EP0646658B1 - Galvanizing bath members effectively protected against the deposition of alloy layers, a process for producing said members, and a method of hot-dip galvanizing that uses said members - Google Patents

Galvanizing bath members effectively protected against the deposition of alloy layers, a process for producing said members, and a method of hot-dip galvanizing that uses said members Download PDF

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Publication number
EP0646658B1
EP0646658B1 EP94113648A EP94113648A EP0646658B1 EP 0646658 B1 EP0646658 B1 EP 0646658B1 EP 94113648 A EP94113648 A EP 94113648A EP 94113648 A EP94113648 A EP 94113648A EP 0646658 B1 EP0646658 B1 EP 0646658B1
Authority
EP
European Patent Office
Prior art keywords
members
galvanizing bath
deposition
alloy layers
molten zinc
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
EP94113648A
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German (de)
English (en)
French (fr)
Other versions
EP0646658A1 (en
Inventor
Hideo Nitta
Yang Gao
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Praxair ST Technology Inc
Praxair Technology Inc
Original Assignee
Praxair ST Technology Inc
Praxair Technology Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by Praxair ST Technology Inc, Praxair Technology Inc filed Critical Praxair ST Technology Inc
Publication of EP0646658A1 publication Critical patent/EP0646658A1/en
Application granted granted Critical
Publication of EP0646658B1 publication Critical patent/EP0646658B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/123—Spraying molten metal
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/02—Tanks; Installations therefor
    • C25D17/04—External supporting frames or structures

