Classifications

• • 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
  • C22C21/10—Alloys based on aluminium with zinc as the next major constituent
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
  • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
  • B22D11/001—Continuous casting of metals, i.e. casting in indefinite lengths of specific alloys
  • B22D11/003—Aluminium alloys
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
  • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
  • B22D11/06—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars
  • B22D11/0622—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars formed by two casting wheels
• • 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
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
  • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
  • C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
  • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
  • C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
  • C22F1/053—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon of alloys with zinc as the next major constituent

Definitions

• the invention relates to the field of thin strips (thickness ⁇ 0.3 mm) of aluminum alloy intended for the manufacture of heat exchangers, in particular those used for the cooling of engines and the air conditioning of the passenger compartment of motor vehicles.
• Aluminum alloy strips for exchangers are used either bare or coated on one or two sides with a brazing alloy.
• the invention relates more particularly to the uncoated strips used for the fins or spacers fixed to tubes or elements in contact with the cooling fluid.
• Aluminum alloys are now very widely used in the manufacture of heat exchangers for the automobile because of their low density, which allows a saving in weight, in particular compared to copper alloys, while ensuring a good thermal conduction, a ease of implementation and good corrosion resistance.
• These exchangers include tubes for the circulation of the internal heating or cooling fluid and fins or spacers to ensure the heat transfer between the internal fluid and the external fluid, and their manufacture is carried out either by mechanical assembly or by brazing.
• the fins or spacers must ensure protection of the tubes against perforation by galvanic effect, that is to say by providing for the fins an alloy having a lower electrochemical corrosion potential than for the tubes, so that the fin acts as a sacrificial anode.
• the most commonly used alloy for tubes being alloy 3003, an alloy of the same type is usually used for the fins with an addition 0.5 to 2% zinc.
• the strips in this type of alloy are generally obtained by semi-continuous casting of a plate, homogenization of this plate, hot rolling, then cold rolling with possibly an intermediate annealing and / or a final annealing. They can also be obtained by continuous casting of bands between two belts ("twin-belt casting") or between two cooled cylinders ("twin-roll casting”). It is known that with this latter technique, in order to obtain a fine-grained structure in Al-Mn alloys, a homogenization of the blank is applied which eliminates the segregation resulting from casting, which leads to a good compromise between the mechanical strength and formability.
• Patent application WO 98/52707 to the applicant describes a process for manufacturing aluminum alloy strips containing at least one of the elements Fe (from 0.15 to 1.5%) or Mn (from 0.35 at 1.9%) with Fe + Mn ⁇ 2.5%, and possibly containing Si ( ⁇ 0.8%), Mg ( ⁇ 0.2%), Cu ( ⁇ 0.2%), Cr ( ⁇ 0 , 2%) or Zn ( ⁇ 0.2%) by continuous casting between cooled and shrunk cylinders to a thickness between 1 and 5 mm, followed by cold rolling, the force applied to the casting cylinders, expressed in tonnes per meter of strip width, being less than 300 + 2000 / e, e being the thickness of the strip expressed in mm.
• the use of these bands for the production of brazed exchanger fins is mentioned.
• Patent application WO 00/05426 of Alcan International describes the manufacture of strips for fins made of aluminum alloy of composition: Fe: 1, -2 - 1.8%,
• Patent applications WO 01/53552 and WO 01/53553 of Alcan International also relate to the manufacture of strips for fins made of iron alloys containing up to 2.4% of iron by continuous casting and very rapid cooling. The aim is to obtain a more negative corrosion potential. Purpose of the invention
• the fins or spacers must play a galvanic protection role of the tubes, they must not however be too deteriorated by corrosion during the life of the exchanger. Indeed, it is necessary to maintain a sufficient integrity of the material, because if it punctures too quickly, the heat exchange will be less effective due to the loss of useful surface. There could even be a separation of the fin and the tube, which would block the thermal conduction between these components.
• the object of the invention is therefore to obtain strips for fins or spacers of aluminum alloy heat exchangers intended in particular for the automotive industry, having both good mechanical strength, good formability and good resistance to perforating corrosion while having the role of a sacrificial anode.
• the subject of the invention is strips of aluminum alloy with a thickness ⁇ 0.3 mm, intended for the manufacture of heat exchangers, of composition (% by weight): Si ⁇ 1.5 Fe ⁇ 2.5 Cu ⁇ 0.8 Mg ⁇ 1.0 Mn: ⁇ 1.8 Zn ⁇ 2.0 In ⁇ 0.2 Sn ⁇ 0.2 Bi ⁇ 0.2 Ti ⁇ 0.2 Cr ⁇ 0.25 Zr ⁇ 0.25 Si + Fe + Mn + Mg> 0.8, other elements ⁇ 0.05 each and ⁇ 0.15 in total, aluminum residue, having a difference in corrosion potential between the surface and the mid-thickness, measured with respect to a saturated calomel electrode according to ASTM G69, d '' at least 10 mV.
• the invention also relates to a method of manufacturing such strips by continuous casting under conditions favoring the formation of segregations at the heart of the strip, possibly hot rolling, cold rolling with possibly one or more intermediate annealing (s). or final from 1 to 20 h at a temperature between 200 and 450 ° C.
• FIG. 1 represents the evolution of the corrosion potential, measured with respect to a saturated calomel electrode, of a strip according to the invention of the alloy of example 1, as a function of the depth with respect to the surface.
• FIG. 2 likewise represents the evolution of the corrosion potential of an alloy strip from Example 2.
• the Applicant has found that by using, for alloys of type 3000 (Al-Mn) or of type 8000 (Al-Fe) with possible addition of zinc, the casting continues under specific casting conditions and with a transformation range suitable, we obtained strips with a corrosion potential gradient in their thickness, and that this property favored lateral propagation rather than perpendicular to the corrosion surface, which ensured the sacrificial effect while avoiding perforation, and therefore deterioration of the fin or the interlayer over time.
