Acta metall, mater. Vol. 42, No. 5, pp.

1763-1768, 1994
Copyright © 1994 Elsevier Science Ltd
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TEM STUDY OF PRECIPITATES IN LASER CLAD Ni-A1

BRONZE
Y. LIU1, M. E. MOCHEL 2, J. MAZUMDER t and K. SHIBATA3
ICenter for Laser Aided Material Processing, Department of Mechanical and Industrial Engineering,
University of Illinois at Urbana-Champaign, 1206 W. Green Street, Urbana, IL 61801, 2Center for
Microanalysis of Materials, Materials Research Laboratory, University of Illinois at Urbana-Champaign,
104 S. Goodwin Avenue, Urbana, IL 61801, U.S.A. and 3Nissan Motor Co. Ltd, Nissan Research Center,
1, Natsushima-cho, Yokosuka 237, Japan

(Received 12 March 1993; in revisedform 28 August 1993)

Abstract--Transmission electron microscopy ('gEM) examination of sheet martensite in laser clad Ni-A1
bronze reveals precipitates with diameter of about 20 nm. It is found that the hardness of the sheet
martensite shows a pronounced decrease with increasing test temperature. Heat treatment at 673 K for
4 h doubled the size of the precipitates. Convergent beam electron diffraction (CBED) and microdiffrac-
tion (MD) in TEM are used to examine the crystal structure of the precipitates in heat treated material.
CBED patterns suggest two point groups: 4/mmm and m 3m. Three MD patterns of the precipitates show
complete agreement with B2 structure. The crystal structure of precipitates in as-clad material is studied
by high resolution electron microscopy (HREM) and optical diffraction. The HREM images are a close
match with simulated images based on a B2 crystal structure model.

1. INTRODUCTION results of morphology, composition and crystal

Laser materials surface modification has been in a
flurry of activity in recent years. Laser cladding is a
process where a stream of powder is injected into a
laser generated molten pool on the metal surface. The
injected powder is melted and then solidified to form
a clad with metallurgical bonding to the metal sub-
strate. The process has been used to extend the
solubility of some rare earth metals to improve the
oxidation resistance of superalloys [1, 2] and to im-
prove wear resistance [3]. Laser clad Ni-AI bronze on
AI alloy AA333, when fabricated as a mechanical
component, has the advantages of high wear resist-
ance at the clad portion and light weight of the
supporting substrate. The laser cladding process and
interface structure have been described in earlier
papers [4, 5]. TEM microstructure characterization of
the cladding [6] indicates that the clad region is sheet
martensite which is a close-packed structure with
predominantly a 9-layer stacking mode. Dislocation
structure and stacking faults in the sheet martensite
are revealed by weak beam (WB) and high resolution
electron microscopy [7].
Precipitates of dimension 20 nm are observed in the
sheet martensite. To the best knowledge of the
authors, no study has appeared in the literature about
the crystal structure and its behaviour. It is well
known that the precipitation behaviour has an im-
portant effect on the mechanical properties. Modern
transmission electron microscopes have the capability
of forming a probe as small as 2 - 1 0 n m which
facilitates the microdiffraction study of nano-grain
sized materials. The present paper describes the
structure study of the precipitates by scanning trans-
mission electron microscopy (STEM), microdiffrac-
tion (MD) and high resolution electron microscopy
(HREM). The effects of heat treatment on precipitate
growth and hardness change will also be reported.
2. EXPERIMENTAL
A detailed description of laser cladding process can
be found in Ref. [4]. The laser cladding processing
parameters which were used to produce the present
TEM samples were as follows: Laser spot size, 4 mm
in diameter; CW CO: laser power, 4.8 kW; traverse
speed, 16.93 mm/s; powder feed rate, 55 g/min; and
helium flow, 0.708 m3/h. For TEM sample prep-
aration the clad material was first cut into 3 mm
diameter and 0.2 mm thick discs and then these discs
were thinned in a 10% H2SO 4 methanol solution by
the twin jet polishing technique. The TEM mi-
croscopy work was done in a Phillips CM12 TEM
and in a Hitachi H-9000 TEM.
3. EXPERIMENTAL RESULTS
3.1. Morphology of precipitates
The precipitates can be observed either in a dark
field [Fig. l(a)] or bright field image [Fig. l(b)]. The
distribution of the precipitates is quite uniform and
every martensite area examined showed similar mor-
phology in the as-clad material. Since no needle-
shape or disk-shape precipitates were found the
precipitates are considered to have spherical shape.
The precipitates showed noticeable growth upon

1763
1764 LIU et al.: PRECIPITATES IN Ni-AI BRONZE

iO0.

