A ZINC OR ZINC-ALLOY COATED STRIP OR STEEL WITH IMPROVED ZINC ADHESION

Abstract

A zinc or zinc-alloy coated rolled steel strip or sheet includes 0.08-0.28 C, 1.4-4.5 Mn, 0.01-0.5 Cr, 0.01-2.5 Si, 0.01-0.6 Al. The steel has a tensile strength of 950-1550 MPa, yield strength of 550-1400 MPa, yield ratio 0.50, and Ri/t4. The microstructure has 70 tempered martensite+bainite, 10 fresh martensite, 2-20 retained austenite, and 20 polygonal ferrite. The steel has a decarburized zone where the C content at a depth of 20 m is not more than 75% of the carbon content in the middle of the steel strip and/or the microhardness at a depth of 20 m is not higher than 75% of the microhardness in the middle of the steel strip. The adhesion of the zinc or zinc alloy coating is 1 or 2 according to SEP 1931.

Claims

1. A zinc or zinc-alloy coated cold rolled steel strip or sheet, a) having a composition comprising of (in wt. %): TABLE-US-00023 C 0.08-0.28 Mn 1.4-4.5 Cr 0.01-0.5 Si 0.01-2.5 Al 0.01-2.0 Si + Al 0.1 Si + Al + Cr 0.4 Nb 0.1 Ti 0.1 Mo 0.5 Ca 0.05 V 0.1 balance Fe apart from impurities; b) fulfilling the following conditions: TABLE-US-00024 TS tensile strength (R.sub.m) 950-1550 MPa YS yield strength (R.sub.p0.2) 350-1400 MPa YR yield ratio (R.sub.p0.2/R.sub.m) 0.35 bendability (Ri/t) 4 c) having a multiphase microstructure comprising (in vol %) TABLE-US-00025 tempered martensite+ bainite 40 fresh martensite 30 retained austenite 2-20 polygonal ferrite 35; and d) having a decarburized zone in which the carbon content at a depth of 20 vim is not more than 75% of the carbon content in the middle of the steel strip or sheet and/or wherein the microhardness at a depth of 20 vim is not higher than 75% of the microhardness in the middle of the steel strip or sheet; e) having a zinc or zinc-alloy coating, wherein the adhesion of the zinc or zinc alloy coating as determined by a drop-ball impact test in accordance with SEP 1931 is 1 or 2.

2. The cold rolled steel strip or sheet according to claim 1, wherein the steel strip has a decarburized zone in which the carbon content at a depth of 20 m is not more than 50% of the carbon content in the middle of the steel strip and/or wherein the microhardness at a depth of 20 m is not higher than 60% of the microhardness in the middle of the steel strip.

3. The cold roll strip or sheet according to claim 1 or 2, a) having a composition comprising of (in wt. %): TABLE-US-00026 C 0.08-0.28 Mn 1.4-4.5 Cr 0.01-0.5 Si 0.01-2.5 Al 0.01-0.6 Si + Al 0.1 Si + Al + Cr 0.4 Nb 0.1 Ti 0.1 Mo 0.5 Ca 0.05 V 0.1 balance Fe apart from impurities; b) fulfilling at least one of the following conditions: TABLE-US-00027 TS tensile strength (R.sub.m) 950-1550 MPa YS yield strength (R.sub.p0.2) 550-1400 MPa YR yield ratio (R.sub.p0.2/R.sub.m) 0.50 bendability (Ri/t) 4; and c) having a multiphase microstructure comprising (in vol %) TABLE-US-00028 tempered martensite+ bainite 50 fresh martensite 10 retained austenite 2-20 polygonal ferrite 10.

4. The cold roll strip or sheet according to claim 3, wherein the composition fulfilling at least one of the following conditions (in wt %): TABLE-US-00029 C 0.1-0.25 Mn 1.4-3 Cr 0.01-0.5 Si 0.1-1 Al 0.01-0.1 Si + Al 0.1 Si + Al + Cr 0.4 Nb 0.008 Ti 0.02 Mo 0.08 Ca 0.005 V 0.02 balance Fe apart from impurities.

5. The cold roll strip or sheet according to claim 3, a) having a composition comprising of (in wt. %): TABLE-US-00030 C 0.08-0.16 Mn 2.0-3.0 Cr 0.1-0.5 Si 0.5-1.2 Al 0.01-0.5 Si + Al 0.1 Si + Al + Cr 0.4 Nb 0.1 Ti 0.1 Mo 0.5 Ca 0.05 V 0.1 balance Fe apart from impurities; and a) fulfilling at least one of the following conditions: TABLE-US-00031 TS tensile strength (R.sub.m) 950-1150 MPa YS yield strength (R.sub.p0.2) 750-1000 MPa YR yield ratio (R.sub.p0.2/R.sub.m) 0.70 bendability (Ri/t) 2

