Se YF Electron Metallography of the Substructure of Martensite in High-Carbon Steels M. OKA axp C. M. WAYMAN ABSTRACT. A transmission electron microscopy and diffraction study of mar- tensite plates in Fe-1.28% C and Fe-1.82% C has been carried out with particular attention to the martensite substructure. For each of these alloys {112}. transfor- mation twins were observed, principally clustered around the martensite midrib region. For the Fe-1.82% C steel planar defects on {110}, were observed, but not for the 1.28% C steel, in which case there is evidence of more than one |112}4 inhomogeneity. For the 1.82% C steel twinning on both {112}, and |110}~ may be involved and regular dislocation arrays are observed. It has proved difficult to isolate the transformation substructure from that caused by accommodation dis- tortion of the growing martensite plates, and for both of the alloys studied the substructures are considerably more complex than expected from the idealized phenomenological crystallographic theory martensite in carbon steels, where the habit planes depend on the austenite carbon content and are roughly classified in the following way. Between 0 and 0.3% C, the habit plane is reported to be IIL :* between 0.4 and 1.4% C the habit is [2254.5 carbon steels containing in excess of 1.5% C exhibit the {259|. habit plane (1). Various orientation rela- tionships between the martensite and austenite have been reported (2-4); that for |2594, martensite isnot known. Crystallographic aspects of the martensite trans- formation in iron alloys have been discussed by Wechsler et al. (5) and Bowles and Mackenzie (6) in the form of a phenomenological theory. For the }225), transformation, Wechsler et al. (5) attempted to explain the crystallography on the basis of alter- native elements of the inhomogencous shear, whereas Bowles and Mackenzie introduced a dilata- tion (6). Neither of these approaches is considered (8) to be adequate. In the former case the predicted direction of the shape deformation differs from that which is observed, and for the Bowles-Mackenzie analysis the predicted orientation relationship ‘The authors are associated with the Department of Mining Metallurgy and Petroleum Engineering, University of Illinois ai Urbana-Champaign, Urbana, Ill, Mu Oka is. presently. at the Institute of Scientific and. Industrial Research, Osaka Univer sits, Osaka, Japan; C.-M. Wayman is presently at the Depart ment of Metellurgy. University of Cambridge, Cambridge, England. Original rhanuscript received 18 November 1968) revised manuscript received 1 April 1969, ‘Subscripts a and m designate austenite and mar. tensite respectively 370 differs from the experimental one (8). The {259}, transformation in carbon steels is not yet understood either theoretically or experimentally Transmission electron microscopy studies of martensite have thus far provided considerable in- formation on its internal structure and morphology, but the overall situation is as yet far from being clear for most iron-base alloys. Kelly and Nutting (9) examined the internal structures of martensite in carbon steels of various carbon contents and reached the following conclusions: Martensite in steels containing less than 0.3% C is needle-like, the direction of the needles being (II1)q; the mar- tensite needles contain only dislocations, and no twins, Martensite containing 1.0 and 1.4% C con- sists of plates, exhibits the {225}, habit plane, and contains {112}, twins which were derived from {110}, according to the Bain correspondence. Nishi- yama and Shimizu (10) reported the existence of {112}, twins in a 0.7% C steel. Only one trans mission clectron microscopy study of carbon steel martensite containing more than 1.5% C has so far been reported (11). Considering this and the present unsatisfactory situation from both the transmission electron microscopy and theoretical point of view (8, 9), the present investigation was undertaken with the purpose of examining in some detail {259| martensite and in further detail {225} martensite in carbon steels. High purity Fe-C steels containing 1.28% C ({225}. habit) and 1.82% C ([259}. habit) were chosen for study. Some of the results reported herein are incon Transactions of the ASM ere 8ol Oka and Waymal clusive in that for either alloy, the “typical” mar. tensite