Effects of competitive anion adsorption

(Br− or Cl−) and semiconducting

properties of the passive films on the
corrosion behavior of the additively
manufactured Ti–6Al–4V alloys Dong-Il
Seo & Jae-Bong Lee
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 Corrosion Science 173 (2020) 108789

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Effects of competitive anion adsorption (Br− or Cl−) and semiconducting T

properties of the passive films on the corrosion behavior of the additively
manufactured Ti–6Al–4V alloys
Dong-Il Seo, Jae-Bong Lee*
School of Advanced Materials Engineering, Kookmin University, 77 Jeongneung-ro, Seongbuk-gu, Seoul 02707, Republic of Korea

A R T I C LE I N FO A B S T R A C T

Keywords: Herein, the corrosion behavior of the additively manufactured (AM) Ti–6Al–4V is investigated based on the
Pitting corrosion relation between the pitting potentials and equilibrium adsorption of the Br− and Cl− anions using potentio-
Additive manufacturing dynamic polarization curves, Mott–Schottky plots, and the Langmuir isotherm model. The Mott–Schottky plots
Ti–6Al–4V are measured using the microdroplet cell technique based on the capacitance of the passive films on each dark
Langmuir isotherm
and bright AM Ti–6Al–4V grain. The pitting potential can be attributed to the doping densities as well as α′ phase
Mott–Schottky plot
distribution and predicted using the equilibrium adsorption coefficient of Br− and Cl−.

1. Introduction SM Ti–6Al–4V alloy. Further, the unfavorable corrosion resistance of

Titanium (Ti) alloys are extensively used in various industries, such
as aerospace, marine, and medical industries, because of its high
strength-to-density ratio and excellent corrosion resistance [1–4]. Re-
cently, the usage of additive manufactured (AM) Ti alloys has become
popular owing to the buy-to-fly ratio advantage, which is approxi-
mately 20:1 compared to the conventional subtractively manufactured
(SM) Ti alloys [5,6]. From the mechanical viewpoint, the strength and
ductility of Ti alloys, such as Ti–6Al–4V, which are fabricated by ad-
ditive manufacturing, are comparable to or greater than those of their
counterparts manufactured by conventional methods owing to their
unique microstructures. However, the corrosion resistance of the AM Ti
alloys with respect to those of the conventionally manufactured Ti al-
loys is still unknown because both these alloys differ with respect to the
direction of stacking and formation of the martensite phase owing to
rapid solidification. The SM Ti–6Al–4V alloys have a dual-phase mi-
crostructure comprising α and β phases, whereas the AM Ti–6Al–4V
alloys contain α, β, and martensite α′ phases generated by rapid cooling
during additive manufacturing [7]. The martensite α′ phase is unstable
and considerably reduces the corrosion resistance of the AM Ti–6Al–4V
alloy [8–11]. Zhang and Attar [9] investigated the recent developments
associated with the selective laser melting of Ti alloys for biomedical
applications. They conducted electrochemical impedance spectroscopy
(EIS) experiments, indicating that the AM Ti–6Al–4V alloy exhibited an
unfavorable corrosion resistance compared with that of the commercial
the AM Ti–6Al–4V is related to the considerably larger content of aci-
cular α′ and smaller content of β-Ti phase in its microstructure com-
pared with those in the microstructure of the SM Ti–6Al–4V. Dai et al.
[10,11] studied the corrosion behavior of the AM Ti–6Al–4V alloy and
observed that the difference between the corrosion rates of the planes
parallel and perpendicular to the substrate can be attributed to the
formation of a “weaker” passive layer on the planes and the higher
portion of acicular martensitic α′ phase along the planes perpendicular
to the substrate. Further, they [12] extended their research to study the
potential of using heat treatment to reduce the α′ volume fraction in the
AM Ti–6Al–4V alloy. They hypothesized that heat treatment will result
in grain refinement and reduction in the volume fraction of the α′
phase. However, their research was limited to studying uniform cor-
rosion, and they did not study the effects of localized corrosion.
The corrosion resistance of the AM Ti–6Al–4V alloy is affected by
the types of ions present in the aqueous solutions. Halide solutions,
especially those containing Cl− or Br− ions, may play an important role
with respect to the reduction of the localized corrosion resistance of the
AM Ti alloys. White et al. [13] investigated the deterioration of native
and anodically grown oxide films on Ti alloys using scanning electro-
chemical microscopy (SECM). They observed that pitting occurred at
significantly lower potentials in Br− solutions compared to that in Cl−
solutions, indicating that Br− is strongly chemisorbed and causes the
dissolution of the oxide film and the growth of pits. Basame et al. re-
ported the susceptibility of Ti to pitting corrosion in aqueous solutions

⁎
Corresponding author.
E-mail address: leejb@kookmin.ac.kr (J.-B. Lee).

