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Electrocrystallization and electrochemical control of crystal growth.

Fundamental considerations and electrodeposition of metals

Article  in  Journal of Physics D Applied Physics · July 2000

DOI: 10.1088/0022-3727/24/2/019

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J. Phys. D: Appl. Phys. 24 (1991) 217-225. Prinled in the UK

Electrocrystallization and
electrochemical control of crystal
growth: fundamental considerations
and electrodeposition of metals

Frank C Walsht and Maura E Herront

t Chemistry Department, Portsmouth Polytechnic, White Swan Road, Portsmouth
*
PO1 ZDT, UK
Chemistly Department, Southampton University, Highfield, Southampton SO9
5 N H , UK
Received 17 July 1990, in final form 13 November 1990

Abstract. The fundamental steps involved in an electrochemical reaction are

reviewed with respect to their role in crystallization at the electrode surface. The
reaction system is seen to be sensitive to the flow environment and the nature of
the electrode surface. The electrode potential can influence many features
including reaction rate, chemical and phase composition, the extent of adsorption,
orientation and texture. Aspects of electrocrystallization are illustrated by
considering cases of metal deposition. Particular emphasis is placed upon the
development of surface roughness and the formation of metal powders during
copper deposition from aqueous acid sulphate solutions.

1. Introduction apparently simple cathodic reduction may be

The term ‘electrocrystallization’ was coined by Fischer
[l] in the 1940s to describe a crystallization process in
which mass transfer is accompanied by charge transfer.
The early development of the subject has been summa-
rized by Bockris and Razumney [ 2 ] . In the present
paper, electrocrystallization may be broadly defined as
the process (or result) of a direct or indirect elec-
trochemical influence on crystallization.
(i) A direct electrochemical influence may be
exerted if the value of the electrode potential dom-
inates the type of nucleation and the growth kinetics
for electrodeposition of a metal.
(ii) Electrochemical reactions may indirectly alter
the local reaction environment (e.g. the pH) and hence
the nature of the reaction product. For example, in
an unbuffered electrolyte the occurrence of hydrogen
evolution as a side reaction at the cathode may result
in the co-deposition of metal oxides/hydroxides in the
metal deposit.
In many processes, both of these influences are experi-
enced to some extent, i.e. there is a significant coupling
between electrochemical and chemical steps in the
overall reaction sequence.
In order to appreciate some of the steps involved
in the overall process of electrocrystallization, an
considered:
Oxd,) + ne- -+ Red(,). (1)
As shown schematically in figure 1, this hetero-
geneous charge transfer reaction takes place at the
interface between an electronic conductor (or semi-
conductor) and a n ionicconductor. Extensive treatments
of the interface region are available elsewhere and con-
sider charge separation resulting in a potential dis-
tribution over the electrical ‘double layer’ (e.g. [3]), as
shown in figure Z(a). Additionally, a concentration pro-
file will exist for each of the eiectrolyte species near the
electrode surface, due to convective diffusion (e.g. [4,
51). This situation arises due to depletion or build-up of
species; in figure 2 ( b ) ,reactant depletion is considered.
At the limiting current, the reaction is under complete
mass transport control and the surface concentration bas
reachedzero. Assuming a (fictitious) linear profile allows
the Nernstian diffusion layer thickness to he defined, BN
isdirectly relatedto themasstransport coefficient, k,and
the diffusion coefficient, D by the equation k , = D/B,.
A third layer, the fluid velocity boundary layer (figure
2 ( c ) ) , develops due to localized differences in electrolyte
convection. The hulk velocity is increasingly retarded as
the electrode surfaceis approached. At the surface itself,
the fluid is stationary relative to the electrode. Assump-
tion of a linear profile allows the Prandtl (hydrodynamic)
boundary layer, B,, to be defined.

