Corrosion Science 46 (2004) 23372354

www.elsevier.com/locate/corsci

The protective nature of passivation lms

on zinc: wetting and surface energy
Tim H. Muster *, Aaron K. Neufeld, Ivan S. Cole
Corrosion Science and Surface Design Team, CSIRO Manufacturing and Infrastructure
Technology, Graham Road, P.O. Box 56, Highett, Victoria 3190, Australia
Received 18 November 2003; accepted 13 January 2004
Available online 5 March 2004

Abstract

The inuence of passivation lm surface chemistry on the atmospheric corrosion of zinc

was investigated. Crystalline oxide compounds replicating natural zinc corrosion products
were deposited from aqueous solution, and grown as coatings on rolled zinc plates. The
energetic properties of the oxide surfaces were characterised by water contact angle deter-
mination and inverse gas chromatography. Water contact angles were determined by liquid
penetration and dynamic Wilhelmy techniques, and a good correlation was observed between
the two methods. In comparison with wetting approaches, inverse gas chromatography was
found to overestimate values for the dispersive contribution to the solid surface energy. Zinc
hydroxychlorides possessed the lowest contact angles whilst naturally formed zinc oxide
hydroxide coatings were the most hydrophobic. The ability of zinc oxidation products to
retain moisture was investigated by correlating wetting data with the criteria for droplet
retention on planar surfaces. The response of the various oxides to rain washing events and
water adsorption processes was discussed. Comparison of the corrosion rates of thin liquid
lms versus droplets was explored experimentally by adjustment of droplet contact angles
through the addition of a non-ionic surfactant. Mass gain data indicated that corrosion rates
decreased with decreasing contact angle, suggesting that hydrophobic surfaces are not nec-
essarily advantageous for improving corrosion performance.
Crown Copyright 2004 Published by Elsevier Ltd. All rights reserved.

Keywords: Zinc; Passive lms; Oxidation products; Contact angle; Surface energy; Runo

*
Corresponding author. Tel.: +61-3-92526293; fax: +61-3-92526253.
E-mail address: tim.muster@csiro.au (T.H. Muster).

0010-938X/$ - see front matter Crown Copyright 2004 Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2004.01.001
2338 T.H. Muster et al. / Corrosion Science 46 (2004) 23372354

1. Introduction

A vast depth of knowledge has been reported concerning the atmospheric corro-
sion of common engineering metals [1,2]. Understanding the corrosion performance
of zinc is particularly relevant due to its widespread usage as a protective coating on
steel. The corrosion resistance of zinc (and metals in general) is strongly related to the
protective nature of surface oxides [3], and therefore, a thorough understanding of the
characteristics of surface oxides is important. The wetting properties of passive lms
are expected to play a number of roles in determining atmospheric corrosion rates,
and may inuence the following: electrolyte lm thicknesses [4], the time-of-wetness
(TOW) [5], the eciency of impurity adsorption [6,7], the rate of runo and the
likelihood of moisture retention [8].
The ability of a surface to wet is largely controlled by the interfacial energy and to
some extent by roughnesses and porosities [7]. Surfaces are classied into two broad
categories, those that are hydrophilic and those that are hydrophobic. Hydrophilic
surfaces possess a high surface energy and permit the spreading of aqueous solutions
such that the three-phase contact angle [9] approaches zero. Hydrophobic surfaces
are low-energy and create high water contact angles approaching or greater than 90,
and therefore droplets tend to bead on the surface. Also, the roughness of surfaces
and the porosity of oxidation products inuence droplet spreading, runo phe-
nomena, salt distribution, and the retention of moisture in pores.
In terms of mass-transport processes, the spreading behaviour of an electrolyte
(i.e. whether droplets or thin lms are formed) will directly inuence both the solid
liquid contact area and the liquidvapour interfacial area. The solidliquid contact
area has a direct inuence on the rates of oxide and metal dissolution, and controls
the access of oxygen and water to cathodic sites [10]. The liquidvapour inter-
face area controls the extent of oxygen/gas diusion and controls bulk evapora-
tion rates. Also, the chemical and physical nature of a surface will change with time,
and therefore wetting phenomena is thought to play a rather dynamic role in
inuencing metal corrosion. For example, work by Cole et al. [11] has shown that the
energy of a zinc surface increases upon its short-term exposure to outdoor environ-
ments.
A supporting study to the present article summarized in the common oxide
compositions (zinc oxide, zinc hydroxychloride, zinc hydroxycarbonate and zinc
hydroxysulphate) that form naturally at the zincenvironment interface, and inves-
tigated the eect of oxide surface charge on corrosion protection [12]. This article
aims to elucidate dierences in the wetting properties of naturally formed oxides, and
emphasise the role of wetting and surface properties in controlling atmospheric
corrosion rates. More specically, the wetting and energetic properties of the syn-
thetic oxides are characterised by contact angle and surface energy determinations.
From information gained from the surface energy studies, the response of each oxide
type to rain events, water adsorption, water runo and evaporation is discussed, and
their inuence on corrosion rates implied.
 T.H. Muster et al. / Corrosion Science 46 (2004) 23372354 2339

