J Polym Eng 2017; aop

Dev K. Mandal, Haripada Bhunia*, Pramod K. Bajpai, Chandrasekhar V. Chaudhari,

Kumar A. Dubey and Lalit Varshney

Morphology, rheology and biodegradation of

oxo-degradable polypropylene/polylactide blends
DOI 10.1515/polyeng-2016-0380 But they are a big source of environmental problems.
Received November 11, 2016; accepted April 1, 2017 After the short-term use, they are thrown to landfill sites.
They get accumulated in the environment at the rate of
Abstract: The blends of polypropylene (PP)/polylactide
60  million metric tons per year worldwide [1]. In India
(PLA) with or without compatibilizer, and with pro-oxi-
particularly, the figure of plastic waste generation was
dant (cobalt stearate/calcium stearate) and pro-oxidant
approximately 5.6 million metric tons per year in 2012 [2].
filled PP were prepared by using the melt blending tech-
It is estimated that the plastic waste generation would rise
nique. Films of these blends were prepared by compres-
to approximately 16.5 million metric tons by 2030, trebling
sion molding. PP85PL15 and PP85PL15MA4  were the
every 10 years. India is the third largest consumer market
optimum blends from the tensile strength point of view.
(behind USA and China) for plastic goods with a consump-
The improvement in the tensile strength of PP85PL15MA4
tion of 12.5 million metric tons per annum. After polyethyl-
blend was achieved by addition of 4 phr compatibilizer.
ene (PE), polypropylene (PP) is an extensively used plastic
Cobalt stearate and calcium stearate were added sepa-
material in the packaging industries like trash bag, food
rately to PP85PL15MA4 blend in 0.2% (w/w) ratio. The
packaging etc. The hydrophobic nature, unavailability of
optimized blends were further characterized by differen-
functional groups and long chain of PP molecules resist
tial scanning calorimetry, X-ray diffraction, rheological
microorganism attack and make it non-biodegradable.
studies, scanning electron microscopy (SEM) and biodeg-
Short-term use and long-term functionality of PP create
radability test. Rheological studies confirmed the pseudo-
huge waste management problems. Recycling is one of
plastic nature of all the blend samples. SEM studies have
the important processes to reduce plastic waste, but it is
revealed that the addition of PLA in PP85PL15 enhances
not efficient and produces inferior quality products. In the
the void and roughness on the blend. All the prepared
last two decades, researchers have been working on the
blends have biodegraded in the composting environment
degradation and biodegradation of PP. Degradation was
and the blend containing pro-oxidant biodegraded to the
improved by (1) blending with biodegradable natural poly-
maximum extent.
mers such as cellulose [3], starch [4–7], poly(lactic) acid
Keywords: biodegradability; polylactide; polypropylene; [8, 9], poly(ε-caprolactone) [10], etc., (2) blending with
pro-oxidant; rheology. stearate of transition metals and (3) isolation and identifi-
cation of microorganisms capable of ­biodegradation [11].
Polylactide (PLA), a linear aliphatic polyester derived

1 Introduction from biomass through bioconversion and polymeriza-

Plastics are widely used in packaging, medical, agri-
cultural, electrical, automobile and manufacturing
industries due to their low cost and desirable physical,
chemical, mechanical, thermal and electrical properties.
*Corresponding author: Haripada Bhunia, Department of Chemical
Engineering, Thapar University, Patiala 147004, Punjab, India,
e-mail: hbhunia@thapar.edu
Dev K. Mandal and Pramod K. Bajpai: Department of Chemical
Engineering, Thapar University, Patiala 147004, Punjab, India
Chandrasekhar V. Chaudhari, Kumar A. Dubey and Lalit Varshney:
Radiation Technology Development Division, Bhabha Atomic
Research Centre, Trombay, Mumbai 400085, India
tion, can be degraded upon disposal in biotic environ-
ment such as bacteria, algae, fungi, etc. [12]. However,
inherent brittleness characteristics, high cost and limited
shelf life restrict its use as a replacement of commercial
synthetic packaging polymer materials. Many research-
ers have reported blending of PLA with linear low density
polyethylene (LLDPE) [13, 14], high density polyethyl-
ene (HDPE) [15], PP [8, 9, 16, 17] and with other aliphatic
polyesters such as poly(ε-caprolactone) [10, 18–20] and
poly(hydroxybutyrate) [21–23]. Most of the blends of these
polymers with PLA are partially immiscible and have poor
mechanical properties. Addition of suitable compatibi-
lizer is helpful in improving the miscibility and mechani-
cal properties of these blends. Over the past decades,