Definitions

  • This invention relates to the development of a means that is effective in preventing the deposition of alloy layers on the surfaces of members, such as sunk rolls and Support rolls, that are used as submerged in zinc baths or zinc-aluminum alloy baths in facilities for the production of galvanized steel plates and sheets. More specifically, the invention relates to galvanizing bath members such as those to be submerged in galvanizing baths that have many chances to contact the molten zinc and which have coatings deposited on their surfaces by thermal spraying in order to impart not only high resistance to the erosive action of the molten zinc but also effective protection against the deposition of alloy layers. The invention also relates to a process for producing said galvanizing bath members, as well as a method of hot-dip galvanizing that uses said bath members.
  • Galvanized steel plates and sheets have primarily been produced by continuous hot-dip galvanizing, in which a steel strip with cleaned surfaces is passed through a molten zinc alloy bath usually containing 0.1 - 0.2% aluminum, has the direction of its travel changed by a sunk (submerged) roll and passes by support rolls, wiping nozzles, etc. to be sent to a heating furnace, where alloying is effected and furnace-cooled to room temperature.
  • the coatings formed by thermal spraying the Conventional oxide ceramics have high resistance not only to the erosive action of molten zinc but also against the deposition of unwanted alloy layers.
  • the thermal expansion coefficient and mechanical strength of the coatings are so small that if they are actually applied to the surfaces of sunk rolls and other steel rolls, cracks will often develop, making them unsuitable as protective coatings.
  • the coatings formed by thermal spraying non-oxide ceramics are as poor in adhesion and mechanical strength as those formed by thermal spraying the oxide ceramics.
  • the addition of metallic components is essential.
  • the coatings formed by thermal spraying the mixtures with Co, Ni or Cr were eroded by either alloying with the galvanizing metal or reacting with diffusing added elements; alternatively, the addition of Co, Ni or Cr promoted the formation of alloy layers deposits on the surface of the coatings.
  • the coating formed by spray fusing the 22% Al-containing iron alloy taught in Unexamined Published Japanese Patent Application (kokai) Hei 5-78801 is an intermetallic compound of the same kind as the alloy layers to be deposited on the roll surface and, hence, the use of this alloy often induced the deposition of unwanted alloy layers.
  • the present invention has been accomplished under these circumstances and has as an object providing such an article for use either submerged in molten zinc baths or in contact with the molten zinc during continuous hot-dip galvanizing that it has a thermal sprayed coating that not only has high resistance to the molten zinc alloy but is also protected effectively against the deposition of unwanted alloy layers.
  • Another object of the invention is to provide a process for producing said article.
  • Still another object of the invention is to provide a method of hot-dip galvanizing that employs said article as a sunk roll or support rolls in the production of galvanized steel plates or sheets and thereby assures maximum protection against the deposition of unwanted alloy layers on the surfaces of those rolls.
  • the present inventors made studies to attain these objects of the invention and formed coatings using various thermal spraying materials. And in order to investigate the deposition profile of unwanted alloy layers formed on the surfaces of the coatings during hot-dip galvanizing, the inventors conducted a simulation with an experimental setup of the type shown in Fig. 1 and to be described below in details in Example 1. Based on the results of the simulation, the inventors analyzed and evaluated the alloy layers that deposited on the surfaces of test samples.
  • Fig. 1 is a schematic section of the experimental setup which was used not only in Examples 1 and 2 but also in Comparative Examples 1 - 4 to simulate the process of the formation of alloy layers on test samples.
  • the alloy layers deposited on the surfaces of sunk rolls and support rolls are mostly made of an intermetallic Zn-Fe-Al compound.
  • the deposition of the Zn-Fe-Al alloy layer starts with the dissolution of iron from the steel strip into the molten zinc alloy, goes through the formation of an Fe- and Al- supersaturated region in the liquid phase between the surfaces of the steel strip and the sunk roll, and ends with the nucleation of the supersaturated metallic components on the roll surface.
  • Papers on nucleation have pointed out that its frequency is generally determined by the matching in Crystalline structure on the surface of the material in which nuclei are to be formed, namely, the crystal matching between the surface of hot material and the precipitate, and by the surface tension of the material.
  • the coating formed by thermal spraying an oxide Ceramic or Mo-base cermet matrix that already has high resistance to the erosive action of molten zinc alloys and to which aluminum has been added in such an amount as to give 0.5 - 10 wt% Al in the as-sprayed state has not only outstanding resistance to molten zinc alloys but it also is protected effectively against the deposition of unwanted alloy layers. If the addition of aluminum is less than 0.5 wt%, the proportion of Al that occupies the coating's surface is too small to assure satisfactory protection against the deposition of unwanted alloy layers; if the addition of aluminum exceeds 10 wt%, aluminum will dissolve out of steel plates or sheets in an excessive amount to potentially cause adverse effects on their quality.
  • the oxide ceramic matrix is spinel (MgAl 2 O 4 ) or zircon (ZrSiO 4 ), the coating formed by thermal spraying it in the presence of the specified amount of Al is not only protected effectively against the deposition of intermetallic compounds but also improved in adherence and mechanical strength.
  • Aluminum has a much lower melting point than ceramics and cermets and if a given amount of aluminum as mixed with a ceramic or cermet powder is thermally sprayed, a significant portion of the sprayed aluminum will be evaporated or lost upon impinging on the substrate surface.
  • the amount of aluminum that remains in the thermal sprayed coating varies with the type of the spray method used and it is necessary to control the feed's formulation in such a way that the amount of residual aluminum will be at a preset level. This is why the range of aluminum addition to ceramics or cermets is specified by "weight percent in the as-sprayed state".
  • Fig. 1 is a schematic presentation of the experimental setup which was used not only in Examples 1 and 2 but also in Comparative Examples 1 - 4. The following description should be read with reference to Fig. 1.
  • a heater 1 holds the interior of a furnace 8 at a predetermined temperature.
  • a crucible 4 placed on a table 6 in the bottom of the furnace 8 contains a molten zinc-aluminum alloy 5.
  • a SUS 403 rod (20 mm ⁇ x 120 mm L) coupled and retained by a rotating shaft 9 is thermally sprayed with Mo-MoB + Al to prepare a thermal sprayed sample 2, which is mounted rotatably in a soft iron cylinder 3 having a window 7.
  • the thermal sprayed sample was rotated for 6 hours and its surface was examined under a microscope (X 30) and the severity of the deposition of alloyed layers was evaluated by counting the number of Zn-Fe-Al base precipitates (number of dross deposits) as identified within the visual field, as well as measuring their size ( size of dross deposits).
  • Example 1 The procedure of Example 1 was repeated except that spinel + Al was substituted as a thermal spraying material.
  • the thermal sprayed sample 2 thus prepared was immersed in the molten Zn-Al bath 5 and the severity of the deposition of alloyed layers was evaluated as in Example 1.
  • Example 2 Using the same experimental setup as in Example 1, the procedure of Example 1 was repeated except that the thermal spraying material was Mo-MoB (Comparative Example 1), Fe-Al (Comparative Example 2), Al 2 O 3 + TiO 2 (Comparative Example 3)and WC-Co(Comparative Example 4). After 6 hours of the experiment, the number of dross deposits was counted and their size was measured.
  • the thermal spraying material was Mo-MoB (Comparative Example 1), Fe-Al (Comparative Example 2), Al 2 O 3 + TiO 2 (Comparative Example 3)and WC-Co(Comparative Example 4).
  • the thermal sprayed coating of the present invention comprises a ceramic or cermet matrix having high resistance to the erosive action of molten zinc alloys and which has aluminum added thereto in an amount of 0.5 - 10 wt% in the as-sprayed composition.
  • the coating offers the advantage that if it is applied to a sunk roll and other bath members that are to be used submerged in the molten zinc bath during Continuous hot-dip galvanizing, those members are not only provided with high resistance to the erosive action of molten zinc alloys but also protected very effectively against the deposition of unwanted alloy layers which would otherwise form on the bath members during galvanizing by the prior art.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Electrochemistry (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Coating With Molten Metal (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
EP94113648A 1993-09-01 1994-08-31 Galvanizing bath members effectively protected against the deposition of alloy layers, a process for producing said members, and a method of hot-dip galvanizing that uses said members Expired - Lifetime EP0646658B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP5240392A JPH0776763A (ja) 1993-09-01 1993-09-01 合金層の付着防止性に優れた亜鉛めっき浴用部材とその製法およびそれを用いる溶融亜鉛めっき法
JP240392/93 1993-09-01

