British Corrosion Journal

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Anodic Behaviour of Tin in Potassium Hydroxide

Solution

N. A. Hampson & N. E. Spencer

To cite this article: N. A. Hampson & N. E. Spencer (1968) Anodic Behaviour of Tin in Potassium
Hydroxide Solution, British Corrosion Journal, 3:1, 1-6, DOI: 10.1179/000705968798326523

To link to this article: https://doi.org/10.1179/000705968798326523

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 ANODIC BEHAVIOUR OF TIN IN POTASSIUM
HYDROXIDE SOLUTION
By N. A. HAMPSON* and N. E. SPENCER*t

Results of galvanostatic polarisation of tin anodes in potassium hydroxide solutions are reported.
The orientation of the anode plays an important part in the observed behaviour. Permanent passivity
occurs when the potential rises to that required for oxygen evolution from a film of stannic oxide, 50-100 . \,
thick. At [KOHl up to and including 7 M, the prepassivation 'active' region of the potential-time beha-
viour conforms to a 'solution-controlled' reaction; at higher [KOH] anode films are formed with less and
less dependence on mass transport in the electrolyte.
Interpretations of the observed behaviours are given.

Introduction of a metal having an anodic product freely soluble in the

It is well established that tin anodes become passive in electrolyte. The time to reach the transition (or passivation
alkaline solution once the potential rises above a critical if the transition is to the process of oxygen evolution), tF, at a
value.l-lo Attainment of the passive state corresponds to the current density i, is often found to conform to
transition between the dissolution of the anode and the
(i - h)t; =k . . (4)
evolution of oxygen from a passive film formed on the anode
surface. It is clear from the literature that the anodic h is the limiting current density below which the transition
behaviour of Sn in alkali is complicated and there has been does not occur. iI, nand k are constant for a particular
some general disagreement regarding the exact nature of the system under specific conditions.
stages preceding passivation. If transition is due to the attainment of a critical concentra-
It is generally agreed, however, that the sequence tion of anode product in the electrolyte layers near the
Sn -? Sn (II) + 2e . (1) electrode and if convection can be supressed, the equation
Sn (II) -? Sn (IV)
20H- -? H20 +
+ 2e
+
-!-02 2e .
. (2)
. (3)
it; = k . . (5)
accounts for the main features of the process. Early wor- follows from the laws of non-steady-state diffusion.l2,13,15,16
kersl,2 considered that the 1st transition, from (1) to (2), The effect of a limited amount of convection can be taken into
corresponded to the solubility limit of stannite in the electro- account when (5) becomes :13-15
lyte layers surrounding the anode. El Wakkad et al.9 con-
sidered that the 1st transition was marked by the formation
(i - i 1) t;
.1.
= k . . (6)
of a very thin (,..... 2 molecules) layer of Sn(OH)2 on the El Din et al,l° reported that Equation (6) applied in the case
electrode surface. El Din & El Wahab10 agree that the 1st of tin in sodium hydroxide.
transition is marked by the presence of Sn(OHh on the This paper records the results of experiments made with
electrode but Shah & Daviesll considered that the direct horizontally and vertically orientated tin electrodes in
formation of stannite occurs at the anode until SnO is potassium hydroxide electrolytes in the range O· 1 to 14 M.
formed on the anode when the capacity for SnO in the electro-
lyte layers surrounding the anode has been exceeded.
For the 2nd transition (permanent passivation) El Wakkad
et al.9 and El Din et al.10 agree that oxygen evolution takes Experimental
place from a film of Sn(OH)4 whereas Shah & Daviesll The polarisation cells, capacity about 25 ml, are shown in
consider that Sn02 is the final solid product at the anode. Fig. 1. Anodes were cut from Sn sheet (99' 95 %) 0·005 in.
El Din et al.lo considered the thermodynamic data for a thick supplied by Johnson, Matthey and Co. Limited.
number of different oxidation reactions and conclude that Anodes were pretreated as follows1? : trichloroethylene
whereas the compound corresponding to Sn(II) in Equations vapour phase degrease; dip (5 sec) in 5~;;; aqueous sulphuric
(1) and (2) could be either SnO or Sn(OH)2, the compound acid; water rinse; polished to a mirror-like finish with pure
corresponding to Sn(IV) in Equations (2) and (3) could only cotton wool lubricated with carbon tetrachloride (other
be Sn(OH)4. lubricants were equally satisfactory e.g. acetone, amyl
A serious objection to transition (passivation) time- acetate, trichloroethylene-none gave any adverse effects on
current density data reported in previous investigations is the experimental reproducibility). The electrical circuit and
neglect of anode orientation.l2-l4 This results in considerable experimental technique have been described in detail else-
doubt being attached to reported current density regions in where.l2,l3 Galvanostatic polarisations were carried out at
which passivation will or will not occur. 220
• In experiments with the most concentrated electrolytes
The 1st transition in the anodisation of Sn, between the maximum current density investigated was O· 6 A cm -2, for
Equations (1) and (2), corresponds to the anodic passivation the most dilute electrolytes (0' 1 M) the maximum current
density was 9 rnA cm -2. The anode overpotential was
* Department of Chemistry, Loughborough University of measured against an unpolarised tin reference electrode using
Technology.
an electrometer (Wayne-Kerr, type M141). Sufficient poten-
t Present address: Joseph Lucas Research Centre, Shirley, tial determining species were present on the reference electrode
Warwickshire.
Manuscript received 3 July, 1967; amended manuscript 12 Sept., to maintain the reference potential, measured by the electro-
1967. meter, at a constant value. The equilibrium potential (in the

