METALS AND MATERIALS, Vol. 4, No. 6 (1998), pp.

1191~1197

Corrosion of Plastics and Composites in Chemical Environments

Hidemitsu Hojo, Ken Tsuda*, Masatoshi Kubouchi* and Dong-Seop Kim**

Engineering Management Department, College of Industrial Technology, Nihon University

1-2-11, Izumi-cho, Narashino-shi, Chiba-ken 275-0006, Japan
*Department of Chemical Engineering, Faculty of Engineering, Tokyo Institute of Technology
2-12-1, Ookayama, Meguro-ku, Tokyo 152-8552, Japan
**Chemistry & Chemical Eng. Div., Korea Institute of Industry & Technology Information
206-9 Cheongryangri-dong, Dongdaeman-ku, Seoul 130-742, Korea

The degradation of polymeric materials with chemical reaction in which the molecular chains is cut is
called corrosion. In this paper the behavior, the forms and mechanisms of corrosion of resins and GFRP
(glass fiber reinforced plastics) under several aqueous solutions are reviewed based on oar experiments.
Three types of corrosion exist: the surface reaction type, the corroded layer forming type and the penetration
type. Each form was determined by the chemical structures of the resin, the reactivity between resins and
environments, and also the diffusivity of environmental media into the resins. The concept of the corrosion rate
of metals could be applied even in plastics and fiber reinforced plastics for each corrosion form.
Key words : corrosion, plastics, FRP, composites, immersion

1. I N T R O D U C T I O N When materials suffer from external environment, e.g.,

light, thermal exposure, radiation, fluid, and mechanical
Plastics, elastomers and composites are being used exposures, chemical structures change and properties are
widely for protecting carbon steel equipments and also deteriorating with a lapse of time. Among these, fluid
as construction materials for components and structures. action is important for polymeric materials used in liquid
Corrosion resistant glass fiber reinforced plastics, (GFRP) environments as in chemical equipments. The degrada-
were introduced to prevent corrosion of towers, vessels, tion in the environment can be classified into physical
tanks and others. Their contribution in various fields of and chemical degradation. The physical degradation is a
the industry is very significant, too. common nature of polymeric materials. Basically it
The corrosion resistance of FRP depends primarily on is due to swelling, but in some cases swelling is
the performance of the resin used as matrix. Though followed by solvation and dissolution. The chemical
plastics and GFRP in general have excellent corrosion degradation, on the other hand, occurs by chemical
resistant properties, the corrosion resistant behavior and reaction between polymer chains and the environment.
the mechanism have not been reasonably elucidated. We describe the chemical degradation of polymeric
Especially, polymeric materials do not have the defini- materials as 'corrosion' which is generally defined as
tion of "corrosion and evaluation index like the "destruction or deterioration of a material by reaction
concept of "corrosion rate" as used in metallic corrosion. with its environment".
This prevents the rational corrosion resistant design with Table 1 shows the probable corrosion reaction of
these materials. polymeric materials under several environments. The
In this paper the corrosion problem of polymeric typical corrosion reactions of GFRP matrix resin in an
materials and composites is described and compared aqueous solution are hydrolysis and oxidation.
with that of metals using the corrosion behaviour and
mechanisms as a model. 3. CORROSION BEHAVIOR

2. D E G R A D A T I O N OF POLYMERIC 3.1. Chemical structures of resins

MATERIALS Fig. I shows the chemical structures of unsaturated
1192 Hidemitsu Hojo et al.

Table 1. Examples of corrosion reactions 3 ' ' ','"'1 ........ u O S0~ lOwt.%
Reaction Environment Chemical structure 9 65% lOwt.%
~ 80~ lOwt.%
Hydrolysis acid & alkali ester, nitrile, amide ~163
v 2 ~7 80oc 20wt.%
acid ester, acetal J. 9 80"C 30wt.%

Oxidation 02, 03, HNO3 ester, aliphatic, =~ 1 ^ . _ /Y o 80% 40wt.%

phenol, ether
Ester interchange alcohol ester
o
Dehydrochlorination high temperature alkyl choloride
e-
(a) e- -2

_3 i , i i i1~1 i i i i iiiii l I i iiiiii i i i Ill

=====================================
...... :::::~:::::::.... ::::~:~:~::~:~.].. 1 10 10 2 10z 104
Immersion time, t (h)
Isophthalic unsaturated polyester resin Fig. 2. Weight change of MTHPA-EP (see Table 2) by
immersion in NaOH.
C=C I C=C I C=C

liquid and resin, the strength of resin decreases as shown

HO-C~ IHO-C IHO'f; in Fig. 3.
C / C / C
By infrared spectroscopic analysis (IR), it was found
that corrosion proceeded with the following reaction.

