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Inhibitor effects of sodium benzoate on corrosion resistance of Al6061-B4C composites in

NaCl and H3BO3 solutions

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2016 Mater. Res. Express 3 126501

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Mater. Res. Express 3 (2016) 126501 doi:10.1088/2053-1591/3/12/126501

PAPER

Inhibitor effects of sodium benzoate on corrosion resistance of


RECEIVED
25 August 2016
Al6061-B4C composites in NaCl and H3BO3 solutions
REVISED
24 October 2016
ACCEPTED FOR PUBLICATION
Rafi-ud-din1, Q A Shafqat2, M Shahzad1, Ejaz Ahmad1, Z Asghar1, Nouman Rafiq2, A H Qureshi1,
3 November 2016 Waqar adil Syed2 and Riffat asim Pasha3
PUBLISHED
1
Materials Division, Pakistan Institute of Nuclear Science and Technology (PINSTECH), Nilore, Islamabad, Pakistan
2 December 2016 2
Department of Physics, International Islamic University, Islamabad, Pakistan
3
Department of Mechanical Engineering, University of Engineering and Technology Taxila, Pakistan
E-mail: rafi_682@yahoo.com and rafiuddin@pinstech.org.pk

Keywords: metal matrix composites, sodium benzoate, electrochemical techniques, corrosion inhibition

Abstract
Sodium benzoate (SB) is used for the first time to inhibit the corrosion of Al6061-B4C composites in
H3BO3 and NaCl solutions. Al6061100−x–x wt% B4C (x=0, 5, and 10) composites are manufactured
by a powder metallurgy route. The corrosion inhibition efficiency of SB is investigated as a function of
the volume fractions of B4C particles by using potentiodynamic polarization and electrochemical
impedance techniques. Without the use of an inhibitor, an increase of the B4C particles in the
composite decreases the corrosion resistance of Al6061-B4C composites. It is found that SB is an
efficient corrosion inhibitor for Al6061-B4C composites in both investigated solutions. The corrosion
inhibition efficiency of SB increases with an increase in B4C content. Since SB is an adsorption type
inhibitor, it is envisaged that an extremely thin layer of molecules adsorbs onto the surface and
suppresses the oxidation and reduction. It is found that the inhibitor effect of SB is more pronounced
in a H3BO3 environment than in NaCl solution. Further, the mechanism of corrosion inhibition by SB
is illustrated by using optical and scanning electron microscopy of corroded samples. It is found that
the adsorption of benzoate ions on the Al surface and its bonding with Al3+ ions forms a hydrophobic
layer on top of the exposed Al surface, which enhances the protection against dissolved boride ions.

Introduction

B4C reinforced aluminum matrix composites offer several advantages due to their high specific strength,
stiffness, wear resistance and low thermal expansion coefficient. Al-B4C composites are widely used as structural
neutron absorbers, as armor plate materials, and as a substrate material for computer hard disks [1–4]. During
recent years, due to the high neutron absorption cross-section of the 10B isotope, Al-B4C composites have been
extensively used as an excellent neutron absorber material to fabricate storage baskets and transport containers
for spent nuclear fuel [5, 6].
In spent nuclear fuel wet storage applications, AA6061-B4C metal matrix composites (MMCs) are exposed
to mildly corrosive borated reactor pool water containing high B in the form of H3BO3 [7]. Among all Al alloys,
Al6061 exhibits excellent formability as well as offering high strength and good corrosion resistance [8].
However, the incorporation of B4C particles into Al6061 alloy degrades the corrosion resistance of such
materials, which is of great concern for nuclear as well as other industrial applications. Moreover, a considerable
amount of research work has been carried out to understand the corrosion behavior of Al-SiC and Al-Al2O3
composites in various environments [9–14]. Nevertheless, studies on the corrosion behavior of AI-B4C
composites, especially in highly corrosive environments such as H3BO3 and NaCl, are very limited. Yu-Mei et al
have investigated the corrosion behavior of Al-B4C composites in 0.5 M K2SO4, 3.5% NaCl and 2500 ppm
boron-containing H3BO3 solutions [15]. In the literature various organic and inorganic compounds have been
suggested for the protection of Al MMCs from corrosion [16, 17]. The organic compound sodium benzoate (SB)
is reported to be an effective corrosion inhibitor for steel, zinc, copper, copper alloys, aluminum and aluminum

© 2016 IOP Publishing Ltd


Mater. Res. Express 3 (2016) 126501 Rafi-ud-din et al

Figure 1. Micrographs of Al6061-B4C compact in (a) as-sintered and (b) as-rolled conditions.

