EP0008706A1 - Lead-alloy coated heat exchanger for a fuel-heated heat source, and process for coating such an exchanger with lead - Google Patents

Lead-alloy coated heat exchanger for a fuel-heated heat source, and process for coating such an exchanger with lead Download PDF

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Publication number
EP0008706A1
EP0008706A1 EP79102942A EP79102942A EP0008706A1 EP 0008706 A1 EP0008706 A1 EP 0008706A1 EP 79102942 A EP79102942 A EP 79102942A EP 79102942 A EP79102942 A EP 79102942A EP 0008706 A1 EP0008706 A1 EP 0008706A1
Authority
EP
European Patent Office
Prior art keywords
lead
fuel
exchanger
antimony
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
EP79102942A
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German (de)
French (fr)
Other versions
EP0008706B1 (en
Inventor
Manfred Lehnert
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.)
Cofrabel Nv
SCHONEWELLE BV
Vaillant Austria GmbH
Vaillant GmbH
Vaillant SARL
Original Assignee
Kw+-Paulus & Co Ltd
Vaillant Austria GmbH
Cofrabel Nv
Joh Vaillant GmbH and Co
Vaillant GmbH
Vaillant SARL
PAULUS K W CO Ltd
Vaillant Ltd
SCHONEWELLE BV
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 Kw+-Paulus & Co Ltd, Vaillant Austria GmbH, Cofrabel Nv, Joh Vaillant GmbH and Co, Vaillant GmbH, Vaillant SARL, PAULUS K W CO Ltd, Vaillant Ltd, SCHONEWELLE BV filed Critical Kw+-Paulus & Co Ltd
Priority to AT79102942T priority Critical patent/ATE977T1/en
Publication of EP0008706A1 publication Critical patent/EP0008706A1/en
Application granted granted Critical
Publication of EP0008706B1 publication Critical patent/EP0008706B1/en
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C11/00—Alloys based on lead
    • C22C11/06—Alloys based on lead with tin as the next major constituent
    • 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/10—Lead or alloys based thereon
    • 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

Definitions

  • the present invention relates to a heat exchanger for a fuel heated heat source.
  • Such heat exchangers have hitherto been provided with a top layer of pure lead.
  • a lead layer has proven to be relatively susceptible to corrosion.
  • tin-copper-antimony lead alloys have become known as white metal 5 and white metal 10, the tin contents of which range from 4.5 to 5.5%, the copper content is between 0.5 and 1.5% , the antimony content from 14.5 to 16.5% and the rest is lead or technical contamination.
  • a lead injection molding alloy has become known from DIN 1741, which contains a tin content of 6% and an antimony content of 9 to 11%, the rest is lead or due to technical reasons Impurities. Furthermore, lead alloys for the graphic arts industry have become known from DIN 16512, the tin contents of which range from 2.5 to 3.5% with a simultaneous antimony content of 3.5 to 4.5%, the rest consisting of lead and technically caused impurities. Other alloys for printing purposes have significantly higher antimony contents or relatively large tin contents.
  • Leaflet "Steel" No. 179 has disclosed a lead bath alloy with up to 2.5% tin and 2% antimony, which is said to improve the adhesion of the lead layer. At the same time, the extraordinarily soft and easy-to-damage pure lead layer becomes harder and more mechanically resistant due to the addition of antimony.
  • the bath temperature can be reduced by 40 to 50 ° C by adding tin and antimony.
  • the object of the present invention is to create a heat exchanger which is distinguished by extremely high corrosion resistance to exhaust gases, in particular exhaust gases containing sulfur dioxide, when the dew point is not reached.
  • the solution to the problem with a heat exchanger of the type specified at the outset is that it is made with a known alloy of 6 to 10% tin, 4.5 to 6.5% antimony, the rest lead and technical contingent impurities is covered.
  • a coating alloy with a content of 8% tin, 5.5% antimony, the remainder lead and technical impurities is particularly advantageous.
  • antimony-containing lead alloys for remaining copper heat exchangers was not obvious in the invention, because in a known case (2.5% Sn, maximum 2% SB) the antimony serves to harden the lead layer and thus the lead layer becomes mechanically more resistant.
  • the method according to the invention for remaining a heat exchanger of a fuel-heated heat source assumes that the heat exchanger consisting of copper sheet (99.9% Cu, 0.015-0.050% P, remainder from technically caused contamination, ie SF-Cu) in the form of a heating shaft with an internal lamella block through which a copper water pipe coil is passed, first immersed in phosphoric acid, then rinsed in water and then immersed in sulfuric acid, followed by a rinse in water, followed by immersion in flux (znC12 in aqueous solution). The next step is immersion in the lead bath, consisting of a lead alloy with 8% tin, 5.5% antimony, the rest of the lead and technical impurities. To remove the salt residue, it must then be immersed in water. Alternatively, the part can be dipped in a 5% aqueous HC1 solution and then rinsed with water.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Coating With Molten Metal (AREA)

Abstract

1. Heat exchangers, which consist entirely or in a major part of copper, which may be alloyed, if desired, for fuel-heated heat sources, characterized in that they are coated with an alloy consisting of 6 to 10 % zinc, 4.5 to 6.5 % antimony (percent by weight in each instance), balance lead and impurities which are present owing to technology.

