U.S. patent number RE44,940 [Application Number 13/863,100] was granted by the patent office on 2014-06-10 for coated hot- and cold-rolled steel sheet comprising a very high resistance after thermal treatment.
This patent grant is currently assigned to ArcelorMittal Atlantique et Lorraine, ArcelorMittal France. The grantee listed for this patent is Arcelormittal Atlantique Et Lorraine, Arcelormittal France. Invention is credited to Jacques Devroc, Jean-Paul Hennechart, Jean-Pierre Laurent, Dominique Spehner.
United States Patent |
RE44,940 |
Laurent , et al. |
June 10, 2014 |
Coated hot- and cold-rolled steel sheet comprising a very high
resistance after thermal treatment
Abstract
Hot-rolled steel sheet which then can be cold-rolled, coated,
the steel in the sheet having the following composition by weight:
0.15%<carbon<0.5% 0.5%<manganese<3%
0.1%<silicon<0.5% 0.01%<chromium<1% titanium<0.2%
aluminum<0.1% phosphorus<0.1% sulfur<0.05%
0.0005%<boron<0.08%, the remainder being iron and impurities
inherent in processing, the shoot ensuring a very high mechanical
resistance after thermal treatment and the aluminum-based coating
ensuring a high resistance to corrosion.
Inventors: |
Laurent; Jean-Pierre (Istres,
FR), Hennechart; Jean-Paul (Floing, FR),
Spehner; Dominique (Sedan, FR), Devroc; Jacques
(Salon de Provence, FR) |
Applicant: |
Name |
City |
State |
Country |
Type |
Arcelormittal France
Arcelormittal Atlantique Et Lorraine |
Saint-Denis
Saint Denis |
N/A
N/A |
FR
FR |
|
|
Assignee: |
ArcelorMittal France
(Saint-Denis, FR)
ArcelorMittal Atlantique et Lorraine (Saint Denis,
FR)
|
Family
ID: |
9528455 |
Appl.
No.: |
13/863,100 |
Filed: |
April 15, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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13205126 |
Aug 8, 2011 |
Re. 44153 |
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Reissue of: |
09350100 |
Jul 9, 1999 |
6296805 |
Oct 2, 2001 |
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Reissue of: |
09350100 |
Jul 9, 1999 |
6296805 |
Oct 2, 2001 |
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Foreign Application Priority Data
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Jul 19, 1998 [FR] |
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98 08793 |
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Current U.S.
Class: |
420/104; 148/531;
148/537; 428/653; 428/939 |
Current CPC
Class: |
C22C
38/38 (20130101); C22C 38/32 (20130101); C21D
8/0278 (20130101); Y10T 428/12757 (20150115); Y10S
428/939 (20130101) |
Current International
Class: |
C21D
8/02 (20060101); C22C 38/18 (20060101); C22C
38/06 (20060101); B32B 15/08 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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382512 |
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Nov 1964 |
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CH |
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1252034 |
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Oct 1967 |
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DE |
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1297906 |
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May 1962 |
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FR |
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2 625 227 |
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Jun 1989 |
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FR |
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09-025551 |
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Jan 1997 |
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JP |
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09-195021 |
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Jul 1997 |
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JP |
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1555374 |
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Apr 1990 |
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SU |
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Primary Examiner: Sample; David
Attorney, Agent or Firm: Baker & Hostetler LLP
Schumaker; David W.
Parent Case Text
.Iadd.Notice: More than one reissue application has been filed for
the reissue of U.S. Pat. No. 6,296,805. This application is a
reissue continuation of U.S. application Ser. No. 13/205,126, filed
Aug. 8, 2011, which is an application for reissue of U.S. Pat. No.
6,296,805. .Iaddend.
Claims
What is claimed is:
.[.1. A hot-rolled coated steel sheet comprising a hot-rolled steel
sheet coated with an aluminum or aluminum alloy coating, wherein
the steel in the sheet comprises the following composition by
weight: 0.15%<carbon<0.5% 0.5%<manganese<3%
0.1%<silicon<0.5% 0.01% <chromium<1% titanium<0.2%
aluminum<0.1% phosphorus<0.1% sulfur<0.05%
0.0005%<boron<0.08%, the remainder being iron and impurities
inherent in processing, and the steel sheet has a very high
mechanical resistance after thermal treatment and the aluminum or
aluminum alloy coating provides a high resistance to corrosion of
the steel sheet..].
