dfrq

lau' eJdeJ'^,^A.r\//:
8 I I I S Z 5 S 6 I ( 0 )V b + t x v J t 8 g 0 S Z 6 t 6 1 0 ) t t + : a u o q d a l {
tuop8ur) pelrun'U N{t tIS'a-rrqsdo.rq5 .l.rnqs.an
a.rq5',{.rnq.m,e
q5
palrrurT dSolouqral erdeg

'crt

A9010NHc3r

VUdVU
')'v
alrsen')pue eLllL{sarqsln)
:sJolrpl

z aunlon

sausodttto)pue spuaErauqod lo YooqpueH

uror,tpaluudau

Ppnsl') pue olou 'H

sluauuor!^ulplnbn
ut sollsodtuolpuespualgrau4od
'sJaul{oa
lo a)ue}stsauuotsojJo)

patrurl ,{SoJouqrel erdeg dq rasaddl

9-60t-LS65g-I :les elalduoJ roJ NgsI

7,-gLe-ls6sg-I.7,etunlo^ roJ NgsI

drergrl qsrttrg or{rruory elge[re^Esl

z awnloA - sattsoduro3 PuB spualg -reur.,(1o4
Jo IooqpupH aqr JoJ pJof,er an8oJetery
.reploq
rq8uidor eql uro{ uorssnurad rorrd
aql
lnoqtl4^ 'uals.{s lp^errtarJo es'g'tep e ur paJotsJo supotudue
dq Jo ruJoJ
due_u1polnqrrlsrpro parnpordar ,perdoeoioqdaq deur
uortecrlqnAsrqryo
rred ou uouelsrsoJruorrnr repun polrrurad w rdacxg .pe^rasor'srq8i.r'11y

palrlurl {SoJouqcale:deg ,T00TA

Xn'UNt 715,arrqsdorggtrnqs,trarq5drnqa,req5

Pelrrurf dSolouqoalBrdeu
^q 7007 ur poqsrlqndtsrr{

^
t-T a

Polymer
of Polymers,
Resistance
Corrosion
in Liquid
BlendsandComPosites
Environments
H. Hoio and K. Tsuda

of PolymericMaterials
of Degradation
4.1 Fundamentals
Plastics,elastomersand compositesare being widely used as constructionmaterials
and aiso as coatingor lining materialsin corrosiveenvironments.Their contribution
to the industriesis quite significant,however,the materialsin contact with the liquid
the
environment causetwo kinds of degradation,one is a physical degradationand
other is a chemicalone.

4.1.1PhysicalDegradation
When plastics are in contact with liquid environments,liquid moleculesalways
p.n.,.",. the materials.As illustratedin Figure 4.1' liquid moleculespenetrateand
diffrrr" betweenthe molecularchains of polymer,then the material causeswelling
which increaseits massand also volume but goesdown the physicaland mechanical
propertiesof the material.
If the polarities of plasticsand liquid are different (polar and non-polar), the liquid
a equilibriumstateaftersomeexposure(Figurea'1(a))'If the polarities
abso.plionreaches
arethe samesuch pol", to polar or non-polarto non-polar,afterswellingthe solvation
",
the
phenomenonoccursand polymer moleculesare coveredwith liquid molecules,then
molecularchainsof polymersaredissolvedphysicallybecauseof looseninginter-molecular
polymers
bonding of the molecularchains (Figure4.1(b)). Examplesof the polarity of
to
resistance
poor
and liquids are shown in Table 4.1. Thus non-polar plasticsshow
hydrocarbonsolventsthat havelow polarity. Crystallinethermoplasticpolymers,however,
will
often show better performancefor such applications.For example' polyethvlene
only dissolvein hydrocarbonsolvents[1].
(PVC)
Thereare someexceptionalintermediateplastics.For example,polyvinvlchloride
(UP)
has
polyester
shows polar behavitur in some degreeto water' and unsaturated
polar group in the structure,but its framework is non-polar'

107

Handbook of polymer Blends and Composites

lo

' s!'u D'rytrrruJ

{swellinge,luiltbriufi)

{ai frillarrfy,:f iriaslil:s anC i}quid ir dJ,{taferf

h.:"
Ll

tt,

lirqr.iro
FFnetraticn.tu"ellingand wtuatirrnJ

is*l!ti urr ff--d {jts*rritriton)

{i:) p+lerityol plasticsene lqurq r+sam*

Figure4'1 Model illustrationof physical

degradationof plasticsby liquid environmenrs

Table4.1 polarityof plurtio

Chemicalgroups

Polar(hydrophilic)
-OH, -COOH,-OCH

"'ffi

NH,,-coo-;-co-o'i,

Non-polar(hydrophobic)

-H, -cH, _cH], _c6H.,

-CONHPlastics

PVA, cellulosicplastics,pA

Liquids

PS,PE,PVC.PA.UP

Acid, alkali) water, alcohol

Organic solvents
(gasoline,CuH,, CCl,,,etc.)

PA: pollamide; pE: polyethy

The degradationof linear type thermoplastics

is controlledmainly by this physicalone,
however,in thermosettingpiastic, with
three-dimensional
srru*ure (so callednerwork
polymers) rhe amount of swelling
is relativery low ,r,a J.p.nas on the
degree of
crosslinking.

108

Corrosion Resistanceof Polymer,Polymer Blendsand Compctsitesin Liqwid Enuironments

As is rvell known, the swellingand the dissolutionof thermoplasticsoccurs in organic
solvents,and the solubilit,vparameteris usedas a measureof solubility and swelling[2]'
The solubility parameter6 is given by:

6=(^E/v)"' =(nrra
)t/')

(4.1)

whereAE is the energyof vaporisation(cal/mol),v= M/d and v is the molecularvolume

(cm3/mol),d the density (g/ml) and M the molecular weight. Solubility parameteris
Maximum solubility of plastics
obtainedfor plastics(6n)and solvents(6r) respectively.
will be att"ined at 6o 6.. Figure 4.2 showsthat volume changeof orthophthalictype
unsaturatedpolyesterresin by immersion into various organic solventsare maximum
when D, is equalto that of resin6o {= 9-11) t3l.A similar relationship,that is, severe
changet..oru at 6o = 65,has beenbbtainedbetweenthe flexural strengthof vinyl ester
g1"r, .n-posites aiter immersionand solubility parameterof organicliquids [4]'

acetone
I

l-pentano

o
E

ethyl

.1

.;
(E

(t)
c
o
='1
U)

0 o l om e t h a n o I

20
10
6, lcal/cm3)1/2

30

Figure4.2 RelationshiPbetweenswelling ratio and solubility parameters of various

liqui ds (rtrt h oPhthalict y p e u n s a t u r a t e dp o l y e s t e rr e s i n , 5 0 ' C )

1.09

Handbook of polymer Blends and Composites

4.1.2 Chemical Degradation
Polymerswhich have some specialfunctional
groups and./orbonds, tend to degrade
by
chemicalreaction in some environmental
conditions,especiallywhen in contact with
liquids [5]' This chemicaldegradationis
considered,, ih. corrosion phenomenon
of
polymeric materials,as in metals.In
a broad sense,.,.orrorio.r,,is defined
as the

Table 4.2 Examplesof corr"r@

Chemical
reaction

Reactivefunctional
group and bond

Hydrolysis

Examplesof plastics
acid, alkali, warer
PMMA, PET,PBT,
(high temperarure)
EP,VE, UP

nitrile

acid, alkali

amide,imide

acid,alkali

urea,urethane,

acid,alkalr

ABS,SAN.CPE-AS
PA, PAI, PI

ether, acetal

siloxane
Oxidation

HNO.,, air
aliphatic,phenol

Transesterification
Dehydrochlorination

acid, alkali

POM, PPO,EC,
CAB,CA, PEEK

Oxidising agent
(O, O.,,conc.
HNO3, NaClO, etc.)
air, O., O,

Rubber,ABS

alcohol,acid, alkali

PET,PBT,ER,
UP,VE

high temperature
conc.H,SO,,

ABS: Acrylonitrile-butadirr,
_rtyrri,;6-eS,
Cl,to
styrenecopolymer;SA!l Sptreye-acrylonitrile;
CA: C"ll"ior|"a-ietate;CAB: Cellulose
acetatebutyrate;EC: Etbyt celluloseiER:Epoxy
,"ri";iii:;;iyamideirnide;
pBT:
Polybutyleneterephtharalei
pEEK: poryethir ether
keione;rnii roryethyrene
terephthalate;pF:phelo.rformardehydL;
pI: poryimide;pirrie, potymetbyr

:::::?'#^1"?,y.'^'^:.?":J?r',bvh":::p-,.p"ry;;;it4i'iio,potvphenvtene
110

Corrosion Resistanceof Polymer,Polymer Blendsand Compositesin Liquid Enuironments

destructionor deteriorationof a materialbecauseof reactionwith its environment.This
deteriorationis also applied to the chemicaldegradationof polymeric materialsand
composites,therefore.uen in plasticsand polymer compositeswith excellentchemical
,.sist"nce,they happento causecorrosionin somesevereenvironmentalcondition'
The probable corrosion reactionsbetween reactivefunctional groups and bonds in
polvmersand chemicalenvironmentsare shown in Table 4'2'
In caseof the resinwithout the esterbond in its structure,no corrosionoccursin acidicor
alkalinesolution.Figure4.3 showsan exampleof epoxy resincuredwith menthanediamine
(MDA-ER, seeFigure4.11) immersedin sodiumhydroxidesolutionat 80 "C [6]'

s
_c
d)
.!
ann
u, Ivw

6
X
F

o
b6u

'r=
C

'10

'100

'1000

10000

time (h)
lmmersion
Figure4.3 Relationshipbetweenretentionof flexural strengthof epoxy resincured
with amine and immersiontime in NaOH solution at 80 "C
(o: 10wt7o, t 20wt"/o,v: 30wt7o, t 40wto/")

Of the corrosionreactionsshown in Table 4.2, the most typical onesare hydrolysisand

oxidation.
a) Hydrolyticcorrosion
Resinsincluding esterbonds (symbol E in Figure 4.4) in main polvmer chain and/or
crosslinkingchain such as unsaturatedpolyesterand epoxy resin cured with acid
anhydride,sufferchemicalattack by acid or alkali, and scissionof polymerchainsoccur
as the resultof hydrolysis.The hydrolytic reactionbv acid or alkali is expressedas,

111

Handbook ctf Polymer Blends and Composites

(a) Orthoor lsophthalic

type unsaturated
polyesterresin

(b) Novolaktypevinylesterresin

--cS1"hfl"trro-. t l

ll

!--

MrHpAE-

E- narHpA
_E _
Crosstinkrng

H,r
r nen- s--,-{!1 d1fl1lr * oo- . -E

ll

E_E-MTHPA-E-

fcljgq1eqgl11,p_e.epoxy
resincuredwithmethyt
retrahydrophthatic
anhydride
(MTHpA)
Figure 4'4 Schematic chemical structures
of cured resins, (a) ctrthoor isophthalic
type
unsaturared polyester.resin, (b)novolak
type vinyl este, resin, (c) bisphenolrype
epoxy
resin cured with methyr-tetrahydrophthatc
anhydriae (MTH'A)

Reaction by acid:
o

^-

,rl , @
+H2O+R-

"( oR'

o
ll e
//
C +OR' .--->R- C'
+ R'OH
\9
H
OH

thisreactionis reversible.

r12

t4 )\

Corrosion Resistanceof PolymeaPolyvnerBlendsand Compositesin Liquid Enuironments

Reactionbv alkali:

oYO

H-

1]o

./ot//o
+ OH-+
C'
\l\

oR'

R-C+OR'------rR-

(4.3)

+ R'O"

C'

oH

oH

This reactionis irreversible.

and
When hvdrolytic corrosionoccurs,the number of esterbondsin the resindecreases
corrosion
carboxylateis producedas a corrosionproduct.The mechanismof hydrolytic
is proved by measuringIR spectrumbeforeand after immersionof resinspecimens[7].
Figure 4.5 shows IR absorption spectrum of three network resins before and after
'C. It is recognisedthat the ester
immersionin 1Owt% sodiumhydroxide solution at 80
peak near to 7720 cm-l becomessmallerand the carboxylateanion peaksat near 1.570
cm-l and 1440 cm 1 appearby immersionfor all resinstested.

