J Polym Environ (2014) 22:5868

DOI 10.1007/s10924-013-0620-0

ORIGINAL PAPER

Bio-based PolyethyleneLignin Composites Containing

a Pro-oxidant/Pro-degradant Additive: Preparation
and Characterization
Sangram K. Samal E. G. Fernandes
Andrea Corti Emo Chiellini

Published online: 9 November 2013

Springer Science+Business Media New York 2013

Abstract Formulations of low cost bio-based oxo-biodegradable polyethylene (PE)/Lignin hybrid polymeric composites were prepared by using ethylene/vinyl acetate (EVA)
copolymer as compatibilizer and a transition metal salt as
oxo-biodegradation promoter. The hybrid composites and
relevant Lignin-free blends were formulated by following a
statistical mixture design. The effect of Lignin, pro-degradant additive, EVA copolymer and their compatibility with
the PE continuous matrix, was evaluated by means of
structural features by attenuated total reflectance, morphological by scanning electron microscopy, thermal by differential scanning calorimetry and thermo-gravimetric
analysis and mechanical properties by an Instron Machine.
The results attained in this study, regarding especially the
thermal and mechanical properties, suggest that bio-based
oxo-biodegradable hybrid composites offer an interesting
way to produce low cost bio-based materials with fairly

S. K. Samal  E. G. Fernandes  A. Corti  E. Chiellini (&)

Laboratory of Bioactive Polymeric Materials for Biomedical and
Environmental Applications (BIOlab), UdR INSTM, Department
of Chemistry and Industrial Chemistry, University of Pisa, Via
Vecchia Livornese 1291, Loc. San Piero a Grado, 56122 Pisa,
Italy
e-mail: emochie@dcci.unipi.it
S. K. Samal
e-mail: sksamalrec@gmail.com
E. G. Fernandes
e-mail: egrillof@gmail.com
A. Corti
e-mail: mcandrea@dcci.unipi.it
Present Address:
S. K. Samal
Polymer Chemistry and Biomaterials Research Group, Ghent
University, Krijgslaan 281, S4-Bis, 9000 Ghent, Belgium

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enhanced properties. The moderate-low cost hybrid materials appear to be attractive for their potential in the mercantile
area of commodities including: packaging, personal care
products, agricultural mulch films and disposable items. This
will constitute a novel added-value contribution aimed at
mitigating the environmental burden caused by plastic waste
items improperly abandoned in the environment.
Keywords Oxo-biodegradation  Lignin  Hybrid
composites  Polyethylene  Eco-compatible plastics

Introduction
The world population is growing exponentially with addition
of almost one billion every current decade. This is expanding
world population demands for feed, food and commodity
items with desired properties [1, 2]. The shortage and cost of
synthetic petrochemical-based polymeric materials has been
raised sharply over last few years [3, 4]. Some synthetic
polymers are refractory to biodegradation or are difficult to
be re-used and/or recycled, and wherever unintentionally
abandoned in the environment tend to accumulate in different
terrestrial and aquatic environmental compartments with
negative impact [5, 6]. Therefore, there are urgent needs to
find effective ways, aimed at providing new visions for novel
materials, revisiting of consolidate ones and propose a correct management of synthetic plastics waste. Its degradation
and disposal options and biodegradation represent a very
important topic of scientific significance on both environmental and economic grounds.
The bio-based products are emerging as an important
component for minimizing energy consumption, waste
generation and accelerate economic development [7, 8]. In
consumer product segments including packaging, health