0022-37271911020217 + 09 $03.500 1991 IOP Publishing Lld 217

F C Walsh and M E Herron

ELECTRODE INTERFACE ELECTROLYTE (i) Solvent (electrolyte) decomposition, e.g. in the

electronic charge ionic
ronduc t i o n transfer r a n d UT t i o n case of an aqueous phase the cell reaction may be

Oxdlrurfl c :
I

O x d Ibulk1
H 2 0 + H, + $ O z .
(ii) Chemical changes which modify the electrolyte
(3)

1o d r o r p t ion

Oxd lrurf 1
composition, e.g. the localized generation of hydroxyl
ions due to oxygen reduction
0 , + 2 H 2 0 + 4e- + 4 0 H -

1 I
(4)
\ f electron t r n n r f e r
or hydrogen evolution
Red (surf I
2H+ + 2e- + H,. (5)

! s u r f a c e diffusion

Redirurf I
(iii) Active dissolution of a surface, which may form

-
soluble or insoluble species, e.g. in the case of nickel
Ni - 2e- Ni2+ (6)
nucleation & growth
J Ni + Z H 2 0 - 2e- + Ni(OH), + 2 H + . (7)
Inass
Redlrurfl - - --
tronrpert
3 Red I b u l k 1
(iv) Direct deposition of a new surface phase, as in
the electrodeposition of metals, e.g.
Figure 1. Steps involved in the process of Cu2+ + 2e- + Cu. (8)
electrocrystallization.The cathodic reaction,
Oxd + m-+ Red is considered schematically. (v) Transformation of a surface phase; e.g. at the
positive pole of a lead-acid battery, the simplified reac-
tion is

It is important to appreciate the disparate dimen-

sions for these three layers near the eiectrode. If broad
ranges are considered:
0.5 nm < c p 2 plane < 1 nm
1pm < 6, < 100pm
0.1 mm < bpC< 1mm.
In the general case, electrocrystallization processes
may be affected by changes in any of these near-eiec-
trode layers. In practice, interactions occur between
these layers giving rise to a complex environment and
the concept of a reaction layer (e.g. [6]).
Figure 1 indicates some of the steps involved in
reaction (1). If thc ovcrall process is considered to be
copper deposition, the steps are:
cuib+"lk; + cui:,,
Cui& + 2e- + CU(,,,~.
The reactant must first be transported via convective
diffusion to the interface (equation (Za)), and this step
may be very sensitive to the hydrodynamic conditions,
i.e. the relative velocity between the electrode and
the electrolyte. Following surface adsorption of cupric
ions, electron transfer occurs (equation (26)). This, in
turn, is followed by surface diffusion of copper atoms
which nucleate, then grow, to form a surface deposit.
In this case, the reaction product remains on the elec-
trode surface. It is important to realize that the elec-
trode potential may exert an influence over any of
these steps.
Electrochemical reactions may affect crystallization
via the following pathways:
P b 0 2 + SO:- + 4H+ + 2e- e PbSO, + 2 H 2 0 . (9)
Perusal of ihese reactions indicaies ihai thc proccss
of electrocrystallization may include:
(i) anodic, cathodic or cell reactions;
(ii) chemical and electrochemical steps;
(iii) soluble or insoluble reactants or products;
(iv) ions and uncharged species, including the sol-
vent;
(v) disappearance, appearance or transformation of
a solid phase;
(vi) phases which remain on the electrode or which
reside in the electrolyte.
In practice, several complications may occur:
(i) The solid phase may be mixed, e.g. it may be
an alloy, a metal/metal oxide composite or combined
(20) crystallographic phases.
(26) (ii) Chemical steps may serve, for example, to (a)
increase the pH, encouraging oxide/hydroxide for-
mation or (6) exceed a solubility limit, leading to
precipitation.
(iii) 'Underpotential' deposition of metallic mono-
layers may occur at potentials more positive than the
open-circuit value, This phenomenon results in the
controlled formation of an essentially two-dimensional
array of adsorbed metal atoms, the surfice coverage
often approximating to a monolayer of adatoms.
(iv) Electrode participation may result in corrosion
with the formation of intermetallics or other metal
compounds.
(v) The surface state and composition may greatly
affect the nature of adsorption and nucleation
processes.