Br. Corros. J.; 1968, Vol. 3, January

 2 Hampson and Spencer: Anodic Behaviour o/Tin in Potassium Hydroxide Solution

B 0·3
F
o·g

0·2
Horizontal
anodes
0'7
>

E 0·1

.0

o
o
F
B
V~rtical
anodu

o A 0·1

2000

FIG. 2. Overpotential vs. time curves

A-A 0'176; !:J.-!:J. 0'141; 0-0 0'106;
.-.0'071; 0-0 0·035 Acm-2
5 M-KOH, horizontal electrodes, 2rc
Inserted curve: log)oi vs. 110.

FIG. 1. Polarisation cells

A Pyrex cell with accurately ground end pressing on to metal anode
B Cathode C Rubber seal D Clips
E Metal anode supported on Perspex base
F Luggin system with reference electrode

absence of added stannite) of the reference electrode con- SnlI'll/SnUl)

formed to
Eh = -0·93 - RT 10geaoH- . . (7)
F
and indicated that the probable reference electrode reaction
was18
SnO + H20 + 2e = Sn + 20H-.
. (8)
In addition to polarisation as far as the point of oxygen
evolution (or continuous anode dissolution), current inter-
ruption experiments,13,17 in which galvanostatic polarisation
was discontinued for sufficient time to allow electrolyte-
soluble anodic products to diffuse away, were made. Surface
films from passivated anodes were examined in the electron
microscope (A.E.!. EM6G): the technique for this has been
described.13
Tin analyses were made by precipitation and weighing
stannic oxide.19
Results
Electrolyte concentrations up to and including 7 M Fig. 4 shows tF vs. current density data-correlated in the form
Horizontal electrodes
Fig. 2 shows typical overpotential-time curves: an initial
'active' portion at relatively low overpotential is terminated
by a rapid rise in potential to that required for oxygen evolu-
tion from the passive anode. Observation of the second
transition, between Equations (2) and (3), was only possible
with the present experimental arrangement at low rates (Fig. 3).
··It is clear that identification of the abrupt potential rise with
the first transition is fully justified; the time taken for this rise
8520 8580 8640 8700
0·2 TIME, sec
o
o
FIG. 3. Overpotential vs. time curves showing 1st and 2nd transition
5M-KOH, horizontal electrodes, 0·018 Acm-2, 22°c
Inserted curve: details of 2nd transition
from the instant of closing the circuit is the first transition
time, tF.
Passivation occurred at all current densities investigated.
of Equation (6). In the lower part of the concentration
range, plots consisted of two rectilinear portions : at low
currents a smaller value of il and a larger value of k was
observed than at higher currents (k2 and i2 designate high
current parameters). The low current portion increased with
increasing [KOHl to extend over the whole experimental
range for concentrations 5 M and 7 M. At 0·1 M the 'low-
current' region was not discernable. Parameters calculated
from Equation (6) for all the systems investigated are shown
in Table I.

