Accelerated Atmospheric Corrosion

Testing Using a Cyclic Wet/Dry

Exposure Test: Aluminum,
Galvanized Steel, and Steel*

S. B. LYON,* G. E. THOMPSON,* J. B. JOHNSON,

G. C. WOOD, * and J. M. FERGUSON**

Abstract
Overhead electrical power transmission conductors, constructed from aluminium wires centrally
reinforced by galvanized steel strands, have been found, in a few isolated instances, to suffer from
internal corrosion, which is associated with the presence of chloride ion, and external corrosion, which
is associated with sulfate ion. A cyclic wet/dry exposure test, with salt spray solutions containing
appropriate ratios of sulfate and chloride ion, was used to simulate these observations. The parameters
of the test are explained, and the performance of the exposed metals are reported in terms of weight
loss and are compared with available data on the atmospheric corrosion of similar materials at industrial
and marine locations. An acceleration of corrosion in the chamber of between 25 to 50 times was
observed. The results are discussed in terms of the solution chemistry of the salt spray as it acts on the
metal surface, with particular regard to the buffering capacity of ammonium and bicarbonate ion. The
reality of the situatien, with regard to atmospheric attack, is considered. It is clear that a true laboratory
model should include a consideration of the chemistry on the surface in conjunction with dilution and
concentration by surface-adsorbed moisture (wetting and drying) in order to represent the outside
environment adequately.

however, is concerned primarily with an evaluation of the accelerated

Introduction test, rather than with a discussion of conductor corrosion. The
chemistry of the salt sprays used is considered only with reference to
At the present time, overhead high-voltage power transmission
the corrosion of the materials from which the conductor is constructed
conductors constructed from aluminium with galvanized steel rein-
(i.e., aluminium, galvanized steel, and steel). The corrosion rates of
forcing (Figure 1) make up a significant proportion of the UK grid. The
these materials in the accelerated test cabinet are compared with
conductor consists of a central core of the hot-dip galvanized steel
published atmospheric corrosion rates of similar metals. A subse-
strands coated in grease to prevent the ingress of water. This is
quent paper deals with galvanic corrosion effects between these
overlaid with up to three exterior layers of ungreased aluminium
materials. 2
stranding, which acts as the conductor. As some of this material is
over 20 years old, the Centra) Electricity Generating Board (CEGB) Conductor Corrosion
and the Local Area Boards have begun a program of line refurbish-
External corrosion of conductors is rarely a problem and is
ment. Most of the removed conductor has been found to be in
usually associated with clamps containing graphited rubber bushes.
excellent condition. Serious external corrosion of the conductors is
Surface corrosion products contain sulfate species (i.e., aluminium
rare and is detectable by visual inspection. 1 However, the conductors
sulfate, and ammonium sulfate), as well as hydrated aluminium
do suffer from localized unseen internal corrosion at a few isolated
oxides and hydroxides. However, a more serious attack occurs
regions. For example, in a 10-km length of line, only a few meters
internally and unseen. This manifests itself as localized (i.e., a few
may be affected. In order to gain insight into the nature of this
cm) attack on the galvanized steel strands. The corrosion products
problem, a program of accelerated testing of the component parts
are incorporated in the grease, which becomes dry, caked, and
was undertaken using a cyclic wet/dry corrosion test to simulate and
useless as a barrier to further moisture ingress. Attack accelerates
accelerate the observed attack. In conductors, cycles of resistive
after the initial deterioration has started. Initially, as the galvanized
heating, while on load, and subsequent cooling can cause concen-
steel zinc layer is anodic to the aluminium, no significant corrosion of
tration of pollutants on the exterior and in the interior. This paper,
the current-carrying strands occurs. However, when the underlying
iron-containing layers are exposed, corrosion of the aluminium
*Submitted for publication September 1986; revised February 1987.
*Corrosion and Protection Center, UMIST, P.O. Box 88, U.K. M60 commences, as it is then anodic to the steel. Analysis of the corrosion
1 QD. product on the galvanized strands revealed the presence of basic
**Central Electricity Research Laboratories, Leatherhead, Surrey, zinc chloride as the only detectable materials (by x-ray diffraction and
UK. inferred from Zn to Cl ratios in an energy dispersive x-ray analyzer).

