polymers

Article
Fully Biodegradable Biocomposites with High
Chicken Feather Content
Ibon Aranberri *, Sarah Montes ID
, Itxaso Azcune, Alaitz Rekondo and Hans-Jürgen Grande
CIDETEC Research Centre, Paseo de Miramón, 196, 20014 Donostia-San Sebastián (Gipuzkoa), Spain;
smontes@cidetec.es (S.M.); iazcune@cidetec.es (I.A.); arekondo@cidetec.es (A.R.); hgrande@cidetec.es (H.-J.G.)
* Correspondence: iaranberri@cidetec.es; Tel.: +34-943-30-90-22

Received: 16 October 2017; Accepted: 8 November 2017; Published: 9 November 2017

Abstract: The aim of this work was to develop new biodegradable polymeric materials with high
loadings of chicken feather (CF). In this study, the effect of CF concentration and the type of biodegradable
matrix on the physical, mechanical and thermal properties of the biocomposites was investigated.
The selected biopolymers were polylactic acid (PLA), polybutyrate adipate terephthalate (PBAT)
and a PLA/thermoplastic copolyester blend. The studied biocomposites were manufactured with
a torque rheometer having a CF content of 50 and 60 wt %. Due to the low tensile strength of CFs,
the resulting materials were penalized in terms of mechanical properties. However, high-loading CF
biocomposites resulted in lightweight and thermal-insulating materials when compared with neat
bioplastics. Additionally, the adhesion between CFs and the PLA matrix was also investigated and
a significant improvement of the wettability of the feathers was obtained with the alkali treatment of
the CFs and the addition of a plasticizer like polyethylene glycol (PEG). Considering all the properties,
these 100% fully biodegradable biocomposites could be adequate for panel components, flooring or
building materials as an alternative to wood–plastic composites, contributing to the valorisation of
chicken feather waste as a renewable material.

Keywords: biodegradable biocomposites; thermoplastics; fibres; chicken feathers

1. Introduction
There is a growing interest in the research and development of new materials obtained
from natural resources as new alternatives to decrease or even replace petroleum-derived plastics.
The incorporation of bio-based fillers into polymeric matrices results in a biocomposite [1]. Natural
fibres such as flax, hemp and sisal have been widely studied as reinforcements for thermoplastics [2].
Animal fibres such as wool [3], silk [4] and horns [5], which are made of proteins, can also be used as
alternative sources of reinforcements and fillers for polymers. All of them represent an opportunity to
make the most of renewable and under-utilized raw materials in new application areas.
The poultry industry (including duck, turkey, goose and chicken breeding) generates a huge amount
of waste each year. Despite figures regarding feather waste generation varying considerably depending
on the source, it is estimated that over 65 million tons of poultry feathers are produced worldwide [6].
According to the European Commission, 13.1 million tons of poultry meat was produced in the European
Union (EU-28) only in 2014 [7], with an estimated generation of 3.1 million tons of feather waste. At present,
the majority of poultry feathers are disposed of in landfills or incinerated, and a minor part converted
into low-nutritional-value animal food. The current solutions do not exploit the opportunity that this
proteinaceous material represents, and more importantly, the management of environmental and health
concerns as overall waste rises.
CFs, which are composed of 90% keratin, are abundant, cheap, biodegradable [8] and provide
an opportunity to replace non-environmentally-friendly raw materials in many applications [9–11].

Polymers 2017, 9, 593; doi:10.3390/polym9110593 www.mdpi.com/journal/polymers

Polymers 2017, 9, 593 2 of 15

Serine is the most abundant amino acid in the keratin structure and contains a hydroxyl side group,
which gives CFs the ability to attract moisture from the air [12]. This particular property makes keratin
an effective material for insulation applications [13]. Despite the low mechanical properties of the
feathers compared to other natural fibres [2], they have been used, for example, as reinforcement in
cement-bonded composites [14], polyurethanes [15], polypropylene (PP)-based composites [16,17]
and recycled PP composites [18,19]. Furthermore, a few studies have been performed reinforcing
PLA with CFs, obtaining fully biodegradable materials [20–22]. Reddy et al. [23] also obtained 100%
biodegradable composites using CFs as matrix and jute fibres as reinforcement. When feathers are
used as fillers it is important to pay attention to the compatibility with the polymer matrix in order
to improve the adhesion with the polymer. According to its amino acid sequence, keratin can be
considered to have both hydrophilic and hydrophobic properties, since 39 out of the 95 amino acids in
the keratin structure are hydrophilic [24]. Several studies have modified the CF [25] and the polymer
matrix [26] for enhancing their compatibility.
Among the aliphatic polyesters, PLA is the most well-known biodegradable polymer and has
the greatest commercial potential due to its good aesthetics, mechanical strength, thermal plasticity,
biocompatibility and ability to be easily processed with natural fibres [27]. PLA is produced from
renewable resources such as corn starch, which is fermented to lactic acid followed by ring-opening
or gradual polycondensation polymerization into PLA [28]. The combination of properties of PLA
makes it an ideal thermoplastic for a wide array of applications, but it still has some drawbacks
when compared to other traditional materials, which are related to its production limitations and
brittleness. The latter has a relatively easy solution, since the processability of the biocomposites can be
addressed by modifying the PLA with plasticizers such as polyethylene glycol (PEG), citrate ester and
glycerol [29]. This is not the case for the former drawback. A huge amount of starting raw material
(e.g., corn) is required for PLA production, and having in mind the food category of corn, economic
and sustainability issues arise. One approach to reduce the required PLA amount while keeping its
benefits is the combination of PLA with natural fibres to create biocomposites.
Among other biodegradable polymers, PBAT is synthesized from fossil fuel-based monomers
and shows similar properties to nonbiodegradable polymers like polyethylene. PBAT is flexible and
has a higher elongation at break than most biodegradable polyesters, such as PLA, being therefore
more suitable for packaging [30].
Bio-Flex® is a commercial product based on polylactic acid and a thermoplastic copolyester, and only
a very few articles have published on this system [31].
Even though several studies regarding biocomposites containing CFs up to 20 wt % and PLA
have been published, to the best of our knowledge, this is the first example of biocomposites obtained
from biodegradable thermoplastics with high loadings of CFs. CF concentrations were selected based
on the highest amount of CFs that was possible to incorporate into the polymer matrices, keeping
an optimum processability of the blends. Hence, the aim of this study was to develop sustainable
biocomposites comprised of 50 and 60 wt % CFs and biodegradable thermoplastic matrices (Figure 1)
contributing to the responsible use of materials and zero-waste policies. The selected polymer matrices
were PLA, PBAT and a PLA/copolyester blend, which are commercially available, biodegradable
and compostable according to EN 13432. Additionally, the effect of the addition of plasticisers to the
composite and alkali pre-treatments of the feathers were investigated. The mechanical properties,
thermal stability and diffusivity of the resulting biocomposites were studied in order to identify
potential applications of these new materials.
 Polymers 2017, 9, 593 3 of 15
Polymers
Polymers 2017,
2017, 9,
9, 593
593 33 of
of 15
15

11 cm
cm

Figure 1.
Figure 1. Chicken feather/PLA
1. Chicken feather/PLA
feather/PLA biocomposite
biocomposite containing
biocomposite containing 50
containing 50 wt
50 wt %
wt % of
% of feather.
of feather.
feather.

2.
2. Materials
Materials and
and Methods
Methods

2.1.
2.1. Materials
Materials
Sanitized
Sanitized CFs
CFs from
from Grupo SADA (Madrid, Spain) Spain) were
were ground
ground in
in a universal cutting mill
Pulverisette 19 (Fritsch, Germany) at a rotor rotational
Pulverisette 19 (Fritsch, Germany) at a rotor rotational speed of 2800 rpm and at aa sieve
sieve insert
insert size
size of
of
11 mm.
mm. According to the optical microscope images (Figure 2), ground feathers showed a wide size
According to the optical microscope images (Figure 2), ground feathers showed a wide size
distribution ranging from
distribution ranging from 100
100 µm
μm to aa few
μm to few mm.
mm. The
The different
different polymers
polymers used
used in
in this
this work
work are
are detailed
detailed
in Table 1. According to the EN 13432,
in Table 1. According to the EN 13432, all
13432, all thethe matrices
the matrices are
matrices are biodegradable
are biodegradable and
biodegradable and compostable.
compostable. Sodium
and compostable. Sodium
hydroxide
hydroxide (NaOH,
hydroxide (NaOH, 97%)
(NaOH, 97%) and
97%) and polyethylene
and polyethylene glycol
polyethylene glycol with
glycolwith molecular
withmolecular weight
molecularweight
weightofof 400
of400 g/mol
g/mol (PEG
400g/mol (PEG 400)
400) were
were
purchased from
purchased from Aldrich
Aldrich (St.
(St.
Aldrich (St. Louis,
Louis, MO,
MO, USA).
USA).