Novolak type vinyl ester resin O O

(c) I~ li
r ? ~ c R-COR' + O H - , ' R-C-O + R'OH (in alkali) (1)
c-c-c-o,k-%c-C%o-c-c-c-o
'~..l I'Wl--W , ~i--~' ,
4-C5-c-C5-o-c-c-c
I ~ , U 99
u L C OH Jn C O
where R and R' indicate hydrocarbon groups.
Bisphenol-A type epoxy resin Other than the ester bonding, amide (-CONH), and
Fig. 1. Basic chemical structures of resins. The sha- ether (-O-) bonds tend to cause corrosion by hydrolysis.
dowed part is easter group. Thermoplastics such as polyamide (nyron), polymethyl-
methacrylate (PMMA), polyoxymethylene (polyacetal)
polyester and epoxy resins which are dealt with in this and polycarbonate are also probable to cause such
paper. Unsaturated polyester resin, (a), has many ester corrosion. Therefore, the more ester bonds, the less
bonds (-COO , indicated as shadowed parts) within the corrosion resistance. However, hydrolytic corrosion
main polymer chain, resulting in the probable attack sites behavior varies from the combination of resin, liquid
by acid and alkaline solutions. Novolak type vinyl ester environment and service or test condition. For example,
resin, (b), has a few bonds at the cross-linking chain. for the case of an amine cured epoxy resin which does
Epoxy resin, (c), has essentially no ester bond within the not have any ester bonds, no corrosion occurs in alkaline
main chain; the ester bonds are tbrmed within cross- solution at any temperature and concentration [1].
linking chain when using acid anhydride type curing
agent [1,2,3]. 3.3. Forms of corrosion
The forms of corrosion observed by the immersion
3.2. Corrosion behavior of resins testing in the chemical environment are classified into
Fig. 2 shows the typical results of the weight change three types, that is, the surface reaction type, the
as a function of immersion time [1,2]. At first the corroded layer forming type and the penetration type.
weight increases by penetration of liquid into the resin, 3.3.1. The surface reaction type
and then decreases by dissolution of the resin into liquid. This form is observed when the reaction rate is so
Finally it increases again by the penetration of liquid high that the dissolution of corroded resin starts directly
into the corroded resin. By the penetration of liquid into at the liquid contacted surface and the corrosion deve-
the resin and/or the hydrolytic reaction between the lops uniformly over the entire surface. This type
 Corrosion of Plastics and Composites in Chemical Environments 1 ] 93

the case of polycarbonate, alicyclic epoxy resin in

v
~- 1.1 . . . . . . . . r . . . . . . . . i ........ i ........ NaOH, and amine cured epoxy resin in HNO~.
t- 3.3.2. The corroded layer forming type
1.0 This type of corrosion is found in isophthalic
unsaturated polyester (iso-UP), novolak type vinyl ester,
0.9
x
and nyron in alkaline solution. Parts of corroded resin
0
~- 0.8 dissolve out and a residual corroded layer with original
bonding to uncorroded resin is formed.
~- 0.7 v 8o~c Zowt.% I ~ ~ Fig. 5 shows examples of the cross section of an
0 9 80'C 30wt.%l }~
'.~
t"- iso-UP specimen corroded by this type in NaOH and
o.8 ,~ Y?I, ....... ............
10 10z 10 3 1 04
KOH solutions. The boundary between the outside
e',,,'

Immersion time, t (h)

discolored layer and the central unchanged region can be
clearly observed. It was tbund by an IR analysis that
Fig. 3. Change of tlexural strength of MTHPA-EP by
corrosion was observed only in the di~olored portion.
immersion in NaOH. The thickness of the unchanged portion was measured
by microscopic or infrared spectroscopic observations,
of corrosion occurs when low molecular weight com- and lhe corrosion thickness defined by Eq. 2 was
ponents are produced by corrosion reaction at a cross- obtained. Fig. 6 shows the relation between the
linking chain. Corroded products dissolve into the ~lution corrosion thickness and the immersion time for the
directly from the surface. Fig. 3 shows an example of this iso-UP immersed in NaOH or KOH solution. In this
type of corrosion behavior. case, corrosion thickness was calculated by substituting
The corrosion lhickness x is calculated as follows,

x = ~ -1 (ho-h) (2)

where h0 is the thickness of the original specimen, and

h is that of the immersed one. Fig. 4 shows the
relationship between the corrosion thickness, x, and the
immersion time, t. A linear relationship
x=klt (3)

is applicable, where k~ is a constant.

