CN109797323B - High-corrosion-resistance multilayer composite aluminum alloy pipe and production method thereof - Google Patents
High-corrosion-resistance multilayer composite aluminum alloy pipe and production method thereof Download PDFInfo
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Abstract
The invention relates to a high corrosion-resistant multilayer composite aluminum alloy pipe and a production method thereof, wherein the high corrosion-resistant multilayer composite aluminum alloy pipe is formed by sequentially laminating a coating layer alloy 1, a barrier layer alloy, a core layer alloy and a coating layer alloy 2 and then rolling and compounding the laminated alloy, wherein the barrier layer alloy consists of the following elements in percentage by mass: 0.5 to 1.0 percent of Si, 0.15 to 0.7 percent of Fe, 1.0 to 2.0 percent of Mn, 0.05 to 0.2 percent of Mg, 1.5 to 3.5 percent of Zn, 0 to 0.15 percent of Cu, other elements with single content less than or equal to 0.05 percent and total content less than or equal to 0.15 percent, and the balance of Al. The barrier layer is an Al-Mn alloy added with a certain content of Zn element and provides a sacrificial protection effect, the optimal Zn content of the barrier layer is 1.5-3.5% by mass fraction, the potential difference between the barrier layer and the core layer is 60-140 mV, the barrier layer provides a protection effect for the core layer, and the corrosion resistance of the material is optimal.
Description
Technical Field
The invention relates to a multilayer composite aluminum alloy pipe and a production method thereof, in particular to a high-corrosion-resistance multilayer composite aluminum alloy pipe suitable for brazing B-shaped pipes, U-shaped pipes, sand leakage pipes and the like of an aluminum radiator and a production method thereof.
Technical Field
The multilayer composite brazing aluminum alloy material is widely applied to heat exchanger systems, such as automobile radiators, intercoolers, air-conditioning condensers, evaporators and the like. The carrier for heat exchange is generally liquid such as water, refrigerating fluid, oil and the like, the liquid is combined with automobile exhaust gas or refrigerant and then flows in a circulating mode in a heat exchanger tube material, so that the material is greatly corroded, once the tube material leaks due to corrosion, the product is scrapped, and therefore the improvement of the corrosion resistance of the multilayer composite brazing aluminum alloy tube material has important significance for the improvement of the service life of the product.
At present, the brazing aluminum alloy for the automobile radiator heat exchanger pipe in China is a three-layer composite pipe, the core material of the brazing aluminum alloy is AA3003 alloy, the brazing aluminum alloy has low strength and poor corrosion resistance after brazing, and the brazing aluminum alloy is easy to fatigue fracture, corrosion leakage and other adverse conditions in the using process.
The CN 101927588A of zhangguojun et al discloses a novel composite brazing aluminum alloy material for an automobile heat exchanger, which also adds a barrier layer structure at one end of a core layer and a cladding layer, thereby improving the corrosion resistance of the material. However, the barrier layer in the invention is made of AA7072 alloy, which reduces the strength of the alloy to a certain extent. And although the AA7072 alloy has lower corrosion potential and can play a good role in anode protection on the core material with the positive potential, the potential difference between the barrier layer and the core layer is not very large, and the AA7072 alloy cannot play a good role in protection under certain special environments.
And an et al CN 103122427a discloses an aluminum alloy composite sheet for brazing and a manufacturing method thereof, wherein a core layer contains a higher Si element, which can consume more waste materials in the production process, reduce raw material cost and energy consumption, but is prone to serious problems such as severe erosion in the high-temperature furnace brazing process. The barrier layer alloy adopts AA1050 and 0.5-3.5% of Zn, and although the barrier layer can play a good role of protecting the core material, the overall strength of the material can be reduced.
Disclosure of Invention
The invention aims to provide a high-corrosion-resistance multilayer composite aluminum alloy pipe for brazing and a production method of the aluminum alloy pipe, so as to overcome the defects in the prior art.