2. Experimental

2.1. Substrate and particle preparation

Rolled zinc plates (Zintane 83, Union Miniere, France) were cleaned using a
commercial surfactant (Neutracon90e, Decon). Wetting experiments were carried out
on both cleaned and synthetic-oxide coated, rolled zinc plates, and also on a series of
synthesised oxide particles. The details for oxide preparations are reported elsewhere
[12]. We make special mention of the sample heterogeneity of the synthetically pas-
sivated plates. XRD revealed that both zinc hydroxychloride and zinc hydroxysul-
phate lms also possessed minor phases of zinc hydroxycarbonate material, whilst zinc
hydroxycarbonate lms showed traces of zinc oxide and some sodium carbonate [12].

2.2. Washburn liquid penetration contact angles

Liquid penetration contact angles of synthesised oxide particles were determined

using the approach of Washburn [13], where the rate of liquid travel through a
particle bed is governed by the Poiseuille and Laplace equations:
h2 reff clv cos hp
1
t 2g
where h is the height of liquid at time t, reff is the eective radius of pores, g is the
liquid viscosity, clv is the liquid surface tension, and hp is the contact angle. The water
contact angle can be obtained from the ratio of liquid penetration rates of water and
a perfectly wetting liquid (cyclohexane), thus avoiding the need for the direct
determination of reff [1416]. For consistent packing of particle beds, a known weight
of each oxide was placed into glass wool plugged glass capillaries (2 mm internal
diameter) and compacted to a constant volume fraction. Packed capillaries were
stored at 40% relative humidity overnight prior to analysis.

2.3. Dynamic Wilhelmy contact angles

The Wilhelmy technique measures the mass (force) of a solid object when sub-
merged and then withdrawn from a liquid [17]. The total force, F , acting on the solid
at any time is the sum of capillary and bouyancy forces. At the point where the
sample and liquid rst contact, the bouyancy force is negligible, and extrapolation by
linear t over the range of submerging and withdrawing data allows the calculation
of the advancing, hA , and receding, hR , contact angles, respectively:
Fcap
cos hA=R 2
pclv
where Fcap is the capillary force and p is the wet perimeter. Advancing and receding
traces were performed on plates with oxide lms using a number of probe liquids:
2340 T.H. Muster et al. / Corrosion Science 46 (2004) 23372354

water, hexane, cyclohexane, formamide and diiodomethane. The perimeter was

measured physically using a micrometer. Studies were also undertaken to estimate
the wet perimeter using the approach of Pepin et al. [18], who based their calcula-
tions on the theory of Fowkes [19]. Pepin and co-workers determined the capillary
forces (F1 and F2 ) for two apolar wetting liquids (i.e. 1-bromonaphthalene and di-
iodomethane). The wet perimeter is solved using Eq. (3).
F1 clv2
F2 a 
0:5
clv1 clv2
p where a 3
clv2 1  a clv1

2.4. Inverse gas chromatography (IGC)

A Hewlett Packard 5890 Series II gas chromatograph was used to obtain the net
retention volumes, VN , for solvent vapour ows through columns lled with synthetic
zinc hydroxideoxide, zinc hydroxychloride and zinc hydroxycarbonate particulates.
Stainless steel chromatographic columns with an internal diameter of 2 mm and
length of approximately 200 mm were cleaned using 10% HNO3 for 1 h, rinsed with
distilled water and oven dried prior to use. The oxide particulates were sieved to a
size 150 lm < x < 300 lm and packed into the columns and compressed by gently
tapping. Glass wool was used to block the ends of the column. To ensure the oxides
were free of moisture prior to characterisation, each system was conditioned by
passing helium gas through the column for 24 h. Experiments were carried out at
elevated temperatures (40150 C) to achieve workable retention times.
The alkane series from pentane (C5 ) to decane (C10 ) were used to determine the
dispersive component (cd ) of the solid surface energy from the slope of a plot of
0:5
RT ln VN against acdl , which is based upon Eq. (4) [1921].
 
0:5 0:5
RT ln VN 2Nacds  cdl c 4

where R is the gas constant, T is the absolute temperature, N is Avogadros number,

a is the cross-sectional surface area of a probe molecule, c is a constant, and cds and cdl
are the dispersive components of surface energy of the solid and the probe,
respectively. The specic, or polar, component of the free energy of adsorption
(DGsp ) was evaluated by comparing the retention volume of both acidic (benzene, di
and tri-chloromethane) and basic (tetrahydrofuran) probes with the retention time of
the alkane probes (Eq. (5)).