plate is rather difficult to characterize and describe. It is clear, however, from the present ) work that a simple system of martensite inhomo- geneity due either to slip or twinning, or both, may not exist, and that the fine structure of mar- tensite is probably complicated by distortion effects (ic. additional inhomogeneities) arising from ac- commodation of the plates by the austenite as they undergo growth. The present results are thus pre- Fic. 1. Transmission electron micrograph of martensite in Fe-1.82% C and selected area diffraction patterns from (b) martensite and (c) austenite, See text for details Volume 62, 1969 LOTT 371substructure of Martensite # Ftc. 2, Transmission electron micrograph of martensite plate in Fe description, Fic, 3, Transmission electron micrograph of martensite in Fe-I.82% C showing (112), twins and {110}, planar defects. See! for discussion. sm Transactions of the ASM ie,\. Oka and Wayman sented in the spirit of documentation and detailing of difficulties that are encountered, rather than generalizations. This is particularly so for the {225}, transformation in Fe-1.28% C. EXPERIMENTAL PROCEDURE Alloys of analyzed composition Fe-1.28 wt % C and Fe-1.82 wt % C were prepared by vacuum melting electrolytic iron and graphite. From hot forged ingots, specimens 30 by 30 by 0.2 mm were cut, polished with metallographic paper, austenit- ized one hour at 1180 C in evacuated quartz cap- sules, and finally water quenched to’ room tem- perature. For the Fe-1.82% C steel about 30% transformed to martensite occurred, whereas for the Fe-1.28% C steel about 80% transformation oc- curred. To check for possible decarburization of the specimens during heat treatment chemical analyses were made. There was no evidence of de- carburization, and metallographic analysis confirmed that graphitization was insignificant The as-quenched specimens were immediately clectropolished in a solution consisting of 50 gms CrO,, 270 ml glacial acetic acid, and 14 ml H.O using the window method. Thin foils were examined at 100 ky in a Hitachi HU-1IC electron microscope equipped with a tilting stage. There was no evidence that martensite formed upon thinning, RESULTS 1.82% C STEEL Observations of {011}, Twins and Planar Defects in Martensite Figure 1a is a transmission electron micrograph of a region of a large martensite plate and Fig Ib is the corresponding selected area diffraction pattern taken from the encircled area in the plate. The electron beam in Fig. 1b is approximately parallel to (010},. Figure Ic is a selected area dif- fraction pattern from the encircled region in the adjacent austenite. As seen in la, there are three prominent sets of striations in the martensite defin- ing directions which are designated as 1, 2, and 3. From stereographic trace analysis, based on Fig. 1b, it was concluded that trace | is parallel to (101). and traces 2 and 3 (the latter relatively wide and in faint contrast) respectively correspond to (101) and (Oll)q. Since streaks normal to trace I can be seen in the diffraction spots designated a and b, the (i01), trace is considered to be due to cither thin twins or stacking faults (j.e. planar defects). From their appearance, the other planar defects on (101) and (011), are also inferred to be thin twins or stacking faults, consistent with @ previous interpre- Volume 62, 1969 re Fic. 4. Transmission electron micrograph showing regular dislocation arrays in martensite in Fe-I.82% C and correspond: ing selected area diffcaction pattern. See text for discussion tation of {011m twins* in tetragonal martensite in Fe-1.82% C11). In the austenite, there are several slip traces parallel to direction D, which is parallel to trace 3 in the martensite, The projected width of the slip traces in the austenite (D) is the same as for trace 3 which is (011),. From Fig. 1¢ and trace analysis, the slip traces D correspond to (111). The approxi- mate parallelism between (111), and (O11). is also verified from the orientation relationship derived from Fig. 1b and le. Trace analysis of the martens- ite habit plane [assumed to be the midrib plane (m-m)] is consistent with the particular habit variant (295).. Further examination of Fig. 1b shows that many of the diffraction spots are accompanied by streaks or extra maxima. The four streaks