The invention provides a high-corrosion-resistance multilayer composite aluminum alloy pipe, which is formed by sequentially laminating a coating layer alloy 1, a barrier layer alloy, a core layer alloy and a coating layer alloy 2 and then rolling and compounding the laminated alloy, and is characterized in that the barrier layer alloy consists of the following elements in percentage by mass: 0.5 to 1.0 percent of silicon (Si), 0.15 to 0.7 percent of iron (Fe), 1.0 to 2.0 percent of manganese (Mn), 0.05 to 0.2 percent of magnesium (Mg), 1.5 to 3.5 percent of zinc (Zn), 0 to 0.15 percent of copper (Cu), other element impurities with the content less than or equal to 0.05 percent and the total content less than or equal to 0.15 percent, and the balance of aluminum (Al).
In the high-corrosion-resistance multilayer composite aluminum alloy pipe, the core layer alloy consists of the following elements in percentage by mass: 0.1 to 0.8 percent of silicon (Si), 0.15 to 0.8 percent of iron (Fe), 0.15 to 0.7 percent of copper (Cu), 0.5 to 1.8 percent of manganese (Mn), 0.1 to 0.45 percent of magnesium (Mg), 0.05 to 0.3 percent of titanium (Ti), other element impurities with the single content of less than or equal to 0.05 percent and the total content of less than or equal to 0.15 percent by weight, and the balance of aluminum (Al).
In the high corrosion-resistant multilayer composite aluminum alloy pipe, the coating layer alloy 1 and the coating layer alloy 2 are conventional brazing layer alloy materials, for example, commercially available AA4343 and AA4045 aluminum alloys are adopted, and the mass fractions of the conventional elements are as follows: 4 to 13 percent of Si, 0.1 to 0.4 percent of Fe, 0.05 to 0.25 percent of Cu, 0 to 0.1 percent of Mn, 0 to 0.1 percent of Zn, other element impurities with single content less than or equal to 0.05 percent and total content less than or equal to 0.15 percent, and the balance of Al.
Furthermore, in the high-corrosion-resistance multilayer composite aluminum alloy pipe, the composite ratio of the barrier layer alloy is 10-25%, the composite ratio of the coating layer alloy 1 is 5-15%, and the composite ratio of the coating layer alloy 2 is 6-15%; the composite ratio is the thickness percentage of a single-layer material in the multi-layer composite material.
Furthermore, the total thickness of the high-corrosion-resistance multilayer composite aluminum alloy pipe is 0.15-0.5 mm.
The second purpose of the invention is to provide a preparation method of a high-corrosion-resistance multilayer composite aluminum alloy pipe, which is characterized by comprising the following steps:
(1) respectively cutting and milling the cast ingots of the barrier layer alloy, the coating layer alloy 1 and the coating layer alloy 2, carrying out homogenization treatment at 520-580 ℃, and then carrying out hot rolling at 470-500 ℃ to reach the required thickness; cutting and milling the core layer alloy cast ingot; (2) according to the requirement of composite ratio, the cladding layer alloy 2, the core layer alloy, the barrier layer alloy and the cladding layer alloy 1 which are processed in the step (1) are laminated from bottom to top; connecting and combining 4 layers of materials, and then hot rolling at 470-500 ℃ to obtain a product with the rolling thickness of 3-5 mm; (3) performing cold rolling on the composite material obtained in the step (2), wherein the rolling thickness is 0.15-0.5 mm; annealing the cold-rolled finished product at 240-300 ℃ for 1-3 h.
The barrier layer alloy consists of the following elements in percentage by mass: 0.5 to 1.0 percent of Si, 0.15 to 0.7 percent of Fe, 1.0 to 2.0 percent of Mn, 0.05 to 0.2 percent of Mg, 1.5 to 3.5 percent of Zn, 0 to 0.15 percent of Cu, other elements with single content less than or equal to 0.05 percent and total content less than or equal to 0.15 percent, and the balance of Al.
