EP1721998A1 - Werkstoff für stranggepresstes Rohr aus Aluminium-Legierung für Wärmetauscher mit natürlichem Kühlmittel - Google Patents

Werkstoff für stranggepresstes Rohr aus Aluminium-Legierung für Wärmetauscher mit natürlichem Kühlmittel Download PDF

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Publication number
EP1721998A1
EP1721998A1 EP06009528A EP06009528A EP1721998A1 EP 1721998 A1 EP1721998 A1 EP 1721998A1 EP 06009528 A EP06009528 A EP 06009528A EP 06009528 A EP06009528 A EP 06009528A EP 1721998 A1 EP1721998 A1 EP 1721998A1
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Prior art keywords
mass
tube material
aluminum alloy
extruded tube
refrigerant
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EP06009528A
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English (en)
French (fr)
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EP1721998B1 (de
Inventor
Junji c/o Furukawa-Sky Aluminium Corp. Ninomiya
Satoshi c/o Furukawa-Sky Aluminium Corp. Tanaka
Kazuhisa c/o Furukawa-Sky Aluminium Kashiwazaki
Kazumi c/o Furukawa-Sky Aluminium Katou
Yoshiyuki c/o Furukawa-Sky Aluminium Oya
Tomohiko c/o Denso Corp. Nakamura
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Denso Corp
Furukawa Sky Aluminum Corp
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Denso Corp
Furukawa Sky Aluminum Corp
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Publication of EP1721998A1 publication Critical patent/EP1721998A1/de
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Ceased legal-status Critical Current
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium

Definitions

  • the present invention relates to an aluminum alloy extruded tube material, which can be used as a structural member to be applied to a heat exchanger in which a refrigerating cycle using a natural refrigerant as typified by carbon dioxide (CO 2 ) as a refrigerant is incorporated, such as a gas conditioner (condenser) for cooling a high temperatures and pressures gas refrigerant which has been heated and compressed in a car air-conditioner.
  • CO 2 carbon dioxide
  • the present invention relates to an aluminum alloy extruded tube material having a plurality of refrigerant-flowing holes.
  • refrigerators each using a natural refrigerant as typified by carbon dioxide as a refrigerant have been under development.
  • Air conditioners employing such refrigerators using carbon dioxide as their refrigerants will have to respond to new requests different from those in using a flon as a conventionally usual refrigerant.
  • an air conditioner using carbon dioxide as a refrigerant has higher working pressures as well as higher refrigerant temperatures when compressed, as compared with those when a flon is employed.
  • the refrigerant may be heated up to a temperature as high as 130 to 200°C at the inlet of the conditioner. Therefore, when carbon dioxide is used as a refrigerant, the conditioner requires better durability at high temperatures and pressures than that in the case where a flon is used as a refrigerant.
  • the conventional, usual heat exchangers employ tube materials having refrigerant-flowing holes for allowing refrigerants to flow through it, particularly aluminum alloy extruded tube materials.
  • tube materials having refrigerant-flowing holes for allowing refrigerants to flow through it, particularly aluminum alloy extruded tube materials.
  • pure aluminum-based alloys as typified by an inexpensive JIS 1050 alloy excellent in extrudability are used.
  • Such a pure aluminum-based alloy has a significantly lowering in mechanical strength under high temperature conditions of 150°C or higher.
  • a tube may be provided with enhanced pressure resistance (pressure-resisting strength) at high temperature by making the wall of the tube much thicker than the case of using a flon.
  • the thick aluminum alloys as described above have not coped with the demands on reductions in weight and thickness of a car air conditioner in recent years.
  • attempts have been conducted to obtain an extruded tube material high in pressure resistance at high temperature while having a thinner wall, by adding an element contributing to improvement in material strength, that is a reinforcing element, to an aluminum alloy to be used in an extruded tube material, thereby to enhance mechanical strength of the aluminum alloy itself for the tube material particularly, the high-temperature strength.
  • the reinforcing element for the aluminum alloy include Cu, Mn, Si, Fe, Ti, and V.
