Electron Microscopy and Diffraction Study of the Carbide

Precipitated at the First Stage of Tempering of

Martensitic Medium Carbon Steel

By Yoshihiko Hirotsu* and Sigemaro Nagakura*

Crystal structure and precipitation mode of the carbide in a martensitic 0.45 wt%C steel tempered at 120 and 200℃

have been studied by means of electron microscopy and selected area diffraction. In both plate-like and lath martensites,

the precipitated carbide is η-Fe2C like the previous case of high carbon steel(Acta Met.,20(1972),645). The crystal

morphology and the orientation relationships between the carbide and the matrix are also the same. In general, the pre-

cipitation occurs along dislocations, but it has been found that grain boundary precipitation also takes place in the

non-parallel lath region and that in fine grains in this region the carbide precipitation does not occur. Some discussions are

given to the crystal structure and the precipitation mode of the carbide.

(Received September 4,1973)

solution kept below 50℃, the specimens were ex-

Ⅰ. Introduction amined with a JEM-200 electron microscope operated

at 200 kV. For comparison, martensitic 1.13%C steel

Previously, the present authors studied the carbide was tempered at 200℃ for 3 hr and examined simi-

precipitated from a martensitic 1.13 wt%C(5.49 larly.

at%C)steel tempered at 120℃ fbr l∼100 days by Since the Ms temperature is known to be as high as

means of electron microscopy and selected area 300℃ for the 0.45%C steel, the carbide precipitation

diffraction(1)∼(3). It was fbund that tie carbide was may take place during quenching. However, such a

not the hexagonal ε-carbide but an orthorhombic case was not found in the present experiment.
carbide. This carbide was isomorphous with Co2C The method of investigation is similar to that

and Co2N, and named asη-carbide of iron orη-Fe2C. employed in the previous study. Many selected area

The orientation relationships between the carbide and electron diffraction patterns were taken with beam

the matrix α" were determined. Also studied were the incidence along important zone axes, and analyzed

crystal morphology and the mode of precipitation. carefully. The lattice parameter determination was

While the martensitic high carbon steel has a texture made by referring to the lattice parameter of TICl

composed of plate-like martensites containing fine evaporated on the specimen surface. Dark field elec-

internal twins, the martensitic low and medium carbon trop microscopy was actively used to investigate the

steel has a texture composed of needle-like or lath morphology and the precipitation mode of the carbide.

martensites containing dislocations with high density.

Such a structural difference may influence the crystal Ⅲ. Results

structure and the mode of precipitation at the first

stage of tempering. According to previous studies(4)(5),

1. Tempered martensite
the precipitates were reported to be e-carbide, although

they were made on alloy steels. Therefore, a detailed The texture of the specimen was inhomogeneous:

study was undertaken for a martensitic plain carbon regions composed ofplate-like martensites and regions

steel of 0.45 wt%C(2.06 at%C). composed of lath martensites were localized. The

plate-like martensites were smaller in size than those

Ⅱ. Experimental in the high carbon steel and sometimes contained fine
transformation twins. On the other hand, two types of

The method of specimen preparation is similar to the lath region were observed extending in a wide range

the previous case of 1.13%C steel. Thin plates(0.13 of 30∼100μm. In the parallel lath regio11, the marten-

mm thick)of zone refined pure iron were carburized sites with the width of 0.2∼0.8μm are elongated along

at 950℃ for 20 min in an activated town gas, aus- about <111>α" direction in groups. Photograph l

tenitized at 1100℃ for 7 hr in a high vacuum and shows approximately(100)α" section of the grains

elongated along about[111]α" In the nonparallel lath

quenched into ice water, followed by immersion in
liquid nitrogen. Martensitic specimens containing region, the grains take complex shapes with the width

O.45%Cwere obtained. Tempering was made in an oil of 0.05∼0.2μm and their long axes are not parallel to

bath kept at 120℃ for 1∼40 day and also at 200℃ one another as shown in Photo.2. The lath grains,

for 1∼3hr. After electrolytic thinning in CrO3-H2PO4 independent of the lath region, are slightly mis-

orientated with adjacent lath grains or in the twin

* Department of Metallurgy relation(6). The dislocation density in the lath grain is

, Tokyo Institute of Tech-
nology, Meguro-ku, Tokyo, Japan. of the order of 1011 cm-2.