Description

Die vorliegende Erfindung bezieht sich auf einen Wärmetauscher für eine brennstoffbeheizte Wärmequelle.The present invention relates to a heat exchanger for a fuel heated heat source.

Solche Wärmetauscher sind bislang mit einer Oberzugsschicht aus reinem Blei versehen worden. Eine derartige Bleischicht hat sich jedoch als relativ korrosionsanfällig erwiesen.Such heat exchangers have hitherto been provided with a top layer of pure lead. However, such a lead layer has proven to be relatively susceptible to corrosion.

Es sind Metallegierungen mit Zinn, Antimon und Blei bekannt. Beispielsweise a s DIN 1703, Seite 20, sind als Weißmetall 5 und Weißmetall 10 Zinn-Kupfer-Antimon-Bleilegierungen bekannt geworden, deren Zinngehalte von 4,5 bis 5,5 % reichen, der Kupfergehalt liegt zwischen 0,5 und 1,5 %, der Antimongehalt von 14,5 bis 16,5 % und der Rest ist Blei bzw. technisch bedingte Verunreinigung.Metal alloys with tin, antimony and lead are known. For example, as DIN 1703, page 20, tin-copper-antimony lead alloys have become known as white metal 5 and white metal 10, the tin contents of which range from 4.5 to 5.5%, the copper content is between 0.5 and 1.5% , the antimony content from 14.5 to 16.5% and the rest is lead or technical contamination.

Aus DIN 1741 ist eine Bleispritzgußlegierung bekanntgeworden die einen Zinngehalt von 6 % und eine Antimongehalt von 9 bis 11 % enthält, der Rest ist Blei bzw. technisch bedingte Verunreinigungen. Weiterhin sind aus DIN 16512 Bleilegierungen für das graphische Gewerbe bekannt geworden, deren Zinngehalte von 2,5 bis 3,5 % bei gleichzeitigem Antimongehalt von 3,5 bis 4,5 % reichen, wobei der Rest aus Blei und technisch bedingten Verunreinigungen besteht. Weitere Legierungen für Druckzwecke weisen wesentlich höhere Antimongehalte bzw. relativ große Zinngehalte auf.A lead injection molding alloy has become known from DIN 1741, which contains a tin content of 6% and an antimony content of 9 to 11%, the rest is lead or due to technical reasons Impurities. Furthermore, lead alloys for the graphic arts industry have become known from DIN 16512, the tin contents of which range from 2.5 to 3.5% with a simultaneous antimony content of 3.5 to 4.5%, the rest consisting of lead and technically caused impurities. Other alloys for printing purposes have significantly higher antimony contents or relatively large tin contents.

Aus Merkblatt "Stahl", Nr. 179, ist eine Bleibadlegierung mit bis zu 2,5 % Zinn und 2 % Antimon bekannt geworden, die eine bessere Haftung der Bleischicht bewirken soll. Zugleich wird die außerordentlich weiche und lei'cht zu beschädigende Reinbleischicht durch den Antimonzusatz härter und mechanisch widerstandsfähiger. Die Badtemperatur kann durch die Zulegierung von Zinn und Antimon um 40 bis 50°C gesenkt werden.Leaflet "Steel", No. 179, has disclosed a lead bath alloy with up to 2.5% tin and 2% antimony, which is said to improve the adhesion of the lead layer. At the same time, the extraordinarily soft and easy-to-damage pure lead layer becomes harder and more mechanically resistant due to the addition of antimony. The bath temperature can be reduced by 40 to 50 ° C by adding tin and antimony.

Der vorliegenden Erfindung liegt die Aufgabe zugrunde, einen Wärmetauscher zu schaffen, der sich durch eine extrem hohe Korrosionsbeständigkeit gegenüber Abgasen, insbesondere schwefeldioxydhaltigen Abgasen, bei einer Unterschreitung des Taupunktes auszeichnet.The object of the present invention is to create a heat exchanger which is distinguished by extremely high corrosion resistance to exhaust gases, in particular exhaust gases containing sulfur dioxide, when the dew point is not reached.

