2. 56
rapid solidification processing (RSP), which improves the corrosion resist-
ance by reducing the scale of the microstructure and effectively distributing
the corrosion more evenly. In addition, RSP may increase the extent of solid
solubility which can be important for the creation of stable, passive films or
allow the use of more active (relative to Mg) alloying elements, such as
certain rare earths.
Active metals, such as magnesium and its alloys, are subject to pitting
corrosion due to the presence of discontinuities in the protective surface
film. Sources of film discontinuities are many, varying from emergent screw
dislocations to macroscopic inclusions [3], some requiring time to activate
before pits are observed [4]. Impurity phases of metals such as Fe, Ni and Cu
are ideal pit initiation sites because of the associated break in the protective
film combined with the low hydrogen overvoltage of the impurity phase.
Microgalvanic corrosion between Mg and these metals is spontaneous in
aqueous solution and accelerated by the presence of chloride ions [5]. Once
initiated, pit growth is auto-catalytic and occurs at an accelerating rate, with
the locally acidic environment preventing repassivation within the pit.
Hydrogen gas is produced at the cathodic sites and can be collected as a
method of determining corrosion rate by stoichiometric calculation with the
overall corrosion reaction [4,5]:
Mg + 2H20 = Mg(OH)z + H2 (1)
Note that, within the pit, the presence of a high concentration of chloride
ions prevents proton recombination initially and produces a locally acidic
solution.
Hydrogen evolution has been used previously [6-9] as a technique for
monitoring the corrosion of active metals, particularly Mg. One aspect of
this method that is quite intriguing is the observed 'negative difference
effect' in which the corrosion rate measured by hydrogen evolution is less
than that measured by weight loss. This effect has been ascribed to a number
of causes, including the loss of metallic Mg particles, monovalent Mg,
undermining and loss of heavy metal impurity particles, and film damage
and repair processes [6,10-15]. Since monovalent Mg has not been
observed, undermining of impurity particles would not necessarily produce
a large difference in weight, metallic Mg particles would not be stable
(would eventually corrode), and film repair is not important in stable pits,
these explanations are less than satisfactory. Two alternative explanations
are offered within the context of the current study. One source of the
difference is the weight loss contribution from second phases, such as
Mg17AI12' which are stable when exposed to the solution. These phases are
ultimately lost with the corrosion product. The second is that, during pitting
57
corrosion, protons are produced within the pit, many of which combine to
form hydrogen gas. However, as the pit grows a significant proportion will
remain as H+in response to the high CI- concentration within the pit, and are
responsible for the increased acidity. Thus, the proportion of protons which
do not eventually combine to form hydrogen gas will cause an apparently
lower corrosion rate when measured by hydrogen evolution.
Early studies of the corrosion resistance of Mg and its alloys in aqueous
environments produced very erratic results. In a classic study, Hanawalt,
Nelson and Peloubet [16] found the inconsistencies to be a result of
extremely small amounts of impurities, one of the most insidious being Fe.
They determined a 'tolerance limit' for Fe in unalloyed Mg of 0.017wt%,
above which the corrosion rate increased markedly beyond the passive rate
of 12 mils per year. The addition of lOwt% AI to the Mg decreased this limit
to 0.0002wt% Fe or lower. In addition, Mn was shown to have a beneficial
effect on the Fe tolerance limit, at concentrations of 0.2wt%Mn for high AI
alloys. No Mn additions were made to the alloys in the current study. More
recent work by Hillis [1] on die-cast material suggested that the sensitivity to
Fe is not as large as the Hanawalt study indicated. This discrepancy may be
due to the difference in coarseness of microstructure between the mold-cast
alloys in Hanawalt's study and the die-cast alloys in Hillis' study. Given this
effect of microstructural scale, it is expected that further refinement, such as
that derived from RSP, will increase the tolerance limit for Fe still more.
This has been observed in other work on Mg alloys [6] and appears to be the
case in the current study in which the tolerance limit is not well defined and is
well above Hanawalt's limit of 0.0002wt%.
