PROCESS FOR MANUFACTURING HIGH STRENGTH STEEL

Information

  • Patent Application
  • 20230272499
  • Publication Number
    20230272499
  • Date Filed
    November 23, 2022
    2 years ago
  • Date Published
    August 31, 2023
    a year ago
Abstract
A method of making high strength steel sheet with a tensile strength of 800 to 1000 MPa and a hole expansion ratio of at least 50%, comprising the steps of reheating a previously cast slab, or retaining the heat from a directly cast slab, above Ar3; hot rolling the slab to final desired thickness; cooling the steel sheet at a rate of 50° C. per second to a temperature less than 400° C.; and winding the steel sheet into a coil.
Description
BACKGROUND

Typically, a direct quenching approach is employed in plate products and hot strip mill products. Tempering is applied in direct quenching of the plate and aging, for example, precipitation strengthening, have been employed after direct quenching in laboratory settings when developing models of precipitation hardening kinetics. Most of the steel produced on hot-strip mills is produced using coiling temperatures exceeding 500° C. This condition restricts the strength attainable in low alloy steels, demands higher alloy content to achieve higher strength levels of interest, or requires additional processing and cost through off-line heat treatment.


In some processes, the process of manufacturing high strength steels with good local formability, for example, bending and hole expansion in the 800 MPa and 1000 MPa tensile strength class is produced without the need for cold rolling.


The present disclosure includes a method of producing high strength steel directly on a hot-strip mill without further thermomechanical processing, for example, cold-rolling and annealing. In some embodiments, the process disclosed includes utilizing low coiling temperature, or “direct quenching,” in a hot strip mill to manufacture high strength steels. In some embodiments, the process described herein includes direct quenching, with reduced or eliminated subsequent thermal treatment, to achieve high strength steels having fine and tough microstructures, for example, acicular ferrite suitable for applications requiring high local formability. In some embodiments, high strength steel is produced, for example, bainite or martensite, directly after quenching. In some embodiments, the strength, ductility, or toughness balance may be modified by subsequent tempering operations, for example, through batch annealing, continuous annealing, or hot-dip coating lines. In some embodiments, steel having fine microstructures is produced while preserving precipitation strengthening elements in the dissolved state for subsequent aging treatment, similar to tempering, for example, through batch annealing, continuous annealing, or hot-dip coating lines. In some embodiments, an aging treatment will be utilized to produce a desired balance of strength, ductility, or toughness.


SUMMARY

A method of making high strength steel sheet with a tensile strength of 800 to 1100 MPa and a hole expansion ratio of at least 50%, comprising the steps of reheating a previously cast slab, or retaining the heat from a directly cast slab, above Ar3; hot rolling the slab to final desired thickness; cooling the steel sheet at a rate of 50° C. per second to a temperature less than 400° C.; and winding the steel sheet into a coil.


A method of making high strength steel sheet having a tensile strength of approximately 800 MPa and a composition of 0.06 weight percent of Carbon, 1.0 weight percent of Mn and 0.1 weight percent of Si, 0.03 weight percent of Ti and 0.0020 weight percent of Boron, comprising the steps of: reheating a previously cast slab, or retaining the heat from a directly cast slab, above Ar3; hot rolling the slab to final desired thickness; cooling the steel sheet at a rate of 50° C. per second to a temperature less than 400° C.; and winding the steel sheet into a coil.


A method of making high strength steel sheet a tensile strength of approximately 1000 MPa and a composition 0.06 weight percent of C, 1.0 weight percent of Mn, 0.1 weight percent of Si, 0.03 weight percent of Ti and 0.0020 weight percent of B, comprising the steps of: reheating a previously cast slab, or retaining the heat from a directly cast slab, above Ar3; hot rolling the slab to final desired thickness; cooling the steel sheet at a rate of 50° C. per second to a temperature less than 400° C.; and winding the steel sheet into a coil.





BRIEF DESCRIPTION OF THE DRAWINGS


FIG. 1 provides a graph showing modeling prior methods of cooling at various positions in a coil.



FIG. 2 provides a graph showing hole expansion as a function of tensile strength for the experimental steels without subsequent annealing.



FIG. 3 provides a graph showing hole expansion as a function of tensile strength for the experimental steels after applying different annealing cycles.



FIG. 4 provides graphs showing the aging response via hardness testing to determine if there was a match to P* modeling, batch annealing paradigm.



FIG. 5 provides graphs showing the aging treatments conducted to determine sensitivity to annealing.



FIG. 6 provides a graph of low temperature aging treatment conducted to temper the microstructure with the goal of improving hole expansion.



FIG. 7 provides a graph showing the batch annealing simulations to determine sensitivity to annealing temperature.



FIG. 8 shows graphs of aging response based on batch annealing.



FIG. 9 shows a graph the aging study results conducted batch annealing simulations with hot spot and cold spot.



FIG. 10 shows graphs of annealing screening to see sensitivity to batch annealing temperatures.



FIG. 11 provides a graph of the annealing simulation with hot spot and cold spot cycle.



FIG. 12 shows graphs of lower anneal temperatures.





DETAILED DESCRIPTION

In some embodiments, the process of manufacturing high strength steels requires developing a ferritic microstructure that is substantially strengthened by precipitation hardening. The principal precipitation hardening prior processes are either titanium based, or vanadium based. These technologies employ common hot-strip mill (HSM) processing, with coiling temperatures of at least 600° C. (1112° F.). Free cooling of a hot coil, as is the conventional practice, inherently results in varying time-temperature history for the different positions in the coil. The extremities of the coil (edges, outer wraps in particular) cool more rapidly than the coil interior. Such variations can be estimated in the prior methods, as shown in FIG. 1. This example is based on initial coiling temperature of 1325° F., 30-inch coil inner diameter, 65.6-inch outer diameter, and 0.371-inch thickness. This has significant implications for the precipitation hardening reactions upon which this material design relies and induces undesirable mechanical property variability.