21 8
 Electrocrystallization

MurW wmei
(4
0' E3
@
0 e c

6N- I=O
Electrode [b
@
50luofed
0 onion

@
1 3 = IL>l2>l1>O

0 @ @ (b)

E) 0
0 6, I

- P0,enll.l
--
4, p l o w I p 8 i l i o n of ~ l o i e s 1opprmch for

COmpOct
toyer
Diffuse layer
Solvoted
COfiO"
cation)

r Yb
-
_ _ _ _ _JPr---'_ _ _ _ _ ~ __..--------

+m-

4> -

(4
4s
r- 0
1.0 2.0 3.0 dP,
+; -0IOnc
4.0
Xinm
5.0 0 I

Flgure 2. Electrolyte layers near the electrode surface. (a) The electrical double layer and the resulting potential field
(caused by charge separation). The case of a negatively charged surface is taken. The q 2 plane is the 'outer Helmholtz
plane'. (b) The concentration boundary layer (arising from diffusion).The depletion of reactant concentration with distance
from the electrode surface is considered. Assumption of a linear profile enables the Nernst diffusion layer thickness, SN to be
defined. (c) The fluid boundary layer (due to fluid shear and flow development). a,, is the Prandtl (hydrodynamic)boundary
layer thickness.

(vi) Roughened surfaces may give rise to electro- points of view [l,2,7-131. Such studies have greatly
catalysis, enhanced surface area or improved mass contributed to our understanding of direct elec-
transfer effects. trocrystallization, including adsorption, nucleation and
(vii) The localized potential and current on the growth processes.
electrode may change the morphology, chemical com- The linear rate of electrocrystallization, U , is
position or phase composition of the products. directly related to the current density, j , according to
(viii) Several competitive electrochemical reactions the expression
may be possible. U = jVm/nF (10)
(ix) Time-dependent effects may be experienced. where V,,, is the molar volume and F is the Faraday
These considerations lead to the recognition that the constant. This relationship shows the importance of the
reaction environment is extremely important. This current density distribution. High localized values will
includes the nature and state of the electrode, the elec- lead to a higher rate of growth, a different growth form
trolyte composition, temperature and flow effects [ 6 ] . or the incidence of a side reaction.
The amount of deposited metal per unit area is the
ratio of the mass per unit area to the molar mass
2. Electrodeposition of metals m = w/M (11)
and is given by Faraday's laws as
This is the most extensively studied field in electro- m = q/nF (12)
crystallization, from both the theoretical and practical where q is the charge density at the electrode surface,

21 9
F C Walsh and M E Herron

ELECTRODE ELECTROLYTE -j m~ r m-2 (4

150 I I I I I
~

'adotom'
I@
cluster
II rurfote
diffusion

0 0.1 0.2 0.3 0.L 0.5 0.6

t/s

+2Ld3
growth

growth
I hemispherical
6
.
centres pyramidal

dendritic

Flgure 3. Some of the steps during the

p!ectroc~,~!=!!iz=t!/nnof a metal onto i) substrate. This 0 0 ?0 20 -
30i t t.l/mr ."
In