Br. Corros. J., 1968, Vol. 3, January

 Hampson and Spencer: Anodic Behaviour o/Tin in Potassium Hydroxide Solution 3
TABLE I
Values of parameters from Equation (6) calculated by the
method of least squares (I.B.M. 1620 computer)
D,S

Low current High current

KOH,M k, Acm-2 sect it, Acm-2 k2, Acm-2 sect i2, Acm-2
N 0'4
I Horizontal
E electrodes
~ 0·1 - - 0·019 (0'0002)
1·0 (0'60) (0·0001) 0·15 0·023
1·5 0·70 0·011 0·23 0·072
2·0 0·78 0·012 0·42 0·081
2·5 1·07 0·010 0·43 0·123
~z 5·0 1·57 0'013 - -
W
Q::
Q:: Vertical
:::>
u electrodes
0·2
0·1 - - 0·0145 (0'0005)
1·0 - - 0·14 0·028
2·0 0·80 0·025 0·41 0·085
5·0 1·40 0·045 - -
7·0 1·60 0·076 - -

Values in parentheses are approximate; dashes indicate that the values were not
calculable from the experimental data.

o·rM
TABLE II
G2 O~ 0·6
(TIME) -t2, sec-1f2 Typical results of current interruption experiments
Horizontal anodes (passivation time, tF) were polarised for
FIG. 4. Passivation time (tF) vs. current density data correlated in
the/orm 0/ Equation (6) time ft, rested and then polarised to the point of passivation,
Horizontal electrodes, 22°c t2. Total polarisation time is (ft + t2). (Rest period 600 sec.)

Current density, tF, t1, t2,

Results of current interruption experiments are shown in Acm-2 sec. sec. sec.
Table II. Provided that sufficient time was allowed to elapse
for the anode products to leave the vicinity of the anode, the 0·1 M-KOH
0·0018 104 45 109
secondary passivation time, t2, was independent of the initial 0·0022 80 30 90
polarisation and approxin1ately equal to tF. 0'0034 30 10 26
2·0 M-KOH
0·078 160 90 176
Vertical electrodes 0·103 93 45 92
Two distinct forms of potential-time curves were observed. 0·14 33 10 32
(a) At relatively high current densities the form was similar 7·0 M-KOH
to Fig. 2. 0·04 3260 1620 2900
(b) At lower current densities, the abrupt potential rise to 0·07 818 390 750
the potential of oxygen evolution was replaced by a small 0·17 118 60 61
0·32 38 15 35
potential increase ('" 20mV) which rapidly (10 sec) subsided
to a value very slightly greater than the Sn(II)/Sn over- 14 M-KOH
potential characteristic of the 'active' anode. Continuous 0·016 147 90 47
dissolution of the anode occurred without passivation. 0·035 68 30 32
0·14 23 15 6
Fluctuations of potential above the anode dissolution potential 0·27 12 5 5
were often observed after the small local potential maximum
particularly at low [KOH]. These were often of fairly large
amplitude (0' 2 V in 0·1 MKOH) and persisted indefinitely. Concentrations greater than 7 M
The relationship between the two behaviours (a) and (b) is
clearly demonstrated by the correlation of the transition Horizontal and vertical electrodes
time-current density data as Equation (6). i vs. tpt curves Fig. 6 shows the results of plotting t pt vs. current density
(Fig. 5), taking tF as the beginning of the potential rise, either for both horizontal and vertical electrodes polarised in
to oxygen discharge overpotential or the small local maximum, concentrated KOH (10 M and 14 M).
are independent of the ultimate result of polarisation, passiva- IF was independent of electrode orientation for the system
tion or continuous anode dissolution. The point of potential in 14 M-KOH and not influenced by rest times in current
rise after the dissolution potential Sn/Sn (II) has been estab- interruption experiments (Table II).
lished marks the same point in the polarisation history; the At 10 M, tF for vertical electrodes was somewhat greater
onset of the first transition. than tF observed with horizontal electrodes. In addition an
Br. Corros. J., 1968, Vol. 3, January
 4 Hampson and Spencer: Anodic Behaviour of Tin in Potassium Hydroxide Solution
10M