The results presented here compare the sensitivity to Fe content of the
corrosion of RSP Mg-AI extrusions to that of conventionally-cast Mg-AI ,
alloys. The extrusions were produced from atomized powder containing
differing Fe levels, between 0.003 and 0.020wt%. The lower sensitivity to Fe
content for the RSP product is explained in terms of microstructural
refinement. In addition, the corrosion forms , rates and products are
characterized.
2. Experimental Procedure
The Mg-15wt%AI extrusions used in this study were produced in a prior
research program [17] by extrusion of RSP atomized powder. AZ31HP, an
experimental high purity version of AZ31B, was used as comparison
material known to display good corrosion resistance in wrought form. The
composition of each of the extrusions, including analyses for Fe and Ni, are
shown in Table 1. The Mg-15wt%AIextrusions were provided as rod 10 mm
in diameter and the AZ31HP as extruded plate 10 mm in thickness. The
amount of oxygen present in the atomizing gas during powder production
3. 58
TABLE 1
Results (wt%) of wet chemical analyses of alloys
Element Extrusion-A Extrusion-B Extrusion-C AZ31HP
AI 14.5 14.5 15.0 2.9
Zn nfa nfa nfa 0.69
Si nla nfa nfa 0.01
Mn nla nfa nfa 0.23
Fe 0.003 0.009 0.020 0.004
Ni 0.001 0.002 0.002 0.005
Sn nfa nfa nla 0.05
Pb nfa nfa nfa 0.03
Cd nfa nfa nla 0.03
Mg bal bal bal bal
Data provided by T. Wilks, Magnesium Elektron Ltd, UK.
nla = not analysed. .
Added oxygen contents ofthe atomizing gas used to produ~e powders for extrusIOns A , Band C
were 1.0 percent, nil and nil respectively with 1.0, 011 a.nd 0.1 percent added oxygen ,
respectively in the collector system. Classification of resultmg powders was done m argon
without added oxygen.
was varied as shown in Table 1. Such low levels of oxygen were necessary to
allow safe handling of the powder.
The corrosion rate of each extrusion was determined by measuring the
rate of hydrogen gas evolution from a specimen when immersed in
3wt%NaCI aqueous solution saturated with Mg(OH).z' All tests . were
conducted at room temperature (22 ± 3°C). The corrosIOn test specImens
were cut into shapes with either square, circular or semicircular cross
section, depending on the product form. All surfaces were then ground on
600 grit silicon carbide paper, thoroughly rinsed in met~anol , followed .by
drying, weighing and dimensional measurement: HandlIng w~s done Wlt~
plastic tweezers and the specimens were stored In sealed plastIC bag~ untIl
tested. During corrosion testing the specimens were suspe~ded In the
solution by polypropylene clips fashioned to contact ~he specu~en. at two
opposing points. The hydrogen evolved from the specImen dUrIng Immer-
sion in the solution was collected in a calibrated burette. Measurements
were made hourly until the corrosion rate stabilized. Selected specimens
were later stripped on their corrosion product by immers~on in boiling 1~%
chromic acid containing 1% silver nitrate and then rinsed In tap water, drIed
and weighed to determine the corrosion rate by weight loss. .
By filtering the used NaCI solution following a tes.t, t~e Ins.oluble
corrosion product of each extrusion was collected.. FollOWIng aIr ~ryIng for
several days, this product was analyzed by X-ray dl~~actometry wlt.h Co K-
alpha radiation using standard techniques with a PhIlIps PW 1700 dIffracto-
meter. The ASTM procedure for the identification of compounds was used.
59
The microstructure of each extrusion was studied in the unetched
condition. Standard metallographic techniques were used with the excep-
tion of the use of MgO powder in deionized water for the final polishing step.
Selected corroded specimens were mounted in transparent epoxy, ground
and polished. Photomicrographs were taken at several different magnifica-
tions of the metal/corrosion product interface. By placing small drops of the
NaCI solution on a polished specimen surface and focussing through the
solution, in situ observation of the corrosion process was carried out and
recorded photographically.
