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Effect of Carbon and Manganese on the Quenching and Partitioning Response of CMnSi Steels
Emmanuel De MOOR,1) John Gordon SPEER,1) David Kidder MATLOCK,1) Jai-Hyun KWAK2) and Seung-Bok LEE2)
1) Advanced Steel Processing and Products Research Center, George S. Ansell Department of Metallurgical and Materials Engineering, Colorado School of Mines, 1500 Illinois Street, Golden, CO 80401 USA. E-mail: edemoor@mines.edu, jspeer@mines.edu, dmatlock@mines.edu 2) POSCO, 700 Gumbo, Gwangyang, Jeonnam, 545-711 South Korea. E-mail: jhkwak@posco.com, sbcreater@posco.com (Received on June 14, 2010; accepted on August 30, 2010 )

CMnSi steel grades with carbon contents ranging from 0.2 to 0.3 wt% and manganese contents of 3 and 5 wt% were Quenched and Partitioned (Q&P). Tensile properties were assessed and retained austenite fractions measured. Intercritically annealed and fully austenitized conditions were studied. The best combinations of tensile strength and total elongation obtained in the 0.2C3Mn1.6Si grade after intercritical annealing were associated with strength levels in the 1 0001 200 MPa range and total elongations ranging from 14 to 20 %. Optimum properties were obtained in the 0.3C3Mn1.6Si steel after full austenitization with tensile strength levels ranging from 1 450 to 1 700 MPa and total elongations ranging from 11 to 18 %. The 0.2C3Mn1.6Si fully austenitized samples also exhibited remarkable strength/ductility combinations albeit at lower strength levels of 1 2001 450 MPa UTS with 915 % total elongation indicating the effectiveness of the manganese addition to develop novel property combinations. KEY WORDS: third generation AHSS; Quenching and Partitioning; martensite; retained austenite.

1. Introduction Quenching and Partitioning (Q&P) is receiving increased attention as a potential processing route to develop socalled third generation advanced high strength sheet steel (AHSS) properties.114) The proposed heat treatment aims at stabilizing retained austenite in martensitic microstructures through decarburization of the martensitic matrix and carbon enrichment of the austenite. The Q&P design identies an optimum quench temperature, QT, corresponding to the greatest fraction of austenite that can be stabilized with the carbon available in the martensite formed during quenching to the QT.1) Carbide formation should be avoided as it may act as a carbon sink. Thus, TRIP steel type compositions may be suitable for Q&P processing, and have been studied by several authors.24,6) The addition of molybdenum to a CMnSi TRIP steel composition has been shown to result in increased austenite stabilization whereas the partial replacement of Si by Al resulted in lower fractions.6) The present work investigates the effect of carbon and manganese modications on the Q&P response of a typical CMnSi TRIP steel composition. Two levels of carbon (0.2 and 0.3 wt%) and manganese (3 and 5 wt%) were

considered. 2. Experimental Procedure The chemical compositions of the investigated laboratory-prepared steel grades are given in Table 1. The material was received as cold rolled sheet with a thickness of 1 mm. Longitudinal tensile specimens were machined according to the ASTM E8 geometry. Specimens were heat treated using salt pots, following the heat treating matrix given in Table 2. A xed reheating time of 2 min was used and the employed reheating temperatures are based on Thermo-Calc thermodynamic calculations shown in Fig. 1 to obtain an intercritical microstructure consisting of 50 vol% intercritical ferrite or a fully austenitized microstructure. The amount of intercritical ferrite was measured using light optical microscopy (LOM) on intercritically annealed and water quenched samples to verify the Thermo-Calc predictions. The results are shown in Table 3. Reasonable agreement was obtained between the predicted and measured volume fractions of intercritical ferrite. To ensure full austenitization, the reheating temperatures were approximately 50C above the predicted Ae3

Table 1. Chemical composition, in wt%, of laboratory prepared steel grades.

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Table 2. Heat Treating Matrix.

Table 3. Volume fraction of intercritical ferrite (% a int) obtained by LOM phase area point counting of annealed and water quenched samples.

