d. Electrochem. Soc., Vol. 138, No. 12, December 1991 9 The ElectrochemicalSociety, Inc.

3633

where K~ is the adsorption equilibrium constant for excess

TEA on adsorbed Cu(II)-TEA. - - - ~ 1 + [3]
From Eq. [A-l] to [A-4], the fractional surface coverage of e3,max rmax K l l ] " 1 + K1 - Cxl 1 + K2 9Cxl
active Cu(II)-TEA is expressed as
where rm~xis the deposition rate at 03..... and r is the depo-
K1 9C~1 K3" Cc 1 sition rate measured at 03.
03 - [1]
I+KI.C~ I+K3.Cc I+K2.Cxl REFERENCES
1. L. N. Schoenberg, This Journal, 119, 1491 (1972).
When the differential coefficient of Eq. [1] is equal to 0, the 2. A. Hung, ibid., 132, 1047 (1985).
m a x i m u m fractional surface coverage can be defined as 3. A. Hung, ibid., 133, 1350 (1986).
03..... The differential equation of 03 by C~1 is 4. F. J. Nuzzi, Plat. Surf. Fin., 70, 51 (1983).
5. M. Paunovic, This Journal, 124, 349 (1977).
d(03) K3 9C~ 6. F. M. Donahue, D. J. Sajkowski, A. C. Bosio, and L. L.
d(C~) 1 + K3" Cc Schafer, ibid., 129, 717 (1982).
7. W. Goldie, Plating, 51, 1069 (1964).
K1 " (1 - KI" K~" 0~1) 8. L. N. Schoenberg, This Journal, 118, 1571 (1971).
= 0 [A-5] 9. K. Kondo, J. Ishikawa, O. Takenaka, T. Matsubara, and
(1 + K1. C~)3. (1 + K2. Cxl)2 M. Irie, ibid., 137, 1859 (1990).
10. R. L. Meek, ibid., 122, 1177 (1975).
From Eq. [A-5] C~ at O3.... is 11. J. F. Fisher and J. L. Hall, Anal. Chem., 39, 1550 (1967).
12. J. M. Bolling and J. L. Hall, J. Am. Chem. Soc., 75, 3953
(1953).
1 [A-6] 13. D. J. Alner and M. A. A. Kahn, J. Chem. Soc., 5265
Cxl(0r,~) = KI 9K2
(1964).
14. A. Nozaki and M. Demori, Nippon Kagaku Zasshi, 84,
Therefore the m a x i m u m fractional surface coverage can 42 (1963).
be expressed as 15. G. S. Smith and J. L. Hoard, J. Am. Chem. Soc., 81, 556
(1959).
K3 "Cr 1
16. J. L. Hall, F. R. Jones, C. E. Delchamps, and C. W. Mc-
03.... 1 + K3" Cc (1 + V~2/K1) 2 [2] williams, ibid., 79, 336t (1957).
17. K. H. Pearson and K. H. Gayer, Inorg. Chem., 3, 476
Since the deposition rate is proportional to the fractional (1964).
surface coverage, the rate related to the concentration of 18. A. Molenaar, M. F. E. Holdrinet, and L. K. H. van Beek,
excess TEA from Eq. [1] and [2] is expressed as Plating, 61, 238 (1974).

The Effect of Chromium Particles on Nickel Electrodeposition

Sandra W. Watson* and Richard P. Waiters*
U.S. Bureau of Mines, Albany Research Center, Albany, Oregon 97321

ABSTRACT
I n order to obtain an u n d e r s t a n d i n g of the mechanism of chromium particle occlusion in electrodeposited stainless-
steel-type coatings, the U.S. Bureau of Mines has studied the effect of chromium particles on nickel electrodeposition. The
chromium particles catalyzed nickel electrodeposition on a vitreous carbon surface. Chromium particle additions, when
added to Watt's-type electrolytes, of 0.33M, 0.67M, and 1.00M NiSO4, shifted the nickel reduction wave to more positive po-
tentials on a vitreous carbon surface. From rotating cylinder electrode studies it was concluded that nickel deposition
with or without chromium particles is a kinetically limited rather than mass-transfer-limited process. Electrochemical im-
pedance spectroscopy experiments with and without chromium particles verified the rate-determining step proposed by
Epelboin, with the Ni+(ads) limiting the nickel electrodeposition. The chromium particles appear to enhance the forma-
tion of this Ni(,d~) intermediate.