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2      D.K. Mandal et al.: Biodegradable PP/PLA blends and their properties
considerable efforts have been made by researchers to
modify polyolefins by the introduction of compatibilizers
like PP grafted maleic anhydride (PP-g-MA) and PE grafted
maleic anhydride [24].
Pro-oxidants are transition metal complexes com-
monly used in the form of stearates such as iron (Fe3+)
stearate, mangnese (Mn2+) stearate and cobalt (Co2+) stea-
rate [25, 26]. Among them, Fe3+ initiates photo-oxidative
degradation, and Mn2+ and Co2+ initiate thermo-oxidative
degradation process, which facilitates the degradation of
pro-oxidant blended samples with the microorganisms.
Pro-oxidants add functional groups to the PP chain. These
functional groups degrade them as hydro-peroxides and
form low molecular weight products such as carboxylic
acid, ketones and alcohol, which are further biodegraded
by the microorganisms aerobically and anaerobically. In
an aerobic condition (presence of air) microorganisms
form CO2, H2O and biomass as products. In an anaerobic
condition (absence of air) microorganisms form CO2, H2O,
CH4 and biomass as products under methanogenic condi-
tion or H2S, CO2 and H2O as products under sulfidogenic
condition [27].
The blending of PP with PLA and pro-oxidant
enhances the degradability of the PP [9, 28]. Therefore,
this type of blends may be used as alternative for the
non-biodegradable PP films in the packaging applica-
tion. There have been several studies to investigate the
mechanical and thermal properties of these blends [29,
30]. But rheological properties of these polymers have
presented an important link between the production of
polymers and their end-use properties [31]. Moreover, sys-
tematic studies of rheological behavior of these polymer
blends are relatively limited but are essential. There has
been no research carried out on pro-oxidant filled PP/
PLA blends, specifically in the field of biodegradability.
In this research work, an attempt has been made to
develop biodegradable packaging film from pro-oxidant
filled PP/PLA blends. Effects of pro-oxidant and PLA
concentration on the mechanical, thermal, morphologi-
cal and rheological properties and biodegradability have
been evaluated. Compatibilizer PP-g-MA was also used to
increase the interaction between PP and PLA.
2 Materials and methods
2.1 Materials
PLA pellets (4032D) of density 1.24 g/cm3 and 2% w/w
D-isomer content were provided by NatureWorks LLC,
Minnetonka, MN, USA. Compatibilizer – maleic anhy-
dride modified PP (Optim P406) of density 0.91 g/cm3
and melting temperature (Tm) 163°C was purchased from
Pluss Polymers Pvt. Ltd., Gurgaon, Haryana, India. PP in
the form of pellets (density 0.9 g/cm3 and melt flow index
(MFI) = 3 g/10  min) was provided by Haldia Petrochemi-
cal Ltd., Haldia, West Bengal, India. Calcium stearate
(6.6–7.4% Ca basis) was procured from Sigma-Aldrich, St.
Louis, MO, USA and used as received. Cobalt stearate (Co,
9–10%) was purchased from Alfa Aesar, Haverhill, MA,
USA. Barium hydroxide, Ba(OH)2 (Mw = 315.47) and cellu-
lose with a particle size ≤20 μm were purchased from S. D.
Fine Chemicals Ltd., Mumbai, Maharashtra, India.
The digested municipal solid waste (mature compost)
having pH 7.2 and C:N ratio of 15.3  was obtained from
the Delhi Jal Board (compost plant) at Okhla, New Delhi,
India. Inorganic materials such as glass, stone, metal etc.
were removed from the compost and screened through a
1  mm mesh sieve. The amount of moisture, total solids
and volatile solids in compost was 19%, 81% and 18%,
respectively.
2.2 Blend preparation
Table 1 shows the composition of PP/PLA blends with
and without compatibilizer and pro-oxidant (calcium
and cobalt stearate) and PP with pro-oxidant, which-
were prepared by melt blending using Internal Mixer
(Haake Poly Lab, Germany). Pro-oxidant based on
calcium and cobalt stearate were also incorporated
in the compatibilized blends and PP. The ingredients
were weighed at a prescribed ratio and manually mixed
before being loaded into the mixer for melt blending.
The amount of pro-oxidant (calcium/cobalt stearate)
used was 0.2  wt%. The ratio of PP/PLA was varied
from 100/0 to 80/20; and in the fixed ratio of 85:15, the
amount of compatibilizer was 2, 4, 6 and 8 phr. The melt
mixing was performed at rotor speed of 60  rpm and
190°C for 4  min. The extrudate was passed through a
two-roll mill with a nip gap of 2  mm, maintaining the
rolls at room temperature.
2.3 Film preparation
The prepared blends were molded into the films (80–85 μm
thick) by compression molding at 180°C and 400 kN/m2
pressure. Teflon sheets were kept in between the mold to
restrict the sticking of molten material with the plates. The
plates were cooled by water.
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Table 1: Blend compositions of different samples.
Sample no.   Polymer/blend code  
PP (wt%)  PLA (wt%)  PP-g-MA (phr)  CaSt (wt%)  CoSt (wt%)
1   PP  
2   PP95PL5  
3   PP90PL10  
4   PP85PL15  
5   PP80PL20  
6   PP85PL15MA2  
7   PP85PL15MA4  
8   PP85PL15MA6  
9   PP85PL15MA8  
10   PP85PL15MA4CoSt0.2  
11   PP85PL15MA4CaSt0.2  
12   PP100CoSt0.2  
13   PP100CaSt0.2  
3 Testing methodologies
3.1 Tensile properties
Tensile properties such as tensile strength at yield and
elongation at break of the film samples were measured
according to ASTM D 882-91  standard [32] on Universal
Testing Machine (Z010, Zwick-Roell, Ulm, Germany). The
rectangular shaped specimens for tensile test were pre-
pared by the strip-sample cutter. The clamp separation
was kept at 100  mm with cross head speed of 12.5  mm/
min. The average values of five specimens of each blend
were reported.
3.2 D
 ifferential scanning calorimetry
Thermal behavior of all the samples was analyzed by
differential scanning calorimetry (DSC) using the instru-
ment 200F3, Netzsch-Geratebau GmbH, Selb, Bavaria,
Germany. A sample weight 5–0 mg was used. The samples
were heated from room temperature to 200°C at 10°C/min
and held for 1 min to remove the thermal history. Subse-
quently, the samples were cooled to −30°C at a cooling rate
of 10°C/min and heated again to 200°C at 10°C/min under
constant nitrogen flow. The second heating scans were
used for analysis. Melting enthalpy (ΔHm) of the samples
was obtained from the area under the melting thermo-
grams. The degree of crystallinity (Xc%) of samples was
calculated by using Eq. (1) [33]:
∆H m
Χ c (%) = × 100
∆Hm (crys)

