EP0902098A1 - Verfahren zum Herstellen eines legierten verzinkten Bleches ohne dzeta phase auf der Oberfläche - Google Patents

Verfahren zum Herstellen eines legierten verzinkten Bleches ohne dzeta phase auf der Oberfläche Download PDF

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Publication number
EP0902098A1
EP0902098A1 EP98402165A EP98402165A EP0902098A1 EP 0902098 A1 EP0902098 A1 EP 0902098A1 EP 98402165 A EP98402165 A EP 98402165A EP 98402165 A EP98402165 A EP 98402165A EP 0902098 A1 EP0902098 A1 EP 0902098A1
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EP
European Patent Office
Prior art keywords
treatment
phase
maximum temperature
galvanized
less
Prior art date
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Granted
Application number
EP98402165A
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English (en)
French (fr)
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EP0902098B1 (de
Inventor
Jean-Michel Prat
Thierry Moreau
Thérèse Six
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.)
Sollac SA
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Sollac SA
Lorraine de Laminage Continu SA SOLLAC
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Application filed by Sollac SA, Lorraine de Laminage Continu SA SOLLAC filed Critical Sollac SA
Publication of EP0902098A1 publication Critical patent/EP0902098A1/de
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/28—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases more than one element being applied in one step

Definitions

  • the invention relates to a sheet of galvanized alloy steel resistant to both dusting and chipping.
  • the invention relates to methods of manufacturing this steel sheet.
  • galvanized alloy in which, after quenching a sheet of steel in a galvanizing, heat treatment of the galvanized steel sheet to achieve a zinc-iron alloy between the galvanizing layer based on zinc and its iron-based substrate.
  • the invention relates more particularly to heat treatment of alliance.
  • the structure of the alloyed galvanized coating obtained by this type of process is generally laminated into several superimposed layers of phases different iron-zinc alloy, richer in zinc near the surface, more rich in iron near the substrate-coating interface.
  • the resulting alloyed galvanized coating considered in all of its thickness, generally has an average iron content of between 8 and 14%.
  • Powdering and flaking are mechanical degradations of the coating which is generally observed under the effect of stresses applied to the sheet in sheet metal stamping operations.
  • Powdering occurs by cracking in the very thickness of the coating, in particular under the effect of compression stresses in the blank holder area of the stamping machine.
  • phase ⁇ The disadvantages of the presence of phase ⁇ are greater on the grades of low carbon steel known as “ULC” (Ultra Low Carbon in English language) ; indeed, on these grades, galvanized coatings or galvanized alloys indeed exhibit a less good adhesion, which increases the risk of chipping at this interface under the effect of shear transmitted by the surface ⁇ phase.
  • ULC Ultra Low Carbon in English language
  • a low carbon steel grade is called either a steel containing less than 5.10 -3 % by weight of carbon, or a steel having a higher carbon content but a large part of which is trapped by additives such as titanium. and / or niobium.
  • the object of the invention is to provide an alloyed galvanized steel sheet. having both good dusting and flaking resistance, particularly without phase ⁇ on the surface and with hard and brittle phases, in particular ⁇ , of minimized thickness.
  • Galvanizing baths generally contain aluminum for control the alloying of the coating within the bath itself; so it is quite classic to find aluminum ( ⁇ 0.5%) in the galvanized layer ally; the aluminum content in the layer is conventionally of the order of 0.2%.
  • the object of the invention is to provide an alloyed galvanized steel sheet. having both good dust and chipping resistance.
  • the invention also aims to limit the formation of background mattes during the galvanizing stage.
  • the continuous production facility for alloyed galvanized sheet according to the invention conventionally comprises a device for galvanizing by soaked in a bath of molten metal and, online, a treatment device thermal alloy.
