May 1995

ELSEVIER Materials Letters 23 ( 1995) 269-272

A computer-simulated electron diffraction analysis of precipitates

in 18Ni ( 350) maraging steel
Xiaodong Li, Zhongda Yin
Department of Metals and Technology, Hat-binInstitute of Technology, Harbin 150001, China

Received 1 March 1995; accepted 6 March 1995

Abstract

A computer-simulated electron diffraction analysis was applied to determine the nature of the strengthening precipitates in
18Ni( 350) maraging steel. The results show that the strengthening is caused by a refined distribution of the rod-shaped Ni,Mo
and pN&Ti precipitates. The computer-simulated electron diffraction analysis is effective in the study of unknown precipitates
in this steel.

1. Introduction 2. Experimental

Maraging steels are a special class of ultrahigh-
strength martensitic steels which are age-hardened by
the precipitation of intermetallic compounds [ 11. Since
their initial development in the late 1950’s, maraging
steels have found a wide range of applications.
Although the general physical metallurgy of these
steels is well understood, there is a diversity of opinion
on the nature of the strengthening precipitates. Differ-
ent results have been reported even on the same mate-
rial and after the same heat treatment. The similarity of
diffraction patterns from the different possible precip-
itate phases makes their identification difficult by a
conventional stereographic approach. Computer-sim-
ulated diffraction analysis has been proved to be a very
powerful method for determining the multiphases
which have a large number of variants of the orientation
relationship [ 2,3]. In order to clarify the nature of the
strengthening precipitates in 18Ni (350) maraging
steel, the electron diffraction patterns are computer-
simulated and compared with the observed electron
diffraction patterns in this paper.
The chemical composition of 18Ni( 350) maraging
steel studied is (wt%): Ni 18.09, Co 12.16, MO 4.54,
Ti 1.27, C 0.04, Si 0.05, Mn 0.03, Fe balance. The
maraging steel was melted in a vacuum induction fur-
nace and the ingots were remelted in a consumable-arc
furnace, and then forged to 4 mm thick sheets. The
forged sheets were solution treated at 820°C for 1 h,
water quenched and then aged at 500°C for 4 h. This
heat treatment was chosen according to the more usual
industrial treatment [ I]. Transmission electron
microscopy (TEM) thin foil specimens were made by
electropolishing using a solution consisting 10% per-
chloric acid in methanol. The TEM studies were carried
out using a Philips CM 12 transmission electron micro-
scope.
3. Results and discussion
Our work has already established that in 18Ni( 350)
maraging steel, Fe-Co and Ni-Mo-Ti zones form dur-

0167-577x/95/$09.50 0 1995 Elsevier Science B.V. All rights reserved

SSDIO167-577x(95)00053-4
270 X. Li, Z. Yin /Materials Letters 23 (1995) 269-272

ing the early stages of ageing, and then Ni,(Mo,Ti)

type intermetallic compounds precipitate in the Ni-
Mo-Ti zones [4,5]. The Ni,(Mo,Ti) intermetallic
compounds have two kinds of crystallographic struc-
tures, one is the orthorhombic Ni,Mo with a = 0.5064
nm, b = 0.4224 nm and c = 0.4448 nm, the other is the
hexagonal v-N&Ti with a = 0.5 101 nm and b = 0.8307
nm [ 31. The strengthening precipitate phase(s) in this
steel should be one or both of them. Different results
have been reported [6-81, however, none of them is
convincing due to the lack of consideration of precip-
itate variants and diffraction-spot coincidence.
In the following, the subscript M represents the mar-
tensite with a body-centered cubic (bee) structure. Fig.
1 shows a typical TEM image and the corresponding
diffraction pattern for the [ OO1lM zone axis of
18Ni( 350) maraging steel aged at 500°C for 4 h. The
TEM image shows that the fine rod-shaped precipitates
are distributed homogeneously, and lie along two dif-
ferent crystallographic directions, which make an angle
of 90”. The strain-field contrast was observed around
the precipitates. The precipitate diffraction spots are
quite complex, and some of them are streaked.
First, suppose Ni,Mo is the strengthening precipitate
phase in this steel. From the analysis of the diffraction
pattern in Fig. 1b, the orientation relationship between
the martensite matrix and Ni,Mo is supposed to be
(Oll)~ll(O1O)~~~~*~ rliii,ll [IOO]Ni3Mo.Thisrela- Fig. I. TEM image (a) and the correspondingdiffractionpattern (b)
for [OOllM zone axis of lSNi(350) maraging steel aged at 500°C
tionship gives rise to twelve possible variants of Ni,Mo
for 4 h.
precipitates relative to the martensite matrix, as shown
in Table 1. Fig. 2 shows the computer-simulated
relative to the martensite matrix, as shown in Table 2.
[OOl], pattern for the N&MO precipitates. The spots
Fig. 3 shows the computer-simulated [OOl] M pattern
from variants 1, 2, 5,7,9 coincide with the spots from
variants 4, 3, 6, 8, 12, 11, respectively. Some of the Table 1
observed spots exactly agree with the simulated spots, The twelve possible variants of Ni,Mo relative to martensite
however, the other observed spots do not agree with
the simulated spots. This indicates that there exists variant Martensite Ni,Mo

