Corrosion Science, Vol. 35, Nos 14, pp. 791-800, 1993 0010-938X/93 $6.00 + 0.

00
Printed in Great Britain. © 1993 Pergamon Press Ltd

IN SITU SYNCHROTRON RADIATION X-RAY

TECHNIQUES FOR STUDIES OF CORROSION AND
PROTECTION

J. ROBINSON* and F. C. WALSHt

* Department of Physics, University of Warwick, Coventry CV4 7AL, U.K.

t Chemistry Department, University of Portsmouth, Portsmouth PO1 2DT, U.K.

Abstract--The importance of synchrotron radiation X-ray diffraction (XRD) and X-ray absorption
spectroscopy (XAS) as probes for the characterisation of corrosion products, surface films and protective
layers is emphasised. In many cases, in situ studies may be carried out to elucidate structural information
about the surface of an electrode in the presence of an intact surface film and the electrolyte under
controlled potential conditions. The versatility of these X-ray techniques in corrosion and protection is
illustrated by the following systems (and X-ray techniques): the phase composition of phosphate coatings
on carbon steel (ex situ XRD), phase transformation of lead dioxide films in 1 M H2SO4 during potential
cycling (in situ XRD) and the structure of passive films on iron in 0.1 M NaCIO4 at constant potential (in
situ XAS).

INTRODUCTION
ADVANCESin our knowledge of corrosion mechanisms and the protective properties
of surface layers or coatings on metals critically depend upon reliable data concern-
ing the metal/electrolyte interface. Traditionally, such information has been ob-
tained via two routes, namely the application of electrochemical methods and
surface spectroscopy techniques. A wide range of powerful electrochemical methods
is available including steady state voltammetry, current and potential step tech-
niques, and frequency response analysis, while rapid developments are taking place
in microelectrode techniques and the implementation of microcomputer instrumen-
tation for the control of experiments together with the acquisition and analysis of
data.
Despite their importance, electrochemical techniques provide only indirect
information on surface structure and it is essential to utilise complementary surface
techniques in order to obtain a balanced view of the physical and chemical effects
which accompany corrosion or the formation/breakdown of protective layers. In
addition to conventional microscopy, a vast array of 'beam' techniques has been
developed over the last two decades. Indeed, the combination of electrochemical
and spectroscopic techniques has resulted in the development of both classical and
novel spectroelectrochemical methods. The majority of these techniques utilise
optical, electron or ion beam irradiation, while the probes include optical, X-ray and
mass spectroscopy devices. Despite the power of these techniques, their application
is limited in some cases by the relatively small degree of information provided on
direct and quantitative surface structure. In addition, the frequent need for high
vacuum conditions greatly restricts the study of realistic electrode/electrolyte en-
vironments and raises the spectre of phase transformation between the electrolyte
environment and the high vacuum chamber of the spectrometer.
791
792 J. ROBINSONand F. C. WALSH

X-Ray techniques provide a particularly important series of structural tools for

electrode studies. 1-3 For example, X-ray diffraction (XRD) can provide information
on phase composition, preferred orientation and texture; X-ray absorption spectro-
scopy (XAS) is capable of yielding information on bond distances, oxidation states
and coordination numbers. These two techniques are therefore complementary in
providing structural information regarding long- and short-range order at a metal
surface. X-Ray techniques may be utilised for in situ studies which permit the surface
to be examined in the presence of an electrolyte film and under controlled potential
conditions. This facilitates the study of dynamic changes under more realistic
environmental conditions. In order to exploit these advantages, however, it is
necessary to pay adequate attention to the design of the electrochemical cell and
to the instrumentation required for synchrotron radiation studies. The use of
such radiation necessitates access to a central facility but provides the critical
advantages of a high degree of penetration through electrolyte films and a choice of
wavelength or energy dispersive geometries. In the field of corrosion and protection
of metals, a recent survey has shown the developing importance of these X-ray
techniques. 4
In this paper, the use of synchrotron radiation X-ray techniques is illustrated by
data taken at the U.K. synchrotron radiation source (SRS) at the SERC Laboratory,
Daresbury.