VN acid=base
DGsp RT ln 5
VN ref
The specic interaction enthalpy, DH sp , was determined by plotting DGsp as a
function of absolute temperature and extrapolating back to T 0 K, at which
DH sp DGsp .
Hamieh et al. [22] recently demonstrated that the value of a is not known with
good accuracy and presented values calculated using various models. For this study,
a values for temperatures higher than 100 C were obtained from the two-dimen-
 T.H. Muster et al. / Corrosion Science 46 (2004) 23372354 2341

sional modelling of van der Waals contributions, whilst an average of values ob-
tained using Kiselev [22] and Cylindrical models was used at lower temperatures [20].

2.5. Droplet spreading and runo

The runo of single water droplets from rolled zinc plates with synthetic oxide
lms was determined as a function of drop size and plate inclination. The samples
were mounted to a tilting beam assembly carrying a digital protractor (PM Pro 360).
Ten to fty microliters droplets of water (18 MX resistivity) were placed onto the
oxide coated zinc samples and the angle of runo recorded.

2.6. Corrosion rates under droplets of varying surface tension

Droplets of NaCl-containing aqueous solutions with masses in the range of 15

1000 mg were placed onto the surface of pre-weighed cleaned rolled zinc sections.
The droplet mass was recorded in grams to ve signicant gures. Corrosion pro-
cesses were allowed to take place under ambient conditions for 16 h, after which the
sections were dried at 70 C and reweighed for mass gain. Two aqueous solutions
containing 1 M NaCl were used, one with the addition of 0.1% Tween80 non-ionic
surfactant.

3. Results and discussion

3.1. Contact angle determination

Table 1 shows the estimated water contact angles for synthesised oxide particles
and synthetic passivation lms on zinc plates. General trends in the ranking of oxide
hydrophobicity showed good agreement, with zinc hydroxychlorides being the most
hydrophilic and zinc oxide the most hydrophobic. Contact angles for zinc hy-
droxysulphate and zinc hydroxycarbonate appear to be of a similar magnitude. For
similar compounds the Wilhelmy technique generally resulted in higher contact
angles, an observation that may be attributed to the inability of the liquid pene-
tration technique to evaluate contact angles greater than 90. Cole et al. [23] reported

Table 1
Average contact angle data for synthetic zinc oxidation products
Oxide Particle Plate
(liquid penetration) (Wilhelmy technique)
hp () hA () hR ()
Zinc oxidehydroxide 88.6 107.8 71.0
Zinc hydroxychloride 76.7 72.8 54.8
Zinc hydroxycarbonate 86.2 89.1 47.2
Zinc hydroxysulphate 86.5 82.9 55.4
2342 T.H. Muster et al. / Corrosion Science 46 (2004) 23372354

sessile drop water contact angles on clean galvanised steel to be in the range of 65
85, and after exposure to various sites, contact angles ranged from 16 to 80.
Considering that sessile drop contact angle measurements generally provide an
intermediate angle between hA and hR , the magnitude of the current data appears to
be in good agreement with that generated by Cole et al. There is some conjecture that
clean metal surfaces should be perfectly wet by water [24]. However, several authors
[25,26] suggest that for various metals (i.e. gold, copper, nickel and steel) that the
contact angle can vary from anywhere between 0 and 90. Certainly, zinc, which
rapidly forms an oxide, appears to possess a nite water contact angle.
The rate of liquid ow through glass capillaries packed with synthesised oxide
particles was consistent with Poiseuille capillary ow theory for both water and
cyclohexane, with the height squared showing a linear relationship with time (Fig. 1).
The estimated eective radius of capillaries ranged from reff 0:14 to 0.62 lm for
zinc hydroxysulphate, which indicates an assumed spherical particle radii of
approximately 12.8 lm. Reproducibility in the rate of liquid penetration was within
5% for repeat runs of the same liquid through particle beds prepared on conse-
cutive days. This provides condence that observed dierences in the rates of pen-
etration reveal clear information concerning the ranking of particle surface energy
properties.
Fig. 2 shows selected raw wetting traces obtained from Wilhelmy balance
experiments. Repeat determinations of dynamic contact angles were found to vary
by less than 3% when altering the wetting rates in the range of 20150 lm s1 . All
presented data was obtained using a wetting rate of 100 lm s1 . The information

Fig. 1. Selected data points showing the liquid penetration height squared (h2 ) as a function of time for
water (lled symbols) and cyclohexane (open symbols) through 3 mm diameter glass capillaries packed

with synthetic oxide particles. ( ) Zinc oxidehydroxide, (r }) Zinc hydroxychloride, (N M) zinc
hydroxycarbonate, (j ) zinc hydroxysulphate.
 T.H. Muster et al. / Corrosion Science 46 (2004) 23372354 2343

Fig. 2. Wilhelmy traces showing mass change as a function of immersion distance for zinc plates with
oxide coatings.

