Composites: Part A 73 (2015) 109115

Contents lists available at ScienceDirect

Composites: Part A
journal homepage: www.elsevier.com/locate/compositesa

PLA/algae composites: Morphology and mechanical properties

Mindaugas Bulota 1, Tatiana Budtova
Mines ParisTech, Centre de Mise en Forme des Matriaux (CEMEF), UMR CNRS 7635, CS 10207, rue Claude Daunesse, 06904 Sophia Antipolis, France

a r t i c l e i n f o a b s t r a c t

Article history: Bio-composites with poly(lactic) acid as matrix and various algae (red, brown and green) as ller were
Received 1 July 2014 prepared via melt mixing. Algae initial size (below 50 lm and between 200 and 400 lm) and concentra-
Received in revised form 4 January 2015 tion (from 2 to 40 wt%) were varied. First, algae morphology, composition and surface properties are anal-
Accepted 2 March 2015
ysed for each algae type. Second, an example of algae particle size decrease during processing is given.
Available online 10 March 2015
Finally, tensile properties of composites are analysed. The surface of algae akes was covered with inor-
ganic salts affecting llermatrix interactions. The Youngs modulus of composites increased at 40 wt%
Keywords:
load of algae as compared with neat PLA although the strain at break and tensile strength decreased.
A. Polymer-matrix composites (PMCs)
B. Mechanical properties
In most cases the inuence of algae type was minor. Larger akes led to better mechanical properties
D. Electron microscopy compared to the smaller ones.
Algae 2015 Elsevier Ltd. All rights reserved.

1. Introduction
Natural bres and llers are an inexhaustible source of biobased
materials: wood our is already used in mass production of wood
plastic composites while cellulosic bres from other plants (ax,
sisal, jute) for the reinforcement of thermoplastic and thermoset
polymers. Algae represent another vast and cheap source of poten-
tial llers for making polymer-matrix composites; however, the
knowledge on the properties of algae-lled composites is very
scarce. Algae biomass is a source of hydrosoluble polysaccharides
(alginate, carrageenan, agarose), and it is mainly used in agricul-
ture, food and cosmetics industries. An uncontrolled proliferation
of algae occurs in coastlines due to environmental problems [1],
thus the use of this waste would be highly appreciated.
There are thousands of different algae species which vary with
respect to the structure and composition [24]. They can be
roughly grouped into three categories: green, brown and red algae.
In terms of structure, algae are similar to land plants and consist of
stiff and strong cellulose-based brils which are embedded in a
soft amorphous matrix. Contrary to plant bres, cellulose con-
tent is less than 10 wt% of the dry mass of algae and the chemical
composition of the matrix as well as the ratios between the con-
stituents greatly vary within the species.
Two main approaches in using algae in composites have been
reported: rst, as llers (not treated, only milled and pulverised)
Corresponding author. Tel.: +33 (0)4 93 95 74 70.
E-mail addresses: mindaugas.bulota@mines-paristech.fr (M. Bulota), tatiana.
budtova@mines-paristech.fr (T. Budtova).
1
Tel.: +33 (0)4 93 95 74 81.
with the goal to decrease both the price and carbon footprint of
polymer and utilise algae waste [1,510] and second, as reinforcing
bres (treated, usually bleached, to keep mainly cellulosic bres
and remove soluble compounds) [1113]. For example, bleached
red algae was melt-mixed with poly(lactic) acid (PLA) and
polypropylene [11] and poly(butylene succinate) [12] resulting in
their improved mechanical properties and the coefcient of ther-
mal expansion. However, the bleaching process is rather laborious
and the yield is low. The benets of using treated algae in polymer
composites are not compensating the additional costs which are
required during bleaching.
Chiellini and co-workers used algae as llers and prepared
poly(vinyl) alcohol (PVA) composites, via lm casting, with green
algae Ulva armoricana powder [1] and steam exploded Zostera mar-
ina [5]. The biodegradability in both cases has been improved. The
addition of Ulva powder up to 30 wt% with particle dimensions
below 150 lm led to the improved mechanical properties of
PVA; above this concentration the cohesion of composites was
poor. The mechanical properties of hybrid composites using
Zostera steam exploded algae were improved only in the presence
of additives such as starch and glycerol [5]. PLA/Zostera composites
were very brittle, hence the highest content of algae was 20 wt%
[5]. Signicantly improved modulus and oxygen barrier properties
of PVA were reported upon the addition of 10 lm size of Zostera
akes [14]. The Youngs modulus of various grades of Mater-Bi,
poly(e-caprolactone) and polyhydroxybutyrate was improved with
the addition of Ulva armoricana particles of 50100 lm [7] and
algae from Sardinia beaches (not specied) [6]. Green algae
(Cladophora) bres, having average length of around 600 lm, have
also been successfully used in the preparation of isocyanate based

