Precipitation Hardening of Ferrite in Commercially Processed Niobium-Bearing HSLA Steels

A. J. DeArdo Basic Metals Processing Research Institute Department of Materials Science and Engineering, University of Pittsburgh, PA15261, USA Tel.: 412-624-9737 Fax: 412-624-1543 Email: deardo@engr.pitt.edu M. Hua Basic Metals Processing Research Institute Department of Materials Science and Engineering, University of Pittsburgh, PA15261, USA Tel.: 412-624-8593 Fax: 412-624-8069 Email: mjhua@pitt.edu C. I. Garcia Basic Metals Processing Research Institute Department of Materials Science and Engineering, University of Pittsburgh, PA15261, USA Tel.: 412-624-9731 Fax: 412-624-1543 Email: garcia@engr.pitt.edu V. Thillou Pipe Mill, EUROPIPE FRANCE S. A. Usine de Dunkerque, Route de Fort-Mardyck, F-59760 Grande-Synthe, France Tel.: +33 (0)3 28 22 60 00 Fax: +33 (0)3 28 22 60 64 Email: veronique.thillou@europipe.com KEY WORDS: Hot Strip, HSLA, Niobium, Precipitation, Strengthening, Yield Strength INTRODUCTION It is well known that the philosophy of thermomechanical processing is to properly condition the structure of the austenite to induce the formation of fine ferrite through the γ to α transformation. The presence of microalloying elements in the steel can greatly enhance this microstructural control by their precipitation prior, during or after the γ to α transformation. The role of Nb in these microstructural events can be summarized as follows: (i) as initial inhibitor of austenite grain coarsening during the reheating of the slabs, (ii) as austenite recrystallization modifier during rolling, (iii) as transformation hardener by controlling the hardenability of the steel and inducing dislocation strengthened forms of ferrite, and (iv) as precipitation hardener in conjunction with the γ to α transformation. In recent years, several authors have indicated that the precipitation behavior which results from the processing of high strength microalloyed (MA) strip steels might be different than that observed in plate steels. For example, some authors reported that after the hot rolling and coiling of low- carbon, low-alloy steels, lower than expected volume fractions of NbC are formed prior to and after the y to a transformation[ 11. Also, there is some evidence in the literature indicating that fine NbC precipitation in austenite may have a contributing effect to the final strength of the steel [ 1,2]. The present study was directed to assess the precipitation behavior in two high strength MA strip steels with different Mn levels. Of particular interest in this study was to differentiate the precipitation that was formed prior to and after the γ to α transformation and to characterize them quantitatively. In addition to the precipitation, other microstructural features such as the dislocation density and grain size were also measured. The quantitative information from these individual microstructural features was used to calculate the

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These samples were etched with 2% Nital to reveal the overall microstructure. then held at 650°C for 0. only one third of the total number of precipitates in a given area can be illuminated by a single set of precipitate reflections [7. then roughing in three passes from 1140°C to 103O°C. This allows low energy.07 C .004 N for steel B. In this study.0. The austenite (fcc) transforms to ferrite (bcc) with a Kurdjumov-Sachs (K-S) relationship. Niobium precipitates can nucleate in ferrite in two different ways: by interphase precipitation which takes place along with the transformation front of y and the precipitation in the ferrite matrix from a so. without doubt. The precipitates nucleated in ferrite can be identified from the orientation relationship between the ferrite and the precipitates reflections in the electron diffraction patterns. Thus. an orientation relationship to the K-S family. Superimposed stereographic projections for the different phases studied with their well-defined relationships were used to aid in the interpretation of the diffraction patterns [9].1. The nominal chemical composition (wt%) of the steels was 0. Electron microscopy Thin foil samples were prepared and examined using a JEM 2OOCX