https://doi.org/10.1016/j.corsci.2020.108789
Received 9 March 2020; Received in revised form 2 June 2020; Accepted 2 June 2020
Available online 05 June 2020
0010-938X/ © 2020 Elsevier Ltd. All rights reserved.
D.-I. Seo and J.-B. Lee
containing more Br− than Cl−, indicating that the equilibrium ad-
sorption coefficient of the former was greater than that of the latter
[14] by 2.5 times using the Langmuir isotherm model [15] based on the
monolayer adsorption of molecules. Further, the competitive adsorp-
tions between Br− and Cl− can be attributed to their pitting potentials.
Therefore, in this study, the corrosion resistance of the AM Ti–6Al–4V
alloy is investigated with respect to the distribution of the α′ phases and
the adsorption of halide ions, including Br− and Cl−. The excellent
corrosion resistance of the Ti alloys can be attributed to the formation
of a concrete passive film, which exhibits n-type semiconducting
properties. Lee and Kim calculated the donor densities of the semi-
conductive passive films of ferritic and austenitic stainless steels using
Mott–Schottky plots [16], which represented the relation between the
pitting potentials and the donor densities of the passive films.
In this study, we investigate the effect of anions, such as Br− and
Cl−, and the semiconducting properties on the corrosion resistance of
the AM Ti–6Al–4V alloy. To further elucidate their relation, the pitting
potentials, doping densities, and equilibrium adsorption coefficients are
investigated using potentiodynamic polarization curves, Mott–Schottky
plots, and the Langmuir isotherm simulation model.
2. Experimental
2.1. Sample and test solution preparation
The AM Ti–6Al–4V alloy was used in this study. The sample was cut
to the dimensions of 26 mm × 25 mm × 2 mm (thickness) and manu-
factured via the directed energy deposition (DED) process (InssTek, MX-
4, Korea) using a laser power of 460 W at a laser scan speed of 0.85 m/
min in an Argon (Ar) gas atmosphere. The alloys were stacked via si-
multaneous injection using a laser with the following powder compo-
sition: C: 0.011, Fe: 0.18, Al: 6.1, V: 3.7, Sn: 0.01, and Ti: Bal, wt%
(produced by AP&C, Canada). All the fabricated samples were wet-
ground using 2000-grit SiC paper, polished with a suspension of 1-μm
alumina powder, washed using double-distilled water, and dried in air.
Before the electrochemical tests, 0.6 M NaCl and 0.6 M NaBr aqueous
solutions were prepared.
For conducting the Mott–Schottky measurements, a pH 8.5 buffer
solution (0.2 M boric acid, 0.05 M citric acid, and 0.1 M tertiary sodium
phosphate solution) was prepared in addition to 0.6 M NaCl and 0.6 M
NaBr aqueous solutions.
2.2. Microstructural characterization
The sample surfaces were etched using a solution containing 10 mL
of HNO3, 5 mL of HF, and 85 mL of H2O for 10 s. An optical microscope
(OM, Nikon Eclipse LV100) was used to characterize all the etched
samples.
Phase identification was performed using a Rigaku D/MAX 2500/PC
X-ray diffraction (XRD) fitted with a Cu∙Kα radiation source. The
samples were scanned at room temperature when 2θ = 30°–90° with a
step size of 1° and a dwell time of 1 min per step. The JADE9 (KSA)
software was used to analyze the XRD results.
The micro-Vickers hardness (Mitutoyo HM-211) was measured to
determine the difference between the α- and α′-phase grains on the AM
Ti–6Al–4V alloy surface.
2.3. Electrochemical measurements
The Gamry PCIB-4750 potentiostat was used for achieving po-
tentiodynamic polarization. Meanwhile, a three-electrode system was
used for performing the electrochemical tests, and the employed
counter electrodes included Pt and Au wires (in case of a microdroplet
cell). A saturated calomel electrode (SCE; 0.242 V vs. standard hy-
drogen electrode) was used to facilitate all the potential measurements.
In addition, a Luggin probe was employed to connect the reference and
2
Corrosion Science 173 (2020) 108789
working electrodes. In this study, micro-electrochemical experiments
were performed using a microdroplet cell [17] because the AM
Ti–6Al–4V alloys exhibit different corrosion resistances depending on
the distribution of the α′ phases. The microdroplet cell technique en-
ables the microelectrode to be aligned to the desired spot of the
working electrode and the direct measurement of local currents during
electrochemical polarization. For performing the microdroplet cell
tests, a capillary tip with a diameter of 330 μm was fabricated and si-
licon paste was used for sealing to prevent the leakage of the solution
from the capillary.
Potentiodynamic polarization tests were performed at a potential of
200 mV, which is lower than the open circuit potential (OCP), to 9.0 V
or the pitting potential at a scan rate of 1 mV/s in aqueous 0.6 M NaCl
and 0.6 M NaBr solutions.
To investigate the effect of the Br− and Cl− ions on the pitting
corrosion of the AM Ti–6Al–4V alloy, potentiodynamic polarization was
performed using microdroplet cell techniques in 0.6 M NaBr at various
concentrations of NaCl aqueous solutions (0.05, 0.3, 0.4, 0.5, 0.6, 0.7,
and 1 M). The equilibrium adsorption coefficients between Br− and Cl−
at each pitting potential in the above aqueous solutions were calculated
using a nonlinear data curve fitting program (Origin 8.0, Origin lab
corporation, USA).
The EIS measurements at the OCP were potentiostatically conducted
at an alternating current (AC) voltage amplitude of 10 mV within the
frequency range of 10−2–105 Hz. The EIS results were analyzed using
the Gamry Echem Analyst software.
During the formation of passive films for performing the
Mott–Schottky measurements, the samples were statically polarized for
2 h and the film formation potential was selected to be 1.0 or 1.5 V. The
capacitance was measured at 1000 Hz using a potentiostat (Gamry
PCIB-4750). The polarization was applied at successive steps of 50 mV,
starting at the film formation potentials in the cathodic direction up to
−2.0 V. To measure the metastable pitting susceptibility, potentiostatic
polarization experiments were conducted at a film formation potential
of 1.0 V for 2 h. The transient currents were collected at a sampling rate
of 1 point/s. The electrochemical measurements were performed in
triplicate for ensuring data reproducibility at 25 °C.
3. Results
3.1. Microstructure studies
The microstructures of the AM Ti–6Al–4V alloys were observed
through OM. Fig. 1 presents the micrographs of the AM Ti–6Al–4V alloy
denoting grains with acicular phases i.e., martensite α′.
Fig. 2 displays the XRD results of the AM Ti–6Al–4V sample, in-
dicating that its phases comprised only α and α′ phases without any β
phase.
To investigate the distribution of the α′ phase in the AM Ti–6Al–4V
alloy, the micro-Vickers hardness test was performed with respect to the
individual dark and bright grains observed via OM. The results showed
that dark grains (335 HV) exhibited greater hardness than the bright
grains (287 HV), indicating that the dark grains contained considerably
more acicular martensite α′ phase than the bright grains.
3.2. Potentiodynamic polarization studies
Fig. 3(a) and (b) show the potentiodynamic polarization curves
(micro-polarization) of dark and bright grains on the surface of the AM
Ti–6Al–4V alloy, as recorded using a microdroplet cell in aqueous 0.6 M
NaCl and 0.6 M NaBr solutions. As shown in Fig. 3(b), in case of 0.6 M
NaBr, the pitting potentials on the dark and bright grain areas were 4.4
( ± 0.04) V and 6.1 ( ± 0.10) V, respectively. The pitting potentials of
the AM Ti–6Al–4V on the dark grain area in 0.6 M NaCl aqueous so-
lution was 8.4 ( ± 0.17) V, and the bright grain area did not exhibit a
pitting corrosion behavior up to the maximum applied potential of
D.-I. Seo and J.-B. Lee
Fig. 1. Optical micrographs of the AM Ti–6Al–4V alloy. The inset is a magnified micrograph of the corresponding sample.
Fig. 2. XRD patterns of the AM Ti–6Al–4V alloy.
9.0 V (Fig. 3(a)). This indicates that the Br− ions cause a lower pitting
resistance with respect to the AM Ti–6Al–4V alloy when compared with
Cl−.
Fig. 4 represents the potentiodynamic polarization (micro-polar-
ization) behavior of the AM Ti–6Al–4V alloy in mixed aqueous solutions
containing various NaBr and NaCl concentrations. The addition of NaCl
(0.05–1 M) results in a positive shift with respect to the pitting poten-
tial. The dependence of the pitting potential on the relative con-
centrations of Br− and Cl− suggests that they compete for surface ad-
sorption sites, which is in agreement with the observations of Basame
[14].
Fig. 5 shows the dependence of pitting potential on the concentra-
tion of Cl− (in 0.6 M NaBr aqueous solutions) using the Langmuir iso-
therm model [15]. The pitting potential increases continuously from
the lowest Cl− concentration (0.05 M) to the highest Cl− concentration
3
Corrosion Science 173 (2020) 108789
(1 M) in 0.6 M NaBr + x M NaCl ( x = 0.05−1M) aqueous solutions.
The calculated equilibrium adsorption coefficients from Fig. 4 are β Br −
=29.6 mM−1 for Br− and βCl− =8.3 mM−1 for Cl−, which is in
agreement with the results of Basame (β Br − =24.7 mM−1 for Br− and
βCl− =9.1 mM−1 for Cl−).
3.3. EIS studies
Fig. 6 and Table 1 show the EIS test results of the AM Ti–6Al–4V
alloys in 0.6 M NaCl and 0.6 M NaBr aqueous solutions. A Randles
circuit model was used to represent an equivalent circuit comprising a
solution resistance (Rs), a charge transfer resistance (Rct), and constant
phase elements (CPEdl). CPE describes the deviation of an electro-
chemical reaction from the ideal capacitor behavior owing to the effects
of surface inhomogeneity and roughness. Brug et al. [18] developed a
relationship between the interfacial capacitance and the CPE. The es-
timated interfacial of capacitance for a Faradaic system is defined as Ceff
= [Q{(Rs+Rct)/(RsRct)}(α−1)]1/α, where Q is the CPE coefficient value,
α is the exponent of CPE ranging from -1 to 1, which is related to non-
uniform current distribution. Accordingly, α in Table 1 represents the
deviation from ideal capacitor, where ideal capacitor response in the
system corresponds to a fitted α value of 1. The capacitance should be
related to film thickness deff according to Eq. (1).
εε0
Ceff =
d eff (1)
where ε is the dielectric constant of a passive film (considered to be 85)
[19], εo is the vacuum permittivity of free space (8.854 × 10−14 F
cm−1). The values of Ceff and deff are presented in Table 1 for different
AM dark or bright grains in 0.6 M NaBr or 0.6 M NaCl solution. The
calculated values of deff can be compared to those given in Ohtsuka
et al. of Ti oxides [20]. It should be noticed that deff of AM bright grains
is higher than that of AM dark grains in both 0.6 M NaBr and 0.6 M
D.-I. Seo and J.-B. Lee
Fig. 3. Potentiodynamic polarization curves of the dark and bright grains of the AM Ti–6Al–4V alloy and optical micrographs of the samples collected after the test
using a microdroplet cell in (a) 0.6 M NaCl and (b) 0.6 M NaBr aqueous solutions.
NaCl solutions while deff in 0.6 M NaCl is higher than that in 0.6 M NaBr
for both AM dark and bright grains. Based on Rct, the dark (Fig. 6(a))
and bright (Fig. 6(b)) grains represent the inferior corrosion resistance
in the 0.6 M NaBr solution compared with that in the 0.6 M NaCl so-
lution.
3.4. Mott–Schottky analysis
The potentiodynamic polarization tests of the AM Ti–6Al–4V alloy
were performed in a pH 8.5 buffer solution (macro-polarization,
Fig. 7(a)) as well as 0.6 M NaCl and 0.6 M NaBr (micro-polarization,
4
Corrosion Science 173 (2020) 108789
Fig. 7(b)) aqueous solutions to determine the film formation potentials
with respect to Mott–Schottky analysis. 1.0 and 1.5 V were considered
to be the film formation potentials in these aqueous solutions.
Fig. 8(a) and (b) show the Mott–Schottky plots (1/C2 versus E) of
the passive films formed on the AM Ti–6Al–4V alloy in aqueous 0.6 M
NaCl and 0.6 M NaBr solutions respectively. The capacitance mea-
surement results with respect to the passive films formed at film for-
mation potentials of 1.0 and 1.5 V show the existence of three potential
ranges (R1–R3) because of different capacitance behaviors with applied
potentials. The AM Ti–6Al–4V exhibits an n-type semiconductor of Ti
oxide layer, as shown by the positive slopes (R2), and is similar to that
D.-I. Seo and J.-B. Lee Corrosion Science 173 (2020) 108789