/1nf\

Before
immersion

w [tr[
:

ffii

After
immersion

\((

\/'

i\ "l'(
:Y
I

?rr0 rr00

'u'''
til:t""
"'rHt..t1tJl-',

rsix)

Figure 4.5 IR spectrumof resin surfacebeforeand after immersionin NaOH solution

ar 80 oC. (a) isophthalictype unsaturatedpolyesterresin,immersed504 h in 10wt%
solution,(b) novolaktype vinylesterresin,immersed504 h in 1Owt% solution,(c)
anhydride
bisphenolrype epoxy resincured with methyl-tetrahydrophthalic
(MTHPA), immersed360 h in 40wt7o solution.

The hydrolytic reaction occurs also in ether,amide and urethanebonds as shown in

T a b l e4 . 3 1 6 , 8 , 9 1 .

1,1.3

Handbook of Polymer Blends and Composites

Table4.3 Examplesof hydrolyri, of pl"rri*

Chain bond
Ester

R-C-O_R'

R-C_OH + HOR'

Polyester

Ether

R-O_R'

ROH + HOR'

Polyether

Amide

R-C-N_R'

6fr

R_C_OH + H"NR'

Polyamide

Urethane

R_O_C-N_R'

6fi

ROH+CO"+H.NR'

Polyurethane

b) Oxidative corrosion
Polymershaving double bondsor etherbonds
in their srrucure and alsomethyl, merhylene
groupsin fatty acidsor phenylgroups,
are openro a*ack by oxidisingagenrslike or,
o,
and H,O,, and also strong oxidisingacids.
In atmosphericenvironment'plasticsaredegraded
graduallyby the actionof o, and sunlight
(ultraviolet rays).This type of corrosive
re"actio'called auto-oxidation occursas:
CHs

r.l

uttravioletrays

- Q H z - C : C H - C H zl - - - *
n
_

+ Oz_ROO.

'oH
-lRo'+
R O O H* R . i _
r Ro. + Roo.+
H2o

where Ro, ROo, ROO., oOH are free radicals.

114

R O O .+ R H

(4.4)

Corrosion Resistanceof Polymer,Polymer Blendsand Compositesin Liquid Enuironments

Oxidising agentssuchasNaClO, KMnOo, ClO, attackthe unsaturatedpositionin resin
structures,and causessevereoxidative corrosion. Corrosion reaction of polymers by
NaCIO is consideredas:
OH
I
R - o - c H z- C H - c H 2 - o -

R + cl-o

(4.5a)

o
il
---> R - O -CH2 - C- CHzO- R + Cl- + HzO

OH
I
R - O - C H z- C H - C H z - O - R + 2 0 C l -

ocl

----> R - O -CH2 - C- C - O- R + 2OHI

cl

(4.sb)

ocl
tl
R-O-CHz-C-C-O-R+
I

cl

NaOH

ocl

ll
- - - - - -R+ - O - C H z - C - O - N a ++ H - C - O - R
I

(4.5c)

cl

Solutionsof oxidising acids like concentratedH,SO4, HNO3, H,CrOo or HrPO.*also

corrode resinsby oxidation other than hydrolysis.Figure 4.6 shows this behaviourof
vinylesterresinimmersedin three acidic solutionsat pH 0.1 and 50'C [10].
to a different
by two or threestages,and eachstagecorresponds
Tensilestrengthdecreases
with time,
mechanismof corrosion.Especiallyat the secondstage,strengthdecreases
stage,
At
the
third
and its degreedependson the type of acid and its oxidisingstrength.
the slopeof the straightline for three acidsare the same,then this stageof corrosionis
controlledbv hydrolysis.
reaction
c) Corrosion by transesterification
P o l y m e r sw i t h e s t e r b o n d s i n a c h e m i c a l s t r u c t u r e w i l l c a u s e c o r r o s i o n b y a
reactionin alcohol environments.The reactionis as follows:
transesterification

115

Handbook of Polymer Blends and Composttes

IUU

c)

OU

=
o

'v

--

;
c
qn
0)"v

o
M

l m m e r s i o nt i m e ( h )

Figure 4'6Yariation of tensilestrengthof novolak type

vinyl esrerresinsby immersion
in pH 0.1 oxidisingacidic solutionsar S0 .C
( : H3PO', : HNO3, : H,CrO.,)

-ROzCCoHaCOzR+ 2RrOH---+ RrOzCCoHqCzORr

+ 2HOR_

(4.6)

where -R is the main chain of resinand R, standsfor an

alkyl group in an alcohol such
as CH-,,C.Hr, 1-CjH7, 1-C4He,for example
In general,the transesterification
reactionby alcohol is consideredto take place under
the existenceof acid or baseas shown as:
HRrcozRz- RsoH or oH- RrcozRs+ HoRz

(4.7)

where, R,, Rz and R, are alkyl groups.

Figure 4'7 shows the weight changeof orthophthalic
type unsaruraredpolyesterresin
versusroot of immersiontime in methanoland -ate,
Jj].
In methanol,after rapid absorption,the weight tends
to decreaseand after drying the
immersedspecimen,the weight losscan be clearlyobserved.
This rype of corrosionis an
exampleof 'penetrationtype corrosion' shown in Figure
4.14 insection 3.

t16

Corrssion Resistanceof Polymer,Polymer Blendsand Compositesin Liqwid Enuironments

10

oc
3
o

{)
Cn
(EU

(lmmersion
11ms)12
151/21
Figure4.7'Weightchangeof orthophthalictype unsaturatedpolyesterresinin the wet
or after drying, immersedin methanol(O:wet, : dry) and water (v: wet, : dry )

of Plastics
4.2 CorrosionResistance
4.2.1 General Tendency
The corrosionrate of plasticsand its compositesaregreatlydependenton the absorption
of water or environmentalliquid and also reactivity.

4.2.1.1 Affinity of Plasticsand Environmental Liquid

The most remarkabledifferencein corrosion behaviourbetweenmetalsand plasticsis
the degreeof liquid absorptioninto the materials.
the averagedistance
An environmentalliquid can easilypenetrateinto the plasticsbecause
liquid.
environmental
of
an
that
of the polymer chain is largerthan
Table 4.4 shows the water absorption of various plasticsmeasuredby ASTM D--570
m e t h o d[ 1 1 ] .
'Water
absorption behaviouris different from plastics,and this is due to' at first, the
polarity.When the polarity of plasticsand environmentalliquid coincides,both molecules
eachother,then the amount of absorbedliquid increaseas describedin Section1.
",rrr.t

71.7

Handbook of Polymer Blends and ComDosites

Table4.4 Waterabsorptionofi*iofrluG
Polystyrene(PS)

Water absorption (24h, wt"/o\

0.20-0.4s
0.01-0.03
Polytetrafluoroethylene(PTFE)
PA (tvpe 6)
Polycarbonate(PC)

0.08-0.09

Besidesthe polarity of plastics,the following

factorsalso affectwarer absorprion:
.

degreeof crosslinking

degreeof crystallinity

presenceof residualhardener,filler,additives,
etc.

The penetrationbehaviourof the liquid is

evaluatedby the diffusion coefficientand the
saturatedliquid contentsin the resin.The diffusion
coefficientof liquid decreases
with
increaseof crosslinkingdensityas shown in
Figure4.g t121.
Moreover,the amount of liquid penetrationinto
the plasticsdecreases,
in general,with
an increaseof degreeof crystallinity
[13].
The diffusioncoefficientsobtainedexperimentally
from the weight changeare shown in
Thble 4.5.
Thesevaluesare dependenton the kind of resin,
temperatureand filler.etc.
118

Corrosion Resistanceof Polymer,Polymer Blendsand Compositesin Liquid Enuironments

_c
N

oc'

56
?

.9

OE
o)
(J

a
f
9?

16
12
I
4
C r o s s l i n k i ndge n s i t y( x10 - ? n o l / c m 3 )

Figure 4.8 Effect of crosslinkingdensityon diffusivity (iso-uP,80 "c, H'o)

Table 4.5 Diffusion coefficients of water in plastics and composites

Diffusion coefficient
Temperature
Plastics
mm2/h
"C
PA6

50

0.012

PA 6iPAR(blend)

50

0.00s

glassbeads)
PA 6 13Owt7o

50

0.011

ER'

80

0.007

ER (50wt% FRP)

80

0.009

UP2

80

0.008

50
Vinyl ester
1cured with acid anhydride, 2 isophthalic type
PAR: polyarylate

0.0t2

4.2.1.2 Reactivity of Plasticswith Liquids

In some combination of resin and environmentalliquid' the degradationby chemical
reactionoccursas shown in Table 4.2.

119

Handboctk of polymer Blends and Combosites

Generally,chainsymmetryand strongintermolecular
secondaryvalencebondswill assure
high glasstransitiontemperature(Tj and aid good
p".t i,rf of polymer chains,thus they
contributeto the chemicalresistanc..in.on,r"rt,
the presen.e.rf ,arrdo-ry ,p"..a p.ndant
groups or flexibilisinggroups decrease
chemical,"rir,"rr.. iB1.
Although thereare many exceptions,one can
usuallypredictthe resistance
of plasticsto
corrosivesfrom knowledgeof the polymer
structure.

4.2.2characteristics
of prasticsandother Materiars
Table 4'6 shows the various physical properties
of metals, ceramicsand plastics

114,15,161.

one can seeeasilyfrom th-istable' that plastics

are light weight, and haverelativelylow
thermal conductivity-and low strengthi.r compariron
with other materials.And one of
the disadvantagesof plasticsin serviceis
the low heat resistance,that is the service
temperaturelimit is below 100 "c in common
thermoplastics.
However,the plasticsthat
show excellentheat resistancehave beendeveloped,
they are known asengineeringplastics
and the limit is about 150-200 oc. In engineering
plastics,the heatdistortionremperature
exceeds200 "c and someplasticsare Jurabre
oc or
over,they are called.super
"i:oo
engineeringplastics'.
Plastics,in general,exhibit an excellentchemical
or corrosion resistance,however,'n
the other hand' they show low burning resistance
and weatherability.
Roughly speaking,plasticsshow high resistance
to acidic environmentsand as suchare
able to be substitutedfor metallic materials,
and they have low resisrancefor organic
solvents,for which metalsshow enoughdurabilitv.

4.2'3 Thermosettingprastics
for corrosionResistant
GFRp
It can be seenfrom Table 4.6 that fluorocarbon
plastics(prFE) show good chemical
resistance
to many environments.However,the flufropl"rti.,
h"u" problemsin strength
and mouldability,they are nor suitablefor making
large-scale
equipmenr,and they are
usually used as a lining' For large scalestructures,
the corrosion resistantglassfibre
reinforcedplastic(GFRp)is suitable.
The typical marrix resinsof GFRP are shown
in Table4.7.

