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The Effect of Marine Sediments on the

Mechanical Properties and Thermal Stability of
Proteinic Biopolymer

AQ6 Ines Zarrad,1,2 Nicolas Montrelay,1 Justin Houessou,1 Rose-Marie Dheilly,1 Jamel Bouaziz,2
AQ1 Michèle Queneudec1
1
University of Picardie Jules Verne, SFR Condorcet CNRS 3417, Research Unit EPROAD, EA 4669,
Engineering of Materials and Process (IMaP), 80000 Amiens, France

2
University of Sfax, Ecole Nationale d’Ingenieurs de Sfax, Laboratoire Chimie Industrielle Il, BP 1173, Sfax,
Tunisia

This article focuses on the valorization of marine sedi-
ments (MS) in proteinic biopolymer (HE) that will gener-
ate HEMS biocomposites. These biocomposites were
developed with various percentages of marine sedi-
ments (0, 5, 15, and 20%) and characterized. Mechanical
properties were examined as a function of the contents
of used marine sediments. The flexural and compressive
modulus increase with the rise of the MS percentage in
the composite. The compressive strength increases
while the flexural and tensile strengths decrease. Fur-
thermore, the HEMS composite was characterized using
Fourier transform infrared spectroscopy and by using
scanning electron microscopy. And the thermal degra-
dation behavior of the composite was investigated by
thermogravimetric analysis coupled with differential
scanning calorimetry. POLYM. COMPOS., 00:000–000, 2015.
C 2015 Society of Plastics Engineers
V of composites to understand the evolution of these proper-
INTRODUCTION
Over the last few years, numerous research projects
have focused on material recovery in the context of sus-
tainable development. The growing demand to substitute
petroleum-based products has increased the focus on bio-
based resources among which biopolymers which are
gaining increasing popularity [1]. Indeed the increase in
fossil energy costs and the environmental concerns have
resulted in new opportunities for the industrial production
of the biodegradable materials based on natural renewable
resources [2]. In addition, the use of biopolymer can
solve the waste disposal problem to a certain extent. Such
biopolymers include those derived from naturally pro-
duced protein, cellulose, starches and other polysaccha-
Correspondence to: Ines Zarrad; e-mail: inesss_zarrad@yahoo.fr
DOI 10.1002/pc.23730
Published online in Wiley Online Library (wileyonlinelibrary.com).
C 2015 Society of Plastics Engineers
V and their particle sizes ranges from 0,08 to 2000 mm. The
rides as well as those synthesized chemically from
naturally derived monomers [3]. The incorporation of an
inorganic filler into an organic matrix leads to the modifi-
cation of strengths and stiffness [4], and to the increase
of physical and thermal properties too [5]. Previous works
show that the incorporation of marine sediments as inor-
ganic fillers in a matrix derived from hemoglobin protein
effectively improved the stiffness, compressive strength
and thermal properties (TGA) of the HEMS biocomposite
[6]. However, the tensile and flexural strengths decreased.
A multiphase model has been developed, which is able to
reproduce the compressive behavior of HEMS [6].
It was necessary to study the morphological properties
ties. The primary purpose of this research is to establish
the correlation between Fourier transform infrared spec-
troscopy (FTIR), the mechanical properties of the compo-
sites and their microstructure. The thermal properties
were also investigated by thermogravimetric analysis
coupled with differential scanning calorimetry (TGA/
DSC) to show the effect of marine sediments on the ther-
mal stability of HEMS biocomposites and to study the
mechanism of their thermal degradation.
EXPERIMENTAL
Materials
In this work, in order to elaborate the biosourced
matrix, a protein of atomized beef blood has been used. It
was obtained from the French company “Vapran” (vepro
95 BHF). Its bulk density is about 1370 kg/m3. The
marine sediments used in this study are extracted from
Dunkirk Harbour. Their bulk density is about 2780 kg/m3

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HESM biocomposite was produced by using the thermo-

compression process reported in previous research [6].
Samples of composites were prepared by adding various
amounts (0, 5, 15, and 20%) of (MS) marine sediments.
The names of these composites are, respectively, HESM
0, HESM 5, HESM 15, and HESM 20%.