In some prior methods, the addition of molybdenum may mitigate the variability for titanium carbide precipitates and in some examples vanadium-based precipitates. It is known that acicular ferrite microstructures offer combinations of strength and toughness. These microstructures are the underpinning of line pipe products. Local formability is effectively a measure of toughness and high strength steels as disclosed herein.


Acicular ferrite can be developed by quenching low carbon steels, and quenching strip to a low temperature before winding in the coiler mitigates the variability in post-coiling cooling. The present disclosure discusses direct quenching steel after hot strip mill processing. In some embodiments, direct quenching may preserve precipitation hardening species in a dissolved state (unprecipitated).


The primary purpose of a hot strip mill is to reheat thick steel slabs into thin sheets with varying thickness. The thick steel slab passes through several rolling mill stands that are driven by powerful motors. The rolled sheets then pass through coilers, thereafter these coils move on to the next process in the plant. From the startup to the end, the steel material undergoes several treatments through each stage that are the main features of a hot strip mill.


The disclosure includes a method of inducing precipitation strengthening reactions under controlled thermal conditions, such as batch annealing, continuous annealing, or adjusting properties with improved uniformity. Additionally, the disclosure includes data showing that annealing quench-and-tempered products are shown to achieve a combination of strength and toughness.


The disclosure is applicable to a broad range of steel hot rolling processes. In some embodiments, the steel is hot rolled while the steel is primarily in its austenitic state and that the rolled strip is subsequently cooled to a temperature low enough, and at a sufficient rate, to achieve acicular ferrite or bainitic structures. In some embodiments, a precursor for final hot rolling can be produced in tandem with final rolling sequence (direct casting and rolling technologies with or without intermediate reheating in advance of the final rolling) or can be produced in an independent facility with the slabs or transfer bars reheated for processing in a hot strip mill.


In some embodiments, the temperature of the final rolling step should be such that the steel is in the austenitic start. This causes the last rolling pass to be completed at a temperature greater than the austenite-to-ferrite transformation temperature, also known as temperature Ar3.


In some embodiments, upon completion of the final rolling step, the steel is rapidly cooled to achieve the desired acicular ferrite and/or bainite microstructure (depending on strength class). The rapid cooling continues until the steel is less than 400° C. The steel strip is then wound into a coil. The rate of rapid cooling should be greater than 50° C/second.


In some embodiments, a secondary treatment process is applied to the steel strip to promote precipitation reactions for strength preservation or increase. In this embodiment, the hot rolled strip should be reheated to a temperature above 500° C. and below the ferrite-to-austenite phase transformation temperature, for example, a temperature Ac1. The appropriate temperature depends on the time duration anticipated for the process employed. For example, continuous annealing of the steel strip will result in shorter heating times than batch annealing of coils. The shorter duration of continuous annealing operations (for hot-dip coated or uncoated strip) allows the strip to approach the Ac1 temperature while achieving the desired properties.


In some embodiments, the steel composition includes carbon. In some embodiments, the steel composition includes carbon in a range of approximately 0.03 to 0.07 weight percent. Carbon levels below approximately 0.03 weight percent will risk the ability to achieve the desired strength level. Higher levels of carbon risk low hole expansion performance and can make the steel prone to the adverse peritectic reaction during continuous casting.


In some embodiments, the steel composition includes manganese. In some embodiments, the steel composition includes manganese in a range of approximately at most 2.0 weight percent. Manganese is one of the more economical strengthening elements that also sequesters sulfur prevent the formation of damaging iron sulfide. A minimum practical level for higher strength steels is approximately 0.5 weight percent, and economics often dictate higher levels to preclude the use of more costly elements. Elevated levels of manganese lead to chemical segregation patterns that can be damaging to performance.


In some embodiments, the steel composition includes molybdenum. In some embodiments, the steel composition includes molybdenum in a range of at most approximately 0.5 weight percent. Molybdenum is a potent strengthening element, but often expensive to employ. It may be chosen to limit the maximum manganese content employed or to add thermal stability to precipitation hardening species. If not technically required, a residual level would be employed for economic reasons.


In some embodiments, the steel composition includes chromium. In some embodiments, the steel composition includes chromium less than approximately 2.0 weight percent. Chromium is a potent strengthening element. Economics often suggest its use after manganese but before molybdenum. It can be used to limit the maximum manganese employed. For this technology, additions less than approximately 2.0 weight percent are appropriate.


In some embodiments, the steel composition includes silicon. In some embodiments, the steel composition includes silicon less than up to approximately 1 weight percent silicon is an efficient strengthening element. Higher levels of silicon can induce surface features on the hot strip that may be objectionable depending on the application. Higher silicon levels can also interfere with galvanizing operations.


In some embodiments, the steel composition includes boron. In some embodiments, the steel composition includes boron less than up to approximately in the range of 10 to 30 parts per million. The strengthening effect can only be assured with use of a nitrogen sequestering element, most typically titanium. The sequestering of nitrogen results in coarse nitride particles that can be damaging to the toughness of the steel. As such, the use of boron alloying may not be appropriate for the most toughness critical applications.


In some embodiments, the steel composition includes titanium. In some embodiments, the steel composition includes titanium as a potent strengthening element. In the context of this disclosure, titanium is principally utilized as a nitrogen sequestering element to facilitate the use of boron, or as a precipitation strengthener for secondary thermal operations. The appropriate level for use in nitrogen sequestration is at a level of 3.4 time the nitrogen content of the steel. A practical maximum addition for the precipitation strengthening consideration would be 0.2 weight percent.


In some embodiments, the steel composition includes vanadium. In some embodiments, the steel composition includes vanadium at approximately 0.2 weight percent. Vanadium can be a potent strengthening element. In the context of this disclosure, the use of vanadium is as a precipitation strengthener for secondary thermal operations.


In some embodiments, the steel composition includes copper. In some embodiments, the steel composition includes copper at approximately in the range of 0.3 to 0.5 weight percent where atmospheric corrosion resistance is desired. Copper is not considered a critical strengthening element. In the context of the disclosure, copper would only be employed when atmospheric weathering resistance is desired. Suitable mechanical properties can be achieved without the need for this costly alloying element. The use of copper must be judicious as it can result in low ductility during hot rolling operations (hot shortness). Depending on the hot rolling process employed, a concurrent nickel addition may be mandatory to mitigate the hot ductility reduction.