Fe

AI

NI

~1 C u

o.o * ' ' " ' " ' ' ' " ' ' ' " ' " to.o
ENERGY (KV)

Fig. 4. An example of STEM EDX spectra of the precipi-

tates in martensite.

Fig. 1. Precipitation behaviour in Ni-A1 bronze clad. (a,b)

TEM dark field image and bright field image of precipitates
in a as-clad foil. (c,d) precipitates in a foil heat treated at
673 K for 4 h.

heating. Figure l(c) and (d) compares the precipitates

observed in a specimen heat treated at 673 K for 4
hours with those in the as-clad materials. The growth
Fig. 5. CBED patterns of precipitates in a foil heat treated
o f the precipitates has a preferred direction and at 673 K for 4 h. (a) [001] zone axis pattern. (b) Dark field
sometimes rod-like precipitates are observed. pattern.
3.2. Thermal differential analysis and hardness
measuremen t above the melting temperature. Figure 2 shows the
Thermal differential analysis ( D T A ) of the as-clad A T - T c u r v e . A valley from 523 to 723 K in the A T - T
material was performed from r o o m temperature to curve of the clad corresponds to the growth of the
precipitates. The hardness, measured as a function of
temperature, is shown in Fig. 3. The decrease in
"PBC*I
2 . 0 0 f
W! : 164.66 mg ..,. ~ t hardness is relatively small from r o o m temperature to
573 K but becomes significant from 573 to 673 K.
1.50 Precipitation growth is responsible for the decrease in
hardness.
~1.00
D 3.3. S T E M E D X composition analysis
0.50 The composition o f the precipitates were examined
with a vacuum generator HBS S T E M fitted with
, , a , a , i • ' • '
energy dispersive X-ray unit. The size of the electron
0"0~00 500 700 900 11001300"1500 probe is about 10 A which is about one twentieth o f
Temperature (K)
the diameter of the precipitate. Figure 4 shows one
Fig. 2. DTA curve of the as clad material.
example of the E D X spectra of the precipitates.
A b o u t 10 precipitates in the as-clad and 10 in the
400 . . . . . . . . . i . . . . . . . . . , . . . . . . . . . , . . . . . . . . . , . . . . . . . . .
heat-treated specimen were examined. Some of the
analysis shows high Cu concentration which is con-
sidered to be due to overlapping of the precipitate
3OO and the matrix. F o u r examples of composition analy-
m
sis are shown in Table 1.
m
r.
o

Table 1. STEM EDX composition analysis of the precipitates in

as-clad specimen and in specimen heat treated with 673 K for 4h
(at.%)
Precipitate AI Si Fe Ni Cu
As-clad 34.3 2.0 24.8 17.4 21.5
10~00 .... 30"0 .... 4:0"0 ..... S'o'O..... 6"0"0.... "700 As-clad 34.4 0.1 29.6 19.6 16.3
Temperature (K) 673K for 4h 31.2 6.2 34.9 13.3 14.4
673 K for 4h 28.5 30.0 6.5 18.9 15.1
Fig. 3. Vickers hardness as a function of testing temperature.
 LIUet al.: PRECIPITATES IN Ni-A1 BRONZE 1765

Fig. 6. Comparison of MD patterns (a) taken from precipitates heat treated at 673 K for 4 h. (b) simulated
patterns with the B2 structure.

