EP2683839A1 - Procédé pour produire un acier formable à haute résistance et acier formable à haute résistance produit par celui-ci - Google Patents
Procédé pour produire un acier formable à haute résistance et acier formable à haute résistance produit par celui-ciInfo
- Publication number
- EP2683839A1 EP2683839A1 EP12708008.3A EP12708008A EP2683839A1 EP 2683839 A1 EP2683839 A1 EP 2683839A1 EP 12708008 A EP12708008 A EP 12708008A EP 2683839 A1 EP2683839 A1 EP 2683839A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- strip
- temperature
- martensite
- steel
- austenite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 60
- 239000010959 steel Substances 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 29
- 230000008569 process Effects 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 229910000734 martensite Inorganic materials 0.000 claims description 51
- 229910052799 carbon Inorganic materials 0.000 claims description 44
- 229910001566 austenite Inorganic materials 0.000 claims description 43
- 238000010791 quenching Methods 0.000 claims description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 32
- 238000001816 cooling Methods 0.000 claims description 23
- 238000000137 annealing Methods 0.000 claims description 20
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- 229910001563 bainite Inorganic materials 0.000 claims description 10
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- 229910000859 α-Fe Inorganic materials 0.000 claims description 9
- 150000001247 metal acetylides Chemical class 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 238000005246 galvanizing Methods 0.000 claims description 5
- 230000000717 retained effect Effects 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 238000003303 reheating Methods 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910001567 cementite Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 241000030538 Thecla Species 0.000 claims 1
- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 6
- 238000000638 solvent extraction Methods 0.000 description 28
- 230000015572 biosynthetic process Effects 0.000 description 27
- 238000007792 addition Methods 0.000 description 26
- 230000009466 transformation Effects 0.000 description 25
- 239000010936 titanium Substances 0.000 description 23
- 239000011572 manganese Substances 0.000 description 20
- 239000000203 mixture Substances 0.000 description 19
- 230000006641 stabilisation Effects 0.000 description 16
- 238000012545 processing Methods 0.000 description 10
- 238000005728 strengthening Methods 0.000 description 9
- 229910045601 alloy Inorganic materials 0.000 description 8
- 239000000956 alloy Substances 0.000 description 8
- 238000005266 casting Methods 0.000 description 8
- 230000001965 increasing effect Effects 0.000 description 8
- 239000004411 aluminium Substances 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 230000001737 promoting effect Effects 0.000 description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 6
- 239000011651 chromium Substances 0.000 description 6
- 235000002908 manganese Nutrition 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000011575 calcium Substances 0.000 description 5
- 230000000171 quenching effect Effects 0.000 description 5
- 238000005496 tempering Methods 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 238000007571 dilatometry Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- QFGIVKNKFPCKAW-UHFFFAOYSA-N [Mn].[C] Chemical compound [Mn].[C] QFGIVKNKFPCKAW-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000005098 hot rolling Methods 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000000979 retarding effect Effects 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000005097 cold rolling Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000002939 deleterious effect Effects 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000010339 dilation Effects 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 229910001562 pearlite Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 238000000844 transformation Methods 0.000 description 2
- ZHSKUOZOLHMKEA-UHFFFAOYSA-N 4-[5-[bis(2-chloroethyl)amino]-1-methylbenzimidazol-2-yl]butanoic acid;hydron;chloride Chemical compound Cl.ClCCN(CCCl)C1=CC=C2N(C)C(CCCC(O)=O)=NC2=C1 ZHSKUOZOLHMKEA-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 241000022563 Rema Species 0.000 description 1
- 229910001035 Soft ferrite Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910000797 Ultra-high-strength steel Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- -1 iron carbides Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 210000001331 nose Anatomy 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
- C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
- C23C2/0224—Two or more thermal pretreatments
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/06—Zinc or cadmium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/008—Martensite
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0278—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips involving a particular surface treatment
Definitions
- the invention relates to a method for producing a steel strip composite and to a steel strip composite produced by said method.
- Enhancement of ductility at elevated strength is desirable for widespread markets.
- automotive industry in particular, where legislation is driving improvements in fuel economy and safety, there is a move towa rds stronger, formable high strength steels.
