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ABSTRACT
Rotating electrodes are used to model flow conditions in electro- The system of metals exposed to flowing natural marine wa-
chemical systems where mass transfer affects the reaction rate. ters is of particular interest. This occurs in engineering applications
Mass transfer correlations are used to relate the model system to that rely on these waters for cooling. Examples include shipboard
the prototype system through equivalence of the limiting current and coastal heat exchange operations. The design of cathodic
densities. This approach is used to apply laboratory polarization protection systems for both cases considers the oxygen reduction
data obtained with rotating cylinder electrodes to corroding sys- reaction to be rate controlling so that mass transfer limitation of
tems in turbulent flow conditions. Results of this technique are the oxygen is observed.
described for cathodic protection design in marine environments.
M=M +ze (1) -
KEY WORDS: laboratory simulation, limiting current, mass trans-
fer, rotating cylinder
0 2 + 2H 2 0 + 4e = 40H (2)
- -
0010-9312/90/000217/$3.00/0
764 © 1990, National Association of Corrosion Engineers CORROSION— September 1990
SCIENCE
w
U
>
c
w
c
o-0
0.1 1 10 100
Current Density (eA/cm2)
FIGURE 1. Potentiodynamic scan of a steel rotating cylinder in seawater showing limiting current
behavior in the cathodic region.
studies. ° A general knowledge of the system hydrodynamics, ge- sion. The cylindrical test cell measured 15.2 cm in diameter. The
ometry, and physical properties permits rapid estimates of limiting electrolyte was aerated natural seawater contained in a thermosta-
current densities through these correlations. ted and isolated recirculating bath. Potentiodynamic scans were
Rotating electrodes provide an experimental toot for studying performed at a scan rate of 0.1 mV/s. Test samples were
these rate processes under turbulent hydrodynamic conditions. 7 prepared for cylindrical stock and measured 1.6 cm in diameter
The rotating cylinder electrode (RCE) has the characteristics of a and 2.0 cm in length. The sample material served as the working
uniform current distribution and velocity profile in the axial direction electrode with a platinized niobium'electrode placed concentrically
with clearly defined hydrodynamics. 8,9 This apparatus is useful in as the counter electrode. A PAR EG&Gt 2) model 273 potentiostat
elucidating velocity-sensitive mechanisms such as erosion—corro- was used with a computer interface for experimental control and
sion where hydrodynamics and mass transfer have a combined data acquisition.
effect on the corrosion rate. 10 '" The mass transfer rate may be
accurately followed in electrochemical systems by measuring the
current passed. RESULTS AND DISCUSSION
Recent modeling efforts in the area of cathodic protection
have reinforced the effectiveness of this approach when applying Correlation of limiting current values to mass transfer rates
laboratory polarization data to the design of cathodic protection and dimensionless group analysis for the rotating cylinder elec-
systems. 12 Polarization data obtained from experiments with rotat- trode were first reported by Eisenberg, Tobias, and Wilke. 3,6
ing electrodes were applied to model corroding systems operating
Sh = 0.079Re 0 70 5e0355 (3)
under turbulent flow conditions where similarity was achieved
through the limiting current densities. Available mass transfer cor-
relations provided the necessary relations to determine limiting Subsequent researchers have demonstrated that correlation
current densities between the service environment and the labora- of limiting current values to mass transfer rates show a similar de-
tory apparatus. Polarization data obtained for exposed materials pendence on these dimensionless groups with slight variation in
with the RCE permitted the calculation of corrosion rates for the the power indexes reported. e The selection of correlating variables
service conditions. and the functional dependence in the correlation for the RCE ap-
pears well established.
An interesting modification of these correlations is obtained
EXPERIMENTAL through the introduction of the friction factor. The Fanning friction
factor is defined as the ratio of the shear at the wall to the velocity
The experimental data were obtained with a rotating cylinder head.' 3
( "Pine Instruments, Grove City, PA. (2 jEG&G Princeton Applied Research (PAR), Princeton, NJ.
V0.70d-0.3nFD0.644v-0.344Cb
Correlations for the friction factor in terms of the Reynolds i, = 0.0791 (11)
number exist for many geometries and flow conditions. 13 • 14 Substi-
tuting such an expression into the correlation for mass transfer
yields a correlation for i L involving hydrodynamic parameters ex- Temperature changes that occur from plant processes or are
plicitly. For the RCE in the turbulent region the following correta- due to fluctuations in ambient conditions produce property
tion exists. e changes that may increase or decrease iL• Increasing temperature
decreases both oxygen solubility and viscosity, but increases diffu-
sivity. These latter two changes would produce higher rates of
f = 0.0794Re - o 3 (5)
2 mass transfer and an expected increase in í L for a given oxygen
concentration. Figure 4 shows the effects of the variation of oxy-
gen solubitity, diffusivity, and viscosity with temperature on limiting
This development provides a relation for the limiting current den- current densities for seawater. Literature values of physical prop-
sity in terms of the rate of momentum transfer as measured by the erty data were used in Equation (11). 17,16 As can be seen from
friction factor.' 0,15 Equation (11), the limiting current density is directly proportional to
the dissolved oxygen coscentration, which decreases with increas-
ReSco.356 (6) ing temperature. In general, gas solubility decreases with increas-
Sh =f ing temperature except near the solution critical point where it then
2
increases. The kinematic viscosity follows the expected linear de-
crease with increasing temperature as observed experimentally for
Similarly for turbulent flow in smooth pipes the friction factor many systems. The diffusivity also follows expected behavior, in-
has been correlated to the Reynolds number. Y3 creasing linearly with increasing temperature as predicted from
hydrodynamic theory.
