EP0245862B1 - Liquid film coating of iron-based metals - Google Patents

Liquid film coating of iron-based metals Download PDF

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Publication number
EP0245862B1
EP0245862B1 EP87107020A EP87107020A EP0245862B1 EP 0245862 B1 EP0245862 B1 EP 0245862B1 EP 87107020 A EP87107020 A EP 87107020A EP 87107020 A EP87107020 A EP 87107020A EP 0245862 B1 EP0245862 B1 EP 0245862B1
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EP
European Patent Office
Prior art keywords
roll
zinc
coating
conveyor
substrate
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
EP87107020A
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German (de)
English (en)
French (fr)
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EP0245862A1 (en
Inventor
Thomas Alan Taylor
Robert Clark Tucker, Jr.
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Union Carbide Corp
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Union Carbide Corp
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Publication of EP0245862A1 publication Critical patent/EP0245862A1/en
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    • 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
    • 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
    • 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
    • C23C2/003—Apparatus
    • C23C2/0034—Details related to elements immersed in bath
    • C23C2/00342—Moving elements, e.g. pumps or mixers
    • C23C2/00344—Means for moving substrates, e.g. immersed rollers or immersed bearings
    • 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
    • C23C2/26—After-treatment
    • C23C2/28—Thermal after-treatment, e.g. treatment in oil bath