3.4. CBED and MD study of the crystal structure axes and take diffraction patterns. The crystal struc-
A 10 nm electron beam, achieved in nano-probe ture of the precipitates was further studied by
mode on the CM 12 TEM, was used to obtain the HREM. It was found that the precipitates are
CBED patterns and M D patterns from a specimen spatially coherent with matrix martensite. One
heat treated at 673 K for 4 h. Figure 5 shows two example H R E M image of the precipitate is shown in
CBED patterns with high symmetry. Two mirrors Fig. 7. The TEM specimen was aligned on the [11~0]
and a four fold axis were observed in Fig. 5(a). The zone axis of the martensite matrix. In both matrix
4 mm symmetry was then tentatively assigned to this and precipitate, well-resolved black or white dots are
pattern. It was also noted that some contrast, as observed. The coherent relationship between the
indicated by the arrow, suggests that the 4 mm sym- precipitate and matrix is also revealed by
metry needs further confirmation. Figure 5(b) is a the optical diffraction patterns which are shown
pattern of the same zone axis with one disk set at in Fig. 8. Note that the zone axis of the precipitate
Bragg reflection condition, called the dark field disk. matches exactly with the [001] zone axis shown in
The contrast feature in this dark field disk suggests a Fig. 6. It is now clear that the coherence
2 mm symmetry. According to Table 2 in Ref. [8]
diffraction group 4ram IR is deduced. Possible point
groups 4/mmm and m3m are deduced from diffrac-
tion group 4ram 1R.
The crystal structure of the precipitates was further
studied by MD. The smallest condenser aperture was
used and the TEM was operated under convergent
beam mode. The tilting experiment was assisted by
using a program which provides the tilting angle from
one zone axis to another zone axis. The three main
zone axis diffraction patterns are shown in Fig. 6(a).
These patterns were indexed by referring to a diffrac-
tion pattern map of a b.c.c, structure. In fact, simu-
lated diffraction patterns with Bz structure in which
A element occupies the corner position and B atoms
occupies the body center position show excellent
agreement with the patterns from TEM [see Fig.
6(b)]. This result suggests that the point group of the
phase is m 3m (cubic structure) but not 4/mmm (tetra-
gonal structure).

3.5. H R E M and optical diffraction study

Since the size of the precipitates in the as-clad Fig. 7. A [11~0] zone axis high resolution image of sheet
martensite in laser clad Ni-A1 bronze. The crystal structures
specimen is very tiny (20 nm in diameter) it is in of martensite and precipitates are revealed in the atomic
practice very difficult to locate high symmetry zone level.
1766 LIU et al.: PRECIPITATES IN Ni-A1 BRONZE

Fig. 8. Optical diffraction patterns taken from a HREM negative. (a) From precipitate, (b) from both
precipitate and matrix, (c) from matrix.

relationship between precipitate and matrix is
precipitate [001]//matrix[11~0] and precipitate
[100]//matrix[0001]. The lattice parameter of the pre-
cipitates was deduced as a = 0.275 nm. If the crystal
is imaged along the [001] zone axis the projected
distance between a corner sited atomic column to its
adjacent body center sited atomic column is 0.194 n m
which is within the resolution limit of the Hitachi
H-9000 with a point to point resolution of 0.19 nm.
Multi-slice H R E M image simulation was performed
with EMS software package [9]. The composition of
the input model of B2 structure is shown in Table 1
where A1 and Si are considered to occupy corner sites
and Ni and Cu body center site. Fe is considered to
occupy both corner and body center sites with a
proper ratio.
The projected potential and images as a function of
defocus are shown in Fig. 9. Near Scherzer defocus
[Fig. 9(d) and (e)] there is a good relation between
projected potential and simulated images where black
dots correspond to atomic columns and near the
second pass band [Fig. 9(i) and (j)] white dots corre-
spond to atomic columns.
The H R E M images were printed using an optical
image processing system with Fourier filter [10].
Figure 10 displays the images as from the negative