simplified schematic shows a solvated ion and idealized

growth geometries.
In terms of local current density
m=
f jdt/nF
the equilibrium between a surface phase on the elec-
trode and a solution phase in contact with it may he
described by the reversible electrode potential, E,. The
driving force for electrocrystallization is provided by
the deviation of the electrode potential from its equi-
librium value, which is known as the overpotential, q:
q=E-E,.
This influential parameter is directly related to the
chemical potential, p and the change in Gibb's
function, AG as follows:
q = Ap/nF
q = AG/mnFA
where m is the amount of material per unit electrode
area A.
The formation of a new phase requires that the
system is in a metastable state. This is achieved by
perturbing the equilibrium via the application of a
potential field, in direct electrocrystallization, or an
alteration in the temperature or composition of the
electrolyte for indirect electrocrystallization.
Figure 4. Analysis of current versus time data for
nucleation of manganese onto vitreous carbon. (a) The
current transient response to the potential step shown.
Electrolyte: 0.5 M MnCI, + 1 M NHCI at 20 "C; electrode:
stationary vitreous carbon disc. (b) Analysis of the
nucleation kinetics for a potential step from -1.30 V SCE to
(13)
-1.66 V SCE. The linear data fit through the origin indicates
an instantaneous type of nucleation: j = current density at
time 1; j,,, = minimum current density; T = time intewal
between j and j,,,.
Such a situation is analogous to crystallization from
a supersaturated solution or condensation from a
supersaturated vapour. Variation of electrode potential
provides an important method for exercising control
(14) over the degree of supersaturation in electrocrystal-
lization processes. On the other hand, poor control of
the potential distribution may lead to changes in the
deposit morphology and growth rate, or even to an
increased rate of side reactions. It should also he noted
(15) that active sites must be available for crystallization to
begin; therefore, adsorption and nucleation steps are
(16) key prerequisites for growth processes (figure 3).
The kinetics of nucleation have been considered in
detail elsewhere [7-121. In a simple approach, the rate
of appearance of stable growth centres is expected to
follow first-order kinetics. The number of active sites,
N c , at time 1, is related to the initial number, N o , by
the expression [13]
N , = No[l - exp(-k.t)] (17)
where k. is the apparent nucleation rate constant.

220

c h a r g e charge mars
tronrfer transfer tronrfer (4
I / polyrryrtoliine
layers a tidger
growth
s p i r a l s , I o y e r r 8 blocks
0 niques to be sure of the nucleation and growth
E, -E
Figure 5. Idealized steady state current density versus
electrode potential curve for metal (e.g. copper) deposition.
(a) Showing the various regions of kinetic control. (b)
indicating the regions of growth various morphologies
There are two obvious limits to this expression. If
k,f % 1 , then exp(-k,f)+ 0 and N , = N o , i.e. the num-
ber of nucleation sites remains constant at its initial
value, This is often referred to as instantaneous
nucleation [14]. On the other hand, when kat is very
small, exp(-k,f) 2 1 - k,t and 1 - exp(-k,?) = k,f so
that N, = Nok,t or N, = k;t, where k: is a modified
nucleation rate constant. The latter case is known as
progressive nucleation [14]. In the absence of mass
transport restrictions the overall current density at time
f is given by [9]
where k is a modified rate constant, A, is the active
area of a single nucleus and U, = dN/df is the rate
of increase in the number of nuclei per unit time.
Instantaneous nucleation is most likely to occur at high
overpotentials due to the increased probability of a
high number of nucleation sites per unit electrode area.
Under these conditions, equation (18) becomes
j = kA(f)No (19)
while for progressive nucleation
j = kAZ(t)No. (20)
In both cases, the growth of three-dimensional nuclei
Electrocrystallization
may be described by considering the rate of increase
in the volume of the nuclei, i.e. dV/df
dV(t)/df = -kVm
A(().
nF
Geometrical considerations for hemispherical nuclei
and a coupling of equation (21) with (19) or (20) yield
for instantaneous nucleation
j = BNofZ (22)
and for progressive nucleation
j = BN,Af' (23)
where B = 2nVik3/n2FZ.
These expressions assume that the growth centres
are independent, i.e. no overlap occurs [U, 161.
Equations (22) and (23) predict that the current tran-
sient (i.e. the I versus f behaviour) should follow a f 2
relationship for instantaneous nucleation and a t3 one
for progressive nucleation. It is therefore possible to
test observed current transients according to these
diagnostic models, with due regard to the assumptions
made in the derivation. In practice, however, other
types of growth patterns (such as two-dimensional layer
growth on instantaneously generated nuclei) can lead
to a similar current density versus time dependence to
that shown in equation (22). It is therefore important
to use microscopy and other electrochemical tech-
geometry.
This approach may be illustrated by a specific
example. The observed current transients for depo-
sition of manganese from an aqueous chloride elec-
trolyte
Mn2+ + 2e- --* Mn (24)
are shown in figure 4(a). The curves show the response
of a static vitreous carbon electrode to a cathodic
potential step from -1.30 V SCE (where negligible reac-
tion occurs) for 4 s to a potential in the range -1.63 V
to -1.67 V. Following a very brief initial spike due to
double-layer charging, the current density rapidly
drops to a low value (approximately 2 mA cm-') then
becomes progressively more negative with time. At
sufficiently long times, the current density tends to a
constant, steady state value. The application of a more
negative potential, i.e. a greater overpotential, pro-
duces a faster increase of current, a larger steady state
value and a shorter transition time to the plateau
region.
These current density transients are characteristic
of nucleation and phase growth of the deposit on the
inert carbon surface. In the present case, hydrogen
evolution occurs as a secondary reaction on the
deposited manganese. However, the partial current
density for this reaction merely amplifies the current
density response without changing its shape. The data
[17] may be analysed by plotting the increase in current
density vs the square of the time interval ( t - t ) 2or
(as shown in figure 4(b)), (j- jmin)'I2 versus t - r. The
221
F C Walsh and M E Herron