http://dx.doi.org/10.1016/j.compositesa.2015.03.001
1359-835X/ 2015 Elsevier Ltd. All rights reserved.
110 M. Bulota, T. Budtova / Composites: Part A 73 (2015) 109115
foams [8]. The notion of algae as ller for thermoplastics has been
also exhibited through international patents [9,10].
The goal of this work was to perform a comprehensive com-
parative study of the morphology and properties of composites
blended with three types of algae, red, brown and green. PLA was
chosen to keep 100% biobased nature of composites. The basic
building block of PLA is lactic acid which is usually produced by
carbohydrate fermentation. Often corn or potato starch is used as
a source of carbohydrates thus rendering PLA fully bio-based poly-
mer. No algae treatment was performed except sieving and select-
ing two populations of particles sizes, below 50 lm and from 200
to 400 lm. All composites were prepared in the same way, via melt
mixing, allowing an adequate comparison between algae types.
First, we characterised the initial algae: we analysed particle size
distribution, their surface morphology and chemical composition
together with bulk algae composition and crystallinity. Then we
performed tensile testing of composites and compared the evolu-
tion of mechanical properties as a function of algae type, concen-
tration and particles size.
2. Materials and methods
2.1. Materials
PLA 3051D produced by NatureWorks (USA) and provided by
Natureplast (France) has been used as matrix. It has melting tem-
perature of around 150165 C, glass transition temperature of 55
65 C and density of 1.25 g/cm3, as provided by the manufacturer.
The composition of this PLA sample is L- and D-lactide in proportion
96% and 4%, respectively. The average molecular weight is
1.6  104 [15].
Three types of algae, green, red and brown, were used as ller.
Algae were collected in the Northwest coast of France in the North
Sea and provided by Universit de Bretagne Occidentale
(University of West Brittany, Brest, France). Algae were dried,
ground and then sieved using standard (ISO 3310-1) sieves from
Retsch GmbH (Germany) prior mixing with polymer matrix. Two
families of sizes were selected: small particles with the largest size
below 50 lm and large particles of 200400 lm.
2.2. Composites preparation
All ingredients were dried in a vacuum oven at 80 C overnight
before mixing; thus moisture content of both algae akes and poly-
mer during processing was close to 0%. Internal mixer Haake
Rheomix 600 (Thermo Fischer Scientic, Germany) was used to
mix PLA and algae at 180 C with rotation speed of 75 rpm for
6 min. Composites with 2, 20 and 40 wt% of algae were prepared.
In total 40 g of material (polymer + ller) was mixed to prepare
one formulation. Neat PLA underwent the same thermomechanical
history as that of composites. All samples were ground in a
Hellweg M50/80 (Hellweg Maschinenbau GmbH, Germany) grin-
der to obtain granules of approximately 13 mm in diameter.
2.3. Mechanical testing
Dumbbell shape bars of 75 mm in the overall length, 2 mm
thick, 10 mm in width at the ends and 5 mm in width at the nar-
row parallel-sided portion were prepared according to ISO 527
