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CORROSIONC)L
201 The NACE International Annual Conference and Exposition
P,O. Box 48-3, C. P,62251 ,Cuernavaca, Mor. Mexico, 0 and Programa de Corrosion del
Golfo de Mexico, UAC,Ave.Agustin Melgar s/n, Campeche, Cam. Mexico.
ABSTRACT
Commercial magnesium anodes were evaluated using ASTM G97-89 as standard test
was also used . Cylindrical samples were cut from the as-cast Mg anodes. Several heat
treatments and different cooling rates were carried out. The anodic efficiency was
above the efficiency showed by the non-treated commercial anodes (as-cast condition).
The efficiency increments were related to the microstructural characteristics i.e particle
size and/or grain size. Also some morphological aspects were considered .The appearance
of second phase particles influences the different forms that the corrosion process
exhibits.
Keywords: Magnesium. Anodes, Heat Treatment, Efficiency.
Copyright
(31996by NACE International. Requests for permission to publish this manuscript in any form. in part or in whole must be made in writing to NACE
International, Conferences Division. P.O. Box 218340. Houston, Texas 77218-8340. The material presented and the views expressed in this
paper are solely those of the author(s) and are not necessarily endorsed by the Association. Printed in the U.S.A.
INTRODUCTION
The increasing demand for cathodic protection in the past few years for commercial
and domestic uses has given rise to widespread interest in new developements and
applications of galavanic anodes. Considerable amount of work has been done in the
past in order to improve the most important properties of the anodes. Considering mainly
the metal purity ) , the alloying elements (23), and backfill material(4). These studies
rarely exceeds 50Y0. This figure is unfavorable compared with that of other anodes, such
as Zn and Al which have current efficiencies better than 907.. Several factors have been
atributed to the low efficiency of the Mg anodes such as the thermal history related to
the structure effects and the alloying elements , changes
(34@) in anion and cation
concentrations which ocurr close to the dissolving Mg suflace and the anodic
electrochemistry 7).
Some significant local consumers of Mg-based sacrificial anodes, and specifically the
mexican national pipeline system are concerned with respect to the casting procedures
and the efficiency of the sacrificial anode materia which now ranges between 30% and
35%. Cathodic protection is now well established and required by law for pipeline
protection. There is, therefore, current interest in improving efficiency of Mg anodes.
Salinas et al.(8) pointed out that the metallurgical features of sacrificial anodes
(i,e.castings conditions, t,eat treatments, etc.) are related to the anode operation potential
and also to their own efficiency. In the Mg anodes, contrary to the requirements for
anode materials, the corrosion occurs by pitting rather by uniform corrosion, shifting the
potential to more electronegative values 9) However a very recent work 0) reported that
pitting was found under a local ) standard that use artificial sea water for the anodes
evaluation. Furthermore, the same authors 0) report that when using the ASTM standrad
for GALVOMAG (trademark of the Dow Chemical Co.) type anodes evaluation, they
201/2
found uniform corrosion, being this difference due to the solution used.
On the other hand, local consumers of Mg anodes pointed out that at present they
have several tons of low-efficiency Mg-anodes already cast in stock and they are
interested that these anodes could be rehabilitated instead of rejecting them. The low-
thus controlling the amount of second phase particles at grain boundaries, by producing
a uniform distribution of impurities in the matrix. The purpose of the present work is to
seek an alternative to improve the efficiency by using heat treatments and/or different
cooling rates in order to use directly the cast anodes instead of refining them, and where
possible, to correlate the microstructural observations with the efficiency obtained.
EXPERIMENTAL PROCEDURE.
A commercial magnesium anode of bulk chemical composition shown in Table 1 was
used for the present work. The chemical analysis was performed using a ICP
spectrometer,JY 24, technique that is strongly recommended from the ASTM standard.
From the this table it is clear that the Fe value is high compared to the typical value of
0.03% reported for these type of anodes. Also the Ni content is above of the typical
value of 0,001 IYO, Several cuttings were performed according to ASTM G97-89 14)in order
to obtain cylindrical anodes, The dimensions of the test anodes were 152x12.7 mm and
special care during their machining was necessary in order to avoid heating. These
anodes were lapped to a 240 grit finish and thoroughly cleaned and weighed, before the
electrochemical evaluation is carried out. In order to assess the effect of heat treatments
on the commercial anode, using the same specimens obtained for the ASTM tests.