Figure
Figure 2. Optical image of ground chicken
chicken feathers.
Figure 2.
2. Optical
Optical image
image of
of ground
ground chicken feathers.
feathers.
Table
Table 1.
1. Properties
Properties of the
of the biopolymers
the biopolymers obtained
biopolymers obtained from
obtained from their
from their technical
their technical datasheets.
technical datasheets.
datasheets.
Table 1. Properties of

Polymer
Polymer Melting
Melting temperature Density
temperature Density
Density
Polymer Type
Type of matrix
of of
Type matrix
Matrix
Melting Supplier
Supplier
Supplier
(sample
(sample code)
code)Code)
(Sample (°C)
(°C) (◦ C)
Temperature 3 ) 33))
(g/cm
(g/cm
(g/cm
NatureWorks
Ingeo 2003D (ING) PLA 145–160 1.24 NatureWorks
NatureWorks
Ingeo
Ingeo 2003D
2003D (ING)
(ING) PLA
PLA 145–160
145–160 1.24
1.24 (Minnetonka, MN, USA)
(Minnetonka,
(Minnetonka,
BASF MN,
MN, USA)
USA)
Ecoflex C1200 (ECO) PBAT 120 1.25–1.27
(Ludwigshafen,BASF
Germany)
Ecoflex C1200
C1200 (ECO)
EcoflexBio-Flex (ECO) PBAT
PBAT 120
120 1.25–1.27
1.25–1.27 FKuRBASF
6611 (BIO) PLA/copolyester blend 150–170 1.29 (Ludwigshafen,
(Willich, Germany)Germany)
(Ludwigshafen, Germany)
FKuR
FKuR
Bio-Flex
Bio-Flex 6611
6611 (BIO)
(BIO) PLA/copolyester
PLA/copolyester blend
blend 150–170
150–170 1.29
1.29 (Willich,
(Willich, Germany)
Germany)
Polymers 2017, 9, 593 4 of 15

2.2. Alkali Treatment of the CFs

CFs were immersed in NaOH solution (5% w/v) for 2 h at room temperature. The feathers were then
washed with distilled water until the rinse water no longer indicated any alkalinity [32]. After washing,
the feathers were kept in an oven at 80 ◦ C for 6 h.

2.3. Biocomposite Preparation

The biocomposites were manufactured using a torque rheometer HAAKE PolyLab QC (Karlsruhe,
Germany). Prior to blending, ground CFs and the polymers were dried at 80 ◦ C for 6 h. The contents of
CF in the biocomposites were 50 and 60 wt %. ING, ECO, BIO biopolymers were first melted at 170, 140
and 170 ◦ C, respectively, and CFs were added later while mixing for 3 min. For the ING/PEG400 blends,
10 wt % of PEG400 was mixed before the CFs were incorporated. The blends were compression-molded in
a Vogt 600T laboratory hot press machine (Maschinen + Technik Vogt GmbH, Möhnesee, Germany) into
sheets of 90 × 90 × 2.1 mm3 . Consolidation was carried out at 200 ◦ C for 3 min and finally, the square
plates were cooled with air. TGA analyses of the biocomposites were performed previously in order to set
the consolidation conditions.

2.4. Characterization of the Biocomposites

2.4.1. Density of the Biocomposites

The density of the biocomposites was determined experimentally according to the ISO 9427 [33].
Three rectangular samples of each composite with a known volume were weighed and the density was
determined as the ratio of the mass to volume. The average and standard deviation were reported.

2.4.2. Water Absorption of Biocomposites

Water absorption of the biocomposites was determined by immersion of the specimens vertically in
distilled water at 25 ◦ C for 24 h (ASTM D570-98) [34]. First, rectangular specimens (24 mm × 12 mm ×
2.1 mm) were cut from tensile testing fracture specimens and air-dried at 60 ◦ C for 24 h, cooled in a desiccator
and weighed (conditioned weight). Then, samples of the biocomposites were soaked in water for 48 h and
wiped with paper to remove the excess of water on the surface of the specimens before weighing (wet weight)
at fixed time intervals. Three specimens were tested with an analytical balance of 0.1 mg precision and the
average and standard deviation were reported. The percentage of water absorption (WA in %) was calculated
using Equation (1):
wet weight − conditioned weight
WA (%) = × 100 (1)
conditioned weight

2.4.3. Thermogravimetric Analysis (TGA)

The thermal stability was measured by thermogravimetric analysis using a TGA Q500 (TA Instruments,
New Castle, DE, USA). Dynamic measurements were performed from 25 to 600 ◦ C at a heating rate of
10 ◦ C/min by using constant nitrogen flow of 60 mL/min to prevent thermal oxidation processes of the
polymer sample. The temperatures at 5%, 10%, 25% and 50% of weight loss were calculated. Sample
weight was approximately 10 mg.

2.4.4. Dynamic Scanning Calorimetry (DSC)

Thermal properties of CFs, ING, BIO, ECO and the biocomposites containing 50 and 60 wt % CFs
were determined with a Discovery DSC 25 auto (TA Instruments, New Castle, DE, USA) at a scan
rate of 10 ◦ C·min−1 over the temperature range 25–200 ◦ C for CF and ING series and −70–200 ◦ C for
ECO and BIO series due to their differences in thermal properties. The measurements were carried
out using 5.00 ± 0.50 mg samples under a nitrogen atmosphere (50 mL·min−1 ). All of the thermal
properties were obtained from the second heating curves in order to evaluate the effect of the filler,
Polymers 2017, 9, 593 5 of 15

as nucleating agent, during the processing. The degree of crystallinity (χc ) was calculated from the
following Equation (2):
100 |∆Hm + ∆Hcc |
χc (%) = × , (2)
w ∆Hom
where ∆Hm and ∆Hcc are the enthalpy of fusion and cold-crystallization at melting and crystallization
temperatures, respectively, w is the weight fraction of neat polymer in the sample and ∆Hm 0 is the

melting enthalpy of the 100% crystalline polymer. ∆Hm 0 was taken as 93.7 and 114 J/g for PLA and

PBAT, respectively. For the BIO series, ∆Hm was also taken as 93.7 J/g after the assumption that
0

Bio-Flex 6611 is mainly based on PLA, and no other melting peak was observed in the analysed range.

2.4.5. Mechanical Testing

The tensile properties of the biocomposites (Young’s modulus, tensile strength, and elongation
at break) were evaluated using a tensile test according to the ISO 527 [35] standard with a universal
testing machine model 3365 (Instron, Norwood, MA, USA) and controlled by Bluehill Lite software
developed by Instron (Norwood, MA, USA). The initial length of the test specimens was 25.4 mm
and a cross-head speed of 10 mm/min was used. The number of tested specimens for the mechanical
properties was 5 for average calculations.

2.4.6. Thermal Diffusivity

The thermal properties were measured utilizing a light flash analyzer (LFA, Nanoflash 447 by
Netzsch, Ahlden, Germany) following the ASTM E1461 [36]. This analyser operated a xenon flash
light that induced a pulse of energy on one side of the sample. Such a pulse increased the sample
temperature and an indium antimonide (InSb) infrared detector measured the temperature response
time to the pulse of energy on the other side of the sample. The response time was used to calculate
the thermal diffusivity.

2.4.7. FE–SEM
The CF/polymer interface was analysed by scanning electron microscopy of the fractured surface
of the composites. The microphotographs were taken with a Carl Zeiss Ultra Plus field-emission–
scanning electron microscope (FE–SEM, Oberkochen, Germany) equipped with an energy dispersive
X-ray spectrometer (EDXS). Prior to FE–SEM analysis, samples were Au-coated.