.[.2. The coated steel sheet according to claim 1, wherein the
composition by weight of the sheet further comprises the following:
0.20%<carbon<0.5% 0.8%<manganese<1.5%
0.1%<silicon<0.35% 0.01%<chromium<1% titanium<0.1%
aluminum<0.1% phosphorus<0.05% sulfur 0.03%
0.0005%<boron<0.01%, the remainder being iron and impurities
inherent in processing..].
.[.3. A heat treated coated steel sheet prepared by subjecting the
coated steel sheet according to claim 2, to an increase in
temperature at a speed in excess of 600.degree. C./second..].
.[.4. A process for producing a casting comprising shaping the
coated steel sheet of claim 2, subjecting the shaped coated steel
sheet to an increase in temperature at a speed in excess of
5.degree. C./sec..].
.[.5. The coated steel sheet according to claim 1, wherein the
ratio of titanium to nitrogen in the steel sheet in weight % is in
excess of 3.42..].
.[.6. A process for producing a casting comprising shaping the
coated steel sheet of claim 5, subjecting the shaped coated steel
sheet to an increase in temperature at a speed in excess of
5.degree. C./sec..].
.[.7. The coated steel sheet according to claim 1, wherein the
aluminum or aluminum alloy coating comprises from 9% to 10% silicon
by weight, from 2% to 3.5% iron by weight, the remainder being
aluminum..].
.[.8. A process for producing a casting comprising shaping the
coated steel sheet of claim 7, subjecting the shaped coated steel
sheet to an increase in temperature at a speed in excess of
5.degree. C./sec..].
.[.9. The coated steel sheet according to claim 1, wherein the
coating comprises from 2% to 4% iron by weight, the remainder being
aluminum..].
.[.10. A process for producing a casting comprising shaping the
coated steel sheet of claim 9, subjecting the shaped coated steel
sheet to an increase in temperature at a speed in excess of
5.degree. C./sec..].
.[.11. A process for producing a casting comprising shaping the
coated steel sheet of claim 1, subjecting the shaped coated steel
sheet to an increase in temperature at a speed in excess of
5.degree. C./second..].
.[.12. The process according to claim 11, wherein the casting is
heated to a temperature in excess of 750.degree. C..].
.[.13. A heat treated coated steel sheet prepared by subjecting the
coated steel sheet according to claim 1 to an increase in
temperature at a speed in excess of 600.degree. C./second..].
.[.14. A land motor vehicle comprising the heat treated coated
steel of claim 13..].
.[.15. A land motor vehicle comprising the coated steel sheet of
claim 1..].
.[.16. A heat treated coated steel sheet prepared by subjecting the
coated steel sheet according to claim 1 to a temperature in excess
of 750.degree. C..].
.Iadd.17. A hot-rolled coated steel sheet comprising a hot-rolled
steel sheet coated with an aluminum or aluminum alloy coating,
wherein said coated steel sheet is in the form of a delivery coil
and the steel in the sheet comprises the following composition by
weight: 0.15%<carbon<0.5% 0.5%<manganese<3%
0.1%<silicon<0.5% 0.01%<chromium<1% titanium<0.2%
aluminum<0.1% phosphorus<0.1% sulfur<0.05%
0.0005%<boron<0.08%, the remainder being iron and impurities
inherent in processing, and the steel sheet has a very high
mechanical resistance in excess of 1500 MPa after thermal treatment
and the aluminum or aluminum alloy coating provides a high
resistance to corrosion of the steel sheet. .Iaddend.
.Iadd.18. The coated steel sheet of claim 17 that is manufactured
by a process comprising providing said hot rolled sheet; and
coating said hot rolled sheet with an aluminum coating or aluminum
alloy coating. .Iaddend.
.Iadd.19. The coated steel sheet of claim 18 wherein said aluminum
or aluminum alloy coating is obtained by hot-dipping and comprises,
before said thermal treatment, a first alloy layer in contact with
the surface of the steel, and a second alloy layer on top of the
first alloy layer. .Iaddend.
.Iadd.20. The coated steel sheet of claim 19 wherein the first
coating layer comprises iron. .Iaddend.
.Iadd.21. The coated steel sheet of claim 19 wherein the second
coating layer comprises iron. .Iaddend.
