Materials 2012, 5, 1084-1113; doi:10.

3390/ma5061084
OPEN ACCESS

materials
ISSN 1996-1944
www.mdpi.com/journal/materials
Article

Glass Fiber Reinforced Polypropylene Mechanical Properties

Enhancement by Adhesion Improvement
Mariana Etcheverry and Silvia E. Barbosa *
Planta Piloto de Ingeniera Qumica, PLAPIQUI (UNS-CONICET), Cno. La Carrindanga Km. 7,
Baha Blanca 8000, Argentina
* Author to whom correspondence should be addressed; E-Mail: [email protected];
Tel.: +54-291-4861700; Fax: +54-291-4871600.
Received: 10 April 2012 / Accepted: 26 May 2012 / Published: 18 June 2012

Abstract: Glass fibers (GF) are the reinforcement agent most used in polypropylene (PP)
based composites, as they have good balance between properties and costs. However, their
final properties are mainly determined by the strength and stability of the polymer-fiber
interphase. Fibers do not act as an effective reinforcing material when the adhesion is weak.
Also, the adhesion between phases can be easily degraded in aggressive environmental
conditions such as high temperatures and/or elevated moisture, and by the stress fields to
which the material may be exposed. Many efforts have been done to improve polymer-glass
fiber adhesion by compatibility enhancement. The most used techniques include
modifications in glass surface, polymer matrix and/or both. However, the results obtained do
not show a good costs/properties improvement relationship. The aim of this work is to
perform an accurate analysis regarding methods for GF/PP adhesion improvement and to
propose a new route based on PP in-situ polymerization onto fibers. This route involves the
modification of fibers with an aluminum alkyl and hydroxy--olefin and from there to enable
the growth of the PP chains using direct metallocenic copolymerization. The adhesion
improvements were further proved by fragmentation test, as well as by mechanical properties
measurements. The strength and toughness increases three times and the interfacial strength
duplicates in PP/GF composites prepared with in-situ polymerized fibers.
Keywords: glass fiber/polypropylene composites; in-situ polymerization; improvement
adhesion; mechanical properties

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1. Introduction
Glass fibers (GF) are the most common reinforcement for polymeric matrix composites. Their
principal advantages are the relationship between their low cost, high tensile strength, high chemical
resistance, and insulating properties. The disadvantages are low tensile modulus, relatively high
specific gravity, sensitivity to abrasion during handling, low fatigue resistance, and high hardness.
E-glass and S-glass are the types of fibers more commonly used in the fiber-reinforced plastic industry.
E-glass fibers have the lowest cost of all commercially available reinforcing GFs, which is the reason
for their widespread use in the fiber-reinforced plastic industry. S-glass, originally developed for
aircraft components and missile casings, has the highest tensile strength among all fibers in use.
However, the compositional difference and higher manufacturing cost make it more expensive than
E-glass [13].
The manufacturing process for GFs includes several steps. Various ingredients in the glass
formulation are first dry mixed and melted in a refractory furnace at about 1,370 C. The molten glass
is exuded through a number of orifices contained in a platinum bushing and rapidly drawn into
filaments of approximately 10 m diameter. A protective coating (size) is then applied on individual
filaments before they are gathered together into strands and wound on a drum. The size is a mixture of
lubricants, which prevent abrasion between the filaments, antistatic agents, which reduce static friction
between the filaments and a binder, which packs the filaments together into a strand. It may also
contain small percentages of a coupling agent that promotes adhesion between fibers and the specific
matrix for which it is formulated [1].
Fiber-reinforced composite materials consist of fibers with high strength and modulus embedded in
a matrix. Both fibers and matrix retain their physical and chemical identities and the new material has
a combination of properties that cannot be achieved with either of the constituents acting alone. In
general, fibers are the main load-carrying members, while the matrix functions are: to transfer stresses
between the fibers, to provide a barrier against an adverse environment, and to protect the fiber surface
from mechanical abrasion [1,3].
Polymer composites have been used in a wide range of industrial applications like aeronautic, naval,
construction, sporting goods, home appliances, furniture, etc. They have been on the market for over fifty
years, and have generally been used to replace materials such as wood, aluminum and steel. Their
advantages over traditional materials include greater mechanical strength, lighter weight, better
dimensional stability, higher dielectric strength and corrosion resistance, and flexibility to improve the
designs [4]. The major advantage of these composites that helped them enter into such a variety of
markets is their high specific property, which is greater than that of metals and ceramics. Nevertheless,
the tailoring of well-bonded and/or durable interphases between the matrix and reinforcement remains a
critical issue in this kind of material. This factor is critical with thermoplastic polymer matrices such as
polyethylene (PE), polypropylene (PP), polyvinylchloride (PVC), polystyrene (PS) and polyamide (PA).
The effectiveness of reinforcement essentially depends on the adhesion between matrix and fiber,
so this is a key factor in determining the final properties of the composite material, particularly its
mechanical properties [1,57]. The fiber-matrix adhesion is confined to a region or third phase
known as interphase, where stress-transfer occurs. The interphase is defined as the tridimensional
region, located between the fiber and the matrix. It is considered as a transition region or third phase

Materials 2012, 5

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with its own characteristics, corresponding neither to fiber properties nor to matrix ones [8]. Wu
postulated that the extent of molecular or local segmental diffusion across the interface determines the
structure of the interfacial zone, which critically affects the mechanical strength of an adhesive bond.
Negligible diffusion will give a sharp interface with weak adhesion. In this case, high adhesive
strength can be expected only when strong polar interactions or chemical bonds exist across it. On the
other hand, if the interphase is relatively thick and gradual as a result of extensive diffusion, a high
adhesive strength will result just by the effect of dispersion forces [9].
2. Methods for Adhesion Improvement
The strengthening of matrix-reinforcement interphases has been the goal of a great amount of
research, particularly in thermoplastic composite materials. Different kinds of treatments are necessary
to improve the interfacial adhesion [10]. Compatibility can be increased by fiber surface treatment,
changes in the polymer matrix or both [1,11]. Among the compatibilizing methodologies, the most
widely used is fiber treatment with coupling agents and techniques for modifying the matrix, such as
alkali treatment, acetylation and graft copolymerization, which are summarized below [12].
2.1. Glass Fiber Treatment
The glass surface modifications by treatment with a coupling agent are used to improve the
fiber/matrix interfacial strength through both physical and chemical bonds, and to protect the fiber
surface from environmental conditions, such as moisture and reactive fluids. Organofunctional silanes
are the most widely used coupling agents for improvement of the interfacial adhesion in
glass-reinforced materials. Their effectiveness depends on the nature and pretreatment of the substrate,
the silane type, the silane layer thickness and the application process. In a relatively dry state, the
proper selection of a silane coupling agent is an effective means of promoting interfacial adhesion and
enhancing mechanical properties. Under wet conditions, however, its effectiveness substantially
depends on the nature of the chemical bond between the silane coupling agent and the primary
constituents, i.e., the GFs and the polymeric matrix. A variety of mechanisms have been proposed to
explain the function of silanes at the interphase. Plueddemann and colleagues were the first to perform
a systematic study of the effectiveness of over a hundred silane coupling agents on the wet strength of
epoxy and polyester laminates [1316]. These data suggest that the primary factors are:

The chemical reactivity of the silane organofunctional group to form covalent bonds with the
polymer matrix.
The primary or secondary chemical bond formation at the glass interface.
The ability of the polymer matrix to diffuse into the silane interphase to form a rigid, tough,
water resistant interpenetrating polymer network as a transition zone between the bulk matrix
and glass reinforcement.

The coupling mechanism of these agents has not been fully clarified, probably because of the
complex nature of the interfacial interactions [1,5,7,11]. The chemical bonding theory states that silane
undergoes a chemical reaction with the surface of inorganic substances to form Si-O-M bonds (where
M is either a Si atom from glass or metallic atom in general). This theory was verified for silanes

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reacting with silica, where the alkoxysilanes undoubtedly formed Si-O-M bonds. Since glass consists
mainly of SiO2, silanol and siloxane groups, they are likely to be present at the GF surface. When
heated, silanol groups decompose into siloxano by releasing water. Also siloxane groups, formed at
moderate temperatures, will rehydrate in the presence of water, to form silanol groups. In any case, the
conditions of glass surfaces depend on the environment, particularly on the moisture content. It can be
expected that a few layers of free water (thickness in the range of the diameter of the water molecule)
remain weakly adsorbed. In unsaturated polyesters-silane-treated GF composites, the interphase
strength depends on the reactivity of the agents to the unsaturated polyesters. This fact strongly
suggests the formation of chemical bonds between the resin and the coupling agents. Instead, the last
ones have less effect on thermoplastic resins, in particular on polyolefins, for which there are no
specific reactions that may involve silanes. Studies on silane coatings include the development of
aminosilane with an unsaturated bond, carboxylic acid functional silane, cationic silane, silyl peroxide,
and aminimide.
Zulkifli investigated the effect of different types of silane and their concentrations in the interphase
chemistry of the filler particle or fiber reinforcement in a polymer matrix and their influences on the
fracture properties. Surface fracture analysis was carried out to determine the level of fiber-matrix
debonding. It was found that physicsorbed silane removing enhances its chemisortion in order to form
bonds with the substrate and improve the fiber-matrix adhesion [17].
Other coupling agents used with GFs are titanium compounds, known as titanates. They are mainly
used to modify the surface of mineral reinforcements such as calcium carbonate, talc, etc. in order to
make them compatible with resins such as PP, PE, PS, and to use them as processing
aids [1,5,16,18,19]. These coupling agents are more effective than silanes with thermoplastic resins
because they have three functional groups compared to only one in the silanes. In addition, titanates
also act as plasticizers to allow higher rates of charges and/or to achieve a better flow. When applied as
a coating, they reduce the viscosity of the system and increase the reinforcement concentration. Their
main disadvantage is the very high cost, which is much higher than that of silanes.
2.2. Matrix Modifications
Another way to improve the thermoplastic/glass fiber interphase is to add a specific modified
polymer to the matrix. Taking into account that polyolefins are highly non-polar, the introduction of
polar functional groups to the PP chains can improve compatibility with polar strengthening and
achieve a homogenous dispersion of additives, fillers and reinforcements. The polar groups in PP
chains are introduced by reactions with species that contain specific functional groups in their
structures, such as ester, carboxylic acid or anhydride groups. This kind of strategy is used for PP/GF
composites in which a maleic anhydride grafted polypropylene (PP-g-MA) is added in order to react
with the amine group of the silanized glass surface [20,21]. A similar methodology was adopted by
Di Benedetto et al. who used oligomers of poly(sulfone) and poly(carbonate) to promote the fiber
bonding with different matrices. In these cases, the coupling proceeds from the reaction between
organic functions of the silanized glass surface and the modified oligomer [22]. Lee et al. [23]
evaluated the ability of hydroxylated polypropylenes to improve the adhesion between pure PP and
glass laminates. They found evidence for chemical bonding between PP-OH and glass surfaces with a

