Journal of Electroanalytical Chemistry 916 (2022) 116375

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Journal of Electroanalytical Chemistry

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Nanobubble formation from ionic vacancies in an electrode reaction on a

fringed disk electrode under a uniform vertical magnetic field – 2.
Measurement of the angular velocity of a vertical magnetohydrodynamic
(MHD) flow by the microbubbles originating from ionic vacancies
Satoshi Takagi a, Takashi Asada a, Yoshinobu Oshikiri b, Makoto Miura c,1, Ryoichi Morimoto d,⇑,
Atsushi Sugiyama e,f,g, Iwao Mogi h, Ryoichi Aogaki i
a
Graduate School of Symbiotic Systems Science and Technology, Fukushima University, 1, Kanayagawa, Fukushima, Fukushima 960-1296, Japan
b
Department of Architectural and Environmental Engineering, Yamagata College of Industry and Technology, 2-2-1, Matsuei, Yamagata, Yamagata 990-2473, Japan
c
Architectural Construction Systems Technology, Hokkaido Polytechnic College, 3-190, Zenibako, Otaru, Hokkaido 047-0292, Japan
d
Saitama Industrial Technology Center, 3-12-18, Kamiaoki, Kawaguchi, Saitama 333-0844, Japan
e
Research Organization for Nano and Life Innovation, Waseda University, 513, Waseda-tsurumaki-cho, Shinjuku-ku, Tokyo 162-0041, Japan
f
National Institute for Materials Science, 1-1, Namiki, Tsukuba, Ibaraki 305-0044, Japan
g
R&D Division, Yoshino Denka Kogyo, Inc., 1-2, Asahi, Yoshikawa, Saitama 342-0008, Japan
h
Institute for Materials Research, Tohoku University, 2-1-1, Katahira, Aoba-ku, Sendai 980-8577, Japan
i
Polytechnic University, 2-20-12, Ryogoku, Sumida-ku, Tokyo 130-0026, Japan

A R T I C L E I N F O A B S T R A C T

Keywords: In an electrode reaction under a uniform vertical magnetic field, due to the tangential Lorentz force by the
Ionic vacancy interaction of the current lines and the magnetic field, a tornado-like rotation accompanied by a radial sec-
Nanobubble ondary flow and numerous microscopic vortexes (micro-magnetohydrodynamic (MHD) flows (micro-MHD
Microbubble flows)) emerges over a disk electrode with an insulator fringe (fringed vertical MHD electrode (fringed-
Copper deposition
VMHDE)). By utilizing as tracers, the microbubble clusters originating from the ionic vacancies created in a
Magnetic field
Vertical MHD flow
solution phase, the angular velocity of the rotation was measured for copper cathodic deposition. As a result,
not always the contribution of the current lines to the rotation but also the contribution of the micro-vortexes
to the mass transfer at the electrode were exactly determined. Namely, 4.71% of the whole current lines drives
the rotation, and 4.67% of the mass flux density of the radial secondary flow is converted to the diffusion cur-
rent by the mixing effect of the micro-MHD flows. Within the experimental error, the product of both values
2:20
103 was in good agreement with the value ð1:76  0:45Þ
103 obtained by the measurement of
the limiting-diffusion-current in Part 1.

1. Introduction
Over several decades, many researchers have been investigating
the analyses of electrochemical reactions using micro-disk-electrodes
under magnetic fields. Some of them we can refer as follows: Electro-
chemical impedance spectroscopy using micro-disk-electrodes in mag-
netic fields was first established by Olivier and coworkers [1–3]. At the
same time, they derived that the steady-state currents measured under
parallel magnetic fields are proportional to B1=3 C4=3 where B is mag-
netic flux density and C is the concentration of the electroactive spe-
cies. The magnetoelectrochemical effects at ultramicro-disk-electrodes
was performed by White and coworkers [4–6], and the magnetic field
effects on the limiting (steady state) current were studied by using cyc-
lic voltammetry in non-aqueous systems containing organic reactants.
They concluded that the magnetic field effect was attributed to the
convective flow caused by the viscous drag of the electrolyte ions