.Iadd.22. The coated steel sheet of claim 17 wherein the aluminum
coating or aluminum alloy coating has a thickness of about 20
micrometers. .Iaddend.
.Iadd.23. The coated steel sheet of claim 17 wherein the steel in
the sheet is treated with calcium. .Iaddend.
.Iadd.24. A coated steel sheet according to claim 17, manufactured
by a process comprising a step of cold-rolling before said aluminum
or aluminum alloy coating. .Iaddend.
.Iadd.25. The coated steel sheet of claim 24 that is composed
predominately of martensite. .Iaddend.
.Iadd.26. The coated steel sheet of claim 24 wherein said
subsequent thermal treatment includes hot-shaping the coated steel
sheet, and cooling the hot-shaped sheet at a rate that produces
martensitic structures, ferrite-martensitic structures , or
ferrite-bainitic structures. .Iaddend.
.Iadd.27. A hot-rolled coated steel sheet comprising a hot-rolled
steel sheet coated with an aluminum or aluminum alloy coating,
wherein the steel in the sheet comprises the following composition
by weight: 0.15%<carbon<0.5% 0.5%<manganese<3%
0.1%<silicon<0.5% 0.01%<chromium<1% titanium<0.2%
aluminum<0.1% phosphorus<0.1% sulfur<0.05%
0.0005%<boron<0.08%, the remainder being iron and impurities
inherent in processing, and the steel sheet has a very high
mechanical resistance in excess of 1500 MPa after a subsequent
thermal treatment, and the aluminum or aluminum alloy coating
provides a high resistance to corrosion and prevents
decarburization during said subsequent thermal treatment of the
steel sheet. .Iaddend.
.Iadd.28. The coated steel sheet of claim 27 that is composed
predominately of martensite. .Iaddend.
.Iadd.29. The coated steel sheet of claim 27 wherein said
subsequent thermal treatment includes hot-shaping the coated steel
sheet, and cooling the hot-shaped sheet at a rate that produces
martensitic structures, ferrite-martensitic structures, or
ferrite-bainitic structures. .Iaddend.
Description
The invention relates to a coated, hot- and cold-rolled steel sheet
comprising a very high resistance after thermal treatment.
In this technical area, the proposed solutions involving an
increase in the mechanical characteristics are accomplished to the
detriment of shaping properties. There is a solution consisting in
separating the shaping properties and those required for use. The
characteristics required for use are obtained through a thermal
treatment subsequent to or concomitant with shaping. In this case,
the proposed sheets are not delivered coated because of problems of
holding power of the coating at the time of thermal treatment.
Coating therefore is performed on finished castings, which requires
a careful cleaning of the surfaces and the hollowed portions. In
addition, the thermal treatment must be performed under a
controlled atmosphere in order to prevent any decarbonization and
oxidation of the metal in the sheet. Steel sheets for thermal
treatment do not have any precoating which requires post-treatments
of scouring, pickling and coating.
At the time of continuous coating of flat hot- and cold-rolled
products, preliminary annealing and cooling preceding or following
the zinc- or aluminum-based coating operation, are used only to
bring the sheet to a temperature close to that of the bath or to
restore the mechanical properties of the sheet degraded at the time
of cold-rolling. These thermal cycles are chosen in terms of the
composition of the steel so that no allotropic transformation takes
place at the time of the thermal cycle, the objective being to
obtain mechanical characteristics similar to those measured on the
steel sheet delivered uncoated.
The purpose of the invention is to produce a hot- or cold-rolled
steel sheet of a desired thickness, coated, and affording extensive
shaping possibilities and which, after thermal treatment performed
on the finished casting, makes it possible to obtain a mechanical
resistance in excess of 1000 MPa, a substantial resistance to
shocks, fatigue, abrasion and wear, while retaining a good
resistance to corrosion as well as a good capacity for painting and
gluing. It also is possible to carry out hot-shaping with hardening
in the tool making it possible to obtain the same properties.
The subject of the invention is a hot-rolled steel sheet, which
then can be cold-rolled, coated, the steel in the sheet having the
following composition by weight: 0.15%<carbon<0.5%
0.5%<manganese<3% 0.1% silicon<0.5%
0.01%<chromium<1% titanium<0.2% aluminum<0.1%
phosphorus<0.01% sulfur<0.05% 0.0005%<boron<0.08%, the
remainder being iron and impurities inherent in processing, the
sheet ensuring a very high mechanical resistance after thermal
treatment and the aluminum-based coating ensuring a high resistance
to corrosion.