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subsequent interfacial interaction. Van den Oevert and Peijs investigated the influence of PP-g-MA on
fatigue behavior in continuous glass-fiber-reinforced polypropylene (GFRPP) composites. In the case
of longitudinal tension-tension fatigue, only in a slightly higher absolute fatigue strength results of the
use of PP-g-MA. In the case of off-axis (shear or transverse) fatigue, improved adhesion as a result of
the use of PP-g-MA results in significantly higher fatigue strength [24].
Rijsdijk et al. [20] investigated the influence of PP-g-MA on monotonic mechanical properties
in continuous GFRPP. Three-point bending tests were performed on 0 and 90 unidirectional
glass-fiber/PP laminates with various weight fractions of PP-g-MA in the PP matrix. These tests
showed an increase in both longitudinal and transverse flexural strength up to 10 wt% PP-g-MA,
whereas at higher PP-g-MA weight fractions, a flexural strength decrease was observed. No significant
influence of PP-g-MA on composite stiffness was found. Additional mechanical tests on unidirectional
glass/PP composites with 0 wt% and 10 wt% PP-g-MA showed only a small increase in
fiber-dominated properties such as longitudinal tensile strength and strain, whereas composite
properties that are governed by the interphase, such as transverse, shear and compressive strength,
showed significant increases as a result of matrix modification and an enhanced interaction between
the GFs and the PP matrix.
Bogoeva-Gaceva et al. also investigated the characterization of a PP-g-MA as an adhesion promoter
for GF composites. They found that the apparent shear strength of single-fiber model composites with
PP-g-MA-modified iPP was increased compared with those with homo-iPP [25].
It is important to note that, during PP-g-MA preparation, melted PP is subject to a grafting reaction
with maleic anhydride in the presence of peroxide initiators. The use of peroxide initiators together
with the required processing conditions causes the formation of products not completely homogeneous
and characterized by a PP degradation, which makes them unsuitable to use as a matrix or, due to the
not guaranteed constant and repeatable properties, as compatibilizing agents in the preparation of
GFRPP. This fact makes PP-g-MA only attractive as an additive to blend with pure PP [26].
2.3. Fiber Treatment and Matrix Modifications
Several studies have been performed in order to determine the influence of the interphase PP/GF on
the mechanical properties by modifying the fibers with -aminopropyltriethoxysilane and various
polymer dispersions (PE/polyurethane), PP, PP/polyurethane and epoxy) with PP-g-MA. The
experimental results showed that physical and chemical interactions established in the composite
improved the interfacial strength values and mechanical properties in all cases [21,2733].
Feller et al. [34,35] investigated a way to increase mechanical properties of PP/GF composites
modifying the fiber/matrix interphase using model multifunctional sizing agents (triethoxy and
chlorodimethyl silane grafted isotactic copolymers of propene and dienes). These polymers were
synthesized through heterogeneous Ziegler-Natta catalysis copolymerization and hydrosilylation with
a Speier catalyst. The resulting multifunctional sizing agents can create chemical bonds with the fiber
surface and co-crystallize with the PP matrix (co-crystallization is obtained between polymers having
very similar chemical and crystalline structures). They found that, for ramificated poly(propene)s it is
possible to adjust the surface free energy with the silane content. The more important interfacial shear
stress was obtained with poly(propene-co-8.5%methyloctadiene-g-chlorodimethylsilane) showing that

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a compromise must be found between the silane content and polymer crystallinity. The main
disadvantage of these methods is the relationship between high-costs and low efficiency.
3. Fiber In-Situ Polymerization as a Route of Adhesion Improvement
PP polarity is so low then the adhesion with GF is bad. As it was shown above, a lot of effort was
done in order to enhance the compatibility between both surfaces, but improvement obtained was low.
Also its viscosity in the molten state is so high that good penetrability in GF mats is impeded. The best
possible adhesion is given by chemical anchorage between the polymer and fiber. Following this idea,
PP was polymerized and chemically bonded on the glass surface [36,37] in our group. This reaction
involves a metallocenic catalysis starting with propylene gas. In this sense, when polymerization is
performed onto the glass-fiber mat, the penetrability of this gas is so high that PP prepreg mats could
be obtained [38].
The experimental reaction route involves an initial contact with methylaluminoxane (MAO) and
hydroxy--olefin (9-decen-1-ol) to generate the anchorage points on the fiber surface, followed by a
propylene polymerization catalyzed by EtInd2ZrCl2 (metallocene)/MAO. The reaction was carried out
onto GFs of about 25 m nominal diameter, provided by Vetrotex Argentina. It should be noted that,
because the extruding glass process takes place at very high temperatures on the surface, hydrolysis
used for all surface modifications, silanization, titanization, and so on, and will also be used as anchor
points for the proposed direct copolymerization in this study. Figure 1 shows the reaction scheme
proposed for the PP grafting molecules onto glass surface.
Figure 1. Scheme proposed for the polypropylene (PP) grafting molecules onto glass surface.
Surface
GlassGlass
fiberFiber
surface

H 2C

OH
OH

CH CH2

OH

MAO
+ MAO
++

CH3
CH

OH

OH
OH

MAO/hydroxy--olefin
MAO/hydroxy-
-olefinbond
bond

Al O
CH2

CH (CH2)8

O Al

O
Al

CH3
O

Al O
O

OH
OH

Polypropylene
Polypropylene
Polypropylene

Al-O-Si
Bond
Al-O-Si
bond

Macromonomer
Macromonomer

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The graft reaction of PP onto GFs includes two steps:

-

Glass-MAO pretreatment. The first step is MAO addition in order to produce an appropriate
concentration of CH3 groups (from the MAO), which subsequently react with the compounds
to be copolymerized (the hydroxy--olefin) through the OH groups. The glass reacts with
MAO through the OH groups anchored on its surface, releasing methane (CH4) and generating
a bond Al-O-Si (glass). The methyl group on the (glass) Si-O-Al-CH3 reacts with the OH of the
hydroxy--olefin, releasing CH4. The final anchorage on the surface, previous to the propylene
polymerization reaction, is AlO3, with one of the O of the AlO3 linked to an alkyl group and the
other two to Si or Al. The addition of a hydroxy--olefin to supply the necessary vinyl-bonds to
initiate the propylene polymerization is performed. It was demonstrated that short
hydroxy--olefins (5-hexen-1-ol) [39] tend to act as Lewis bases; however the use of
long-chain hydroxy--olefins (9-decen-1-ol,10-undecen-1-ol) is preferred to assure a low level
of poisoning [40].
Reaction of the glass surface with hydroxy--olefin. After the MAO reaction to the glass
surface, hydroxy--olefin is added. The hydroxy--olefin reacts with the MAO-CH3 groups
with evolution of methane and the setting of terminal vinyl groups to the glass. Then, a
copolymerization reaction can be initiated from these macrocomonomers. The propylene
(CH3CH=CH2) molecules are attached via catalytic polymerization using EtInd2ZrCl2
(metallocene)/MAO. The MAO is included in the metallocenic catalyst to alkylate the
metallocene, and to generate and stabilize the cationic active zirconocene. As a result, PP chains
grow by copolymerization of propylene with the vinyl group of the Al-O(CH2)n-C=CH2,
remaining chemically bonded to the glass. Finally, the polymer precipitates by acidified ethanol
aggregate. Details of the experimental procedure are described in previous works [36,38]. This
reaction scheme (Figure 1) was further proved by consistent evidence obtained by combining
scanning electron microscopy techniques (SEM) with X-ray energy dispersive analysis (EDX).

The hydroxy--olefin concentration used in each case was calculated in order to ensure the activity
of the metallocene catalyst. The metallocene concentration remained constant. Therefore, the reaction
variables were selected aimed to obtain a high level of PP coverage on the glass surface by chemical
bonding between them. Table 1 summarizes the nomenclature of all reactions performed, where the
concentrations in percentage were calculated following the calculations explained in reference [37].
The experimental methodology, as well as the techniques used for characterization, are schematically
described in Figure 2.
Table 1. Nomenclature of all reactions performed.
Name
F0
F0.5%
F1%
F1.5%
F2%

Hydroxy--olefin [L]
---50
100
150
200

Total MAO [mL]

---10
10
12
12

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Figure 2. Experimental methodology.
GLASS FIBERS

COPOLIMERIZATION REACTION

1- Fibers are placed inside the reactor. It is closed,

reactives added and propylene copolymerization reaction
begins.

