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Surface & Coatings Technology 205 (2010) 928935

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Surface & Coatings Technology


j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / s u r f c o a t

Pre-treatment of Zn surfaces for droplet corrosion studies


N.S. Azmat a,b,c,, K.D. Ralston b,c, I.S. Cole a
a
CSIRO Materials Science and Engineering, Clayton, Victoria, Australia
b
Department of Materials Engineering, Monash University, Clayton, Victoria, Australia
c
ARC Centre of Excellence for Design in Light Metals, Monash University, Clayton, Victoria, Australia

a r t i c l e i n f o a b s t r a c t

Article history: In this work, the signicance of pre-treatment techniques to prepare stable and reproducible surfaces for
Received 30 June 2010 corrosion and coatings studies on zinc-based materials is presented. The stability and consistency of Zn
Accepted in revised form 16 August 2010 surface lms were investigated using chemical and physical pre-treatment methods, whereas the
Available online 20 August 2010
effectiveness of pre-treatments was assessed by water contact angle measurements using droplet proles.
Morphology and composition of pre-treated Zn surfaces were investigated using scanning electron
Keywords:
microscopy (SEM) and energy dispersive spectroscopy (EDS). Chemical etchants, such as HNO3 (acidic)
Zn
Surface pre-treatment
and NaOH (alkaline), were found to be aggressive towards the Zn metal surface and responsible for the
Wettability formation of various oxides of inhomogeneous thickness. Air plasma pre-treatment proved to be effective in
Roughness removal of hydrocarbon contaminants, leaving the surface highly hydrophilic irrespective of the fact that the
SEM-EDS thickness and roughness of native surface oxides remained unchanged. Zn surfaces pre-treated with organic
XPS solvents were found to be hydrophobic in nature in contrast to Zn surfaces pre-treated with abrasives like
SiC paper, which were found to be relatively hydrophobic. Further, SEM-EDS analysis showed contamination
of these surfaces with SiC. As expected the last surface pre-treatment step exerts a large inuence over the
nal characteristics of the surface lm when a number of pre-treatments are applied sequentially to the
same surface. This work demonstrates that Zn surfaces pre-treated with diamond particles of sizes 9, 6, 3 and
1 m show a moderate hydrophobic character. SEM-EDS analysis showed that surface lms prepared via
diamond polishing are uncontaminated. Additionally, surface lm thickness was estimated using Auger
signals produced during X-ray Photoelectron Spectroscopy (XPS). Surface depth proling through depth
sputtering revealed that the surface lm is composed of ZnO and had a thickness of 1.98 nm. Specically, the
objective of this study is to lay the groundwork for future research on Zn corrosion in which consistent and
reproducible surfaces are paramount to produce meaningful results. However, this work may also nd more
general utility in showing how different surface pre-treatments affect surface reactivity and in turn could
impact adhesion to Zn or other metal surfaces.
Crown Copyright 2010 Published by Elsevier B.V. All rights reserved.

1. Introduction of a ne lm of moisture from the central drop appears driven by both


changes in the contact angle and the occurrence of cathodic reactions
Zn possesses a relatively active redox potential and as such Zn at the drop edge [69]. Finally, cathodic reaction rates are highly
coatings are commonly used to prevent corrosion of a substrate dependent on oxygen concentration and thus on the diffusion path
material in various cathodic protection schemes [13]. A major factor length from the air through the droplet edge to the metal surface
promoting Zn corrosion is the deposition of marine and industrial which in turn is dependent on the contact angle [5]. Thus the contact
aerosols from the atmosphere [4]. The dynamics and chemistry of angle directly inuences drop movement, surface cleaning, the
aerosols once they contact the surface are greatly inuenced by the occurrence of secondary spreading and the oxygen concentration in
local contact angle, drop movement/run off, secondary spreading and a drop over a corroding surface.
oxygen diffusion. Drop movement (which promotes surface cleaning) Further, the contact angle and surface energy will be determined
occurs when a drop reaches a critical size and this size is determined by the development of oxides on the Zn surface. A variety of oxides,
by the difference between the receding and advancing contact angle hydroxides and carbonate lms develop when an aqueous solution
of the drop [5]. Secondary spreading which refers to the propagation contacts a native Zn surface. These lms can consist of combinations
of different components and previous studies have shown that the
initial surface products that form on Zn are either ZnO [10,11] or Zn
Corresponding author. Gate 5, Normanby Road, Clayton, Victoria 3168, Australia.
Tel.: + 61 3 95452975; fax: + 61 3 95452059.
(OH)2 [12,13]. However, a dual layer composed of ZnO and Zn(OH)2
E-mail addresses: Nasia.Shahzad@csiro.au, Nasia.Shahzad@eng.monash.edu.au [11,12,14,15] may form and in some instances the layer has been
(N.S. Azmat). reported to consist of two types of ZnO [11,12,14,16]. More recent