Fig. 4. Potentiodynamic polarization curves of dark grains of the AM

Ti–6Al–4V alloy obtained using a microdroplet cell in aqueous mixed solutions
containing 0.6 M NaBr with various concentrations of NaCl.

Fig. 6. The EIS results represented by the Bode plots of (a) dark grains and (b)
bright grains in the AM Ti–6Al–4V alloy in 0.6 M NaCl and 0.6 M NaBr aqueous
solutions. The inset equivalent circuit is used to fit the impedance spectra.

4. Discussion

Fig. 5. Epit as a function of NaCl concentration in solutions containing a fixed 4.1. Effect of competitive anions (Br− or Cl−) on the corrosion resistance of
concentration of NaBr (0.6 M). The dashed lines correspond to Epit measured in the AM Ti–6Al–4V
solutions containing either 0.6 M NaCl (Epit=8.4VSCE) or 0.6 M NaBr
(Epit = 4.4 VSCE) at 25 °C. The solid red line through the data corresponds to the
To understand the effect of the types of halide ions (Cl− and Br−) on
theoretical fit (Eq. 1) obtained by assuming a Langmuir isotherm for the
competitive adsorption of Br− and Cl−. (For interpretation of the references to
the corrosion resistance of the AM Ti–6Al–4V alloy, the pitting poten-
colour in this figure legend, the reader is referred to the web version of this tials in case of bright or dark grains were measured using potentiody-
article). namic polarization curves, as shown in Fig. 3(a) and (b). The results
show that the pitting potentials in case of a 0.6 M NaBr solution is lower
than those of a 0.6 M NaCl solution in bright (low α′ phase) and dark
of the SM Ti–6Al–4V alloys, as examined by Ibriş et al. [21]. Based on
(high α′ phase) grains. Fig. 4 shows the dependence of the pitting po-
the slopes (R2) in Fig. 8, the calculated donor densities (Table 2) are
tential of the AM Ti–6Al–4V alloy in 0.6 M NaBr solution and x M NaCl
1018–1019, which are comparable to those calculated by Krawiec et al.
( x = 0.05–1 M). The pitting potentials increased with increasing Cl−
[22]. Fig. 9 shows the plot of current density versus time using po-
concentrations from 4.4 ( ± 0.09) V to 7.2 ( ± 0.20) V in the solution.
tentiostatic polarization at 1.0 V in an aqueous pH 8.5 buffer solution as
The dependence of the pitting potential on the concentration of Cl−
well as 0.6 M NaCl and 0.6 M NaBr solutions. These results denote the
can be modeled by assuming a Langmuir isotherm [15] for the ad-
variations in transient current density. The incidence of current den-
sorption of anions on the oxide film surface and the linear relation
sities and the height of the individual current density transients sig-
between pitting potential and the coverage of Cl−. According to this
nificantly decreased in the following order: 0.6 M NaBr, 0.6 M NaCl,
model, the equilibrium adsorption coefficients between Br− and Cl−
and buffer (pH 8.5) solutions, indicating that the presence of Br− ions
can be derived using Eq. (2) [14].
leads to more metastable pits and eventually to a higher metastable
pitting susceptibility when compared with those observed in case of Cl− sat−
Epit (ΓBr −, ΓCl−) = Epit (ΓBr )
ions. This can be attributed to the higher adsorption coefficient of Br−.
Fig. 10 shows the effect of Br− or Cl− having bright or dark grains, sat− ⎛ β Br − [Br −] ⎞⎟
+ Ω Br − ΓBr ⎜1 −
respectively, on the donor densities at film formation potentials of 1.0 V ⎝ 1 + β Br − [Br −] + β − [Cl−]
Cl ⎠
(Fig. 9(a)) and 1.5 V (Fig. 9(b)). Br− has more influence on the donor β − [Cl−]
densities at film formation potentials of 1.0 and 1.5 V than Cl−, in- − ΩCl− ΓClsat− ⎛⎜ Cl
− −
⎞⎟
dicating a facilitated deterioration of the oxide film. ⎝ 1 + β Br − [Br ] + βCl− [Cl ] ⎠ (2)
sat−
where Epit (ΓBr ) represents the pitting potential when the surface is
completely covered by Br−, Ω Br − is a proportionality constant that

5
D.-I. Seo and J.-B. Lee Corrosion Science 173 (2020) 108789

Table 1
Fitting parameters of the EIS measured in 0.6 M NaBr and 0.6 M NaCl aqueous solutions for the Ti–6Al–4V samples produced by the AM processes.
RS (Ωcm2) Rct (kΩcm2) α CPEdl, Q (Ω−1∙cm-2∙Secα) Ceff (μFcm−2) deff (nm)

−6
AM dark grains (0.6 M NaBr) 4.30 (± 0.38) 12.5 (± 0.12) 0.8714 44.25 (± 0.34) × 10 12.9 (±0.05) 5.84 (±0.02)
AM dark grains (0.6 M NaCl) 4.23 (± 0.41) 44.2 (± 0.39) 0.8792 25.42 (± 0.15) × 10−6 7.24 (±0.04) 10.4 (±0.06)
AM bright grains (0.6 M NaBr) 4.18 (± 0.37) 21.5 (± 0.21) 0.8748 40.56 (± 0.29) × 10−6 11.7 (±0.05) 6.44 (±0.03)
AM bright grains (0.6 M NaCl) 4.26 (± 0.42) 90.6 (± 0.22) 0.8707 23.15 (± 0.12) × 10−6 5.88 (±0.05) 12.8 (±0.10)

※ AM (additive manufacturing).