S$; S:, Ss, Su, from trace analysis, correspond _to presumably twins or faults on (113)q, (T13)m; (112)m, and (112)m Planar defects on these planes are not in contrast in Fig. 1a and were not observed when the speci- men was tilted up to six degrees. The “island” designated B in Fig. la near the martensite midrib is retained austenite. ‘The results just described suggest that |O1I|. twins or faults or both are involved in the formation of martensite plates in a Fe-1.82% C steel. {O11}, faulting or twinning has also been observed in an Fe-3% Cr-1.5% C alloy which has a habit plane be- tween {225}, and {259|, (12), and this work will be published shortly. Planar defects on $0111. in {225} martensite plates in Fe-8% Cr-1.1% C have also For the variant considered (701), (101) and (O11), are all possible twin planes, 373Te lO Substructure of Martensite Fig. 5. Martensite plate in Fe-I.82% C exhibiting internal subboundaries. and selected area diffraction patterns from (b) martes ite and (c) austenite, An enlargement of the plate area to the right is shown in (2), See text for details, been reported (8, 13) but in this case the martens- ite tetragonality is somewhat lower, and the separa- tion of reciprocal lattice points, if due to twinning, is more difficult to ascertain. Observation on the Midrib Region Figure 2a is a transmission electron micrograph showing the midrib region and adjacent area of a martensite plate in Fe-1.82% C, and the insert, 374 Fig. 2b, is a selected area diffraction pattern taken from the midrib region (encircled area). Figure 2b shows a twinned pattern; streaks normal to (112). twins (trace A) are consistent with the observed thinness of the twins (~100 A), which in this case are nearly parallel to the electron beam; the mid: rib trace for this plate is (7, 11, 10),. which is (295 from the Bain correspondence. The midrib region of the plate shown in Fig. 2a consists of a high Transactions of the ASM a. Oka and Waymari density of (112), twins, as has been reported for other ferrous martensites. However the same plate also exhibits another system of planar defects, designated by trace B, exhibiting four extinction ringes which are parallel to the defects themselves. Fic. 5D Trace analysis based on Fig. 2b suggests that B corresponds to (T01),.™ It is thus inferred that the plate contains (101), faults, besides the (112), twins corresponding to the midrib region, Figure 3 is another example of a martensite plate showing fine (112). twins confined to the midrib region, and in addition {110|, planar defects There are actually three planar defects, designated by traces 1, 2, and 3. From the twin spots on the diffraction pattern trace 1 is due to (112)q twins. From trace analysis trace 2 corresponds to (101)q, and trace 3 corresponds to (10T),. The habit plane trace, assumed given by the midrib trace, is (295). working backwards from the Bain correspondence. In addition, it can be deduced that (112),, (101)q, and (101)., are derived respectively from (101)., (1M), and (1T1,. Since (111), and (111), are not mirror planes, the traces (101), and (101). are un- likely to represent twins with equivalent lattice correspondences (11). The two examples, Fig, 2 and * In addition to (TOT), the plane (701) also lies inthe same trace, "But relative to the electron beam, (201]q, (101). is in- clined 70° whereas (TOI). makes an angle of 19°” The projected ‘width of he planar defects (trace B) Is approximately 400 A Considering that the number of extinction fringes corresponding, to trace Bis 4 to 5, and that the extinction distance for the (110) reflection in alpha irgn is 270A (Id), if the Toul thickness is, Sssumed (0 be’ 1500 A, the inclitation of trace B is calculated to be about 70°, confirming that trace B corresponds to (101), and not 01). Fic. 6. Transmission electron micrograph of martensite plate in Fe-1.82% C showing a diffrence in substructure in regions “M," and "M,", Volume 62, 1969 ——— 3753, provide new information, namely that both {112}. twins and {011j,, twins or faults are involved in the formation of martensite plates having a habit plane near {259}. Fic. 7, Typical transmission electron micrograph of mattens- itein Fe-1.28%C NS ee Substructure of Martensite Dislocations in Martensite Plates Figure da is a transmission electron micrograph of a region of