EP0950127B1 - Protection amelioree contre la corrosion galvanique - Google Patents

Protection amelioree contre la corrosion galvanique Download PDF

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Publication number
EP0950127B1
EP0950127B1 EP97945553A EP97945553A EP0950127B1 EP 0950127 B1 EP0950127 B1 EP 0950127B1 EP 97945553 A EP97945553 A EP 97945553A EP 97945553 A EP97945553 A EP 97945553A EP 0950127 B1 EP0950127 B1 EP 0950127B1
Authority
EP
European Patent Office
Prior art keywords
noble metal
metal member
aluminum
less noble
less
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.)
Expired - Lifetime
Application number
EP97945553A
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German (de)
English (en)
Other versions
EP0950127A1 (fr
Inventor
Thomas J. Garosshen
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.)
Carrier Corp
Original Assignee
Carrier Corp
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Filing date
Publication date
Priority claimed from US08/734,146 external-priority patent/US6578628B1/en
Application filed by Carrier Corp filed Critical Carrier Corp
Publication of EP0950127A1 publication Critical patent/EP0950127A1/fr
Application granted granted Critical
Publication of EP0950127B1 publication Critical patent/EP0950127B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F19/00—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers
    • F28F19/02—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings
    • F28F19/06—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings of metal
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process