PHOSPHATE LAYERS ON CARBON STEEL

The formation of protective phosphate coatings on steel is routinely applied as a
pretreatment technique prior to the application of organic paint coatings, particu-
larly for automotive finishes. 5'6 The mechanism of phosphating is complex and
involves the time-dependent interplay of several chemical and electrochemical
processes. The result is a thin (typically 0.2-5/~m) coating which contains two major
phases corresponding to hydrated forms of insoluble tertiary metal phosphates:
hopeite, Zna(PO4)2" 4H20 and phosphophyllite, Zn2(Fe,Mn)(PO4)2.4H20.
It is generally accepted that the structure and phase composition of the phosphate
layer plays a pivotal role in the protective properties of the resultant coating system.
Hence, several groups have attempted to correlate the proportion of hopeite and
phosphophyllite with corrosion resistance. 7's For example, Miyawaki and
co-workers7 have suggested that the ratio P / P + H is a useful figure of merit, where
P = intensity of diffraction from the (100) plane of phosphophyllite at an interplanar
(d) spacing of 8.84 ~ and H = that from the (020) place of hopeite at d -- 9.04 ,~. The
application of such a simple figure of merit has proved controversial and often
inappropriate. 8'9 However, it is essential to determine the phase composition in
order to progress understanding of this coating system.
X-Ray tube radiation (typically using a chromium or copper target) has been used
by many workers. 7'9 It suffers, however, from long data acquisition times and is not
capable of yielding rapid, high quality powder diffraction data from modern
automotive phosphate coatings which are often thin (typically 0.2-1 gm), particu-
larly in the early stages of deposition.
The electrolyte used in this investigation was a commercially available phosphat-
ing solution (Granodine 6005) based upon zinc phosphate and phosphoric acid. The
freshly prepared solution also contained manganese, together with nitrate and nitrite
accelerators, and was operated at a temperature of 45°C. The (0.45%) carbon steel
 Synchrotron radiation X-ray techniques for corrosion studies 793

12 I i I ] I I

10
° ,

\
'~o 8
0.2
x
6
I---
Z E

~ ,~ _
t.J

1.0 V - - - - - L~A'--~ ~

f I , I

0 5 10 15 20 25 30 35
2e/deg
FIG. 1. Ex situ XRD pattern from a steel surfacewhich has been phosphated at controlled
potentials (vs SCE) for 5 min.

was wet polished on 600 grade silicon carbide paper before use. Coatings were
produced by immersion of 20 mm x 100 mm x 1 mm panels. The freshly prepared
phosphate layers were washed in distilled water, air dried and then desiccated before
X-ray diffraction studies. Powder X R D data was taken on Station 9.1 of the SRS
using a fixed 8° angle of incidence and monochromatic radiation (2 = 1.005 ,~).
Diffraction patterns were typically obtained in approximately 45 min over a scatter-
ing angle (20) range of 5-60 ° using a scanning diffractometer equipped with a solid
state detector.
Anodic polarisation studies showed a complex current vs potential
relationship, 1° which displayed a marked sweep rate dependence. Rapid changes in
the current may be attributed to dissolution/precipitation and recrystallisation
effects within the phosphate layers. The reverse potential sweep shows that the
anodic formation of phosphate is an irreversible process and the films were stable in
air, facilitating a study of the dry films intact on the mild steel. The complex
behaviour shown by the present solution precludes any simple analysis (in contrast to
report studies on synthetic electrolytes. 11
The effect of controlled potential deposition on the XRD pattern is shown in
Fig. 1. The application of potentials more positive than the open circuit value
[ca - 0 . 6 0 V(SCE)] resulted in higher diffraction intensities from phosphophyllite
planes with a decrease in those due to hopeite. In fact, the use of a wide range of
potentials [ - 0 . 1 to +1.6 V(SCE)] allowed a wide range of P / P + H ratios to be
obtained, from pure hopeite at very negative potentials (P ~ zero) to pure
phosphophyllite ( H -+ zero) at very positive potentials. 10 Thus, cathodic protection
of the steel prevents dissolution of the surface and favours hopeite, which is formed
from solution-phase zinc ions.
It was also possible to apply partial cathodic protection by galvanic coupling of
the steel to pure zinc sheet having the same area. As Fig. 2 shows, the steel shows a
higher hopeite level than in the case of open circuit samples; the corresponding zinc
794 J. ROBINSONand F. C. WALSH