  • an element for easily reinforcing the material may be Cu that contributes to improvement in strength by forming a solid solution. Hitherto, therefore, attempts have been conducted to use an aluminum alloy for an extruded tube material with the addition of a larger amount of Cu than the conventional one.
  • the content of Cu as an alloy element in an aluminum alloy for the tube material may be increased, thereby to easily improve the mechanical strength of such a tube material. In other words, pressure resistance at high temperature required for the tube material can be easily enhanced.
  • the content of Cu is simply raised. That is, when an aluminum alloy having a large amount of Cu is subjected to a high refrigerant temperature of 130 to 200°C as described above, the amount of solid-solution Cu around a grain boundary decreases as a Cu-Al-series intermetallic compound precipitates in the grain boundary, thereby causing a Cu-shortage layer.
  • an electric potential difference may be caused between a portion having a high Cu content (Cu-rich portion) in the grain boundary and a Cu-shortage layer of the grain boundary, so occurrence of corrosion at the grain boundary is apt to occur.
  • the aluminum alloy added with a large amount of Cu has difficulty in retaining its corrosion resistance satisfactorily, as well as difficulty in obtaining good extrudability.
  • the present invention resides in an aluminum alloy extruded tube material for a heat exchanger using a natural refrigerant, which is composed of an aluminum alloy comprising 0.1 to 0.5% by mass of Si, 0.3 to 0.8% by mass of Fe, 0.5 to 1.5% by mass of Mn, 0.05 to 0.25% by mass of Cu, 0.05 to 0.25% by mass of Ti, and 0.05 to 0.30% by mass of V, the balance being aluminum and an unavoidable impurity(s).
  • the inventors of the present invention have conducted experiments and studies in detail with respect to the correlation of corrosion resistance, mechanical strength, and strength after thermal history, with the composition of the alloy elements of the aluminum alloy extruded tube material. Consequently, the inventors of the present invention found that high pressure resistance at high temperature as well as high strength after thermal history can be obtained while sufficient corrosion resistance is retained, when the amounts of Si, Fe, Mn, Cu, Ti, and V as alloy elements to be added are appropriately adjusted, particularly the appropriate amounts of Cu, Ti, and V are simultaneously added. The present invention has been attained based on the above finding.
  • the content of manganese (Mn) is 0.5 to 1.5% by mass.
  • Mn may be crystallized or precipitated as an Al-Mn-series intermetallic compound and contribute to enhancement in mechanical strength after brazing. Further, Mn is an element which is coexistent with Si to generate an Al-Mn-Si-series intermetallic compound, to thereby enhance the mechanical strength. Further, the addition of Mn makes an electric potential of the aluminum alloy noble, and the electric potential difference with a fin can be increased by previously adding Mn in a tube material when the fin is provided on the outer surface of the tube material, thereby enhancing external-corrosion resistance. For surely attaining those effects, Mn should be added in an amount of 0.5% by mass or more, preferably 0.7% by mass or more. Further, if a large amount of Mn is added, extrudability may be lowered.
  • the addition of Si prevents lowering of extrudability, so that Mn in an amount of 0.5% by mass or more, or 0.7% by mass or more, may cause no particular trouble.
  • the content of Mn exceeds 1.5% by mass, lowering of extrudability may be inevitable even though the material contains Si.
  • the upper limit of the Mn content is defined as 1.5% by mass.
  • the content of silicon (Si) is 0.1 to 0.5% by mass.
  • a crystallized or precipitated product of an Al-Mn-series intermetallic compound (an Al compound containing only Mn, e.g. Al 6 Mn), which can be generated by the addition of Mn, may contribute to improvement in mechanical strength after brazing.
  • the crystallized or precipitated product of the Al-Mn-series intermetallic compound can conspicuously lower extrudability by raising an extrusion contact pressure.
  • the addition of Si allows the generation of an Al-Mn-Si-series intermetallic compound, as a consequence the generation of an Al-Mn-series intermetallic compound too much as compared to a necessary amount can be prevented, and the extrusion contact pressure can be lowered.
  • the addition of Si in conjunction with the addition of Mn can prevent lowering of extrudability.