  • the alloying device therefore comprises strip running means having, in the running direction, a rising strand, a support and tape guide roller at the top of the installation (in English: "top roll”), and a downward strand.
  • the rising strand is positioned directly above the galvanizing bath and strip wiping means, which are part of the galvanizing device.
  • the heat treatment means include for example temperature rise means and a holding oven.
  • Heat treatment means and cooling means are known in themselves and are not described here in detail.
  • the alloying is carried out during a single stage of heat treatment, unlike the processes described in documents JP 02 194157 A and JP 07 034213 A from SUMITOMO, JP 08 165 550, JP 05 320 853 A and JP 61 223 174 A from NIPPON STEEL.
  • the process according to the invention is specially adapted for the preparation of galvanized alloyed layers on steel sheets known as "without interstitial” (in English language “Intersticial Free” or “IF”) and stampable; we hear by stampable IF steel of the grades “IF”, or “IF (Ti, Nb)", “IF (Ti, B)", or “IF (Ti)", ie "IF” steels without other elements of addition (such as Ti and / or Nb, B) than those intended to trap carbon and / or nitrogen.
  • the bath therefore essentially contains zinc, aluminum to control the alloy in the bath, iron resulting from the dissolution of the strip and inevitable residual impurities; this bath can also contain flowering agents, such as lead, antimony or bismuth; the aluminum content by weight in the bath is between 0.10 and 0.135%; the proportions of nickel and chromium from impurities are much less than 0.02% and 0.1% by weight, respectively.
  • the alloying heat treatment means At the outlet of the galvanizing device and after spinning, using the alloying heat treatment means, then continuously heating the tape up to a maximum temperature greater than or equal to 490 ° C, while maintaining suitable temperature and treatment time conditions on the one hand to obtain a complete alloy ( ⁇ without phase ⁇ ) of the coating of galvanizing with strip steel on the other hand so that the content average iron in the alloy coating obtained does not exceed 6 g / m2.
  • the maximum temperature reached by the strip during this treatment is understood between 490 ° C and 510 ° C, if possible between 495 ° C and 505 ° C.
  • the strip is then cooled. sheet metal at a temperature low enough that the coating is not deteriorated when the tape passes over the tape support roller Summit ; this temperature is generally less than or equal to 300 ° C.
  • a strip is then obtained in a single heat treatment step.
  • galvanized alloy steel very resistant to both chipping and dusting.
  • This steel strip resists chipping because the proportion of phase ⁇ in surface is below the detectable threshold; the goal of low proportion of phase ⁇ is reached according to the invention whatever the duration of the treatment because the maximum treatment temperature is greater than or equal to 490 ° C, as illustrated in example 1 below.
  • This steel strip resists dusting because the amount of iron contained in the coating is less than or equal to 6 g / m2, as illustrated Example 2 below.
  • the maximum heat treatment temperature is below 490 ° C, for example in the range 450 ° C-490 ° C as in the prior art, depending on the duration of treatment, there is a risk of maintaining too much significant phase ⁇ on the surface of the coating, which is detrimental to the resistance to chipping, in particular in the case of stampable IF steels.
  • the quantity iron content in the coating may be greater than 6 g / m2, which is detrimental to the powder resistance as illustrated in Example 2.
  • the process for obtaining an almost alloyed galvanized coating without phase ⁇ and with a layer of minimum thickness of hard phases and brittle, especially ⁇ is advantageous, especially compared to the processes already cited and described in documents JP 02 194 157 A and JP 08 165 550 A, because, according to the invention, only one processing step is carried out thermal, which is much more economical and productive.
