Materials and Corrosion 2012, 63, No. 8 DOI: 10.1002/maco.

201106225 707

A new theory for the negative difference effect in magnesium

corrosion
S. Bender*, J. Goellner, A. Heyn and S. Schmigalla

An unusual feature known as the negative difference effect (NDE) can be

observed in magnesium when recording corrosion current density–potential
curves. More hydrogen is evolved at a more positive potential which does not
occur in conventional metals. Several models have been proposed in the
literature in order to explain the phenomenon of NDE. They succeed in
explaining some effects, and fail to deal with others. A new model, which
explains the NDE by two electron consuming processes, is presented in this
paper. By potentiostatic investigations of magnesium in a chloride electrolyte,
measurements of hydrogen evolution and chemical analysis of the electrolyte
the new model was experimentally verified.

1 Introduction this model is no possible explanation for NDE. The dissolution of

magnesium involving monovalent ions is the most cited and
Magnesium exhibits a very strange electrochemical phenomenon discussed model [2, 12]. Convincing evidence for Mg(I) has been
known as the negative difference effect (NDE) [1, 2]. For most forthcoming from the work of Atrens et al. [13] while a recent
metals, the hydrogen evolution decreases with an increase of the study by Williams et al. [14] and Swiatowska et al. [15] showed no
applied potential or current density. However, for magnesium, it evidence for a Mg(I) intermediate.
is found experimentally that, with increasing potential, both the
magnesium corrosion rate and also the hydrogen evolution rate
2 Effect of NDE
increase. This is the basic feature of the NDE, which has the
consequence that the weight loss calculated with Faraday’s law is
The effect of the NDE can be seen on the current-potential-curves
lower than the experimentally determined weight loss. Several
in Fig. 1. The normal anodic and cathodic reactions are shown by
models have been presented in order to explain this phenomenon
the black solid curve marked Ia(Mg) and Ic(H2). This is the case
[3]. The main models published about the NDE of magnesium are
for normal electrochemical polarization behaviour and would also
based on the breakdown of a protective film [4–8] or the formation
be expected for magnesium. But it is found experimentally
of magnesium hydride [9]. These models try to explain only the
(dashed line) that, with increasing potential E, the hydrogen
effect of the strange hydrogen evolution. No explanation is given
evolution increases instead of decreasing along the expected
for the difference in the weight loss calculated with Faraday’s law
curve Ic(H2).
and the gravimetrically determined weight loss. Another model
Simultaneously, the anodic dissolution increases stronger
tries to explain the NDE by the presence of imbedded secondary
than expected. The effect that the measured hydrogen evolution is
phase particles [10, 11]. This model describes the NDE exclusively
greater than the expected hydrogen evolution is designated as the
for alloys of magnesium. But just on pure magnesium the
NDE. Furthermore, for anodic dissolution of magnesium, the
‘strange’ hydrogen evolution behaviour arises as the polarization
experimentally determined weight loss is greater than that
current density or potential becomes more positive. Therefore,
calculated using Faraday’s law.

S. Bender
Institut für Lacke und Farben e.V., Fichtestr. 29, 39112 Magdeburg 3 Previous explanations of the NDE
(Germany)
E-mail: susanne.bender@lackinstitut.de 3.1 Model of the partially protective surface film

J. Goellner, A. Heyn, S. Schmigalla
Otto-von-Guericke-Universität Magdeburg, IWF, P.O. Box 4120, 39016
Magdeburg (Germany)
A. Heyn
BAM – Bundesanstalt für Materialforschung und -prüfung, Fachgruppe
6.1, Unter den Eichen 87, 12205 Berlin (Germany)
In this model the effect of NDE is described with the breakdown
of a partially protective surface film on the magnesium alloy at
anodic polarization [4–8]. This is shown schematically in Fig. 2.
In Fig. 2 can be seen that at potential E, which is more
negative than the free corrosion potential or at lower corrosion
current I, a protective reaction layer covered the surface.

