EP0837296A1 - Heat exchanger of aluminum alloy - Google Patents

Heat exchanger of aluminum alloy Download PDF

Info

Publication number
EP0837296A1
EP0837296A1 EP97918343A EP97918343A EP0837296A1 EP 0837296 A1 EP0837296 A1 EP 0837296A1 EP 97918343 A EP97918343 A EP 97918343A EP 97918343 A EP97918343 A EP 97918343A EP 0837296 A1 EP0837296 A1 EP 0837296A1
Authority
EP
European Patent Office
Prior art keywords
amount
less
brazing
aluminum alloy
heat exchanger
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP97918343A
Other languages
German (de)
French (fr)
Other versions
EP0837296B1 (en
EP0837296A4 (en
Inventor
Takeyoshi Doko
Koji Okada
Takeshi Iguchi
Takaaki Sakane
Yoshihiro Kinoshita
Taketoshi Toyama
Akira Uchikawa
Satoshi Nohira
Homare Koutate
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Furukawa Electric Co Ltd
Denso Corp
Original Assignee
Furukawa Electric Co Ltd
Denso Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Furukawa Electric Co Ltd, Denso Corp filed Critical Furukawa Electric Co Ltd
Publication of EP0837296A1 publication Critical patent/EP0837296A1/en
Publication of EP0837296A4 publication Critical patent/EP0837296A4/en
Application granted granted Critical
Publication of EP0837296B1 publication Critical patent/EP0837296B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28HEAT EXCHANGE IN GENERAL
    • F28FDETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F9/00Casings; Header boxes; Auxiliary supports for elements; Auxiliary members within casings
    • F28F9/02Header boxes; End plates
    • F28F9/0219Arrangements for sealing end plates into casing or header box; Header box sub-elements
    • F28F9/0224Header boxes formed by sealing end plates into covers
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28HEAT EXCHANGE IN GENERAL
    • F28FDETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F21/00Constructions of heat-exchange apparatus characterised by the selection of particular materials
    • F28F21/08Constructions of heat-exchange apparatus characterised by the selection of particular materials of metal
    • F28F21/081Heat exchange elements made from metals or metal alloys
    • F28F21/084Heat exchange elements made from metals or metal alloys from aluminium or aluminium alloys
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28HEAT EXCHANGE IN GENERAL
    • F28FDETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F9/00Casings; Header boxes; Auxiliary supports for elements; Auxiliary members within casings
    • F28F9/02Header boxes; End plates
    • F28F9/0234Header boxes; End plates having a second heat exchanger disposed there within, e.g. oil cooler