Trans. JIM 1974 Vol. 15

130 Carbide Precipitated at the First Stage of Tempering of Martensitic Medium Carbon Steel

The lattice parameters of the tempered martensite martensites were weak at the tempering of 120℃ but

were found to be almost equal for the above three types became clear and fairly strong at 200℃. The parallel
of martensite. Also they were little influenced by the lath regions and fairly large martensites in the non-
tempering temperature and time. In Table 1, the ob- parallel lath regions gave weak carbide spots. On the
served lattice parameters and the axial ratios of the

0.45%Csteel tempered at 120 and 200℃ are shown

and compared with those of the tempered 1.13%C

martensite. The values of the 0.45%C steel are slightly

smaller than those of the 1.13%C steel at the tem-

pering of 120℃, but they are equal at the tempering of

200℃.

2. Precipitated carbide

Electron diffraction patterns of the precipitated

carbide in the tempered 0.45%C steel were similar to

those in the tempered 1.13%C steel. The diffraction

spots due to the carbide precipitated in the plate-like

Photo.3 Electron diffraction pattern from plate-like

martensite in 0.45%C steel tempered at

120℃ for 40 days. Beam//[010]η//[011]M.

Photo.1 Parallel lath martensites in 0.45%C steel

tempered at 200℃ for 3 hr. Figure shows

approximately(100)α" section of the grains

elongated along about[111]α".

Photo.4 Electron diffraction pattern from lath

martensite in 0.45%C steel tempered at

120℃ for 20 days. Beam//[121]η//[113]M.M,

Photo.2 Non-parallel lath martensites in 0.45%C Tand η represent matrix, twin and η-carbide,

steel tempered at 200℃ for 3 hr. respectively.

Table 1 Lattice parameters and axial ratios of tempered martensite.

 Yoshihiko Hirotsu and Sigemaro Nagakura 131

diffraction condition is almost satisfied for the funda-

other hand, fine martensites in the non-parallel lath
mental reflections 220η and 220η as well as for the
regions did not give any diffraction spot. Photographs
superstructure reflections 110η and 110η. Appearance
3and 4 reproduce typical diffraction patterns from a
of the 110η and 110η spots ls the most clear indicatioll
plate-like martensite tempered at 120℃ for 40 days
of the ordered arrangement of carbon atoms in the
and from a grain in the parallel lath region tempered at

120℃ for 20 days, respectively. All the diffraction

spots due to the precipitates could satisfactorily be

interpreted on the basis of η-Fe2C. In Table 2, the

observed lattice parameters are tabulated for the

carbide in the plate-like and the lath martensites

tempered at 120 and 200℃. The values for the carbide

in the 1.13%C steel tempered under the same condi-

tions are also shown for comparison. They agree

with one another within the experimental error.

The orientatioll relatiollships betweenη-Fe2C and

matrix α"were determined as

(1)
They are the same as the relationships previously

observed in the high carbon steel.

The superstructure re$ections ofη-Fe2C appeared

in the diffraction patterns from both of the plate-1ike

and lath mertemstes. Photographs 5(a)and 6(a)show

diffraction patterns containing the superstructure

reflections, while Photo. 5(b),6(b)and 6(c)are xnicro-

photometer curves along the directions AB, CD and

EF in Photo.5(a)and 6(a). In these patterns, the

Photo.5(a)Electron diffraction pattern from plate- Photo. 6(a)Electron diffraction pattern from plate-

like 0.45%C martensite tempered at 200℃ hke 0.45%C martensite tempered at 200℃

for 3 hr. Beam//[110]η//[010]M. F refers to for 3 hr. Beam//[111]η//[120]M. O and T

the fundamental spot and S to the superstruc- represent reflections from surface oxide and

ture spot. (b)Microphotometer curve along twm, respectively.(b)and(c)Microphoto-

the line AB in(a). Peaks due to the super- meter curves along the lines CD and EF in

structure spots are clearly observed. (a),respectively.

132 Carbide Precipitated at the First Stage of Tempering of Martensitic Medium Carbon Steel

Table 2 Lattice parameters of η-Fe2C.

