EP0950127A1 - Protection amelioree contre la corrosion galvanique - Google Patents
Protection amelioree contre la corrosion galvaniqueInfo
- Publication number
- EP0950127A1 EP0950127A1 EP97945553A EP97945553A EP0950127A1 EP 0950127 A1 EP0950127 A1 EP 0950127A1 EP 97945553 A EP97945553 A EP 97945553A EP 97945553 A EP97945553 A EP 97945553A EP 0950127 A1 EP0950127 A1 EP 0950127A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- aluminum
- recited
- less noble
- noble metal
- consists essentially
- 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
Links
- 238000005260 corrosion Methods 0.000 title claims abstract description 13
- 230000007797 corrosion Effects 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 22
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 22
- 238000000576 coating method Methods 0.000 claims description 21
- 239000011248 coating agent Substances 0.000 claims description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 229910000838 Al alloy Inorganic materials 0.000 claims description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005229 chemical vapour deposition Methods 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 238000009713 electroplating Methods 0.000 claims description 2
- 238000005240 physical vapour deposition Methods 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 2
- 229910052749 magnesium Inorganic materials 0.000 claims 2
- 239000011777 magnesium Substances 0.000 claims 2
- 229910052718 tin Inorganic materials 0.000 claims 2
- 239000011135 tin Substances 0.000 claims 2
- 229910000611 Zinc aluminium Inorganic materials 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 claims 1
- 239000000956 alloy Substances 0.000 claims 1
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 claims 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims 1
- -1 cadium Substances 0.000 claims 1
- 238000009792 diffusion process Methods 0.000 claims 1
- 238000007591 painting process Methods 0.000 claims 1
- 238000005019 vapor deposition process Methods 0.000 claims 1
- 150000002739 metals Chemical class 0.000 abstract description 10
- 239000000463 material Substances 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000011253 protective coating Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 238000005269 aluminizing Methods 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RRXGIIMOBNNXDK-UHFFFAOYSA-N [Mg].[Sn] Chemical compound [Mg].[Sn] RRXGIIMOBNNXDK-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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 cf 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.
- the present invention provides an advanced galvanic corrosion protection method.
- the outer surface of the more noble metal is treated with a metal which is galvanically compatible with the less noble metal to form a protective layer between the two dissimilar metals which prevents the reduction reaction of the galvanic couple from occurring.
- the invention greatly reduces the oxidation reduction process which occurs when two dissimilar metals are in contact with one another in the presence of an electrolyte.
- FIG. 1 is a perspective view of a heat exchanger incorporating heat exchanger tubes treated in accordance with the present invention.
- 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 3 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 ease 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 greatly 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 the 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.
- 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 must 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.
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)
Abstract
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 true EP0950127A1 (fr) | 1999-10-20 |
| EP0950127B1 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)
| 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)
| 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 |
-
1997
- 1997-09-30 WO PCT/US1997/018122 patent/WO1998017841A1/fr not_active Ceased
- 1997-09-30 CN CNA2007100886648A patent/CN101063206A/zh active Pending
- 1997-09-30 EP EP97945553A patent/EP0950127B1/fr not_active Expired - Lifetime
- 1997-09-30 BR BR9712540-7A patent/BR9712540A/pt not_active Application Discontinuation
- 1997-09-30 CN CN97198948A patent/CN1234079A/zh active Pending
- 1997-09-30 KR KR1019997003467A patent/KR100334213B1/ko not_active Expired - Fee Related
- 1997-09-30 DE DE69733317T patent/DE69733317T2/de not_active Expired - Lifetime
- 1997-09-30 ES ES97945553T patent/ES2238731T3/es not_active Expired - Lifetime
- 1997-09-30 JP JP10519413A patent/JP2001502757A/ja active Pending
- 1997-10-06 ZA ZA9708931A patent/ZA978931B/xx unknown
- 1997-10-20 ID IDP973477A patent/ID18594A/id unknown
- 1997-10-20 EG EG110297A patent/EG22317A/xx active
- 1997-11-01 SA SA97180556A patent/SA97180556B1/ar unknown
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9817841A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| ZA978931B (en) | 1998-04-17 |
| JP2001502757A (ja) | 2001-02-27 |
| CN101063206A (zh) | 2007-10-31 |
| KR20000052682A (ko) | 2000-08-25 |
| ID18594A (id) | 1998-04-23 |
| EP0950127B1 (fr) | 2005-05-18 |
| 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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