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MATERIALS RESEARCH

The effect of heat treatment on the corrosion behavior

of amorphous Mg–Ni–Nd alloys
C. H. Kam and Y. Lia)
Department of Materials Science, National University of Singapore, Singapore 119260
S. C. Ng, A. Wee, and J. S. Pan
Department of Physics, National University of Singapore, Singapore 119260
H. Jones
Department of Engineering Materials, University of Sheffield, Sheffield, United Kingdom
(Received 30 March 1998; accepted 21 September 1998)

The effect of heat treatment on the corrosion behavior of seven amorphous melt-spun Mg–Ni–Nd
alloys containing 10–20 at.% Ni and 5–15 at.% Nd has been studied. Hydrogen evolution testing
was used to determine the dissolution rate of the heat-treated specimens immersed in a 3% NaCl
solution saturated with Mg(OH)2 . The dissolution rates of the partially crystallized specimens were
found to be lower than those of the untreated specimens, while the fully crystallized specimens
exhibited marked deterioration of corrosion resistance. X-ray diffraction (XRD) and transmission
electron microscopy (TEM) studies on the heat-treated specimens revealed precipitation of Mg3 Nd,
Mg12 Nd, and Mg2 Ni phases during the crystallization. TEM results show that the partially
crystallized structure consists of uniform dispersion of either Mg3 Nd or Mg2 Ni in the amorphous
matrix. In contrast, multiple phases precipitate in the fully crystallized specimen.

I. INTRODUCTION an understanding of the response of their corrosion behavior

1
In 1988, a new class of amorphous Mg-based ternary
metallic glasses with a wide range of compositions
generally represented by Mg–TM – Ln (Ln ­ Y, Ce, or
Nd; TM ­ Ni, Cu, or Zn) was initiated. Rapidly increasing
interest in these metallic glasses was stimulated as a result,
mainly because of their several attractive properties includ-
ing a wide supercooled liquid region before crystallization,2
large glass-forming ability (GFA),2 high tensile strength,
good ductility, and corrosion resistance.3 For instance, the
temperature interval of the supercooled liquid region is as
large as 69 K for Mg65 Cu25 Y10 .2 Bulk amorphous Mg–
Cu–Y4 and Mg –Ni– Nd5 alloys with diameters as large as
4 and 3.5 mm, respectively, have been reported. The
tensile fracture strength of as-spun ribbons is in the range
of 535 to 850 MPa which is significantly higher than for
conventional Mg-based casting or wrought alloys.6
It has been well recognized that metallic glasses formed
by rapid solidification processing (RSP) have a chemically
homogeneous amorphous structure which is practically free
from crystalline defects, thus giving a higher corrosion
resistance than their crystalline counterparts. The chemical
heterogeneity introduced by crystallization, precipitation,
and segregation during thermal exposure, however, can
cause a marked deterioration of the corrosion resistance
of heat-treated metallic glasses. Therefore, successful ex-
ploitation of the attractive properties possessed by the
Mg-based metallic glasses depends to a significant extent on
toward heat treatment. The main focus of the present work
is to report the dissolution rates of amorphous Mg– Ni–Nd
alloys before and after heat treatment using the hydrogen
evolution testing method. The results are correlated with
the associated crystallization processes induced by the
heat treatment which were investigated by a combination
of x-ray diffraction (XRD), transmission electron micros-
copy (TEM), scanning electron microscopy (SEM).
II. EXPERIMENTAL
The details of the production of seven Mg– Ni–Nd
alloys with compositions given in Table I and of their
ribbons with thickness of 30 to 50 mm and width 1 to
2 mm using the melt-spinning technique have been reported
previously.5,6 Heat treatment of the amorphous ribbons
was conducted in quartz ampoules filled with argon gas.
Hydrogen evolution during corrosion immersion tests was
applied to determine the dissolution rate and to prepare the
corroded specimens for SEM and XPS studies, respectively.
These tests were carried out in 600 ml of 3% NaCl solution
saturated with Mg(OH)2 , which were prepared from de-
ionized water and Analar grade salts. All the test solutions
had a pH of 10.4 throughout and were maintained at 25 6
TABLE I. Chemical compositions of alloys investigated
(balance Mg).
Alloy No. 1 2 3 4 5 6 8

a)
Ni, at.% 10.4 14.6 10.1 15.5 19.9 18.2 19.9
Address all correspondence to this author. Nd, at.% 10.2 9.6 15.0 15.2 5.1 5.3 14.8
e-mail: masliy@nus.edu.sg