η-carbide lattice. In Photo.6(a)and(c), the super- carbide particles are seen to precipitate along the lath

structure reflections 011η and 211η are also observed boundaries with the size of about 50×50 A2. By com-

faintly just in the middle of the fundamental reflections paring the precipitation modes in Photo.7and 8(c),
121η and 101η, and 101η and 321η, respectively. we can say that the carbide precipitation is heavily

suppressed in the non-parallel laths.

3. Mode of the carbide precipitation

Photograph 7 reproduces a 210η dark field electron Ⅳ. Discussion

micrograph of the carbide in a large grain in the

parallel lath martensites tempered at 200℃ for 3 hr. In the present study, it was shown that the carbide
The carbide particles with the size of about 70×50A2 precipitated at the first stage of tempering is η-Fe2C,
are observed to line up with intervals of 50∼100 A. independent of the carbon content and the martensite
The precipitation was found to occur along disloca- texture. However, the tempering of the fine non-
tion lines. In general, the precipitation mode iri the parallel laths did not provide any carbide pattern.

plate-like and the parallel lath martensite was similar Since the lattice parameters of the matrix is inde-

to the case of high carbon steel, but the number of pendent of the martensite texture, carbon atoms in the
carbide particles was about 1/5-1/3 of that in the high fine laths must be in some thermally stable positions.

carbon steel. This may be mainly due to the difference Dislocations provide such positions, but calculation

in the carbon content. shows that the dislocations with density as high as

Diffraction spots due to the carbide could not be

observed in fine grains in the non-parallel lath region,

but in relatively large grains they could be observed,

especially in the case of tempering at 200℃. An

example is shown in Photos.8(a),(b)and(c). Photo-

graph 8(a)is a bright field image of the non-parallel

lath region in a specimen tempered at 200℃ for 3 hr,

(b)the corresponding diffraction pattern with beam

incidence along nearly[010]η, and(c)the dark field

image taken with 101η , spot. In(c), most of theη-

Photo.8 Precipitation of η-carbide particles along

grain boundaries in the non-parallel laths

Photo. 7 Dark field image showing η-carbide partides tempered at 200℃ for 3 hr.(a)Bright field
in a fairly large grain in parallel laths image,(b)corresponding diffraction pattern
tempered at 200℃ for 3 hr. Taken with 210η with beam//[010]η//[011]M, and(c)dark field

reflection. image taken with 101η reflection.

 Yoshihiko Hirotsu and Sigemaro Nagakura 133

1012 cm-2 can absorb only the carbon atoms corre- can make mirror crystals B and D with respect to the

sponding to the order of 0.01 wt%C(0.05 at%C). We (001)α" plane, and further we can make mirror crystals
could not find any diffuse scattering or diffraction A',B', C'and D'with respect to the crystals A, B, C

spots other than the matrix spots in the electron and D by taking(010)α" and(100)α" as the mirror

diffraction patterns. Therefore, both the short and planes. Owing to the crystal symmetry of η-Fe2C,
long range orderings of carbon atoms(7)do not seem however, B'and A, A'and B, D'and C, and C'and D

to take place in the tempered fine laths. As seen in are respectively identical. Okamoto and Shimizu(8)

Photo.2, the image of such region is very complex. first pointed out that such mirror carbide crystals exist

It is considered that a detailed investigation is neces- in the tempered martensitic carbon steel. Their

sary for the structure of the fine laths. existence was also confirmed in our study. They

The α" and bα" axes are crystallographically egttiva- sometimes provide overlapped diffraction patterns and

lent. Therefore, the following orientation relationships disturb the observation of the superstructure spots of

can be derived from(1). the carbide. Figure 2 represents schematically the

diffraction pattern with beam incidence along[120]α"

(2) The large open circles represent the matrix spots,. the

In Fig. 1, A and C represent schematically the carbide small filled ones the carbide spots from the crystal A,

crystals precipitated with the orientation relationships the small open ones the carbide spots from the crystal

(1) and (2), respectively. For the respective crystals we B,and the small double circles the carbide spots com-

mon to A and B. The diffraction spots from the two

crystals come close on the line PP'parallel to[001]α".