A CAMSCAN Series 2 scanning electron microscope (SEM), in conjunc-
tion with a LINK Systems X-ray Digital Analyzer, was enlisted to find and
identify impurity phases that could have been responsible for the large
differences in corrosion behaviour between the three Mg-15wt%AI extru-
sions. The method adopted to locate these phases was to allow a polished
surface to corrode in the salt solution for approximately 30 minutes, rinse in
methanol and dry. Cathodic particles were then located in the secondary
electron imaging mode by a 'halo' of corrosion debris. Photomicrographs
were taken at several magnifications in both secondary and backscattered
modes and X-ray energy spectra were recorded for selected areas of each
microstructure to characterize the various phases present.
3. Results
3.1 Corrosion Rates
Plots of the corrosion rates (average of two or three specimens per
condition) determined by hydrogen evolution are shown in Figure 1. The
corrosion rates were evaluated, assuming an alloy density of 1.8 X 103 kg/
m3
, from the equation:
C.R. (mpy) = 2150.64(v/AT) (2)
where V is volume of hydrogen evolved in ml , A is surface area of specimen
surface in square centimetres and T is immersion time interval in hours.
Equation (2) is based on the overall corrosion reaction (1). Study ofthe plots
reveals substantial differences in the steady state corrosion rates of the three
Mg-15wt%AI extrusions. These are shown in Table 2. The results are
probably affected by the formation of a proportionate amount of AI-
containing corrosion product. Due to its higher valence, aluminum can form
1.5 moles of hydrogen per mole of metal , and the apparent corrosion rate
predicted by equation (2) may be slightly higher than that for unalloyed
magnesium.
4. 60
a
a
N
Q)
U.
oe.C')
a
a
a
«
Q)
a;-u.
~ u.0
~OJ 0
a .,.a a
0 a
2-CD
c..
::c a
~
a
«
en
E.CII
E
t=
c
0
'iii...CII
E
.s
C
.9
;
'0
'"
0
'"Z
~0
«)
"0
"....
~
:>
.D
.=
".§
!:
0
.~
"E
.§
'0
!:
0
"B
!:
:>
""'co
'"
'"!:
.9
;
'0
>
"!:
"0/)
0
....
"0
>-
..c:
>-
.D
"0
"!:
.§
....
".,"0
'"
'"'"B
e
!:
0
'v;
0
....
:5u
'":>
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co
t:
19
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61
TABLE 2
Measured stable corrosion rates (mils per yr) of RSP Mg-15wt%AI and wrought ingot AZ31 HP
alloys (mpy)
Extrusion Instantaneous
(hydrogen)
EWLCR (hydrogen) True (weight loss)
Extrusion-A
Extrusion-B
Extrusion-C
AZ31HP
4
178
2267
5
4
167
1691
10
7
196
2030
13
By measuring the cumulative volume of hydrogen evolved from each
specimen, the equivalent weight loss corrosion rate (EWLCR) could be
determined for proper comparison with actual weight loss data. Plots of the
EWLCR are shown in Figure 2 with the points for the weight loss data. The
actual (true) weight loss corrosion rates, determined gravimetrically, were
evaluated from:
EWLCR (mpy) = 191601O.S(W/ST) (3)
where W is weight loss in grams, S is surface area in square centimetres and T
= total immersion time in hours.
The closed point symbols in the plot are actual weight loss data for
comparison.
The effect of Fe content on the corrosion rate is shown in Figure 3 by
plotting the true weight loss corrosion rates of the three Mg-1Swt%AI
extrusions against Fe content. The three data points indicate an exponential
dependence on Fe content. Figure 3 also includes the data of Hanawalt [16]
for mold-cast Mg-lOwt%AI alloys. The fitted curves show a difference in
corrosion rate of at least two orders of magnitude between the two sets of
results for Fe contents less than O.OOSwt%.
3.2 Identification of Corrosion Products:
Mg(OH)z (brucite) was identified as the dominant corrosion product for all
alloys tested and the only corrosion product for AZ31HP. X-ray peaks
corresponding to MgJ7AIJ2 were also identified in the corrosion product of
the RS Mg-1Swt%AI extrusions. Diffraction peaks from an unidentified
third phase were also observed, corresponding to the following d-spacings
(Angstoms): 8.1S, 4.09, 2.60 and 1.S3. These displayed some degree of peak
broadening. It is likely that other peaks of low intensity belonging to this
phase were present but these coincided with those of the other compounds.