available from the Wilhelmy trace can be summarised by the following [17]: (1)
displacement of the trace in the positive force direction indicates a decreased contact
angle, (2) the distance between the advancing (lower) and receding (higher) traces is a
measure of the contact angle hysteresis, (3) the slope of the trace is characteristic of
the bouyancy force and is directly related to the perimeter of the solid, and (4)
uctuations in the data are due to physical heterogeneities of the sample. Advancing
contact angles increased as zinc hydroxychloride < zinc hydroxysulphate < zinc hy-
droxycarbonate < zinc oxide. Receding contact angles were 2540 lower than the
corresponding advancing angles, including the as-received zinc oxidehydroxide
sample. Roughening of the plate surface occurred during the application of syn-
thesised zinc oxidation compounds, as was evidenced by increased uctuations in the
advancing wetting traces when compared to the as-received zinc oxidehydroxide
plates.
The determination of accurate dynamic contact angles is dependent upon the
estimation of the wet perimeter [27]. Three approaches of obtaining wet perimeter
were considered in the present study. Firstly, the plate perimeters were measured
using a micrometer. Secondly, plates were immersed into liquids (cyclohexane and
hexane) that were assumed to perfectly wet the solid, and the perimeter calculated as
p F =clv . Thirdly, the use of two non-polar liquids using the Pepin et al. [18] ap-
proach. Table 2 provides the wet perimeter details for the rst two approaches. Wet
perimeters determined using both cyclohexane and hexane were in good agreement
and showed that the porosities and roughnesses of the oxide coated plates increased
by less than 7% compared to the micrometer measurements. Of the synthesised oxide
coatings, if would appear that zinc hydroxychloride and zinc hydroxysulphate
compounds have a higher roughness and/or porosity than zinc oxidehydroxide and
zinc hydroxycarbonate coatings. Mention should be made that the third approach to
2344 T.H. Muster et al. / Corrosion Science 46 (2004) 23372354

Table 2
Perimeter measurements and wet perimeter estimates
Physical perimeter Perfect wetting Perfect wetting:
(mm) perimeter (mm) physical
Zinc oxidehydroxide 41.34 41.22 0.13 0.997
Zinc hydroxychloride 41.28 43.87 0.25 1.063
Zinc hydroxycarbonate 41.10 40.86 0.43 0.994
Zinc hydroxysulphate 41.24 43.65 0.10 1.058

wet perimeter determination appears to be problematic, returning unrealistic and

negative values.

3.2. Inverse gas chromatography (IGC)

The ow of non-polar alkane vapours through particle beds of zinc hydroxy-

chloride and zinc hydroxycarbonate allowed the estimation of cds DGsp and DH sp
values (Table 3). However, long retention times for the transport of non-polar
hydrocarbon vapours through the zinc hydroxideoxide column provided unusable
and inconclusive data. Even at 100 C, data was collected for C5 C7 hydrocarbons,
whilst C8 vapour was not detected after 75 min. Also, the decomposition of zinc
hydroxide, which occurs at around 120130 C, restricted the use of higher experi-
mental temperatures. For zinc hydroxycarbonate and zinc hydroxychloride particles
exposed to alkane vapour over a range of temperatures, plots of RT ln VN against
acdl 0:5 provided a linear correlation with a squared regression R2 > 0:997. The
value of cds at 100 C for zinc hydroxychloride was 43 mN m1 , which was signi-
cantly lower than the value of 91 mN m1 for zinc hydroxycarbonate at the same
temperature. The high estimated value of cds (>90 mN m1 ) from IGC would suggest
perfect wetting by water [28]. However, the wetting results (Table 1) show that this
clearly does not occur.
The calculated values of DGsp are associated with the polar contributions to the
solid surface energy, and the more negative its value, the stronger the acidbase
interactions between the adsorbent solid and the adsorbate. Zinc hydroxychloride
showed strong acid characteristics as the specic interactions between the stationary
solid phase and the acidic probes (benzene) were low, and were eectively zero for

Table 3
Surface energy and interaction energy data obtained from inverse gas chromatography
Oxide cds (100 C) DGsp (100 C) (kJ mol1 ) DH sp (kJ mol1 )
(mN m1 )
C6 H6 CHCl3 CH2 Cl2 THF C6 H6 CH2 Cl2 THF
Zinc hydroxychloride 43 0.6
0 Very 12.1 2
high
Zinc hydroxycarbonate 91 2.1 0.3 13.6 5.1 2 1.6
 T.H. Muster et al. / Corrosion Science 46 (2004) 23372354 2345