6. The cold roll strip or sheet according to claim 3, a) having a composition comprising of (in wt. %): TABLE-US-00032 C 0.15-0.25 Mn 1.0-2.0 Cr 0.1-0.5 Si 0.1-0.5 Al 0.01-0.5 Si + Al 0.1 Si + Al + Cr 0.4 Nb 0.1 Ti 0.1 Mo 0.5 Ca 0.05 V 0.1 balance Fe apart from impurities; and b) fulfilling at least one of the following conditions: TABLE-US-00033 TS tensile strength (R.sub.m) 1300-1550 MPa YS yield strength (R.sub.p0.2) 1000-1300 MPa YR yield ratio (R.sub.p0.2/R.sub.m) 0.70 bendability (Ri/t) 4

7. The cold roll strip or sheet according to claim 3, a) having a composition comprising of (in wt. %): TABLE-US-00034 C 0.15-0.25 Mn 2.0-3.0 Cr 0.1-0.5 Si 1-2.0 Al 0.01-0.5 Si + Al 0.1 Si + Al + Cr 0.4 Nb 0.1 Ti 0.1 Mo 0.5 Ca 0.05 V <0.1 balance Fe apart from impurities; and b) fulfilling at least one of the following conditions: TABLE-US-00035 TS tensile strength (R.sub.m) 1100-1300 MPa YS yield strength (R.sub.p0.2) 900-1100 MPa YR yield ratio (R.sub.p0.2/R.sub.m) 0.70 bendability (Ri/t) 3.

8. The cold roll strip or sheet according to claim 3, a) having a composition comprising of (in wt. %): TABLE-US-00036 C 0.10-0.20 Mn 2.0-3.0 Cr 0.1-0.5 Si 0.2-0.9 Al 0.01-0.5 Si + Al 0.1 Si + Al + Cr 0.4 Nb 0.1 Ti 0.1 Mo 0.5 Ca 0.05 V 0.1 balance Fe apart from impurities; and b) fulfilling at least one of the following conditions: TABLE-US-00037 TS tensile strength (R.sub.m) 900-1100 MPa YS yield strength (R.sub.p0.2) 600-800 MPa YR yield ratio (R.sub.p0.2/R.sub.m) 0.65 bendability (Ri/t) 2.5.

9. The cold roll strip or sheet according to any one of claims 3-8, wherein TABLE-US-00038 Al 0.1.

10. The cold roll strip or sheet according to claim to any one of claim 1 or 2, a) having a composition comprising of (in wt. %): TABLE-US-00039 C 0.08-0.28 Mn 1.4-4.5 Cr 0.01-0.5 Si 0.01-2.5 Al 0.5-2.0 Mn + Cr 1.7-5.0 Nb 0.1 Ti 0.1 Mo 0.5 Ca 0.05 V 0.1 balance Fe apart from impurities; and b) fulfilling at least one of the following conditions: TABLE-US-00040 TS tensile strength (R.sub.m) 950-1350 MPa YS yield strength (R.sub.p0.2) 350-1150 MPa YR yield ratio (R.sub.p0.2/R.sub.m) 0.35 bendability (Ri/t) 4 c) having a multiphase microstructure comprising (in vol %) TABLE-US-00041 tempered martensite + 40 bainite fresh martensite 10-30 retained austenite 2-20 polygonal ferrite 10-35.

11. The cold roll strip or sheet according to claim 10, a) having a composition comprising of (in wt. %): TABLE-US-00042 C 0.12-0.20 Mn 1.9-2.6 Cr 0.15-0.3 Si 0.3-0.8 Al 0.8-1.2 Nb 0.008 Ti 0.02 Mo 0.08 Ca 0.005 V 0.02 balance Fe apart from impurities: and b) fulfilling at least one of the following conditions: TABLE-US-00043 TS tensile strength (R.sub.m) 950-1150 MPa YS yield strength (R.sub.p0.2) 350-600 MPa YR yield ratio (R.sub.p0.2/R.sub.m) 0.38 bendability (Ri/t) 4.

12. A method of producing a zinc or zinc-alloy coated steel strip or sheet comprising the following steps: i. providing a cold rolled steel sheet or strip having a nominal composition as defined by item a) in any one of the preceding claims; ii. heating the sheet or strip to a temperature in the range of 650-900 C. in a reducing atmosphere with an optional change of atmosphere to an oxidizing atmosphere in a temperature range lying between 650 and 900 C.; iii. soaking the sheet or strip at temperature in the range of 780-1000 C. for a duration of 40 s to 180 s in a nitrogen atmosphere containing <5 vol. % hydrogen; iv. injecting steam during the soaking step iii) to bring CO>1 vol. %; v. cooling the strip or sheet at a rate in the range of 10-400 C./s to a temperature between 200 and 500 C. followed by isothermal holding for 50-10000 s before coating; vi. coating the strip or sheet with a zinc or a zinc-alloy coating; and vii. optionally galvannealing to alloy the coating into the steel strip.