Insoluble particles suspended in an electrolyte during
plating can be occluded in an electrodeposited coating
(1-3). The Bureau of Mines has been successful in produc-
ing stainless steel coatings on low-alloy steel substrates by
heat-treating an electrodeposited binary alloy of nickel
and iron with occluded chromium particles (4-6). As a first
step in u n d e r s t a n d i n g the mechanism of this particle oc-
clusion, the effect of chromium particles on nickel electro-
deposition has been studied.
Previous studies by Bazzard and Boden (7) concluded
that chromium particle occlusion occurs as a result of col-
lisions of the particles with the cathode surface. The
changes Bazzard and Boden observed in the polarization
behavior and increased current at a fixed potential were at-
tributed to the increased surface area due to the particles
and an increased surface ion activity. The latter effect re-
sulted from fresh solution brought to the surface by the
stationary film of liquid on each particle. Bazzard and
Boden also considered the effect of having conductive
chromium particles within the electric field. Due to the
small size of the particles, substantial polarization of them
* Electrochemical Society Active Member.
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did not occur. However, a local anode and cathode were
set up on each particle in accordance with its position in
the electric field. The conductive chromium particle af-
fected the electric field gradient as it approached the cath-
ode, resulting in a local rise of the c u r r e n t of the cathode.
This local rise in current ensured rapid incorporation of
the chromium particle. However, no large-scale electro-
phoretic or electrochemical effect was involved in the par-
ticle occlusion process, according to Bazzard and Boden.
This study sought to examine the effect of the chromium
particles on the mechanism of nickel deposition from a
sulfate electrolyte during the occlusion process.
Experimental
All research was conducted in a three=electrode, modi-
fied Greene cell with a volume of 1000 ml. The experimen-
tal cell resided in a temperature-controlled water bath reg-
ulated at 70~ The experimental cell was purged with
nitrogen gas prior to the experiments. A small rod of vitre-
ous carbon embedded in glass with an exposed surface
area of 0.08 cm 2 was used as the stationary working elec-
trode (cathode) for the slow sweep studies, while a rotating
cylinder electrode of vitreous carbon (0.665 cm 2 surface
 3634 J. Electrochem. Soc., V o l . 1 3 8 , N o . 12, D e c e m b e r 1 9 9 1 9 The Electrochemical Society, Inc.