  • Si can be provided in a solid-solution state in a matrix or generate an Al-Mn-Si-series intermetallic compound, thereby exhibiting an enhancing effect on the mechanical strength after brazing.
  • the tube material should contain Si in an amount of 0.1 % by mass or more.
  • the content of Si is preferably 0.2% by mass or more, more preferably 0.3% by mass or more.
  • Si when Si is contained excessively, Si, which is solely crystallized, may conspicuously shorten the operable life of an extrusion die and may lower the melting point of the alloy, thereby melting the material at the time of brazing. Besides, the formation of a crystallized product may lower the extrudability.
  • the strength at room temperature when the alloy is subjected to a high refrigerant temperature of about 130 to 200°C, the strength at room temperature may significantly reduce in comparison with one before the alloy is subjected to that high temperature. In addition, the high-temperature strength in a high-temperature region of higher than 130°C can be significantly reduced.
  • the upper limit of Si content should be 0.5% by mass.
  • the content of iron (Fe) is 0.3 to 0.8% by mass.
  • Fe can be crystallized or precipitated as an intermetallic compound, to improve the mechanical strength after brazing.
  • Fe can improve the extrudability by forming an Al-Mn-Fe-series or Al-Mn-Fe-Si-series intermetallic compound.
  • the content of Fe should be 0.1 % by mass or more, preferably 0.3% by mass or more.
  • a Fe-containing intermetallic compound may be crystallized from the surface of the tube material and accelerate the rate of corrosion, thereby lowering the extrudability.
  • the content of Fe should be 0.8% by mass or less.
  • the tube material contains 0.05 to 0.25% by mass of cupper (Cu), 0.05 to 0.25% by mass of titanium (Ti), and 0.05 to 0.30% by mass of vanadium (V), respectively.
  • the addition of Cu alone may enhance the strength after brazing by allowing Cu to be in a solid-solution state in a matrix; and further, it may make an electric potential of the tube material noble, to enlarge the electric potential difference between the tube material and a fin when the fin material is provided on the outer surface of the tube material, to remarkably enhance the external corrosion resistance.
  • the amount of Cu to be added should be 0.05% by mass or more.
  • the amount of Cu to be added is preferably 0.1 % by mass or more.
  • the addition of Ti alone may contribute to enhance corrosion resistance, particularly pitting corrosion resistance. That is, Ti added to an aluminum alloy can be distributed into high-concentration regions and low-concentration regions on its concentration, which are distributed in a layered structure in which the regions are laminated in alternation in the direction along the sheet thickness. Then, a low-Ti concentration region can be preferentially corroded, compared with a high-Ti concentration region, thereby allowing the formation of corrosion into a layered structure to prevent the progress of corrosion in the direction along the sheet thickness. As a result, pitting corrosion resistance is improved. For sufficiently attaining such improving effect on pitting corrosion resistance, the content of Ti should be 0.05% by mass or more.
  • the addition of Cu in an amount of 0.05% by mass or more may lead to a conspicuous lowering of corrosion resistance, because of an increase in sensitivity to grain boundary corrosion when the alloy is subjected to a high temperature of 130 to 200°C after heating for brazing.
  • Ti and V are added together with the addition of Cu in an amount of 0.05% by mass or more, and it is possible not only to improve pitting corrosion resistance but also to suppress the sensitivity to grain boundary corrosion due to the addition of Cu. The reason that an inhibitory effect on the sensitivity to grain boundary corrosion can be obtained by simultaneously adding Ti and V when Cu is added, will be considered as follows.
  • the alloy when Ti is added, the alloy is in a state of a layered structure in which high-Ti concentration layers (Ti-rich layers) and low-Ti concentration layers are laminated one after another.
  • the simultaneous addition of V allows V to be incorporated into the Ti-rich layer, thereby causing a TiN rich layer.
  • the Ti/N rich layer comes across the grain boundary, and the grain boundary within the range being traversed by the Ti/N rich layer can be of a noble electric potential due to the Ti/V rich layers.
  • the grain boundary when Cu is added alone, the grain boundary can be of a Cu shortage phase to cause an ignoble potential, thereby causing increase in the sensitivity to grain boundary corrosion.