120

()

rr

q)
tr
q)

n{

oE

v :

o- -f

;S

Y60

\J

Zo

Xi.

.O

a?

co
NI

g^x
Elt

rrl

tOI
6l

co
$
V

(,

.l

c.l

rrl

tJ.

.'l
N

"n

o\

t-

t-r

co
'\o

c.l

...!
\o

oo

rh

t-

oq c\

a)

.o

co
oo

r)

;
a

't'

N
N

co
co

Y
N

.o

Y
aO

o\

i: =

EI
sl
;l
E=l
QJ\

:! |

'*-t

!Fl
\ca

*<

5tI
3;l
ss I

ill
S:I
{ll
'bs

sFt
FS
:\

x-:
Asr

.tq

*S
- { :c/)
-

x\
:s

R\l

9y

.3 ;v
L : \

.q: .'l-i
Y)i

E i

c5

Corrosion Resistanceof Polymer,Polymer Blendsand Compositesin Liquid Enuironments

la

IO

IE
la
lE"
l=

IE

t;

lI
li

ls
I:
r'l

IE

li
q)

1,2r

Handbook of Polymer Blends and Composites

Table 4.7 Matrix resinsof GFRP

Chemicalstructures

Unsaturated
Polyester
restn

ool

n o ] ' -H=Hl -I#

i- i- : -na r. { - !- f r - , - n I

1""

!:!"r-'

lr

I:

H,

l:'"'
"n'

{ s h a d e dp a n r n o r t h o p h t h a lar cc i d t y p e l

B i sp h e n ottype

j-{.

/-,i\,,

//

i--4

!.

}-( s n a d e dp a n i n o r t h o p h t h a iai {c i d t V p e , r

HET@acid
type
l s h a d e dp a n r n o n h . F h t h a l tac . r d t ! , p e J

Vinylester
Bisphenot
A type
restn

Novolaktype

-H O^{ 'H, ' -

' H,
! !'
-?1r!' {" =
" , . . - . ' - , = 1 - , . , 1r i * ; "
fo_cH

j"'

l"'

Har<H

j"'

/-.---f_.11-___f_4
utl " L_(*lr o. ," \=.r
t-

Hl-lnr7.H!(-c-cJo{,
nr]
u
o

("

Cycloaliphatic
type
(Alicyclic
diepoxy
carboxylate)

Ff_{
(d,U

Fo+_i+r,
H:^.t-

"{]'-"-I}"
-'"-l-t-'='.'
J/'
1\n',-f

- "fli'7-\
.-l

122

f..-,"

Corrosion Resistanceof Polymer,Polymer Blendsand Compositesin Liquid Enuironments

4.2.3.1 IJnsaturated Polyester Resin
Unsaturatedpolyesterresin (UP) is most frequentlyusedas a matrix for FRP becauseit
is rransparenrand has excellentmouldability and good mechanicalproperties.By
controlling the amountsof styrenemonomer,acceleratorand catalyst,the resin can be
hardenedin wide rangeof temperaturesand time.
Corrosion resistanceof this resin dependsmainly on the number of esterbonds in the
resin.This is due to rhe fact that the estergroup is degradableeasilyby hydrolysis,and
then the lower the concentrationof estergroup the higherthe corrosionresistance.
The chemical structuresof typical ortbophthalic type UP are shown in Figure 4.9' and
orher typesof UP with different structuresas the shadedpart of ortbo-UP inTable 4.7,
are also shown in the table.

nr\
ill
HHH

3-o-.-3'-o-8-":.-8-"]_3'-r-",
Br"-o*E
H H
lHr
H' tCt H s
| |
l - l H-z
cH:'

7\
\:/

l CHe
)'

Figure4.9 Chemicalsrructureof orthophthalictype unsaturatedpolyesterresin

(a) Ortbophthalic type UP

This type of resinis most popular for the GFRPmatrix, however,it is not consideredas
a corrosion resistantresin becausethis it is degradatedeasilvby hydrolysisin alkaline
solutionsat normal temperatures,and water and acidicsolutionsat high temperatures.
(b) Isophthalictype UP
of isophthalictypeUP is higherthan that of orthophthalictype
The hydrolysisresistance
UP.Thus the resinis widely usedfor generalcorrosionresistantequipmentsand tanks.
(c) Bisphenoltype UP
to many chemicalliquid
Bisphenoltype UP has good heat and corrosionresistances
environments.This is becauseof low numbersof esterbonds and sterichindranceto
liquid penetrationaround the esterbonding.

123

Handbook of Polymer Blends and Composites

(d) HET acid type Up
This resin has excellentcorrosion resistance.
to oxidising acids such as nitric acid,
nitric acid/hydrofluoricacid mixture, etc. The
resin is u"sedfor example,as GFRp
lining for acid pickling tank of chrome plating
[17).

4.2.3.2Vinyl EsterResrn
vinyl esterresinsare made by reactinga.liquid
epoxy resin with unsaruratedorganic
acid, e'g', methacrylicacid, to terminaL theii
molecut", *iih reacriveestergroups.
In the previouslymentionedUP resins,carbon
double bonds (c=c) locatedat random
on a molecularchain, and estergroups also
exist ,"p.ur"dly in *"in chain. In vinyr
esterresins,however,both endsof the molecule
"
hru. doubiecarbon
bonding,and the
estergroup existsadjacentto them.
"
Thereare a few unreacteddouble bonds,and
the esterbondingrs not includedin a main
chain but they contain only one bond ai each
end of the resin molecule.
Therefore'thenumberof esterbondsis low, and this
resinshowsexcellentcorrosionresistance.
(a) Bisphenoltype vinyl esterresin
This resinis manufacturedfrom standardbisphenol
A-basedliquid epoxy resinand
is typified by a tensileelongationat break of
5-6"/",combinedwith a heat deflection
temperature(HDT) of 100_120oC.From the corrosion
point of view, it resistswell.
many aggressive
chemicals[1g].
(b) Novolak type vinyl esrerresin
This resin usesa novolak epoxy resin as its starting
agent.The resultingvinyl ester
resinhas highercrosslinkingdensitythan the
blsphlnoi-Atyp. ..rirrr. This provides
high resistanceto penetrationof chemicalsinto
rhe matrix, and it has a superior
resistanceto liquid environments.The heat
resistanceis also higher,and is HDT of
140-150 oc, and it is a lirtle more brittle than
bisphenotifp" resin [19].

4.2.3.3EpoxyResrn
Epoxy resin(ER)containsmore than two epoxygroups
(oxilanegroups)in eachmolecule
chain' There are many typesaccordingto the
chemicalstructureand molecularweight.
The epoxy group is reactedwith hard-eneror
curing agent,and then three-dimensional
crosslinkednetwork polymersare formed_

1,24

Corrosion Resistanceof Polymer,Polymer Blendsand Compositesin Liquid Enuironments

The most widely usedepoxy resinsare made by reactionwith either'bisphenol-Aor a
novolak phenolic resin with epichlorohydrin.Aliphatic amines,aromatic amines and
acid anhydridecan be usedas hardeners.
The characteristicpropertiesof epoxy resin are:
(1) The resin showsa wide rangeof propertiesfrom liquid to solid states.
(2) The resinperformancechangesgreatlywith combinationsof the resinand hardener.
to the acid, and that
For example,the resincuredwith aminesshowspoor resistance
cured with acid anhydrideis weak to the alkali.
(3) The resin is slow to cure, and requiresa post cure.
(4) Excellentadhesiveand electricinsulationperformanceare expected.
(5) The resin showslow shrinkageduring and after the curing process,comparedto
UP resins.

4.2.3.4 Furan Resin

and
This resinhasa furan ring producedfrom furfuryl alcohol(2-hydroxymethyl-furan)
furfural (2-furaldehyde).
The resin is relativelybrittle comparedwith UP resin,howeverit has excellentstrength
at high temperatures.
it showshigh durability to acidsand alkalis,
For the propertiesof corrosionresistance,
ketones,
and halogenidehydrocarbonswhere
and also organic solventssuch as esters,
UP resinsshow poor resistance.
Therefore,this resin is one of the best plasticsfor using in a liquid mixture of a severe
to note that the resinis
corrosiveacid and an organic solvent.However,it is necessary
extremelyweak for oxidisingchemicals.

4.2.3.5 Phenolic Resin

by the reaction
The resinis one oldestthermosetsknown as Bakelite,and is synthesised
of the phenol and formaldehyde.

125

Handbook of Polymer Blends and Composites

This type of resin has a problem in the moulding process,
becausethey are powder
(novolak)or high viscosityliquid (resol),and the poiymerisatio'
pro..r. is condensation,
and so the resinneedshigh temperature,and prerst.rres.
At the beginningof 1970,theresoltype phenolresinwith high
volatileand low viscosity
was developedand then usedas FRP has increasedrapidly.thi,
l, calledas rhe secondgenerationphenolicresin.
One of the most superiorcharacteristics
of phenolicresin is inflammability and also it
doesnot generatepoisongasesif it burn. Therefore,its usagein
building and for equipment
for public rransportationis beingexpanded.
In general,the resin shows relativelygood resistanceto acids
but poor performancein
alkalis' Table4.8 showsphysicaland mechanicalpropertiesof
corrosionresisrantresins

119,201.

Table 4.8 Various properties of corrosion resistant resins

UP
Ortho

Iso

Bis-A

Vinyl
ester

6-9

7-9

7.5-8.5

7-8

<3

65-90

80-95

90-100

101107

110130

Water absorption
(%)

0.2-0.3

0.150.25

0.150.2s

0.150.20

0.1-0.2

0.3-0.8

Flexural strengrh
(MPa)

60-130 70-130

80-130

100150

140

59-83

Tensilestrength
(MPa)

40-80

50-80

60-80

70-90

74

35-59

Impact srrengrh
(lzod) (J/m)

5-30

8-30

20-34

25-80

I1-27

Property
Shrinkage(%)

HDT ("C)

MTHPA: methyl-tetra hydrophthalic anhydride

126

trvrffinr
I r'n"'ot

1)
1LJ_L/

Corrosion Resistanceof PolymeaPolymer Blendsand Compositesin Liquid Enuironments

4.3 CorrosionBehaviourof Polymersand Composites

4.3.1 Corrosion Forms and Mechanisms of Resins
4.3.1.1 Corrosion Behaviour
mainly with reference
The corrosionbehaviourand mechanismof polymersarediscussed
to typical matrix resinsfor GFRP.
Isophthalictype UP (iso-UP)and bisphenol-Atype ER shown in Table 4.7 were used.
Iso-UPwascrosslinkedby styrene,and epoxywascuredwith phthalicanhydride(methyldiamine
tetrahydrophthalicanhydride: MTHPA) or menthanediamine(p-menthane-1.,8,
4.10,
the
structures
of
and
: MDA). The structuresof the hardenersare shown in Figure
crosslinkedresinsare shown in Figure4.11.