5M I 10 14",
0·5
I J ,
I I ,
I, I
0·4 o-s ,.,
16
/
~

II
III

It I
<{
II I-
i tel I
~ 0·3
w 0·4
19 ~
o til
I II I
E
I-
Z
W «
u II I
0:=
~ 0.2
0:=
2M
>•.
t-
i" p'
• f!
(J
(j)
I
••:f/ ,/
Z
~ 0·3

• FI I
:/1 "
f! c;-
Q-2
(TIME) -'12,
0'4
sec-'t2
0·6 0·8 " t'
I'
19 ./
FIG. 5. Passivation time (tF) vs. current density data correlated in 0-1
It I
theform of Equation (6) !.I ,<
Vertical electrodes, 22°c J.~ /..,
increase in integral passivation time was observed due to the
~
inclusion of rests in the polarisation schedule (current inter- 0'2 0-4 0'6
ruption experiments) for both horizontal and vertical elec- (TIME)_1/2,sec- ~2

trodes. FIG. 6. Passivation time (tF) vs. current density data correlated in
the form of Equation (6)
Structure of the anode film on passive anodes Horizontal (0) and vertical (e) electrodes, 22°c

Films, duplex, consisted of a thick, poorly adherent, layer

overlaying a strongly adherent film. (b) The reaction is independent of anode product transport
The thin (50-100 A) film was composed of very small via the electrolyte, anode products being retained on the
crystals, the small crystallite size made selected area diffraction electrode from the instant of closing the circuit (14 M-KOH).
patterns somewhat difficult to obtain. From the few areas Electrometric data does not conform to Equation (6) (extra-
which gave diffraction patterns these conformed to Sn02. polation of the limited rectilinear regions to infinite time of
The thick 'loose' film was generally amorphous; selected area polarisation yields a negative limiting current density-
diffraction patterns, obtained only with great difficulty, impossible to interpret on mass transport theory applied to
conformed to 5 SnO' 2H20. Films from anodes passivated the electrolyte phase). Transition times are independent
in 14 M-KOH were similar although the thick film had better of anode orientation and unaffected by rests in the polarisa-
adhesion. tion schedule.
At the intermediate concentration (10 M) the anodic
behaviour shows some of the features of (a) and (b) classifi-
Discussion cations.
Anode behaviour can be classified in terms of two extreme Selected area diffraction patterns of the Sn(lI) films cor-
types. respond to 5 SnO' 2H20, however the presence of other
(a) The reaction is completely dominated by anode product Sn(lI) compounds having a crystallite size too small to
transport via the electrolyte (7 M-KOH and below). Current diffract the electron beam is not precluded. The constitution
density vs. IF data follow IF! relationships of the form of the thin Sn(IV) film, Sn02, is much more definite. The
Equation (6) with positive intercepts, iI, on the current thinness of the Sn02 film is reflected by the relatively short
density axis which correspond to infinite times of polarisation. time between the 1st and 2nd transition (Fig. 3).
F or the same electrolyte, iI in the case of vertical electrodes is It is suggested that the electrode reaction sequence conforms
greater than that for horizontal electrodes and reflects the to the following scheme:
additional modes of mass transport available for the vertical (i) Electron transfer,
systems. Under certain conditions vertical electrodes under- Sn +
20H- = Sn(OH)2 2e. .' . (9) +
go c:>ntinuous corrosion. Changes in the rectilinear slopes (The identity of the initial Sn(lI) product is inferred by analogy
of i vs. IF! lines (Figs 4 and 5) at a fixed [KOHl indicate with other systems, e.g. Zn in KOH.l3 The product might
a change in the reaction causing transition. As [KOHl is be stannous oxide, SnO or SnO' H20, but this seems less
increased, the change occurs at progressively higher current likely.)
densities. Current interruption experiments confirm that (ii) Chemical reaction to form the final product potassium
anode products formed prior to passivation are removed stannite
from the vicinity of the electrode by the electrolyte. Sn(OH)2 +
OH- = HSn02 H20 . (10) +
Br. Corros. J., 1968, Vol. 3, January
 Hampson and Spencer: Anodic Behaviour of Tin in Potassium Hydroxide
(iii) Electrode is 'blocked' with Sn(ll) when the capacity of
the electrolyte layers surrounding the electrode for either