3. Results and Discussions

3.1. Density
One of the main reasons of using biocomposites containing a high concentration of CF is the
high-density reduction that is expected due to the low density of these feathers. Compared to other
natural fibres like wool 1.31 g/cm3 , jute 1.3 g/cm3 and coir 1.2 g/cm3 , the density of the chicken feather
fibres ranges between 0.8 g/cm3 [37] and 0.9 g/cm3 [38]. This variation may be due to the different
source of feathers. Hence, chicken feather inclusion in a thermoplastic matrix could potentially lower
biocomposite density more than any other reinforcing natural fibre.
In Table 2 are summarised density values and the percent reduction of the biocomposites
compared to the neat polymers. The density values determined for the processed ING, ECO and BIO
matrices are 1.16, 1.22 and 1.28 g/cm3 , respectively. As expected, the addition of CFs decreased the
density values of all the biocomposites, as has been reported by other researchers [39]. The higher
density of the neat matrix (ECO and BIO), the more pronounced was the reduction of the composite
material. The addition of 50 wt % of CF led to 13.11% and 15.63% density reductions, whereas the
addition of 60 wt % of CF lead to 17.21% and 20.31%, respectively.
 Polymers 2017, 9, 593 6 of 15
Polymers 2017, 9, 593 6 of 15

Table 2. Density values and percentage of density reduction of the biocomposites compared to
Tableneat polymer.
2. Density values and percentage of density reduction of the biocomposites compared to neat polymer.
Polymer/CF Density % of Density reduction
Matrix Polymer/CF Density % of Density Reduction
Matrix ratio (g/cm 3) Compared to neat polymer
Ratio (g/cm3 ) Compared to Neat
100/0 1.16 - Polymer
ING 100/0
50/50 1.16
1.10 - 5.17
ING 50/50
40/60 1.10
1.00 5.1713.79
40/60 1.00 13.79
100/0 1.22 -
ECO 100/0
50/50 1.22
1.06 - 13.11
ECO 50/50 1.06 13.11
40/60
40/60 1.01
1.01 17.2117.21
100/0 1.28 -
100/0 1.28 -
BIO BIO 50/50
50/50 1.08
1.08 15.6315.63
49604960 1.02
1.02 20.3120.31

Thereduction
The reductionisisattributed
attributedto
tothe
thehigh
highvoid
voidvolume
volumeof
ofthe
thebiocomposites
biocompositesdue
dueto
tothe
thepresence
presenceof
of
thehollow
the hollowstructure
structureofofthe
theCFs
CFs[40]
[40]which
whichwere
werepreserved
preservedafter
afterthe
the compression
compression molding
molding conditions.
conditions.

3.2.Water
3.2. WaterAbsorption
Absorption
Inorder
In order toto study
study the dimensional stabilitystability of
of the
thebiocomposites,
biocomposites,all allsamples
sampleswere
wereimmersed
immersed in
water at 25 °C◦ for 48 h. Figure 3 shows the water gain after 24 and 48 h of
in water at 25 C for 48 h. Figure 3 shows the water gain after 24 and 48 h of immersion of water.immersion of water. The
water
The absorption
water absorption of the
of thecomposite
composite samples
samples waswascalculated
calculatedwith
with(1).
(1).The
The water
water gain in the
the neat
neat
polymersafter
polymers after24 24hhwaswas0.46%,
0.46%,1.1%1.1%and
and0.32%
0.32%for
forING,
ING,BIO
BIOandandECO,
ECO,respectively.
respectively.These
Theselow
lowvalues
values
wereexpected
were expected since
since the the polymeric
polymeric matrices
matrices are hydrophobic.
are hydrophobic. After 48After 48 h of immersion,
h of immersion, all the
all the composite
composite
samples samples
gained watergained
in the water in the range
range between between
12.5–14.5% for12.5–14.5%
50 wt % and for16.6–17.6%
50 wt % andfor 16.6–17.6%
60 wt % of CF.for
60can
As wt % of CF.
been seen,As thecan been
mass seen,of
uptake the
themass uptake of the
biocomposites biocomposites
increased as the CFincreased
loading andas the immersion
CF loading
and increased.
time the immersion time increased.
The water gain of theThe water gain
composites of the composites
is mainly attributed toisthemainly attributed
hydrophilic to the
polymer
hydrophilic
backbone polymer
of the CF [41]. backbone
ING-based of the CF [41]. ING-based
composites showed thecomposites
highest water showed the highest
absorption. water
This effect
absorption. This effect is probably due to neat PLA samples containing
is probably due to neat PLA samples containing more polar groups in the polymer chain than the more polar groups in the
polymer
other chainmatrices.
polymer than theThese other results
polymerarematrices. These
in agreement results
with are in published
the results agreementby with the results
Carrillo et al.,
published
in which the byaddition
Carrillo of et CFs
al., inpromotes
which the addition
water of CFs promotes
absorption water absorption
in biocomposites in biocomposites
based on PLA [20,39] and
based on PLA
polyolefins [39].[20,39] and polyolefins [39].

Figure 3. Water absorption of the polymers and biocomposites after 24 h (black) and 48 h (white) of
Figure 3. Water absorption of the polymers and biocomposites after 24 h (black) and 48 h (white) of
immersion in water at 25 ◦ C.
immersion in water at 25 °C.
Polymers 2017, 9, 593 7 of 15

3.3. Polymers
Thermogravimetric
2017, 9, 593
Analysis (TGA) 7 of 15

The thermal stability of neat polymers and polymer/CF biocomposites was investigated with
3.3. Thermogravimetric Analysis (TGA)
TGA. The TGA curves presented in Figure 4a–c show thermal decomposition of CFs, neat polymers
(ING, ECO Theandthermal
BIO)stability
and theofCF-containing
neat polymers biocomposites.
and polymer/CFThe biocomposites
weight loss was investigated
of the with
CFs is represented
TGA. The TGA curves presented in Figure 4a–c show thermal decomposition of CFs,
in the three figures as reference. Three weight-loss steps can be seen in the case of CFs. The weight loss neat polymers
(ING, ECO and BIO) and the CF-containing biocomposites. The weight loss of the CFs is represented
in the first stage, from 50 to 250 ◦ C, is due to the evaporation of absorbed water from the hydrophilic
in the three figures as reference. Three weight-loss steps can be seen in the case of CFs. The weight
groups of the CFs; the second step, with a higher rate, between 250 and 400 ◦ C, undergoes degradation
loss in the first stage, from 50 to 250 °C, is due to the evaporation of absorbed water from the
associated withgroups
hydrophilic the destruction
of the CFs; theofsecond
disulphide bonds
step, with andrate,
a higher the between
elimination of 400
250 and H2 S°C,originating
undergoes from
amino acid cysteine [42]; and from 400 ◦ C onwards, the keratin partially decomposes. According
degradation associated with the destruction of disulphide bonds and the elimination of H2S
to Figure 4a–c, from
originating the biocomposites
amino acid cysteinealso degrade
[42]; andthrough
from 400three°Cstages and the
onwards, the keratin
degradation starting
partially
temperature
decomposes. depends
According on the type 4a–c,
to Figure of matrix. The degradation
the biocomposites starting
also degrade temperature
through of and
three stages the ING
the and
degradation starting
the corresponding temperature
biocomposites depends
is slightly on the
lower thantype
that of matrix.
of ECO andTheBIOdegradation starting
and their biocomposites.
Moreover, the degradation rate is faster for ING-based biocomposites. All biocomposites are and
temperature of the ING and the corresponding biocomposites is slightly lower than that of ECO thermally
BIO
stable and230–240
until their biocomposites. Moreover, thecomposites
◦ C; at this temperature, degradation begin
rate is thermal
faster fordegradation
ING-based biocomposites.
due to presence of
All biocomposites are thermally stable until 230–240 °C; at this temperature, composites begin
CFs also in three stages. For temperatures above 400 ◦ C, all the polymer matrices were completely
thermal degradation due to presence of CFs also in three stages. For temperatures above 400 °C, all
decomposed and an inorganic residue coming from the CFs was left behind after the decompositions
the polymer matrices were completely decomposed and an inorganic residue coming from the CFs
of the
wasCF-containing
left behind after composites. Composites
the decompositions of the containing
CF-containing 60composites.
wt % CF started degrading
Composites containingat lower
temperatures
60 wt % CFthan composites
started degradingcontaining 50 wt % CFthan
at lower temperatures duecomposites
to the higher keratin50content.
containing wt % CFThese
due toresults
are in agreement with previous studies of PLA/CF biocomposites containing
the higher keratin content. These results are in agreement with previous studies of PLA/CF up to 10 wt % [21] and
30 wt % of CFs [25].
biocomposites containing up to 10 wt % [21] and 30 wt % of CFs [25].