Mechanical Testing
Tensile Testing. The tensile experiments were carried
out using ISO 527-1 on a Shimadzu AGX tensile testing
machine with an extensometer type SSG50-
10SHIMADZU. Trapezium software was used for the
machine control and data acquisition. Tensile tests were
performed at a constant cross-head speed of 2 mm/min.
FIG. 1. FTIR of Marine sediment (MS), Protein, HEMS 0% and
Three point Bending Testing. Flexural properties of HEMS 15%. [Color figure can be viewed in the online issue, which is
available at wileyonlinelibrary.com.]
composites were measured by ISO 14125 at a cross-head
speed of 3 mm/min using the same machine as for the Fourier Transform Infrared Spectroscopy (FTIR) Analysis
tensile tests.
FT-IR spectra of marine sediments, protein, pure bio-
polymer, and HESM composites were recorded in the
Compressive Tests. Compressive tests were conducted wave number range of 648–4000 cm21 using FTIR Ana-
using WDW-10E Microcomputer-controlled electronic lyser (Pestige 21 Shimadzu) with a spectral resolution of
universal testing at a cross-head speed of 3 mm/min. 4 cm21 and scan times of 100. FTIR analysis requires the
mixing of 1 mg of composite with 100 mg of KBr.
Hardness. The Hardness test of the composites was
done with Hardmatic Mitutoyo shore D long leg type.
Thermal Analysis
The hardness measurement can determine the relative
resistance that opposes a surface to the penetration of a The TGA/DSC measurement was conducted by using
cone with a rounded tip (D scale). a SETERAM Ligne 96 TGA apparatus to investigate the

FIG. 2. Scanning electron microscope of marine sediments.

2 POLYMER COMPOSITES—2015 DOI 10.1002/pc

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TABLE 1. Mechanical test results of HESM composites as a function of MS percentage.

MS Tensile Young’s Flexural Flexural Compressive Compressive

Percentage Strength (MPa) modulus (MPa) strength (MPa) modulus (MPa) yield stress (MPa) modulus (MPa) Hardness

0 13,9 6 2,3 1600 6 61 30,61 6 4,24 1402 6 110 32 6 2,82 667 6 61 60 6 2

5 8,14 6 2,52 1450 6 164 19,16 6 1,3 1625 6 41 32,055 6 1,25 773,80 6 84 63,33 6 0,57
15 7,04 6 1,71 1580 6 125 19,19 6 1,21 1619 6 131 38,66 6 4,71 953,79 6 45 69,66 6 1,52
20 3,21 6 1,27 2120 6 296 16,47 6 1,22 1805 6 55 36,43 6 0,32 954,54 6 64 73 6 2

thermal degradation behavior. Samples were heated from
25 to 8008C at a heating rate of 108C/min and under a
helium flow at 80 ml/min.
Scanning Electron Microscopy
The morphology of various samples, which were
obtained after flexural tests, was studied by means of scan-
ning electron microscopy. To make observation easier, the
samples were initially dried and then covered with a thin
layer of vacuum-sputtered gold, which acted as a conductor.
Micrographs were derived using a PHILIPS FEG XL 30
microscope, which exhibited the particularity of being
coupled to an X-ray spectrometer; this set-up enabled, by
means of EDX analysis, determining the atomic composi-
tion of a sample.
RESULTS AND DISCUSSION
Fourier Transform Infrared Spectroscopy (FTIR) Analysis
F1 Figure 1 shows the FTIR spectra of samples of the
marine sediment, the protein, the HE biopolymer and
HEMS 5% and HESM 15% biocomposites.
Marine sediments (MS) have a complex composition
F2 as shown in Fig. 2. They contain clays (smectite, illite,
kaolinite, and chlorite) and quartz [7].
The MS spectrum shows characteristic peaks 1078,
1029, and 1008 cm21 due to the SiO stretching of Kaolin-
ite and Montmorillonite (MMT). The anti symmetric
FIG. 3. Scanning electron microscope of HEMS 15% composite
(1003).
stretching of these groups are assigned to bands at 1032
and 1008 cm21 [8–10]. The 690 cm21 peak is due to SiO
perpendicular deformation [8]. The 3616 cm21 peak
belongs to OAH stretching of the inner hydroxyl related to
kaolinite and MMT [8, 10]. The 3693 cm21 peak is attrib-
uted to the stretching vibration mode of inner surface
hydroxyls located at the surface of octahedral oxygen of
the adjacent kaolinite layer [11]. The 3437 cm21 band and
the 1645 cm21 peak are due to HAOH bending [12]. The
peaks observed at 910 and 792 cm211 are due to the bend-
ing and translation modes of inner surface hydroxyls of
kaolinite [8]. The peaks observed at 792, 690, 775, and
1078 cm21 can be attributed to quartz [13]. The bands
observed at 1427 and 871 cm21 are attributed to asymmet-
ric stretching of CO22
3 [14]. The peaks observed at 2953,
2920, and 2850 cm21 are attributed to CAH stretching.
The symmetric stretching of CH2 is assigned to the peak at
2850 cm21, while the antisymmetric stretching of CH3 and
CH2 are assigned to peaks at 2953 and 2920 cm21, respec-
tively. While standard HE biopolymer shows a band at
1616–1693 cm21 This band is centred at 1640 cm21 and it
can be attributed to C@O vibration of amide I [2]. The
band at 1489–1570 cm21 is centered at 1542 cm21 and it
is due to NAH bending of amide II[ [2]. The peak
observed at 1400 cm21 belongs to CAN stretching of
amide III [4]. Observed peaks at 667, 692, and 783 cm21
can be attributed to NAH vibration in the polymer [10]. A
broad band observed at 3282–3520 cm21 centred at 3400
cm21 may be attributed to hydrogen bridges between the
oxygen atoms of the carbonyl C@O and the hydrogen
atoms of the amine NAH [15]. The peak observed at 2960
cm21 belongs to CAH stretching [16].
The infrared spectra of HESM biocomposite showed a
shift of band corresponding to hydrogen bridges of 3400
cm21 to 3410, and 3444 cm21 for HEMS 0%, HEMS 5%
and HEMS 15% respectively. In addition, the peak of
AOH at 3616 cm21 disappeared from the spectrum of
HEMS compared to the spectrum of MS. The HAOH
bending band of MS appeared in the spectrum of HEMS
and was broadened.
However, from the infrared spectra of the HEMS bio-
composite, no new chemical bond between (MS) marine
sediments and matrix is observed. Moreover, it is difficult
to deduct from these measurements the complete absence
of those chemical bonds, which can be hidden by the
complexity of infrared spectra of both the marine sedi-
ments and the matrix, which have a large number of func-
tions and linkages in their structure [2].