13. The method according to claim 12, wherein the soaking temperature in step iii) is in the range of 830-890 C.

14. The method according to claim 12, wherein the soaking temperature in step iii) is above A.sub.c3 as defined by: A.sub.c3=910-203*C.sup.1/215.2 Ni30 Mn+44.7 Si+104 V+31.5 Mo+13.1 W.

15. The method according to claim 14, wherein the soaking temperature in step iii) is above A.sub.c3+20 C.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0029] FIG. 1 shows a metallographic picture of a sample subjected to steam injection during soaking.

[0030] FIG. 2 shows metallographic picture of a sample without steam injection during soaking.

[0031] FIG. 3 shows a graph of the C-content from the surface towards the centre according to an example of the invention.

[0032] FIG. 4 shows a graph of the microhardness from the surface towards the centre according to an example of the invention.

DETAILED DESCRIPTION

[0033] The invention is described in the paragraphs that follow.

Composition

[0034] The steel sheet or strip has a composition consisting of the following alloying elements (in wt. %):

TABLE-US-00005 C 0.08-0.28 Mn 1.4-4.5 Cr 0.01-0.5 Si 0.01-2.5 Al 0.01-0.6 Si + Al 0.1 Si + Al + Cr 0.4 Nb 0.1 Ti 0.1 Mo 0.5 Ca 0.05 V 0.1 [0035] balance Fe apart from impurities.

[0036] The importance of the separate elements and their interaction with each other as well as the limitations of the chemical ingredients of the claimed alloy are briefly explained in the following. All percentages for the chemical composition of the steel are given in weight % (wt. %) throughout the description. Upper and lower limits of the individual elements can be freely combined within the limits set out in the claims. The arithmetic precision of the numerical values can be increased by one or two digits for all values given in the present application. Hence, a value of given as e.g. 0.1% can also be expressed as 0.10 or 0.100%. The amounts of the microstructural constituents are given in volume % (vol. %).

C: 0.08-0.28%

[0037] C stabilizes the austenite and is important for obtaining sufficient carbon within the retained austenite phase. C is also important for obtaining the desired strength level. Generally, an increase of the tensile strength in the order of 100 MPa per 0.1% C can be expected. When C is lower than 0.08% it is difficult to attain a tensile strength of 950 MPa. If C exceeds 0.28%, then the weldability is impaired. The upper limit may thus be 0.26, 0.24, 0.22, 0.20 or 0.18%. The lower limit may be 0.10, 0.12, 0.14, or 0.16%.

Mn: 1.4-4.5%

[0038] Manganese is a solid solution strengthening element, which stabilises the austenite by lowering the M.sub.s temperature and prevents ferrite and pearlite to be formed during cooling. In addition, Mn lowers the A.sub.c3 temperature and is important for the austenite stability. At a content of less than 1.5% it might be difficult to obtain the desired amount of retained austenite, a tensile strength of 950 MPa and the austenitizing temperature might be too high for conventional industrial annealing lines. In addition, at lower contents it may be difficult to avoid the formation of polygonal ferrite. However, if the amount of Mn is higher than 4.5%, problems with segregation may occur because Mn accumulates in the liquid phase and causes banding, resulting in a potentially deteriorated workability. The upper limit may therefore be 4.2, 4.0, 3.8, 3.6, 3.4, 3.2, 3.0, 2.8, 2.6, or 2.4%. The lower limit may be 1.5, 1.7, 1.9, 2.1, 2.3, or 2.5%.

Cr: 0.01-0.5%

[0039] Cr is effective in increasing the strength of the steel sheet. Cr is an element that forms ferrite and retards the formation of pearlite and bainite. The A.sub.c3 temperature and the M.sub.s temperature are only slightly lowered with increasing Cr content. Cr results in an increased amount of stabilized retained austenite. When above 0.5% it may impair surface finish of the steel, and therefore the amount of Cr is limited to 0.5%. The upper limit may be 0.45 or 0.40, 0.35, 0.30 or 0.25%. The lower limit may be 0.01, 0.03, 0.05, 0.07, 0.10, 0.15, 0.20 or 0.25%. Preferably, a deliberate addition of Cr is not conducted according to the present invention.

Si: 0.01-2.5%

[0040] Si acts as a solid solution strengthening element and is important for securing the strength of the thin steel strip. Si suppresses the cementite precipitation and is essential for austenite stabilization. However, if the content is too high, then too much silicon oxides will form on the strip surface, which may lead to cladding on the rolls in the CAL and, as a result there of, to surface defects on subsequently produced steel sheets. The upper limit is therefore 2.5% and may be restricted to 2.4, 2.2, 2.0, 1.8 or 1.6%. The lower limit may be 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.60, 0.80 or 1.0%.

Al: 0.01-0.6%

[0041] Al promotes ferrite formation and is also commonly used as a deoxidizer. Al, like Si, is not soluble in the cementite and therefore it considerably delays the cementite formation during bainite formation. In addition, galvanization and reduced susceptibility to Liquid metal embrittlement can be improved. Additions of Al result in a remarkable increase in the carbon content in the retained austenite.