  • the Ti/V rich layer alters the grain boundary so that the boundary has a noble electric potential. Thus, the grain boundary corrosion becomes difficult to progress, and the sensitivity to grain boundary corrosion may be thus prevented.
  • Ti should be added in an amount of 0.05% by mass or more, particularly preferably 0.1 % by mass or more.
  • V should be added in an amount of 0.05% by mass or more.
  • the amount of Ti to be added exceeds 0.25% by mass, the extrudability of the material is prohibited by the formation of a giant compound upon casting, thereby resulting in difficulty in obtaining a healthy material for extrusion.
  • the amount of V to be added exceeds 0.30% by mass, the extrudability of the material is prohibited by the formation of a giant compound upon casting, thereby resulting in difficulty in obtaining a healthy material for extrusion and also prohibiting the corrosion resistance of the resultant extruded tube material.
  • the content of Cu exceeds 0.25% by mass, the preventing effects on the sensitivity to grain boundary corrosion by Ti and V cannot be obtained.
  • the room temperature strength after the material is subjected to refrigerant temperatures (130 to 200°C) for a long period of time is conspicuously reduced, as compared with the room temperature strength before the material is subjected to the refrigerant temperatures.
  • the tube material contains 0.05 to 0.25% by mass of Ti, 0.05 to 0.30% by mass of V, and 0.05 to 0.25% by mass of Cu.
  • balance other than the respective elements described above may be Al and an unavoidable impurity(s).
  • an aluminum alloy molten liquid is provided in a usual manner to attain the element composition described above, and then the resultant molten liquid is subjected to casting in a usual manner, and the method is not particularly limited.
  • the ingot is preferably subjected to a homogenization treatment in advance. Afterwards, at least before extruding, a soaking treatment may be carried out, and followed by extruding. Further, heating methods or heating conditions, structures of heating furnaces, and the like for the above homogenization treatment and soaking treatment are not particularly limited.
  • the form after extruded is not particularly limited, and any of appropriate extruded forms can be selected depending on, for example, the shape of a heat exchanger to which the resultant tube is applied.
  • a multiple hollow die in the form of a hollow may be used for the extrusion in a favorable manner.
  • an extrusion method (system) for extruding is not particularly limited, and any of usual methods can be suitably applied in combination with the shape after extruded and the like.
  • the extruded material that can be obtained, for example, in the manner as described above, can be used as a material for a heat exchanger, and it can be generally used as a material for a tube for flowing a refrigerant (heat medium) through it.
  • Such an extruded tube material may be generally assembled with other members (e.g., a fin material and a header) and then brazed by brazing when used as a part of a heat exchanger.
  • the conditions of atmosphere, heat temperature, time period, and the like upon brazing are not particularly limited, and also the brazing method is not particularly limited.
  • the heat exchanger thus obtained can be efficiently manufactured because its tube material has good extrudability, and the exchanger has high pressure resisting property and good corrosion resistance. Therefore, the heat exchanger can exhibit good durability even in a car or the like, for example, when used under a severe corrosive environment.
  • the extruded tube material of the present invention may be directly used in a heat exchanger as it is.
  • a sacrificial material made of a material having an ignoble electric potential compared with that of the tube material may be provided on the outer surface of the extruded tube material, to further improve corrosion resistance, thereby forming a tube having a sacrificial material, which can also be used in heat exchangers.
  • the sacrificial materials that can be used include metal Zn, and an Al-Zn alloy.
  • a concrete method of forming the sacrificial material on the surface of an extruded tube material, and the thickness or the like of the sacrificial material are not particularly limited, and they may be determined similarly to those of the usual aluminum alloy tube material having a sacrificial material for heat exchangers.
  • the extruded tube material of the present invention for a heat exchanger is not limited to one having a single hole as a refrigerant-flowing hole, but it may be in the form to give a multi-hole tube having a plurality of refrigerant-flowing holes.
  • the tube material of the present invention is excellent in extrudability, and a multi-hole extruded tube material can be prepared in an easy manner.