a martensite plate in Fe-1.82% C showing dislocations; Fig. 4b (insert) is the corre. sponding selected area diffraction pattern. From 4, the foil is in an approximate [110], orientation, and a nearly two-beam_ situation exists, the con. trast being due to the (110) reflection, From trace analysis the dislocations parallel to traces 1 and 2 in Fig. 4a are parallel to [111]_ and (TT1], respec tively. Similar dislocation arrays in martensite plates in Fe-Ni alloys have been observed previously (II, 12). If the diffraction spots in Fig. 4b are care- fully examined, each is seen to be accompanied by streaks or additional spots; however, the streaks (or additional spots) in Fig. 4b cannot be due to disloca- tions (Fig. 4a) and in fact must result from thin twins, stacking faults or some other planar defect Trace analysis of the streaks in Fig. 4b gave in conclusive results although a given streak direction (or more properly its projection in the plane of the diffraction pattern) is consistent with either a 1112), oF {110}, trace. Further Aspects Some other characteristics of martensite plates in the 1.82% C steel are shown in Fig. 5 and 6. igure Sa shows a martensite plate. which for purposes of the present discussion is arbitrarily divided into three regions: M;, Mz and Ms. Se lected area diffraction patterns were taken from both the martensite and austenite in the indicated encircled areas, and are given as Fig. Sb and Se Fic. 8. Transmission electcon micrograph of Fe-I.28% C martensite plate showing slight orientation difference about miiib region 376 Transactions of the ASMFic. 9, Transmission electron micrograph of martensite plate in Fe-.28% C and selected area diffraction pattern. See text for discussion respectively. In the M, region relatively thick (011). twins parallel to trace T, originate at an apparent midrib region and extend rightwards to the inter- phase boundary, However these twins are not ob- served in either the Mz or M, regions of the plate, even after tilting the specimen. The twins T, in the M, region are parallel to trace D, corresponding to dislocations in the austenite, region A. This im- plies that (O11). | (111)., and is consistent with the particular variant of the Kurdjumov-Sachs orienta- tion relationship involving the close-packed planes of the two lattices since the habit plane variant is specifically (295),, from trace analysis. In addition to the (011), twins T,, there are also planar defects T, in the M, region which correspond to (101)q. Te thus represents either thin twins or stacking faults. Itis possible that the M, and Mo regions represent Volume 62, 1969 gee the original martensite plate, because of the paral- lelism between the “boundaries” I) and [:, and that the Ms region corresponds to a subsequent thickening process.* Note that the interphase bound- ary 1; is not parallel to the midrib, It thus appears that the main martensite plate consists of three more or less parallel regions. The branch plate B to the left corresponds to (529), from trace analysis, and is thus another variant. Figure 5d is an enlarge- ment of an area near the encircled region of the martensite plate showing a definite fringe contrast associated with both traces T, and Ts Figure 6 is another example of a martensite plate in Fe-1.82% C showing a difference in sub- structure in two regions M, and Mz separated by a midrib. The striations in region Mo correspond to (101)_ and region A is austenite 1.28% C STEEL Figure 7 shows a typical transmission electron micrograph of martensite in a quenched 1.28% C steel. The parallel striations within the plates were found without exception to be due to {112}, twins ‘of thicknesses in the range 50-900 A. Generally the boundaries of the martensite plates are ill- defined because of virtually complete transforma- tion, numerous extinction contours, etc. Similar internal structures have been observed in martens- ite in a 1% C steel (7) and in a 0.7% C steel (8), both of which exhibit the {225}, habit plane. Figure 8 is a transmission electron micrograph of a large martensite plate which appears to be sub- divided into two parts designated M, and M: by the midrib region m-m. Planar defects parallel to two directions (traces 1 and 2) can be seen clearly in region M, and faintly in region M,. From a selected area diffraction