[0042] For some applications it may also be suitable to limit Al to 0.01-0.6%. Here the upper limit can may be set to 0.5, 0.4, 0.3, 0.2, or 0.1% and the lower limit may be set to 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, or 0.1%. If Al is used for deoxidation only then the upper level may then be 0.09, 0.08, 0.07 or 0.06%. For securing a certain effect the lower level may set to 0.03 or 0.04%.

[0043] For other applications it may be suitable to limit Al to 0.5-2.0%. Here the upper limit can further be set to 2.0, 1.8, 1.7, 1.6, 1.5, 1.4, 1.3, 1.2, or 1.1% and the lower limit may be set to 0.5, 0.6, 0.7, 0.8, or 0.9%.

Si+Al0.1%-2%

[0044] Si and Al suppress the cementite precipitation during bainite formation. Their combined content is therefore preferably at least 0.1%. The lower limit may be set to 0.1, 0.2, 0.3, 0.4, or 0.5%. The upper limit may be set to 2%.

Si+Al+Cr0.4%-2.5%

[0045] A certain amount of these elements is beneficial for the formation of austenite. Their combined content should therefore be at least 0.4%. The lower limit can be 0.5, 0.6 or 0.7%. The upper limit may be set to 2.5%.

Mn+Cr 1.7-5.0%

[0046] Manganese and Chromium affects the hardenability of the steel. Their combined content should therefore be within the range of 1.7-5.0%.

Optional Elements

Mo0.5%

[0047] Molybdenum is a powerful hardenability agent. It may further enhance the benefits of NbC precipitates by reducing the carbide coarsening kinetics. The steel may therefore contain Mo in an amount up to 0.5%. The upper limit may be restricted to 0.4, 0.3, 0.2, or 0.1%. A deliberate addition of Mo is not necessary according to the present invention. The upper limit may therefore be restricted to 0.01%.

Nb: 0.1%

[0048] Nb is commonly used in low alloyed steels for improving strength and toughness, because of its influence on the grain size. Nb increases the strength elongation balance by refining the matrix microstructure and the retained austenite phase due to precipitation of NbC. The steel may contain Nb in an amount of 0.1%. The upper limit may be restricted to 0.09, 0.07, 0.05, 0.03, or 0.01%. A deliberate addition of Nb is not necessary according to the present invention. The upper limit may therefore be restricted to 0.004%.

V: 0.1%

[0049] The function of V is similar to that of Nb in that it contributes to precipitation hardening and grain refinement. The steel may contain V in an amount of 0.1%. The upper limit may be restricted to 0.09, 0.07, 0.05, 0.03, or 0.01%. A deliberate addition of V is not necessary according to the present invention. The upper limit may therefore be restricted to 0.01%.

Ti: 0.1%

[0050] Ti is commonly used in low alloyed steels for improving strength and toughness, because of its influence on the grain size by forming carbides, nitrides or carbonitrides. In particular, Ti is a strong nitride former and can be used to bind the nitrogen in the steel. However, the effect tends to be saturated above 0.1%. The upper limit may be restricted to 0.09, 0.07, 0.05, 0.03, or 0.01%. A deliberate addition of Ti is not necessary according to the present invention. The upper limit may therefore be restricted to 0.005%.

Ca0.05

[0051] Ca may be used for the modification of the non-metallic inclusions. The upper limit is 0.05% and may be set to 0.04, 0.03, 0.01%. A deliberate addition of Ca is not necessary according to the present invention. The upper limit may therefore be restricted to 0.005%.

Impurities

Cu: 0.06%

[0052] Cu is an undesired impurity element that is restricted to 0.06% by careful selection of the scrap used.

Ni: 0.08%

[0053] Ni is also an undesired impurity element that is restricted to 0.08% by careful selection of the scrap used.

B: 0.0006%

[0054] B is an undesired impurity element that is restricted to 0.006% by careful selection of the scrap used. B increases hardness but may come at a cost of reduced bendability and is therefore not desirable in the present suggested steel. B may further make scrap recycling more difficult and an addition of B may also deteriorate workability. A deliberate addition of B is therefore not desired according to the present invention.

[0055] Other impurity elements may be comprised in the steel in normal occurring amounts. However, it is preferred to limit the amounts of P, S, As, Zr, Sn to the following optional maximum contents: [0056] P: 0.02% [0057] S: 0.005% [0058] As0.010% [0059] Zr0.006% [0060] Sn0.015%

[0061] It is also preferred to control the nitrogen content to the range: [0062] N: 0.015%, preferably 0.003-0.008%

[0063] In this range a stable fixation of the nitrogen can be achieved.

[0064] Oxygen and hydrogen can further be limited to [0065] O: 0.0003 [0066] H: 0.0020

Microstructure

[0067] The microstructural constituents are in the following expressed in volume % (vol. %).