0257-8972/$ see front matter. Crown Copyright 2010 Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2010.08.065
N.S. Azmat et al. / Surface & Coatings Technology 205 (2010) 928935 929

work indicates that under a saline drop the most common oxides Table 1
formed on Zn are simonkolleite (Zn5(OH)8(Cl2).H2O), gordaite Pre-treatment methods utilised to prepare the Zn surface.

(NaZn4Cl(OH)6SO4.6H2O), boyleite ((Zn, Mg)SO4.4H2O), and hydro- Pre-treatment code Pre-treatment applied to the zinc surface
zincite (Zn5(CO3)2(OH)6). Simonkolleite and hydrozincite have
T1 Solvent cleaning
signicantly different properties from each other and from ZnO and T2 Physical abrasion
Zn(OH)2 in terms of isoelectric point and wettability [7,17,18]. Thus, T3 Plasma cleaning
small changes in surface oxide chemistry may have a signicant T4 Acid etching
T5 Alkaline etching
impact on the contact angle and surface energy and in turn runoff,
T6 Physical abrasion, diamond polishing, and plasma cleaning
secondary spreading and oxygen diffusion. To protect Zn surfaces T7 Diamond polishing, plasma cleaning
from corrosion, different methods of surface processing and barrier T8 Diamond polishing
coating formation are used which include surface structuring by
monolayer adsorption, ultrathin layer deposition and metal surface
conversion by chemical pre-treatment [19]. 5 min at room temperature. Pre-treatment T5 was carried out by
The important role of and the required surface pre-treatment immersing the Zn metal sample in 1 M solution of NaOH (BDH) for
necessary for the formation of homogeneous surface layers, which can 3 min at 70 4 C. T6 is based on a sequence of three pre-treatment
provide a considerable binding effect for organic coatings and in turn steps and consisted of wet grinding the zinc surface with SiC paper
corrosion protection have been identied [20,21]. Standard industrial (grit 800, 1000, 2400, and 4000) followed by diamond polishing with
surface pre-treatments, such as chromate conversion coatings or Zn- pastes of particle sizes 9, 6, 3, and 1 m and exposure to high RF air
phosphatation [22] are increasingly being replaced by new thin lm plasma for 30 s at an air pressure of 500 mtorr. T7 was a sequence of
conversion treatments to enhance corrosion protection, promote two pre-treatment steps polishing the metal coupons with diamond
adhesion and lower surface roughness [19]. Passivation and corrosion pastes of particle sizes 9, 6, 3, and 1 m followed by exposure to high
resistance of Zn metal are strongly related to the protective nature of RF air plasma for 30 s at an air pressure of 500 mtorr. T8 was
surface oxides; therefore, development of knowledge related to the accomplished by polishing with diamond paste of particle sizes 9, 6, 3
stability of Zn surface oxide lms against various surface pre- and 1 m in blue lubricant (Struers).
treatments is signicant [23].
This work was undertaken to nd a reproducible surface pre- 2.2. Quantication of surface reactivity
treatment for Zn surfaces to be used for subsequent droplet corrosion
studies. To accomplish this objective a detailed characterisation of a The reactivity of Zn surfaces as a function of various pre-
range of surface pre-treatments (physical and chemical) was carried treatments was determined using contact angle measurements. Zn
out to obtain uncontaminated and stable Zn surface oxides of known metal samples, pre-treated with physical and chemical methods
thickness and roughness. The present work was designed to identify (summarised in Table 1), were exposed to a laboratory atmosphere
the surface pre-treatments that lead to the formation of stable and and sessile water contact angle were subsequently measured as a
consistent Zn surface oxides, which will make a surface suitable for function of time for times up to 120 h. The rst reading for the contact