Itu 7:1 ,*'-',

HsN-9-{r X 'cHs
.\--/
C*.
(b)

Figure4.10 Chemicalstructuresof hardenersfor ER. (a) MTHPA(methyl

tetrahydrophthalicanhydride,(b) MDA(p-menthane-1,8-diamine)

As mentionedin Section2.3 the polyesterresin (iso-UP)(a)has many ester bonds

(-COO-) within the main chainthat are the attacksitesby acid and alkalinesolutions.
Bisphenol-Atype epoxy resinhas essentiallyno esterbond within the main chain but is
crosslinkedby esterbonds in MTHPA-ER and by C-N bonds in MDA-ER.
Figure4.12 showsthe typical resultsof weight changesas a function of immersiontime
16, 21). Basically,at first, weight increasesby penetrationof liquid into the resin,and
by dissolutionof the resin into the liquid and finally increasesagain by
then decreases
penetrationof liquid into corrodedresin.By penetrationof liquid into the resinand/or a
as shown in
hydrolysisreactionbetweenliquid and resin,the strengthof resindecreases
Figure4.13.

1.27

Handbook of Polymer Blends and Composites

H2
?
p-o-c-c-o-c-c?
Hrl
_

^ l l

v-3

(dJ

iH
--.lu^n-n-n-n
rrlv
v
v
v
Hr
I

(b)

cH. -

-i{-,!o-c-cH i
HroH\
cHgv
9Ht
--------:--;
-i \
- - - f rcH,i
F t t s i Yn
?H
Il - , ,/--\
N-ql
',_, XrrZ__.-__-{
;H2c-c_c_o_
------------,,r,
i, _I__
I
- o-- c - c H Z '
i^I.: I
HrJH

cHs

H-------\-^
lHrC-C-C-olH2c-?-c-o-

(c)
Figure4.11 chemical strucures of cured Up and ER. (a) iso-Up,(b) MTHPA-ER,
(c) MDA-ER

128

Corrosion Resistanceof Polymer,Polymer Blendsand Compositesin Liquid Enuironments

t oe
c

P
o.a
0)

3
E 00
r:I)
(5 -U.4
-C

10

100

1000

lmmerstontime (h)
Figure4.12 Weight changeof iso-uP immersedin 10 wt% NaOH solution.

( 2 0" c . 5 0 ' c , 8 0 ' c )

1 .. 1
O)
0)

'11. . 0

(u 0 .
x
o

- 0.
;
o
c)
E

0
0

.l
I

10

'ro2

103
l m m e r s i o nt i m e ( h )

104

Figure4.13 Changeof flexural strengthof MTHPA-ER immersedin NaOH solution'

'C 10 wt7", 80 'C 20 wt"h'
( 50 "C 10 wt7o, r 65 "C 1'0wt"/o, 80
o 80 "C 30 wt%, 80 "C 40 wt%)

1,29

Handbook of Polymer Blends and Composites

By infrared specroscopicanalysis(IR), it
was confirmed that corosion occurred with
the hydrolysisreacion of esterbondine shown
in Tables 4.2 and 4.3.

However, hydrolytic corrosion behaviour is

different from the combination of resin,
liquid environmentand other serviceor test
condition. In an amine cured epoxy resin,
which does not have any ester bonds, no corrosion
occursin alkaline Jvrqrrvrr
solution 4r
at any
temperatureand concentrationas shown in Figure
4,3 t6l.
4.3.1.2 Forms of Corrosion
The forms of corrosionobservedby the immersion
testingin chemicalenvironmentare
classifiedinto threetl'pes,there
surfacereaction,yp"].orrorion layer forming
type
"r.
and penerrationtype as illustrated
in Figure4.14 t221.

liquid

liquid

Surfacereactiontype

Corrosion
layer
formingtype

liquid

Penetration
type

Figure4,I4Three typesof corrosion

(a) The surfacereactlonrype

This form is observedwhen the corrosionproduct
can be dissolvedinto the liquid at
the liquid contactedsurfaceand the corrosion
developsuniformly overentiresurface.
This type of corrosionoccurswhen low molecular
*.igr.i.""rponents are produced
by a corrosionreactionat both the main chain
and th" ."rorr-linkingchain.corrosion
productsdissolveinto the solution directly
from the ,u.f"...
The corrosionthicknessx is calcularedas follows:
7,,
x=1\no-h)

(4.8)

where ho is the thicknessof the original specimen,

and h is that of rhe immersedone.

130

Corrosion Resistanceof Polymer,Polymer Blendsand Compositesin Liquid Enuironments

Figure4.15 showsthe relationshipbetweencorrosionthicknessand immersiontime t. A
linear relationshipis obtained:

(4.e)

x=kf
where k, is a constant.

This type of corrosionbehaviourcorrespondsto uniform generalcorrosionof metals

[23]. The sametype of corrosionis observedfor PC, alicyclicepoxy resinin sodium
hydroxide,and aminecured epoxy resinin nitric acid.
(b) The corrosionlayer forming type
This type of corrosionwas recognisedin isophthalicunsaturatedpolyester,novolak
type vinyl esterin alkalinesolution.
Part of the resindissolvesout and the residualpart is left as a corrosionlayer where
the initial chemicalbonds are maintained.

3oo
o
a

o)
C

E+o
'o;
o

20

400

800

1200

l m m e r s i o nt i m e ( h )
Figure4.15 Changeof corrosionthicknessof MTHPA-ER by immersionin NaOH
oc 10 wt"/o, 80 "c 1.0wt"h, a 80 'c 20 wt"/",
solution. ( 50 'c 10 wt7o, v 65
o 80'C 30wt%. 80"C 40 wt%)

Figure 4.16 shows examplesof crosssectionsof the specimenscorroded by this type.

The specimenswere immersedin sodium and potassiumhydroxide solutions[21].

131

Handbook of Polymer Blends and Compostes

specimen
discolored
layer;

ff
(bi

tu

Figure4'16 cross sectionof iso-uP specimens

immersedin 50 wt% NaoH solution,
500 h(a), and 60 wt% KOH solution, 71h(b), g0
at
"C
(Reproducedwith permission
from H. Hojo, K. Tsuda and i. ()gasawara, Aduanced
composite Materiars, 1991, 1, 55,Figure 6.
@Japan society for composite
Materials, Japan, 19 9 1)

The boundary betweenthe outsidediscoloured

portion and the central unchanged
portion is clearlyobserved.It was found by
infrared analysisthat the corrosionwas
observedonly in the discolouredportion.
The thicknessof unchangedportion is measured
by microscopicobservationor
infrared spe*roscopy,and the corrosion thickness
defined Cy rqurrron (4.g) was
calculated'Figure 4.17 shows the relationship
betweencorrosion thicknessand
immersiontime for iso-up immersedin sodiurnhydroxide
solution.
The corrosionthicknessx is proportionarto the
root of immersiontime, r:
x = kztl/2 or x2 = kst
where k, and k., are both constant.

r32

(4.10)

Corrosion Resistanceof Polymer,Polymer Blendsand Compositesin Liqwid Enuironments

E
5,

u,
th

(Da
cl
-v.

c
'o
o
o

10

'100

1000

l m m e r s i o nt i m e ( h )
Figure4.L7 Changeof corrosionlayer thicknessof iso-UPby immersionin 10 wt7"
NaOH solutionat 80'C

This crosslinkingmolecularchain consistsof highly stableC-C bonds, so those

molecularchainsare preservedevenafter hydrolysingthe esterbonds,and residual
corrosionproductsform a corrodedlayer.
Equation (4.10) meansthat the corroded layer makes a resistantlayer to the
penetrationof solution by diffusion and the reactionoccursat the interfacebetween
the corrodedlayerand the non-corrodedresin.This behaviouris the sameas'l7agner's
paraboliclaw for high temperatureoxidation of metals[23].
In contrast,if the sameresinsare immersedin potassiumhydroxide solution' highly
swelledporous corrodedlayer are formed shown as Figure4.16(b).
For potassiumhydroxidethe swelledand corrodedlayerdoesnot behaveas a barrier
for the diffusion of solution.Then the relationshipbetweenthe corrosionthickness
and immersiontime followsthe rectilinearlaw the sameas in Equations10.4-10.9.
This agreeswith the behaviourof metalswhich producesa rough oxide film in high
temperatureoxidation.
(c) The penetrationtype
This type of corrosion is observedin eponv resincured with amine such as MDA-ER
by a rwo-step
immersedin sulphuric acidl22). The corrosionbehaviouris characterised
reachesan
and
processin diffusion and reaction.The solution penetratesinto the resin
owing to the initiation of a corrosive
equilibrium state,and then the strengthdecreases

133

Handbook of Polymer Blends and Composites

reactionasshown in Figure4.18. In this type,
the amounrof saturatedliquid absorption
is important as shown in Figure 4.19. And
the penetrationdepth .rn b. -."rur"d by
tracing sulphur aromsin sulphuricacid with
an X-ray microanalyser.
The depth y was
proportional to root of (t_t,,),where t,, is
incubationtime.

' l 1 ' 4f
-

40

JA

s- 3 0

11.2 c

.l e
lt oa
t;
ll xo . e= -

.9
G'

tzo

loo#

o
G)

IE
lo.ac

o)

.t 1o
c
o

lo

t^ ^;
lu.z c
l0)

6o)

0*

/2
/2
( | m mersion ti me11
1y-r11

Figure4.18 change of weight and flexural

strengthof MDA-ER immersedin
10 wt"/" H,SO+ solution at B0 C
^4

1.2

tD,
CI
0)

1.0

U)

_ o0 . 8

;G

x
(D00 . 6
o

o
o

-c 0) . 4
.9
9
9 01 a

CJ

11)

05

10 15 zv
zJ
C ha ng e o f w e i g h t
AA

30

35

40

(o'6)

Figure4'19 Relationshipbetweenretention
of flexural strengthand weight changefor

( s0.c10w.7o,^
'#3iJ*,i.1.?3131"J11*,
, 80"c20wt%)

1,34

in Liquid Enuironments
Corrosion Resistanceof Polymer,Polymer Blendsand Composites
type uP immersed
The sametype of corrosionhas beenobservedfor orthophthalic
plastics'
in boiline *ur.r. This type of corrosionis characteristicin

4.3.1.3 Corrosion Mechanisms

by relativevaluesof
The forms of corrosion as shown in Figure 4.14 are determined
4'9'
reactionrate (R) and diffusion rate (D) as shown in Table

f uAl" q.g Mechanism of the three forms of corrosion

Solubility of
Reactionrate (R)
Form of corrosion
product
corrosion
and Diffusion
rate (D)

distinct boundarY
Corrosion Iayer
forming type

indistinct
boundary

Penetration tYPe

"'lrrrta"ry ttetweencorrosion loyn' on@

.WhenD..R, reactantliquid which reachesvirgin resin by diffusion is dissipated

layer forming
immediatelyty,.".tloo, ih"r, the'surfacereactiontype'or'corrosion
product
of
corrosion
solubility
by
iyf", u..,rr. th. diff.r"n.. b.r*..n both forms is caused
'surface
on
observed'
is
reactiontype'
i" riqrria.If the produ6 has high solubility,the
'corrosionlayer forming type' is observed'
the other hand, in caseof low solubility,the
latge diffusion rate and the
If D>>R, reactantliquid penetratesinto the resin with a
region is locatedin a part of
corrosion reactionproceedsslowly.Thereforethe reacted
'penetrationtype"
ihe tiquid penetratedregion.This behaviouris that of
gradually with liquid penetration'
If D and R are comparable,degradationproceeds
This type was observedin the PA-H,SO+system[24]'
determineswhich of the three
The number of repeatedunits (n) is also a factor that
'surface
if n = 0 the
forms is observed.In .fo"y ,.ri.r, .,r..d with phthalic anhydride,

13s

Handbook ctf polymer Blends and Composites

reactiontype' was observed,while if n>1,
the 'corrosionlayerforming type,was revealed
[25]' Becauseof the severe.nt".rgl.-.rr1 of ,h. long p.ly;
.;;in, rhe corrosionproducts
were difficult to dissolve.