Fig. 8. Mott–Schottky plots for the passive films formed on the AM Ti–6Al–4V
with film formation potentials of 1.0 VSCE or 1.5 VSCE in (a) 0.6 M NaCl and (b)
Fig. 7. Potentiodynamic polarization curves of the AM Ti–6Al–4V alloys for 0.6 M NaBr aqueous solutions.
determining the appropriate film formation potentials in a buffer (pH 8.5) as
well as 0.6 M NaCl and 0.6 M NaBr aqueous solutions.
higher equilibrium adsorption coefficient of Br−, which is 3.6 times
greater than that of Cl−. This higher equilibrium adsorption coefficient
describes the sensitivity of the pitting potential to the surface con-
of Br− can be attributed to the more aggressive attack on the passive
centration of Br−, ΓBr sat−
is the surface concentration of Br−, β Br − is the
film of the AM Ti–6Al–4V alloy.
equilibrium adsorption coefficient of Br−, [Br −] is the molar con-
centration of Br−, ΩCl− is a proportionality constant that describes the
sensitivity of the pitting potential to the surface concentration of Cl−, 4.2. Effect of microstructures (α′ phases) on the corrosion resistance of the
ΓClsat− is the surface concentration of Cl−, βCl− is the equilibrium ad- AM Ti–6Al–4V alloy in halide ion solutions using Mott–Schottky plots
sorption coefficient of Cl−, and [Cl−] is the molar concentration of Cl−.
sat−
In Eq. (1), the pitting potential (Epit (ΓBr ) ) estimated in saturated
The α′ phase formed in the AM Ti–6Al–4V alloy during the AM
NaBr is 4.4 V and the values of Ω Br − ΓBr sat−
and ΩCl− ΓClsat− in mixed Br− and
process [16,22] is known as an acicular martensitic structure; this
Cl− solutions are 20.7 and 11.8 V, respectively, as obtained by Basame
structure is associated with the rapid cooling of spots that occurred
[14]. Using the nonlinear curve fitting technique (Fig. 5), the equili-
after being exposed to an energy source such as a laser [23,24]. The
brium adsorption coefficient of Br− and Cl−, i.e., β Br − and βCl−, are
XRD results of the AM Ti–6Al–4V alloy identify only α or α′ phases
calculated as 29.6 mM−1 for Br− and 8.3 mM−1 for Cl−, respectively,
without any β phase. The α and α′ phases in the AM Ti–6Al–4V are not
which are similar to the values obtained by Basame [7]. This indicates
easily distinguished based on XRD peaks because both the phases have
that more Br− can be adsorbed on the oxide surface than Cl− due to the
the same HCP structure [25]. To identify the α and α′ phases, micro-

6
D.-I. Seo and J.-B. Lee Corrosion Science 173 (2020) 108789

Table 2
The Mott–Schottky data at the film formation potentials (1.0 VSCE and 1.5 VSCE)
for bright and dark grains of the AM Ti–6Al–4V in 0.6 M NaCl and 0.6 M NaBr
aqueous solutions.
Donor density (× 1018 cm−3)

Film formation 1.0 VSCE 1.5 VSCE

potential
Bright grains Dark grains Bright grains Dark grains

pH 8.5 buffer 7.05 7.08 3.17 3.75

solution ( ± 0.09) ( ± 0.12) ( ± 0.20) ( ± 0.25)
NaCl 7.35 10.9 4.45 4.72
( ± 0.15) ( ± 0.10) ( ± 0.12) ( ± 0.14)
NaBr 11.4 16.4 5.18 7.26
( ± 0.24) ( ± 0.38) ( ± 0.33) ( ± 0.47)

Fig. 9. The potentiostatic polarization results represented by the plot of current

density versus time for the AM Ti–6Al–4V alloys at an applied potential of
1.0 VSCE in a buffer (pH 8.5) as well as 0.6 M NaCl and 0.6 M NaBr aqueous
solutions.
Vickers hardness test was performed on the dark grain (more α′ and less
α phases) and the bright grain (less α′ phases and more α phases), in-
dicating that the former is harder than the latter. The EIS results
(Table 1) show that the dark grain had a lower corrosion resistance
compared to that of the bright grain in Rct. Furthermore, the dark and
bright grains show less corrosion resistance in the NaBr aqueous solu-
tion when compared with those in NaCl aqueous solution.
To further understand these results, Mott–Schottky analysis was
separately performed on the dark and bright grain areas of the AM
Ti–6Al–4V alloys in 0.6 M NaCl and 0.6 M NaBr aqueous solutions using
the microdroplet cell technique [17]. The different donor densities on
the individual dark and bright grain areas of the AM Ti–6Al–4V alloys
for n-type semiconductors can be calculated using Eq. (3). [19,25–27].
1 2 ⎛ kT ⎞
= E − Efb −
Csc2 εε0 eND ⎝ e ⎠
where ε is the dielectric constant of a passive film (considered to be 85)
[19], εo is the vacuum permittivity of free space (8.854 × 10−14 F
cm−1), e is the electron charge, ND is the donor density, Efb is the flat
band potential, k is the Boltzman constant, and T is the absolute tem-
perature. ND can be determined based on the slopes of the Mott–-
Schottky plots.
Table 2 shows a higher donor density and a lower pitting potential
in 0.6 M NaBr when compared with those in 0.6 M NaCl. This phe-
nomenon can be explained using the point defect model (PDM) [28].
According to PDM, the passive film contains several point defects, in-
cluding oxygen and/or cation vacancies, which serve as donors and
acceptors, respectively. Therefore, an increased donor density in the
passive film may be considered to be an increase in oxygen vacancies.
Fig. 10. Donor densities of the AM Ti–6Al–4V alloy on the individual bright
and dark grains in an aqueous buffer (pH 8.5) as well as 0.6 M NaCl and 0.6 M
NaBr solutions at film formation potentials of (a) 1.0 VSCE and (b) 1.5 VSCE.
Meanwhile, halide ions may absorb into a surface oxygen vacancy and
the system can respond to the loss of the oxygen vacancy by acquiring a
positive charge. This causes the generation of cation vacancy/oxygen
vacancy pairs according to the following Schottky pair reaction:
χ
Null ⇔ VMχ' + ( ) V ''O
2 (4)
Here, VMχ′ and V ′′O represents a cation vacancy and an oxygen vacancy,
respectively.
The newly generated oxygen vacancies can react with additional
halide ions at the film/solution interface to generate more oxygen and
cation vacancies. Therefore, the rate of generation of cation vacancies
increases with an increase in the adsorption of halide ions. The newly
(3) generated cation vacancies are transported across the barrier layer and
are annihilated by the emission of cations from the metal into the film
as follows:
m + VMχ′ → MM + VM + χe' (5)
where m is a metal atom, MM is a metal cation at a cation site, and VM is
a vacancy in the metal phase.
If this annihilation reaction cannot consume the cation vacancies
arriving at the metal/film interface, the excess vacancies will condense,
form voids, and result in a local detachment of the film from the un-
derlying metal substrate. Thus, the passive film cannot grow on the
locally detached sites. Pits are formed if a sufficiently high local tensile
stress is applied in the locally dissolved sites in the passive film.
Therefore, the halide ion concentration may increase the cation

7
D.-I. Seo and J.-B. Lee
vacancy concentration at the film/solution interface, generating pits
due to the formation of voids at the metal/film interface. Hence, with
respect to the susceptibility of the localized corrosion resistance, the
pitting corrosion of the AM Ti–6Al–4V alloy was attributed to the high
equilibrium adsorption coefficient of Br− and the high α′ phase dis-
tribution.
5. Conclusions
The results of this study indicated that the pitting corrosion of the
AM Ti–6Al–4V alloy was determined based on the equilibrium ad-
sorption coefficient, the donor density obtained using the
Mott–Schottky plots, and the α′ phase distribution obtained via the
micro-Vickers hardness test. The pitting potentials of the areas of bright
and dark grains were measured using the microdroplet cell technique.
The pitting potentials of Br− and Cl− can be predicted using the
Langmuir isotherm simulation to obtain their equilibrium adsorption
coefficients. By considering a competitive adsorption model between
Br− and Cl−, the higher equilibrium adsorption coefficient of Br− can
be attributed to the more aggressive attack on the passive film of the
AM Ti–6Al–4V alloy. The AM Ti–6Al–4V alloy with a higher α′ phase
distribution contained more defects, which are associated with the
higher donor density on the passive film observed using Mott–Schottky
plots. This phenomenon was explained using PDM.
CRediT authorship contribution statement
Dong-Il Seo: Investigation, Data curation, Software, Writing - ori-
ginal draft, Visualization. Jae-Bong Lee: Conceptualization,
Methodology, Resources, Writing - review & editing, Supervision,
Project administration, Funding acquisition.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
This work was supported by the Technology Innovation Program
(20006868, Standard Development for Corrosion testings of Additive
Manufactured (3D Printing) Bio-metallic material) funded By the
Ministry of Trade, Industry & Energy (MOTIE, Korea).
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 CHAPTER XXVIII.
DEATH OF OMAR.