1638 J. Mater. Res., Vol. 14, No. 4, Apr 1999  1999 Materials Research Society
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 C. H. Kam et al.: The effect of heat treatment on the corrosion behavior of amorphous Mg – Ni – Nd alloys

0.1 ±C in a constant temperature bath. For the hydrogen in Table II, and results for alloy 3, 6, and 8 ribbons are
evolution measurements, specimens were held vertically by shown in Figs. 1 and 2. All the specimens heat-treated
plastic clips in a calibrated hydrogen collection tube placed at low temperature and for short duration exhibit 20 to
over the corroding specimens. The dissolution rates in mpy 80% reduction in dissolution rates in comparison with
(mils per year) were calculated by means of the following the untreated ribbons. For examples, the dissolution rate
formula, assuming an alloy density of 1.8 gycm3 , of alloy 3 ribbon heat-treated at 170 ±C for 30 min was
VH 281 mpy in a test duration of 6 h. This was reduced further,
dissolution rate smpyd ­ 2150 , (1) by heat treatment at 180 ±C for 30 min to 51 mpy, in
AT
contrast to 333 mpy for the same sample without heat
where VH ­ volume of hydrogen evolved in ml, A ­
treatment [Fig. 1(a)]. Alloy 8 ribbon without heat treatment
surface area of specimen in cm2 , and T ­ test duration
gave a dissolution rate as low as 38 mpy at 6 h test
in hours.
duration, which showed a reduction down to 17 mpy on
For the characterization studies, ribbons immersed for
heat treatment at 220 ±C for 30 min for the same 6 h
30 min were carefully handled using clean plastic tweezers
test duration [Fig. 1(c)]. However, Fig. 2 shows that heat
and dried in air after draining the excess solution onto tissue
treatment at high temperature gave a sharp increase in
paper.
dissolution rate at shorter test durations. For example,
Thin foil specimens for TEM were produced using a
the dissolution rate of alloy 3 heat-treated at 250 ±C for
Gatan 600 Duomill operating at 6 keV, 1 mA, and grazing
15 min was 8160 mpy, in contrast with that of 370 mpy
angle of 15±, with a cold stage to prevent any further
for specimen heat-treated at 170 ±C for 30 min at a test
heating during milling. The resulting thin foil specimens
duration of 30 min; the dissolution rate of alloy 6 specimen
were examined in a 100 kV JEOL transmission electron
heat-treated at 250 ±C for 15 min was 1460 mpy, compared
microscope. X-ray diffraction and SEM studies were per-
with that of 390 mpy for a specimen heat-treated at 150 ±C
formed in a Philips 1700 diffractometer using Cu Ka as
for 30 min at a test duration of 2 h.
radiation source and JEOL 50 equipment, respectively.
B. XRD results
III. RESULTS
Selected XRD results for alloys 3, 6, and 8 after
A. Results of hydrogen evolution tests heat treatment are shown in Figs. 3(a), 3(b), and 3(c),
Dissolution rates as a function of test duration up to respectively. These results demonstrate clearly the progres-
6 h for each alloy before and after heat treatment are listed sive transition from typical amorphous, through partially
TABLE II. Dissolution rate as a function of test duration in a 3% NaCl solution saturated with Mg(OH)2 for Mg – Ni – Nd alloys heat-treated
to various conditions.

Dissolution rate (mpy)

Test duration (h) 0.5 1 1.5 2 3 4 5 6

Alloy no. Heat treatment conditions

1 Before heat treatment 438 403 379 339 348 301 285
180 ±C for 30 min 404 380 354 342 295 272 253 232
250 ±C for 15 min 91 152 182 190 200 182 167
2 Before heat treatment 1025 926 820 731
210 ±C for 30 min 399 432 421 365
220 ±C for 30 min 232 216 177 149 120 100
3 Before heat treatment 539 400 382 372 334 345 333
170 ±C for 30 min 374 333 318 312 305 302 291 281
180 ±C for 30 min 35 58 79 76 72 61 51
4 Before heat treatment 481 440 356 288 243 212 179
185 ±C for 10 min 468 425 340 287 227 186 153 128
200 ±C for 15 min 243 213 182 152 132 129 109 91
5 Before heat treatment 496 503 428 358
140 ±C for 30 min 386 329 309 271
160 ±C for 30 min 80 100 115 113 84 66 53 45
6 Before heat treatment 653 683 589 532
150 ±C for 30 min 501 516 442 391 310 254 218 140
190 ±C for 15 min 332 249 194 159 115 88 73 61
8 Before heat treatment 60 63 56 51 44 38
185 ±C for 10 min 43 36 38 32 28
220 ±C for 30 min 31 31 26 24 19 17