(a) (b) (c)

Figure 4. TGA curves of (a) ING-based biocomposites; (b) ECO-based biocomposites and (c) BIO-
Figure 4. TGA curves of (a) ING-based biocomposites; (b) ECO-based biocomposites and (c) BIO-
based biocomposites.
based biocomposites.
In Table 3, the 5%, 25% and 50% weight-loss temperatures are listed for all the specimens shown
inInFigure
Table4a–c.
3, the 5%, 25% and 50% weight-loss temperatures are listed for all the specimens shown
in Figure 4a–c.
Table 3. Thermal characterization of the neat polymers and biocomposites.
Table 3. Thermal characterization
Samples T (5%) (°C) of the neat polymers
T (25%) (°C) and biocomposites.
T (50%) (°C)
CF 191 276 325
Samples
ING (5%) (◦ C)
T323 T (25%) ◦
345 ( C) T (50%) ◦
358 ( C)
ING/CF (50/50)
CF 238191 305
276 322
325
ING/CF ING
(40/60) 231323 302
345 321
358
ING/CF
ECO (50/50) 352238 305
386 322
398
ING/CF
ECO/CF (40/60)
(50/50) 236231 302
330 321
377
ECO/CFECO
(40/60) 227352 386
316 398
369
ECO/CF
BIO (50/50) 314236 330
339 377
353
ECO/CF (40/60) 227 316 369
BIO/CF (50/50) 239 304 323
BIO 314 339 353
BIO/CF (40/60) 221 303 325
BIO/CF (50/50) 239 304 323
BIO/CF (40/60) 221 303 325
Polymers 2017, 9, 593 8 of 15
Polymers 2017, 9, 593 8 of 15
3.4. DSC Analysis
In order
3.4. DSC to study the effect of the CFs on the thermal properties of the neat polymers, DSC
Analysis
analysis of CFs, neat polymers and the corresponding biocomposites was performed. For CFs (shown
In order
in Figure 5a–ctoasstudy the effect
reference), of thelow-temperature
a large CFs on the thermalendothermic
properties ofpeakthe neat
waspolymers,
observedDSC at 77analysis of
°C. This
CFs, neat polymers and the corresponding biocomposites was performed.
peak ranges from 30 to 130 °C approximately and shows the amount of bound water in the keratin For CFs (shown in Figure 5a–c
as reference),
structure, anda on
large low-temperature
occasion is referredendothermic peak was observed
as the “denaturation” at 77 ◦ C.
temperature. This peak
Figure rangesthe
5a shows from
DSC30
to 130 ◦ C approximately and shows the amount of bound water in the keratin structure, and on occasion is
curves of CF/ING biocomposites. The glass transition temperature decreased from 53.6 to 47.4 °C and
referred as the “denaturation” temperature. Figure 5a shows the DSC curves
increased to 55.6 °C with addition of 50 and 60 wt % of CF, respectively. This lack of trend of the Tg of CF/ING biocomposites.
The glass transition ◦ and increased to 55.6 ◦ C with addition of
of PLA may be due temperature decreased
to: (i) heterogeneity offrom 53.6 to 47.4
the material. TheChigh concentration of CF may contribute
50 and 60 wt % of CF, respectively. This lack of trend
to a poor mixture of both phases; (ii) the DSC thermogram of the CFs of the T g of PLA maymaybe affect
due to:the(i)output
heterogeneity
of the Tofg
values of the biocomposites; and (iii) high disparity in the thermal properties of the differentthe
the material. The high concentration of CF may contribute to a poor mixture of both phases; (ii) DSC
part of
thermogram
the of the CFs may affect the output of the Tg values of the biocomposites; and (iii) high disparity
feathers [43].
in theForthermal
the ECOproperties of the different
series shown in Figure part
5b,ofthe
theTfeathers [43].and the ΔHm, Tm and the degree of the
g increased
For the of
crystallinity ECO theseries shown in Figure
biocomposites decreased5b, the
in theTg increased
presence of and theIn
CFs. ∆H m, T
this m andsince
series, the degree of the
the melting
crystallinity of the biocomposites decreased in the presence of CFs. In
temperatures of the samples were between 116.8 and 120.4 °C, the DSC curve of the CFs in this rangethis series, since the melting
temperatures ◦ C, the DSC curve of the CFs in this range
overlaps with of
thethe
DSC samples
curveswereof thebetween 116.8affecting
ECO series, and 120.4the measurements of the melting enthalpy.
overlaps with 5c
In Figure thethe
DSC DSCcurves of the
curves ECO
of the BIO series,
seriesaffecting the measurements
are shown. All the samplesofbasedthe melting enthalpy.
on a copolymer
In Figure 5c the DSC curves of the BIO series are shown. All the samples
that contains PLA showed two Tg, both increasing significantly after addition of 50 and 60 wt % of based on a copolymer
that contains
CFs. PLA showed
The melting two Tg ,Tboth
temperatures increasing
m increased significantly
slightly and ΔH after addition of more
m decreased 50 andthan
60 wt50%. % of The
CFs.
crystallinity of PLA in theTBIO
The melting temperatures m increased slightly and
series increased from∆H30.5%
m decreased
to 36.0%more thanthe
when 50%. The crystallinity
biocomposite was
of PLA in the BIO series increased from 30.5% to 36.0% when the biocomposite
reinforced with 60 wt % of CFs, observing the same effect as observed in the ING series. According was reinforced with
60 [44,45],
to wt % ofthere
CFs, observing
are two main the same
factorseffect as observed
affecting in the INGof
the crystallinity series. According
polymer to [44,45],
composites: there are
(i) additives
two main factors affecting the crystallinity of polymer composites: (i) additives
having a nucleating effect that results in an increased crystallinity, and (ii) additives hindering the having a nucleating
effect that results
migration in an increased
and diffusion of polymer crystallinity,
chains toand the (ii) additives
surface of the hindering
growingthe migration
polymer and lowering
crystal, diffusion
of polymer chains to the surface of the growing polymer crystal, lowering crystallinity.
crystallinity.

(a) (b) (c)

Figure 5. DSC curves of (a) ING-based biocomposites; (b) ECO-based biocomposites and (c) BIO-based
Figure 5. DSC curves of (a) ING-based biocomposites; (b) ECO-based biocomposites and (c) BIO-
biocomposites.
based biocomposites.

The crystallinity was found to increase in the ING and BIO series, both containing PLA, in
The crystallinity was found to increase in the ING and BIO series, both containing PLA, in agreement
agreement with Cheng [20], who reported that chicken feather fibres play the role having a nucleating
with Cheng [20], who reported that chicken feather fibres play the role having a nucleating effect in PLA.
effect in PLA. In the same study, it was observed that the crystallization peaks became narrower with
In the same study, it was observed that the crystallization peaks became narrower with the addition of
the addition of up to 10 wt % of CFs, indicating an increase of the crystallization rate. A similar effect
up to 10 wt % of CFs, indicating an increase of the crystallization rate. A similar effect was observed for
was observed for the ING/CF (50/50) biocomposite. However, a broader crystallization peak was
the ING/CF (50/50) biocomposite. However, a broader crystallization peak was found for the ING/CF
found for the ING/CF (40/60), probably due to a more heterogeneous crystallization process, which
(40/60),
can probably due
be attributed to ato a moreCF
higher heterogeneous crystallization
loading. Regarding process, which
the ECO-based can be attributed
biocomposites, to a higher
the crystallinity
CF loading. Regarding the ECO-based biocomposites, the crystallinity decreased. In this
decreased. In this case, the addition of CFs may disrupt the crystallite formation of PBAT due case, the addition
to the
of CFs may disrupt the crystallite formation of PBAT due to the increasing of viscosity, hence
increasing of viscosity, hence leading to less-ordered and smaller crystals. Detailed results of the leading
to less-ordered
thermal andobtained
properties smaller crystals.
from DSC Detailed results of the
are summarized thermal
in Table 4. properties obtained from DSC are
summarized in Table 4.
Polymers 2017, 9, 593 9 of 15

Polymers 2017, 9, 593 9 of 15

Table 4. Thermal properties of ING, ECO, BIO and their corresponding biocomposites.