[0068] The cold rolled steel sheets of the present invention have a microstructure comprising at least 70% tempered martensite (TM) and bainite (B). And further, at most 10% fresh martensite (FM) and at most 20% polygonal ferrite (PF).

[0069] Retained austenite is a prerequisite for obtaining the desired TRIP effect. The amount of retained austenite should therefore be in the range of 2-20%, preferably 5-15%. The amount of retained austenite was measured by means of the saturation magnetization method described in detail in Proc. Int. Conf. on TRIP-aided high strength ferrous alloys (2002), Ghent, Belgium, p. 61-64.

[0070] Depending on the Al content the tempered martensite (TM) and bainite (B), the fresh martensite (FM) and the polygonal ferrite (PF) can be further limited as described below.

A Microstructure of Steels Having A1 in the Range 0.01-0.6 can Further be Limited.

[0071] The microstructure comprising at least 70% tempered martensite (TM) and bainite (B). The lower limit may restrict to at least 70%, 75%, or 80%.

[0072] And further, at most 10% fresh martensite (FM). The upper limit may be restricted 8% or 5%. Small amounts of fresh martensite may improve edge flangeability and local ductility. The lower limit may be restricted 1% or 2%. These un-tempered martensite particles are often in close contact with the retained austenite particles, and they are therefore often referred to as martensite-austenite (MA) particles.

[0073] Polygonal ferrite (PF) should further be limited to 20%, preferably 10%, 5%, 3% or 1%. Most preferably, the low Al steel is free from PF.

[0074] Retained austenite as described above.

Mechanical Properties

[0075] The mechanical properties of the claimed steel are important, and the following requirements should be fulfilled:

TABLE-US-00006 TS tensile strength (R.sub.m) 950-1550 MPa YS yield strength (Rp.sub.0.2) 550-1400 MPa YR yield ratio (Rp.sub.0.2/R.sub.m) 0.50 bendability (Ri/t) 4

[0076] The R.sub.m, R.sub.p0.2 values are derived according to the European norm EN 10002 Part 1, wherein the samples are taken in the longitudinal direction of the strip.

[0077] The bendability is evaluated by the ratio of the limiting bending radius (Ri), which is defined as the minimum bending radius with no occurrence of cracks, and the sheet thickness, (t). For this purpose, a 90 V-shaped block is used to bend the steel sheet in accordance with JIS Z2248. The value obtained by dividing the limit bending radius with the thickness (Ri/t) should be less than 4, preferably less than 3. Using steam injection to raise CO above 10000 ppm during soaking can improve the bendability by 10-30% compared to the same grade without steam injection.

[0078] Bendability may be 4, 3.5, 3, 2.5, or 2. Lower limit may be 1, 1.5, or 2.

[0079] The yield ratio YR is defined by dividing the yield strength YS with the tensile strength TS.

[0080] Depending on the A1 content the mechanical properties can be further limited.

[0081] Mechanical properties of steels having A1 in the range 0.01-0.6 can further be limited to:

TABLE-US-00007 TS tensile strength (R.sub.m) 950-1550 MPa YS yield strength (Rp.sub.0.2) 550-1400 MPa YR yield ratio (Rp.sub.0.2/R.sub.m) 0.50 bendability (Ri/t) 4;

[0082] The lower limit for YR of steels having Al in the range of 0.01-0.6, can further be set to 0.70, 0.75, 0.76, 0.77, or 0.78.

Decarburized Zone and Microhardness

[0083] The steel has a decarburized zone in which the carbon content at a depth of 20 m is not more than 75% by weight of the carbon content in the middle of the steel strip. The carbon content at depth 20 m can further be set to not more than 50%, 40% or 30% of the carbon content in the middle of the steel strip.

[0084] The microhardness at a depth of 20 m is not higher than 75% of the microhardness in the middle of the steel strip. The microhardness at a depth of 20 m can further be set to not higher than 70%, 60% or 50% of the microhardness in the middle of the steel strip.

[0085] The decarburised zone improves zinc adhesion, bendability of the steel, and reduces the risk of liquid metal embrittlement.

Zinc Coating

[0086] The steel sheet or strip comprises a zinc or a zinc-alloy coating. The coating can be applied by Hot Dip Galvanizing (GI), galvannealing (GA) or through Electrogalyanizing (EG).

[0087] A zinc alloy coating may comprise in weight %: [0088] at least one of:

TABLE-US-00008 Mg 0.1-10 Al 0.1-10 Sn 1-10 [0089] Balance Zn and impurities.

[0090] A galyannealed coating can contain 5-20 wt. % of diffused Fe.

Zinc Adhesion

[0091] The decarburised zone improves zinc adhesion of the steel. The steel therefore has a Zn-adhesion of 1 or 2 as determined by a drop-ball impact test according to SEP 1931: Prfung der Haftung von Zinkberzgen auf feuerverzinktem Feinblech, Kugelschlagprfung, 1991.

