EP0235067B1 - Procédé de revêtement protecteur de produits sidérurgiques - Google Patents

Procédé de revêtement protecteur de produits sidérurgiques Download PDF

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Publication number
EP0235067B1
EP0235067B1 EP87470003A EP87470003A EP0235067B1 EP 0235067 B1 EP0235067 B1 EP 0235067B1 EP 87470003 A EP87470003 A EP 87470003A EP 87470003 A EP87470003 A EP 87470003A EP 0235067 B1 EP0235067 B1 EP 0235067B1
Authority
EP
European Patent Office
Prior art keywords
scale
layer
product
zinc
protective material
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
EP87470003A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0235067A1 (fr
Inventor
Danièle Quantin
Francisco Galdon
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.)
Institut de Recherches de la Siderurgie Francaise IRSID
Original Assignee
Institut de Recherches de la Siderurgie Francaise IRSID
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Institut de Recherches de la Siderurgie Francaise IRSID filed Critical Institut de Recherches de la Siderurgie Francaise IRSID
Priority to AT87470003T priority Critical patent/ATE53071T1/de
Publication of EP0235067A1 publication Critical patent/EP0235067A1/fr
Application granted granted Critical
Publication of EP0235067B1 publication Critical patent/EP0235067B1/fr
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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
    • E04C5/00—Reinforcing elements, e.g. for concrete; Auxiliary elements therefor
    • E04C5/01—Reinforcing elements of metal, e.g. with non-structural coatings
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/68—Temporary coatings or embedding materials applied before or during heat treatment
    • C21D1/72—Temporary coatings or embedding materials applied before or during heat treatment during chemical change of surfaces
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06—Zinc or cadmium or alloys based thereon
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12583—Component contains compound of adjacent metal
    • Y10T428/1259—Oxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12785—Group IIB metal-base component
    • Y10T428/12792—Zn-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12785—Group IIB metal-base component
    • Y10T428/12792—Zn-base component
    • Y10T428/12799—Next to Fe-base component [e.g., galvanized]