0010-9312/87/00332/$3.00/0
Vol. 43, No. 12, December 1987 1987, National Association of Corrosion Engineers 719
 mm
O Aluminium
Galvanised
steel
FIGURE 1 Schematic diagram of a transverse section
of galvanized steel reinforced aluminium conductor.
The corrosion product on the aluminium is aluminium hydroxide and
basic aluminium chloride. These analyses indicate that the chloride
ion is primarily responsible for attack in the conductor interiors.'
Experimental Details
Materials
Wire samples of aluminium and galvanized steel (3.18-mm
diameter) were obtained by disassembly of a conductor exposed for
25 years in an industrial environment. The central reinforcing core of
the conductors was coated in a layer of grease, which was removed
from the galvanized steel and the adjacent aluminium strands by
vapor degreasing in trichlorethane; after which, both materials
showed no sign of corrosion and both retained a shiny appearance.
Steel samples were prepared from the galvanized strands by
removal of the zinc-rich coating in boiling 30% NaOH. The magnetite
film, which results from this treatment, was removed by abrading with
600-grit SiC paper.
The electrical grade aluminium was in excess of 99% pure, with
maximum permissible levels of iron plus copper totaling less than
0.3%. The steel strands were specified on a combination of strength
and galvanizing thickness. They had a Vickers hardness between
410 and 420 and a coating, applied by hot-dip galvanizing, with an
average total thickness of 40 m. About one-half of this thickness
was contributed by the various zinc-iron intermetallic layers adjacent
to the steel base and one-half by the outer, relatively pure eta-layer.
A representative transverse section is shown in Figure 2.
Test Method
The test method is similar to that described by Timmins. 3 It uses
an intermittent wet/dry cycle and consists of a compressed air supply,
two test cabinets (each 0.32 m 3 in volume), a control unit, and two
salt solution reservoirs, one for each cabinet. Selection of a salt mist
or an air draught for drying was performed by solenoid valves under
control of a time switch. The salt solution was drawn into the cabinets
and atomized by a venturi nozzle. The cabinets were heated to 35
1 C during drying, but were allowed to cool naturally during misting.
Specimens were placed around the periphery of the cabinets on
either of the two tiers and were subjected to a repeating cycle of a 1-h
salt spray and a 1-h drying (Figure 3). This differs from the time
schedule used by Timmins by increasing the number of wet/dry
cycles in a 24-h period from 6 to 12. The change was made to further
accelerate the effects of wetting and drying, as experienced by a
conductor. Using this procedure, specimens became visibly wet
within about 5 min of the onset of misting, and the specimens became
surface dry at the end of the drying cycle, at which point, the relative
humidity in the cabinets next to the specimens had dropped to --35%
720 CORROSIONNACE
FIGURE 2 Optical micrograph of a section of galva-
nized steel, showing the layers formed by the hot-dip
process.
Salt spray
Air draught
'nozzle (vertical)
er
rl
H H
e e
all a
t t
e e
r r
Specimen positions
2 tiers about edges
er
FIGURE 3 Schematic diagram of the salt spray test
chamber in plan view.
(wet/dry bulb hygrometer). This level is below the relative humidity of
water in equilibrium with the individual salts used in the sprays, 75 to
80%, thereby implying the absence of a continuous surface elec-
trolyte layer on the specimens; this level is well below the level at
which Barton considers atmospheric corrosion to occur. 5 The com-
positions of the two salt spray solutions used in this work are given
in Table 1 and are justified below.
Harrison, Tickel, and Barraclough have criticized continuous
salt spray tests, based on the sole use of NaCl, as being unreliable
for accelerating atmospheric corrosion in industrial environments."
This results from the absence of both ammonium and sulfate species,
which they found present in the atmosphere, and on naturally
weathered steel, and to the effects of wet/dry cycling in nature that
are not reproduced in a continuous spray. They found that a solution
containing 3.5% ammonium sulfate and 0.25% sodium chloride was
more effective. This work was extended by Timmins 3 who recom-
mended dilution of the above mixture while using intermittent
spraying. His preferred solution was used in this work (high sulfate)
to simulate the exterior environment of the conductor (i.e., an
industrial atmosphere). However, it was not found to reproduce the
corrosion products observed at the center of the naturally exposed
conductors (i.e., the chloride-containing species). Accordingly, an-
other solution (high chloride) was chosen, and was found to be more
successful in this regard.
 TABLE 1 Charcteristics of Salt Solutions

Concentratlon of pH of Solutlon Relative Humidlty Over

Solution (NH4)2SO4 NaCI Aerated Deaerated Saturated Solution

High 0.35% 0.05% 5.2 5.4 80%

Sulfate (26.5mM) (8.5mM)

High 0.05% 0.35% 5.4 5.95 75%

Chloride (3.8mM) (59.8mM)

During preliminary weight loss trails, the corrosion rate of pure

zinc coupons was found to vary only slightly as a function of the
solution flow rate during the misting period, but not with the position
inside the cabinet, provided the spray was centrally placed. This
variation was minimized when the solution flow was restricted to
between 600 and 700 mUh.