area) was used for the rotating cylinder and electrochemi-
cal i m p ed an ce spectroscopy (EIS) studies. The reference
electrode was a saturated calomel electrode (SCE) con-
nected to the Greene cell by a Luggin probe assembly. An
inert counterelectrode of graphite rod, generating H ~ as its
product at the anode (the anodic reaction was the
breakdown of H20 to form H § and O~), was used. There-
fore, the potentiostatic scans were limited to a region
(-0.45 to -0.85 V SCE) where the pH (approximately 4) did
not change during experiments.
Electrolytes were composed of nickel sulfate, enough so-
dium sulfate to maintain the sulfate ion concentration con-
stant at 1M, and 0.65M boric acid. Commercially available
c h r o m i u m powder (>99% Cr) was used in this study. The
particles were of a spherical shape with a size distribution
of 0.3 to 60 ~tm diam; the majority of the particles were
1~2 ~m in diam as determined by image analysis on a scan-
ning electron microscope. Slow-sweep polarization stud-
ies of nickel electrolytes at three concentrations of NiSO4,
0.33M, 0.67M, and 1.00M, with the addition of 0.1 and 4.2
volume percent (v/o) c h r o m i u m particles, were conducted.
(When a tenfold increase from 0.1 v/o to 1 v/o did not show
a clear trend in 0.33M NiSO4 electrolyte, a 40 to 50-fold in-
crease was tried. A good suspension of the particles in the
electrolyte was obtained at 4.2 v/o.) The electrolyte concen-
tration of 0.67M NiSO4 with and without 4.2 v/o chromium
particle additions was used for the rotating cylinder elec-
trode and EIS studies. The rotating cylinder experiments
were conducted at rotation rates of 500, 1000, 1500, and
2000 rpm. Some EIS experiments were also conducted at
room temperature.
The slow potentiodynamic polarizations, sweep rates of
1 mV/s, were performed with a P A R I Model 371 potentio-
stat, P AR Model 175 universal programmer, Fluke multi-
meter, HP computers, and in-house software. I m p e d an ce
spectra were acquired in the frequency range of 100 kHz
to 5 mHz with a r m s peak value of i0 mV using a Solar-
tron 1286 electrochemical interface, Solartron 1255 HF
frequency response analyzer, a H P computer, and
"ACDRIVE ''2 software. I m p e d a n c e data were taken under
potentiostatic control at -0.4, -0.6, -0.7, and -0.8 V SCE.
Results and Discussion
S l o w s w e e p c u r v e s . - - O n the small vitreous carbon elec-
trode the full forward scan beginning at 0 to -1.5 V SCE
exhibited a limited current region (near -0.7 V SCE) fol-
lowed by hydrogen reduction (Fig. 1). The addition of
chromium particles affected the shape of the nickel reduc-
tion wave (increasing the length of the limited current re-
gion) for some of the concentrations of nickel electrolyte,
and displaced the wave to more positive potentials for all
of the concentrations. The positive displacement (depo-
]Reference to specific trade names is made for identification
only and does not imply endorsement by the Bureau of Mines.
2 Purchased from Dr. Peter Searson, The Johns Hopkins Uni-
versity.
Table I. Nickel reduction wave displacement with
addition of Cr particles.
Ni concentration Reduction wave
M/1 displacement mV
Volume percent Cr
0.1 4.2
0.33 50 100
0.67 55 110
1.00 70 150
larization) was greater for 4.2 v/o c h r o m i u m than that for
0.1 v/o chromium. The greatest displacement occurred for
1M NiSO4 containing a 4.2 Wo addition of chromium parti-
cles, as Table I indicates.
These trends also have been observed by M. Metzger and
H. H. Tombrink (8) in their studies on the addition of SiC
and colloidal graphite particles to a nickel sulfamate elec-
trolyte. The shifts in reduction potentials were attributed
to an increase in the active surface area by the adsorbed
particles on the cathode. Metzger and Tombrink reported
no change in the form of the reduction wave, only a poten-
tial displacement. Figure 2 shows an example of the re-
sults obtained during this study on the forward scans in
the limited current region (-0.45 to 0.85 V SCE), which
were in agreement with Metzger and Tombrink. The major
shifts in reduction potential were only observed during the
nucleation of the nickel deposit onto the foreign substrate
(forward scan only). However, reverse scans, Fig. 3, exhibit
no shift in the reduction potentials but do show increases
in the current. Once a Ni deposit was formed and growing
(reverse scan), the particles did not cause any further signifi-
cant shifts in reduction potential. These results are consist-
ent with the suggestion by Bazzard and Boden (7) that the
concentration of nickel ions near the cathode is increased
as the particles approach the cathode. Each collision of the
particle with the cathode has the effect of momentarily in-
creasing both the surface area of the cathode and the
nickel activity at the surface.
R o t a t i n g c y l i n d e r electrode s t u d i e s . - - I n general, the
presence of c h r o m i u m particles increased the limiting cur-
rent during nucleation at all rotation rates (r Direct com-
parison to data with the stationary electrode was not possi-
ble, since the poor reproducibility of the rotating electrode
was believed to be caused by the heterogeneous nature of
the reduction reaction. The observed limiting current plot-
ted vs. r 213 did not produce a straight line, indicating that
the limiting current was i n d ep en d en t of mass transport at
rotation rates from 500 to 2000 rpm. These results are con-
sistent with rotating ring-disk electrode studies of Andri-
cacos et al. (9), who concluded that agitation does not af-
fect the nickel deposition reaction. For the Andricacos

