Dissertation Review Form

-for members of the Dissertation Commission-

Please write a review of the dissertation taking the following criteria into account, where
appropriate:

- General remarks
- The significance and status of the dissertation in the field
- The sufficiency and quality of the material
- The adequacy of the methods used
- The validity of results
- The logic of the dissertation’s structure
- The knowledge and use of literature in the field
- The project’s contribution to the research area
- The author’s input into the achievement of the dissertation results
- Language
- The shortcomings of the manuscript

Name of the Ph.D. Candidate: Mr. Sai Krishna Padamata

Planned Date of Graduation: September, year: 2020

Title of the Dissertation: « Electrolysis of cryolite-alumina melts and suspensions with

oxygen evolving electrodes.»

Would you please elaborate upon your review with reference to the criteria as mentioned
above in the box below. Please add extra pages if needed

Page 1 of 7
The Dissertation of Sai Krishna Padamata is connected with one of the focal problems of the
development of inert anodes for aluminium reduction cell, vertical electrode cell along with a
wettable cathode in low-temperature melts. Although the physics of the electrodes in low-
temperature is still under investigation, the extraordinary phenomenon of their application is still
very scarce, and it needed to be elucidated. Cu-based alloys are considered promising candidates
(along with Fe-Ni alloys) as an inert anode’s material in aluminium reduction cells with low-
temperature electrolytes. Low-temperature alumina suspension electrolytes were found to reduce
impurities in aluminium produced, and the behaviour of alumina in the melts was examined. In
this research, the anode behaviour of Cu-Al-based electrodes and cathode behaviour of the
tungsten electrode in low-temperature KF-AlF3 melts were tested. The alumina dissolution and
sedimentation rate in KF-AlF3 melts were analyzed at different conditions.
However, successful applications require a controllable generation of low-temperature
electrolysis processes with the desired quality of metal that is presently restricted because of
limited knowledge on the low-temperature melts. This is why the number of investigations of
low-temperature melts appearing in scientific literature is growing almost exponentially at the
present time. Against the background of information flow on this topic, the contribution presented
in the Dissertation by Sai Krishna Padamata is impressive and adds considerable novelty into the
understanding of the Electrolysis of cryolite-alumina melts and suspensions with oxygen-evolving
electrodes. The following new observations and regularities reported by Sai Krishna Padamata
can be highlighted:
• This work reports on first observation the development of inert anodes for
aluminium reduction cell for industries and the application of the inert anodes
for environmental concerns, energy, and cost-efficient. According to a
conventional approach, the inert anodes can only be fully efficient when used in
vertical electrode cells along with a wettable cathode in low-temperature melts.
Thus, Cu-based alloys (along with Fe-Ni alloys) as an inert anodes’ material in
aluminium reduction cells with low-temperature electrolytes are used in the
reduction of impurities in aluminium production, and by examining the
behaviour of alumina in the melts. The introduction of the alumina suspension
particles in the electrolyte seems to be an excellent way to solve this problem by
suppressing the convective transfer of corrosion products.