- Hig h strength a nd ultrahig h strength strip steel provides a utomotive man ufacturers potentia l for down weig hting of the body in white and the opportunity for countering weight increases arising from the move to electric and hybrid vehicles.
- high and ultrahigh strength steels play a critical role in determining the crash worthiness of modern passenger vehicles.
- enha ncement of d uctility is realised either by using composite effects (Dua l Phase or DP steels) or by using deformation induced transformation of retained austenite (TRIP steels). Both composite hardening and transformation induced plasticity mechanisms can measurably enhance the ductility of predominantly ferritic steels.
- the enha ncement of ductility which may be achieved i n th is way is l imited to a rou nd 1.5 (for DP) to 2 (for TRIP) times that of conventional C-Mn steels at equivalent strength .
- the strength level that may be achieved in commercial, ferritic-matrix DP and TRIP steels is also limited (TRIP to around 800MPa and DP to around lOOOMPa).
- Extreme enhancement of tensile ductility may also be achieved by utilising high a lloy (predomina ntly manga nese) additions to sta bilise austenite (Twinning Induced Plasticity or TWIP steels) .
- Austenite is inherently more ductile than ferrite and twinning provides a very effective work hardening mechanism.
- Such steels may achieve very high elongations (typically 50%) at very high strengths (typically lOOOMPa).
- the improvement in elongation may be typically 5x that of a conventional C-Mn steel.
- the yield strength is comparatively low and large strains need to be uniformly imposed to achieve high strength in the formed component.
- the extremely high levels of alloy make large scale production over conventional process problematic.
- austenite is simply chemically stabilised by large additions of Mn.
- strength-ductility combinations can be ach ieved i n th is way, processi ng ha s proven to be difficult since hard, brittle martensitic phases are developed in intermediate product. This renders further processi ng , such a s cold rol l i ng , d ifficu lt at d i mensions releva nt to com flarea l processing.
- alloy costs are high due to the high manganese content.
- a method for producing a quenched and pa rtitioned steel by providing a cold rolled a nd a nnea led steel strip containing (in weight %) :
- annealing process comprises the following steps:
- a cold-rolled strip is provided by the conventional and known processes of casting, hot-rolling and cold-rolling.
- the casting process may involve thick slab casting (sla b thickness between 150 a nd 350 mm), thin sla b-casting (slab thickness below 150 mm, usually between 50 and 100 mm) or even strip casting.
- Cold rolling is also a conventional and known process.
- the composition of the steel according to the invention is a balanced composition comprising medium carbon and moderate manganese additions.
- the cold rolled steel is heated to form austenite, either partially or fully, followed by quenching to a temperature between the ma rtensite start temperature (M s ) a nd the ma rtensite finish temperature (M f ), thereby creating a controlled amount of martensite and retained austenite.
- the manganese additions result in stabilisation of an austenite fraction during cooling from the annea ling temperature and the subsequent ca rbon enrichment further sta bilises the austenite fraction.
- Combined stabilisation via C and Mn additions enables alloying with either element to be restricted to reasonable limits lead ing to cost and processability advantages.
- the steel is then subjected to a thermal treatment to partition carbon from the martensite into the austenite.
- the carbon enrichment of the austenite fraction is achieved by partitioning from martensite or low temperature bainitic transformation or preferably a combination of both.
- the formation of ca rbides is su pp ressed a nd the a uste n ite is sta b i l ised rather tha n decom posed .
- Combined stabilisation with partitioning and bainitic transformation enables the amount of austenite and the microstructure in which it is embedded to be optimised.
- the bainitic transformation also leads to ca rbon enrichment of the remaining a ustenite because the formation of carbides is suppressed. All compositions are given in weight percentages, unless otherwise indicated.
- the final microstructure of the steel comprises martensite, bainite and carbon- enriched austenite and, if Ti ⁇ Ac 3 , equiaxed ferrite.
- the stabilisation of austenite results in the steel exhibiting improved ductility relative to traditional high strength steels.