Definitions

  • This invention pertains to apparatus and processes for protective coating of iron-containing metals such as processes and apparatus for the continuous hot-dip galvanizing of iron-based sheet metal.
  • the corrosion of iron-based metals can be mitigated by coating the metal with a protective metal coating material, i.e., an anodic or cathodic metal such as zinc, tin, aluminum, lead, or mixtures or alloys thereof.
  • a protective metal coating material i.e., an anodic or cathodic metal such as zinc, tin, aluminum, lead, or mixtures or alloys thereof.
  • Anodic materials, such as zinc are sacrificial and thereby provide corrosion protection to the underlying substrate whereas cathodic materials typically serve as barrier layers.
  • the deposition of these metals on an iron-based metal substrate is herein referred to as a "protective metal coating process".
  • the protective metal coating process can be conducted by immersing the substrate into a vessel containing the molten protective metal coating material for the coating or by spraying or otherwise applying a liquid film of the protective metal coating material on the substrate.
  • Galvanizing is a widely practiced process for liquid film coating and is conventionally practiced by immersing the metal substrate into a vessel containing molten zinc and then removing the metal substrate from the vessel to effect the coating ("hot-dip" process).
  • hot-dip a process for galvanizing sheet metal
  • the sheet metal is removed vertically from the molten zinc and passed over a tower roll which enables the movement of the sheet to be redirected.
  • the tower roll may be positioned about 10 to 80 meters above the vessel containing the molten zinc. This distance is selected on the basis of the time required, under the rate of movement of the sheet, for the zinc coating to solidify sufficiently so that the zinc does not transfer to the tower roll.
  • the zinc or other protective metal coating material contacting the roll may be molten, semi-solid, or solid. Even when solid, but while still hot, the protective metal coating material can transfer to a roll since the full strength of the coating has not developed. That is, the coating may be characterized as being in a plastic state and is subject to being transferred to a roll surface.
  • galvannealing has found acceptance in providing galvanized coatings having a substantial absence of spangles as well as superior mechanical properties.
  • the zinc-coated substrate exiting the molten zinc bath is heated for a sufficient time to enable a zinc-iron alloy to be formed.
  • the alloy has a relatively uniform matte finish, that can readily be painted, providing a finish of an acceptable quality to a discriminating consumer.
  • the distance between the vessel containing the molten zinc and the tower roll is selected such that the zinc coating is solidified sufficiently prior to the contact of the sheet with the tower roll that a transfer of the zinc to the tower roll surface does not occur.
  • the installation of an intervening galvannealing unit results in shortening the distance that cooling can occur before the sheet metal contacts the tower roll. If the normal production speed is maintained, then the zinc does not sufficiently solidify prior to contacting the tower roll. This contact has been found to adversely affect the quality of the finish. For instance, deposits of zinc develop on the tower roll and cause a marring of the sheet metal surface or even a perforation of the sheet surface.
  • an endless casting belt which is used as a mould of a continuous casting machine for the casting of metals, in particular aluminum or zinc or alloys thereof, and which has a ceramic coating of A l 2O3, CaZrO3, A l 2O3 ⁇ MgO, ZrSiO4 or A l 2O3 ⁇ TiO2 deposited in several thin layers in a total thickness of 100 to 600 ⁇ m.
  • This roll is provided with a ceramic cover layer of A l 2O3, ZrO2, TiO2, MgO, SiO2 with a thickness of 20 to 30 mm to prevent or resist chemical reaction of the roll with the molten liquid.
  • EP-A-0 158 474 Besides a metal roll for use in molten salt bath descaling processes is known (EP-A-0 158 474), which roll has a ceramic coating consisting of ZrO2, A l 2O3, MgO or MgZrO3 or of a combination of two or more thereof and having a thickness of 0.127 to 0.762 mm.
  • the present invention in conformity with one aspect thereof, provides for a roll or conveyor with an overlay of refractory oxide ceramic, selected from at least one of, alone or in combination, zirconia, alumina, yttria, chromia, magnesia and titania, in a thickness of between 20 and 700 ⁇ m on at least a part of the surface of said roll or conveyor which has a substructure, wherein an undercoat, comprising at least one of nickel, iron and cobalt based alloy of the type MCrA l Y, is provided immediately below the refractory oxide overlay, M being at least one of nickel, iron and cobalt.
  • refractory oxide ceramic selected from at least one of, alone or in combination, zirconia, alumina, yttria, chromia, magnesia and titania
  • a further aspect of the subject invention is the application of a roll or of a conveyor comprising a substructure and an overlay of refractory oxide ceramic having a thickness in the range of between 20 and 700 ⁇ m, for contacting, in the ambient atmosphere, an iron based metal substrate having a protective coating of zinc thereon, which has been applied by a liquid film coating technique, with contact occurring while the coating is viscous or plastic, wherein said overlay is provided on at least that portion of the surface of the roll or conveyor intended to contact the zinc coating, and wherein said refractory oxide ceramic consists of zirconia stabilized with from 6 to 10 percent yttria.
  • the present invention further is concerned with an apparatus for liquid film coating of iron-based substrates with a protective metal coating of zinc comprising a liquid zinc applying zone and a roll positioned after the zone for directing the movement of the substrate, wherein the roll is a roll as defined above.
  • An aspect of the present invention also is a process for the liquid film coating of an iron-based substrate with protective metal coating material comprising applying molten zinc to the substrate to provide a coating on said substrate and contacting said coated substrate with a surface of the roll or conveyor as defined above.
  • the roll according to this invention can be used in apparatus for the liquid film coating of sheet metal in a continuous manner.
  • the conveyor of this invention may comprise narrow strips that are substantially perpendicular to the movement of the conveyor which strips are movable in respect to one another or a loose woven mesh.
  • the protective metal coating may be capable of transfer to a surface when it is in a liquid or even solid state, i.e. when it has not yet cooled or solidified sufficiently or it can be said that the protective metal coating is in a viscous or plastic state.
  • the mechanism of transfer of the protective metal coating material to the tower roll is not well understood and is probably dependent on the specific composition of both the coating and the surface of the tower roll.
  • the temperature of the protective metal coating material in particular is very important.
  • the protective metal coating material, as it first comes in contact with the tower roll surface is usually below its solidus temperature, but may be between the solidus and liquidus temperatures in some instances; i.e., part of the material may be solid and part liquid. In either event, the material is in a highly plastic or viscous state and is easily transferred to the roll surface. Transfer may occur as the result of either adhesion or abrasion.