subsequent corrosion studies, with a focus on surface stability, angle was taken 5 min after the pre-treatment due to practical
consistency, efciency, reproducibility, and hydrophobicity achieved limitations. Pre-treated Zn metal coupons were mounted on the
after various pre-treatments. However, more generally this work may motorized stage of an automated goniometer and droplet proles
also prove relevant to organic coating and adhesion studies, with were obtained using a FTA robotics controller equipped with a video
different pre-treatments causing different interfacial energies, which camera and commercial software (FTA32). Contact angle measure-
could have direct consequences for adhesion. In the present work, ments were obtained using high purity water (resistivity N18 M cm
contact angles () were measured as a function of time to assess the and surface tension of 72.8 mN/m at 20 C). Sessile droplets (2 L)
effectiveness of pre-treatments and reactivity of Zn surfaces. were placed on the metal surface at the rate of 0.2 L/s using a
Composition of surface layers was analysed through SEM-EDS and microsyringe (Hamilton, 100 L). Images of the droplet were taken
surface roughness was investigated through non-contact surface using RS170 camera (North American NTSC standard, 60 Hz) with
prolometry, whereas thickness of surface oxide layer was estimated frame grabber (FG4: MuTech MV-510). All measurements were done
through XPS. The results indicate that the objectives of stability, in triplicate and carried out at room temperature (23 1 C).
consistency, reproducibility and moderate hydrophobicity of Zn
surface layers are achievable using trivial yet suitable surface pre- 2.3. FIB-SEM-EDS analysis
treatment techniques.
The possible existence of and the extent of surface contamination
2. Experimental methods i.e., abrasive and dust particles on pre-treated Zn surfaces were
analysed using SEM-EDS. SEM images and EDS compositional spectra
2.1. Preparation of Zn substrates of Zn surfaces were obtained using a Philips XL30 FESEM with a
LinkISIS X-ray analysis system. The FESEM works under continuously
A number of commonly used pre-treatments (chemical and variable accelerating voltage over the range of 0.230 kV and the
physical), presented in Table 1, were utilised to assess the reactivity spatial resolution of instrument is 0.2 m in X, Y plane and 10 nm in Z
of a Zn surface (99.96%, Union Miniere France). The pre-treatment plane. Cross sections of pre-treated Zn metal were obtained through
routines under study are described in the following. Pre-treatment T1 milling of the surface using xT Nova Nanolab200, Focused Ion Beam
consisted of degreasing the Zn surface with acetone (Merck), followed (FIB) miller and SEM system tted with an EDS detector. The FIB used
by scrubbing with detergent (Decon Neutracon), rinsing with high a Gallium Liquid Metal Ion Source (LMIS) working in the range of 5
purity water (resistivity N18 M cm), and nally rinsing with ethanol 30 kV and had a spatial resolution of b1.0 nm at 30 kV, 1.1 nm at
(CSR). Pre-treatment T2 was carried out by progressive mechanical 15 kV and 2.5 nm at 1 kV. The resolution for ion milling was 7 nm at
wet grinding of the Zn surface using SiC paper (grit 800, 1000, 2400, 30 kV and 1 pA. The instrument is equipped with three gas injection
and 4000). Pre-treatment T3 was carried out in a plasma chamber systems which consist of Pt deposition, I2 enhanced etch and SiO2
(Harrick); metal samples were exposed to air plasma at 500 mtorr air deposition. The gas precursor used for the Pt deposition was (CH3)3-
pressure for 30 s at high radio-frequency (RF). T4 was performed by CH3C5H4Pt. A thin platinum strip (1 m in thickness) was deposited
immersing the Zn metal sample in a 10% HNO3 (Fluka) solution for on the pre-treated Zn surface at 0.3 nA (30 kV) as a protection layer
930 N.S. Azmat et al. / Surface & Coatings Technology 205 (2010) 928935