- Ca rbon (C) provides solid solution strengthening, enhances hardenability (thus enabling avoidance of high temperature transformations at cooling rates achievable in conventional annealing lines) and, when dissolved in austenite, promotes the retention of austenite at room temperature. Above 0.4wt% C the propensity for formation of brittle high carbon martensite increases.
- a preferable upper limit for the manganese content is 3.5%.
- Sil icon (Si) add ition provides sol id solution strengthen ing th us ena bl ing the attainment of high strength and promotes the stabilisation of austenite. Si very effectively retards the formation of carbides during overaging thus keeping carbon in solution for stabilisation of austenite. Ferrite and hard phases such as bainite and martensite exhibit improved ductility in the absence of carbides. Free carbon, not trapped in carbides, may be partitioned to austenite.
- the imposed addition of Si should be below a certain level : Si may be added i n the ra nge of between 0.5 to lwt% when combined with Al addition . In the absence of Al additions beyond the level needed for deoxidation Si should be maintained in the range of between 1 to 2wt%.
- Aluminium is usually already added in small quantities of at most 0.1% and preferably at most 0.05% to liquid steel for the purpose of deoxidation by forming alumina. Ideally, the total aluminium content in the steel is between 0.01 and 0.08% if aluminium is only added for desoxidation. In the right quantity it also provides an acceleration of the bainite transformation. Al also retards the formation of carbides thus keeping carbon in solution for pa rtitioning to a ustenite a nd promoting the sta bi lisation of a ustenite.
- a maximum value of 1.5wt% is imposed for castability purposes because higher Al-contents lead to poisoning of casting mould slag and consequently an increase in mould slag viscosity leading to incorrect heat transfer and lubrication during casting. Aluminium alone delivers low strength . Therefore, if Al is used a bove levels required for deoxidation it should always be in combination with Si.
- Niobium (Nb) if added, is added in small amounts of up to 0.1% or more preferably of u p to 0.05wt%. It is added for austenitic grain refinement during hot rolling. If combined with a suitable rolling schedule, it promotes transformation on the run-out-table, and thus finer and a more homogeneous grain size in the hot-rolled intermediate product which is then subsequently cold-rolled.
- Titanium (Ti) ca n be used to form fine precipitates in the ferritic component of mixed microstructures thus increasing strength and promoting uniformity of strength at the microstructural scale and in turn good stretched edge ductility.
- Ti is below 0.1%.
- Molybdenum is used to increase hardenability thus retarding the formation of high temperature transformation products on cooling to the quench temperature. Additions of Mo may therefore allow the utilisation of lower cooling rates more readily achieved in full-scale production lines or to achieve the desired structure and properties in heavier gauge strip.
- the use of Mo is to be preferred over the use of Cr when UHS is required since in addition to enhancing hardenability Mo provides additional solid solution strengthening. Mo is also known to retard coarsening of fine strengthening precipitates thus promoting thermal stability precipitation strengthening variants. For reasons of cost less than 0.5wt% is preferable.
- V Vanadium
- V is used to increase hardenability thus retarding the formation of high temperature transformation products on cooling to the quench temperature.
- V may combine with C or N or both to form fine strengthening precipitates thus increasing strength and promoting uniformity in strength at the microstructural sca le i n mixed microstructures and in turn improved stretched edge ductility.
- V addition up to 0.4wt% is effective. Higher additions are undesirable for reasons of cost and because excessive levels of precipitation tie up high amounts of C. Since free C is required for austenite stabilisation too high V requires increased C addition.
- V is below 0.1%.
- Phosphorus (P) is used to suppress the formation of pearlite d uring cooling, to suppress carbide formation and thereby promote the partitioning of carbon to austenite resulting in austenite stabilisation.
- P addition is known to cause embrittlement at hot-rolling temperatures and to lead to reduced toughness in martensitic UHSS.
- P may also lead to problems in spot welding of the final product. For these reasons P is limited to a maximum of 0.08wt% and more preferably to a maximum of 0.02wt%.
- S is an impurity which may embrittle the intermediate or final product. S should be limited to a maximum level of 0.01wt% and more preferably to at most 0.005wt%.