Production of Cold Rolled Strip

[0092] The steel can be produced by making steel slabs of the conventional metallurgy by converter melting and secondary metallurgy with the composition suggested above. The slabs are hot rolled in austenitic range to a hot rolled strip. Preferably by reheating the slab to a temperature between 1000 C. and 1280 C., rolling the slab completely in the austenitic range wherein the hot rolling finishing temperature is greater than or equal to 850 C. to obtain the hot rolled steel strip. Thereafter the hot rolled strip is coiled at a coiling temperature in the range of 500-700 C. Optionally subjecting the coiled strip to a scale removal process, such as pickling. The coiled strip is thereafter batch annealed at a temperature in the range of 500 650 C., preferably 550-650 C., for a duration of 5-30 h. Thereafter cold rolling the batch annealed steel strip with a reduction rate between 35 and 90%, preferably around 40-60% reduction.

Annealing and Coating of Cold Rolled Strip

[0093] The cold rolled strips can e.g. be treated in a Continuously Annealing Line (CAL) and subsequent Continuous Electroplating Line (CEL) or in a Hot Dip Galvanizing Line (HDGL).

[0094] The annealing and coating include the steps: [0095] i) Providing a cold rolled steel sheet or strip having a nominal composition as described in the section Composition or the section Exemplary compositions and mechanical properties. [0096] ii) heating the sheet or strip to a temperature in the range of 650-900 C. in a reducing atmosphere with an optional change of atmosphere to an oxidizing atmosphere in a temperature range lying between 650 and 900 C. The heating can be e.g. be done in a heating furnace such as a Direct Fired Furnace (DFF) or Non-Oxidizing Furnace (NOF). [0097] iii) Soaking the sheet or strip at temperature in the range of 780-1000 C. for a duration of 40 s to 180 s in a nitrogen atmosphere containing <5 vol. % hydrogen. The soaking furnace can e.g. be radiant tube furnace.

[0098] The soaking temperature is a preferably in the range of 830-890 C.

[0099] The soaking temperature is preferably above A.sub.c3 as defined by: A.sub.c3=910-203*C.sup.1/215.2Ni30 Mn+44.7 Si+104 V+31.5 Mo+13.1 W. The soaking temperature may be least A.sub.c3+20 C. or at least A.sub.c3+30 C.

[0100] The upper limit of hydrogen may be 5.0, 4.5, 4.0, 3.5, 3.0, 2.5, 2.0, 1.7, or 1.5%. The lower limit of hydrogen may be 0.1, 0.5, 1.0, 1.2, or 1.3%. [0101] iv) Injecting steam during the soaking step iii) to bring CO>1 vol. % and to create a decarburized zone. The CO content can e.g. be controlled by measuring the CO level in the exhaust gases from the soaking furnace.

[0102] The upper limit of CO may be 2% or 1.5%. [0103] v) Cooling the strip or sheet at a rate in the range of 10-400 C./s to a temperature between 200 and 500 C. followed by isothermal holding for 50-10000 s before coating. The cooling of the strip can e.g. be done by slow jet cooling followed by rapid jet cooling.

[0104] The end temperature of cooling and the holding temperature may be above or below Ms. Ms can be defined by the formula: Ms=692-502*(C+0.68N).sup.0.537*Mn14*Si+20*A111*Cr.

[0105] The lower time of the isothermal holding may be set to 50, or 100 s. The upper time of may be 10000, 5000, 1000, or 500 s. The lower temperature of the isothermal holding may be 200, 250, 300, or 330 C. The upper temperature may be 500, 450, or 400 C. [0106] vi) Coating the strip or sheet with a zinc or a zinc-alloy coating. The coating can e.g. be applied by Hot Dip Galvanizing (GI), Galvannealing (GA), or Electrogalvanizing (EG). [0107] vii) Optionally galvannealing (GA) to alloy the coating into the steel strip. If the coating is applied with Hot Dip Galvanizing, the strip or sheet can be annealed to alloy the coating into the steel strip or sheet.

[0108] The galvannealing may be performed at temperatures in the range of 450-600 C.

Exemplary Compositions and Mechanical Properties

[0109] The microstructure and the mechanical properties of example 1-5 can be limited according to the restrictions disclosure for steels having Al in the range of 0.01-0.6 as discussed above, whereas the microstructure and the mechanical properties of example 6 and 7 can be limited according to the restrictions disclosure for steels having M in the range of 0.5-2.0 as discussed above.

[0110] Zinc adhesion and decarburised zone as discussed above.

[0111] According to a first example the steel: [0112] a) having a composition comprising of (in wt. %):

TABLE-US-00009 C 0.08-0.28 Mn 1.4-4.5 Cr 0.01-0.5 Si 0.01-2.5 Al 0.01-0.6 Si + Al 0.1 Si + Al + Cr 0.4 Nb 0.1 Ti 0.1 Mo 0.5 Ca 0.05 V 0.1 [0113] balance Fe apart from impurities; and [0114] b) fulfilling at least one of the following conditions:

TABLE-US-00010 TS tensile strength (R.sub.m) 950-1550 MPa YS yield strength (Rp.sub.0.2) 550-1400 MPa YR yield ratio (Rp.sub.0.2/R.sub.m) 0.50 bendability (Ri/t) 4.