experiment the base chamber pressure was kept at approximately


5 1010 mbar during data acquisition. The samples were xed on the
standard VG Escalab holder stub supported by an XYZ manipulator.
The surface was irradiated with Mg K (1253.6 eV) X-rays incident at
an angle of 90 with respect to the surface normal. X-ray excited
photoelectron and Auger electron spectra were recorded using VG
310F Scanning Auger Microscope. XPS spectra were recorded for C 1s,
O 1s and Zn LMM spectra at pass energy of 20 eV. Depth sputtering
was performed using an Ar+ beam at an energy of 3 keV with a
current density of 3 /cm2.

3. Results

3.1. Surface reactivity as determined using water contact angle


measurements
Fig. 1. Water contact angle vs. time after applying various methods of surface pre-
treatment to Zn metal. The reactivity of Zn surfaces after various pre-treatments has been
assessed using water contact angle measurements. To investigate the
for the subsequent milling. The milling was performed with a beam of stability and consistency of pre-treatment methods, contact angle
Ga2+ ions using an accelerating voltage of 30 kV and a milling current data has been plotted as a function of time in Fig. 1. Solvent cleaning
of 3 nA. was observed to have no signicant effect on wettability of Zn
surfaces, as the contact angle remained relatively unchanged (101
2 deg) with time.
2.4. Measurement of Zn surface roughness
Physical abrasion does not cause signicant changes in the contact
angle, as the rst value was found to be (74 1 deg) and values were
Roughness is an important surface feature that may inuence the
observed to increase slowly with time to approximately 97 deg.
apparent corrosion rate by varying the effective surface area.
Plasma cleaning produced comparatively lower contact angle (28
Therefore, surfaces used for atmospheric studies should have
2 deg) which reaches near saturation in the rst 56 h and then
standardised surface roughness. Surface roughness and waviness
continues to saturate slowly over the whole time scale. Consequently,
were measured using a 3D non-contact AltiSurf 500 prolometer
constant values in the contact angle have not been observed in the
tted with built in softwares (Altisurf and AltiMap). A beam of white
case of plasma cleaning.
light (quartz halogen) was focused through a lens onto the Zn surface,
The wettability of Zn surfaces after immersion in acid etchant
which displays a high level of axial chromatic aberration. Line proles
indicates that a relatively lower contact angle (25 3) which
were recorded after each polishing step (9, 6, 3, and 1 m) using
increases with time-eventual contact angle stability was not observed.
300 m probe which has a spatial resolution of 0.5 m and a depth
Optical images taken after acid etching show the modication of the
resolution of 10 nm. Line proles of these surfaces were recorded at a
Zn surface chemically i.e. the Zn surface is covered by various oxides
frequency of 1000 Hz using spacing of 1 m.
(Fig. 2a). Similarly, after alkaline etching a comparatively lower
contact angle (52 1) has been obtained but the Zn surface is
2.5. Determination of oxide chemistry and thickness modied chemically (Fig. 2b).
Pre-treatments T6 (physical abrasion, diamond polishing, and
To minimize the number of variables and complexity involved in plasma cleaning) and T7 (diamond polishing and plasma cleaning)
atmospheric corrosion experiments, it is necessary to have consistent show similar trends. In the case of pre-treatments T6 and T7, the
and reproducible starting surface oxide chemistry. The composition of initial contact angles were 20 3 deg and 26 1, respectively. A
native Zn surface oxides was investigated using XPS depth proling relative stability in the contact angles was observed after 20 h in both
through depth sputtering. As a complimentary investigation, the the T6 and T7 pre-treatments. Furthermore, Zn surfaces pre-treated
thickness of native surface oxides was estimated using Auger signals with a diamond polish demonstrate quick saturation of the contact
which may have some effect on setting the surface energetics. In this angle at ~64 2 deg within 5 h of pre-treatment.