transmission electron microscope operating at 200 Kv. reducing the free energy of activation for the formation of critically sized nuclei and maximizing diffusion [6].0. interphase precipitates nucleate on only one of the three possible ferrite cube planes as a result of a preferred nucleation at the γ/α interphase boundary. Although both types of precipitates nucleated in ferrite obey the B-N relationship. this consists of concentric circles superimposed randomly on illuminated negatives to avoid any printing contrast errors. The transformation temperature. The ferrite grain structure was investigated by measuring etched samples with a computer controlled image analysis system BioQuant IV.0. France.strength properties and to compare these to the measured properties of the steels. Ar3. immobile interface to develop between fcc and bcc. Specimens from the fully processed steels were sectioned for microstructural analysis and mechanical testing. NbCN precipitates in the ferrite will exhibit the Baker-Nutting (B-N) relationship: (l00)MX 2 (100)α and [001]MX 2 [011]α [5].8].33 Mn . Processing The samples used in this study were rolled from 70 mm down to 10 mm on the experimental hot rolling mill at CRDM. The strain-induced precipitates of NbCN in austenite have a simple cube-cube lattice relationship with austenite: [l00]MC 2 [100]γ & [010]MC 2 [010]γ.called super-saturated ferrite. The crystallographic orientation adopted will be the one that allows good matching with both phases reducing the interface energy. Ferrite will exhibit that rational orientation relationship to at least one austenite grain. and 0. it is very difficult to attribute. The quantitative assessment of the dislocation density was done by measuring from a series of TEM micrographs the total projected length of dislocation line per unit area.025 Nb . the precipitates formed in austenite would be related to the ferrite by the K-S relationship when observed at room temperature.0.2mm and chemical electropolishing with solutions of distilled water + H2O2 (30% vol. and 790°C for steel B. Sections parallel to the rolling direction were machined into standard tensile samples and tested at CDRM.07 C . EXPERIMENTAL PROCEDURE The materials used in this investigation were continuously cast slab sections provided by Sollac. The dislocation density is taken as ρ = R / (At) = 2N / (L·t) with units cm/cm3.0.02 Nb . 2 or 5 hours.1 Mn . The results of this analysis will be presented and discussed in this paper. N is the number of intersections with dislocations by random lines of length L per unit area A [4.) + HF and distilled water + HNO3 + HCI + HF. Because of the multi-variance in nature of that K-S relationship. The Ar3 for steel A was measured to be 835°C. Consequently.004 N for steel A. t is the foil thickness. The specimen preparation involved mechanical thinning to a thickness of about 0. and have a random relationship with the other austenite grains. Optical microscopy Specimens for optical microstructural analysis were prepared using standard metallographic procedures. The specimens were then either air cooled or accelerated cooled to 680°C at a cooling rate of 5O”C/s. respectively and then ACRT. during the ACRT was measured for both steels.4]. where A is the area of the foil containing the dislocation line length R. In this study Hilliard’s method was used. Sollac. because of the trivariant nature of supersaturated precipitation in ferrite. Carbon extraction replica specimens were not used in this study due to the lack of reliability of the extraction efficiency and the impossibility to determine the exact origin of the precipitates [3. 10]. Fringes of thickness extinction contours in the 4 MS&T 2004 Conference Proceedings . The hot strip mill processing schedule was as follows: (i) reheating at 1200°C. The final foil specimens were prepared from punched discs by twin jet polishing at 50V and 45 mA using 10% perchloric acid in acetic acid at room temperature. and (ii) finishing in three passes from 928°C to 892°C. it was essential to use tilting techniques for all the work conducted on the TEM not only to obtain the proper contrast but also to avoid false interpretation of the results and to insure the nature of the precipitation.