- Chromium (Cr) and nickel (Ni) may be used to increase hardenability thus retarding the formation of high temperature transformation products on cooling to the quench temperature. Additions of Cr and/or Ni may therefore allow the utilisation of lower cooling rates more readily achieved in full-scale production lines or to achieve the desired structure and properties in heavier gauge strip. Cr and/or Ni should be limited to a level of less than lwt% for reasons of cost and preferably to levels of 0.5wt% or less and more preferably below 0.1%.
- Boron (B) may be used to improve hardenability and, in particular, to prevent the formation of ferrite on cooling from a fully austenitic soaking temperature. B should be limited to 50ppm because above these levels further addition is ineffective.
- Antimony (Sb) may be used to enhance the wettability of zinc during hot dip galvanising. Addition should be limited to 0.06wt% or less.
- Calcium (Ca) may be required to avoid clogging during casting and may be beneficial for modifying the morphology of MnS inclusion. Globular inclusions are known to be less detrimental to stretched edge ductility than highly elongated inclusions. If used, then addition should preferably be made to the level of 30ppm or less. Additions above 0.05% lead to the formation of coarse inclusions detrimental to ductility and toughness.
- N itrogen may be used, in combination with V, to form fine strengthening precipitates imparting strength and promoting uniformity in strength at the microstructural scale and in turn good stretched edge ductility. Additions should be limited to 150ppm or less.
- the annealing step starts with reheating to an annealing temperature (Ti) .
- Ti may be above or below Ac 3 . If Ti is below Ac 3 the resulting ferrite fraction leads to a lower strength and may introduce heterogeneity in strength at a microstructural scale. Local differences in strength lower the ratio of yield to tensile strength and lead to poor stretched edge ductility and bendability. It is therefore preferable that Ti is above Ac 3 .
- the phrase "above Ac 3" means that the microstructure is austenitic at TV
- the equilibrium transformation temperature Ae 3 is only determined by the composition, the value of the corresponding Ac 3 temperature is not a constant value as its value depends among others on the heating rate during which Ac 3 is measured and the starting microstructure of the steel.
- T 2 The rapid cooling to T 2 (CR1) is required to avoid the formation of high temperature transformation phases.
- the specific rate required depends upon the steel chemistry and corresponds to the critical cooling rate for avoidance of ferrite and pearlite noses in the relevant CCT diagram.
- the critical rate decreases with increasing Ti above Ac 3 .
- CR1 i.e. the cooling rate over the temperature interval 800-500°C from Ti to T 2 is between 30 to 80 °C/s.
- T 2 should be chosen low enough to deliver partial transformation to martensite, but not so low as to cause complete transformation to martensite.
- T 2 is chosen to deliver a volume fraction of martensite of between 50 to 90% (in volume) and preferably an a ustenite fraction of at least vol.5%.
- the dependency of the martensitic transformation start temperature (M s ) on composition means that T 2 will also depend upon chemistry.
- a martensite fraction of 60 - 85 vol.% is chosen.
- Holding at T 3 is needed to enrich the remaining austenite in carbon via a bainitic transformation or carbon partitioning or both.
- Higher isothermal holding temperatures may be advantageous since increased rates of carbon diffusion may make feasible shorter isothermal holds.
- Several processes occur d uring isothermal holding including tempering of martensite, diffusion of carbon from the martensite fraction to the rema ining a ustenite, the precipitation of ca rbides a nd the formation of ba inite.
- T 3 is chosen so as to give a suitable rate of transformation to bainite or rate of partitioning or both.
- the specific temperature will be dependent upon alloy composition and will preferably fall in a range expressed by: (Ms-70) ⁇ T 3 ⁇ (Ms+ 150), and preferably T 3 ⁇ (Ms+50)
- the correct balance of isothermal holding temperature and isothermal holding time must be chosen for each composition. These can be determined by means of dilatometry as described hereinbelow.
- carbides may lock up carbon which would otherwise be available for stabilisation of austenite and should therefore preferably be avoided. Furthermore, coarse Fe 3 C carbides may lead to a deterioration in tensile ductility and/or stretched edge ductility.
- the levels of Si or Si/AI must be suitably tuned to retard carbide formation for the duration of the isothermal hold.