temperature and LOM was conducted to verify the absence of intercritical ferrite. The quench temperatures were calculated according to the approach proposed by Speer et al.1) assuming full carbon depletion of the martensite and homogenization throughout the austenite in the absence of cementite or transition carbide formation. Fully stable austenite is assumed at the quench temperature and during partitioning. The results are shown in Fig. 2(a) for intercritical annealing and in Fig. 2(b) for full austenitization. Quench temperatures 20C above or below the calculated optimum QT, and also 250C were included in some cases. Quenching was done in Durferrit AS 140 heat treating salt for quench temperatures above 160C. Quenching to lower temperatures was done using organic Paratherm NF heat transfer uid. Initial heat treatments were conducted for each QT with tensile specimens having a spot welded thermocouple, connected to a data recorder in order to assess the quench time required to reach the desired quench temperature. It was found that the desired QT was obtained after a quenching time of 10 s for quenching in salt, whereas 18 s were required for quenching in the oil bath to the lower quench temperatures. The heat lost during transfer from the quench bath to the partitioning bath, amounting to 20C in some cases, was also taken into account. Partitioning was done for 10, 30, and 100 s at 400C and for 10 s at 450C. Following partitioning, the samples were water quenched to room temperature. Tensile testing was done on an electro-mechanical tensile machine at a constant strain rate of 5.6 10 4/s, with a 2 inch (50.8 mm) 50% extensometer. Two samples were tested for each heat treating condition. Measured yield strengths were based on the 0.2% offset method, uniform strains were determined as the engineering strain at the peak load used for UTS calculation, and total strains to failure were obtained from the extensometer output at nal fracture. All samples were observed to fail within the specied extensometer gage length. The retained austenite content was measured for each microstructure using X-ray diffraction (XRD). The samples were lightly ground to remove surface oxides followed by chemical thinning for 3 min using a solution of 50 parts water, 50 parts 30% hydrogen peroxide, 1 part hydrouoric acid. The XRD analysis was performed on a Phillips X-pert diffractometer operating at 45 kV and 40 mA, using an 2011 ISIJ
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Fig. 1. Thermo-Calc predicted equilibrium phase distributions for the three alloys.

Xcelerator detector, ltered copper radiation, and a 1 degree slit. Quantication of the austenite content employed four austenite peaks and four ferrite/martensite peaks: {111}, {200}, {220}, {311} and {110}, {200}, {211}, {220}, respectively. A 2-theta scan was run from 40 to 105 degrees. Each sample was run twice. Data were analyzed using Prot software to produce integrated intensity values. The volume fractions of retained austenite were calculated according to the SAE method.15) 3. Results and Discussion 3.1. Intercritically Annealed Steels The tensile properties obtained in the intercritically annealed and Q&P processed microstructures are given in Table 4 for the 0.2C3Mn1.6Si composition. The retained austenite fractions and carbon contents measured by XRD are also given in the table. The same properties are given for the 0.3C3Mn1.6Si and 0.3C5Mn1.6Si steels in Table 5 and Table 6, respectively. Tensile strength levels of 9851 190 MPa are combined with total elongations ranging from 14 to 20% in the 0.2C3Mn1.6Si grade. The 0.3C3Mn1.6Si grade exhibits tensile strength levels of 875910 MPa with total elongations of 1418% whereas the properties in the 0.3C5Mn1.6Si grade range from 1 110 to 1 175 MPa tensile strength and 7 to 15% total elongation. A low yield to tensile ratio is observed in the 0.2C3Mn1.6Si grade and the ratio increases with increased C and Mn alloying. Lower retained austenite fractions are measured than were predicted assuming full carbon depletion of the martensite as shown in Fig. 2. High austenite carbon contents are observed indicating carbon enrichment. Representative SEM micrographs of the microstructure of a 0.2C3Mn1.6Si intercritically annealed Q&P sample, with a QT of 185C, PT of 400C and Pt of 30 s are given in Fig. 3. Austenite pools and laths are ob-

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Fig. 2. Calculated retained austenite fractions as a function of quench temperature assuming full carbon partitioning for a) intercritical annealing and b) full austenitization.

Table 4. Yield strength (YS), ultimate tensile strength (UTS), uniform elongation (UE), total elongation (TE), retained austenite fraction (fg ret) and carbon content obtained for the intercritically annealed 0.2C3Mn1.6Si grade.

Table 5. Yield strength (YS), ultimate tensile strength (UTS), uniform elongation (UE), total elongation (TE), retained austenite fraction (fg ret) and carbon content obtained for the intercritically annealed 0.3C3Mn1.6Si grade.

Table 6. Yield strength (YS), ultimate tensile strength (UTS), uniform elongation (UE), total elongation (TE), retained austenite fraction (fg ret) and carbon content obtained for the intercritically annealed 0.3C5Mn1.6Si grade.

served. Spherical particles are present in the intercritical ferrite which are believed to be cementite that was not dissolved during intercritical annealing. Figure 4 shows an
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SEM micrograph of an intercritically annealed and water quenched 0.3C5Mn1.6Si sample where the remnants of the predecessor pearlitic microstructure are clearly ob 2011 ISIJ