Definitions

  • the present invention relates to a heat exchanger made of an aluminum alloy, and more particularly to a heat exchanger with a radiator and an oil cooler integrated that is produced by using aluminum alloy brazing sheets.
  • a heat exchanger having a radiator and an oil cooler in combination is manufactured by assembling a radiator core part (10) and an oil cooler part (11) (oil passages (7) formed by joining brazing sheets (8) are illustrated in a simplified manner in the drawings) and then mechanically associating them with tanks (6), for example, as shown perspectively in Fig. 4.
  • the radiator is made up of the radiator core part (10), comprising flat tubes (3), thin fins (1), side supports (12), and headers (4), and the tanks (6).
  • Each of the corrugated thin fins (1) is formed between the flat tubes (3), with the corrugated thin fin integrated with the flat tubes, and the ends of the flat tubes (3) are open to space (2) formed by the headers (4) and the tanks (6), so that a high-temperature refrigerant is passed from the space in one tank through the flat tubes (3) to another space (2) of the other tank (6), to recirculate the refrigerant, whose temperature has been lowered due to the heat exchange at the tubes (3) and the fins (1).
  • the radiator part is assembled as follows: as the tube material and the header material, brazing sheets are used, wherein the core material is, for example, JIS 3003 alloy; the inner side on the core material, that is, the side to which the refrigerant constantly contacts is coated with JIS 7072 alloy as a lining material; and the outer side on the core material is clad with a usual filler material, such as JIS 4045; and the tubes and the headers are integrated with corrugated fins and other members by brazing.
  • the core material is, for example, JIS 3003 alloy
  • the inner side on the core material that is, the side to which the refrigerant constantly contacts
  • JIS 7072 alloy as a lining material
  • the outer side on the core material is clad with a usual filler material, such as JIS 4045
  • the tubes and the headers are integrated with corrugated fins and other members by brazing.
  • the oil passages (7) formed by joining the brazing sheets (8) extend through the space in the tank (2), and an oil having a high temperature passing through the passages (7) is cooled with the refrigerant passing through the space (2).
  • brazing sheets are used, wherein, as the core material, for example, JIS 3003 alloy is used; the outer side on the core material, that is, the side to which the refrigerant constantly contacts is clad, for example, with JIS 7072 alloy, and the inner side on the core material is clad, usually, with a filler material, such as JIS 4045.
  • the brazing sheets are brazed by heating them to a temperature of about 600 °C.
  • the radiator part and the oil cooler part are assembled by brazing at a temperature of about 600 °C.
  • the brazing is carried out, for example, by the flux brazing method or the non-corrosive flux brazing method, wherein a non-corrosive flux is used.
  • the tank (6) is generally made of a resin material, and the tank (6) has to be attached in a step separated from the step of assembling the radiator part and the oil cooler part by brazing, so that there is a difficulty that additional step is required. Further, in such a heat exchanger, the part between the resin tank (6) and the header (4) that is fastened, is required to be caulked through a resin packing (5) or the like, which leads to a defect that crevice corrosion is apt to take place at the boundary between the resin packing (5) and the header (4).
  • Heat exchangers for automobiles are removed when the automobiles are disassembled, and they are melted as aluminum alloys for recycling.
  • the heat exchanger has, as the tank (6), a tank made of resin, the resin tank has to be removed purposely when the automobile is disassembled, and that becomes a bottleneck in the recycling process.
  • the tank also be made of an aluminum alloy and be assembled simultaneously by the brazing technique.
  • the oil cooler part is brazed with it covered with the tank. Therefore, if the brazing of the oil cooler is incomplete, it cannot be repaired anymore. Thus, it is required that the brazing be effected completely, but it is conventionally difficult due to the following reason. Since the oil cooler part is covered with the tank, the temperature of the brazing is not elevated satisfactorily, and defective brazing is apt to occur. Further, if the heating is carried out to elevate the temperature satisfactorily so as not to cause defective brazing, the brazing temperature is elevated excessively for the radiator part, and thus inconveniently the filler material diffuses into the radiator tubes and the fins. Further, in the oil cooler, since the brazed part is in contact with a refrigerant, local corrosion is apt to occur due to the potential difference between the brazed part and the core material part. This problem cannot be solved by brazing by the conventional brazing technique.
  • an object of the present invention is to provide a heat exchanger that is made of an aluminum alloy by using an aluminum material instead of a resin tank, can be easily recycled, is excellent in corrosion resistance, and can be produced without requiring a step of caulking a tank.
  • the radiator part and the oil cooler part can be assembled integrally in one step brazing.
  • Fig. 1 is a perspective view, partly in cross section, of an embodiment of the heat exchanger of the present invention with a radiator and an oil cooler integrated.
  • Fig. 2 is an illustrative view of an oil cooler part of another embodiment of the heat exchanger of the present invention made of an aluminum alloy.
  • Fig. 3 is an illustrative view of an oil cooler part of still another embodiment of the heat exchanger of the present invention made of an aluminum alloy.
  • Fig. 4 is a perspective view of a conventional heat exchanger having a radiator and an oil cooler in combination.
  • Fig. 5 is a perspective view of the conventional radiator.
  • Fig. 1 is an embodiment of a heat exchanger of the present invention made of an aluminum alloy with a radiator and an oil cooler integrated by brazing (a double pipe-type, brazing-type heat exchanger), wherein instead of a resin tank (6) shown in Fig. 4, a tank (13) in which brazing sheets of an aluminum alloy are used is employed, and a header (4) of a radiator core part and the tank (13) are assembled by one step by brazing-heating. Accordingly a packing (5) as used in the prior art is not required.
  • the tank is made of an aluminum alloy and its joining is made by the brazing method, crevice corrosion between the tank and the header does not occur, and when the exchanger is recovered as waste refuse, the tank can also be recycled as an aluminum material without dismounting it. Further, since the header and the tank are integrated by one step of brazing, a step of caulking the tank is not required.
  • Fig. 1 the same reference numerals are used to indicate the corresponding parts of Fig. 4.
  • the present invention is directed to the thus integral heat exchanger and as the brazing alloy of the brazing sheets (e.g., the above brazing sheets (8) in Fig. 1) used for the oil cooler, an aluminum alloy containing Si in an amount from more than 7.0 wt% to 12.0 wt%, Fe in an amount from more than 0.05 wt% to 0.5 wt%, Cu in an amount from more than 0.4 wt% to 8.0 wt%, Zn in an amount from more than 0.5 wt% to 10.0 wt%, and the balance of aluminum and inevitable impurities, additionally plus one or both of In in an amount from more than 0.002 wt% to 0.3 wt% and Sn in an amount from more than 0.002 wt% to 0.3 wt% for low-temperature brazing, is used.
  • the brazing alloy of the brazing sheets e.g., the above brazing sheets (8) in Fig. 1
  • This aluminum alloy is an alloy suggested as a low-temperature brazing alloy, for example, in JP-A ("JP-A" means unexamined published Japanese patent application) No. 90442/1995. The reason why brazing sheets clad with the brazing alloy having the above specified composition are used in the present production method is described below.
  • the amount of Si to be added is desirably 8.0 to 11.0 wt%.
  • Fe functions to make the crystals fine to make high the strength of the fillet of the brazed joint when the brazing alloy is melted and is then allowed to solidify and if its amount is 0.05 wt% or less, the effect is not satisfactorily exhibited.
  • the brazing alloy is solidified, Fe forms intermetallic compounds, which act as starting points of corrosion. Accordingly, in view of the balance between the effect of making the crystals fine and the corrosiveness, the upper limit of the amount of Fe is 0.5 wt% and the amount of Fe is preferably 0.2 wt% or less in view of the corrosiveness.
  • Cu lowers the melting point of the alloy to improve the brazing alloy flow property. Further Cu serves to increase the outer corrosion resistance of the filler material. Since the brazed parts of the oil cooler come in direct contact with a refrigerant, the outer corrosion resistance is required. Here, in view of the corrosion resistance, if the amount of Cu is 0.4 wt% or less, its effect is not satisfactory. To secure stable brazing properties, the amount of Cu to be added is over 1.0 wt%.
  • the brazing alloy will not be suitable as a filler material used for brazing sheets for the heat exchanger. Therefore, when the amount of Cu is over 1.0 wt% but 8.0 wt%, preferably 4.0 wt% or less to take the workability in rolling into account, and particularly from 1.0 to 3.5 wt%, stable properties are exhibited.
  • the addition of Zn lowers the melting point of the alloy to stabilize the brazing properties. Further, a conventional brazing alloy wherein Cu is added as in the present invention had the problem that the electric potential of the brazing alloy becomes nobler than that of the core and the outer corrosion occurs in a pitted pattern and at a high speed. The addition of Zn in this invention lowers the electric potential of the brazing alloy to bring the electric potential of the brazing alloy near to the electric potential of the core alloy to improve the corrosion resistance.
  • the brazing alloy is not suitable as a filler material to be used for brazing sheets for the heat exchanger.
  • the amount of Zn to be added is desirably over 2.0 wt%, and taking the workability in rolling into account, the amount of Zn to be added is desirably 6.0 wt% or less, preferably 5.0 wt% or less.
  • In and Sn make the electric potential of the filler material base to improve the corrosion resistance of the members constituting refrigerant passages. In and Sn are added to assist the effect of Zn. If its amount is 0.002 wt% or less, its effect is not satisfactory whereas if its amount is over 0.3 wt%, the workability in rolling of the alloy is lowered.
  • inevitable impurities other elements may be contained if the amounts are 0.30 wt% or less respectively, and the amounts are desirably 0.05 wt% or less respectively.
  • typical inevitable impurities include Ni, Cr, Zr, Ti, Mg, etc. which are often added into brazing sheets.
  • the filler materials of the brazing sheets used in the heat exchangers in the embodiments (1) and (2) stated above may be changed to the following filler materials (hereinafter referred to as third to sixth filler materials, respectively).