J Polym Environ (2014) 22:5868

care products, agricultural mulch films and disposable

items, these materials are experiencing ever growing
attention and requests [9]. Hence, in recent years, there is
an increasing interest for bio-based polymeric materials
and for synthetic polymers with unique physical and
functional properties [10]. The loading of a synthetic
polymer with natural fillers is considered to be an effective
method for the attainment of bio-based composite materials
and relevant plastic items whose properties could be more
environmentally friendly with substantial saving of fossil
fuel feedstock used in the production of the synthetic
polymeric materials [11, 12]. This strategy is also usually
cheaper with lower time-consuming impact [13, 14].
Polyethylene (PE) is the largest produced and consumed
polyolefin in its different grades convertible to a wide variety
of commodities including flexible and semi-flexible plastic
items. The various grade of polyethylene [low density
(LDPE), linear low density (LLDPE) and high density
(HDPE)] are available in the market. In its various grades PE is
regarded as a synthetic biostable polymer with slow propensity to degradation in the various environmental compartments. Its structural reengineering by addition of natural fillers
as well as bio-based pro-oxidant/pro-degradant additives is
aimed at designing plastic items within the concept of a controllable service life. The production nowadays of plastic
items destined to last as long as they serve is a strategy
aimed at covering the environmentally compatible plastic
items by ever growing attention to needs for bio-based
materials desirably not interfering with food and feed chains.
The Lignin is considered as one of the most abundant
renewable biopolymers next to cellulose and is important
due to its renewable nature, low cost, easy availability, and
fairly ease of chemical and mechanical modifications, which
are also recognized as eco-compatible [1517]. It is a readily
available material characterized by low-density, low abrasive features and relatively inexpensive. These features
make it interesting as organic filler viable to replacing the
inorganic ones [18, 19]. In recent years, there is an increasing
interest to explore the novel applications of Lignin as a
potential source of a bioactive components in the food and
pharmaceutical industry. Lignins are polar network polymers consisting of on average of 12 hydroxyl groups per
monomeric unit [20]. The problem usually faced is the poor
miscibility of Lignin with apolar synthetic polymers such as
polyolefins [21]. High interfacial tension and the lack of
interfacial adhesion combined with the high viscosity of the
components are the crucial barriers to the achievement of the
desired degree of dispersion in synthetic polymers and natural composites. The use of plastics filled with Lignin
extracted from agricultural waste is holding a great potential
in the design and production of eco-compatible plastic
commodities. The organosolv Lignin from the Alcell alkalyne process has found some use in replacing up to 30 wt% of

59

phenolformaldehyde resins in wafer board, plywood and

particleboard. Blends of acid extracted Lignin with selected
thermoplastics similar to those prepared with the Organocell
Lignin are also of interest.
In the present work, composites based on PE and Lignins were formulated using as compatibilizer ethylene/
vinyl acetate copolymer (EVA). In order to evaluate the
effect of Lignin on the properties of PE formulations followed a statistical screening experiment. The effect of
Lignin, EVA compatibilizer and addition of a pro-oxidant/
pro-degradant component was evaluated by means of
morphological, thermal and mechanical properties.

Experimental Section
Materials
The key material used as filler in this investigation was the
Lignin recovered by acid precipitation process. The Lignin,
a dark brown free flowing powder, was recovered as byproduct of tannin extraction from chestnut tree wood
(Fig. 1a). Riblene FF33 a low density polyethylene
[LDPE (9002-88-4)] in pellet shape with a MFI (190 C/
2.16 kg) = 0.8 g 10 min-1 and density = 0.92 g cm-3 at
23 C, was kindly supplied by Polimeri Europa, Italy.
ELVAX 3185 a poly (ethylene-co-vinyl acetate) (EVA
24937-78-8) with 33 wt% vinyl acetate, MFI (190 C/
2.16 kg) = 43 g 10 min-1; density = 0.96 g cm-3, and
melting point (Tm) 61 C was supplied by DuPont. The
pro-oxidant/pro-degradant additive (TDPA) DCP562
(T6), MFI (125 C/2.16 kg) = 2328 g 10 min-1 (it is a
proprietary masterbatch containing organic salts of transition metals, stabilizers and fillers loaded in LDPE resin
matrix) was kindly supplied by EPI Environmental Technologies Inc. (EPI), Canada [22].
Formulation of Bio-based Composites Lignin/
Polyethylene-Statistical Mixture Design (SMD)
Polyethylene and Lignin (Fig. 1a) are polymers of different
structural features and polarity, (the former being a linear
full carbon backbone polymer consisting of 2030 (C2, C4)
branches/1,000 C atoms whereas the latter is a natural
network heteropolymer. Consequently they are not compatible for blending and need a compatibilizer susceptible
to interact and establish at least dispersion links between
the two incompatible polymeric materials. A copolymer
containing both EVA units [18] as non-polar and polar
segments, respectively was selected as compatibilizer. The
formulations followed a constrained mixture statistical
design. The evaluated variables are the proportion of each

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J Polym Environ (2014) 22:5868