200 J I I I I I I I I I I I I I I I I I I tl I I I~.J~l li 10 t ] t I I t t
j/

//
0
,~
04
-50
E
~ -
< -300 < -15
E E
E~ Q // f 4.2 vol
o -550 (3 ~z" 0o.11 Vol
Vo~ _ ,~ pert
percent Cr
percent Cr
/
--800 I I It It Illll t I -40 I t I I~l I I
-1.50 -1.00 -.500 0 -850 -600 -450
POTENTIAL V (SCE) POTENTIAL mV(SCE)
Fig, 1. Full forward and reverse scans of nickel electrodeposition Fig. 2. Limited forward scans of nickel electrodeposition with chro-
without chromium particles from 0.67M NiS04 electrolyte. mium particle additions from 1M NiS04 electrolyte.

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 J. Electrochem. Soc., Vol. 138,No. 12, December19919 TheElectrochemicalSociety,Inc. 3635
10 I I i I I l i 2

0 Slow Step's Resistance--/

No Or
E
o Vol percentCr ~ ~ " ~ Pseudocapacitance
< -15
~1 - m

~ , . Double-
0
~3 Fast Step "~ Layer
Capacftance
0I: i I I I V~ perclnt Crl 0 ResTstunce ~

Solution ~ /
Resistance
-40 i (Rs)
-850 -600 -450 0 I I
POTENTIAL mV(SCE)
-2 0 2 4 6
LOG (af)
Fig. 3. Limited reverse scans of nickel electrodeposition with chro- Fig. 5. Typical Bode plot of EIS displaying resistance and capaci-
mium particle additions from 1M NiS04 electrolyte. tance components.

data a plot of log Ni c u r r e n t d e n s i t y vs. e l e c t r o d e potential b e e n p r o p o s e d to o c c u r at low p H (pH of 1.5 to 3), w h e r e

