+

WO1998017841A1 - Protection amelioree contre la corrosion galvanique - Google Patents

Protection amelioree contre la corrosion galvanique Download PDF

Info

Publication number
WO1998017841A1
WO1998017841A1 PCT/US1997/018122 US9718122W WO9817841A1 WO 1998017841 A1 WO1998017841 A1 WO 1998017841A1 US 9718122 W US9718122 W US 9718122W WO 9817841 A1 WO9817841 A1 WO 9817841A1
Authority
WO
WIPO (PCT)
Prior art keywords
aluminum
recited
less noble
noble metal
consists essentially
Prior art date
Application number
PCT/US1997/018122
Other languages
English (en)
Inventor
Thomas J. Garosshen
Original Assignee
Carrier Corporation
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
Priority claimed from US08/734,146 external-priority patent/US6578628B1/en
Application filed by Carrier Corporation filed Critical Carrier Corporation
Priority to DE69733317T priority Critical patent/DE69733317T2/de
Priority to JP10519413A priority patent/JP2001502757A/ja
Priority to BR9712540-7A priority patent/BR9712540A/pt
Priority to EP97945553A priority patent/EP0950127B1/fr
Publication of WO1998017841A1 publication Critical patent/WO1998017841A1/fr

Links

Classifications

    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28HEAT EXCHANGE IN GENERAL
    • F28FDETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F19/00Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers
    • F28F19/02Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings
    • F28F19/06Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings of metal
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C30/00Coating 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Prevention Of Electric Corrosion (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

Procédé permettant de limiter la corrosion galvanique de métaux dissemblables en contact l'un avec l'autre et consistant à revêtir la surface exposée du métal le plus noble avec un métal plus compatible du point de vue galvanique avec le métal le moins noble.
PCT/US1997/018122 1996-10-21 1997-09-30 Protection amelioree contre la corrosion galvanique WO1998017841A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
DE69733317T DE69733317T2 (de) 1996-10-21 1997-09-30 Fortgeschrittene galvanische korrosionsschutz
JP10519413A JP2001502757A (ja) 1996-10-21 1997-09-30 発展した電解腐食保護
BR9712540-7A BR9712540A (pt) 1996-10-21 1997-09-30 Processo de prevenção de corroção galv‰nica de uma superficie,e, trocador de calor.
EP97945553A EP0950127B1 (fr) 1996-10-21 1997-09-30 Protection amelioree contre la corrosion galvanique

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US73414596A 1996-10-21 1996-10-21
US08/734,145 1996-10-21
US08/734,146 1996-10-21
US08/734,146 US6578628B1 (en) 1996-10-21 1996-10-21 Article exhibiting increased resistance to galvanic corrosion

Publications (1)

Publication Number Publication Date
WO1998017841A1 true WO1998017841A1 (fr) 1998-04-30

Family

ID=27112678

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1997/018122 WO1998017841A1 (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)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000050664A1 (fr) * 1999-02-26 2000-08-31 Carrier Corporation Article faisant preuve d'une resistance amelioree a la corrosion galvanique
WO2001000903A3 (fr) * 1999-06-30 2001-03-01 Volvo Personvagnar Ab Dispositif permettant de reduire la corrosion galvanique entre composants metalliques
WO2016100640A1 (fr) * 2014-12-17 2016-06-23 Carrier Corporation Échangeur de chaleur en alliage d'aluminium
US10422593B2 (en) 2012-04-12 2019-09-24 Carrier Corporation Sacrificial aluminum fins for failure mode protection of an aluminum heat exchanger
WO2020132202A1 (fr) * 2018-12-19 2020-06-25 Carrier Corporation Échangeur de chaleur avec tube plaqué d'alliage d'aluminium et son procédé de fabrication
WO2020132237A1 (fr) * 2018-12-19 2020-06-25 Carrier Corporation Échangeur de chaleur doté de générateur de turbulence sacrificiel

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100567801B1 (ko) * 2004-11-01 2006-04-05 엘지전자 주식회사 냉장고용 열 교환기 및 이의 냉매관 제조방법
KR101400170B1 (ko) * 2013-09-03 2014-05-28 주식회사 안성에이치이산업 격판을 이용한 열교환기용 파손방지 및 보호장치
KR101462150B1 (ko) * 2013-09-03 2014-11-14 주식회사 안성에이치이산업 이중격판을 이용한 열교환기용 파손방지 및 보호장치
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

Citations (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
EP0263592A1 (fr) * 1986-09-04 1988-04-13 Showa Aluminum Kabushiki Kaisha Procédé de fabrication d'échangeurs de chaleur résistant à la corrosion
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

Patent Citations (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
EP0263592A1 (fr) * 1986-09-04 1988-04-13 Showa Aluminum Kabushiki Kaisha Procédé de fabrication d'échangeurs de chaleur résistant à la corrosion
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

