EP1233079B1 - Tôle en acier émaillé formé à froid et structure émaillée contenant un composant d'une tôle d'acier - Google Patents

Tôle en acier émaillé formé à froid et structure émaillée contenant un composant d'une tôle d'acier Download PDF

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Publication number
EP1233079B1
EP1233079B1 EP01200567A EP01200567A EP1233079B1 EP 1233079 B1 EP1233079 B1 EP 1233079B1 EP 01200567 A EP01200567 A EP 01200567A EP 01200567 A EP01200567 A EP 01200567A EP 1233079 B1 EP1233079 B1 EP 1233079B1
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EP
European Patent Office
Prior art keywords
steel sheet
max
sheet according
enamelling
steel
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
EP01200567A
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German (de)
English (en)
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EP1233079A1 (fr
Inventor
Lambertus Jacobus Van Benschop
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.)
Tata Steel Ijmuiden BV
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Tata Steel Ijmuiden BV
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Publication date
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Priority to ES01200567T priority Critical patent/ES2383168T3/es
Priority to AT01200567T priority patent/ATE553224T1/de
Priority to EP01200567A priority patent/EP1233079B1/fr
Publication of EP1233079A1 publication Critical patent/EP1233079A1/fr
Application granted granted Critical
Publication of EP1233079B1 publication Critical patent/EP1233079B1/fr
Anticipated expiration legal-status Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
    • 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
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/04—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing
    • C21D8/0478—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing involving a particular surface treatment