for data collected at 100 and 1600 r p m coincided. Within the H&ds) is strongly b o n d e d to t h e surface and acts as an
t h e r a n g e of rotation rates for this B u r e a u of Mines study, i n h i b i t o r for h y d r o g e n evolution. T h e E p e l b o i n m e c h a n -
it appears that t h e l i m i t i n g current is related to a kinetic ism gives a v e r y simplistic d e s c r i p t i o n of this h y d r o g e n
r a t e - d e t e r m i n i n g step d u r i n g nickel n u c l e a t i o n on the vit- e v o l u t i o n reaction on t h e c o a t e d Ni surface (reactions [1]
reous c a r b o n surface. and [5]-[7]). A m o r e d e s c r i p t i v e m e c h a n i s m of p r o t o n dis-
c h a r g e f o l l o w e d by r a t e - d e t e r m i n i n g electrodic d e s o r p t i o n
E I S s t u d i e s . - - T o further e l u c i d a t e t h e effect of t h e chro- is g i v e n by K o b o s e w and N e k r a s s o w (12).
m i u m particles on t h e m e c h a n i s m of nickel n u c l e a t i o n on E p e l b o i n et al. m e c h a n i s m
a v i t r e o u s c a r b o n surface and s u b s e q u e n t d e p o s i t i o n of
the nickel coating, E I S was p e r f o r m e d , T h e shapes of all of 2H § + 2e- --->H2 [1]
our B o d e plots are characteristic of a capacitor and resistor
in parallel rather t h a n in series. F r o m our E I S studies we Ni +2 + e- --~ Ni(~d~) [2]
f o u n d nickel e l e c t r o d e p o s i t i o n to be a multi-step reaction .+
Nl(.d~) + e- ---*Ni ~ [3]
process i n v o l v i n g first a c h a r g e transfer reaction, a surface-
a d s o r b e d i n t e r m e d i a t e p r o d u c e d by the c h a r g e transfer re- Ni(~ds>+ Ni +2 + 2e- --->Ni ~ + Ni(~as) [4]
action, and t h e s u b s e q u e n t r e m o v a l of the a d s o r b e d inter-
m e d i a t e b y a s e c o n d or p o s s i b l y third reaction. The equiv- 9+ ) + H + + e - ---> Nl(ads
Nl(ads "+ ) + H(ads
, ) [5]
alent circuit w h i c h d e s c r i b e s t h e electrical r e s p o n s e of an 2H%d~) --~ H2 [6]
e l e c t r o c h e m i c a l r e a c t i o n w i t h a strongly a d s o r b e d inter-
m e d i a t e is s h o w n in Fig. 4. I n this circuit R~ r e p r e s e n t s the "+ ) + S(ads
Nl(ads * ) + e- --->Ni + S(included) [7]
solution resistance (including IR drop), Rc~ is t h e charge
t r a n s f e r resistance, and CADSand RADSare c o m p o n e n t s that T h e Nltad, "§ ) species, p r o b a b l y a h y d r o x i d e or an oxy-
c o n t a i n t h e c o n t r i b u t i o n of surface c o v e r a g e of t h e ad- h y d r o x i d e , plays a vital role in t h e E p e l b o i n m e c h a n i s m .
sorbed i n t e r m e d i a t e and t h e rate of desorption. T h e s e Matulis and Slizys (13) also report that nickel deposits
electrical r e s p o n s e s for t h e e l e c t r o c h e m i c a l reaction can from a N i O H § ion species in the p H r a n g e of 4.0 to 4.2. The
be e x t r a c t e d f r o m t h e B o d e plot. B e g i n n i n g at the low-fre- E I S and slow s w e e p data f r o m this r e s e a r c h s u p p o r t the
q u e n c y e n d of t h e B o d e plot (Fig. 5), the resistance of the E p e l b o i n m e c h a n i s m . The N y q u i s t plots, w i t h and w i t h o u t
slow, r a t e - d e t e r m i n i n g step (RADs) is f o l l o w e d by the pseu- c h r o m i u m particles, d i s p l a y e d the two i n d u c t i v e loops
d o c a p a c i t a n c e s (CADs), fast step, charge transfer resistance (shown in Fig. 6) m e n t i o n e d by E p e l b o i n and Wiart (14).
(RcT), and last t h e total resistance of t h e solution i n c l u d i n g T h e N y q u i s t plots d e m o n s t r a t e d that two s u c c e s s i v e
I R d r o p (Rs)- e l e c t r o n transfer reactions o c c u r r e d d u r i n g nickel reduc-
A possible m e c h a n i s m for this multi-step nickel electro- tion regardless of t h e p r e s e n c e of t h e c h r o m i u m particles.
d e p o s i t i o n f r o m a sulfate electrolyte was first p r o p o s e d by Also, the variation of log of c u r r e n t w i t h log of nickel con-
E p e l b o i n et al. (10), w i t h m o r e d i s c u s s i o n by Chassaing c e n t r a t i o n for the slow s w e e p data is first-order in nickel
et al. (11). In our case at t h e h i g h e r p H of 4, steps [2]-[4] are
the m o s t likely reactions to be occurring. Steps [5]-[7] h a v e 13 i i

c~ E
c- 7 0 0 O0 0 0 0 0
0 0
R S O 0 0
A
oo 0
o 0
RADS O 0
0
~E 0
0
N 8
0
,
-3
10 20 2g.4

Fig. 4. An equivalent circuit which describes the electrical response

of the electrochemical reaction for nickel electrodeposition. Fig. 6. Nyquist plot showing two inductive loops.
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 3636 J. Electrochem. Soc., Vol. 138, No. 12, December 1991 9 The Electrochemical Society, Inc.