  • Adhesive transfer occurs when a chemical bond forms between the protective metal coating and the tower roll surface which is stronger than the internal cohesive strength of the coating or the bond of the coating to its substrate.
  • Abrasive transfer may occur when an asperity, harder than the protective metal coating, scoops out coating material. The tendency for any of these mechanisms to operate diminishes as the temperature of the coating material decreases because the strength of the coating increases with decreasing temperature. Once a small amount of protective metal coating material has transferred to the tower roll surface, additional material may build-up on this transferred material, eventually forming large lumps which may damage the coated sheet material.
  • the rolls of this invention can be used in a variety of applications in a number of protective metal coating processes.
  • the liquid film coating processes include hot-dip processes and spraying processes.
  • hot dip processes the metal to be treated is immersed into a vessel containing molten protective metal coating material and is withdrawn in a generally upward direction. Most frequently in continuous processes, the metal is withdrawn vertically and passes to a tower roll. The metal is then redirected and passes over various rolls in a further cooling section after which it may be subjected to further treatments or packaged for use.
  • Another type of hot-dip process involves removing the metal from the vessel to a substantially horizontal conveyor for transporting and cooling. This process is often used when applying the protective metal coating material to pieces of metal rather than continuous sheets of metal.
  • the conveyor system may comprise rollers in accordance with this invention or a continuous conveyor in accordance with this invention.
  • the molten protective metal coating material is sprayed to contact the metal substrate.
  • the protective metal coating material solidifies immediately upon contact with the cooler metal substrate.
  • this invention can still be useful if the protective metal coating material is capable of transfer.
  • the most commonly used protective metal coating materials include zinc, aluminum, aluminum-zinc alloy, and aluminum-silicon alloy although tin, terne metal (lead and tin), copper and copper alloys can be applied using the liquid film coating technique.
  • the metal substrate is an iron-based metal and is often cast iron or steel and has a sufficiently high softening temperature that it is not adversely affected by the temperatures required for the application of the molten protective metal coating material.
  • the form of the metal substrate may vary depending upon the ultimate need. For instance, the substrate may be in the form of a continuous sheet, wire or screen or it could be in the form of the final product such as a molded part or a cast article.
  • the protective metal coating material for the application of the liquid film to the metal substrate is at a temperature to provide the desired rheological properties for forming a coating of the desired thickness.
  • the temperature range will vary depending upon the nature of the protective metal coating material. However, temperatures should be avoided at which the metal substrate becomes unduly adversely affected.
  • the nature of the protective metal coating material can also be affected by the time of contact with the molten protective metal coating material in a hot-dip process.
  • the cooled substrate may be further heat treated by maintaining the substrate in a heating zone under temperatures for chemical interaction or recrystallization.
  • the heating in galvannealing permits chemical interactions to occur between zinc and iron.
  • the temperature and duration of the heating will vary depending on the desired result.
  • the liquid film coating may be contacted with a nucleating agent which promotes the formation of smaller crystal structures, i.e., microspangles.
  • a nucleating agent which promotes the formation of smaller crystal structures, i.e., microspangles.
  • commercial galvanizing processes exist in which the metal removed from the molten-zinc is sprayed with finely-divided zinc to provide nucleation sites.
  • the protective metal coating material when contacting the rolls in accordance with this invention, is often at a temperature at which the protective metal coating material has begun to solidify. In some instances, the protective metal coating material will be semi-solid or in the solid, but plastic state, and will be capable of transferring protective metal coating material to an iron surface upon contact.
  • At least the portion of the lateral surface of the roll that is to contact the coated metal substrate is a refractory oxide having a relatively low thermal conductivity selected from alumina, magnesia, zirconia, chromia, titania, yttria, and mixtures thereof.
  • the preferred oxides exhibit a good thermal shock resistance.
  • the refractory oxide often exhibits a thermal conductivity at 100°C of less than about 0.42 W/(cm ⁇ K) (0.1 cal((sec x cm x °C) preferably less than about 0.042 W/(cm ⁇ K) (0.01, cal/(sec x cm x °C)), and frequently has a coefficient of thermal expansion of less than about 1 x 10 ⁇ 5 per °C.
  • Zirconia surfaces are often desirable because of the combination of mechanical strength, shock resistance, and low thermal conductivity.
  • the surface is an yttria stabilized zirconia, i.e., zirconia containing about 6 to 10, say, about 8, weight percent yttria.
  • Figure 1 is a schematic depiction of a cross-section of a hot-dip galvanizing apparatus having a galvannealing section and a tower roll in accordance with the invention.
  • FIG. 2 is a schematic depiction of a tower roll in accordance with this invention.
  • Figure 3 is a schematic depiction of a break-away section of the surface of a tower roll in accordance with this invention.
  • Figure 4 is a schematic depiction of a horizontal galvanizing mill using a conveyor in accordance with this invention.
  • vessel 100 is externally heated and contains molten zinc 102.
  • Roll 104 is positioned below the surface of the molten zinc 102 and is adapted to receive sheet metal 106.
  • sheet metal has been pretreated to facilitate the galvanizing process. These pretreatment processes include annealing, chemical cleaning (e.g., with sulfuric acid), flame cleaning or combinations thereof.
  • the sheet metal 106 passes underneath roll 104 and is directed vertically from vessel 100. Above vessel 100 and on both sides of the sheet metal are air knives 108 which serve to remove excess molten zinc from the sheet metal.
  • the sheet metal 106 may then passes through a galvannealing unit 110.
  • the galvannealing unit may be gas fired or electrically heated to a temperature sufficient to enable a zinc and iron alloy to form.
  • This alloy provides a matte finish rather than macrospangling associated with zinc coatings.
  • This zinc and iron alloy generally forms as a solid.
  • the sheet metal 106 may then contact a guide roll 112 and then tower roll 114 where it is redirected horizontally and is typically fed into a cooling tower section (not depicted) of the mill.
  • the cooling tower section may contain a number of rolls for supporting the sheet metal and moving the sheet metal to further processing.