2 29. MPa 437 440 503 487 490 365 455 Elongation.1% A B Condition AC + coil (0h) AC + coil (2h) AC + coil (0h) AC + coil (2h) AC + coil (5h) ACRT ACRT YS. In addition.2 31.5 4.2 8. a CRDM’s computer program [14].3 3. Atom probe/Field ion microscopy APFIM was used to determine both the composition of the Nb precipitates and the distribution of soluble Nb in the structure. Steel B typically exhibited a larger and less uniform ferrite grain sizes than those observed in steel A. Table 1.4 12.1 6.0 Mean intercept Measured (µm) 5. The results from this analysis revealed that the microstructure in steel A after ACRT was equiaxed ferrite with small amounts of pearlite.2 A B A B MS&T 2004 Conference Proceedings 5 . The specimen of the material studied is prepared in a needle-like form with an end radius of typically 50 to 100 nm.0/3. The measured grain sizes are in good agreement with those predicted by Structura. Identification of the individual imaged atoms becomes possible.two beam diffraction conditions were used to determine the foil thickness [11. This enables the three dimensional structure of the material to be imaged in atomic detail and also provides the source of ions for analysis by mass spectrometry.8 3.3 5. In the FIM.4 5. the results from Table 1 also indicate that the tensile properties did not change with holding time at the coiling temperature.6/3.8 3. The average measured ferrite grain sizes after ACRT and/or after AC are reported in Table 2.6 4. % 31. This technique is a combination of a field ion microscope and a mass spectrometer of single ion sensitivity. The dimensions of the particles were measured from high resolution centered dark field micrographs. Successive atom layers of material may be ionized and removed from the specimen surface by the process of field evaporation. Details of the sample preparation and operation of this technique are given elsewhere [13].5 Microstructural Analysis The first level of microstructural analysis was conducted using optical metallography.7 28. Typically around 200 particles in austenite and 700 to 2500 in ferrite were quantitatively measured from each sample condition.2/1. As expected.7 15. Tensile Properties Steel A: Mn=0.3 10.9 3. the steel with the higher Mn content exhibited higher tensile properties than the steel with the lower Mn content for a given processing condition. Table 2.1 37.9 5. the ferrite was less equiaxed and had more pearlite.0/1.8 3. positively charged gas ions generated by the process of field ionization are used to produce images of the atoms on the surface of a solid specimen.5 41.9/1. The maximum and minimum holding times during the isothermal treatments represent a time-temperature envelope which could be somewhat representative of the inner and outer wraps of an industrial coil.2 5. Row spacing measurements were made averaging around 150 counts per condition. Measurements for particle size or interphase row spacings were made by viewing through a magnifying eye piece marked with grids the original micrographic negative plates on a lighted table. 12]. Predicted and measured ferrite grain size and dislocation density Steel Condition AC + coil (0h) AC + coil (2h) AC + coil (0h) AC + coil (2h) AC + coil (5h) ACRT ACRT Mean intercept predicted by Structura (µm) 5. MPa 382 385 430 428 427 298 357 TS.2 31.7/4.6 Dislocation density Average/Std Dev (109 cm-2) 5. independent of the Mn content.3 8.3/3. RESULTS AND DISCUSSION Mechanical properties The results from the tensile properties are presented in Table 1. For steel B.3% B: Mn=1.8 8.

8 2. while Figure 3 shows general matrix precipitation. For example.8 2. However. After 2 hours holding. (i)in general random precipitation. The general random precipitation in austenite was typical of steel A.2 5.4 6. All the carbides are in the form of films at the ferrite grain boundaries. The average size and location of the precipitates observed are shown in Table 3.7 2.9 2.6 6.9 NM NM 6. and (ii) in deformation bands.7 1. In steel A with no holding time. while steel B exhibited the two types of precipitation. the precipitation of NbC observed on the deformation bands was detected only in the air cooled specimens.1 3. The results are shown in Table 2. Figure 1.3 3. The third level of microstructural analysis involved the use of TEM.2 5. These observations were confirmed by TEM examination. From this analysis the dislocation density in each specimen after a given condition was determined. while 90 ∀ 20 nm for steel B. The SEM results showed that in steel B. The average size of these precipitates was in the order of 3 nm. and hence there was no sufficient time for their precipitation at the deformation bands.0 A B ACRT Volume fraction of precipitates In order to get a better understanding of the amount of Nb precipitated. -790°C).The second level of microstructural analysis was conducted by SEM.0 5.1 NM NM 2. This type of