Fig. 1 a Isolation of Lignin from water extracted Castanea sativa chestnut fibers, b mixture space for three components in the PELigninEVA
blend and c microtensile specimen shape and dimensions

component in the polymer composite taking into account

that the levels of each component of mixture are dependent
of the levels of the other components. The design space for
formulations of the PE based mixtures compatibilized with
EVA is a triangle as shown in the Fig. 1b. This space was
constrained on the components PE, compatibilizer EVA
and Lignin proportions with the lower and upper values
bound 0.5 B x1 B 1, 0 B x2 B 0.2, and 0 B x3 B 0.3,
respectively. The content of pro-oxidant/pro-degradant
additive was fixed at a 10 wt% in relation to the amount of
the PE in the formulation. Mixture compositions and
samples identification codes are presented in Table 1.
Scheffe-type models are canonical polynomial equations
that can be used with variables that are expressed as proportions as in the case of a mixture design. These models
are simple in the form, yet are extremely versatile in terms
of modeling the linear and nonlinear blending properties of
the constituents in the mixtures. Equations 1 and 2 represent the linear and quadratic models that can be applied to
the number of the selectively performed formulations.

Quadratic model : y^ b1 x1 b2 x2 b3 x3 b12 x1 x2

Linear model: y^ b1 x1 b2 x2 b3 x3 e

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b13 x1 x3 b23 x2 x3 e

where, y^ is the predicted response, x1 is PE, x2 is EVA, and

x3 is Lignin, whereas bis are coefficients and e is the
estimated error.
Table 1 Compositions (wt%) and sample identification codes of biobased polymeric composites containing a pro-oxidant/pro-degradant
additive (TDPA)
Sample

PE

TDPA

EVA

La

PEI-1

90

10

PEIL-2

63

30

PEIV-3
PEIVL-4

72
45

8
5

20
20

0
30

PEIVL-5

67.5

7.5

10

15

PEIV-6

76.5

8.5

15

PEIVL-7

54

10

30

PEIVL-8

58.5

7.5

20

15

PEIV-9

81

10

Lignin

J Polym Environ (2014) 22:5868

Processing of the Composite PELignin Mixtures By

Brabender
All formulation components were initially dried at 60 C
for 48 h in a laboratory oven equipped for forced air circulation before melt processing. Dried materials were
mixed and melted in a torque rheometer W 50 EHT with
roller blade at 165 C by 7 min at 60 rpm.
Compression Moulding
To obtain films with a thickness around 200250 lm mixed
materials were compression moulded in a laboratory mould
press Collin (model P 200E) equipped with a water-cooling
system. A mass of 4.2 g was placed in a teflonated mould and
the press plates were allowed to heat up to 165 C and
maintained isothermically for 3 min at 15 MPa (150 bar).
After completion of the desired press time the molded samples
were held under compression while the platen heaters were
turned off and a cooling water line was fully opened to cool
down the sample. The resulted thin films were stored in plastic
bag under vacuum and kept at -4 C to prevent possible oxodegradation before submitting them to testing evaluations.
Characterization
Morphological Analysis By Scanning Electron Microscopy
(SEM)
The cross-section morphologies of film blends, as aimed at
assessing components compatibility and homogeneity were
accomplished with a JEOL (JSM-5600LV) scanning electron microscope (SEM) at the required magnification and
with accelerating voltage of 14 kV. The film samples frozen in liquid nitrogen were fractured and sputtered with
gold before SEM observation.
Attenuated Total Reflectance (ATR-FTIR)
The ATR-FTIR is very useful interrogating technique for
the structural assessment of polymer samples that are too
opaque or too thick for standard transmission methods. The
sample is placed onto the horizontal face of the internal
reflectance crystal where total internal reflection occurs
along the crystal-sample interface. Typically, the reflected
radiation penetrates the sample to a depth of only a few
microns. The present investigation was performed with
Jasco FTIR-4100, Crystal Ge (IR penetration 0.66 lm).
Mechanical Tests
The tensile properties were carried out in accordance with
the procedures outlined in ASTM D1708-93 standard test