Page 2 of 7
• In this research, the author tested the anode behaviour of Cu-Al-based electrodes,
and the cathode behaviour of the tungsten electrode in low-temperature KF-AlF3
melts, and he also analyzed the alumina dissolution, and sedimentation rate in
KF-AlF3 melts at different conditions. In the first stage, the tests were conducted
to characterize the electrochemical behaviour of Cu-Al-based anodes. The
effects of the temperature, the particle size, the phase composition of the
dispersed material, and its volume fraction in the suspension on the dissolution
kinetics, as well as the sedimentation velocity, were studied.
• A part of this work was devoted to experimental verification of the anodic
behaviour of Cu-Al based electrode in low temperature melts at different
conditions like alumina volume fraction, CR value, and the temperature was
investigated along with the cathode process on W electrode in low temperature
melts using cyclic voltammetry and chronopotentiometry techniques. This is the
experimental model pretending to highlight the effects of the electrode process in
KF-AlF3-Al2O3 melts. (comprehensive overview of the experimental procedure
and techniques, as well as explanations of the, is given in Chapter 3 of the
Dissertation). This part of the work is performed in a classical approach by
application of three-electrode cell, as shown in figure 11 was used to perform the
experimental studies. High purity graphite crucible was also used to contain KF-
AlF3-Al2O3 (5wt. %) melt. The crucible also acted as a counter electrode. The
Al/AlF3 reference electrode was utilized, which was connected to the measuring
device using a tungsten rod. The reference electrode had a porous BN tube
containing the liquid aluminium and KF-AlF3 melt. Autolab PGSTAT302n
potentiostat equipped with a 20A booster and controlled by NOVA 2.1.2
software was used to carry out the Electrolysis. Electrolysis was conducted using
the Chrono potentiometric method. Stationary polarization was performed for
0.005 to 1.5 A/cm2 current densities, where the recording was made with 30 µs
of current interruption time after a 120s current passage to determine the ohmic
voltage drop (IR). Cyclic voltammetry was performed at 0.05 V/s scan rate to
examine the possible anodic reactions. Some outstanding results have been
obtained describing the Stationary state polarization describes reasonably the
polarization in melts (φ=0) occurring with cell voltage U between 2.5 and 3.1 V
for all the anode composition. The voltage was changed due to the oxide layer
formation and the changes in its structure and composition. The voltage was
altered due to the oxide layer formation and the changes in its structure and
composition. The stationary galvanostatic polarization curves (figure 17) were
recorded in melts (φ=0) and suspensions with φ=0.12 and 0.15. The time to
reach the quasi-stationary state was about 100 seconds. Page 3 of 7
In the non-stationary study at a low sweep rate of 0.05 V/s (figure 18), the anode A1 has an
unexpected highest current density as the alloy of this composition is more prone to passivation
due to the formation of dielectric oxides. Thus, the presence of significant transport difficulties
that may be created by the presence of a concentrated suspension. The aforementioned high
current density confirms the possibility of the anode oxidation product dissolution.
• In XRD studies, Cyclic voltammetry was performed on anodes at 700 and 800
°C in melts saturated with alumina at CR = 1.2 -1.5. Records from
Voltammograms were carried out to reveal the response of anode with the
change in potential at 0.05 V/s. In this subpart, the reversible potentials and the
stationary potentials at i=0.4 A cm-2 are obtained through the galvanostatic
process for 1.2≤CR≤1.5 (Fig. 22). Consequently, an increase in the CR results in
the more negative of the anodic potential and evolution of oxygen at low current
densities.
• The results, which are extremely important for the understanding of experimental
studies were also carried out in Stationary galvanostatic polarization of Cu-Al
anode over several melts with different cryolite ratios from 1.2 to 1.5 at 700, 750
and 800 °C to study the kinetic parameters of oxygen evolution. Therefore, the
anodic current density ia, and the anodic potential Ea (vs. Al reference electrode)
were recorded during the experiment. The obtained polarization curves are
presented in figure 23.
For the purpose of finding the total overvoltage, it has been demonstrated the
relationship between the decomposition to the activation and the concentration
components. And, the linear section on the graph was considered as an activation
component of the overvoltage. It was extrapolated to higher values of i. The rest
part was considered as the concentration component. The obtained results for
CR=1.2 and T=750 and 800 °C are presented in figure 24. The experimental
values of the concentration overvoltage ηconc(exp.) were estimated and were
compared with the values calculated according to the Eq. (23), from which the
limiting current density was also found.
In the cathode process in the KF-AlF3-Al2O3 system part, the experiments were
performed at 800℃ melts with CR (1.2-1.5). The electrochemical behaviour is
investigated using cyclic voltammetry and chronopotentiometry. The processes
were tested in the melts with CR values of 1.3, 1.4, and 1.5, and the potential
sweep rates (ν) was between 0.01 and 0.2 V.s-1. The cathode peaks associated
with the aluminium reduction (Al) depending on the potential sweep rate and CR
values were observed between -0.125 and -0.240 V (vs. Al) for all the CR
values. Typical cyclic voltammograms (CV) obtained on W in KF − AlF3 melts
at 800°C are shown in figure 31. Page 4 of 7
 • In Chapter 4, Mr. Sai Krishna Padamata goal was to provide a complete
understanding of the dissolution rate and sedimentation of alumina in KFAlF3
melts and suspensions. The effects of the temperature, particle size and phase
composition of the dispersed material and its volume fraction in the suspension
on the dissolution kinetics and the sedimentation velocity were studied. The
experiments were carried out over the melts with cryolite ratios 1.3 and 1.5 in
the range of 750 - 850 °C. Three different types of aluminium oxide were also
used, and the electrolytes were synthesized at 900 °C from the dried individual
chemically pure (p.a.) salts KF and AlF3. Drying lasted for 4 hours at 400 °C.
For dissolution and sedimentation studies, three types of materials were chosen.
• The studies in this Chapter have shown the effect of temperature on the
dissolution kinetics at different concentrations of O2- ions are presented in figure
39. The findings state that in terms of dissolution rate, the increase in
temperature is preferable as well as using alumina with small particles and
electrolytes with higher cryolite ratios.
The influence of the temperature on the sedimentation kinetics of the suspension
based on 1.3KF-AlF3 melt with volume fractions φ=0.1 was also given in figure
45 shows that the suspensions were stable or quasi-stable at φ values of 0.25,
0.20 and 0.10 with SGA, α-Al2O3 and MA alumina respectively. The critical
effect on the stability is influenced by the particle size and the density of the
particles. The sedimentation velocity and the Reynolds number, have shown to
highly rely on the temperature, alumina volume fraction, and properties.