• This potential gradient is at least 10 mV. According to a hypothesis put forward by the inventors, this difference could be linked to the presence, for the particular casting conditions selected, of segregations at the center of the strip, a phenomenon that is usually sought to avoid, and which leads to differences in composition. in solid solution in the thickness of the strips.
• the zinc content varies depending on the alloy used for the tubes, so as to obtain a difference in electrochemical potential between the tubes and the fins that is sufficient to allow the fin to fulfill its role as a sacrificial anode. , and not too high to avoid too rapid deterioration.
• indium, tin and / or bismuth can also be added up to a content of 0.2%.
• the zinc content is preferably between 1.0 and 1.5%.
• tubes of Al-Mn ps alloy loaded with copper such as for example the alloys with more than 0.4%> of copper described in patent application EP 1075935 of the applicant, the zinc content must rather be kept below 0.8%.
• the copper content is preferably kept below 0.5% o.
• the possible addition of titanium up to 0.2%, zirconium up to 0.25% and / or chromium up to 0.25% makes it possible to improve the heat resistance ("resistance SAG") of the alloy.
• the alloy used is an alloy of the type
• silicon preferably beyond 0.5% and up to 1% contributes to increasing the solidification interval of the alloy, which promotes the appearance of segregation during casting. Above 1%, there is a risk of reaching the burning temperature of the alloy during the brazing operation of the exchanger.
• a particularly suitable composition range is as follows: Si: 0.8 - 1.5 Fe: 0.7 - 1.3 Mn ⁇ 0.1 Cu ⁇ 0.1 Mg ⁇ 0.1 and, preferably, Si: 1.0 - 1.3 and Fe: 0.9 - 1.2.
• the method of manufacturing the strips according to the invention comprises the development of the alloy from a charge adjusted to obtain the desired alloy composition.
• the metal is then continuously cast in the form of a strip of thickness between 1 and 30 mm, either by casting between belts between 12 and 30 mm, or, preferably, by casting between two cooled and hooped cylinders, at a thickness between 1 and 12 mm.
• casting parameters are chosen which favor the appearance of relatively large segregations at the heart of the cast strip. In the case of casting between rolls, this requires that the contact between the metal and the cooled rolls is the best possible, so as to increase the thermal gradient at the surface of the metal during casting, which promotes segregation.
• the various parameters on which one can act are in particular the length of the arc of contact between the metal and the cylinders, the force exerted by the cylinders during casting and the temperature of the frets of the cylinders.
• a high contact arc preferably greater than 60 mm, is favorable for the formation of segregations. It is likewise a high effort, preferably greater than 100 + 2000 / and / m of width of the cast strip, e being the thickness of the cast strip expressed in mm.
• the temperature of the frets must be as low as possible, preferably less than 100 ° C.
• the casting strip is optionally, in the case of casting between belts, hot rolled, and then cold rolled. On the other hand, the strip cast between cylinders is directly cold rolled.
• the final thickness is small enough, it is necessary to provide at least one intermediate annealing at a temperature between 200 and 450 ° C. If the metal is to be delivered in the annealed condition, the laminated strip is annealed at a temperature between 200 and 450 ° C. In the case where the metal is delivered in the work hardened state, the transformation range is adapted so that the reduction rate is adjusted to the target work hardening rate.
• the strips according to the invention make it possible to produce fins or spacers of heat exchangers having a high mechanical strength, which makes it possible to reduce the thickness compared to a fin or a spacer according to the prior art, while keeping good formability.
• the fin or the spacer plays its sacrificial role, but corrosion progresses laterally parallel to the surface, which prevents or delays perforation, ensures the integrity of the tube-fin assembly, and therefore a heat exchange continued.
• the strips have a coarse-grained microstructure, which is favorable to heat resistance during brazing.
• a 5 mm thick strip was cast on a Jumbo 3Cm TM continuous casting installation from the company Pechiney Rhenalu, at a width of 1420 mm, with a force between the cylinders of 780 1, a contact arc of 70 mm and a temperature of cylinder frets of 70 ° C.
• the strip was then cold rolled in one pass to the thickness 0.7 mm, then subjected to an intermediate annealing of 12 h in an air oven programmed at 520 ° C to bring the metal to a temperature of l '' 380 ° C, and cold rolled in three passes up to 130 ⁇ m.
• the first part of the strip underwent a restorative annealing of 2 h at 350 ° C, then a rolling up to 100 ⁇ m.
• a second part underwent a recrystallization annealing of 2 h at 400 ° C, then a rolling up to 100 ⁇ m.
• a third part underwent the same annealing, but rolling up to 75 ⁇ m.
• strips of alloy 3003 with zinc of composition were manufactured:
• the metal obtained by continuous casting has both better mechanical strength and better elongation than the metal obtained from traditional casting.
• the evolution of the corrosion potential in the thickness was measured, relative to a saturated calomel electrode according to the ASTM G69 standard. We can see in the figure the presence, below the surface, and on a depth of about 15 ⁇ m, of an area in which the potential evolves rapidly from -890 mV to -870 mV.
• a 6.1 mm thick strip was cast on a Davy TM continuous casting installation from the company Pechiney Eurofoil, at a width of 1740 mm, with a force between the cylinders of 550 t, a contact arc of 60 mm and a temperature of the frets of the cylinders of 42 ° C.
• the strip was then cold rolled to the thickness of 80 ⁇ m, to obtain an H19 type metallurgical state.
• the mechanical characteristics of this strip are as follows:
• this metal produced by continuous casting, has an excellent compromise between mechanical strength and elongation.
• a typical brazing cycle was then applied to the metal, in an oven under a nitrogen atmosphere, comprising a 2-minute plateau at 600 ° C.
• the elastic limit after brazing, R 0 equal to 53 MPa is significantly higher than that obtained for strips of alloy 3003 traditionally used, obtained by conventional casting (of the order of 40-45 MPa). From the point of view of corrosion resistance, we find on these alloys 8xxx, as we can see in Figure 2, and always in connection with the casting process used, an evolution of the corrosion potential in the thickness of the metal, the beneficial nature of which was explained above for 3xxx alloys.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• Materials Engineering (AREA)
• Metallurgy (AREA)
• Organic Chemistry (AREA)
• Crystallography & Structural Chemistry (AREA)
• Thermal Sciences (AREA)
• Physics & Mathematics (AREA)
• Continuous Casting (AREA)
• Conductive Materials (AREA)
• Separation By Low-Temperature Treatments (AREA)
• Prevention Of Electric Corrosion (AREA)
• Heat Treatment Of Sheet Steel (AREA)
• Metal Rolling (AREA)
• Laminated Bodies (AREA)