Definitions

  • the invention relates to the protection of the surface of steel products formed at a relatively high temperature.
  • a preferred application of the invention relates to long products and, typically but not limited to, the protection of concrete reinforcing bars.
  • the temperature at the end of production of the concrete rods at the exit from the finishing stands of the rolling mills is usually of the order of 900 to 1000 ° C.
  • the concrete reinforcing bars are then cooled, put on hold, then resumed to be cut to length.
  • concrete reinforcing bars are not considered as noble products and do not undergo any protective treatment.
  • hot dip galvanizing requires, barring exceptions (JP-A-54/133438), a prior pickling of the round with acid, because the scale is a barrier to the galvanizing reaction.
  • Calamine also opposes electrolytic deposition, or the apposition of a film-forming material, preceded by the formation of a primer layer, either by heat treatment (US-A-3085 034), or by reaction. of the bare surface with an acid solution of metallic sulphates (GB-A-1153 202) or by steam (Review of Current Litterature on the paint and allied Industries, vol. 22, n ° 129, May-June 1949, p. 265).
  • the object of the invention is to propose a protective coating process for steel products which is effective and economical, and free from the abovementioned drawbacks.
  • the invention achieves its object by the fact that the product is produced hot and the speed of its accelerated cooling is controlled from a temperature of the order of 900 to 1000 ° C. up to a temperature of 600 to 550 ° C. approximately, so that the thickness of the resulting scale which forms naturally on the surface is less than an adhesion threshold, characteristic of the metal from which the product is made and of its temperature at the end of production, and then deposited, directly on the layer of scale thus formed, a protective material.
  • the cooling of the product after its shaping is controlled, so that the average thickness of the scale layer formed during cooling does not exceed approximately 8 ⁇ m .
  • the expression "hot” refers to the temperatures, known to those skilled in the art, which result in the rapid formation of a layer of scale.
  • the invention goes against the prejudice firmly established for the skilled person, prejudice according to which the scale which naturally forms during the production of the hot product, is absolutely incompatible with the adhesion of a surface layer of material protective. Indeed, it has been surprisingly discovered that, according to the invention, when the formation of scale is controlled, this layer may have characteristics (of adhesion and roughness in particular) which make it possible to apply it directly (ie without pickling, but without excessive waiting which would degrade the surface) a perfectly adherent protective coating.
  • the protective coating is a layer of a material intended to form itself a barrier between the metal surface, covered with scale, and the atmosphere (without the intervention of a chemical reaction mique between said material and the scale, unlike the document FR-A-2 029 285 cited above).
  • Controlling the formation of scale involves controlling the cooling: rapid cooling (by soaking in water, for example) is particularly favorable because it avoids maintaining the metal surface for too long at a relatively high temperature, conducive to the rapid development of scale.
  • the cooling control is often easier with long products, especially of relatively small section, than with flat products.
  • the invention finds a particularly advantageous application in the context of installations for the production of concrete reinforcing bars where an accelerated cooling device exists.
  • TORSID [ R ] the concrete rod is quenched by a sheath of water, while passing through a cooling tube. Subsequent natural heating from the core leaves the product surface at 400-500 ° C at the outlet of the rolling train.
  • the bars are hot cut and placed laterally on an air-cooling table, allowing the temperature to drop to appreciably ambient temperature, with a view to resuming them, for exact lengthening and leaving the installation. .
  • the fresh scale covering the concrete rods (with an average thickness of 2 to 3 ⁇ m) allows direct coating with a layer of protective material.
  • the coating is a zinc metallization by spraying, because this technique can take place over a wide range of temperatures, which makes it possible to treat the bars at any stage of their cooling on the cooling table.
  • the method according to the invention is all the more economical since not only does it avoid the descaling step, but it is inserted locally in a generally uncluttered zone of the installation and is inserted in a passive phase of the round cooling process.
  • the average thickness of the zinc coating is advantageously of the order of 20 to 40 ⁇ m, to provide sufficient protection. A much greater thickness can lead, in the case of folding of the coated round, to cracking of the coating. However, it should be noted that, even when cracked, the zinc coating provides protection (sacrificial type this time).
  • zinc and aluminum alloys can be used instead of zinc (the latter entering in proportion up to 20%), easier to apply and having better resistance.
  • the preferred alloy is the Dunois alloy (90% Zn - 10% AI).
  • the holding of the protective coating directly applied to the scale is conditioned by the adhesion of the scale and the quality of its surface.
  • adhesion covers two aspects: the adhesion before application of the protective coating, which is linked to the adhesion of the oxide layer during its growth, during the accelerated cooling of the raw product, and the adhesion to the during the forming of the coated product, which is linked to the deformation ability of the oxides during mechanical deformation of the coated product (for example, by bending the ends of the concrete bars).
  • the oxide formation takes place with an increase in volume (x 1.7 to 2) compared to the metal which gave it birth. Therefore, at the metal / scale interface, the oxide is in compression and the metal in tension. All of these accumulated stresses are resolved without breaking for thin calamines (a few micrometers) and all the better since the structure of the oxides is said to be decomposed (accelerated cooling to approximately 600-550 ° C. then slowed down to room temperature - but in a generally weak oxidizing atmosphere). For thick calamines (greater than about 10 ⁇ m), the stresses are absorbed by oxides ruptures and detachments at the interface. So, without external mechanical stresses for simple reasons of growth, a scale, to be non-degraded, must be thin (a few ⁇ m). Generally, until about 6-8 pm, there is no break.
  • the limiting thickness increases.
  • the metallic coating does not come off with the oxide during a deformation, its thickness must be less than a limit value, which has never been quantified, during experiments on concrete rods, in below 8 ⁇ m.
  • the surface of the scale must be rough, clean and regular. These qualities most often depend on the stages of prior shaping of the product. In the case of long products (and particularly concrete reinforcing bars), the surface roughness after shaping in rolling trains, is generally important (very often very superior to that of flat products which require a more careful surface quality). The cleanliness and regularity of the surface are then ensured if the installation of the coating takes place, in accordance with the invention, directly on the oxide which has just been formed, without unnecessary waiting.
  • this adhesion threshold is defined as the maximum value of the calamine thickness which simultaneously satisfies these two aspects, therefore the more severe of the two. In this case, it is that relating to the adhesion of scale during formation on a straight rectilinear product of manufacture and whose said maximum value reaches approximately 8 ⁇ m.
  • the thickness of scale "C” formed in accordance with the invention was measured on concrete bars “M” obtained by the “TORSID” process.
  • the average thickness is 1 to 2 ⁇ m, with, very locally, extra thicknesses of up to 12 ⁇ m. Micrographs have confirmed that the oxide layer is very adherent and that the appearance of the external surface is tormented, with significant roughness.
  • the concrete bars previously examined were zinc-plated by spraying with a gun.
  • a series of samples received an "R" coating with an average thickness of 60 ⁇ m.
  • a second series received a coating with an average thickness of 200 ⁇ m.
  • Micrographs of the rounds of test 1 made it possible to note an excellent penetration of zinc R into all the crevices of the scale 'C' and of the surface of the metal M; very good adhesion of the coating to the scale; a very good compactness of the coating and a very rough external appearance, suggesting good bonding with the concrete.
  • test 1 The rounds of test 1 were tested in a salt spray under the following standard conditions: temperature of 35 ° C and water at 5% NaCl (50 g / I).
  • the rounds coated with the Dunois alloy held better than those coated with pure zinc (fig. 3 b).
  • Shaped circles and rectilinear circles have similar resistance to salt spray for a coating of the same type: in particular, there is no appearance of rust in the chipped zone of the shaped circles surface protection ).
EP87470003A 1986-02-06 1987-02-03 Procédé de revêtement protecteur de produits sidérurgiques Expired - Lifetime EP0235067B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87470003T ATE53071T1 (de) 1986-02-06 1987-02-03 Verfahren zum aufbringen von schutzueberzuegen auf metallurgischen produkten.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8601636A FR2593831B1 (fr) 1986-02-06 1986-02-06 Procede de revetement protecteur d'un produit en fer ou en acier et produit revetu
FR8601636 1986-02-06