Figure 2. The XRD spectra of sintered and rolled Al6061-B4C composite.

alloys [18]. SB inhibits corrosion by reducing the free energy of the system and impeding the passage of metal
ion–atoms from the lattice into the solution [19]. There are many reports which involve the inhibition effect of
SB on various metals. However, the inhibition effect of SB on Al6061-B4C composites is reported for the first
time in the present work.
The main objective of the present work is to investigate the corrosion susceptibility of Al6061-B4C
composites with respect to different B4C particle levels in H3BO3 and NaCl solutions. This is done in detail by
employing potentiodynamic polarization (PDP) and electrochemical impedance spectroscopy (EIS) techniques.
SB is tested for the first time as a corrosion inhibitor for Al6061-B4C composites in H3BO3 and NaCl solutions.
The corrosion inhibition effects of SB as a function of B4C particle volume fractions are investigated by using the
aforementioned techniques.

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Mater. Res. Express 3 (2016) 126501 Rafi-ud-din et al

Table 1. The densities of Al6061–x wt% B4C (x=0, 5, 10, 20, 30, 40) composite powders after sintering at different temperatures.

Sintered density (g cm−3)

Sample Green density (g cm−3) 585 oC 610 oC 630 oC

Al6061 alloy 2.58 2.59 2.62 2.64


AA6061+05% B4C 2.50 2.59 2.63 2.65
AA6061+10% B4C 2.43 2.49 2.58 2.62
AA6061+20% B4C 2.31 2.35 2.52 2.55
AA6061+30% B4C 2.25 2.26 2.40 2.46
AA6061+40% B4C 2.19 2.20 2.32 2.43

Experiment

Fine, gas atomized Al6061 alloy powder with a mean particle size of 19 μm and boron carbide powder with a
mean particle size of 8 μm were milled for 2 h in a planetary ball mill PM 4, developed by RETSCH (Germany).
The milling was performed at 200 rpm under argon atmosphere and compacted into disk-type compacts of
19 mm diameter and larger size rectangular compacts (60×40 mm) with zinc stearate as the die lubricant.
Sintering was performed at three temperatures for 1 h holding time under N2 atmosphere using a flow rate of
5 l min−1 and a dew point temperature of less than −42 °C. The density of the sintered compacts was measured
by the Archimedes principle. The sintered Al6061-B4C composite compacts were homogenized at 525 °C for
1 h. After homogenization, compacts were hot rolled with a thickness reduction of 5%–15% per pass. The
sintered compacts after rolling were sectioned from the longitudinal cross-section for metallographic and
corrosion studies. X-ray diffraction (XRD) patterns of sintered and rolled composites were obtained using a
powder x-ray diffractometer (Rigaku). Prior to corrosion tests, the surfaces of the specimens were ground up to
P1200 grit SiC finish using water as a lubricant, degreased with isopropyl alcohol in an ultrasonic bath and dried
in warm air. The polished surface of the Al6061-B4C was examined under an Olympus BX51 optical microscope.
The samples after corrosion testing were examined using a scanning electron microscope (LEO 440). The
macroscopic hardness of the sintered and rolled Al6061-B4C composites was measured on a Rockwell B (HRB)
testing machine, using an initial load of 10 kgf and a major load of 90 kgf with a 1/16 inch steel ball indenter. The
given values of hardness were the average of five measurements on each sample.
Electrochemical measurements were carried out at ambient temperature (around 21 °C) in a conventional
three-electrode electrolytic cell. The solutions used were 2500 ppm boron-containing H3BO3 with and without
0.5 M SB, and 3.5% NaCl with and without 0.5 M SB. The working electrode was in the form of a rectangular
composite sample with a geometric working area of 1 cm2. These samples were prepared using a mechanical
process of wet sanding with SiC papers of up to 1200 grit. An Ag/AgCl electrode and a platinum electrode are
used as the reference and counter electrodes, respectively. Prior to EIS and PDP measurements, the samples were
immersed in the solution for 15 min to reach a steady open circuit potential. Electrochemical impedance curves
were obtained by applying a sinusoidal potential of 10 mV in amplitude, in the frequency range from 100 mHz
to 1 MHz. PDP tests were performed at a scan rate of 10 mV s−1.