2 - The reaction ends when the flow of propylene is

stopped.

3- PP precipitates by addition of ethanol acidified solution.

This solution also deactivates the catalyst and breaks down
the MAO, generating methane and AlCl3.

- Morphological SEM/ EDX

CHARACTERIZATION

- T hermal DSC TGA

- H ydrophobicity test

In order to determine the reaction occurrence, a comparative study was performed on fiber surfaces
after strong PP extraction. In a previous work, screening experiments were performed using extremely
low and high hydroxy--olefin concentrations, 0.4 and 4%, respectively. In these studies, it was
demonstrated that propylene effectively copolymerizes onto fiber surfaces and the final morphology
depends on the hydroxy--olefin amount used during the reaction [36,41].
4. Morphological Aspects of in Situ Polymerized Fiber Glass
Figure 3 shows the scanning electron micrograph of GFs without any treatment and its
corresponding EDX spectrum, which is used as standard. Peaks of Si, O, Al and Ca for the E-glass
fiber chemical composition can be seen. Note that the peak of C is undetectable, so it is not possible to
establish an initial C/Si ratio. A complete morphological study was performed on all reaction products

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in order to optimize the alcohol concentration that maximizes the PP-glass adhesion. Figures 47 show
the fiber surfaces after in-situ polymerization for all hydroxy--olefin concentrations. The EDX
spectra are also included to verify the nature of the species attached to the fibers; and to allow a rough
estimation of their relative amounts. In all cases, the polymers attached to the fibers appear as white
particles in the SEM micrographs. From the EDX spectra, it is clear that the C peak increases notably
after polymerization.
Figure 3. Scanning electron micrograph (SEM) of the sample F0 (2,000) with its
corresponding EDX spectrum.

Figure 4. SEM micrographs for sample F0.5% and its corresponding EDX spectrum.
(a) 600 and (b) 2,000.

Materials 2012, 5
Figure 5. SEM micrographs for sample F1% and its corresponding EDX spectrum.
(a) 600; (b) 6,000; (c) and (d) 10,000.

Figure 6. SEM micrographs for sample F1.5% and its corresponding EDX spectrum.
(a) 200; (b) 600; (c) 2,000 and (d) 6,000.

1093

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Figure 7. SEM micrographs for sample F2% and its corresponding EDX spectrum.
(a) 200, (b) 2,000 and (c) 6,000.

For all in-situ polymerizations, the EDX spectra show large C peaks and obviously O, Al, Si and Ca.
The C peak corresponds to PP adhered to the glass surface. Note that in some cases, when the amount
of C is very large (F1% in Figure 5) the typical peaks from the fiber (Si, Al, O) are relatively reduced,
as expected. In low magnification, the micrographs show that the degree of coverage for different
concentrations of hydroxy--olefin used is different.
In extreme conditions (F0.5% and F2%) the coverage is not homogeneous, presenting zones with
larger polymer agglomerates. At high magnifications, it is evident that the polymer onto fibers presents
different morphologies. These crystalline forms are typical of the crystallization during polymerization
of polyolefins, particularly PP. Wunderlich shows similar results for PP, where the difference between
the spherical macroscopic crystalline forms attached to the polymer is first generated and then
crystallized, nucleated by a particle of the catalyst. The smaller rod-shaped particles are those where
the crystallization occurs as the polymer is formed [42,43].
Taking into account that the objective is the improvement of adhesion, a homogeneous polymer
layer on the fibers is needed. F1% and F1.5% samples show the highest degree of coverage while
F0.5% and F2% samples have agglomerated polymer. The greater the amount of hydroxy--olefin, the
greater the number of anchor points and the lower the PP chain length. Aaltonen et al. [44,45], report
that an increase in the concentration of hydroxy--olefin reduces the rate of consumption of propylene
when other polymerization conditions are kept constant..
From these results it appears that the length of the PP chains decreases when the concentration of
hydroxy--olefin increases. These observations also agree with the EDX results. Comparing the EDX
spectra, it is clear that in all polymerizations the C peak appears, but its relative intensity is much
greater for conditions F1% and F1.5% that for F0.5% and F2% samples.
Thermal characterization of the polymer grafted onto fibers was performed by Differential
Scanning Calorimetry (DSC) and Thermogravimetrical analysis (TGA). Figure 8 shows the DSC
thermograms of the PP grafted onto fibers with different percentages of hydroxy--olefin and
compared with untreated fibers. Low melting temperatures (110122 C) in PP copolymerized onto

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fibers is typical of -PP metallocene polymerization. TGA gives the evidence that molecules grafted
onto the fibers at the optimal condition are PP ones. The thermograms obtained allow the evaluation of
the mass changes that occur at different temperatures, indicating the transformations taking place at all
times. Figure 9 shows the weight loss as a function of temperature. Degradation of PP can be observed
at 425 C whereas commercial PP degrades at approximately 450 C.
Figure 8. Differential Scanning Calorimetry (DSC) thermograms of the polymer grafted
onto the GFs with different hydroxy--olefin concentrations.

Figure 9. Thermogravimetrical analysis (TGA) thermograms for the sample (a) PP

commercial and (b) PP graft MF1%.

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Figure 10. SEM micrograph (2,000) and photograph of hydrophobicity test of:
(a) untreated fibers and (b) copolymerized fibers.