Fig. 2. Chemically modied Zn surface after immersion in 10% HNO3 solution (a), 1 M NaOH solution at 70 4 C (b).
N.S. Azmat et al. / Surface & Coatings Technology 205 (2010) 928935 931

3.2. Contamination of the Zn surface papers are routinely used for surface preparation of a number of
materials and contamination with SiC and the possible impact on
Zn surfaces which have a favourable hydrophobic character must subsequent surface interactions is not widely appreciated. In contrast,
be clean enough to carry out subsequent corrosion experiments. The Fig. 4 suggests that the Zn surfaces prepared using routine T8
word clean means free from grease, oils, oxides, dust, and abrasive (diamond polishing) are contamination free or at least free of SiC
particles. Therefore, a contamination free Zn surface is desired for contamination. Obviously the presence of embedded SiC particles
atmospheric corrosion studies to limit the number of complicating could have an impact on droplet spreading and may generally
variables involved. SEM-EDS analysis (Fig. 3) reveals that Zn surfaces interfere with atmospheric/aerosol studies which inherently involve
pre-treated using routines T2 (physical abrasion) and T6 (physical on small length scales. As a compliment, 0.55 m deep cross sections
abrasion, diamond polishing, and plasma cleaning) are contaminated of polished Zn surface was analysed through FIB-SEM milling and no
with embedded SiC particles from the grinding papers. SiC grinding deformation was observed in the grain structure.

Fig. 3. SEM-EDS analysis of the Zn surface contaminated with SiC particles.


932 N.S. Azmat et al. / Surface & Coatings Technology 205 (2010) 928935

Fig. 4. .SEM-EDS analysis of Zn surface pre-treated with diamond particles.

3.3. Roughness of Zn surface oxide polish with only small decreases in roughness after polishing with 3
and 1 m. Not surprisingly experimental results show a gradual
Standardisation of surface roughness is necessary for subsequent decrease in roughness Ra and increase in smoothness of the zinc
corrosion work to limit the number of variables involved and thus surface after each polishing step i.e. 9, 6, 3 and 1 m diamond paste.
help simplify interpretation. The roughness data has been sum-
marised in Table 2. Surface roughness measured through non-contact 3.4. Chemistry of Zn surface oxide
surface prolometry (Fig. 5) demonstrates a gradual decrease in the
roughness of Zn surfaces prepared using routine T8 (diamond The exact chemistry of a surface oxide will impact droplet-surface
polishing). These results are not altogether surprising in trend but interactions as previously described. As such the creation of a
do show a rather dramatic change in surface roughness after the 6 m standard reproducible surface oxide is a paramount prerequisite to
N.S. Azmat et al. / Surface & Coatings Technology 205 (2010) 928935 933

Table 2 Table 3
Roughness and waviness of the Zn surface pre-treated with diamond particles (pre- Atomic ratios of chemical species present on the outer surface layer of polished Zn
treatment T8). metal relative to the total concentration of O (X/O).

Zinc surface nish Roughness (Ra) m Waviness (Wa) m Chemical species Atomic ratio Tentative assignment

Unpolished 0.556 0.204 Zn 0.327


9 m diamond paste 0.471 0.275 O 1.000
6 m diamond paste 0.066 0.051 C1 + C2 1.069 CHx (hydrocarbon)
3 m diamond paste 0.043 0.010 C3 0.153 CO
1 m diamond paste 0.032 0.006 C4 0.002 C=O
C5 0.137 OC = O