Results and discussion

Figure 1 shows optical micrographs of sintered as well as rolled Al6061-B4C composite. The microstructure
clearly indicates the homogeneity in the distribution of reinforcement in the matrix alloy and no segregation
takes place at a particular region. It appears that some of the larger B4C particles can break up into smaller
particles as a result of hot rolling, as presented in figure 1. It is evident from the micrographs that the most of the
reinforcements get oriented along the rolling direction on hot rolling of sintered composites. XRD investigations
were carried out to determine the phase constituents of the sintered as well as rolled composites. Figure 2
presents typical XRD patterns from sintered as well as rolled composites, and they confirm the presence of Al
and B4C as the major constituents.
Table 1 shows the sintered densities of composites at 585, 610 and 630 °C. The density increases with an
increase in sintering temperature. Higher relative densities are achieved at higher sintering temperature. This
can be explained by equation (1), showing the dependence of diffusion on sintering temperature (Porter and
Easterling 1980). Hence, a denser structure is achieved at higher sintering temperature (German 1996) [20],
D = Do exp ( - Q RT ) (1)

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Mater. Res. Express 3 (2016) 126501 Rafi-ud-din et al

Figure 3. (a) Sinterability curves of Al6061–x wt% B4C (x=0, 5, 10, 20, 30, 40) and (b) hardness of Al6061–x wt% B4C (x=0, 5, 10,
20, 30, 40) sintered at 630 °C.

where D is the diffusion coefficient, Do is constant, Q is the activation energy, R is Boltzmann’s constant and T is
the temperature. According to the above equation, the self-diffusion coefficient increases greatly as T increases.
The diffusion coefficient, also called diffusivity, is an important parameter indicative of diffusion mobility. The
higher the diffusivity, the faster the Al particles will diffuse into each other. It is also pertinent to mention here
that in the present case, supersolidus liquid-phase sintering (SLPS) is performed. The presence of a high-
diffusivity Al liquid usually provides for rapid sintering densification. During SLPS, the viscosity of the solid–
liquid mixture decreases as the liquid volume fraction increases, so more liquid makes for faster sintering.
Consequently, temperature is a main determinant of sintered density and higher temperature is an effective
method to attain a high sintering quality. It is well established that the milling process in composite powders is
accelerated compared with unreinforced alloy. In composite powders, the local deformation in the vicinity of
reinforcement particles is enhanced, promoting the fracture process and diminishing the ductility of the
composite powder. In addition, the small hard reinforcement particles in the powder mixture act as milling
agents and increasing B4C content results in a more brittle manner and lower powder particle size under the
same milling conditions. During the milling process, the density of dislocations increases due to the presence of
hard ceramic particles. The formation of additional dislocations is mainly as a result of the difference between
the coefficient of thermal expansion of the matrix and reinforcement [21]. Though the sub-grain size decreases
at high dislocation density, the crystallite size can be reduced at higher concentrations of B4C particles. The hard
B4C particles hinder dislocation movements, leading to an increase in dislocation density [22]. Therefore, it is
estimated that high reinforcement content should accelerate the sintering process. The sinterability of sintered

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Mater. Res. Express 3 (2016) 126501 Rafi-ud-din et al

Figure 4. PDP curves in (a) NaCl solution and (b) NaCl plus SB inhibitor.

compacts is evaluated by the following equation:

Ø = rs - rg r th - rg (2)

where ρs, ρg, and ρth are sintered, green, and theoretical densities, respectively. The sinterability gives
information about how much sintered density is close to the theoretical density. It is evident in equation (2) that
it is effectively the ratio of the sintered density and theoretical density. The theoretical density of the composites
is calculated in accordance with the rule of mixtures considering the composition of composites. The results
show that the sinterability of composite powders decreases with an increase in reinforcement content
(figure 3(a)). This is mainly due to reducing compressibility, as discussed earlier, leading to lower metal–metal
contacts. Figure 3(b) clearly indicates that both in sintered and rolled conditions, the hardness increases with
increased B4C content. However, for a given B4C content, rolled composites possess higher hardness compared
to the sintered ones. This may be mainly attributed to the higher hardness of the reinforcements. The Vickers
hardness of B4C is 38 GPa [23], which is very high when compared to that of Al6061. The small volume
expansion of the B4C particles renders the plastic deformation of alloy particles. The dislocation densities
increase those results in higher resistance to plastic deformation, leading to improved hardness [21, 22, 24].
The PDP curves in sodium chloride and boric acid solutions are given in figures 4(a) and 5(a), respectively,
while the curves in the same two solutions with SB inhibitor are given in figures 4(b) and 5(b), respectively. The
results reveal that in both solutions the additions of B4C shift the free corrosion potential to a more anodic value,
indicating higher thermodynamic affinity towards oxidation and corrosion. The kinetics of reactions are not any
different and the Tafel analysis (table 2) shows that the corrosion rate increases as B4C particles are added to the
composite. Moreover, table 2 shows that the corrosion rates are comparatively higher in chloride solution than

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Mater. Res. Express 3 (2016) 126501 Rafi-ud-din et al

Figure 5. PDP curves in (a) boric acid solution and (b) boric acid plus SB inhibitor.

in boric acid solution, probably due to the stability of the oxide layer on the aluminum matrix in the presence of
an oxidizing environment (boric acid solution). The addition of inhibitor in both solutions lowers the corrosion
rate, which is in agreement with the observed increase in corrosion resistance with the addition of inhibitor as
observed during EIS analysis. SB is an adsorption type inhibitor. This type of inhibitor forms an extremely thin
layer of molecules that adsorb onto the surface and suppress the oxidation and reduction. The potentiodynamic
curves in figures 4(b) and 5(b) and their data in table 2 show that both oxidation and reduction reactions are
suppressed. The effect is more pronounced in the boric acid environment as indicated by the decrease in the beta
A and beta C slopes. The presence of chloride ions not only weakens the oxide layer on Al, but also the adsorbed
benzoate layer, making the inhibitor less effective.
The results of EIS in a boric acid environment, both with and without a SB inhibitor, are shown in
figures 6(a) and (b). Figure 6(a) indicates that the area under impedance spectra which is proportional to the
quantitative value of resistance to corrosion is the sample that is highest in Al and decreases with the addition of
boron carbide. Nevertheless, it is evident in figure 6(b) that the addition of an inhibitor increases the area under
impedance spectra for all three conditions, which implies that the corrosion resistance of composites is
enhanced by the addition of an inhibitor. Moreover, the Nyquist curves of 10% B4C condition in both
uninhibited and inhibited conditions are not much different. One plausible explanation for this behavior is that
the results of PDP and EIS experiments have been taken after 15 min of immersion time for all conditions for the
sake of consistency, which in general show a good trend. However, as the concentration of B4C increases, the
activity of the system increases, thus it is quite possible that the 10% B4C condition in EIS measurement is not
fully at equilibrium in the uninhibited condition. The PDP which clearly indicates the inhibiting effects of SB is

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Mater. Res. Express 3 (2016) 126501 Rafi-ud-din et al

Table 2. Tafel analysis derived from polarization curves.