61

method using a Universal Testing Machine Instron (model

5564) with a load cell of 2 kN and pneumatic grips. Microtensile test specimens were cut from films obtained
from compression molding and dimensions are indicated in
the Fig. 1c. Prior test, the specimens were preconditioned
inside desiccators containing saturated solutions of magnesium nitrate (ca. 53 % RH at 25 C) by 48 h (ASTM
E104-02).
At least 11 specimens for each sample formulation were
tested and the average value was reported. The average and
standard deviation values were considered by statistical
analysis (ANOVA). A digital micrometer was used to
monitor film thickness averaged from five measurements
at different points along the specimen length. Measurements were performed under a crosshead speed set at
1 mm min-1.
Thermo-Gravimetric Analysis (TGA)
Thermo-gravimetric analysis experiments were carried out
in a thermogravimetric analyzer of the TA Instrument
model Series Q500 with the software Universal TA analysis. Samples of 715 mg were loaded in a furnace constantly purged with air or nitrogen gas at 60 mL min-1
flow rate. TGA traces were recorded at a scansion rate of
10 C min-1 from 30 to 800 C. The TGA temperature
was calibrated with three standards and weights comprised
between 100 and 1,000 mg.
Differential Scanning Calorimetry (DSC)
Thermodynamic parameters of the various blend samples
were assessed by using a differential scanning calorimeter
(DSC) from Mettler Toledo, model DSC822 equipped with
a STAR software. Samples of 310 mg were weighed in
standard 40 lL aluminum pan and an empty pan was used
as reference. DSC temperature calibration was performed
using indium, lead and zinc standards and energy calibration using indium standard. Measurements were performed
(in accordance with the ASTM D 3418 standard method)
under nitrogen flow rate of 80 mL min-1 according to the
following protocol:
1.
2.
3.

First heating scan from -50 to 160 C at 10 C min-1

and 3 min of isotherm at the end.
First cooling scan from 160 to -50 C at
100 C min-1 and 3 min of isotherm at the end.
Second heating scan from -50 to 300 C at
10 C min-1.

Typically, 1st heating temperature scan erases any prior

thermal history of the sample, in the following cooling scan
a well defined thermal history will be established and
finally, the 2nd heating scan will permite to evaluate the

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thermodynamic parameters of the materials such as melting

point (Tm), crystallization temperature (Tc) and glass
transition temperature (Tg).
Oxidation Potential
Oxidation of the blend samples was performed by using a
DSC from Mettler Toledo, model DSC822 with STAR
software. Samples size of 310 mg were weighed in standard 40 lL aluminium pan and an empty pan was used as
reference. DSC temperature calibration was performed

J Polym Environ (2014) 22:5868

using indium, lead and zinc standards and energy calibration using indium standard. Measurements were performed
in isotherm mode at a temperature of 180 C under different atmospheric conditions including nitrogen, air and
oxygen at flow rate of 80 mL min-1.
Statistical Analysis
The Students t test was used when statistical significance
of differences between average values of two independent
groups at 95 % confidence (p \ 0.05) was determined.

Fig. 2 SEM photomicrographs of PEIL-2 (a, b), PEIVL-4 (c, d) and PEIVL-8 (e, f) at magnifications of 9500 and 91,500, respectively

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Results and Discussion

Morphological Analysis by Scanning Electron
Microscopy (SEM)
In Table 1 are reported the compositions of the various
composite formulations with a Lignin filler content comprised between 15 and 30 wt% and EVA comprised
between 10 and 20 wt% and the TDPA additive comprised
between 5 and 10 wt% with a 10 wt% with respect to the
content of PE. The SEM photomicrographs of PELignin
based composite formulations, additivated with 10 wt% of
TDPA additive with respect to the PE content, are shown in
Fig. 2. PEIL-2 (Fig. 2a, b) showed morphological features
typical of immiscible systems, as attributable to the
hydrophobic and hydrophilic characteristics of PE which
are incompatible with the partially hydrophilic polar
character of Lignin. It can be observed in fact that Lignin
dispersed phase is not homogeneous in size and its interfacial adhesion with PE continuous matrix is poor. The
morphologies of PETDPALigninEVA composites
(Fig. 2cf) are very similar suggesting that at an EVA/
Lignin 2/3 ratio by weight (PEIVL-4) a reasonable interaction between these two components does occur analogously to what is happening for the sample PEIVL-8, in
which the weight ratio EVA/Lignin is doubled with respect
to PEIVL-4.
Mechanical Tests
Tensile properties of PELignin based composites additivated with TDPA are reported in Table 2 and represented
for a bird new vision in Fig. 3. The mean deviation of six
replicates was calculated by using Students t test at 95 %
of confidence. The elastic modulus (EM), obtained by the
tangent at 1.5 % of strain is reported together with, tensile
strength (TSB) and elongation at break (EB). The results

