EP0245862A1 - Liquid film coating of iron-based metals - Google Patents
Liquid film coating of iron-based metals Download PDFInfo
- Publication number
- EP0245862A1 EP0245862A1 EP87107020A EP87107020A EP0245862A1 EP 0245862 A1 EP0245862 A1 EP 0245862A1 EP 87107020 A EP87107020 A EP 87107020A EP 87107020 A EP87107020 A EP 87107020A EP 0245862 A1 EP0245862 A1 EP 0245862A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- roll
- coating material
- protective metal
- metal coating
- 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.)
- Granted
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 123
- 239000002184 metal Substances 0.000 title claims abstract description 123
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000007788 liquid Substances 0.000 title claims abstract description 22
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 19
- 239000007888 film coating Substances 0.000 title claims description 14
- 238000009501 film coating Methods 0.000 title claims description 14
- 150000002739 metals Chemical class 0.000 title description 6
- 238000000576 coating method Methods 0.000 claims abstract description 84
- 239000011248 coating agent Substances 0.000 claims abstract description 74
- 230000001681 protective effect Effects 0.000 claims abstract description 58
- 239000000463 material Substances 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 51
- 230000008569 process Effects 0.000 claims abstract description 37
- 239000000758 substrate Substances 0.000 claims abstract description 32
- 239000000919 ceramic Substances 0.000 claims abstract description 8
- 239000011701 zinc Substances 0.000 claims description 41
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 40
- 229910052725 zinc Inorganic materials 0.000 claims description 38
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 229910000531 Co alloy Inorganic materials 0.000 claims description 2
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052574 oxide ceramic Inorganic materials 0.000 claims 3
- 239000011224 oxide ceramic Substances 0.000 claims 3
- 229910052804 chromium Inorganic materials 0.000 claims 1
- 239000011651 chromium Substances 0.000 claims 1
- 238000012546 transfer Methods 0.000 abstract description 15
- 238000001816 cooling Methods 0.000 abstract description 10
- 230000002411 adverse Effects 0.000 abstract description 4
- 230000004888 barrier function Effects 0.000 abstract description 4
- 238000005244 galvannealing Methods 0.000 description 14
- 238000005246 galvanizing Methods 0.000 description 11
- 239000010959 steel Substances 0.000 description 10
- 229910000831 Steel Inorganic materials 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000007921 spray Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000005507 spraying Methods 0.000 description 5
- 229910001297 Zn alloy Inorganic materials 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000005474 detonation Methods 0.000 description 4
- 230000035939 shock Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 2
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001208 Crucible steel Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- FJMNNXLGOUYVHO-UHFFFAOYSA-N aluminum zinc Chemical compound [Al].[Zn] FJMNNXLGOUYVHO-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000000788 chromium alloy Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003028 elevating effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- -1 i.e. Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910001120 nichrome Inorganic materials 0.000 description 1
- 229910000623 nickel–chromium alloy Inorganic materials 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004901 spalling Methods 0.000 description 1
- 229910000648 terne Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910003470 tongbaite Inorganic materials 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Images
Classifications
-
- 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.
- the rolls to contact the protective metal coating material comprise a body defining a surface for contact with the protective metal coated metal which body is adapted to be rotated around its axis wherein at least that portion of the surface intended to contact the metal is a ceramic surface or barrier system.
- the ceramic surface or barrier is a refractory oxide and has thickness of at least about 20 microns.
- the roll can be used in apparatus for the liquid film coating of sheet metal in a continuous manner.
- This invention also relates to processes for the liquid film coating of metal in which the metal is contacted with molten protective metal coating material to provide a coating of the protective metal coating material on the metal, and thereafter contacting the metal with a roll in accordance with this invention for purposes of directing the metal in a desired direction, said contact occurring while the protective metal coating is capable of transfer.
- the protective metal coated material contacts a continuous conveyor and the contact surface of the conveyer is a ceramic surface system.
- the conveyor 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 such as alumina, magnesia, zirconia, chromia, titania, silica, and the like 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 0.1, preferably less than about 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.
- 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.
- the 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 preferably 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. Often the thickness of the overlay is about 25 to 700, say, about 50 to 500, microns.
- 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 microns 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 may or may not have an undercoating.
- Undercoatings for instance, composed of nickel, iron or cobalt based alloy with resistance to oxidation, can often provide enhanced bond strength and improved thermal shock resistance.
- Particularly useful undercoating materials include nickel-aluminum or nickel-chromium alloys and the MCrAl and MCrAlY alloys in which M is nickel, cobalt, iron, or any conbination thereof.
- Alternative undercoats that may be used consist of a mixture of metals and oxides, or graded structures that consist of a first layer of pure metal with continuous or discontinuous additions of oxide with increasing volume fraction of oxide toward the outer surface.
