Corrosion Science, Vol. 33, No. 8, pp.

1203-1226, 1992
Printed in Great Britain.

0010-938X/92 $5.00 + 0.00

~ 1992 Pergamon PressLtd

A S T U D Y OF C O R R O S I O N I N I T I A T I O N ON P O L Y I M I D E
COATINGS
F. BELLUCCI, L. NICODEMO, T. MONETTA, M. J. KLOPPERS* a n d R. M. LATANISION*
Department of Materials and Production Engineering, University of Naples, Piazzale Tecchio,
80125 Naples, Italy
*The H. H. Uhlig Corrosion Laboratory, Massachusetts Institute of Technology, Cambridge,
MA 02139, U.S.A.
Abstract--The protective properties of thin polyimide (PI) films on aluminum and iron metallic substrates
were studied using a.c. and d.c. electrochemical techniques. The effects of storage time, film thickness,
and the synergistic effect of temperature (80C) and relative humidity (85 %) on the lifetime of the PI were
investigated. The results obtained can be summarized as follows: (i) early failure was observed for the
PI/AI samples tested directly after curing, while extended lifetime was observed for samples stored in a
desiccator for 2 months before testing, (ii) early failure was also observed for the PI/Fe samples even after
storage in a desiccator before testing, (iii) the lifetime increases by increasing the film thickness, and (iv)
temperature and relative humidity (RH) dramaticallyaffect failure. A mathematical model is presented to
relate coating failure to salt uptake by the PI. By applying this model to the experimental findings, an
estimate of the heterogeneities or defects in the PIs is given.
INTRODUCTION
CORROSION p h e n o m e n a affecting m i c r o - e l e c t r o n i c s circuitry a n d d e v i c e s a r e t h e s a m e
as t h o s e e n c o u n t e r e d with o t h e r e n g i n e e r i n g systems. T h e m a i n d i f f e r e n c e is t h e v e r y
low c o r r o s i o n r a t e (of t h e o r d e r o f p A cm -2) t h a t e l e c t r o n i c circuitry can t o l e r a t e
b e f o r e failure. 1
E l e c t r o c h e m i c a l failure o f d e v i c e s was w i d e l y r e p o r t e d in the l i t e r a t u r e a n d
a t t r i b u t e d to ionic c o n t a m i n a n t s , t h e r e l a t i v e h u m i d i t y ( R H ) a n d the a p p l i e d electric
field. 2-5 P r o t e c t i o n o f m e t a l l i c circuitry f r o m aggressive species is o b t a i n e d b y t h e use
of p o l y m e r i c ( e p o x i e s , silicones a n d p o l y i m i d e s ) o r c e r a m i c e n c a p s u l a t i n g
materials. 6
P r o t e c t i o n f r o m the e n v i r o n m e n t is critical to d e v i c e p e r f o r m a n c e , since the
ingress o f m o i s t u r e a n d o t h e r c o n t a m i n a n t s can result in c h e m i c a l a t t a c k o f t h e chip
m e t a l l i z a t i o n o r can a l t e r the e l e c t r i c a l c h a r a c t e r i s t i c s o f the d e v i c e . l - 7 It has b e e n
s h o w n 2'7"8 t h a t i n t e g r a t e d circuit ( I C ) chips m a y fail d u r i n g service d u e to c o r r o s i o n
at the p o l y m e r / m e t a l i n t e r f a c e . D e v i c e r e l i a b i l i t y o f t e n d e p e n d s o n t h e r a t e o f a r r i v a l
o f ionic c o n t a m i n a n t s at t h e p a c k a g i n g / m e t a l l i c circuitry i n t e r f a c e . 1-5 T h e techn o l o g y r e l a t e d to p a c k a g i n g r a t h e r t h a n the i n c r e a s i n g chip d e n s i t y m a y b e t h e issue
limiting d e v i c e p e r f o r m a n c e . 6
T h e m e c h a n i s m by which an o r g a n i c c o a t i n g p r o t e c t s a m e t a l l i c m a t e r i a l f r o m the
e n v i r o n m e n t is a c o m p l e x a n d n o t well u n d e r s t o o d p r o c e s s . S o r p t i o n a n d t r a n s p o r t of
c h a r g e d (ions) a n d u n c h a r g e d ( w a t e r , o x y g e n ) species affect t h e c o r r o s i o n b e h a v i o r
o f t h e p o l y m e r i c / m e t a l l i c s y s t e m . 9-12 M a n y p r o p e r t i e s o f p o l y m e r s ( p r o c e s s a b i l i t y ;

Manuscript received 23 July 1991; in amended form 11 November 1991.

1203

1204

F. BELLUCCIet al.

electrical p r o p e r t i e s ; c h e m i c a l , t h e r m a l , m e c h a n i c a l a n d e n v i r o n m e n t a l stability)
affect t h e i r suitability a n d reliability as p r o t e c t i v e o r g a n i c coatings. 13,14
In this p a p e r the use o f P M D A - O D A * P I as an o r g a n i c low d i e l e c t r i c c o n s t a n t
p a c k a g i n g m a t e r i a l ( m u l t i l e v e l d i e l e c t r i c ) in m i c r o - e l e c t r o n i c s was i n v e s t i g a t e d . PIs
( p o l y i m i d e s ) a r e a class o f p o l y m e r s with a high glass t r a n s i t i o n t e m p e r a t u r e Tg, (e.g.
325C for B T D A - O D A * a n d 400C for P M D A - O D A ) a n d an o p e n m o l e c u l a r
s t r u c t u r e which m a k e s p e r m e a t i o n o f w a t e r m o l e c u l e s a n d o x y g e n i n e v i t a b l e . 15-21 In
a d d i t i o n , t h e p r e s e n c e o f c o n t a m i n a n t ions ( N a +, C I - ) a n d gases (SO2, H2S, etc.), in
high h u m i d i t y e n v i r o n m e n t s , can result in the i n i t i a t i o n of c o r r o s i o n . 1-5 A n u n d e r s t a n d i n g o f the c o r r o s i o n b e h a v i o r o f t h e P I / m e t a l l i c s y s t e m , m a y t h e r e f o r e r e p r e s e n t
the r a t e d e t e r m i n i n g step in i m p r o v i n g t h e r e l i a b i l i t y o f ICs.
M a n y p a p e r s h a v e a d d r e s s e d t h e i n t e r r a c i a l i n t e r a c t i o n b e t w e e n PI a n d
m e t a l s , 22-26 w h e r e a s the e n v i r o n m e n t a l d e g r a d a t i o n o f the P I / m e t a l l i c s u b s t r a t e
s y s t e m is less well d o c u m e n t e d , z7 T h e p u r p o s e of t h e w o r k d e s c r i b e d h e r e i n is to
p r o v i d e an u n d e r s t a n d i n g o f t h e p r o t e c t i v e p r o p e r t i e s of t h e P I on the A I a n d F e
m e t a l l i c s u b s t r a t e s using a.c. ( i m p e d a n c e s p e c t r o s c o p y ) a n d d.c. ( p o l a r i z a t i o n
resistance method) electrochemical techniques. The thickness of the PI investigated
( P M D A - O D A ) , v a r i e d b e t w e e n 1 a n d 3 / ~ m in t h e case o f the PI/A1 s y s t e m , a n d
b e t w e e n 5 a n d 15/~m in the case of t h e P I / F e s y s t e m , r e s p e c t i v e l y . This p a p e r will
a d d r e s s t h e effect of: (i) s t o r a g e t i m e , (ii) film thickness a n d (iii) t e m p e r a t u r e a n d R H
on c o a t i n g p e r f o r m a n c e . In a d d i t i o n , an a t t e m p t will b e m a d e to clarify the role of
ionic c o n t a m i n a n t s on lifetime a n d to r e l a t e failure to t h e ionic diffusion across t h e
PI. A m a t h e m a t i c a l m o d e l is p r e s e n t e d t h a t allows the d i s c r i m i n a t i o n b e t w e e n
failure d u e to e l e c t r o l y t e s p e n e t r a t i o n t h r o u g h r e d u c e d p a t h w a y s (defects o r h e t e r o g e n e i t i e s ) o f the c o a t i n g , a n d failure d u e to t h e i n t e r f a c i a l a d h e s i o n loss.
E X P E R I M E N T A L METHOD
Coating preparation
Commercially available PMDA-ODA was investigated in this paper. PMDA-ODA is the synthetic
analogue of Kapton PI. Polyamic acid as PI precursor was supplied by E. I. du Pont de Nemours and
Company, as the amic acid solution of poly [N,N'-(p,p'-oxydiphenylene) pyromellitimide]. The polymer
film of interest was deposited on a 2.5" (6.35 cm) diameter wafer using the spin coating technique
(6000 rpm for 90 s) and then cured. A r-stage cure (135C for 10 min in air) followed by a final curing step
at 400C for 45 min in nitrogen was adopted.

