WO2023240965A1 - 一种平行流冷凝器用集流管料及其制备方法和应用 - Google Patents

一种平行流冷凝器用集流管料及其制备方法和应用 Download PDF

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WO2023240965A1
WO2023240965A1 PCT/CN2022/139624 CN2022139624W WO2023240965A1 WO 2023240965 A1 WO2023240965 A1 WO 2023240965A1 CN 2022139624 W CN2022139624 W CN 2022139624W WO 2023240965 A1 WO2023240965 A1 WO 2023240965A1
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Prior art keywords
parallel flow
flow condenser
header
core layer
alloy
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PCT/CN2022/139624
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English (en)
French (fr)
Inventor
郭飞跃
卢紫琼
黄美艳
吴佳丽
桂良宝
王立新
李洪伟
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乳源东阳光优艾希杰精箔有限公司
韶关东阳光科技研发有限公司
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Publication of WO2023240965A1 publication Critical patent/WO2023240965A1/zh

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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B39/00—Evaporators; Condensers
    • F25B39/04—Condensers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
    • F28F21/08—Constructions of heat-exchange apparatus characterised by the selection of particular materials of metal
    • F28F21/081—Heat exchange elements made from metals or metal alloys
    • F28F21/084—Heat exchange elements made from metals or metal alloys from aluminium or aluminium alloys
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B2339/00—Details of evaporators; Details of condensers
    • F25B2339/04—Details of condensers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/40—Solar thermal energy, e.g. solar towers

Definitions

  • the present invention relates to the technical field of alloys for heat exchangers, and more specifically, to a header material for a parallel flow condenser and its preparation method and application.
  • parallel flow heat exchangers have been widely used as condensers and evaporators in the fields of automotive air conditioners and commercial air conditioners due to their high pressure resistance, large heat exchange area, and high heat dissipation efficiency.
  • the parallel flow heat exchanger is assembled and brazed by using zinc-sprayed extruded porous tubes (MPE tubes for short), composite fin foils, header tubes made of high-frequency welding, plugging caps, side plates, etc.
  • MPE tubes zinc-sprayed extruded porous tubes
  • composite fin foils composite fin foils
  • header tubes made of high-frequency welding
  • plugging caps plugging caps
  • side plates etc.
  • the 4XXX alloy brazing material on the surface of the header, composite fin foil, and plug cap melts and flows, and after cooling, is connected with the MPE pipe to form a whole.
  • the header is one of the important components of the condenser in the air conditioning system.
  • the refrigerant gas in the air conditioner is compressed by the compressor to produce high-temperature and high-pressure gas. After being dissipated and condensed by the condenser, it becomes a low-temperature and high-pressure liquid, which enters the header. flow.
  • the corrosion resistance of the collecting pipe material directly affects the overall service life of the condenser. With the development of heat exchangers in the direction of miniaturization and lightweight, the thickness of collector pipe materials has also shown a trend of thinning, which has also put forward higher requirements for the pressure resistance and corrosion resistance performance indicators of collector pipe materials.
  • the collector pipe material is composed of an outer layer alloy and a core layer alloy.
  • the composition of the outer layer alloy is 4XXX series aluminum alloy + 1wt.% Zn
  • the core layer alloy is 3003 series aluminum alloy.
  • the outer layer of 4XXX alloy brazing material contains about 1wt.% zinc. Its main purpose is to use the zinc element to effectively reduce the potential of the aluminum alloy electrode and be corroded preferentially, thereby protecting the core layer of the collector pipe from being corroded and perforated preferentially, thereby achieving extended The purpose of condenser service life.
  • the zinc in the brazing material flows with the 4XXX brazing material part to the welding angle connecting the header and the MPE pipe.
  • the actual Zn content remaining in the outer layer of the collector after brazing will be far less than 1%, and the thickness of the outer brazing layer will also be greatly reduced, resulting in a significant reduction in the potential difference between the outer layer and the core layer of the collector.
  • the sacrificial anode protection effect of the brazing layer on the core layer of the collector tube will be greatly weakened, and it will be difficult to meet the long-term requirement of the parallel flow condenser SWAAT corrosion test without perforation.
  • the present invention provides a header pipe material for a parallel flow condenser.
  • Another object of the present invention is to provide a method for preparing the above-mentioned header material for a parallel flow condenser.
  • Another object of the present invention is to provide the application of the above-mentioned header material for parallel flow condenser.
