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Characterisation of fibrepolymer interactions

and transcrystallinity in short keratin


fibrepolypropylene composites
J. R. Barone* and N. T. Gregoire
Short fibre reinforced composites were made from keratin fibres obtained from poultry feathers.
The matrix material was either polypropylene or a blend of polypropylene and maleic anhydride
modified polypropylene (MaPP). In general, the addition of MaPP to polypropylene (PP) did not
alter the tensile properties of the blend in a significant way. When not using MaPP, composites
had lower breaking stresses than samples without fibres. However, MaPP at concentrations of
.4 wt-% enhanced the breaking stress of the composites to above the value without fibres.
Concurrent thermal analysis using differential scanning calorimetry (DSC) showed a distinct
increase in the amount of transcrystallinity in the composites at MaPP concentrations greater than
4 wt-%. Scanning electron microscopy (SEM) revealed increased interactions between the
protein fibres and the PP/MaPP matrix. Annealing showed that more large polymer crystals near
the fibres were not enough to increase stress transfer across the interface.
Keywords: Composites, Polypropylene, Maleic anhydride, DSC, Properties

Introduction
Agricultural fibres, such as cellulose and protein fibres,
provide an environmentally friendly reinforcement
option for commodity thermoplastic materials such as
polyethylene (PE)1,2 and polypropylene (PP)312 and are
a pathway to obtain materials from sustainable
resources. Agricultural fibres typically are of lower
density than inorganic reinforcements such as talc, glass
or calcium carbonate. The absolute physical properties
of agricultural fibres might not be as high as inorganic
reinforcements, but specific or density normalised
properties are comparable with inorganic fillers.
Agricultural fibres are polymeric and have densities
lower than inorganic fibres so synthetic polymers can be
reinforced with little or no cost to unit weight.
The key to successful enhancement of polymers with
fibres of higher modulus or strength is to achieve good
polymer/fibre interaction.13 Good fibre/polymer interaction can be expected if the two components are
chemically compatible. Plant based cellulosic fibres such
as wood, flax, jute and sisal, and inorganic fibres and
fillers are hydrophilic. However, commodity thermoplastics such as PP are hydrophobic. To get chemical
compatibility between the two, additives such as
coupling agents or compatibilisers are used.1,2,7,13
Maleic anhydride has been used to increase the properties of cellulose fibre reinforced PE1,2 and PP.49 In most

USDA/ARS/ANRI/EMBUL, BARC West, Bldg. 012, Rm. 13, 10300


Baltimore Ave., Beltsville, MD 20705, USA
*Corresponding author, email baronej@ba.ars.usda.gov

2006 Institute of Materials, Minerals and Mining


Published by Maney on behalf of the Institute
Received 19 June 2006; accepted 10 August 2006
DOI 10.1179/174328906X146478

cases, ultimate strength of the composites increased at


maleic anhydride concentrations of 0.12%, depending
on the maleic anhydride substitution in the olefin and
the concentration of maleic anhydride modified olefin in
the composite. Scanning electron microscopy (SEM)
revealed increased fibre/polymer interactions.1,4,5
Protein fibres are mixed hydrophobic/hydrophilic
depending on the amino acid sequence. Keratin fibres
obtained from poultry feathers have ,60% hydrophobic
amino acids in the amino acid sequence, with the
balance being hydrophilic amino acids.14 So it can be
expected that there will be some chemical compatibility
between PP and feather keratin fibres. Recently, Barone
and Schmidt showed that it was possible to increase the
tensile properties of low density polyethylene (LDPE)
using keratin feather fibre without the use of coupling
agents or compatibilisers.15 SEM showed good fibre/
polymer interaction.
Maleic anhydride modified polypropylene (MaPP)
has been used in keratin feather fibrePP composites.
Bullions et al. used MaPP to increase interactions
between PP and a mix of keratin feather fibre and kraft
pulp fibre.10 Schuster made MaPPkeratin feather fibre
composites and observed an increase in properties over
neat PP.11 The proposed interaction mechanism between
MaPP and the fibres is hydrogen bonding between
hydroxyl groups on the MaPP and fibre and covalent
bonding between hydroxyl groups on the fibre and the
carbonyl on the maleic anhydride. The PP portion of the
MaPP is free to entangle with the PP composite matrix.
Investigation of the fibre surface in PP and cellulose
fibre composites shows a transcrystalline layer develops.7,8,12 The fibre surface serves as a nucleation site for