The polymer fiber coverage after in-situ polymerization and previous to composite preparation was
qualitatively determined by a hydrophilic/hidrophobic test. The results are interpreted in terms of
surface energy (or activity) change due to the attached material to GF. This technique includes the
immersion of fibers in a mixture of two immiscible liquids with different polarity and density.
A mixture of 50% v/v hexane/water was used in these tests. The densities at 20 C were: hexane
0.675 g/cm3 and water 1 g/cm3. The GF surface behaves, initially, hydrophilicly since its superficial
hydroxyl groups tend to form hydrogen bonds with water. However, such hydrophilicity should
disappear as a consequence of the surface copolymerization and the resulting PP coverage. The
different morphology exhibited by the fiber surface before and after copolymerization with 1%
hydroxy--olefin is shown in Figure 10. The complete PP coverage onto the GF is apparent from the
comparison of Figure 10a, b. This is consistent with possible surface activity variations that occurred
with the polymerization onto the fibers. Untreated GF, which have surface hydroxy groups [1], are
hydrophilic, hence they sunk in water, as their density is 2.5 times greater. However, propylene
copolymerized fibers remained at the water-hexane interphase. Since the coating is non-polar, the
fibers became more compatible with the organic phase. Then, as Figure 10 clearly shows, the
attraction forces of the organic phase are greater than the gravity effect, showing that the GF surface
energy radically changed. This simple test gives a qualitative but strong indication of the surface
change that occurred to the fibers with the copolymerization treatment.

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5. Adhesion Improvement Assessing

5.1. Theoretical Background
Fragmentation tests were used to assess whether the polymerization technique increments the
interfacial adhesion. Interfacial shear strength (ISS) is the result of static equilibrium between the
tension force acting on the fiber and the shear force transferred through the interface of the matrix to
the fiber [46,47]. According to the Kelly-Tyson approach [48], this value is defined as
ISS =

fb ( Lc ) d

(1)

2 Lc

where fb ( Lc ) is the mean fiber strength at the critical length, Lc, and d is the diameter of the fiber.
The value of the critical fragment length can be determined from the average length at saturation
(Ls), assuming that the distribution of the fiber fragment lengths at the end of the rupture process is
quasi-symmetrical:
Lc =

4
Ls
3

(2)

It is clear, from Equation (1) that the calculation of ISS implies that it is known how the fiber
strength depends on the fiber length. In the present work, this relation was experimentally assessed by
carrying out single filament tensile tests following ASTM 3379 standard [49]. These tests were
conducted at a given gauge length and the data were fitted by a two-parameter Weibull distribution.
According to the weakest link approximation, it is assumed that a fiber of a length L is formed by N
independent links of arbitrary unit lengths L0, each link failing or surviving at a given stress level,
independent of its neighbors. The strength distribution of each link is also described by a simple
Weibull distribution, characterized by identical shape parameters. Then, the Weibull cumulative
distribution function F(), and the corresponding average strength,

m
F ( ) = 1 exp L
0

fb

L
( L ) = 0
L0

1
m

1 +
m

fb ( Lc )

, respectively, are given by:

(3)

(4)

where is the Gamma function. The scale (0) and shape (m) parameters of the Weibull distribution
were estimated from strength data determined at one single gauge length by fitting the distribution of
failure probability. The fiber tensile strength at any gauge length needed for the calculation of ISS was
finally calculated on the basis of Equation 4.
The mechanical strength of the fibers was measured on the starting sample; untreated and only
MAO treated fibers. Notably, the latter study is to analyze whether the attack with MAO produces any
change in the fibers resistance. These changes may stem from a possible smoothing, including
micro-cracks, surface hardening etc. Importantly, a preliminary observation with SEM/EDX of the
fibers only attacked with MAO was done and the results are shown in Figure 11.

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Figure 11. SEM micrographs of the sample MAO-F and its corresponding EDX spectrum.
(a) 2,000 and (b) 6,000.

In principle, it can be seen that a very smooth surface with a metallic brightness due to the
aluminum oxide layer is formed. Its appearance in general does not differ from that of the starting GFs.
Microcracks are not observed, however the final conclusion will only be possible by measuring the
mechanical properties of the fibers. In turn, the EDX spectrum shows that treatment with MAO does
not introduce major changes in the surface composition of fibers with respect to the starting GFs. No C
peak can be seen and the Al/Si is maintained. Only an increase of peak O is observed, which is
expectable due to the formation of the oxide. The fibers were characterized mechanically using tensile
tests according to ASTM 1557. The fiber diameter was measured under an optical microscope.
Average mechanical properties of fibers and their diameters are summarized in Table 2 where it can be
seen that, in principle, the fibers remain unchanged, because the changes in mechanical properties are
within the experimental error of measurements.

Table 2. Average mechanical properties of fibers and their diameters.

Diameter
[m]
26.8 1.8
25.1 1.0

Fiber
GF
MAO-GF

Young Modulus
E [GPa]
46.11 5.7
48.71 4.2

Strength at break Elongation at break

(b) [MPa]
[%]
1,688 206
3.02 0.29
1,516 163
2.94 0.42

Table 3. Weibull parameters for a reference length L0 = 25 mm [50].

Fiber
MF0
MAO-GF

Scale parameter
0 [MPa]
1,556
1,361

Shape parameter
m
2.36
2.92

0.122
0.029

0.976
0.986

Materials 2012, 5

1099
Figure 12. Weibull plot of untreated and MAO-treated fibers [50].
1,0

0,8

F()

0,6

0,4

F0
0,2

FMAO

0,0
0,0 0,2 0,4 0,6 0,8 1,0 1,2 1,4 1,6 1,8 2,0 2,2 2,4

(Mpa )
Tensile tests on both untreated and MAO treated single GFs were performed to determine their
strength. The strength data were statistically treated according to the Weibull distribution. The results
are summarized in Figure 12. It is worth to note that the MAO treatment induced only a slight decrease
in the fiber tensile strength as documented by the small reduction in the Weibull scale parameter, r0,
reported in Table 3. At the same time, a slight increase of the Weibull shape parameter was found, m,
wich accounts for a somewhat sharper distribution of strength values of the treated fibers around an
average value. These results are in agreement with the morphological observations reported above and
provide further evidence that MAO treatment does actually induce very limited fiber damage. The
effects of this small reduction of the fiber strength on the interfacial adhesion have been taken into
account by considering the actual values of the fiber strength at the critical length [50].
5.2. Interfacial Shear Strength Evaluation
The interfacial adhesion was determined by single fiber fragmentation tests, carried out on model
composites consisting of a single GF embedded in a PP matrix. Microcomposite samples were
prepared by compression molding. Fibers were carefully aligned between two PP films and in turn
sandwiched between two stainless steel sheets. Microcomposites were prepared using untreated and
treated fibers with 0.5%, 1.0%, 1.5% and 2.0% of hydroxy--olefin, and they were named PP/F
(% hydroxy--olefin)/PP. Single fiber fragmentation tests were performed on model composites
consisting of a single fiber embedded in a polymeric matrix. It was measured at room temperature by
using a custom-made apparatus as shown in Figure 13 [50,51]. The mean fiber length, Ls, was
measured by means of an image analyzer system, as proposed by Ohsawa et al. [52].
An example of the fiber failure appearance is reported in Figure 14 for PP/F0/PP and PP/F1.0/PP.
For the untreated fibers (Figure 14a), the interfacial debonding appears to be the dominant failure
mechanism, thus indicating low-adhesion conditions. On the other hand, a different failure behavior is
observed for microcomposites with fibers previously treated with 1.0% of hydroxy--olefin. Here, a