Specimen Preparation
Samples were cut to -70 mm in length and were vapor
degreased in trichiorethane. After weighing accurately to 0.2 mg and
prior to placement in the cabinet, the specimens were stored in a
desiccator in individual polythene bags. To simulate crevices, a
3-mm-diameter inert polyolefin rod was wound with the specimen.
The ends were then sealed by dipping in a 3 to 1 ratio of beeswax and
colophony resin (BDH), leaving -50 mm exposed.
Specimens were exposed in batches of 10 for periods of 340,
680, and 1020 h to give 30 specimens per material per solution.
During exposure, the specimens were turned from end-to-end and
back-to-front at weekly intervals to ensure uniform exposure on all
surfaces. After removal from the cabinet, the plastic was taken off the
samples, and the wax/resin mixture was removed by melting. At this
stage, sufficient corrosion product was collected from each batch of
samples for analysis by x-ray powder diffractometry. The amount of
corrosion of each sample was determined by weight loss measure-
ments. The corrosion products were stripped chemica!ly. Aluminium
was cleaned in a five times diluted version of the hot chromic/phos-
phoric acid solution, 9 galvanized steel (i.e., mainly zinc) with satu-
rated ammonium acetate, 10 and steel with inhibited HCI, 9 both at
room temperature. Corrections for dissolution of the base metal were
performed according to the ASTM Standard. 9

Results
Aluminium
The most visible corrosion product occurred in and spread out
from the crevices formed between the specimen and the plastic
spiral. The most heavily corroded example, after a 1020-h exposure
to the high-sulfate solution, is shown in Figure 4(a). At the end of the
wet part of the cycle, a gel-like corrosion product could be seen in the
corroded regions, which, by the end of the drying cycle, had become
a dry white powder. Figures 5 and 6 show the appearance of the
galvanized steel and steel specimens, respectively, after a 1020-h
exposure in the high-sulfate cabinet.
The variation of weight loss per unit area against time of
exposure is shown in Figure 7, which displays an increase of
corrosion with time. The average corrosion rate in the high-sulfate
solution was 32 g/m 2 /1000 h, but the regression line did not pass
through the origin, implying that corrosion was initially slower than
this value. In the high-chloride solution, the corrosion rate was 6
g/m 2 /1 000 h, about five times less than in the previous case. Optical
micrographs of typical pitted areas show clearly that in the high-
sulfate solution, the pits were relatively shallow, 200 m, tending to
spread laterally [Figure 4(b)]; whereas, in the high-chloride solution,
after a 1020-h exposure, the pits were more than twice as deep, 600
FIGURE 4 (a) Optical macrograph of aluminium cor-
.m, and were relatively narrow [Figure 4(c)].
roded for 1020 h in the high-sulfate solution, showing a
Corrosion products, identified by x-ray diffraction after exposure
low-magnification view of the external surf ace. (b) Optical
in the solutions, are listed in Table 2. In both cases, only hydrated
basic aluminium chiorides could be positively identified, although the micrograph of aluminum corroded for 1020 h in the
degree of hydration in the high-sulfate solution was less. Additionally, high-sulfate solution, showing a transverse section
some amorphous material was present, inferred by fogging of the through a shallow pit. (c) Optical micrograph of alumi-
x-ray film at low angles. This product was presumably a form of nium corroded for 1020 h in the high-chloride solution,
hydrated alumina. showing a transverse section through a deep pit.