Several cooling rates were used (i.e.50, 400 and 1000 OC/seg.) under an argon
atmosphere, using several holding times. The heating temperature was 400C, and from
this all the cooling rates were carried out. Also, two ageing treatments were performed
using 400C and 300C as the solution temperatures at different times ranging from 1.8
to 57.6 ks, than quench in water. The ageing temperature was 250 and 150C
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respectively at different holding times (from 1,8 to 57.6 ks.) Table 2 shows all the thermal
treatments been carried out in this work. Metallographic specimens were prepared and
photomicrographs were taken with Olympus PMG3 optical and a JEOL 6400 scanning
electron microscope equipped with an energy dispersive X-ray spectrometer. The
sacrificial anodes with and without heat treatment were evaluated electrochemical
according to ASTM G97-89 with the standard laboratory test method for magnesium
sacrificial anodes for underground applications 14) For this purpose, a known direct
current is passed through a test cell connected in series (galvanostatically method). Each
test cell consists of a preweighed magnesium anode specimen, a steel pot container,
and a solution of CaS04+Mg(OH)z. The specimens oxidation potential is measured
several times during the 14-day test and one hour after the current is turned off. At the
conclusion of the test, each specimen is cleaned and weighed, The ampere-hours
obtained per unit mass of specimen lost are calculated. The values obtained are shown
in Table 2, these values represent an average from 5 test specimen. Also ,the closed and
open circuit potential average values are shown. Attached to this arrangement the
electrochemical impedance technique (EIS) was used to follow the process and this is
an alternative that allow to study the changes at the interphase metal/solution, and from
this to determine the causes that may affect the corrosion behavior of the anodes. The
were generated over the frequency range of 100 mHz to 10 kHz, using a 10 mV peak-to-
peak AC perturbation. Using a software package from B. Boukamp 13), the results
obatined were processed. After assesment of the current efficiency, the specimens were
observed under a scanmng electron microscope (SEM) at 25 kV.
approximately of 10Opm, in the center of the anode (figure 1a). The microstructure mainly
consists of columnar grains of a-Mg. Few precipitates were observed at the interior of
the columnar grains at the equiaxed grains and at the grain boundaries (figure 1b). The
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microanalysis detected that the precipitates observed were mainly rich in Fe and
Mn(similar to the inset EDAX pattern in figure 2a). The heat treatments carried out in the
as-cast anodes modified substantial the microstructure and the microanalysis of the
precipitates. Figure 2a shows a micrograph obtained when the as-cast anode was heat
treated and cooled in air, showing columnar type structure with a substructure inside this
columnar grains with very fine precipitates, but these precipitates are concentrated near
the grain boundaries. Microanalysis indicate the presence of Fe and Mn in these fine
precipitates, and relatively high concentration of Mn being segregated as a second
phase particle ( the diagram is shown in the inset), Figure 2b, is the microstructure
obtained from the anode being solution treated at 300 C and then aged during 28.8Ks
at 150 C, It shows a needle-like structure associated with very fine precipitates, finely
distributed in the matrix, and the microanalysis showed the presence of Fe, Mn, Mg and
Al (the diagram is shown in the inset), The formation of Al and Mg particles at the grain
boundaries, indicates that this treatment may have redissolved the Fe-Mn particles to form
Mn rich second phase particles. Table 3, shows a resume of the main microstructural
parameters being observed and measured for the different heat treatment carried out
and table 2a shows the efficiency values obtained, From the data it can be observeda
that the efficiency increases as the particle size tend to decrease, specifically with ageing
treatments been carried at 300C. The morphology changes to spherical and the
chemistry of these particles changes with the appearance of compound of A1-Mg at the
grain boundaries help to obtain a higher efficiency. This situation may be due to the
presence of A1-Mg compounds at the grain boundaries acting as-local cathodes with
respect to the matix It has been reported that the benefit of Al is likely related to the
nature of an oxide of the type Mg-Al-oxide (Mg-rich) which is thinner with increasing Al
content 15) Also there is strong tendency for Al to form a stable passive film in certain
type of electrolyte, and there is lack of galvanic action between Mg and Al in Mg-alloys.