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FIG. 4. Scanning electron microscope of HEMS 15% (5003).
Mechanical Test Results
The effects of marine sediments contents in the range
of 0, 5, 15, and 20% on the mechanical properties of
T1 HEMS composites are given in Table 1.
It can be seen that when 20% of MS was added, the
young’s modulus increased by 32,5%. The flexural modu-
lus and compressive modulus increase with the addition of
SM too. In fact, increased MS content causes modulus
growth. The presence of 20% of sediments in the compos-
ite causes a modulus increase: 28% for the flexural modu-
lus and 43% for the compressive one respectively. The
modulus improvement can be explained by the hardness of
FIG. 5. Scanning electron micrographs of MS and matrix adhesion in HEMS composites (50003).
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sediment particles which have much higher stiffness values
than the matrix [11, 17, 18] and which are in larger num-
bers and are well dispersed in the matrix (Fig. 3). F3
The compressive strengths of the Composite increases
with the rise of MS too. The addition of 15% MS
improves the compressive strength by about 20%, which
may be explained by the fact that the exerted vertical
load is supported by the matrix and the hardness of the
particles [6, 19]. This may also explain the improvement
of the shore hardness of the composites with the addition
of MS. Contrarily, the tensile strength of the composite
decreases with MS contents. For example the addition of
15% MS in the matrix, results in a decrease of 59 % with
regard to tensile strength of pure HE polymer. This
decrease can be attributed to the existence of defects such
as voids [5, 20]. Indeed, with the increase of filler con-
tents, the size of voids formed when the polymer matrix
becomes detached from the filler particles due to the
deformation will become critically large and may initiate
the main crack [21, 22] (Fig. 4). F4
In addition Fig. 5 shows a slightly good adherence F5
between the matrix and the sediments. A specimen with
5% of substitution reveals a better adhesion with a mini-
mum of voids in the interface between the matrix and the
marine sediments. But with a substitution of about 15 and
20%, SEM micrographs shows, in addition to the increase
of number of interfaces, a weak adherence due to the pres-
ence of several voids in the interface and inside the
DOI 10.1002/pc
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FIG. 6. TGA and DTG curves of neat polymer HEMS 0%. [Color fig-
ure can be viewed in the online issue, which is available at wileyonline-
library.com.]
sediments, which can explain the decrease of the tensile
strength with the rise of marine sediments contents [23].
The adherence observed by using SEM is considered as a
physical adherence due to nature of sediments (clay), char-
acterized by their cohesive properties. Moreover, all inter-
faces observed by using SEM confirm that no chemical
bonds developed between the matrix and the sediments.
As expected, the flexural strength decreased by 37%
when adding 15% MS, which is close to the expected
value of 39% deduced from tensile and compressive
strength, since in the flexural testing the specimen was
induced to uniaxial compression as well as tensile stress,
acting simultaneously in the opposite directions [1]
The Thermal Stability of the Biocomposite
The behaviour of the thermal degradation of the Com-
posites was investigated by using thermogravimetric anal-
FIG. 7. TGA and DTG curves of HEMS 5%. [Color figure can be
viewed in the online issue, which is available at wileyonlinelibrary.com.]
DOI 10.1002/pc
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FIG. 8. TGA and DTG curves of neat polymer HEMS 15%. [Color
figure can be viewed in the online issue, which is available at wileyonli-
nelibrary.com.]
ysis coupled with differential scanning calorimetry (TGA/
DSC). TGA curves and their corresponding DTG curves
of pure biopolymer (HEMS 0%) and of 5 and 15%
HEMS composites are respectively shown in Figs. 6–8. F6 F7
The detailed parameters to evaluate the degradation are F8
listed in Table 2. Three weight losses are observed for T2
the pure polymer and its composites. The first weight loss