This type corresponds to the general corrosion of
metals [4]. The same type of corrosion is observed in

--'--
I-I 9 80~
9 80"(;
40wt.% ]
30wt.% I. . 9
E / " zowt. l
60 I / J 8~176 lowt.%l
x II L v 65~ 10wt.%l

4O
t-

= 20
.o
O0
o
c
0 400 800 1 200
Immersion time, t(h) Fig. 5. Cross sectional photos of an iso-UP specimen
Fig. 4. Change of corrosion thickness of MTHPA-EP immersed in (a) 50 wt.% NaOH, 500h, and (b) 60 wt.%
by immersion in NaOH. KOH, 71h, at 80~
1194 Hidemitsu Hojo et al.

H/z~
I I I l
o ester bond
=~ 500 Before ~ m a i n chain
X 9 O optiqal
microscope KO c o r r o s l o n ~ ~cross link
/k IR analysis
O"O i I I /
,- 100
(J

~" 50
e- ( ~ ~ ~ " - ' - COr r odi ng zone
o
o /,~! 2 Iso-UP swelling zone
o 10 l I I
u 5 10 50 100 500 1000 uncorroded zone

Immersion time, t (h)

case 2 case 1
Fig. 6. Change of corrosion thickness of the iso-UP by
immersion in NaOH and KOH.

the thickness of! the central changed region into h in

Eq. 2. In NaOH solution, the corrosion thickness x is
in proportion to the square root of the immersion time residual corroded layer
as. lZig. 7. Corrosion process of corroded layer forming type.
x=k2t m o r x2=kz't (4)
corresponds to the case which forms the weak and/or
where k2 is a constant. This resin was cross-linked by coarse layer (case 1), and the novolak resin to the case
the styrene which brings the cross-linking molecular which forms the strong and/or tight layer (case 2).
chains with highly stable C-C bonds. Those molecular 3.3.3. The penetration type
chains are maintained with high molecular weight even This type of corrosion is seen in amine cured epoxy
though the easter bonds are disconnected by the resin immersed in H 2 8 0 4 . The corrosion form is
hydrolysis, and make a corroded layer. Eq. 4 means that characterized by a two-step process of diffusion and
the corroded layer makes a resistant layer to the reaction. The solution penetrates into the resin to reach
penetration of solution and the reaction occurs at the an equilibrium stage, and then its strength decreases
interface. In this case, the reaction rate is higher than the owing to the initiation of corrosive reaction as shown in
diffusion rate of liquid in the resin. This behavior Figs. 8 and 9.
corresponds to the Wagner's parabolic law for high In this type, the penetration depth is important, and
temperature oxidation of metals [4]. the depth can be measured by tracing S atoms in the
In contrast, if the same resin is immersed in KOH specimen immersed in H2SO4 with an X-ray micro-
solution, a highly swelled porous corroded layer is analyzer. Fig. 10 shows the change of the penetration
formed as shown in Fig. 5(b). The swelled and corroded
layer does not behave as a barrier for the diffusion 4O
of solution. Thus the relation between the corrosion A A ~ m,

thickness and immersion time (Fig. 6) follows a t--

30
rectilinear law as Eq. 3. This corresponds to the beha-
i=
vior of metals which produce a rough oxide film during 20
0
high temperature oxidation. ,W
,.i.
The corroded layer of iso-UP immersed into NaOH or r 10
KOH has no strength. It does, however, have strength in t..)
novolak resin. This is because it has ester bonds only at I I I I I
cross-linking chains, and also complicated three- 0 10 20 30 40 50 60
dimensional configuration. Or.mersion time) 1/2, ~- (~-)
The corrosion model for the corroded layer forming Fig. 8. Weight change of MDA-EP (see Table 2) by
type is shown in Fig. 7. In this figure, the iso-UP immersion in 10 wt.% H2SO 4 at 80~
 Corrosion of Plastics and Composites in Chemical Environments ] ] 95