the case of CHCl3 . The basic probe, THF, had a strong specic interaction with the
acidic moieties on the solid phase and did not diuse through the column (data not
shown) at any temperature conducted. Zinc hydroxycarbonate showed slightly in-
creased interactions with acidic probe molecules when compared to zinc hydroxy-
chloride, indicating that it possesses more basic characteristics. In contrast to zinc
hydroxychloride, interactions between THF and zinc hydroxycarbonate were mea-
surable, indicating a lesser degree of surface acidity.
The value of DH sp describes the energy of interaction between the probe molecule
and the solid phase independently of temperature-based entropic eects. The esti-
mates of DH sp provided in Table 3 suggest that the interaction energy between the
acidic probes (benzene/CH2 Cl2 ) and zinc hydroxychloride exceeds that for the zinc
hydroxycarbonate. This trend is in contrast to that observed for DGsp values ob-
tained with the same acidic probes, an observation that is attributed to the high
entropic dependence of adsorption onto zinc hydroxychloride surfaces (see Fig. 3).
Fig. 3 also shows that the free energy of interaction between zinc hydroxycarbonate
and THF probe molecules has a positive slope, suggesting an increase in entropy
with temperature. All other interactions possessed negative slopes and show a de-
crease in entropy with temperature.

3.3. Surface energy determinations

Tables 4 and 5 present the estimates of surface energy values calculated from
contact angle using a number of approaches as outlined in Appendix A. Whilst
considerable variations were obtained in the estimated surface energy values, each

Fig. 3. Plot of the specic free energy of various polar probe molecules adsorbing onto synthetic zinc

oxide particles: () benzene adsorption onto zinc hydroxychloride, ( ) benzene adsorption onto zinc
hydroxycarbonate, (}) CH2 Cl2 adsorption onto zinc hydroxycarbonate, and (M) THF adsorption onto
zinc hydroxycarbonate.
2346 T.H. Muster et al. / Corrosion Science 46 (2004) 23372354

Table 4
Surface energy data derived from (1) the equation of state approach of Li, Kwok and Neumann [28,45], (2)
acidbase approach of Van Oss et al. [30], and (3) the reciprocal mean approach of Wu [29]
Oxide Particle csv (mN m1 ) Plate csv (mN m1 )
1 2 3 1 2 3
Zinc oxidehydroxide 30.1 20.5 43.2 18.4 18.8 53.3
Zinc hydroxychloride 37.6 22.7 45.3 40.0 28.2 31.1
Zinc hydroxycarbonate 31.6 17.2 38.8 29.8 17.0 34.2
Zinc hydroxysulphate 31.4 17.0 37.6 33.7 22.9 35.8

Table 5
Surface energy data derived from acidbase theory approach of Van Oss et al. [30]
System Particle Plate
cLVW
sv c
s c
s cLVW
sv c
s c
s
(mN m1 ) (mN m1 ) (mN m1 ) (mN m1 ) (mN m1 ) (mN m1 )
Zinc oxidehydroxide 15.34 0.80 8.45 16.32 0.40 3.67
Zinc hydroxychloride 15.89 0.58 20.01 21.94 0.51 18.84
Zinc hydroxycarbonate 13.32 0.17 22.71 13.36 0.28 11.92
Zinc hydroxysulphate 13.12 0.25 14.74 19.39 0.24 12.81

calculation method was able to rank the surface properties of the studied systems
into a similar but not identical order. In addition, a good correlation was observed
between calculations made for particulate and plate systems. It would appear from
this study that the surface energy of common zinc surfaces found in the environment
are in the range of 2040 mN m1 . These values are in agreement with a previous
study by Cole et al. [23].
Given that the zinc oxidehydroxide system was found to exhibit the highest
water contact angles (Table 1), it would appear that estimations using Wus ap-
proach [29] overestimate the surface energy for this particular system. It was noted
that the specic components of surface energy calculated using this approach sig-
nicantly outweighed dispersive contributions, a result that is not probable. For
example, the dispersive component of the surface energy for zinc hydroxycarbonate
was just 0.4 mN m1 of the total predicted energy of 38.4 mN m1 . Therefore, we
suggest that the information provided in Table 4 be used with caution.
A breakdown of the surface energy components calculated using the Van Oss
et al. [30] approach is provided in Table 5. Lifshitzvan der Waals dispersive energies
were in the range of 1322 mN m1 , values signicantly lower than those obtained
using IGC. A series of authors have published data comparing the non-polar
component to the surface energy estimated using IGC and wetting techniques [31
33]. In each case the value of cd is higher for IGC, a result that is attributed to the
contrasting mechanisms of adsorption [34]. Wetting experiments are based on the
interactions between a surface and a bulk liquid, whilst IGC measures the interaction
between innitely diluted gas molecules and surface. It follows that gas adsorption
has the ability to target high-energy sites whereas wetting experiments provide an
 T.H. Muster et al. / Corrosion Science 46 (2004) 23372354 2347

average of the interactions over a macroscopic area. It follows that the particularly
high value of cd estimated for zinc hydroxycarbonate, may be a result of the ability
of non-polar probe molecule targeting.