(shape 1BA) standard using injection moulding machine Haake
Minijet II (Thermo Fischer Scientic, Germany) using injection
and holding pressure of 400 bar and 300 bar, respectively. Both
injection and holding time was 10 s. Samples were melted at
180 C for 5 min prior injection.
Tensile tests were carried out on a tensile testing machine Zwick
(Zwick GmbH, Germany) Z 2.5 equipped with a 2.0 kN load cell
according to ISO 527 with the testing speed of 1.2 mm/min. All
the samples were conditioned for at least 72 h prior the testing in
controlled environment (23 C, 50% RH). At least 5 samples of each
formulation were tested. The errors were around 4% for the Youngs
modulus, 2% for tensile strength and 9% for the strain at break. The
mechanical characteristics are discussed taking into account the
statistical signicance of 95%.
2.4. Thermogravimetric analysis (TGA)
TGA was performed by Arkema, Cerdato, France and carried out
using Netzsch TG 209F1 (Netzsch GmbH, Germany) analyser. Each
sample was heated from 25 C to 550 C at a heating rate of 10 C/
min under nitrogen ow.
2.5. Scanning electron microscopy (SEM) and energy dispersive
spectroscopy (EDS)
Samples were platinum sputtered in a sputter coater Quorum
Q150T ES (Quorum Technologies Ltd, UK) to obtain a layer of about
7 nm prior the imaging. SEM Supra 40 (Carl Zeiss AG, Germany)
was operating at accelerating voltage of 3 kV. EDS was carried
out using SEM XL 30 (Philips, The Netherlands) coupled with EDS
detector and operating at a voltage of 15 kV; no coating was made.
The weight fraction of chemical elements was averaged from at
least 5 specimens.
2.6. Optical microscopy
Optical microscope Leica DM 4500 P (Leica microsystems
GmbH, Germany) operating in transmission mode and coupled
with Archimed 4.2 software (Microvision Instruments, France)
was used to analyse the surface area of algae particles before and
after processing (mixing followed by injection). Algae were oven
dried at 80 C in vacuum prior the measurements. For each for-
mulation at least 200 algae particles were analysed. The surface
area distribution of algae particles in a composite after the process-
ing was measured by dissolving PLA in chloroform, casting the dis-
persion of particles on a microscope glass slide and evaporating the
solvent.
2.7. Fourier transform infrared spectroscopy (FT-IR)
FT-IR spectra of dry samples have been acquired with a Tensor
27 (Bruker Optics Inc., MN, USA) spectrometer operating in the
range from 400 cm 1 to 4000 cm 1. The baseline correction was
done using built-in software.
2.8. X-ray diffraction (XRD)
XRD measurements have been carried out using Siemens D500
(Siemens AG, Germany) X-ray diffractometer with Cu Ka source
operating at a wavelength of 1.54 nm. Data have been collected
at the scattering angle (2h) between 5 and 60 at incremental step
of 0.1, and step acquisition time was 128 s. The data were ltered
using Fourier transforms and peak tting (Gausian).
3. Results and discussion
3.1. Characterisation of algae
The thermal behaviour of algae used is shown in Fig. 1. The rst
mass loss occurs for all types of algae around 60 C and can be
 M. Bulota, T. Budtova / Composites: Part A 73 (2015) 109115 111