A.H. XXIII. A.D. 644.

It was now the eleventh year of Omar’s

Caliphate, and though fifty-five years of Omar performs pilgrimage;
age (according to others over sixty) he was end of a.h. XXIII. October,
a.d. 644.
full of vigour and vigilant in the discharge
of the vast responsibilities that devolved upon him.[418] In the last
month of the twenty-third year of the Hegira, he journeyed, as was
his wont, to Mecca; and taking on this occasion the Widows of
Mahomet in his suite, performed with them the rites of the annual
Pilgrimage. He had returned but a few days to Medîna, when his
reign came to a tragical and untimely end.
A Persian slave, Feroze, called more
familiarly Abu Lulû, had been brought by Abu Lulû, a Persian slave,
Moghîra from Irâc. Carried off a prisoner in promises to make a windmill.
his youth by the Romans, he had early embraced Christianity; and
now, captured from them by the Moslems, his fate was to endure a
second captivity as Moghîra’s slave. When the crowd of prisoners
was marched into Medîna from the battle of Nehâvend (which is said
to have been his birthplace) he gave vent to his grief; the sight
opened springs of tenderness long pent up, and stroking the heads
of the little ones, he exclaimed: ‘Verily, Omar hath consumed my
bowels!’ He practised the trade of a carpenter; and Moghîra, as his
owner, shared the profit. Meeting Omar in the market-place,[419] he
cried out, ‘Commander of the Faithful! right me of my wrong, for
verily Moghîra hath assessed me heavily.’ ‘At how much?’ asked the
Caliph. ‘At two dirhems a day.’ ‘And what is thy trade?’ ‘A carpenter,
designer, and worker in iron.’ ‘It is not much,’ replied Omar, ‘for a
clever artificer like thee. I am told that thou couldst make for me a
mill driven by the wind.’ ‘It is true.’ ‘Come then,’ continued the Caliph,
‘and make me such a mill that shall be driven by the wind.’ ‘If
spared,’ said the captive in a surly voice, ‘I will make a mill for thee,
the fame whereof shall reach from the East even to the far West;’
and he went on his way. Omar remarked, as he passed on, the
sullen demeanour of Abu Lulû:—‘That slave,’ he said, ‘spoke
threateningly to me just now.’[420]
Next morning, when the people
assembled in the Great Mosque for the Omar mortally wounded by
Abu Lulû.
early matin prayer, Abu Lulû mingled with
the front rank of the worshippers. Omar entered, and, as was
customary with the Imâm who led the prayers, took his stand in
advance of the congregation, having his back towards them. He had
no sooner called out the first words, Allah Akbar, than Abu Lulû
rushed upon him, and with a sharp blade inflicted six wounds in
different parts of his body. Then he ran wildly about, killing some and
wounding others, and at last stabbed himself to death. Omar, who
had fallen to the ground, was borne into his house, which adjoined
the Mosque, sufficiently composed to desire that Abd al Rahmân
should proceed with the service. When it was ended, Omar
summoned him to his bedside, and signified his intention of
nominating him to the Caliphate. ‘Is this obligatory upon me?’
inquired Abd al Rahmân. ‘Nay, by the Lord!’ said Omar, ‘thou art
free.’ ‘That being so,’ he replied, ‘I never will accept the burden.’[421]
‘Then stanch my wound,’ said the dying Caliph (for life was ebbing
fast through a great gash below the navel), ‘and stay me while I
commit my trust unto a company of men that were faithful unto their
Prophet, and with whom their Prophet was well pleased.’ So he
named together with Abd al Rahmân, other
four, namely Aly, Othmân, Zobeir, and Sád, Omar appoints Electors to
as the chiefest among the Companions of choose successor.
Mahomet, to be the electors of his successor, and called them to his
bedside. When they appeared, he proceeded thus:—‘Wait for your
brother Talha (who was absent for the moment from Medîna) three
days; if he arrive, take him for the sixth; if not, ye are to decide the
matter between you.’ Then, addressing each in turn, he warned them
of the grave responsibility attaching to their office as Electors, and
the danger to the elected one of favouring unduly his own clan and
family. ‘O Aly, if the choice fall upon thee, see that thou exalt not the
Beni Hâshim above their fellows. And thou, Othmân, if thou art
elected, or Sád, beware that thou set not thy kinsmen over the necks
of men. Arise, go forth, deliberate and then decide. Meanwhile
Soheib shall lead the public prayers.’[422] When they had departed,
he called Abu Talha, a warrior of note, to him:[423] ‘Go, stand,’ he
said, ‘before their door, and suffer no man to enter in unto them.’
After a while he proceeded solemnly, addressing those around him:
—‘To him who shall succeed, give it as my dying bequest that he be
kind to the Men of this city, which gave a home to us and to the
Faith; that he make much of their virtues, and pass lightly by their
faults. And bid him treat well the Arab tribes, for verily they are the
backbone of Islam; the tithe that he taketh from them, let him give it
back unto the same for the nourishment of their poor. And the Jews
and Christians, let him faithfully fulfil the covenant of the Prophet with
them.[424] O Lord, I have finished my course. And now to him that
cometh after me I leave the kingdom and the Caliphate firmly
stablished and at peace.’ Then he lay down quietly and rested for a
time.
After a while he bade his son go forth,
and see who it was that had wounded him. Omar desires to be interred
beside the Prophet.
Being told that it was Abu Lulû, he
exclaimed:—‘Praise be to the Lord that it was not one who had ever
bowed down before Him, even once, in prayer! Now, Abdallah, my
son, go in unto Ayesha, and ask her leave that I be buried in her
chamber by the side of the Prophet, and by the side of Abu Bekr. If
she refuse, then bury me by the other Moslems, in the graveyard of
Backî.[425] And list thee, Abdallah, if they disagree’ (for he too was to
have a voice in the election) ‘then be thou with the majority; or, if the
votes be equal, then choose thou that side on which is Abd al
Rahmân. Now let the people come in.’ Crowds had assembled at the
door; and, permission having been given, they approached to make
obeisance. As they passed in and out, Omar asked whether any
leading man had joined in conspiring against him. ‘The Lord forbid!’
was the loud response of all, in horror at the very word. . For this
burying-ground, see Life of Mahomet, p. 208.
 Among the rest, Aly came forward to
inquire; and as he sat by the bedside, the Omar’s death.
son of Abbâs came up. Omar, who
dreaded the factious spirit of the latter, said: ‘O Ibn Abbâs, art thou
with me in this matter?’ He signified assent, whereupon Omar added
earnestly: ‘See that thou deceive me not, thou and thy fellows.[426]
Now, Abdallah, my son, raise up my head from the pillow, and then
lay it gently on the ground:[427] peradventure the Lord may in mercy
take me thus, this night, for I fear the horrors of the rising sun.’ A
physician gave him to drink of date-water; but it oozed through the
wound unchanged; and so also with a draught of milk. Which when
the physician saw, he said: ‘I perceive that the wound is mortal:
make now thy testament, O Commander of the Faithful.’ ‘That,’ said
Omar, ‘have I done already.’ As he lay, his head resting on the
bosom of his son, he recited this couplet:—
It had gone hard with my soul, if I had not been a Moslem;
But verily all the appointed prayers have I observed, and fasted.

