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Composites

Science and Technology

51 (1997)

565-571

ELSEVIER

PII:

SO266-3538(97)00017-l

 

0

1997

Elsevier

Science

Lmited

Printed

in Northern

Ireland.

All

rights

reserved

0266-3538/97/$17.00

0 2 6 6 - 3 5 3 8 / 9 7 / $ 1 7

INFLUENCE

OF

MOISTURE

ON

THE

THERMAL

AND

MECHANICAL

PROPERTIES

OF

AUTOCLAVED

AND

OVEN-CURED

KEVLAR-49/EPOXY

LAMINATES

“School of Electrical

and

M.

Akay,”

S. Kong

Ah

Mud*

&

A.

Stanley’

Mechanical

Engineering,

“Shorts Brothers

plc,

University of

BT37

Airport

OQB,

Road,

Ulster at Jordanstown, UK

Belfast BT3

9DZ,

UK

Newtownabbey,

Co. Antrim,

Abstract

Moisture

(Received

23 August

absorption

behaviour

and

1996; revised

the

influence

14 November

1996; accepted

11 December

1996)

of

clearly

(Twaron)/epoxy-resin

demonstrated*

for

laminates

2 mm

thick

of

aramid-fibre

60~01%

fibre

moisture on the thermal and mechanical properties of

content.

Unlike

other

high-performance

fibres

such

as

Kevlar-49/epoxy-resin laminates have been studied.

carbon

and

glass

fibres,

aramid

fibres

are

strongly

The laminates were prepared by two different routes,

hygroscopic

and

often

to

a much

greater

extent

than

namely autoclauing and oven-curing, and their

the

matrices

 

in

composites.

For

instance,

a maximum

properties were compared. The oven-cured laminates

moisture

absorption,

M,,,, of approximately

2 wt%

was

contained a greater percentage of voids which resulted

reported2,3

at

70-8o”C/lOO%

RH

for

epoxy

resins

of

in a greater amount of moisture absorption and higher

approximately

120°C

cure

temperature.

The

values

for

values of moisture diffusivity. Moisture absorption

the

associated

unidirectional

aramid-fibrelepoxy-resin

caused an associated depression in the glass-transition

composites

were

approximately

 

4%2,4,5

or

7%.’

A

temperature and deterioration in mechanical properties.

maximum

moisture

content

of

6%

was

reported6

by

Furthermore, two distinct relaxation transitions were

the

manufacturers

for

Kevlar-49

at

room

indicated beyond a certain level of moisture absorption.

temperature/96%

RH.

Moisture

diffusion

coefficients,

Strongly hygroscopic Keular fibre is considered to

D,

of

approximately

3 X lo-’

mm2 ss’

(Ref.

3)

and

provide an easy route for moisture ingress and led to

mm2 ss’

(Refs

3

and

5)

were

recorded

for

the observed inhomogeneity in the plasticisation of

2 X lop6 epoxy

resin

and

Kevlar-fibre/epoxy-resin

composites,

specimens. 0 1997 Elsevier Science Limited

respectively.

 

A

certain

level

of

imbibed

moisture

may

improve

Keywords: Kevlar-fibre/epoxy-resin laminates, mois-

the

mechanical

properties

of

composites

by

relieving

ture absorption, glass-transition

temperature,

double

thermal

stresses

generated

by

the

differences

between

transitions, mechanical properties

the

coefficients

of

thermal

expansion

of

the

fibre

and

the

resin

as

the

matrix

cools

from

the

curing

temperature.

For

instance,

 

improvements

 

in

tensile

1 INTRODUCTION

strength

and

modulus

were

indicated7

for

a composite

In

Kevlar-reinforced

composites

the

hygroscopic

nature

of

both

the

resin

and

the

fibre

must

be

considered.

Water

absorption

by

epoxy

resins

varies

depending

on

the

resin

type

and

the

curing

system.

Work’

has

shown

that

the

water

absorption

may

differ

by

a factor

of

10 between

different

epoxy

resins,

and

to

a

factor

of

up

to

three

for

the

same

resin

with

a

different

curing

agent.