⇑ Corresponding author.
E-mail addresses: s1871001@ipc.fukushima-u.ac.jp (S. Takagi), tasada@sss.fukushima-u.ac.jp (T. Asada), oshikiri@yamagata-cit.ac.jp (Y. Oshikiri), miura.makoto@tohoku-pc.ac.
jp (M. Miura), morimotoryoichi@mbn.nifty.com (R. Morimoto), sugiyama@aoni.waseda.jp, a.sugiyama@yoshinodenka.com (A. Sugiyama), iwao.mogi.d4@tohoku.ac.jp (I. Mogi),
ryoaochan@aol.com (R. Aogaki).
1
Present affiliation: Architectural Construction Systems Technology, Tohoku Polytechnic College, 26, Tsukidate Hagisawa Dobashi, Kurihara, Miyagi 987-2223, Japan.

https://doi.org/10.1016/j.jelechem.2022.116375
Received 3 November 2021; Received in revised form 10 April 2022; Accepted 28 April 2022
Available online 02 May 2022
1572-6657/© 2022 Elsevier B.V. All rights reserved.
S. Takagi et al. Journal of Electroanalytical Chemistry 916 (2022) 116375

Nomenclature

List of symbols ζII z-coordinate normalized by lII , ζII ≡ z=lII

!
i current density (A m−2) ∼
! Ω angular velocity of the rotational boundary layer (s−1)
B magnetic flux density (T)
! Gi ðζII Þ function of ζII for vin on a rigid or free surface
fϕ tangential Lorentz force per unit volume (N m−3)
! ρ solution density (kg m−3)
f ϕ tangential component of f ϕ (N m−3)
ν kinematic viscosity (m2 s−1)
I electrolytic current (A)
Dm diffusion coefficient (m2 s−1)
r radial coordinate (m)
Cm ðz ¼ 1Þ bulk concentration of Cu2+ ion (mol m−3)
z axial coordinate (m)
! ! ɛ mixing coefficient of micro-MHD flows
θ angle between the vectors of i and B
zm electron number transferring in an electrode reaction
R electrode radius (m)
0 F Faraday constant (=96,500 C mol−1)
R outer radius of the fringe (m)
γ VMHDE cell constant of VMHDE
vin tagential velocity component of the inner area of the
Lfre coefficient of the diffusion current on the free surface de-
electrode (m s−1)
fined by Eq. (8b) (A mol−2 m6 T−1)
vin ð0Þ tangential component within the radial boundary layer
M rotational coefficient of Lorentz force defined by Eq. (7b)
(m s−1)
(s−1 A-1 T−1)
vout tangential component of the outer area of the electrode
N fre rotational coefficient of the diffusion current on the free
(m s−1)
electrode surface defined by Eq. (9b) (s−1 mol−2 m6 T−2)
lII height of the rotational boundary layer (m)
ρcorr correlation coefficient of a linear regression

accelerated by the magnetic force. Recently, electrodeposition of cop- and oxygen gas evolutions [28–30]. The microbubbles result from
per on a conically shaped diamagnetic electrode under a vertical mag- the collisions of nanobubbles in the rotational boundary layer [10].
netic field has been examined by Mutschke and coworkers [7]. As for Here, the nanobubbles are produced by the collisions of ionic vacan-
magnet arrays of small cylindrical magnets, deposit patterns of catho- cies with the same sign in micro-MHD flows. On the other hand, the
dic electrodeposition reflecting the non-uniform magnetic field has collisions between ionic vacancies with opposite signs lead to the pair
been studies by Dunne and Coey. [8,9].
When a uniform vertical magnetic field is applied to a disk elec-
trode with an insulator fringe (fringed vertical magnetohydrodynamic
(MHD) electrode (fringed-VMHDE)), as shown in Fig. 1, a tornado-like
macroscopic rotation called vertical MHD flow (VMHD flow) emerges
over the electrode. As shown in Fig. 1, a VMHD flow is composed of
two parts; an upper cylindrical rotation (rotational-boundary-layer-
flow), and a lower radial secondary flow (radial-boundary-layer-flow),
so that as a whole, an ascending spiral stream arises from the elec-
trode, and the electrode surface is covered with ionic vacancies of
the same sign created in the electrode reaction. Due to the role of
atomic-scale lubricant of ionic vacancy, the surface is always kept free
without friction, while the surface of the insulator fringe is rigid with
friction, reducing the centrifugal force of the cylindrical rotation to
zero. As a result, losing the balance with the centrifugal force, the
residual pressure gradient induces an inward radial secondary flow,
forming the radial boundary layer with a vacancy layer on the elec-
trode [10].
A solvated ionic vacancy composing the vacancy layer is a free
space of the order of 0:1 nm enveloped by polarized solvent molecules,
which are further surrounded by an oppositely charged ionic cloud,
which arises from the conservations of the linear momentum and elec-
tric charge during the electron transfer [11,12]. The lifetime is about 1
s [13,14], and the nanobubbles arising from the collisions of ionic
vacancies [15] are specifically adsorbed on a copper electrode surface
to cause the three dimensional (3D) dendritic growth of copper deposit
[16]. As mentioned above, the atomic-level lubricants, i.e., ionic
vacancies drastically decrease the viscosity of the solution, so that in
copper cathodic deposition under a vertical magnetic field, micro-
scopic vortexes called micro- and nano-MHD flows are self-organized
on and in a vacancy layer, yielding chiral screw dislocations
[17–26]. The micro-MHD flows have been also optically observed by
Mogi and coworkers, where from the upper side, special tracers slowly
Fig. 1. Schematic of a VMHD flow on a fringed-VMHDE. A, copper disk
approached in rotation with the VMHD flow toward the tops of the
electrode; B, doughnut-shaped fringe of VMHDE; C, rotational-boundary-
micro-MHD flows, being scattered by them in drawing zigzag loci
layer-flow; D, radial-boundary-layer-flow.δ, thickness of the radial boundary
[27]. layer ( < 0:1 mm); lII , height of the rotational boundary layer (several mm) vin ,
The existence of the ionic vacancy has been experimentally vali- inner tangential velocity on the electrode; vout , outer tangential velocity on the
dated by observing microbubble clusters unrelated with hydrogen ! !
fringe; B , magnetic flux density, i , current density; z, z-axis.