Positive identification of this phase was not achieved, although the ASTM
5. 10000,~--------------------------------~--------------------------'
• C - 0.020%Fe
~ 1000
.sQ)
-;
II:
c:
o
VI
o
~
o
o
VI
VI
o
-I
-.c
OJ
Q)
;:
0-
W
100
10
B - 0.009%Fe
AZ31 HP (0.004%Fe)
_ _ _ _t
A - 0.003%Fe
o 100 200
Immersion Time (hrs)
FIGURE 2 Effect of immersion time on equivalent weight loss corrosion rates as determined by hydrogen evolution (solid lines) with symbols
representing data from direct weight loss experiments.
>-
a.
E
Q)
-;
II:
c:
o
VI
g
o
o
VI
VI
o
-I
.1:
OJ
Q)
;:
ra
~
u
<I:
10000 r'----------------------------------------------------------------,
1000
100
10
III RS Mg-15AI
• Slow-cooled Mg-10AI [4]
0.010 0.020
Fe level (%)
FIGURE 3 Effect of iron content upon true weight loss corrosion rate for RS Mg-15wt. % Al (present work) compared with results of Hanawalt [4]
for conventionally cast Mg-lOwt. %Al.
0
tv
0
(;.l
6. 64
search manual showed it to closely match those of Mg6AI2C03(OH)16.4H20
(hydrotalcite) . The match was generally good, except that the c-dimension
of the hexagonal hydrotalcite unit cell appeared slightly compressed (by
about 5%) compared to the tabulated value. This may be a result of the
substitution of chloride ions for hydroxyl ions in the lattice, which has been
similarly suggested for Mg(OHh [5, 18].
Cathodic second phases in the microstructures were identified by X-ray
diffractometry of saw filings from each alloy. The data revealed only
metallic magnesium in AZ31HP and metallic magnesium plus Mg17A112 in
the RS Mg-15wt% AI extrusions. Intensity calculations, based on the peak
areas, showed that the relative volume fractions of Mg17A11 2 in the Mg-
15wt%AI extrusions were within 10 percent of one another.
3.3 Light Optical Microstructures
The longitudinal microstructures of the extrusions are shown in Figures 4a-
c. The scale and character of the RSP extrusions are similar in all but two
respects. The first is the amount of interparticle oxide, which appears dark in
the micrographs. Extrusion A contained the largest amount of oxide while
extrusion B contained the least which corresponds to the amount of oxygen
present in the argon atomizing gas. The oxide level appeared not to affect
the corrosion rate. The second is the presence of hard, spherical particles in
extrusion B (Figure 4b). Previous analysis showed these particles to be
enriched in aluminum [17], and it is likely that they are powder particles
containing a somewhat higher volume fraction of Mg17AI12 than the
remaining matrix. Poor mixing in the crucible could have caused a small
proportion of the atomized powder to have a higher AI-content, with only a
small reduction in the AI-content of the bulk. The particles, in some cases,
exhibit substantial plasticity, being elongated by the extrusion process
(Figure 4b). It has been shown [19] that unalloyed Mg17AI12 is very brittle
below about 400°C. Since the extrusion took place at 200°C or less, the
particles would have fractured if they were composed entirely of Mg17AI12'
as was observed in the AZ31HP samples.
3.4 Metaliographic Sections of Corroded Specimens
The sections failed to reveal any microstructural feature causing preferential
corrosion for any of the extrusions. Nonetheless, there was a lack of attack
of the spherical particles in extrusion B and they were observed to be spalled
unaltered with the corrosion product in several cases (Figure 5). This
indicates that the AI-content in the particles may have been high enough to
induce passivation by a compound more stable than the usual Mg(OHh-
Recent work [2, 20] has shown that AI-contents in excess of approximately
30wt% induce very good corrosion resistance. While pitting was the primary
65
(a)
(b)
(c)
FIGURE 4 Light optical microstructures: (a) Mg-15wt. %Al-O.003wt. %Fe (extrusion A), (b)
Mg-15wt .% Al-O.009wt. % Fe (extrusion B) and (c) Mg-15wt. % Al-O.020wt. %Fe (extrusion C).