Definitions

  • the invention relates to cold reduced enamelling steel sheet.
  • Cold reduced enamelling steel sheet is frequently used to fabricate products such as domestic appliances. During fabrication of such products, the steel sheet material is usually coated with an enamel layer. It is then desirable to obtain an enamel layer with good adhesion to the steel sheet, and with at most only a few visible defects such as fish scale patterns. It is known that the resistance to fish scale formation can be improved by a synergistic effect of boron and nitrogen content in cold reduced steel sheet when boron in an amount of 83 ppm by weight or more and nitrogen in an amount of 89 ppm by weight or more, are present in the steel sheet.
  • an enamelling steel sheet with a minimum of alloying elements that has deep drawing properties which are sufficiently good. After applying and firing white enamel, the steel sheet is essentially free from fish scale defects, and the enamel adhesion is satisfactory.
  • JP 57 104627 relates to the manufacture of cold rolled soft steel plate with superior press formability by continuous annealing.
  • a steel slab consisting of ⁇ 0.010% C, 0.05 - 0.30% Mn, ⁇ 0.070% Sol. Al., ⁇ 0.0050 N, 0.0010 - 0.0050% B and the balance Fe with inevitable impurities in hot rolled at 850-900°C finish temperature and coiled at 550 - 720°C.
  • This hot rolled coil is de-scaled, cold rolled at ⁇ 60% ordinary reduction ratio and continuously annealed.
  • the publication does not refer to an enamelling steel and does not mention the combined effect of B and N and of P and Cu. It does not disclose Cu as an alloying element.
  • US 4,576,657 relates to a process of manufacturing a cold rolled steel sheet having excellent press-formability which overcomes drawbacks in the prior art in the production of the cold rolled steel sheet for press working, and enables the treatment at at a temperature of 800 - 1,100°C, which is far lower than that of the prior art.
  • This publication does not refer to an enamelling steel and in particular does not mention the combined effect of B and N and of P and Cu. It is silent on the presence of Cu as an alloying element.
  • JP 08 199299 relates to a steel for porcelain enamelling, excellent in fish scale resistance, black speck resistance and ageing resistance.
  • the steel has a composition consisting of, by weight ratio, ⁇ 0.004% C, ⁇ 0.2% Mn, 0.003 - 0.025 P, ⁇ 0.02% S, 0.006 - 0.05% Cu, ⁇ 0.004% N, ⁇ 0.03% O, > 0.02% B and the balance Fe with inevitable impurities.
  • the B content in the disclosure steel is higher than 0.002%, corresponding to higher than 200 ppm. According to this publication, it is further desirable to set Cu/P to 3 - 5 as a desirable range.
  • the combination of B and N in the steel of the invention enables formation of precipitates that help suppress the formation of fish scales.
  • the atomic ratio B/N should be more than 0.80. It is now found that the mechanical properties, in particular deep drawing properties, are better if the amount of excess B above the atomic ratio B/N of 1.00 is limited to at most 83/6 ppm by weight. The recrystallisation temperature is also lower in that case. Thus, when the B-content exceeds B max , the mechanical properties are unnecessarily deteriorating. This deterioration is currently thought to be related to the presence of acid soluble B in the steel matrix.
  • Oxygen can be present in the steel sheet after oxygen steel making process typically up to an amount of 35 ppm.
  • oxygen is not added to extra amounts, since it might form unnecessary precipitates that are unfavourable for the mechanical properties.
  • the amount of acid soluble Al should be limited to at most 300 ppm. Deep drawing properties may improve as the amount of Alas is kept low as possible, preferably lower than 150 ppm.
  • the total amount of Al that may be present in the steel depends primarily on the oxygen content. The total amount of Al is preferably sufficiently high to bind essentially all the oxygen that is present in the steel sheet.
  • Mn is important for forming MnS precipitates, and MnO precipitates in the case that not all oxygen is already bound by Al. S may be, and in practice often is present in the steel sheet as unintentional element. A significant effect is obtained when at least 0.10 wt. % of Mn is present in the steel sheet. Preferably, the amount of Mn is at least 0.23 wt. % to gain full advantage of this alloying element. However, for maintaining sufficient deep drawing capability of the steel sheet, the Mn content should be kept to a maximum of 0.50 wt. %.
  • the steel sheet also contains:
  • an atomic ratio Cu/P of between 1.00 and 1.50 is preferred, since under this condition in most cases the pickling behaviour is sufficiently good, with less Cu added to the alloy.
  • B min N ⁇ 0.90 ⁇ 10.8/14.
  • B/N the atomic ratio
  • B min N ⁇ 1.00 ⁇ 10.8/14.
  • the atomic ratio B/N is higher than 1.00. It has been found that a small excess of B can be tolerated regarding the mechanical properties, with the advantage that it ensures that all N is indeed precipitated. Herewith the formation of fish scales is essentially fully suppressed.
  • the steel sheet comprises:
  • the steel sheet comprises less than 89 ppm N. It has been found that the amount of added B can then be reduced while the formation of fish scale defects is nevertheless sufficiently reduced.
  • the steel sheet comprises less than 89 ppm N
  • B max N ⁇ 1.20 ⁇ 10.8/14.
  • the Cu max P ⁇ 1.50 ⁇ 63.6/31.
  • the maximum amount of C in the steel sheet is 50 ppm by weight.
  • the ageing properties are better suited.
  • the maximum amount of C is 40 ppm.
  • the amount of C in the steel sheet is lower than 30 ppm by weight.
  • the strengthening of the steel sheet by ageing is maximised.
  • the cold reduced enamelling steel sheet has a composition of C, Mn, Al, S, N, B, Cu, P in the amounts as specified above, the balance being Fe and unintentional and/or inevitable impurities such as O, Si.
  • the steel sheet as described above has a grain size according to ASTM of 9.5 units or less.
  • ASTM ASTM of 9.5 units or less.
  • the yield strength is between 140 MPa and 190 MPa
  • the tensile strength is between 270 MPa and 350 MPa
  • the elongation to fracture is at least 35 %, all numbers measured in cross sectional direction to rolling in annealed, unaged and 1 % temper rolled condition.
  • the steel sheet can have an r-value (at 90° to rolling direction) of higher than 1.85, and/or an n-value exceeding 0.233.
  • the invention is applicable to an enamelled structure comprising at least one component made of the above described steel sheet, provided with an enamel layer.
  • Cold reduced enamelling steel sheet can be produced by preparing a suitable steel melt and casting the melt into a slab.
  • the production process can include operations of hot rolling the slab, pickling the rolled product, cold rolling, annealing, temper rolling.
  • cold rolling can be applied to a reduction exceeding 50 %, or exceeding 70 %, and in an embodiment not exceeding 90 %.
  • annealing can be performed to a temperature between the recrystallisation temperature of the rolled sheet and the Ar 3 temperature. Annealing may be performed as coil annealing, continuous annealing, or any suitable type of annealing.
  • temper rolling may be performed to a reduction between 0.5 % and 2 %.
  • the embodiments of the invention are, however, not limited to these operations and conditions.
  • the atomic ratio B/N is also included in Table I.
  • the melts were cast and hot rolled, with a finishing temperature of 930 °C. Then the sheets were cooled at a velocity of 20 °C/s, and coiled at a temperature of 690 °C.
  • the sheets were pickled at a temperature of 70 °C, and cold rolled to three reductions of 75 %, 80 %, and 85 % (corresponding to respective final thicknesses of 1.0 mm, 0.8 mm, and 0.6 mm) for each type.
  • the recrystallisation temperature for tight coil annealing was determined for each type for various reductions using a heating rate of 2.4 ⁇ 10 -5 /sec in HN x . Each sample was heated to a certain temperature, and cooled, and successively heated to a temperature 10° above the previous temperature. After each cooling step, a microscopic study of the microstructure of the sample was performed to determine whether recrystallisation had occurred. The thus found recrystallisation temperatures are given in °C in the following Table II. Table II Type Cold reduced by: 75% 80% 85% Ref. 640 640 640 1 640 640 640 2 610 620 620 It has been found that the presence of B does not result in an increase of the recrystallisation temperature. This is believed to be a result of no free B being present in the steel sheets.
  • each type of thus obtained and rolled steel sheet was tight-coil annealed at 640 °C using a heating rate of 2.4 ⁇ 10 -5 /sec, and after cooling down to room temperature subsequently temper rolled to a 1 % reduction.
  • White enamel was applied to these steel sheets, using various firing temperatures between 780 and 860°C.
  • the reference steel sheet showed a high abundance of fish scales after application of white enamel, while none of the steel sheets of types 1 or 2 suffered from visible fish scale defects. This shows that in cold rolled sheet even a low B content of 64 ppm can be sufficient to suppress fish scale formation, as long as the amount of B is carefully adapted to the amount of N that is present in the steel sheet. Also, the adhesion of the white enamel was excellent.
  • Table IV shows results of mechanical tests of temper rolled (1 %) non-aged sheet sheets. The results are average results obtained on 75, 80, and 85 % cold reduced sheets, measured in the transverse direction, according to the small Euronorm using a small rod from the sheet.
  • R p denotes yield strength
  • R m is the tensile strength
  • a g is the uniform elongation
  • a 80 the elongation to fracture.
  • transverse r -value 90°
  • n -value (90°) and n -value.
  • Both types 1 and 2 being embodiments of the invention have better mechanical properties than the reference steel sheet.
  • the elongation percentages of steel type 1 slightly exceed those of type 2.
  • Type 1 contains more Al as than type 2, yet type 1 has slightly better mechanical properties. The present understanding is that this shows the onset of the adverse effect of excess B, since in type 2 both the absolute amount of B as well as the atomic ratio B/N are higher than those of type 1.
  • An embodiment of the enamelling steel sheet according to the invention has also been prepared in a production plant.
  • the spectroscopically analysed composition is given in Table V.
  • the cast melt was hot rolled, and cold rolled to a cold reduction of 80 % and a final thickness of 0.9 mm.
  • the cold rolled steel sheet was coil annealed to a temperature of 650°C, and subsequently cooled down to room temperature and temper rolled by 0.8 %.
  • the grain size in cross section to rolling direction was determined to be 9.0 ASTM units using the ASTM standard.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Heat Treatment Of Sheet Steel (AREA)