  • the technical solution adopted by the present invention is:
  • a collector pipe material for a parallel flow condenser which is composed of an outer layer alloy and a core layer alloy. It is characterized in that the outer layer alloy includes the following mass percentage components: silicon: 0.8 to 1.3%, iron: 0.05 ⁇ 0.25%, copper: ⁇ 0.1%, manganese: ⁇ 0.05%, magnesium: ⁇ 0.03%, zinc: 0.85 ⁇ 1.15%, titanium: ⁇ 0.05%; the total proportion of other impurities is not greater than 0.15%, the balance of aluminum;
  • the core layer alloy includes the following mass percentage components: silicon: 0.05 ⁇ 0.12%, iron: 0.05 ⁇ 0.18%, copper: 0.05 ⁇ 0.2%, manganese: 1.0 ⁇ 1.5%, magnesium: ⁇ 0.03%, zinc: ⁇ 0.1%, titanium: ⁇ 0.05%; the total proportion of other impurities is not greater than 0.15%, the balance is aluminum.
  • the present invention creatively breaks through the limitation of the traditional outer layer 4XXX+1%Zn alloy and designs the outer layer alloy of the collector tube material to 3003MOD+1%Zn.
  • the parallel flow condenser of the present invention is made of pipes by high-frequency welding of collector pipe materials, and then used in conjunction with MPE pipes with silicon layers and zinc layers (SiZnFlux extruded porous pipes for short).
  • the outer alloy of the header has a low silicon content and does not melt during high-temperature brazing, that is, there is no brazing layer on the surface, the silicon layer on the surface of the SiZnFlux extruded porous tube melts during brazing, and the header can still be combined with The gaps between the extruded porous tubes are filled and fully connected into a whole.
  • the outer alloy will not melt.
  • the actual zinc content of the outer layer of the collector is still about 1%, and the thickness of the outer layer will not become thinner.
  • the potential difference between the outer layer and the core layer of the collector Compared with before brazing, it will not drop significantly, and it can still play a good sacrificial anode protection role for the core layer of the current collector.
  • the zinc content in the outer alloy is controlled to be 0.85 to 1.15%.
  • the inventor's research found that if the zinc content drops below 0.85%, the potential difference between the outer layer and the core layer of the collector pipe material is relatively small, and the sacrificial anode cannot effectively protect the core layer; if the zinc content exceeds 1.15% , The zinc content in the outer layer of the collecting pipe material is too high, which will lead to poor corrosion resistance of the outer layer itself.
  • the silicon content in the outer alloy is controlled to be 0.8 to 1.3%.
  • the inventor's research found that the maximum solubility of silicon in aluminum alloys is 1.65%, which can play a very good role in solid solution strengthening and improving the strength of aluminum alloys; if the silicon content drops below 0.8%, the outer alloy of the header pipe material will The effect of solid solution strengthening of silicon on improving strength is not significant; if the silicon content exceeds 1.3%, the silicon content in the outer layer of the collector pipe material is too high, which may cause the silicon not to be completely dissolved in the aluminum alloy matrix, and may also cause the outer layer itself to Corrosion resistance becomes worse.
  • the iron content in the outer alloy is controlled to 0.05-0.25%.
  • the inventor's research found that if the iron content exceeds 0.25%, it is easy to form a large amount of Al-Fe-Si phase rich in iron and silicon with silicon. A local galvanic reaction is formed between the Al-Fe-Si phase and aluminum, causing the area to be blocked. It is corroded away preferentially to form pitting corrosion, thereby reducing the corrosion resistance of the alloy; since the raw material used for aluminum alloys is 99.7% ordinary aluminum ingots, there are inevitably elements such as iron and silicon. If the iron content drops below 0.05%, the production cost will increase. Too high.
  • the copper content in the outer alloy is controlled to ⁇ 0.1%.
  • the inventor's research found that copper can significantly increase the strength and electrode potential of aluminum alloys, which is exactly the opposite of zinc reducing the electrode potential of aluminum alloys. If the copper content exceeds 0.1%, copper will significantly increase the electrode potential of the outer alloy, partially offsetting the sacrificial anode protection effect of the zinc element.
  • the magnesium content in the outer layer alloy is controlled to ⁇ 0.03%.
  • the inventor's research found that if the magnesium content exceeds 0.03%, magnesium will evaporate during high-temperature brazing and chemically react with the flux (main component is KFAl 4 ) during nitrogen shielded welding, which may easily cause poor brazing.
  • the individual mass percentage of other impurity elements is ⁇ 0.05%.