precipitation was not observed in the AC specimens. The results shown in this table are consistent with the TEM observations regarding the amount of precipitation observed in a given sample condition. Average size and location of NbCN precipitates observed (NM = not measured) Steel A B Condition AC + coil (0h) AC + coil (2h) AC + coil (0h) AC + coil (2h) AC + coil (5h) ACRT Precipitate type γ grain boundary γ grain boundary γ grain boundary γ grain boundary γ grain boundary γ grain boundary γ matrix α interphase α matrix γ grain boundary γ matrix γ deformation bands α interphase α matrix Average size. samples ACRT after hot rolling exhibited larger amount of precipitation than samples AC to the coiling 6 MS&T 2004 Conference Proceedings . This seems to indicate that this mode of precipitation occurred in the delay time between the finishing rolling temperature (TFR -892°C) and the transformation temperature to ferrite (T.0 2. 4. Figure 2 shows typical interphase precipitation observed. The majority of the precipitates appear to have been nucleated in austenite and to a much lesser extent in the ferrite matrix. the pearlite is mostly in the form of lamellae up to the 2 hour holding (lamellae spacing = 200 to 350 nm).0 3. This observation is consistent with previous results from isothermal transformation studies that have been presented in a separate publication [15]. Table 3. The row spacing for the interphase precipitation in ferrite was measured to be approximately 175 ∀ 39 nm for steel A. the volume fraction of the precipitates for a given processing condition was determined using the precipitate extraction residue method. especially those nucleated on the deformation bands in austenite. After the 5 hour holding the lamellae appears to be undergoing spheroidization. these specimens were rapidly cooled from the finishing rolling temperature to the coiling temperature.1 1. nm 2. That is. The results from this analysis are shown in Table 4.3 4.6 5.9 2. Further TEM analysis in the AC + coiled specimens did not revealed any evidence that precipitation in ferrite took place.5 2.0 Standard Deviation.9 1. carbides were observed in the form of elongated thick films at ferrite grain boundaries and in the form of a few pearlite colonies. nm 7. no pearlite was detected. Modes of precipitation observed The results from the TEM investigation did not reveal the presence of any large undissolved particles or large carbonitrides formed during solidification. The precipitation in austenite seems to have taken place in two forms. The results from this table indicate that the precipitates are very small. a possible explanation for this behavior is that. Samples from both steels A and B which were ACRT after hot deformation exhibited interphase and general random matrix precipitation in ferrite. The average size distribution of about 2400 particles measured is shown in Fig.

Table 4. Results from the extraction residue method Steel A B Condition AC + coil ACRT AC + coil ACRT Total Nb in steel composition. ppm 90 170 120 190 MS&T 2004 Conference Proceedings 7 . ppm 190 190 280 280 Total Nb precipitated. Similar trend was observed for steel B. Figure 1. The results from Table 4 showed that in steel A. while only about 47% precipitated after AC + coil. Dark field TEM micrograph showing precipitates nucleated on γ deformation bands.temperature after rolling. 68% after ACRT and 43% after AC + coil. approximately 90% of the Nb is precipitated after ACRT.

5.05+(%Mn))] d -0. it was considered that the pearlite contribution was negligible. and α is a numerical factor dependent of the crystal structure taken as 0. From the microstructural observations.896/(0. The results from this analysis revealed that the stoichiometry of the precipitates was close to NbC.. Dark field TEM micrograph showing interphase precipitation. A more detailed 8 MS&T 2004 Conference Proceedings . where b is the Burgers vector of a dislocation. Composition of precipitates The fourth level of microstructural analysis was conducted using APFIM to determine the composition of the precipitates. From these expressions.5 c) ∆YS dislocation = α · G · b · ρ 0. For the other microstructural features the following relations were developed: a) ∆YS Peierls-Nabarro + ∆YSsolid solution = 48 + 32.. The APFIM analysis also showed that Nb and C atoms were present in solid solution in the matrix and at the grain boundaries. the calculated YS for the AC specimens which showed only precipitation formed in austenite was 375 MPa for steel A and 440 MPa for steel B.248Η10 -7 cm.Figure 2.38. G is the shear modulus. b = 0. These values are in good agreement with the measured YS shown in Table 1.30(%C)+ [0. Mechanical properties assessment The various microstructural contributions to the strength of the steels can be calculated from the optical and TEM measurements.5 (%Mn) + 84 (%C) in MPa [16] b) ∆YS grain size = ky.

