Degradation of an organomineral coating Ann. Chim. Sci. Mat, 1998,23, pp.

397-400

ELECTROCHEMICAL STUDY OF THE DEGRADATION OF AN

ORGANOMINERAL COATING : POLARIZATION RESISTANCE AND
ELECTROCHEMICAL IMPEDANCE SPECTROSCOPY MEASUREMENTS

N. POMMIER, L. THIERY*, M.P. GIGANDET’*, M. TACHEZ**

Laboratoire d’Electrochimie et des Systkmes Microdispersks, Route de Gray, 25030 Besaqon, Cedex, France
* SociBt6 Continentale Parker, 51 rue Pierre, B.P. 310,921ll Clichy Cedex, France
** Institut Universitaire de Technologie, Iaboratoire & Corrosion et de Traitements de Surfaces, B.P. 1559, 25009
Besancon Cedex, France

Summa~ : The corrosion behaviour of chromated zinc with an organomineral coating, was studied by
electrochemical measurements (polarization resistance and electrochemical impedance spectroscopy @IS.))
in a corrosive environment for extended time periods. During this time, the impedance spectra will change as
the coating properties deteriorate and corrosion occurs at the metal/coating interface. The change of
parameters such as b, % and fb are very useful for the analysis of coating damage.

R&urn6 : Etude 6lectrochimique de la dkgradation d’un rev&tement organomintral : r&stance de

stion et spectroscopic d’imptiance Clectrochimique. Le comportement du zinc chromate
recouvert d’une fit&ion organomin&ale a 6tB Btudit dans un environnement corrosif par des mesures
de r&stance de polarisation et par spectroscopic d’impkdance blectrochimique. Les diagrammes
d’imptdance montrent, avec le temps d’immersion, une dkgradation du revCtement et l’apparition des
processus de corrosion 2 l’interface m&al/rev&ement. L’Ctude des variations de Rpo, % et f,, s’avbre
trbs utile pour analyser la ddgradation du rev&tement.

1. INTRODUCTION

Protection against corrosion, particularly in the automotive industry, is presently ruled by stricter and
stricter standards. To fight against the corrosion of steel, the part which is to be protected receives a zinc layer
by an electrochemical treatment, a layer of chromic passivation and in recent years an organomineral finish.
Continental Parker, which was associated with this study, uses an organomineral finish with a polymer
base and anticorrosion mineral pigments as a final layer. This finishing layer is then capable of resisting
temperature variations, mechanical and chemical attacks and frictions.
At the laboratory stage, the application of stationary and non-stationary electrochemical techniques is
of great interest in order to determine the corrosion resistance of steel which is zinc-coated, then chromated
and which finally receives an organomineral film finish. Following this, dif%rent protective coat&s can be
chosen, optimized and classified.

Reprints : M.P. GIGANDET, Laboratoire de Corrosion et Traitements de Surfaces, 32 rue Mbgevand, 25030
Besanp Cedex, France
398 N. Pommier et al.

Presentday non-electrochemicaltests are too long and results rely on purely subjective observation.
Electrochemicalmethods are particularly interestingbecausetests are not long and can also show a trend even
if they cannot reproducecorrosionphenomena.

2. EXPERIMENTAL CONDITIONS AND TECHNIOUES

Various tests were carried out on electrogalvanizedsteel plates which had undergone a chromating
treatment with an organomineral finish. The electrolytesusedwere industrial ones.
The electrolytical medium selectedfor electrochemicaltests is composedas follows :
NaCl : 30 g/L ; NarS04 : 15 glL ; pH = 4,8. (Mechanical agitation : 250 rev/mm)
Polarization resistance measurements were carried out in potentiostatic mode with a
e potentiostat/galvanostatB PGP 201 (Tacussel),using Voltamasterl for Windows. The scan speedis 0,83
mV/s and the amplitude was set to f 10 mV. The polarization resistancebeing in inverseratio to the speedof
corrosion, this will allow us to estimatethe corrosion resistanceof a protective coating.
The electrochemicalimpedancemeasurementswere performed in the 100 kHa/O,l Hz range using an
EG&G Princeton Applied ResearchCorp., model 6310 impedance system. The amplitude of the sinusoidal
voltage signalwas kept at 10 mV.
The electrochemicalcell is made of a saturatedcalomel electrode(S.C.E.) as a referenceelectrodeand
a platinum electrodeas a counter-electrode.The exposedarea of the working electrodeis 4,9 cm*.