100 with polymer matrix and hence affects matrixller interactions.

Red
Furthermore, it may induce chemical reactions in the matrix itself:
90
Green for example, transition metals, such as iron, zinc or copper, can
80 react with PLA upon heating and result in chain scission due to
70 Brown transesterication [18]. EDS was carried out in order to elucidate
the composition of the matter present on the surface of algae
Weight (%)

60 100
50 90
40 80
30 70
20 60
150 200 250 300
10
0
0 100 200 300 400
Temperature (C)
Fig. 1. TGA for green, brown and red algae akes of 200400 lm. Inset: zoom at the
temperature interval corresponding to the highest mass loss.
associated with the degradation of chlorophyll as it is known to
degrade at temperatures as low as 60 C [16]; the following mass
loss is due to water evaporation. Hemicelluloses and cellulose start
degrading at about 220 C and 315 C, respectively [17]. Thus the
inection points at temperatures 209, 218 and 230 C,
corresponding to green, brown and red algae, could be linked with
the degradation of hemicelluloses (see inset of Fig. 1). The incline
of the mass loss curve of red algae in a range of 200250 C is stee-
per than that of green and brown algae, indicating different chemi-
cal composition, and hence faster degradation kinetics. The residue
of inorganic matter in algae varies around 4550 wt%, due to high
content of salts and other impurities as also reported in the litera-
ture [10,11].
Optical micrograph (Fig. 2) shows a representative example of
initial red algae large particles of 200400 lm after sieving.
Brown and green algae are of very similar shapes, see Fig. S1 in
Supporting Information. Algae are in the form of at brittle akes.
Particle size distribution before and after compounding will be dis-
cussed in the section on composite properties.
The surface of algae particles is shown in SEM micrographs, Fig. 3,
which also depicts ake-like layered morphology of algae. Algae
ake surfaces are covered with crystals (insets of Fig. 3a and b)
which are inorganic compounds as it will be shown with EDS analy-
ses below. Contrary to the brown and green algae, barely any crystal
can be seen on the surface of the red ones (Fig. 3c).
The presence of various contaminants (inorganic compo-
nents) on the surface of algae is important as it is in direct contact
akes; carbon, hydrogen and oxygen are not shown in order to
focus on the composition of inorganic components only. Fig. 4
shows that various elements, mostly metals, are present on the
surface of algae. EDS analysis exhibited the presence of various ele-
ments on the surface of red algae also, but in smaller amount:
around 48 wt% versus 54 and 75 wt% for green and brown
algae, respectively. The most abundant elements are potassium
(K), chlorine (Cl), sulphur (S), sodium (Na), calcium (Ca) and nitro-
gen (N), as Fig. 4 shows. Some smaller amounts of magnesium
500
(Mg), phosphor (P) and tiny fractions of silicon (Si), aluminium
(Al) and iron (Fe) were also found.
FTIR spectra were recorded from green, brown and red algae
(Fig. 5) since the composition may inuence the mechanical prop-
erties of the composite. The chemical composition of algae varies
with respect to type and, in general, with other aspects such as cli-
mate conditions [2]. A signicant part of algae consist of hemi-
celluloses (Fig. 5): the absorption bands at 1055 cm 1 and
1026 cm 1 correspond to rhamnose and to a glucan, respec-
tively. The band at 1084 cm 1 could be associated with CAC
vibrations in starch. The broadening of the green algae spectrum
at 1120 cm 1 arises from the CAOAC vibrations in cellulose [19].
The sulphated groups are known to be at 800850 cm 1,
1250 cm 1 and 1370 cm 1 [20]. Amines NAH stretch is manifested
as vibrations at 3350 and 3450 cm 1, they are present in green
and red algae but missing in brown. Similarly, a band at
1540 cm 1 which corresponds to NAH bending [21] is not pre-
sent for brown algae but is detected in red and green. This corre-
lates well with the results found in EDS analysis which shows
higher amount of nitrogen in red and green algae than in brown.
Carboxylic groups corresponding to the wavenumber of 1600
1690 cm 1 are present in all cases. A distinct broad band in the
spectrum of red algae is visible at 12301250 cm 1 which can
be linked with P@O [20] and S@O [22], the latest could be asso-
ciated with sulfonate groups which are present in carrageenan of
red algae. In overall, IR spectra shows that green and brown algae
are similar in terms of composition, while red algae have some
distinct differences which correlates well with the literature
[24,23].
XRD spectra were recorded to scrutinize the structure of algae
akes, Fig. 6. A number of peaks correspond to various salt crystals
which are present on the surface of akes (see also Fig. 1). Peaks
are visible for both green and brown algae, Fig. 6; however, red
algae showed no peaks and thus no spectra are shown.
Although it has been reported in the literature that red algae
contain crystalline cellulose imbedded in an amorphous matrix,
it was not detected in this study probably due to low content
and low packing of brils [24]. Peaks located at 2h (1 1  0) 14.8
and 2h (2 0 0) 22.2 can be associated with cellulose I [25]. The
intensity of the peaks is rather weak since the amount of cellulose
in algae is relatively low, i.e. 57% [2]. In overall, brown and green
algae exhibit similar diffraction patterns supporting the idea of
having similar structure and similar mineral salts. This also agrees
with the ndings from FT-IR spectra, Fig. 5.