 
 

For

a given

composite

material

system,

the

moisture

absorption

behaviour

is dictated

by

the

conditions

of

temperature

 

and

relative

humidity

(RH).

This

was

* Present address: Chemical Process Technology Depart- ment, Singapore Polytechnic, 500 Dover Road, Singapore

0513.

of

approximately

65 ~01%

fibre

content

based

on

a

unidirectional

tape

prepreg

containing

Kevlar-49

and

TGMDA/DDS

epoxy

resin

following

three

weeks’

 

immersion

in

water.

At

higher

 

levels

of

moisture

absorption,

however,

deterioration

due

to

resin

plasticisation,

interface

failure

and

fibre

degradation

 

can

occur.

For

epoxy

resins,

a

drop

in

the

glass-transition

temperature

 

(T,)

of

15-20°C

per

1%

moisture

pickup

have

been

widely

reported.xm’0

Matrix

plasticisation

and

matrix/fibre

 

interface

deg-

radation

have

been

shown

to influence

the

mechanical

properties

of aramid-fibre/epoxy-resin

 

composites.

An

approximately

35%

loss

in

the

room-temperature

flexural

strength

was

observed”

in

Kevlar-49/epoxy-

resin

laminates

at

5%

moisture

uptake,

apparently

as

a

result

of

the

ease

of

fibre

buckling

in

a plasticised

at 5% moisture uptake, apparently as a result of the ease of fibre buckling in a

565

566

M. Akay

et

al.

matrix.

Work

on

Twaron-HM

aramid-fibre/epoxy-

 

by

ultrasonic

C-scanning

in

a

water

 

immersion

tank.

resin

composites

indicated

an

approximately

50%

Void

contents

of

-1%

in

autoclave-cured

panels

and

decrease

in

both

the

interlaminar

shear

strength

and

>

2%

in

oven-cured

panels

were

detected.

Poor

in

the

elastic

modulus

obtained

under

short-beam

surface

finish

was

in evidence

in oven-cured

panels.

bending

with

5%

moisture

absorption,

 

with

untreated

 

fibres.

Considerable

improvements

were

observed,

2.2

Test

methods

 

apparently,

with

fibres

which

had

surface

treatment.

The

specimens

were

cut

from

the

panels

with

a

The

composites

suffered

only

5-15%

moisture-

diamond-tipped

saw

such

that

the

long

directions

of

induced

reduction

 

in

compressive

strengths,

greater

the

specimens

were

parallel

to

the

warp

direction

of

deteriorations

occurring

in

the

specimens

with

the

the

fibres.

 

untreated

aramid

fibres.

 

The

specimens

were

pre-dried

 

in

a vacuum

oven

at

 

Kevlar-49/epoxy-resin

composites

have

also

shown

80°C

for

20 h

and

cooled

to

room

temperature

under

substantial

effects

of moisture

on

the

transverse

tensile

vacuum.

The

pre-dried

and

weighed

specimens

were

properties:

deterioration

 

of

14%

in

the

elastic

hygrothermally

conditioned

 

in

an

environmental

modulus,

35%

in

the

strength

and

27%

in

the

chamber

at

approximately

70°C

and

95%

relative

elongation

to

failure

were

 

indicated

 

from

tests

humidity.

Specimens

 

were

periodically

removed

from

conducted

at

room

temperature

 

for

specimens

the

chamber,

surface

moisture

 

wiped

off,

and

containing

approximately

5%

moisture.

At

such

high

re-weighed

to

determine,

by

weight,

the

moisture

moisture

contents,

 

failure

mechanisms

 

due

to

filament

content

and

the

equilibrium

 

moisture

content.

splitting

as

well

as

matrix

plasticisation

and

interface

Diffusivity

(D)

was

determined

 

from

the

initial

slope

degradation

were

observed.

Since

only

a 12%

strength

of

the

curves

of

moisture

absorbed

 

versus

(time

of

degradation

was

estimatedI

 

for

Kevlar-49

fibres

after

conditioning)1’2

curves,

by

using

the

Fickian

1 year’s

exposure

 

to

65”C/lOO%

RH,

it

was

there-

relationship”

without

correcting

 

for

‘edge

effects’.

fore

concluded

that

the

hydrolytically-induced

fibre

Some

of the

specimens

had

to

be

immersed

in water

at

strength

deterioration

would

not

be

too

serious

under

70°C

in

order

to

achieve

larger

quantities

of

moisture

typical

in-service

 

environmental

conditions.