In some embodiments, the steel composition includes nickel. In some embodiments, the steel composition includes nickel at approximately the level of one-half the copper addition. This level has been found suitable for mitigating the low ductility at hot rolling temperatures. Nickel additions can be employed for strengthening, toughening, or to mitigate low ductility during hot rolling. In the context of the disclosure, nickel would only be employed as a companion to copper additions when atmospheric weathering resistance is desired. Suitable mechanical properties can be achieved without the need for this costly alloying element.


In some embodiments, the steel composition includes a tensile strength of approximately 800 MPa, a very economical steel composition would be approximately (all values in weight percent): 0.06C-1.0Mn-0.1Si-0.03Ti-0.0020B; with no additional intentional additions. Using a similar alloy design for nominally 1000 MPa tensile strength, the composition would be approximately (all values in weight percent): 0.06C-1.0Mn-0.1Si-0.03Ti-0.0020B; with no additional intentional additions. Alternative designs without boron additions can be considered. For example, 800 MPa tensile strength steel would be expected with a composition of approximately (all values in weight percent): 0.06C-1.5Mn-0.1Si, with no additional intentional additions. To reach the 1000 MPa tensile strength level the manganese level would be increased to its practical maximum of 2.0 weight percent and chromium would be added at a level of 0.5 weight percent.


As described herein, direct-quenching is a first step of the heat treatment operation with subsequent tempering occurring in a different process step (batch annealing, continuous annealing). This approach does not rely on precipitation hardening reactions and is an alternative implementation of known quench-and-temper concepts.



FIG. 2 illustrates the combination of two key properties of primary interest: hole expansion and tensile strength. FIG. 2 illustrates a graph showing hole expansion as a function of tensile strength. The graphs show properties of the steel manufactured according to an embodiment of the process of the present disclosure in the as-direct-quenched condition and after annealing. The present disclosure is configured to produce steel having at least 800 MPa tensile strength, with hole expansion of at least 50%. The graphs shown in FIG. 2 show properties without subsequent annealing, the second graph shows properties after applying different annealing cycles. The graphs in FIG. 2 illustrate that there are various batches that produced good hole expansion at tensile strength greater than 800MPa.


The following examples are intended to illustrate various aspects of the present disclosure and are not intended to limit the scope of the disclosure. Many different steel alloys were considered. The strength of the direct-quenched product can be expected to vary as a function of composition. Table 1 shows a regression model for tensile strength as a function of composition. The data is sorted by ascending P-Value, placing the elements of most significance to the regression at the top of the list (higher P-Value means higher probability of random contribution).


Table 1 illustrates regression results of tensile strength vs composition for as-direct-quenched plates.














TABLE 1







Standard Error





Term
Coefficient
of the Coefficient
T-Value
P-Value
VIF




















Constant
322.2
80.1
4.02
0



C
3688
665
5.55
0
2.35


B
82830
16566
5.00
0
2.48


Mn
130.1
38.9
3.35
0.002
1.87


Mo
256
126
2.03
0.048
3.40


Cr
118.7
67.7
1.75
0.086
3.90


Cb
−435
320
−1.36
0.180
2.38


Si
64.9
59.2
1.10
0.278
2.90


Cu
158
492
0.32
0.749
74.05


Ni
−192
850
−0.23
0.822
64.92


V
−14
443
−0.03
0.975
1.68


Ti
1
208
0
0.997
2.27









The inclusion of C, B, Mn, Mo, and Cr are utilized to increase the hardenability of the steel. In some embodiments, the contribution of Cb, particularly as indicated by a negative coefficient, reflects this element's contribution to grain size refinement and a negative contribution to hardenability. In some embodiments, Cu and Ni additions, while expected to contribute to hardenability, were not reported as reliable contributors (quite high P-Value). Similarly, in some embodiments, V and Ti had high P-Values. This condition is reasonable for V and Ti since their contributions in these steels is primarily through precipitation hardening, which is not expected to be active in the as-quenched condition. It is through subsequent aging treatments that V and Ti, as well as Cb, will contribute to strength preservation or increase.


Tables 2 and 3 illustrate data from Campaign 1. Plates were hot rolled and direct quenched to room temperature. Heat compositions (all values in weight percent).


























TABLE 2





Heat
Note
C
Mn
P
S
Si
Cu
Ni
Cr
Mo
V
Ti
Al
N
Cb
B
Pcm







8774A
HIC Steel
0.046
1.07
0.009
0.0031
0.20
0.30
0.20
0.50
0.01
0.005
0.015
0.03
0.0051
0.030
0.0002
0.151


8774B
Development:
0.047
1.08
0.008
0.0026
0.20
0.30
0.20
0.51
0.01
0.005
0.015
0.04
0.0052
0.059
0.0002
0.153


8774C
Based on
0.047
1.08
0.008
0.0026
0.20
0.30
0.20
0.51
0.01
0.005
0.015
0.04
0.0049
0.090
0.0002
0.153


8775B
lower Mn
0.043
0.80
0.009
0.0030
0.19
0.02
0.01
0.24
0.01
0.005
0.014
0.03
0.0048
0.061
0.0002
0.105


8775C

0.046
0.80
0.009
0.0023
0.19
0.02
0.01
0.48
0.01
0.005
0.014
0.03
0.0048
0.062
0.0002
0.120






















TABLE 3









Uni.
Total
Hole



Thickness
YS
UTS
Elong.
Elong.
Expansion*


Heat
(in.)
(MPa)
(MPa)
(%)
(%)
(%)







8774A
0.250
502
684
10.0
28.4
69


8774B
0.250
488
685
10.1
30.7
69


8774C
0.250
541
730
 9.5
28.3
52


8775B
0.250
455
631
12.7
30.9
94


8775C
0.250
482
641
11.7
32.5
79





*plates were ground to 5 mm thick prior to hole expansion testing.






Tables 4 and 5 illustrate data from Campaign 2. Plate was hot rolled and direct quenched to room temperature. Subsequently did aging treatments to determine sensitivity to annealing.

