63

showed PEI-1 EM value was ca. 142 MPa, whereas PEIV9 (81 %PE-9 %TDPA-10 % EVA) showed the highest EM
value (ca. 168 MPa) with the lowest value (ca. 107 MPa)
recorded for PEIVL-4 formulation (45 %PE-5 %TDPA20 %EVA-30 %Lignin). This result suggests that the
decreasing in the EM values depends on the interaction of
TDPA additive with the others two components used in the
formulation. TSB value recorded for PEI-1 was ca. 9 MPa
corresponding to a decreasing of 25 % in confront to its
TDPA additive-free counterpart.
Attenuated Total Reflectance (ATR-FTIR)
The ATR-FTIR spectra of PELignin based composites
containing TDPA additive are represented in Fig. 4. The
PE band associated to the crystalline portion appears at
721 cm-1. Besides, apparently no effect of TDPA additive was observed in the freshly prepared films. The
additive TDPA can promote oxidation of PE by the action
of a fairly long time exposure to heat and/or UV radiation. Changes are detectable principally in the carbonyl
(1,800 and 1,600 cm-1) and hydroxyl (3,500 and
2,500 cm-1) absorptions recorded by in the FTIR
spectrum.
Thermo-Gravimetric Analysis (TGA)
Typical TGA traces of PELignin based composites with
pro-oxidant/pro-degradant TDPA additive in nitrogen and
air atmosphere are presented in Fig. 5a, b and relevant
TGA data are collected in Tables 3 and 4.
Sample PEI-1 containing 10 wt% of TDPA is more
stable than the pristine PE (PE-1). Besides, PEI-1 gives
raise to thermal oxidation in only one step while PE-1
presented three steps. From the comparison of TGA traces
PEI-1 with that of PEIVL-7 (54 wt% PE, 6 wt% TDPA,
10 wt% EVA, 30 wt% Lignin) one can detect a profile

Table 2 Tensile properties of PELignin based blends additivated with TDPA pro-oxidant/pro-degradant
Sample

Tangent modulusa (MPa)

Tensile strengthb (MPa)

Elongationb (%)

PEI-1

142.2 9.1

9.4 0.1

437.6 26.2

PEIL-2

134.2 11.6

6.5 0.4

003.8 00.4

PEIV-3

117.2 6.2

9.7 0.4

504.0 44.8

PEIVL-4

107.4 6.8

5.2 0.4

006.9 1.0

PEIVL-5

140.8 6.0

5.7 0.5

009.9 1.0

PEIV-6

114.2 2.7

8.72 0.8

418.0 99.5

PEIVL-7

120.8 13.8

6.7 0.4

004.2 0.6

PEIVL-8

113.8 04.3

6.0 0.4

010.3 01.4

PEIV-9

168.2 09.6

8.9 0 0.4

468.4 50.4

At 1.5 % of strain

At break

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Fig. 3 Tensile properties of PELignin based blends containing TDPA additive. a Youngs modulus (EM), b tensile strength at break (TSB),
c elongation at break (EB)

Fig. 4 ATR-FTIR spectra of PELignin based composites containing TDPA additive. a PELignin binary composites, b PEEVA binary
blends, and c PEEVALignin ternary composites

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65

Fig. 5 Typical TGA traces of PELignin based composites containing TDPA additive in nitrogen (a) air and (b) atmosphere. Experimental and
simulated TGA traces of blends and pristine components in air atmosphere (cf)

nearer to that of TDPA containing sample than that of

pristine PE-1.
The TDPA containing samples are more stable in
nitrogen atmosphere, while the same samples are less stable in air atmosphere. These results suggest that either
TDPA is favouring Lignin degradation or there is a synergistic effect of both components on the PE thermal-oxidation. As the effect of additive TDPA is more significant
in the air atmosphere, experimental and simulated TGA
traces of additivated PELignin based composites were
assessed by comparing them with pristine components in
air atmosphere (Fig. 5cf). The significant effect of the
TDPA in the PE matrix can be observed in the Fig. 5c.