  • the first and second filler materials can be used at a brazing temperature of higher than 570 °C, but 585 °C or lower.
  • the filler materials are described below in detail.
  • a third filler material which can be used for a heat exchanger of the present invention made of an aluminum alloy is an Al alloy filler material containing Si in an amount from more than 7.0 wt% to 12.0 wt%, Cu in an amount from more than 0.4 wt% to 8.0 wt%, Fe in an amount from more than 0.05 wt% to 0.5 wt%, one kind or two or more kind elements selected from a group consisting of Zn in an amount from more than 0.5 wt% to 6.0 wt%, In in an amount of 0.3 wt% or less (preferably from 0.01 to 0.3 wt%), and Sn in an amount of 0.3 wt% or less (preferably from 0.01 to 0.3 wt%); and one kind or two or more kind elements selected from a group consisting of Li in an amount of 1.0 wt% or less (preferably from 0.1 to 0.5 wt%), Na in an amount of 0.2 wt% or less (preferably from 0.003 to 0.1
  • a fourth filler material for a heat exchanger made of an aluminum alloy of the present invention is an Al alloy filler material containing, in addition to the composition of the above third filler material, Mn in an amount from more than 0.05 wt% to 1.2 wt%.
  • a fifth filler material for a heat exchanger made of an aluminum alloy in the present invention is an Al alloy filler material containing Si in an amount from more than 7.0 wt% to 12.0 wt%, Cu in an amount from more than 0.4 wt% to 8.0 wt%, Fe in an amount from more than 0.05 wt% to 0.5 wt%, one kind or two kind elements selected from a group consisting of Ga in an amount of 1.0 wt% or less, and Ge in an amount of 2.0 wt% or less; and one kind or two or more kind elements selected from a group consisting of Li, Na, K, Ca, Sr, Ba, Bi, Be, Ni, Cr, Ti, Zr and V, in an amount of Li 1.0 wt% or less, Bi 0.5 wt% or less, Ni 0.6 wt% or less, and Na, K, Ca, Sr, Ba, Be, Cr, Ti, Zr or V 0.2 wt% or less; the balance being Al and inevitable impurities.
  • a sixth filler material for a heat exchanger made of an aluminum alloy of the present invention is an Al alloy filler material containing, in addition to the composition of the above fifth filler material, Mn in an amount from more than 0.05 wt% to 1.2 wt%.
  • Preferable amounts to be added respectively for Ga, Ge, Li, Na, K, Ca, Sr, Ba, Bi, Be, Ni, Cr, Ti, Zr, and V in the fourth to sixth filler materials are same as those previously mentioned in the third filler material.
  • the addition of Ga and/or Ge is effective to make base the potential of the filler material and hence to improve the corrosion resistance of a refrigerant passage component by such a sacrifice anode effect.
  • the addition of Ga and/or Ge also functions to reduce the potential of the filler material containing Cu to a value close to the potential of a core alloy, and hence to improve the corrosion resistance.
  • Ga and/or Ge can be added to assist the additional effect of Zn, In and/or Sn, or in place of them.
  • the amount of Ga is more than 1.0 wt% or the amount of Ge is more than 2.0 wt%, the self-corrosion resistance of the filler material is reduced, which may degrade the workability in rolling of the alloy.
  • Li, Na, K, Ca, Ba, Sr, Be, and Bi are effective to improve the flowability, that is, the brazing properties of the Al alloy filler material by forming a brittle oxide or a low melting point compound on the surface of the filler material to facilitate the breakage of the oxide film.
  • the amount of Li is more than 1.0 wt%, that of Bi is more than 0.5 wt%, or that of Na, K, Ca, Sr, Ba and Be is more than 0.2 wt% respectively, the workability in rolling of the alloy may be degraded.
  • Mn, Ni, Cr, Ti, Zr, and V function to form an intermetallic compound upon solidification of the filler material after being melted and hence to increase the strength of a brazing portion.
  • the amount of Mn is 0.05 wt% or less, the additional effect may be insufficient, while when the amount of Mn is more than 1.2 wt%, that of Ni is more than 0.6 wt%, or that of Cr, Ti, Zr and V is more than 0.2 wt% respectively, the workability in rolling of the Al alloy may be degraded.
  • the third to sixth filler materials for a heat exchanger made of an aluminum alloy in the present invention can also be used at a brazing temperature higher than 570 °C but to 585 °C. These filler materials are suitable for assembling a radiator and oil cooler integrated type heat exchanger.
  • the brazing sheet may be a sacrificial-material-coated brazing sheet having a three-layer structure.
  • a clad ratio of the filler material in the brazing sheets is not particularly different from that in the usual material, and there is no restriction on the amount of clad. It is recommended that a filler material is clad in an amount sufficient to brazing-joint.
  • the aluminum alloy of the radiator and the tank in the heat exchanger made of an aluminum alloy of the present invention is not particularly restricted. Any of generally used aluminum alloys and aluminum alloy brazing sheets as well as brazing sheets wherein the filler material used for the oil cooler of the present invention is used can be used.
  • the brazing conditions employed in the present invention may be usual conditions under which the radiator can be brazed without any problems. That is, there is no particular restriction and, for example, the flux brazing method and the non-corrosive flux brazing wherein a non-corrosive flux is used can be used. For example, assembling, cleaning, and, if required, applying a flux before the brazing may be carried out in a usual manner.
  • Fig. 2 In the present invention, so long as the radiator and the oil cooler are integrated, there is no particular restriction on the type of the heat exchanger made of an aluminum alloy and various types can be formed. Examples of the heat exchanger are illustrated in Figs. 2 and 3.
  • the oil cooler part shown in Fig. 2 is of a double pipe type having an inner pipe and an outer pipe.
  • the radiator core part In Fig. 2, the radiator core part is omitted since it may be basically the same as that in Fig. 1.
  • Fig. 2 (14) indicates a tubular oil cooler, which comprises an inner pipe (15) and an outer pipe (16). (19) indicates an aluminum alloy tank.
  • the same reference numerals as those in Fig. 1 are used to indicate the corresponding same parts.
  • (17) indicates a pipe and (18) indicates a connector. As shown in Fig.
  • the aluminum alloy tank (19) is made of brazing sheets and is brazed integrally to a header plate (4).
  • the inside of the outer pipe (16) is made of the filler material having the specified composition according to the present invention.
  • Fig. 3 shows another embodiment of the oil cooler part that is of a multi-plate type.
  • (20) indicates an oil cooler
  • (21) indicates inner fins
  • (22) indicates a tube plate
  • (23) indicates an aluminum alloy tank made of brazing sheets, the same reference numerals as those in Fig. 2 being used to indicate the corresponding same parts.
  • the inside of the tube plate (22) is made of a brazing sheet clad with the specified filler material according to the present invention.
  • the tank (23) is brazed integrally to the header plate (4).
  • the following shows an example for the first and second filler material.
  • the materials of the radiator are shown in Table 1.
  • the tubes of the radiator were tubes electroseamed by using the tube material shown in Table 1.
  • brazing sheets having the following constitution were used.
  • the brazing sheets were made by press molding O-material plates having a thickness of 0.6 mm, wherein the core material was an Al-0.5wt%Si-0.3wt%Fe-0.5wt%Cu-1.1wt%Mn alloy, the sacrificial material outside the core material of an Al-2wt%Zn alloy was clad thereon, and the brazing alloy inside the core material shown in Table 2, was clad thereon in amounts of 10% for the total thickness respectively.
  • Example of the present invention A1 10.2 0.08 2.5 3.9 - - balance B1 9.2 0.12 0.7 1.1 - - balance C1 9.9 0.09 1.6 2.2 - - balance D1 10.1 0.10 3.8 4.3 - - balance E1 8.5 0.09 2.6 2.5 0.02 - balance F1 10.5 0.28 2.4 4.6 - 0.02 balance Comparative Example G1 10.0 0.07 - 3.0 - - balance H1 5.6 0.15 1.5 3.4 - - balance I1 9.9 0.08 2.6 0.2 - - balance Conventional Example J1 8.5 0.41 - - - - balance K1 10.1 0.42 - - - - balance (wt%)
  • the corrosion test was performed in such a way that from the oil cooler a part that had no leakage defect was cut out, the end of the part was masked, the part was immersed for 5 months in a tap water to which Cu 2+ ions had been added to give a concentration 10 ppm, and cycles of 80 °C x 8 hours and room temperature x 16 hours were repeated. The state of formation of corrosion around the brazed section was examined in cross section.
  • the temperature reached at brazing was lower than 600 °C, that was 570 to 585 °C, the brazing of the oil cooler was good and no leakage defect occurred because of the use of the filler material for low-temperature at this part. Further, the potential difference between the brazing alloy and the core material alloy in any of these Examples was within 100 mV. As a result, through-hole corrosion did not occur in the corrosion test.
  • the following shows an example for the third to sixth filler materials.
  • brazing metals having compositions shown in Tables 4 and 5 were clad on one surface of a core material (Al-0.27wt%Si-0.42wt%Fe-1.1wt%Mn-0.52wt%Cu alloy), to prepare brazing sheets having the thickness of 0.50 mm.
  • the brazing sheets were subjected to thermal refining under the specification of JIS grade H14 and the clad ratio of the filler material was 10%. No.
  • brazing sheets were subjected to the following brazing test by heating at a brazing temperature shown in Tables 6 and 7.
  • the brazing sheet was taken as a lower sheet and a sheet (thickness: 0.5 mm) of an Al-1.2wt%Si-0.25wt%Fe-0.4wt%Cu-1.1wt%Mn alloy-H14 material was taken as an upper sheet.
  • the lower sheet was assembled with the upper sheet in the form of a T joint.
  • a brazing portion of the T joint was coated with a liquid containing a potassium fluoride series flux at a concentration of 10% and heated in a N 2 gas to be thus brazed.
  • 50 pieces of T joints were prepared for each brazing sheet. The number of occurrence of incomplete brazing of the T joints was estimated by visual inspection. Complete brazed T joints were then subjected to tensile test to check the breaking point of each T joint for examining the strength of each brazing portion.
  • the examples A2 to V2 for the present invention exhibit good brazing property even at 575 °C that is a temperature lower than the conventional method. Therefore, with the filler material in the present invention, it is possible to satisfactorily assemble a radiator and oil cooler integrated type heat exchanger made of an aluminum alloy, without causing brazing defects even when the temperature of brazing is not elevated so high due to the tank that covers the oil cooler part.
  • the heat exchanger produced in accordance with the present invention does not use a resin tank, the heat exchanger is characterized in that it is readily recycled, the corrosion resistance is excellent, and a step of caulking the tank is not required to produce the heat exchanger.