  • the outer layer alloy includes the following mass percentage components: silicon: 0.84 ⁇ 1.26%, iron 0.07 ⁇ 0.23%, copper: ⁇ 0.05%, manganese: ⁇ 0.04%, magnesium: ⁇ 0.02%, zinc 0.87 ⁇ 1.14%, titanium ⁇ 0.04%; the total proportion of other impurities is not greater than 0.15%, the balance is aluminum.
  • the outer layer alloy includes the following mass percentage components: silicon: 0.93 ⁇ 1.13%, iron 0.10 ⁇ 0.19%, copper: ⁇ 0.05%, manganese: ⁇ 0.04%, magnesium: ⁇ 0.02%, zinc 0.94 ⁇ 1.08%, titanium ⁇ 0.04%; the total proportion of other impurities is not greater than 0.15%, and the balance is aluminum.
  • the iron-silicon ratio is usually designed at a ratio of about 3:1, and the silicon content and iron content are usually about 0.15 to 0.25% and 0.45 to 0.65% respectively.
  • High content control When the silicon and iron content are high, when the outer alloy layer is corroded away, the corrosion will enter the 3003 core layer, and the corrosion rate of the core layer will accelerate. In the core layer alloy of the present invention, the silicon content and iron content are reduced to 0.05-0.12% and 0.05-0.18% respectively.
  • Silicon and iron are inevitable impurity elements in 3XXX aluminum alloys. If the silicon or iron content drops below 0.05%, high-purity aluminum ingot raw materials must be used for smelting, resulting in higher production costs.
  • the magnesium content in the core layer alloy is controlled to be ⁇ 0.03%; if the magnesium content exceeds 0.03%, magnesium will evaporate during high-temperature brazing and chemically react with the flux (main component is KFAl 4 ) during nitrogen shielded welding, causing Poor brazing.
  • the core layer alloy includes the following mass percentage components: silicon: 0.06 ⁇ 0.10%, iron 0.07 ⁇ 0.16%, copper: 0.07 ⁇ 0.18%, manganese: 1.02 ⁇ 1.44%, magnesium: ⁇ 0.02%, zinc ⁇ 0.04%, titanium ⁇ 0.04%; the total proportion of other impurities is not greater than 0.15%, and the balance is aluminum.
  • the core layer alloy includes the following mass percentage components: silicon: 0.08 ⁇ 0.09%, iron: 0.09 ⁇ 0.13%, copper: 0.09 ⁇ 0.15%, manganese: 1.14 ⁇ 1.37%, magnesium: ⁇ 0.02% , zinc ⁇ 0.04%, titanium ⁇ 0.04%; the total proportion of other impurities is not greater than 0.15%, and the balance is aluminum.
  • the thickness of the header material for parallel flow condenser is 1.0-2.5 mm.
  • the thickness of the outer alloy layer is 3.5% to 13% of the thickness of the header material for the parallel flow condenser.
  • the thickness of the outer alloy layer is within this ratio range, which can not only ensure the thickness of the core layer of the collector tube material to ensure the overall strength, but also ensure that the potential difference between the outer layer and the core layer of the collector tube material after brazing will not exceed Small, the outer layer can play a good sacrificial anode protection role for the core layer.
  • the thickness of the outer alloy is higher than this ratio range, the thickness of the core layer will be insufficient, resulting in insufficient strength of the collector pipe material; when the thickness of the outer alloy is lower than this ratio range, the thickness of the outer layer will be too thin and the outer layer will not be able to align with the core.
  • the layer plays a good sacrificial anode protection role.
  • the present invention also protects the preparation method of the above-mentioned header pipe material for parallel flow condenser, which includes the following steps:
  • the thickness of the outer layer plate ingot is 400-500mm, and the thickness of the core layer plate ingot is 360-500mm.
  • the thickness of the outer plate is 22.5-55 mm.
  • the controlled milling amount of the milling surface is 8 to 10 mm/each surface.
  • the hot rolling composite is to produce a composite strip coil with a thickness of 3.5 to 6 mm.
  • the invention also protects a header, which is made from the above header material for parallel flow condenser through high-frequency welding.
  • the invention also protects the use of the aforementioned headers in parallel flow condensers equipped with SiZnFlux extruded porous tubes.
  • the present invention develops a header material for parallel flow condensers. After high-frequency brazing to form a header, it can be used in parallel flow condensers equipped with SiZnFlux extruded porous tubes. Through the specific metal component content in the outer layer alloy and core layer alloy, the corrosion resistance of the header material for parallel flow condensers is greatly improved.