2
S. Takagi et al. Journal of Electroanalytical Chemistry 916 (2022) 116375

annihilations of them, releasing their saved solvation energies as heat

[31,32].
In Part 1 [10], the formation process of the radial secondary flow in
the radial boundary layer by the rotation of a VMHD flow in the rota-
tional boundary layer has been theoretically clarified, so that two
kinds of equations of the limiting-diffusion-currents on rigid and free
surfaces have been derived, which are proportional to
   
! 2 !
 B Cm ðz ¼ 1Þ where  B  is the absolute value of the applied mag-
netic flux density and Cm ðz ¼ 1Þ is the bulk concentration of the elec-
troactive species. Then, from the criterion that the diffusion current on
a free surface covered with ionic vacancies is larger than or equal to
the current on a rigid conventional surface at the same magnetic field,
it has been concluded that ionic vacancies with the same sign do not
collide in a vacancy layer. In view of the repulsion of Coulomb’s force
between ionic vacancies with the same sign, it is quite reasonable. By
the hydrodynamic force overcoming the Coulomb’s force, the collision
occurs in upward micro-MHD flows, yielding nanobubbles. The
nanobubbles further collide with each other in the rotation of the
Fig. 2. Primary current distribution over a fringed-VMHDE. A, disk electrode;
upper rotational boundary layer, preparing microbubble clusters for 0
B, fringe; R, electrode radius; R , outer radius of fringe; x, x-axis; z, z-axis; lII ,
the optical observation. Therefore, as will be shown in Fig. 5a, the fact ! !
height of the rotational boundary layer; B , magnetic flux density, i , current
that the observed clusters are not pasted on the electrode center but  ! !
density; θ , angle between the vectors, i and B . The semicircle of break line
circulate around it is important evidence that the microbubbles are describes the cross section of a hemisphere with a radius of the outer radius of
not created in the radial boundary layer but created in the rotational 0
fringe r ¼ R ; where r is the radial coordinate.
boundary layer. However, from the measurement of the diffusion cur-
rents in Part 1 [10], we cannot determine each parameters concerning
the mixing effect of the micro-MHD flows and the macroscopic rota- of the hemisphere. The current value integrated over the surface is
tion but can only determine the product of them. Namely, the product equalized to the total current jI j.
of the mixing coefficient of the micro-MHD flows and the cell constant !  
1   
of VMHDE ɛγ VMHDE ¼ ð1:76  0:45Þ
103 , where ɛ≈2:79
102 and
4πr 2  i  ¼ I  ð1Þ
2
γ VMHDE ≈ð6:38  1:94Þ
102 are estimated.
The current density at a distance r from the electrode center is thus
In the present paper, firstly, we observe the evolution processes of a
written by
microbubble cluster and hydrogen bubbles on a copper VMHDE, and
! jI j
clarify the difference between their evolution modes. Secondarily,  
i¼ ð2Þ
measuring the limiting diffusion current and the angular velocities of 2πr 2
the microbubble clusters circulating with the rotational-boundary- On the other hand, the tangential Lorentz force per unit volume is
layer-flow, we directly determine the parameters concerning the diffu- given by
sion current and the rotation ɛ and γ VMHDE . Then, for validating the ! ! 
   !
measurement, the product of the determined parameters ɛγ VMHDE is
compared with that mentioned above. Finally, we propose a new
method using the microbubbles for the microscopic flow visualization