20 [ 1 I r i i

15 m

o
g
x

-g8
0
L.J
~o
~ ,~o

~ N

-/x__._
[ I

5 10 15 20 25 30 5
2O/deg
FIG. 2. Ex situ XRD patterns of a steel surfacefollowinggalvaniccouplingof steel and zinc
for 5 min in a phosphatingsolution, showingthe presence of both hopeite and phosphophyl-
lite.

sample showed only hopeite. It is clear from these results that electrode potential is a
major variable which affects the control of phase composition and that synchrotron
radiation provides a powerful analytical tool for these thin coatings.

PHASE TRANSFORMATIONS IN LEAD DIOXIDE/LEAD SULPHATE FILMS

Lead dioxide surfaces are widely used in electrochemical technology as positive
electrodes in the lead-acid battery and as anodes in electrosynthesis cells. 12 In
sulphuric acid, potential cycling of lead dioxide to lead sulphate has been extensively
studied using a wide variety of electrochemical techniques 13'a4 and by ex situ
XRD. 15'a6 In order to follow the structural changes under realistic conditions,
however, it is necessary to apply an in situ technique.
In situ X R D studies were carried out on Station 7.4 of the SRS and more detailed
information about the instrumentation is provided elsewhere, tT'xs Data were
acquired in the reflection mode using X-ray radiation with a wavelength of 1.307/~
and an incident angle of 4 ° with a data collection time of 10 min. A 120 ° CPS detector
facilitated continuous acquisition of data over a wide scattering angle (20) range. The
purpose-built cell utilised a 6 mm diameter platinum disc working electrode which
was precoated with a lead oxide film. Lead dioxide was deposited from an aqueous
solution of 0.1 M lead nitrate at a temperature of 298 K and at controlled pH. 19,20A
special feature of the cell was the ability to perform electrochemical changes in the
presence of a thick electrolyte film by gently expanding the flexible 'cling-film'
window via an increased electrolyte pressure. For X-ray studies, however, the
window was collapsed to leave a thin (typically 100 pm) electrolyte film in order to
minimise problems with X-ray absorption and scatter.
Cyclic voltammetry of an a-PbO2 layer 2° (deposited on platinum with a charge
density of 2.15 C cm-2) in 1 M H2SO4 revealed a well defined cathodic peak which
had an associated charge density of 0.16 C cm -2, corresponding to only a 7%
 Synchrotronradiation X-ray techniques for corrosion studies 795

5"01 ' O~ I I i I

N 2.0
- - Pt~

o~I'01 ~
0 -- i- -I I
20 25 30 35 L.O ~.5
2e/deg
Fro. 3. XRD patterns of a lead dioxidefilmon platinum. (a) Ex situ, freshlyprepared film
of a-PbO2. (b) In situ at the open circuitpotential in 1 M HzSO4. (c) In situ after steppingthe
potential to 1.25 V(SCE). (d) In situ after reoxidation at 1.55 V(SCE). a, a-PbO2; fl,
fl-PbO2; S, PbSO4.