- 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 when used, frequently has a thickness of at least 20 microns, e.g., between about 20 to 500, say, about 50 to 250, microns.
- 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 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 microns 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 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. Attempts were made to remove the buildup using 120 grit aluminum oxide sandpaper with very little success. The roll face temperature was measured during operation and found to be about 980°F. The roll was removed from service after about 39 days of operation. This illustrates the unsatisfactory performance of a state-of-the-art conventional overlay.
- 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 microns.
- An overlay of an yttria-stabilized zirconia (ZrO2-8Y2O3) was deposited by plasma to a thickness of 325 microns. The surface was finished to less than 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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Abstract
Description
- 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. 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. These types of processes are herein referred to as "liquid film coating" processes.
- Galvanizing (zinc coating) 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). Typically in continuous processes 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. In these processes, 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. In general, 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.
- Further information about applying protective metal coatings can be found in "THE MAKING, SHAPING AND TREATING OF STEEL", Tenth Edition, 1985, Association of Iron and Steel Engineers/United States Steel Corporation, herein incorporated by reference.
- With the current emphasis on corrosion resistance in the automotive and other industries, protective metal coating processes, especially galvanizing, are sought-after treatments for iron-based materials for fabrication. In many such applications the protective metal coating must be painted and the resulting finish must be very smooth to meet the approval of the ultimate consumer. Unfortunately, galvanized finishes are characterized by crystal structures that provide large relief patterns, referred to as "spangles", which are difficult to paint without their crystal pattern showing through the paint.
- Recently a process modification referred to as galvannealing has found acceptance in providing galvanized coatings having a substantial absence of spangles as well as superior mechanical properties. In the galvannealing process, 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.
- Difficulties exist when adapting the conventional galvanizing processes to utilize the galvannealing technique. As stated earlier, 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.
- Proposals to eliminate the deposits on the tower roll have included cooling the tower roll, externally with water or internally with water or a glycol solution. By cooling the tower roll, it was thought that the cooler surface would have less affinity for the zinc and that the chilling would result in the spalling of any transferred zinc particles from the roll. This procedure proved to be unsuccessful. Pick-up still occurred, and variations in the temperature over the surface of the roll resulted, in some instances, in buckling or warping of the sheet metal. Direct spraying of the galvanized sheet metal also proved to be unsuccessful due to temperature differentials that cause the sheet metal to buckle or warp. Another proposal has been to scrape the surface of the tower roll with a blade to remove any accumulated zinc. This approach has not been effective in adequately removing the zinc and the problems continue. It is also possible to reduce the rate of production of the galvanized metal or to modify the equipment by further elevating the tower roll to allow for sufficient cooling to prevent zinc transfer. The first alternative is unattractive due to the reduced production capacity and the latter alternative suffers from substantial capital costs in revamping existing facilities.
- The most common practice has been the periodic maintenance and/or replacement of tower rolls. However, because of the location of the tower rolls and the heat in the vicinity of the tower rolls due to their location in the mill, this procedure is difficult, time consuming, and results in lost production and spotty quality.
- By this invention processes and apparatus have been provided that enable iron-based metals having protective metal coatings applied thereon by a liquid film coating technique to contact rolls such as tower rolls, conveyor rolls, guide rolls and the like while the protective metal coating material has not yet cooled or solidified sufficiently to avoid transfer of the protective metal coating material to ordinary roll surfaces without transfer of materal so that acceptable finishes can be obtained i.e., undue amounts of the protective metal coatings do not transfer to the rolls. Accordingly, conventional galvanizing mills can be modified to include a galvannealing unit yet still use the existing tower roll configuration and production rates when using this invention. This invention is also useful in other types of mills.
- In accordance with this invention the rolls to contact the protective metal coating material, comprise a body defining a surface for contact with the protective metal coated metal which body is adapted to be rotated around its axis wherein at least that portion of the surface intended to contact the metal is a ceramic surface or barrier system. The ceramic surface or barrier is a refractory oxide and has thickness of at least about 20 microns. Advantageously, the roll can be used in apparatus for the liquid film coating of sheet metal in a continuous manner.
- This invention also relates to processes for the liquid film coating of metal in which the metal is contacted with molten protective metal coating material to provide a coating of the protective metal coating material on the metal, and thereafter contacting the metal with a roll in accordance with this invention for purposes of directing the metal in a desired direction, said contact occurring while the protective metal coating is capable of transfer.
- In another aspect of the invention, the protective metal coated material contacts a continuous conveyor and the contact surface of the conveyer is a ceramic surface system. The conveyor 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.
- As stated above, 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. In 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.
- In the spraying process, the molten protective metal coating material is sprayed to contact the metal substrate. Often when using the spraying process, the protective metal coating material solidifies immediately upon contact with the cooler metal substrate. However, in such situation, 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. For instance, 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.