another kind of precipitate phase, v-Ni,Ti. However, 1 (Oll)[lil] (010) [ 1001

the existence of Ni,Mo phase cannot be determined 2 (Oll)[Til] (010) [ 1001
because all of the spots from the Ni,Mo precipitates 3 (oii)[iiil (010) [ 1001
perhaps coincide with the spots from the q-Ni,Ti pre- 4 (OTl)[ill] (010) [ 1001
5 (iio)[iiij (010) [ 1001
cipitates.
6 (iio)[iiij (010) [ 1001
Next, suppose r]-Ni,Ti is the strengthening precipi- 7 (iio)[iiil (010) [loo]
tate phase in this steel. According to Fig. 1b, the pos- 8 (iio)[iii 1 (010) [ 1001
sible orientation relationship between the martensite 9 (ioi)[iiil (010) [ 1001
matrix and q-Ni,Ti is (Oll),ll (OOO1),,igTi, 10 (ioi)[iii) (010) [ 1001
11 (ioi)~iiil (010) [loo]
[lill~II[llZOl~~is~i. This relationship also gives
12 (ioi)[iiil (010)[1001
rise to twelve possible variants of q-Ni,Ti precipitates
 X. Li. 2. Yin /Materials Letters 23 (1995) 269-272 211

an interplanar spacing of 0.0864 nm, corresponds to

the (432) Ni,Mo or the (4046) q-N&Ti spots. The
(432) Ni,Mo spot is strong while the (4046) q-N&Ti
spot is very weak and often not present [ 81. Although
T T the spot indicated by the arrow in Fig. lb is far from
the center spot, its intensity is still very strong, indicat-
l
ing the existence of Ni,Mo phase.
In addition to the above spots, there exist extra spots
at the ( 1 f 0), and (001 jM locations in Fig. lb. The
T T
spots at the { f i O}, locations result from the marten-
site-martensite double diffraction. The spots at the
{001 }Mlocations are due to the BZtype ordering in the
martensite matrix and the ( 110) reflections from sur-
Fig. 2. Computer-simulated [ 001 I M pattern for the Ni,Mo precipi- face Fe304 [ 3,9].
tates. (0) mattensite, (A) variants 1, 4, (V) variants 2, 3, (A) The long axis of the Ni,Mo and q-Ni,Ti precipitates
variants 5.6, (7) variant 7,8, (0) variants 9.12, (=) variants 10, is the ( 11 l)M direction. Streaks form when the Ewald
11.
sphere intersects planar regions of diffuse scattering in
Table 2
reciprocal space normal to the long axis of the precip-
The twelve possible variants of V-Ni,Ti relative to martensite itates. Therefore, the precipitate spots in Fig. lb were
observed to be streaked.
variant Martensite V-NisTi It has been pointed out that Ni,Mo and v-Ni,Ti pre-
1 (oii)[iii] (0001)[11201 cipitates are favored because of the good lattice fit with
2 (oii)[iil] (0001)[11201 bee martensite [ 3,101. Based on the lattice parameters
3 (oii)[iii] (0001)[11201 of these structures, the lattice mismatch along the close-
4 (oii)[iii] (0001)[11201
packed directions in the close-packed planes of the
5 (iio)[iii] (0001) [ llZO]
Ni,Mo phase and the martensite matrix is 1.48%, and
6 (iio)[iiii cooo11 I 11201
7 (iio)[iii] (Oool)[llZO] that of the qNi,Ti phase and the martensite matrix is
8 (iio)[iii] (Oool)[llZO] 2.22%. An edge dislocation with b = f (111) approx-
9 (ioi)[iii] (oool)[ llZO1 imately every 35 planes would accommodate the spac-
10 (ioi)[iii] (oool)[ 11201 ing differences between the Ni,Mo phase and the
11 (ioi)[iii] (oool)t llZO]
12 (ioi) [iii] (oool)1llZO]