  • the zinc and iron alloy may be a solid, it can still be capable of being transferred.
  • a tower roll 200 is generally shown.
  • the tower roll has lateral surface 202, annular support structure 204, and spokes 206 which terminate at drive shaft 208.
  • Drive shaft 208 may be adapted for mechanical communication with a motor for the purposes of rotating the drive roll at a desired speed to move the sheet metal. In some mills, however, the tower roll is not driven.
  • Figure 3 illustrates an embodiment of the invention wherein the refractory oxide at the lateral surface of the tower roll is provided as an overlay or coating 302 over an intermediate overlay or coating 304 which improves the bonding and thermal shock resistance of the refractory oxide overlay on the tower roll.
  • the intermediate overlay is shown as being bonded to a metal substructure 306 which can provide the form of the tower roll 200 as shown in Figure 2.
  • iron-based articles 400 are transported by conveyor 402 having drive roller 404 and end roller 406 into molten zinc 408 contained in vessel 410.
  • Articles are removed from vessel 410 by conveyor 412 having drive roller 414 and end roller 416.
  • Both conveyors 402 and 412 are constructed of steel mesh.
  • Articles 400 are then passed to conveyor 418 having a loose interlocking, wire mesh structure as depicted in the inset.
  • This conveyor is fabricated of steel having a refractory oxide overlay.
  • Conveyor 418 is powered by drive rolls 420 and 422.
  • the rolls in accordance with this invention have an overlay of a refractory oxide material and have a mechanically strong and relatively inexpensive substructure, e.g., an iron or steel substructure.
  • the refractory oxide overlay need not be thick in order to obtain the benefits of the invention.
  • the thickness of the overlay is between 20 and 700 ⁇ m, and preferably from 50 to 500 ⁇ m.
  • the overlay may be applied in any convenient manner and commercial services exist for applying refractory oxide overlays.
  • the refractory oxide is typically applied through the use of a thermal spray process such as the plasma or detonation gun techniques.
  • the refractory oxide when applied by the plasma process, is typically provided in the form of a finely divided powder, e.g., in the range of about 5 to 100 ⁇ m in average particle size.
  • the application of the refractory oxide with the plasma process is desirably sufficient to provide a coating density of at least about 80 percent, and often at least about 85 to 88 percent.
  • the density is achieved by adjusting the gas flow, gas composition, amperage, voltage, torch to work distance and the like as is commonly practiced in the industry. The specific parameters that are used will vary with the design of the plasma torch used for the deposition.
  • thermal spray techniques such as disclosed in U.S. Patent Numbers 2,858,411 and 3,016,447 and detonation gun techniques such as disclosed in U.S. Patent Numbers 2,714,563 and 2,950,867 have been mentioned as possible methods of deposition of the overlays, it should be recognized that other thermal spray techniques can be used as well. These include the so-called “high velocity” plasma and “hypersonic” combustion spray processes as well as various flame spray processes. These and similar techniques are part of the "thermal spray" family of deposition technologies. Other technologies such as physical vapor deposition or chemical vapor deposition may also be applicable.
  • the oxide overlay has an undercoating comprising at least one of nickel, iron and cobalt based alloys of the type MCrAlY in which M is nickel, cobalt, iron, or any combination thereof.
  • Such an undercoating has resistance to oxidation, and it provides enhanced bond strength and improved thermal shock resistance.
  • the undercoatings can also be applied using suitable processes, e.g., the thermal spray process such as the detonation gun and plasma techniques.
  • the undercoating frequently has a thickness of at least 20 ⁇ m, e.g., between about 20 to 500 ⁇ m and preferably, about 50 to 250 ⁇ m.
  • the undercoat preferably has sufficient roughness to enhance the bonding to the refractory oxide overlay.
  • the surface of the steel superstructure should be cleaned and preferably roughened, e.g., by grit blasting.
  • the refractory oxide is applied, it is generally desired to finish the surface to produce a smooth surface.
  • This finishing can be accomplished by any suitable means such as grinding, belt sanding honing and the like.
  • a surface finish of less than 0.51 ⁇ m (20 microinches) rms is preferred.
  • a tower roll having a diameter of 60 inches (1.524 meters) with an 84 inch (2.134 meters) wide lateral surface and constructed with steel was overlayed (coated) to a thickness of 75 to 100 ⁇ m with a chrome carbide-nichrome overlay [Cr3C2+20(Ni-20Cr)] (prefix numbers refer to weight percent) applied using a detonation gun.
  • the overlay was finished to 0.15 to 0.25 ⁇ m (6 to 10 microinches) rms.
  • the tower roll was used in a galvanizing mill having a galvannealing unit and is similar to that depicted in Figure 1.
  • the distance between the molten zinc surface in the hot-dip vessel to the tower roll was about 30 meters and the distance from the top of the galvannealing unit and the tower roll was about 18 meters.
  • the galvannealing unit was about 3 meters above the molten zinc surface. Only ambient cooling was provided between the top of the galvannealing unit and the tower roll. The galvannealing unit was not being operated over the entire duration of the test using this tower roll. Rather, over some periods of time, the mill was producing the standard spangled product. After nine days pickup was visible on the entire roll face in the form of pinhead size zinc spots with smeared tails in the direction of strip travel. After an additional three days of operation, massive buildup on the roll had occurred.
  • a steel roll having a 5 inch (12.7 cm.) diameter and an 84 inch (2.134 meters) lateral surface was undercoated with a plasma deposited MCrAlY coating having a composition of 32Ni-21Cr-8Al-0.5Y-balance Co with a thickness of about 75 ⁇ m.
  • An overlay of an yttria-stabilized zirconia (ZrO2-8Y2O3) was deposited by plasma to a thickness of 325 ⁇ m. The surface was finished to less than 0.51 ⁇ m (20 microinches) rms.
  • the roll was placed in the same facility as the tower roll in Example 1 at a position immediately below the tower roll.
  • the roll was held against the sheet metal at a force comparable to or slightly higher than the force of the sheet metal on the tower roll.
  • a tendency to pick-up zinc on the surface was observed. Even so, the transferred material did not appear to agglomerate to such a size that the quality of the finish on the metal contacting the surface of the roll was deleteriously affected.
  • zinc no longer appeared to collect on the roll, and in fact, that zinc which transferred to the surface of the roll seemed to be lost.
  • After a period of six months the roll was removed from service with no evidence of zinc pickup and little or no wear on the roll face.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Thermal Sciences (AREA)
  • Coating With Molten Metal (AREA)
  • Coating Apparatus (AREA)
EP87107020A 1986-05-15 1987-05-14 Liquid film coating of iron-based metals Expired - Lifetime EP0245862B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US86344886A 1986-05-15 1986-05-15
US863448 1986-05-15

