Interface properties and their

influence on short fibre

composites
E. M/IDER and K-H. FREITAG

(Academy of Sciences of the GDR, GDR)

The single fibre pull-out method has been used to characterize the interfacial
shear strength in the glass fibre/polypropylene system. Interfacial shear
strengths were found to be significantly dependent on modifications of the
polypropylene matrix, while sizings applied to the fibres had no influence on
the adhesion forces. Interfacial shear strength results obtained using the
single fibre pull-out method are compared with those estimated from the
stress/strain curve.

Key words: composite materials; fibre~matrix interface; interfacial shear

strength; single fibre pull-out tests; surface treatment; glass fibres; poly-
prop ylene ma trices

Fibre-reinforced polymers include a very wide range of formed. The other end of the molecule is designed to
types. At one extreme there are low-performance react chemically with one of the reactants in the ther-
moulding compounds, which when finally moulded moplastic or thermosetting resin. The chemical compo-
contain fibres with lengths of 1 mm or less. At the other sition of this part of the sizing molecule is consequently
extreme are continuously aligned fibre laminates with dependent on the polymer matrix.
performances outclassing the best metal alloys. All of
them consist of at least three phases. Two of these, the This concept is illustrated in Fig. 1. In practice, more
reinforcing fibres and the polymer matrix, are reason- than a monolayer of sizing is present on the fibre
ably well characterized. The third phase, the interface - surface. Thus there is a chemisorbed layer at the fibre
or, more correctly, the intermediate phase between the surface, and a less well-bound, physisorbed, layer on
fibres and matrix - is little known and understood. top. The combined chemisorbed and physisorbed
layers are quite distinct from the fibres and matrix and
Fibre-reinforced composites are generally character- constitute the interphase.
ized and evaluated by means of various standard
tensile, flexural and fatigue tests performed on actual
composite specimens. Although these tests provide \ \ \/ \
valuable information about the macroscopic properties Bulk polymer CHz CIH2 CH CH2
of the composite, their results are strongly dependent I o I CH
0 I NH / I
on such factors as specimen geometry, fibre/matrix R\I ~ o ~ S i c - o . . 2 . j O " 0
volume ratio and fibre aspect ratio. Direct information ~Si- R bt~ R ~H
about the fibre/matrix interface cannot be obtained by # R /H--;O, /
such means. ~.\ ~ 0-..~.! ? H" ~Si/O\.i/I.
Physisorbed R/St ~/bt~ 0 / S t - 0 \ ~\
layer 0 R R R
In order to ensure efficient transfer of stress between H/ RI
fibres and matrix, the fibres are surface-treated or Interphase
R R R /SL...
'sized' or, in the case of a non-polar matrix, modified. ~1 \ k/o I O. R
The function of sizing agents and their reactions and Si_ _Si-- O--Si . 0 \ \Si/__
Chemisorbedloyer 0 / "~0 ~
"., \
0 i
~ H.~.O /H
interactions with the fibres and polymer have been
reviewed recently by Ishida 1. In the case of glass fibres,
the silanol end of the sizing agent molecule is attracted --
\ O?si/1_
Si Si Si
/
Si - -
to the glass surface where it forms a bond, probably by Gloss fibre
hydrogen bonding through OH groups which are
normally present on the surface of silica-based glasses Fig. 1 Schematic of the chemical structure of the interphase
or possibly sometimes an Si-O-Si bond may be between a fibre and a polymer (after Ishida 1)