Samples
The metallic substrates for corrosion testing were aluminum produced by electron beam evaporation
of aluminum onto silicon wafers and pure (99.998%) Fe. The aluminum deposition was carried out at a
vacuum base pressure of about 10-8 Torr. The thickness of the deposit was typically 1000 ,~. The
silicon/aluminum (Si/AI) wafers and the iron metallic substrate were subsequently spin coated with the PI
as described above.
Apparatus
The experimental apparatus for the electrochemical investigation consisted of a perspex cylinder
attached to the surface of a coated substrate in order to create a vessel to hold the electrolyte. The coated
metal was the working electrode. A saturated calomel electrode (SCE) was used as the reference
electrode. All reported potentials are referred to the latter electrode. A platinum foil was used as the
counter electrode. Except where otherwise specified, specimens were stored for 2 months in a desiccator
*PMDA-ODA is made from pyromellitic dianhydride (PMDA) and oxydianiline (ODA) while
BTDA-ODA is made from benzophenone tetracarboxylic dianhydride (BTDA) and oxydianiline.

Corrosion initiation on polyimide coatings

1205

before testing. Samples tested were those which did not exhibit any pinholes according to the following
test.
After storage in a desiccator for 2 months, the samples were assumed as being dry and the film
capacitance, G , was determined using the impedance spectroscopy (a.c.) technique (see below) and the
apparatus described above. Mercury was used as the electrolyte in order to avoid water and salt
contamination of the specimen (exposure to an aqueous salt solution before the start of the test may lead
to an initiation of the degradation process, with resultant artificially short measured lifetime). Two
different impedance spectra were observed among the samples investigated. The first exhibited resistive
components at low frequencies, while the second showed pure capacitive behavior even at 1 mHz. The
resistive component observed in the former case was attributed to pinholes or diffuse heterogeneities. The
samples that exhibited a resistive component were considered as defective and were discarded.

Methods
Electrochemical impedance spectroscopy was performed at the corrosion potential in the case of
aqueous solutions of NaCl (see below), and at zero applied potential when mercury was used as the
electrolyte. Experimental tests were carried out using a Schlumberger Solartron 1250 Frequency
Response Analyzer connected to a Solartron 1286 potentiostat. The analyser was controlled by a HewlettPackard desktop computer. Usually, 10 points were measured for each decade of frequency. The
frequency used ranged between 65 kHz and 1 mHz. The amplitude of the superimposed potential was
5 inV.
The polarization resistance method, developed by Stern and Geary 2s from the earlier work of Wagner
and Traud, 29 is currently applied to painted metals and is considered, to some extent, a non-destructive
test. This test method is, however, destructive (to some extent) in nature because ion movement is forced
through the paint film in one direction or another (depending on the polarity of the d.c. applied voltage),
causing acceleration or deceleration of corrosion degradation of the painted metal. To reduce this effect,
the overpotential applied in the polarization resistance method was l0 mV periodically reversed to
balance ion movement in the anodic and cathodic reaction. Since the original relationship only applies in
the absence of ohmic potential drop, which is not the case under study, the terminology 'pseudopolarization resistance' will be used to describe these measurements. The pseudo-polarization resistance
of the coated sample was evaluated by measuring the steady-state current after an anodic and cathodic
polarization of 10 mV has been applied. The value taken was the average of three measurements.
Air saturated sodium chloride (up to 0.5 M) was the test solution in the cases where an aqueous
electrolyte was employed. It was prepared from reagent grade material and distilled water (18 MI) cm
resistivity). The temperature was 20 +_ lC.
The transparent nature of the PI allowed visual evaluation of the delamination area as a function of the
immersion time without perturbing the system under study. The delamination area was measured by
taking periodically pictures of the specimens and evaluating the number and the area of each corrosion
spots observed.

EXPERIMENTAL

RESULTS AND DISCUSSION

A survey of the literature revealed that corrosion failure of electronic materials

a n d d e v i c e s is a c o m p l e x a n d n o t w e l l u n d e r s t o o d m a t t e r , o f t e n d e p e n d e n t o n t h e R H
a n d o n t h e e l e c t r i c a l s t a t e o f t h e e q u i p m e n t . ~-6 N o e x p e r i m e n t a l w o r k , h o w e v e r , h a s
been reported describing the electrochemical and corrosion properties of PI/metallic
s u b s t r a t e s d e s p i t e t h e e x t e n s i v e u s e o f P I as d i e l e c t r i c in t h e p a c k a g i n g o f i n t e g r a t e d
c i r c u i t s . 6-s'13 S o m e e x p e r i m e n t a l r e s u l t s d e s c r i b i n g t h e e l e c t r o c h e m i c a l a n d c o r r o s i o n b e h a v i o r o f P I / A 1 a n d P I / F e s y s t e m s i n a e r a t e d N a C I s o l u t i o n as a f u n c t i o n o f
immersion time by using the impedance spectroscopy and the polarization resistance
techniques are described below.

The PI/AI system

The effect of storage time. M e t a l l i c s u b s t r a t e s (Si/A1) w e r e i d e n t i c a l l y p r o c e s s e d
and spin coated with PI (1.2/~m thick). Some specimens were immersed in aerated

1206

F. BELLUCC! et al.
10
E
u

1.2 ~m PI/AI 0.5 M NaCI, Sample "A"

Od

8
ld

"...,

..."...::::!::;:.

J=
0

3d

,.

"":ilh,"
"h.

6
................

8d

---:

"'~.

........................ ,,,.,,.
, .:~

_o
2

-1

log o~, rad s

100

a)

12 pm PI/'AI 0.5 M NaCI, Sample

80

Od

, . . - " : : ::..
:~:

""

60

"

'

.........

.'

.:::"

l d

_~
=m 40

'

'

...:

.."

"'

"" . . . . . .

14d

"" "
'""
".'""..:.., .::::i ..................... "'"'"

.."

'

'
i

-2

. "8d

"'.' 3d

20

rO.
0

"

" "

G)

..,

- ' . "-

'

2
log co, rad s

4
-1

FIG. 1. (a) Bode plot as a function o f immersion time for the 1.2/xm thick PI/AI system
(sample A ) in air-saturated 0.5 M NaC1 at room temperature; (b) phase angle plot as a

function of immersion time for the 1.2/~m thick PI/AI system (sample A) in air-saturated
0.5 M NaC1 at room temperature.