4. Discussion

4.1. Forms of moisture on surfaces

Using the information obtained from wetting studies, we now consider the
inuence of zinc passivation lm surface chemistry on the formation of moisture
layers under atmospheric conditions. Aqueous environments on exterior metal sur-
faces are generally established by either rain or through water adsorption processes.
We concentrate rstly on the deposition of moisture by rain. Where light rain is
concerned, the spreading behaviour of individual droplets will be determined by the
surface energy, roughness and porosity. That is, if the energy of the surface is high,
droplets impacting on the surface will tend to spread and form a thin continuous lm
of moisture. In contrast, light rain on a low-energy hydrophobic surfaces will yield
discrete droplets with a nite contact angle. For this reason hydrophobic surfaces
tend to favour more isolated forms of corrosion damage whereas hydrophilic sur-
faces favour general corrosion mechanisms.
The ability of a surface to retain droplets is not solely dependent upon the
hydrophobicity of a surface, rather it is the dierence between the advancing and
receding contact angles that provides the resistance against a droplet sliding down an
inclined surface [8]. At an innitely low wetting rate the critical angle, ac , leading to
droplet sliding is given as:
qgV sin ac wclv cos hR  cos hA 6
where q is the liquid density, g is the acceleration due to gravity, V is the droplet
volume, w is the width of the droplet, clv is the liquid surface tension and hA and hR
are the advancing and receding contact angles, respectively.
As rain becomes heavier, droplets impacting a surface tend to coalesce as repre-
sented in Fig. 4. Once the droplet size reaches a critical size, gravitational forces
overcome the adhesional forces of the droplet to the zinc and runo occurs (see
contact area dependence of Eq. (6)). When rain events reach a critical ux, forced
wetting of a surface occurs and a sheet of moisture will cover the surface. However,
when the wetting event halts on a hydrophobic surface, the thin lm ruptures and the
liquid attempts to recede to form disconnected droplets. The ability of a thin lm to
avoid rupturing is controlled by the disjoining pressure and the ability of the water to
spread over the surface [35]. The dewetting of surfaces by the growth of dry regions
has been described by Kheshgi and Scriven [36]. As will become clear later, rain is
not highly detrimental to the corrosion performance of zinc as it performs an
important function in washing salt contaminants from the surface. It has been
suggested that the pH of the rainwater and the total solids content of the air appear
to have more signicance than the time-of-wetness [37].
2348 T.H. Muster et al. / Corrosion Science 46 (2004) 23372354

Fig. 4. The spray wetting of contaminated zinc surfaces with electrolyte: (a) impacting droplets were
approximately 500 lm in size and exhibited an equilibrium contact angle in the order of 65 (sessile drop),
(b) the continued spraying led to droplet growth and the eventually combining of adjacent droplets.

Since values of hA and hR are available from dynamic wetting experiments, the
ability of zinc surfaces with synthetic oxide lms to control droplet runo was
investigated with respect to Eq. (6). A plot of sin ac versus cos hR  cos hA (Fig. 5)
shows a positive correlation between the angle of runo and the hysteresis in the
dynamic wetting traces. The data in Fig. 5 also provides an appreciation of the in-
creased energy required for the removal of small droplets from a surface.
Given the data on the oxide surface properties, some hypotheses can be made
concerning the ability of the studied zinc oxidation species to retain moisture on
surfaces after rain events. Zinc with naturally forming oxidehydroxide surface lms
are relatively hydrophobic and for rolled zinc, exhibit a large contact angle hyster-
esis. Therefore, moisture on the surface exists as individual droplets that are not
easily removed. Zinc hydroxycarbonate lms appear to behave similarly to zinc
oxidehydroxide lms in that droplets adhere to the surface remarkably well (see
Fig. 5). However, the contact angle of the zinc hydroxycarbonate is lower than the
 T.H. Muster et al. / Corrosion Science 46 (2004) 23372354 2349

Fig. 5. Correlation between the dynamic contact angle of oxide coated zinc plates and the tilt-angle of zinc
plates required for visible movement of 30 and 50 ll droplets.