linear dependence at high overpotentials indicates niques have been employed which include one or more
instantaneous nucleation according to equation (22), of the following parameters under controlled con-
followed by three-dimensional growth under charge centration and fluid velocity conditions:
transfer control. The relatively small dependence of
the steady state current density upon overpotential may (i) Current at a controlled potential (the potentio-
suggest that overlap of growth centres and formation static technique) [20, 211.
of a continuous layer are followed by a thickening (ii) Electrode potential, under constant current
process which is partially mass transport controlled. (galvanostatic) control [18, 19, 22, 231.
This approach may be readily extended to the con- (iii) Surface morphology, as revealed by, for
sideration of diffusion-controlled nucleation kinetics example, optical microscopy or scanning electron
and the effects of overlap [15, 161. However, such microscopy [18, 241.
simple electrochemical measurements should be comp- (iv) Surface roughness, typically measured by a
lemented by structural (e.g. microscopic) studies to stylus traversing profile meter [24, 251.
confirm the prevalence and size of nuclei and to exam- As an illustration, the development of surface rough-
ine the geometry of growth. ness during copper deposition from an acid sulphate
So far, the case of short-term, charge-transfer-con- solution (1.5M H2SO4) may be considered. Such
trolled nucleation has been considered. There are two studies have been described [16] using potentiostatic
related consequences as the overpotential is increased, control of a rotating cylinder electrode (RCE) at a tem-
i.e. as the potential is made more negative (figure 5). perature of 22°C (figure 6).
Both the kinetics and the deposit morphology change. The active surface for these studies was a copper
The current density increases due to the faster rate foil which had been preplated with a compact copper
of charge transfer, according to Tafel kinetics as an
approximation
jcr = i oexp(-Lu,nFq/RT) (25)
where j o and aCare characteristic kinetic parameters
known as the exchange current density and the
.
.
A
>
..
,
:
.
f:a,,,"uLc
r...
Llall>,c,
...r . : ....
C~,C,,,CLC,,~.
*.
A 5
.L.
LIIG
........-~....:^,
*-wG,~'"LcL1L'"'