a systemic study on aerosol chemistrysurface interactions. Taking interpretation. Therefore, in order to perform meaningful droplet
this into consideration, the composition of outer surface layer corrosion studies we need reproducible surface conditions. Given the
(Table 3) and thickness of the surface lm present on a polished Zn small size of aerosols any variation in the initial surface conditions
surface were characterised by XPS depth proling through depth may cause signicant differences in results and interpretation.
sputtering. Fig. 6a shows the Zn LMM Auger signal [24,25] in the XPS The following surface conditions are necessary for a consequential
spectra of a polished Zn surface as a function of etch cycle. The study of dropletsurface interactions:
thickness of surface oxide layer can be estimated using the following
o A constant contact angle throughout the period of experimenta-
expression [26]:
tion which helps eliminate the effects from a changing contact
I = I0 expd = 1 angle with surface exposure time.
o Minimization of surface contaminants and deformation of grain
structure to prevent subsequent interactions and variation in
where I is the intensity of the XPS signal for the ZnO peak, I0 is the
surface properties. The most effective way to accomplish this is to
intensity of the XPS signal for the pure Zn metal peak, stands for
minimize the level of contamination (a higher level of contami-
electron inelastic mean free path and d stands for the thickness of the
nants may result in a higher contact angle) and maintain the
ZnO layer. This expression allows the calculation of layer thickness,
surface grain structure constant.
provided the layers are less than ~3 thick [26]. The value of electron
o Constant chemical composition of the initial surface oxides.
inelastic mean free path of ZnO calculated for Zn LMM using the
o Reproducible surface roughness to avoid variation in effective area
TPP-2 M formula is 2.0 nm [27]. Fig. 6b and c shows the determination
which would impact perceived corrosion rate.
of Io and I from the XPS spectrums of pure Zn metal and oxidized Zn
metal, respectively. The value of I0 corresponds to the peak height of Applied surface pre-treatment can exert a large inuence on
pure metal after the removal of carbon and the oxide. The value of I is surface features such as hydrophobicity, level of contamination, oxide
the height of the zinc oxide peak at a time at which the oxygen signal chemistry and roughness. Therefore, standardisation of the Zn surface
is maximised (Fig. 6c and d) and carbon decreased below 10% of the is desired and necessary for future corrosion studies on the effect of
initial value (17th etch cycle after 1852 s as shown in Fig. 6e). industrial and acidied marine droplets (aerosols).
To achieve the rst objective Zn surfaces need to be moderately
4. Discussion hydrophobic so that droplets can sit for hours without a considerable
change in the contact angle. Therefore, the reactivity of the Zn surface
The contact angle between the droplet edge and Zn surface is an was tested against various physical and chemical pre-treatments.
important parameter which may affect drop movement, the occur- Wettability measurements have indicated that chemical pre-treat-
rence of secondary spreading and the oxygen concentration in a ments (acidic and alkaline) are capable of a reasonable reduction in
droplet. Contact angle is readily inuenced by the surface conditions the contact angle but at the same time are responsible for introducing
such as oxide chemistry, roughness and the level of contamination undesirable side effects by altering the Zn surface chemically as
these may impact corrosion rates. There is a signicant number of various oxides of variable texture appear on the surface (Fig. 2).
variables involved in droplet corrosion studies e.g. drop chemistry, Results indicate that air plasma pre-treatment is able to remove
drop size and pH. However, if possible it is desirable to limit the hydrocarbon contamination leaving the surface highly hydrophilic
number of variables associated with the substrate to help simplify and leads to lower contact angles, which increase with time.

Fig. 5. Gradual decrease in surface roughness (Ra) of Zn polished with diamond particles of various sizes (9, 6, 3 and 1 m).
934 N.S. Azmat et al. / Surface & Coatings Technology 205 (2010) 928935

Fig. 6. a. XPS Zn LMM spectra of the Zn surface pre-treated using T8 routine: Oxidized Zn at 1st etch cycle after 10 s, (b) pure Zn metal at 77th etch cycle after 46,715.9 s. b. XPS Zn
LMM spectrum of pure metal demonstrating the calculation of I0 for Zn surface pre-treated using T8 routine. c. XPS Zn LMM spectrum of oxidized metal demonstrating the calculation
of I for Zn surface pre-treated using T8 routine. d. XPS spectrum demonstrating the maximised oxygen signal at 17th etch level after 1852 s for Zn surface pre-treated using T8
routine. e. XPS C 1s spectra showing the removal of C from the Zn surface pre-treated using T8 routine.