The low efficiencies found were related to the presence of insoluble particles of Fe-
Mn (Fe-rich) that together with the presence of Mn segregated as a second phase,
observed directly on samples been cooled in air and/or furanace, These precipitates and
segregates are not uniformly distributed, in some places the Mn was segregated and in
other regions only the Fe-Mn particles were observed on the grain boundaries, indicating
201/5
that during the corrosion test they act as a local galvanic microcells of strong cathodic
nature.
Since a complete discussion of the application of the EIS to corrosion studies is
beyond the scope of this paper, the reader is referred to the literature for more thorough
treatments 1617). However from the Nyquist presentation of the EIS data obtained for the
anodes exposed were adjusted to the electrochemical model of the double-layer (R[RQ]
[RQ] ). Figure 3 (a, b,c and d) represents the different electrochemical parameters being
respectively Rt, the resistance to the charge transference; Rp, represents the resistance
of the porous-layer; Cp the capacitance of the layer and Cdl, the capacitance of the
double-layer, all these parameters are shown as a function of time (duration of the test)
and are also realted to the different anode condition i.e. as-cast and heat treated.
Figure 3a shows the Rt value as a function of time, it can be observed that in the
anodes with low efficiency this value increases, this suggests that the formation of a
crystalline film of Mg(OH)z is forming and trying to consolidate, but Cp and Rp values
decrease, these may induce to think that the layer is not very adherent (Figs.3band
c) The anodes with high efficiency (around 50 Yof), the Rt values do not change with
time. Figure 3b, represents the Rp value as a function of time, it shows that for all the
treated anodes this value decreases, meaning that the porous-layer tends to consolidate
with time, For the as-cast nd the aged 300C/28.8Ks anodes, this value increases and
this may induce that the film is not well formed and is not adherent. Figure 3C represents
the Cp value as a function of time. The anodes being aged (300C and 400C, 1.8 Ks.)
and furnance cooled, showed no variation, and the anodes as-cast and aged at 300C
during 28.8Ks increases during the first seven days of the test, indicating that the
insulating properties of the film formed are not so good. The same behavior is observed
by the anode being cooled in air, but after the seven day of test, Further, from the seven
day to the fourteen day of test, the Cp value decreases, which suggests that the layer
is not well formed and it is not adherent. Finally, the Cdl value is shown in figure 3d. The
anodes being aged 300C during 18 Ks and 28.8Ks, showed a decrease of the Cdl value
which indicates a uniform corrosion. The rest of the anodes showed an increase in this
value, which suggests a localized or non-uniform corrosion.
Regarding the efficiency obtained related with the electrochemical parametres it can
201/6
be said that the anodes with low and intermediate efficiency showed an increase of the
Cdl values, and the anodes with high efficiency showed a decrease of the Cdl value.
The other parametres do not correlate with the efficiencies obtained. These results
indicate, the EIS measured the uniform corrosion only of the aged anodes relatively
accurately and when localized corrosion is manifested this technique is not very
adequate. Similar results have been previously reported for Mg 16>1g),
and in those cases
the authors attributed to this to either an anomalous valence effect due to the existance
undermining action. This is probably to occur because the particle, i.e. the Fe-Mn-rich
impurity phase, is cathodic to the surrounding Mg matrix, which corrodes rapidly at this
particle boundary by galvanic action, The particle subsequently falls out, resulting in a
mass loss much higher than that due only to the dissolution that is measured using EIS.