Upon reading this Dissertation, the remarks arose, which mostly concern the dissolution rate,
sedimentation, and behaviour of alumina in KF-AlF3 melts. As a whole, the description alumina
melts, and suspensions with oxygen are extremely interesting. The original reading paper
mentioned above gives the same opinion. Derivation of the parametric decay expression lacks
clarity, while the explanation of the physical-mechanical mechanism is not convincing. It is stated
that the influence of the dispersed phase volume fraction and the anode material on the current-
voltage characteristics at stationary and non-stationary polarization, the phase composition of the
oxide layer, and the features of the formation of the oxide layer on the surface of the material were
studied. It was found that an increase in alumina volume fraction leads to an appreciable decrease
in apparent limiting current density of the oxygen evolution and the metal oxidation as well. It also
leads to the drastic increase in the resistance due to several reasons: the accumulation of anode
oxidation products and bubbles in the anode layer, the growth of oxide layer, the structural
changes, and the decrease in the active surface area.

Page 5 of 7
The most abundant compounds in all oxide layers are Cu2O and CuAlO2. The 90Cu-10Al anode,
the aluminium oxide suspension based on the KF-AlF3-Al2O3 system with a volume fraction no
more than 0.12 (with five μm Al2O3) at a temperature of at least 750 °C are recommended for
further studies. The author of this Dissertation confirms pertinence of his technique that the
aluminium reduction can be performed using 90Cu-Al anode and wettable tungsten cathode at CR
1.4 and T 800 °C. High purity aluminium can be produced using SGA and adequately protected
current leads. Remarkable is comparing the obtained results, data based on the physicochemical
properties of KF-AlF3 melts, the current density in anodes (A1-A3), the concentration of
overvoltage, and cyclic voltammetry records allow excellent agreement. Although more studies
are needed to further verify these models on other materials and conditions, the performed
successful attempt indicates that this new model can become an excellent alternative method to
produce aluminium.
Summarizing, the candidate for a Ph.D. degree has performed a large amount of insightful
research and obtained new original results, which broaden our understanding of the physical
mechanisms of the Electrolysis of cryolite -alumina melts and suspension with oxygen-evolving
electrodes. The Dissertation work has been performed at a high scientific level. All crucial results
presented in the Dissertation are published in peer-review journals. Judging by the Dissertation,
the candidate Sai Krishna Padamata merits the Ph.D. Degree.

Prof. Mouhamadou A. Diop, Ph.D., P.Eng.

School of Metallurgy
Institute of Light Metal Metallurgy
No.3-11, Wenhua Road, Shenyang, China 110819.
TEL: +86 24 8368 6381
FAX: +86 24 8368 6381
E-mail: [email protected]

Page 6 of 7
Name of the Dissertation Commission Member: Dr. Mouhamadou Aziz Diop

Chair / Function: Associate-Professor at Northeastern University (China)

Date: 2020-05-15

Signature: …………………………… *
* No signature required when submitted per email.
Please send the completed form to the Head of Department of Highly Qualified
Personnel Training Grigorieva O.A. e-mail:[email protected], tel. +7 (391) 206-22-
62, address: 79/10 Svobodny pr., Room P6-16, 660041 Krasnoyarsk, Russia

Page 7 of 7