  • the average corrosion pit depth of the SWAAT 700h corrosion test after brazing is ⁇ 0.12mm.
  • the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in this technical field.
  • Embodiments 1 to 5 respectively provide a collector pipe material, which is composed of an outer layer alloy and a core layer alloy.
  • the compositions of the outer layer alloy and core layer alloy are shown in Table 1.
  • the preparation method of the collector pipe material is as follows:
  • outer layer ingots with a thickness of 400 ⁇ 500mm and thickness of 360 ⁇ 360mm are respectively obtained.
  • the smelting temperature is controlled at 740 ⁇ 780°C. After the raw materials are melted, the stirring, slag removal, and component sampling tests are passed, and then the aluminum liquid is poured into the static furnace;
  • Refining Use N2 to refine in a static furnace for 10 to 12 minutes, then stir, remove slag, and let stand for 5 to 10 minutes;
  • the core layer board ingots are sawed, heated and milled to obtain core layer board ingots to be welded and assembled;
  • the milling surface control milling amount is 8 ⁇ 10mm/each surface
  • the metal temperature is controlled at 480 ⁇ 510°C and maintained for 1 ⁇ 3 hours;
  • Hot rolling multi-pass rolling, final rolling temperature ⁇ 350°C;
  • the temperature of the core plate ingot is controlled at 600 to 610°C for 10 to 15 hours;
  • the metal temperature is controlled at 480 ⁇ 510°C and maintained for 1 ⁇ 3 hours;
  • Hot rolling multi-pass rolling, the final rolling temperature is controlled at 260 ⁇ 300°C;
  • Cold rolling multi-pass rolling, rolling to the intermediate thickness, annealing and cooling, and then rolling to the required finished product thickness;
  • the thickness of the header material prepared in the embodiment is 1.5 mm, in which the outer layer alloys of embodiments 1 to 5 account for 8.1%, 6.3%, 7.5%, 8.8% and 9.6% respectively.
  • Comparative Examples 1 to 5 respectively provide a collector pipe material, which is composed of an outer layer alloy and a core layer alloy.
  • the compositions of the outer layer alloy and core layer alloy are shown in Table 2.
  • the preparation method of the collector pipe material is the same as that in the embodiment. .
  • the thickness of the header material prepared in the comparative example is 1.5mm, in which the outer layer alloys of comparative examples 1 to 5 account for 9.5%, 7.7%, 6.5%, 8.3% and 9.1% respectively.
  • Corrosion resistance For headers made by high-frequency welding, conduct high-temperature simulated brazing at 600°C ⁇ 5 minutes, and then conduct a SWAAT 700h corrosion test according to ASTM G85-2011 test standards, and then take 20 corrosion points to calculate the average corrosion pit. Depth, the smaller the depth of the corrosion pit, the better the corrosion resistance.
  • the collector pipe materials of each embodiment of the present invention have good mechanical properties before and after brazing.
  • the tensile strength before brazing is ⁇ 164MPa
  • the tensile strength after brazing is ⁇ 115MPa.
  • the header pipe materials of Examples 1 to 5 made by high-frequency welding have good corrosion resistance after brazing.
  • the average corrosion pit depth of the SWAAT 700h corrosion test is ⁇ 0.12mm.