Definitions

  • This invention relates generally to protecting metals from a corrosive environment, and more specifically to protecting copper-aluminum heat exchangers for use in air conditioners.
  • Galvanic corrosion occurs when two dissimilar metals make contact with one another in the presence of an electrolyte thereby forming a galvanic couple.
  • the more noble metal (higher on the galvanic series) provides the surface area for the reduction reaction and the less noble metal (lower on the galvanic series) corrodes in an oxidation process.
  • the oxidation occurs in the greatest amount at the interface of the two metals but may also occur at some distance away from the actual interface.
  • the most common electrolyte is salt water in the air. A fine salt water mist may be blown inland for up to fifty miles from the coast. Sulfur dioxide from industrial pollution also creates an electrolyte when it combines with moisture in the air.
  • a common method of preventing galvanic corrosion has been to coat the exposed surfaces of the metals with various types of paint.
  • These protective coatings have met with only limited success for a number of reasons.
  • the main problem with coatings is that their effectiveness at preventing corrosion is degraded by exposure to the environment such as ultraviolet light and acid rain.
  • Another common problem is that the coating materials often do not adhere well to the metal substrates and eventually flake off or erode away exposing the metal substrates.
  • such protective coatings are somewhat porous and allow the electrolyte to penetrate the surface of the substrates and connect the galvanic couple.
  • the application of protective coatings to the surfaces of certain articles can negatively affect their performance.
  • Japanese patent publication JP 53 132 449 A discloses a heat exchanger manufactured from an iron pipe and aluminum fins wherein the entire assembly is coated with an aluminum braze clad.
  • British patent publication GB 2 284 882 A discloses a fin and tube heat exchanger manufactured from a tube, preferably steel, which is coated with a metallic coating, in particular a soft malleable metallic coating, to provide a corrosion barrier on the tube to prevent corrosion of the tube itself and to improve bonding between the tube and the fins.
  • French patent publication FR 2 179 317 A discloses a heat exchanger manufactured from copper tubes and aluminum fins wherein the tube is coated with a solder applied via a hot dip process to a thickness of 20 to 50 micrometers.
  • Japanese patent publication JP 63 034 495 A discloses a heat exchanger having aluminum fins and an aluminum alloy tube which is flame-coated with an aluminum alloy braze which may contain zinc.
  • the present invention relates to an advanced galvanic corrosion protection method.
  • an article made of two metals, one being more noble than the other the outer surface of the more noble metal is treated with a metal which is more galvanically compatible the with less noble metal than the more noble metal is galvanically compatible with the less noble metal prior to assembly to form a protective layer on the surface of the more noble metal and between the less noble metal and the more noble metal whereby galvanic corrosion of the less noble metal is reduced.
  • the invention greatly reduces the oxidation reduction process which causes corrosion of the less noble metal, for example an aluminum fin mounted on a copper tube of a heat exchanger, in the presence of an electrolyte.
  • the present invention will be described in to providing for galvanic corrosion protection of a copper-aluminum heat exchanger.
  • the present invention is not limited to this specific example and could be used in connection with a number of arrangements where dissimilar metals are in contact with one another in the presence of an electrolyte.
  • FIG. 1 illustrates a fin/tube heat exchanger 10 of the type typically used in air conditioning units.
  • the heat exchanger includes one or more flow circuits for carrying refrigerant through the heat exchanger unit.
  • the heat exchanger 10 contains a single flow circuit tube 2 consisting of an inlet line and an outlet line 4 which are connected at one end of the heat exchanger 10 by means of a 90° tube bend 5. It should be evident, however, that more circuits may be added to the unit depending upon the demands of the system.
  • the unit further includes a series of fins 6 comprising radial disposed plate like elements spaced along the length of the flow circuit. The fins 6 are supported in the assembly between a pair of end plates 7 and 8 to define a gas flow passage through which a gas passes over the extension of the tube 2 and between the spaced fins 6.
  • heat exchangers of this type are commonly exposed in use to corrosive environments.
  • heat exchangers of this type are fabricated utilizing copper tubes for the circuit flow tubes and aluminum for the fins.
  • the fins are disposed in contact with the tubes and draw heat away from the tubes through conductive heat transfer and then dissipate the heat through convective heat transfer to the gas (commonly air) flowing over the tubes.
  • Copper is utilized in tube construction because of its good heat transfer properties, general resistance to corrosion, and case of repair.
  • the fins are fabricated from aluminum because of its good heat transfer properties, ease of fabrication, and low cost. Heat exchangers fabricated entirely from copper, as well as entirely from aluminum, are utilized in certain applications to avoid the problems of galvanic corrosion but at the cost of trades characterized above.
  • Aluminum is significantly lower on the galvanic series, i.e. less noble, than copper. It is for this reason that the aluminum oxidizes or corrodes when it is in contact with copper in the presence of an electrolyte.
  • the interface of the tube and fin is where the galvanic couple is made and where the corrosion of the aluminum fins occurs. Once the fin has corroded at the intersection the fin is no longer in contact with the tube and thus the heat exchanger efficiency is gready reduced because the fin loses its ability to conduct heat away from the tube.
  • the exposed surfaces of the tubes 2 are coated or enriched with aluminum or a metal more galvanically compatible with aluminum.
  • Aluminum is the best candidate material since a galvanic couple will not form between the aluminum coating and the aluminum fins 6.
  • active metals such as zinc, tin magnesium, gallium, cadmium and lead will also reduce the extent of the galvanic couple and thus the rate of oxidation of the fin material.
  • the coating or surface enrichment of the copper tubes 12 with aluminum is accomplished prior to the assembly of he heat exchanger 10.
  • the aluminizing of copper is a well known practice and can be accomplished to a degree precision so as to virtually eliminate the above cited problems with conventional coating for corrosion protection.
  • Several processes for aluminizing the copper tubes are known in industry and contemplared by the present invention.
  • the coating processes include hot dipping, electroplating, aluminum filled painting and slurries, and thermal spraying.
  • the surface enrichment processes include ion vapor deposition, chemical vapor deposition, and physical vapor deposition.
  • the critical aspect of the present invention is the production of a uniform coating of aluminum over the entire surface of the flow circuit tubes 2. Regardless of the process contemplated the variables of tube surface preparation, tube preheat temperature, coating composition, and coating thickness must be carefully controlled to achieve the proper results of the present invention.
  • the preparation of the exposed surfaces of the tube is preferred to remove the surface oxide layer from the copper to ensure that the coating material will adhere well to the tube.
  • a number of surface preparation processes are known in industry and include the use of reducing gases, fluxes and shot blasting.
  • the tube preheat temperatures should be controlled between 24 C and 600 C to prevent the dissolution of copper and to limit intermetallic growth during the coating process.
  • the coating have high ductility to allow for the subsequent assembly of the heat exchanger without damaging the coating.
  • the ductility of the coating is determined in part by the coating composition and the thickness of the coating.
  • any metallic composition more galvanically compatible with the fin material than the tube material would slow the oxidation rate of the fins 6, while the ideal coating material would exactly match the fin material.
  • Certain aluminum alloys are considered for use in the present invention and they comprise aluminum combined with silicon and aluminum combined with zinc.
  • the coating should advantageously be thick enough to prevent the penetration of the electrolyte. However, as any coating has a somewhat negative effect on the heat transfer of the unit, excessively thick protective layer should be avoided.
  • the optimal range of thickness contemplated by the present invention is .1 mils to 2 mils (2.5 to 51 micrometers).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Prevention Of Electric Corrosion (AREA)
  • Electroplating Methods And Accessories (AREA)