7. 66
FIGURE 5 Hard spherical particle spalled with corrosion product without significant
corrosive attack.
mode of corrosion in all specimens, those with the lowest Fe content,
AZ31HP and extrusion A, experienced less severe attack.
3.5 In Situ Observation of Corrosion
The corrosion of the extrusions was observed to proceed by two different
modes, pitting and filiformt. These are shown in Figure 6. Pitting was
indicated by slow hydrogen bubble growth and discharge at specific sites in
the microstructure, although the exact nucleation sites were not identifiable.
The'bubbles would nucleate very quickly (within 10 seconds), slowly grow to
a critical size in the course of minutes, and detach, after which the process
would repeat. At the most active sites, usually an Fe-rich particle, a 'halo'
[21] of corrosion product and debris was observed to develop around the
site. The corrosion product was usually fractured (Figure 7), and was found
to be enriched in Mg and chlorine by SEM analysis. Upon rinsing, the sites
appeared light gray to the naked eye. The filiform corrosion was charac-
terized by small, meandering trenches, in which the head would rapidly
t The filaments were not filiform corrosion in the classic sense in that no surface coating was
present and it occurred in complete immersion. Filiform corrosion is usually defined as
occurring in humid air beneath coatings (viz. paint) [22]. Its formation on bare metal exposed to
bulk solution has scarcely been reported [3, 10] and it seems likely that a different mechanism
may be operative.
(a)
•
(b)
• ••II· ~ ~.
•"
,"
..
.. «
. .-•
.,.
: ~...:'.
." ."
.. . . . " >
..... .
. '.,.
" -
'.
67
1' •
• !...e . 'It ': :. " ..1
C-. ~ --
.~ " '.II .. '" •
: ... ' .
' . .~.•'.. .' . ~
.. ~ ..
~ .. . O.5h1m
." I. '.
"
....
....-:- . ~
''e ......, ..4 ' . • !tr
.. ' "" "" .. • •..
FIGURE 6 In situ observation of corrosion of extrusion B: (a) 15 seconds exposure to
solution , (b) 210 seconds exposure. Dark circles are hydrogen bubbles which are slowly
growing. Wavy features are "filiform" corrosion.
8. 68
FIGURE 7 Scanning electron micrograph of corrosion product imbedded in a filament trail.
evolve tiny hydrogen bubbles in a continuous stream and leave behind a trail
of imbedded corrosion product. Figure 8 portrays this process as it occurred
in extrusion B. It is also notable that the filiform corrosion occurred
preferentially in the extrusion direction of the longitudinal section, perhaps
finding propagation more easy along the interparticle oxide/metal interface.
This was verified by placing an intentional scratch nonparallel to the
extrusion direction and observing filiform branches to extend from the
scratch in the extrusion direction. Filiform corrosion appeared to nucleate at
any significant surface discontinuity, particularly the specimen corners.
3.6 Scanning Electron Microscopy:
Although general surveys of the slightly corroded specimens by SEM
revealed no Fe-rich particles in extrusions A or AZ31HP, a number were
found on extrusions Band C. Subsequent SEMIEDAX analysis of the
particles in extrusion B showed them to contain primarily Fe (with trace Mn,
V, Cr or Ni) . Figure 8 shows a typical Fe-rich particle in extrusion B with
results of EDAX analysis. Analysis of cathodic particles in extrusion C
indicated they were also Fe-rich, Figure 9. This might be expected from the
chemical analyses of the extrusions. In some cases, the size of the Fe-rich
69
(a)
UF
c U
~ c aC U 'i F
}. I .~ ~ fI v ,':, !
t-......!!'-LJ!111I...-~~. ~-'-'--::::. J;~~, .... ... . ~.' .........l "'.. A
1+. 880 k eU 10•0 >
FS= 16K ch 25L+= 101+9 cts
r1Ef11 : f'lG15AL EXT?,- FE-RICH PARTICLE
(b)
FIGURE 8 (a) EDAX spectrum of Fe-rich particle in extrusion B. (b) electron micrographs
of partIcle (secondary electron Image on left, back-scattered image on right).