0.5 M NaCI immediately after curing (sample 'A'), while others were first stored in a
desiccator for 2 months before testing (sample 'B').
Figure l(a) and (b) show the Bode and the phase angle plots for sample A as a
function of immersion time. The rest potential E0 was also recorded. The E 0 vs time
behavior will be analysed in a subsequent section together with the film capacitance,
Cf time decay plot.
After 1 day of immersion, the film response departs, at low frequencies, from a
purely capacitive behavior ( - 1 slope on the Bode plot). The resistive component at
low frequencies is associated with the film resistance Rf. The value observed is of the
order of 107 ~r~ c m 2 . Failure by corrosion of the metallic substrate has been observed
for a great number of cases as soon as Rf falls below 107 ~ cm2. 3
After 8 days of immersion, the Rf falls below the criterion value and, as expected,
a more complex impedance spectrum is observed. In this latter case the Bode and
phase angle plots show two time constants (rf for the film and rot for the metal), given
by:
r f ----R f C f ; "t'ct = R t C d

(1)

where Cf is the film capacitance, Rt is the charge transfer resistance and Cd the double

Corrosion initiation on polyimide coatings

1207

10
1.2 ttm PI/AI 0.5 M NaCl, Sample "B"

0-30d
47d .......

.... .........::.
.... "::=.

53d"":;:.:: ..
"'--...........
":~??:.

r-

60d............ii ~:.,.~,.
"~qh =.

N_

'%.

o
2
-2

4
-I

log

co, r a d s

100

80

. . . .

47d"

...... .-

......

.' 53d

-..

~ 6o
'6o~

i"

~ 40

-"
.' : . . . . . ,

ID

..
........"

20

I1,
0
-2

log co, rad s

4
-1

FIG. 2. (a) Bode plot as a function of immersion time for the 1.2/~m thick PI/AI system
(sample B) in air-saturated 0.5 M NaCI at room temperature; (b) phase angle plot as a
function of immersion time for the 1.2/~m thick PI/AI system (sample B) in air-saturated
0.5 M NaCI at room temperature.

layer capacitance, respectively. The time constant at higher frequencies is due to the
film if rf < lrct, which is usually the case. The experimental results reported in Fig.
l(b) show that with prolonged immersion time (14 days) diffusional processes within
pores in the film were taking place.
Results of sample B are reported in Fig. 2(a) and (b). As can be seen, the Bode
and phase angle plots exhibit the same features as those exhibited by sample A but on
a different time scale. Pure capacitive behavior is observed for immersion times up to
30 days, followed by the appearance of a resistive component with prolonged
immersion while two time constants can be seen at longer immersion times (53 days).
Also in this case, a second time constant was observed when the film resistance fell
below 107 ~ cm 2. No diffusional processes were observed in this case even after 92
days of immersion. The latter data were omitted for the sake of simplicity.
The impedance response over the lifetime of the film reported in Figs 1 and 2 can
be related to the various stages of degradation at the PI/A1 interface. Initially, the
film acts as a pure dielectric separating the metallic substrate from the aggressive
external environment. This behavior results in purely capacitive behavior (see for
example Fig. la after i day immersion and Fig. 2a for immersion times up to 30 days).
The second step is water and ion uptake within the film, either homogeneously

1208

F. BELLUCCI et al.

101

1.2 p.m PI/AI 0.5 M NaCI

Sample "A"

o
.

10 0

10 "1

f,,

"~ lo-2
10 -a

FIG. 3.

100

le "B"

200

300

400

500

time, h
D e l a m i n a t i o n a r e a as a f u n c t i o n o f i m m e r s i o n t i m e f o r t h e s a m p l e s A a n d B ,
r e s p e c t i v e l y in a e r a t e d 0.5 M N a C 1 s o l u t i o n at r o o m t e m p e r a t u r e .

through the film or heterogeneously due to defects. At this stage the water and ion
uptake can modify the capacitive response leading to either one (see Figs la and 2a
up to 3 and 47 days of immersion, respectively) or two time constants (Figs la and 2a
after 8 and 53 days, respectively). Two time constants are indicative of the first
separation of film and metal substrate properties. With continued immersion, the
film resistance decreases due to both water and ionic species that are absorbed into
the film. 9 At longer immersion times, the rate of diffusion of species through pores in
the film may become comparable with the charge transfer process and a diffusional
response may appear (see Fig. 1 after 14 days).
The time of failure was taken as the time required to separate the film and the
metal response. On this basis, the sample A exhibits a lifetime ranging between 3 and
8 days, while the lifetime of sample B ranges from 47 to 53 days. There is not a simple
explanation for such a macroscopic difference in lifetime between otherwise similar
samples. An attempt is given in the following section to explain this result, while a
deeper analysis will be presented in the Mathematical model section.
The electrochemical and corrosion behavior described in Figs 1 and 2 indicates
that the curing and processing of PI may affect the environmental degradation of the
PI/AI system. Residual stress, due to curing, and osmotic stress, arising when the PI
is exposed to an aqueous NaC1 solution due to trapped water at the interface, can
contribute to a local microcracked area through which ions can easily diffuse to reach
the AI interface. Samples stored in a desiccator can release both thermal stress and
trapped solvent and water. Water and solvent release may also enhance the adhesion
of the PI at the metallic interface leading to an extended lifetime. Even if both
samples did not exhibit any pinholes according to the test described in the experimental section, the reliability of the coatings was somewhat different. The more time
allowed for sample equilibration in the desiccator, the better the sample performed.
The rate of delamination (evaluated as described in the experimental section) and
the type of corrosion observed were also different. Sample A corroded more
homogeneously whereas sample B showed few localized black corrosion spots. This
phenomenon can be clearly seen by the presence of a diffusion tail on the phase angle
plot at low frequencies after 14 days of immersion in NaCI (Fig. lb). The higher rate
of delaminated area for sample A as shown in Fig. 3, supports the conclusion that
corrosion is taking place over the entire surface.

Corrosion initiation on polyimide coatings

10

1209

2.4 ~m PI/AI 0.5 M NaCI

0d..
8

25d

.... ..
':::~: . . . . . . . . . . .
"-1:.>

.E

"':::.: : : : : .

N_----:

~3o~....................
4

......
................ ".i:::::,

-N-

" " . %..

log
FIG. 4.

2
e), tad s

4
-1

Bode plot as a function o f immersion time for a 2.4/~m thick PI/AI system in
air-saturated 0.5 M NaCI at room temperature.

The effect of film thickness. The effect of the coating thickness on the coating
lifetime was also investigated. Two Si/AI samples were coated with 1.2 and 2.4/~m
thick PI, respectively. These samples were processed according to the procedure
described above and stored in a desiccator for 2 months before use. The electrochemical behavior exhibited by the 1.2/~m thick coated sample was similar to that
reported in Fig. 2 and is omitted for the sake of simplicity. The Bode plot for the
2.4/~m film in aerated 0.5 M NaCI solution at room temperature is shown in Fig. 4.
Departure from a pure capacitive behavior was observed after 25 days of
immersion. A second time constant characterizing the onset of an interracial
electrochemical process was observed after 130 days. This time was taken as the
sample lifetime. The rate of delamination and the distribution of corrosion spots
were similar to those observed for sample B. As can be seen from the Bode plot,
coating degradation occurs when R e falls below 107 ~ cm 2. This observation is in
agreement with the previous results. In the mathematical section an attempt will be
given to relate the observed macroscopic difference in the lifetime experimentally
observed for the PI/A1 samples to the coating's structure and thickness, and to the
interracial adhesion loss.
The effect of temperature and RH. The synergistic effect of the temperature and
R H was investigated by carrying out impedance spectra at 80C and 85% RH. These
conditions are the same as those used in one of the accelerated tests adopted to
evaluate chip failure. 6 Samples were stored in a desiccator for 2 months prior to
usage. Mercury was used as the electrolyte in order to avoid salt contamination. This
technique is similar to the experimental technique adopted by Leidheiser. 11 This
technique is commonly used to measure the degradation of coatings without
exposing the specimen to an aqueous electrolyte during the measurement. The
mercury provides electrical contact to the sample surface (through an immersed Pt
electrode) but can be easily removed in order to expose the specimen at 80C and
85% RH.
Results are shown in Fig. 5(a) and (b) in the form of Bode and phase angle plots.
After 8 days of exposure at 80C and 85% RH, the film departs from a pure capacitive
behavior and a resistive component at low frequencies (of the order of 107 ~ cm 2)

1210

F. BELLUCCI et al.
10

'
1,2 ~m PI/AI 80

C, 85% RH

'

2d

"',

8d

J
O
t-

- . . . .