  • the aluminum alloy extruded tube material of the present invention for a heat exchanger using a natural refrigerant can exhibit remarkably excellent corrosion resistance even in a corrosive environment, as well as high pressure resistance at high temperature, while showing high room-temperature strength after thermal history applied. Therefore, the tube material of the present invention can provide a tube for flowing a refrigerant in a heat exchanger, which uses a natural refrigerant as typified by carbon dioxide, and which has a thinner wall and sufficient durability. Therefore, the tube material of the present invention is preferable as a tube material for a heat exchanger subjected to severe corrosive environments such as a car air-conditioner.
  • Each of Al alloys having the respective element composition as shown by Nos. 1 to 19 in Table 1 below was molten and then subjected to casting in a usual manner, to cast into a billet of diameter 200 mm.
  • the resultant billet was subjected to a homogenization treatment under the conditions of retaining at 610°C for 4 hours, followed by cutting into a length of 1,000 mm, to give a billet for extrusion.
  • the thus-obtained billet was again heated to 500°C and then extruded through a mandrel die, thereby preparing a multi-hole tube material having 20 holes.
  • the surface of the thus-obtained multi-hole tube was subjected to a sandblasting method, to make it rough with approximately 10 ⁇ m in a center line average roughness (height) (Ra). Then, metal Zn as a sacrificial material was sprayed onto the resultant surface.
  • the method of spraying was an electric arc spraying method, under the spraying conditions of thermal source temperature 4,000°C and particle velocity 75 m/s. The amount of metal Zn covered was adjusted to about 9 g/m 2 . In this way, the extruded multi-hole tube covered with the metal Zn was obtained, followed by cutting into a piece of length 100 mm.
  • a clad fin (thickness 0.1 mm) that was prepared by cladding a JIS 4343 alloy in a cladding amount of 10% by mass on a JIS 3003 alloy added with 2% by mass of Zn, was corrugated, and followed by assembling with the multi-hole tube, to give an assemble having a shape as shown in Fig. 1.
  • reference numerals 1 and 2 each represent a multi-hole tube, and 3 represents a fin corrugated.
  • the thus-assembled test piece was subjected to brazing by heating at 600°C for 3 minutes, under a nitrogen atmosphere. After that, an additional thermal history of 180°C x 48 hours was applied thereto, to prepare a test piece for corrosion.
  • the CASS test was carried out for 1,500 hours according to JIS H8601. After the CASS test, a fin was cut off from the test piece, and then the corrosion product on the tube was removed, followed by measuring the depth of pitting corrosion of the tube material with an optical microscope. Further, for the pitting corrosion cite, the cross section of the tube was observed with an optical microscope. Table 1 shows grain boundary corrosion, if observed, and the results of the CASS test. Further, the tube material obtained as described above was examined for mechanical strength, and evaluated for extrudability. The results are shown in Table 1.
  • the resultant billet was subjected to a homogenization treatment under the conditions of retaining at 610°C for 4 hours, followed by cutting into a length of 1,000 mm, to give a billet for extrusion.
  • the thus-obtained billet was again heated to 500°C and then extruded through a mandrel die, thereby preparing a multi-hole tube material having 20 holes.
  • the thus-obtained tube materials were subjected to brazing by heating at 600°C for 3 min under a nitrogen atmosphere, followed by applying thermal history 180°C, for any time period of 24 hours, 150 hours, 500 hours, 700 hours, 1,000 hours, or 2,000 hours, thereby to prepare test pieces for evaluation of mechanical strength properties. After each thermal history, the room-temperature strength was measured in a state after each material was left standing to cool to the room temperature. The results are shown in Table 3. Table 2 Classification No.
  • the multi-hole tube materials of Nos. 21 to 31 of Examples according to the present invention did not show any decrease in the room-temperature strength even after a thermal history for 24 to 2,000 hours at 180°C.
  • the contents of Si and Cu were too high over the ranges defined in the present invention, a conspicuous decrease in the room-temperature strength was observed when the heating time was long.
  • the contents of Cu and Mn were too high over the ranges defined in the present invention, a conspicuous decrease in the room-temperature strength was observed when the heating time was long, similarly.