- the partitioning temperature and time are chosen such as to optimise the enrichment of ca rbon in the austenite but without creation of deleterious microstructures during the isothermal hold.
- the strip is cooled to ambient temperature.
- the strip may also be coated with zinc or other such metallic layers using a suita ble method of deposition either in-line or in a following process step.
- the cold rolled strip contains at least 0.25% C and at least 0.03% Al.
- a lower limit of 0.25wt% is placed on C because below this level the desired combinations of strength and ductility may not be achieved.
- Si is preferred to that of Al such that a minimum silicon content of lwt% and a max maximum aluminium content of 0.5 wt% is defined.
- Si provides substantial strengthening allowing the achievement of ultra high strength, more effectively su ppresses ca rbide formation ena bl ing longer isotherma l holds without formation of large volumes of coarse iron carbides, and because it does not accelerate bainite formation to the same extent as Al thus preventing excessive formation of bainite and enabling higher strengths to be achieved.
- Strength-Ductility data for a range of production C-Mn steels including ferritic forming steels and quenched martensitic steels have been used to generate a base-line strength-ductility decay for conventional strip steels. The data conform to the expression :
- e ca icuiated is the total elongation (expressed as % engineering strain)
- UTS is the ultimate tensile strength
- k is a constant which for tensile test pieces with 80 mm gauge and thickness 1 mm is 250000.
- elongations are measured at d ifferent ga uge or thickness then they must be converted to an equ iva lent elongation at 80mm ga uge a nd 1 mm thick or the a bove expression must be fit to base-line data measured at that alternative gauge/thickness combination using appropriate values of the constants. Conversion of tensile ductility can be performed using accepted procedures (ISO Norm 2566/1-2) when the geometries corresponding to the measured and to be calculated elongations are know :
- e 2 is the required elongation for a gauge length of L 2 with a cross section of A 2
- ei is the known elongation measured for a gauge length of U with a cross section of Ai and the exponent m is a material constant here assumed to be equal to 0.4.
- the quenched and partitioned steel has an e-ratio of at least 1.8 wherein the e-ratio is defined as emeasured/e C aicuiated a nd wherein e ca icuiated is calculated according to equation (1) and wherein e me asured is the elongation measured from an 80mm gauge length sample at 1mm thick (or measured at some other geometry and converted to an equivalent elongation on an 80mm gauge at 1mm thick using expression (2)).
- the tensile strength of the steel according to the invention is at least 900 MPa. This strength regime is of interest since it provides significant opportunity for down-gauging and is a strength regime for which formability is most limited. Ductility levels a re at least 1.8x or more tha n that of conventiona l C-Mn steels at equivalent strength.
- the yield to tensile strength ratio is 0.6 or higher. More preferably the ratio is at least 0.65 or even higher. Low yield to tensile strength ratios are associated with poor bendability and edge cracking sensitivity. Performance is often dependent on yield strength, anti-intrusion components for instance require high yield strength. High yield to tensile strength ratios ensure strength uniformity in the formed part, especially in forming operations which apply localised strain such as bending, or hole expansion.
- the metal or metal alloy coating is zinc, aluminium, magnesium or alloys thereof.
- the steel is afforded sacrificial corrosion protection since the zinc and aluminium will oxidise in preference to iron in the steel.
- the partitioning temperature and time are chosen such as to optimise the enrichment of carbon in the austenite but without creation of deleterious microstructures during the isothermal hold.
- the temperature and time can be determined using dilatometry as follows:
- t 2 may be between 10 and 500 seconds, but for practical purposes in commercial annealing lines t 2 is preferably in the range of 20 to 180 s or even 20 to 100 s.
- the specimen can be cooled naturally or acceleratedly to room temperature; no fast quench is needed. If during this cooling the dilatation curve shows that the martensite formation re-starts at a temperature in the range from (Ms - 20) to 120°C, then a correct degree of stabilisation has been achieved. In the case that the martensite formation recommences at a temperature ⁇ 120°C, it means that the stabilisation is too strong and the martensite has a very high carbon content compared to the bulk concentration.