"..
"'""-..

""'..

~8~i..... .... "......::....

.........:::!iii::..
'";;:::,

O~

2
-2

2
log

co, raft s

-1

100
2d"

.....

..................................

8O

8d

......-" '

0
~lU

..." ................

..

~ 60
d
~ 40

,....:.

.,." ...... ..,..

,."

:'""" "..

." "18d
......

20

O.

0
-2

2
log

co, r a d

4
s

-1

Fla. 5. (a) Bode plot as a function of exposure time at 80C and 85% R H for a 1 . 2 # m thick
PI/A1 system: the impedance m e a s u r e m e n t s were carried out in Hg as the electrolyte;
(b) phase angle plot as a function of exposure time at 80C and 85% R H for a 1.2/~m thick
PI/AI system. The impedance m e a s u r e m e n t s were carried out in Hg as electrolyte.

was observed. After 18 days of exposure, a second time constant was observed. At
the same time black corrosion spots were visually detected.
The appearance of the second time constant probably indicates the onset of an
electrochemical process at the PI/AI interface. The impedance spectra were carried
out using mercury as the electrolyte; C1- ion contamination could not result from the
experimental procedure adopted. There are, however, two possible routes for ionic
contamination, namely (i) surface contamination due to handling, and (ii) residual
impurities coming from the PI itself. The synergistic action of the high temperature
and R H enhance ionic diffusion which ultimately leads to early failure of the PI/AI
system. It should be also pointed out, however, that the similarites between the Bode
plots observed with mercury as the electrolyte and with an air-saturated 0.5 M
aqueous solution of NaCI, do not necessarily mean that the same degradation
process is occurring in both cases.

The PI/Fe system

The corrosion behavior of PI/Fe samples was investigated by using the pseudopolarization resistance method and the impedance spectroscopy. Experiments were

Corrosion initiation on polyimide coatings

18r
oE

107 f

10 6

n, fl"

1211

5 /am PI/Fe 0.5 M NaCI

lO s
10 4

200

400

600

time,
FIG. 6.

800

Polarization resistance Rp as a function of immersion time for the 5 #m thick PI/Fe

system in air-saturated 0.5 M NaCl at room temperature.

carried out only on samples stored in a desiccator for 2 months. The Rp measurements were p e r f o r m e d on three different specimens in order to assess reproducibility
of data.
Figures 6 and 7 show the Rp as a function of the immersion time for Fe samples
coated with 5 and 15 # m PI, respectively. Results reported in these figures clearly
indicate the lack of reproducibility. Variation of one or two orders of magnitude in
the values of Rp at the same immersion time were observed among otherwise similar
samples. The values of Rp and its change with immersion time are commonly used
indicators of p o o r protection according to the criterion reported in the literature. 3
D e e p e r insight on the corrosion process taking place at the PI/Fe interface can be
obtained by the impedance spectroscopy technique, as will be shown below.
As for the PI/A1 system, the experimental findings will be reported in terms of
Bode and phase angle plot as a function of immersion time. Figure 8(a) and (b) shows
the data for the 5/xm thick PI while the data for the 15/~m samples are reported in

I0 s

15 I~m PI/Fe 0.5 M NaCt

10 7

E
u
E
.=
0

10 6

.
a.

105

104

,
0

200

400

600

800

time, h
FIG. 7.

Polarization resistance Rp as a function of immersion time for the 15 Ftm thick

PI/Fe system in air-saturated 0.5 M NaC1 at room temperature.

F. BELLUCC[ et al.

1212
,

5 pm PI/Fe 0.5 M NaCI

0d

',..,..

3d

,,., ........ .,....

....... . ......

.=:: . . . .

...............

...

"
""'.....

lh

.,...
"" ' " ,, . . . . ?

log Z

log Z

log Z

.....

_o
2
-2

log co, rad s

100

-1

5 lam PI/Fe 0 5 M NaCI

....I
........

80

Od ."

.?'
.'

60

...:,i.."'

lh "

40

"

20

3d .........................:::ii..::::

....... "

."
' ".. , . . : = : : . . . . . . "

0
-2

."
'" '
I

2
log co, tad s

4
-1

FIG. 8. (a) Bode plot as a function of immersion time for the 5/~m thick PI/Fe system in
air-saturated 0.5 M NaCI at room temperature; (b) phase angle plot as a function of
immersion time for the 5 #m thick PI/Fe system in air-saturated 0.5 M NaCI at room
temperature.

Fig. 9(a) and (b). A quick departure from a purely capacitive behavior for the PI/Fe
system compared to that of the PI/AI system is observed. Two time constants were
clearly observed after 1 and 5 h of immersion for the 5 and 15 # m films, respectively.
The observation of a second time constant indicates the onset of a corrosion process
occurring at the metallic substrate. The results of Figs 8(b) and 9(b) show that, after 3
days of immersion, a diffusional process within pores in the film is taking place. As in
the case of the PI/AI system, the time of failure was taken as the time required to
separate the film and the metal response. On this basis, the 5 ktm coated Fe sample
exhibits a lifetime of 1 h, while the lifetime for the thicker sample is 5 h. Both
lifetimes are of orders of magnitude lower than those exhibited by the coated and
stored A1 samples. The metallic substrate, thus, can affect the corrosion behavior of
the PI/metallic system in aerated 0.5 M NaC1 solution. As will be shown in a
subsequent section, the dielectric properties of PI are not affected by the metallic
substrate when exposed to a dry environment.

Dielectric properties of applied PI

In this section the dielectric properties of the coating will be discussed as they

Corrosion initiation on polyimidecoatings

,

1213

15 lam PI/Fe 0,5 M NaCI

E
O

Od

5h

,,C
O

.......:::::iiiiiii?-....
..

3d

"-,..

......
.::;:::::.
o

2
-2

log co, rad s ' l

100
15 I.tm PI/Fe 0.5 M NaCI
(I)

.=
IO}
O
"O

C
a

80
0d

60
40

0
fO.

..."

20
0
-2

.,.:: ":
. . . i : : z' ..'=
..

.."'

5h .........-..i:i:i.....'...: ::::'::""
3d

..

"..i:)"

".-.--.
I

2
log o~, rad s

-1

FIG. 9. (a) Bode plot as a function of immersion time for the 15/~m thick PI/AI system in
air-saturated 0.5 M NaCI at room temperature; (b) phase angle plot as a function of
immersion time for the 15 #m thick PI/AI system in air-saturated 0.5 M NaCI at room
temperature.

relate to the corrosion of the metallic substrate, to the water and salt uptake and to
the film thickness.

Film capacitance and rest potential time decays The variation of rest potential and
the film capacitance as a function of immersion time for the PI/A1 system (samples A
and B) and for the PI/Fe system are reported in the form of a double plot in Figs 10
and 11, and in Figs 12 and 13, respectively. The values of Cf were obtained from the
high frequency part of the Bode plot. These values were in good agreement with the
values as calculated at the frequency of 6.5 kHz where the reactive component of the
total impedance approaches the value 1/(2:rfCf). In Figs 10 and 11 are also reported:
(i) the pitting potential of pure A1 in neutral aerated 0.5 M NaC1 equal to
- 7 0 0 mV(SCE) (arrow on the right hand scale), 31 and (ii) the time at which black
corrosion spots were visually observed (arrow on the upper scale). The latter time is
also reported for the PI/Fe system in Figs 12 and 13.
Both PI/AI samples (A and B) exhibited the same capacitance value after
immersion in the test solution (3.89 nF cm-2). The rest potential, however, was quite
different. Sample A exhibited a potential of - 7 6 0 mV whereas sample B exhibited a

1214

F. BELLUCCIet al.
s.o

......