Beta A V dec–1 Beta C V dec–1 Icorr (A cm–2) Ecorr (mv) Corrosion rate (mpy)

NaCl

Al6061 alloy 0.20 0.14 7.00E-07 −847.00 0.513


AA6061 + 05% B4C 0.04 0.42 1.64E-06 −622.00 1.060
AA6061 + 10% B4C 0.06 0.00 3.72E-06 −785.00 2.415

NaCl+Na benzoate

AA6061 0.02 0.19 3.20E-07 −718.00 0.200


AA6061 + 05% B4C 0.05 0.40 1.58E-06 −605.00 0.850
AA6061 + 10% B4C 0.06 0.65 2.08E-06 −762.00 1.349

Boric acid

AA6061 0.17 0.43 2.29E-06 −397.00 1.485


AA6061 + 05% B4C 0.24 0.24 2.04E-06 −467.00 2.338
AA6061 + 10% B4C 0.26 0.68 6.82E-06 −342.00 4.420

Boric acid+Na benzoate

AA6061 0.30 0.08 1.03E-06 −472.00 0.670


AA6061 + 05% B4C 0.15 0.26 1.01E-03 −622.00 1.060
AA6061 + 10% B4C 0.40 0.23 1.98E-06 −471.00 1.288

not as much affected by this because it is performed up to a much higher/lower (±250 mV) DC potential than
the 10 mV AC excitation potential of EIS.
The electrochemical impedance spectra in 3.5% NaCl solution are given in figures 7(a) and (b). As observed
in the boric acid environment, the resistance to corrosion decreases with the addition of boron carbide, and the
addition of SB increases the resistance to corrosion. The sizes of the impedance spectra are a lot different in the
two solution environments, but as the fitted curves in figures 6 and 7 show, the underlying mechanisms are
probably the same. The fitted model has been sketched in figure 8. The model contains two resistances, Ru and
Rp, and one constant phase element, Ø. Where Ru is uncompensated resistance, Rp is polarization resistance and
Ø is the constant phase element which behaves like an imperfect capacitor and whose impedence, Z, is given by
the formula below equation (2) where Y0 is the capacitance and α is the exponent. Thus the constant phase
element (CPE) behaves as a true capacitor when the exponent α is zero.
1
Z= (3)
( jw )a Yo

The imperfection of the constant phase element is due to the presence of double layer capacitance, surface
roughness and non-uniform current distribution. The fine oxide layer on Al which is locally broken at the sites
of boron carbide reinforcement could be the origin of this imperfection in addition to unavoidable causes as
mentioned above. The parameters of the fitted EIS model have been given imperfection of constant phase
element due to the presence of double layer capacitance, surface roughness and non-uniform current
distribution. The parameters of the fitted EIS model have been given in table 3. The parameters shown in table 3
give the contribution of the solution resistance Ru and the polarization resistance Rp to the overall impedance.
The results show that with the addition of B4C, the system drifts away from ideal capacitive behavior (i.e. α=1)
towards resistive behavior (i.e. α=0). The values of the α exponent decrease, i.e. the imperfection of the
capacitor increases with the addition of reinforcement, possibly due to the rupture of the oxide film. Similarly, in
a chloride environment, which is detrimental to the oxide layer, the imperfection of the capacitor system
increases.
SB is an organic inhibitor. Like other organic inhibitors, their protection mechanism is through adsorption
and the formation of a hydrophobic layer on the surface of a metal, in which the active ion (benzoate) bonds with
the metal ion Al+3 in this case. Through this hydrophobic layer both anodic and cathodic reactions are inhibited.
The Tafel curves shown in figures 4 and 5 clearly show that both anodic and cathodic reactions are inhibited by
SB. The exact composition of the layer is difficult to determine due to its organic nature and fine thickness. The
optical and SEM images shown in figures 9(a) and (c) show the surface of the composite after corrosion testing in
uninhibited solution while the images shown in figures 9(b) and (d) are of the sample tested in inhibited
solution. It is evident that there is much less boride ion induced damage to the oxide layer (Al2O3) in the

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Mater. Res. Express 3 (2016) 126501 Rafi-ud-din et al

Figure 6. Fitted Nyquist plot in boric acid (a) and boric acid with SB (b) solutions.