TABLE 4





Note
C
Mn
P
S
Si
Cu
Ni
Cr
Mo
V
Ti
Al
N
Cb
B
Pcm







Stock slab
.064
1.82
.013
.0032
.06
.01
.04
.03
.00
.020
.112
.02
.0047
.063
.0001
.162


from HSMM


















Studies




















TABLE 5








Uni.



Thickness (in.)
YS (MPa)
UTS (MPa)
Elong. (%)
Total Elong. (%)







0.250
577
784
7.6
23.2





No hole expansion testing conducted.







FIG. 4 provides graphs of an aging response via hardness testing to determine if there was a match to P* modeling. Batch annealing paradigm times were 1 hour through 48 hours, 3600 s to 172800 s. Hardness tests conducted using HRA scale, converted to HRC.


Tables 6 and 7 illustrate data from Campaign 3. Plates were hot rolled and direct quenched.


























TABLE 6





Heat
Note
C
Mn
p
S
Si
Cu
Ni
Cr
Mo
V
Ti
Al
N
Cb
B
Pcm







8709
USSC
0.048
 1.65
 0.010
0.0050
0.28 
0.30 
0.15 
0.30 
0.20
0.02 
0.020 
0.034
0.0071
0.085 
0.0003
0.189


8710
X70
0.044
 1.68
 0.010
0.0043
0.29 
0.30 
0.15 
0.45 
0.01
0.02 
0.021 
0.036
0.0061
0.084 
0.0002
0.182


8711
Lab
0.050
 1.64
 0.010
0.0045
0.29 
0.28 
0.15 
0.45 
0.15
0.02 
0.021 
0.030
0.0071
0.089 
0.0002
0.194


8712
Heats
0.035
 1.93
 0.010
0.0043
0.30 
0.31 
0.15 
0.46 
0.01
0.02 
0.022 
0.030
0.0054
0.087 
0.0001
0.185


8713

0.047
 1.91
 0.010
0.0045
0.30 
0.30 
0.15 
0.45 
0.15
0.02 
0.020 
0.042
0.0070
0.085 
0.0003
0.206


8714

0.048
 1.88
 0.010
0.0043
0.30 
0.30 
0.15 
0.44 
0.01
0.02 
0.026 
0.032
0.0070
0.086 
0.0016
0.202


9183
LTO
0.093
1.412
0.0131
0.0042
0.394
0.031
0.011
0.0637
0.07
0.0552
0.0072
0.036
0.0082
0.0319

0.19 


Plate B
X65


















9183
Lab
0.093
1.412
0.0131
0.0042
0.394
0.031
0.011
0.0637
0.07
0.0552
0.0072
0.036
0.0082
0.0319

0.19 


Plate D
Heats


















9184

0.082
1.362
0.0095
0.0021
0.405
0.03
0.01
0.032
0.081
0.0647
0.0006
0.028
0.0072
0.020

0.18 


Plate B



















9184

0.082
1.362
0.0095
0.0021
0.405
0.03
0.01
0.032
0.081
0.0647
0.0006
0.028
0.0072
0.020

0.18 


Plate C



















9184

0.082
1.362
0.0095
0.0021
0.405
0.03
0.01
0.032
0.081
0.0647
0.0006
0.028
0.0072
0.020

0.18 


Plate D






















TABLE 7









Uni.
Total
Hole



Thickness
YS
UTS
Elong.
Elong.
Expansion*


Heat
(in.)
(MPa)
(MPa)
(%)
(%)
(%)





















8709
0.25
697
861
6.0
21.9
54


8710
0.25
613
793
6.7
23.6
67


8711
0.25
674
861
6.8
22.8
46


8712
0.25
622
798
5.5
14.3
79


8713
0.25
670
849
6.2

60


8714
0.25
863
1000 
3.8
16.8
46


9183 Plate B
0.25
577
851
10.3
23.8
25


9183 Plate D
0.178 
568
859
7.9
14.3
34


9184 Plate B
0.25
726
882
3.6
17.7
42


9184 Plate C
0.17
524
792
9.0
16.2
42


9184 Plate D
0.18
540
798
9.6
20.8
43





*0.250″ thick plates ground to 5 mm prior to hole expansion testing.






Tables 8 and 9 illustrate data from Campaign 4. Hot rolled to heavy gauge and initial testing conducted.


























TABLE 8





Heat
Note
C
Mn
P
S
Si
Cu
Ni
Cr
Mo
V
Ti
Al
N
Cb
B
Pcm







8709
USSC
0.048
1.65 
0.010 
0.0050
0.28 
0.30 
0.15 
0.30 
0.20 
0.02 
0.020 
0.034
0.0071
0.085 
0.0003
0.189


8710
X70
0.044
1.68 
0.010 
0.0043
0.29 
0.30 
0.15 
0.45 
0.01 
0.02 
0.021 
0.036
0.0061
0.084 
0.0002
0.182


8711
Lab
0.050
1.64 
0.010 
0.0045
0.29 
0.28 
0.15 
0.45 
0.15 
0.02 
0.021 
0.030
0.0071
0.089 
0.0002
0.194


8712
Heats
0.035
1.93 
0.010 
0.0043
0.30 
0.31 
0.15 
0.46 
0.01 
0.02 
0.022 
0.030
0.0054
0.087 
0.0001
0.185


8713

0.047
1.91 
0.010 
0.0045
0.30 
0.30 
0.15 
0.45 
0.15 
0.02 
0.020 
0.042
0.0070
0.085 
0.0003
0.206


8714

0.048
1.88 
0.010 
0.0043
0.30 
0.30 
0.15 
0.44 
0.01 
0.02 
0.026 
0.032
0.0070
0.086 
0.0016
0.202


9183
LTO
0.093
1.412
0.0131
0.0042
0.394
0.031
0.011
0.0637
0.07 
0.0552
0.0072
0.036
0.0082
0.0319

0.19 


Plate B
X65


















9183
Lab
0.093
1.412
0.0131
0.0042
0.394
0.031
0.011
0.0637
0.07 
0.0552
0.0072
0.036
0.0082
0.0319

0.19 


Plate D
Heats


















9184

0.082
1.362
0.0095
0.0021
0.405
0.03
0.01
0.032
0.081
0.0647
0.0006
0.028
0.0072
0.020