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Heat-Exchange Devices With Radiators And Conduit Assemblies (AREA)
  • Details Of Heat-Exchange And Heat-Transfer (AREA)

Abstract

There is disclosed a heat exchanger made of an aluminum alloy having a radiator part (10) and an oil cooler part (11) in combination and manufactured integrally by the brazing method, wherein a refrigerant tank (13) for covering and sealing the oil cooler part is made of an aluminum alloy, an aluminum alloy containing Si in an amount from more than 7.0 wt% to 12.0 wt%, Fe in an amount from more than 0.05 wt% to 0.5 wt%, Cu in an amount from more than 0.4 wt% to 8.0 wt%, Zn in an amount from more than 0.5 wt% to 10.0 wt%, and the balance of aluminum and inevitable impurities is used as a filler material of brazing sheets that are used for the oil cooler part and are brazed in the tank, and the refrigerant tank is assembled integrally with the radiator part and the oil cooler part by brazing with the brazing material. The heat exchanger made of an aluminum alloy by using an aluminum material instead of a resin tank, can be easily recycled, is excellent in corrosion resistance, and can be manufactured without requiring a step of caulking a tank.

Description

TECHNICAL FIELD
The present invention relates to a heat exchanger made of an aluminum alloy, and more particularly to a heat exchanger with a radiator and an oil cooler integrated that is produced by using aluminum alloy brazing sheets.
BACKGROUND ART
A heat exchanger having a radiator and an oil cooler in combination is manufactured by assembling a radiator core part (10) and an oil cooler part (11) (oil passages (7) formed by joining brazing sheets (8) are illustrated in a simplified manner in the drawings) and then mechanically associating them with tanks (6), for example, as shown perspectively in Fig. 4.
Herein, as is apparent from Fig.5 showing a perspective view, the radiator is made up of the radiator core part (10), comprising flat tubes (3), thin fins (1), side supports (12), and headers (4), and the tanks (6). Each of the corrugated thin fins (1) is formed between the flat tubes (3), with the corrugated thin fin integrated with the flat tubes, and the ends of the flat tubes (3) are open to space (2) formed by the headers (4) and the tanks (6), so that a high-temperature refrigerant is passed from the space in one tank through the flat tubes (3) to another space (2) of the other tank (6), to recirculate the refrigerant, whose temperature has been lowered due to the heat exchange at the tubes (3) and the fins (1).
The radiator part is assembled as follows: as the tube material and the header material, brazing sheets are used, wherein the core material is, for example, JIS 3003 alloy; the inner side on the core material, that is, the side to which the refrigerant constantly contacts is coated with JIS 7072 alloy as a lining material; and the outer side on the core material is clad with a usual filler material, such as JIS 4045; and the tubes and the headers are integrated with corrugated fins and other members by brazing.
In the oil cooler part (11), the oil passages (7) formed by joining the brazing sheets (8) extend through the space in the tank (2), and an oil having a high temperature passing through the passages (7) is cooled with the refrigerant passing through the space (2). For forming the oil passages, brazing sheets are used, wherein, as the core material, for example, JIS 3003 alloy is used; the outer side on the core material, that is, the side to which the refrigerant constantly contacts is clad, for example, with JIS 7072 alloy, and the inner side on the core material is clad, usually, with a filler material, such as JIS 4045. Generally the brazing sheets are brazed by heating them to a temperature of about 600 °C.
Thus, the radiator part and the oil cooler part are assembled by brazing at a temperature of about 600 °C. The brazing is carried out, for example, by the flux brazing method or the non-corrosive flux brazing method, wherein a non-corrosive flux is used.
However, conventionally the tank (6) is generally made of a resin material, and the tank (6) has to be attached in a step separated from the step of assembling the radiator part and the oil cooler part by brazing, so that there is a difficulty that additional step is required. Further, in such a heat exchanger, the part between the resin tank (6) and the header (4) that is fastened, is required to be caulked through a resin packing (5) or the like, which leads to a defect that crevice corrosion is apt to take place at the boundary between the resin packing (5) and the header (4).
Further, in recent years, recycling of material has attracted attention in view of effective use of resources on the earth. Heat exchangers for automobiles are removed when the automobiles are disassembled, and they are melted as aluminum alloys for recycling. However, as shown in Fig. 4, when the heat exchanger has, as the tank (6), a tank made of resin, the resin tank has to be removed purposely when the automobile is disassembled, and that becomes a bottleneck in the recycling process.
Therefore, it is desirable that the tank also be made of an aluminum alloy and be assembled simultaneously by the brazing technique. However, after that brazing, the oil cooler part is brazed with it covered with the tank. Therefore, if the brazing of the oil cooler is incomplete, it cannot be repaired anymore. Thus, it is required that the brazing be effected completely, but it is conventionally difficult due to the following reason. Since the oil cooler part is covered with the tank, the temperature of the brazing is not elevated satisfactorily, and defective brazing is apt to occur. Further, if the heating is carried out to elevate the temperature satisfactorily so as not to cause defective brazing, the brazing temperature is elevated excessively for the radiator part, and thus inconveniently the filler material diffuses into the radiator tubes and the fins. Further, in the oil cooler, since the brazed part is in contact with a refrigerant, local corrosion is apt to occur due to the potential difference between the brazed part and the core material part. This problem cannot be solved by brazing by the conventional brazing technique.
Therefore, an object of the present invention is to provide a heat exchanger that is made of an aluminum alloy by using an aluminum material instead of a resin tank, can be easily recycled, is excellent in corrosion resistance, and can be produced without requiring a step of caulking a tank.
Other and further objects, features, and advantages of the invention will appear more fully from the following description, taken in connection with the accompanying drawings.
DISCLOSURE OF INVENTION
The above object has been attained by providing a heat exchanger made of an aluminum alloy having the following constitution.
According to the present invention there are provided:
  • (1) A heat exchanger made of an aluminum alloy having a radiator part and an oil cooler part in combination and assembled integrally by the brazing method, wherein a refrigerant tank for covering and sealing said oil cooler part is made of an aluminum alloy, an aluminum alloy containing Si in an amount from more than 7.0 wt% to 12.0 wt%, Fe in an amount from more than 0.05 wt% to 0.5 wt%, Cu in an amount from more than 0.4 wt% to 8.0 wt%, Zn in an amount from more than 0.5 wt% to 10.0 wt%, and the balance of aluminum and inevitable impurities is used as a filler material of brazing sheets that are used for said oil cooler part and are brazed in said tank, and said refrigerant tank is assembled integrally with said radiator part and said oil cooler part by brazing with said brazing material; and
  • (2) A heat exchanger made of an aluminum alloy having a radiator part and an oil cooler part in combination and assembled integrally by the brazing method, wherein a refrigerant tank for covering and sealing said oil cooler part is made of an aluminum alloy, an aluminum alloy containing Si in an amount from more than 7.0 wt% to 12.0 wt%, Fe in an amount from more than 0.05 wt% to 0.5 wt%, Cu in an amount from more than 0.4 wt% to 8.0 wt%, Zn in an amount from more than 0.5 wt% to 10.0 wt%, one or both of In in an amount from more than 0.002 wt% to 0.3 wt% and Sn in an amount from more than 0.002 wt% to 0.3 wt%, and the balance of aluminum and inevitable impurities is used as a filler material of brazing sheets that are used for said oil cooler part and are brazed in said tank, and said refrigerant tank is assembled integrally with said radiator part and said oil cooler part by brazing with said brazing material.
  • In this invention, the radiator part and the oil cooler part can be assembled integrally in one step brazing.
    BRIEF DESCRIPTION OF DRAWINGS
    Fig. 1 is a perspective view, partly in cross section, of an embodiment of the heat exchanger of the present invention with a radiator and an oil cooler integrated.
    Fig. 2 is an illustrative view of an oil cooler part of another embodiment of the heat exchanger of the present invention made of an aluminum alloy.
    Fig. 3 is an illustrative view of an oil cooler part of still another embodiment of the heat exchanger of the present invention made of an aluminum alloy.
    Fig. 4 is a perspective view of a conventional heat exchanger having a radiator and an oil cooler in combination.
    Fig. 5 is a perspective view of the conventional radiator.
    BEST MODE FOR CARRYING OUT THE INVENTION
    Now, the present invention is described in detail referring to the drawing.
    Fig. 1 is an embodiment of a heat exchanger of the present invention made of an aluminum alloy with a radiator and an oil cooler integrated by brazing (a double pipe-type, brazing-type heat exchanger), wherein instead of a resin tank (6) shown in Fig. 4, a tank (13) in which brazing sheets of an aluminum alloy are used is employed, and a header (4) of a radiator core part and the tank (13) are assembled by one step by brazing-heating. Accordingly a packing (5) as used in the prior art is not required. In the present invention, since the tank is made of an aluminum alloy and its joining is made by the brazing method, crevice corrosion between the tank and the header does not occur, and when the exchanger is recovered as waste refuse, the tank can also be recycled as an aluminum material without dismounting it. Further, since the header and the tank are integrated by one step of brazing, a step of caulking the tank is not required. In passing, in Fig. 1, the same reference numerals are used to indicate the corresponding parts of Fig. 4.
    The present invention is directed to the thus integral heat exchanger and as the brazing alloy of the brazing sheets (e.g., the above brazing sheets (8) in Fig. 1) used for the oil cooler, an aluminum alloy containing Si in an amount from more than 7.0 wt% to 12.0 wt%, Fe in an amount from more than 0.05 wt% to 0.5 wt%, Cu in an amount from more than 0.4 wt% to 8.0 wt%, Zn in an amount from more than 0.5 wt% to 10.0 wt%, and the balance of aluminum and inevitable impurities, additionally plus one or both of In in an amount from more than 0.002 wt% to 0.3 wt% and Sn in an amount from more than 0.002 wt% to 0.3 wt% for low-temperature brazing, is used. This aluminum alloy is an alloy suggested as a low-temperature brazing alloy, for example, in JP-A ("JP-A" means unexamined published Japanese patent application) No. 90442/1995. The reason why brazing sheets clad with the brazing alloy having the above specified composition are used in the present production method is described below.