Claims (11)

  1. Tôle en acier émaillé formé à froid constituée par (en ppm en poids sauf spécification contraire) :
    5 ≤ C ≤ 90 ;
    0,10 ≤ Mn ≤ 0,50 (% en poids) ;
    Alas ≤ 300 (Al soluble dans l'acide) ;
    O ≤ 35 ;
    S ≤ 350 ;
    30 ≤ N ≤ 110 ;
    Bmin < B ≤ Bmax ;
    où Bmin = N x 0,80 x 10,8/14 et Bmax = N x 10,8/14 + 83/6 ;
    50 ≤ P ≤ 160 ; en combinaison avec
    Cumin ≤ Cu ≤ Cumax ;
    où Cumin P x 1,00 x 63,6/31 et Cumax = P x 2,00 x 63,6/31 ; le reste étant du Fe et des impuretés non souhaitables et/ou inévitables.
  2. Tôle d'acier selon la revendication 1, dans laquelle Bmin = N x 0,90 x 10,8/14.
  3. Tôle d'acier selon la revendication 1 ou 2, dans laquelle Bmin = N x 1,00 x 10,8/14.
  4. Tôle d'acier selon la revendication 1, 2, ou 3, dans laquelle
    45 ≤ N ≤ 110.
  5. Tôle d'acier selon la revendication 1, 2, ou 3, dans laquelle
    30 ≤ N < 89.
  6. Tôle d'acier selon la revendication 5, dans laquelle
    Bmax = N x 1,20 x 10,8/14.
  7. Tôle d'acier selon l'une quelconque des revendications 1 à 6, dans laquelle Cumax = P x 1,50 x 63,6/31.
  8. Tôle d'acier selon l'une quelconque des revendications 1 à 7, dans laquelle la quantité maximale de C est de 30 ppm en poids.
  9. Tôle en acier émaillé formé à froid ayant une composition de C, Mn, Al, S, N, B, Cu, P en les quantités spécifiées dans l'une quelconque des revendications 1 à 8, le reste étant du Fe et des impuretés non souhaitables et/ou inévitables telles qu'O, Si.
  10. Tôle d'acier selon l'une quelconque des revendications précédentes, dans laquelle la taille de grains selon ASTM est de 9,5 unités ou moins.
  11. Tôle d'acier selon l'une quelconque des revendications précédentes, dans laquelle la limite d'élasticité est comprise entre 140 MPa et 190 MPa, la résistance à la traction est comprise entre 270 MPa et 350 MPa, et l'allongement à la rupture est d'au moins 35 %.
EP01200567A 2001-02-16 2001-02-16 Tôle en acier émaillé formé à froid et structure émaillée contenant un composant d'une tôle d'acier Expired - Lifetime EP1233079B1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
ES01200567T ES2383168T3 (es) 2001-02-16 2001-02-16 Chapa delgada de acero esmaltado, reducido en frío, y una estructura esmaltada que comprende un componente de una chapa delgada de acero parecida
AT01200567T ATE553224T1 (de) 2001-02-16 2001-02-16 Kaltverformtes emailliertes stahlblech und emaillierte struktur mit einem bestandteil von einem solchen stahlblech
EP01200567A EP1233079B1 (fr) 2001-02-16 2001-02-16 Tôle en acier émaillé formé à froid et structure émaillée contenant un composant d'une tôle d'acier