i incubation time. This type of corrosion is a characteristic

i i i i i ,
form in plastics.
1.0
r

P 4. THE FACTORS DETERMINING EACH

t,o
0.8
FORM OF CORROSION
3

m
0.6 The number of repeated unit (n in Fig. 1) are also a
factor which determines which of the three forms is the
0.4 correct one. The number n was changed in epoxy resin
e- I I I I I i shown in Fig. l(c), and was cured with phthalic
0 1000 2000 3000
re" Immersion time, t (h) anhydride. In case of n=0, the surface reaction type
corrosion was observed, while n L>_.1, the corroded layer
F i g . 9. Change
of flexural strength of MDA-EP by
forming type was revealed [5]. Because of the severe
immersion in 10 wt.% H a S O 4 at 80"C.
entanglement of the long chain polymer structure, the
corrosion products were difficult to be dissolved.
1.0 i , i i A concept of corrosion rate can be applicable to each
corrosion form. The equations of corrosion rate are
oE 0.8
summarized in Table 2 taking into account the chemical
,.- 0.6 structures, reactivity and diffusivity.
o
Three forms of corrosion can be understood from the
g 0.4 view point of diffusion and reaction rate. When
"o
r diffusion rate (( reaction rate, corrosion behavior obeys
o 0.2
the surface reaction type or the corroded layer forming
o I
type. If the cured resin is decomposed at cross-linking
0 5 10 15 20 2'5 30 sites in the main chain, and produces low molecular
(Immersion time) l/z, ~- ( ~ ' ) weight products, the surface reaction type occurs. And if
Fig. 10. Penetration depth of S atom in MDA-EP imm- the chain of cured resin is partially broken, corrosion
ersed in 10 wt.%, 80~ H 2 S O 4. products maintain a relatively high molecular weight,
and then the corroded layer forming type will be
depth with the immersion time. The depth is observed. When diffusion rate)) reaction rate, the
proportional to the square root of (t-to), where L is the penetration type can be expected.

Table 2. Forms and rate equations of corrosion for thermosetts

Reaction rate (R) & Corrosion rate
Form of corrosion Resin Environment
Diffusion rate (D) equation
Bisphenol A type EP cured with MTHPA NaOH x ec t
Bisphenol A type EP cured with PA (n=0) KOH x ~:n t
Surface reaction type D<<R
Bisphenol A type EP cured with MDA HNO3 x ~x t
Alicyclic type EP cured with PA NaOH x ~: t
lsophthalic UP KOH x oct
Isophthalic UP NaOH x c~ I:~/~
Corroded layer D << R Isophthalic UP HNO3 x ~ t v2
forming type Orthophthalic UP NaOH w ~: (t-to)1/2
Bisphenol A type EP cured with PA (n_~l) KOH
Novolak type VE NaOH, KOH x oc i m
Orthophthalic UP Boiling water w oc (t-to)v2
Penetration type D >> R Bisphenol A type EP cured with MDA H2SO 4 y ~ (t-to)l:z
t: immersion time, to: incubation time, x: corrosion thickness, w: amount of dissolute y: penetration depth, EP: epoxy resin,
UP: unsaturated polyester, VE: vinyl ester resin, MTHPA: methyl-tetrahydrophthalic anhydride, PA: phthalic anhydride and
MDA: p-menthane- 1,8-diamine.
1196 Hidemitsu Hojo et aL

5. C O R R O S I O N BEHAVIOR OF I0C i i i !

COMPOSITES Vf=40.2 %
g"" 8c ~.o,,
Corrosion resistance of GFRP is initially determined
by the performance of a matrix resin, but ultimately it is
controlled by the performance of fiber/resin interface at
the later stage. The example which gives the effect of
.s 60
Creepi-rupture~
9\ _ ",c-, I mmersion
~ ' ~ , j - - ~ - -