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Characterisation of fibrepolymer interactions and transcrystallinity

polymer crystals and the crystals that form at the fibre


surface are different from the crystals formed in the bulk
polymer. This means that the polymer volume immediately surrounding the fibres has properties different from
the bulk polymer. The transcrystallinity can be affected
by shear deformation at the fibre/polymer interface, the
chemical nature of the interface and the cooling rate
after processing.7,8,12,16 Joseph et al. performed a very
complete study on the properties of the transcrystalline
layer in PP/sisal composites.7 The study showed that the
addition of a urethane compatibiliser initiated crystallisation at the fibre/polymer interface in a short amount
of time, similar to using shear deformation at the
interface. Crystallisation at the interface occurred over
much longer time periods in absence of shear deformation or compatibiliser. The melting point and amount of
crystallinity as studied by differential scanning calorimetry (DSC) increased with fibre and compatibiliser
content. Nunez et al. showed that a b crystalline fraction
appeared at the PP/wood flour interface when cooled
quickly from the melt.8 These researchers also showed
that the melting point and crystalline fraction increased
with filler and MaPP content.
In the present paper, keratin feather fibre of 0.2 cm
length is incorporated into blends of PP and MaPP with
the MaPP content varying from 0 to 10 wt-%. The
physical properties of the composites are characterised
using tensile testing, DSC and SEM. Fibrepolymer
interactions are assessed in terms of the transcrystallinity
that develops at the interface.

Experimental
Keratin feather fibre
Keratin feather fibre was obtained from Featherfiber
(Nixa, MO) using a process patented by the United
States Department of Agriculture (USDA).17 The
feather fibre was semicrystalline and had a diameter of
,5 mm and a density of 0.89 g cm23 (Ref. 15). A more
detailed description of feather fibre can be found
elsewhere.10,11,15,18 Fraser and MacRae report modulus
values of 3.4 and 5.2 GPa and yield stress values of 100
and 200 MPa at relative humidity values of 100 and 65%
respectively for feather rachis.19 Modulus and strength
values of polyolefins are less than the feather values, so
reinforcement of polyolefins with keratin feather fibre is
possible.
Fibres of 0.2 cm length were made by grinding
feather fibre using a Retsch ZM 1000 centrifugal
grinder. The rotational velocity of the instrument was
15 000 rev min21 and contained a torque feedback so as
not to feed in too much material and overload the
motor. The fibre was fed in slowly to avoid motor
overload and to minimise frictional heating of the
instrument and the fibre. Sieving analysis and SEM
imaging of the fibres showed that the majority of the
fibres were in the 0.2 cm length range with a few
percentages of smaller fine particles.

Composite preparation
The PP was ExxonMobil PP9505E1, a random copolymer PP with melt flow index (MFI)530 g/10 min at
230uC and 2.16 kg. The MaPP is ExxonMobil Exxelor
PO1020 and had a reported maleic anhydride substitution of 0.51.0 wt-%. The fibre fraction of the composites was held constant at 20 wt-%. The MaPP content

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represented the amount of MaPP relative to the total


sample weight. The blends were prepared by mixing PP/
MaPP in ratios of 100:0, 98:2, 96:4, 94:6, 92:8 and 90:10.
Composites were prepared by dry blending the PP and
MaPP at PP/MaPP ratios of 100:0, 97.5:2.5, 95:5,
92.5:7.5, 90:10 and 87.5:12.5. The polymer was first
added into a Brabender mixing head set at 160uC and
rotating at 75 rev min21. Immediately after adding the
polymer, 20 wt-% keratin feather fibre was added into
the mixing head. The total sample weight of each
composite was 40 g, which represented a degree of fill of
70% of the total volume of the mixing head. The melt
temperature was monitored independently. The polymer
control samples all achieved melt temperatures of
,174uC and the composites all achieved melt temperatures of ,183uC. The total mixing time for each sample
was 15 min.
Following mixing, each sample was sandwiched
between Teflon coated aluminium foil and pressed into
three thin sheets in a Carver Press Autofour/30 Model
4394 at 180uC and 1 MPa for 18 s. The film was then
removed and cooled under an aluminium block until it
reached room temperature. After pressing, each thin film
was inspected to note feather fibre dispersion. Previous
work showed that pressing did not affect fibre dispersion.15,20 Good dispersion was observed in all cases.
To prepare samples for testing, the three thin sheets
were cut into quarters, stacked on top of each other,
sandwiched between Teflon coated aluminium foil, and
pressed in the Carver Press at 180uC and 0.7 MPa for
1.5 min. After pressing, the films were air cooled until
they reached room temperature. The resulting plates
were ,0.3 cm in thickness. Type 4 dogbone samples for
testing according to ASTM D638 were machined from
the plates.