Sample Tg1 (°C) Tg2 (°C) ΔΗcc (J/g) Tm (°C) ΔHm (J/g) χ (%)
Table 4. Thermal properties of ING, ECO, BIO and their corresponding biocomposites.
ING 53.6 19.5 147.6 22.7 3.48
ING/CF (50/50) 47.4 ◦ 15.2 144.6◦ 17.9 5.78
Sample T g1 (◦ C) T g2 ( C) ∆Hcc (J/g) T m ( C) ∆H m (J/g) χ (%)
ING/CF (40/60) 55.6 9.00 147.4 11.8 7.50
ING 53.6 19.5 147.6 22.7 3.48
ECO −34.1 120.4 9.8 8.60
ING/CF (50/50) 47.4 15.2 144.6 17.9 5.78
ECO/CF
ING/CF (50/50)
(40/60) −30.4 55.6 9.00 116.8
147.4 4.3
11.8 7.54
7.50
ECO/CFECO(40/60) −30.7
−34.1 116.6
120.4 2.7
9.8 5.92
8.60
ECO/CF
BIO (50/50) −
−37.830.4 58.7 116.8
176.9 4.3
28.6 7.54
30.5
ECO/CF (40/60) −30.7 116.6 2.7 5.92
BIO/CF (50/50) −33.1 65.6 178.7 14.4 30.7
BIO −37.8 58.7 176.9 28.6 30.5
BIO/CF (40/60)
BIO/CF (50/50) −32.1
−33.1 64.8 65.6 178.5
178.7 13.5
14.4 36.0
30.7
BIO/CF (40/60) −32.1 64.8 178.5 13.5 36.0
3.5. Mechanical Properties of the Biocomposites
3.5. Mechanical
Previous work Properties
by of the Biocomposites
Cheung [46] proved that the mechanical properties of chicken feather
fibre/PLA biocomposites were determined
Previous work by Cheung [46] proved that bythethemechanical
feather loading. As of
properties a matter
chickenof fact, the
feather tensile
fibre/PLA
biocomposites were determined by the feather loading. As a matter of fact, the tensile strengththe
strength of PLA decreases with increasing the content of CF, which is ascribed to the fact that of
strength of CF is insufficient. Cheng et al. [21] investigated 2, 5, 8 and 10 wt
PLA decreases with increasing the content of CF, which is ascribed to the fact that the strength of CF % feather concentration
and
is showed that
insufficient. evenetthough
Cheng al. [21]the tensile properties
investigated 2, 5, 8 andof the composites
10 wt % featherwere improved and
concentration withshowed
2 and 5
wt %
that loading
even though compared
the tensiletoproperties
the neat of PLA, increasing were
the composites feather amountwith
improved resulted
2 andin 5 wta significant
% loading
worsening of the mechanical properties. Therefore, it was expected
compared to the neat PLA, increasing feather amount resulted in a significant worsening that 50 and 60 wt % of feather
of the
content could
mechanical decreaseTherefore,
properties. the mechanical
it wasproperties
expected that considerably.
50 and 60 wtThe %three polymer
of feather matrices
content couldthat have
decrease
been
the investigated
mechanical in this considerably.
properties work have different
The threeinitialpolymer mechanical properties
matrices that have been andinvestigated
thus have shown in this
different performance upon the addition of CFs.
work have different initial mechanical properties and thus have shown different performance upon
Under some
the addition of CFs. conditions, alkali treatment could significantly improve adhesion at the interface
and Under
contribute
sometoconditions,
penetrate alkali
the fibre into the
treatment couldpolymer matrix.improve
significantly Alkali treatment’s
adhesion at main purpose
the interface andis
to remove some wax and oils, thereby increasing surface roughness and reducing
contribute to penetrate the fibre into the polymer matrix. Alkali treatment’s main purpose is to remove its hydrophilic
naturewax
some [47].and oils, thereby increasing surface roughness and reducing its hydrophilic nature [47].
Figures
Figures 6–86–8 show
show how
how three
three main
main variables
variables affectaffect the
the mechanical
mechanical properties
properties (Young’s
(Young’s modulus,
modulus,
tensile strength and elongation at break) of the biocomposites: (1)
tensile strength and elongation at break) of the biocomposites: (1) the type of the polymer the type of the polymer matrix,
matrix,
(2) the
(2) the CF
CF content
content andand (3)
(3) the
the alkali
alkali treatment
treatmentof ofthe
thefeathers
feathersand
andblending
blendingof ofING
INGwith
withPEG.PEG.
In Figure 6, the Young’s moduli of the biocomposites are presented.
In Figure 6, the Young’s moduli of the biocomposites are presented. This parameter measures This parameter measuresthe
the stiffness of the materials. ING and BIO showed a similar trend
stiffness of the materials. ING and BIO showed a similar trend upon the addition of CFs. upon the addition of CFs.

Figure 6. Young’s
Figure 6. Young’s moduli
moduli values
values of
of neat
neat polymers
polymers and
and the
the different
different biocomposites
biocomposites containing
containing 50
50 and
and
60 wt % of CFs.
60 wt % of CFs.
Polymers 2017, 9, 593 10 of 15
Polymers 2017, 9, 593 10 of 15

For biocomposites based on ING, the addition of 50 wt % of CFs has no major effect on the
Young’s
For modulus compared
biocomposites based to on
the ING,
neat polymer. Evenof
the addition when
50 wt alkali-treated
% of CFs has CFsno and PEG effect
major as plasticiser
on the
were added, only a minor increase was observed, reaching a maximum value
Young’s modulus compared to the neat polymer. Even when alkali-treated CFs and PEG as plasticiser of 2.1 GPa. However,
increasing
were added,the feather
only a minor loading,
increasethat
wasis, observed,
the ING/CF (40/60)a maximum
reaching biocomposite,value showed a pronounced
of 2.1 GPa. However,
decrease of Young’s modulus of 20%.
increasing the feather loading, that is, the ING/CF (40/60) biocomposite, showed a pronounced
For ECO/CF
decrease of Young’s biocomposites,
modulus of 20%. the reference value of the neat polymer is lower than that of ING
and BIO and hence,
For ECO/CF the effect of reinforcing
biocomposites, the referenceECO withof
value CFthe
is substantial.
neat polymer The Young’s
is lower moduli
than are
that of 70,
ING
300 and 670 MPa for 0, 50 and 60 wt % of CFs, respectively, with an increase up
and BIO and hence, the effect of reinforcing ECO with CF is substantial. The Young’s moduli are 70, to 1000%. For BIO/CF
biocomposites,
300 and 670 MPaadding feathers
for 0, 50 and 60has wt %a positive effect, but aswith
of CFs, respectively, observed in theup
an increase first
to case,
1000%. theForincrease
BIO/CFof
CF loading to 60 wt % is detrimental. The differences observed on the trends
biocomposites, adding feathers has a positive effect, but as observed in the first case, the increase of CF of the mechanical
properties
loading of wt
to 60 the%biocomposites
is detrimental.are Theprobably
differencesdueobserved
to the different degrees
on the trends of compatibility
of the between
mechanical properties
thethe
of matrices and the feathers.
biocomposites are probably due to the different degrees of compatibility between the matrices
In Figure
and the feathers. 7, the tensile strengths of the biocomposites are shown. This property is a measurement
of theInforce
Figurerequired to break
7, the tensile the material
strengths per unit area.
of the biocomposites areFor all the
shown. series,
This the effect
property on the tensile
is a measurement of
the force required to break the material per unit area. For all the series, the effect on the tensile strengtha
strength was similar, decreasing when 50 and 60 wt % of CF was added. This effect is probably
combination
was of the high
similar, decreasing whenCF 50 content
and 60 wt and
% ofhence
CF waspoor mixing
added. This between the components,
effect is probably a combination andoflow
the
adhesion between the matrices and the fibres [43]. For ING/CF specimens,
high CF content and hence poor mixing between the components, and low adhesion between the matrices the alkali treatment of
the CFs increased the tensile strength, with respect to the composite with untreated
and the fibres [43]. For ING/CF specimens, the alkali treatment of the CFs increased the tensile strength, CFs, from 13.7 to
24 MPa.
with respect to the composite with untreated CFs, from 13.7 to 24 MPa.

Figure 7. Tensile strength values of neat polymers and the different biocomposites containing 50 and
60 wt % of CFs.