Materials 2012, 5

1100

radial matrix crack or mixed radial-conical cracks occur (Figure 14b). This behavior is an indication of
a somewhat better fiber matrix-adhesion, as reported by Pegoretti et al. [51,53]. From Figure 14 also
clearly shows that the number of fiber fragments increases with the interfacial adhesion, resulting in a
shorter critical length, as summarized in Table 4.

Figure 13. Single fiber fragmentation test set up.

Figure 14. Optical microphotographs (4) from fragmented fibers in microcomposites

(a) PP/F0/PP and (b) PP/F1%/PP.

Table 4. Average fiber critical length, Lc and Interfacial shear strength (ISS) for all
composites [50].
Sample
PP/F0/PP
PP/F1%/PP
PP/F1.5%/PP
PP/F2%/PP

Average fiber critical length,

Lc [mm]
8.43 1.85
4.10 0.64
4.94 1.19
4.49 0.34

Interfacial shear strength ISS

[MPa]
3.5 0.8
7.4 1.1
5.8 1.4
6.5 0.5

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1101

Figure 14 shows the appearance of microcomposites after the fragmentation test for samples
prepared using untreated fibers and treated fibers in optimum condition (1% hydroxy--olefin). These
photographs, taken with optical microscopy equipment, indicate that in the untreated fibers, the
segments are long, the remaining space between segments is shaped cylindrically and the crack
appears to have spread into the matrix (Figure 14a). Moreover, in the case of fiber microcomposites
copolymers, the segments are significantly shorter and the space segment-segment has a different
shape, similar to that of a double truncated cone whose vertex is set off from the ends of the fiber
segments. Additionally, the crack is spread widely in the matrix (Figure 14b). In the literature three
possible failure modes from fragmentation tests are reported. Debonding failure, where the crack
propagates parallel to the interphase, is the typical case of a very poor adhesion with low interfacial
resistance. If the resistance is higher, the crack can propagate to the array before the fiber falls away.
This behavior manifests itself in a disk perpendicular to the rupture of the fiber, and interfacial
resistance is typical of socks. The third case, when adherence is very good, a cone-type fracture is
observed with a vertex at both ends of the broken fibers. Importantly, the behavior intermediate
between those described presents as a combination of these patterns of fracture [53]. Figure 15 shows
these models schematically. Clearly, the results obtained (shown in Figure 14) describe two extreme
cases. No adherence seems to be the dominant failure mechanism in the case of PP/F0/PP
microcomposites showing poor interfacial adhesion, on the contrary, the samples that have broken
polymerized matrix-radial cone type fractures from the interface of the fiber indicate a marked
improvement in adhesion.

Figure 15. Fracture model proposed for simple fragmentation test [53].

In the same table, the interfacial shear strength, calculated in accordance to Equation (1), is also
reported. The adhesion markedly increases when fibers with in-situ polymerization are considered. For
microcomposites obtained with polymerized fibers using 1% of hydroxy--olefin, an ISS value more
than two times higher than that of the untreated fibers is observed. On the other hand, it appears that

Materials 2012, 5

1102

the improvement of interfacial adhesion decreases as the amount of hydroxy--olefin used in

polymerization decreases. This behavior could be explained in terms of a competition between the
length of the growing PP chains and the number of anchorage points generated on the fiber surface. In
fact, the higher the amount of hydroxy--olefin, the higher the number of anchorage points and the
lower the PP chain length. The anchorage is formed by the reaction between the hydroxyl groups of
the hydroxy--olefin and the aluminoxane from MAO, which is bonded to the glass surface [50]. Then,
as the hydroxy--olefin concentration increases, the number of anchorage points also increases.
However, the presence of hydroxy--olefin (a polar compound) results in a decrease of the catalysts
activity. Aaltonen et al. [44,45] showed that the synthesis of hydroxyl group containing polyolefins
with metallocene/methylaluminoxane catalysts displayed a polymerization rate with decay type
kinetics. In particular, these authors reported that an increase of hydroxy--olefin concentration reduced
the consumption rate of propylene when the other polymerization conditions were kept constant. Hence,
it appears from their results that the PP chain length between anchorage points decreases with the
hydroxy--olefin concentration. Since interfacial adhesion is developed mostly by PP molecular
entanglements, the incidence of changes in chain lengths should be more important than the number of
anchorage points.
5.3. Microcomposites Interphase Characterization
After the fragmentation test, the morphology of cryogenically obtained fracture surfaces of
microcomposites was analyzed by SEM. Figure 16 shows the appearance of both untreated and treated
samples with different concentrations of hydroxy--olefin, as observed at 6,000 magnifications. For
the sample PP/F0/PP, the neat fiber pullout and the absence of polymer attached to the fiber surface
clearly indicate a very limited adhesion between PP and the fiber (Figure 16a). On the other hand, the
fracture surfaces of microcomposites made with in situ polymerized fibers show features indicating a
better fiber-matrix adhesion. In fact, as documented in Figures 16be, PP partially adheres to the fiber
surface. Figure 17, at higher magnification, also shows that PP is adhered to the the fiber surface of
F1.0 and F1.5 samples. The increment in adhesion is also demonstrated by the radial fracture cracks
emanating from the fiber interface (Figures 16d, e and 17b). This latter feature indicates that the
PP-glass interface strength is more stable than the PPPP entanglements and the fracture occurs in the
PP region around the fibers, not at the interface.
Details of the fiber-matrix interphase for the two best conditions (1% and 1.5%) are shown in
Figure 17. In these it is clear that the fiber-matrix bond is retained after the fracture (micro-void).
Much of the polymer bonding remains and is evenly distributed on the fiber surface. Major approaches
in other areas of the fiber surface after fracture (Figure 18) confirm the earlier observations. The
polymer is evenly distributed on the fiber surface and is seen as a bump smaller than 200 nanometers.
This is consistent with the polymer attaching to the surface and then splitting at room temperature and
returning to its curled up structure.
These observations support the hypothesis that the fracture in the fiber microcomposites
copolymers preferably occurs in the polymer mass surrounding the fiber, with the entanglement
breaking off rather than splitting between the glass and the polymer, confirming that the technical
compatibility proposal greatly improves adhesion.