Vol. 43, No. 12, December 1987 721

 N
E E
o rn
s 0
rn
FIGURE 5 Optical macrograph of galvanized steel
corroded for 1020 h in the high-sulfate solution.
FIGURE 6 Optical macrograph of steel corroded for
1020 h In the high-sulfate solution.
Galvanized Steel
Prior to exposure of the underlying steel, corrosion of the
galvanized steel is primarily concerned with the behavior of the
layered structure of the hot-dipped coating (Figure 2). Initially, the
attack occurs relatively uniformly on the outer zinc or eta-layer;
however, as the underlying intermetallic layers are exposed, the
corrosion tends to proceed perpendicular to the macroscopic sur-
face, i.e., between the dendritic grains in the coating. An aggressive
solution may then have access to the steel substrate at an early
stage, well before the entire coating is breached. Under these
circumstances, however, galvanic action will stil] protectthe steel for
a distance of -2 to 3 mm.
The corrosion data are presented in Figure 8 and show an
increase in weight loss with exposure time. Linear regression about
the mean showed that there was no significant difference in the
corrosion rates (160 g/m 2 /1 000 h) in either solution; however, neither
regression line passed through the origin. This implies that the
corrosion passed through the origin. This suggests that the corrosion
occurred initially at a relatively slow rate in the high-sulfate solution
but proceeded more quickly in the high-chloride solution. In the laffer
case, virtually all of the eta-layer of galvanizing was removed during
the first 340 h of exposure.
After exposure, all specimens had become covered in an
adherent, white corrosion product (Figure 5), occasionally stained
orange because of iron corrosion on severely attacked specimens.
This attack was apparently uniform with no obvious increase near the
crevices. When the corrosion product was stripped off, any remaining
722 CORROSIONNACE
rn
Exposure time (hours)
FIGURE 7 Graph of weight loss per unit area against
time for aluminium specimens (scatter bands shown).
eta-layer material appeared light grey, while the underlying interme-
tallic layers appeared dark grey. Corrosion products are listed in
Table 2. After exposure in the high-sulfate solution, three compounds
could be identified: hydrated zinc ammonium sulfate, a complex zinc
hydroxy-chloro-sulfate hydrate, and zinc hydroxide in relatively minor
amounts. In the high-chloride solution, basic zinc chloride, the
complex compound above, and zinc oxide were observed after 340
h of exposure. However, after 1020 h, only zinc oxide could be
identified.
Steel
The corrosion of the various specimens in the solutions is
presented in Figure 9, which shows an increase in the weight loss
with the exposure time. The regression line of corrosion in the
high-sulfate solution did not pass through the origin, unlike the
corresponding line for the high-chloride solution, implying that the
corrosion may have been initially slower in the sulfate. The corrosion
rate in the high-sulfate solution was 2300 g/m 2 /1 000 h but only 1600
g/m 2 /1000 h in the high-chloride solution. The crevices appeared to
have no influence on the course of the attack. After exposure in the
cabinets, all samples were covered by a loosely adherent layer of
rust, as shown in Figure 6. This material was identified as mainly a
mixture of geothite and lepidocrocite (Table 2).
Discussion
Aluminium
Generally, in the presence of aggressive anions, aluminium
corrodes by pitting, concentrated at local disruptions in the oxide film
where the environment can reach the metal at transiently revealed
sites." Foley and his coworkers 12,13 have shown that the chemical
nature of the anions in the solution affects the pitting process, with
chloride being particularly aggressive and sulfate much less aggres-
sive. Once attack has become established, the local chemistry in the
pit changes substantially as a result of the metal ion hydrolysis, which
lowers the pH, and the aggressive anion ingress. Under atmospheric
attack, apart from various hydrated aluminas (e.g., gibbsite and
bayerite), Barton 5 reported amorphous basic aluminium chloride as
products in marine environments, but only in very severely polluted
industrial environments (i.e., by S0 2 ) is amorphous basic aluminium
sulfate found.
In both spray solutions used in this work, there is sufficient
chloride ion present to promote the observed pitting of the speci-
mens. However, despite the relatively high concentration of ammo-
nium sulfate in the high-sulfate solution, the corrosion products do not
include any basic aluminium sulfate. The presence, in addition to
basic chlorides, of an amorphous component, arises from the
 TABLE 2 Corrosion Products Appearing in Test

Specimen Solutlon Corroslon Product Referenoe or JCPDS Card

Aluminum High After a 1020-h exposure:

Sutlate AICI3 4AI(OH)3 4H 2 0 15-713

High After a 1020exposure:

Chloride AICI3 4AI(OH)3 7.5H 2 0 27-11

In both After a 1020-h exposure:

solutions Amorphous material

Galvanized High After a 1020-h exposure:

Steel Sulate Zn12(OH),5(SO4)3CI3(H20)5 (16)
High Sulfate Zn(OH)2 12-479
High Sulfate (NH,)ZZnSO; 6H 2 o 18-138

High After a 340-h exposure:

Chloride ZnCl2 4Zn(OH) 2 7-155
High Chloride Zn12(OH)15(SO,)3CI3(H20)5 (16)
High Chloride ZnO 5-664
After a 1020-h exposure:
High Chloride ZnO 5-664

Steel After a 1020-h exposure:

In both FeO(OH)goethite 29-713
solutions Feo(OH)lepidocrocite 8-98

(N.B. (NH 4) 2 SO 4 , NH 4 NaSO 4 , NH 4CI, and NaCI were also observed in the diffraction pattems.)

fV
E
rn High chloride
E .2
z 0
v L
0
O rn
_
Q m
S
.2
d
rn o

Exposure time (hours)

High sulphate

iPI Al
Exposure time (hours) FIGURE 9 Graph of weight loss per unit area against
time for steel specimens (scatter bands shown).