reduction of the PbO2. On the reverse scan, only a small anodic current was
observed, showing that reoxidation of the PbSO4 is a slow process under these
conditions. On the second and third cycles, the peaks all diminished, showing a
growing reluctance for the PbSO4 to reoxidise. Potential step experiments showed
that holding the potential at 1.55 V(SCE) resulted in significant oxidation and
reduction currents. In view of the slow phase transformations and the lack of
information about structure from voltammetry, a series of in situ experiments were
carried out under potential step conditions.
Figure 3(a) shows an in situ X R D pattern of the freshly deposited film on the Pt
and it is clear that the a-PbO2 phase predominates. When this film was held at the
open circuit potential [1.34 V(SCE)] in sulphuric acid, self-discharge reactions
occurred and additional PbSO4 peaks are evident [Fig. 3(b)]. In the present
experiments, the lead oxide film was put through a controlled potential sequence.
When the electrode was stepped to 1.25 V, the PbSO4 content increased [Fig. 3(c)].
Finally, the film was stepped to a potential of 1.55 V and held there for 15 min. The
diffractogram obtained [Fig. 3(d)] shows the appearance of fl-PbO2, while the
a-PbO2 and PbSO4 peaks diminish. A single reduction/oxidation cycle has resulted
in the conversion of a- to fl-PbO2 and demonstrates the incomplete reversibility of
the PbO2/PbSO4 couple, the limited extent to which the PbO2 film is reduced and a
slow rate of conversion of PbSO4 to P b 0 2 at a potential of 1.55 V.
A second series of experiments investigated more extensive phase changes. A
sequence of 50 potential steps between the potential limits of 0.65 and 1.55 V was
undertaken. The resulting diffraction patterns (Fig. 4) demonstrate the progressive
transformation of a-PbO2 to fl-PhO2 such that the K-phase can hardly be detected
after the 20th cycle. A closer inspection of the data (and visual observation of the
electrode) shows that the film is damaged by this treatment; some cracking occurs
and the Pt substrate peaks are more evident. 2°

PASSIVE OXIDE LAYERS ON IRON AND IRON/CHROMIUM ALLOYS

The passivity of iron and its alloys is of both fundamental and technological
importance in corrosion science. Unfortunately, the thin. amorphous nature of such
796 J. ROBINSONand F. C. WALSH

10
./3 ' /3 '_ Pt I I D I
tY 8
.,a:

v)
l.--
Z 6 . s s ~ P~ ss p~ ~ e~
._.m,
0

4
v3

2 sss~ J[ Pt (~ (b.)-
¢.y
0
Z
o
i i I I
20 25 30 35 /,0 /*5
2eldeg
FIG. 4. XRD patterns for an a-PbO2 layer on platinum. (a) Ex situ after preparation.
(b) In situ at the open circuit potential in 1 M H2SO4. (c) In-situ after reduction at
0.65 V(SCE). (d) In situ after reoxidationat 1.55V. (e) In situ after fourth potential cycleat
0.65 V. (f) In situ after fourth potential cycleat 1.55 V. (g) In situ after the twentieth cycle
at 1.55 V.

passive films and their lack of long-range order renders analysis difficult. Consider-
able progress has been made via the application of ex situ techniques such as electron
diffraction and X-ray photoelectron spectroscopy. However, such techniques
necessitate removal of the sample from the normal electrolyte to an ultra high
vacuum. Such a transfer, which results in a loss of the electrode/electrolyte interface
and loss of potential control, inevitably leads to both chemical and structural
changes. Consequently, doubts always exist concerning the relevance of the analysis
obtained.
The possibility of using ex situ EXAFS (extended X-ray absorption edge fine
structure) to probe the structure of a passive film on iron was demonstrated in 1982. 21
Subsequent in situ investigations, e.g. Ref. 22, have shown qualitative changes in the
EXAFS spectra due to the passivation, but a detailed structural analysis has been
precluded by a relatively poor signal-to-noise ratio and the contribution of unpassi-
vated metal to the EXAFS. Early attempts at a structural analysis 21 indicated F e - O
bond lengths which were intermediate between those of 7-Fe203 and y - F e O O H . The
authors proposed that the film was not a stoichiometric oxide or hydroxide and that
water was incorporated into the passive layer. Recently Kerkar et a/. 23'24 have
undertaken a more detailed investigation and their findings are reviewed here.
The samples used were prepared by thermal evaporation of 10-20/~ iron, under
vacuum, onto a 23/~m Mylar film, using a gold interlayer to promote good electrical
contact and satisfactory adhesion. The cell design 24 utilised the working electrode as
a window, through which the incident X-rays (7 keV) entered (and fluorescent X-
rays left) the cell in order to minimise absorption in the electrolyte. The secondary
electrode was a platinum gauze and a saturated calomel reference electrode (SCE)
was mounted in a separate compartment. An important feature of these studies is the
use of thin iron (and F e - C r ) films which completely passivate and hence remove any
complications due to the contributions of the Fe substrate to the EXAFS, together
with a detection system which discriminated against scatter from the electrolyte.
I n situ XAS spectra at both the Fe and Cr K-edges were recorded for Fe and
F e - C r alloys (up to 25% Cr) electrochemically passivated in 0.1 M NaC104. Samples
 Synchrotron radiation X-ray techniques for corrosion studies 797

i I ' I ' I ; I

30-

20

10

5 7 9 11
k/~ -1
Fie. 5. k 3 weighted Fe K-edge EXAFS spectra of: (a) passive film on Fe at 0.8 V(SCE) in
0.1 M NaCIO4: (b) a-FeOOH: (c) 7-FeOOH; (d) a-FezO 3.