4.3.2 Corrosion Behaviour of Blended polymers

The incompatiblepolvmer blend which consists
of a continuousphaseand a dispersed
one can be expectedto show unique corrosion
behaviour.Becauseeach phaseshows
differentdurability ro corrosion by environmentar
liquid [26, 27, 2gl.

4.3.2.1BlendSystems
The materialsdiscussed
are pA, pc, pAR, modified-polyphenylene
ether(ppE),pBT and
polymer blendswith thesecomponents;
i.e. pA/pAR, pA/ppE, pBT/pc and pA/pc.
The
durability of thesecomponentswereconfirmed
experime"JLi""a arelistedin Thble 4.10.
Thesesystemsall consistof continuousphase/dispersed
ph"r..

t"rt" O.tOtn. Olrubt,tr,

ot.o

Alkali

4.3.2.2 Corrosion Behaviour

The corrosionbehaviourof polymer blends
are roughly groupedinro accelerated
types
and improved ones[29].
(a) Acceleratedtype
The blends with easily degradabledispersed
phase and high corrosion resisranr
continuousphaseare classifiedinto this type
of corrosion;rheseare pA/pAR (s0/50),
PBT/PCand PA/PC(50/50)in alkalinesolution.
In thesefl.ndr, the dispersedphase
is degradedfirst and then the continuousphase
adjacentto the dispersedphaseis
alsodegraded,though the continuousphasesho*r
rrigrr,.rirr"n.. to corrosionwhen
135

CctrrosionResistanceof Polymer,Polymer Blendsand Compositesin Liquid Enuironments

(a)

(b)

Figure 4.20 Morphology of PfuPAR(50/50)blend polymer.(a) beforeimmersion'

'C
(b) after immersionin 1'0Y.NaOH solution,528 h' 50
(Reproducedwith permissionfrom M. Kubowcbi,K.Isuda, K. Yamazakiand H' Hoio,
of MaterialsScience,
Japan,1995,32,3, 135,Figure3. O The
Journalof the Scrilety
Societyof MaterialsScience,
Japan' 199-5)

they exist as a neat resin. Then many holes with larger diameterthan that of the
original dispersedphaseare generatedby corrosionas shown in Figure 4'20 126l'
The corrosion behaviour of a blend of PC/PA (75125)in alkaline solution is also
classifiedinto this type. In this case,continuousphase(PC) is easilydegradableand
The continuousphasewas degraded
the dispersedphase(PA)showsgood resistance.
more quicklyih"n neatPC resinas shown in Figure4.27 andthe dispersedPA phase
is left in the corrosionlayer.The corrosionrate of (PC/PA'75125)blend was higher
PA
than that of neat PC resin althoughthe blend containedhigh corrosionresistant
continuous
the
than
pC
earlier
phase
degraded
adjacentto the dispersedPA
resin.The
pC phase.This was becauseof the existenceof an interphaselayer betweenthe
continuousPC phaseand the dispersedPA phase'
(b) lmproved type
The othertype of corrosionobservedwith incompatiblepolymerblendswas the case
In this type, the interphase
in which corrosionwas reducedrather than accelerated.
showeda small effecton the corrosionrate.
pA/pAR and PA/PPEblends in acidic solution show this type of corrosion. The
the
degradablecontinuousphaseincludescorrosion resistantdispersedphase'and

t37

Handbook of polymer Blends and ComDosites

o.7
E
E

NA

a
a
o

0.5

o.4

=
o
o
o
I
o

n2

o.2

0 . 1|

ol

100 200 300 4oo soo- oboJbo

l m m e r s i o nt i m e ( h )

Figure4.21 changeof corrosionthickness

with immersiontime in 20% NaoH
solution at 50 oC, ( pC, o pC/pA(75l25)
blend polvmert.

dispersedparticulate phase showed

an obstructive effect on permeation
of the
environmentalsolution.
lr:y lvgiSht change data, diffusion coefficientsw e r e o b t a i n e d a s s h o w n i n
Table 4.11. The diffusion coefficients
of sulphuric a c i d d e c r e a s ew i t h i n c r e a s i n s
dispersedphasecontenr.

Table4.11Diffusiott.o.ffffi
Ratio of continuous phaseto
dispersedphase
6 . 8x 1 0 r l
4.6 x 1013

4 . 0x 1 0 r l
3 . 5x 1 0 1 3

The blendsof corrosionresistantcontinuous

phaseand degradabledispersedphase
with low conrent were also grouped into
this improved-type.In this case,rhe role
of
interphaselayer in blends on corrosion
was negligible,then the corrosion rate
was
dominatedby the continuousphase.For
a blendolpirpin
tiotiolin alkalinesolution.

138

Corrosion Resistanceof Polymer,Polymer Blendsand Compositesin Liquid Enuironments

few weight changeswere observedevenafter long-termimmersion.This tendencywas
phase,includingthe interphaselayer,existsin isolationin
observedwhen the dispersed
the continuous phase.So that, when dispersedphasecontent increases,the isolation
effect becameunavailable,then the corrosion rate increaseddramatically' This
phenomenonw,rsobservedwith PA/PAR(50/50)in alkalines6lution [29].

4.3.3CorrosionBehaviourof GFRP
of GFRPis initially determinedby the performanceof matrix resin,
Corrosionresisrance
but it is also controlledbv that of fibre/resininterfaceand fibre itself.

4.3.3.1 Effect of tnterface Between Fibre and Resin

In general,the surfaceof the glassfibre is treatedwith couplingagentto increasethe strength
and there are manv different types are
of interface.Common couplersare organosilanes,
towards the glassand the organic
is
oriented
molecule
available.The silaneporrion of the
portion is orientedtowards the resin of the composite[30]. The interfaceis degradableby
easilyinto the materialthroughthe interfaceby capillary
hydrolysis[31], and liquid penetrates
of
fibre orientationon corrosionrate [32].
effect
the
action.Figure4.22 shows

7.O

E 5.0
;g t
,^

E"fz

E an
.9
*, 2.O
d
o 1.0

0.0
0

100 200 300 400 500 600 700 800

(h)
lmmersiontime

Figure 4.22 Changeof corrosion thicknessof unidirectional GFRP with matrix of

'C'
bir-pn cured with MTHPA by immersion in 10wt7o NaOH solution at 80
( parallelto fibre axis, o perpendiculardirectionto fibre axis)'

1,39

Handbook of Polymer Blends and Composites

The unidirectionalGFRP with matrix of bis-A
type ER cured with.MTHpA specimens
wereimmersedin sodiumhydroxide solution.
Thii systemwas rhe corrosionlayer forming
type' and the thicknessof the corrosionlayer
was -."rur.d in the directionof fibre axis
and the perpendiculardirection.corrosion thickness
gro-r-or. quickly in the direction
of fibre axisthan the perpendiculardirection.The
reaition betweencouplerand liquid is
also a factor to causedebondingof matrix from
fibre and biisterformarion
[33, 341.
4.3.3.2 Corrosion of GlassFibre
(1) Mechanismof ion removal
[35]
a. Effect of warer
Alkali silicateglassesdealkarisein the presence
of warer as folrows:
:Si-O Na + H,O -- Si_OH
+ Na*OH
The alkali producedfurther attacksthe Si-o-si

bonds_

Adding alkalineearthoxides(cao) in placeof

alkali oxidesimprovesthe chemical
durability by decreasingthe numb., of ,urf"ce
sodium ions.
b. Effect of acid
Acidsleachout nonsiliceousions preferentially,
leavinghighly poroussilicaglass.
:Si-O M + H* -+=Si_OH
+ M*
c. Effect of alkali
Alkalis attack the silica network and concentrated
alkali solutionsdissolvethe
glassitself.
=Si-O-Si=+ OH- * =Si_O-+ =Si_OH
Adding zrrO improvesthe durability to alkali
by forming the insolublefilm of
hydratedZrrO.
(2) Glassfibresfor FRp
Severaltypesof glassfibre for composiresare produced
as shown in Table4.12, and
most common is E.glass[36]. This glassconrains
few alkali metal elemerr,r,
h",
excellentwater resistance.Thus it is used for
"nd
electricalfields. c glasscontains
alkali
metalelements,and is widely usedfor acid resistant
GFRPbut haspoor water resistance.
s glassis widely usedin the aerospaceindustry
becauseof its excellenrsrrength.It also
has excellentcorrosionresistance
but is very expensivecomparedto E glass,thus it
is
not usedas an anti-corrosionmatrix
t37]. Alkali resisranr1ittl gt"r, showsexcellenr
resisrance
to alkali' it is usedfor GRC (glassfibre reinforced
cemenr).
740

Enuironments
Corrosion Resistanceof Polymer,Polymer Blendsand Compositesin Liquid
4J2 E""mples of chemical composition of glass fibres (wt.%)
AR glass
S glass
C glass
E glass
Component
T"bl"

sio.

5s.2

65.0

65.0

Al.or

14.8

4.0

25.0

CaO

78.7

14.0

Mgo
Bro,

a1
J.J

3.0

7.3

5.0

NarO+K,O

0.5

8.5

60.7

10.0
16.5

21's

S g/ass:high strength glass

in 2 mol/l
Figure4.23 showsthe degradationbehaviourof E and C glassfibre mat
weight
glass
the
E
in
but
nitric acid at 80 "C t38]. C glassshowsgood resistance,
acid
severelybecausethe component of E glassis dissolvedinto strong
decreases
only boron oxide but alsocalcium,
[3g]. The corrosionprocessis the removalof not
strength
aluminium,and magnesiumions from the glass.By corrosionof fibre their
in strongacid with a spiralcrack [40]'
also decreases

110
l e 1oor
.9

90

0)

= 80
o
q)

o)

IU

60
50
0

2oo

4 0 0 6 0 0 8 0 0 10 0 0 12 0 0
time(h)
lmmersion

oc'
Hrso4, 80
Figure4.23 Veight changeof E- and c-glassmat immersedin 2 mol/l
(o E-glassmat, C- glassmat).

t41,

Handbook of polymer Blends and

Composites
Examplesof corrosion behaviour
of GFRp are shown in Figure 4.24.
There are
three stagesof degradation,the first
stage,isdue to the degradationof
matrix,
the
secondone is due to that of the interface
betweenmatrix-and glassfibre, and
the
third one is due to fibre itself;th"
,..o.,J ,t"g. d.gr.J;;;;;,
.ro.cialry predominant
[a1]' The secondandthird stagesbeginearlie.
*lrh increaseof fibre content
In general,corrosion behaviouror
[42].
cinp depends;;;.;;p.
of marrix resin and
glassfibre [43].

.;l

o)

al
o^
=U
o
c

o
L

I I

.:

c
0)

d)

0
10

1oo

r ot--ilr

tmmersion time (h)

10

10

Figure 4'24 change of tensile strength

of E-glass-matvinyl
'2 estercomposiresimmersed
in variousenvironmentsat 50
"c. ( 10 wto/oHCl, o
wt"l"NaoH, t 70 wtT"
NaOH, glasscontents:40.2volo/o,_urri*,
J.ryl .rt.r r.rin;

4.4 CorrosionResistanceData
The durabilityof plasticsto liquid
corrosiveenvironmenrs
havebeendiscussed
extensively
in the literature[44,4s,46,47,48, +1,
sl, s2,53] and ,r,. ,".rr.ri.rr sheets
of manufacturers.
Tables 4'13 and 4'14 show corrosion
resistancedata forcommon plastics
engineeringplastics[53]. Tabre4.15
[47] and,
shows them
L r r L ' r rfor
r J ' ru
corros
orroslon reslstant

55, 55].

resins [54,

Table 4'15 shows only a rough

tendencyof corrosion resistance,
becausecorrosion
behaviour is dependentof t.rip.rr,u..,-ion.entration
of chemicalsand conta* time
Figures 4'25 and 4'26 show the-e""mpl.
of changerf fr;;;i;rrength
with immersion
time [45, 52,57].