The core layer alloy consists of the following elements in percentage by mass: 0.1 to 0.8 percent of Si, 0.15 to 0.8 percent of Fe, 0.15 to 0.7 percent of Cu, 0.5 to 1.8 percent of Mn, 0.1 to 0.45 percent of Mg, 0.05 to 0.3 percent of Ti, other elements with single content less than or equal to 0.05 percent and total content less than or equal to 0.15 percent by weight, and the balance of Al.
The coating layer alloy 1 and the coating layer alloy 2 are conventional brazing layer alloy materials, for example, commercially available AA4343 and AA4045 aluminum alloys are adopted, and the mass fractions of the conventional elements are as follows: 4 to 13 percent of Si, 0.1 to 0.4 percent of Fe, 0.05 to 0.25 percent of Cu, 0 to 0.1 percent of Mn, 0 to 0.1 percent of Zn, other element impurities with single content less than or equal to 0.05 percent and total content less than or equal to 0.15 percent, and the balance of Al.
The composite ratio of the barrier layer alloy is 10-25%, the composite ratio of the coating layer alloy 1 is 5-15%, and the composite ratio of the coating layer alloy 2 is 6-15%; the composite ratio is the thickness percentage of a single-layer material in the multi-layer composite material.
Further, the preparation method of the high corrosion-resistant multilayer composite aluminum alloy pipe further comprises the following smelting process of the barrier layer alloy and the core layer alloy: selecting aluminum materials, zinc materials, magnesium materials, silicon powder, Al-50% of Cu and Al-10% of Mn intermediate alloy materials as raw materials, and respectively smelting in a melting furnace according to the component proportion of the barrier layer alloy and the core layer alloy, wherein the smelting and casting temperature is 720-780 ℃; adding a deslagging agent, and deslagging; and casting to obtain a barrier layer alloy ingot or a core layer alloy ingot.
The aluminum material is a high-purity aluminum (Al) material with the mass fraction of more than or equal to 99.95 percent; the zinc material is a high-purity zinc (Zn) material with the mass fraction of more than or equal to 99.7 percent; the magnesium material is a high-purity magnesium (Mg) material with the mass fraction of more than or equal to 99.7 percent; the silicon powder is high-purity silicon (Si) powder with the mass fraction of more than or equal to 99.7%.
According to the high-corrosion-resistance multilayer composite aluminum alloy pipe, a barrier layer structure is added in a traditional three-layer composite structure; the core layer is prepared by common 3-series Al-Mn alloy with a small amount of Mg element and Si element, provides main strength support for the material, forms a certain aging strengthening effect to improve the mechanical property of the material under the condition of not influencing the brazing of the coating layer, and the yield strength and the tensile strength after brazing respectively reach over 55MPa and 165MPa, and respectively reach over 75MPa and 185MPa after two weeks of natural aging; the barrier layer is an Al-Mn alloy added with a certain content of Zn element, the optimal content of Zn is 1.5-3.5 mass percent, the optimal corrosion potential difference between the barrier layer and the core layer is 60-140 mV, a good sacrificial protection effect is provided for the core layer, and the corrosion resistance of the material is greatly improved by the anode protection effect of the core layer generated by the potential difference between the barrier layer and the core layer; and a certain amount of Mg element is added into the barrier layer, so that the overall strength of the material is not reduced after a layer of barrier layer is added, the cladding layers on two sides are Al-Si alloy and are connected with other materials for brazing, and the brazing performance of the material is not influenced. Therefore, the high-corrosion-resistance multilayer composite brazing aluminum alloy pipe can effectively generate sacrificial anode protection, so that the corrosion resistance of the side of the barrier layer is improved, the diffusion of core layer elements to the coating layer can be prevented, and the strength of the material is improved under the condition of ensuring the brazing performance of the material.
Drawings
Fig. 1 is a schematic structural diagram of the high corrosion resistance multilayer composite aluminum alloy pipe of the invention.
Wherein: 1-cladding alloy 1, 2-barrier alloy, 3-core alloy, 4-cladding alloy 2.