pattern and trace analysis, trace 1 corresponds to (112)q and trace 2 corre- sponds to (112),. The midrib trace falls close to 374)q, which from the Bain correspondence is (252),. The faint contrast in region Mz relative to that in region M, is evidently a result of a small lattice misorientation In the plate shown in Fig. 9a (112), twins (trace 1) are verified by the diffraction spots and accom- panying streaks in the corresponding diffraction pattern, Fig. 9b. These twins are confined to the vicinity’ of the midrib region of the plate in Fig. 9a. From the selected area diffraction pattern the mid- rib plane trace is (374). which corresponds to (252),; trace 2 corresponds to (T12),. The various light ‘colored “islands” within the plate A, B, and C may be retained austenite, but considering the parallelisms of the straight boundaries of the islands ‘Because of the diffuseness of the boundary I, it does not appear likely that the regions 2 and 3 correspond to two inde- pendently formed plates which have grown together. According {o the present work and other work (12) impingent boundaries are relatively sharp even when viewed at oblique incidence. 377with (112). it is possible that these regions corre- spond to (112), twins in reversed contrast. In general the {225} plates shown in Fig. 7, 8, and 9 suggest the existence of two types of {112}. twin- ning in each plate. In contrast to the results ob- tained for {259}, plates in Fe-1.82% C there was no definite evidence of a {110}. inhomogeneity in the 1225}, plates in Fe-1.82% C. DISCUSSION AND CONCLUSIONS The feasibility of {110} stacking faults in bee metals has been argued (16, 17), however twinning on {110} is not possible for bec materials since these planes are mirror planes. On the other hand if tetragonality exists, one can expect twinning to occur on certain of the {110} planes (18), and the existence of {110} twins in bet martensite in Fe- 1.82% C was reported recently by the authors (11) The fact that tetragonal martensite (c/a = 1.08) in a 1.82% C steel contains {110}. twins or faults or both, in addition to the usual 112}. transformation twins raises several issues. First the question arises as to whether the |110j twins are transformation twins, or result from accommodation distortion of the growing martensite plates—icc., plastic defor- mation. Secondly, if the |I10} twins are indeed transformation twins, it must be considered from the Bain relationship that the {110} twins are derived from a {11} plane in the austenite. Since the octahedral planes are not mirror planes, the {110} twin related regions in the martensite do not have equivalent lattice correspondences, as seems to be the case when |112{ transformation twinning is in- volved (7). In other words, the {011} twins are not consistent with the generation of adjacent twin- related martensite regions whose Bain contraction axes are variants of one another. Such consistency always obtains for the commonly observed {112} transformation twins, which are derived from {110} mirror planes in the austenite, Thus if the [O11] twins on the martensite are transformation twins their theoretical significance remains obscure at present. For {011} twinning the shear magnitude (11) is only 0.154 (c/a = 1.08) in contrast to values near 0.71 for {112} twinning. Thus if {011} twinning were the preferred transformation twinning mode, it is difficult to explain the presence of {112{ twins (in the same plate) involving the substantially larger shear. On the other hand, if the {011} twins are formed by accommodation, the overall situation appears easier to assess. The transformation twins would be of the {112} type to maintain equivalent correspondences whereas the {011{ twins would represent a rather easy mode of accommodation distortion because of the low shear strain involved. It has been demonstrated that {011} twins can propagate through |112) twins (26) without diffi 378 Substructure of Martensite culty, thus strengthening the view that the {011} twins may be due to accommodation effects. There is also the consideration that the mechani- cal deformation modes of the martensite in the 1.82% C steel may be related to the preference of {O11} twins or faults to {112} twins (in the latter thickening stages of plates) in a way similar to the transition from {112} twinning