142

Corrosion Resistanceof Polymer,Polymer Blendsand Compctsitesin Liquid Enuironments

Resin

Table 4.13 Corrosion resistanceof common plastics

PP
PS PM- ABS PE
PVC
MA

PU

MF

U
U
U

Liquid
S

L]

IT

tJ

U
U

LJ

IT

s-Q

Q-u

U
U

q-o

Sodiumhydroxide(RT)

S o d i u mh y d r o x i d et H T )

TJ

Q-u

U
U

U
U

N n c a c i d ( L C , RT)

N ric acid (HC, HT)

acidtLC,RT)
Sulphuric
acid(HC, HT)
Sulphuric

Hydrochloricacid (LC, RT)

acid(HC. HT)
Hvdrochloric

Anrmonia gas (HT)

Acetone

Ethvl alcohol

Formic acid

LJ

Acetic acid
Ethyl acetate
Diethyl ether
Benzene
Formaldehyde
Methyl ethyl ketone
Gasoline
Sodium hypochlorite (HT)

Carbondisulphide

Q-u

Q-u
s-Q

SQ

a
a
a

s-Q s-Q Q-r1 S

s-Q s-Q I T Q-u
s-Q s-Q U Q-u
a
Q-u a
s-Q s-Q
U
U
Q-u Q-u s-Q a
s-Q
s-Q s-Q S
a
Q-u s-Q U
S-U
Q-u Q-u S
s-Q s-Q U Q-u

L]

LI

U
U

U
U

U
U

L]

a
a

a
a

s-Q U
s-Q s-Q
U

s-Q s-Q Q-u Q-u

S

II

s-Q s-Q

U
U

I1

II
LJ

tl
L]

II

tl

resin,
St ktltf*ttry,
Q: Questionable, U: IJnsatisfactory, MF: Melamine forntaldehyde
temperature
Higb
HT:
LC: low concentration, HC: concentrated,

Table 4.16 gives more detailed data which include the effect of temperature and
concentration.Miasa and others showedthesedata with a plot of temperatureversus
concentrationas shown in Figure4.27 [58].

143

Handboctk of polymer Blends and Composztes

q

rr,l

(t

v)

(h

tt

(t)

ra

tt)

(h

(t)

D
R

(t)

th

(t

ah

rn

ta

rt)

(a

r-a

ct)

(h

th

V)

rh

(h

(a

(t

(t

(h

th

A)

v)

(a)

\
<
\s

ra

rt)

th

\3

6
Q

-,-l

(t

I
lr

00

IF

t-

(.) I

r'l

t+

q
q

c)

lj

FF

rt

rh

L
th

(t)

(t

ra

ct)

v)

L)

(t

(t

(t

(h

th

tt)

ct)

q)

(t

tt)

rh

(h

tt)

(t)

*'
S

(t

t)

(t)

(a

rt)

U)

rh

rh

\t)

U)

v)

(t)

tt)

rh

(t)

v)

tt)

(a

(h

|ss

tiUS
YiSIY

(h

th

(h

ol

a.

s s* $

ss s s

t^

"

$fl-p

J A

.r

(a

rn

D D

;)

(a

lU)

sa*.::
F\ s h

; $.: S

I
n

(.)
()

o\

B
N

"rN

co

- r 5\o
>Ffr
a.)

>-

O
cg

A]
9l

(J

ALf)

tJ)

---

ul
<l

-l

c
g

rr. I

r.

^-

lG's i

;.

:.si

cJl

-4

FC\

(t

o\

()

!,U *S
S.T FT

t.

(J

(J

y!

o\

ts B

xB

o\

I
Xa
Y-\
H:

c\

c\

p
"
\

qi*
sca:

tJ)

II

144

erQJv
i-}

<s;

\0

()

n;i

tf

\+\

;l *s

l
(a

C')

t-

-l

k
k

F
r i < F.]

'ii

ra

th

lN *s
:5:i
\
if ,t s
\

a)

i. =
* s\ l i
<s
rA.<

il

CorrctsirmResistanceof Polymer,Polymer Blendsand Compositesin Liquid Enuironments

Table 4.15 Corrosion resistanceof corrosion resistantresins
Inorganic
acids

Liquids

Organic
acids

Oxidative
chemicals

Alkalis

Organic
solvents

3-4

-)

Resins
UnsaturatedPolvester
Isophthalictype

Bisphenoltype

HET-acid type"'

Bis-tvpe

Novolak tvpe

1
J

1
I

1
J

RT curing

a
J

Heat curing

A
.1

.+

.1

Vinylester

Epoxy

Phenolic

1
a

1
Furan
^'chlorendicacid, RT: Room temperature,L:

;R
E

Excellent,2: Good, .3:Poor,4: Very poor

1 10
10

70

60

50
0

'100

200
300
l m m e r s i o nt i m e ( d a y )

400

Figure4.25 Changeof flexural strengthof novolak type vinyl esterresinin75 w,r.o/"

H2SO4(o) and 35 wt% HCI solution( ) at 40 "C

1.45

Handbook of Polymer Blends and Composites

s
DI

o)

120
100

;(

BO

E 60

bis-UP

f
X

o
E

40
20

. \.iso-Up
_t\\

orthor -^\t---UP !El'\

d)

4
6
8
10 12
l m m e r s i o nt i m e ( m o n t h )

4A
t-

Figure 4.26 Change of flexuralstrengthof ER andUp resinsin 25 wt"/o acetic acid

s o l u t i o na t 9 9 ' C

Table 4.16 corrosion resistanceof corrosion resistantroi*

Liquids
Hydrochloric
acid
Sulphuric
acid

Nitric acid

Sodium
hydroxide

to/ \
\/ol

Benzene
Kerosene

Iso-UP

Bis-UP

70

80
80
100
80

10
20
25
50

70
60

75

NR

50

20
40
10
25
50
10

Acetic acid

Maximum operating tem rerature (oC

Conc.

25
70
100
100

50

JU

HET-UP Nov.-VE'3
80
100
80
100

80
80

90

100

100

90
60
80

90

80
25
70
50

50

25

60
40

60

80
70

NR

NR

60

2S

NR

NR

NR

NR

NR

NR

NR

25

100

i00

NR

60
50
80
100
100
30

100
30

100
60

70
70
50
100
100
60

25

NR

NR

50

NR

50

70

80

80

NR
NR

70
70

80

oNouolak type
uinyl ester resin

146

Bis-VE

Corrosion Resistanceof Polymer,Polymer Blendsand Compositesin Liquid Enuironments

120
^t)

100

E
- 80
6
bou

A
+rr

20

Bis-VE
30
20
10
(%)
Concentration

120
100
o
=
$
L
(l)

o-

t-

80

OU

40
)n

Nov-VE
30

20

10

(%)
Concentration
120
(J
o
a

o-

E
{)

100
B
'

80
60

A\

\!

40

20

Bis-UP

10

.
\|
\|
"r1

20

30

\ l

40

(%)
Concentration

Figure4.27 Temperaturevs. concentrationdiagramsfor threetypesof resin in HCI'

(RegionA: satisfactory,B: questionable,C: unsatisfactory)

t47

Handbook of polymer Blends and ComDosrtes

4.5 Designingof CorrosionResistant

Structure
4.5. 1 Laminate Construction
The corrosion resistanceof GFRPdepends
essentiallyon the corrosionresistanceproperry
of resin used as a matrix' GFRP in
contuct with a corrosivechemicalenvironment
is
protectedby the performanceand
also thicknessor ,.rin
a corrosion barrier.
",
The corrosionresistantGFRP structure-of
equipmentsuchas tanks, towers,vessers
and
pipes'is usuallycomposedof a surface
g"l .o"t oir"rin-rr.i in*r layer and
an
intermediate
resin-richrayerto prevenrcorrosion
and also.ahi;h ,;;;;;;h our., layer
ro preserverhe
structure'A surface.resin-rich
inner layerthicker rir" o.i3 -m is
made
wirh
resinmore
than 85 wt"/o andacid resistantc-glr*
o, syntheticsurfacingmat (veil).The intermediate
layer is madeof at leasttwo rayers"o
f 4s0g/m2E d"r; ;;;p;d
strandmat impregnated

ili":iJr::t;f

;:""'

rheouier
ii.o-fo-r'i'ofarternating-r-"ii,-'?,.,
or
"'u',u,"1luv..

purposeof ",u,f"'.ll; l'JiT,'ffi:'ilff:l ii;:J',,i i?::H,Hi r:,:..'*H

i#;
moulding,impactingandtemperature
vanation.

In principle'innerand intermediate
corrosionbarrierof laminatecorresponds
to an idea
of corrosionallowancein the thickness
of steel,rru.rrr"r. rlom the designingpoint
of
view,it is importanttochoose
propercorrosion
resistant
,"rir,
t"-inate
structure
and
also
thickness
requiredtt t:T:.:]ife. rigure 4.28 illustrat.,
rh. typicalcorrosionresistanr
laminateconsrru*ionof_GFRp.
riguiri'.zl
of resinlining or coatrng
usedin steelequipmenr.
In resinlining,glass*?*:."rr
flakeri"i"g"*"*ft.
lr-^Ci-gusedwidery.
In somecorrosivecondition,so called_dual
laminate,which is a
thermoplastics
sheetlike PVC' pP,PVDB fluorocarbonplastics combinationof
as an inner liner and
externalGFRPstructures,
is used.
4.5.2 RateEquations and Life prediction
4.5.2.1Equationsof Corrosion Rate
[21]
f.t$*L:itrcorrosion

ratedefinedby an increasing
rareof corrosionthickness,
can

s*
? = k.xo.c0
ut

(4.11)

where x is thickness.of corroded part.,

t is immersion time, k is rate constant,
c is
concentrarionof liquid, and c and p
are consranrs.

r48

Handbook of polymer Blends and Composites

The rate constantft can be represented
by Arrhenius,equation:
k= hexp(-E/RT)
where A, is frequencyfactor,E is activation

(4.12)
energy,R is gasconstantand T is temperature.

Let us consider,at first, if C and T are

constant.
In the caseof 'surface.reaction
type', the corrosionrate is independent
of x, that is a _ 0
in Equation (4'11) ' thus the Equation (4.9)
canbe obtained.tn th. caseof .corrosion
layer forming type', if the corrosionlayer
showsthe resistan..,., p"rr.rration of liquid
and it increaseswith the thicknessof
th. layer,the u"lu" oio = _1 and the Equation
(4'10) can bederived'Ifthe resistance
ofthe layerto p.n.rr"rion ofliquid can
beneglected,
the sametype of equation as Equation (a.9)
holds. This behaviourwas recognisedfor
iso-uP immersedin potassiumhydroxide
solution rrro*.,l;-Fig,rr. 4.16(b\.
From the experimentsunder various
concentrationsand temperatures,the
second,
following equarionsare obtained:
(a) Epoxy resincured with MTHpA
in sodium hydroxide solurion:

x = Azexp(-o+++
/ T)co.s6. t

(4.13)

(b) IsophthalicUp in l}wtTo NaOH

solurion:

x = Asexp(-e+zo
t T)r,,,

(4.14)

(c) IsophthalicUP in potassiumhydroxide

solution at B0 oC:
x=A.C.t

(4.15)

From theseequations'the thicknessof

corrosionlayer or dissolvedpart afterimmersion
at arbitrary concentration
temperaturecan be predicted.The equations
.and
of corrosion
rate are summarisedin Table
4.17 [2I,60].