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708 Bender, Goellner, Heyn, and Schmigalla
Figure 1. Schematic illustration of the anodic Ia(Mg) and the cathodic
Ic(H2) partial reactions for the expected (solid line) and the
experimentally found (dashed line) polarization behaviour
Figure 2. Model of the partially protective surface film [5]
Therefore, there is a low dissolution of the magnesium. If the
potential E or the corrosion current I become more positive,
the breakdown of the reaction layer increases. Thus, more
magnesium goes into solution and more hydrogen develops.
3.2 Model of the monovalent magnesium ion
Song and Atrens [2] consider that the monovalent magnesium ion
(Mgþ), which is formed during the aqueous corrosion of
magnesium should be involved in the NDE as shown in Fig. 3.
Monovalent magnesium ions are produced as intermediate
species [Eq. (1)], which react chemically with water to evolve
hydrogen, Eq. (2).
Mg ! Mgþ þ e

2 Mgþ þ 2Hþ ! 2 Mgþþ þ H2
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Materials and Corrosion 2012, 63, No. 8
Figure 3. Model of the monovalent magnesium ion [2]
3.3 Model of undermining particles
The particle undermining model explains the NDE with the
falling out of nobler precipitations and phases during anodic
dissolution [10, 11]. The precipitates and phases are cathodic to
the magnesium matrix. Therefore, microgalvanic corrosion
occurs on the phase boundaries, particles were undermined
and fall out. An increased hydrogen evolution and a difference in
weight loss can be observed during anodic polarization. This is
shown schematically in Fig. 4.
3.4 Model of the formation of magnesium hydride
The formation of magnesium hydride (MgH2) was proposed by
Gulbrandsen [9]. MgH2 forms on the surface during magnesium
dissolution. This species is not stable in contact with water and
reacts chemically to form hydrogen, Fig. 5.
4 New explanation of the NDE
Resulting from our own examinations and considerations the
following explanation of the NDE arises: If the magnesium is in
contact with water it sends immediately ions (Mgþþ) into solution,
as shown in Eq. (3). The electrons (2e
) remain free in the metal.
anodic reaction Mg ! Mgþþ þ 2e
(3)
The magnesium ion could also leave its atomic site as a
monovalent ion. Then it would exist as an unstable intermediate
(1)
(2) Figure 4. Model of the particle undermining [11]
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Materials and Corrosion 2012, 63, No. 8
Figure 5. Model of the magnesium hydride formation [9]
species with a short lifetime, Eq. (1). After giving up the second
electron [Eq. (4)], the magnesium ion would leave the metal
surface. It is presently not known under which conditions one or
the other reaction has priority.
anodic reaction Mg ! Mgþ þ e
(1)
anodic reaction Mgþ ! Mgþþ þ e
(4)
For the new theory it is not essential, if monovalent
magnesium ions initially leave the metal and are oxidized
electrochemically in a second step to bivalent magnesium ions, or
if bivalent magnesium ions go immediately into solution. In every
case an appropriate number of electrons remains in the metal.
The reaction will stop since the electrostatic forces (positive ions
in the electrolyte, negative charge carriers in the metal) prevent a
charge separation. An electron consuming process is necessary
for the further dissolution of the metal to occur. The electron