to slip, as has been documented for cubic martensite with a {3, 15, 10) habit plane (21). Jt is of comparative interest to note that martensite in an Fe-3% Cr-1.5% C alloy (c/a = 1,072), whose habit plane (19) lies between (252), and (295)., has essentially the same axial ratio as the 1.82% C steel (c/a = 1.08). However, in the latter case 011} planar defects (or twins) were observed much more frequently. Since Cr apparently lowers the austenite stacking fault energy in steels (20), it thus appears that not only the magnitude of the martensite tetragonality but also the austenite stacking fault energy may be re- sponsible factors, insofar as 4011] twinning in mar- tensite is concerned. Various arguments concerning the martensite midrib have been presented; these basically center around the two points that the mi sents the basic initiation plane of the transformation (21), or that the midrib represents an impingement region between two martensite plates (22). It has been shown that a high density of {112|q transfor mation twins exists near the central (midrib) region of martensite plates in Fe-Ni alloys (15, 23, 24), In the present investigation, for the 1.82% C steel the midrib of tetragonal martensite consists of a region of {112} twins where the / index in {hkl} is 2. Moreover, although |110{ twins are observed in the plates, only {112} twins are found near the midrib region. Tamura et al. (25) considered in some de- tail the observation that (112), twins specifically were associated with plates of a (3, 15, 10), habit in Fe-Ni-C alloys, and made the following points: (I) for c/a = 1.04 the magnitude of the twinning shear ‘on (112)« where the / index is 2 or 3 is about 0.70. However for twins of variants (211) or (121) the mag- nitude is 0.72, ie., (112)q twinning is energetically preferable. (2) In addition, when the position of car- bon in the martensite is taken into consideration, if twinning occurs on the (112), plane the carbon atoms are able 10 move homogeneously to the stable positions ['f, '/2, 0] or [0, 0, 'f2]. However for (121) or (211) twinning, the carbon atoms must un dergo shuifles in order to reach the stable interstitial positions, As to the |225| transformation in Fe-1.28% Cc only planar defects or twins on {112}, were ob served: there was no definite evidence of {0Illx twinning. However it should be considered that more than one type of {112} inhomogeneity is in general observed in a given plate of {225| habit Unfortunately, again, it is not possible to identify Transactions of the ASMOka and Wayman with or deny the association of the observed inho- mogeneities with the transformation mechanism per se, Substantial additional work is required to estab- lish the “typical” transformation substructure of a “typical” [225| plate, as revealed by transmission electron microscopy, before a critical comparison be- tween observations and the phenomenological the- ories can be made. In particular the role of accom- modation distortion must be established and if pos- sible separated from the true transformation sub- structure. This applies to both the Fe-1.28% C and Fe-1.82% C steels, ACKNOWLEDGMENTS This work was sponsored by the U. S. Army Re- search Office (Durham) Contract ARO 956 and the support of that agency is gratefully acknowledged. We are indebted to Professor K. Shimizu for @ num- ber of useful comments on the manuseript, and wish to thank Dr. T. G. Nilan and the Applied Research Laboratory of the United States Steel Corp. for providing the high purity Fe-C alloys used in this work REFERENCES. 1. A.B, Greninger and A. R. Troiano, Trans AIME, 140 (1940) 307. 2. G. V, Kurdjumow and G. Sachs, Z Physik, 64 (1930) 325. 5. Z. Nishiyama, Sci Rep Tohoku Univ, 23 (1934) 637 4. A.B, Greninger and A, R. Troiano, J Metals, 185 (1949) 590. 5. M. S. Wechsler, D. S. Lieberman and T. A. Read, Trans ‘AIME, 197 (1983) 1303. 6.4. S, Bowles and J. K. Mackenzie, Acta Met, 2 (1954) 129. 7.C.M, Wayman, Introduction to the Crystallography” of Martensite Transformations, Macmillan, New York, 1964. 8. A.J. Morton and C, M, Wayman, Acta Met, 14 (1963) 1567. 9. P.M. Kelly and J, Nutiing, Proc Royal Soc (London), 2594 (1960) 45, 10, Z. Nishiyama and K. Shimizv, Bull Japan Inst Metals, 2 (1963) 153. 11. M, Oka and C. 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