Publications (2)

Publication Number Publication Date
EP0245862A1 EP0245862A1 (en) 1987-11-19
EP0245862B1 true EP0245862B1 (en) 1991-09-25

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EP87107020A Expired - Lifetime EP0245862B1 (en) 1986-05-15 1987-05-14 Liquid film coating of iron-based metals

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EP (1) EP0245862B1 (ko)
JP (1) JP2584627B2 (ko)
KR (1) KR920002008B1 (ko)
CA (1) CA1302805C (ko)
DE (1) DE3773256D1 (ko)

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JP3356889B2 (ja) * 1994-08-26 2002-12-16 プラクスエア エス ティ テクノロジー インコーポレイテッド 耐久性に優れたハースロール
JP3312709B2 (ja) * 1994-10-24 2002-08-12 新日本製鐵株式会社 連続溶融亜鉛メッキ用浸漬ロール
JP4354315B2 (ja) 2004-03-22 2009-10-28 東芝機械株式会社 アルミニウム溶湯接触部材およびその製造方法
JP4499024B2 (ja) 2005-12-02 2010-07-07 東芝機械株式会社 アルミダイカスト用給湯管およびその製造方法
CN101410205B (zh) 2006-03-24 2011-04-06 东芝机械株式会社 铝压铸用熔液供给管
DE102016218947A1 (de) 2016-04-28 2017-11-02 Sms Group Gmbh Bauteil für eine Schmelztauchbeschichtungsanlage und Verfahren zum Herstellen eines solchen
CN108374138A (zh) * 2018-03-27 2018-08-07 苏州富博宏新材料科技有限公司 一种用于钛合金的材料的表面镀锡装置
DE102018212540A1 (de) * 2018-07-27 2020-01-30 Bayerische Motoren Werke Aktiengesellschaft Verfahren zum Beschichten eines Kraftfahrzeugrohbauteils sowie Kraftfahrzeugrohbauteil

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Also Published As

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KR870011269A (ko) 1987-12-22
JP2584627B2 (ja) 1997-02-26
DE3773256D1 (de) 1991-10-31
EP0245862A1 (en) 1987-11-19
KR920002008B1 (ko) 1992-03-09
JPS6324049A (ja) 1988-02-01
CA1302805C (en) 1992-06-09

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