3. RESULTS AND DISCUSSION

3.1. Shapeof imnedancediagrams and accessibleparameters

Impedance diagrams of organomineral coatings (Placedin a hot air drying oven for 1 hour at 12OOC)
representedin the complex plane (Nyquist) are character&d, after extrapolation, by two capacitive loops
more or less well defined. Figure 1 (page 3) shows the experimental impedance diagram after 4 hours of
immersion. The behaviour of such an interface can be describedby the equivalent electrical diagram built on
the porous model. Most of data reported in the literature agreewith this model [l-5]. lbe high frequency loop
(H.F) of the impedancediagram is relative to the protective coating, whereas the low frequency (LF) part
representsthe faradic processthat develops on the bare metal through the pores and/or the discontinuitiesof
the film. Different valuescan be found :
Rpo (Qcmz) is the pore resistanceresulting from the formation of ionically conducting paths across the
coating. Rr (Q.cmz)is the polarization resistanceof the area at the metaYcoatinginterface at which corrosion
occurs. According to Man&d 131,Deflorian & al [4] and McIntyre [5], these two parameters are related to
the delaminated area & (also called disbondedor wetted area expressedas a dimensionlessquantity) by :

R = R$ =p.d (,) R, = $ (2) , D=+ (3)

p Ad A, ’ d

where p is the resistivityof the coating (sZ.m).IQ” is the correspondingquantity for the bare metal.
A delamination ratio D is calculatedwhich is based on the ratio of the delaminatedarea & (at which
corrosionis assumedto occur) and the exposedarea A. The delaminationratio is given by the equation (3).

3.2. Timedeuendenceof%,

h is the resistanceof the pores and/or of the discontinuitiesof the film and is defined by equation (1).
Experimentalresults are shown in figure 2 page 3.
& decreaseswith immersiontime. This showsa rapid uptake of the electrolyte in the pores and/or the
defects of the fihn. The change in slope observed after ten hours of immersion is due to the formation of
corrosion products that slow down the advance of the electrolyte in the film. The decrease of G with
 Degradation of an organomineral coating 399

immersion time is due to (according to equation (1)) a decrease in the resistivity p of the coating and/or an
increase of the delaminated area &.
r

z 6000
6000
6i 4500
c
x 3000

1500

I
0 5000 10000 15000 6 i0 4b 6b i0 lb0 li0
Reg) inohm.cm2 Immersion time in hours
Figure I : experimental impedance diagram (organo- Figure 2 : time dependence of the pore.
-mineral coating) after 4 hours of immersion resistance Q.

600 -
“E
9 600-
s
2 400-
.6
2 200-

o- +
1, ., , ( ., ., I
Li 2b .lO 6b 6b 160 rio 0 20 40 60 60 100 120
Immersion time in hours Immersion time in hours
Figure 3 : hme dependence of the polarization Figure 4 : time dependence of the breakpoint
resistance :% frequency : fb

3.3. Time deuendence of R,

Rr, is the polarization resistance at the metal/coating interface, related to & by equation (2).
Experimental results are shown in figure 3. The polarization resistance that is in inverse ratio to a speed of
corrosion gives informations concerning the corrosion resistance of the coating.
A decrease of R+, with immersion time therefore shows a decrease of the corrosion resistance of our
system. Rr being, according to equation (2), in inverse ratio to the delaminated area, the decrease of the Rr
value clearly shows an increase of A.I and therefore of D
After 20 hours of immersion, the Rr value is still relatively high (in the range of 350 kR.cm*),
compared with a chromating which in the same electrolytic medium is already completely deteriorated, which
means that the coating will protect against corrosion durably.