Almost all the anodes after the ASTM tests showed a non-uniform corrosion
appearnce when viewed with the naked eye or under low-magnification, The surface of
these specimens was observed more closely. Figure 4a is an SEM photomicrograph
showing the anode in the as-cast condition after ASTM test. As can be observed,
corrosion of Mg occurs preferentially in regions rich in second phase often subject to
localized segregation, elemental depletion or precipitation. Corrosion in these regions is
by pitting, forming a step-like pattern. The pits were quite deep and in many cases
showed cracks at their base, Figure 4b, shows the surface appearnce of an anode heat
treated (aged 400C, 18 Ks), with a very low efficiency (27.5Yo). It can be observed that
the corrosion pattern is almost similar to the pattern showed for the anode as-cast
(fig, 1a), i.e. pitting, forming a step-like pattern. Figure 4c, it is an anode heat treated
(furnance cooled,4000C/28 .8Ks), and shows a pitted region. Such pits are very deep and
certainly indicates accelerated non-uniform corrosive attack at high energy locations (i.e
grain boundaries and/or precipitates). Figure 4d, shows a uniform corrosion attack,
founded in the anodes heat treated (aged 300 C,28.8Ks), with high efficiencies (i,e.60%
or more) .This pattern was obtained inside the pits uniformly distributed along the anode.
This uniform attack was observed in almost all the anodes heat treated with high
efficiencies. Few spherical particles were founded, roughly lpm in diameter, such
particles were rich Fe-Mn and widely distributed over the surface. Inducing a relatively
201/7
uniform attack.
From the results obtained in this work and considering recent reports 12>13),
values
higher than 50% of efficiency were obtained, and these values are directly related to the
according with the particle and/or grain size measured in the as-cast anodes, the cooling
rate varied from 103K/s ( roughly 5pm in particle size) to 1021@ (roughly 10pm in particle
size), meaning a considerable refinement of the microstructure compared with the as-cast
anodes, that have particle and/or garin size of about 10O#m or bigger. On the other
hand, impurities such as Cu and Ni, and second-phase particles rich in Fe and Al were
partially dissolved by the heat treatment (aged). This gives rise to an incraese in their
efficiency and a uniform corrosion rather to localized corrosion (pitting).
CONCLUSIONS
1.Using certain specific heat treatments the efficiency of the Mg anodes were
imporved, and with this it is posssible to control the amount and size of the precipitates
and of the second phase particles localized at grain boundaries and at inside the matrix.
2. Lower efficiency was realated to the presence of Mn rich second phase particles
were corrosion ocurrs along a narrow region at the grain boundaries.
3.When uniform corrosion was observed on the tested anodes, the EIS technique is
a reliable method to evalute the corrosion process. Anodes with a non-uniform attack this
parametres. The solutior, could be the usage of an alterantive casting processes 12)and
heat treatments.
ACKNOWLEDGEMENTS
The authors are grateful for their technical support of L.A. Nunez, J. L.Albarran,
A. Gonzalez and O. Flores. This work was supported by the Programa de Corrosion del
Golfo de Mexico-Universidad Autonoma de Campeche and the Facultad de Quimica-
UNAM, Mexico.
201/8
REFERENCES.
1.H.A.Robinson and P.F.George, Corrosion,10(6) (1954), p.182.
2. H.A. Robinson, Trans. J. Electrochem. Soc.,90(1946), p.485.
3.J. D. Hanawalt, C. E, Nelson and J. A, Peloubet, Corrosion studies of Mg and its
15,A.Joshi and R.E. Lewis,in Advances in Mg Alloys and Composites, eds. H. Paris and
Corrosion Science, in Electrochemical Corrosion Testing (ASTM STP 727) ,F. Mansfeld and
U. Bertocci, Eds. (Philadelpia, PA:ASTM 1981), p,l 10.
18,R.L.Pettey, W. Davidson and J. Kleinberg,The Anodic Oxidation of Magnesium
Metal: Evidence for the Existence of Unipositive Magnesium, J.1 of the American
Anodically in Neutral and Acidic Solutions, J.of the Electrochemical Socl 10 (5) 1963,p.357
201/9
FIGURE AND TABLE CAPTIONS
Figure 1a.As-cast columnar-type microstructure with cell grains inside the columnar
grains.
Figure 1b. Detail of the as-cast microstructure. Cell grains observed inside the columnar
grains with fine particles and/or precipitates inside the grains.