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low retained austenite volume fractions measured by XRD, and further characterization of the austenite fractions by other techniques may be helpful. The cementite observed in Fig. 3, believed to be inherited from the prior microstructure due to insufcient dissolution during intercritical annealing, lowers the carbon available in the intercritical austenite, reducing the potential for austenite retention by Q&P. A clear correlation between the measured volume fractions of retained austenite and the strain hardening behavior is not apparent, and thus the role of retained austenite in ne microstructures is perhaps not fully understood. Further work is needed to understand the mechanical behavior of these microstructures. Stressstrain and instantaneous strain hardening as a function of true strain curves are given in Fig. 6 for the intercritically annealed 0.3C3Mn1.6Si steel for a QT of 140C. Clearly higher yield strengths and lower strain hardening are obtained as compared to the 0.2C3Mn1.6Si grades. Fairly low fractions of retained austenite were again measured. Figure 7 shows stressstrain curves and instantaneous strain hardening as a function of true strain for the 0.3C5Mn1.6Si grades for a xed QT of 70C. High yield strengths and limited strain hardening are obtained. The stressstrain curves and strain hardening behavior observed in Fig. 6 and Fig. 7 is similar to the behavior of tempered Dual Phase steels.4) 3.2. Fully Austenitized Steels Tensile properties, austenite fractions and carbon contents obtained after full austenitization and Q&P processing are given in Tables 7 through 9. Tensile strength levels of 1 2251 450 MPa and total elongations of 915% are obtained in the 0.2C3Mn1.6Si grade, and 1 4201 710 MPa and 217% in the 0.3C3Mn1.6Si grade. The 0.3C 5Mn1.6Si grades exhibit low ductility in most cases. Retained austenite fractions between 4 and 9 vol% are obtained in the 0.2C3Mn1.6Si grade whereas fractions ranging from 1 to 15 vol% are obtained in the 0.3C3Mn 1.6Si grade. A peak in austenite fraction is observed with partitioning time in most cases in the latter grade. It can be noted that much more austenite is stabilized following full austenitization as compared to intercritical annealing in this grade. A pronounced effect of QT is observed for the austenite fraction stabilized in the 0.3C5Mn1.6Si grade with the highest tested QT resulting in the highest volume fraction of about 14 vol%. Representative microstructures are presented in Figs. 8 through 10. Large spherical precipitates are absent which suggests that the austenitizing treatment was successful in dissolving the cementite of the prior microstructure. Thick-lm-like austenite is observed in the microstructure of the 0.2C3Mn1.6Si grade quenched to 210C and partitioned at 400C for 120 s as indicated by the arrows in Fig. 8. Some ne precipitates are observed in the martensitic regions. Similar observations are made for the 0.3C3Mn1.6Si Q&P grade (QT 200C, PT 400C and Pt 30 s) shown in Fig. 9. Flat featureless regions are observed in the micrograph of the 0.3C5Mn1.6Si Q&P grade (QT 160C, PT 400C and Pt 30 s) shown in Fig. 10, presumably indicative of fresh martensite where carbon depletion through tempering or partitioning did not take place to a signicant extent.
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Fig. 3. SEM images of a 0.2C3Mn1.6Si sample reheated to 725C for 120 s, quenched to 185C and partitioned at 400C for 30 s followed by nal water quenching. 2% nital etched. Image (a) shows undissolved carbides and image (b) shows retained austenite regions (highlighted by arrows) adjacent to martensite.

Fig. 4. SEM image of a 0.3C5Mn1.6Si sample reheated to 660C for 120 s and water quenched. 2% nital etched.

served. Undissolved cementite was present in the intercritical microstructures of all grades, for the annealing conditions employed in this work. It is clear from Table 4 by the large difference between UTS and YS that the intercritically annealed Q&P processed 0.2C3Mn1.6Si samples exhibit signicant strain hardening as also observed by the stressstrain curves and instantaneous n-values4) plotted as a function of true strain in Fig. 5 for a QT of 165C and various partitioning conditions. The tensile strength levels decrease with increasing partitioning time and temperature, whereas ductility increases. The n-values decrease with strain after passing through a maximum. This strain hardening behavior may be somewhat unexpected especially given the fairly 2011 ISIJ

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Fig. 5. (a) Stressstrain curves and (b) plots of instantaneous strain hardening as a function of true strain for the intercritically annealed 0.2C3Mn1.6Si grade for a QT of 165C for the indicated partitioning conditions temperature and time. The retained austenite volume fractions are also given.

Fig. 6. (a) Stressstrain curves and (b) plots of instantaneous strain hardening as a function of true strain for the intercritically annealed 0.3C3Mn1.6Si grade for a QT of 140C for different partitioning conditions.

Fig. 7. Stressstrain curves for the 0.3C5Mn1.6Si alloy for a reheating temperature of 660C and QT of 70C for different partitioning conditions.