The other characteristics of the invention are: the composition by
weight of the sheet preferably is the following:
0.20%<carbon<0.5% 0.8%<manganese<1.5% 0.1%
silicon<0.35% 0.01%<chromium<1% titanium<0.1%
aluminum<0.1% phosphorus<0.05% sulfur<0.03%
0.0005%<boron<0.01%, the remainder being iron and impurities
inherent in processing. in the composition by weight of the sheet,
the titanium content with respect to the nitrogen content is in
excess of 3.42, the boron no longer being able to be combined with
the nitrogen. the metal bath for the coating contains in its basic
composition by weight, from 9% to 10% silicon, from 2% to 3.5%
iron, the remainder being aluminum. the metal bath for the coating
contains in its basic composition by weight, from 2% to 4% iron,
the remainder being aluminum.
The invention also concerns a process for producing a casting
starting from the coated sheet in which, after shaping, the coating
of the casting is subjected to an increase in temperature at a
speed in excess of 5.degree. C./second, which may exceed
600.degree. C./second.
A further characteristic of the process is: the coating and the
casting are heated to a temperature in excess of 750.degree. C.
The invention also concerns the use of the hot-rolled steel sheet
which then can be cold-rolled and coated, for structural and/or
anti-intrusion or substructure castings for a land motor vehicle,
such as, for example, a bumper bar, a door reinforcement, a wheel
spoke.
The description which follows wilt make the invention clearly
understood.
The sheet according to the invention which derives, by reason of
its processing, from a hot-rolling mill, possibly may be
cold-rerolled again depending on the final thickness desired. It
then is coated with an aluminum-based coating, for example by
dipping in a bath containing, in addition, from 8% to 11% silicon,
from 2% to 4% iron, the sheet having a high mechanical resistance
after thermal treatment and a high resistance to corrosion, as well
as a good capacity for painting and gluing.
The coating has in particular the function of protecting the basic
sheet against hot as well as cold corrosion. The mechanical
characteristics in the delivery state of the sheet according to the
invention allow a great variety of shaping, in particular a deep
stamping. The thermal treatment applied at the time of a
hot-shaping process or alter shaping makes it possible to obtain
high mechanical characteristics which may exceed 1500 MPa for
mechanical resistance and 1200 MPa for the limit of elasticity. The
final mechanical characteristics are adjustable and depend on the
carbon content of the steel and on the thermal treatment.
At the time of thermal treatment performed on a finished casting or
at the time of a hot-shaping process, the coating forms a layer
having a substantial resistance to abrasion, wear, fatigue, shock,
as well as a good resistance to corrosion and a good capacity for
painting and gluing.
According to the invention, the steel the weight composition of
which is the following: 0.15%<carbon<0.5%
0.5%<manganese<3% 0.1%<silicon <0.5%
0.01%<chromium<1% titanium<0.2% aluminum<0.1%
phosphorus<0.1% sulfur<0.05% 0.0005%<boron<0.08%, the
remainder being iron and impurities inherent in processing, is
processed in the form of a hot-rolled and possibly cold-rolled
sheet to obtain the desired thickness. The steel sheet then is
coated by dipping, after pickling, in an aluminum bath containing
either from 8% to 11% silicon and 2% to 4% iron, or from 2% to 4%
iron, or even in an aluminum bath preferably containing from 9% to
10% silicon and 2% to 3.5% iron.
In an example of implementation of a coating of the sheet by
dipping in a metal bath containing an aluminum alloy comprising a
proportion of approximately 90% aluminum, the coating layer
comprises a first alloy layer in contact with the surface of the
steel. This layer, directly in contact with the surface of the
sheet, is highly alloyed with iron.
A second coating layer, on top of the first, contains approximately
90% aluminum and may contain silicon and a small amount of iron,
depending on the composition of the bath.
The first alloy layer may crack when the sheet is shaped for the
manufacture of castings.
According to the invention, after the shaping of the casting, the
coating is subjected to an increase in temperature at a speed in
excess of 5.degree. C./second, which may exceed 600.degree.
C./second. This rise in temperature makes possible a rapid
remelting of the aluminum which fills in the cracks generated by
the operation of shaping of the casting.