Composite testing
Composite samples were allowed to sit at ambient
conditions for one week before testing. Uniaxial tensile
testing was performed using a Com-Ten Industries 95 RC
Test System. The applied test speed was 2.5 cm min21.
Four samples of each composite were tested.

Thermal analysis
The thermal properties of the polymers and composites
were assessed using DSC. A TA Instruments DSC 910s
was used according to the procedures outlined in ASTM
D3417 and D3418. Sample sizes of ,5 mg were used in a
N2 atmosphere. The first heating cycle proceeded from
30 to 225uC at 10uC min21. The first heating cycle was
followed by a cooling cycle from 225uC back down to
20uC. The cooling rate could not be controlled. The
heater simply shut off and the DSC cell cooled to 30uC.
Although there may have been some variation in the
cooling step from sample to sample, the room temperature was always 20uC; so it was assumed that the cooling
steps were similar. A second heating cycle then
proceeded from 30 to 225uC. Peak assignments and
areas were determined according to the ASTM procedures. The first heating cycle yielded information about
the state of the polymer as a function of processing
conditions. The heat of fusion of the first heating cycle
DQm,1 and the melting temperature during the first
heating cycle Tm,1 were determined because these values
relate to the crystalline structure of the as tested
composite. The crystalline fraction of each polymer

Barone and Gregoire

1 Tensile modulus versus MaPP concentration for PP


20 wt-% 0.1 cm keratin feather fibre composites

and composite after the first heating cycle X1 was


determined from the DSC results using
X1 ~

DQm,1
DQf (1{mf )

(1)

where DQf is the theoretical heat of fusion of 100%


crystalline
PP,
DQf5(5798 J mol21)/(42 g mol21)5
21
138 J g (Ref. 21), and mf is the mass fraction of fibre.
Joseph et al. determined the crystallinity of PP
composites in a similar manner.7

Characterisation of fibrepolymer interactions and transcrystallinity

2 Peak stress versus MaPP concentration for PP20 wt-%


0.1 cm keratin feather fibre composites

MaPP for the blends. There was perhaps a minimal


enhancement of the elastic modulus as a function of
increasing MaPP concentration at a constant fibre
loading. The peak stress and strain at peak stress
showed noticeable differences as MaPP concentration
increased as shown in Figs. 2 and 3 respectively. The
addition of MaPP to PP did not affect the peak stress.
At low MaPP concentration, the composite peak stress
was lower than the PP/MaPP blends. However, the peak
stress of the composites was increasing with increasing

Scanning electron microscopy (SEM)


The fracture surfaces were excised from the failed tensile
bars using a scalpel blade and transferred into a
modified specimen carrier. The specimen carrier was
known as an indium vise because the dissected pieces
were clamped between sheets of indium metal and
plunge cooled in liquid nitrogen to 2196uC. The cooled
holder was then transferred to an Oxford CT1500 HF
cryopreparation system attached to a Hitachi S-4100
SEM. The sample temperature was raised to 290uC for
10 min to remove surface water from the sample surface.
The sample was then cooled to below 2120uC and
coated with ,5 nm of platinum metal using a magnetron sputter coater. Coated samples were transferred to
the cold stage in the SEM at 2170uC and observed with
an electron beam accelerating voltage of 2 kV.

Results and discussion


Effect of MaPP on tensile properties
Figure 1 shows the elastic modulus of the PP/MaPP
blends and PP/MaPP/20 wt-% keratin fibre composites.
The percentage of MaPP relative to the total amount of
PP or PP/fibre was kept constant to note how the
replacement of PP with fibre affected tensile properties.
However, on a phr basis, the samples had overlapping
ranges, 014 phr MaPP for the composites and 011 phr

3 Strain at peak stress versus MaPP concentration for


PP20 wt-% 0.1 cm keratin feather fibre composites

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4 Melting temperature from DSC first heating cycle Tm,1


versus MaPP concentration

MaPP concentration. At MaPP concentrations .4 wt-%,


the peak stress increased discontinuously to peak stress
values above the PP/MaPP blends. There did not
appear to be a strong dependence of stress on MaPP
concentration above 4 wt-%, indicating that this may
have been the limiting value necessary to get optimal
fibrepolymer interactions. It should be noted that the
samples with higher MaPP contents had some surface
freckles after moulding and it was possible that this
may have contributed to a premature failure. Therefore,
theoretical peak stress values could be higher than the
ones reported if samples could be prepared to avoid
surface anomalies.
In Fig. 3, the strain at peak stress did not appear to be
greatly dependent on MaPP concentration for the PP/
MaPP blends. The blends were more ductile than the
fibre composites. For the composites, the strain immediately decreased upon introduction of MaPP but slowly
increased with increasing MaPP back to the 0 wt-%
MaPP value. This indicated that better fibrepolymer
interactions required more strain to break. Therefore,
addition of MaPP increased not only the strength but
also the toughness of the composites.