in magnetoelectrochemistry.
2. Theory
The radial current distribution on a disk electrode under a vertical
f ϕ  ¼  i  B sinθ ð3Þ
!
where θ is the angle between the vectors of the current density i and
!
the magnetic flux density B . Since the thickness of a radial boundary
layer δ formed by the secondary flow is much smaller than the radius
of the disk electrode R, i.e., δ ≪ R; for the radial boundary layer and
a certain area outside it, i.e., the rotational boundary layer, θ ¼ π=2
can be assumed, so that substituting Eq. (2) into Eq. (3), we have the
equation of the Lorentz force.
magnetic field yields a macroscopic rotation. In an electrode reaction   
under a vertical magnetic field, as shown in Fig. 1, a tornado-like  !
upward rotation called VMHD flow emerges over a disk electrode with
an insulator fringe (fringed-VMHDE). The main part of the rotation of
the rotational-boundary-layer-flow is stably sustained by Lorentz
force. At the surface, however, the friction of the fringe ceases the rota-
tion, reducing the centrifugal force down to zero, so that the residual
pressure gradient inwardly induces a radial secondary flow, forming a
radial boundary layer. To conserve the continuity of the incompress-
ible solution, an upward-flow-component slowly arises from the
radial-boundary-layer-flow.
In accordance with the theory of primary current distribution [33],
on a disk electrode, the current lines are radially distributed. Near the
electrode surface, the current lines acquire the components parallel to
the electrode surface, which generate a tangential Lorentz force. It in
turn induces a rotation of the solution near the electrode. As shown
in Fig. 2, near the electrode surface, a radius r of a hemisphere is iden-
tified with the radial coordinate in a cylindrical polar coordinate sys-
γ VMHDE I  B 
f ϕ ≡ ð4Þ
2πr 2
!
where f ϕ is the tangential component of f ϕ , and γ VMHDE is a cell constant
introduced to express the ratio of the current lines participating in the
rotation to the whole current lines.
To formulate the rotation, we use cylindrical polar coordinates r, ϕ
and z on a stationary disk electrode at z ¼ 0. We denote the velocity
component in the tangential direction by v. In view of axial symmetry,
the derivations concerning ϕ may be dropped from the Navier-Stokes
equation in steady state, and due to low electric conductivity, in a
macroscopic scale, the electromagnetic induction except for the Lor-
entz force in an electrolyte solution is disregarded.
As shown in Fig. 1, the vertical MHD flow is expressed by a thick
rotational boundary layer and a thin radial boundary layer. The rota-
tional boundary layer is further divided into inside and outside areas
! of the electrode (Fig. 3), where the latter corresponds to the insula-
 
tem, and the current density  i  takes a constant value at the surface tor-fringe-part. For the inside area of the rotational boundary layer,

3
S. Takagi et al. Journal of Electroanalytical Chemistry 916 (2022) 116375

as shown in Fig. 2, since based on electromagnetic theory, the current where Grig ðζ II Þ is a function of ζ II on the rigid fringe surface.
lines are assumed parallel to the magnetic field, Lorentz force becomes At the outer boundary of the rotational boundary layer ζ II ¼ 1, and
∼
zero. Therefore, the equation for the tangential velocity component of outside the electrode area, the solution rotates in a velocity of R Ω,
the inside area is expressed by ∼
where Grig ð1Þ ¼ 1: Therefore, substituting the relationship vout ¼ R Ω
@ 1 @