0010-4361/90/050397-06 © 1990 Butterworth-Heinemann Ltd

COMPOSITES. VOLUME 21 . NUMBER 5. SEPTEMBER 1990 397
Characterizing the interphase
Work carried out to date at the authors' Institute has
been concerned with the characterization of surfaces of
numerous solids with regard to proton or electron
exchange properties, chiefly using electrokinetic and
wetting measurements.
The need to understand more fully the role of the
fibre/matrix interface has led to the introduction of
experimental techniques specifically designed to
measure the interfacial shear strength. Direct measure-
ment of the interracial shear strength of a fibre/resin
composite is usually accomplished by a pull-out test.
From the whole pull-out curve it is possible to measure,
for example, the energy absorption G i per unit area.
Careful control of pull-out experiments enables inde-
pendent measurements to be made of an interface yield
stress and an interface work of fracture at the instant of
debonding. Frictional shears can also be measured and,
due to Poisson's shrinkage effects in the fibre, an
average shear can be identified as well as a maximum
shear. After debonding, pull-out is controlled by
friction. These various mechanisms interact in a
complex manner during the pull-out tests.
Calculations of the interracial shear strength have been
carried out in the literature by assuming the maximal
pull-out length at fracture areas as IJ2 or by measuring
the fibre length distribution in fibre fragmentation
tests, extrapolating to the critical fibre length Ic and
calculating xi from:
rf
Ti = ~ " Ofu
These methods are not discussed in this paper.
EXPERIMENTAL
Materials and testing
P o l y p r o p y l e n e (PP) was employed as the matrix
material, and the four modifications used are listed in
Table 1. Single production glass fibres, prepared in the
authors' laboratory, with diameters between 30 and 50
~tm were used; Table 2 gives details of the sizing agents
employed. The fibres were handled with extreme care
so that the lengths used in the experiments did not
become contaminated.
Pull-out test specimens were prepared by first
mounting the glass fibres on a frame. The fibres were
then embedded singly in a _pool of liquid or molten

Table 1. Interfacial shear strengths of modified polypropylenes with unsized glass fibres

Polymeric material r Fd Td
(Ixm) (N) (MPa)

(1) Polybond 1001 (modified PP) (PPgrafted with 5 wt% acrylic acid) 20 3.93 21.35
(2) Mosten 52512 (irradiated) (PPhomopolymer, irradiated with electron 22 2.33 11.63
beams, dose: 30 kGy)
(3) Mosten 52512 (homopolymer) blended with 10 wt% modified PP(1) 23 1.11 8.39
(4) Mosten 52512 (PPhomopolymer) 24 0.85 4.91

Table 2. Interfacial shear strengths of PP homopolymer (4) and modified PP (3) with different glass
treatments

PP Glass treatment
1;d S V q
Sizing no Silane coupling agents Binder (MPa) (MPa) (%) (MPa)

(4) PPS 63 Amino/vinyl-silane Modified PO/PURdispersion 2.6 0.8 35.4 0.5

(4) PPS 65 Amino/vinyl-silane Modified PO/PURdispersion 2.2 0.8 35.9 0.4
(3) PPS 34 Amino/vinyl-silane PO dispersion 5.3 0.7 13.2 0.5
(3) PPS 36 Amino/vinyl-silane PO dispersion 7.3 2.0 29.5 1.5
(3) PPS 37 Amino/vinyl-silane PO/PUR dispersion 6.0 0.8 13.8 0.6
(3) PPS 63 Amino/vinyl-silane Modified PO/PURdispersion 5.2 0.7 13.3 0.4
(3) PPS 65 Amino/vinyl-silane Modified PO/PURdispersion 5.2 0.8 15.7 0.4
(3) PPS 71 Vinyl/Dynasilan IMEO PO/PUR dispersion 4.7 0.5 9.8 0.2
(3) PPS 74 Modified aminosilane PO/PURdispersion 5.8 0.8 13.4 0.6
(3) PPS 76 Modified aminosilane PO/PURdispersion 5.4 0.7 13.5 0.5

s standard deviation
v variation coefficient
2 x q width of the confidence interval for mean (S = 95%)

398 COMPOSITES . SEPTEMBER 1990

 the true embedded length2. Another problem which
was discussed by Piggott and co-workers3 was the free
length of the fibre extending from the surface of the
resin to the grip. The free length was set at 1 mm,
~ Upperfibre clamp which reduced the compliance4. Great care was also
taken in embedding the fibres so that they were sym-
metrically surrounded by the matrix bead, thus mini-
/ / ~ ,~ Fibre mizing flexural stresses in the fibre during pull-out.