consumption in magnesium happens by the discharging of
hydrogen ions, as can be seen in Eq. (5).
cathodic reaction 2Hþ þ 2e
! H2 (5)
The source for the hydrogen ions (more exactly the hydronium
ion H3Oþ) in neutral solutions (pH 7) is the dissociated water, as
shown in Eq. (6). For simplicity in the literature the symbol Hþ
is used instead of H3Oþ in the equations because this proton is
the part of the hydronium ion that participates in the reactions
discussed in the text. But Hþ does not exist by itself due to a
high electrical field resulting in the formation of a hydronium
ion H3Oþ [16, 17].
dissociation H2 O ! OH
þ Hþ (6)
Because of secondary reactions magnesium ions react with
the hydroxide ions as seen in Eq. (7).
product formation Mgþþ þ 2OH
! MgðOHÞ2 (7)
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A new theory for the negative difference effect in Mg corrosion 709
If magnesium corrosion is investigated by external polariza-
tion, electrons are consumed by the potentiostat and more
magnesium ions go into solution. These additional magnesium
ions react with the hydroxide ions of the dissociated water. As a
consequence, the equilibrium between water and its ions is
disturbed and the reaction goes stronger in one direction. The
non-equilibrium of the dissociated water is balanced after the
principle of Le Chatelier and Braun [see 18] as seen in Eq. (8).
H2 O ! OH
þ Hþ
# (8)
Mgþþ
Because of the product formation between magnesium ions
and hydroxide ions [Eq. (7)], the hydrogen ions of the dissociated
water are left over. Therefore, an acid is produced which
discharges the free electrons on the surface, in addition to the
potentiostatic discharge. As more magnesium ions go into
solution by anodic polarization, more hydroxide ions from
dissociated water react with the magnesium ions and stronger
water dissociation occurs. Therefore, electrons are consumed by
external polarization with the potentiostat and by hydrogen ions
from the dissociated water. The dissolution of magnesium
increases rapidly. This further disturbs the non-equilibrium of
the dissociated water and an increasing hydrogen evolution can
be noticed.
The new model can be seen in Fig. 6 as a schematic
illustration. The dashed arrows on the magnesium represent the
electron consumption by external polarization (potentiostat) and
the electron consumption by hydrogen ions (acidic corrosion).
The aqueous electrolyte is dissociated into hydrogen and
hydroxide ions. Magnesium ions, which go into solution by
contact with water, react with the hydroxide ions of the dissociated
water. The hydrogen ions are discharged on the metal surface and
molecular hydrogen forms.
With this new model it can be shown that the effects of NDE,
strong hydrogen evolution by anodic polarization, and the
difference between the calculated and the measured weight loss
have their reasons in the increased discharge of hydrogen ions.
Due to anodic polarization of magnesium, more electrons are
consumed by the potentiostat and more magnesium ions go into
solution. The electron consumption by the potentiostat can be
measured as an electric current. The magnesium irons react with
the hydroxide ions of the dissociated water to form magnesium
Figure 6. Schematic illustration of the new model for explanation of
the NDE
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710 Bender, Goellner, Heyn, and Schmigalla Materials and Corrosion 2012, 63, No. 8