FIGURE 8 Graph of weight loss per unit area against

time for galvanized steel specimens (scatter bands shown).
non-crystalline hydrated alumina, which would be expected to form
from the initially developed gel-like material.
Corrosion of aluminium, in terms of weight loss, is accelerated
in the cabinet by between 80 and 50 times over atmospheric
exposure (comparing industrial and marine environments with the
high-sulfate and high-chloride solutions, respectively.) However, pits
propagated during the tests at rates between 300 and 600 times
faster than in the atmosphere (Table 3). Thus, despite the high-
chloride solution being apparently five times less aggressive than the
high-sulfate solution in terms of weight loss, it was more than twice
as aggressive in terms of maximum depth of the pit obtained.
As the localized corrosion of aluminium is dependent on the
solution chemistry in and around the pits, a consideration of the bulk
solution chemistry of the salt sprays used here is unlikely to explain
the observed behavior completely. However, Ross and Callaghan 14
investigated the effects of ammonium sulfate as a corrodent of steel
and concluded that its apparent high-aggressivity results from the
lower surface tension of ammonium hydroxide, formed at cathodic
sites, permitting the solution to spread over the surface more easily.
In this case, the cathodic sites will be in the region immediately
adjacent to the pits, associated with intermetallic compounds and
other segregates. Additionally, the high-sulfate solution is about
one-half as saturated, with respect to its solute species compared
with the high-chloride solution. This would imply that the former is
likely to wet the specimen more effectively during the mist cycle and
is likely to remain a concentrated solution on the surface longer
during drying, thus providing more opportunity for corrosion to occur
around the edges of pits, making them shallow and promoting pit
coalescence, which would allow the pit solution to be more readily
washed away during the next mist cycle. If such a process is absent
during corrosion using the high-chloride solution, the pit solution will
be retained inside the interiors and will not evaporate readily,
resulting in the long narrow pits observed here.
Galvanized Steel
The corrosion of zinc is at a minimum in near neutral and
alkaline solutions; i.e., from pH 6 to 12.5. At higher pH values, the
corrosion increases substantially because of the formation of the
zincate ion, while in solutions with lower pH values, the zinc corrodes
freely, giving the zinc ion Zn 2 +. Corrosion products formed by natural
exposure s are based on various forms of zinc hydroxide. Further
reaction leads to the formation of basic carbonates, basic sulfates,
and basic chlorides, depending on the amount of the pollutant
species present. However, the actual corrosion products formed
during the spray test include species not normally found in nature.