3.2. Algae size evolution, morphology and degradation behaviour in

200 m composites

Optical microscopy was used to analyse the size of algae akes

Fig. 2. Optical micrograph of red algae akes of 200400 lm after sieving. in injected composites and compare with the initial dimensions of
112 M. Bulota, T. Budtova / Composites: Part A 73 (2015) 109115

Fig. 3. SEM micrographs of algae akes: (a) green (200400 lm), (b) brown (<50 lm), (c) red (200400 lm).

~28.5
100% Brown algae
3.2 N 4.7 N
90%
1.0 Fe 0.6
4.4 Green algae
14.1
7.4 Ca 7.8 Fe ~40.7
80% 0.8 Si
0.5 Al 2.3 Ca

Intensity (a.u.)
1.4
4.6 Na 4.4
70% 5.6 0.2 0.3
4.3 Mg Si
7.9

~20.5
60% 3.4 P Al
2.3 ~9.8

~22.2

~36.2
~24.8

~31.8
50% 28,2
2.2
Na
~50.3
11.1 S ~14.8 ~45.7 ~58.6
40% 15.6 Mg
30% 10.2 Cl P ~19.8
~9.5
~11.8
20% 7.8 S
24.1
10% 11.3 Cl 5 10 15 20 25 30 35 40 45 50 55 60
K 7.8
0% K Angle 2
Green Brown Red Fig. 6. XRD patterns of green and brown algae (Gaussian tting).

Fig. 4. The composition of inorganic compounds on the surface of green, brown and
red algae resulting from EDS analysis. The elements are depicted in the same order
in each column. Numbers correspond to the weight per cent fraction calculated
towards the total value of inorganic compounds. (For interpretation of the Table 1
references to colour in this gure legend, the reader is referred to the web version The surface area (lm2) of green algae akes in 20 wt% composite prior and after
of this article.) injection.

Range of initial sizes <50 lm 200400 lm

after sieving
Initial After injection Initial After injection
green algae ~1084 ~1055 Maximal 3170 2156 307,380 19,057
brown algae ~1120 ~1026 Average 582 239 8390 1252
Arbitrary units (a. u.)

red algae
~1620-1640

maximum value was taken as the surface area of a largest ake

~1453
~1546

~930
~1378

measured and the mean value was calculated as an arithmetic

~844
~891

average.
In both cases, the initial size of surface area decreased after
~1149 processing due to mechanical stresses acting upon ller, similarly
~1227
~1416

to what has been observed for natural bres [26,27]. An addi-

1800 1600 1400
Wavenumber (cm-1)
Fig. 5. FT-IR spectra of green, brown and red algae.
algae. Since algae particles have irregular geometrical shape
(Fig. 2), their surface area was measured. An example for 20 wt%
green algae/PLA composite is shown in Table 1 for two initial sizes
of akes and detailed size distribution of the initial particles and
after processing is shown in Supporting Information, Fig. S2. The
tional reason of particles breakage is their weakening because
of chlorophyll degradation starting at low temperature (Fig. 1).
The difference in average particle surface area between the two
1200 1000 800
groups prior mixing was approximately 14 times, after processing
it decreased to 5. Larger akes tend to break more during pro-
cessing. The average surface area decreased by 2.5 and 6.7 times
for the initial akes with the size below 50 lm and between 200
and 400 lm akes, respectively. If roughly approximating an
algae ake by a disc, then an average equivalent radius would
decrease from 27 to 17 lm for the initial akes with the size
below 50 lm and from 103 to 40 lm for the initial akes of
200400 lm.
An example of a cross-section of a 20 wt% green algae/PLA com-
posite with initial particle size below 50 lm is presented in Fig. 7a
 M. Bulota, T. Budtova / Composites: Part A 73 (2015) 109115 113

a b

100 m 10 m

Fig. 7. SEM micrographs of fracture surface of green algae/PLA composites with the initial particle size below 50 lm: (a) with 20 wt% algae; (b) zoom on particle with 2 wt%
algae.