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• 2001
  • 2001-11-19 FR FR0114948A patent/FR2832497B1/fr not_active Expired - Fee Related
• 2002
  • 2002-11-12 US US10/495,118 patent/US7811394B2/en not_active Expired - Fee Related
  • 2002-11-12 DE DE60211011T patent/DE60211011T2/de not_active Expired - Lifetime
  • 2002-11-12 DE DE02790555T patent/DE02790555T1/de active Pending
  • 2002-11-12 JP JP2003545854A patent/JP4484241B2/ja not_active Expired - Fee Related
  • 2002-11-12 WO PCT/FR2002/003866 patent/WO2003044235A2/fr active IP Right Grant
  • 2002-11-12 AU AU2002365952A patent/AU2002365952A1/en not_active Abandoned
  • 2002-11-12 EP EP02790555A patent/EP1446511B1/de not_active Expired - Lifetime
  • 2002-11-12 ES ES02790555T patent/ES2263841T3/es not_active Expired - Lifetime
  • 2002-11-12 AT AT02790555T patent/ATE324470T1/de not_active IP Right Cessation
  • 2002-11-12 CA CA2467681A patent/CA2467681C/fr not_active Expired - Fee Related
• 2006
  • 2006-06-23 US US11/473,177 patent/US20060260723A1/en not_active Abandoned

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