This

ingress.

 

corroborates

the

manufacturer’s

 

account’

that

 

Pre-dried

specimens

and

specimens

with

various

moisture-conditioned

Kevlar

fibres

do

not

suffer

any

moisture

contents

were

tested

for

dynamic

mechanical

significant

loss

of strength

or

stiffness.

 

thermal

properties,

and

mechanical

 

properties.

Mono-

 

Moisture

absorption

behaviour

and

the

influence

of

tonic

mechanical

tests

were

conducted

at

ambient

moisture

on

the

thermal

and

mechanical

properties

temperature

( = 2O”C),

and

the

results

presented

here

are

studied

here

for

autoclave-cured

and

oven-cured

are

an

average

of

at

least

five

measurements

for

the

Kevlar-49/epoxy-resin

laminates.

Oven

curing

is

a less

static

tests

and

three

measurements

 

for

the

dynamic

costly

production

route

but

may

require

surface

filling

mechanical

thermal

analysis

(DMTA).

 

if the

part

is subsequently

to

be

painted.

 

Compression

tests

were

conducted

in

accordance

 

with

ASTM

D695

at

1.3 mm

mini’

 

loading

rate

on

2

EXPERIMENTAL

 

specimens

of

12.7 mm

width

and

80mm

length,

with

 

the

aid

of

an

antibuckling

device.

The

specimens

for

2.1

Materials

and

preparation

 

compressive

strength

measurements

were

end-tabbed

Laminates

of

flat

 

panels

were

prepared

from

(a)

with

glass-fibre/epoxy,

 

leaving

an

unsupported

speci-

Kevlar

49-285

fibre

and

Fiberite

MXM

7714

epoxy

men

surface

area

of

12.7 mm

X 4.8

mm.

The

specim-

resin

and

(b)

Kevlar

49-285

fibre

and

Brochier

1454

ens

for

the

modulus

measurements

 

were

not

epoxy

resin.

The

 

prepregs

were

in

four-harness

(or

end-tabbed,

since

the

load

was

only

taken

up

to

crowfoot

satin)

fabric

form

with

-48

~01%

fibre

one-third

of the

average

compressive

 

failure

load,

and

content.

 

the

extent

of

compression

was

monitored

with

an

 

Laminates

were

produced

by

autoclave

curing

and

extensometer

attached

to

the

specimen.

 

oven

curing,

for

comparison.

 

Each

panel,

-3.0

mm

X

Interlaminar

shear

tests

were

conducted

ac-

240

mm

x 400 mm,

consisted

of 10 plies.

The

stack

was

cordance

with

ASTM

D2344:

the

specimens

in of 6.4 mm

bagged,

debulked

 

under

vacuum

at

the

five-

and

width

and

25.4

mm

length

were

loaded

in

three-point

lo-ply

stages,

and

then

cured.

Autoclave

settings

were

bending

on

a support

span

of four

times

the

specimen

127

+ 5°C

310 z!=35 kPa

and

2 h.

Oven

curing

was

also

thickness

at

1.3 mm

mini’.

The

central

loading

nose

conducted

at

127°C

for

2 h.

A

vacuum

of

760 mmHg

and

the

support

pins

were

approximately

6 mm

and

( -

100 kPa)

was

applied

to the

debulked

stack

of plies

3 mm

in diameter,

respectively.

 

throughout

the

oven

cure

cycle.

The

heating

and

The

flexural

test

was

conducted

 

in

accordance

with

cooling

of the

production

chamber

were

maintained

at

ASTM

D790:

the

specimens

 

of

12.5 mm

width

and

-2~5°C

min -’

in

both

cases.

Laminates

of

-2.8

and

127 mm

length

were

loaded

in

four-point

bending

(a

3.3 mm

oven

thickness

were

curing,

respectively.

produced

The

panels

by

autoclave

and

were

inspected

double-point

support

span

loading

with

of

80 mm)

a load

at

1 mm

span

mm-‘.

of 40 mm The

and

a

loading

and

the

support

pins

Influence

of moisture

on thermal

were

approximately

6 mm

in

diameter.