Vol. 43, No. 12, December 1987 723

 TABLE 3 Corrosion Rates in Cabinets and the Atmosphere from a concentrated solution containing Zn 2 + ions, as observed. At
cathodic sites, the pH will rise only slightly during the drying phase as
Materlal Exposure Corroslon Rate Reterence ammonium ion is in excess to produced hydroxyl; i.e., the buffering
capacity of the solution is adequate.
Aluminum Cabinet: In the high-chloride solution, however, the amount of ammo-
High sulfate
general 250 gm -2y ' This work nium ion available to buffer the system is much less. For the first 340
pitting 2200 m-y' This work h of exposure, 11 mmol dm -3 of Zn 2 + is produced per cycle, and
High chloride
general 50 gm -2 y' This work twice this amount of hydroxyl ion. In this case, the pH in the cathodic
pitting 5000 m-y ' This work regions is buffered at a more alkaline level, 9.5, during the wet cycle
Naturel:
Industrial
and the bicarbonate/carbon dioxide equilibrium is much more impor-
general 3 gm -Z y' 23 tant. At the sites of precipitation of zinc hydroxide, however, the pH
pitting 5-10 my' 23
is similar to that in the high-sulfate solutions, but only 1% of the total
Marine
general 1-1.6 gm -zy 23 corroded zinc is in the solution, as shown in Table 4. During in the
pitting 4-13 m-y' 23 drying cycle, much less zinc hydroxide dissolves. Thus, the main
Galvanized Cabinet: product, in the initial stages at least, is the form of zinc hydroxide,
Steel High sulfate 200 my' This work which is stable in a solution containing 60 mmol dm -3 of Cl ion (i.e.,
-
High chloride
(340 h) 540 my' This work basic zinc chloride). 16 At cathodic sites, the buffering capacity of the
(340-1020 h) 205 m-y' This work ammonium ion is overwhelmed, during continued production of
Zinc Naturel:
Industrial 2-16 m-y - ' 23 hydroxide ion, and the pH control will depend on the rate that CO 2
(average) 6.5 my ' 19 dissolves in the surface solution to provide a source of bicarbonate
Marine 0.5-8 m-y ' 23
19
ion. The pH rises during this time, and observation of ZnO as a solid
(v. high Cl - ) 8-35 my'
product, after extended periods of exposure, implies that conditions
Steel Cabinet: were sufficiently alkaline for zincate ion to be present in substantial
High sulfate 2400 my' This work
High chloride 1800 my ' This work amounts; i.e., pH 12 and above.
Naturel: The corrosion rates of the galvanized steel in this work are
Industrial 25-175 m-y' 23
Marine 25-105 my 1 23 compared with the values for the atmospheric occurring, this
comparison is valid, and the behavior of the intermetallic layers is
generally similar in atmospheres contaminated by S0 2 . 19 In the
high-sulfate solution, the zinc corroded 30 times faster than an
This can be explained by considering the bulk solution chemistry and average value for corrosion in an industrial environment, though the
its interaction with the zinc surface. Calculated values of surface pH values ranged from 100 to only 12 times faster. Taking the middle
values and metal ion concentrations are presented in Table 4 and are range, an acceleration factor of 25 to 50 times can be equated with
used to explain the formation of the observed corrosion products. The an exposure of one to two weeks in the cabinet, being equivalent to
method used is summarized in the Appendix section and is justified an exposure of one year in the atmosphere. The high-chloride
below. cabinet test, however, was significantly more aggressive than this
It is apparent from Table 2 that the exposure conditions in the when compared with the values taken from the corrosion at marine
two cabinets were completely different. The major corrosion product sites (an acceleration factor of between 70 and 1000). After the
observed during exposure to the high-sulfate solution, the complex intermetallic layers were exposed, the corrosion rate feil by a factor
hydroxy-sulphato-chloro hydrate, has been found to form as an of 3. However, since no data appear to exist concerning the
evaporite. 16 However, ZnO, the major product after corrosion in the corrosion rate of the intermetallic layers specifically in a marine
high-chloride solution, can form by precipitation from an alkaline atmosphere, no direct measure of acceleration can be deduced.
solution containing Zn(OH) -2 4 ions, possibly resulting in passivation
Steel
of the surface, leading to a reduction in the zinc corrosion rate." Any
According to Barton, 5 the atmospheric corrosion mechanisms
consideration of the solution chemistry effects must result in an
for iron in the presence of sulfate and chloride species are similar and
explanation of these observations.
are based on reaction of the aggressive species with the metal,
At the zinc surface, the solution pH is controlled primarily by the
initially producing Fe e . This then undergoes further oxidation and
ammonium ion/ammonia and the bicarbonate ion/carbon dioxide
hydrolysis with the resulting precipitation of the usually observed
equilibria (the solution in the mist can be considered to be fully atmospheric corrosion products (geothite, lepidocrocite, and magne-
aerated), as well as the self-dissociation of the metal hydroxide. If the
tite), which are generally non-protective. 2
system has undergone steady-state corrosion during the wet cycle,
Although the high-sulfate solution is more aggressive than the
the pH in the vicinity of the precipitating zinc hydroxide, i.e., between
high-chloride solution, the corrosion mechanism is probably similar.
the cathodic and anodic sites, as well as the amount of zinc ions in
If the solution chemistry in the region where the iron corrosion
solution, can be calculated by a consideration of these equilibria.
Additionally, the buffering capacity of the solution will restrict the rise products are forming is considered, the low-solubility product of ferric
hydroxide indicates that the pH values of both solutions will be similar
in pH at cathodic sites, and this can also be evluated. The
during the wet cycle (Table 4). As the surface dries out, virtually no
assumptions implicit in the method given in the Appendix are: (1) all
corrosion product redissolves during concentration of the salt solu-
the solution that arrives on the metal surface during the course of one
tions. Therefore, the observation that the corrosion rates and the
cycle is retained, (2) the anodic and cathodic sites are well separated,
products after cabinet exposure in either solution are similar, is not
and (3) all the reactions considered are at equilibrium.
unexpected. The increased aggressivity of the high-sulfate solution
During corrosion in the high-sulfate solution, 3.8 mmol dm -3
may result from a surface tension effect mentioned previously. 14
of Zn 2 + ions are produced at anodic sites, and twice this amount of
Comparing the corrosion rates in the cabinets with those under
hydroxyl ion is produced at the cathodic sites (this has been
atmospheric exposure conctitions (Table 3) gives an acceleration
calculated by converting the weight loss per wet/dry cycle into
factor of between 15 and 100 times, a similar range of acceleration
solution concentrations, assuming no loss from the surface). While
as evident for zinc corrosion, and it again implies that cabinet
the solution is being sprayed, its buffering capacity prevents the pH
exposures of 1 to 2 weeks can be equated with an external exposure
at the cathodic sites rising beyond --8.4, while in the regions where
of 1 year.
the hydroxide is precipitating, the pH is lower (-7.3) with 7% of the
corroded zinc in the solution, as summarized in Table 4. However,
Comparison of Cabinet Results with
during the drying cycle, as the solution concentrates, more zinc
hydroxide dissolves. If equilibrium conditions are assumed, all the Atmospheric Exposure
zinc will have been dissolved before the surface dries out; hence, the Comparisons between accelerated testing in a cabinet using a
resulting solid species wilt be those expected to form by precipitation salt spray and natural weathering exposures must be approached