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP01200567A EP1233079B1 (fr) 2001-02-16 2001-02-16 Tôle en acier émaillé formé à froid et structure émaillée contenant un composant d'une tôle d'acier

Publications (2)

Publication Number Publication Date
EP1233079A1 EP1233079A1 (fr) 2002-08-21
EP1233079B1 true EP1233079B1 (fr) 2012-04-11

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Application Number Title Priority Date Filing Date
EP01200567A Expired - Lifetime EP1233079B1 (fr) 2001-02-16 2001-02-16 Tôle en acier émaillé formé à froid et structure émaillée contenant un composant d'une tôle d'acier

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EP (1) EP1233079B1 (fr)
AT (1) ATE553224T1 (fr)
ES (1) ES2383168T3 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE306569T1 (de) 2001-10-29 2005-10-15 Nippon Steel Corp Stahlblech zur glasemaillierung mit hervorragender bearbeitbarkeit und fischschuppenbeständigkeit und herstellungsverfahren dafür
ES2667198T3 (es) * 2013-04-15 2018-05-10 Tata Steel Ijmuiden Bv Chapa de acero esmaltado reducido en frío, método para su producción y uso de dicho acero
EP3526359A1 (fr) * 2016-10-17 2019-08-21 Tata Steel IJmuiden B.V. Substrat en acier pour pièces peintes
WO2021091878A1 (fr) * 2019-11-04 2021-05-14 Ak Steel Properties, Inc. Tôle d'acier émaillée laminée à froid présentant une aptitude au formage améliorée

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57104627A (en) * 1980-12-19 1982-06-29 Nippon Kokan Kk <Nkk> Manufacture of cold rolled soft steel plate with superior press formability by continuous annealing
JPS6045689B2 (ja) * 1982-02-19 1985-10-11 川崎製鉄株式会社 プレス成形性にすぐれた冷延鋼板の製造方法
JPH0759735B2 (ja) * 1988-07-20 1995-06-28 川崎製鉄株式会社 耐泡・黒点欠陥に優れた直接一回掛けほうろう用鋼板
KR100221349B1 (ko) * 1994-02-17 1999-09-15 에모또 간지 가공성이 우수한 비시효성 캔용 강판의 제조방법
JP3067569B2 (ja) * 1995-01-25 2000-07-17 日本鋼管株式会社 耐爪とび性、耐黒点性および耐時効性に優れたほうろう用鋼
CN1152340A (zh) * 1995-03-27 1997-06-18 新日本制铁株式会社 具有改进疲劳性能的超低碳冷轧钢板和镀锌钢板及其生产工艺
JP3293424B2 (ja) * 1995-09-25 2002-06-17 日本鋼管株式会社 非ｉｆ鋼系非時効性極低炭素冷延鋼板の製造法
JP3377155B2 (ja) * 1996-02-26 2003-02-17 日本鋼管株式会社 極低炭素缶用鋼板の製造方法

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Publication number Publication date
EP1233079A1 (fr) 2002-08-21
ES2383168T3 (es) 2012-06-18
ATE553224T1 (de) 2012-04-15

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