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Abstract

一种平行流冷凝器用集流管料及其制备方法和应用；平行流冷凝器用集流管料中，外层合金包括如下组分：硅：0.8~1.3%，铁：0.05~0.25%,铜：≤0.1%，锰：≤0.05%，镁：≤0.03%，锌：0.85~1.15％，钛：≤0.05％；铝余量；芯层合金包括如下组分：硅：0.05~0.12%，铁：0.05~0.18%，铜：0.05~0.2%,锰：1.0~1.5%，镁：≤0.03%，锌：≤0.1%，钛：≤0.05％；铝余量；通过外层合金和芯层合金中的特定的金属组分含量，使得集流管料的耐腐蚀性大幅改善，可应用于配有SiZnFlux挤压多孔管的平行流冷凝器。

Description

一种平行流冷凝器用集流管料及其制备方法和应用 技术领域
本发明涉及热交换器用合金技术领域，更具体的，涉及一种平行流冷凝器用集流管料及其制备方法和应用。
背景技术
近年来，平行流热交换器由于耐压强度高、热交换面积大、散热效率高等优点，被广泛用作汽车空调和商用空调领域的冷凝器、蒸发器。平行流热交换器是采用表面喷锌挤压多孔管(简称MPE管)、复合翅片箔、高频焊接制成的集流管、堵帽、边板等一起组装、钎焊而成。在590～605℃钎焊温度下，集流管、复合翅片箔、堵帽表面的4XXX合金钎料熔化、流动，冷却后与MPE管等连接成一个整体。
集流管是空调系统中冷凝器的重要组成部件之一，空调中的冷媒气体经过压缩机压缩后产生高温高压的气体，通过冷凝器散热冷凝后变为低温高压的液体，进入集流管集流。集流管料的耐腐蚀性能直接影响冷凝器的整体使用寿命。随着热交换器向着小型化、轻量化的方向发展，集流管料的厚度也呈现减薄化趋势，对集流管料的耐压和耐腐蚀性能指标也提出了更高的要求。
通常集流管料由外层合金和芯层合金复合而成，其中外层合金的组成为4XXX系铝合金+1wt.％Zn，芯层合金为3003系铝合金。外层4XXX合金钎焊材含1wt.％左右的锌，其主要目的是利用锌元素能有效降低铝合金电极电位、优先被腐蚀，从而保护集流管料芯层不被优先腐蚀穿孔，达到延长冷凝器使用寿命的目的。但是在钎焊过程中，外层4XXX+1％Zn钎焊层熔化后，在毛细作用下，钎料中的锌随着4XXX钎料部分流到集流管与MPE管连接的焊角处，钎焊后集流管外层残留的实际Zn含量将远远低于1％，而且外层钎焊层厚度也会大幅减薄，导致集流管外层、芯层的电位差将大幅减小，钎焊层对集流管芯层的牺牲阳极保护作用将大幅减弱，很难满足平行流冷凝器SWAAT腐蚀试验长时间不穿孔的要求。
因此，需要开发出一种耐腐蚀性更优的平行流冷凝器用的集流管料。
发明内容
本发明为克服上述现有技术所述的腐蚀性能差的缺陷，提供一种平行流冷凝器用集流管料。
本发明的另一目的在于提供上述平行流冷凝器用集流管料的制备方法。
本发明的另一目的在于提供上述平行流冷凝器用集流管料的应用。
为解决上述技术问题，本发明采用的技术方案是：
一种平行流冷凝器用集流管料，由外层合金和芯层合金复合而成，其特征在于，所述外层合金包括如下质量百分比的组分：硅：0.8～1.3％，铁：0.05～0.25％，铜：≤0.1％，锰：≤0.05％，镁：≤0.03％，锌：0.85～1.15％，钛：≤0.05％；其它杂质合计比例不大于0.15％，铝余量；
所述芯层合金包括如下质量百分比的组分：硅：0.05～0.12％，铁：0.05～0.18％，铜：0.05～0.2％，锰：1.0～1.5％，镁：≤0.03％，锌：≤0.1％，钛：≤0.05％；其它杂质合计比例不大于0.15％，铝余量。
发明人研究发现，对于集流管料，外层合金和芯层合金的电位差越大，集流管料的耐腐蚀性能越优。为了进一步提高集流管料外层和芯层的电位差，本发明创造性地突破传统外层4XXX+1％Zn合金的限制，将集流管料的外层合金设计为3003MOD+1％Zn。在实际的平行流冷凝器应用中，本发明的平行流冷凝器用集流管料高频焊接制管后，与带硅层和锌层的MPE管(简称SiZnFlux挤压多孔管)配合使用。虽然集流管的外层合金硅含量较低、高温钎焊时不熔化，即表面不带钎焊层，但是钎焊时SiZnFlux挤压多孔管表面的硅层熔化，一样可以将集流管与挤压多孔管之间的间隙填充饱满连接成一个整体。在钎焊过程中，外层合金不会熔化，钎焊后集流管外层的实际锌含量还是1％左右，而且外层厚度不会减薄，和集流管芯层之间的电位差跟钎焊前相比不会明显下降，仍然可以对集流管芯层起着良好的牺牲阳极保护作用。