724 CORROSIONNACE
 TABLE 4 - Catculations of Solution pH and Metal Ion Concentration
Bufrered pH at
Solodon Cond@IOns
Cathodic Shot
High As sprayed Zn - 8.38
Sulfate Fe - 9.84
10x concentrated Zn - 8.45
Fe - 10.70
50x concentrated Zn - 8.46
Fe-11.37
Saturated Zn - 8.46
Fe-11.97
High As sprayed Zn - 9.56
Sulfate Fe-I0.66
10x concentrated Zn - 10.50
Fe-11.66
50x concentrated Zn - 11.49
Fe - 12.36
Saturated Zn - 11.79
Fe - 12.66
with caution because of the substantially different conditions under
which both take place. Recent advances, of which this test is one,
now place more emphasis on humidity and condensation cycling
(wetting and drying) than had been previously done; this was an
attempt to simulate intermittent wetting and drying under natural
conditions. Closer accordance with reality can be assigned to this
kind of approach.
Consideration of the solution conditions on the surface of a
corroding specimen is also necessary. In this work, there is littie
apparent difference between the corrosion rates of steel using either
solution and no detectable difference in corrosion product, as
assessed by x-ray diffraction. This is reflected in the data quoted in
Table 3 and is caused by the comparable corrosion mechanisms
acting to produce nearly identical surface conditions. The surface
chemistry may be similar to that formed during atmospheric expo-
sure, in which case, the test cabinet conditions are a valid model for
steel corrosion.
For zinc, however, the situation is different. A substantial part of
the corrosion product formed during the wet part of the cycle does
redissolve during the dry cycle as the high-sulfate solution concen-
trates. This is not the case during the concentration phase with the
high-chloride solution. Additionally, with this latter solution, the
surface pH rises significantly during the drying phase, and the
resulting corrosion products and corrosion rates are substantially
different from the former situation. Under natural exposure, the
buffering capacity of a surface moisture film will be primarily caused
by the carbon dioxide/bicarbonate equilibrium, and thus when zinc
corrodes in the atmosphere, carbon dioxide is absorbed on an
alkaline surface to form basic zinc carbonates. 5 These are not
observed in this cabinet test because the salts in the spray
overwhelm this reaction. Therefore, the test used is not representa-
tive of the atmospheric attack.
In the case of aluminium exposures, bulk surface chemistry
effects cannot effectively explain the differences in the corrosive
attack with the two solutions, as continuing corrosion of aluminium is
dependent on local solution chemistry. However, the substantial
difference between the corrosion rates observed in the high-sulfate
and high-chloride solutions is evidence that local pit chemistry is
dependent, to some extent, on the composition of the bulk solution.
Based on corrosion products which were found naturally in conduc-
tors exposed for 25 years, the high-sulfate solution, used generally to
represent an industrial atmosphere, adequately reflects the external
environment. However, it does not simulate the circumstances
prevailing in the interior of a conductor, where the local environment
contains a higher concentration of chloride ions. This situation is
modeled more effectively by the high-chloride solution. However, as
galvanic interactions between the adjacent aluminium and the
galvanized steel strands are of primary importance, this will be
considered in more detail in a subsequent paper. 2
It is important to consider what is required from an accelerated
test when devising a new one or when using an existing one. If only
a proving test for various materials is needed, it may not matter if the
simulation in the cabinet is not a good representation of the
Vol. 43, No. 12, December 1987 725
pH During Formatlon % Metal Ion
of Hydroxide In Solutlon
Zn2' - 7.30 6.7%
Fe3 - 4.24 <10-" %
Zn2+ - 7.00 26%
Fe3` - 4.00 <10 -4 %
Zn2* - 6.76 78%
Fe3 -3.80 <10-4 %
Zn2 - 6.46 M dissolved
Fe"-3.68
Zn2' - 7.47 1%
Fe3 -4.38 <10 -4