Sn(OH)2 (Equation 9) or HSn02- (Equation 10) is exceeded.
The electrode is 'blocked' by a solid film based on SnO. The
film might be, and certainly contains, 5SnO' ZH20.
(iv) First transition occurs when the potential of the
'blocked' electrode rises to that required for the formation of
Sn02.
SnO + ZOH- = Sn02 + H20 + Ze. .' (11)
(v) Second transition occurs on the completion of a coherent
film of Sn02 and the potential rises to that required for
oxygen evolution.
The two successive reactions (i), Equation (9), and (ii),
Equation (10), are consistent with the observed breaks in the
i vs. t fit lines Figs 4 and 5. Transition is due to the attain-
ment of the critical concentration of either Sn(OH)2 or
HSn02-. At high current density the critical concentration
of Sn(OH)2 is obtained before the critical concentration of
HSn02-. At low current density the conversion of Sn(OH)2
into HSn02- by Equation (10) offsets the accumulation of
Sn(OH)2 to such an extent that the critical concentration
of HSn02- is attained first. The accumulation of critical
concentrations of both Sn(OH)2 and HSn02- follow the laws
of non-steady-state diffusion modified for limited amounts
of convection (on the experimental time scale employed in
these experiments). Transition, due to attainment of the
solubility limit of either Sn(OHh or HSn02-, follows tp!
equations as is observed in practice. The break in the; vs.
tpt curves occurs at the current at which transition may be due
to reaching the solubility limit of either Sn(OH)2 or HSn02-.
The limiting current density, iI, represents the rate of removal
of anode products other than by diffusion in the electrolyte.
The extrapolated current density, ;2, represents the rate of
conversion of Sn(OH)2 into HSn02- under steady-state
conditions (no net accumulation of Sn(OH)2).
The effects of modes of mass transport other than diffusion
(convection) is indicated by comparing horizontal and
vertical electrode systems. Convection increases limiting
current density but has little effect upon k (Table I); both of
these observations conform to expectations and have been
discussed in detail.13,15 A major difference in the anodic
behaviour of horizontal and vertical electrode systems is the
continuous corrosion of vertical electrodes at low current
density. When diffusion is the only mode of mass transport,
every final anode product (except OH- discharge) irrespective
of current will ultimately reach the critical concentration
required for a process transition: horizontal electrodes will
therefore ultimately passivate. Vertical electrodes, subject to
convection may depassivate if the passivating species is removed
more quickly than it is formed. It is suggested that when the
critical concentration of Sn(ll) is reached, Sn02 forms but
being more acidic10 dissolves more rapidly in KOH than
Sn(II): hence depassivation may occur and the anode corrodes
continuously. The small 'rise and fall' in the overpotential-
time behaviour reflects the 'formation and removal' of
Sn(IV) at the anode and marks the first transition (Fig. 5).
The greater [KOH] the more readily Sn02 is likely to dissolve
(at least up to a limit of [KOH]), thus the current at which
continuous corrosion of vertical electrodes occurs should
increase with [KOH] as observed. A 'similar mechanism
accounts for the potential oscillations after the small hump.
If the faradaic current density is sufficiently high, a· local
concentration of Sn(IV) may build up until it is removed by
turbulent flow, e.g. eddy currents (oscillations were never
Br. Corros. J., 1968, Vol. 3, January
Solution 5
observed at horizontal electrodes). Oscillations in potential
follow these local concentrations variations.
The results of experiments with 14 M-KOH are unexpected
in view of the solubility curve of SnO in KOH, Fig. 7, since
appreciable solubility of SnO in high [KOtl] is indicated.
One explanation, adsorption of anode product at the electrode,
receives support from Tafel plots. These indicate that the
reaction is charge-transfer controlled (e.g. Fig. Z - insert), and
a value of the charge-transfer coefficient lX, '" O· 9, suggests
adsorption of SnO at the electrode.20