- partitioning temperature T 3 By varying the partitioning temperature T 3 and repeat above the required partitioning time will a lso va ry. Increasing the partitioning temperature resu lts in a decrease in partitioning time t 2 and to a higher degree of tempering of the martensite formed during the quench.
- the metallic coating is provided by hot- dip galvanising or by electro-galvanising.
- Figure 1 shows the schematic annealing schedule indicating the meaning of Ti, T 2 and T 3 , ti and t 2 , and of CR1 and CR2.
- Figure 2a and 2b show a set of result of the dilatometric experiments to determine the quench temperature and the partitioning time.
- Figure 2a shows the temperature as a fu nctio n of ti me for a steel havi ng 3.5% M n w h ich was q uenched to a quench temperature of 280°C and reheated to a partitioning temperature of 330°C (triangle) and 440°C (circle). The sample was held at the partitioning temperature for 20 seconds. The quenching temperature resulting in the required amount of martensite is determined on the basis of the base curve (NC-III, sq ua re).
- Fig ure 2b shows the d ilatation of the samples for these conditions.
- the base curve, with a full quench to room temperature allows to determine Ms (about 315°C).
- the partitioning step for 20s at 330°C shows no dilation of the sample, which means that no bainite is formed, carbon is partitioned and the martensite is only marginally tempered.
- the transformation to martensite re-starts at temperatures lower tha n the quench temperature of 280°C, namely at 250°C, which ind icates that the austenite has been stabilized d ue to carbon partitioning.
- Increased partition times at 330°C show that the transformation to martensite re-starts at lower temperatures than 250°C.
- Table 2 shows the results of various thermal cycles with the steels of Table 1. These results show that (I-VI) :
- composition G delivers a very la rge extension of ductility (typically 2.2 times that of a conventional C-Mn steel) at strengths ra ng i ng fro m 850 to 1050 M Pa .
- H oweve r, th is is o n ly true w he n the a n nea ling temperature Ti is chosen below the preferred range, (Ac 3 -40 to Ac 3 +40 such that a high fraction of ferrite is retained in the final structure. From table 2 it is apparent that, in these cases (cycles 31-32, although ductility is at the desired level, the ratio of YS to UTS drops below the desired level to approximately 0.4.
- both direct quenching to room temperature and direct quenching to room temperature followed by an isothermal hold at a higher temperature deliver strengths in the desired range but do not deliver ductility above the desired minimum level.
- composition A when directly quenched to room temperature delivers strength in the desired range but ductility below the desired minimum (cycle 4).
- Composition A when quenched to a T 2 above the M s temperature and subjected to isothermal holding at the same temperature delivers strength greatly below the desired range and ductility below the desired minimum (cycle 3).
- Composition A when quenched to a T 2 below the M s temperature and subjected to isothermal holding at some higher temperature delivers strengths in the approximate range 950 to lOOOMPa and ductilities below the desired minimum (thermal cycles 1-2).
- Compositions B, C, D, F and H each enable the desired property range to be achieved even if T 2 is set such that no martensite is formed during the initial quench (cycles 8, 12, 13, 16, 17, 36 and 37) but in all cases the isothermal holding time at T 3 is unacceptably long to be practical or economical in a continuous annealing process.
- compositions B, D and F each enable the desired property range to be achieved if T 2 is set such that the desired fraction of martensite is formed during the initial quench (cycles 6, 15, 22) and if an isothermal holding temperature (T 3 ) and the holding time at this temperature are set at suitable levels.
- compositions C and H each return effectively zero ductility results when subjected to processing involving a deep quench (low T 2 ) a nd isothermal hold times at T 3 sufficiently short for conventional CA process (cycles 10-11 and 34-35) due to the formation of brittle, high carbon martensite in the final structure.
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Abstract
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EP12708008.3A EP2683839B1 (fr) | 2011-03-07 | 2012-03-07 | Procédé pour produire un acier formable à haute résistance et acier formable à haute résistance produit par celui-ci |
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EP12708008.3A EP2683839B1 (fr) | 2011-03-07 | 2012-03-07 | Procédé pour produire un acier formable à haute résistance et acier formable à haute résistance produit par celui-ci |
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