RESULTS AND DISCUSSION

Fig. 4 shows a typical pull-out curve obtained when the
force applied to the fibre is plotted as a function of the

I
L Lower fibre
~>..] ~ Paper tab
clamp

o= c
Fig. 2 Arrangementof fibre pull-outtest in an Instronmachine
LL

~ ~ b ~ ~ ture

D
Polymerbead o Displacement
Fig.4 Typicalpull-outcurve
Fig. 3 Extendedembeddedlength,producedby a meniscus,
and potentialruptureof the meniscusbeforedebonding
resin to depths in the range 0.1-4 mm with the fibre
axis perpendicular to the surface. The resin was
allowed to harden, either by chemical reaction or
cooling, and the fibres with attached polymer beads
were then heated under a nitrogen atmosphere at
180°C followed by air cooling. The fibre was then cut
off at one side of the polymer bead, where the bead
touched the fibre. On the other side of the polymer
bead a paper tab was glued around the fibre 1 mm
above the bead to prevent fibre slip during the test.
To test the interphase, the fibre was pulled out of the
polymer at a speed of 5 mm min-1 in an Instron
machine as shown in Fig. 2.

Special precautions
There is a problem that limits the usefulness of any
method that requires partial immersion of the fibre
with melt or liquid. If the fibre surface is appreciably
wetted, there will be an elevated meniscus formed
around the fibre. The resin coating is thinner in the
meniscus region and may rupture prior to debonding
(Fig. 3). As a result, a cone of resin is left behind on the
surface of the fibre after pull-out, indicating cohesive
failure prior to adhesive debonding at the interface.
Although this premature rupture does not invalidate a
subsequent pull-out curve, it does require the inspec- Fig. 5 (a) Surfaceof a fibre after single fibre pull-out; and (b)
tion of every specimen after debonding to determine surface of a sizedfibre

COMPOSITES.SEPTEMBER1990 399
displacement of the fibre-pulling mechanism, relative consisting of 30 fibre/droplet specimens, is shown in
to the matrix. In the region OA the displacement is Fig. 8. There is a small distribution width between 629
entirely due to elastic effects. About 45 % of this and 962 ~tm and 453 and 824 ~tm, and therefore the
displacement is due to the fibre free length stretching, influence of the embedded length L on the force F d
and 10% is due to stretching of the fibre in the required to cause adhesion failure (discussed as a
polymer. At point A, the adhesion between the fibre linearly increasing region for very short embedded
and the polymer breaks down, and fibre sliding begins.
This leads to relaxation of the force in the region AB.
Between B and C, there is a 'stick-up' motion normally
observed in frictional sliding. At point C, sliding
decreases constantly, until the fibre emerges from the
polymer surface at point D. The distance OD is equal
to the embedded length in an ideal experiment, where
the polymer surface is smooth and no material is
plucked from the surface during the pull-out process. In Adhesive frocture Cohesive fr0cture
this paper the authors report measurements with glass
fibre-reinforced polypropylenes (vP).
Fig. 5 shows the resin left behind on the surface of the
fibre after single fibre pull-out and an untreated glass
fibre without polymer. Fig. 6 presents the fracture
surfaces of a chemically coupled glass fibre-reinforced
PP and an uncoupled glass fibre-reinforced PP. For
comparison purposes the model representation for the
fracture mechanical behaviour at the interphase, Shear void Shear craze Shear crack
described by Friedrich 6, is shown in Fig. 7.
Fig. 7 Fracture m e c h a n i c a l b e h a v i o u r o f f i b r e - r e i n f o r c e d
The embedded length of each fibre was measured t h e r m o p l a s t i c s d e s c r i b e d by Friedrich 8
microscopically before the pull-out test. The embedded
fibre length distributions for two compound-samples,
Xmi n = 6 2 9 p m
3O Xma x = 9 6 2 IJm

o~ $ = 9 2 . 4 pm
v = 11.9%

2o

n-I0

500 1000
a Embedded fibre length, L (pm)