    In the above brazing alloy, Si lowers the melting point of the alloy. If its amount is 7.0 wt% or less, the melting point is not lowered satisfactorily whereas if its amount is over 12.0 wt%, the melting point is elevated contrarily and therefore the brazing properties are deteriorated. In particular, taking the brazing flow property into account, the amount of Si to be added is desirably 8.0 to 11.0 wt%.
    Fe functions to make the crystals fine to make high the strength of the fillet of the brazed joint when the brazing alloy is melted and is then allowed to solidify and if its amount is 0.05 wt% or less, the effect is not satisfactorily exhibited. When the brazing alloy is solidified, Fe forms intermetallic compounds, which act as starting points of corrosion. Accordingly, in view of the balance between the effect of making the crystals fine and the corrosiveness, the upper limit of the amount of Fe is 0.5 wt% and the amount of Fe is preferably 0.2 wt% or less in view of the corrosiveness.
    Cu lowers the melting point of the alloy to improve the brazing alloy flow property. Further Cu serves to increase the outer corrosion resistance of the filler material. Since the brazed parts of the oil cooler come in direct contact with a refrigerant, the outer corrosion resistance is required. Here, in view of the corrosion resistance, if the amount of Cu is 0.4 wt% or less, its effect is not satisfactory. To secure stable brazing properties, the amount of Cu to be added is over 1.0 wt%. If the amount of Cu is over 8.0 wt%, since the electric potential of the brazing alloy becomes noble to make members constituting refrigerant passages preferentially corroded, that is, to make the corrosion resistance lowered and the workability in rolling of the alloy is lowered, the brazing alloy will not be suitable as a filler material used for brazing sheets for the heat exchanger. Therefore, when the amount of Cu is over 1.0 wt% but 8.0 wt%, preferably 4.0 wt% or less to take the workability in rolling into account, and particularly from 1.0 to 3.5 wt%, stable properties are exhibited.
    The addition of Zn lowers the melting point of the alloy to stabilize the brazing properties. Further, a conventional brazing alloy wherein Cu is added as in the present invention had the problem that the electric potential of the brazing alloy becomes nobler than that of the core and the outer corrosion occurs in a pitted pattern and at a high speed. The addition of Zn in this invention lowers the electric potential of the brazing alloy to bring the electric potential of the brazing alloy near to the electric potential of the core alloy to improve the corrosion resistance. However, if its amount is 0.5 wt% or less, its effect is not satisfactory whereas if its amount is over 10.0 wt%, since the corrosion resistance of the brazing alloy itself is lowered and the workability in rolling of the alloy is lowered, the brazing alloy is not suitable as a filler material to be used for brazing sheets for the heat exchanger. Although the above range is within the present invention, taking the brazing alloy flow properties into account, in the present alloy, the amount of Zn to be added is desirably over 2.0 wt%, and taking the workability in rolling into account, the amount of Zn to be added is desirably 6.0 wt% or less, preferably 5.0 wt% or less.
    In and Sn make the electric potential of the filler material base to improve the corrosion resistance of the members constituting refrigerant passages. In and Sn are added to assist the effect of Zn. If its amount is 0.002 wt% or less, its effect is not satisfactory whereas if its amount is over 0.3 wt%, the workability in rolling of the alloy is lowered.
    As inevitable impurities, other elements may be contained if the amounts are 0.30 wt% or less respectively, and the amounts are desirably 0.05 wt% or less respectively. Herein typical inevitable impurities include Ni, Cr, Zr, Ti, Mg, etc. which are often added into brazing sheets.
    In the present invention, the filler materials of the brazing sheets used in the heat exchangers in the embodiments (1) and (2) stated above (the first and second filler materials, respectively) may be changed to the following filler materials (hereinafter referred to as third to sixth filler materials, respectively). The first and second filler materials can be used at a brazing temperature of higher than 570 °C, but 585 °C or lower.
    The filler materials are described below in detail.
    A third filler material which can be used for a heat exchanger of the present invention made of an aluminum alloy is an Al alloy filler material containing Si in an amount from more than 7.0 wt% to 12.0 wt%, Cu in an amount from more than 0.4 wt% to 8.0 wt%, Fe in an amount from more than 0.05 wt% to 0.5 wt%, one kind or two or more kind elements selected from a group consisting of Zn in an amount from more than 0.5 wt% to 6.0 wt%, In in an amount of 0.3 wt% or less (preferably from 0.01 to 0.3 wt%), and Sn in an amount of 0.3 wt% or less (preferably from 0.01 to 0.3 wt%); and
       one kind or two or more kind elements selected from a group consisting of Li in an amount of 1.0 wt% or less (preferably from 0.1 to 0.5 wt%), Na in an amount of 0.2 wt% or less (preferably from 0.003 to 0.1 wt%), K in an amount of 0.2 wt% or less (preferably from 0.003 to 0.1 wt%), Ca in an amount of 0.2 wt% or less (preferably from 0.003 to 0.1 wt%), Sr in an amount of 0.2 wt% or less (preferably from 0.003 to 0.1 wt%), Ba in an amount of 0.2 wt% or less (preferably from 0.003 to 0.1 wt%), Bi in an amount of 0.5 wt% or less (preferably from 0.1 to 0.3 wt%), Be in an amount of 0.2 wt% or less (preferably from 0.003 to 0.1 wt%), Ni in an amount of 0.6 wt% or less (preferably from 0.05 to 0.3 wt%), Cr in an amount of 0.2 wt% or less (preferably from 0.003 to 0.1 wt%), Ti in an amount of 0.2 wt% or less (preferably from 0.003 to 0.1 wt%), Zr in an amount of 0.2 wt% or less (preferably from 0.003 to 0.1 wt%), V in an amount of 0.2 wt% or less (preferably from 0.003 to 0.1 wt%), Ga in an amount of 1.0 wt% or less (preferably from 0.3 to 0.9 wt%), and Ge in an amount of 2.0 wt% or less (preferably from 0.2 to 1.9 wt%);
       the balance being Al and inevitable impurities. A fourth filler material for a heat exchanger made of an aluminum alloy of the present invention is an Al alloy filler material containing, in addition to the composition of the above third filler material, Mn in an amount from more than 0.05 wt% to 1.2 wt%.
    A fifth filler material for a heat exchanger made of an aluminum alloy in the present invention is an Al alloy filler material containing Si in an amount from more than 7.0 wt% to 12.0 wt%, Cu in an amount from more than 0.4 wt% to 8.0 wt%, Fe in an amount from more than 0.05 wt% to 0.5 wt%, one kind or two kind elements selected from a group consisting of Ga in an amount of 1.0 wt% or less, and Ge in an amount of 2.0 wt% or less; and
       one kind or two or more kind elements selected from a group consisting of Li, Na, K, Ca, Sr, Ba, Bi, Be, Ni, Cr, Ti, Zr and V, in an amount of Li 1.0 wt% or less, Bi 0.5 wt% or less, Ni 0.6 wt% or less, and Na, K, Ca, Sr, Ba, Be, Cr, Ti, Zr or V 0.2 wt% or less; the balance being Al and inevitable impurities.
    Further, a sixth filler material for a heat exchanger made of an aluminum alloy of the present invention is an Al alloy filler material containing, in addition to the composition of the above fifth filler material, Mn in an amount from more than 0.05 wt% to 1.2 wt%.
    Preferable amounts to be added respectively for Ga, Ge, Li, Na, K, Ca, Sr, Ba, Bi, Be, Ni, Cr, Ti, Zr, and V in the fourth to sixth filler materials are same as those previously mentioned in the third filler material.
    The technical significance and function of components in the composition of the third to sixth filler materials are described below in detail. The components that are common with the first and second filler materials have the same technical significance and function.
    The addition of Ga and/or Ge is effective to make base the potential of the filler material and hence to improve the corrosion resistance of a refrigerant passage component by such a sacrifice anode effect. The addition of Ga and/or Ge also functions to reduce the potential of the filler material containing Cu to a value close to the potential of a core alloy, and hence to improve the corrosion resistance. Ga and/or Ge can be added to assist the additional effect of Zn, In and/or Sn, or in place of them. When the amount of Ga is more than 1.0 wt% or the amount of Ge is more than 2.0 wt%, the self-corrosion resistance of the filler material is reduced, which may degrade the workability in rolling of the alloy.
    Li, Na, K, Ca, Ba, Sr, Be, and Bi are effective to improve the flowability, that is, the brazing properties of the Al alloy filler material by forming a brittle oxide or a low melting point compound on the surface of the filler material to facilitate the breakage of the oxide film. When the amount of Li is more than 1.0 wt%, that of Bi is more than 0.5 wt%, or that of Na, K, Ca, Sr, Ba and Be is more than 0.2 wt% respectively, the workability in rolling of the alloy may be degraded.
    Mn, Ni, Cr, Ti, Zr, and V function to form an intermetallic compound upon solidification of the filler material after being melted and hence to increase the strength of a brazing portion. When the amount of Mn is 0.05 wt% or less, the additional effect may be insufficient, while when the amount of Mn is more than 1.2 wt%, that of Ni is more than 0.6 wt%, or that of Cr, Ti, Zr and V is more than 0.2 wt% respectively, the workability in rolling of the Al alloy may be degraded.
    Similarly to the first and second filler materials, the third to sixth filler materials for a heat exchanger made of an aluminum alloy in the present invention can also be used at a brazing temperature higher than 570 °C but to 585 °C. These filler materials are suitable for assembling a radiator and oil cooler integrated type heat exchanger.
    The above is the reason of the restriction on the components of the brazing alloy of the brazing sheets of the oil cooler used in the present invention whereas there is no particular restriction on the alloy of the core material. It is recommended to use an aluminum alloy generally used for brazing sheets. However, to improve the corrosion resistance, preferably the amounts of Zn and Cu in the filler material are adjusted to bring the potential (natural potential) difference between the filler material and the core material to 100 mV or less. If required, the brazing sheet may be a sacrificial-material-coated brazing sheet having a three-layer structure. A clad ratio of the filler material in the brazing sheets is not particularly different from that in the usual material, and there is no restriction on the amount of clad. It is recommended that a filler material is clad in an amount sufficient to brazing-joint.
    The aluminum alloy of the radiator and the tank in the heat exchanger made of an aluminum alloy of the present invention is not particularly restricted. Any of generally used aluminum alloys and aluminum alloy brazing sheets as well as brazing sheets wherein the filler material used for the oil cooler of the present invention is used can be used.
    Herein, the brazing conditions employed in the present invention may be usual conditions under which the radiator can be brazed without any problems. That is, there is no particular restriction and, for example, the flux brazing method and the non-corrosive flux brazing wherein a non-corrosive flux is used can be used. For example, assembling, cleaning, and, if required, applying a flux before the brazing may be carried out in a usual manner.