were mounted in the cell and were cathodised at negative potentials to remove any
air-formed oxide. Prior to anodisation, the cell was flushed with clean electrolyte,
whilst maintaining the electrode potential and purging with argon, in order to
eliminate any ferrous ions that had been introduced into the solution by the cathodic
pretreatment.
The XAS spectra were obtained on Station 8.1 at the SRS, Daresbury. The
monochromator on this station was a double crystal instrument with a bent first
crystal and a post-monochromator Pt-coated mirror to provide a high photon flux at
the sample. The spectra of model compounds were obtained in the conventional
transmission mode whilst fluorescence detection, with a 13 element solid state Ge
(Canberra) detector, was used for the passive films. The fluorescence yield XAS
spectra of the passive films were obtained by mounting the cell vertically at an angle
of about 45° to the incident X-ray beam and positioning the detector in the plane of
the storage ring making an angle of 45 ° to the sample. For good quality spectra,
suitable for EXAFS analysis, typically about eight identical scans, each of 45 min
duration, were inspected then summed prior to analysis.
XANES (X-ray absorption near edge structure) spectra at the Fe K-edge of an
electrochemically passivated Fe film showed that the spectrum for the passive film
was more like that for the oxyhydroxides than the oxides. These results therefore
lend support to the idea that the passive film has a structure like that of an
oxyhydroxide.
Figure 5 shows k 3 weighted EXAFS spectra of an iron sample passivated at 0.8
V(SCE) in 0.1 M NaC104 (as well as spectra for a number of model compounds).
Again, the similarity appears to be closest between the data for the passive film and
oxyhydroxides, though the passive film shows less long-range order.
In the original study, 23 Kerkar et al. found that to fit the EXAFS of the passive
films two shells were required, involving six oxygen atoms at 2.01 A and six iron
atoms at 3.02 ,~. These shell radii do not of themselves permit easy identification of
798 J. ROBINSON and F. C. WALSH

i I I I i I

20

/, 5 6 7 8 9 10
k/~-1
FIG. 6. Fourier filtered EXAFS spectra for the passive film. (a) Compared to the
calculated contribution to the EXAFS of the first two shells. (b) a-FeOOH. (c) y-FeOOH.

the structure. In most iron oxides and oxyhydroxides, the basic building unit is an
octahedron of oxygen atoms surrounding the iron centre and therefore the radii of
the first shells are very similar. Whilst the radii of the second shells range from 2.95 ,~
for a-Fe203 to 3.08 ~ for y-FeOOH, the greatest variation occurs in the third shell.
This arises from the different ways the FeO6 octahedra are joined to form the
extended three-dimensional structure. For the a-oxyhydroxide, and both forms of
the oxide, there is a shell containing iron atoms at between 3.3 and 3.5 & from the
absorber, and its presence is clearly observed in the EXAFS. For the y-oxyhydroxide
no such shell exists, nor was any evidence for such a shell obtained for the passive
films. These observations were used to support the idea that the structure of the
passive film on iron is similar to that of y-FeOOH, i.e. FeO6 octahedra linked
together by sharing edges and not faces or corners.
Analysis of EXAFS data for Fe and alloys containing 25% Cr electrochemically
passivated in NaCIO4 solutions have shown that the presence of Cr has only a slight
effect. The films on pure Fe were also studied as a function of the electrode potential
and there appeared to be no variation in structure with potential, though of course
there is an increase in the film thickness with increasing passivation voltage.
The overall conclusion from these results is that for the passive film on Fe, the
basic structure is similar to that of y-FeOOH, except that the second shell radius was
shorter, and the overall structure significantly more disordered. Further analysis of
the data allows a more detailed consideration of the structure of the passive layer.
The likening of the passive film to y-FeOOH depends essentially on the absence
of a contribution from Fe backscattering at about 3.5 &. However, Fig. 6 shows a
comparison of the Fourier filtered EXAFS spectrum for the passive film and the
calculated contributions to the EXACS spectra for a-FeO O H and y-FeOOH from
the first two shells. The similarity now appears to be greater with the a- rather than
the y-form of the oxyhydroxide. The Debye-Waller factors for the passive film were
 Synchrotron radiation X-ray techniques for corrosion studies 799