Materials 2012, 5

Figure 16. SEM microphotographs (6,000) from cryogenic fracture surface of different
microcomposites: (a) PP/F0/PP; (b) PP/F0.5%/PP; (c) PP/F1%/PP; (d) PP/F1.5%/PP;
(e) PP/F2%/PP [51].

1103

Materials 2012, 5

1104

Figure 17. SEM micrographs (20,000) of the composites (a) PP/F1%/PP and
(b) PP/F1.5%/PP [51].

Figure 18. SEM micrographs (40,000) of fiber surface after cryogenic fracture of
PP/F1%/PP [51].

6. Mechanical Properties of PP/GF/PP Composites

Tensile mechanical behavior of laminated PP/GF/PP was evaluated using unidirectional arrays.
The mechanical properties obtained were interpreted according to the adhesion results and
phenomenological evidence.
The tensile behavior of composite materials is difficult to predict, as the fracture mechanics are so
complex. Is known that the composite shows a marked anisotropy, that is to say, its properties vary
significantly when measured in different directions. This usually arises because the harder constituent
is in a fibrous form with the fiber axes preferentially aligned in particular directions [3]. Hence,

Materials 2012, 5

1105

samples were prepared with uni-axially oriented continuous fibers, where the rule of mixtures can be
used to predict modulus and strength. According to this rule, the mechanical strength for continuous,
uni-axially oriented fiber composites is just based on the properties of each component and the relative
concentration and orientation of the fibers. These approaches assume that the charge transfer is
complete and the variations in adhesion between the fiber and the matrix are not taken into account.
For this reason, they are, in principle, more suitable to predict the modulus value than the mechanical
strength. The elastic modulus is measured as the slope of the stress-strain curve at low deformation, as
the charge transfer is less critical in this property determination. Very low deformation materials react
to an atomic-molecular level separately. However, the mechanical strength is the maximum tension
that the material can resist, and it usually occurs at higher deformation, where charge transfer is a
decisive factor, and consequently, adhesion influences its value. It is remarkable that the mechanical
strength values, calculated from rule of mixture, assume full adhesion and thus overestimate the actual
value. This problem is most evident in the case of transverse mechanical resistance, where the matrix
strip of the fibers goes through the interface. For this reason the equation arises only as an
approximation. Tensile tests were carried out on PP, GF and composite samples. Table 5 summarizes
the mechanical properties of the PP matrix and the fibers used in the composites. Note that these
values are used as parameters, because they were measured under similar conditions with samples of
equal size.

Table 5. Mechanical properties of PP and GFs.

Property
E [MPa]
u [MPa]
y [%]
b [%]

PP
685 69.6
25.7 1.7
10.0 1.8
412 92

GF
47,600 2,015
234 31.3
---2.6 0.9

The fiber concentration of the tensile specimens was measured by weight difference before and
after washing them. The achieved weight and volumetric fractions are summarized in Table 6 [41].

Table 6. Average concentration of fiber composites.

Fraction [%]
Volume
Weight

PP/GF/PP
53.8 5.9
76.4 4.35

PP/MAO-GF/PP
50.8 4.8
74.2 3.66

PP/COP-GF/PP
46.6 5.3
70.8 4.58

Continuous parallel fiber PP/GF composites, containing about 1800 aligned GF, were prepared by
compression molding in a hydraulic press. The fibers were carefully aligned and compounded by
sandwiching them within two PP sheets. Before compounding, the GF received different surface
conditioning: no pretreatment, in situ polymerization and just MAO treated surface. These composites
were named PP/GF/PP, PP/COP-GF/PP and PP/MAO-GF/PP, respectively. Rectangular specimens for
tensile tests were obtained by careful cutting with a sharp blade in order to have net edges and
minimize errors during experimental tensile measurements.

Materials 2012, 5

1106

The fracture shape, as well as the morphological features of fiber surface and microcomposites
subjected to mechanical tests were studied by SEM. Figure 19 shows tensile stress-strain curves for all
the composites tested, PP/GF/PP, PP/MAO-GF/PP and PP/COP-GF/PP. The corresponding properties
are summarized in Table 7.

Table 7. Mechanical properties for the composites PP/GF/PP.

Property
E [MPa]
u [MPa]
y [%]
b [%]
Toughness [J]

PP/GF/PP
8,125 1,060
101.6 14.1
2.5 0.8
14.1 8.3
12,654 1,100

PP/MAO-GF/PP
8,4911,029
103.4 12.3
1.6 0.4
16.56 6.4
12,054 512

PP/COP-GF/PP
8,852 1,017
104.7 11.1
6.8 0.9
35 7.2
38,579 1,600

The possible occurrence of fiber damage caused by the MAO attack was studied in a previous
study [50], in which tensile stress-strain tests on both untreated and MAO treated single GFs were done.
The strength data, statistically treated according to the Weibull distribution, showed that MAO induced
only a slight decrease in the fiber tensile strength, indicating that a very small fiber damage could
occur in the presence of MAO. This trend is also confirmed for composite samples, since only a small
variation in strength and elongation properties was observed for composites having either untreated
and MAO treated fibers (Figure 19).

Figure 19. Stress-strain curves of PP/GF/PP composites.

From the strain-dependent tensile behavior, it is observed that the mechanical strength of PP/GF/PP
and PP/MAO-GF/PP composites is reached at 1 to 3% deformation; while for PP/COP-GF/PP, the
deformation is close to 7%, i.e., three times larger. This is related to the composite fracture mechanism.