for Ni,Ti precipitates. The spots from variant 1, 2, 5,

7,9 coincide with the spots from variants 4,3,6,8, 12,
11, respectively. The observed spots exactly agree with
the simulated spots, confirming the existence of v-
Ni,Ti phase. When Figs. 2 and 3 superimpose, it was
found that all of the spots from the Ni,Mo precipitates
coincide with the spots from the q-N&Ti precipitates
while only parts of the spots from the v-N&Ti precip-
itates coincide with the spots from the Ni,Mo precipi-
tates. Therefore, according to Figs. lb, 2 and 3, the
existence of q-NigTi phase can be confirmed while that
A I
of Ni,Mo phase cannot.
Fig. 3. Computer-simulated [OOl lM pattern for the V-Ni,Ti precip-
In order to determine if Ni,Mo phase does exist, the itates. (@) martensite, (A) variants 1.4, (V) variants 2, 3, (A)
high-order spots of precipitates were carefully ana- variants 5.6, (V) variants 7, 8, (Cl) variants 9, 12, (W) variants
lyzed. The spot indicated by the arrow in Fig. lb, with 10.11.
212 X. Li. Z. Yin/Materials Letters 23 (1995) 269-272

martensite matrix, and approximately every 25 planes References

would do between the q-Ni,Ti phase and the martensite
matrix. The Ni,Mo precipitates with lengths less than
about 17 nm and the q-Ni,Ti precipitates with length
less than 11 nm would be coherent with the martensite
matrix, longer ones being semicoherent.
Acknowledgement
The authors gratefully acknowledge the financial
[tl R.F. Decker and S. Floreen, in: Maraging steels: recent
developments and applications, ed. R.K. Wilson (The Metals
Society, Pennsylvania, 1988) p. I.
f21 C.S. Lee, J.W. Kim,C.N. Parkand Y.G. Kim, ScriptaMeta~l.
Mater. 24 ( 1990) 639.
[ 31 V.K. Vasudevan, S.J. Kim and CM. Wayman, Metall. Trans.
A 21 (1990) 2655.
I41 X.D. Li, Z.D. Yin, H.B. Li, T.C. Lei, M.L. Liu, X.W. Liu and
M.Z. Jin, Mater. Chem. Phys. 33 (1993) 277.
I51 X. Li, Ph.D. Thesis, Harbin Institute of Technology, Harbin
(1993) p. 40.

support provided by the National Natural Science L61U.K. Viswanathan, G.K. Dey and M.K. Asundi, Metall. Trans.
A 24 (1993) 2429.
Foundation of China throughout this investiga- 171 U.K. Viswanathan, T.R.G. Kutty and C. Ganguly, Metall.
tion. Trans. A 24 (1993) 2653.
I81 J. Zhu, H. Li and L. Zhang, Acta Metall. Sinica 22 (1986)
A304.
191 S. Spooner, H.J. Rack and D. Kalish, Metall. Trans. 2 ( 1971)
2306.
[lOI K. Shimizu and H. Okamoto. Trans. Japan. Inst. Met. 12
(1971) 270.