0016] S2: Adjust the temperature of the metal liquid to 1060 - 1120 °C, then add zinc blocks and fluxes to the temperature-adjusted metal liquid, and then heat up to 1100 - 1160 °C, and keep melting for 10 - 20 min to obtain an alloy liquid.

[0017] S3: Adjust the composition of the alloy liquid until the composition of the alloy liquid is as follows:

[0018] Cu 53 - 57%, Al 2.0 - 5.0%, Si 1.0 - 3.0%, Ni 9.0 - 13.0%, Fe 0.5 - 2.5%, impurities ≤ 0.8%, and the balance is Zn;

[0019] S4: Pour the qualified alloy liquid into a mold, and after crystallization and solidification, draw out an ingot by traction to obtain the product.

[0020] Further, the melting equipment is an intermediate frequency induction furnace.

[0021] Further, the purity of the electrolytic copper plates is 99.99%; the purity of the remelted aluminum ingots is 99.5%; the proportion of iron in the aluminum-iron master alloy is 25%; the purity of the electrolytic nickel plates is 99.5%; the purity of the silicon blocks is 99.4%.

[0022] Further, the flux is composed of CaCO3, SiO2 and NaCl.

[0023] Further, the addition amount of the flux in S1 is 0.2 - 0.3% of the total mass of the remaining materials.

[0024] Further, the traction drawing parameters in S4 are: drawing length 8 mm, drawing speed 16 mm / s, reverse push waiting time 0.5 s, reverse push length 0.6 mm, and residence time 12 s.

[0025] The beneficial effects of the present invention are as follows:

[0026] 1. The copper alloy prepared by the present invention has better thermal conductivity. When mass-producing glass wine bottles under the same working conditions, the working temperature is only 470°C, which is lower than 500°C of the vermicular graphite cast iron mold. The lower working temperature speeds up the solidification rate of the glass melt, and the production rhythm of glass wine bottles per minute is increased by 2 - 3 groups, improving the production efficiency.

[0027] 2. The surface roughness of the glass wine bottle mold prepared from the copper alloy in the present invention is lower, and the surface of the finally produced glass wine bottle is also smoother.

[0028] 3. The glass wine bottle mold prepared from the copper alloy in the present invention has excellent high-temperature oxidation resistance. The excellent high-temperature oxidation resistance reduces the number of mold repairs, and the production efficiency is improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 FIG. 15 is an external view of the copper alloy ingot for the glass wine bottle mold prepared in Example 1;

[0030] Figure 2 FIG. 19 is a metallographic structure diagram of the copper alloy for the glass wine bottle mold prepared in Example 1;

[0031] Figure 3 FIG. 23 is a schematic diagram of the glass wine bottle mold prepared from the copper alloy for the glass wine bottle mold prepared in Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0032] The following describes in detail the specific implementation manners of the present invention in conjunction with the embodiments.

[0033] Example 1

[0034] A copper alloy for a glass wine bottle mold includes the following components by mass percentage:

[0035] Cu 55.73%, Al 3.57%, Si 2.15%, Ni 11.37%, Fe 0.76%, impurities ≤ 0.8%, and the balance is Zn.

[0036] The copper alloy for the glass wine bottle mold in this example is prepared through the following steps:

[0037] S1: Add electrolytic copper plates with a purity of 99.99%, remelted aluminum ingots with a purity of 99.5%, aluminum-iron (25%) master alloy, electrolytic nickel plates with a purity of 99.5% and silicon blocks with a purity of 99.4% into a 750 kg medium-frequency induction furnace. The electrolytic copper plates, remelted aluminum ingots, aluminum-iron (25%) master alloy and electrolytic nickel plates are all small pieces of 2 kg per piece, and the silicon blocks are small pieces of 0.5 kg per piece. Then add a flux (composed of equal-mass mixture of CaCO3, SiO2 and NaCl) accounting for 0.25% of the total mass of the above materials. Then increase the power of the medium-frequency induction furnace and raise the temperature to 1150 °C for smelting until the materials are completely melted to obtain molten metal.

[0038] S2: Reduce the power of the medium-frequency induction furnace to lower the temperature of the molten metal to 1100 °C. Then add zinc blocks (5 kg per piece) and flux (the same as above) to the temperature-adjusted molten metal, then raise the temperature to 1150 °C and keep it warm for smelting for 10 min. Subsequently, adjust the medium-frequency induction furnace to the holding state, let it stand for 5 min, and skim off the floating slag on the surface of the molten metal to obtain alloy liquid.