Figure 2a. Microstructure obtained from theanode aircooled (4000 C/28.8 Ks), Columnar-
type microstructure with a substructure inside the columnar grains with fine precipitates.
The EDAX pattern shows the presence of Fe and Mn in these fine precipitates.
Figure 2b. Microstructure obtained after the anode was aged (3000 C/28.8 Ks).the
microstructure observed is a needle-like associated with fine precipitates finely distributed
in the matrix. EDAX pattern show the presence of Al, Mg, Fe and Mn in the fine particles,
Figure 3a and 3b. Represent the electrochemical values Rt and Rp as a function of the
testing time.
Figure3c and 3d. Represent the electrochemical values Cp and Cdl as a function of the
testing time.
Figure 4a. SEM micrograph showing the anode in the as-cast condition after the ASTM
test, It can be observed that the corrosion is by pitting.
Figure4b.SEM micrograph from the anode aged (4000C/18 Ks), after the test. Showing
a similar corrosion pattern as figure 4a,
Figure 4c. SEM micrograph obtained from the anode heat treated (furnance cooled
4000 C/28.8 Ks).The surface corroded shows pits, that indicates a accelerated non-uniform
corrosion.
Figure 4d. SEM micrograph showing the anode aged (3000 C/28.8Ks), after the ASTM
201/10
Table 1.Chemical Analysis of the Commercial Mg Anode (in wTXO).
cooled
201/11
Table 2. Electrochemical Efficiency of the Anodes After Thermal Treatments.
Circuit
CONDITION EFFICIENCY Potential(mVj
(%)(a) (b)
open closed
201/12
Figure 1a. As-cast columnar type microstructure with cell garins inside the columnar
grains.
Figure 1b. Detail of the as-cast microstructure. Cell grains observed inside the
columnar grains with fine particles and/or precipitates.
201/13
Figure 2a, Microstructure obtained from an anode cooled in air (4000 C/28.8Ks).
Columnar-type microstructure with a substructure inside the columnar grains with fine
precipitates. The EDAX pattern shows the presence of Fe and Mn in these fine
precipitates.
Figure 2b, Microstructure obtained after the anode was aged (3000 C/28 .8Ks) .The
microstructure observed is a needle-like associated with fine precipitates finely
distributed in matrix. EDAX pattern show the presence of Al, Mg, Fe and Mn in the fine
particles.
201/14
1,600
1,400
f
1,200
/
/
1,000 -As-cast
/
ii y fc 400 C/8hrs.
/
800 /
*aged 300 C/5hrs.
+ ac 400 C/8hrs.
/
600 / *aged 400 C/5hrs
200 /----
. -,
k-. > -
0 5 10 15
time (days) Figure 3a
2,500 + As cast
-F fc 400 C/8hrs.
1,500
1,000
500
-o 5 10 15
201/15
0,0071
x
0.006
0,005
+ aged 300 C/8hrs
~ 0.004 + As-cast
-X ac 400 C/8hrs
+ f~ 4oo C/8hr~
0.002
0.001
n
-o 5 10 15
time (days) figute3c
0.0016
0.0014
\
0.0012
% fc 400 C/8hrs,
0.0008
+ as-cast
l--
* aged 300 C/8hrs.
0.0006
. + aged 400 C/5hrs.
-------- .-
0.0004
0.0002
01
o 5 10 15
time (days)
Figure 3d
201/16
Figure 4a.SEM micrograph showing the anode in the as-cast condition after the ASTM
test. It can be observed that the corrosion is by pitting.
Figure 4b. SEM micrograph from the anode aged (4000C/18Ks), after the test.lt
shows a similar corrosion pattern as fig.4a.
201/17
Figure 4c. SEM micrograph obtained from the anode furnance cooled
(4000 C/28.8 Ks).The corroded surface shows pits, indicating a accelerated non-
uniform corrosion.
.,,* .,
w
.
,.
.
. . .
..
-,.
. . F
k-. j. ,,
&
,
,,.
F+..
-
-. .
.
Figure 4d.SEM micrograph showing the anode aged (3000 C/28.8 Ks),after the ASTM
test. It can be observed a uniform corrosion pattern.
201/18