Publications (2)

Publication Number Publication Date
EP0646658A1 EP0646658A1 (en) 1995-04-05
EP0646658B1 true EP0646658B1 (en) 1996-11-06

Family

ID=17058803

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94113648A Expired - Lifetime EP0646658B1 (en) 1993-09-01 1994-08-31 Galvanizing bath members effectively protected against the deposition of alloy layers, a process for producing said members, and a method of hot-dip galvanizing that uses said members

Country Status (6)

Country Link
EP (1) EP0646658B1 (ja)
JP (1) JPH0776763A (ja)
KR (1) KR950008724A (ja)
CN (1) CN1055509C (ja)
DE (1) DE69400856T2 (ja)
TW (1) TW287207B (ja)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10147897C1 (de) * 2001-09-28 2003-01-23 Epcos Ag Verfahren zum galvanischen Aufbringen von Kontaktschichten auf keramische Bauelemente
JP4408649B2 (ja) * 2003-04-30 2010-02-03 Ｊｆｅスチール株式会社 耐ドロス付着性に優れた溶融金属めっき浴用浸漬部材
CN101734222B (zh) * 2008-11-12 2012-11-07 晨星软件研发(深圳)有限公司 监控装置及其运作方法
GB2484302A (en) * 2010-10-05 2012-04-11 Rotalok Security Ltd Seal comprising RFID tag and RFID reader with random number generator
CN114686796B (zh) * 2020-12-31 2024-02-13 安泰天龙钨钼科技有限公司 一种耐磨耐腐蚀涂层材料、涂层及其制备方法
CN117564387B (zh) * 2024-01-15 2024-03-15 烟台大学 旋转热浸连接及增材制备异种金属复合结构的方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DZ1422A1 (fr) * 1989-06-09 2004-09-13 Galva Lorraine Procédé, enciente et installation pour le revêtement continu/intermittent d'objets par passage desdits objets à travers une masse liquide d'un produitde revêtement.
CN1071709A (zh) * 1991-10-18 1993-05-05 中国人民解放军兰州军区空军后勤部科技开发中心 复合材料热镀锌槽

Also Published As

Publication number Publication date
JPH0776763A (ja) 1995-03-20
DE69400856D1 (de) 1996-12-12
EP0646658A1 (en) 1995-04-05
TW287207B (ja) 1996-10-01
CN1055509C (zh) 2000-08-16
CN1107522A (zh) 1995-08-30
KR950008724A (ko) 1995-04-19
DE69400856T2 (de) 1997-05-22

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