Zn2' - 7.26 2.7%
Fe3' - 4.20 <10 -4
Zn2' - 7.04 7.5%
Fe3+ - 4.04 <10 -4 %
Znz + - 6.93 12.4%
Fe3 - 3.96 <10 -4 %
atmospheric attack. Provided the system is reproducible and gives
an adequate acceleration, such a test may be useful for ranking or for
quality control. The test described here is particularly useful because
the parameters (solution composition, and the wet and dry times) can
be altered readily. On the basis of the high-sulfate solution, the test
provides an acceleration factor of between 25 and 50 times for the
corrosion of aluminium, steel, and zinc (i.e., the eta-layer of the
galvanized steel) compared with atmospheric corrosion rates.
If a model test is desired, however, then thought must be given
to the nature of the electrolyte solution on the surface under natural
conditions. Any model should encompass at least a consideration of
the following: (1) steady-state corrosion on the surface in the
presence of a moisture film; (2) increasing corrosion as this surface
film dries out (concentrates); (3) cessation of corrosion after the
relative humidity has dropped below that level required to maintain a
moisture film; and (4) increasing corrosion on initial re-wetting.
Whereas, a conventional continuous salt spray test only reflects
Consideration (1), a wet/dry test has the potential to also take into
account Considerations (2) through (4). It the relative importance of
wet and dry periods are assessed correctly, then the test is more
likely to reproduce natural corrosion products and morphologies.
Information about whether corrosion under a continuous dilute
electrolyte film of moisture, or corrosion in the latter stages of drying
of a film of concentrated pollutant species, is the dominant factor in
atmospheric attack will help to clarify the correct conditions. In the
present work, neither solution provides a complete basis, and
alterations to their compositions could be considered. The buffering
capacity of the high-sulfate solution can be reduced by substitution of
ammonium ion with sodium ion, and bicarbonate ion additions could
be made to both solutions to simulate natural buffering capacity and
to encourage the appearance of carbonate corrosion products.
Within the requirement to provide some degree of acceleration of
attack, the solutions could be made much more dilute. Such effects
as repeated surface drying 21 can substantially increase the concen-
tration of aggressive species in the electrolyte film.
Conclusions
1. The wet/dry cycle test used accelerates the average corro-
sion rates of zinc (i.e., the eta-layer of galvanized steel), steel, and
aluminium by between 25 and 50 times compared with atmospheric
attack.
2. The solutions used, high-sulfate and high-chloride solutions,
provide an approximate simulation of atmospheric attack on steel,
although neither provides a true simulation of atmospheric attack on
zinc (or galvanized steel). It is not clear which situation holds true for
aluminium because of the localized nature of corrosion on this metal;
nevertheless, the mode of attack is controlled by the bulk solution
chemistry.
3. Modifications to the solutions, including dilution, adjustments
in the ratios of Cl - and SO 42- , partial substitution of Na + for NH 4 +
and further additions of HCO 3 - and CO 3 2 - , to simulate the effects of
atmospheric CO 2 , should provide a more pertinent model for natura)
exposure of zinc, which may also be applicable for other metals.


Acknowledgments (Zn2+) final = (a + b)/2 (Fe3 +) final = (a + b)/3

This work was financed by a research grant provided by Central
Electricity Research Laboratories. Thanks are due to A. Y. M. Peng From Equilibria (3): K 3 = 12 (a + b)/2/(H + )
for measuring and photographing the pit depths in the aluminium. a + b = (OH - ) produced at cathodic sites.

Appendix Solve for (H+) as above by elimination of a and b.

The solution pH and the equilibrium metal ion concentrations
were calculated from the following equilibria: 22

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726 CORROSIONNACE