Sample"A"
Cf

----a---

......

1000

/~
[

"m

E
u

>

,,

c
O"

4,0

.......

3'50"1

........

100

.......

101
time,

, .

102

-lO0O

O"

FIG. 10. Rest potential, Eo, and film capacitance, Cf, as a function of immersion time for
the 1.2 # m thick PI/A1 system (sample A) in air-saturated 0.5 M NaCI solution at room
temperature.

potential of - 2 2 0 mV. The less noble potential is very close to the AI pitting
potential. This indicates the presence of reduced pathways for the external salt
solution. These pathways could be either holes invisible to the impedance test with
the mercury electrolyte described in the experimental section, or may be due to
diffuse heterogeneities. The value of Cf, however, indicates that the PI was not yet
affected by the corrosion process at the interface. This is because the electrochemical
reaction taking place at the metallic interface occurs at low rates as described below.
Pure AI in aerated 0.5 M NaCI solution exhibits a mixed potential equal to
- 1 2 0 0 mV(SCE). 31 The AI corrosion rate, even in high NaC1 concentration, is
negligible due to the poor catalytic behavior of the A1 for the oxygen cathodic
reduction. 31 Significant corrosion rates can only be observed at potential values
above the pitting potential [ - 7 0 0 mV(SCE)]. It can be concluded that - 7 6 0 mV as
rest potential may well be compatible with low corrosion rate. After 1 day of
immersion, a potential of - 6 4 0 mV(SCE) (above the pitting potential) and a film
s,o

;.2.~,~, Pi#,io:~ MNa5', ..... ~ ...... t000

Sample "B"

~,
E
u

I~

4,5

,,

O"

o
I,M

4,0

3,5

. . . . . ". . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

0 "1

10 0

10 1

time,

10 2

10 3

-1000

10'

FIG. 11. Rest potential, E0, and film capacitance, Cf, as a function of immersion time for
the 1.2 # m thick PI/AI system (sample B) in air-saturated 0.5 M NaCl solution at room
temperature.

Corrosion initiation on polyimide coatings

. . . . . . .

. . . . . . .

. . . . . . . .

. . . . . . . .

1215

-400

5 p.m PI/Fe 0.5 M NaCI

1,4

E
o

t,I.
P

1,2
-600

E
-

t.o

1,0

0,8

0-2

10-1

10 0

101

-800
O-

102

t, hr
FIG. 12, Rest potential, E0, and film capacitance, Cf, as a function of immersion time for
the 5/~m thick PI/Fe system in air-saturated 0.5 M NaC1 solution at room temperature.

capacitance of 4.19 nF cm-2 were observed. Both trends indicate the occurrence of a
degradation process at the AI interface. Even if no visual corrosion spots were
observed, the tendency of the PI/AI system is towards early failure.
The observed increase of the rest potential with time may be due to: (i) presence
of cathodic sites (PI itself, contaminants on the metallic substrate, aluminum
compound formed during the curing of PI), (ii) macroscopic defects originated by
microcracks due to unreleased stress, and (iii) A1 surface heterogeneities. For
prolonged immersion, the rest potential varied between -700 and -587 mV while
the film capacitance reached a maximum value of 4.8 and then decreased to 4.6 nF
cm -2. At this stage, black corrosion spots were visually detected.
Figure 11 shows the results of sample B. The time decay of both E 0 and Cf
exhibited a less dramatic behavior. A constant Cfwas measured up to 120 h followed
by a smooth increase from 120 to 456 h of immersion. A sharp increase was then
observed with a maximum value (4.87 nF cm -2) very close to that of sample A. It is
remarkable to observe the occurrence of the sharp decrease of E0 [from -480 to
-900 mV(SCE)] at roughly the same time where a sharp increase in Cewas observed.
0,46

~,

........, ........ , ........, ........, . . . . . . . 400

15 urn PI/Fe 0.5 M NaCI

0,44
E

~=.
o"

~_~

0,42

-'~\

Cf

~ = o

>

-6oo

o,4o

E
=o

0,38

0'3602

.............................
10 "1 10 o
101
lime,

102

-800
10-

FIG. 13. Rest potential, E0, and film capacitance, Cf, as a function of immersion time for
the 15/~m thick PI/Fe system in air-saturated 0.5 M NaCI solution at room temperature.

1216

F. BELLUCCIet al.

The lowest potential measured in this case [ - 9 0 0 mV(SCE)] may be ascribed to the
absence of impurities at the interface or to the reduced contaminations in the curing
process. Oxygen reduction on pure AI is a very slow process. Thus, also in this case
cathodic sites were operating. Once the pitting potential is established, the electrochemical degradation is fast and failure (black spots) can be detected.
At longer immersion time, sample B exhibited behavior different than that of
sample A. An increase of the rest potential was observed with a final value of
- 9 0 mV. This result, in conjunction with the impedance response (absence of a
diffusive component in the phase angle plot), can be explained assuming that the
cathodic and anodic sites were separated. The anodic sites correspond to the points
at which corrosion spots were observed, while the rest of the metallic surface acts as
the cathode. Sample A showed a stable rest potential even after corrosion spots were
observed. This trend together with the appearance of a diffusive tail (see Fig. 1 at low
frequencies) indicates that anodic and cathodic area coincides. The degradation of
the PI/AI system seem to be dispersed rather than localized in this case.
The time behavior of the film capacitance exhibited by the PI/Fe systems is similar
to that shown by the sample A, as described above. A sharp increase in the film
capacitance (from 0.82 to 1.4 nF cm -2) was observed for early immersion followed
by a sharp decrease at longer immersion. Also in this case it is remarkable to observe
the occurrence of the sharp increase of Cf at the same time where a decrease of the
rest potential was observed. Both samples exhibit a continuous decrease of Eo that
appears more pronounced for the sample with the thinner coating. A potential of
- 6 2 0 mV(SCE), a value close to the corrosion potential of pure iron in aerated 0.5 M
NaCI solution, was observed after 1 h of immersion. This result indicates that the salt
solution has penetrated through the coating reaching the metallic interface. At this
stage the corrosion process can initiate. The value of Cf, 1.07 nF cm -2, indicates that
the PI has been affected by the electrochemical reaction. Even if no visual corrosion
spots were observed, the tendency of the PI/Fe system is toward early failure. Black
corrosion spots were visually observed after 35 h of immersion.
The time decay of the 15/~m coated Fe sample is less dramatic. Penetration of the
electrolyte through holes or heterogeneities occurs at a reduced rate due to the
increased thickness and visible corrosion spots were observed after 120 h of
immersion in the test solution.
The results described in these figures show a close analogy between reliability and
film capacitance. A rise in capacitance preceded visible breakdown: Cf measurements could, thus, be used as a non-destructive test to detect early failure of organic
packaging materials on metallic substrate.
Capacitance measurements have also been used to determine the effective
lifetime of a coating.32 A rise in film capacitance preceding visible film breakdown in
aerated artificial sea-water was reported in the literature and ascribed to a different
mode of water uptake in the coating. 32-35 A detailed discussion on the mode of water
uptake is described in the subsequent section.

Water uptake. The dielectric properties of a coating varies as water is taken up.
The film capacitance increases as a function of the immersion time in NaCl solutions.
This increase in capacitance has been associated with water penetration into the
coating. 32

Corrosion initiation on polyimide coatings

1217

Film "capacitance'of dr; supp'orted 'Pl

..,,'

'?,
E

Pl/Fe
c =4.57.
j,"

ii
C

o"

u,O0

,e/"

...J ..'"
f/ ..,'"
z~.'..oO."

....'""