hydroxide. Due to this secondary reaction the equilibrium

between water and its ions is disturbed. The non-equilibrium of
the dissociated water is balanced immediately by the additional
dissociation of the water into hydrogen and hydroxide ions. The
chemical equilibrium is disturbed mainly in the phase boundary,
i.e., the hydrogen ions are reduced in the electrochemical double
layer and no acidification of the bulk electrolyte can be measured
with a pH-meter. The acid is always produced on the phase
boundary, which, in addition to the potentiostat, consumes the
electrons. Therefore, more hydrogen develops on the magnesium
surface. This second electron consumption process can be seen
by the formation of gas bubbles and can only be measured by the
simple hydrogen evolution technique. Therefore, the corrosion of
magnesium alloys depends on two cathodic processes.

5 Verification of the new model

5.1 Experimental

Tests for the experimental verification of the new model were

performed with pure magnesium. The composition of the
material is listed in Table 1.
The specimens were acquired in the form of cubes with an Figure 7. Measuring cell for investigation of hydrogen evolution as a
edge length of 1 cm. They were ground on all sides with 1200-grit function of the applied potential and pH value of solution (electrolyte:
SiC-paper and equipped with an electrical contact. The contact 0.01 M NaCl, pHstart3.5)
area was isolated from the electrolyte with a lacquer. A special
measuring cell (Fig. 7) was used for potentiostatic measurements.
This cell ensures simultaneously the polarization of the To prepare balance sheets for the measurements, the
magnesium specimen, the measurement of hydrogen gas, and amounts of the magnesium ions, the collected hydrogen gas,
the measurement of the pH-value. and the current flow were converted to number of particles N. The
The potentiostatic measurements were carried out for 2 h number of particles N is an extensive, dimensionless quantity
with a standard three-electrode set-up in an acidic NaCl which describes the absolute number of electrons, H2 molecules,
solution (0.01 M, pHstart 3,5). The pH reduction to the value of and Mg ions in the system. The basis of the calculations from
3.5 was accomplished with acetic acid. A saturated Ag/AgCl measurement to number of particles N is listed in Table 2.
(EH ¼ 197 mV) electrode was used as reference and platinum as According to calculations, N(Q) represents the number of
counter electrode. All potentiostatic tests were performed with particles for charge, N(H2) shows the number of particles for
electrochemical potentials which are 200 and 600 mV more hydrogen gas and N(cMg) the number of particles for magnesium
positive than the corresponding open circuit potential. A burette ions in the electrolyte. The constants used are the elementary
was placed upon the specimen in order to collect the hydrogen charge e with a value of 1.602176487  10
19 C, the valence z
gas. The burette had a 0.02 mL scaling and was filled with for magnesium with a value of 2, the pressure p with a value
electrolyte up to the zero-millilitre-level before beginning of the of 101 325 Pa, the Avogadro constant NA with a value of
tests. The volume of the electrolyte used in the potentiostatic tests 6.02214179  1023 mol
1, gas constant R with 8.314472 J/mol  K,
was always 675 mL. The surface area of the specimens of pure
magnesium was always about 5 cm2 because of one isolated
contact area. The cell contained a stirrer in order to avoid Table 2. Mathematic basis for calculation the number of particles N
hydrogen bubbles on the specimen surface and a pH gradient in from measurement
the electrolyte. The current flow on ammeter I, the collected Measurements Current Hydrogen gas Magnesium
hydrogen gas DVH2 in the burette, the quantity of magnesium ions
ions in the electrolyte cMg, and the change of pH in the electrolyte l [A] VH2 [ml] þþ
CMg [mg]
DpH were recorded after every potentiostatic test. The atomic
absorption spectroscopy (AAS) analysis was carried out by an Z7200
m
external vendor. Q¼ lðdtÞ pV ¼ NRT M¼
n
0

Table 1. Chemical composition of used material (wt%) Q ¼ eNe N ¼ NA n N ¼ NA n

Material Al Zn Mn Si Fe Cu Mg Q pVNA CMg NA
NðQÞ ¼ NðH2 Þ ¼ NðCMg Þ ¼
ze RT M
Magnesium 0.009 0.025 0.020 0.035 0.024 0.005 Balance

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Materials and Corrosion 2012, 63, No. 8
the temperature T with 298.15 K, and the molar mass M for
magnesium with 24.31 g/mol.
5.2 Results and discussion
The calculated number of particles for magnesium ions in the
electrolyte N(cMg), for charge N(Q), for hydrogen evolution N(H2),
and for the sum of N(Q) þ N(H2) are shown in Fig. 8. These
measurements were done at a hold potential with a value of