0.18 


Plate B



















9184

0.082
1.362
0.0095
0.0021
0.405
0.03
0.01
0.032
0.081
0.0647
0.0006
0.028
0.0072
0.020

0.18 


Plate C



















9184

0.082
1.362
0.0095
0.0021
0.405
0.03
0.01
0.032
0.081
0.0647
0.0006
0.028
0.0072
0.020

0.18 


Plate D





















TABLE 9







YS
UTS
Uni.
Total


Heat
Thickness (in.)
(MPa)
(MPa)
Elong. (%)
Elong. (%)




















9081a
0.268
620
863
7.6
19.4


9081b
0.265
643
879
7.0
22.2


9082a
0.259
633
816
6.1
20.1


9082b
0.257
809
978
3.7
14.9


9083a
0.263
581
789
7.7
24.2


9083b
0.261
610
805
6.8
18.6


9084a
0.261
567
792
7.1
22.9









Table 10 provides data for plates that were ground to 5 mm thick to facilitate hole expansion tests. Subsize longitudinal tensile specimens extracted from edges and tested.















TABLE 10









Uni.

Hole



Thickness
YS
UTS
Elong.
Total Elong.
Expansion


Heat
(in.)
(MPa)
(MPa)
(%)
(%)
(%)







9081a
0.197
715
908
5.5
19.8
46


9081b
0.197
606
823
7.1
19.9
50


9082a
0.198
717
896
5.0
16.8
66


9082b
0.202
698
872
5.3
17.9
67


9083a
0.200
701
880
5.4
17.2
58


9083b
0.198
647
828
6.7
19.8
66


9084a





56










FIG. 5 shows graphs of an aging treatment conducted to determine sensitivity to annealing. All tests were conducted in salt pots and hardness measure by HRA. Converted to VHN to allow more direct estimation of tensile strength. FIGS. 6 and 7 simulate batch annealing of hot spots and cold spots subjected to a low temperature aging treatment conducted to temper the microstructure with the goal of improving hole expansion.


Table 11 illustrates hole expansion after low temperature temper treatments.










TABLE 11








Hole Expansion (%)










Heat
Before tempering
Hot Spot, 272° F.
Cold Spot, 185° F.





9081a
46
41
40


9081b
50
48
54


9082a
66
68
69


9082b
67
78
68


9083a
58
60
66


9083b
66
56
58


9084a
56
60
53









Tables 12 and 13 illustrate data from Campaign 5. Plates hot rolled and direct quenched to room temperature.



















TABLE 12







Heat
Note
Alloy
C
Mn
P
S
Si
Cu
Ni
Cr





8976
Existing
FW11
0.062
1.648
0.009
0.0033
0.181
0.017
0.099
0.2


8977
Line Pipe
FM25
0.054
1.52
0.015
0,0037
0.233
0.016
0.139
0.202


9026
Grades
XM02
0.053
1.51
0.011
0.0025
0.198
0.021
0.02
0.03


9027

FM22
0.055
1.507
0.012
0.0044
0.21
0.02
0.019
0.19


9028

FW18
0.053
1.494
0.011
0.0043
0.197
0.099
0.201
0.25



















Heat
Note
Mo
V
Ti
Al
N
Cb
B
Pcm





8976
Existing
0.141
0.039
0.012
0.031
0.0059
0.051

0.1762


8977
Line Pipe
0.149
0.0025
0.0118
0.033
0.0055
0.075

0.1612


9026
Grades
0.011
0.0021
0.0149
0.033
0.0048
0.0861

0.1389


9027

0.013
0.0023
0.0166
0.031
0.0044
0.0837

0.1493


9028

0.151
0.04
0.016
0.03
0.005
0.05

0.1691
























TABLE 13







Finishing



Uni.
Total
Hole




Temp.
Thickness
YS
UTS
Elong.
Elong.
Expansion


Heat
Note
(º F.)
(in.)
(MPa)
(MPa)
(%)
(%)
(%)























8976
Plate A
1515
0.172
573
797
8.8
22.3
57



Plate B
1605
0.178
597
813
8.2
20.7
55


8977
Plate A
1525
0.172
562
767
9.5
22.8
60



Plate B
1600
0.177
572
770
8.8
22.9
56


9026
Plate A
1520
0.170
534
715
11.0
22.9
68



Plate B
1610
0.176
541
713
10.7
24.9
77


9027
Plate A
1520
0.170
563
728
10.8
26.1
67



Plate B
1625
0.175
543
734
10.3
26.0
57


9028
Plate A
1525
0.169
578
782
8.7
20.8
72



Plate B
1595
0.175
590
785
8.9
23.3
65









Tables 14 and 15 illustrate data from Campaign 6. Plates were hot rolled and quenched to room temperature.


























TABLE 14





Heat
Note
C
Mn
P
S
S
Cu
Ni
Cr
Mo
V
Ti
Al
N
Cb
B
Pcm







8709
USSC
0.048
1.645
0.010
0.0050
0.282
0.296
0.146
0.299
0.196
0.0220
0.020
0.034
0.0071
0.085
0.0003
0.189


8710
X70 Trials
0.044
1.677
0.010
0.0043
0.293
0.296
0.148
0.451
0.014
0.0220
0.021
0.036
0.0061
0.084
0.0002
0.182


8711

0.050
1.644
0.010
0.0045
0.292
0.278
0.147
0.453
0.146
0.0210
0.021
0.030
0.0071
0.089
0.0002
0.194


8712

0.035
1.930
0.010
0.0043
0.295
0.308
0.145
0.455
0.011
0.0230
0.022
0.030
0.0054
0.087
0.0001
0.185


8713

0.047
1.910
0.010
0.0045
0.300
0.299
0.150
0.446
0.152
0.0220
0.020
0.042
0.0070
0.085
0.0003
0.206