Publications (2)

Publication Number Publication Date
EP0235067A1 EP0235067A1 (fr) 1987-09-02
EP0235067B1 true EP0235067B1 (fr) 1990-05-23

Family

ID=9331869

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87470003A Expired - Lifetime EP0235067B1 (fr) 1986-02-06 1987-02-03 Procédé de revêtement protecteur de produits sidérurgiques

Country Status (15)

Country Link
US (2) US4801338A (el)
EP (1) EP0235067B1 (el)
JP (1) JPS63121650A (el)
KR (1) KR920001388B1 (el)
CN (1) CN1018658B (el)
AT (1) ATE53071T1 (el)
BR (1) BR8700518A (el)
CA (1) CA1293163C (el)
DE (1) DE3762887D1 (el)
ES (1) ES2016111B3 (el)
FR (1) FR2593831B1 (el)
GR (1) GR3000713T3 (el)
IN (1) IN169271B (el)
MX (1) MX168070B (el)
PT (1) PT84250B (el)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01263255A (ja) * 1988-04-14 1989-10-19 Nippon Aen Kogyo Kk 高付着溶融アルミニウム−亜鉛合金めっき方法
US5449563A (en) * 1994-05-20 1995-09-12 Cominco Ltd. Galvanic protection of rebar by zinc wire
US5909984A (en) * 1997-02-15 1999-06-08 Matthews; Mike R. Pile forming system and method of using the same
US20060000183A1 (en) * 2001-12-20 2006-01-05 Farwest Steel Corporation Method and apparatus for anticorrosive coating
US7086897B2 (en) * 2004-11-18 2006-08-08 John Mezzalingua Associates, Inc. Compression connector and method of use
JP7158197B2 (ja) * 2018-07-30 2022-10-21 前田建設工業株式会社 鉄筋の耐食性を向上させた金属系防食被膜の生成方法
JP7312583B2 (ja) * 2019-03-22 2023-07-21 株式会社栗本鐵工所 鋳鉄管およびその製造方法
JP7285667B2 (ja) * 2019-03-22 2023-06-02 株式会社栗本鐵工所 鋳鉄管の製造方法および鋳鉄管の表面防食方法