And so, in a low voice, he kept Nov. 3, a.d. 644.

repeating the name of the Lord, and the
short Moslem creed, until his spirit passed away. It was the 26th of
Dzul Hijj, the 23rd year of the Hegira. He had reigned for the space
of ten years and a half.[428]
So died Omar, next to the Prophet the
greatest in the of Islam; for it was all within Achievements of his
these ten years that, by his wisdom, Calphate.
patience, and vigour, the dominion was achieved over Syria, Egypt,
and Persia, which Islam has ever since maintained. Abu Bekr beat
down the apostate tribes; but at his death the armies of Islam had
but just crossed the Syrian frontier. Omar began his reign the master
only of Arabia. He died the Caliph of an empire embracing Persia,
Egypt, and some of the fairest provinces of the Byzantine throne. Yet
throughout this marvellous fortune he never lost the equipoise of a
wise and sober judgment, nor exalted himself above the frugal and
familiar style of the Arab Chief. ‘Where is the Caliph?’ would the
visitor from distant provinces inquire, as he looked around the court
of the Great Mosque; and all the while the monarch sat in homely
guise before him.
The features of Omar’s life it requires
but few lines to sketch. Simplicity and duty Character of Omar.
were his guiding principles. Impartiality and
devotion characterised the discharge of his great office; and the
responsibility so weighed upon him that at times he would exclaim,
‘O that my mother had not borne me; would that I had been this stalk
of grass instead!’ Of a fiery and impatient temper, he was noted in
his youth, and even during the later days of the Prophet’s life, as the
stern advocate of vengeance. Ever ready to unsheathe the sword, it
was he who, after the battle of Bedr, advised that the prisoners
should all be put to death. But age, as well as weight of office, had
mellowed the asperity of his nature.[429] His sense of justice was
strong. And excepting the treatment of Khâlid, whom he pursued
with an ungenerous resentment, no act of tyranny or injustice is
recorded against him; and even in this matter his enmity took its rise
in Khâlid’s unscrupulous treatment of a fallen foe. The choice of his
captains and governors was free from favouritism; and (the
appointment of Moghîra and Ammâr excepted) singularly fortunate.
The different tribes and bodies in the empire, representing interests
the most diverse, reposed in his integrity the utmost confidence, and
his strong arm maintained the discipline of law and empire. A certain
weakness is discernible in his change of governors at the factious
seats of Bussorah and Kûfa. But even so, the conflicting claims of
Bedouin and Coreish were kept by him in check, and never dared to
disturb Islam till he had passed away. The more distinguished of the
Companions he kept around him at Medîna, partly, no doubt, to
strengthen his counsels, and partly (as he would say) from
unwillingness to lower their dignity by placing them in an office
subordinate to himself.[430] Whip in hand, he perambulated the
streets and markets of Medîna, ready to punish the offenders on the
spot; and it became a proverb,—‘Omar’s whip is more terrible than
another’s sword.’ But with all this he was tender-hearted, and
numberless acts of kindness are recorded, such as relieving the
wants of the widow and the fatherless.[431]
 Omar was the first who assumed the
title Ameer al Momenîn, or ‘Commander of The first called Commander
the Faithful.’ Caliph (Successor) of the of the Faithful.
Prophet of the Lord, was, he said, ‘too long and cumbersome a
name, while the other was easier and more fit for common use.’
According to his desire, Omar was
buried side by side with the Prophet and Burial of Omar.
Abu Bekr, in the chamber of Ayesha.
Soheib, as presiding over the public prayers, performed the funeral
service, and the five Electors, with Abdallah, the Caliph’s son,
lowered the body into its last resting-place.
The Moslem annalist may well sigh as
he bids farewell to the strong and single- Faction and schism in
minded Caliph; and enters on the troubled prospect.
sea of self-seeking faction, strife, and schism, which opens with the
Caliphate of his successor.
 CHAPTER XXIX.
ELECTION OF OTHMAN.

DZUL HIJJ, A.H. XXIII.—MOHARRAM, A.H. XXIX.

NOVEMBER, A.D. 644.