Another advantage of the invention lies in the fact that the
diffusion of the iron in the coating will be initiated at high
temperature. One thus will have a better cohesion between coating
and steel in the sheet. In another form of the invention, the
thermal treatment may be performed locally, in heavily deformed
zones.
In an example of implementation, the steel sheet according to the
invention containing 0.21% carbon, 1.14% manganese, 0.020%
phosphorus, 0.0038% sulfur, 0.25% silicon, 0.040% aluminum, 0.009%
copper, 0.020% nickel, 0.18% chromium, 0.0040% nitrogen, 0.032%
titanium, 0.003% boron, 0.0050% calcium is coated with an
aluminum-based layer about 20 .mu.m in thickness.
According to the invention the sheet, in the delivery state in a
coil or in sheeting, the thickness of which may range between 0.25
mm and 15 mm, has good shaping properties and a good resistance to
corrosion as well as a good capacity for painting or gluing.
The sheet, a coated siderurgic product, has a substantial
resistance to corrosion in the delivery state, during shaping and
thermal treatments as well as during usage of the finished casting.
After thermal treatment, a substantial mechanical resistance, which
may exceed 1500 MPa, is obtained. The presence of the coating at
the time of thermal treatment of the castings makes it possible to
prevent any decarbonization of the base metal as well as any
oxidation. That is an undeniable advantage, in particular in the
case of hot-shaping. Furthermore, heating of the treated casting
does not require a furnace having a controlled atmosphere to
prevent a decarbonization.
Thermal treatment of the metal in the sheet consists in a heating
at a temperature ranging between Ac1, starting temperature of
austenitic transformation, for example 750.degree. C. and
1200.degree. C., in a furnace, for a period which depends on the
temperature to be reached and the thickness of the casting sheet.
The composition is optimized so as to limit the enlargement of the
grains at the time of thermal treatment. If the structure sought is
completely martensitic, the holding temperature should be in excess
of Ac3, for example 840.degree. C., ending temperature of
austenitic formation. The temperature holding should be followed by
a cooling adjusted to the final structure sought. For a completely
martensitic structure and for a steel having the composition of the
example, the speed of cooling should be in excess of the critical
speed of hardening which is 27.degree. C./s for an austenitizing at
900.degree. C. for 5 min., the sheet having a thickness of
approximately 1 mm.
It also is possible to obtain in particular ferrito-bainitic or
ferrito-martensitic structures, by a heating at a temperature
ranging between Ac1, for example 750.degree. C. and Ac3, for
example 840.degree. C., followed by an appropriate cooling.
According to the level of resistance to be achieved and the thermal
treatment applied, one or several of these phases is/are present in
variable proportions. For the highest resistance levels, the
structure is composed predominantly of martensite.
Chromium, manganese, boron and carbon are added, in the composition
of the steel according to the invention, for their effect on
hardenability. In addition, carbon makes it possible to achieve
high mechanical characteristics thanks to its effect on the
hardness of the martensite.
Aluminum is introduced into the composition in order to trap oxygen
and to protect the effectiveness of the boron.
Titanium, the ratio of the content of which with respect to the
nitrogen content should be in excess of 3.42, is introduced in
order to prevent combining of the boron with the nitrogen, the
nitrogen being combined with titanium.
The alloying elements, Mn, Cr, B, make possible a hardenability
allowing hardening in the stampers or the use of mild hardening
fluids limiting deformation of the castings at the time of thermal
treatment. In addition, the composition according to the invention
is optimized from the point of view of weldability.
The steel in the sheet may undergo a treatment for globularization
of sulfides performed with calcium, which has the effect of
improving the fatigue resistance of the sheet.
The steel is particularly suited to the production of structural
and anti-intrusion castings.
The proposed coating makes it possible to avoid different
surface-preparation operations such as for steel sheets for thermal
treatment not having any coating.
The modulation of thermal treatment parameters makes it possible to
achieve, with a given composition, different levels of hot and cold
sheet resistance according to the thickness sought.
At the time of thermal treatment, the base coating, of aluminum for
example, is transformed into a layer alloyed with iron and
comprising different phases depending on the thermal treatment and
having a considerable hardness which may exceed 600 HV100 g.
Table 2 presents an example of maximal resistance of the steel
sheet according to the invention after thermal treatment.
TABLE-US-00001 Thermal treatment Rm (MPa) 850.degree. C./5 min.
1695 990.degree. C./5 min. 1675 950.degree. C./5 min. 1665
* * * * *