[0039] S3: Take a sample from the middle of the furnace chamber for spectral analysis of the composition of the alloy liquid, and then fine-tune the composition of the alloy liquid according to the test results until the composition of the alloy liquid is as follows:

[0040] Cu 55.73%, Al 3.57%, Si 2.15%, Ni 11.37%, Fe 0.76%, impurities ≤ 0.8%, Zn balance.

[0041] S4: Transfer the qualified alloy liquid into the L-shaped holding furnace (750 kg) of the horizontal continuous casting production line, skim off the floating slag on the surface of the alloy liquid, add dry charcoal to cover and isolate the air, and control the temperature of the alloy liquid in the L-shaped holding furnace at 1100 °C. Install a mold on the lower part of the L-shaped holding furnace, and install a graphite mold with a diameter of Φ205 on the inner wall of the mold. Indirectly cool the alloy liquid through circulating cooling water inside the mold. The alloy liquid cools and solidifies into a solid state, and is pulled out by a traction machine with set drawing parameters to obtain an ingot. The traction and drawing of the traction machine are: drawing length 8 mm, drawing speed 16 mm / s, reverse push waiting time 0.5 s, reverse push length 0.6 mm, residence time 12 s.

[0042] Example 2

[0043] A copper alloy for glass wine bottle molds comprises the following components in mass percentage:

[0044] Cu 53.11%, Al 5.02%, Si 1.08%, Ni 13.04%, Fe 0.56%, impurities ≤ 0.8%, Zn balance.

[0045] The copper alloy for glass wine bottle molds in this example is prepared through the following steps:

[0046] S1: Add electrolytic copper plates with a purity of 99.99%, remelted aluminum ingots with a purity of 99.5%, aluminum-iron (25%) master alloy, electrolytic nickel plates with a purity of 99.5%, and silicon blocks with a purity of 99.4% into a 750 kg intermediate frequency induction furnace. The electrolytic copper plates, remelted aluminum ingots, aluminum-iron (25%) master alloy, and electrolytic nickel plates are all small pieces of 2 kg per piece, and the silicon blocks are small pieces of 0.5 kg per piece. Then add a flux (composed of equal mass mixture of CaCO3, SiO2, and NaCl) accounting for 0.2% of the total mass of the above materials, and then increase the power of the intermediate frequency induction furnace, raise the temperature to 1100 °C, and carry out smelting to completely melt the materials to obtain molten metal.

[0047] S2: Reduce the power of the intermediate frequency induction furnace to lower the temperature of the molten metal to 1060 °C. Then add zinc blocks (5 kg per piece) and flux (the same as above) to the temperature-adjusted molten metal, and then raise the temperature to 1100 °C and keep it warm for smelting for 15 min. Subsequently, adjust the intermediate frequency induction furnace to the heat preservation state, let it stand for 5 min, and skim off the floating slag on the surface of the molten metal to obtain alloy liquid.

[0048] S3: Take a sample from the middle of the furnace chamber for spectral analysis of the composition of the alloy liquid, and then fine-tune the composition of the alloy liquid according to the test results until the composition of the alloy liquid is as follows:

[0049] Cu 53.11%, Al 5.02%, Si 1.08%, Ni 13.04%, Fe 0.56%, impurities ≤ 0.8%, and the balance is Zn.

[0050] S4: Transfer the qualified alloy liquid into the L-shaped holding furnace (750 kg) of the horizontal continuous casting production line, skim off the floating slag on the surface of the alloy liquid, add dry charcoal to cover and isolate the air, and control the temperature of the alloy liquid in the L-shaped holding furnace at 1060 °C. Install a mold in the lower part of the L-shaped holding furnace, and install a graphite mold with a diameter of Φ205 on the inner wall of the mold. The alloy liquid is indirectly cooled by circulating cooling water inside the mold, and the alloy liquid cools and solidifies into a solid state, and is pulled out by a traction machine with set drawing parameters to obtain an ingot. The traction and drawing parameters of the traction machine are: drawing length 8 mm, drawing speed 16 mm / s, reverse push waiting time 0.5 s, reverse push length 0.6 mm, and residence time 12 s.

[0051] Example 3

[0052] A copper alloy for glass wine bottle molds, comprising the following components in mass percentage:

[0053] Cu 57.03%, Al 2.04%, Si 3.01%, Ni 9.11%, Fe 2.52%, impurities ≤ 0.8%, and the balance is Zn.