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 C. H. Kam et al.: The effect of heat treatment on the corrosion behavior of amorphous Mg – Ni – Nd alloys
FIG. 1. Dissolution rate as a function of duration of immersion in 3%
NaCl solution saturated with Mg(OH)2 for (a) alloy 3, (b) alloy 6, and
(c) alloy 8 before and after prior heat treatment.
crystallized, and finally to fully crystallized as the tem-
perature of heat treatment was increased. Figure 3(a) shows
that the alloy 3 ribbons heat-treated at 170 ±C for 30 min
remain essentially amorphous. For the partially crystallized
alloy 3 ribbons obtained by heat treatment for 30 min at
180 ±C shown in Fig. 3(a), prominent peaks corresponding
to Mg3 Nd phase superimpose themselves onto the amor-
phous pattern, indicating coexistence of Mg3 Nd precipitates
in the amorphous matrix. The fully crystallized pattern
from the sample heat-treated at 250 ±C for 15 min, on the
1640 J. Mater. Res., Vol. 14, No. 4, Apr 1999
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FIG. 2. Dissolution rate as a function of duration of immersion in 3%
NaCl solution saturated with Mg(OH)2 for alloys 3, 6, and 8 showing
contrast between dissolution rate of amorphous specimen before heat
treatment and that of fully crystallized specimen after the prior heat
treatments indicated.
other hand, shows only Mg3 Nd phase and absence of an
amorphous structure. Similarly, alloy 6 ribbons heat-treated
at 150 ±C for 30 min remain fully amorphous [Fig. 3(b)].
Partial crystallization as a result of heat treatment at 190 ±C
for 10 min gave peaks corresponding to Mg2 Ni phase
together with the amorphous structure while two phases,
Mg2 Ni and Mg12 Nd, appear in the fully crystallized pattern
for ribbons heat-treated at 250 ±C for 30 min. Figure 3(c)
shows that alloy 8 ribbons heat-treated at 185 ±C for
10 min were fully amorphous while those heated at 220 ±C
for 30 min and 300 ±C for 30 min were essentially fully
crystalline with Mg3 Nd phase predominant and probably
with Mg2 Ni also.
C. TEM results
The crystallization processes associated with heat treat-
ment under various conditions which result in precipitation
of intermetallic phases have been investigated for alloy 3
and alloy 6 ribbons. The results are shown in Figs. 4 and
5, respectively. For alloy 3 ribbons heated at 170 ±C for
30 min, a small quantity of fine spherulites is distributed in
the amorphous matrix as seen in Fig. 4(a). The typically
intense amorphous ring and a few bright spots in the
corresponding diffraction pattern in Fig. 4(b) confirm that
some crystalline phase is present with the amorphous
structure. Heat treatment of the alloy 3 ribbons at 180 ±C
for 30 min resulted in the partially crystallized structure
shown in Fig. 4(c) comprising a uniform dispersion of fine
spherulites having size ranging from 30 to 150 nm in the
amorphous matrix. The spherulites can be identified as
Mg3 Nd phase using the corresponding diffraction pattern
shown in Fig. 4(d). It is worth noting that the superim-
position of the dispersive bright spots onto the intense
amorphous rings is consistent with the XRD result in
Fig. 3(a). As illustrated in Figs. 4(e) and 4(f), further heat
 C. H. Kam et al.: The effect of heat treatment on the corrosion behavior of amorphous Mg – Ni – Nd alloys
FIG. 3. XRD results for (a) alloy 3, (b) alloy 6, and (c) alloy 8,
showing the transition from completely amorphous as-spun to partially
crystallized and fully crystallized accompanied by precipitation of
different phases as a result of heat treatment at successively higher
temperatures.
treatment at the higher temperature of 250 ±C for 15 min
finally led to full crystallization, resulting in the formation
of nanosized spherulites of mainly Mg3 Nd together with
other unidentified phases. Note that the absence of strong
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XRD peaks for the unidentified phases in Fig. 3(a) probably
indicates that the other phases were present in relatively
small amounts.
Similar crystallization processes were observed for
alloy 6 specimens undergoing various heat treatment
schemes as illustrated in Figs. 5(a) to 5(f). Figure 5(a)
shows the coexistence of single elongated needlelike
phase, identified as Mg2 Ni using the corresponding
diffraction pattern in Fig. 5(b), in the amorphous matrix
for alloy 6 ribbons heat-treated at 150 ±C for 30 min.
Heat treatment of alloy 6 ribbons at the higher tem-
perature of 190 ±C for 10 min resulted in an increased
amount of Mg2 Ni phase embedded within the amorphous
matrix as shown in Figs. 5(c) and 5(d). Figure 5(e) shows
that heat treatment of alloy 6 ribbons at 250 ±C for 15 min
finally led to precipitation of multiple phases consisting
mainly of Mg2 Ni and Mg12 Nd as shown by the diffraction
pattern in Fig. 5(f).
Results for alloy 8 specimens after heat treatment are
also shown in Figs. 6(a) to 6(d). Heat treatment at 220 ±C
for 30 min resulted in precipitation of nanosized Mg3 Nd
spherulites as shown in Figs. 6(a) and 6(b). Additionally,
as shown by the diffraction pattern in Fig. 6(d), Mg2 Ni
precipitates in the specimen heat-treated at the higher
temperature of 300 ±C for 30 min.
D. SEM results
Figures 7(a) and 7(b) compare the surface corrosion
morphologies after 30 min immersion in 3% NaCl solution
saturated with Mg(OH)2 of alloy 3 ribbons before and after
prior heat treatment at 180 ±C for 30 min, which gives
Mg3 Nd spherulites within the amorphous matrix [Fig. 4(a)].
The corroded surface of the unheat-treated sample shown in
Fig. 7(a) is characterized by localized attack which results
in high density of perforations surrounded by voluminous
corrosion product. In contrast the corroded surface of
heat-treated ribbon shown in Fig. 7(b) consists mainly of
voluminous corrosion product distributed uniformly over
the surface. The corrosive attack is relatively more homo-
geneous with lower perforation density after heat treatment
in comparison with the one before heat treatment.
IV. DISCUSSION
The detrimental effects of Ni together with Fe and
Cu on corrosion resistance of crystalline Mg alloys
have been long attributed to microgalvanic reactions
between Ni, Fe, or Cu-based dispersoids and the a-Mg
matrix. Hanawalt et al.8 have studied extensively the effect
of trace amounts of Ni and Fe on corrosion resistance
of Mg-based crystalline alloys. Their study showed that
when the amount of Ni, Fe, or Cu in the alloys exceeds
a tolerance value, typically 100 ppm, the corrosion rate
increased sharply to over 2000 mpy. Although all our
samples have much higher Ni content well over 100 ppm,
1641
 C. H. Kam et al.: The effect of heat treatment on the corrosion behavior of amorphous Mg – Ni – Nd alloys