3.4. Representation of Bode/Method ofthe breakpoint freauencv 131161

E.I.S. data should be displayed as Bode plots in which the logarithm of the magnitude of the
impedance modulus 1ZI and the phase angle Q are plotted versus the logarithm of the applied frequency f.
Variations of parameter such as the breakpoint frequency fb, which is the frequency at which the phase angle
0 equals 45” can be used to follow the deterioration of a protective coating during its exposure to a corrosive
environment. The representation of the phase angle as a function of frequency is a very sensitive indicator for
the analysis of coating damage. fb is the frequency theoritically obtained for a transition between a capacitive
region (of slope - 1 on the Bode diagram) and a resistive region with no slope.
400 N. Pommier et al.

fb is given by :
fa --.Lz (Hz) (4)
2.Z.E.E0 p

where a is the dielectric constant of the coating and aa is the dielectric constant of free space. The
determination of fb from the representationof Bode aUowsus to draw the fb vs immersiontime plot, This curve
is shown in figure 4 page 3.
An increaseof fb with immersiontime can be discussedfrom the equation (4). This relation showsthat
fb dependsupon the ratio D/p. The increaseof fb seemsto be due to an increaseof D and/or a decreaseof the
resistivity of the coating.
However, in that reasoningwe do not take into accountthe dielectricconstant of the coating that must
increase,the electrolyte penetrating in the pores and/or in the defects of the film. If we consider that the
resistivity of the film decreaseswith immersiontime and therefore with the deterioration of the film itself, it is
possibleto supposethat the increaseof E makes up for the decreaseof the resistivity of the film. In that case,
fr,would not dependupon the delamination ratio D and would be written :

fb =f:.D (5) avec fz = (2.a.&.~,)-’

This hypothesisis then corroboratedwith theoritical impedancespectra which have been simulated by
a computer for a polymer coating with a thicknessof 10 pm as a function of the delaminatiou ratio D=wA at
which corrosionoccurs [3]. It has been assumedby the authors that D increasedfrom lo4 to 1.
The change of slope observed is therefore due to the formation of corrosion products that develop
during the immersion and (( lock 1)the electrochemicalreactions.Variations in &,, h and fb that are related to
the delaminated area A,r (and therefore to D) clearly show that the area on which corrosion occurs increases
quickly during the first 10 to 15 hours of immersion. The changeof slopefor longer immersiontimes indicates
a filling in the pores by corrosionproducts.

4. CONCLUSION

Polarization resistancemeasurementscarried out in various conditions on zinc, chromating and the

organomineral finish show that this technique can be used in the laboratory in order to edmate the corrosion
resistanceof thesedifferent types of protective coatings.
The use of electrochemicalimpedancespectroscopyallowed us to follow successfullythe deterioration
ofthe organomineralcoating during its exposureto a corrosiveenvironment.
The results obtained show that it is possible to dissociatethe contribution of the coating from the
faradic processoccuring in the corrosion process.
The characteristicvalues for the state of deterioration of the film such as G, Rr, and fb were thus
determined. The analysis of the variations of these parameters allowed us a better understanding of the
deterioration of various coatings on zinc used in the automotive industry.
Finally, the breakpoint frequency method (fb) is particularly quick and well adjusted for the detection
of any deterioration of the protective coating.

5. REFERENCES

[I] M. Kendig, F. Mansfeld and S.Tsa’i,Corrosion Science, 23, 317, 1983

[2] M. Kendig and J. SculJy,Corrosion, 46,22, 1990
[3] F. Mansfeld, Journal ofApplied Electrochem., z 187, 1995
[4] F. Deflorian et al, Electrochemicu ACM, 39, 1945, 1993
[5] John McIntyre, Ha. Q. Plum, Progress in Ornanic Coatings, 27,201, 1996
[6] F. Mar&Id and C.H. Tsai, Corrosion, a 958, 1991