Figure 88 shows
Figure shows the theelongation
elongationatatbreak
breakofofthe
thedifferent
differentsamples.
samples.The Theelongation
elongation atat break,
break, which
which is
is the ratio between changed length and initial length after breakage, showed
the ratio between changed length and initial length after breakage, showed a dramatic decrease with CFsa dramatic decrease
with CFs less
obtaining obtaining
ductileless ductileThe
materials. materials. The most
most obvious caseobvious case is the
is the ECO/CF ECO/CF
series, varying series, varying the
the elongation at
elongation
break at break
from 570% for from 570%tofor
pure ECO pure
2.5% forECO to 2.5%
ECO/CF for ECO/CF
(50/50). When the(50/50). When of
percentage thethe
percentage
CF loading ofwas
the
CF loading
increased wasseries,
in this increased in this series,
the elongation the further
at break elongation at break
decreased. Forfurther decreased.
all the series, whenFor the all the series,
percentage of
when the percentage of CF was 50 wt %, the ductility of the biocomposites decreased,
CF was 50 wt %, the ductility of the biocomposites decreased, which indicates that the CFs had hardened which indicates
the
that the CFs had
biocomposites andhardened the biocomposites
reduced their ductility. For theand
INGreduced their
series, no ductility.
clear effect ofFor
thethe ING
alkali series, no
treatment or clear
PEG
effect of the alkali treatment or PEG was observed. When the CF loading was
was observed. When the CF loading was increased to 60 wt %, the elongation at break of ING/CF (40/60)increased to 60 wt %,
the elongation
and ECO/CF (40/60)at break wasofreduced.
ING/CF The (40/60) and ECO/CF
elongation at break(40/60) was reduced.
of ING/CF The not
(40/60) was elongation at break
further reduced.
of ING/CF (40/60) was not further reduced.
Polymers 2017, 9, 593 11 of 15
Polymers 2017,9,9,593
Polymers2017, 593 1111ofof1515

Figure 8. Elongation-at-break values of neat polymers and the different biocomposites containing
50Figure Elongation-at-break
and 608.8.
wt % of CFs. values of neat polymers and the different biocomposites containing 50
Figure Elongation-at-break values of neat polymers and the different biocomposites containing
and 60 wt % of CFs.
50 and 60 wt % of CFs.
3.6. Morphology of the Biocomposites
3.6.
3.6.Morphology
Morphologyofofthe theBiocomposites
Biocomposites
The effects of the two different treatments on the adhesion between the PLA matrix and CFs were
The
Theeffects
investigated effects ofofthe
by FE–SEM. thetwo different
differenttreatments
Micrographs
two of raw CFs
treatments ononthetheadhesion
and NaOH-treated
adhesion between
betweenCFsthe PLA
are
the PLA matrix
shown matrixin and
andCFs
Figure CFs were
9a,b,
were
investigated
respectively. by
investigatedAsbycan FE–SEM. Micrographs
be observed,
FE–SEM. of raw
alkali treatment
Micrographs of raw CFsCFs and
increases NaOH-treated
the roughness
and NaOH-treated CFs
CFs are
of are shown
the shown in Figure
CFs, increasing
in Figurethe 9a,b,
9a,b,
respectively.
respectively. As can be observed, alkali treatment increases the roughness of the CFs, increasingthe
surface area ofAsthe can be
fibres observed,
available alkali
for treatment
contact to theincreases
matrix. the roughness
Bismarck et al.of the
[48] CFs,
also increasing
observed this the
surface
effect
surface area
areaofof
in natural the fibres
fibres.
the available
Additionally,
fibres availableforalkali
contact
for to the
to matrix.
treatment
contact thealso Bismarck
removes
matrix. et al. [48]
et al.also
hydrophilic
Bismarck observed
components
[48] this
also observed effect
located this
onineffect
natural
the fibrefibres.
surface
in natural Additionally,
[47].
fibres. The alkali treatment
micrographs
Additionally, ofalso
alkali treatment theremoves
fractured hydrophilic
also removes surface ofcomponents
hydrophilicthe untreated located
components on
CF/ING the
located
fibre
on thesurface
biocomposites fibre[47].
can Theseen
be
surface micrographs
in Figure
[47]. of
9c.the
The micrographs This fractured
figure surface
of shows
the of the untreated
individual
fractured ofCF/ING
CFs, which
surface biocomposites
the indicates
untreated that the
CF/ING
can
fibres be seen in
have been not
biocomposites Figure 9c.
can mixed This
be seenwell figure shows
with the
in Figure 9c.matrixindividual
due toshows
This figure CFs, which
a lowindividual indicates
adhesion between that
CFs, which the fibres
the indicates have
matrix and been
thatthethe
not
fibres. mixed
fibresAshave
can well
be
been with
seen the
notin matrix
Figure
mixed 9d,
well due
the
withtoING/NaOH–CF
athelow adhesion
matrix between
duebiocomposites
to the matrix
a low adhesion aand
showbetween good thedispersion
fibres.
the matrixAsofcan
and thebe
the
seen
NaOH–CFs in Figure
fibres. As in 9d,
canthe the
beING ING/NaOH–CF
seenmatrix compared
in Figure biocomposites
9d, the to the appearance
ING/NaOH–CF show a good dispersion
of the ING/CFshow
biocomposites of the
biocomposites NaOH–CFs in
(Figure 9c),
a good dispersion the
of the
ING
enhancingmatrix
NaOH–CFs thecompared
inCF tomatrix
thewettability
ING the appearance
incompared
the polymer oftothe
theING/CF
matrix
appearance biocomposites
and improving
of the ING/CF (Figure 9c), enhancing
the biocomposites
tensile strength ofthethe
(Figure CF
9c),
wettability
biocomposites. in the
In polymer
the case matrix
of the and improving
biocomposites the
containing tensile
the strength
PEG,
enhancing the CF wettability in the polymer matrix and improving the tensile strength of the seeof the
Figure biocomposites.
9e; chicken In
fibresthe case
were
ofbiocomposites.
the biocomposites
completely covered bycontaining
In the the of thethe
casepolymer, PEG,
however,
biocompositessee Figure 9e; chicken
nocontaining
improvement fibres were
in thesee
the PEG, tensilecompletely
Figure strength covered
and
9e; chicken bywere
modulus
fibres the
polymer,
was however, no improvement in the tensile strength and modulus
observed.covered by the polymer, however, no improvement in the tensile strength and modulus
completely was observed.
was observed.

(a) (b)
(a) (b)
Figure 9. Cont.
 Polymers 2017, 9, 593 12 of 15
Polymers 2017, 9, 593 12 of 15
Polymers 2017, 9, 593 12 of 15

(c) (d) (e)

(c) (d) (e)
Figure
Figure9.9. FE–SEM
FE–SEMimages
images of
of (a)
(a) untreated
untreated CFs;
CFs; (b)
(b) NaOH-treated CFs; (c)
NaOH-treated CFs; (c) fractured
fractured ING/CF
ING/CF (50/50);
(50/50);
(d)
Figure fractured
9. FE–SEM ING/NaOH–CF
images of (a) (50/50)
untreatedand (e)
CFs; fractured
(b) PEG–ING/CF
NaOH-treated CFs;
(d) fractured ING/NaOH–CF (50/50) and (e) fractured PEG–ING/CF (50/50).(50/50).
(c) fractured ING/CF (50/50);
(d) fractured ING/NaOH–CF (50/50) and (e) fractured PEG–ING/CF (50/50).
3.7.
3.7.Thermal
ThermalDiffusivity
Diffusivity
3.7. Thermal Diffusivity
Thermal
Thermaldiffusivity
diffusivitymeasures
measuresthe therate
rateatatwhich
whichheat heatflows
flowsthrough
through a material.
a material. It isItaismeasure
a measureof
theThermal
raterate
of the
diffusivity
at which
at which a body measures
withwith
a body
the rate at which
a non-uniform
a non-uniform
heat flows
temperature
temperature
through
reaches aamaterial.
a state
reaches of thermal
state
It isequilibrium.
of thermal
a measure of
The
equilibrium.
themeasured
rate at which a
thermal body with
diffusivitya non-uniform
of the temperature
biocomposites at 25 reaches
°C and ◦a state
containingof
The measured thermal diffusivity of the biocomposites at 25 C and containing 50 wt % of CFs are
thermal
50 wt equilibrium.
% of CFs are The
shown
measured
in Figurethermal diffusivity of the biocompositeswereat 25 °C and containing 50 wt %of ofthe
CFsbiocomposites
are shown
shown in10. It can
Figure be seen
10. that
It can bewhen
seenthe CFs
that when added,
the CFs thewere thermal
added, diffusivity
the thermal diffusivity of the
in Figure
was 10. It can
reduced. Thebe seen thatdiffusivity
when the CFs were added, the thermal diffusivity of9.5%
the biocomposites
biocomposites wasthermal
reduced. The thermal reduction varied
diffusivity from
reduction 5%varied
for INGfromand 5% for BIO
for ING andto9.5%18.9%
for
wasforreduced.
ECO. TheCFs
The thermal
showed diffusivity
a reduction
hollow varied from 5%
honeycomb-shaped for ING which
structure, and 9.5% for as
acted BIOairtoand18.9%heat
BIO to 18.9% for ECO. The CFs showed a hollow honeycomb-shaped structure, which acted as air
forinsulators
ECO. ThecausingCFs showed
a a hollow
decrease of honeycomb-shaped
thermal diffusivity of thestructure, whichbiocomposites
CF-containing acted as air and [40].heat
These
and heat insulators causing a decrease of thermal diffusivity of the CF-containing biocomposites [40].
insulators
results causing
mean that a biocomposites
decrease of thermal diffusivity
containing of the
CFs will CF-containing
require timebiocomposites
longerlonger totime
be heated or[40]. These
cooled than
These results mean that biocomposites containing CFs will require to be heated or cooled
results
the mean that
unfilled biocomposites
polymer, containing
indicating that CFs
the will require longer
CF-reinforced time to beshow
biocomposites heated or cooledthermal
improved than
than the unfilled polymer, indicating that the CF-reinforced biocomposites show improved thermal
theinsulation
unfilled properties.
polymer, Qin, indicating that the aCF-reinforced
X. [13] reported similar trend when biocomposites
PLA sheets were showreinforced
improved with thermal
CF mats.
insulation properties. Qin, X. [13] reported a similar trend when PLA sheets were reinforced with
insulation properties. Qin, X. [13] reported a similar trend when PLA sheets were reinforced with CF mats.
CF mats.
0.16
0.16
0.14
0.14
0.12
Diffusivity (mm2/s)