Claims (4)

  1. Procédé de réduction de la corrosion galvanique d'un premier élément d'un métal moins noble dans un assemblage avec un second élément d'un métal plus noble lorsque l'assemblage est exposé à un électrolyte, le premier élément de métal moins noble assemblé ayant une surface en contact avec une surface exposée du second élément de métal plus noble, comprenant l'étape de traitement de la surface exposée du second élément de métal plus noble avec un métal galvaniquement plus compatible avec le premier élément de métal moins noble que le second élément de métal plus noble est galvaniquement compatible avec le premier élément de métal moins noble avant l'assemblage du premier élément de métal moins noble avec le second élément de métal plus noble par lequel une couche protectrice est formée sur la surface exposée du second élément de métal plus noble et entre le premier élément de métal moins noble et le second élément de métal plus noble, dans lequel le second élément de métal plus noble est constitué essentiellement de cuivre, le premier élément de métal moins noble est constitué essentiellement d'aluminium, et le métal de traitement comprend un métal choisi parmi le groupe composé de l'aluminium, d'un alliage d'aluminium contenant du silicium, d'un alliage d'aluminium contenant du zinc, du zinc, de l'étain, du magnésium, du gallium, du cadmium, du plomb et de combinaisons de ceux-ci.
  2. Procédé selon la revendication 1, caractérisé en ce que l'assemblage est un échangeur thermique dans lequel le second élément de métal plus noble est un tube de transfert thermique et le premier élément de métal moins noble est au moins une ailette métallique assemblée sur la surface externe dudit tube de transfert thermique.
  3. Procédé selon la revendication 1 où 2, dans lequel l'étape de traitement inclut un processus de revêtement choisi parmi un processus de métallisation par immersion, un processus de dépôt électrolytique, un processus de peinture ou un processus de revêtement à diffusion.
  4. Procédé selon l'une quelconque des revendications précédentes dans lequel la couche de métal de traitement présente une épaisseur comprise entre 0,0001 pouce et 0,002 pouce (2,5 à 51 micromètres).
EP97945553A 1996-10-21 1997-09-30 Protection amelioree contre la corrosion galvanique Expired - Lifetime EP0950127B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US73414596A 1996-10-21 1996-10-21
US734146 1996-10-21
US08/734,146 US6578628B1 (en) 1996-10-21 1996-10-21 Article exhibiting increased resistance to galvanic corrosion
US734145 1996-10-21
PCT/US1997/018122 WO1998017841A1 (fr) 1996-10-21 1997-09-30 Protection amelioree contre la corrosion galvanique

Publications (2)

Publication Number Publication Date
EP0950127A1 EP0950127A1 (fr) 1999-10-20
EP0950127B1 true EP0950127B1 (fr) 2005-05-18

Family

ID=27112678

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97945553A Expired - Lifetime EP0950127B1 (fr) 1996-10-21 1997-09-30 Protection amelioree contre la corrosion galvanique

Country Status (12)