...'""P I / A I
c =3.24

o"**"

0,25
l/L,

0,50

0,75

1.tm

-t

FIG. 14. Film capacitance, Cf, as a function of the reciprocal of the PI film thickness for dry
PI/AI and PI/Fe systems at room temperature.

The amount of water taken up by the coating can be calculated from the
capacitance values using the following relationship: 33
Xv = 100 log (Cf,t/Cf,o)
log 80

(2)

where Xv is the volume percentage of water taken up by the film, and Cf,t and Cf,o are
the film capacitances at time t and zero, respectively. Equation (2) was derived
assuming: (i) a linear relationship between the permittivity of the polymer-water
system and those of the pure components, (ii) a random distribution of water, and
(iii) a linear relationship between permittivity and capacitance. Reasonable agreement between water uptake determined gravimetrically and calculated using
equation (2) was observed for relatively small amounts of water taken up. 34 Poor
agreement was observed at higher water content. 35
By applying equation (2) to the data reported in this paper for the 1.2 (sample A
and B) and 2.4pm thick PI, an estimate of water uptake equal to 2.7% vol/vol 4 wt%
was obtained. This result in conjunction with the values of the rest potential, suggests
a different distribution mode of the water in sample A that leads to an early failure of
this sample when immersed in the salt solution. The water taken up by the 5 and 15
/xm PI was equal to 4.7% vol/vol (7.0 wt.%). The water taken up by the PI coated on
AI is in the range of the values for PI reported in the literature. 17-21Somewhat higher
is the value of the water taken up by the PI coated on Fe. This result may suggest that
the additional water taken up by the PI/Fe system can be distributed into the coating
(holes) or at the polymer/metallic interface.

The effect of coating thickness. Assuming that the PI behaves as a pure capacitor,
the permittivity e can be calculated by the following equation:
1

Cf : CE0 ~

(3)

where Cf is the film capacitance in nF c m - 2 e0 is the absolute permittivity (8.854

10-14 F cm-2), and L is the film thickness in cm. Figure 14 shows the capacitance Cf
as a function of 1/L for the dry PI/AI and PI/Fe systems investigated. The experimen-

1218

F. BELLUCCIet al.

tal points lie on a straight line that extrapolates to the origin of the axis in agreement
with equation (3). The estimated relative permittivity is equal to 3.24 and 4.57 in the
case of the PI/A1 and PI/Fe systems, respectively. These values are the range of the
data reported in the literature for PI. 7"37 The AI and Fe metallic substrates,
therefore, do not affect the PI dielectric behavior at least when the PI is in the dry
state.
The effect o f NaCI. An increase of the coating capacitance for prolonged
immersion in salt solution has been reported in the literature and attributed to an
increase in the water uptake or to a different mode of the water distribution into the
film. 32'35 Since this rise preceded visible breakdown, it can be concluded that water
uptake and its distribution into the PI is affected by the salt content of the film and the
salt transport through the PI. The follwing arguments support this hypothesis.
When a coated metal is immersed in an aqueous salt solution, the first step of the
overall degradation process is water and salt uptake. Water and salt uptake in a
homogeneous free standing polymeric film of thickness L can be described according
to Fick's law by using the dimensionless time variable r = t D / L 2 (D is the diffusion
coefficient). 38 The thermodynamic equilibrium between the external and internal
(film) solution, occurs for r - 1. Accordingly, the time required to saturate a
supported PI film of thickness L (neglecting the effect of the metallic substrate), is
given by:
t -> (2L)-----f2
D

(4)

The diffusion coefficient D of water and of CI- across PI have been reported in
the literature as 2 10 -9 cm 2 s - l , 17"20'21 and 1 10 -13 cm 2 s - l , 39 respectively.
A 1.2/~m thick PI film will be, thus, saturated by the water and the CI- after 29 s and
160 h, respectively. The latter time is of the same order of magnitude as the time at
which the rise in the film capacitance was observed (see Fig. 11). Since ions are taken
up by a polymeric material with their hydration shell, the latter result suggests that
the observed rise in capacitance could be attributed to the ion bound water. It is
assumed also in this case that a random distribution of the ion bound water exists in
the PI. Thus, equation (2) can still be applied.
Due to the low dielectric constant of the polymer-water-salt solution (of the
order of 10 in this case) 4 water molecules are weakly bound to the ions. At this time,
the homogeneous dispersed water in the film may cluster with the water associated to
the absorbed ions leading to macroscopic clusters. If such clusters are in contact, they
may create paths of reduced ionic resistance through which CI- can easily reach the
metallic interface to initiate pitting. Of course, the greater the external NaC1
concentration, the larger the number of columns that can be developed and the
shorter the lifetime.
The time to saturate a 2.4 p m thick film with water and NaC1 according to
equation (4), is 115 s and 27 days, respectively. Also in this case the lifetime
experimentally observed in 0.5 M NaCI (130 days) was greater than the time required
to saturate the 2.4 ,um film with NaC1 in agreement with the previous result. In
addition, this result supports the idea that the 1.2 and the 2.4 p m thick films can be
considered homogeneous as far as the water and the salt uptake are concerned. If
heterogeneities are present salt can easily reach the interface through the pores and

Corrosion initiation on polyimide coatings

1219

early failure is expected. This aspect will be dealt with in the mathematical model
section.
The time to saturate a 5 and 15/~m thick film with water and NaCI according to
equation (4), is 500 s and 115 days, and 1.2 h and 3 years, respectively. The
experimentally short lifetime observed in the case of the PI/Fe system clearly
indicates the presence of diffuse heterogeneities or pores through which the salt
solution can easily diffuse to reach the metallic interface. Early failure is, thus,
expected in this case. An estimate of the pore sizes that can account for the early
failure observed in this case will be attempted in the next section.
Using a reasonable value of the activation energy (46 kJ mole -1) for ionic
diffusion in polymers, 41 a 10-fold increase in D is expected if the temperature is
increased from 20 to 85C. From equation (4), this in turn leads to a 10-fold decrease
in the saturation time. If salt uptake is the rate determining step in the degradation of
the interface, a 10-fold decrease in the lifetime of the device is expected. Experimentally, a 5-fold decrease was observed (Fig. 5) in the 85C test. This correlates well
(within a factor of two) with the predicted value. This descrepancy could be,
probably, ascribed to both the approximate value of the activation energy used and
to a non uniform contaminants distribution into the PI.
Mathematical model

In this section an attempt will be made to introduce and to discuss the concept and
the role of pores as related to the coating lifetime. The aim of this section is to relate
coating lifetime to coating properties such as porosity, tortuosity factor, C1- ion
diffusion and distribution coefficient, and coating thickness. Two approaches will be
presented and discussed. In the first one it will be assumed that the solution filling the
heterogeneities or pores is not in thermodynamic equilibrium with the electrolyte
solution dissolved in the homogeneous part of the film, while in a second approach
thermodynamic equilibrium is assumed. Before discussing these models some
preliminary concepts will be introduced.
As reported above, coating breakdown is related to the underfilm corrosion
process. This process can take place when all the necessary ingredients, i.e. water,
oxygen and electrolyte (C1-) are available at the interface. Water, oxygen and ions
are taken up into the PI film at a rate depending on their diffusion coefficient, D.
Each sorption process is based on the following first and second Fick's law:
J = - D --OC
Ox
OC
Ot

02C

D -

Ox2

(5)

(6)

where J is the solute flux over a distance x, C the concentration and D is either the
water, the oxygen or the chloride ion diffusion coefficient.
In order to obtain the amount of penetrant (water, oxygen and chloride ion)
taken up by the coating as a function of the time as well as its equilibrium value,
equation (6) must be solved with the appropriate boundary conditions. The thermodynamic equilibrium rather than the kinetics of solute uptake, will be assumed in this
paper as the parameter that affects interfacial coating breakdown. As already
reported, the thermodynamic equilibrium between the external and internal (film)