[0054] The copper alloy for the glass wine bottle mold in this embodiment is prepared through the following steps:

[0055] S1: Add electrolytic copper plates with a purity of 99.99%, remelted aluminum ingots with a purity of 99.5%, aluminum-iron (25%) master alloy, electrolytic nickel plates with a purity of 99.5%, and silicon blocks with a purity of 99.4% into a 750 kg medium-frequency induction furnace. The electrolytic copper plates, remelted aluminum ingots, aluminum-iron (25%) master alloy, and electrolytic nickel plates are all small pieces of 2 kg per piece, and the silicon blocks are small pieces of 0.5 kg per piece. Then add a flux (composed of equal-mass mixture of CaCO3, SiO2, and NaCl) accounting for 0.3% of the total mass of the above materials. Then increase the power of the medium-frequency induction furnace and raise the temperature to 1160 °C for smelting until the materials are completely melted to obtain molten metal;

[0056] S2: Reduce the power of the medium-frequency induction furnace to lower the temperature of the molten metal to 1120 °C. Then add zinc blocks (5 kg per piece) and flux (the same as above) to the temperature-adjusted molten metal, and then raise the temperature to 1160 °C for heat preservation smelting for 20 min. Subsequently, adjust the medium-frequency induction furnace to the heat preservation state, let it stand for 5 min, and skim off the floating slag on the surface of the molten metal to obtain alloy liquid;

[0057] S3: Take a sample from the middle of the furnace chamber for spectral analysis of the composition of the alloy liquid, and then fine-tune the composition of the alloy liquid according to the test results until the composition of the alloy liquid is as follows:

[0058] Cu 57.03%, Al 2.04%, Si 3.01%, Ni 9.11%, Fe 2.52%, impurities ≤ 0.8%, Zn the balance;

[0059] S4: Transfer the qualified alloy liquid to the L-type heat preservation furnace (750 kg) of the horizontal continuous casting production line, skim off the floating slag on the surface of the alloy liquid, add dry charcoal to cover and isolate the air, and control the temperature of the alloy liquid in the L-type heat preservation furnace at 1120 °C. Install a mold in the lower part of the L-type heat preservation furnace, and install a graphite mold with a diameter of Φ205 on the inner wall of the mold. The alloy liquid is indirectly cooled by circulating cooling water inside the mold. The alloy liquid cools and solidifies into a solid state, and an ingot is drawn out by a traction machine with set drawing parameters, thus obtaining; the traction and drawing by the traction machine are with a drawing length of 8 mm, a drawing speed of 16 mm / s, a reverse push waiting time of 0.5 s, a reverse push length of 0.6 mm, and a residence time of 12 s.

[0060] Experimental example

[0061] Saw the ingot obtained in Example 1 into ingots 400 mm long by a sawing machine, and turn off the skin of the ingot by an ordinary lathe (single-side machining 1 mm). The ingot after skin turning is as Figure 1 shown, and the ingot metallographic structure is as Figure 2As shown. Then, the ingot is cut in half longitudinally by a sawing machine to obtain a mold blank, and the mold blank is processed into a copper alloy glass wine bottle mold by a high-precision CNC machining center, as Figure 3 shown. Then, a vermicular graphite cast iron for molds commercially available is made into a cast iron glass wine bottle mold according to the same method. The density, specific heat capacity, thermal diffusivity, thermal conductivity, etc. of the two glass wine bottle molds are tested according to the test methods described in ASTM E1269-11, GB / T1432-1996, and GB / T22588-2008. The test instruments are a thermal conductivity meter (LFA467), an analytical balance (PX224ZH), and a differential scanning calorimeter (DSC25); the results are shown in Table 1.

[0062] Table 1 Thermal conductivity parameters and density of copper alloy and vermicular graphite cast iron molds

[0063] Glass wine bottle mold material name <![CDATA[Density g / cm 3 > Specific heat capacity J / (g*℃) <![CDATA[Thermal diffusivity mm 2 / s]]> Thermal conductivity W / (m*K) Copper alloy 7.8 0.48 25.79 97.62 Vermicular graphite cast iron 7.0 0.62 8.35 36.42

[0064] It can be seen from Table 1 that the copper alloy mold prepared by the present invention has better thermal conductivity. When mass-producing glass wine bottles under the same working conditions, the working temperature of the vermicular graphite cast iron mold is about 500 °C, and the working temperature of the copper alloy mold is about 470 °C. The lower working temperature speeds up the solidification rate of the glass melt, and the production rhythm of glass wine bottles produced per minute is increased by 2-3 groups, improving the production efficiency.