Country Link
EP (1) EP0950127B1 (fr)
JP (1) JP2001502757A (fr)
KR (1) KR100334213B1 (fr)
CN (2) CN101063206A (fr)
BR (1) BR9712540A (fr)
DE (1) DE69733317T2 (fr)
EG (1) EG22317A (fr)
ES (1) ES2238731T3 (fr)
ID (1) ID18594A (fr)
SA (1) SA97180556B1 (fr)
WO (1) WO1998017841A1 (fr)
ZA (1) ZA978931B (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6325138B1 (en) * 1996-10-21 2001-12-04 Carrier Corporation Article exhibiting improved resistance to galvanic corrosion
SE524615C2 (sv) * 1999-06-30 2004-09-07 Volvo Personvagnar Ab Arrangemang för minskning av galvanisk korrosion mellan metallkomponenter
KR100567801B1 (ko) * 2004-11-01 2006-04-05 엘지전자 주식회사 냉장고용 열 교환기 및 이의 냉매관 제조방법
US10422593B2 (en) 2012-04-12 2019-09-24 Carrier Corporation Sacrificial aluminum fins for failure mode protection of an aluminum heat exchanger
KR101462150B1 (ko) * 2013-09-03 2014-11-14 주식회사 안성에이치이산업 이중격판을 이용한 열교환기용 파손방지 및 보호장치
KR101400170B1 (ko) * 2013-09-03 2014-05-28 주식회사 안성에이치이산업 격판을 이용한 열교환기용 파손방지 및 보호장치
WO2016100640A1 (fr) * 2014-12-17 2016-06-23 Carrier Corporation Échangeur de chaleur en alliage d'aluminium
US12050067B2 (en) 2018-12-19 2024-07-30 Carrier Corporation Heat exchanger with aluminum alloy clad tube and method of manufacture
US20210302112A1 (en) * 2018-12-19 2021-09-30 Carrier Corporation Heat exchanger with sacrificial turbulator
JP6923099B1 (ja) * 2021-03-23 2021-08-18 秋田県 異種金属接合体およびその製造方法

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2179317A5 (fr) * 1972-04-06 1973-11-16 Chausson Usines Sa
JPS53132449A (en) * 1977-04-25 1978-11-18 Showa Aluminium Co Ltd Preparation of aluminium finnloaded iron pipe
JPS5777894A (en) * 1980-10-31 1982-05-15 Tsuchiya Mfg Co Ltd Manufacturing of heat exchanger
JPS5849898A (ja) * 1981-09-18 1983-03-24 Mitsubishi Heavy Ind Ltd 熱交換器の製造方法
JPS5995397A (ja) * 1982-11-20 1984-06-01 Nippon Radiator Co Ltd アルミニウム製熱交換器コア
JPS59100399A (ja) * 1982-12-01 1984-06-09 Nippon Radiator Co Ltd アルミニウム製熱交換器
JPS60121264A (ja) * 1983-12-06 1985-06-28 Nippon Mining Co Ltd 耐食性に優れたフインを有するラジエ−タ−の製造方法
JPS60194291A (ja) * 1984-03-16 1985-10-02 Hitachi Plant Eng & Constr Co Ltd 熱交換器
JPS60245787A (ja) * 1984-05-18 1985-12-05 Matsushita Electric Ind Co Ltd 熱交換器
JPS6334495A (ja) * 1986-07-29 1988-02-15 Nippon Denso Co Ltd アルミニウム熱交換器
JPS6363567A (ja) * 1986-09-04 1988-03-19 Showa Alum Corp 耐食性の優れた熱交換器の製造方法
JPH03255895A (ja) * 1990-03-02 1991-11-14 Hitachi Cable Ltd 車両用熱交換器の製造方法
JPH04190096A (ja) * 1990-11-24 1992-07-08 Sky Alum Co Ltd 熱交換器
GB2284882A (en) * 1993-11-24 1995-06-21 John Taylor Engineering Limite Coated finned tube heat exchanger

Also Published As

Publication number Publication date
ZA978931B (en) 1998-04-17
JP2001502757A (ja) 2001-02-27
EP0950127A1 (fr) 1999-10-20
CN101063206A (zh) 2007-10-31
KR20000052682A (ko) 2000-08-25
ID18594A (id) 1998-04-23
SA97180556B1 (ar) 2006-08-06
EG22317A (en) 2002-12-31
CN1234079A (zh) 1999-11-03
ES2238731T3 (es) 2005-09-01
DE69733317D1 (de) 2005-06-23
KR100334213B1 (ko) 2002-05-02
BR9712540A (pt) 1999-10-19
WO1998017841A1 (fr) 1998-04-30
DE69733317T2 (de) 2006-01-19

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