[0115] According to a second example the steel: [0116] a) having a composition comprising of (in wt. %):

TABLE-US-00011 C 0.08-0.16 Mn 2.0-3.0 Cr 0.1-0.5 Si 0.5-1.2 Al 0.01-0.5 Si + Al 0.1 Si + Al + Cr 0.4 Nb 0.1 Ti 0.1 Mo 0.5 Ca 0.05 V 0.1 [0117] balance Fe apart from impurities; and [0118] b) fulfilling at least one of the following conditions:

TABLE-US-00012 TS tensile strength (R.sub.m) 950-1150 MPa YS yield strength (R.sub.p0.2) 750-1000 MPa YR yield ratio (R.sub.p0.2/R.sub.m) 0.70 bendability (Ri/t) <2.

[0119] According to a third example the steel: [0120] a) having a composition comprising of (in wt.

TABLE-US-00013 C 0.15-0.25 Mn 1.0-2.0 Cr 0.1-0.5 Si 0.1-0.5 Al 0.01-0.5 Si + Al 0.1 Si + Al + Cr 0.4 Nb 0.1 Ti 0.1 Mo 0.5 Ca 0.05 V 0.1 [0121] balance Fe apart from impurities; and [0122] b) fulfilling at least one of the following conditions:

TABLE-US-00014 TS tensile strength (R.sub.m) 1300-1550 MPa YS yield strength (R.sub.p0.2) 1000-1300 MPa YR yield ratio (R.sub.p0.2/R.sub.m) 0.70 bendability (Ri/t) 4.

[0123] According to a fourth example the steel: [0124] a) having a composition comprising of (in wt. %):

TABLE-US-00015 C 0.15-0.25 Mn 2.0-3.0 Cr 0.1-0.5 Si 1-2.0 Al 0.01-0.5 Si + Al 0.1 Si + Al + Cr 0.4 Nb 0.1 Ti 0.1 Mo 0.5 Ca 0.05 V 0.1 [0125] balance Fe apart from impurities; and [0126] b) fulfilling at least one of the following conditions:

TABLE-US-00016 TS tensile strength (R.sub.m) 1100-1300 MPa YS yield strength (R.sub.p0.2) 500-1100 MPa YR yield ratio (R.sub.p0.2/R.sub.m) 0.70 bendability (Ri/t) 3.

[0127] According to a fifth example the steel: [0128] a) having a composition comprising of (in wt.

TABLE-US-00017 C 0.10-0.20 Mn 2.0-3.0 Cr 0.1-0.5 Si 0.2-0.9 Al 0.01-0.5 Si + Al 0.1 Si + Al + Cr 0.4 Nb 0.1 Ti 0.1 Mo 0.5 Ca 0.05 V 0.1 [0129] balance Fe apart from impurities; and [0130] b) fulfilling at least one of the following conditions:

TABLE-US-00018 TS tensile strength (R.sub.m) 900-1100 MPa YS yield strength (R.sub.p0.2) 600-800 MPa YR yield ratio (R.sub.p0.2/R.sub.m) 0.65 bendability (Ri/t) 2.5.

EXAMPLE

[0131] Five steels A-E were produced by conventional metallurgy by converter melting and secondary metallurgy. The compositions are shown in table 1, further elements were present only as impurities, and below the lowest levels specified in the present description. The compositions are shown in Table 1.

TABLE-US-00019 TABLE 1 Steel C N Mn Cr Si Al A 0.108 0.0035 2.66 0.185 0.85 0.044 B 0.221 0.005 1.47 0.378 0.13 0.042 C 0.196 0.0035 2.49 0.027 1.47 0.052 D 0.153 0.0059 2.31 0.238 0.42 0.051 E* 0.168 0.0031 2.31 0.228 0.44 0.958

[0132] *Steels based on E have a composition outside the scope of the present claims,

[0133] The steels were continuously cast and cut into slabs. The slabs were reheated and hot rolled in austenitic range to a thickness of about 2.8 mm. The hot rolling finishing temperature was about 900 C. The hot rolled steel strips where thereafter coiled at a coiling temperature of 630 C. The coiled hot rolled strips were pickled and batch annealed at about 624 C. for 10 hours in order to reduce the tensile strength of the hot rolled strip and thereby reducing the cold rolling forces. The strips were thereafter cold rolled in a five stand cold rolling mill to a final thickness of about 1.4 mm.