Xmi n = 4 5 3 p m
Xma x = 8 2 4 p m
30 s = 101.4pm
v = 14.6 %

zo

a: I0

500 1000
b Embedded fibre length, L ( pm )

Fig. 6 Fracture s u r f a c e of glass fibre-reinforced PP: (a) c h e m i - Fig. 8 Embedded fibre length distribution for two samples of
c a l l y coupled; a n d (b) uncoupled modified PP (3) w i t h glass fibres (linear classified)

400 COMPOSITES . SEPTEMBER 1990

 4
1;d - -
2~x. rf. L
where rf is the fibre radius. This shear-lag analysis is
limited to the case of an elastic fibre and a plastic
(i) interface yielding at constant stress xj. The interracial
shear strengths of samples comprising unsized glass
fibres and modified pps are reported in Table 1.
Table 1 evidences the possibility of varying the interfa-
cial shear strength by using a modified polymer; the
polymer blend (3) (see Table 1) is usually used in short
fibre-reinforced compounds for practical applications.
Additionally, these compounds with modified eps
contain functionalized glass fibres. Table 2 presents the
interracial shear strengths of this polymer blend (3) and
a PP homopolymer (4) as a function of glass treatments.
Fig. 10 demonstrates a clear demarkation between
modified and unmodified PPs; however, there is no real
difference between the various sizes. The extent of the
error bars indicates that there is a large standard
deviation in the sample PPS 36, but it does not really
perform consistently better than the other sizes in a
modified PP matrix.
Zz (z)
The results obtained in this study were checked using
the concept developed by Bowyer and Bader 7, Ram-
steiner and Theysohn 8 and Mittal and Gupta 9 to
estimate the interracial bond strength from the stress/
strain curve. Mittal and Gupta 9 based their analysis on
the stress/strain relation of a single sample of the
composite with fibres aligned along the load axis and
argued that, since the interface may not be stressed to
\ its limiting value at low strains, a linear relationship has
to be assumed between the applied tensile stress and
the interfacial shear strength x. While Bowyer and
Bader 7 assumed x to be constant and equal to the
\ interracial shear strength at all strains, the present
analysis has led to the assumption that x = K.o~ where
K = 0.211° and l~ = Ee.rf.cJx.
Fig. 11 presents the measured stress/strain curves, and
\ gives calculated values of x and l~. Compared with the
data from pull-out tests (Fig. 10) the agreement is

[
,\
\ P P blend (3), treated
glass fibres

~ ~ ~ . I I

0.5 1.0 1.5 2.0 i

6~
Pulled-out distonce (ram)
Fig. 9 Mean pull-out curves of different PPdroplet]glass fibre
samples (see Table 1 for description of polymer blends) 5 ~2
Q_ PP h o r n o p o l y m e r ( 4 ) ,
treated glass fibres
4

lengths and a 'plateau' region 5 or as a function of L '/~

(Reference 3)) is neglected.
Samples were prepared of different modified PPs and
glass fibres either unsized or sized with various sizing
formulations. Fig. 9 shows the mean pull-out curves of
different ees with unsized glass fibres. The debonding
load F d and the embedded length L can be related to Fig. 10 Comparison of interfacial shear strengths of PP
the interracial shear strength xd by the equation homopolymer (4) and PP blend (3) and treated glass fibres

C O M P O S I T E S . S E P T E M B E R 1990 401
 s t r e n g t h . B o n d s t r e n g t h s in t h e PP/glass fibre s y s t e m
w e r e f o u n d to b e significantly d e p e n d e n t o n t h e m o d i f i -
c a t i o n s o f t h e PP. S u r f a c e t r e a t m e n t o f t h e glass fibres
2000 d i d n o t r e s u l t in d i f f e r e n t a d h e s i o n forces. If t h e
i n t e r r a c i a l s h e a r s t r e n g t h Xd is s m a l l in t h e t e s t e d
s y s t e m , o n l y t h e large i n f l u e n c e o f t h e m o d i f i e d m a t r i x
is d i s c e r n i b l e a n d t h e small i n f l u e n c e o f t h e sizing is n o t
noticeable.