together with a zoom on one particle in 2 wt% green algae/PLA temperatures in composites can be seen in Fig. 8: it corresponds
composite (Fig. 7b). Very similar fracture modes were recorded to the inorganic salts present in algae in large quantities and corre-
for composites with red and brown algae; an example of fracture sponds well to algae TGA results (Fig. 1).
of 40% red algae/PLA composite with the initial particle size 200
400 lm is shown in Supporting Information, Fig. S3. PLA shows
3.3. Composite mechanical properties
brittle fracture. The matrix distortion after removal of an algal ake
is minor and a gap between ller particle and matrix can be
The results of tensile testing are presented in Fig. 9a and b for
observed implying poor llermatrix adhesion. This could be a
composites prepared from algae with the initial particle size below
result of incompatibility of the hydrophilic ller and the hydropho-
50 lm. A constant decrease in tensile strength can be observed
bic matrix as well as the presence of various inorganic salts on the
upon every addition of algae akes and at 40 wt% load it
surface of algae akes as demonstrated earlier. Some pull-outs can
reaches about half of the neat PLA value. The Youngs modulus
be observed (Fig. 7a). One of the ways of improving the adhesion
decreases at 2 wt% of algae, remains the same for 20 wt% compos-
between algae akes and polymer matrix could consist of remov-
ites and increases at 40 wt% reaching the same or slightly
ing salts from algae surface by the appropriate chemical treatment.
higher than neat PLA value, suggesting the presence of
The balance between the potential gain in composite mechanical
percolated system above 20 wt% of ller (compare Figs. 7a and S3
properties and the increase of the price because of the additional
in Supporting Information). The percolation threshold for the algae
treatment has to be studied.
composites studied should be high due low aspect ratio. Strain at
Composite degradation behaviour is affected by the addition of
break increases at low algae concentration (2 wt%) but then
algae akes as demonstrated in Fig. 8. Neat PLA starts degrading at
decreases substantially and equals less than 50% of neat PLA value.
approximately 337 C, while the main degradation of algae com-
Similar behaviour has been also observed for composites with
posites occurs at lower temperatures: 298, 317 and 327 C for
Zostera algae dispersed in PVA [5]. The increase of strain at break
20 wt% loads of brown, green and red algae, respectively. The com-
could be due to the presence of very small particles that act as local
posites with red algae are slightly more thermally stable as com-
stress concentrates. For the case of small particles, the values and
pared with green and brown ones. The beginning of mass loss in
trends obtained practically do not depend on algae type; small dis-
composites can be detected around 180 C which corresponds to
crepancies seen are practically within the experimental errors.
the degradation of algae as shown in Fig. 1. Contrary to the neat
Composites prepared with algae akes of larger initial size,
PLA, 1012% of residual weight still remaining at high
200400 lm, Fig. 9c and d, showed similar trends for red and
brown algae as compared to composites with smaller akes.
Several differences can be detected for green algae composites.
100 First, contrary to the composites with small akes, Fig. 9a, the
90 Youngs modulus of composites with large green algae particles
does not decrease with the increase of ller concentration while
80 PLA with red and brown it does, for both initial sizes, Fig. 9c. Second,
70 Youngs modulus with 40 wt% of green algae is higher than that
with red and with brown and is also higher than those with small
Weight (%)