8714

0.048
1.884
0.010
0.0043
0.304
0.299
0.150
0.444
0.011
0.0200
0.026
0.032
0.0070
0.086
0.0016
0.202


8681A
Lab HTP-
0.037
1.582
0.011
0.0056
0.195
0.030
0.024
0.283
0.016
0.0020
0.015
0.028
0.0066
0.087
 0.000
0.140


8681B
Type Heats,
0.057
1.564
0.011
0.0054
0.194
0.030
0.024
0.282
0.016
0.0020
0.015
0.026
0.0065
0.085
0.0001
0.159


8682A
C-Cr Study
0.032
1.614
0.012
0.0041
0.202
0.031
0.008
0.501
0.016
0.0030
0.015
0.031
0.0050
0.088
0.0001
0.148


8682B

0.056
1.643
0.010
0.0040
0.209
0.031
0.008
0.503
0.015
0.0030
0.016
0.028
0.0046
0.090
0.0001
0.174


8683A

0.027
0.572
0.011
0.0050
0.199
0.031
0.008
0.705
0.013
0.0030
0.015
0.029
0.0057
0.090
0.0001
0.151


8683B

0.050
1.561
0.010
0.0050
0.198
0.030
0.008
0.700
0.013
0.0030
0.015
0.026
0.0057
0.088
0.0001
0.173






















TABLE 15









Uni.
Total
Hole



Thickness
YS
UTS
Elong.
Elong.
Expansion


Heat
(in.)
(MPa)
(MPa)
(%)
(%)
(%)





















8709
0.173
626
819
7.2
19.3
42


8710
0.171
618
799
8.1
22.1
52


8711
0.171
643
848
7.5
19.8
40


8712
0.170
611
785
7.6
21.6
61


8713
0.169
661
843
7.0
19.4
52


8714*
0.170
573
758
7.4
19.5
49


8681A**
0.174
568
703
9.5
23.9
63


8681B
0.172
557
742
10.1
24.6
49


8682A
0.170
567
701
8.3
22.2
78


8682B
0.170
580
778
9.1
23.6
55


8683A
0.169
555
701
8.1
20.4
71


8683B
0.167
592
784
8.3
21.5
49





*Not properly direct quenched, speed under sprays too high.


**Delay during rolling resulted in ultra-low finishing temperature.






Tables 16 and 17 illustrate a direct quench portion of 780 development bainitic approach. Lab heats hot rolled with two different finishing temperatures and direct quenched to room temperature.


























TABLE 16





Heat
Note
C
Mn
P
S
Si
Cu
Ni
Cr
Mo
V
Ti
Al
N
Cb
B
Pcm







9304
FM37
0.058
1.548
0.012 
0.0034
0.245
0.02 
0.01 
0.033
0.217
0.0016
0.023
0.031
0.0067
0.09 
0.002 
0.171



Base


















9305
Low N
0.062
1.617
0.011 
0.0034
0.248
0.02 
0.011
0.034
0.22
0.0016
0.024
0.033
0.0035
0.092 
0.0019
0.178



FM37


















9306
FM 37,
0.059
1.58
0.011 
0.0036
0.241
0.019
0.01 
0.033
0.218
0.0015
0.024
0.032
0.0037
0.045 
0.0018
0.172



low N, Nb


















9307
Mesplont
0.063
1.585
0.012 
0.0031
0.253
0.02 
0.01 
0.033
0.149
0.0015
0.023
0.031
0.0036
0.045 
0.0019
0.173



low N


















9308
Babbit
0.04 
1.779
0.0099
0.0037
0.247
0.019
0.011
0.034
0.294
0.0018
0.023
0.031
0.0067
0.06 
0.002 
0.170



1992


















9309
Nunakawa
0.11 
1.604
0.011 
0.0029
0.519
0.02 
0.01 
0.486
0.011
0.002 
0.071
0.032
0.0034
0.0022
0.0004
0.236



1985
























TABLE 17











Uni.
Total
Hole




Finishing
Thickness
YS
UTS
Elong.
Elong.
Expansion


Heat
Note
Temp. (º F.)
(in.)
(MPa)
(MPa)
(%)
(%)
(%)























9304
Plate A
1545
0.185
714
901
6.7
15.5
40



Plate H
1650
0.184
816
995
5.0
11.1
34


9305
Plate A
1555
0.182
663
878
6.7
14.8
41



Plate H
1665
0.184
779
1013
5.5
12.1
37


9306
Plate A
1520
0.182
746
911
3.6
10.8
35



Plate H
1635
0.181

1023
4.5
11.0
38


9307
Plate A
1555
0.179
787
945
4.6
11.4
55



Plate H
1640
0.180
850
1022
5.2
12.6
35


9308
Plate A
1540
0.180
756
898
4.5
11.3
44



Plate H.
1650
0.177
861
976
4.7
11.2
46


9309
Plate A
1530
0.178
796
1068
5.5
10.8
24



Plate H
1625
0.175
862
1162
5.1
11.8
30










FIG. 8 provides graphs showing an aging response based on batch annealing paradigm. In this embodiment, batch annealing was conducted to determine sensitivity to the annealing temperature, for example, heat at 100° F./hr., hold 24 hours, furnace cool.



FIG. 9 shows results based on the aging study results, conducted batch annealing simulations with hot spot and cold spot. In some embodiments, the hot spot temperature was 1100° F., around peak aging with Mo steels, overaging without Mo. In some embodiments, the cold spot was 1000° F., below peak aging, if peak aging was 24 hours at 1000° F.


Table 18 shows results based on the aging study results, conducted batch annealing simulations with hot spot and cold spot, a hot spot of 1100° F. was tested at approximately peak aging with Mo steels, overaging without Mo. In addition, a cold spot of 1000° F. was tested. This is below peak aging if peak aging was 24 hours at 1000° F.