1700 mVAg/AgCl. It corresponds to a potential, which is 200 mV
more positive than the free corrosion potential of magnesium
(
1900 mVAg/AgCl).
The represented bars show that the calculated number of
magnesium ions in the electrolyte N(cMg) reached for all
measurements the highest values. N(cMg) has similar values
for all measurements. The lowest values resulting from the
number N(Q). If the numbers of particles of charge N(Q) will be
compared with the number of particles from hydrogen evolution
then the latter have considerably higher values. Most electrons
from magnesium were consumed by acid corrosion than by
external polarization with potentiostat on this hold potential
(
1700 mVAg/AgCl). It can be seen a great hydrogen evolution on
the specimens. The value of the sum from N(Q) þ N(H2) is equal
to the value of N(cMg). This is evidence, that two electron
consumption processes have taken place to dissolute magnesium.
One can be measured with the flowing current and the other can
be measured by collecting the hydrogen evolution. The amount of
magnesium ions in the electrolyte corresponds to the amount of
the sum of hydrogen gas and charge.
The calculated number of particles for magnesium ions in
the electrolyte N(cMg), for charge N(Q), for hydrogen evolution
N(H2), and for sum of N(Q) þ N(H2) can be seen in Fig. 9.
To adjust a constant value of
1300 mVAg/AgCl on the
specimens, it was necessary to polarize from the free corrosion
potential by over 600 mV in the anodic direction. The highest
number of particles could be found for the magnesium ions
in the electrolyte N(cMg). Furthermore, it can be seen that
the calculated number of particles for magnesium ions in the
electrolyte N(cMg) varied strongly for every measurement.
The number of particles from charge N(Q) are higher than the
Figure 8. Number of particles N for three potentiostatic tests at a
potential of
1700 mVAg/AgCl, which corresponds to a potential
200 mV more positive than the free corrosion potential (conditions:
0.01 M NaCl, pHstart3.5, t ¼ 120 min, N(cMg): number of particles for
magnesium ions in the electrolyte, N(Q): number of particles for charge,
N(H2): number of particles for hydrogen evolution)
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A new theory for the negative difference effect in Mg corrosion 711
Figure 9. Number of particles N for three potentiostatic tests at a
potential of
1300 mVAg/AgCl, which corresponds to a potential 600 mV
more positive than the free corrosion potential (conditions: 0.01 M
NaCl, pHstart3.5, t ¼ 120 min, N(cMg): number of particles for magnesium
ions in the electrolyte, N(Q): number of particles for charge, N(H2):
number of particles for hydrogen evolution)
number of particles from hydrogen gas N(H2) for potentials of

1300 mVAg/AgCl. The increase of the number of particles
from charge N(Q) is expected, but that the number of particles
from hydrogen gas N(H2) is lower than N(Q) is experimentally
found. Because of the strong dissolution of magnesium on this
positive potential, a great amount of hydrogen bubbles forms on
the magnesium surface. The hydrogen bubbles do not leave the
magnesium surface completely, so that the surface is partly
covered with a layer of hydrogen bubbles, which impedes the
further dissolution. A magnetic stirrer was used during every
measurement, so a complete isolation of the magnesium
surface could be prevented, but not a temporary hindering of
the dissolution and hydrogen evolution. In every case the sum
of the number of particles from hydrogen evolution N(H2) and
from charge N(Q) corresponds to the number of particles
from magnesium ions in the electrolyte N(cMg). However, if
the dissolution of the magnesium specimen on these positive
potentials is lower because of the hydrogen bubbles on the
surface, in sum the amount of N(cMg) corresponds to N(Q) plus
N(H2). So magnesium dissolution resulting from external
polarization depends on two-electron consumption processes,
namely the electron consumption by the potentiostat and the
discharge of hydrogen ions (acidic corrosion).
The single measurement values resulting from potentiostatic
investigations in dependence of hold potential EH are listed in
Table 3. It shows the pH-value of electrolyte at the beginning
(pHstart) and at the end (pHend) of the measurement, the
collected hydrogen gas VH2, the magnesium ions in the
electrolyte cMg, and the corresponding numbers of particles
N(Q), N(H2), and N(cMg).
In Table 3 it can be seen that the pH of the electrolyte changes
only a little at the end of every measurement due to magnesium
dissolution. The collected hydrogen gas and the determined
magnesium ions from the electrolyte increase with increasing
hold potential EH. Furthermore, the values of charge increase
with increasing potential EH. According to those values, the
calculated number of particles for charge N(Q), for hydrogen
N(H2), and for magnesium ions N(cMg) increase if the potential
becomes more positive.
ß 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
712 Bender, Goellner, Heyn, and Schmigalla Materials and Corrosion 2012, 63, No. 8

Table 3. Values of measurement for potentiostatic dissolution of magnesium in dependence of applied hold potential (EH ¼
1700 and

1300 mVAg/AgCl) in 0.01 M NaCl at pHstart3.5 over a time interval of 120 min (N(CMg) number of particles for magnesium ions in the
electrolyte, N(Q): number of particles for charge, N(H2): number of particles for hydrogen evolution)

Nr. EH pHstart pHend VH2 OMg Q N(Q) N(H2) N(QMg)