0.12
0.10
Diffusivity (mm2/s)

0.10
0.08
0.08
0.06
0.06
0.04
0.04
0.02
0.02
0.00
0.00 ING ING/CF ECO ECO/CF BIO BIO/CF
ING (50/50) ECO
ING/CF (50/50) BIO
ECO/CF (50/50)
BIO/CF
(50/50) (50/50) (50/50)

Figure 10. Diffusivity values of neat polymers and polymers reinforced with 50 wt % CFs.
Figure 10. Diffusivity values of neat polymers and polymers reinforced with 50 wt % CFs.
Figure 10. Diffusivity values of neat polymers and polymers reinforced with 50 wt % CFs.
4. Conclusions
4. Conclusions
In this work, fully biodegradable biocomposites with 50 and 60 wt % of CFs were successfully
4. Conclusions
In this and
developed work, fully
their biodegradable
density, biocomposites
water absorption, thermalwith 50 andmechanical
stability, 60 wt % of properties
CFs were successfully
and thermal
In this
developed work,
and fully
their biodegradable
density,
diffusivity were investigated. water biocomposites
absorption, with
thermal 50 and
stability,60 wt % of
mechanical CFs were successfully
properties and thermal
developed and
diffusivity their
were density, water
investigated. absorption, thermal stability, mechanical properties
CF/polymer biocomposites with high content of CF showed a decrease in density values unlike and thermal
diffusivity were
any CF/polymer
other investigated.
naturalbiocomposites with high
or synthetic fibres, content
forming of CF showed
lightweight a decrease in density
fully biodegradable values
materials. unlike
Regarding
anyCF/polymer biocomposites
other natural or syntheticwith high
fibres, content
forming of CF showed
lightweight fullya biodegradable
decrease in density valuesRegarding
materials. unlike
anywater
otherabsorption,
natural or the
synthetic fibres, forming
biocomposites gainedlightweight
from 12% tofully17% biodegradable
of weight aftermaterials. Regarding
48 h of immersion, due
water absorption,
to the theamino
hydrophilic biocomposites gained
acid groups from
found 12%structure
in the to 17% ofofweight after 48 h of immersion, due
the feathers.
to the hydrophilic amino acid groups found in the structure of the feathers.
Polymers 2017, 9, 593 13 of 15

water absorption, the biocomposites gained from 12% to 17% of weight after 48 h of immersion, due to
the hydrophilic amino acid groups found in the structure of the feathers.
The thermogravimetric curves revealed that the thermal stability of the biocomposites is lowered
by the addition of feathers, due to their high content of thermally unstable keratin.
Mechanical properties of the CF-containing biocomposites showed lower tensile strength and
lower elongation-at-break values compared to those of neat polymers, whereas the elastic moduli
depended on the matrix type. The elastic moduli of the biocomposites were increased for ECO- and
BIO-based biocomposites due to the low values of the neat polymers. In these cases, the biocomposites
became stiffer. In the ING series, the moduli were not affected by the addition of the CFs for the
ING/CF (50/50) biocomposite.
The presence of honeycomb structures in CFs provides air- and heat-insulating capabilities to the
biocomposites, lowering the thermal diffusivity of the biocomposites. The results showed that the CFs
could be considered as isolator components in buildings to reduce heat transfer and hence decrease
energy consumption.
Taking into account the overall properties observed, these materials could be used as an alternative to
wood–plastic composites in medium-density fibreboards (MDF) composites [49], decking materials and
many other applications [50], in which low density, low thermal diffusivity and low water absorption are
also required.
This approach would contribute to a more efficient use of natural resources and take advantage of
this material that is produced in huge amounts and is currently underutilized by the poultry industry. It is
intended that the use of 100% biodegradable materials will contribute to sustainability and a reduction in
the environmental impact associated with the disposal of non-biodegradable polymers.

Acknowledgments: This work was supported by KaRMA2020 project. This project has received funding from
the European Union’s Horizon 2020 Research and Innovation program under Grant Agreement n◦ 723268.
Author Contributions: Ibon Aranberri and Sarah Montes performed the experiments and wrote the paper;
Itxaso Azcune conceived and designed the experiments and contributed on the interpretation of the results and
Alaitz Rekondo and Hans-Jürgen Grande contributed on the final discussion of the results.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Mohanty, A.; Misra, M.; Drzal, L. Natural Fibers, Biopolymers and Biocomposites; CRC Press, Taylor & Francis:
Boca Ratón, FL, USA, 2005; pp. 1–36. ISBN 9780849317415.
2. Pickering, K.L.; Efendy, M.G.A.; Le, T.M. A review of recent developments in natural fibre composite and
their mechanical performance. Compos. Part A Appl. Sci. Manuf. 2016, 83, 98–112. [CrossRef]
3. Conzatti, L.; Giunco, F.; Stagnaro, P.; Patrucco, A.; Marano, C.; Rink, M.; Marsano, E. Composites based on
polypropylene and short wool fibres. Compos. Part A Appl. Sci. Manuf. 2013, 47, 165–171. [CrossRef]
4. Alam, A.K.M.M.; Shubhra, Q.T.H.; Al-Imran, G.; Barai, S.; Islam, M.R.; Rahman, M.M. Preparation and
characterization of natural silk fiber-reinforced polypropylene and synthetic E-glass fiber-reinforced polypropylene
composites: A comparative study. J. Compos. Mater. 2011, 45, 2301–2308. [CrossRef]
5. Kumar, D.; Boopathy, S.R.; Sangeetha, D.; Bharathiraja, G. Investigation of Mechanical Properties of Horn
Powder-Filled Epoxy Composite. J. Mech. Eng. 2017, 63, 138–147. [CrossRef]
6. Zhao, W.; Yang, R.; Zhang, Y.; Wu, L. Sustainable and practical utilization of feather keratin by a novel
physicochemical pretreatment: High density steam flash-explosion. Green Chem. 2012, 14, 3352–3360.
[CrossRef]
7. European Commission. Available online: http://ec.europa.eu/agriculture/poultry_en (accessed on 9 November 2017).
8. Korniłłowicz-Kowalska, T.; Bohacz, J. Biodegradation of keratin waste: Theory and practical aspects.
Waste Manag. 2011, 31, 1689–1701. [CrossRef] [PubMed]
9. Reddy, N. Non-food industrial applications of poultry feathers. Waste Manag. 2015, 45, 91–107. [CrossRef]
[PubMed]
Polymers 2017, 9, 593 14 of 15