Detailed Description
The present invention is further illustrated by the following examples, which should be construed as being merely illustrative and not limitative of the remainder of the disclosure, wherein the non-illustrations in the examples are carried out in accordance with common sense and common technique.
In the examples of the present invention and the comparative examples, the symbol "-" indicates that this element was not added.
Examples A1, A2, B1 to B4, comparative examples A3, A4, B5, B6
Examples A1, A2, B1-B4 and comparative examples A3, A4, B5, B6 are examples of melting alloy materials. Selecting a high-purity aluminum (Al) material with the purity of 99.99 percent (mass fraction, the same below), a zinc (Zn) material with the purity of 99.9 percent, a magnesium (Mg) material with the purity of 99.9 percent, silicon (Si) powder with the purity of 99.9 percent and intermediate alloy materials of Al-50 percent Cu and Al-10 percent Mn as raw materials, respectively proportioning the raw materials according to the components of the barrier layer alloy and the core layer alloy listed in the tables 1 and 2, and smelting in a melting furnace, wherein the casting temperature is 720-780 ℃; adding a deslagging agent, and deslagging; casting into a barrier layer alloy ingot, a coating layer alloy ingot and a core layer alloy ingot; and then carrying out homogenizing annealing on the ingot at 550 ℃ for 10h to obtain the required core layer alloy ingot and barrier layer alloy ingot.
TABLE 1 composition of the alloy composition of the barrier layer (wt%)
| Numbering | Si | Fe | Mn | Cu | Mg | Zn | Al |
| Example A1 | 0.71 | 0.21 | 1.48 | 0.1 | 0.15 | 3.08 | Balance of |
| Example A2 | 0.74 | 0.33 | 1.24 | 0.08 | 0.06 | 2.45 | Balance of |
| Comparative example A3 | 0.82 | 0.22 | 1.60 | 0.05 | 0.16 | 0.88 | Balance of |
| Comparative example A4 | 0.84 | 0.40 | 1.70 | 0.11 | 0.11 | 4.64 | Balance of |
TABLE 2 composition of alloy composition for core layer (wt%)
Examples 1 to 6 and comparative examples 1 to 5
Cutting and milling the barrier layer alloy ingot obtained in the embodiments A1 to A4 and the core layer alloy ingot obtained in the embodiments B1 to B6, and removing a riser and a skin; after face milling, heating to 480 ℃ in an annealing furnace for homogenization treatment, preserving heat for 2-4 h, carrying out hot rolling at 470-500 ℃, and rolling to be 10-40 mm thin according to different compound rates at the final rolling temperature of 340 ℃; cutting and milling an outsourced coating alloy cast ingot to remove a dead head and a skin; according to the composite ratio listed in the table 3, the 1-cladding alloy 1, the 2-barrier layer alloy, the 3-core layer alloy and the 4-cladding layer alloy 2 are sequentially laminated, connected and combined, heated to 480 ℃ in an annealing furnace, insulated for 2-4 hours, subjected to hot rolling, and rolled to the thickness of 3-5 mm; and then cold rolling, wherein the pass working rate of a finished product is 80-95%, the thickness of the finished product is reduced to 0.15-0.5 mm, and finally annealing is carried out at 240-300 ℃ for 1-3 h to reach a finished product state.
TABLE 3 composition of the finished examples and comparative examples (wt%)
The materials of the examples and the comparative examples in table 3 were subjected to simulated brazing, and tested for mechanical properties, brazing properties and corrosion properties at different times after brazing: the yield strength and the tensile strength are detected by a GB/T228-2002 metal material room temperature tensile test method; the corrosion performance is detected by adopting an OY aqueous solution circulation experiment method, and the corrosion time is 8 weeks.