TABLE 1. A COMPARISON OF THE CRYSTALLOGRAPHIC RADIAL DISTRIBUTION FUNCTIONS AROUND

THEFe ATOMSIN a-FeOOH WITHSTRUCTURALPARAMETERSDERIVEDFROMEXAFS DATAAND
FOR THE PASSIVE FILM FORMED ON Fe AT A POTENTIAL OF 0 . 8 V ( S C E ) IN 0 . 1 M NaCIO 4

a-FeOOH
Passive film
Crystallographic data EXAFS data EXAFS data

Atom N r[A] N r[A] 202[A2] N r[A] 2a2[A 2]

O 2 1.953 3 1.94 0.(107 2.5 1.91 0.005

O 1 1.954
O 2 2.089 3 2.10 0.007 3.1 2.08 0.(107
O 1 2.093
Fe 2 3.010 2 2.99 0.01(I 2.2 2.93 0.004
Fe 2 3.281 2 3.22 0.010 3.7 3. l 1 0.008
Fe 4 3.459 4 3.39 (I.(11(I

N = coordination number; r = distance from the central atom; 2a2 = Debye-Waller

factor; a = disorder parameter.

f o u n d to be very m u c h larger than for the oxyhydroxide; whilst this may imply
significant disorder, it could also m e a n that the simple two-shell m o d e l used is
incorrect. T o test this, the E X A F S spectra were re-analysed, allowing the two shells
to be split into two c o m p o n e n t s . Statistically significant i m p r o v e m e n t s in the fits were
o b t a i n e d and the new structural p a r a m e t e r s are given in Table 1, where they are
c o m p a r e d with those of a - F e O O H .
It can be seen that the p a r a m e t e r s relating to the F e - O distances are very similar
to those of a - F e O O H , t h o u g h the F e - F e distances are a little different. A n F e - F e
distance of about 2.9 A typically implies o c t a h e d r a sharing faces, whilst a value
a r o u n d 3.1 A indicates edge sharing. A value a r o u n d 3.5 A would imply c o r n e r
sharing, as is observed in a - F e O O H but, as has already been seen, this is absent for
the passive film. This analysis would therefore imply that there is both edge and face
sharing but no sharing of corners. T h e r e f o r e , the film does not a p p e a r to be really
like either of the oxyhydroxides, or indeed any of the d o c u m e n t e d oxides.

CLOSURE
T h r o u g h o u t the 1980s, a new generation of X-ray scattering and absorption
techniques emerged. The possibility of in situ X R D and X A S studies has been
accelerated by the increasing access to s y n c h r o t r o n radiation sources, by the
d e v e l o p m e n t of suitable electrochemical cells and via practical experience. These
d e v e l o p m e n t s are set to continue rapidly in the 1990s and the following trends m a y be
anticipated as a result of new d e v e l o p m e n t s in detector design and the commission-
ing of 'third g e n e r a t i o n ' s y n c h r o t r o n sources:

(1) the c o m b i n a t i o n of the c o m p l e m e n t a r y , in situ techniques of X R D and X A S ;

(2) rapid X R D and E X A F S data collection and energy dispersive techniques;
(3) the e m e r g e n c e of imaging techniques.
Additionally, our knowledge of corrosion films and surface films on metals must
increase as E X A F S modelling improves and m o r e extensive databases on surface
corrosion products emerge.
800 J. ROBINSON and F. C. WALSH

Acknowledgements--The studies reported in this paper were assisted by financial support from the SERC
and the cooperation of staff at the SERC Daresbury Laboratory. Contributions to the experimental work
were made by Drs S. E. Doyle, M. E. Herron, A. H. Nahl6, M. Kerkar and K. J. Roberts. Part of the work
has been supported by Johnson Matthey Technology Centre.