rv ¼ 0in into Eq. (6a), and using Eq. (4), we can derive the equation of the
@r r @r ð5aÞ angular velocity.
for 0 ≤ r ≤ R and 0 ≤ z ≤ lII   
∼  !
where lII is the height of the rotational boundary layer, and vin implies
the tangential component of the velocity at the inside area, having the
following function form.
∼ M≡
v ðζII Þ ¼ r Ω Gfre ðζII Þ
in
ð5bÞ
for 0≤r ≤R and 0 ≤ ζII ≤ 1
∼ the sign  corresponds to anticlockwise and clockwise rotations,
where Ω is the angular velocity of the rotation, Gfre ðζ II Þ is a function of
ζ II on a free surface of the electrode, and ζ II is the z-coordinate normal-
ized by the height of the rotational boundary layer lII , ζ II ≡ z=lII . As men-
tioned above, the thickness of the radial boundary layer δ is much
smaller than the height of the rotational boundary layer lII , δ ≪ lII , so
that the tangential component within the radial boundary layer is
expressed by vin ð0Þ, where ζ II ð¼ δ=lII Þ≈0.
The rotation of the inside area vin of the rotational boundary layer is
induced by the rotation of the outside area vout . Outside the electrode
Ω ¼ M I  B  ð7aÞ
where M is the rotational coefficient expressed by
γ VMHDE
ð7bÞ
2πρνR
where the rotational direction is defined by the right-handed system;
respectively. In Fig. 3, the tangential velocity distributions inside and
outside the electrode area are schematically illustrated.
As mentioned above, the insulator fringe surrounding the electrode
makes a pressure gradient toward the electrode center, which induces
an inward radial secondary flow on the electrode surface (radial-
boundary-layer-flow). Solving the mass balance equation in the radial
boundary layer, in Part 1 [10], we obtained the following limiting-dif-
fusion-current-equation on the free surface without friction covered
with ionic vacancies.
area, as discussed in Eq. (4), a constant Lorentz force f ϕ emerges, so  
! 2
that we get the following equation. jI j ¼ Lfre  B Cm ðz ¼ 1Þ ð8aÞ

@ 1 @ 1 The coefficient of the diffusion current Lfre is expressed by.

ðrvout Þ ¼  f ϕ
@r r @r ρν ð6aÞ  1
0 ν
for R≤r ≤R and 0 ≤ z ≤ lII Lfre ≡ 0:688ðzm F Þ2 R3 ρ1 ɛγ VMHDE ð8bÞ
Dm
0
where ρ is the density, ν is the kinematic viscosity, and R is the outer
where zm is the transferring electron number, F is Faraday constant, ν is
radius of the fringe. vout is the tangential component outside the elec-
the kinematic viscosity, Dm is the diffusion coefficient, ɛ is the mixing
trode area on the insulator fringe, so that the function form is given by
coefficient implying the mass transfer efficiency by the micro MHD
∼
vout ðζ II Þ ¼ R Ω Grig ðζII Þ flows, R is the radius of the disk electrode, and ρ is the solution density.
0
ð6bÞ From Eq. (8b), the unknown product ɛγ VMHDE is obtained from Lfre , as
for R ≤ r ≤ R and 0 ≤ ζII ≤ 1
follws.
 
ν
ɛγ VMHDE ¼ 1:45ðzm F Þ2 R3 Lfre ρ ð8cÞ
Dm
Measuring the limiting-diffusion-currents against various magnetic
flux densities and bulk concentrations in copper cathodic deposition
with fringed copper VMHDE’s, we obtained the average value and
its standard deviation Lfre = (3:34  0:86Þ
108 A mol−2 m6 T−1 in
Part 1 [10]. Using the value of Lfre as well as the other data at 27℃;
zm ¼ 2, F ¼ 96500 C mol−1, Dm ¼ 6:67
1010 m2 s−1,
ν ¼ 8:90
107 m2 s−1, ρ ¼ 1:01
103 kg m−3 and R ¼ 1:0
103
m, we derived the value of the product
ɛγ VMHDE ¼ ð1:76  0:45Þ
103 .
Substituting Eq. (8a) into Eq. (7a), we get another equation of the
angular velocity of the rotation on the free electrode surface.
 2
∼ !
Ω ¼ N fre  B  Cm ðz ¼ 1Þ2 ð9aÞ

where the rotational coefficient of the diffusion current on the free elec-
trode surface N fre is expressed by
 1
ν

1 2
N fre ≡ 0:109 ν1 ɛγ 2
VMHDE zm FRρ ð9bÞ
Dm
∼
From the measurements of the angular velocity Ω and the limiting-
Fig. 3. Schematic of the tangential velocity distribution over a disk electrode diffusion-current jI j, using Eqs. (7a) and (9a), we can separately deter-
surrounded by an insulator fringe at the outer boundary of the rotational mine the values of ɛ and γ VMHDE . Namely, from Eq. (7b), we obtain.
boundary layer ðz ¼ lII Þ. A, electrode; B, fringe; R, electrode radius; R0 , outer
! γ VMHDE ¼ 2πρνRM ð10Þ
fringe radius; z, z-axis; B , magnetic flux density; lII , height of the rotational
boundary layer; v , inner tangential component of velocity on the electrode;
in
From Eq. (9b), we get.
vout , outer tangential component of velocity on the fringe.