    In the present invention, so long as the radiator and the oil cooler are integrated, there is no particular restriction on the type of the heat exchanger made of an aluminum alloy and various types can be formed. Examples of the heat exchanger are illustrated in Figs. 2 and 3. The oil cooler part shown in Fig. 2 is of a double pipe type having an inner pipe and an outer pipe. In Fig. 2, the radiator core part is omitted since it may be basically the same as that in Fig. 1. In Fig. 2, (14) indicates a tubular oil cooler, which comprises an inner pipe (15) and an outer pipe (16). (19) indicates an aluminum alloy tank. The same reference numerals as those in Fig. 1 are used to indicate the corresponding same parts. (17) indicates a pipe and (18) indicates a connector. As shown in Fig. 2, the aluminum alloy tank (19) is made of brazing sheets and is brazed integrally to a header plate (4). Herein, the inside of the outer pipe (16) is made of the filler material having the specified composition according to the present invention. Fig. 3 shows another embodiment of the oil cooler part that is of a multi-plate type. In Fig. 3, (20) indicates an oil cooler, (21) indicates inner fins, (22) indicates a tube plate, and (23) indicates an aluminum alloy tank made of brazing sheets, the same reference numerals as those in Fig. 2 being used to indicate the corresponding same parts. In Fig. 3, the inside of the tube plate (22) is made of a brazing sheet clad with the specified filler material according to the present invention. In Fig. 3, the tank (23) is brazed integrally to the header plate (4).
    EXAMPLE
    The present invention is specifically described with reference to the following examples, but the present invention is not restricted to the following examples.
    Example 1
    First, the following shows an example for the first and second filler material.
    A heat exchanger wherein a radiator and an oil cooler were integrally formed as shown in Fig. 1 and the tank material was aluminum alloy brazing sheets was produced under heating conditions of 600 °C x 5 min. Any packings were not used. The materials of the radiator are shown in Table 1. The tubes of the radiator were tubes electroseamed by using the tube material shown in Table 1. As the material for the oil cooler, brazing sheets having the following constitution were used. In their constitution, the brazing sheets were made by press molding O-material plates having a thickness of 0.6 mm, wherein the core material was an Al-0.5wt%Si-0.3wt%Fe-0.5wt%Cu-1.1wt%Mn alloy, the sacrificial material outside the core material of an Al-2wt%Zn alloy was clad thereon, and the brazing alloy inside the core material shown in Table 2, was clad thereon in amounts of 10% for the total thickness respectively.
    The oil cooler part was cut from the obtained heat exchanger and the leakage test and the corrosion test were performed.
    Member Constitution Plate thickness Refining
    Tube material (three layers) filler material:[4045 alloy](10%) 0.25 mm H-14-material
    core material: Al-0.5wt%Si-0.3wt%Fe-0.5wt%Cu-1.1wt%Mn
    lining material:Al-1.5wt%Zn(15%)
    Fin material (bear) Al-0.2wt%Si-0.2wt%Fe-0.1wt%Cu-1wt%Mn-1wt%Zn 0.07 mm H-14-material
    Header material (two layers) filler material:[4045 alloy](7%) 1.5 mm O-material
    core material: 3003 alloy
    Side support material (two layers) filler material:[4045 alloy](7%) 1.5 mm O-material
    core material: 3003 alloy
    Tank material (two layers) filler material:[4045 alloy](7%) 1.5 mm O-material
    core material: 3003 alloy
    No. Si Fe Cu Zn In Sn Al
    Example of the present invention A1 10.2 0.08 2.5 3.9 - - balance
    B1 9.2 0.12 0.7 1.1 - - balance
    C1 9.9 0.09 1.6 2.2 - - balance
    D1 10.1 0.10 3.8 4.3 - - balance
    E1 8.5 0.09 2.6 2.5 0.02 - balance
    F1 10.5 0.28 2.4 4.6 - 0.02 balance
    Comparative Example G1 10.0 0.07 - 3.0 - - balance
    H1 5.6 0.15 1.5 3.4 - - balance
    I1 9.9 0.08 2.6 0.2 - - balance
    Conventional Example J1 8.5 0.41 - - - - balance
    K1 10.1 0.42 - - - - balance
    (wt%)
    The corrosion test was performed in such a way that from the oil cooler a part that had no leakage defect was cut out, the end of the part was masked, the part was immersed for 5 months in a tap water to which Cu2+ ions had been added to give a concentration 10 ppm, and cycles of 80 °C x 8 hours and room temperature x 16 hours were repeated. The state of formation of corrosion around the brazed section was examined in cross section.
    The results are shown in Table 3.
    No. Leakage test result of the oil cooler Result of the corrosion test
    Example of the present invention A1 No leakage defect No through-hole corrosion
    B1 No leakage defect No through-hole corrosion
    C1 No leakage defect No through-hole corrosion
    D1 No leakage defect No through-hole corrosion
    E1 No leakage defect No through-hole corrosion
    F1 No leakage defect No through-hole corrosion
    Comparative Example G1 No leakage defect Through-hole corrosion occurred
    H1 Leakage defects occurred No through-hole corrosion
    I1 No leakage defect Through-hole corrosion occurred
    Conventional Example J1 Leakage defects occurred Though-hole corrosion occurred
    K1 Leakage defects occurred Through-hole corrosion occurred
    Since the oil cooler part was covered with the heater tank in Examples A1 to F1, the temperature reached at brazing was lower than 600 °C, that was 570 to 585 °C, the brazing of the oil cooler was good and no leakage defect occurred because of the use of the filler material for low-temperature at this part. Further, the potential difference between the brazing alloy and the core material alloy in any of these Examples was within 100 mV. As a result, through-hole corrosion did not occur in the corrosion test.
    In contrast, in Comparative Example H1, wherein the amount of Si was smaller than that of the present invention, and in the prior art Examples J1 and K1, wherein Cu and Zn were not contained, the oil coolers were brazed incompletely, and leakaging parts were recognized in the leakage test.
    Further, in Comparative Examples G1 and I1 and the prior art Examples J1 and K1, wherein Cu and Zn were outside the present invention, the potential difference between the brazing alloy and the core material was over 100 mV. As a result, through-hole corrosions occurred in the corrosion test.
    Example 2
    The following shows an example for the third to sixth filler materials.
    Each of brazing metals having compositions shown in Tables 4 and 5 was clad on one surface of a core material (Al-0.27wt%Si-0.42wt%Fe-1.1wt%Mn-0.52wt%Cu alloy), to prepare brazing sheets having the thickness of 0.50 mm. The brazing sheets were subjected to thermal refining under the specification of JIS grade H14 and the clad ratio of the filler material was 10%.
    No. Composition of the aluminum alloy filler material (wt%)
    Si Cu Fe Zn In Sn Ga Ge Mn Al
    Example of the present invention A2 10.4 2.25 0.19 4.05 - - - - - Li 0.19 balance
    B2 10.4 2.25 0.19 4.05 - - - - - Li 0.47 balance
    C2 10.4 2.25 0.19 4.05 - - - - - Li 0.83 balance
    D2 10.4 2.25 0.19 4.05 0.21 - - - - Na 0.05 balance
    E2 10.4 2.25 0.19 4.05 - 0.18 - - - K 0.04 balance
    F2 10.4 2.25 0.19 4.05 - - 0.87 - - Ca 0.05 balance
    G2 10.4 2.25 0.19 4.05 - - - 0.65 - Sr 0.03 balance
    H2 10.4 2.25 0.19 - 0.15 - 0.70 1.52 - Ba 0.04 balance
    I2 10.4 2.25 0.19 4.05 - - - - - Bi 0.09 balance
    J2 10.4 2.25 0.19 2.04 0.04 0.03 - - - Bi 0.21 balance
    K2 10.4 2.25 0.19 4.05 - - - 0.24 - Be 0.09 balance
    L2 10.4 2.25 0.19 2.04 - - 0.49 - - Ni 0.10 balance
    M2 10.4 2.25 0.19 1.45 - - 0.75 - - Cr 0.04 balance
    N2 10.4 2.25 0.19 2.04 - - - 0.31 - Ti 0.08 balance
    No. Composition of the aluminum alloy filler material (wt%)
    Si Cu Fe Zn In Sn Ga Ge Mn Al
    Example of the present invention O2 10.4 2.25 0.19 2.04 - - - 0.66 - Zr 0.05 balance
    P2 10.4 2.25 0.19 1.67 - - - 1.52 - V 0.09 balance
    Q2 10.4 2.25 0.19 - - - 0.87 - - Li 0.22 balance
    R2 10.4 2.25 0.19 - - - - 0.66 - Ca 0.15 balance
    S2 10.4 2.25 0.19 4.05 - - - - 0.30 Li 0.53 balance
    T2 10.4 2.25 0.19 4.05 - - - - 0.61 Sr 0.19 balance
    U2 10.4 2.25 0.19 - - - 0.81 - 0.30 Li 0.72 balance
    V2 10.4 2.25 0.19 - - - - 1.85 0.81 Be 0.17 balance
    Comparative Example a 5.3 0.91 0.28 2.30 balance
    b 10.4 - 0.19 4.30 balance
    Each of the above brazing sheets was subjected to the following brazing test by heating at a brazing temperature shown in Tables 6 and 7.
    The brazing sheet was taken as a lower sheet and a sheet (thickness: 0.5 mm) of an Al-1.2wt%Si-0.25wt%Fe-0.4wt%Cu-1.1wt%Mn alloy-H14 material was taken as an upper sheet. The lower sheet was assembled with the upper sheet in the form of a T joint. A brazing portion of the T joint was coated with a liquid containing a potassium fluoride series flux at a concentration of 10% and heated in a N2 gas to be thus brazed. In this brazing test, 50 pieces of T joints were prepared for each brazing sheet. The number of occurrence of incomplete brazing of the T joints was estimated by visual inspection. Complete brazed T joints were then subjected to tensile test to check the breaking point of each T joint for examining the strength of each brazing portion.
    The results are shown in Tables 6 and 7.
    No. Brazing temperature (°C) Characters after brazing
    Brazing property Fillet strength
    Number of occurence of incomplete brazing of T joints Braking points of T joints
    Example of the present invention A2 575 absence brazing portion X
    B2 575 absence brazing portion X
    C2 575 absence brazing portion X
    D2 575 absence brazing portion X
    E2 575 absence brazing portion X
    F2 575 absence brazing portion X
    G2 575 absence brazing portion X
    H2 575 absence brazing portion X
    I2 575 absence brazing portion X
    J2 575 absence brazing portion X
    K2 575 absence brazing portion X
    L2 575 5 base material O
    M2 575 2 base material O
    N2 575 3 base material O
    No. Brazing temperature (°C) Characters after brazing
    Brazing property Fillet strength
    Number of occurence of incomplete brazing of T joints Braking points of T joints
    Example of the present invention O2 575 6 base material O
    P2 575 4 base material O
    Q2 575 absence brazing portion X
    R2 575 absence brazing portion X
    S2 575 absence brazing portion X
    T2 575 absence brazing portion X
    U2 575 absence brazing portion X
    V2 575 absence brazing portion X
    Comparative Example a 575 50 Brazing could not be done so that the tests could not be done.
    b 575 50 ditto
    As is apparent from the results shown in Tables 6 and 7, the examples A2 to V2 for the present invention exhibit good brazing property even at 575 °C that is a temperature lower than the conventional method. Therefore, with the filler material in the present invention, it is possible to satisfactorily assemble a radiator and oil cooler integrated type heat exchanger made of an aluminum alloy, without causing brazing defects even when the temperature of brazing is not elevated so high due to the tank that covers the oil cooler part.
    INDUSTRIAL APPLICABILITY
    Since the heat exchanger produced in accordance with the present invention does not use a resin tank, the heat exchanger is characterized in that it is readily recycled, the corrosion resistance is excellent, and a step of caulking the tank is not required to produce the heat exchanger.
    Having described our invention as related to the present embodiments, it is our intention that the invention not be limited by any of the details of the description, unless otherwise specified, but rather be construed broadly within its spirit and scope as set out in the accompanying claims.