FIG. 4. Bright-field TEM micrographs and corresponding diffraction patterns for alloy 3 heat-treated under the following conditions:
(a, b) 170 ±C for 30 min, (c, d) 180 ±C for 30 min, and (e, f ) 250 ±C for 15 min.

the present results show that their dissolution corrosion rates
for the fully amorphous alloys are well below 2000 mpy
(Table II). The low dissolution rate of our present alloys
containing a high content of Ni (at least larger than 5 at.%)
can certainly be attributed to the fact that all the samples
are fully amorphous so that no Ni-containing particles were
present and all Ni atoms are embedded in the Mg matrix.
It is notable that alloy 8 with the highest amount of total
alloying content of Ni and Nd among the samples studied
had the lowest dissolution rate. This shows clearly that the
detrimental effects of Ni can be significantly reduced if
the microgalvanic effect is eliminated even when the Ni
content in the Mg alloy is high.
As expected, the corrosion rates increased sharply
to well over 2000 mpy (Fig. 2) when the samples were
fully crystallized to give a mixture of Mg2 Ni and Mg12 Nd
(or Mg3 Nd) present after heat treatment at high tem-
peratures [Figs. 4(e), 4(f), 5(e), 5(f), and 6(c, d)]. The
sharp increase in corrosion dissolution rates can be at-
tributed to microgalvanic effects between the crystalline
phases Mg2 Ni and Mg3 Nd or Mg12 Nd which have different
electrochemical potentials. This is consistent with other
observations of Rugg et al.7 and that in rapidly solidified
Ni containing Mg–Mn microcrystalline alloys there were
still microgalvanic reactions between the Mg –Mn matrix
and the interpenetrating network of Mg2 Ni, which results
in poor corrosion resistance.
However, it is necessary to explain why some of the
partially crystallized samples in the present study showed
even lower dissolution rate than corresponding fully amor-
phous samples (Fig. 1). For example, after heat treatment at
190 ±C for 15 min, our XRD [Fig. 3(b)] and TEM results
[Figs. 5(c, d)] showed that large amounts of needlelike
Mg2 Ni were present in the amorphous matrix of alloy 6
ribbon. However, its corrosion rate was one-third of that of
the corresponding amorphous sample (Table II). It is also
notable that alloy 8, which has the highest Ni as well as Nd
content among the alloys, showed a similar trend of reduced
corrosion rate for the partially amorphous sample after heat
treatment [Fig. 1(c)]. The corrosion rate reduced further