9. 70
region was much smaller than the secondary electron image would suggest,
due to a reaction layer surrounding the particle (Figure 9).
4. Discussion
To understand the corrosion behavior of the alloys and the reason for the
strong influence of Fe content, the mode of dissolution must be discerned.
Some insight can be gained by study of the dependence of corrosion rate on
immersion time shown in Figures 1 and 2. A notable feature of the curves is
the rise in dissolution rate during the initial 5 to 10 hours. This behavior is
most evident in specimens Band C, which contained the highest Fe
concentrations, 0.009 and 0.020wt%, respectively. Since pitting was visually
observed on these specimens, the initial rise is probably a result of pit
initiation and formation at certain favorable sites on the surface. Once the
pits are well developed, i.e. increasing in depth rather than diameter, the
corrosion rate will be limited by ion transfer into and out of the pit and will
stabilize. The increase in rate for Band C may also be related to the delayed
activation or exposure of pitting sites. Once all the available sites are active,
the stable corrosion rate for the specimen will depend largely on their
number and size. If one assumes that the principal active sites are due to Fe
particles, then for particles above a critical size, there should be a
correspondence of corrosion rate with the number of pitting sites. There is
also an effect of particle size in that larger particles will provide more surface
for the liberation of hydrogen gas and produce a larger local current density
around the particle. Thus, the presence of either larger or more Fe particles
in extrusion C accounts for its higher corrosion rate and corresponds with
the wet chemical analysis. Unfortunately, because of the very low concen-
trations of Fe, only very few particles can be located on a specimen of
manageable size. In addition, some pit-initiating particles are probably lost
in the corrosion process once the pit has developed and undermined the
particle. Simple calculation shows that Mg-15wt%AI, containing
0.009wt%Fe, will contain only 27 pure Fe particles of 10 !-tm diameter in a
cross section of one square centimetre. Thus, insufficient numbers of
particles were located for statistical characterization of particle size and
number distributions.
Comparison of the actual weight loss corrosion rates with the EWLCR
values from the hydrogen evolution tests showed good correspondence for
all alloys (Figure 2), and demonstrated the validity of the technique.
However, in all cases there was a consistent negative deviation from the true
weight loss values of the corrosion rate determined by hydrogen evolution.
This type of deviation has been noted previously in tests of this type and is
generally attributed to the negative difference effect [6, 10-15]. In the
present study, a large proportion of the weight loss discrepancy can be
71
(a) F
,
I, I
I
;
I
,.
" ~9 F
I
t
~ S C C C M
r ZiI
,
1 i 1 r n I n
!.f. 880 ko::U 10.0 >FS= 16K ,~h 25!.f= 395 C"t$
r'lEN1: r'16 1SAL E::<Tl I) FE PARTICLE CErHER
(b)
1.0mm
FIGURE 9 (a) EDAX spectrum of Fe-rich particle with reaction zone in extrusion C.
(b) Back-scattered electron image of particle.
10. 72
accounted for by assuming that the Mg17A112 particles are not dissolved. The
presence of Mg17A112 in the corrosion product filtrate and the observation of
barely visible shiny particles in the corrosion product (Figure 10) supports
this assumption.
The effect of Fe content on the corrosion rate, plotted in Figure 3, with the
results of Hanawalt for lOwt%AI shows that processing route also has a
strong effect:!:. Hanawalt's alloys were cast in refractory molds, in which the
alloys solidified at typically low rates. The comparison thus indicates that a
higher solidification rate decreases the sensitivity to Fe content. This
improvement has also been observed in other RSP Mg alloys [22, 23], in die
cast Mg-AI alloys [1, 5], for RSP AI-base alloys [24], and has been generally
explained in terms of reduced segregation. Rapid solidification may reduce
both the size of cathodic second phases, and their volume fraction, by
solubility extension. Counter to this effect, for Mg-AI alloys, is the presence
of AI, which increases the amount of Fe-bearing phase by compound
formation.