    Claims (10)

    1. A heat exchanger made of an aluminum alloy having a radiator part and an oil cooler part in combination and manufactured integrally by the brazing method, wherein a refrigerant tank for covering and sealing said oil cooler part is made of an aluminum alloy, an aluminum alloy containing Si in an amount from more than 7.0 wt% to 12.0 wt%, Fe in an amount from more than 0.05 wt% to 0.5 wt%, Cu in an amount from more than 0.4 wt% to 8.0 wt%, Zn in an amount from more than 0.5 wt% to 10.0 wt%, and the balance of aluminum and inevitable impurities is used as a filler material of brazing sheets that are used for said oil cooler part and are brazed in said tank, and said refrigerant tank is assembled integrally with said radiator part and said oil cooler part by brazing with said brazing material.
    2. The heat exchanger made of an aluminum alloy as claimed in claim 1, wherein the refrigerant tank is brazed and assembled integrally with a header plate of the radiator part, without using a packing.
    3. The heat exchanger made of an aluminum alloy as claimed in claim 1, wherein the heat exchanger is a double pipe-type, brazing-type heat exchanger, a inside-outside double pipe type heat exchanger, or a multi-plate type heat exchanger.
    4. A heat exchanger made of an aluminum alloy having a radiator part and an oil cooler part in combination and manufactured integrally by the brazing method, wherein a refrigerant tank for covering and sealing said oil cooler part is made of an aluminum alloy, an aluminum alloy containing Si in an amount from more than 7.0 wt% to 12.0 wt%, Fe in an amount from more than 0.05 wt% to 0.5 wt%, Cu in an amount from more than 0.4 wt% to 8.0 wt%, Zn in an amount from more than 0.5 wt% to 10.0 wt%, one or both of In in an amount from more than 0.002 wt% to 0.3 wt% and Sn in an amount from more than 0.002 wt% to 0.3 wt%, and the balance of aluminum and inevitable impurities is used as a filler material of brazing sheets that are used for said oil cooler part and are brazed in said tank, and said refrigerant tank is assembled integrally with said radiator part and said oil cooler part by brazing with said brazing material.
    5. The heat exchanger made of an aluminum alloy as claimed in claim 4, wherein the refrigerant tank is brazed and assembled integrally with a header plate of the radiator part, without using a packing.
    6. The heat exchanger made of an aluminum alloy as claimed in claim 4, wherein the heat exchanger is a double pipe-type, brazing-type heat exchanger, a inside-outside double pipe type heat exchanger, or a multi-plate type heat exchanger.
    7. A heat exchanger made of an aluminum alloy, wherein instead of the filler material in claim 1, an aluminum alloy containing Si in an amount from more than 7.0 wt% to 12.0 wt%, Cu in an amount from more than 0.4 wt% to 8.0 wt%, Fe in an amount from more than 0.05 wt% to 0.5 wt%, one kind or two or more kind elements selected from a group consisting of Zn in an amount from more than 0.5 wt% to 6.0 wt%, In in an amount of 0.3 wt% or less, and Sn in an amount of 0.3 wt% or less; and
         one kind or two or more kind elements selected from a group consisting of Li in an amount of 1.0 wt% or less, Na in an amount of 0.2 wt% or less, K in an amount of 0.2 wt% or less, Ca in an amount of 0.2 wt% or less, Sr in an amount of 0.2 wt% or less, Ba in an amount of 0.2 wt% or less, Bi in an amount of 0.5 wt% or less, Be in an amount of 0.2 wt% or less, Ni in an amount of 0.6 wt% or less, Cr in an amount of 0.2 wt% or less, Ti in an amount of 0.2 wt% or less, Zr in an amount of 0.2 wt% or less, V in an amount of 0.2 wt% or less, Ga in an amount of 1.0 wt% or less, and Ge in an amount of 2.0 wt% or less;
         the balance being Al and inevitable impurities, is used as the filler material.
    8. A heat exchanger made of an aluminum alloy, wherein instead of the filler material in claim 1, an aluminum alloy containing Si in an amount from more than 7.0 wt% to 12.0 wt%, Cu in an amount from more than 0.4 wt% to 8.0 wt%, Fe in an amount from more than 0.05 wt% to 0.5 wt%, Mn in an amount from more than 0.05 wt% to 1.2 wt%, one kind or two or more kind elements selected from a group consisting of Zn in an amount from more than 0.5 wt% to 6.0 wt%, In in an amount of 0.3 wt% or less, and Sn in an amount of 0.3 wt% or less; and
         one kind or two or more kind elements selected from a group consisting of Li in an amount of 1.0 wt% or less, Na in an amount of 0.2 wt% or less, K in an amount of 0.2 wt% or less, Ca in an amount of 0.2 wt% or less, Sr in an amount of 0.2 wt% or less, Ba in an amount of 0.2 wt% or less, Bi in an amount of 0.5 wt% or less, Be in an amount of 0.2 wt% or less, Ni in an amount of 0.6 wt% or less, Cr in an amount of 0.2 wt% or less, Ti in an amount of 0.2 wt% or less, Zr in an amount of 0.2 wt% or less, V in an amount of 0.2 wt% or less, Ga in an amount of 1.0 wt% or less, and Ge in an amount of 2.0 wt% or less;
         the balance being Al and inevitable impurities, is used as the filler material.
    9. A heat exchanger made of an aluminum alloy, wherein instead of the filler material in claim 1, an aluminum alloy containing Si in an amount from more than 7.0 wt% to 12.0 wt%, Cu in an amount from more than 0.4 wt% to 8.0 wt%, Fe in an amount from more than 0.05 wt% to 0.5 wt%, one kind or two kind elements selected from a group consisting of Ga in an amount of 1.0 wt% or less, and Ge in an amount of 2.0 wt% or less; and
         one kind or two or more kind elements selected from a group consisting of Li in an amount of 1.0 wt% or less, Na in an amount of 0.2 wt% or less, K in an amount of 0.2 wt% or less, Ca in an amount of 0.2 wt% or less, Sr in an amount of 0.2 wt% or less, Ba in an amount of 0.2 wt% or less, Bi in an amount of 0.5 wt% or less, Be in an amount of 0.2 wt% or less, Ni in an amount of 0.6 wt% or less, Cr in an amount of 0.2 wt% or less, Ti in an amount of 0.2 wt% or less, Zr in an amount of 0.2 wt% or less, and V in an amount of 0.2 wt% or less;
         the balance being Al and inevitable impurities, is used as the filler material.
    10. A heat exchanger made of an aluminum alloy , wherein instead of the filler material in claim 1, an aluminum alloy containing Si in an amount from more than 7.0 wt% to 12.0 wt%, Cu in an amount from more than 0.4 wt% to 8.0 wt%, Fe in an amount from more than 0.05 wt% to 0.5 wt%, Mn in an amount from more than 0.05 wt% to 1.2 wt%, one kind or two kind elements selected from a group consisting of Ga in an amount of 1.0 wt% or less, and Ge in an amount of 2.0 wt% or less; and
         one kind or two or more kind elements selected from a group consisting of Li in an amount of 1.0 wt% or less, Na in an amount of 0.2 wt% or less, K in an amount of 0.2 wt% or less, Ca in an amount of 0.2 wt% or less, Sr in an amount of 0.2 wt% or less, Ba in an amount of 0.2 wt% or less, Bi in an amount of 0.5 wt% or less, Be in an amount of 0.2 wt% or less, Ni in an amount of 0.6 wt% or less, Cr in an amount of 0.2 wt% or less, Ti in an amount of 0.2 wt% or less, Zr in an amount of 0.2 wt% or less, and V in an amount of 0.2 wt% or less;
         the balance being Al and inevitable impurities, is used as the filler material.
    EP97918343A 1996-05-02 1997-04-30 Heat exchanger of aluminum alloy Expired - Lifetime EP0837296B1 (en)

    Applications Claiming Priority (4)

    Application Number Priority Date Filing Date Title
    JP8111546A JPH09296996A (en) 1996-05-02 1996-05-02 Heat exchanger made of aluminum alloy
    JP111546/96 1996-05-02
    JP11154696 1996-05-02
    PCT/JP1997/001491 WO1997042457A1 (en) 1996-05-02 1997-04-30 Heat exchanger of aluminum alloy

    Publications (3)

    Publication Number Publication Date
    EP0837296A1 true EP0837296A1 (en) 1998-04-22
    EP0837296A4 EP0837296A4 (en) 1999-04-28
    EP0837296B1 EP0837296B1 (en) 2003-04-09

    Family

    ID=14564128

    Family Applications (1)

    Application Number Title Priority Date Filing Date
    EP97918343A Expired - Lifetime EP0837296B1 (en) 1996-05-02 1997-04-30 Heat exchanger of aluminum alloy