What arrangement Omar might have

made for a successor, had his end come The Electors.
less suddenly upon him, it is perhaps
unnecessary to inquire. But some more definite choice he would, in
all probability, have signified. We know that the perils of disunion
hung heavily on his mind. The unbridled arrogance of the numerous
powerful tribes settled in Kûfa and Bussorah, flushed with the glory
and the spoils of war, was already felt a danger; while family rivalries
amongst the Coreish themselves were beginning to weaken their
hold over the people which had hitherto been absolute. So much is
plain, that (Abd al Rahmân perhaps excepted) Omar saw none
amongst them endowed with sufficient power and influence, after his
death, to hold the reins of government. There was none, at least, so
prominent as to take the acknowledged lead. Again, the mode of
nomination or election proper to Islam, was as yet all uncertain. Abu
Bekr had on his death-bed named Omar his successor; but the
higher precedent of Mahomet, who appointed no one to take his
place, but simply named Abu Bekr, when he fell sick, to lead the
prayers, was doubtful. Had Abu Obeida been yet alive, Omar
declared that he would have chosen him; and the succession now
offered to Abd al Rahmân was (as we have seen) declined. Weak
and faint from the assassin’s dagger, the emergency came upon the
dying Caliph altogether unprepared to meet it. So, relieving himself
of the responsibility, he fell upon the expedient of nominating the six
chiefest Companions, on one or other of whom he knew that the
choice must needs fall, to be the Electors of a successor from
amongst themselves. These were Abd al Rahmân, Othmân, Aly,
Sád, Zobeir, and Talha. A seventh was added in the person of his
son Abdallah, who, himself excluded from election,[432] was (in case
the conclave were divided) to have the casting vote; and this his
father desired him to give on whichever side Abd al Rahmân might
be. Talha was absent, and did not return until the election had been
made.
Omar hoped, no doubt, that the
Successor thus chosen would be strong in Character of the Electors.
the support of his Electors. But he had not
calculated on the frailty of human nature; and selfish ends proved
more powerful than loyalty to Islam. Abd al Rahmân was the only
real patriot amongst them. Talha, Zobeir, and Sád, not yet beyond
the age of fifty, had none of them any special reason to aspire to the
Caliphate. They were all warriors of renown. Zobeir was closely
related to the Prophet. Sád was the nephew of Mahomet’s mother;
but his recall from Kûfa (although Omar had declared it to involve no
discredit) could not but in some measure tarnish the fame of the
conqueror of Medâin. Aly, a few years younger, had by far the
strongest claims of kinship (whatever these might be); for he was at
once the son of Mahomet’s uncle, the widowed husband of Fâtima,
and the father of the Prophet’s only surviving grandsons. He had
hitherto, from his inactive temperament, remained passive at the
Caliph’s court; but, possessed of a quick and high intelligence, he
had ever held a distinguished place in the counsels of Omar. The
time was now come, when, in the absence of any leading competitor,
his claims could no longer fail to be recognised by those around him;
or, without want of spirit, to be asserted by himself. Othmân was the
only real rival. His years carried weight, for he was now close on
seventy. Handsome and attractive in person and carriage, he gained
the hand of Rockeya, the Prophet’s daughter. She died while the
battle of Bedr was being fought. Shortly after, he married her sister
Omm Kolthûm; and when she, too, died, Mahomet used to say he
loved Othmân so dearly that, if another daughter had remained, he
would have given her also to him. But with all this, his character had
vital defects. Of a close and selfish disposition, his will was soft and
yielding. And of all the competitors, Othmân probably had the least
capacity for dominating the unruly elements of the Moslem empire.
 The Electors, when appointed by Omar,
retired at once to an adjoining chamber, Electors’ conclave. Three
and forthwith fell into such loud and hot days’ fruitless discussion.
discussion, that Abdallah exclaimed, ‘Good heavens! all this tumult,
and my father still alive!’ Omar, overhearing it, desired that they
should wait till his decease, and then again assemble. So after his
death and burial, Micdâd, a veteran citizen appointed by the
deceased Caliph to the duty, gathered the Electors in the treasury
chamber attached to Ayesha’s house, Abu Talha keeping watch at
the door with a guard of fifty men.[433] Omar’s order was that the
choice should not be delayed beyond the third day, so that his
successor might be declared by the fourth at latest; and he signified
the urgency of the business in the empire’s interest, by saying that if
the minority then resisted, they should be beheaded on the spot.
When the Electors came together, each pressed hotly the claim of
his own party, and two days were wasted in unprofitable wrangling.
Abd al Rahmân spent his nights in visiting the leading citizens, and
the governors and chief men from the provinces (who, having come
for the yearly pilgrimage, had not yet departed to their several posts)
and in sounding their views. On the third day, Abu Talha warned the
Electors that he would allow no further delay, and that the decision
must be come to by the following morning. To bring the matter,
therefore, to an issue, Abd al Rahmân offered to forego his own
claim to the Caliphate, if only the rest would abide by his decision.
They all agreed but Aly, who at first was silent. At last Aly said: ‘First
give me thy word that thou wilt not regard kith nor kin, but the right
alone and the people’s weal.’ ‘And I,’ rejoined Abd al Rahmân, ‘ask
thee first to give me thy troth that thou wilt abide by my choice, and
against all dissentients wilt support the same.’ Aly assented, and
thus the matter rested in the hands of Abd al Rahmân.
That night Abd al Rahmân did not close
his eyes. The contest was narrowed Abd al Rahmân acts as
between the houses of Hâshim and Umpire.
Omeyya, in the persons of Aly and Othmân, and their influence with
the electoral body was fairly equal.[434] Abd al Rahmân was closeted
with each of the Electors alone in turn. Zobeir was in favour of Aly;
how Sád voted is not certain. With Aly and Othmân, separately, Abd
al Rahmân was long in secret conference. Each pressed his own
claim; but each also admitted the claim of the other to be the next in
weight to his own. The morning broke upon them thus engaged; and
now the nomination must be made.
The Great Mosque overflowed with
expectant worshippers, who crowded in Othmân elected Caliph.
unusual number to the morning service.
Abd al Rahmân addressed them thus:—‘The people think that the
governors, chiefs, and captains should, without further waiting, return
to their respective posts. Wherefore advise me now in this matter.’
Ammâr, the late governor of Kûfa, said: ‘If it be thy desire that there
be no division in the land, then salute Aly, Caliph!’ and Micdâd
affirmed the same. ‘Nay,’ cried Abu Sarh, ‘if it be thy desire that there
be no division, then salute Othmân!’ and Abu Rabia affirmed the
same. Ammâr turned contemptuously on Abu Sarh; who, repaying
scorn with scorn, said: ‘And pray, Ammâr, how long hast thou been
counsellor to the Moslems? Let the Beni Hâshim and Omeyya speak
for themselves.’ But Ammâr would not be silent, and, continuing to
press the claims of Aly, asked why the government should pass
away from the Prophet’s line. Whereupon one of the Beni Makhzûm
(a Coreishite tribe) cried angrily: ‘Thou passest beyond thy bounds,
O son of Sommeyya; who art thou, thus to counsel the Coreish?’[435]
Sád, seeing that the strife was waxing warm, said to Abd al Rahmân:
‘Finish thy work at once, or the flames of discord will burst forth.’
‘Silence, ye people!’ cried Abd al Rahmân—‘Be quiet, or ye will bring
evil upon yourselves. The determination of this matter resteth with
me.’ So saying, he called Aly to the front, and thus addressed him:
‘Dost thou bind thyself by the covenant of the Lord, to do all
according to the Book of the Lord, the example of the Prophet, and
the precedent of his Successors?’ ‘I hope,’ responded Aly, ‘that I
should do so; I will act according to the best of my knowledge and
ability.’ Then he put the same question to Othmân, who answered
unconditionally,—‘Yea, I will.’ Whereupon, either dissatisfied with
Aly’s hesitating answer, or having already decided in his mind
against him, Abd al Rahmân raised his face toward heaven, and
taking Othmân by the hand, prayed thus aloud:—‘O Lord, do thou
hearken now and bear me witness. Verily the burden that is around
my neck, the same I place around the neck of Othmân.’ So saying,
he saluted him as Caliph, and all the people followed his example.
It was the first day of the new year, the
twenty-fourth of the Hegira. After receiving Othmân’s inaugural address,
3d Moharram, a.h. XXIV.
the homage of the people, a process in Nov. 7, a.d. 644.
which two or three days were occupied,
Othmân ascended the pulpit, and made a brief and modest speech.
[436] ‘The first attempt,’ he said, ‘was always difficult, for he was
unused to speak in public. It would be his duty in the future to
address them, and the Lord would teach him.’
Though Aly, like the rest, took the oath
of allegiance to Othmân, yet his party were Aly swears allegiance.
much displeased, and he himself
upbraided Abd al Rahmân bitterly with the desire to keep the
supreme power out of the Prophet’s house and brotherhood.
‘Beware,’ said Abd al Rahmân, with a prophetic warning: ‘take heed
lest, thus speaking, thou makest not a way against thyself, whereof
thou shalt repent hereafter.’ And so Aly passed out with the words of
Joseph on his lips; ‘Surely patience becometh me. The Lord is my
helper against that which ye devise.’[437] Shortly after, Talha returned
to Medîna. Othmân acquainted him with what had happened. As his
vote would have ruled the majority, Othmân declared that if he
dissented, he was prepared even then to resign the Caliphate. But
on learning that all the people had agreed, Talha also swore
allegiance.
The choice of Abd al Rahmân laid the
seeds of disaster for Islam at large, and for The choice unfortunate for
the Caliphate in particular. It led to Islam; faith.
but made in good

dissensions which for years bathed the

Moslem world in blood, threatened the very existence of the faith,
and to this day divide believers in a hopeless and embittered schism.
But Abd al Rahmân could hardly have anticipated the wanton, weak,
and wavering policy of Othmân which slowly but surely brought such
results about. There is no reason to think that, in discharging his
functions as Umpire, he acted otherwise than loyally and for the
best.[438]
An embarrassing incident followed immediately on the accession
of Othmân. Some one told Obeidallah, son
of the deceased Caliph, that Abu Lulû had Murder of Hormuzân, and
been seen some days before in private affair of Omar’s son.
converse with Hormuzân the Persian prince, and with a Christian
slave belonging to Sád; and that when surprised the three
separated, dropping a poniard such as that with which the assassin
had wounded Omar. Rashly assuming a conspiracy, the infuriated
son rushed with drawn sword to avenge his father’s death, and slew
both the prince and the slave. Sád, incensed at the loss of his slave,
seized Obeidallah, still reeking with his victims’ blood, and carried
him, as the murderer of a believer (for Hormuzân had professed the
Moslem faith) before the Caliph.
A council was called. There was not a tittle of evidence, or
presumption even, against the prince. Aly delivered his opinion that,
according to the law of God, Obeidallah must be put to death, as
having slain a believer without due cause. Others were shocked at
the proposal:—‘But yesterday,’ they said, ‘the Commander of the
Faithful was slain, and to-day thou wilt put his son to death!’ Moved
by the appeal, Othmân assumed the responsibility of naming a
money compensation in lieu of blood, and this he paid himself. Some
feeling was excited, and people said that the Caliph was already
departing from the strict letter of the law. Ziâd ibn Lebîd, a poet of
Medîna, satirised both the murderer and the Caliph who had let him
off, in stinging verse. But he was silenced; the matter dropped, and
there is no reason to think that in the end Othmân’s action was
generally disapproved.[439]
One of the first acts by which Othmân
signalised his accession was to increase Othmân increases stipends.
the stipends of the chief men all round, by
the addition to each of one hundred dirhems. The act, no doubt, was
popular, but it gave promise of extravagance in the new
administration.
 CHAPTER XXX.
CALIPHATE OF OTHMAN. GENERAL REVIEW.