外层合金中控制锌含量为0.85～1.15％。发明人研究发现，若锌含量降到0.85％以下，集流管料外层和芯层之间的电位差比较小，起不到很好的牺牲阳极保护芯层作用；若锌含量超出1.15％，集流管料外层含锌量过高，将导致外层自身耐腐蚀性变差。
外层合金中控制硅含量为0.8～1.3％。发明人研究发现，硅在铝合金中的最大溶解度为1.65％，可以起到很好的固溶强化提高铝合金强度的作用；若硅含量降 到0.8％以下，集流管料外层合金中硅的固溶强化提高强度的效果不显著；若硅含量超出1.3％，集流管料外层硅含量过高，可能导致硅不能完全固溶在铝合金基体中，而且还会导致外层自身耐腐蚀性变差。
外层合金中控制铁含量为0.05-0.25％。发明人研究发现，若铁含量超出0.25％，容易与硅形成大量富含铁、硅的Al-Fe-Si相，Al-Fe-Si相与铝之间形成局部原电池反应，导致该区域被优先腐蚀掉，形成点腐蚀，从而降低了合金的耐腐蚀性能；由于铝合金使用的原材料99.7％普铝锭中不可避免存在铁、硅等元素，若铁含量降到0.05％以下，则生产成本过高。
外层合金中控制铜含量≤0.1％。发明人研究发现，铜可以显著提高铝合金的强度和电极电位，与锌降低铝合金的电极电位正好相反。若铜含量超出0.1％，铜将显著提升外层合金的电极电位，部分抵销了锌元素的牺牲阳极保护作用。
外层合金中控制镁含量≤0.03％。发明人研究发现，若镁含量超出0.03％，由于镁在高温钎焊时会蒸发出来，在氮气保护焊时与钎剂(主要成分为KFAl 4)发生化学反应，容易造成钎焊不良。
通过外层合金中的各组分配比协同作用，为平行流冷凝器整体的耐腐蚀性能提高起到了基础性的支撑作用。
优选地，所述外层合金中，其他杂质元素单个质量百分比≤0.05％。
优选地，所述外层合金包括如下质量百分比的组分：硅：0.84～1.26％，铁0.07～0.23％，铜：≤0.05％，锰：≤0.04％，镁：≤0.02％，锌0.87～1.14％，钛≤0.04％；其它杂质合计比例不大于0.15％，铝余量。
更优选地，所述外层合金包括如下质量百分比的组分：硅：0.93～1.13％，铁0.10～0.19％，铜：≤0.05％，锰：≤0.04％，镁：≤0.02％，锌0.94～1.08％，钛≤0.04％；其它杂质合计比例不大于0.15％，铝余量。
传统的3003合金为了获得细小的再结晶晶粒和良好的成形性能，铁硅比通常按3﹕1左右的比例设计，硅含量、铁含量通常分别按0.15～0.25％、0.45～0.65％左右的高含量控制。当硅、铁含量较高时，当外层合金被腐蚀掉后，腐蚀进入3003芯层，芯层腐蚀速度会加快。本发明的芯层合金中，硅含量、铁含量分别降低至0.05～0.12％、0.05～0.18％。通过采用低硅、低铁设计，当腐蚀进入芯层合金后，芯层腐蚀速度将大大减缓，从而进一步延长了集流管料的使用寿命。硅、铁是3XXX铝合金中不可避免的杂质元素，若硅或铁含量降到0.05％以下，则熔 炼必须使用高纯度的铝锭原材料，生产成本较高。
芯层合金中控制镁含量为≤0.03％；若镁含量超出0.03％，由于镁在高温钎焊时会蒸发出来，在氮气保护焊时与钎剂(主要成分为KFAl 4)发生化学反应，造成钎焊不良。
优选地，所述芯层合金包括如下质量百分比的组分：硅：0.06～0.10％，铁0.07～0.16％，铜：0.07～0.18％，锰：1.02～1.44％，镁：≤0.02％，锌≤0.04％，钛≤0.04％；其它杂质合计比例不大于0.15％，铝余量。
更优选地，所述芯层合金包括如下质量百分比的组分：硅：0.08～0.09％，铁：0.09～0.13％，铜：0.09～0.15％，锰：1.14～1.37％，镁：≤0.02％，锌≤0.04％，钛≤0.04％；其它杂质合计比例不大于0.15％，铝余量。
优选地，所述平行流冷凝器用集流管料的厚度为1.0～2.5mm。
优选地，所述外层合金的厚度为平行流冷凝器用集流管料的厚度的3.5～13％。
外层合金的厚度在此比例范围内，既可以保证集流管料的芯层厚度从而保证整体强度，也可以保证钎焊后集流管料外层与芯层之间的电位差不会过小，外层可以对芯层起到良好的牺牲阳极保护作用。外层合金的厚度高于此比例范围时，将会造成芯层厚度不足导致集流管料强度不足；外层合金的厚度低于此比例范围时，外层厚度太薄，外层不能对芯层起到良好的牺牲阳极保护作用。