    Country Status (6)

    Country Link
    EP (1) EP0837296B1 (en)
    JP (1) JPH09296996A (en)
    KR (1) KR100295587B1 (en)
    CN (1) CN1131414C (en)
    DE (1) DE69720634T2 (en)
    WO (1) WO1997042457A1 (en)

    Families Citing this family (9)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    JP2007101088A (en) * 2005-10-05 2007-04-19 Calsonic Kansei Corp Tank structure for heat exchanger
    JP4825507B2 (en) * 2005-12-08 2011-11-30 古河スカイ株式会社 Aluminum alloy brazing sheet
    JP5049488B2 (en) * 2005-12-08 2012-10-17 古河スカイ株式会社 Method for producing aluminum alloy brazing sheet
    WO2008067970A1 (en) * 2006-12-04 2008-06-12 Behr Gmbh & Co. Kg Casing for holding a fluid for a heat exchanger, method for producing a casing of this type and heat exchanger
    FR2991036B1 (en) * 2012-05-22 2022-03-11 Valeo Systemes Thermiques MANIFOLD PLATE FOR A MANIFOLD BOX OF A MOTOR VEHICLE HEAT EXCHANGER
    DE102016116265A1 (en) 2016-08-31 2018-03-01 Faurecia Emissions Control Technologies, Germany Gmbh Solder based on copper and use of the solder material
    JP6711317B2 (en) * 2017-06-13 2020-06-17 株式会社デンソー Heat exchanger
    CN108225427B (en) * 2018-01-10 2020-07-28 浙江银轮机械股份有限公司 Brazing evaluation system of oil cooler under low vacuum condition
    DE102018109233A1 (en) 2018-04-18 2019-10-24 Hanon Systems System for connecting housing elements of a device for heat transfer

    Citations (4)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US4211827A (en) * 1979-03-15 1980-07-08 Swiss Aluminium Ltd. Al-Si-Sn Alloy clad composite
    JPH04161798A (en) * 1990-10-26 1992-06-05 Showa Alum Corp Double tube heat exchanger
    EP0637481A1 (en) * 1993-08-03 1995-02-08 The Furukawa Electric Co., Ltd. Aluminum alloy brazing material and brazing sheet for heat-exchangers and method for fabricating aluminum alloy heat-exchangers
    US5422191A (en) * 1994-02-14 1995-06-06 Kaiser Aluminum & Chemical Corporation Aluminum-lithium filler alloy for brazing

    Family Cites Families (5)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    JP2875281B2 (en) * 1989-05-15 1999-03-31 カルソニック株式会社 How to attach oil cooler to radiator tank
    JP3183523B2 (en) * 1991-02-04 2001-07-09 カルソニックカンセイ株式会社 Pipe tank for aluminum heat exchanger with built-in oil cooler and method of manufacturing the same
    JPH0630689U (en) * 1992-09-21 1994-04-22 カルソニック株式会社 Oil cooler mounting structure
    JP2570381Y2 (en) * 1992-09-21 1998-05-06 カルソニック株式会社 Oil cooler mounting structure
    JPH0790442A (en) 1993-09-06 1995-04-04 Furukawa Electric Co Ltd:The Aluminum alloy brazing sheet for heat exchanger and manufacture of aluminum alloy-made heat exchanger

    Patent Citations (4)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US4211827A (en) * 1979-03-15 1980-07-08 Swiss Aluminium Ltd. Al-Si-Sn Alloy clad composite
    JPH04161798A (en) * 1990-10-26 1992-06-05 Showa Alum Corp Double tube heat exchanger
    EP0637481A1 (en) * 1993-08-03 1995-02-08 The Furukawa Electric Co., Ltd. Aluminum alloy brazing material and brazing sheet for heat-exchangers and method for fabricating aluminum alloy heat-exchangers
    US5422191A (en) * 1994-02-14 1995-06-06 Kaiser Aluminum & Chemical Corporation Aluminum-lithium filler alloy for brazing

    Non-Patent Citations (2)

    * Cited by examiner, † Cited by third party
    Title
    PATENT ABSTRACTS OF JAPAN vol. 016, no. 456 (M-1314), 22 September 1992 -& JP 04 161798 A (SHOWA ALUM CORP), 5 June 1992 *
    See also references of WO9742457A1 *

    Also Published As

    Publication number Publication date
    CN1190458A (en) 1998-08-12
    EP0837296B1 (en) 2003-04-09
    DE69720634D1 (en) 2003-05-15
    DE69720634T2 (en) 2003-12-18
    JPH09296996A (en) 1997-11-18
    KR100295587B1 (en) 2001-11-05
    EP0837296A4 (en) 1999-04-28
    CN1131414C (en) 2003-12-17
    WO1997042457A1 (en) 1997-11-13
    KR19990028645A (en) 1999-04-15

    Similar Documents

    Publication Publication Date Title
    KR0184019B1 (en) Aluminum alloy brazing material and brazing sheet for heat-exchanges
    US6261706B1 (en) Aluminum alloy clad material for heat exchangers exhibiting high strength and excellent corrosion resistance
    US4991647A (en) Heat exchanger
    US6523605B2 (en) Heat exchanger made of an aluminum alloy
    JP2008303405A (en) Aluminum alloy material for header plate of heat exchanger, and soldering body for heat exchanger
    JP2014519413A (en) Alloy for heat exchange tube with internal protective cladding and brazed turbulator
    BR0107965B1 (en) fin load material for heat exchanger, its production process and the process of forming a brazed brazed article.
    JP4916334B2 (en) Aluminum alloy clad material for heat exchangers with excellent strength and brazing
    EP0837296A1 (en) Heat exchanger of aluminum alloy
    US5518070A (en) Stacked tube type heat exchanger
    EP0867682A2 (en) Al-alloy heat exchanger
    JP2005314719A (en) Aluminum alloy clad material for automotive heat exchanger
    JPH10249580A (en) Al alloy filler metal and manufacture of al alloy made heat exchanger
    JP2004076145A (en) Sacrificial material for heat exchanger, and clad material made of aluminum alloy for heat exchanger
    JP3876180B2 (en) Aluminum alloy three-layer clad material
    JP4236187B2 (en) Aluminum alloy clad material for automotive heat exchanger
    JP2007182602A (en) Aluminum brazing alloy with suppressed erosion during brazing, brazing sheet using the same, header pipe for heat exchanger, and heat exchanger
    JP2990027B2 (en) Method of manufacturing aluminum alloy brazing sheet for heat exchanger
    JP3243188B2 (en) Aluminum alloy clad material for heat exchangers with excellent alkali corrosion resistance
    JP2007113030A (en) High strength aluminum alloy with excellent brazability, high strength aluminum alloy sheet and heat exchanger
    JP4475617B2 (en) Aluminum alloy clad material for heat exchangers with excellent corrosion resistance
    JP3536065B2 (en) Aluminum alloy brazing sheet strip for forming a tube by bending
    JPH0797651A (en) Production of aluminum alloy brazing sheet for heat exchanger and heat exchanger made of aluminum alloy
    JPH1072635A (en) Aluminum alloy clad material for heat exchanger, excellent in alkaline corrosion resistance
    JP3538507B2 (en) Aluminum alloy clad material for heat exchanger with excellent alkali corrosion resistance

    Legal Events

    Date Code Title Description
    PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

    Free format text: ORIGINAL CODE: 0009012

    AK Designated contracting states

    Kind code of ref document: A1

    Designated state(s): DE FR GB IT

    17P Request for examination filed

    Effective date: 19980331

    A4 Supplementary search report drawn up and despatched

    Effective date: 19990315

    AK Designated contracting states

    Kind code of ref document: A4

    Designated state(s): DE FR GB IT

    17Q First examination report despatched

    Effective date: 20010122

    GRAH Despatch of communication of intention to grant a patent

    Free format text: ORIGINAL CODE: EPIDOS IGRA

    GRAH Despatch of communication of intention to grant a patent

    Free format text: ORIGINAL CODE: EPIDOS IGRA

    GRAA (expected) grant

    Free format text: ORIGINAL CODE: 0009210

    AK Designated contracting states

    Designated state(s): DE FR GB IT

    REG Reference to a national code

    Ref country code: GB

    Ref legal event code: FG4D

    ET Fr: translation filed
    REG Reference to a national code

    Ref country code: FR

    Ref legal event code: TP

    PLBE No opposition filed within time limit

    Free format text: ORIGINAL CODE: 0009261

    STAA Information on the status of an ep patent application or granted ep patent

    Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

    26N No opposition filed

    Effective date: 20040112

    REG Reference to a national code

    Ref country code: GB

    Ref legal event code: 732E

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: DE

    Payment date: 20070426

    Year of fee payment: 11

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: GB

    Payment date: 20070425

    Year of fee payment: 11

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: IT

    Payment date: 20070521

    Year of fee payment: 11

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: FR

    Payment date: 20070411

    Year of fee payment: 11

    GBPC Gb: european patent ceased through non-payment of renewal fee

    Effective date: 20080430

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: DE

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20081101

    REG Reference to a national code

    Ref country code: FR

    Ref legal event code: ST

    Effective date: 20081231

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: FR

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20080430

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: GB

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20080430

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: IT

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20080430