4
S. Takagi et al. Journal of Electroanalytical Chemistry 916 (2022) 116375

 
1 ν
ɛγ 2
VMHDE ¼ ðzm FRÞ2 νρ2 N fre ð11Þ
0:109 Dm
Therefore, from the values of M and N fre obtained by the measure-
∼
ment of the angular velocity of microbubble clusters Ω at a current jI j
 
!
under a magnetic flux density  B , we can determine the exact values
of ɛ and γ VMHDE without any assumptions.

3. Experiment

The measurement of the angular velocity was carried out by using

copper electrodeposition in various concentrations of CuSO4 + 500
mol m−3 H2SO4 solutions. Water was prepared by a pure water pro-
duction system (Millipore filter Co.). The CuSO4 and H2SO4 were in
analytical grade (Wako pure chemical Co.). The VMHDE was made
of a copper disk of 2 mm diameter (oxygen-free copper, 99.99% purity,
Nilaco Co.) equipped with a 2 mm-wide fringe of @ Teflon. To prevent
natural convection, it was set in a downward direction. The counter
electrode was a copper ring of 25 mm diameter wound with a copper
rod of 2 mm diameter, which was placed at a distance of 30 mm from
the VMHDE. A copper rod of 1 mm diameter was used as a reference
electrode. The limiting-diffusion-current was measured by applying
an overpotential of 400 mV under a given magnetic field. The elec-
trodes were connected to a potentio-galvanostat (PS-2000, TOHO
Technical Research Co., Ltd.), whose leads were connected to a mea-
suring instrument (NR-2000, KEYENCE Co.). As shown in Fig. 4, the
whole electrode system was settled at the place of a uniform magnetic
field selected in the bore space of 10 T-cryocooled superconducting Fig. 5. Comparison of the motion of microbubble cluster and hydrogen gas
bubbles in copper deposition under a vertical magnetic field. a, Sequential
magnet at the High Field Laboratory for Superconducting Materials,
images of a rotating microbubble cluster observed at an overpotential of -400
Institute for Materials Research, Tohoku University. The rotation of
mV and a magnetic flux density 8 T. 1, t ¼ 0:0 s; 2, t ¼ 0:2 s; 3, t ¼ 0:3 s; 4,
the microbubble clusters was optically observed through the bottom t ¼ 0:5 s, where t ¼ 0:0 s corresponds to t ¼ 60:7 s after starting the reaction.
of the electrolysis cell from below by a USB digital microscope with b, Hydrogen gas bubbles observed at an overpotential of 800 mV and a
30 frames/s with 500 megapixels (Dino-Lite Premier 500 M, AnMo magnetic flux density of 10 T. 1, t ¼ 12 s after starting the reaction; 2, t ¼ 72 s.
Electronics Corp.). Prior to the measurements, the images of a The radius of the copper electrode is 1 mm, and the width of the fringe is 2
microbubble cluster and hydrogen bubbles were taken to compare mm. The solution contains 30 mol m−3 CuSO4 and 300 mol m−3 H2SO4.
with the formation processes.

4. Results and discussion

Differently from the hydrogen or oxygen gas bubbles stuck on an

Fig. 4. Configuration of the experimental apparatus. A, magnet bore space; B,
electrolysis cell; C, CCD camera; D, magnet. W.E., fringed-VMHDE; C.E.,
! !
counter electrode; R.E., reference electrode; B , magnetic flux density; G ,
gravity field. The horizontal break line indicates the magnetic field center.
electrode surface, the microbubble clusters occur at a distance from
the electrode surface. From the viewpoint of flow visualization, we
can expect that the motions of the former and latter bubbles reflect
the differences of the flow modes in the radial boundary layer and
the rotational boundary layer, respectively. Fig. 5a shows the sequen-
tial images of a rotating microbubble cluster observed in copper catho-
dic deposition at an overpotential of 400 mV at 8 T. After several
circulations, it faded from view by ascending with an upward flow (ro-
tational-boundary-layer-flow). Beyond 600 mV, hydrogen gas bub-
bles were newly evolved. Then, at an overpotential of 800 mV, as
shown in Fig. 5b, an agglomerate of the gas bubbles was formed from
the individual bubbles on a copper electrode surface. The smaller
hemispherical bubbles of order of 0:1 mm circulated on the electrode
surface, being gathered to form a larger domed bubble in rotation at
the electrode center by the radial secondary flow (radial-boundary-
layer-flow). Such rotational motions of the hemispherical bubbles
and the domed bubble adhered on the electrode surface strongly sug-
gest the existence of a vacancy layer without viscosity. Due to the lack
of ionic vacancies, the bubbles stuck to the electrode edge stay in the
same positions. Although the present experiment was carried out
under a uniform magnetic field, under a non-uniform magnetic field,
for the present case of cathodic copper deposition in a paramagnetic
cupric sulfate solution, it should be careful about the effect of field gra-