native oxide and wets somewhat easier (Table 1). The similarity in the physical and
wet perimeter determined using a perfectly wetting liquid seem to suggest that the
hydroxycarbonate layers deposited on the surface of rolled zinc have a low porosity.
This result would correspond with the many reports of zinc hydroxycarbonates
protecting zinc by forming a low-porosity insoluble lm [38]. Zinc hydroxychloride
coatings appear to wet easily, have signicant porosity and allow droplets to runo
easily. Surfaces consisting of zinc hydroxychloride will wash easily based upon self-
cleaning theory [39], allowing the removal of any soluble salts in the process. The
properties of zinc hydroxysulphate surfaces appear to fall between the extremes of
zinc hydroxycarbonate and zinc hydroxychloride surfaces. The energetic properties
of zinc hydroxysulphates resemble those of the hydroxycarbonates but appear to be
more porous and allow droplets to runo easier.
In addition to rain events, aqueous lms can be formed by water adsorption
processes, which can occur through a variety of mechanisms [40]. Firstly, there is
specically adsorbed water on the surface, which can remain even at low relative
humidity but will only consist of a few moisture layers. The amount of uptake for
adsorption is directly related to (i) the surface area of the material, (ii) the energetics
of the interaction between the surface and water molecules, and (iii) the relative
humidity. Vernon [41] found that the relative humidity in the presence of sulphur
dioxide showed marked increases in corrosion rate of zinc, rstly above 60%RH, and
then at >90%RH. He referred to these as primary and secondary critical humidities.
Secondly, condensation of moisture onto a metal surface occurs when the air tem-
perature drops below the dew point or the when the temperature of a metal is below
that of the air temperature at high humidity [37]. The formation of dew is a common
occurrence and is enhanced by, the presence of surface porosity, increased surface
roughness, surfaces that dissipate heat easily (i.e. thin sheet), and the presence of
impurities that act as nucleation sites for condensation. Clean zinc surfaces have
2350 T.H. Muster et al. / Corrosion Science 46 (2004) 23372354

been reported to result in the formation of evenly distributed dew droplets [42]. The
third mechanism for water adsorption discussed is thought to be the most important.
Highly soluble salts such as MgCl2 and NaCl deliquesce above a critical relative
humidity. That is, they absorb moisture from the atmosphere and dissolve into that
moisture, eventually forming an electrolyte droplet. Due to the ability of chloride
ions to breakdown passive lms, it is the latter method of water uptake that provides
the major threat to the onset of corrosion. Considering that adhesion theories [7]
predict that high-energy surfaces have a higher anity to adsorb and retain par-
ticulate materials, the hydrophobicity of passive lms will almost certainly inuence
real corrosion rates. Therefore, a more hydrophilic surface such as zinc hydroxy-
chloride may be more susceptible to adsorbing hydroscopic salts than a more
hydrophobic surface such as zinc oxide. This assumption is yet to be evaluated.

4.2. The inuence of droplet spreading on corrosion rate

It is commonly thought that hydrophobic surfaces are advantageous for

increasing corrosion resistance, a view that seems to originate from the protective
nature of chromate conversion coatings, which are inherently hydrophobic [4345].
The main advantages being that low-energy hydrophobic surfaces reduce the contact
area between the electrolyte and the metal surface, and that pores are less prone to
aqueous penetration. However, where conversion coatings are required in the ab-
sence of an organic topcoat, highly hydrophilic surfaces may oer advantages in
terms of dispersing salt and increasing evaporation rates. More hydrophobic oxide
surfaces such as stainless steel and chromate coatings have a habit of corroding more
severally in specic locations, and forming colonies of pits around areas of primary
attack [46,47]. To the authors knowledge there have been no comprehensive studies
comparing the aggressiveness of the corrosive environments created in droplets of
varying contact angle in the 10500 ll range. Here we explored the possibility of
using non-ionic surfactant additions to decrease the droplet contact angle and
therefore allow the inuence of wetting on corrosion rate to be explored. Fig. 6
shows the corrosion severity, represented as a mass gain, as a function of both
droplet size and non-ionic surfactant addition. The data suggests that for droplet
volumes greater than approximately 70 ll, more corrosion occurred under the
droplets with no added surfactant (i.e. a surface with poorer wetting properties).
Therefore, whilst an increased corrosion rate may result from a greater oxygen
concentration in the thin lm (increased thermodynamic driving force for the elec-
trochemical reactions [37]), under the present conditions, the increased evaporation
rate of the thin lm was able to reduce the overall corrosion rate. This is not to say
that this trend will hold for variations in metal substrate, droplet chemistry, or va-
pour conditions. Other studies have shown that pitting corrosion is enhanced by thin
lms when compared to the bulk [46], an observation attributed to increased con-
centrations of oxygen and chloride ions. Another related study by Gilbert and
Hadden [48] reported that for a constant total volume of electrolyte, the corrosion
rate of zinc under high humidity conditions increased as the size of the water droplets
decreased. Further studies are required to better understand the dependence of
 T.H. Muster et al. / Corrosion Science 46 (2004) 23372354 2351


Fig. 6. Corrosion severity (mass gain) dependence upon contact angle: ( ) droplets of 1 M NaCl with no
added surfactant placed on rolled zinc, () droplets of 1 M NaCl with a lowered contact angle due to the
addition of 0.1% Tween80 non-ionic surfactant.

corrosion rates on wetting properties, and the way in which surface energy aects the
corrosion mechanisms.