REFERENCES
1500 1 Ishida, It. 'A review of recent progress in the studies of molecu-
x~ / PPblend (3), with lar and microstructure of coupling agents and their functions in
,~I different surface composites, coatings and adhesive joints' Polymer Composites 5
treotrnent of gloss fibres (1984) pp 101-123
2 Miller, B., Marl, P. and Rebenfeld, L. 'A microbond method for
determination of the shear strength of a fiber/resin interface'

7
~f' 1;=6.24 MPo,/c = O.26mm
Composites Sci and Techno128 (1987) pp 17-32
3 Piggott, M.R. et al. 'Mechanical interactions in the interphasial
region of fibre reinforced thermosets' in Composite Interfaces
edited by H. Ishida and J.L. Koenig (Proc 1st Int Conf on
IO00
/ Composite Interfaces, Cleveland, OH, 27-30 May 1986)
4 Piggott, M.R. and Chua, P.S. 'Recent studies of the glass-fiber-
polymer interphase' Ind Eng Chem Research 26 No 4 (1987) pp

/ 672-677
5 Chua, P.S. and Piggott, M.R. 'The glass fiber-polymer interface:
II. work of fracture and shear stresses' Composites Sci and
Techno122 (1985) pp 107-119
6 Friedrich, K. 'Fracture mechanical behaviour of short fiber
reinforced thermoplastics' Fortschr-Ber VDI-Z 18 No 18 (1984)
500
7 Bowyer, W.It. and Bader, M.G. 'On the reinforcement of
1; = 1.74 MPo,/c =0.91 mm thermoplastics by imperfectly aligned discontinuous fibres' J
Mater Sci 7 (1972) p1315
8 Ramsteiner, F. and Theysohn, W. 'Tensile and impact strengths
PP homopolymer(4) with of unidirectional short fibre-reinforced thermoplastics' Compos-
treated gloss fibres
ites 10 (1979) p 111
9 Mittal, R.K. and Gupta, V.B. 'The strength of the fiber-polymer
7" interfaces in short glass fiber-reinforced polypropylenes'J Mater
I00 Sci 17 (1982) p 3179
10 Gupta, V.B. et al. 'Interfacial shear stress in a short glass fiber-
i i i
reinforced polypropylene sheet' Composites Sci and Technol 28
0.002 0.004 0.006 0.008 0.010 0.012
(1987) pp 45-56
Strain, E 11 Gupta, V.B. et aL 'Some studies on glass fiber-reinforced poly-
Fig. 11 Stress/strain curves for PP/glass fibres at low strains propylene. Part II: Mechanical properties and their dependence
on fiber length, interfacial adhesion and fiber dispersion'
Polymer Composites 10 (1989) pp 16-27
satisfactory, taking into consideration the compliance
o f t h e p u l l - o u t tests.
A U THORS
D r M~ider, to w h o m c o r r e s p o n d e n c e s h o u l d b e
CONCLUSIONS
a d d r e s s e d , a n d D r F r e i t a g a r e b o t h with t h e I n s t i t u t e o f
T h e single f i b r e p u l l - o u t m e t h o d c a n b e u s e d to o b t a i n P o l y m e r T e c h n o l o g y o f t h e A c a d e m y o f Sciences o f t h e
sensitive m e a s u r e m e n t s o f t h e i n t e r r a c i a l s h e a r G D R , H o h e S t r a f e 6, D r e s d e n 8010, G D R .

402 COMPOSITES . SEPTEMBER 1990