and higher pearlite content. NbC precipitation observed in the AC+coil specimens was formed prior to the γ to α transformation.study of the contribution of the various metallurgical factors on the mechanical properties of high strength strip steels has been published elsewhere [15]. CONCLUSIONS The results from this investigation lead to the following conclusions: 1. Figure 3. MS&T 2004 Conference Proceedings 9 . This behavior explains the observed constant tensile properties with coiling treatments. In summary. Interphase and general matrix NbC precipitation in ferrite were only observed in the ACRT specimens. higher dislocation density. 2. 4. 3. promotes smaller ferrite grain size. No further precipitation took place during the coiling treatments. from this analysis it appears that the fine precipitation which occurred in the austenite does not have a strong strengthening effect. Fine NbC precipitation formed in austenite was found in the two steels investigated. Bright field and dark field TEM images showing matrix precipitation.. Similar results have been observed by Sato et al. [19]. Strain induced precipitation formed on prior austenite deformation bands was found only in the ACRT specimens with the higher Mn content. The increase in Mn content lowers the transformation temperature. Fine precipitation in austenite does not appear to contribute to the yield strength of the steels for the processing and steel compositions used in this study.

W. E. Poieuer and C.49. Sato and M. K. 18. 7.. REFERENCES 1. W. 13. Cullity. Hua. Trans Tech Publications Ltd. p. Lopez. 6. p. Edington. Itman. B. 16. Yield. Miller and G. Van Nostrand Co (1976). ISI Special Report 81 (1963).1. A. Private Communication on an Internal Report from CRDM-Sollac-Usinor (France). P. p. V. Sc. Perdrix. K. S. M. The authors also wish to thank Dr. Cardoso. Atom Probe Microanalysis: Principles and Applications to Materials Problems. 14. Brossard. Baker. and A. 8. F. H-J Kestenbach. Hirsch et al. J. Precipitation Processes in Steels. for stimulating discussions. p. and R. G. 4. C. Electron Microscopy of Thin Crystals. 1998. Garcia. K. Rodriguez-lbalbe. Eds. 10 MS&T 2004 Conference Proceedings . IS1 Special Report 64 (1959). Flow and Fracture of Polycrystals (1983).207. Rodriguez-lbalbe. E. N.M. DeArdo. Thillou extends her thanks to Dr. Krieger Publishing Co (1965). 9. p. Mater. 11 (1973). T. Lapointe and T. I. J. Piette. 65 (1978). M. I. B. F. Mrs V. Trans Tech Publications Ltd. I. Jack. Baker. Lee from POSCO Pohang (Korea). J. Gladman. 2. Gutierrez and B. M. Metallurgical Transactions A. 7A (1976). p. Piette. p. Smith. p. N. Pickering and T. 77 (1991). 17. 12.Haasen (1979). 1998. Thillou.915. D.235.10. Elements of X-Ray Diffraction. Gutierrez and B. D. N. D. Lopez. 27 (1975). Baker and J. Davenport. B. 19. Jack and K. Eds. 5.ACKNOWLEDGEMENTS The authors wish to thank the R&D division of SOLLAC (USINOR France) and the CRDM –Research center of SOLLAC. Edited by P. J. Practical Electron Microscopy in Materials Science.W. R. A.in Dunkerque (France) for sponsoring this work and permission to publish this paper. M. C. Materials Research Society (1989). Nutting.1337. Suehiro. C.731. and Techn. 16 (1982). Microalloying in Steels. R.21. H. T. Journal of Metals. and H-J Kestenbach.1. p. A. H. W. p. 3. Strength of Metals & Alloys. Tetsu-to-Hagane. Materials Science and Engineering A. T. for carrying out the precipitate extraction experiments.. K. pp. An Integrated Model for Microstructural Evolution in the Hot Strip Mill and Mechanical Properties Prediction of Plain and Microalloyed C-Mn Hot Strip. P. Science Progress. Miner.M. 13 (1997). p. Baker. Perdrix. L. R. Metal Science. 10. Microalloying in Steels. Hornbogen.675.312-318. p.493. 15. J. 11. Piette and Dr. Addison-Wesley Publishing Company (l978). ibid. Honeycombe. Deshayes from the CRDM.