FIGURE 10 Cross-section of metal/corrosion product interface in extrusion B showing shiny
Mg17A11 2 particles in corrosion product.
:j: The comparison between 10 and 15wt%AI is valid in this case because Hanawalt clearly
showed that higher Al contents exaggerate the effect of Fe in mold-cast alloys. It is therefore, a
conservative comparison.
73
The solubility of Fe in Mg is extremely limited and they form no
compounds [25]. Therefore, the addition of aluminum to Fe-contaminated
Mg would readily produce precipitation of AI-Fe compound(s) which have
melting points well above alloy melt temperatures (assuming no ternary
compounds). This would result in solid AI-Fe particles suspended in the melt
to be incorporated into the Mg-AI powder particles resulting from atomiza-
tion. Subsequent consolidation/extrusion of the powder would produce a
fine dispersion of Mg17AI12 precipitates, as indicated by the X-ray results, in
a Mg matrix, with occasional Fe-rich particles. Thus, RS of impure Mg-
15wt%AI causes the Fe-rich particles to be in contact with Mg17AI12
precipitates encased by a Mg matrix. In contrast, conventional slow
solidification rates will result in large dendrites of relatively pure Mg
surrounded by interdendritic Mg/Mg17AI12 eutectic. When an Fe-rich
particle is placed in the microstructure, the developing pit will likely
incorporate dendritic regions enriched in Mg. These two scenarios are
illustrated in Figure 11. There are three advantages, from a microgalvanic
corrosion viewpoint, of the RSP microstructure: (1) the Mg17AI12 precipi-
tates are passivated and apparently not dissolved to an appreciable extent by
the solution. This creates a more tortuous path for ion transfer around the
particles during matrix dissolution in a pit; (2) the precipitates are left
imbedded in the corrosion product, possibly with some degree of inter-
connectivity, and may lend strength to the product which retards spalling;
(3) a high density of the particles may alter the composition of the protective
film which forms naturally in an aqueous environment to one which is more
stable.
Conclusions
1. The aqueous corrosion rate of RSP Mg-15wt%AI alloy is markedly
augmented by minute quantities of iron, as shown earlier for mold and
die cast alloys of this system.
2. Rapid solidification decreases the sensitivity of corrosion rate of Mg-AI
alloys to iron impurity content. This is considered to result from the
presence of passive precipitates in the microstructure which diminish ion
transfer within pits, stabilize the passive surface film, and strengthen the
corrosion product.
3. Filiform-like corrosion is observed, but is probably not a major contri-
buting mode of corrosion in this case.
4. Magnesium hydroxide is the dominant corrosion product. Another
compound is also produced by the RSP Mg-15wt%AI alloys which may
be a form of hydrotalcite.
11. 74
Corrosion Pit
Fe Particle
Solution
Corrosion Pit
Spalled
~ ____Corrosion
• Product
(a)
Pits Containing Corrosion
________ Product and Passivated
Solution
(b)
FIGURE 11 Schematic corrosion pit formation in: (a) conventionally-solidified coarse
microstructure with large Mg17AI12 particles not shown; (b) rapidly-solidified microstructure
with fine distribution of Mg-AI precipitates.
75
Acknowledgements
This work was the result of the 1989 F.M. Beckett Memorial Award for
overseas summer study provided by the Electrochemical Society and was
conducted at the University of Sheffield, Sheffield, England. Sincere
appreciation is expressed to the Electrochemical Society for providing this
opportunity, and to the faculty, staff and students at the University of
Sheffield for their cooperation and guidance. In particular, the contri-
butions of Elaine Leith, Robert Edyvean and David Rugg are gratefully
acknowledged for their advice and prior research relating to this work. The
RSP powder was atomized by Metalloys Ltd., as part of a study sponsored
by the Aluminium Powder Co. Ltd., Magnesium Elektron Ltd., Shell
Research Ltd. and the U.K. Department of Trade and Industry.
References
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