becomes more negative, the overall reaction rate

becomes increasingly dominated by the rate at which
metal ions reach the cathode. Eventually, this mass
transport control becomes complete and the reaction
rate reaches a constant maximum value known as the
limiting current density, j L
jL= kLnFcb (26)
where kL,the mass transport coefficient, depends upon
electrode geometry and flow conditions and cb is the
bulk concentration of metal ions. At intermediate over-
potentials, the observed current density shows a depen-
dence npon charge transfer and mass transfer effects
such that [ S , 61
1Jj = l/jm + l/jL. (27)
At sufficiently negative overpotentials, a n additional
reaction such as hydrogen evolution takes place (figure
5(n)). As shown in figure 5(b) the overpotential also
affects the nature of the electrodeposit. The general
trend is towards increasing surface roughness as the
potential becomes more negative. In particular, dis-
persed, powdery deposits are common in the vicinity
of the limiting current density [18, 191. This change in
the deposit morphology has important technological
implications. For example, electroplating demands Figure 6. Experimental arrangement lor potentiostatical y
compact, smooth and adherent deposits which are fav- controllea deposition 01 copper at a rotating cylinder
oured by a low overpotential, while metal powders electrode. (a) section, (b) pan. A, anode: C. cathooe
may be deliberately manufactured by applying a high contact (orJsh); RCE. rotating cy inder e ectrode: S,
intermittent scraper, LC, ,Lggin capillary probe; P,
overpotential. The development of roughness and y ,(cathode) potential; 1. current;
potentiostat power ~ ~ p p l E.
increased surface area for growing electrodeposits has D. cathoae deposit: WE, worming electrode; RE, relerence
been studied by several groups. A wide variety of tech- e ectrode; CE, comer electrode.

222
 Electroctystallization

70 i 6

60

50

40

30

20

10

0
0 0.1 0.2 0.3 0.4 0.5 0.6 O.? 00
-E /V vs SCE

Figure 7. Current versus electrode potential curves for electrodeposition of

copper onto a rotating copper cylinder electrode. The curves show results
for surfaces which have been produced by potentiostatic deposition (under
complete mass transpolt control) at -0.600 V SCE for set times. Electrolyte:
0.014 M CuS04 + 1.5 M H2S04at 22 "C. Linear potential sweep at
25 mV s-', RCE detai1s:diameter 6.3 cm, active length 4.3 cm, rotational
speed 6 Hz,
deposit to minimize nucleation effects. The cupric ion the potentials corresponding to the limiting potential
concentration is stabilized via the use of a soluble cop- plateau, i.e. when the rate of metal deposition is under
per anode at the 0.014 M level and the turbulent hydro- partial or complete mass transport control. This is
dynamics are controlled by adjustment of the rotation demonstrated by the current transients in figure 9. The
speed of the RCE. development of roughness may be suppressed by the
The steady state current potential curves shown in addition of certain organics to the electrolyte. The
figure 7 were obtained on deposits which had been resulting adsorption onto the metal deposit greatly
grown for various times (0 to 120 min) at a potential modifies the current-time behaviour. This is illustrated
corresponding to the central region of the limiting cur- for the case of thiourea in figure 10.
rent plateau (-0.600V SCE). The observed limiting Finally, it is important to realize that roughened
current is clearly higher for the prolonged deposition deposits of metal may significantly affect the prevailing
times, due to development of a roughened surface fluid dynamics, due to an increased shear at the elec-
which has both a higher active area, A , and a larger trode surface resulting in microturbulence. For the RCE
mass transport coefficient, kL: in turbulent flow, it is found that the observed limiting
I , = jLA = k,AnFc,. current depends upon the peripheral cylinder velocity,
(28) U,as follows [26, 271:
The time development of roughness in the limiting
current region may be followed directly (figure 8). The ILa U". (29)
transition may be subdivided into three sequential In the present case, x = 0 . 7 4 for the initial, hydro-
zones: dynamically smooth RCE and x = 1 for a significantly
(i) an initial period where the current is steady and roughened surface (figure 11). These values compare
equal to the value for a smooth deposit; closely with literature values of 0.70 and 1.0 [26].
(ii) a period where a steady rise occurs with an Such studies have both fundamental and tech-
eventual decline in slope; nological implications. They provide:
(iii) a final zone where the current is high and rela-
(i) A method for the continuous monitoring of the
tively steady.
development of roughness during mass-transport-con-
An increase in the rotation speed serves to decrease trolled metal deposition.
the initial period, increase the rate at which current (ii) Direct measurement of the rate of mass trans-
increases and elevate its final value at long times. The port to smooth RCES and those of developing rough-
abrupt effect of deposit removal is shown for one ness.
rotation speed; the current is rapidly decreased to a (iii) A controlled hydrodynamic technique for the
value corresponding to a smooth deposit, as expected investigation of electrolyte additives.
(211. (iv) The basis of a method for continuous powder
Such roughness development only occurs near or at formation.