本发明还保护上述平行流冷凝器用集流管料的制备方法，包括如下步骤：
S1.按照外层合金和芯层合金的组分含量，分别进行调配，经熔炼、精炼、除气、扒渣、铸造，分别制得外层板锭和芯层板锭；
S2.对外层板锭进行锯头、铣面、加热、热轧、剪切，制得外层板块；
对芯层板锭进行锯头、铣面，制得待焊合组装的芯层板锭；
S3.将清洗后的外层板块和待焊合组装的芯层板锭叠放，采用钢带捆绑，经加热、热轧复合、冷轧、中间退火、再次冷轧、清洗、分切，得到所述平行流冷凝器用集流管料。
优选地，所述外层板锭的厚度为400～500mm，所述芯层板锭的厚度为360～500mm。
优选地，所述外层板块的厚度为22.5～55mm。
优选地，所述铣面控制铣削量为8～10mm/每面。
优选地，所述热轧复合为制得3.5～6mm厚度的复合带卷。
本发明还保护一种集流管，由上述平行流冷凝器用集流管料经高频焊接制得。
本发明还保护上述集流管在平行流冷凝器中的应用，所述平行流冷凝器配有SiZnFlux挤压多孔管。
与现有技术相比，本发明的有益效果是：
本发明开发了一种平行流冷凝器用集流管料，经高频钎焊制成集流管后可用于配有SiZnFlux挤压多孔管的平行流冷凝器。通过外层合金和芯层合金中特定的金属组分含量，使得平行流冷凝器用集流管料的耐腐蚀性大幅改善，钎焊后SWAAT 700h腐蚀试验平均腐蚀坑深度≤0.12mm。
具体实施方式
下面结合具体实施方式对本发明作进一步的说明。
除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
实施例1～5
实施例1～5分别提供一种集流管料，由外层合金和芯层合金复合而成，外层合金和芯层合金的组成见表1，集流管料的制备方法如下：
S1.按照外层合金和芯层合金的组分含量，分别进行调配，经熔炼、精炼、除气、扒渣、铸造，分别制得厚度为400～500mm的外层板锭和厚度为360～500mm的芯层板锭；
熔炼：熔炼温度控制在740～780℃，待原材料熔化后，搅拌、扒渣、成分取样检测合格后，将铝液倒入静置炉；
精炼：在静置炉采用N 2精炼10～12分钟，然后搅拌、扒渣、静置5～10分钟；
铸造：成分取样检测合格后，静置炉中的铝液经在线除气、过滤，并采用Al-Ti-B丝在线晶粒细化，铸造成板锭。
S2.对外层板锭进行锯头、铣面、加热、热轧、剪切，制得厚度为22.5～55mm的外层板块；
对芯层板锭进行锯头、均热、铣面，制得待焊合组装的芯层板锭；
铣面控制铣削量为8～10mm/每面；
加热：金属温度控制在480～510℃，保持1～3小时；
热轧：多道次轧制，终轧温度≥350℃；
剪切：冷却至300℃开始切板；
均热：芯材板锭均热金属温度控制在600～610℃，保持10～15小时；
S3.将清洗后的外层板块和待焊合组装的芯层板锭叠放好(通常外层板块放上面、芯层板锭放下面)，采用钢带捆绑，经加热、热轧复合，制得3.5～6mm厚度的复合带卷，再进行冷轧，中间退火，再次冷轧、清洗、分切，得到集流管料；
加热：金属温度控制在480～510℃，保持1～3小时；
热轧：多道次轧制，终轧温度控制在260～300℃；
冷轧：多道次轧制，轧至中退厚度，退火冷却后，再轧至要求的成品厚度；
中间退火：金属温度控制在350～450℃，保持2～3小时。
实施例制得的集流管料的厚度为1.5mm，其中实施例1～5的外层合金分别占8.1％、6.3％、7.5％、8.8％、9.6％。
表1 实施例1～5的外层合金和芯层合金的组分组成(wt.％)
Figure PCTCN2022139624-appb-000001
Figure PCTCN2022139624-appb-000002
对比例1～5
对比例1～5分别提供一种集流管料，由外层合金和芯层合金复合而成，外层合金和芯层合金的组成见表2，集流管料的制备方法与实施例相同。
对比例制得的集流管料的厚度为1.5mm，其中对比例1～5的外层合金分别占9.5％、7.7％、6.5％、8.3％、9.1％。
表2 对比例1～5的外层合金和芯层合金的组分组成(wt.％)
Figure PCTCN2022139624-appb-000003