- When the protective metal coating materials are characterized by spangles such as galvanized coatings, the liquid film coating may be contacted with a nucleating agent which promotes the formation of smaller crystal structures, i.e., microspangles. For example, 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 such as alumina, magnesia, zirconia, chromia, titania, silica, and the like 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 0.1, preferably less than about 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. Most preferably, 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.
- Figure 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.
- With reference to Figure 1,
vessel 100 is externally heated and containsmolten zinc 102.Roll 104 is positioned below the surface of themolten zinc 102 and is adapted to receivesheet metal 106. Generally the 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 underneathroll 104 and is directed vertically fromvessel 100. Abovevessel 100 and on both sides of the sheet metal areair knives 108 which serve to remove excess molten zinc from the sheet metal. - The
sheet metal 106 may then passes through agalvannealing 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. Thesheet metal 106 may then contact aguide roll 112 and then towerroll 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. Although the zinc and iron alloy may be a solid, it can still be capable of being transferred. - With reference to Figure 2, a
tower roll 200 is generally shown. The tower roll haslateral surface 202,annular support structure 204, andspokes 206 which terminate atdrive shaft 208. Driveshaft 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 orcoating 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 ametal substructure 306 which can provide the form of thetower roll 200 as shown in Figure 2. - With reference to Figure 4, iron-based
articles 400 are transported byconveyor 402 havingdrive roller 404 andend roller 406 intomolten zinc 408 contained invessel 410. Articles are removed fromvessel 410 byconveyor 412 havingdrive roller 414 andend roller 416. Bothconveyors Articles 400 are then passed toconveyor 418 having a loose interlocking, wire mesh structure as depicted in the inset. The 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 preferably 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. Often the thickness of the overlay is about 25 to 700, say, about 50 to 500, microns.
- 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 microns 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.
- Although plasma 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 may or may not have an undercoating. Undercoatings, for instance, composed of nickel, iron or cobalt based alloy with resistance to oxidation, can often provide enhanced bond strength and improved thermal shock resistance. Particularly useful undercoating materials include nickel-aluminum or nickel-chromium alloys and the MCrAl and MCrAlY alloys in which M is nickel, cobalt, iron, or any conbination thereof. Alternative undercoats that may be used consist of a mixture of metals and oxides, or graded structures that consist of a first layer of pure metal with continuous or discontinuous additions of oxide with increasing volume fraction of oxide toward the outer surface.
- 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, when used, frequently has a thickness of at least 20 microns, e.g., between about 20 to 500, say, about 50 to 250, microns.
- When an undercoat is used, it is preferred that it have sufficient roughness to enhance the bonding to the refractory oxide overlay. Regardless of whether the steel superstructure is to be undercoated its surface should be cleaned and preferably roughened, e.g., by grit blasting.
- Once 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 20 microinches rms is preferred.
- The following examples are provided to further illustrate the invention and are not intended to be in limitation thereof.
- 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 microns 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 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. Attempts were made to remove the buildup using 120 grit aluminum oxide sandpaper with very little success. The roll face temperature was measured during operation and found to be about 980°F. The roll was removed from service after about 39 days of operation. This illustrates the unsatisfactory performance of a state-of-the-art conventional overlay.
- 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 microns. An overlay of an yttria-stabilized zirconia (ZrO₂-8Y₂O₃) was deposited by plasma to a thickness of 325 microns. The surface was finished to less than 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. When first placing the roll into service, 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. After further use of the roll, 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. There was some grooving at the edge of the strip because the roll has been performing so successfully it was used to guide this strip across the tower roll by applying more pressure to one edge than the other. During this period of service a variety of strip product was run, including standard-spangled and galvannealed.