10. Yin, J.; Rastogi, S.; Terry, A.E.; Popescu, C. Self-organization of polypeptides obtained on dissolution of
feather keratins in superheated water. Biomacromolecules 2007, 8, 800–806. [CrossRef] [PubMed]
11. Yin, X.C.; Li, F.Y.; He, Y.F.; Wang, Y.; Wang, R.M. Study on effective extraction of chicken feather keratin and
their films for controlling drug release. Biomater. Sci. 2013, 1, 528–536. [CrossRef]
12. Schmidt, W.F.; Line, M.J. Physical and chemical structures of poultry feather fiber fractions in fiber process
development. In Proceedings of the 1996 TAPPI Nonwovens Conference, Charlotte, NC, USA, 11–13 March 1996;
pp. 135–141.
13. Qin, X. Chicken Feather Fibre Mat/PLA Composites for Thermal Insulation. Master’s Thesis, University of Waikato,
Hamilton, New Zealand, 2015.
14. Acda, M.N. Waste chicken feather as reinforcement in cement-bonded composites. Philipp. J. Sci. 2010, 139, 161–166.
15. Saucedo-Rivalcoba, V.; Martínez-Hernández, A.L.; Martínez-Barrera, G.; Velasco-Santos, C.; Castaño, V.M.
(Chicken feathers keratin)/polyurethane membranes. Appl. Phys. A 2011, 104, 219–228. [CrossRef]
16. Reddy, N.; Yang, Y. Light-weight polypropylene composites reinforced with whole chicken feathers. J. Appl.
Polym. Sci. 2010, 116, 3668–3675. [CrossRef]
17. Huda, S.; Yang, Y. Composites from ground quill and polypropylene. Compos. Sci. Technol. 2008, 68, 790–798.
[CrossRef]
18. Jiménez-Cervantes, E.; Velasco-Santos, C.; Martínez-Hernández, A.L.; Rivera-Armenta, J.L.; Mendoza-Martínez, A.M.;
Castaño, V.M. Composites from chicken feathers quill and recycled polypropylene. J. Compos. Mater. 2015, 49, 275–283.
19. Yang, Y.; Reddy, N. Utilizing discarded plastic bags as matrix material for composites reinforced with chicken
feathers. J. Appl. Polym. Sci. 2013, 130, 307–312. [CrossRef]
20. Cañavate, J.; Aymerich, J.; Garrido, N.; Colom, X.; Macanás, J.; Molins, G.; Álvarez, M.D.; Carrillo, F.
Properties and optimal manufacturing conditions of chicken feather/poly(lactic acid) biocomposites.
J. Compos. Mater. 2016, 50, 1671–1683. [CrossRef]
21. Cheng, S.; Lau, K.T.; Liu, T.; Zhao, Y.; Lam, P.M.; Yin, Y. Mechanical and thermal properties of chicken feather
fiber/PLA Green composites. Compos. Part B Eng. 2009, 40, 650–654. [CrossRef]
22. Baba, B.O.; Özmen, U. Preparation and mechanical characterization of chicken feather/PLA composites.
Polym. Compos. 2015, 38, 837–845. [CrossRef]
23. Reddy, N.; Jiang, J.; Yang, Y. Biodegradable composites containing chicken feathers as matrix and jute fibers
as reinforcement. J. Polym. Environ. 2014, 22, 310–317. [CrossRef]
24. Arai, K.M.; Takahashi, R.; Yokote, Y.; Akahane, K. Amino-acid sequence of feather keratin from fowl.
Eur. J. Biochem. 1983, 132, 501–507. [CrossRef] [PubMed]
25. Huda, M.S.; Schmidt, W.F.; Misra, M.; Drzal, L.T. Effect of fiber surface treatment of poultry feather fibers on
the properties of their polymer matrix composites. J. Appl. Polym. Sci. 2013, 128, 1117–1124. [CrossRef]
26. Ghani, S.A.; Tan, S.J.; Yeng, T.S. Properties of chicken feather fiber-filled low density polyethylene composites:
The effect of polyethylene grafted maleic anhydride. Polym. Plast. Technol. Eng. 2013, 52, 495–500. [CrossRef]
27. Kuma, P.; Bajpai, P.K.; Singh, I.; Madaan, J. Development and characterization of PLA-based green composites:
A review. J. Thermoplast. Compos. Mater. 2012, 10, 1–30.
28. Masutani, K.; Kimura, Y. PLA Synthesis. From the Monomer to the Polymer. In Poly(lactic acid) Science and
Technology: Processing, Properties, Additives and Applications; RSC: London, UK, 2014.
29. Martin, O.; Avérous, L. Poly(lactic acid): Plasticization and properties of biodegradable multiphase system.
Polymer 2001, 45, 6209–6219. [CrossRef]
30. Bordes, P.; Pollet, E.; Avérous, L. Nano-biocomposites: Biodegradable polyester/nanoclay systems. Prog. Polym. Sci.
2009, 34, 125–155. [CrossRef]
31. Briassoulis, D.; Babou, E.; Hiskakis, M. Degradation Behaviour and Field Performance of Experimental
Biodegradable Drip Irrigation Systems. J. Polym. Environ. 2011, 19, 341–361. [CrossRef]
32. Islam, M.S.; Pickering, K.L.; Foreman, N.J. Influence of Alkali Treatment on the Interfacial and Physico-
Mechanical Properties of Industrial Hemp Fibre Reinforced Polylactic Acid Composites. Compos. Part A
Appl. Sci. Manuf. 2010, 41, 596–603. [CrossRef]
33. ISO 9427:2003. Wood-Based Panels. Determination of Density; International Organization for Standardization:
Geneva, Switzerland, 2003.
34. ASTM D570-98. Standard Test Method for Water Absorption of Plastics; ASTM International: West Conshohocken,
PA, USA, 2010.
Polymers 2017, 9, 593 15 of 15

35. ISO 527-1:2012. Plastics—Determination of Tensile Properties; International Organization for Standardization:
Geneva, Switzerland, 2012.
36. ASTM E1461-13. Standard Test Method for Thermal Diffusivity by the Flash Method; ASTM International:
West Conshohocken, PA, USA, 2013.
37. Barone, J.R.; Schmidt, W.F. Polyethylene reinforced with keratin fibers obtained from chicken feathers.
Compos. Sci. Technol. 2005, 65, 173–181. [CrossRef]
38. Carrillo, F.; Rahalli, A.; Cañavate, J.; Colom, X. Composites from keratin biofibers. Study of compatibility
using polyolephinic matrices. In Proceedings of the 15th European Conference on Composite Materials
(ECCM-15) Conference, Venice, Italy, 24–28 June 2012; pp. 1–15.
39. Carrillo, F.; Rahhali, A.; Cañavate, J.; Colom, X. Biocomposites using waste whole chicken feathers and
thermoplastic matrices. J. Reinf. Plast. Compos. 2013, 32, 1419–1429. [CrossRef]
40. Reddy, N.; Yang, Y. Structure and Properties of Chicken Feather Barbs as Natural Protein Fibers. J. Polym. Environ.
2007, 15, 81–87. [CrossRef]
41. Barone, J.R.; Gregoire, N.T. Characterization of fibre-polymer interactions and transcrystallity in short keratin
fiber-polypropylene composites. Plast. Rubber Compos. 2006, 35, 287–293. [CrossRef]
42. Martínez-Hernández, A.L.; Velasco-Santos, C.; de Icaza, M.; Castaño, V.M. Microstructural characterization
of keratin fibres from chicken feathers. Int. J. Environ. Pollut. 2005, 23, 162–178. [CrossRef]
43. Takahashi, K.; Yakamoto, H.; Yokote, Y.; Hattori, M. Thermal Behavior of Fowl Feather Keratin. Biosci. Biotechnol.
Biochem. 2004, 68, 1875–1881. [CrossRef] [PubMed]
44. Huda, M.S.; Drzal, L.T.; Mohanty, A.K.; Misra, M. Chopped glass and recycled newspaper as reinforcement
fibers in injection molded poly(lactic acid) (PLA) composites: A comparative study. Compos. Sci. Technol.
2006, 66, 1813–1824. [CrossRef]
45. Houshyar, S.; Shanks, R.A.; Hodzic, A. The effect of fiber concentration on mechanical and thermal properties
of fiber-reinforced polypropylene composites. J. Appl. Polym. Sci. 2005, 96, 2260–2272. [CrossRef]
46. Cheung, H.Y.; Lau, K.T.; Tao, X.M.; Hui, D. A potential material for tissue engineering: Silkworm silk/PLA
biocomposite. Compos. Part B Eng. 2008, 39, 1026–1033. [CrossRef]
47. Ghani, S.A.; Jahari, M.H.; Soo-Jin, T. Effects of sodium hydroxide treatment on the properties of low-density
polyethylene composites filled with chicken feather fiber. J. Vinyl Addit. Technol. 2014, 20, 36–41. [CrossRef]
48. Bismarck, A.; Mohanty, A.K.; Aranberri-Askargorta, I.; Czapla, S.; Misra, M.; Hinrichsen, G.; Springer, J.
Surface characterization of natural fibers; surface properties and the water up-take behavior of modified
sisal and coir fibers. Green Chem. 2001, 3, 100–107. [CrossRef]
49. Winandy, J.E.; Muehl, J.H.; Micales, J.A.; Raina, A.; Schmidt, W. Potential of chicken feather fibre in wood
MDF composites. In Proceedings of the EcoComp, London, UK, 1–2 September 2003; p. 20.
50. Peter, S. Material Revolution: Sustainable and Multi-Purpose Materials for Design and Architecture; Birkhäuser:
Basel, Switzerland, 2011; ISBN 13:978-3034606639.

© 2017 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).