Erfindungsgemäß besteht die Lösung der Aufgabe bei einem Wärmetauscher der eingangs näher bezeichneten Art darin, daß er mit einer an sich bekannten Legierung aus 6 bis 10 % Zinn, 4,5 bis 6,5 % Antimon, Rest Blei und technisch bedingte Verunreinigungen überzogen ist. Besonders vorteilhaft ist eine überzuglegierung mit einem Gehalt von 8 % Zinn, 5,5 % Antimon, Rest Blei und technisch bedingte Verunreinigungen.According to the invention, the solution to the problem with a heat exchanger of the type specified at the outset is that it is made with a known alloy of 6 to 10% tin, 4.5 to 6.5% antimony, the rest lead and technical contingent impurities is covered. A coating alloy with a content of 8% tin, 5.5% antimony, the remainder lead and technical impurities is particularly advantageous.

Es hat sich herausgestellt, daß mit diesen Bleilegierungen eine unerwartet gute Korrosionsbeständigkeit gegen feuchte schwefeldioxydhaltige Abgase ergibt.It has been found that, with these lead alloys, there is an unexpectedly good corrosion resistance to moist exhaust gases containing sulfur dioxide.

Die Verwendung antimonhaltiger Bleilegierungen zum Verbleien von kupfernen Wärmetauschern hat bei der Erfindung nicht nahegelegen, weil in einem bekannten Fall (2,5 % Sn, maximal 2 % SB) das Antimon zur Härtung der Bleischicht dient und damit die Bleischicht mechanisch widerstandsfähiger wird.The use of antimony-containing lead alloys for remaining copper heat exchangers was not obvious in the invention, because in a known case (2.5% Sn, maximum 2% SB) the antimony serves to harden the lead layer and thus the lead layer becomes mechanically more resistant.

Auf diese beiden Merkmale kommt es bei der Korrosionsbeständigkeit überhaupt nicht an, da eine mechanische Einwirkung auf die Verbleiungsschicht nicht stattfindet. Auch die bekannten Antimon-Bleilegierungen für Druckzwecke können nicht ohne weiteres auf die Erfindung übertragen werden, da es bei Druckmetallegierungen nicht auf gute Korrosionsbeständigkeit ankommt, sondern nur auf leichte Gießbarkeit und guten Abdruck.These two features are of no importance in terms of corrosion resistance, since there is no mechanical influence on the lead layer. The known antimony lead alloys for printing purposes can not be readily transferred to the invention, since good corrosion resistance is not important for printing metal alloys, but only easy castability and good impression.

Das erfindungsgemäße Verfahren zum Verbleien eines Wärmetauschers einer brennstoffbeheizten Wärmequelle geht davon aus, daß der aus Kupferblech (99,9 % Cu, 0,015 - 0,050 % P, Rest aus technisch bedingterVerunreinigung, d. h. SF-Cu) bestehende Wärmetauscher in Form eines Heizschachtes mit innenliegendem Lamellenblock, durch den eine Wasserrohrschlange aus Kupfer geführt ist, zuerst in Phosphorsäure getaucht, dann in Wasser gespult und anschließend in Schwefelsäure getaucht wird, worauf eine Spülung in Wasser stattfindet, an das sich ein Tauchen in Flußmittel (znC12 in wäßriger Lösung) anschließt. Als nächstesfolgt das Eintauchen in das Bleibad, bestehend aus einer Bleilegierung mit 8 % Zinn, 5,5 % Antimon, Rest Blei und technisch bedingte Verunreinigungen. Zur Entfernung der Salzreste muß anschließend in Wasser getaucht werden. Alternativ kann nach dem Verbleien das Teil in eine 5 %ige wäßrige HC1-Lösung getaucht und nachfolgend mit Wasser gespült werden.The method according to the invention for remaining a heat exchanger of a fuel-heated heat source assumes that the heat exchanger consisting of copper sheet (99.9% Cu, 0.015-0.050% P, remainder from technically caused contamination, ie SF-Cu) in the form of a heating shaft with an internal lamella block through which a copper water pipe coil is passed, first immersed in phosphoric acid, then rinsed in water and then immersed in sulfuric acid, followed by a rinse in water, followed by immersion in flux (znC12 in aqueous solution). The next step is immersion in the lead bath, consisting of a lead alloy with 8% tin, 5.5% antimony, the rest of the lead and technical impurities. To remove the salt residue, it must then be immersed in water. Alternatively, the part can be dipped in a 5% aqueous HC1 solution and then rinsed with water.