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1055872A (fr) * 1951-03-28 1954-02-23 Commission Administrative Du P élément de construction en acier résistant à la corrosion et procédé de revêtement des constructions
US3085034A (en) * 1958-07-10 1963-04-09 Polymer Processes Inc Coating process
FR1360754A (fr) * 1963-03-12 1964-05-15 Procédé pour protéger contre la corrosion les aciers utilisés dans les ouvrages précontraints
NL133681C (el) * 1966-02-18 1900-01-01
FR2029285A5 (en) * 1969-01-23 1970-10-16 Borax Francais Protecting rolled or forged steel pro- - ucts against corrosion
BE737682A (en) * 1969-08-19 1970-02-19 Wire rod manufacturing process
US3700505A (en) * 1971-01-11 1972-10-24 Jerome J Kanter Coating ferrous base metal articles
JPS56503B2 (el) * 1972-08-10 1981-01-08
US3925579A (en) * 1974-05-24 1975-12-09 Armco Steel Corp Method of coating low alloy steels
BE817338A (fr) * 1974-07-05 1975-01-06 Procede et installation pour le traitement de fil machine.
BE826201A (fr) * 1975-02-28 1975-06-16 Perfectionnement a un procede et a une installation de refroidissement de produits en acier lamines
FI751200A (el) * 1975-04-22 1976-10-23 Ovako Oy
JPS54133438A (en) * 1978-04-08 1979-10-17 Nippon Steel Corp Manufacture of plated steel sheet
DE2820289C2 (de) * 1978-05-10 1986-09-18 Leybold-Heraeus GmbH, 5000 Köln Verfahren zum Beschichten von metallischen Substraten mit Legierungsschichten bei erhöhter Substrattemperatur
US4242153A (en) * 1978-10-16 1980-12-30 Morgan Construction Company Methods for hot rolling and treating rod
BE874599A (fr) * 1979-03-02 1979-09-03 Centre Rech Metallurgique Procede de fabrication d'une bande d'acier revetue
US4297150A (en) * 1979-07-07 1981-10-27 The British Petroleum Company Limited Protective metal oxide films on metal or alloy substrate surfaces susceptible to coking, corrosion or catalytic activity
US4425383A (en) * 1982-07-06 1984-01-10 Xerox Corporation Process for oxidation of carrier particles
JPS6126763A (ja) * 1984-07-17 1986-02-06 Nippon Steel Corp 高密着性溶射被膜の形成方法
JPS6137959A (ja) * 1984-07-27 1986-02-22 Nippon Steel Corp 薄鋼板上の溶射被膜形成方法

Also Published As

Publication number Publication date
FR2593831B1 (fr) 1994-01-21
CA1293163C (fr) 1991-12-17
ATE53071T1 (de) 1990-06-15
CN1018658B (zh) 1992-10-14
GR3000713T3 (en) 1991-10-10
KR870008038A (ko) 1987-09-23
IN169271B (el) 1991-09-21
EP0235067A1 (fr) 1987-09-02
JPS63121650A (ja) 1988-05-25
PT84250B (pt) 1989-09-14
MX168070B (es) 1993-05-03
US5066548A (en) 1991-11-19
CN87102165A (zh) 1987-12-09
BR8700518A (pt) 1987-12-08
DE3762887D1 (de) 1990-06-28
US4801338A (en) 1989-01-31
PT84250A (fr) 1987-03-01
FR2593831A1 (fr) 1987-08-07
ES2016111B3 (es) 1990-10-16
KR920001388B1 (ko) 1992-02-13

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