Table II. Pseudocapocitances. Whether the c h r o m i u m particles were delivering more

metallic ions or more adsorbed intermediate cannot be de-
Pseudo- Pseudo- termined. However, if the corrosion proposed by Bazzard
Potentiostated capacitance capacitance and Boden (7) occurred on the c h r o m i u m particles, then
potential Temperature w/o Cr particles w/Cr particles there is a possibility of nickel reduction on the particle sur-
(V SCE) (~ (~F/cm2) (~F/cm2)
faces in solution. Although no unambiguous evidence
exists of nickel plating on the c h r o m i u m particles in solu-
-0.4 70 486 186
-0.6 70 377 126 tion, analyses of particles remaining in the electrolyte after
-0.7 70 83 100 extensive plating indicate the presence of nickel on the
-0.8 70 83 84 particles.
-0.7 31 313 NM
-0.8 31 166 NM
-0.4 24 NM 515 Double-layer c a p a c i t a n c e . - - T h e double-layer capaci-
-0.7 24 NM 676 tance values tabulated in Table III were calculated from
the slope of a plot of angular frequency vs. imaginary ad-
NM: Not measured. mittance rather than from the Bode plots because of preci-
sion. The order of magnitude for double-layer capacitance
values was checked and confirmed by a Bode plot calcula-
Table III. Double-layer capacitance. tion. These double-layer capacitance values are one order
of magnitude smaller than values previously reported by
Double-layer Double-layer o~ther researchers (10-16). Volk and Fischer (15) reported a
capacitance capacitance double-layer capacitance value of 50 ~F/cm 2 at 25~ using
without Cr with Cr
Potential, particles particles oscillographic m e a s u r e m e n t of the ohmic drop after
(V SCE) (~F/cm2) (~F/cm2) switching the current on; Kruglikov et al. (16) derived a
value of 60 txF/cm2 at 30~ using a potential decay method;
-0.4 4.4 2.1 and Epelboin and Wiart (14) calculated a value of
-0.6 4.2 2.3 70 ~F/cm 2 by a least squares method from the elements of
-0.7 3.6 2.1
-0.8 3.7 2.5 a representative circuit to fit impedance experimental data
measured at 30~
In order to investigate the apparent differences between
concentration, suggesting that the Ni § is reduced one our results and the above-mentioned literature values,
electron at a time. Epelboin's Nyquist plots were digitized and analyzed with
The pseudocapacitance was interpreted as a measure of our " A C D R I V E " software. Our analyses indicate that
the adsorbed intermediate Ni~ads). The pseudocapacitances Epelboin's double-layer capacitance corresponds, both in
calculated from the Bode plots are shown in Table II. The frequency range and magnitude, to our pseudocapacitance
pseudocapacitance is determined by extending the slopes region. We were not able to determine double-layer capaci-
for the pseudocapacitance and slow step resistances until tance values from Epelboin's data due to lack of high-fre-
the slopes cross; the cutoff frequency and resistance are quency data. Perhaps the current technology of direct cal-
determined at this crossover point. The pseudocapaci- culation of double-layer capacitance from impedance data
tance is the reciprocal of the product of cutoff frequency gives a more precise value than transient techniques with
and resistance. The pseudocapacitance was also very tem- many assumptions and the use of slower responding oscil-
perature-dependent; note the elevated values at the lower loscopes employed by the researchers in the 1960s. Re-
temperature. The temperature dependence of these ca- gardless of the cause, we believe that previous results for
pacitance values clearly shows that these capacitances are double-layer capacitance values for nickel reduction via
pseudocapaeitances. Pseudocapaeitance is temperature- the adsorbed intermediate m ech an i sm reflect the pseudo-
dependent, whereas double-layer capacitance is not tem- capacitance associated with the adsorption of the interme-
perature-dependent. The double4ayer capacitance values diate.
at the lower temperatures were the same as the values at There appears to be a weak potential dependence of the
70~ double-layer capacitance without chromium particles,
Comparisons of the Bode p l o t s at the various potentials, whereas the double-layer values with Cr particles have no
both with and without c h r o m i u m particles, indicated that potential dependence. The double-layer capacitance is
at the same potential, viz., -0.4 V SCE, the pseudocapaci- probably potential-independent in the presence of chro-
tance appeared more pronounced when the chromium m i u m particles because of the excess Ni § and/or Ni~ds~
particles were not present. The pseudocapacitances of provided to the surface over the entire potential range
Table II support this observation. The pseudocapacitance studied.
values are larger without c h r o m i u m particles at potentials
prior to the nickel electrodeposition at -0.7 V SCE. After T i m e constants.--The slope of a plot of the product of
the adsorbed intermediate is formed on the substrate to es- imaginary i m p ed an ce x angular frequency vs. real imped-
tablish the slow rate-determining step, the nickel deposi- ance yields the time constants of a reaction step, and the y
tion can proceed. Thus, the pseudocapacitance values be- intercept is equivalent to the resistance for this reaction
come equivalent for either case, with or without chromium step. The time constant data with and without chromium
particles, at approximately -0.7 V SCE. The role of the particles are tabulated in Tables IV and V. The time con-
c h r o m i u m particles therefore was to reduce the potential stant analysis clearly indicated the positive potential shift
required for the establishment of the surface adsorbed in the reduction mechanism. The more defined time con-
species. stants (time constant value does not change with potential)