There is little difference between simulated TGA trace of

PEI-1 and that of pristine PE (PE-1), which is more
detectable above ca. 450 C. In addition, thermal-oxidation
traces recorded by TGA on all samples, nearly overlapped
that of PEI-1. In conclusion, the role of TDPA additive was
more significant than that played by the Lignin in affecting
the properties of the relevant blends.
The kinetics of the thermal degradation was studied
applying the Broido integral method [23]. The apparent
activation energy (Ea) was obtained in the temperature
range close to derivative peak of the main reaction process
(469483 C) attributed to the PE chain breakdown by
oxidation according a first order kinetic model. The weight

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Table 3 Activation energy (Ea) relevant to thermal-oxidation of PE

Lignin based composites containing TDPA
Sample

Ea
(kJ mol-1)

Sample

Ea
(kJ mol-1)

Sample

Ea
(kJ mol-1)

PE-1

98.6

PEIV-3

74.7

PEIVL-7

35.8

TDPA

29.1

PEIVL-4

46.9

PEIVL-8

58.8

PEI-1

29.2

PEIVL-5

52.3

PEIV-9

84.7

PEIL-2

38.1

PEIV-6

68.8

Differential Scanning Calorimetry (DSC)

fraction of the molecules not yet decomposed (y) is defined

by the following Eq. (3),
y wt  w1 =w0  w1

where w0, wt and w? are the sample weight taken initially,

at time t, and at the end of thermal decomposition,
respectively. The Broido et al. [23] Eq. (4) is
ln1=y Ea =RT constant

accelerate the oxidation process. The samples with lower

Ea values are represented by the formulations with higher
content of Lignin (PEIL-2, PEIVL-4 and PEIVL-7).

where R is the universal gas constant and T is the absolute

temperature.
Apparent activation energies (Ea) relevant to the thermal-oxidation of PELignin based blends additivated with
TDPA were obtained. The 358375 C temperature range
corresponds to the first weight loss of pristine PE (PE-1).
Ea values are reported in Table 3 and represented in Fig. 6a
to the benefit of a bird new vision. Fitting correlation
coefficients were in the 0.99400.9999 range. The highest
value was about 99 kJ mol-1 for the pristine PE (PE-1)
followed by binary blends with EVA (PEIV-3 am PEIV-9).
On the other hand, Ea values of both TDPA and PEI-1 were
around 29 kJ mol-1. As expected the presence of the prooxidant/pro-degradant speeds up the oxidation and
decomposition of PE. The presence of EVA substantially
mitigate the effect of TDPA, whereas the Lignin tends to

In Tables 4, 5 and 6 are collected the thermodynamic data

as recorded by the DSC traces. Melting temperatures of PE
in the composites as attained in the first heating ranged
from 110 to 112 C. The variable in the present formulations is TDPA additive that was maintained at a ratio 1/9
with respect to PE that in the total of formulations changed
between 10 wt% in PEI-1, 5 wt% in PEIVL-4, which
correspond to 1.8 and 1.4 wt% of the inorganic pro-oxidant/pro-degradant transition metal ion. Consequently, this
substance seems do not give rise to any influence in the
crystalline organization of PE.
Oxidation of PELignin Hybrid Blends
Degradation of polyethylene in the presence of oxygen
does occur according to steps implying first of all the
uptake of oxygen by a free radical chain mechanism followed by degradation pathways promoted by photophysical
(Norrish 1 and Norrish 2) and thermal inputs. These lead to
breakdown of the polymer backbone with formation of a
number of oxygenated functional groups including hydroxyl, carbonyl and carboxylic moieties
In the present study different samples of the PE
Lignin were submitted to thermal oxidation in the melt
at 130 C under different environmental conditions
(nitrogen, air and oxygen) in isothermal mode in DSC
apparatus while no significant oxidation was detected in
1 h of heating at 130 C for all the analysed samples
(pristine PE, PEI-1 and PEL-2) in nitrogen atmosphere
the oxidation was recorded instead after 5 and 25 min

Table 4 Thermodynamic properties of PELignin based composites additivated with TDPA pro-oxidant/pro-degradant additive from 1st
heating DSC scan
DTm1 (C)

Tm2 (C)

DHm2 (J g-1)

DTm2 (C)

Xc (%)