Effect of MaPP on thermal properties


The effect of MaPP and fibres on PP Tm,1 and X1 is
shown in Figs. 4 and 5 respectively. The PP/MaPP
blends had increased Tm,1 up to 6 wt-% MaPP; then the
Tm,1 values decreased at ,6 wt-% MaPP. The fraction
of crystallinity showed a similar trend with maximum
values at ,2 wt-% MaPP. For pure MaPP, Tm,15
163.48uC and X150.57. Therefore, the PPMaPP blends
reached a maximum in Tm,1 and X1 at 26 wt-% MaPP,
with the maximum values being higher than pure
PP9505E1 or MaPP PO1020. At greater MaPP concentrations, the PP matrix has inhibited crystallinity
probably because of a branched chain architecture that
the blends assume.

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5 Fraction crystallinity from DSC first heating cycle X1


versus MaPP concentration

For the composites, the melting temperature increased


quickly from 0 to 6 wt-% MaPP; then the melting
temperature increase was much slower at MaPP
concentrations of .6 wt-%, i.e. the thermal behaviour
appeared to reach a limiting value for Tm,1 with
increasing MaPP concentration. The PPMaPP blends
and composites showed a similar trend in Tm,1 up to 4
6 wt-% MaPP. At greater MaPP concentration, the
composites had greater X1 and Tm,1 values. Larger X1
and Tm,1 values meant that there were more large
crystals in the composites. Figure 5 shows that the
crystalline fraction of the composites increased up to 4
6 wt-% MaPP, and then there was a discontinuous
increase in the crystallinity of the composite after which
the crystalline fraction remained relatively unchanged.
The same dependence on MaPP was observed in the
peak stress characteristics of the composites. The fibre
loading was kept constant for each composite, so the
fibre surface area for crystal nucleation was the same.
Liu et al. increased the wood flour content in composites
and saw increased crystallinity because of increased
nucleating surface.22 Again, MaPP loading of ,4 wt-%
was a critical point in the PPzMaPP/fibre composites.
However, unlike the blends without fibres, an increased
crystallinity was observed because of the presence of
fibres.

Observation of fibre/polymer interactions


Figure 6 shows the fracture surface of a 0 wt-% MaPP
composite magnified 62000. At 0 wt-% MaPP, there
was little fibrepolymer interaction. There were voids in
the polymer matrix left by fibres that pulled-out and
voids around identifiable fibres. The fibres had clean
surfaces, indicating that the PP did not adhere to the
fibre. Figure 7a shows a macroscopic view of the
fracture surface of a 4 wt-% MaPP composite at
6300. There were voids where pulled-out fibres once
resided. Closer inspection of the surface at 61000 as

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Characterisation of fibrepolymer interactions and transcrystallinity

6 Image (SEM) of tensile bar fracture surface for 0 wt-%


MaPP composite at
62000

8 Image (SEM) of tensile bar fracture surface for 6 wt-%


MaPP composite at
63000

shown in Fig. 7b shows that some fibres were strongly


adhered to the PP matrix. At 6 wt-% MaPP, the fibres
were also strongly adhered to the polymer matrix as
shown in Fig. 8 for a fracture surface magnified 63000.
There were not many voids from a macroscopic view.
The micrographs showed that, concurrent to the
thermal analysis and physical property data, a definitive
transition in the properties of the composites occurred
after 4 wt-% MaPP. This concentration was high
enough for most of the fibres to bind to the matrix
whereas anything less did not provide enough material
for all of the fibres to bind and there was still some fibre
pull-out.