TABLE 18





Alloy
Condition
YS
UTS
TE
HE




















9304
DQ
714
901
15.5
40



Cold Spot
803
864

35



Hot Spot
737
786

39


9305
DQ
663
878
14.8
41



Cold Spot
833
894

35



Hot Spot
785
803

40


9306
DQ
746
911
10.8
35



Cold Spot
832
879

36



Hot Spot
769
804

35


9307
DQ
787
945
11.4
55



Cold Spot
823
866

38



Hot Spot
737
780

42


9308
DQ
756
898
11.3
44



Cold Spot
823
871

42



Hot Spot
780
810

39


9309
DQ
796
1068
10.8
24



Cold Spot
899
960

32



Hot Spot
751
801

33









Tables 19 and 20 show results of direct quench portion of HR780 development, hybrid of FM13 and KSL 780R. The data includes lab heats for CAL/HD grades. Plates were hot rolled with different finishing temperatures and direct quenched to room temperature.


























TABLE 19





Heat
Note
C
Mn
P
S
Si
Cu
Ni
Cr
Mo
V
Ti
Al
N
Cb
B
Pcm







9324
FM13
0.053
1.819
0.012
0.0024
0.117
0.022
0.01 
0.044
0.005 
0.003
0.109 
0.031
0.0068
0.034 
0.0004
0.154


9325
FM13 + Si
0.055
1.827
0.011
0.0023
0.52 
0.021
0.01 
0.044
0.005 
0.003
0.109 
0.034
0.0071
0.034 
0.0004
0.170


9326
FM13 +
0.055
1.792
0.011
0.0022
0.52 
0.021
0.011
0.042
0.0056
0.003
0.111 
0.032
0.0065
0.053 
0.0004
0.168



Si + Nb


















9327
FM13 + Si +
0.056
1.788
0.012
0.002
0.513
0.021
0.01 
0.042
0.0054
0.004
0.175 
0.034
0.0064
0.053 
0.0004
0.169



Nb + Ti


















9328
KSL780R +
0.084
1.793
0.012
0.0021
0.508
0.021
0.011
0.042
0.0055
0.004
0.175 
0.033
0.0065
0.053 
0.0004
0.197



Mn + Si


















9329
KY06
0.085
1.855
0.012
0.0021
0.873
0.021
0.01 
0.042
0.0051
0.002
0.0016
0.034
0.0067
0.0044
0.0004
0.213


9330
KT24
0.075
1.899
0.012
0.002 
0.101
0.02 
0.011
0.198
0.171 
0.002
0.0008
0.03 
0.0067
0.0038
0.0004
0.198
























TABLE 20











Uni.
Total
Hole




Finishing
Thickness
YS
UTS
Elong.
Elong.
Expansion


Heat
Note
Temp. (º F.)
(in.)
(MPa)
(MPa)
(%)
(%)
(%)























9324
Plate C
1520
0.185
600
789
7.8
17.8
61



Plate J
1630

615
788
7.6
14.6
47


9325
Plate C
1505

622
832
7.9
17.4
54



Plate I
1630

639
834
6.9
15.2
42


9326
Plate C
1505

618
828
8.0
18.1
52



Plate H
1630

562
828
6.0
14.7
41


9327
Plate C
1515

639
834
8.2
17.1
52



Plate H
1650

482
835
6.5
16.2
47


9328
Plate C
1580

635
886
8.6
16.9
34



Plate H
1635

615
868
7.0
14.3
37


9329
Plate C
1480

512
866
11.5
19.9
19



Plate H
1615

591
973
7.4
15.0
29


9330
Plate C
1615

756
975
3.6
10.2
46



Plate H
1750

846
1037
4.3
11.5
42










FIG. 10 shows graphs of an annealing screening to determine sensitivity to batch annealing temperatures of 900, 1000, 1100, 1200° F. at 24 hours. FIG. 11 shows a batch annealing simulation with hot spot and cold spot cycle. Table 21 includes data from a batch annealing simulation with hot spot and cold spot cycle.














TABLE 21





Alloy
Condition
YS (MPa)
UTS (MPa)
TE (%)
HE (%)




















24
DQ
600
789
17.8
61



CS
783
838
21.1
42



HS
747
794
21.0
58


25
DQ
622
832
17.4
54



CS
815
876
20.9
37



HS
773
820
23.2
38


26
DQ
618
828
18.1
52



CS
819
875
20.7
37



HS
765
816
23.2
37


27
DQ
639
834
17.1
52



CS
852
914
21.7
40



HS
821
862
22.7
48


28
DQ
635
886
16.9
34



CS
848
911
20.1
40



HS
793
846
20.2
42


29
DQ
512
866
19.9
19



700CS
593
758
20.8
42



800HS
579
705
23.3
47



650CS
648
840
19.5
80



750HS
639
783
22.5
65


30
DQ
756
975
10.2
46



700CS
725
793
12.9
69



800HS
710
779
16.1
72



650CS
803
911
14.4
93



750HS
842
904
16.4
86










FIG. 12 shows data for lower anneal temperatures in Heat 30, 900° F. for 24 hours results in approximately 755 MPa. Table 22 illustrates a direct quench portion of HR780 development including Ti with different N levels. These heats were for tuning FM13/FM44. Lab heats hot rolled and direct quenched to room temperature.


















TABLE 22







Heat
Note
C
Mn
P
S
Si
Cu
Ni
Cr





9420A
Low Ti,
0.0676
1.93735
0.01192
0.00153
0.49234
0.02033
0.01034
0.04169



Mid N










9420B
Mid Ti
0.0672
1.94201
0.01166
0.0015
0.49923
0.02077
0.0103
0.04158



Mid N










9420C
High Ti,
0.0682
1.9289
0.01144
0.00154
0.49305
0.02023
0.01018
0.04111



Mid N










9435A
Low Ti
0.0601
1.86559
0.01151
0.0014
0.47612
0.01718
0.00998
0.04111



Low N










9435B
Mid Ti,
0.0603
1.86451
0.01147
0.00349
0.47401
0.01716
0.00997
0.04111



Low N










9435C
High Ti,
0.0587
1.87687
0.01097
0.00136
0.48274
0.01764
0.00945
0.04096



Low N





Heat
Note
Mo
V
Ti
Al
N
Cb
B
Pcm





9420A
Low Ti,
0.0055
0.00991
0.07823
0.04935
0.0066
0.03283
0.00028
0.187



Mid N










9420B
Mid Ti
0.0056
0.01044
0.10243
0.05149
0.00643
0.0328
0.0003
0.187



Mid N










9420C
High Ti,
0.00532
0.01051
0.12744
0.05083
0.0059
0.0318
0.00028
0.187



Mid N










9435A
Low Ti
0.00509
0.00906
0.07126
0.03824
0.00425
0.03242
0.00026
0.175



Low N










9435B
Mid Ti,
0.00517
0.00937
0.09294
0.0376
0.00449
0.03256
0.00027
0.175



Low N










9435C
High Ti,
0.00484
0.00993
0.1167
0.03667
0.00443
0.03167
0.00026
0.174



Low N









Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard variation found in their respective testing measurements.