A.H. XXIV.-XXXV. A.D. 645–656.

Having now traced the progress of

Islam to its firm establishment in the world, Dynastic issues of the
I do not propose to pursue the history of its Caliphate.
conquests and further spread, otherwise than in a very brief and
general way; but shall confine what remains of this work chiefly to a
review of the facts bearing on the dynastic issues of the Caliphate.
The reign of Othmân lasted twelve
years. It is usual to say that the first six Causes of Othmân’s
were popular, and the last six the reverse; unpopularity:
that is to say, that, during the latter half, the tide turned, and,
discontent ripening into sedition, the storm burst at length with fatal
force upon the aged Caliph. This is true if we look at the outward
appearance. But in reality the causes of unpopularity were busily at
work from the very beginning. These were twofold: first, antagonism
between the Arab nation at large and the Coreish; secondly, jealousy
between the house of Hâshim, and that of Abd Shems (the
Omeyyads) to which Othmân and Muâvia belonged.
The Arab soldiery, flushed with the
glory and the fruits of victory, were I. Antagonism between Arab
tribes at large and Coreish.
scattered all over the empire. In Syria, they
were held in check by the powerful hand of Muâvia, whose authority
was strengthened by the larger settlement there than elsewhere of
influential citizens from Mecca and Medîna. In every other province,
conscious of their power, the Arab tribes were rapidly getting the bit
between their teeth. Their arrogant and factious spirit found its focus
at Kûfa and Bussorah in both of which cities, indeed, it had already
ominously shown itself during the reign of Omar; for even he had not
been able effectually to curb it there. Impatience of control on the
part of the Arabs was based partly on the spread of Islam having
been due to the prowess of their arms; and partly on the brotherhood
of the faith, in virtue of which all believers, and specially those of
Arab blood, stood on the common ground of civil equality. The
Caliph, it is true, as successor to the Prophet, was absolute,
uncontrolled by any constitutional authority whatever. But even he,
yielding to the sentiment, not only took counsel on all critical
occasions with the leading men around him, but, as a rule, held
himself bound by the popular voice at large, and enjoined the same
upon his lieutenants in the provinces. And so it was that in the recall
of Sád, the arraigning of Abu Mûsa, and other concessions to the
clamour of the citizens of Bussorah and Kûfa, Omar had already set
a baneful lesson to his successor, and given to those constituencies
a foretaste of power which they were not slow to take advantage of.
Thus the turbulent spirit grew from day to day—a spirit of opposition
to all authority, and of impatience in particular of the pretensions of
the Coreish.
The second cause, though less
threatening to Islam, was more insidious, II. Aly and the house of
Hâshim jealous of Othmân
and fraught with greater danger to the and the house of Omeyya.
Caliphate and the person of Othmân
himself. Had the Coreish rallied loyally around the throne, the Arab
factions might have been nipped in the bud. But the weakness of
Othmân, and the partiality with which he favoured his own friends
and relatives, stirred the jealousy of the house of Hâshim, which
began vaunting the claims of Aly and the Prophet’s family, and
depreciating the Omeyyad branch to which the Caliph belonged.
That branch, unfortunately for the Omeyyads, had been the tardiest
to recognise the mission of Mahomet; and the kinsmen on whom
Othmân now lavished his favours had been the most inveterate in
their opposition to it. Every unfavourable expression uttered by the
Prophet during that period of bitter enmity was now raked up against
them, and used to blacken their names, and to cast discredit on a
government which promoted them to power and honour. Thus the
Coreish were divided; rivalry paralysed their influence, and Othmân
lost the support which would otherwise have enabled him to check
the machinations of the Arab malcontents. Still worse, Aly and his
party lent themselves to the disloyal policy of the Bedouin faction,
which was fast sapping the foundations of the Caliphate, and which,
as Aly should have foreseen, would in the end recoil against himself.
[440]

It was not, however, till the later part of

Othmân’s reign that these influences, Factious spirit diverted by
military service.
though early at work, assumed dangerous
prominence. Their retardation was in great measure due to the
military operations, which, busily pursued in all directions by the
Moslem arms, diverted attention from domestic trouble. Campaigns
were annually prosecuted, with more or less vigour, throughout the
twelve years of Othmân’s Caliphate. A very brief outline of them will
suffice.
In Persia, as we have seen, the
Mussulman invasion had resulted hitherto Operations in Persia.
rather in the dispersion of great armies
than in the effectual reduction of the country. Most of the provinces
resented the first imposition of tribute, and rose against their new
masters, one after another, in repeated and sometimes long-
continued rebellion. Expeditions were time after time equipped from
Kûfa and Bussorah to crush these risings, from the Caspian Sea and
the Oxus to the shores of the Indian Ocean, and even as far as
Kabul.[441] It was not till near the close of Othmân’s reign that the
Moslem yoke was firmly settled on the neck of Persia. In the eighth
year of his Caliphate, Yezdegird died; and
thereafter, though in a desultory and a.h. XXXI. a.d. 652.
sporadic fashion opposition might still
survive, anything like national or dynastic antagonism was at an end.
Success, indeed, did not invariably attend the Moslem arms. The
progress, on the whole, was steadily forward; but there were
reverses, and these sometimes of a serious type. In the year a.h. 32,
the Turks on the western shore of the Caspian had an advantage, in
which the Arab leaders and a great body of the veterans were slain.
To retrieve the disaster, Othmân ordered levies from Syria to cross
Mesopotamia and reinforce the Kûfan army. Bad blood bred between
the two; the Syrians refused to serve under the captain of the rival
body; and an altercation ensued which nearly led to bloodshed. This,
adds the historian, was the first symptom of the breach between the
Kûfans and the men of Syria, which subsequently broke out into
prolonged hostilities. About the same time, a whole army was lost in
deep snow upon the heights of Kermân, only two men escaping to
tell the tale. There were also very serious reverses in Turkestan. But
Arabia continued to cast forth its swarms of fighting tribes in such
vast numbers, and the wild fanaticism of the faith still rolled so
rapidly onward, that these and similar disasters soon disappeared in
the swelling tide of conquest.
Excepting raids of little import, Syria
had for some time past enjoyed rest,[442] Syria, Asia Minor, and
Armenia. a.h. XXV. a.d. 646.
when suddenly in the second year of this
Caliphate, Muâvia was startled by the approach of an army from
Asia Minor, which he had not the means to oppose. Othmân ordered
troops to pass over from the eastern provinces, and eight thousand
volunteers soon joined the Syrian army. Thus reinforced, the Arabs
repulsed the Byzantine attack. Following up their success, they
overran Asia Minor, and, piercing the heart of Armenia, joined their
comrades on the Persian border within sight of the Caspian. Thence
they penetrated as far north as Tiflis, and even to the shores of the
Black Sea. Thereafter hostilities were renewed for a long period
every summer; and eventually, aided by naval expeditions from the
ports of Africa, the Syrian generals pushed forward their conquests
in the Levant and Asia Minor, enlarged their coasts, and
strengthened their border.
In Africa, I have already noticed the
desperate attack made early in the reign of Africa. a.h. XXV. a.d. 646.
Othmân on Alexandria from seaward. The
Byzantine forces, for a little while, regained possession of the city,
but (as we have before related) were finally driven out by Amru; and
against the Moslem power in Egypt no further attack was made. The
Imperial arms, however, were still active in Africa; and along the
northern shores of the Mediterranean, strong Arab columns were
long actively engaged. Among the chiefs who had joined the
Egyptian army was Abu Sarh,[443] already noticed as the foster-
brother of Othmân. He did not bear an enviable reputation in Islam;