A more likely explanation is that the product of the electron
transfer reaction Equation (9), is only slowly soluble in very
concentrated (14 M)KOH and remains as a solid phase on the
anode. If the dissolution of Sn(OHh proceeded via various
hydrated intermediates, the rate of dissolution in 14 M-KOH,
in which the concentration of free water is very small, might
be very slow indeed. Supporting evidence for this suggestion
is the observation that the attainment of equilibrium between
SnO and 14 M-KOH is slow. In addition with electrolytes of
a higher concentration of free water (10 M) there was some
dependence of tF on electrode orientation' and evidence of
anode product transport in the electrolyte.
8 12
KOH CONCN., tel
FIG. 7. Solubility curve for SnO in KOH (4 weeks equilibrium
time)
2rc
Conclusions
At [KOH] up to and including 7 M, anodic behaviour is
broadly typical of a metal with an anodic product freely
soluble in the electrolyte. At higher [KOH], anode films are
formed with less and less dependence on mass transport in
the electrolyte.
For the Sn-Sn(ll) process two successive reactions occur at
the interphase. The first, electron transfer, in which an
initial Sn(lI) product, probably Sn(OH)2, is formed, is followed
by a second in which stannite is produced.
Transition to the Sn(II)-Sn(IV) process occurs when the
anode is 'blocked' by hydrated oxide. Electrode blocking
may be due to the attainment of a critical concentration of
either the initial Sn(ll) product (at high current density) or
stannite (at low current density).
6 Hampson and Spencer: Anodic Behaviour o/Tin
Transition to the discharge of OH - when the electrode is
passive occurs when a thin (50-100 A) film of Sn02 covers the
anode. Vertically orientated anodes may depassivate to
undergo continuous corrosion at low current densities when
convection supplies sufficient OH- to remove Sn02 as
stannate. This process is associated with fluctuations of
potential if complicated flow patterns develop. When
passivation occurs, the charge required to bring about the
2nd transition after the 1st has occurred is relatively small.
In very concentrated KOH electrolytes anode films form
References
1. Goldschmidt, H., & Ekardt, E., Z. phys. Chem., 56, 385, 1906
2. Foerster, F., & Dalch, M.,Z.Elektrochem.,angew.phys. Chem.,
1909, 16, 599
3. Newbery, E., J. chem. Soc., 1916, p. 1066
4. Hansel, G., & Gravel, A., Z. Elektrochem., angew. phys. Chem.,
1935, 41, 314
5. Kerr, R., J. chem. Soc. Ind., Lond., 1938, 57, 405
6. Bachvalow,G. T., J. apple Chem., Moscow, 1941, 14,469
7. Bachvalow, G. T., & Titov, P. S., Khim. ref. Zh., 1941, 4, 85
8. Bianchi, G., Chim. Ind., 1947, 29, 295
9. EI Wakkad, S. E. S., EI Din, A. M. Shams, & Sayed, J. A.,
J. chem. Soc., 1954, p. 3103
10. EI Din, A. M. Shams, & El Wahab, F. M. Abd, Electrochim.
Acta, 1964, 9, 883
11. Shah, S. N., & Davies, D. E., Electrochim. Acta, 1963, 8, 663
12. Hampson, N. A., & Tarbox, M. J., J. electrochem. Soc., 1963,
110, 95
in Potassium Hydroxide Solution
fronl the instant of closing the circuit. The reason for this
behaviour is obscure; it,might be connected with adsorption
of SnO at the interphase or alternatively with the low speed
of solution of Sn(lI) oxides or hydroxides in the electrolyte.
Acknowledgment
The authors wish to thank Mr. F. Sheldon (Joseph Lucas
Ltd.) for technical assistance with the electron microscopy and
Professor R. F. Phillips and Dr. R. Taylor for their continued
interest and provision of facilities.
13. Hampson, N. A., Tarbox, M. J., Lilley,J. T., & Farr, J. P. G.,
Electrochem. Technol., 1964, 2, 309
14. Eisenberg, M., Electrochem. Technol., 1965, 3, 340
15. Hampson, N. A., Jones, P. C., & Phillips, R. F., Can. J. Chem.,
1967, 45, 2093
16. Levich, V. G., Fiziko Khemiceskaja Gidrodinamika, Moscow,
1952
17. Farr, J. P. G., & Hampson, N. A., Electrochem. Technol., in
press
18. Latimer, W. M., 'Oxidation Potentials', 1953. (New York:
Prentice Hall)
19. Vogel, A. I., 'Textbook of quantitative inorganic analysis',
Third Ed., 1961, 503 (London: Longmans)
20. Randles, J. E. B., Trans. Symp. on Electrode Processes (1959),
1961 (Ed. E. Yeager), (New York: J. Wiley & Sons)
Br. Corros. J., 1968, Vol. 3, January