Table IV. Time constant data without Cr particles.

Step Slower step Slowest step

Potentiostated time time time
potential constant resistance constant resistance constant resistance
(V SCE) (s) (~-cm 2) (s) (~-cm 2) (s) (~-cm 2)

-0.4 NA NA NA NA NA NA
-0.6 7,6 x 10-6 2.3 NA NA NA NA
-0.7 9.3 • 10-6 2.8 1.1 • 10 3 19.6 NA NA
-0.8 9.8 x 10 6 2.6 1.6 • 10 6 6.2 NA NA

NA: data are not obtainable from the graph.

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 J. Electrochem. Soc., Vol. 138, No. 12, December 1991 9 The Electrochemical Society, Inc. 3637

Table V. Time constantdata with Cr particles.

Step Slower step Slowest step

Potentiostated time time time
potential constant resistance constant resistance constant resistance
(V SCE) (s) (~t-cm2) (s) (~-cm 2) (s) (tl-em 2)

-0.4 1.8 • 19-4 11.5 NA NA NA NA

-0.6 8.5 • 10-6 3.5 1.6 • 10-3 49.5 NA NA
-0.7 9.1 • 10-6 3.4 1.7 • 10-~ 12.4 0.9 15
-0.8 8.7 • 10-6 3.3 1.7 • 10_3 7.5 0.7 7.3

NA: data are not obtainable from the graph.

s u g g e s t that t h e c h r o m i u m particles w e r e catalyzing the s e n t e d at t h e Seattle, WA M e e t i n g of the Society, Oct.

nickel e l e c t r o d e p o s i t i o n by e n h a n c i n g the f o r m a t i o n of the
Ni~+ads~ i n t e r m e d i a t e . With Cr particles, t h e t i m e c o n s t a n t
v a l u e for the first (fastest) step was a p p r o x i m a t e l y
9 • 10 -6 s, and 1.7 • 10 _3 s for the slower step for all poten-
tiostated potentials of -0.6, -0.7, and - 0 . 8 V SCE. On t h e
o t h e r hand, w i t h o u t Cr only the first step was defined at
9.3 • 10 -8 to 9.8 • 10-6s for p o t e n t i o s t a t e d potentials of
-0.7 and - 0 . 8 V SCE; t h e slower t i m e c o n s t a n t was not in-
d e p e n d e n t of potential. T h e s e results suggest that the
c h r o m i u m particles w e r e catalyzing t h e s e slower steps.
P e r h a p s this slowest step, only defined w h e n c h r o m i u m
particles w e r e present, at p o t e n t i o s t a t e d potentials of -0.7
and - 0 . 8 V S C E i n v o l v e s a H~ads) species as well as Ni~ad~~in
reactions s u c h as steps [5]-[7] in the E p e l b o i n (10, 11, 14)
m e c h a n i s m or K o b o s e w and N e k r a s s o w (12) m e c h a n i s m .
Conclusions
I n conclusion, w i t h or w i t h o u t c h r o m i u m particles,
nickel e l e c t r o d e p o s i t i o n is kinetically limited rather t h a n
mass-transfer-limited. All results s u p p o r t t h e m e c h a n i s m
p r o p o s e d by E p e l b o i n et al. in w h i c h t h e Ni § is r e d u c e d
one e l e c t r o n at a t i m e and the Ni~ds~ i n t e r m e d i a t e limits the
nickel e l e c t r o d e p o s i t i o n . C h r o m i u m particles catalyze
nickel d e p o s i t i o n onto a foreign substrate. C h r o m i u m par-
ticles a p p e a r to e n h a n c e t h e f o r m a t i o n of a Ni(+~ds~i n t e r m e -
diate. The c h r o m i u m particles c o u l d be acting as an addi-
tional surface site for t h e Ni~ads~ i n t e r m e d i a t e to form, or
p r o v i d i n g an increase in the Ni +2 c o n c e n t r a t i o n at the sur-
face, or d e l i v e r i n g t h e Ni(aa~~i n t e r m e d i a t e to the surface.
M a n u s c r i p t s u b m i t t e d M a r c h 14, 1991; revised m a n u -
script r e c e i v e d J u n e 25, 1991. This was P a p e r 361 pre-
14-19, 1991.
The U.S Bureau of Mines assisted in meeting the publica-
tion costs of this article.
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On the Electronic Conduction in Dry Thin Films of Prussian Blue,