4. 5.2.2 Life prediction

If the Equations (4'13-4.15) are obtained,
the life basedon flexural strengthcan
be
estimatedas follows [6,611.
The apparentflexural strengthsu' after immersion
is expressedas:

150

CorrosictnResistanceof Polymer,Polymer Blendsand Cctmpositesin Liquid Enuironments

E-glasschoppedstrand mat layer

Figure4.28 Typical laminateconstructionfor corrosiveenvironmentuse

i'

(a) Resinlining

(b) Flakelining

Figure4.29 Exampleof resin lining and glassflake lining for steelequipment

1,49

Corrosion Resistanceof Polymer,Polymer Blendsand Compositesin Liquid Enuironments

table 4.77 Rate equations of corrosion for various resin/liquid systems
Rate
Form of
Liquid
Resin
equation
corrosion
Surface
reaction

rype

Corrosion
layer
forming

Bis-A tvoe ER cured with MTHPA

NaOH

x[t

Bis-Atype ER cured with PA(n=0)

KOH

xllt

Bis-A tvpe ER cured with MDA

HNOs

xut

Alicyclictype ER curedwith PA

NaOH

xl.rt

lsophthalicUP

KOH

xpt

IsophthalicUP

NaOH

xU tl/2

IsophthalicUP

HNO,

xp t"2

Orthophthalic UP

NaOH

rype

Bis-Atvoe ER curedwith PA (n>1)

Penetration
type

KOH

Novolak type VE

NaOH. KOH

Ortbophthalic UP

Boilingwater

Bis-A type ER cured with MDA

wp (t-to)t/2

H,SO4

xp tt"
wpr (t-to)t/2

,p 1t-t,,)',,

t: immersiontime, t^: incubationtime' x: corrosionthickness,w: amowntof

dissolute,y: penetration delttb, Bis-A: bispbenolA

3PI

( 4.1,61

sR = ------t

"

zbho-

and P
where hs, b andl are thickness,width and spanof the specimenbeforeimmersion,
is breakingload in flexural test after immersionrespectively'
The true flexural srrengthsu is equalto that of the original resins' thus:
3Pl

sB=sBo=

-2*)'
z(b-zx)(ho

(4.r7)

Therefore'
In caseof corrosionlayerformingtype,the strengthof the layerwas neglected'
sr'/sur:
strength
flexural
of
retention
the
Equations(4.16) and (4.171give
,

sa

J=..-........_=-

sB()

lt

\/,

\0-/-x)\no-zx)

t]

(4.18)

OnO

151

Handbook of Polymer Blends and ComDctsites

1.1
10
c

c)

09

ah

08
f

0.7
u.o

c
o
c)

tr

0.5
04
U-J

1O-1t

10 - ' 0

4n

e x p ( _ 9 4 4 4 t Tc;o s 6t 1 r r ;
Figure4.30 Master curveof strengthchange
of MTHpA-ER immersedin NaOH solution.
(o 50 'C, 10 wt"/o,r 55 oC, 10 wt;/o, g0 oC,
10 wto/o, g0 " C , 2 0 w t Y o ,
v 80 oC, 30 wto/o, g0 oC, 40 wt./"\

As the retentionof strength su'/sur:varies

only with x, a mastercurvecan be obtained
by
plotting S with the right t"r- ol Equarions
(4.134.1s). The examprefor MTHPA_ER
immersedin sodium hydroxide rolulion
are shown i., ngur. +.:0.
By using this master curve' the retention
of strength after long term immersion at
any
concentrationand temperaturecan be predicted.
For of resinin which the strengthdecreases
abruptly after liquid absorptionasshown in Figure
4'19,the saturatedweight gain givesthe useful
information fo, th. life predictionof resin.
4.5.3 Factors Affecting

Corrosion

The corrosion resistanceof GFRP depends

essentiallyon the performanceof resinmatrix,
however,there are many factors which will
affect ,ir. .or.orion behaviour and form
of
the material.Thesefactorsare:
1. Chemicalstructureof resin
a) Reactivefunctionalgroup and bond as
shown in Table4.2 in section1 and their
concenrrarion[71.

752

Corrosion Resistanceof Pctlymer,Polymer Blendsand Compositesin Liquid Enuironments

concsntrationof ester
improveswith decreasing
For example,corrosionresistance
bonding in hvdrolYsis1621.
b) Constitutionalisomersuch as iso, ortho [62].
c) Number of repeatedunits, n, in Figure4.9 in Section3, molecularchain length [25].
d) Carboxylic acid
Thereexistscarboxylicacid in anhydridecuresepoxy and unsaturatedpolyester
resins.Corrosion rate normalisedwith ester concentration(dx/dt)(1/Ct2)is
proportionalro a concentrationof carboxylicacid C6ol as shown in Figure4.3L
[63]. Cc^ givesa degreeof aciditv of the resin'

10'2

10-3
.J

x
r n -4

rl
U

10-5

01

10

C o n c e n t r a t i o no f c a r b o x y l i ca c i d ( m o l / l )
Figure4.31 Relationshipbetweencorrosionrate normalisedwith esterconcentration
.o.r..ntrarion of caiboxylic acid in bis-A ER with short main chain (o), and long
oC,KOH solution)
"n-d
main chain ( ). (80

153

Handbook of Polymer Blends and Composites

e) Sterichindrance
Aromaticring and bulky sidegroup will prevent
the corrosionof resinby covering
the molecularchain.
f)

Degreeof cure [53,64]and crossrinking

density[65] (Figure4.g in Section4.2)

g) Residualsubsrance
monomer'curing agent'crosslinkingagent,
reactioninitiator of hardener
[66].
h) corrosion produ*' corrodedlayer (Figur
e 4.r4 in section4.3) t211.
2. Serviceor tesr condition
a) Temperatureand temperaturegradient
Diffusion rate and alsoreactionrate are increased
with increasrng
temperatureof
environment[67, 6gl as shownin Figure
4.32 [6,71.
when large temperaturedifferencesexists
betweeninner liquid and outer atmosphere,
vapour diffusion insidethe materialare accelerated,
this i, *"t., vapour diffusion
[591.

o
o

Ol

'a
al

0 .0 1

2 8 x 1O 3

e.oxto3
1r (K1)

3 .2 x 10 - 3

Figure 4.32Effect of temperatureon corrosion

rare of MTHPA_ER immersedin
10wtT" NaOH solution

154

Corrosion Resistanceof PolymeaPo\vner Blendsand Compositesin Liqwid Enuironments

b) Concentrationof solution
As increaseof concentration,corrosion rate are affectedbecauseof increasing
reactivity and decreasingdiffusivity [4,6]. Figure 4.33 shows an effect of
concentrationon corrosionrate [63|.

-1

10'

IU

E
(E
c

: n-3
tu

th

n-4

j 0 - u ,, , " j

'10

C o n c e n t r a t i o no f K O H s o l n . ( m o l / l )
Figure 4.33 Effect of concentration on corrosion rare of bis-A ER cured with acid
anhydride.(Accelerator: none,o amine,a srannousoctoate)

c) pH [7,701
d) Flow velocity
In a turbulent flow region, corrosion rate increasesin comparisonwith that of
static immersion(Reynoldsnumber,Re = 0) as shown in Figure 4.34 [71], and
erosion-corrosionoccursin high velocity flow of liquid and especiallyin solidliquid mixture flow [72,731.

155

Handbook of Polymer Blends and Composites

U .U O

E
g0r
o

0.04

*-4

oo
OD
E$
+O

-ru
oe,
o

0 . 02

(!

'10

50
100
l m m e r s i o nt i m e ( h )

500

Figure4.34 Effect of flow velocityon amount of dissolvedcarbon from vinyl ester

resin immersedin 55 oC,2|wto/oNaOH solution.
(o immersion(Re=0), Re=9.8x 103)

e) Stress
Similarphenomenonasstresscorrosionof metalsis found on GFRPcorrosion.Liquid
absorptionand corrosiongenerallyincreaseunder tensileloading
[74]. Figure4.35
shows an effect of stresson the retention of tensilestrengthof E-glassui.ryl erte,
compositesafter creeptestingrn 10'/' sodiumhydroxidesolution,and the higherthe
creepapplied stress,the earlierthe strengthreductionof the material
[34].
The resultsof both the immersiontestand the creep-rupturetest arecomparedin
Figure4.36.The retentionof tensilestrengthversusimmersiontime in immersion
testand the ratio of appliedstressto initial tensilesrrengthversusrupruretime in
creep-rupturetest performedin sodium hydroxide solution, are presente
d [41,
75]. The behaviouris essentiallythe sameindependentof test merhods,but the
transitiontime from the first stage(I) to the secondone (II) is extremelyaffected
by stresscondition under immersion testing. Therefore,stressacceleratesthe
corrosion of GFRP significantly.This stresscorrosion phenomenonmeansthat
conventionalimmersiontestwithout loadingarenot alwayssufficientto evaluate
the corrosionresisrance
of the compositematerials.

1.56

Corrosion Resistanceof PolymeaPolymer Blendsand Cctmpositesin Liquid Enuironments

;
C.

120
100

80

a
C)

OU

a
c

40

20

'c
0)

10

10-1

d)

102

103

lmmersiontime (h)

Figure 4.35 Effect of creepapplied stress(o) on retention of tensilestrengthfor vinyl

estercomposites(glasscontent:40.2vol/") immersedin 65 "C, 10 wto/"NaOH solution
(a o=49 MPa, o=98 MPa, I o=147 MPa)

'1 0

i0
'u^
(IjIJ

t^

on
a
0.2

1o'1

io
102
t i m e( h )

io3

Figure4.36 Correlationbetweenimmersiontest and creep-rupturetest for vinyl ester

composites(glasscontent:4}.2vol%) in 50 oC, 10 wt"h NaOH solution.
( immersiontest, o creep-rupturetest)

t57

Handbook of Polymer Blends and Composites

Acknowledgement
The authors would like,to acknowledgethe contribution
of Dr. TetsuyaSakai for his
assistance
in preparingthe manuscript.

References
7.

F. R. Jonesin ReinforcedplasticsDurability, Ed., G. pritchard,\woodhead

PublishingLtd., Cambridge, 199g,97.

2'

L' T' Butt and D. C. Wright: lJseof Polymers in Cbemicalplant

Constructic.tn.
Applied SciencepublishersLtd., London, England,19g0, g.

3'

H. Hojo, K. ogasawara,\7. L. chang and K. Tsuda,Aduances

in composite
Materials,1994,3, 4, 34I.

4.

R. C. Allen, PolymerEngineering
and Science,1979,19,
5,329.

5'

W' SchnabeI,Polymer Degradation - Principlesand Practica.l

Applicatictns.
HanserInternational,Munich, Germany,19g2.

6.

H. Hojo, K. Tsuda,K. ogasawaraand T. Takizawain polymeric

Materialsfor
corrosion control, Acs symposiumseries,No. 322, Eds.,
R. A. Dickie and F. L.
Floyd, AmericanChemicalSociety,Washington,DC, 1986,314.