A

linear

variable

differential

transformer

(LVDT)

was

employed

during

initial

loading

of

the

specimens

in

order

to

obtain

accurate

deflection

measurements.

 

The

dynamic

mechanical

thermal

properties

were

determined

by

means

of

a DuPont

983

DMA

at

1 Hz

and

a

temperature

sweep

rate

of

3°C min-’

in

the

temperature

 

range

20-200°C.

The

test

pieces

of

approximately

10mm

width

and

60 mm

length

were

supported

 

at

clamping

lengths

of

approximately

 

30 mm.

The

sinusoidal

oscillation

amplitudes

were

set

at

0.3 mm

and

the

Poisson’s

ratio

was

assumed

to

be

0.35

for

the

materials.

 

3

RESULTS

 

AND

DISCUSSION

 

3.1

Moisture

absorption

bebaviour

The

results

of

the

moisture

 

ingress

measurements

are

presented

 

in

Figs

1

and

2,

and

Table

1.

These

are

similar

to

the

previously

published

data2-5,‘3

for

both

the

maximum

moisture

content,

M,,,,

and

the

diffusivity,

D,

although

the

diffusivity

values

presented

here

are

only

rough

estimates

since

the

curves

of

moisture

weight

gain

versus

(time

of

exposure)“’

did

not

produce

very

obvious

initial

straight

lines

(i.e.

non-Fickian).

 

A

comparison

of

the

data

for

the

autoclaved

and

oven-cured

specimens

clearly

indicates

the

influence

of void

content

 

on

moisture

absorption.

As

with

other

systems,

e.g.

graphite-fibre/epoxy-resin,‘6

greater

values

of

D and

ZU, resulted

in specimens

with

greater

void

content.

3.2

Influence

of

moisture

on

the

dynamic

 

mechanical

thermal

behaviour

 

The

introduction

of

water

into

polymers

reduces

the

glass-transition

temperature

 

(TJ

and

the

maximum

tan

6

peak

height

as

a

result

of

plasticisation.

The

and mechanical

properties

567

a,

g

-6

.e

85

E

$7

B

P

a

.g

z

7

 

w

l

4

c

3

2

1

 

0

5

10

15

20

25

30

 

Exposure

time

(tin)

Fig. 2. Moisture absorption

for: (m) Fiber&e (autoclaved), (+) Brochier (autoclaved),

curves

(0)

(*)

at 70°C and

100%

RH

Fiberite

Brochier

(oven

(oven

cured),

cured).

 

Specimens

of -3

mm X 12.5 mm X 127 mm.

 

decrease

in

the

tan

S peak

height

is

an

indication

of

uneven

plasticisation

 

throughout

the

specimen

and

is

often

accompanied

 

by

a broadening

of

the

peak.

The

lack

of

uniformity

in

the

material

can

reach

a

significant

of

was

absorption,

the

distinct

proportion

relaxation

may

transitions.

and

lead

to

the

generation

Such

a phenomenon

level

were

most

of moisture

observed

notably

observed

dynamic

here:

two

beyond

a certain

distinct

mechanical

transitions

properties,

in

in

the

tan

6 traces

(see

Figs

3 and

4). The

positions

of the

tan

S maxima

indicate

the

presence

of

two

regions

in

the

material:

a

region

plasticised

by

moisture

and

another

which

remains

almost

unplasticised.

The

results

presented

in

Figs

5

and

6

and

Table

2

show

that

the

glass-transition

temperatures

(obtained

from

the

tan

S

traces),

the

rate

of

depression

in

Tg with

moisture,

and

the

moisture

level

at

which

double

transition

peaks

emerged

 

are

different

for

the

two

resin

systems:

Tg values

were

approximately

115°C

and

12o”C,

and

Tg depressions

 

were

approximately

 

15°C

and

10°C

per

1%

moisture

pickup

for

the

Brochier

 

and

Fiberite

 

resins,

respectively,

although

the

3.5 /

I

decrease

in

Tg for

the

Fiberite

system

was

almost

 

negligible

for

the

initial

1%

moisture

ingress.