F. BELLUCClet al.

1220

External electrolyte
~i c19 ;4
........
~ ~ ~ m e :if:r (d)
i '

"::ijii!::l~
i

(c)

F~. 15. Schematic of the coatingmetallicinterfaceshowingthe differenttype of pores.

solution, occurs for r -> 1, while the time required to saturate a supported film of
thickness L is given by equation (4). Since the C1- diffuse into the PI at the lowest
rate compared to those of water and oxygen, then the time required to reach
equilibrium between the CI- dissolved into the PI and the CI- of the external
electrolyte is the rate determining step for corrosion to occur at the PI/metallic
interface. This time is defined as the minimum (coating) lifetime, MLT and is given
by:
M L T - (2L)2
D

(7)

In effect, the MLT corresponds to the time required for the electrolyte to reach
the maximum concentration at the coating/metallic interface. The time at which this
interface fails can be no less than the MLT, but it can be very much larger, depending
upon the Cl- ion concentration at the coating/metal interface, the kinetics of the
interfacial corrosion and delamination rate, for example.
If the coating is homogeneous, then the diffusion coefficient to be inserted into
equation (7) is the chloride ion homogeneous diffusion coefficient into the PI fully
saturated with water. If the coating is heterogeneous, then the diffusion coefficient to
be used in conjunction with equation (7) must take into account: (i) the salt
transported into the pores, (ii) the salt transported into the homogeneous part of the
coating, and (iii) the salt transport between the volume of solution filling the pores
and the homogeneous part of the coating. In each of these cases, equations (5) and
(6) must be modified appropriately to account for these additional effects. Before
addressing these issues, two extreme cases will be analysed first: (i) a homogeneous
film of thickness L fully saturated with water, and (ii) a stagnant water layer of
thickness L separating the metallic interface from the environment. The latter case
can be considered equivalent to that of a coating fully porous. In the first case D =
Ds, f while in the second case D = Ds,w, where Ds, e and Ds,w represent the CIdiffusion coefficient in the homogeneous film and in water, respectively. The
minimum lifetime of a coating, therefore, varies between MLTw = (2L)2/Ds,w and
MLTf = (2L)2/Ds,f.
The real situation differs from the above two limiting cases. The coating will
contain, to some extent, pores of not well defined geometry and structure such as
those schematically reported in Fig. 15 as (a), (b), (c), (d) and (e). It should be

Corrosion initiationon polyimidecoatings

1221

appreciated that the MLT for cases (a), (d) and (e), are expected to be of the same
order of magnitude since in each case the electrolyte must penetrate the same
effective path length through homogeneous film. On the other hand, the ultimate
failure of the interface is likely to occur more readily for case (a), which includes the
interface between the coating and substrate than for either case (d) or (e) which are
removed from the interface. In order to account for the presence of such pores in the
mathematical model, the coating porosity 0 can be defined as: 0 = Vp/V T, where Vp
and VT are the volume of pores and the nominal volume of the coating, respectively.
No pores size distribution will be considered in the present investigation.
In the first approach it is assumed that only pores of the type (b) and (e) exist. In
addition it is further assumed that the pores diameter, dp, is large enough to neglect
the flux of CI- from the solution filling the pores to the pores wall (homogeneous part
of the coating). According to the schematic of Fig. 15, the flux N is assumed to be
much less than the flux J. First and second Fick's law describing salt uptake into these
pores are still given by equations (5) and (6). The time to saturate the continuous
pores is much smaller than the time required to saturate the homogeneous part of the
film. In this case the MLT, is given by:
MLT = (2L)2vP
DS,W

(8)

where Vp is a pore tortuosity factor defined as the ratio between the real path length
and the nominal thickness [rp = 1 for (c) type pores and rp > 1 for (b) type pores].
The MLT is, thus, a function of rp and of L 2, and does not depend on the porosity 0.
As second approach, it is assumed that equilibrium exists at any time t between
the homogeneous part of the coating and the electrolyte solution filling the pores.
The unsteady state processes of interest are, in this case, those occurring into the
homogeneous part and into the pores of the film. The solute flux into the homogeneous film, Jr, and into the pores, Jp (first Fick's law), can be written as:
j f = _ D s , f (1 -- O) Off

rf

Jp

(9)

OX

0 OC
-Ds,w - - - Vp Ox

(10)

where rf and rp are the film and pores tortuosity factor, respectively. Due to the
thermodynamic equilibrium between the solution filling the pores and the solution
homogeneously dissolved into the film, the electrolyte concentration into the film,
Cf, is given by: Cf -- KC, where K is the distribution coefficient that is assumed
constant with the concentration.
After some manipulations, the second Fick's law describing the uptake of salt
into the pores can be written as:
OC _ De q O2C
Ot
OX2

where Deq is an equivalent diffusion coefficient given by:

(11)

1222

F. BELLUCCI et al.

10 3

P /AI
.......

102
o

....-"

"B"

100

.............

...............
101

......." .......

102

" " ....

'

..-=

./"
..... .......

.............J"""
O=10' -8 ..............
...........

.................

. ..........

..........-'"

13 0

.............
"

. ...... -9
......... 0=10

..-"....

''''y''
:.O ":~A
. . . . . . . . . . . . . . . "'"""""''

101
,.~

.........
0"~0

-7

............. 0=10

..;

..e .......... P I / F e
0.5 M NaCI
.

101

10 2

L, p m

FIG. 16. M L T in days as a function of L for different values of 0 for the PI in presence of
0.5 M NaCI. In the same Fig. the experimental lifetime for the PI/A1 (samples A and B) and
the PI/Fe system in air-saturated 0.5 M NaCI at room temperature are also reported.

D~ f K ( 1 - 0) + Dsw ~
Deq =

K(1 - . 0 ) + 0

'r.

(12)

Due to the assumption made on the constancy of K with the concentration, equation
(11) is equivalent to equation (6). The MLT is, thus, given by:
MLT-

(2L)2

(13)

Oeq

Equation (13) shows that the MLT depends, in this case, on L 2 and on the
equivalent diffusion coefficient, O e q that is depending on the porosity 0, on the
distribution coefficient K, on the tortuosity factors, re and I'p, and on the C1diffusion coefficient in the water and into the homogeneous part of the film.
Equation (12) well describes the two limiting cases of 0 ~ 1 and 0 --~ 0 mentioned
above. In the former c a s e Deq --~ Ds,w (layer of water of thickness L), in the latter
c a s e O e q ~ D s , f (homogeneous film of thickness L).
The M L T theoretical findings obtained above (equations 8 and 13) can be
compared with the lifetime experimentally observed for the systems investigated in
this paper. In order to compare theory with experiments a criteria for the failure of a
coating should be available. Different criteria have been reported in the literature to
assess coating breakdown as related to water or salt taken up by the coating for
prolonged immersion in NaC1 solutions. 32'3s'36 Two different paint behavior types
were described in the literature, which were independent of the method to determine
coating lifetime.35'36 The first showed a decrease in lifetime with an increase in NaCI
concentration, 35 while the second showed the opposite behavior. 36 The appearance
of a second time constant in the Bode (or phase angle) plot was used as the criterion
to determine lifetime "in this paper. The second time constant is associated with an
electrochemical reaction at the coating/metallic interface. These values for the PI/AI
system (samples A and B) and for the PI/Fe system are shown in Fig. 16 as a function
of the film thickness on a log-log plot.