increased transcrystallinity at the fibre/polymer interface


that results in an increased stress at break.23
To test this, annealing experiments were performed on
PP and PP/20 wt-% 0.2 cm keratin fiber composites not
containing MaPP. In this manner, pure PP was used but
the transcrystallinity affected through thermal treatment
rather than chemical treatment with maleic anhydride.
PP9505E1 and a composite of PP9505E1 and 20 wt-%
0.2 cm keratin feather fibre were prepared and annealed
at 0.93Tm5135uC in a convection oven for 8 h. At the
end of 8 h, the oven was turned off and allowed to
slowly cool to room temperature. The results of the
annealed PP and annealed PP/20 wt-% 0.2 cm fibre
composites are plotted in Figs. 15 as open and closed
squares respectively. The DSC first heating cycle curves
for the annealed and unannealed PP and PP composites
without MaPP are shown in Fig. 9. Analysis of the DSC
curves in Fig. 9 shows that annealing did not measurably affect the average melt temperature Tm,1, depicted
as the middle of the peak and plotted in Fig. 4.
However, annealing removed the low Tm,1 or small
crystal size fraction thus narrowing the crystal size
distribution. Addition of fibres further narrowed the
crystal size distribution after annealing. Annealing the
pure PP increased the percentage of crystallinity as
shown in Fig. 5. Annealing the PPfibre composite
increased the percentage of crystallinity even further to

Effect of crystallinity on properties


The increased crystallinity observed in the PPzMaPP/
fibre composites manifested as an increased stress to
break. The data in Figs. 2, 4 and 5 suggested that an
increased population of large crystals resided near the
fibres. SEM analysis showed increased fibrepolymer
interactions. The purpose of maleic anhydride is to
increase chemical interactions between the hydrophobic
PP and hydrophilic fibres (in the case of cellulosic or
glass fibres) or partially hydrophilic fibres (in the case
of keratin). However, the results obtained in the
present study suggest that there may be a physical
mechanism of interaction manifesting through an

7 Image (SEM) of tensile bar fracture surface for 4 wt-% MaPP composite at a 6300 and b

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9 DSC first heating cycle curves for annealed and unannealed PP9505E1 and PP9505E1/20 wt-% 0.2 cm keratin fibre
composites: no MaPP is used in this experiment

the values obtained with MaPP and no annealing, so


addition of fibres again acts as a preferential nucleating
surface. Although the crystallinity of an annealed composite was similar to that of a composite with .4 wt-%
MaPP, there was no increase in peak stress. In fact, there
was a decrease in the peak stress of the annealed
composite. Therefore, for PPkeratin fibre composites,
an increased transcrystallinity and larger crystals near the
fibre/polymer interface are not sufficient criteria for stress
transfer across the interface. While this feature of the
transcrystalline region has been shown to increase
physical fibrepolymer interactions and therefore
increase stress to break in the case of PP, increased
chemical interactions, i.e. use of MaPP, is required to get
increased stress at break.23 It was possible that the
crystallinity values obtained in the annealed composite
were enough to overcome any chemical interactions
between the fibre and polymer and pulled the matrix from
the fibre surface, as has been observed previously.23
The key to polymer composites is still efficient stress
transfer across the fibre/polymer interface through
increased adhesion, so the higher yield stress fibres can
bear more load. The role of the transcrystalline layer in
increasing the composite properties is still arguable.
Wang and Hwang argue that after fibre debonding,
larger transcrystalline layers provide more friction
between fibre and polymer.16 Research has shown that
thick transcrystalline layers have increased fibre
polymer interactions, which manifest as lower fragment
lengths in single fibre fragment tests.12 The results shown
in the present study indicated that the increased peak
stress of the composites with .4 wt-% MaPP may have
been partially because of a thick transcrystalline region,
i.e. more large crystals near the fibres. However, the
increased fibre/polymer adhesion from maleic anhydride, as shown first hand by the SEM images, created
much more efficient stress transfer across the interface so
the fibres could bear load.

Conclusions
Although an increased population of large crystals near
a polymer/fibre interface can physically increase stress

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transfer across that interface, for the PP composites


studied here, increased chemical interactions are also
needed for this efficient stress transfer. This was
performed using maleic anhydride modified PP. SEM
analysis showed this increased interaction and it
manifested as increased stress at break. Thermal analysis
showed that increasing MaPP concentration gave an
increased crystallinity with larger crystals in the transcrystalline region. The presence of fibres further
increased crystallinity and resulted in larger crystals
near the fibres. Best properties were observed at MaPP
concentrations of .4 wt-% but increasing MaPP further
did not have a marked effect on physical properties.

Acknowledgements
Mention of trade names or commercial products in this
article is solely for the purpose of providing specific
information and does not imply recommendation or
endorsement by the US Department of Agriculture. The
present paper is based on a presentation at the
AutoPolymers workshop held in Charleston, SC, USA
in October 2005.

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