[mV] [ml] [mg] [As]  1013  1013  1013

1
1700 3.46 3.58 1.30 1.67 2.340 7.30 32.0 41.4

2
1700 3.42 3.61 1.59 2.10 3.137 9.79 39.1 52.0
3
1700 3.50 3.72 1.57 2.25 4.798 15.0 38.6 55.7
1
1300 3.47 3.83 2.08 4.13 19.10 59.6 51.2 102
2
1300 3.49 3.95 2.49 5.91 24.89 77.7 61.3 146
3
1300 3.50 3.91 1.73 4.03 19.03 59.4 42.6 99.8

6 Summary (ii) The model was verified by a complex investigation of the

As a central point of this paper a new model was suggested which
describes the NDE using a special analysis of the cathodic
process. The principle question, about the source of the great
amount of hydrogen gas evolving during anodic polarization, has
been answered. If magnesium is investigated using electro-
chemical techniques with external polarization, it must be taken
into account that the corrosion of magnesium alloys depends on
two cathodic processes. One results from the external polarization
and can be measured as a current flow on the ammeter and the
other results from the enrichment of hydrogen ions and can be
seen by the formation of gas bubbles on the magnesium surface.
Therefore, the difference between the measured weight loss and
the weight loss calculated by Faraday’s Law is expected because
the electron consumption by acidic corrosion is not included in
Faraday’s law. To determine the true weight loss, it is necessary to
add to the calculated weight loss the weight loss resulting from
local acidic corrosion in the boundary layer. Investigations of
the corrosion of magnesium using an external polarization that
is 200 or 600 mV more positive than its free corrosion potential
show that the amount of magnesium ions in the electrolyte
corresponds to the amount of the sum of current flow and the
collected hydrogen gas.
7 Conclusion
The aim of this paper was to clarify the corrosion mechanism
under potentiostatic control and the curious effect that
the rate of hydrogen evolution increases with the anodic
polarization of the electrode. This is known in the literature as
the NDE.
(i) A new model was reported, which explains the NDE
for magnesium and magnesium alloys. It shows that
the corrosion of magnesium depends on two cathodic
processes. One can be measured as a current flow on the
ammeter and the other can be seen by the formation of gas
bubbles.
current flow, the number of Mg ions, and the number of
evolving H2 molecules. The condition N(cMg) ¼ N(H2) þ N(Q)
was shown to hold true.
(iii) The NDE should be regarded as a common process in the
corrosion of magnesium.
(iv) Electrochemical techniques should be further used to
distinguish and compare different magnesium alloys. These
methods can monitor the change of corrosion rate in real
time rather than at an average rate.
8 References
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[2] G. L. Song, A. Atrens, Adv. Eng. Mater. 1999, 1, 11.
[3] G. Song, Adv. Eng. Mater. 2005, 7, 563.
[4] A. Kisza, J. Kazmierczak, B. Borresen, G. M. Haarberg,
R. Tunold, J. Appl. Electrochem. 1995, 25, 940.
[5] R. Tunold, H. Holtan, M.-B. Hägg Berge, A. Lasson,
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[6] L. M. Petrova, V. V. Krasnoyarskii, Prot. Met. 1990, 26, 633.
[7] P. F. King, J. Electrochem. Soc. 1966, 113, 536.
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[11] G. L. Makar, J. Kruger, A. Joshi, Proceedings Annual Meeting of
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nesium Alloys and Composites, Phoenix, Arizona, 26.01. 1988,
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[12] S. Bender, J. Goellner, A. Atrens, Adv. Eng. Mater. 2008, 10,
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[13] A. Atrens, W. Dietzel, Adv. Eng. Mater. 2007, 9, 292.
[14] G. Williams, H. N. McMurray, J. Electrochem. Soc. 2008, 155,
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[15] J. Swiatowska, P. Volovitch, K. Ogle, Corros. Sci. 2010, 52,
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[16] M. Eigen, Angew. Chem. 1963, 12, 489.
[17] S. Bender, PhD thesis, Otto-von-Guericke University
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[18] U. Grigull, Int. J. Heat Mass Transfer 1963, 7, 23.

(Received: May 20, 2011) W6225

(Accepted: June 15, 2011)

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