Claims (3)

1. Wärmetauscher für brennstoffbeheizte Wärmequellen, dadurch gekennzeichnet, daß er mit einer Legierung aus Zinn 6 - 10 %, Antimon 4,5 - 6,5 %, Rest Blei und technisch bedingte Verunreinigungen überzogen ist.1. Heat exchanger for fuel-heated heat sources, characterized in that it is coated with an alloy of tin 6-10%, antimony 4.5-6.5%, the rest lead and technically caused impurities. 2. Wärmetauscher für brennstoffbeheizte Wärmequellen nach Anspruch 1, dadurch gekennzeichnet, daß er mit einer Legierung aus 8 % Zinne, 5,5 % Antimon, Rest Blei und technisch bedingte Verunreinigungen überzogen ist.2. Heat exchanger for fuel-heated heat sources according to claim 1, characterized in that it is coated with an alloy of 8% tin, 5.5% antimony, the rest of lead and technically caused impurities. 3. Verfahren zum Verbleien eines Wärmetauschers einer brenr stoffbeheizten Wärmequelle unter Verwendung einer Metall legierung nach Ansprüchen 1 oder 2, gekennzeichnet durct folgende Schritte: 1. Tauchen in H3P04 2. Tauchen in H20 3. Tauchen in H2S04 4. Tauchen in H20 5. Tauchen in ZnC12 6. Tauchen in das Bleibad nach Anspruch 1 oder 2 7. Tauchen in H20 3. Method for remaining a heat exchanger of a fuel-heated heat source using a metal alloy according to claims 1 or 2, characterized by the following steps: 1. Diving in H3P04 2. Diving in H20 3. Diving in H2S04 4. Diving in H20 5. Diving in ZnC12 6. Diving into the lead bath according to claim 1 or 2 7. Diving in H20
EP79102942A 1978-08-29 1979-08-13 Lead-alloy coated heat exchanger for a fuel-heated heat source, and process for coating such an exchanger with lead Expired EP0008706B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT79102942T ATE977T1 (en) 1978-08-29 1979-08-13 LEAD ALLOY COVERED HEAT EXCHANGER FOR FUEL HEATED HEAT SOURCE AND METHOD OF LEADING SUCH HEAT EXCHANGER.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE7825644 1978-08-29
DE7825644U 1978-08-29

Publications (2)

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EP0008706A1 true EP0008706A1 (en) 1980-03-19
EP0008706B1 EP0008706B1 (en) 1982-05-05

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AT (1) ATE977T1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2473693A1 (en) * 1980-01-14 1981-07-17 Erhardt Gerard Composite coaxial tubes for refrigeration of corrosive liquids - involving copper, lead and polyethylene components
FR2549494A1 (en) * 1983-07-19 1985-01-25 Vaillant Sarl Process for coating with lead structural components which have copper and steel surfaces
WO1996036749A1 (en) * 1995-05-16 1996-11-21 Valeo Térmico, S.A. Process for the protection against external corrosion in copper-based heat exchangers

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105648377B (en) * 2016-01-21 2017-12-29 国网山东省电力公司电力科学研究院 A kind of long timeliness, reusable hot-dip aluminum zinc magnesium alloy fluxing agent

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE137897C (en) *
DE319734C (en) * 1915-08-25 1920-03-11 Clayton Mark Process for the production of zinc-containing protective coatings on metal objects
GB555154A (en) * 1942-02-04 1943-08-06 Fry S Metal Foundries Ltd Improvements in and relating to soldering
FR886010A (en) * 1941-09-10 1943-10-01 Hermes Patentverwertungs Gmbh Metal protection of copper or copper alloy objects, in particular on wires for rubber-insulated electrical conduits
DE1533431A1 (en) * 1965-04-30 1969-07-10 Yawata Iron & Steel Co Plating bath for coating objects made of iron and steel
FR2279859A1 (en) * 1974-07-22 1976-02-20 Armco Steel Corp STEEL ARTICLES COATED WITH A LEAD LAYER

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE137897C (en) *
DE319734C (en) * 1915-08-25 1920-03-11 Clayton Mark Process for the production of zinc-containing protective coatings on metal objects
FR886010A (en) * 1941-09-10 1943-10-01 Hermes Patentverwertungs Gmbh Metal protection of copper or copper alloy objects, in particular on wires for rubber-insulated electrical conduits
GB555154A (en) * 1942-02-04 1943-08-06 Fry S Metal Foundries Ltd Improvements in and relating to soldering
DE1533431A1 (en) * 1965-04-30 1969-07-10 Yawata Iron & Steel Co Plating bath for coating objects made of iron and steel
FR2279859A1 (en) * 1974-07-22 1976-02-20 Armco Steel Corp STEEL ARTICLES COATED WITH A LEAD LAYER

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2473693A1 (en) * 1980-01-14 1981-07-17 Erhardt Gerard Composite coaxial tubes for refrigeration of corrosive liquids - involving copper, lead and polyethylene components
FR2549494A1 (en) * 1983-07-19 1985-01-25 Vaillant Sarl Process for coating with lead structural components which have copper and steel surfaces
WO1996036749A1 (en) * 1995-05-16 1996-11-21 Valeo Térmico, S.A. Process for the protection against external corrosion in copper-based heat exchangers

Also Published As

Publication number Publication date
ATE977T1 (en) 1982-05-15
EP0008706B1 (en) 1982-05-05

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