Prussian Yellow, and Everitt's Salt
Anthony Xidis and Vernon D. Neff
Department of Chemistry and the Liquid Crystal Institute, Kent State University, Kent, Ohio 44242

ABSTRACT
E l e c t r o n c o n d u c t i v i t i e s are r e p o r t e d for dry thin films of P r u s s i a n b l u e and its c o m p l e t e l y o x i d i z e d and r e d u c e d
forms, P r u s s i a n y e l l o w and Everitt's salt. It has b e e n d i s c o v e r e d that desiccated P r u s s i a n b l u e films are n o n - o h m i c in the
sense t h a t significant e l e c t r o n c o n d u c t i o n does not o c c u r b e l o w a t h r e s h o l d voltage of ca. -+ 0.5 V. P r u s s i a n y e l l o w and
Everitt's salt are o h m i c and do not h a v e a c o n d u c t i o n threshold. The conductivities, as d e t e r m i n e d f r o m t h e slopes of t h e
i-V curves, are essentially the s a m e for P r u s s i a n yellow, Everitt's salt, and P r u s s i a n b l u e a b o v e the voltage threshold, and
are ca. 5 x 10 -7 (~ cm) -1. T h e solid state v o l t a m m o g r a m of a w e t film is also c o n s i d e r e d in t e r m s of the p e r s i s t e n c e of t h e
t h r e s h o l d a n d t h e o n s e t of e l e c t r o c h e m i s t r y . We p r o p o s e a qualitative e x p l a n a t i o n for the t h r e s h o l d voltage based on t h e
a s s u m p t i o n t h a t t h e " v a l e n c e b a n d " (ferric ferrocyanide) is c o m p l e t e l y o c c u p i e d and that t h e a p p l i e d voltage injects elec-
trons into t h e " c o n d u c t i o n b a n d " (ferrous ferricyanide).

S i n c e t h e classic d i s c u s s i o n of R o b i n and Day on m i x e d related h e x a c y a n i d e s , t h e r e has b e e n c o n s i d e r a b l e interest

v a l e n c e crystals, P r u s s i a n b l u e has b e e n r e g a r d e d as the in the electronic and ionic c o n d u c t i v i t y of this class of
p r o t o t y p e e x a m p l e of a m i x e d - v a l e n c e transition m e t a l c o m p o u n d s . U n d e r c o n d i t i o n s w h e r e ionic t r a n s p o r t is fa-
h e x a c y a n i d e (1). D u r i n g t h e p a s t decade, f o l l o w i n g the dis- cilitated, as w i t h t h i n films of P r u s s i a n b l u e (ferric ferro-
c o v e r y of t h e e l e c t r o c h e m i c a l activity of P r u s s i a n b l u e and c y a n i d e or PB) in a q u e o u s p o t a s s i u m ion solutions, it is
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