For

both

material

systems,

the

effect

of plasticisation

reached

a

maximum

level

at

approximately

2.5%

moisture

content

such

that

no

further

significant

decrease

in

Tg

and

in

the

maximum

tan

6 peak

height

was

indicated

with

the

additional

moisture

ingress.

 

Two

distinct

transition

peaks

were

observable

 

at approximately

1%

and

2%

moisture

contents

for

the

Brochier

and

Fiberite

systems,

respectively.

 
 

I

The

apparent

 

existence

of

two

phases

with

distinct

0

5

10

15

20

25

relaxation

transition

behaviour

has

been

observed

 

by

 

Exposure

time

(h”?

others

and

various

reasons

offered:

 

Fig. 1. Moisture absorption curves at 70°C and 95% RH for:

(m) Fiberite (autoclaved),

(0) Fiberite

(oven

cured),

(+)

1.

An

incomplete

further

cure

of

the

matrix

which

may

the

thermal

Brochier (autoclaved),

(*)

Brochier (oven cured). Specim-

undergo

 

curing

during

ens of -3 mm X 10 mm X 60 mm. Best-line

fits are shown for

analysis

and

may

thus

generate

a

second

tan

6

 

the Fiberite

data.

peak

at

a

higher

temperature.”

In

this

study,

568

M. Akay

et

al.

 

Table

1. Moisture

absorption

parameters

 
 

Specimen

type

 

Conditions

WI,,,(%

by weight)

D

X

10”

(mm’s_‘)

 
 

(temperature/RH)

 
 

Fiber& (autoclave cured)

 

7O”C/95 %

RH

2.5

2.9

Fiberite (autoclave cured)

7OYZ/lOO% RH

 

4.1

Fiberite (oven cured)

7o”C/95 % RH

3.2

8.6

Fiberite (oven cured)

70+/100% RH

4.3

Brochier (autoclave cured)

7o”C/9S%

RH

2.7

3.3

Brochier (autoclave cured)

7O”C/lOO%

RH

5.5

Brochier (oven cured)

7O”C/9S%

RH

3.0

4.8

Brochier (oven cured)

7O”C/lOO%

RH

6.5

representative

 

specimens

were

post-cured

at

of

testing

increases.

The

authors

have

ignored,

127°C for

a further

2 h

in

order

to

ensure

that

for

instance,

the

fact

that

one

of

their

tan

6

curing

was

complete.

 

The

dynamic

 

peaks

does

not

actually

disappear

but

remains

mechanical/thermal

 

analysis

traces

of

the

as

a shoulder

attached

to

the

other

one

as

the

post-cured

specimens

 

produced

only

a

&2”C

 

rate

of

heating

or

the

frequency

of

the

testing

variation

in

TX, which

is

well

within

the

increases.

 

experimental

scatter.

 

The

specimens

used

in

the

thermogravimetric

 

2. A

different

level

of

plasticisation

 

of

the

analysis

(TGA)

had

to

be

cut

into

very

small

 

fibre/matrix

interface

compared

with

the

bulk

of

dimensions

and

hence

cannot

be

considered

to

the

matrix.lx

 

maintain

the

integrity

of the

bulk

composite.

In

3. influence

An

of

the

absorbed

water

not

bonded

 

any

case

the

TGA

traces

at

different

 

to

the

polymer

network.‘”

 

temperature-scan

rates

indicate

insignificant

 

4.

Drying

of

the

specimen

during

the

dynamic

 

variations

in

the

moisture

content,

and

yet

are

mechanical/thermal

 

analysis.*“,*’

 

employed

to

support

the

occurrence

or

disap-

The

last

explanation

is strongly

argued

for

in recent

 

pearance

 

of a second

tan

6 peak

under

different

work

by

Chateauminois

et

~1.”

conducted

on

a

temperature-scan

rates.

glass-fibre/epoxy-matrix

 

composite

with

a

T,

of

The

use

of

aluminium

foil

to

limit

moisture

approximately

 

180°C. Their

experimental

findings

 

losses

results,

during

DMTA