Corrosion initiation on polyimidecoatings

1223

The difference in the lifetime experimentally observed in the case of PI/A1

(samples A and B) and PI/Fe systems could be ascribed, according to equation (8), to
the presence of macroscopic defects characterized by a difference (by orders of
magnitude) of the tortuosity factor. It is reasonable, however, that due to the small
values of the thickness L, rp is probably of the order of 1, therefore the experimental
lifetime values cannot be ascribed to different tortuosity factors among the samples
investigated. At the same time it should be pointed out that pores with d p - L can be
considered as large defects. Although this approach fails in describing the experimental lifetime findings, an estimate of rp and of dp were obtained. These estimates
will be used to evaluate the M L T values as shown below.
To compare the M L T as calculated by the second approach (equations 12 and 13)
with the experimental lifetime, it is reasonable to assume, rf - ~p - 1 as described
above. The diffusion and distribution coefficient of CI- across PI have been reported
in the literature as 1 10-13 cm 2 s - 1 and 0.01 39 while the CI- diffusion coefficient in
water is equal to 1.5 10 -5 cm2s-1. On these bases, the theoretical MLT values as a
function of L are reported in Fig. 16 for different values of the porosity 0. As can be
seen, the experimental lifetime data for the sample A (PI/AI system) lie in the
vicinity of the M L T values for 0 -- 0, while those of sample B lie well above the M L T
values for 0 = 0. This result indicates that both the PI/A1 samples (A and B) can be
assumed as homogeneous as far as the CI- ion diffusion across the PI is concerned in
spite of the shorter lifetime exhibited by sample A. This result is also consistent with
the test carried out with the mercury as the electrolyte that revealed the absence of
macroscopic defects. If, on the other hand, heterogeneities such as pores (b) are
present in the case of sample A, the order of magnitude of these invisible 'holes' must
be very low as will be shown later.
As reported above, the time at which failure is observed can be larger than the
MLT depending on the type and on the pores distribution into the PIs. The
macroscopic difference in the lifetime observed for samples A and B, could be
attributed, therefore, to a greater number of (a) type pores in sample A. Unreleased
water or solvent trapped at the interface, may have acted as a source of stress
reducing the adhesion between the polymer and the metallic substrate leading to
such interfacial defects. In these defects water can easily accumulate, thus providing
the medium in which the C1- ions coming from the homogeneous part of the coating
can concentrate up to its equilibrium value that is 0.5 M. In the presence of this high
CI- ion concentration, A1 corrodes at a high rate leading to the early failure of the
PI/A1 system. Although it is not possible at this time to discriminate between the two
possible degradation mechanisms [via distributed thin type (b) pores or via interfacial (a) type defects], the early failure observed for sample A can be attributed to a
poor interfacial adhesion rather than originated from large coating defects due to
processing.
Quite different is the behavior of the PI/Fe system. The experimental lifetime
values lie well below the M L T value for 0 = 0. The experimental lifetime well
coincide with the M L T values obtained assuming a porosity 0 = 10 - 7 . The presence
of (b) and (e) type pores can, thus, account for early failure observed in this case. An
estimate of the pores size diameter, dp, can be attempted on the basis of the following
argument. A coating containing n (c) type pores of diameter dp (for 1 cm 2 of nominal
coating surface) is characterized by a value of 0 ----nd 2. SEM carried out on PI of
comparable thickness did not reveal any kind of visible defects of the order of less

1224

F. BELLUCCIet al.

than 0.1/~m. It can be concluded that a porous film with 0 = 10-7 is compatible with a
number of pores n > 103. Diffuse heterogeneities rather than macroscopic defects
are, therefore, responsible for the corrosion behavior of the PI/Fe system. Such
invisible pores formed during the processing of the PI dramatically affect the PI/Fe
lifetime.
The theoretical analysis presented above allows the prediction that heterogeneities as small as 0.1 ktm (that are difficult to detect even at SEM) can reduce the
MLT of thin film by orders of magnitude. In addition, a method has also been
established to distinguish between failure due to defects into the coating [(b) and (c)
pores], from failure due to the loss of interfacial adhesion [(a) defects] depending
upon their position with respect to the MLT values for 0 = 0. The closer are the
experimental lifetime data to the M L T values for 0 = 0, the larger is the metallic
surface involved in the interracial corrosion process and the greater is the number of
(a) type heterogeneities. As ultimate goal of this analysis, an estimate of the
minimum pore size diameter for homogeneity (0 = 0) is also presented.
For 0 ~ 0, i.e. for extremely narrow pores, the mass balance applied to a shell of
thickness dx leads to:
OC
32C
N.Trdp
Sp ~ = SpDs, w ~Ox --

(14)

where N is the flux of solute from the inner of the pore to the solid film, Sp and dp are
the pore surface and diameter, respectively. In order to solve equation (14) an
expression for the flux N must be used to avoid the simultaneous solution of Fick's
second law into the pores and into the homogeneous part of the film. It is assumed
that the flux N is expressed by the film penetration theory, i.e. N = KCX/(Ds.f/Jrt),
where K is the distribution coefficient. Upon substitution of this expression into
equation (14) and after some manipulation, one has:

OC- DswO2C
Ot
Ox 2

KC ~-~p/~S~'f
~ Jrt "

By introducing the following dimensionless variable: 7 =

tDs,w/L z, equation (15) yields:

07_
Or*

027
O(X*)2

(15)

C/C=, x* = x/L and r* =

4 K L / Dsf
~

7d--pp~ / D ~ *

(16)

Equation (16) differs from Fick's second law. The difference is due to the second
term on the right hand side. This term becomes important when the ratio dp/L is such
that:
dp

4 K

/ Ds,r

(17)

Equation (17) allows estimation of the order of magnitude of the pores diameter foc
which all the solute entering into the pore is adsorbed into the homogeneous film.
This case is not of practical interest since the time to saturate this pore will be equal to
infinity due to the use of the film penetration theory. It is suitable to estimate the
pores size for r* - I and for a 1/tm thick film. On the basis of the diffusion coefficient

Corrosion initiation on polyimide coatings

1225

values r e p o r t e d above, d p = 10 -6 # m . This value is in the range of atomic distances.

T h e conclusion is drawn that a coating can be considered as h o m o g e n e o u s f r o m the
mass transport point of view when heterogeneities with dp as large as atomic
distances are present. O n the basis of this result and on the fact that the lifetime of the
sample A lie in the vicinity of the M L T values for 0 = 0, it can be concluded that
sample A can be assumed as h o m o g e n e o u s .
It should be pointed out, h o w e v e r , that the validity of the m o d e l discussed so far
is restricted to the assumptions of: (1) validity of Fick's law, (ii) equilibrium b e t w e e n
the s o l u t i o n filling the pores and that h o m o g e n e o u s l y dispersed into the film, (iii)
constant distribution coefficient K with the concentration, and (iv) absence of fixed
charge in the polymeric matrix.
CONCLUSIONS
(1) T h e lifetime of the PI/A1 system in aerated 0.5 M NaCl solution increases if
the samples are stored in a desiccator after curing. This process allows the release of
both the water and the solvent t r a p p e d in the PI as a result of the curing schedule and
the processing of the PI itself.
(2) T h e lifetime decreases with decreasing film thickness, and increasing temperature. C o r r o s i o n at the PI/metallic interface depends on the ionic rather than on
the water arrival at the metallic substrate.
(3) T h e capacitance of the PI exhibits a rise at a given time when i m m e r s e d in
NaCI. This increase was explained assuming clustering b e t w e e n the water h o m o geneously dispersed in the film and the i o n - b o u n d water.
(4) T h e metallic substrate does not affect the dielectric properties of the dry PI
for the thin (1.2 ~ m ) and the thick (15/~m) film investigated.
(5) T h e role of pores and the c o n c e p t of M L T is introduced and used to explain
the lifetime experimentally o b s e r v e d in the case of the PI/AI and PI/Fe systems.
(6) Interracial failure due to adhesion loss (interfacial defects) can be discriminate f r o m failure due to pores present in the coating if use is m a d e of the M L T
concept.
Acknowledgements--The authors wish to thank Professor S. D. Senturia of the Microsystem Laboratory

Technology of MIT for providing the PI/AI and the PI/Fe samples. The financial support of CNR
(Progetto Finalizzato Chimica Fine e Secondaria II) is also gratefully acknowledged.
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