Fig. 9. Simulated HREM images with the B2 structure as a function of defocus. (a) Projected electrostatic
potential, (b) - 36 nm, (c) - 40 nm, (d) - 44 nm, (e) - 48 nm, (f) - 52 nm, (g) - 56 nm, (h) - 60 nm, (i)
- 6 4 nm, (j) - 6 8 nm, (k) - 7 2 nm and (1) - 7 6 nm. Other parameters for image calculation are foil
thickness 10.8 nm, defocus spread = 2 nm, beam semidivergenee angle = 0.9 m radian, Cs = 0.9 mm and
accelerating voltage = 300 KV.
 LIU et al.: PRECIPITATES IN Ni-A1 BRONZE
Fig. 10. HREM images of the precipitates in as-clad. (a)
Image as printed from negative, and (b) image processed by
an optical image processing system. The unfiltered and
filtered diffraction patterns are attached to corresponding
image.
and filtered by placing a mask at the focal plane of
the objective lens. The image contrast changes from
place to place due to local strain. Two images which
could be matched to the simulated images are found
and shown in Fig. 11. The different strength of the
white dots in Fig. 1 l(b) represents ordering of the
b.c.c, structure i.e. the B2 structure.
1 nm
Fig. 11. Two images printed from TEM negatives. (a)
Defocus = --64 nm, and (b) defocus = - 6 8 nm. Simulated
images were taken from Fig. 9(i) and (j).
1767
4. DISCUSSION
Selected area diffraction (SAD) in TEM has been
used to identify crystal structures for several decades.
The difference between SAD and M D is that the area
in the specimen contributing to the diffraction pattern
is, in SAD, controlled by an aperture, while in M D
the electron beam is focused on the specimen. The
practical working dimension for SAD is 1 tim or
larger because of the spherical abberation in the
objective lens. The MD technique, however, can
focus the electron probe down to 0.3 nm in dedicated
STEM [11] and 1.5 nm in conventional TEM [12]. As
the probe size goes down in conventional TEM the
intensity also goes down significantly. Another
difficulty in taking M D from a small precipitate in the
tilting procedure is that the area being examined can
easily go out of sight with tilting. The best way of
performing a tilting experiment is to use a program
which can give the tilting angles of the double tilting
stage for tilting along a Kikuchi line [13].
It is known that supersaturated solid solution may
decompose to different precipitates when subjected to
aging at different temperatures. Since CBED, M D
and H R E M study indicates that the crystal structures
of the precipitates resulting from room temperature
and at 673 K aging are the same, the B2 precipitates
are considered to be the equilibrium precipitates in
the temperature range examined. One comment
worth mentioning is that the two components in the
B2 structure have an atomic ratio of 1:1. However,
STEM EDX analysis has shown that there are four
major elements AI, Fe, Ni and Cu in the precipitates
in the as-clad specimen. The B2 structure model has
been constructed by considering A1 as one com-
ponent, and Ni, Cu and Fe as the other. This
consideration is based on the assumption that the B 2
compounds are formed with maximum heat of for-
mation. By referring to Smithells Metals Reference
Book [14] one obtains the heats of formation in
kJ/g-at to be NiAI: 59.2; CuAI: 20; FeAI: 27.2; CuNi:
1.84; FeNi: 4.35; FeCu: no compounds and very
small solubility. Apparently a formula (NiFeCu)~
(A1)] produces maximum heat of formation. Some of,
most likely, Fe atoms will go to the A1 site to attain
the ratio 1:1 to form the B2 compound. It is noted
that the precipitates in specimens heat-treated at
674 K contain more Si which is possibly from the
substrate which contains about 9wt% Si. Based on
the same principle of heat of formation a B2 com-
pound with a formula (NiFeCuh (AISi)t is expected.
Several strengthening mechanisms such as solid-
solution hardening, precipitation hardening, struc-
ture hardening and dislocation hardening have been
proposed for the strength of martensites. The current
sheet martensite contains several elements and TEM
study has revealed the existence of dislocations,
stacking faults and precipitates. All the four strength-
ening mechanisms mentioned above will contribute,
to some extent, to the strength of the sheet marten-
1768 LIU et al.: PRECIPITATES IN Ni-A1 BRONZE
site. However, a high density of dislocations and
stacking faults was observed at both room tempera-
ture and 673 K and no noticeable change in configur-
ation between room temperature and 673 K was
found. This suggests that the dislocations and stack-
ing faults are stable in the temperature range exam-
ined. It is then considered that the drop in hardness
is due to the growth of precipitates which involves
two mechanisms, solid-solution hardening and pre-
cipitation hardening. The growth of a precipitate can
proceed by either subtracting solute atoms from the
saturated matrix or dissolving smaller precipitates
and both reduce the strength of martensite.
It is interesting to note that both the annihilation
of dislocation dipoles and the growth of precipitates
are controlled by diffusion process. However, the
driving force for dislocation annihilation is from the
elastic filed of the dislocations and is much smaller
than the driving force arising from the interface
energy between the precipitates and the matrix.
Therefore precipitation growth is more important in
affecting mechanical behaviour in the low tempera-
ture range. The structure of the sheet martensite is
stabilized by the precipitation. The reverse transform-
ation temperature of the sheet martensite is expected
to be much higher than M~ (starting temperature of
martensite transformation).
5. CONCLUSIONS
TEM CBED, M D and H R E M techniques were
used to investigate the crystal structure of the precipi-
tates in laser clad Ni-AI bronze. It was clearly shown
that the precipitates have the B2 structure. DTA study
and TEM morphology examination of the precipi-
tates suggest that the growth of the precipitates upon
heat treatment is responsible for the decrease in
hardness.
Acknowledgements--The TEM electron microscopy was
performed in the center for Microanalysis of Materials,
University of Illinois, which is supported by the U.S.
Department of Energy under contract DEFG02-91-
ER45439. During this research Dr J. A. Eades provided very
instructive information and guidance for conducting the
MD and CBED study which is highly acknowledged.
Authors also wish to express sincere thanks to Professor
J. M. Gibson for his advice in taking the HREM images.
This work was made possible by a grant from Nissan Motor
Co. Ltd.
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