8.2

27.2

111.3

115.1

79.5

42.8

6.1

30.5

111.1

107.4

79.3

39.0

41.4

10.6

31.5

111.3

97.4

76.2

37.6

PEIVL-4

41.1

7.1

33.0

110.2

81.5

96.7

30.5

PEIVL-5

42.2

7.7

33.7

110.7

103.6

75.4

38.7

PEIV-6

42.5

11.4

42.6

111.4

102.3

75.1

39.2

PEIVL-7
PEIVL-8

42.0
41.5

6.9
9.3

32.2
27.5

110.9
111.2

83.4
87.7

81.2
73.2

31.1
33.4

PEIV-9

45.4

7.1

26.3

112.5

101.1

78.3

37.1

Sample

Tm1 (C)

PEI-1

43.4

PEIL-2

43.9

PEIV-3

DHm1 (J g-1)

Tm melting temperatures, DTm, DHm range of temperature and change in enthalpy, Xc degree of crystallinity

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Fig. 6 a Graphic of Ea of thermo-oxidation of PELignin based blends with TDPA, DSC traces of PELignin based composites additivated with
TDPA additive, b 1st heating scan, c 1st cooling scan, and d 2nd heating scan

Table 5 Thermodynamic properties of PELignin based composites additivated TDPA pro-oxidant/pro-degradant additive from 1st cooling
DSC scan
Sample

Tc1 (C)

DHc1 (J g-1)

DTc1 (C)

Tc2 (C)

DHc2 (J g-1)

DTc2 (C)

Tc3 (C)

DHc3 (J g-1)

DTc3 (C)

Xc (%)

PEI_1

61.2

23.2

43.9

98.9

89.7

36.5

38.9

PEIL_2

61.1

8.6

24.6

98.5

62.73

39.4

24.5

PEIV_3

44.9

6.8

26.1

61.8

12.7

20.9

99.1

72.2

37.1

31.6

PEIVL_4

43.6

4.4

28.7

60.9

4.8

14.6

98.5

39.0

41.9

16.6

PEIVL_5

44.3

3.9

21.2

61.0

15.4

23.3

99.1

66.9

41.7

29.7

PEIV_6

44.0

6.7

29.5

61.0

16.4

22.2

98.6

77.4

38.5

34.5

PEIVL_7
PEIVL_8

43.4
44.2

3.0
6.3

20.9
30.5

61.5
61.7

8.8
9.2

20.5
19.8

99.4
99.2

46.3
56.5

38.2
39.0

19.8
24.4

PEIV_9

44.1

3.4

14.2

61.6

13.1

20.3

99.0

76.2

39.4

31.7

Tc crystallization temperature, DTc, DHc temperature range and enthalpy of crystallization, Xc degree of crystallinity

for the samples treated in oxygen and air atmosphere

condition, respectively.

Conclusions
The results attained in the present study suggest that Lignin, as waste of tannin extraction from chestnut wood, can
be used to engineer low cost composites based on LDPE as

continuous matrix containing a pro-oxidant/pro-degradant

additive. The incorporation of this last additive enhances
the oxidation process of the full carbon continuous matrix
of bio-based hybrid composites. This low moderate cost
materials are of potential interest for the fabrication of
plastic items characterized by a controlled service life in
application segments such as packaging, personal care
products, agricultural mulch films, disposable items. The
combination of a filler from renewable resources with a

123

68

J Polym Environ (2014) 22:5868

Table 6 Thermodynamic parameters of PELignin based composites additivated TDPA pro-oxidant/pro-degradant additive from 2nd heating
DSC scan
Sample

Tm (C)

DHm (J g-1)

DTm (C)

Xc (%)

PEI_1

110.4

124.7

125.8

43.0

PEIL_2

111.1

76.9

92.1

26.5

PEIV_3

110.1

101.8

113.8

35.1

PEIVL_4

110.5

56.0

115.8

19.3

PEIVL_5

110.6

88.1

103.3

30.4

PEIV_6

111.1

101.4

105.8

34.9

PEIVL_7
PEIVL_8

110.3
110.5

56.9
71.5

86.2
97.6

19.5
24.6

PEIV_9

111.0

96.3

102.7

33.1

Tm melting temperatures, DTm, DHm range of temperature and change in enthalpy, Xc degree of crystallinity

green pro-oxidant/pro-degradant additive would then

enable to drop the negative environmental impact bound to
mass plastic items attainable by polymeric materials based
on fossil fuel feedstock.
Acknowledgments The results reported in the present paper were
obtained within the framework of the research activities implemented
in Bionanopack project funded by the Italian Minister of Industry.

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