REFERENCES
1. J. ROBINSON, in Electrochemistry (ed. D. PLETCHER), Vol. 9, p. 101. Royal Society of Chemistry
Special Publications (1984).
2. H. D. ABRUNA(ed.), Electrochemical Interfaces, Modern Techniques for In-Situ Interface Characteri-
sation. VCH, Cambridge (1990).
3. L. R. SHARPE, W. R. HEINEMANand R. C. ELDER, Chem. Rev. 90, 705 (1990).
4. F. C. WALSH and A. H. NAHLE,The application of X-ray techniques to studies of corrosion and
protection. Proc. U.K. Corrosion '90, Esher, U.K. (29-31 October 1990).
5. D. B. FREEMAN,PhosphatingandMetalPretreatment. Woodhead-Faulkner, Cambridge (1986).
6. G. LORIN, Phosphating of Metals. Finishing Publications, Middlesex (1974).
7. T. MIYAWAKI,H. OKITA, S. UMEHARAand M. OKABE, Proc. Interfinish 80, 303 (1980).
8. D.B. FREEMAN,K. BROWN, M. O. W. RICHARDSONand H. TIONG, Finishing, p. 27 (August 1984).
9. M. O. W. RICHARDSONand D. R. GABE, Trans. Inst. Met. Finish. 68, 99 (1990).
10. A. H. NAHLE, F. C. WALSH,J. ROBINSON, S. E. DOYLE and K. J. ROBERTS,in preparation for Trans.
Inst. Met. Finish.
11. K. A. AKANNI, C. P. S. JOHAL and D. R. GABE, Trans. Inst. Met. Finish. 62, 64 (1984); Proc. llth
World Congr. Metal Finish. (Interfinish '84), p. 474 (1984).
12. D. PLETCHER and F. C. WALSH,Industrial Electrochemistry, 2nd Edn. Chapman & Hall, London
(1990).
13. J. P. POHLand H. RICKERTin Electrodes of Conductive Metal Oxides (ed. A. TRASAaTI),Part A, p. 183.
Elsevier, Amsterdam (1980).
14. T. F. SHARPE,in Encyclopedia of Electrochemistry of the Elements (ed. A. J. BARD),VOI. 1. Marcel
Dekker, New York (1973).
15. H. NGUYENCONG, A. EJJENNE, J. BRENETand P. FABER,J. appl. Electrochem. 11,373 (1981).
16. Z. TAKEHARA,K. KANAMURAand M. KAWANAMI,J. electrochem. Soc. 137,800 (1990).
17. N. BARLOW,C. BRENNAN, S. E. DOYLE, G. N. GREAVES,M. MILLER, A. H. NAHLE, K. J. ROBERTS,J.
ROBINSON, J. N. SHERWOODand F. C. WALSH, Rev. Sci. Instrum. 60, 2386 (1989).
18. M.E. HERRON, S. E. DOYLE, K. J. ROBERTS,J. ROBINSONand F. C. WALSH,Rev. Sci. Instrum. 63,950
(1992).
19. S.E. DOYLE, M. E. HERRON, K. J. ROBERTS,J. ROBINSONand F. C. WALSH, Phase Transitions 39, 135
(1992).
20. M. E. I-{ERRON,D. PLETCHERand F. C. WALSH, J. electroanal. Chem. 332, 183 (1992).
21. G. G. LONG, J. KRUGER, D. R. BLACKand M. KURIYAMA,J. electroanal. Chem. 150, 603 (1982).
22. M. E. KORDESCHand R. W. HOFFMAN, Nucl. Instrum. Meth. 222, 347 (1984).
23. M. KERKAR, J. ROBINSONand A. J. FORTY, Faraday Discuss. chem. Soc. 89, 31 (1990).
24. J. ROBINSON, X-ray absorption spectroscopy in the study of corrosion and passivation, Electrochem.
Soc. Meeting, Phoenix, Arizona, U.S.A. (13-18 October 1991); Proc. electrochem. Soc. (eds A.
DAVENPORTand J. GORDON), New Jersey (1992).