[0065] The surface roughness of the glass wine bottles produced by the two glass wine bottle molds was detected using a Japanese Mitutoyo roughness meter (SV3200), and the results are shown in Table 2.

[0066] Table 2 Surface roughness of glass wine bottles produced by molds of two materials

[0067] Glass wine bottle mold material name Ra(μm) Rz(μm) Copper alloy 0.1119 0.7028 Vermicular graphite cast iron 0.4035 1.9336

[0068] It can be seen from Table 2 that the surface of the glass wine bottle mold prepared with the copper alloy in the present invention is smoother, and the surface of the finally produced glass wine bottle is also smoother.

[0069] The oxidation resistance of the two glass wine bottle molds is tested according to the method described in HB5258-2000. The test equipment is a high-temperature electric furnace (HDX-4-12), and the test condition is to keep the temperature at 500 °C for 200 h. The results are shown in Table 3.

[0070] Table 3 Oxidation resistance of two glass wine bottle molds

[0071] Glass wine bottle mold material name Oxidation weight gain (g) <![CDATA[Average oxidation weight gain per unit area (g / m 2 )]]> Copper alloy 0.0006 2.988 Vermicular graphite cast iron 0.0067 33.567

[0072] As can be seen from Table 3, the glass wine bottle mold prepared from the copper alloy of the present invention has excellent high-temperature oxidation resistance. In actual production, when vermicular graphite cast iron molds are used to mass-produce glass wine bottles, for every 6 shifts of production (two shifts per day), the molds need to be repaired 3 to 4 times. However, for copper alloy molds, for every 6 shifts of production (two shifts per day), only 1 to 2 repairs are needed; the excellent high-temperature oxidation resistance reduces the number of mold repairs, and the production efficiency is improved.

[0073] Although the specific implementation manners of the present invention have been described in detail in conjunction with the embodiments, it should not be construed as a limitation on the protection scope of this patent. Within the scope described in the claims, various modifications and deformations that can be made by those skilled in the art without creative efforts still fall within the protection scope of this patent.

Claims

1. A copper alloy for glass wine bottle molds, characterized in that, Comprising components with the following mass percentages: Cu 55.73%, Al 3.57%, Si 2.15%, Ni 11.37%, Fe 0.76%, impurities ≤ 0.8%, balance Zn; The copper alloy for the glass wine bottle mold is obtained through the following steps: S1: Put electrolytic copper plates, remelted aluminum ingots, aluminum-iron master alloy, electrolytic nickel plates, silicon blocks and fluxes into the melting equipment, heat up to 1100 - 1160 °C to completely melt the materials to obtain molten metal; S2: Adjust the temperature of the molten metal to 1060 - 1120 °C, then add zinc blocks and fluxes to the temperature-adjusted molten metal, and then heat up to 1100 - 1160 °C, keep warm and melt for 10 - 20 min to obtain alloy liquid; S3: Adjust the composition of the alloy liquid until the composition of the alloy liquid is as follows: Cu 55.73%, Al 3.57%, Si 2.15%, Ni 11.37%, Fe 0.76%, impurities ≤ 0.8%, balance Zn; S4: Pour the qualified alloy liquid into the mold, after crystallization and solidification, draw out the ingot by traction, and that's it; The traction and drawing parameters are: drawing length 8 mm, drawing speed 16 mm / s, reverse push waiting time 0.5 s, reverse push length 0.6 mm, residence time 12 s.

2. The copper alloy for the glass wine bottle mold according to claim 1, wherein: The melting equipment is an intermediate frequency induction furnace.

3. The copper alloy for the glass wine bottle mold according to claim 1, wherein: The purity of the electrolytic copper plates is 99.99%; the purity of the remelted aluminum ingots is 99.5%; the proportion of iron in the aluminum-iron master alloy is 25%; the purity of the electrolytic nickel plates is 99.5%; the purity of the silicon blocks is 99.4%.

4. The copper alloy for glass wine bottle molds according to claim 1, characterized in that: The flux is composed of CaCO3, SiO2 and NaCl.

5. The copper alloy for glass wine bottle molds according to claim 4, wherein: The addition amount of the flux in S1 is 0.2 - 0.3% of the total mass of the remaining materials.

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