TABLE 4 test results of the performance of the examples and comparative examples after brazing at 603 ℃ for 3min
TABLE 5 results of natural aging performance test at 603 ℃ for 3min after brazing in examples and comparative examples
| Numbering | Yield strength Rp0.2(MPa) | Tensile Strength Rm (MPa) | Elongation (%) |
| Example 1 | 86.5 | 197.2 | 13.1 |
| Example 2 | 79.1 | 190.1 | 14.7 |
| Example 3 | 84.6 | 198.0 | 15.4 |
| Example 4 | 82.8 | 193.7 | 13.5 |
| Example 5 | 78.6 | 188.2 | 14.2 |
| Example 6 | 79.5 | 186.6 | 15.0 |
| Comparative example 1 | 62.6 | 173.9 | 13.7 |
| Comparative example 2 | 95.0 | 206.6 | 11.4 |
| Comparative example 3 | 88.0 | 200.3 | 14.7 |
| Comparative example 4 | 80.7 | 185.8 | 13.5 |
| Comparative example 5 | 81.8 | 187.8 | 12.5 |
As can be seen from the above tables 4 and 5, examples 1 to 6 of the present invention have high mechanical properties, excellent corrosion properties, and good brazing properties. The Mg element can improve the mechanical property of the material, and has an aging strengthening effect with the Mg2Si phase generated by the Si element, so that the core layer contains a certain amount of the Mg element, which is beneficial to improving the mechanical property of the material. Comparative example 1 the core layer does not contain Mg element, so its post-weld mechanical properties are lower. However, the content of the Mg element is too high, the Mg element in the core layer can diffuse into the cladding layer in the brazing process to influence the brazing performance of the material, and for example, the defects of insufficient solder and the like can appear in comparative example 2, so that the content of the Mg in the core layer is 0.1-0.45%. Zn element can reduce the corrosion potential of the material, the Zn element is added into the barrier layer to enable the corrosion potential of the barrier layer to be lower, and cathodic current generated by the sacrificial anode protects the core layer from being corroded. Comparative example 3 is a conventional 3-layer material, and the core layer is directly corroded without the presence of a barrier layer, so that the corrosion resistance is poor. Comparative example 4 had a barrier layer, but the Zn content was too low to provide good protection. Comparative example 5 is that the Zn content is too high, the barrier layer is excessively sacrificed, and the corrosion itself is accelerated, so that the Zn element of the barrier layer is optimally 1.5 to 3.5%.
Claims (9)
1. The high-corrosion-resistance multilayer composite aluminum alloy pipe is formed by sequentially laminating and rolling a coating layer alloy 1, a barrier layer alloy, a core layer alloy and a coating layer alloy 2, and is characterized in that the barrier layer alloy consists of the following elements in percentage by mass: 0.5 to 1.0 percent of Si, 0.15 to 0.7 percent of Fe, 1.0 to 2.0 percent of Mn, 0.15 to 0.2 percent of Mg, 1.5 to 3.5 percent of Zn, 0 to 0.15 percent of Cu, other elements with single content less than or equal to 0.05 percent and total content less than or equal to 0.15 percent, and the balance of Al;
the core layer alloy consists of the following elements in percentage by mass: 0.1 to 0.8 percent of Si, 0.15 to 0.8 percent of Fe, 0.15 to 0.46 percent of Cu, 0.5 to 1.8 percent of Mn, 0.35 to 0.45 percent of Mg, 0.05 to 0.3 percent of Ti, other elements with single content less than or equal to 0.05 percent and total content less than or equal to 0.15 percent by weight, and the balance of Al.
2. The high corrosion-resistant multi-layer composite aluminum alloy pipe as recited in claim 1, wherein said clad alloy 1 and clad alloy 2 are braze alloy materials.
3. The high-corrosion-resistance multilayer composite aluminum alloy pipe as claimed in any one of claims 1 to 2, wherein the composite ratio of the barrier layer alloy is 10% to 25%, the composite ratio of the coating layer alloy 1 is 5% to 15%, and the composite ratio of the coating layer alloy 2 is 6% to 15%.
4. The high-corrosion-resistance multilayer composite aluminum alloy pipe as recited in claim 3, wherein the total thickness of the multilayer composite aluminum alloy pipe is 0.15-0.5 mm.