Claims (24)
Applications Claiming Priority (2)
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US86344886A | 1986-05-15 | 1986-05-15 | |
US863448 | 1986-05-15 |
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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 (en) |
JP (1) | JP2584627B2 (en) |
KR (1) | KR920002008B1 (en) |
CA (1) | CA1302805C (en) |
DE (1) | DE3773256D1 (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0492500A2 (en) * | 1990-12-24 | 1992-07-01 | BEHRINGWERKE Aktiengesellschaft | Protecting plasmodium falciparum hybrid proteins, containing partial sequences of malaria antigens HRPII and SERP |
EP0698672A1 (en) * | 1994-08-26 | 1996-02-28 | Praxair S.T. Technology, Inc. | Hearth roll with superior indurance capacity |
EP0712939A3 (en) * | 1994-10-24 | 1996-05-29 | Praxair S.T. Technology, Inc. | Pot roll for continuous hot-dip galvanizing |
DE102016218947A1 (en) | 2016-04-28 | 2017-11-02 | Sms Group Gmbh | Component for a hot dip coating plant and method for producing such |
CN108374138A (en) * | 2018-03-27 | 2018-08-07 | 苏州富博宏新材料科技有限公司 | A kind of surface tin-plating device of material for titanium alloy |
CN112218968A (en) * | 2018-07-27 | 2021-01-12 | 宝马股份公司 | Method for coating a motor vehicle blank and motor vehicle blank |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
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JP4354315B2 (en) | 2004-03-22 | 2009-10-28 | 東芝機械株式会社 | Aluminum melt contact member and method of manufacturing the same |
JP4499024B2 (en) | 2005-12-02 | 2010-07-07 | 東芝機械株式会社 | Hot water supply pipe for aluminum die casting and method for manufacturing the same |
US8580187B2 (en) | 2006-03-24 | 2013-11-12 | Toshiba Kikai Kabushiki Kaisha | Melt supply pipe for aluminum die casting |
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CH574285A5 (en) * | 1974-03-20 | 1976-04-15 | Alusuisse | Refractory coating for continuous casting mould moving bands - comprises layers of refractory covered with resin filled with fine inorg matl |
JPS5456943A (en) * | 1977-10-15 | 1979-05-08 | Asahi Glass Co Ltd | One side molten metal plating device |
JPS5740885A (en) * | 1980-08-25 | 1982-03-06 | Nippon Denso Co | Ignition plug |
JPS57174440A (en) * | 1981-04-20 | 1982-10-27 | Nisshin Steel Co Ltd | Member for molten metallic bath |
JPS5925966A (en) * | 1982-08-03 | 1984-02-10 | Nippon Steel Corp | Material for equipment in galvanizing bath |
JPS6029457A (en) * | 1983-07-29 | 1985-02-14 | Nippon Steel Corp | Member with high corrosion resistance immersed in hot galvanizing bath |
US4581073A (en) * | 1984-04-10 | 1986-04-08 | Allegheny Ludlum Steel Corporation | Method for descaling metal strip |
JPH06137955A (en) * | 1992-10-22 | 1994-05-20 | Furukawa Electric Co Ltd:The | Pipe temperature measuring apparatus |
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1987
- 1987-04-30 CA CA000536063A patent/CA1302805C/en not_active Expired - Lifetime
- 1987-05-14 KR KR1019870004833A patent/KR920002008B1/en not_active IP Right Cessation
- 1987-05-14 JP JP62116050A patent/JP2584627B2/en not_active Expired - Lifetime
- 1987-05-14 DE DE8787107020T patent/DE3773256D1/en not_active Expired - Lifetime
- 1987-05-14 EP EP87107020A patent/EP0245862B1/en not_active Expired - Lifetime
Non-Patent Citations (1)
Title |
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PATENT ABSTRACTS OF JAPAN, unexamined applications, C field, vol. 9, no. 153, June 27, 1985 THE PATENT OFFICE JAPANESE GOVERNMENT page 6 C 288 & JP-A-60-29 457 ( shin nippon seitetsu k.k. ) * |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0492500A2 (en) * | 1990-12-24 | 1992-07-01 | BEHRINGWERKE Aktiengesellschaft | Protecting plasmodium falciparum hybrid proteins, containing partial sequences of malaria antigens HRPII and SERP |
EP0492500A3 (en) * | 1990-12-24 | 1993-02-10 | Behringwerke Aktiengesellschaft | Protecting plasmodium falciparum hybrid proteins, containing partial sequences of malaria antigens hrpii and serp |
CN1062316C (en) * | 1994-08-25 | 2001-02-21 | 普拉塞尔·S·T·技术有限公司 | Hearth roll with superior indurance capacity |
EP0698672A1 (en) * | 1994-08-26 | 1996-02-28 | Praxair S.T. Technology, Inc. | Hearth roll with superior indurance capacity |
EP0712939A3 (en) * | 1994-10-24 | 1996-05-29 | Praxair S.T. Technology, Inc. | Pot roll for continuous hot-dip galvanizing |
DE102016218947A1 (en) | 2016-04-28 | 2017-11-02 | Sms Group Gmbh | Component for a hot dip coating plant and method for producing such |
CN108374138A (en) * | 2018-03-27 | 2018-08-07 | 苏州富博宏新材料科技有限公司 | A kind of surface tin-plating device of material for titanium alloy |
CN112218968A (en) * | 2018-07-27 | 2021-01-12 | 宝马股份公司 | Method for coating a motor vehicle blank and motor vehicle blank |
Also Published As
Publication number | Publication date |
---|---|
CA1302805C (en) | 1992-06-09 |
JPS6324049A (en) | 1988-02-01 |
KR870011269A (en) | 1987-12-22 |
DE3773256D1 (en) | 1991-10-31 |
KR920002008B1 (en) | 1992-03-09 |
JP2584627B2 (en) | 1997-02-26 |
EP0245862B1 (en) | 1991-09-25 |
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