inhibited solution. It is known that anions destabilize the oxide layer on Al and induce localized (pitting)
corrosion [25]. This pitting exposes the underlying virgin metal surface and the process continues. The
adsorption of benzoate ions on the Al surface and their bonding with Al2+ ions forms a hydrophobic layer on top
of the exposed Al surface. This enhances the protection against dissolved boride ions which have to first weaken
this organic hydrophobic layer before attacking the Al2O3 layer.
The SEM images in figure 10 at higher magnification and spot EDX analysis confirm that the visibly
destabilized features on the specimen surface are indeed oxide chips of Al and once they are removed, localized
corrosion initiates at these sites. Figure 10 shows the two types of oxides observed after corrosion experiments,
i.e. Al oxide involving only Al and O (figure 10(b)), while figure 10(a) shows a Al-Mg mixed oxide involving (Al-
Mg-O). Figure 10 also shows that the B4C particles are cathodic to the Al matrix as indicated by the corroded
boundary around them (location indicated by white arrow).

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Mater. Res. Express 3 (2016) 126501 Rafi-ud-din et al

Figure 7. Fitted Nyquist plot in NaCl (a) and NaCl with SB (b) solutions.

Figure 8. Equivalent electronic circuit model for EIS data fitting.

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Mater. Res. Express 3 (2016) 126501 Rafi-ud-din et al

Table 3. Parameter values of the fitted model.

Rp (ohm) Ru (ohm) Yo (μs sa) α

NaCl

Al6061 alloy 3131 0.86 158.5 0.85


AA6061 + 05% B4C 1783 0.85 148.8 0.79
AA6061 + 10% B4C 926 0.85 216.3 0.74

NaCl+Na benzoate

AA6061 3105 0.64 147.2 0.89


AA6061 + 05% B4C 1902 0.65 165.4 0.85
AA6061 + 10% B4C 902 0.70 256.4 0.82

Boric acid

AA6061 241 90 1.56 38.25 0.94


AA6061 + 05% B4C 113 55 1.95 35.78 0.89
AA6061 + 10% B4C 9379 0.98 31.47 0.89

Boric acid+Na benzoate

AA6061 247 10 1.85 88.24 0.94


AA6061 + 05% B4C 132 40 1.89 98.63 0.88
AA6061 + 10% B4C 3087 1.95 95.32 0.82

Figure 9. (a) and (c) Optical and SEM images of the corroded surface of Al6061/10 wt% B4C composite in uninhibited boric acid
solution, and (b) and (d) optical and SEM images of the corroded surface of Al6061-B4C composite in an inhibited boric acid
solution.

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Mater. Res. Express 3 (2016) 126501 Rafi-ud-din et al

Figure 10. SEM images of the corroded surface of the Al6061-B4C composite at higher magnification in boric acid solution and the
corresponding spot EDX analysis.

Conclusions

In the present study, SB is tested for the first time as a corrosion inhibitor for Al6061-B4C composites in H3BO3
and NaCl solutions. The Al6061100−x–x wt% B4C (x=0, 5, and 10) composites are manufactured by a powder
metallurgy process. The effects of B4C content on the corrosion behavior of composites in H3BO3 and NaCl
solutions were investigated using PDP and EIS techniques. Our key findings are as follows.

• The sinterability of composite powders decreases and the hardness of sintered compacts increases with an
increase in hard B4C contents, particularly above 10 wt%.
• Both polarization and impedance results show that SB is an efficient corrosion inhibitor for Al6061-B4C
composites in H3BO3 and NaCl solutions. The addition of inhibitor to both solutions lowers the corrosion
rate by suppressing both oxidation and reduction reactions.
• In the absence of SB, an increase of B4C content shifts the free corrosion potential to a more anodic value,
indicating higher thermodynamic affinity towards oxidation and corrosion. On the other hand, the corrosion
inhibition efficiency of SB increases with an increase in B4C content.
• The corrosion inhibition efficiency of SB is more pronounced in H3BO3 solution than NaCl. The presence of
chloride ions not only weakens the oxide layer on the Al alloy, but also the adsorbed benzoate layer, making
the inhibitor less effective.

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Mater. Res. Express 3 (2016) 126501 Rafi-ud-din et al

• The adsorption of benzoate ions forms a hydrophobic layer on top of the exposed Al surface that enhances the
protection against dissolved boride or chloride ions.
• The introduction of SB can be a promising way to provide active corrosion protection to the MMCs used in
spent nuclear fuel wet storage applications.

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