5. The preparation method of the high-corrosion-resistance multilayer composite aluminum alloy pipe is characterized by comprising the following steps of: (1) respectively cutting and milling the cast ingots of the barrier layer alloy, the coating layer alloy 1 and the coating layer alloy 2, carrying out homogenization treatment at 520-580 ℃, and then carrying out hot rolling at 470-500 ℃ to reach the required thickness; cutting and milling the core layer alloy cast ingot; (2) according to the requirement of composite ratio, the cladding layer alloy 2, the core layer alloy, the barrier layer alloy and the cladding layer alloy 1 which are processed in the step (1) are laminated from bottom to top; connecting and combining 4 layers of materials, and then hot rolling at 470-500 ℃ to obtain a product with the rolling thickness of 3-5 mm; (3) performing cold rolling on the composite material obtained in the step (2), wherein the rolling thickness is 0.15-0.5 mm; annealing the cold-rolled finished product at 240-300 ℃ for 1-3 h;
the barrier layer alloy consists of the following elements in percentage by mass: 0.5 to 1.0 percent of Si, 0.15 to 0.7 percent of Fe, 1.0 to 2.0 percent of Mn, 0.15 to 0.2 percent of Mg, 1.5 to 3.5 percent of Zn, 0 to 0.15 percent of Cu, other elements with single content less than or equal to 0.05 percent and total content less than or equal to 0.15 percent, and the balance of Al;
the core layer alloy consists of the following elements in percentage by mass: 0.1 to 0.8 percent of Si, 0.15 to 0.8 percent of Fe, 0.15 to 0.46 percent of Cu, 0.5 to 1.8 percent of Mn, 0.35 to 0.45 percent of Mg, 0.05 to 0.3 percent of Ti, other elements with single content less than or equal to 0.05 percent and total content less than or equal to 0.15 percent by weight, and the balance of Al.
6. The method according to claim 5, wherein the clad alloy 1 and the clad alloy 2 are brazing alloy materials.
7. The method according to any one of claims 5 to 6, wherein the composition ratio of the barrier layer alloy is 10% to 25%, the composition ratio of the coating layer alloy 1 is 5% to 15%, and the composition ratio of the coating layer alloy 2 is 6% to 15%.
8. The method of claim 5, further comprising a melting process of the barrier layer alloy and the core layer alloy: selecting aluminum materials, zinc materials, magnesium materials, silicon powder, Al-50% of Cu and Al-10% of Mn intermediate alloy materials as raw materials, and respectively smelting in a melting furnace according to the component proportion of the barrier layer alloy and the core layer alloy, wherein the smelting and casting temperature is 720-780 ℃; adding a deslagging agent, and deslagging; and casting to obtain a barrier layer alloy ingot or a core layer alloy ingot.
9. The preparation method of claim 8, wherein the aluminum material is a high-purity aluminum material with a mass fraction of not less than 99.95%; the zinc material is a high-purity zinc material with the mass fraction of more than or equal to 99.7 percent; the magnesium material is a high-purity magnesium material with the mass fraction of more than or equal to 99.7 percent; the silicon powder is high-purity silicon powder with the mass fraction of more than or equal to 99.7%.
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| CN114592193A (en) * | 2020-12-04 | 2022-06-07 | 中国石油化工股份有限公司 | Sacrificial anode and cathode protector for oil pipe and preparation method thereof |
| WO2023087957A1 (en) * | 2021-11-18 | 2023-05-25 | 格朗吉斯铝业（上海）有限公司 | Aluminum pipe, manufacturing method therefor, and full aluminum heat exchanger |
| CN117002104A (en) * | 2022-04-27 | 2023-11-07 | 杭州三花微通道换热器有限公司 | Heat exchange tube for heat exchanger and heat exchanger |
| CN114771049B (en) * | 2022-04-29 | 2024-04-09 | 无锡金洋铝业有限公司 | Corrosion-resistant aluminum brazing composite plate and preparation method thereof |
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