  • the method according to the invention does not provide for any cooling intermediate, especially below 400 ° C, during the heat treatment ; cooling only takes place at the end of the treatment thermal.
  • the alloying process according to the invention starts from a galvanized sheet, that is to say coated with a layer based on unalloyed zinc, and not with a sheet coated with a zinc-iron alloy already formed as in document WO 90 02043 A; moreover, the duration of the heat treatment according to the invention is much shorter than those described in this document, which is, at obviously, advantageous in terms of productivity.
  • the purpose of this example is to illustrate the advantage of carrying out the treatment thermal alloy at a maximum temperature greater than or equal to 490 ° C, according to the invention.
  • each sample is brought to a maximum temperature of treatment, then maintained at this temperature for a period which may reach 70 seconds.
  • the following is carried out: X-ray diffractometry, detection and identification of phases ⁇ , ⁇ and ⁇ so as to identify the holding time at the end of which the phases ⁇ , ⁇ and ⁇ and the holding time after which the phase disappears ⁇ ; the lower detection limit is around 5% for phase ⁇ , around 7 to 8% for phase ⁇ and for phase ⁇ .
  • Alloying treatments are thus carried out at 440 ° C, 450 ° C, 460 ° C, 470 ° C, 480 ° C, 490 ° C, 500 ° C, 510 ° C, 520 ° C, 530 ° C, 540 ° C, 550 ° C and 560 ° C.
  • the abscissa is plotted, for each temperature, the holding time after which the phases apparaissent, ⁇ and ⁇ appear and the holding time after which phase ⁇ disappears.
  • the hatched area limited by the points ⁇ corresponds to the domain of existence of phase ⁇ ; it can be seen that, according to the invention, if the alloying treatment temperature is greater than or equal to 490 ° C, the phase ⁇ does not appear detectably during processing, whatever the duration of maintenance at the maximum temperature, within the limit of one minute about.
  • the duration of treatment can be set regardless of the temperature of processing, which facilitates the piloting of the alloying step; hold time at the maximum treatment temperature is preferably less than one minute.
  • the purpose of this example is to illustrate the advantage of maintaining the temperature and the duration of the alloying heat treatment at sufficiently low values to limit the average iron content of the coating to a lower value or equal to 6 g / m2.
  • FIG. 2 shows the results obtained, temperature (° C) on the abscissa and iron content (g / m2) on the ordinate; we aknowledge that the curve obtained has an inflection point around 500 ° C.
  • the surface is degreased and the sample is weighed; the sample is then covered with a sheet of Teflon ® on both sides then fully stamped by driving a punch into a suitable die for shaping a cup; the bucket obtained is ultrasonically cleaned then weighed again; we calculate the difference in weight which we divide by the initial sample area; the result expressed in g / m2 reflects the dusting of the coating layer.
  • Figure 3 shows the results obtained, iron content (g / m2) on the abscissa and dusting (g / m2) of the coating layer on the ordinate;
  • the average iron content of the coating should be limited to a value less than or equal to 6 g / m2; with reference to FIG. 2, in the case of a holding time of 15 seconds, it can be seen that this objective is achieved if the maximum temperature (T max. ) reached during the treatment is less than or equal to 510 ° C. .
  • Example 1 By combining the teaching of Example 1, which concerns the absence of phase ⁇ when T max. ⁇ 490 ° C, which concerns the delay in the appearance of phases ⁇ and ⁇ if, in addition, T max. ⁇ 510 ° C, it appears that the range 490 ° C-510 ° C offers the most advantageous conditions for achieving the objectives of the invention.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Coating With Molten Metal (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
EP98402165A 1997-09-09 1998-09-02 Verfahren zum Herstellen eines legierten verzinkten Bleches ohne dzeta phase auf der Oberfläche Revoked EP0902098B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9711144 1997-09-09
FR9711144A FR2768157B1 (fr) 1997-09-09 1997-09-09 Tole d'acier galvanise allie, procedes et installation pour la fabrication d'une telle tole