Figure PCTCN2022139624-appb-000004
性能测试
对上述实施例及对比例所制得的集流管进行性能测试，具体方法如下：
力学性能：对钎焊前、后的集流管料分别进行抗拉强度的测试，钎焊条件为按600℃×5min进行高温模拟钎焊，抗拉强度按照GB/T 228.1-2010《金属材料拉伸试验第1部分：室温试验方法》进行制样、室温下进行测试。
耐腐蚀性能：对高频焊接制成的集流管，按600℃×5min进行高温模拟钎焊， 然后按ASTM G85-2011试验标准进行SWAAT 700h腐蚀试验，然后取20个腐蚀点计算平均腐蚀坑深度，腐蚀坑深度越小，说明耐腐蚀性能越优。
实施例和对比例的测试结果见表3。
表3 实施例和对比例的测试结果
Figure PCTCN2022139624-appb-000005
根据表3的测试结果，可以看出，本发明各实施例的集流管料在钎焊前后均具有良好的力学性能，钎焊前抗拉强度≥164MPa，钎焊后抗拉强度≥115MPa，满足平行流冷凝器使用的强度要求。
根据耐腐蚀性能测试结果，实施例1～5的集流管料经高频焊接制成的集流管钎焊后具有良好的耐腐蚀性能，SWAAT 700h腐蚀试验平均腐蚀坑深度≤0.12mm。
显然，本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明权利要求的保护范围之内。

Claims (10)

  1. 一种平行流冷凝器用集流管料，由外层合金和芯层合金复合而成，其特征在于，所述外层合金包括如下质量百分比的组分：硅：0.8～1.3％，铁：0.05～0.25％，铜：≤0.1％，锰：≤0.05％，镁：≤0.03％，锌：0.85～1.15％，钛：≤0.05％；其它杂质合计比例不大于0.15％，铝余量；
    所述芯层合金包括如下质量百分比的组分：硅：0.05～0.12％，铁：0.05～0.18％，铜：0.05～0.2％，锰：1.0～1.5％，镁：≤0.03％，锌：≤0.1％，钛：≤0.05％；其它杂质合计比例不大于0.15％，铝余量。
  2. 根据权利要求1所述平行流冷凝器用集流管料，其特征在于，所述平行流冷凝器用集流管料的厚度为1.0～2.5mm。
  3. 根据权利要求1所述平行流冷凝器用集流管料，其特征在于，所述外层合金的厚度为平行流冷凝器用集流管料厚度的3.5～13％。
  4. 根据权利要求1所述平行流冷凝器用集流管料，其特征在于，所述外层合金包括如下质量百分比的组分：硅：0.84～1.26％，铁0.07～0.23％，铜：≤0.05％，锰：≤0.04％，镁：≤0.02％，锌0.87～1.14％，钛≤0.04％；其它杂质合计比例不大于0.15％，铝余量。
  5. 根据权利要求1所述平行流冷凝器用集流管料，其特征在于，所述芯层合金包括如下质量百分比的组分：硅：0.06～0.10％，铁0.07～0.16％，铜：0.07～0.18％，锰：1.02～1.44％，镁：≤0.02％，锌≤0.04％，钛≤0.04％；其它杂质合计比例不大于0.15％，铝余量。
  6. 权利要求1～5任一项所述平行流冷凝器用集流管料的制备方法，其特征在于，包括如下步骤：
    S1.按照外层合金和芯层合金的组分含量，分别进行调配，经熔炼、精炼、除气、扒渣、铸造，分别制得外层板锭和芯层板锭；
    S2.对外层板锭进行锯头、铣面、加热、热轧、剪切，制得外层板块；
    对芯层板锭进行锯头、均热、铣面，得到待焊合组装的芯层板锭；
    S3.将清洗后的外层板块和待焊合组装的芯层板锭叠放，采用钢带捆绑，经加热、热轧复合、冷轧、中间退火、再次冷轧、清洗、分切，得到所述平行流冷凝器用集流管料。
  7. 根据权利要求6所述制备方法，其特征在于，所述外层板锭的厚度为400～500mm，所述芯层板锭的厚度为360～500mm。
  8. 根据权利要求6所述制备方法，其特征在于，所述铣面控制铣削量为8-10mm/每面；所述热轧复合为制得3.5～6mm厚度的复合带卷。
  9. 一种集流管，其特征在于，由权利要求1～5任一项所述平行流冷凝器用集流管料经高频焊接制得。
  10. 权利要求9所述集流管在平行流冷凝器中的应用，所述平行流冷凝器配有SiZnFlux挤压多孔管。
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