the interface on the degradation behavior of GFRP is tn 20 ,o

shown in Fig. 11 [6]. This is the result of creep-rupture NoOH (50"C)
I I I I I
tests for resin and GFRP in NaOH. There are three q ;2 10-I I 10 102 103
stages of degradation for GFRP; the first stage is due to Time (h)
the degradation of matrix, the second one is due to that
Fig. 12. Correlation between immersion test and creep
of the interface between matrix and fiber, and the third
rupture test at 50~
one is due to fiber itself. The reduction of strength in the
second stage is promoted by increasing the glass
contents, meaning the increase of the interfacial area. sufficient to evaluate the corrosion resistance of the com-
The results of both the immersion test and the creep- posites [6,7].
rupture test are compared in Fig. :12. The rentention of The GFRP specimens of amine cured epoxy resin (Fig.
tensile strength versus immersion time in immersion test,
and the ratio of applied stress to initial tensile strength
versus rupture time in the creep-rupture test, were 20 . . . . . . . . . . . . 1
represented. The behavior is essentially the same ~ O~
independent of test methods, but the transition time from .~ ---O-- HNO3 (2mol/I)
, ~ -20 ~ . -""-El3--HzSO4 (2tool/I)
the first stage to the second one is extremely affected by ~ HaPO 4(2mol/I)
the loading condition. -40 --o-- NaOH (2mol/l)
--E]--H20 ( - )
Consequently, stress accelerates the corrosion of com-
posites significantly. This phenomenon is called "stress
~ -60 )-( NaNOa(2tool/I)
--,e-- H2O2 (30wt%)
t~ -"-~::P"-HCIO4 (2mol/I)
corrosion" as in metals. This also means that conven- f~ - 8 0 + KMn04 (0.33mol/I)
tional immersion tests without loading are not always -loo ~_. . . . . . . I
0 400 800 1200
Immesion time, t (h)
, , , , ' 1250
120 ""(X)~ _ NoOH (50"C) Fig. 13. Weight change of matrix resin (MDA-EP) in
GFRP by immersion in several aqueous environments at
80~

z7o ~ ' ~ - - - -
80
1oo

~ 50

qC-2 I
10-I I
I I
10 102
I
103
I I

Creep r u p t u r e t i m e , t ( h )
Fig. l l . Creep rupture curves of vinyl easter resin and
its GFRP with various glass contents in 1() wt.% NaOH Fig. 14. Observation of MDA-EP-GFRP specimen after
at 50~ immersion in 4 mol/1 HNO3 at 80~ 100 h.
 Corrosion of Plastics and Composites in Chemical Environments 1 197

l(c)) were immersed in various liquid environments at and composites, it was discovered that the concept
80~ Fig. 13 shows the weight change of the part of of corrosion rate in metals could be applied also to
matrix resin in GFRP. After a certain period of polymeric materials and GFRP. Moreover, a possibility of
immersion in HNO3 and H202 solutions, extremely applying the corrosion behavior of composites to disposal
severe degradation could be observed, namely resin is and recycling their waste was pointed out.
dissolved out completely and only glass fiber remains as
shown in Fig. 14. This means that this corrosion process REFERENCES
will be available to the disposal and recycling of GFRP's
waste [8]. 1. H. Hojo, K. Tsuda, K. Ogasawara and T. Takizawa,
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6. EROSION-CORROSION DAMAGE Control (eds., R. A. Dickio and F. L. Floyd), p. 314, Am.
Chem. Soc. (1986).
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Mater. 1, 55 (1991).
metals are used under the conditions in which erosion
3. H. Hojo, K. Tsuda and D. S. Kim, Corros. Eng. 38, 689
and corrosion occur simultaneously.
(1989).
Even though the polymeric materials are corroded as 4, H. H. Uhlig, Corrosion Handbook, p. 16, John Wiley &
mentioned above, the possibility of erosion-corrosion Sons Inc. (1969).
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accelerated each other [3,9,10,11]. Conf. in Organic Coatings Sci. and Tech., p. 221,
Athens (1977).
7. C O N C L U S I O N S 7. H. Hojo and K. Tsuda, Proc. 34th Ann. Tech. Conf.
Reinforced Plastics~Composites Inc., p. 13-B, SPI (1979).
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Recent industrial materials are being used under
Composites Letters 4, 13 (1995).
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9. D. S. Kim, K. Tsuda and H. Hc>io, Corros. Eng. 40, 405
corrosive environment. In order to prevent the corrosion (1991).
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Regarding the problem relating to the corrosion of Japan 35, 32 (1998).
mechanism and the corrosion resistant design of plastics