5. Conclusions

The ability of metals to wet has been shown to vary with the chemistry of its
surface oxide. Contact angle determinations using liquid penetration and Wilhelmy
balance techniques were able to systematically rank the oxides in order of their
wetting properties. Naturally forming zinc oxidehydroxide lms appear to be more
hydrophobic than zinc hydroxycarbonates and zinc hydroxysulphates. Zinc hy-
droxychloride oxidation products appear to give zinc the most hydrophilic nature.
The conversion of contact angle data to solid surface energies using various ap-
proaches provided values in the range of 2040 mN m1 for the oxidised zinc sur-
faces. Inverse Gas Chromatography provided insights into the acidbase nature of
zinc hydroxychloride and zinc hydroxycarbonate compounds, but appeared to
overestimate the Lifshitzvan der Waals component of the surface energy.
Data from wet perimeter measurements on passivated zinc plates suggested that
zinc hydroxychlorides and zinc hydroxysulphates possess a greater porosity than
zinc oxidehydroxide and zinc hydroxycarbonate lms. Further work will be re-
quired to verify the eects of roughness and porosity on controlling the wetting
properties of zinc surface oxides.
The ability of zinc to retain droplets on its surface was shown to be a function of
the wetting properties of the surface oxide, the angle of inclination, and the drop size.
Preliminary experiments have shown that thin moisture lms can be less corrosive
than droplets possessing a nite contact angle. A more detailed study is required to
better understand links between droplet form and corrosion rate.
2352 T.H. Muster et al. / Corrosion Science 46 (2004) 23372354

Acknowledgements

Our appreciation is extended to Pon Kao (CSIRO, Manufacturing and Infra-

structure Technology) for his time and assistance with inverse gas chromatography
measurements.

Appendix A. The conversion of contact angle data to surface energy values

Many approaches have been used to convert the information gained from contact
angle determination into estimating the surface energy values of solids. At present,
there are two dominating approaches; those that suggest that the total surface energy
is made up of non-polar (dispersive) and polar (acidbase) components [19,30], and
secondly, those that suggest that the intermolecular characteristics of the liquid play
little part in determining the magnitude of the contact angle, and consequently an
equation of state approach is proposed [28]. The approaches used in this study are
detailed below.
Surface tension components approach 1: Van Oss et al. [30] proposed that the solid
surface energy is a sum of cLVW
s and acidbase contributions, cAB
s , and is related to
the contact angle through Eq. (A.1):
 LVW LVW 0:5   0:5   0:5 1
cs clv cs clv cs clv 2cos h0:5 A:1
where c 
I and ci represent the acid and base energy components, respectively.
Diiodomethane was used as a probe liquid to determine the Lifshitzvan der
Waals net dispersive component of the solid surface energy, cLVW
s using the approach
of Van Oss et al. [30], and is calculated using Eq. (A.2):
2
1 cos hadv
cLVW
s cLVW
lv A:2
4
where cLVW
lv is the Lifshitzvan der Waals net component to the diiodomethane
surface tension.
The acid and base contributions to the surface energy were calculated from the
contact angle data of water and formamide. The values used for the Lifshitzvan der
Waals and acidbase components of liquid surface tensions are given in Table 6.
Surface tension components approach 2: An alternative method for estimating the
polar contributions to the solid surface energy was proposed by Wu [29], where the
non-polar, cdi and polar, cpi contributions to the surface energy could be related to
the contact angle via a reciprocal mean approach to describe the work of adhesion
between two phases:
 d d 
cs clv cps cplv
Wad 4 d cs clv  cdlv 1 cos h A:3
cs cdvl cps cpvl
which was solved using the contact angle data for two liquids with known non-polar
and polar components to their surface tension (i.e. water and formamide).
 T.H. Muster et al. / Corrosion Science 46 (2004) 23372354 2353

Table 6
Surface tension and viscosity data for liquids from Van Oss et al. [30]
Liquid clv cLVW
lv cAB
lv c
lv c
lv g (Pa s)
(mN m1 ) (mN m1 ) (mN m1 ) (mN m1 ) (mN m1 )
Water 72.8 21.8 51.0 25.5 25.5 0.089
Diiodomethane 50.8 50.8
0
0 0 0.028
Formamide 58.0 39.0 19.0 2.28 39.6 0.0455
1-bromonaphthalene 44.4 44.4 0 0 0 0.0489
Cyclohexane 25.0 25.0 0 0 0 0.0895
Hexane 18.4 18.4 0 0 0 0.0298

Equation of state approach 1: Li and Neumann [49] presented an equation of state

approach to calculate solid surface energies based upon combining a modication of
Berthelots rule with experimental data.
r
c 2
cos hY 1 2 sv ebclv csv A:4
clv
where the empirically determined value of b 0:0001247 (m mN1 )2 and hY is
Youngs contact angle.
Equation of state approach 2: A similar equation to (A.4) was later published by
Kwok and Neumann [28], which yields essentially identical values for solid surface
energy:
r
c
cos hY 1 2 sv 1  bclv  csv 2 A:5
clv
where the value of b 0:0001057 (m mN1 )2 .

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