Materials 2012, 5

1107

In the first two, the whole composite fracture occurs by fiber breakage, at < 3%, without any matrix
contribution to resistance due to the low matrix-fiber adhesion. On the other hand, for copolymerized
fiber composites, the fibers start breaking at about 2% strain (Figure 19), according to the main break
strain of GF. However, the strain (at which strength is achieved) increases up to 7%, and can be
attributed to a greater matrix/fiber adhesion. As was demonstrated above, the copolymerized fiber
breaks into much smaller segments than samples containing untreated fibers. Then, although the first
fracture occurs at the same strain for both treated and untreated fibers, the treated ones keep breaking
as the deformation increases over this strain. This is due to the more effective matrix/fiber load transfer
that requires greater energy consumption to fracture. In composites with polymerized fibers, GF/PP
interface essentially resists by chemical anchorage. Once the fibers fracture, composites do not break
immediately. This fact can be assigned to the greater stability of the glass-PP interface as compared to
PP-PP entanglement resistance.
The composite initially contains continuous and aligned fibers, but once the first fiber fracture
occurs, it gradually converts into a short fiber composite. Here the fiber fragments remain aligned with
the load direction and well attached to the matrix. As the strain increases, each fiber fragment bears a
growing stress up to its rupture limit. Significantly, the rate at which the load is transferred to the fibers
decreases as voids begin to form and grow at the fiber tips. Figure 20 outlines this mechanism.
It is clear that fibers always break at their fracture limit, however the mechanism for crack
propagation, and consequently the composite mechanical strength, will be quite dependent on the
fiber/matrix adhesion. When adhesion is low (composites with untreated fiber) the crack propagates
mainly by fiber debonding. It results in fewer and relatively longer fiber segments. Instead, when
polymerized (treated) fibers are used, cracks spread radially, preventing the fiber pullout. In this case,
the propagating crack finds a greater amount of bonded fiber fragments in its way; so more energy is
needed to break (or evade) them and allow the crack to grow. Therefore, when a large amount of short
and well-adhered fiber segments are present, a considerable barrier to crack propagation is set,
essentially by increments of the fissure path tortuosity. The proposed mechanism justifies the
increment in elongation at break (more than twice for polymerized fiber samples as compared to
PP/GF/PP and PP/MAO-GF/PP), as is shown in Figure 20. Also, the toughness, calculated as the
composite energy to break from the area under the stress-deformation curve, resulted three times
greater for the treated fiber samples (see Table 7). Furthermore, the elongation at yield (related to the
energy required to generate cracks) indicated that PP/COP-GF/PP needed 5% more elongation than
composites with non-copolymerized fibers to initiate cracks.
This evidence further validates the proposed mechanism. Other authors found similar behaviors, but
attributed it to the ability of coupling agents to change the matrix nature, which could act as
impediment of crack propagation. These authors did not report an increase in the strain at which the
maximum stress occurs, but proposed just an increase of matrix ductility by the coupling agent use as
the main cause of improvement [5456].
In order to corroborate the proposed fracture mechanism, and the adhesion enhancement, SEM
characterization of specimens after tensile tests was carried out. Figure 21 shows the fractured sample
surfaces of PP/GF/PP, PP/MAO-GF/PP and PP/COP-GF/PP. It is clear from Figure 21a, b that
untreated and MAO treated composites breaks mainly by fiber debonding, hence PP remains
unchanged. On the other hand, in PP/COP-GF/PP samples, the PP presents a lot of holes evenly

Materials 2012, 5

1108

distributed throughout the sample, indicating that fibers pull the matrix before composite fracture
(Figure 21c). This is consistent with the greater resistance of chemical anchorage relative to PP
molecular entanglements. Moreover, the less regular overall fracture is consistent with a greater
resistance to breakage. Also, PP patches remain adhered to the fiber surface after the composite
fracture (see Figure 22). The observed behavior agrees with the above-proposed model. Here the
interphase presents a micro-damage mode of debonding accompanied by matrix cracks and promotes a
stronger adhesion between matrix and fibers. The result is better resistance to development of damage
and thus higher normal tensile stress. The interface debonding can reduce the effect of the matrix crack.
The breakage (instead of debonding) of several small fiber bundles triggers larger matrix cracks, causing
their propagation along the longitudinal direction. Table 7 also shows the tensile modulus from
non-polymerized and polymerized samples. As it is expected, no appreciable variation is observed since
this is a zero strain property and neither fiber nor matrix modulus changed after treatment.
From these results it is clear that the in-situ polymerization technique improves the compatibility
between phases allowing for more ductile composite materials without affecting their rigidity.

Figure 20. Scheme proposed to explain the stress-strain behavior of PP/COP-GF/PP composites.

Figure 21. SEM micrograph of composites after tensile break with different
magnifications (a) PP/GF/PP at 53 and 270; (b) PP/MAO-GF/PP at 53 and 270, and
(c) PP/COP-GF/PP at 53.

Materials 2012, 5

1109
Figure 21. Cont.

Figure 22. SEM micrographs of PP/COP-GF/PP at: (a) 2,000 and (b) 4,000.

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1110

7. Conclusions
The technique of in-situ metallocenic polymerization of propylene onto a GF surface resulted in a
promising route to increase the adhesion between PP matrix and GF reinforcement since an enhanced
compatibility between them can be obtained. The main conclusions of this work are:
-

PP can be copolymerized onto GFs by using metallocene catalyst.

PP chains grow from the glass surface and enhance the adhesion by entanglements with PP
matrix in polymer composites.
The amount of PP polymerized onto the fiber and the interfacial adhesion seems to have
optimal conditions regarding either the PP coverage or the interfacial shear strength measured.
The interfacial shear strength of PP/GF composites, measured by the fragmentation test, is
considerably improved (up to a factor of 2.1) with respect to the case of untreated
fiber-PP composites.
The radial matrix crack developed during fragmentation tests indicates a good matrix fiber
adhesion for all in situ polymerized fibers.
The polymer remains attached to the fiber surface after cryogenic fracture for all the samples
subjected to polymerization.
Uniaxial composites PP-copolymerized GF presents considerably higher ductility and
toughness without detriment of strength, with respect to the composites prepared with untreated
fibers. These improved properties are assigned only to the increased adhesion caused by
molecular entanglements between the PP-grafted GF and PP matrix.
The MAO pretreatment does not change the PP/GF mechanical properties, since both the
adhesion and fiber properties remain unchanged.
This treatment strongly modifies the composite fracture behavior. The interface fiber
debonding is the main mechanism for untreated fiber composites, while PP disentanglement
accounts for the breakage of polymerized fiber composites.

The in-situ polymerization method is clearly a very good approach to improve the compatibility
between GFs and PP. The adhesion enhancement as well as the mechanical properties improvements
were demonstrated with the evidences shown above. It also seems to be a promissory method to obtain
PP prepregs to increase the performance of PP/GF composites by using mat reinforcements.

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