  • Conventional Example No. 36 the mechanical strength was conspicuously insufficient, regardless of before or after applying the thermal history.
  • the resultant billet was subjected to a homogenization treatment under the conditions of at 610°C for 4 hours, followed by cutting into a length of 1,000 mm, to give a billet for extrusion.
  • the thus-obtained billet was again heated to 500°C and then extruded through a mandrel die, thereby preparing a multi-hole tube material having 20 holes.
  • the thus-obtained tube materials were subjected to brazing by heating at 600°C for 3 min under a nitrogen atmosphere, to prepare test pieces for evaluation of high-temperature strength. Then, each of the test pieces was heated to any temperature at 80°C, 100°C, 130°C, 150°C, or 180°C, followed by retaining for 15 minutes, and the mechanical strength was measured for each sample at said temperature. The results are shown in Table 5. Table 4 Classification No.
  • each of the multi-hole tube materials of Nos. 41 to 51 of Examples according to the present invention showed a slight decrease in the high-temperature strength at each retention temperature of 130, 150, and 180°C.
  • Comparative Example Nos. 52 and 53 since the contents of Si and Cu were too high over the ranges defined in the present invention, a conspicuous reduction in the high-temperature strength at each of the above temperatures was observed.
  • Comparative Example Nos. 54 and 55 since the contents of Cu and Mn were too high over the ranges defined in the present invention, a conspicuous reduction in the high-temperature strength at each of the above temperatures was observed, similarly.
  • Conventional Example No. 56 in addition to the insufficient room-temperature strength from the beginning, the reduction in the high-temperature strength at each temperature was conspicuous.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Extrusion Of Metal (AREA)
EP20060009528 2005-05-10 2006-05-09 Stranggepresstes Rohrteil aus Aluminium-Legierung für Wärmetauscher mit natürlichem Kühlmittel Ceased EP1721998B1 (de)

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JP2005137845A JP4634854B2 (ja) 2005-05-10 2005-05-10 自然冷媒用熱交換器のアルミニウム合金押出しチューブ材

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EP1721998A1 true EP1721998A1 (de) 2006-11-15
EP1721998B1 EP1721998B1 (de) 2010-10-27

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1892308A1 (de) * 2006-08-24 2008-02-27 Furukawa-Sky Aluminum Corp. Aluminium-Werkstoff für Rohre von Kraftfahrzeug-Wärmetauschern
EP2832873A4 (de) * 2012-03-27 2015-06-24 Mitsubishi Aluminium Wärmeübertragungsrohr und verfahren zur herstellung davon
WO2021196482A1 (zh) * 2020-03-31 2021-10-07 江苏亨通电力特种导线有限公司 空调连接管用高性能铝材及其制备方法

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JP4955418B2 (ja) * 2007-02-26 2012-06-20 古河スカイ株式会社 自然冷媒用熱交換器に用いられるアルミニウム合金押出材
JP5030276B2 (ja) * 2007-04-09 2012-09-19 古河スカイ株式会社 熱交換器用アルミニウム合金配管材及びその製造方法
JP5653233B2 (ja) * 2011-01-20 2015-01-14 日本軽金属株式会社 押出性と耐粒界腐食性に優れた微細孔中空形材用アルミニウム合金とその製造方法
JP5882615B2 (ja) * 2011-06-30 2016-03-09 株式会社Uacj エアコン用アルミニウム合金製内面溝付き管及びその溝付き管を備えるエアコン並びにアルミニウム合金内面溝付き管の製造方法及びエアコン用アルミニウム内面溝付き管の製造方法
CN109097636A (zh) * 2018-09-10 2018-12-28 招商局铝业(重庆)有限公司 一种烘焙器具用铝合金及其制备方法
JP7521943B2 (ja) 2020-06-11 2024-07-24 株式会社Uacj 熱交換器用アルミニウム合金押出多穴チューブ及びその製造方法
JP7521942B2 (ja) 2020-06-11 2024-07-24 株式会社Uacj 熱交換器用アルミニウム合金押出多穴チューブ及びその製造方法

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