Since the one is the weak superstructure spot and the

other the strong fundamental one, the former is usually

masked by the latter, resulting in the array of spots

with a rather strong intensity on the line PP'. Strictly

speaking, however, the reciprocal lattice planes

containing the filled and open circles are not the same
but incline mutually by about 2°. Therefore, by careful

adjustment of the specimen orientation and the use of

parallel incident beam, we can obtain the diffraction

pattern contributed only by the crystal A. Photograph

6is an example taken under such condition. The weak

superstructure spots and the strong fundamental spots

are observed to line up alternatively along the line EF

with an equal interval.

Fig.1 Schematic illustration of the possible orienta-
According to the observation of many diffraction
tion relationships between η-carbide and

matrix α". Crystals B and D are mirror crystals patterns ofη-carbide, the observed intensity of the
of A and C with respect to(001)α" plane, while superstructure spots due to the carbide was weaker
A',B'and C', D' are mirror crystals of A, B
than the calculated one. For example, ratios of the
and C, D with respect to(010)α" and(100)α"
superstructure reflection intensity to the fundamental
planes, respectively, but A'and B, B'and A, C'
reflection intensity,I(110η)/I(220η)and I(011η)/I(101η),
and D, and D'and C are respectively identical

because of the crystal symmetry of η-Fe2C. were observed to be 1/2-1/3 of the calculated. In the
In the figure, crystal axes are right-handed.
η-carbide lattice, carbon atoms occupy the octahedral
interstices(0,0,0)and (1/2,1/2,1/2)(3). However, the

structure in which the carbon atoms occupy the other

octahedral interstices(0,1/2,0)and(1/2,0, 1/2)is possible・

In both of the structure, the carbon atoms make

straight chains along the[001]η direction. Therefore, it

is possible that the same carbon atom chains do not

continue throughout the crystal but break with limited

length so as to divide the crystal into domains with

respect to the carbon atom arrangement. In such a

case, the superstructure reflections are weakened. The

weakening is also brought about if the carbide com-

position deviates from the stoichiometric composition

Fe2C. As another possible reason, we can mention the
Fig.2 Schematic illustration of diffraction pattern

from theη-carbide crystals A and B in Fig.1 effect of the electron state. If the electron state of the
with beam incidence along[120]α". Large open carbon atom is negative, the lowest order reflection
cirdes:matrix, small mled circles:A, small
110,,becomes weaker than the calculated(9)∼(11), since
open circles:B, double circles:common to A
it appears at the low angle position, sin θ/λ=0.158
and B. Actually, the reciprocal lattice planes
A-1(θ:Bragg angle,λ:wavelength). At present, it is
containing small open and filled circles are

inclined mutually by about 2°. unable to make clear the reason for the weakness in
 134 Carbide Precipitated at the First Stage of Tempering of Martensitic Medium Carbon Steel

superstructure reflection intensity, because an accurate the orientation relationships between the carbide and
determination of the structure factor from the spot the matrix are the same as those found in tempered
intensity in electron diffraction pattern is difficult. martensitic high carbon steel.
Barton and Gale(12)has rcported the existence of a (2) Generally, the precipitation occurs along dis-
llew iron carbide on the basis of an X-ray difhaction locations, but the grain boundary precipitation takes
study of synthesized iron carbide. According to them, place in the non-parallel lath regions.
the synthesized carbide is monoclinic with lattice (3) No diffraction spots due to the carbide crystals
parameters a=2.794, C=4.360 A and γ=120.92°. are observed from the area of fine non-parallel laths.
This can be transformed to an orthorhombic lattice
Acknowledgment
with parameters a'=2a sin(γ/2)=4.862, b'=c=4.360

and c'=2a cos(γ/2)=2.755 A, wllere a'and c'axes are The present authors wish to express their thanks to
on the closed packed pseudo-hexagonal plane. The Professor M. Kikuchi for his valuable discussions.
axial ratio a'/c'is 1.765, which is larger than the

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than √3. Therefore, the deviation from the hexagonal Tech. Iron and Steel, Tokyo (1970);Trans. Iron Steel
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suggested that Barton and Gale's carbide is closely
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