[0134] The cold rolled steel strips were conveyed to a Hot Dip Galvanizing Line. The strips were heated to a temperature of 800 C. in a Non-Oxidizing Furnace in a reducing atmosphere. The strips were thereafter conveyed to a soaking furnace and soaked at temperatures and conditions according to Table 2. Each steel A, . . . , E was treated with steam injection as of the invention and without steam injection as a reference. The inventive steels denoted by A1, . . . , D1, E1*, and the reference steels by A2, E2. The base atmosphere was N2+1.9 vol % H2. The CO content was determined by measuring the exhaust gas. For the steels A2, . . . , E2 that was soaked without steam injection the CO content were below 2000 ppm. For the steam injected steels A1, . . . E1, the amount of steam injected was regulated such that the CO content reached above 10000 ppm.

[0135] After soaking the steels were cooled by slow jet cooling (SJC) followed by rapid jet cooling (RJC), the end temperatures for SJC and RJC are shown in Table 2. The strips were isothermal held at the end temperature rapid jet cooling at about 180 s and thereafter Hot Dip Galvanized to apply a zinc coating. The process parameters are shown in table 2.

TABLE-US-00020 TABLE 2 Soaking Soaking CO Hold temp time Steam Exhaust SJC RJC time Steel ( C.) (s) Atmosphere injection (ppm) ( C.) ( C). (s) A1 850 120 N2+ 1.9% H2 Yes >10000 750 390 180 A2 850 120 N2+ 1.9% H2 No <2000 750 390 180 B1 850 120 N2+ 1.9% H2 Yes >10000 700 250 180 B2 850 120 N2+ 1.9% H2 No <2000 700 250 180 C1 850 120 N2+ 1.9% H2 Yes >10000 700 350 180 C2 850 120 N2+ 1.9% H2 No <2000 700 350 180 D1 850 120 N2+ 1.9% H2 Yes >10000 750 380 180 D2 850 120 N2+ 1.9% H2 No <2000 750 380 180 E1* 860 120 N2+ 1.9% H2 Yes >10000 750 400 180 E2* 860 120 N2+ 1.9% H2 No <2000 750 400 180

[0136] Zinc adhesion was determined by a drop-ball impact test according to SEP 1931: Prfung der Haftung von Zinkberzgen auf feuerverzinktem Feinblech, Kugelschlagprfung, 1991.

[0137] The decarburised zone was examined for steel C1 (>10000 ppm CO) and compared to C2 (<2000 ppm CO). This can be seen in FIG. 1, which shows the decarburised zone of C1 and FIG. 2 which shows the lack of a decarburised zone in C2. FIG. 3 shows a graph of the C-content from the surface towards the centre of C1 compared to C2. And FIG. 4 shows a graph of the microhardness from the surface towards the centre of C1 compared to C2.

[0138] The mechanical properties are shown in table 3. As can be seen the Zinc adhesion and the bending properties are much improved in the steels A1, . . . , E1 soaked at >10000 ppm CO compared to those A2, . . . , E2 soaked at <2000 ppm CO.

TABLE-US-00021 TABLE 3 Zn YR Total El Adhesion YS TS R.sub.p0.2/ Unif. JIS (SEP Steel R.sub.p0.2 R.sub.m R.sub.m El JIS (A50) Ri/t 1931) A.sub.c3 A1 848 1048 0.81 7.8 13.2 1.8 2 800 A2 942 1082 0.87 6.6 11.5 2.6 4 800 B1 1176 1517 0.78 3.7 6.4 3.7 1 776 B2 1216 1484 0.82 3.3 5.8 4.4 4 776 C1 928 1193 0.78 9.9 15.7 2.6 1 811 C2 859 1207 0.71 10.4 16.4 3.5 3 811 D1 722 995 0.73 8.9 15.0 2.2 1 778 D2 734 1007 0.73 8.9 15.2 3.0 4 778 E1* 394 984 0.40 12.2 16.0 3.4 1 775 E2* 396 985 0.40 12.2 16.1 4.8 4 775

[0139] Yield strength YS and tensile strength TS were derived according to the European norm EN 10002 Part 1. The samples were taken in the longitudinal direction of the strip. The total elongation (A.sub.50) is derived in accordance with the Japanese Industrial Standard JIS Z 2241: 2011, wherein the samples are taken in the transversal direction of the strip.

[0140] Samples of the produced strips were subjected to V bend test in accordance with JIS Z2248 to find out the limiting bending radius (Ri). The samples were examined both by eye and under optical microscope with 25 times magnification in order to investigate the occurrence of cracks. Ri is the largest radius in which the material shows no cracks after three bending tests. Ri/t was determined by dividing the limiting bending radius (Ri) with the thickness of the cold rolled strip (t).

[0141] A.sub.c3 was determined by the formula:

A.sub.c3=910203*C.sup.1/215.2 Ni30 Mn+44.7 Si+104 V+31.5 Mo+13.1 W.

[0142] The microstructures of the A1, B1, D1 and E1 was determined and are shown in Table 4.

TABLE-US-00022 TABLE 4 A1 B1 C1 D1 E1* Bainite + Tempered >85% ~95% >70% ~85% ~45% Martensite Fresh martensite ~5% <15% ~5% ~20% Retained austenite ~5% ~5% <15% ~10% ~10% Polygonal ferrite ~25%