f = 0.316Re-0.25 (7)
The dominant effect on the limiting current density is not ob-
vious in all cases as the physical property dependence varies with
This relation cas be substituted into the following mass transfer the specific correlation used. Using Equation (11) to predict limit-
correlation for turbulent flow in smooth pipes. 7 ing current densities at different temperatures, one obtains values
of 0.93, 1.02, and 1.1 mA/cm 2 for temperatures of 30, 38, and
52°C, respectively. This represents an 18% increase in limiting
Sh = 0.023Re 08 Sc 1 '3 (8)
current density over a 20° temperature range.
Experimental results obtained for the oxygen reduction reac-
The resulting expression provides a correlation for the limiting cur- tion on titanium in natural seawater showed agreement between
rent in terms of the friction factor for turbulent flow in pipes. predicted and experimental values to within the 10% error
assumed for the correlation. This demonstrates the ability of such
Sh = 0.073fRe l05 Sc V3 (9) correlations to account for physical property variation with temper-
ature as it affects limiting current densities.
Figure 2 shows the dependence of the limiting current density Formation of insulating films on the electrode material also
on the product of the friction factor and the Reynolds number for has an effect on the value of the limiting current density. Oxide
the RCE and for a smooth pipe as described by the respective films, biofilms, or accumulation of reaction products may occur on
correlations. the surface and impede the transport of reactant to the surface for
reaction. In the case of natural marine waters, calcareous salts
Figure 3 displays values of wall shear calculated from friction can precipitate and deposit on the reaction surface. Deposition is
factors and limiting current densities predicted from correlations for related to the length of time of exposure to the electrolyte, its com-
the rotating cylinder electrode and for the smooth pipe. The plot
position, and its velocity. High shear rates may prevent or remove
shows that 'L increases with increasing walt shear. Comparison of
such deposits. 19 Deposits are generally included as a time-depen-
the limiting current densities between these two systems for com- dent effect along with concentration stabilization of anodic and ca-
parable values of wall shear indicates that significantly higher val- thodic species. In conducting polarization studies, data may be
ues of i L are predicted for the RCE. The use of shear values to obtained over a short or long period of time. The long-term data
establish the similarity between different geometries has been sug- for many common metals exposed to marine waters shows defi-
gested for the study of velocity-dependent corrosion mechanisms nite changes in the current-potential relation with increasing time
such as erosion-corrosion. 101 For cases where the corrosion of exposure up to 120 days or more. 20 The effects observed with
mechanism is known to exhibit mass transfer limitation and the
90:10 copper:nickel on exposure to flowing seawater include a
flow regimes are comparable, it appears that mass transfer rates,
continuous drift of E co , r to more positive potentials and a decrease
or equivalently the limiting current densities, should be used as the
in the magnitude of the cathodic current densities to very low val-
similarity variable.
ues. A shift in E core of 200 mV and a reduction in i L from 2 mA/cm 2
Correlation of i L has also been made to include a surface to 1.5 µA/cm 2 was reported after 120 days of exposure. 2°
roughness parameter, X. 16 The effect of hydrodynamics on the rate of a corrosion reac-
tion in a system exhibiting mass transfer limited kinetics was con-
X
sidered in estimating current requirements for cathodic protection
R)_2
v
i, = nFc (1.25 + 576 log () °644 u (10) design. The objective was to relate polarization data obtained in
the laboratory under mass transfer limited conditions to the limiting
current values that would be obtained in steam condensars using
The extent to which temperature, dissolved oxygen concen- natural marine waters for cooling. An example of this approach is
tration, and velocity interrelate and affect the value of the limiting provided by the case of a condenser tube that has the following
current density as determined from empirical correlations may be mass transfer correlation given for fully developed turbulent flow. 7
analyzed through the dimensionless groups Re, Sc, and Sh. Equa-
tion (11) shows the dependence of the limiting current density on
the physical properties more explicitly. Sh = 0.023Re ° 6 Sc 12 (12)
Correlated Values of 1 L at 25 C °
FIGURE 2. Values of limiting current densities for the rotating cylinder electrode and for a single tube
predicted from correlations expressed in terms of the Fanning friction factor.
u
E
r. (dynes/cm)
FIGURE 3. Values of limiting current densities and walt shear calculated for the rotating cylinder
electrode and the smooth pipe in seawater at 25°C. Wall shear values are calculated from Equation
(4) with Equations (5) and (7). Corresponding i L values are calculated from Equations (3) and (8).
0-1
25 30 35 40 45 h
Tesperature ('C)
FIGURE 4. The variation of kinematic viscosity, oxygen solubility and diffusivity with temperature for
seawater.
3000
á
UI
1000
Sh (25° C)
1 L (25° C)
•- Sh (52° C )
•--- 1,. (52° C )
FIGURE 5. Relation of flow conditions in the service environment to the rotor speed of the rotating
cylinder electrode. A comparison between the superficial velocity and the predicted rotor speed
obtained by equating the limiting current densities or the Sherwood numbers.
ACKNOWLEDGMENT APPENDIX A
REFERENCES