is related to the adsorbed ethanol, the second is the onset
degradation of polymer which is related to thermal
decomposition of weak linkages and impurities, and the
third is the decomposition of the HE main chains [3, 16].
The three weight losses occurred at 61, 258, and 3218C in
the pure polymer HE, at 59, 259, and 3218C in the case
of the 5% HEMS biocomposite and at 93, 261, and
3258C in the case of the 15% HEMS biocomposite. It
was found that, compared with pure polymer particles,
the HEMS biocomposite particles exhibited a better ther-
mal stability. Indeed the of total weight loss for neat
polymer, HEMS 5 and HEMS 15% were 75,9, 71,7, and
54%, respectively, instead of 72 and 64,6% (deducted by
linear interpolation based on the total weight losses at
100%) for HEMS 5 and HEMS15% [6]. In addition, the
onset degradation rates of HEMS 0, HEMS5, and HEMS
15% which are 0,05, 0,03, and 0,02% min21 8C21
decrease when the percentages of marine sediments rise
in the mixture. The limitation of degradation rates of
composites compared to the pure polymer can be
explained by impeding the diffusion of gaseous decompo-
sition products [24]. This improvement in the thermal sta-
bility of composites (Polymer and clay) has been reported
in several studies [4, 5].
The heat changes of the pure HE and its composites
HEMS 5% and HEMS15% were tested by TGA/DSC and
DSC curves are shown in Fig. 9. A main endothermic F9
peak appears in the DSC curves of the neat polymer and
its composites. This endothermic peak, corresponding to
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TABLE 2. TGA and DSC results of the biocomposites.
Samples Dm1 Dm2 Dm3 Tmax1
HESM 0% 20,43% 15,20% 40,26% 61
HESM 5% 19,30% 14,13% 38,23% 59
HESM 15% 11,23% 5,80% 37,91% 93
FIG. 9. DSC curves of neat polymer HEMS 0% and biocomposites
HEMS 5% and HEMS 15%. [Color figure can be viewed in the online
issue, which is available at wileyonlinelibrary.com.]
15, 14, and 5.80% mass losses and 15.88, 13.35, and 3.124
mVs/mg decomposition enthalpies for the pure polymer
HE, HEMS 5 and HEMS 15%, respectively, corresponding
to the onset degradation of the composite indicates the
chain scission process via hydrolysis [16]. The decrease of
heat dissipation is due to the introduction of inorganic
compounds into organic material, which improves the ther-
mal stability [12] by impeding the diffusion of gaseous
decomposition products [24]. Multiple endothermic peaks
appear in DSC curves centred at 3218C for both HEMS
0% and HEMS 5% respectively, which can be attributed to
the second composite degradation as a sequential degrada-
tion; but the peaks related to this degradation disappear in
the case of HEMS 15%. This can also be explained by the
presence of the clay particles, which limits the release of
gases from decomposition. The endothermic peak showed
in DSC curves of HEMS 5% and HEMS 15% at 527 and
5628C, respectively, can be attributed to the dehydroxyla-
tion of clays (kaolinite) and to the decomposition of calcite
of marine sediments. Putting all of TGA/DSC results
together demonstrates that the HEMS biocomposite has a
better stability than the pure HE.
CONCLUSION
The biocomposites HESM based on beef hemoglobin
protein and marine sediments (MS) were prepared using
thermo-compression molding. The presence of (MS) phases
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The onset degradation DH
(8C) Tmax1 (8C) Tmax1 (8C) rate (% min218C) (mVs/mg)
258 321 0,05 15,88
259 321 0,03 13,35
262 325 0,02 3,124
in matrix was supported by FTIR and SEM analyses. The
addition of (MS) in the matrix increases the stiffness, hard-
ness and compressive strength of the composite, but the
flexural and tensile strengths decrease. The correlation
between the microstructure and the mechanical behaviour
was investigated. The results showed that when the per-
centage of substitution rises, adhesion becomes weaker due
to the presence of voids on the interface matrix/MS. SEM
micrographs also reveal a good dispersion of marine sedi-
ments in the matrix, which can explain the improvement
of the modulus. (TGA/DSC) showed a significant improve-
ment in the thermal stability of the composite.
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