Non-Patent Citations (11)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 7901, Derwent World Patents Index; Class M21, AN 79-00793B, XP002053341 *
DATABASE WPI Section Ch Week 8604, Derwent World Patents Index; Class J08, AN 86-024451, XP002053343 *
DATABASE WPI Section Ch Week 8812, Derwent World Patents Index; Class J08, AN 88-081220, XP002053342 *
PATENT ABSTRACTS OF JAPAN vol. 006, no. 163 (M - 152) 26 August 1982 (1982-08-26) *
PATENT ABSTRACTS OF JAPAN vol. 007, no. 133 (M - 221) 10 June 1983 (1983-06-10) *
PATENT ABSTRACTS OF JAPAN vol. 008, no. 207 (M - 327) 21 September 1984 (1984-09-21) *
PATENT ABSTRACTS OF JAPAN vol. 008, no. 216 (M - 329) 3 October 1984 (1984-10-03) *
PATENT ABSTRACTS OF JAPAN vol. 009, no. 271 (C - 311) 29 October 1985 (1985-10-29) *
PATENT ABSTRACTS OF JAPAN vol. 010, no. 044 (M - 455) 21 February 1986 (1986-02-21) *
PATENT ABSTRACTS OF JAPAN vol. 016, no. 057 (M - 1210) 13 February 1992 (1992-02-13) *
PATENT ABSTRACTS OF JAPAN vol. 016, no. 515 (M - 1329) 23 October 1992 (1992-10-23) *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000050664A1 (fr) * 1999-02-26 2000-08-31 Carrier Corporation Article faisant preuve d'une resistance amelioree a la corrosion galvanique
WO2001000903A3 (fr) * 1999-06-30 2001-03-01 Volvo Personvagnar Ab Dispositif permettant de reduire la corrosion galvanique entre composants metalliques
US6673469B2 (en) 1999-06-30 2004-01-06 Volvo Personvagnar Ab Arrangement for decreasing galvanic corrosion between metal components
US10422593B2 (en) 2012-04-12 2019-09-24 Carrier Corporation Sacrificial aluminum fins for failure mode protection of an aluminum heat exchanger
WO2016100640A1 (fr) * 2014-12-17 2016-06-23 Carrier Corporation Échangeur de chaleur en alliage d'aluminium
US10473411B2 (en) 2014-12-17 2019-11-12 Carrier Corporation Aluminum alloy finned heat exchanger
WO2020132202A1 (fr) * 2018-12-19 2020-06-25 Carrier Corporation Échangeur de chaleur avec tube plaqué d'alliage d'aluminium et son procédé de fabrication
WO2020132237A1 (fr) * 2018-12-19 2020-06-25 Carrier Corporation Échangeur de chaleur doté de générateur de turbulence sacrificiel
US12050067B2 (en) 2018-12-19 2024-07-30 Carrier Corporation Heat exchanger with aluminum alloy clad tube and method of manufacture

Also Published As

Publication number Publication date
ZA978931B (en) 1998-04-17
JP2001502757A (ja) 2001-02-27
KR100334213B1 (ko) 2002-05-02
ES2238731T3 (es) 2005-09-01
ID18594A (id) 1998-04-23
SA97180556B1 (ar) 2006-08-06
DE69733317D1 (de) 2005-06-23
EP0950127B1 (fr) 2005-05-18
KR20000052682A (ko) 2000-08-25
BR9712540A (pt) 1999-10-19
CN1234079A (zh) 1999-11-03
EP0950127A1 (fr) 1999-10-20
EG22317A (en) 2002-12-31
DE69733317T2 (de) 2006-01-19
CN101063206A (zh) 2007-10-31

Similar Documents

Publication Publication Date Title
US6325138B1 (en) Article exhibiting improved resistance to galvanic corrosion
JPS61184395A (ja) アルミニウム製熱交換器の防食処理法
EP0950127B1 (fr) Protection amelioree contre la corrosion galvanique
JPS61186164A (ja) アルミニウム製熱交換器の製造方法
JP4796362B2 (ja) Lng気化器用伝熱管およびその製造方法
US6578628B1 (en) Article exhibiting increased resistance to galvanic corrosion
JPH01225761A (ja) 溶融金属めっき浴用部材
MXPA99003645A (en) Advanced galvanic corrosion protection
EP1192295B1 (fr) ARTICLE POSSéDANT UNE RéSISTANCE AMéLIORée à LA CORROSION DU TYPE NID DE FOURMIS
JP4773780B2 (ja) Lng気化器用伝熱管とそれを用いたlng気化器
US4775004A (en) Copper radiator for motor cars excellent in corrosion resistance and method of manufacturing
JP4480257B2 (ja) 耐応力腐食割れ性に優れた燃料タンク用表面被覆オーステナイト系ステンレス鋼
JPS60230953A (ja) 熱交換器用アルミニウム材製複合板
JP3151152B2 (ja) 耐食性に優れたエバボレータ
JPH10113613A (ja) 防食塗膜の塗装方法
JP2001164381A (ja) 耐硫酸露点腐食性に優れた複合被覆部材およびその製造方法
JPH048514B2 (fr)
KR100865212B1 (ko) Lng 기화기용 전열관, 그의 제조방법 및 그러한 전열관을 이용한 lng 기화기
JPH03255895A (ja) 車両用熱交換器の製造方法
JPS62138695A (ja) ラジエ−タ用フイン材
KR910006779B1 (ko) 열교환기 핀 및 그 제조방법
JPH046283A (ja) 高耐食性放熱フィン材およびその製造方法
JPS59214640A (ja) 熱交換器用内面防食塗装皮膜付き銅合金管
JPS6311696A (ja) 耐食性および塗装性に優れた積層型複合めっき鋼板の製造法
JPH07138770A (ja) 複層被覆鋼板

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 97198948.6

Country of ref document: CN

AK Designated states

Kind code of ref document: A1

Designated state(s): BR CN JP KR MX SG

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1997945553

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 1998 519413

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: PA/a/1999/003645

Country of ref document: MX

Ref document number: 1019997003467

Country of ref document: KR

WWP Wipo information: published in national office

Ref document number: 1997945553

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1019997003467

Country of ref document: KR

WWG Wipo information: grant in national office

Ref document number: 1019997003467

Country of ref document: KR

WWG Wipo information: grant in national office

Ref document number: 1997945553

Country of ref document: EP

点击 这是indexloc提供的php浏览器服务,不要输入任何密码和下载