Wettability results do not show a consistent contact angles over a As a tentative conclusion, diamond polishing is capable of producing
certain period of time, which makes this pre-treatment, unsuitable for moderately hydrophobic Zn surface which makes this pre-treatment
droplet corrosion experiments. suitable for droplet corrosion experiments.
With consideration to the physical pre-treatments, solvent clean- SEM-EDS analysis carried out on the Zn surface polished with
ing only removes grease and oils but does not change the diamond particles does not show any contaminant present on the
hydrophobicity as evident from the contact angle measurements surface (Fig. 4). Further, cross-sectional analysis of polished Zn surface
(101 2). Solvent cleaning has no effect on the contact angle or through FIB-SEM does not show any distortion in the grain structure
reducing the surface roughness. Physical abrasion with SiC paper does which is encouraging evidence in regards to the second objective of
not indicate consistency in the contact angle and SEM-EDS analysis minimizing the variation in contamination levels on the surface and
shows that SiC particles are responsible for the contamination of Zn maintaining a constant surface grain structure.
surface lms (Fig. 3). Auger signal in XPS depth proling through depth sputtering were
Wettability results indicate that in sequential pre-treatments (no. utilised to examine the chemistry and thickness of native Zn surface
of pre-treatments applied in a series) the general behaviour of the oxides developed after diamond polishing. Analysis of the Zn 2p
surface depends on the last step, therefore the trend of contact angle photoelectron spectra does not distinguish between Zno and Zn2+
growth is similar in diamond polish followed by plasma cleaning and species [28]. Similarly, the O 1s photo-peak alone cannot be reliably
grinding followed by polishing and plasma cleaning. Both of these used for this purpose [15,29,30] due to the presence of oxygen
pre-treatments are not useful in achieving the goal of moderate containing hydrocarbons contamination. However, the Zn LMM Auger
hydrophobicity and cleanness as consistency in the contact angle is signal [24,25] can be used when the difference between the kinetic
not observed. energies of the metallic (261.1 eV) and oxidized (265.9 eV) zinc is
Zn surface prepared by polishing with diamond particles (9, 6, 3 more than 4 eV [25]. Given the reported range of ZnO thickness on
and 1 m) demonstrated efcient evolution of contact angles polished surfaces (1.52.5 nm [31]), this appears to be a reasonable
eventually saturating at 64 2 degrees, which reects the stability, estimate for our purposes. As the surfaces are moderately hydropho-
and moderate hydrophobicity of surface oxides. Additionally, bic and covered by a thin layer of adventitious hydrocarbons,
diamond polishing reduces the preparation time considerably as the consideration of the role hydrocarbon contamination plays in the
saturation in contact angles in achieved within 5 h of pre-treatment. signal attenuation is necessary. XPS depth proling results indicate
N.S. Azmat et al. / Surface & Coatings Technology 205 (2010) 928935 935

that the Zn surface pre-treated with diamond particles is covered with smoothness. Finally, the abrasive particles like SiC may contaminate
a very thin layer of ZnO having an estimated thickness of 1.98 nm the surface oxide lms.
which is in excellent agreement with literature [31].
Roughness is an important surface feature which can be Future work
responsible for varying corrosion rates depending upon surface
nishing conditions. For our purpose Zn surface roughness not only We are able to prepare a stable and reproducible Zn surface by
needs to be constant for droplet corrosion studies but also an polishing with diamond particles (9, 6, 3, and 1 m) which will be
important parameter to consider for the volume loss studies after used to study atmospheric corrosion of Zn under droplets of various
corrosion experiments. Smooth surface is a pre-requisite for recording sizes and chemistries. These surfaces will enable us to place stable
3D proles of the Zn surface acting as a base line. Gradual polishing of droplets (with no considerable change in contact angles) for 612 h so
the Zn surface with diamond particles decreases the surface that we can compare laboratory work with the eld exposures where
roughness (Ra) considerably, which makes it suitable to act as a marine and industrial droplets/aerosols can exist for 212 h depend-
base line in volume loss measurements (Fig. 5). ing on the day/night cycles and atmospheric conditions.
It has been demonstrated that the Zn surface polished with
diamond particles is highly suitable for droplet corrosion experi-
Acknowledgements
ments. Diamond polishing is proved to be an efcient method of
surface preparation which makes the Zn surface stable, consistent,
We would like to thank John Ward (CSIRO Materials Science and
and moderately hydrophobic with a negligible level of contamination.
Engineering) for his time and assistance with SEM-EDS and
In addition, the surface features, e.g. surface chemistry and roughness
prolometry work.
have also been standardised so that variation in surface conditions can
be minimized for subsequent droplet corrosion experiments.
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