223
F C Walsh and M E Herron

-j,/mn cm-’ (4 -j 1 m~ m-2

120 10 70 I I I

-E/V vrSCE

100 8 60 - 0.300
0.600

80
6 0.550

60
L
LO 0.500

2
20

0 0 0.450
0 LO 80 120 160 ZOO
0.350
t/min o i 10.300
0 LO 80 120 160 200
t p i n
Figure 9. Potentiostatic growth of copper deposits at
various cathode potentials, showing that a significant
roughness development only occurs at potentials
corresponding to partial or complete mass transport
control. Other conditions as in figure 7

20

16

16
70 t -I6
16

12

10

0 60 120 180 240

L t/min
Figure 10. The effect of thiourea additions on development
2 of surface roughness, shown by the current versus time
behaviour under potentiostatic control for a rotating cylinder
electrode: E = -0.600 V versus SCE, w = 340 RPM. Other
0 conditions as in figure 7.
0 LO 80 120 160 200
t/min

Figure 0. Potentiostatic growth of copper deposits under

complete mass-transport-controlledconditions. (a) The
current transient for various rotational speeds and the
effect of abrupt deposit removal (via scraping) at a
rotational speed of 6 Hz. The shading indicates the limits of
reproducibility for ten separate experiments. (b) The time
development of average roughness of the surface (as
measured by a traversing stylus instrument). Other
conditions as in figure 7.
3. Conclusion
This paper has attempted to outline the fundamental
steps which occur in electrocrystallization and the fac-
tors which may affect the process. Emphasis has been
placed upon the longer-term growth of metal deposits.
In particular, the use of a controlled flow environment

224

Figure 11. The effect of developing roughness on the
limiting current density versus rotational speed relationship,
showing the importance of the time allowed for roughness
development prior to these trials. Other conditions as for
figure 10.
(via the rotating cylinder electrode) allows the dev-
elopment of roughened deposits under the control of
mass transport to be studied using a number of tech-
niques. The morphology and mass transport charac-
teristics of these deposits are sensitive to many
parameters including electrolyte composition and tem-
perature, the prevailing fluid flow, cathode potential,
the electrode surface state and the deposition time.
The fundamental and technological importance of
electrocrystallization is much wider than the deposition
of metals, and in a subsequent paper the scope will be
diversified to include:
(i) the deposition of insoluble inorganic compounds
(e.g. zinc phosphates on steel);
(ii) the deposition of conducting organic polymers
(e.g. polypyrrole on stainless steel); and
(iii) reversible film transformation (e.g. lead diox-
ide to lead sulphate on platinum).
In all cases, electrochemical measurements will be
coupled with complementary structural techniques
(such as x-ray diffraction).
Acknowledgments
The authors are grateful to Miss M Gonsalves and Dr
D Pletcher (University of Southampton) who provided
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Electrocrystallization
data and research facilities. Early studies of metal
deposition on rotating cylinder electrodes were per-
formed in Dr D R Gabe’s laboratory at Loughborough
University of Technology. The work described has
been sponsored by SERC and ICI.
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