5
S. Takagi et al.
dient force on hydrogen gas bubbles acting as diamagnetic voids
[8,34].
In Fig. 6, the difference of the formation process between the
microbubble cluster and the hydrogen-gas-bubble is schematically
illustrated: Fig. 6a represents the formation and rotation of the
microbubble clusters in the upper rotational-boundary-layer-flow. On
Journal of Electroanalytical Chemistry 916 (2022) 116375
bles may arise from the cavitation in a high-speed rotation of the solu-
tion. Using Eq. (10) together with the other data such as diffusion
coefficient and kinematic viscosity mentioned above, we have
γ VMHDE ¼ 4:71
102 ð13Þ
∼
Then, in Fig. 8, in accordance with Eq. (9a), the angular velocity Ω
the other hand, as shown in Fig. 6b, the hydrogen-gas-bubbles gather-  2
!
ing to the electrode center in rotation visualize the lower radial-bound-
ary-layer-flow in a spiral mode on the free surface.
∼
In Fig. 7, according to Eq. (7a), we plotted the angular velocity Ω of
the microbubble cluster against the product of the current and the
was plotted against  B  Cm ðz ¼ 1Þ2 . The plot is also in good agree-
ment with a straight line passing through the origin with the correla-
tion coefficient ρcorr ¼ 0:9973; so that from the slope of the plot, we get
the rotational coefficient.
  
 ! N fre ¼ 3:516
104 s1 mol2 m6 T2
magnetic flux density I  B . All the data follow a straight line passing
ð14Þ
through the origin with the correlation coefficient ρcorr ¼ 0:9932, so for ρcorr ¼ 0:9973
that as the slope of the plot, we obtained the rotational coefficient in Substituting the other data as well as Eq. (14) into Eq. (11), we
the following. obtain
4
ɛγ 2
VMHDE ¼ 1:04
10 ð15Þ
M ¼ 8:393
103 s1 A1 T1 for ρcorr ¼ 0:9932 ð12Þ
Substitution of Eq. (13) into Eq. (15) leads to
At the same time, because the rotational frequency is, at most, of
order of several 10 rpm, we can deny the possibility that the microbub-

Fig. 6. Difference of the formation process between microbubble clusters in the upper rotational-boundary-layer-flow and an agglomerate of hydrogen bubbles in
the lower radial-boundary-layer-flow. a, Formation of microbubble clusters by the collisions in the rotational-boundary layer-flow. b, Formation of the
!
agglomerates of hydrogen bubbles in the radial-boundary-layer-flow. A, electrode; B, fringe; C, rotational-boundary-layer-flow; D, radial-boundary-layer-flow. B ,
!
magnetic flux density; i , current density; z, z-axis; yellow sphere, microbubble arising from nanobubbles; the smaller and larger blue hemispheres, hydrogen
bubble stuck to the electrode and their agglomerate.

6
S. Takagi et al. Journal of Electroanalytical Chemistry 916 (2022) 116375

ɛγ VMHDE ¼ 2:20
103 ð17Þ

Within the experimental error, the value of Eq. (17) agrees with the
average value with the standard deviation ɛγ VMHDE ¼ ð1:76  0:45Þ

103 obtained from the limiting-diffusion-currents measured by the
several experiments in Part 1 [10].
∼
As the angular velocity Ω is defined outside the radial boundary
layer, this experimental result indicates that the microbubble clusters
are evolved in the rotational boundary layer. All the rotations of the
microbubbles observed did not contain such scatterings by the micro-
scopic vortexes of the micro MHD flows as reported by Mogi et al [27],
which also suggests that as have been discussed initially, the measured
rotations occur in the upper part of the rotational boundary layer far
from micro MHD flows.