7'

K' ogasawara'K. Tsudaand H. Hojo,

Journarof the Japansocietyfor
CompositeMaterials, 1986,12, 1, 16.

8.

R. B. seymour,Plasticsus.corrosiues,
John wiley & Sons,New york,19g2,36.

9'

M' ModestiandF Simioni,porymerEngineeringandscience,7996,36,17,2173.

10' Koatsu Gas Hoan-Kyokai, Handbook of corrosion Resistant

FRp, Tokyo,Japan,
1993,35.
71. Modern PlasticsEncyclopedia,19g5,62, 10A, 44g.
1,2. N. Takahashi,Master thesisin Tokyo Instiruteof Technolo
gy, 1996, g9.
13. H. r7. starkweather,Jr, G. E. Moorew, E. Hansen,T.
M. Roder and R. E.
J.
Brooks,lournal of polymer Science,1956,21, 1g9.

158

Corrosion Resistanceof Polymer,Polymer Blendsand Compositesin Liquid Enuironments

74. Report for Eualuationand Designof FRPAimed to Apply to Eqaipmentfor
Preseruationof Enuironment,Engineering
Promotion Association,Tokyo, Japan,
Report,ENAA 1993-1,1994,9.
15. Guidancefor Non-metallic Materials Selectioz,Subcommitteeof Polymeric
Materials,The Plant MaterialsEngineeringcommitee, PMEC, The societyof
ChemicalEngineers,
Tokyo,Japan,1994,2-5-12.
16. R. B. Seymour,Plasticsuersuscorrosiues,wiley Interscience,New york, usA,
1992,131.
17. Application Technologyof organic Materials for cbemical Equipment,
Subcommitteeof PolymericMaterials,The Plant MaterialsEngineering
Committee,PMEC, The Societyof ChemicalEngineers,Tokyo, Japan,1996,
Nanjing, China,122.
18. P.Kelly in ReinforcedPlasticsDurability, Ed., G. Pritchard,tX/oodhead
PublishingLtd., Cambridge,England, 1998,282.
19. PracticalEncyclopediaof Plastic.s,
Ed., F. lde, Sangyochosakai,Tokyo, 1993.229.
20. Introduction to FRP,Ed., M. Miyari, JapanReinforcedPlasticsSociety,Tokyo,
Japan,1992,52.
21. H. Hojo, K. Tsudaand K. ogasawara,Adt,ancedcompositeMaterials,1991,
1,55.
22. H. Hojo, K Tsudaand K. Ogasawara,Presentedat the InternationalSymposium
on Fibre ReinforcedPlastics/composite
Marerials,Nanjing, china, 1988, Paper
No.45.
23. The CorrosionHandbooA,Ed., H. H. Uhlig, John rViley & SonsInc., New york,
1969,16.
24. H. Sembokuya,M. Kubouchi, K. Okamura, K. Tsudaand H. Hojo, lournal of
the Societyof CorrosionEngineering,Japan,2000, 49, 8, 494.
25. H. Hojo, K. Tsudaand K. Ogasawara,ReinforcedPlastics(Japan),'1.988,34,49.
26. M. Kubouchi, K. Tsuda,K. Yamazakiand H. Hojo, Jowrnalof the Societyof
MaterialsSciencelapan, 1995, 32,3, 133.
27. J. H. cho, M. Kubouchi,J. Xu andK. Tsuda,lournal of the society of Materials
Scienceof Japan, 1998, 35, 6, 309.

1.s9

Handbook of Polymer Blends and Composites

28. J. H. Cho, M. Kubouchi and K. Tsuda,Journal of the Societyof Materials
Scienceof lapan, 1999, 36, 5, 272.
29. J. H. cho, H. Sembokuya,M. Kubouchi and K. Tsuda,Presentedat the Regional
Symposiumon ChemicalEngineering,Songkhal,Thailand, 1999, C16-1.
30. D. P. seraphim,D. E. Barr,w r. chen and G. P. Schmittin AduanceTbermctset
CompositesIndustrial and CommercialApplications,Ed.,J. M. Margolis, Van
Nostrand Reinhold,New York, USA, 1986, 139.
31. M. Baschein Interfacesin composlles,ASTM stp. 452, Americansocietyfor
Testingand Materials,1968, 145.
32. T. Tomiyama,Corrosion Behauiourof FRP Boltsusing Notched Bar, Graduation
Thesis,Departmentof ChemicalEngineering,Tokyo Institute of Technology, 1997.
33. F. R. Jonesin ReinforcedPlasticsDurability, Ed., G. pritchard,Woodhead
PublishingLtd., Cambridge,England,1998, 84.
34' CompositeSystemin Materials,Ed., H. Hojo, Materials ScienceSocietyof Japan,
Shokabo,Tokyo,Japan,1993,195.
35. B. E. Ramachandran,
B. C. Pai and N. Balasubramanian,
!ournal of the
American CeramicSociety,7980, 63, 112,1.
36. Introduction to FRP,Ed., M. Miyari, JapanReinforcedPlasticsSociety,Tokyo,
Japan,1987,56.
37. P. A. Schweitzer,Mechanical and Corrosion-ResistantPropertiesof Plasticsand
Elastomers,Marcel Dekker,Inc., New York, USA, 2000, 176.
38. T. Maruyama, study of DecompositionBehauiourand.v/asteTreatmentof
Epoxy Resinsand FRP,Master Thesis,Departmentof chemical Engineering,
Tokyo Instituteof Technology,1.997.
39. G. Pritchardin ReinforcedPlasticsDwrability,Ed., G. Pritchard,woodhead
PublishingLtd., Cambridge,England,1998, 52.
40. B. Das, B. D. Tucker and J. c.
24,6606.

'warson,
Journal of Materialssciettce,1991,26,

41. H. Hojo and K. Tsuda,Presentedat the 34th Annual TechnicalConference,

ReinforcedPlastics/Composites
Instituteand SPI,New Orleans,LA, 1J5A,1979,
Section13-B.

1.60

Corrosion Resistanceof Polymer,Po\nner Blendsand Compositesin Liquid Enuironments

42. H. E. Atkinson,MechanicalEngineering,1962,84,6, 62.
43. D. Santrachand R. Matzeg,Presentedat the 46th SPICompositeInstitute's
Annual Conference,L991.,Washington,DC, USA, 1991,1-A11,.
44. N. E. Hamner,CorrosionData Suruey,NonmetalsSection,National Association
of Colrosion Engineers,Houston, USA, 1975.
45. Koatus Gas Hoan-Kyokai, Handbook for CorrosionResistantFRP, Tokyo,
Japan,1983.
46. P. A. Schweitzer,Corrosion ResistanceTables:Metals, Plastics,Nonmetallics and
Rubbers,2ndEdition,Marcel Dekker,Inc., New York, USA, 1985.
47. R. B. Seymour,Plasticsus. Corrosiues,JohnWiley Interscience,New York,

u sA ,1 9 8 2 .
48. ReinforcedPlasticsDurability, Ed., G. Pritchard,lVoodheadPublishingLtd.,
Cambridge,England,1998.
49. P. A. Schweitzer,Mecbanical and Corrosion-ResistantPropertiesof Plasticsand
Elastomers,Marcel Dekker,Inc., New York, USA, 2000.
50. The Possibilityof Application of FRPfor Main Processin CbemicalPlants,
EngineeringPromotionAssociation,Tokyo, Japan,Report No. ENAA 1991-1,1992.
51. Guidelinefor Non-metallicMaterialsSelection,Subcommitteeof polymeric
materials,The Plant MaterialsEngineeringCommittee,PMEC, The Societyof
ChemicalEngineers,Tokyo, Japan,Tokyo, Japan,1994.
52. Guidelineon PRP Tank for Tank Truck and Tank Container to Transport
Poisr,tnous
of Toxic Liquid, Japan ReinforcedPlasticsSociety,Tokyo, Japan,1.993.
EnsingerGmbH & Co., Nufringen,
53. TechnicalData Sheet,CbemicalResistance,
Germany.
54. Koatsu Gas Hoan Kyokai, Handbook for CorrosionResistantFRP, Tokyo,
Japan,1983,56.
55. The Possibilxyof Application o/FRP for Main Processin ChemicalPlants,
EngineeringPromotion Association,Tokyo, Japan,Report No. ENAA 1990-7,
7997,7.

t51

Handbook of Polymer Blends and Composites

56' vinyl Ester Resin,Ed., Researchgroup of vinyr esrer
resin,Kagakukogyo-NippoSha,Tokyo,Japan,1993.317.
57' vinyl Ester Resin,Ed., Researchgroup of vinyl ester
resin,Kagakukogyo-NippoSha,Tokyo,Japan,1993,259.
58' The Possibility of Application of FRP
for Main processin Chemical plants,
EngineeringPromotion Association,Tokyo,
Japan,ReportNo. ENAA -1991-1
'- - -'
1992,59.
59' JIS K 7012:1999,Glass-fibre-reinforced
thermosettingresinchemical-resistant
tanks,1999.
60. H. Hojo, K. Tsuda,M. Kubouchiand D.S.Kim,
Metarsand Materiars,.J.99g,4,
1,191.
61' H. Hojo, K Tsudaand H. Ishizuka,
Journarof the Japanesesctcietyfor
CompositeMaterials, 1991, 17. 6. 243.
62. H. Updegraff,M. J. Doyle and E. Kerle,presented
at the 24thAnnual
J.
conference,SpvReinforcedplastics/composites
Division, washington,D.c.,

us{, 1969,g_A.

63. H. Hojo, K. ogasawaraand H. Ishizuka,Reinforcedprastics

(Japan),19gg,34,
)49

64. G. H. Arian, Materialsperformance,1.990,29,g,73.

65' T' Akaoka and K. \Tatanabe,Reinforcedprastics
(!apan),1970,16,2,70.
66. T. Sakai,S. ono, M. Kubouchi, K. Tsudaand H.
Hojo, Journal of the Materials
ScienceSocietyof Japan, 2000,37, 5,24G.

67. T. R' Bott and A. J. Barker, Transactictnsof the Institute

ctf chemical Engineers,
1 9 6 9 , 4 7 ,T 1 9 5 .

6 8 . T' w. cowlev and M. A. Robertson,Materiarsperformance,

1991, 30,7, 46.
69. s. okuda and T' Iguchi, Aduancesin organic coating
scienceancrrechnorogy,
1979,4,257.

/ u . L. Prian and A. Barkatt,

lournal of MaterialsScience,1999, 34, 76,3977.

162

Corrosion Resistanceof Polymer,Poly,rnerBlendsand Compositesin Liquid Enuironments

71. H. Hojo, K. Tsuda,K. Ogasawaraand K. Mishima, Presentedat the 4th
lnternationalConferenceon CompositeN{aterials,Tokyo, Japan, 1982,1017.
72. H. Hojo, K. Tsudaand D. S. Kim, CorrosionEngineering,1989,38,12, 689.
73. D. S. Kim, K. Tsudaand H. Hojo, lowrnal of the MaterialsScienceSocietyof
Japan,1998, 35, 1, 32.
74. J. M. Marshall, G. P. Marshall and R. P. Pinzelli,Presentedat the 37th Annual
TechnicalConferenceof the SPI/Reinforced
Plastics/Composites
Institute,
rWashington,
DC, USA, 1982,Session
9-C, L.
75. H. Hojo, M. Koyama and K. Tsuda,Presentedat the 3rd International
Conference
in OrganicCoatingsand TechnologSAthens,Greece,1977,221.

163

Handbook of Polymer Blends and Composites

r64