Also, any numerical range recited herein is intended to include all sub-ranges subsumed therein. For example, a range of “1 to 10” is intended to include all sub-ranges between (and including) the recited minimum value of 1 and the recited maximum value of 10, that is, having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10.


In this application, the use of the singular includes the plural and plural encompasses singular, unless specifically stated otherwise. In addition, in this application, the use of “or” means “and/or” unless specifically stated otherwise, even though “and/or” may be explicitly used in certain instances. In this application and the appended claims, the articles “a,” “an,” and “the” include plural referents unless expressly and unequivocally limited to one referent.


As used herein, “including,” “containing” and like terms are understood in the context of this application to be synonymous with “comprising” and are therefore open-ended and do not exclude the presence of additional undescribed or unrecited elements, materials, phases or method steps. As used herein, “consisting of” is understood in the context of this application to exclude the presence of any unspecified element, material, phase, or method step. As used herein, “consisting essentially of” is understood in the context of this application to include the specified elements, materials, phases, or method steps, where applicable, and to also include any unspecified elements, materials, phases, or method steps that do not materially affect the basic or novel characteristics of the disclosure.


Whereas particular embodiments of this invention have been described above for purposes of illustration, it will be evident to those skilled in the art that numerous variations of the details of the present invention may be made without departing from the invention as defined in the appended claims.

Claims
  • 1. A method of making high strength steel sheet with a tensile strength of 800 to 1100 MPa and a hole expansion ratio of at least 50%, comprising the steps of: reheating a previously cast slab, or retaining the heat from a directly cast slab, above Ar3;hot rolling the slab to final desired thickness; cooling the steel sheet at a rate of 50° C. per second to a temperature less than 400° C.; andwinding the steel sheet into a coil.
  • 2. The method of making high strength steel according to claim 1, wherein the temperature Ar3 is a temperature greater than the austenite-to-ferrite transformation temperature.
  • 3. The method of making high strength steel according to claim 1, further comprising cooling the steel sheet to an acicular ferrite structure.
  • 4. The method of making high strength steel according to claim 1, further comprising cooling the steel sheet to a bainitic structure.
  • 5. The method of making high strength steel according to claim 1, further comprising the application of a secondary treatment to the steel sheet to promote precipitation reactions for strength preservation or an increase in strength.
  • 6. The method of making high strength steel according to claim 5, further comprising reheating the steel coil to a temperature below Ac1.
  • 7. The method of making high strength steel according to claim 6, wherein the temperature Ac1 is a temperature above 500° C. and below the ferrite-to-austenite phase transformation temperature.
  • 8. The method of making high strength steel according to claim 6, wherein the temperature depends on a time duration anticipated for a process employed.
  • 9. The method of making high strength steel according to claim 6, further comprising continuous annealing of the steel sheet to achieve reduced heating times.
  • 10. The method of making high strength steel according to claim 9, wherein the reduced duration of the heating time during the continuous annealing allows for the steel sheet to approach a temperature Ac1 temperature while achieving the desired properties.
  • 11. A method of making high strength steel sheet having a tensile strength of approximately 800 MPa and a composition of 0.06 weight percent of Carbon, 1.0 weight percent of Mn and 0.1 weight percent of Si, 0.03 weight percent of Ti and 0.0020 weight percent of boron, comprising the steps of: reheating a previously cast slab, or retaining the heat from a directly cast slab, above Ar3;than 400° C.; andhot rolling the slab to final desired thickness;cooling the steel sheet at a rate of 50° C. per second to a temperature less winding the steel sheet into a coil.
  • 12. The method of making high strength steel according to claim 11, further comprising cooling the steel sheet to an acicular ferrite.
  • 13. The method of making high strength steel according to claim 11, further comprising a applying a secondary treatment to the steel sheet to promote precipitation reactions for strength preservation or an increase in strength.
  • 14. The method of making high strength steel according to claim 13, further comprising reheating the steel coil to a temperature below Act.
  • 15. The method of making high strength steel according to claim 14, wherein the temperature Ac1 is a temperature above 500° C. and below the ferrite-to-austenite phase transformation temperature.
  • 16. The method of making high strength steel according to claim 11, wherein the temperature depends on a time duration anticipated for a process employed.
  • 17. The method of making high strength steel according to claim 11, further comprising continuous annealing of the steel sheet to achieve reduced heating times.
  • 18. The method of making high strength steel according to claim 17, wherein the reduced duration of the heating time during the continuous annealing allows for the steel sheet to approach a temperature Ac1 temperature while achieving the desired properties.
  • 19. A method of making high strength steel sheet a tensile strength of approximately 1000 MPa and a composition 0.06 weight percent of C, 1.0 weight percent of Mn, 0.1 weight percent of Si, 0.03 weight percent of Ti and 0.0020 weight percent of B, comprising the steps of: slab, above Ar3;than 400° C.; andreheating a previously cast slab, or retaining the heat from a directly cast hot rolling the slab to final desired thickness;cooling the steel sheet at a rate of 50° C. per second to a temperature less winding the steel sheet into a coil.
CROSS-REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional Patent Application No. 63/283,090, filed Nov. 24, 2021, which is incorporated herein by reference.

Provisional Applications (1)
Number Date Country
63283090 Nov 2021 US