5. Conclusions

∼
The angular velocity of a VMHD flow Ω is expressed by two inde-
pendent equations Eqs. (7a) and (9a) of a VMHD flow; the former
  comes from the Lorentz force rotating the upper part of the flow
∼ !
Fig. 7. Plot of the angular velocity Ω against jI j B  for the microbubble ∼ (the rotational boundary layer), and the latter is derived from the dif-
clusters observed on a copper fringed-VMHDE in copper deposition. Ω,
−1 fusion current in the lower part on the electrode (the radial boundary
 
angular velocity of the VMHD flow (s ); jI j, absolute value of the current (A);
! layer). Therefore, from the measurement of the angular velocity and
 B , absolute value of the applied magnetic flux density from 1 T to 10 T; ○,
Cm ðz ¼ 1Þ ¼ 30 mol m−3; □, Cm ðz ¼ 1Þ ¼ 40 mol m−3, where Cm ðz ¼ 1Þ is
the bulk concentration of Cu2+ ion in a CuSO4 + 500 mol m−3 H2SO4 solution
(mol m−3). The slope value of the plot is M ¼ 8:393
103 s−1 A-1 T−1 for
ρcorr ¼ 0:9932.
the limiting-diffusion-current, we can determine the cell constant
γ VMHDE defined by the current line distribution over the electrode
and the mixing coefficient ɛ concerning the microscopic vortexes
called micro-MHD flows formed on the electrode surface. Then, it
was clarified that 4.71% of the whole current lines participates in
the rotation of the vertical MHD flow, and that the micro-MHD flows
convert 4.67% of the mass flux of the radial-boundary-layer-flow to
the diffusion current at the electrode. The accuracy of the values
was validated by the agreement within the experimental error of their
product ɛγ VMHDE ¼ 2:20
103 with the value
ɛγ VMHDE ¼ ð1:76  0:45Þ
103 obtained from the various measure-

ments of the limiting-diffusion-current in Part 1. Namely, with suffi-
cient accuracy, this method can be applied to the analysis of a
VMHD flow. The obtained data strongly indicate that the microbubbles
optically observed are created from the collisions of the nanobubbles
in the rotational boundary layer over the micro-MHD flows in the
radial boundary layer. Finally, we point out that the present technique
is also applicable to the microscopic flow-visualization of other types
of MHD electrodes except for fringed-VMHDE.
CRediT authorship contribution statement
Satoshi Takagi: Formal analysis, Investigation, Writing – review &
editing. Takashi Asada: Supervision. Yoshinobu Oshikiri: Methodol-
ogy, Validation, Formal analysis, Investigation, Resources, Writing –
 2 review & editing, Visualization, Project administration. Makoto
∼ !
Fig. 8. Plot of the angular velocity Ω against  B  Cm ðz ¼ 1Þ2 for the Miura: Methodology, Validation, Formal analysis, Investigation, Writ-
microbubble ∼ clusters observed on a copper fringed-VMHDE in copper ing – review & editing, Visualization. Ryoichi Morimoto: Formal
deposition. Ω, angular
 velocity of the VMHD flow on the free electrode analysis, Data curation, Writing – review & editing. Atsushi
!
surface (s−1);  B , absolute value of the applied magnetic flux density from 1
T to 10 T; Cm ðz ¼ 1Þ, bulk concentration of Cu2+ ion in a CuSO4 + 500 mol
m−3 H2SO4 solution (mol m−3). ○, Cm ðz ¼ 1Þ ¼ 30 mol m−3; □,
Cm ðz ¼ 1Þ ¼ 40 mol m−3. The slope value of the plot is N fre ¼ 3:516
104
s−1 mol−2 m6 T−2 for ρcorr ¼ 0:9973.
ɛ ¼ 4:67
102
The data obtained in Eq. (16) satisfies the limiting condition
ɛ ≥ 2:79
102 obtained in Part 1 [10]. From Eqs. (13) and (16), the
product ɛγ VMHDE is given by
Sugiyama: Methodology, Validation, Formal analysis, Investigation,
Writing – review & editing, Visualization. Iwao Mogi: Resources.
Ryoichi Aogaki: Conceptualization, Methodology, Validation, Writ-
ing – original draft, Supervision.
Declaration of Competing Interest
ð16Þ
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.
7
S. Takagi et al.
Acknowledgements
The authors thank the Tsukuba Magnet Laboratory, National Insti-
tute for Materials Science (NIMS), Tsukuba Japan and the High Field
Laboratory for Superconducting Materials, and Institute for Materials
Research (IMR), Tohoku University for financial support and access
to superconducting magnets. The authors also thank the various sup-
ports and suggestions of experimental data from Dr. M. Miura,
Polytechnic Center Kimitsu, Mr. K. Motomura, Polytechnic University
and Prof. Y. Yamauchi, the University of Queensland.
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