60 20 wt% particles. The reason could be partially associated with higher crys-
50 Green talline cellulose content in green algae [24,23]. Third, while strain
at break decreases at higher weight fractions for all types of com-
40
20 wt% posites, it increased at 2 wt% load for small akes.
30 Brown Overall, the addition of algae akes resulted in a decrease of
tensile strength in all cases from 65 MPa of neat PLA to around
20
20 wt% 30 MPa at 40 wt% of ller irrespectively to the algae type or parti-
10 Red cle size. For all composite formulations except green algae, the
0 Youngs modulus at 40 wt% load reaches approximately the same
0 100 200 300 400 500 value as that of neat PLA, i.e. around 2.6 MPa; with 40 wt% large
green algae akes Youngs modulus exceed that of neat PLA by
Temperature (C)
circa 25%. The main governing factor of the mechanical properties
Fig. 8. TGA curves of 20 wt% algae/PLA composites, initial size of akes was is the weight fraction of ller, and to some extent, the size of
200400 lm. particles.
114 M. Bulota, T. Budtova / Composites: Part A 73 (2015) 109115
Fig. 9. The mechanical properties of algae/PLA composites with the initial size of particles (a) and (b) below 50 lm and (c), (d) between 200 and 400 lm. Columns represent
tensile strength; Youngs modulus and strain at break are shown as points.
4. Conclusions
Biocomposites with different types of algae as ller have been
prepared by melt mixing with PLA. The mechanical behaviour of
injected composites was investigated as a function of the type of
algae (green, red and brown), their concentration (from 0 to
40 wt%) and the initial size of the particles. We demonstrated that
algae particles have a ake-like structure and contain a large
amount of inorganic substances (45 wt%), mainly present as
mineral crystals on the surface. Algae hydrophilicity and inorganic
substances on their surface resulted in poor adhesion between the
ller and the matrix. All studied algae akes break during the pro-
cessing: large particles break more than the small ones, however,
in the conditions used the difference between the initially large
and small particles remained in injected composites.
The difference in structure and composition with respect to
algae type cannot be fully exploited due to poor llermatrix inter-
actions, i.e. poor stress transfer. In overall, except for the compos-
ites with large green algae particles, all tensile mechanical
characteristics of composites decreased with the increase of algae
concentration. Larger particles resulted in slightly better mechani-
cal properties as compared with the smaller ones, and the Youngs
modulus of composites with 40 wt% large green algae particles
exceeded that of the neat PLA. The results obtained show that
depending on the application, algae can be used as ller in
thermoplastic composites up to at least 40 wt% loading, since the
stiffness of materials can be maintained. Further work should focus
on the improvement of adhesion between ller and matrix, conse-
quently tailoring of the algae type and particle size in order to opti-
mise composite mechanical performance.
Acknowledgments
The work has been performed within the frame of the Industrial
Chair in Bioplastics, organised by CEMEF/Mines ParisTech and
supported by Arkema, LOreal, Nestl, PSA and Schneider Electric.
We are grateful to prof. E. Desland, Universit de Bretagne
Occidentale, Brest, France, for providing algae and Arkema,
Cerdato, France for carrying out TGA characterisation.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.compositesa.
2015.03.001.
References
[1] Chiellini E, Cinelli P, Ilieva VI, Martera M. Biodegradable thermoplastic
composites based on polyvinyl alcohol and algae. Biomacromolecules
2008;9(3):100713.
[2] Hoek C, Mann D, Jahns HM. Algae: an introduction to phycology. Cambridge
University Press; 1995.
[3] Graham LE, Graham JM, Wilcox LW. Algae. Benjamin-Cummings Publishing
Company; 2009.
 M. Bulota, T. Budtova / Composites: Part A 73 (2015) 109115
[4] Dodge JD. The ne structure of algal cells. Elsevier Science; 2012.