Remarkable tensile strength levels are found in combination with signicant ductility levels in the 0.2C3Mn1.6Si and 0.3C3Mn1.6Si Q&P steels resulting from pronounced strain hardening as shown in Fig. 11. A signicant effect of partitioning time and temperature on strength and ductility is observed. Low ductility was exhibited by the 0.3C5Mn1.6Si steel with numerous samples failing before yielding. The low ductility may be related to the untempered martensitic regions in the microstructure as shown in Fig. 10. Given the low retained austenite fractions obtained, the quench temperature and partitioning conditions may not have been optimized for this steel.

3.3. Comparison with Other Studies The tensile properties obtained in this work are summarized in Fig. 12, plotting total elongation versus tensile strength. It is clear that high strength levels are combined with signicant ductility in the 0.2C3Mn1.6Si intercritically annealed Q&P heat treated grade and in the 0.2C3Mn1.6Si and 0.3C3Mn1.6Si grades after full austenitization. The properties are compared with other proposed third generation AHSS processing routes in Fig. 13. The different approaches have been reviewed in16) and include ultrane Dual Phase grades obtained through special hot deformation practices,17,18) modied TRIP processing through either alloying1921) or austempering modications,3,22,23) bainite where judicious alloying is employed to reduce the bainite transformation to lower temperatures2429) in order to obtain ultrane microstructures, and TWIP/TRIP alloys with lower manganese levels than typically observed for second generation austenitic alloys.3033) Previously reported properties resulting from Q&P processing of a variety of compositions are also given.24,68) Multiple sample geometries and sizes were employed in these studies and, in order to facilitate comparison, the literature data were corrected for sample geometry and size according to the ISO 2566/1-1984(E) standard34) to an ASTM E8 sample geometry. It is clear from Fig. 13 that exceptional properties have been developed through Q&P processing in the present work, when compared to other promising approaches. Some of these properties are within the desired range for future 3rd generation AHSS steels. Tensile
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Table 7. Yield strength (YS), ultimate tensile strength (UTS), uniform elongation (UE), total elongation (TE), retained austenite fraction (fg ret) and carbon content obtained for the fully austenitized 0.2C3Mn1.6Si grade.

Table 8. Yield strength (YS), ultimate tensile strength (UTS), uniform elongation (UE), total elongation (TE), retained austenite fraction (fg ret) and carbon content obtained for the fully austenitized 0.3C3Mn1.6Si grade.

Table 9. Yield strength (YS), ultimate tensile strength (UTS), uniform elongation (UE), total elongation (TE), retained austenite fraction (fg ret) and carbon content obtained for the fully austenitized 0.3C5Mn1.6Si grade.

strength levels above 2 GPa with appreciably high ductility have also been developed through Q&P heat treating of a 0.41C1.30Mn1.27Si1.01Ni0.56Cr alloy.7) 4. Conclusions Three grades with different carbon and manganese contents were heat treated through quenching and partitioning. Tensile properties were assessed and retained austenite fractions and carbon contents were determined by XRD analysis. High strength in combination with signicant ductility was exhibited in particular by the 0.2C3Mn1.6Si and 0.3C3Mn1.6Si grades after full austenitization. Novel property combinations were obtained in the present research. The results also point out the need to understand 2011 ISIJ
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Fig. 8. SEM image of a 0.2C3Mn1.6Si sample reheated to 840C for 120 s, quenched to 210C and partitioned at 400C for 30 s followed by nal water quenching. Retained austenite regions are indicated by the arrows. 2% nital etched.

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Fig. 9. SEM image of a 0.3C3Mn1.6Si sample reheated to 820C for 120 s, quenched to 200C and partitioned at 400C for 30 s followed by nal water quenching. 2% nital etched.

Fig. 10. SEM image of a 0.3C5Mn1.6Si sample reheated to 780C for 120 s, quenched to 160C and partitioned at 400C for 30 s followed by nal water quenching. 2% nital etched.

Fig. 11. Stressstrain curves and plots of instantaneous strain hardening as a function of true strain for the a) fully austenitized 0.2C3Mn1.6Si grade for a QT of 250C and b) fully austenitized 0.3C3Mn1.6Si grade for a quench temperature of 200C and different partitioning conditions.

Fig. 12. Tensile properties obtained for the three alloys following a) intercritical annealing and b) full austenitization represented on total elongation versus tensile strength diagrams.

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Fig. 13. Situation of properties obtained in current research with respect to other proposed third generation AHSS development routes.16) The data were collected from literature and corrected according to ISO 2566/1-1984(E)34) to the ASTM E8 geometry.

better the structure/property relationships in Q&P steels; in particular the contribution of small retained austenite fractions to strain hardening. Acknowledgements POSCO is gratefully acknowledged for providing material and nancial support. The sponsors of the Advanced Steel Processing and Products Research Center are acknowledged for their continued support to overall operations of the center.
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