Publications (2)

Publication Number Publication Date
EP0902098A1 true EP0902098A1 (de) 1999-03-17
EP0902098B1 EP0902098B1 (de) 2002-08-14

Family

ID=9510860

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98402165A Revoked EP0902098B1 (de) 1997-09-09 1998-09-02 Verfahren zum Herstellen eines legierten verzinkten Bleches ohne dzeta phase auf der Oberfläche

Country Status (7)

Country Link
EP (1) EP0902098B1 (de)
AT (1) ATE222300T1 (de)
BR (1) BR9803937A (de)
CA (1) CA2246858C (de)
DE (1) DE69807165T2 (de)
ES (1) ES2181142T3 (de)
FR (1) FR2768157B1 (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4282541A1 (de) 2022-05-23 2023-11-29 John Cockerill S.A. Verfahren und anlage zum aufbringen einer flüssigen beschichtung auf ein kontinuierlich durchlaufendes und abwärtsgerichtetes band

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0413855A (ja) * 1990-04-27 1992-01-17 Nisshin Steel Co Ltd 加工性に優れた合金化溶融亜鉛めつき鋼板及びその製造方法
JPH05263210A (ja) * 1992-03-19 1993-10-12 Kobe Steel Ltd スポット溶接性に優れた溶融亜鉛・アルミニウム合金 めっき鋼板の製造方法
JPH0688192A (ja) * 1991-08-28 1994-03-29 Nisshin Steel Co Ltd 加工性に優れた合金化溶融亜鉛めっき鋼板及びその製造方法
JPH0913147A (ja) * 1995-06-28 1997-01-14 Nippon Steel Corp 成型性及びめっき密着性に優れた高強度合金化溶融亜鉛めっき鋼板およびその製造方法

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5789468A (en) * 1980-11-22 1982-06-03 Nisshin Steel Co Ltd Continuous hot-dipping apparatus
JPS61223174A (ja) * 1985-03-28 1986-10-03 Sumitomo Metal Ind Ltd 合金化溶融亜鉛めつき鋼板の製造方法
US4913746A (en) * 1988-08-29 1990-04-03 Lehigh University Method of producing a Zn-Fe galvanneal on a steel substrate
JPH0639680B2 (ja) * 1989-01-20 1994-05-25 住友金属工業株式会社 加工性に優れたガルバニール鋼板とその製造方法および装置
JP2824345B2 (ja) * 1991-05-10 1998-11-11 三菱重工業株式会社 溶融亜鉛めっき鋼板の合金化装置
JPH05320853A (ja) * 1992-05-22 1993-12-07 Nippon Steel Corp めっき密着性の良好な合金化溶融亜鉛めっき鋼板の製造法
JP2707952B2 (ja) * 1993-07-19 1998-02-04 住友金属工業株式会社 界面密着性に優れた合金化溶融Ｚｎめっき鋼板およびその製造方法
JPH0748662A (ja) * 1993-08-06 1995-02-21 Nippon Steel Corp めっき密着性、外観性に優れた溶融亜鉛めっき鋼板の製造法
JPH08165550A (ja) * 1994-12-13 1996-06-25 Nippon Steel Corp 耐フレーキング性に優れた合金化溶融亜鉛めっき鋼板の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0413855A (ja) * 1990-04-27 1992-01-17 Nisshin Steel Co Ltd 加工性に優れた合金化溶融亜鉛めつき鋼板及びその製造方法
JPH0688192A (ja) * 1991-08-28 1994-03-29 Nisshin Steel Co Ltd 加工性に優れた合金化溶融亜鉛めっき鋼板及びその製造方法
JPH05263210A (ja) * 1992-03-19 1993-10-12 Kobe Steel Ltd スポット溶接性に優れた溶融亜鉛・アルミニウム合金 めっき鋼板の製造方法
JPH0913147A (ja) * 1995-06-28 1997-01-14 Nippon Steel Corp 成型性及びめっき密着性に優れた高強度合金化溶融亜鉛めっき鋼板およびその製造方法

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 016, no. 168 (C - 0932) 22 April 1992 (1992-04-22) *
PATENT ABSTRACTS OF JAPAN vol. 018, no. 040 (C - 1155) 21 January 1994 (1994-01-21) *
PATENT ABSTRACTS OF JAPAN vol. 018, no. 351 (C - 1220) 4 July 1994 (1994-07-04) *
PATENT ABSTRACTS OF JAPAN vol. 097, no. 005 30 May 1997 (1997-05-30) *

Also Published As

Publication number Publication date
CA2246858A1 (fr) 1999-03-09
CA2246858C (fr) 2008-11-18
BR9803937A (pt) 1999-12-14
DE69807165T2 (de) 2004-05-19
FR2768157B1 (fr) 2001-05-11
ES2181142T3 (es) 2003-02-16
EP0902098B1 (de) 2002-08-14
DE69807165D1 (de) 2002-09-19
ATE222300T1 (de) 2002-08-15
FR2768157A1 (fr) 1999-03-12

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