[5] Chiellini E, Cinelli P, Ilieva VI, Zimbardi F, Kanellopoulos N, Wilde B, et al.
Hybrid composites based on bres of marine origin. Int J Mater Prod Technol
2009;36(14):4761.
[6] Iannace S, Nocilla G, Nicolais L. Biocomposites based on sea algae bers and
biodegradable thermoplastic matrices. J Appl Polym Sci 1999;73(4):58392.
[7] Barghini A, Ivanova VI, Imam SH, Chiellini E. Poly-(e-caprolactone) (PCL) and
poly(hydroxy-butyrate) (PHB) blends containing seaweed bers: morphology
and thermal-mechanical properties. J Polym Sci, Part A: Polym Chem 2010;
48(23):52828.
[8] Johnson M, Shivkumar S. Filamentous green algae additions to isocyanate
based foams. J Appl Polym Sci 2004;93(5):246977.
[9] Shi B, Wang JH. Algae-blended compositions for thermoplastic articles.
EP2424937A2, 2013.
[10] Han SO, Kim HS, Yoo YJ, Seo YB, Lee MW. Seaweed ber-reinforced
biocomposite and method for producing the same using high-temperature
grinding. EP2079794A1, 2012.
[11] Sim K, Han S, Seo Y. Dynamic mechanical and thermal properties of red algae
ber reinforced poly(lactic acid) biocomposites. Macromol Res 2010;18(5):
48995.
[12] Lee MW, Han SO, Seo YB. Red algae bre/poly(butylene succinate)
biocomposites: the effect of bre content on their mechanical and thermal
properties. Compos Sci Technol 2008;68(6):126672.
[13] Ferrero B, Fombuena V, Fenollar O, Boronat T, Balart R. Development of natural
ber-reinforced plastics (NFRP) based on biobased polyethylene and waste
bers from Posidonia oceanica seaweed. Polym Compos 2014. http://
dx.doi.org/10.1002/pc.23042.
[14] Sapalidis AA, Katsaros FK, Romanos GE, Kakizis NK, Kanellopoulos NK.
Preparation and characterization of novel poly-(vinyl alcohol)Zostera akes
composites for packaging applications. Composites, Part B 2007;38(3):
398404.
[15] Modi S, Koelling K, Vodovotz Y. Miscibility of poly(3-hydroxybutyrate-co-3-
hydroxyvalerate) with high molecular weight poly(lactic acid) blends
determined by thermal analysis. J Appl Polym Sci 2012;124(4):307481.
115
[16] Weemaes CA, Ooms V, Van Loey AM, Hendrickx ME. Kinetics of chlorophyll
degradation and color loss in heated broccoli juice. J Agric Food Chem 1999;
47:24049.
[17] Yang H, Yan R, Chen H, Lee DH, Zheng C. Characteristics of hemicellulose,
cellulose and lignin pyrolysis. Fuel 2007;86:17818.
[18] Cam D, Marucci M. Inuence of residual monomers and metals on poly (L-
lactide) thermal stability. Polymer 1997;38(9):187984.
[19] Kacurakova M, Capek P, Sasinkova V. FT-IR study of plant cell wall model
compounds: pectic polysaccharides and hemicelluloses. Carbohydr Polym
2000;43(2):195203.
[20] Rochas C, Lahaye M, YaphSulfate W. Content of carrageenan and agar
determined by infrared spectroscopy. Botanica Marina 1986;29(4):335.
[21] Murdock JN, Wetzel DL. FT-IR microspectroscopy enhances biological and
ecological analysis of algae. Appl Spectrosc Rev 2009;44(4):33561.
[22] Sekkal M, Legrand P, Huvenne JP, Verdus MC. The use of FTIR
microspectrometry as a new tool for the identication in situ of
polygalactanes in red seaweeds. J Mol Struct 1993;294:22730.
[23] Percival E, McDowell RH. Algal walls composition and biosynthesis. In:
Tanner W, Loewus F, editors. Plant Carbohydrates II SE 12, vol. 13/B. Berlin
Heidelberg: Springer; 1981. p. 277316.
[24] Tsekos I, Reiss H-D. Occurrence of the putative microbril-synthesizing
complexes (linear terminal complexes) in the plasma membrane of the
epiphytic marine red alga Erythrocladia subintegra Rosenv. Protoplasma
1992;169:5767.
[25] Poletto M, Pistor V, Zattera AJ. Structural characteristics and thermal
properties of native cellulose. In: Van de Ven T, Gdbout L, editors. Cellulose-
fundamental aspects. InTech; 2013. p. 4568.
[26] Le Moigne N, van den Oever M, Budtova T. A statistical analysis of bre size
and shape distribution after compounding in composites reinforced by natural
bres. Composites, Part A 2011;42(10):154250.
[27] Le Duc A, Vergnes B, Budtova T. Polypropylene/natural bres composites:
analysis of bre dimensions after compounding and observations of bre
rupture by rheo-optics. Composites, Part A 2011;42(11):172737.