1642 J. Mater. Res., Vol. 14, No. 4, Apr 1999

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 C. H. Kam et al.: The effect of heat treatment on the corrosion behavior of amorphous Mg – Ni – Nd alloys

FIG. 5. Bright-field TEM micrographs and corresponding diffraction patterns for melt-spun alloy 6 heat-treated under the following conditions:
(a, b) 150 ±C for 30 min; (c, d) 190 ±C for 10 min; (e, f ) 250 ±C for 15 min.

to half of its original value compared with the untreated
fully amorphous sample. This shows that crystalline Mg2 Ni
present on a sufficiently fine scale in an amorphous matrix
which is protective has only a limited effect on the corrosion
performance.
The beneficial effects of rare earth additions on the
corrosion properties of rapidly solidified crystalline Mg
alloy are well documented.7 In the present study alloy 3 had
a high content of Ni with a low content of Nd, while alloy 6
had a low content of Ni with a low content of Nd while alloy
8 had a high content of both Ni and Nd. The dissolution
rates of alloys 3 and 6 whether fully or partially amorphous
are, however, quite comparable (Table II) and alloy 8 has
the lowest corrosion dissolution rate. Precipitates of Mg2 Ni
in the amorphous matrix of alloy 6 or Mg12 Nd in the
amorphous matrix of alloy 3 did not make very much
difference to their corrosion dissolution rates (Table II).
The effect of Nd on the corrosion resistance of our present
amorphous alloys is thus not clearly shown by our results.
Formation of a protective film on the surface of the
heat-treated samples may not be the reason for the de-
crease in corrosion dissolution rate after treatment. Our
preliminary XPS studies9 showed that, qualitatively, heat
treatment has not caused significant change in the com-
position of oxide film of the sample. The corrosion prod-
ucts were also similar for the samples with and without
heat treatment. Rigorous quantitative analysis is neces-
sary to evaluate whether the structure and composition
of the oxide film change during heat treatment and cor-
rosion. Also, an in-depth assessment of the protective
nature of the oxide film formed on the heat-treated sam-
ples could be accomplished by application of electro-
chemical techniques.
V. CONCLUSIONS
Amorphous Mg–Ni–Nd alloys partially crystallized
specimens by heat treatment give low dissolution rates
in 3% NaCl solution compared to before heat treatment,

J. Mater. Res., Vol. 14, No. 4, Apr 1999 1643

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 C. H. Kam et al.: The effect of heat treatment on the corrosion behavior of amorphous Mg – Ni – Nd alloys

FIG. 6. Bright-field TEM micrographs and corresponding diffraction patterns for melt-spun alloy 8 heat-treated under the following conditions:
(a, b) 220 ±C for 30 min; (c, d) 300 ±C for 30 min.

FIG. 7. SEM micrographs for alloy 3 ribbons after immersion in a 3% NaCl solution for 30 min: (a) with no prior heat treatment and
(b) with prior heat treatment at 180 ±C for 30 min.

while in contrast, fully crystallized specimens exhibited
relatively high dissolution rates. The former result is not
associated with any protective surface film formation and
can be attributed to low corrosion current between finely
distributed intermetallic phase and the amorphous matrix.
The latter result, on the other hand, is attributed to mi-
crogalvanic action between the multiple crystallized phases
then present.
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1644 J. Mater. Res., Vol. 14, No. 4, Apr 1999

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