D.K. Mandal et al.: Biodegradable PP/PLA blends and their properties      3
Composition
100  0  0  0  0
95  5  0  0  0
90  10  0  0  0
85  15  0  0  0
80  20  0  0  0
85  15  2  0  0
85  15  4  0  0
85  15  6  0  0
85  15  8  0  0
85  15  4  0  0.2
85  15  4  0.2  0
100  0  0  0  0.2
100  0  0  0.2  0
where ΔHm(crys) is the melting enthalpy of 100% crystalline
PP (163 J/g) [33]. The melting enthalpy of 100% crystalline
PLA was taken as 93 J/g [29].
3.3 X-ray diffraction
Crystallographic structural information of all the samples
was gathered using X-ray diffraction (XRD) measurements
by using an instrument Philips Xpert diffractometer,
Almelo, Netherlands. During the tests, measurements
were carried out in the diffraction angle range 5° < 2θ < 60°
with monochromatic CuKα radiation of a wavelength
1.5418 Å and operating at 40 kV and 20 mA. The scanning
speed was 5°/min with 2θ values reproduced within ±0.02°
variation. From XRD analysis, percentage of crystallinity
(Xc%) was determined according to Eq. (2) [34].
Ic
Xc (%) = × 100 (2)
Ic + Ia

where Ic and Ia are integrated intensities corresponding to
crystalline and amorphous phases, respectively.
3.4 Rheology
Rheological behavior of all the samples was studied by
a dynamic oscillatory rheometerin the melt state using
an Anton Paar parallel plate rheometer (MCR 102, Graz,
Austria) equipped with 25 mm diameter and 1 mm gap at
190°C. The samples were directly loaded under nitrogen
(1)
atmosphere. At first, a strain sweep test was performed
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4      D.K. Mandal et al.: Biodegradable PP/PLA blends and their properties
for each sample to determine the linear viscoelastic (LVE)
region from the initial strain value of 0.01 to the final strain
value of 1000% with a frequency of 1 rad/s. The frequency
sweep test was performed in the LVE region (γ = 1%) with
the frequency range of 0.01–500 rad/s.
3.5 Scanning electron microscopy
Fractured surface morphology of all the samples was
observed by using scanning electron microscopy (SEM;
JEOL JSM 6510-LV, Tokyo, Japan). All samples were cryo-
genic brittle fractured. To avoid the charging effect and to
enhance the emission of the secondary electrons, all the
samples were coated with 15 mm gold film. The accelera-
tion voltage was 20 kV.
3.6 Biodegradation
Biodegradation study was conducted by estimating the
cumulative amount of CO2 produced from the samples
according to the guidelines of ASTM standard D5338-11
[35]. Test samples in the form of films having dimension
of 2 × 2  cm2 were used. The sample with weight of 1  g
was incubated in a compositing vessel of 1  l at 58 ± 2°C
in three replicates for 45  days with the flow rate of air
Figure 1: Schematic diagram of aerobic biodegradability testing apparatus. (A) CO2-free air supply with flow measuring arrangement.
(B) Composting vessels with temperature controlling mechanism and (C) CO2 gas absorbing vessels.
(CO2 free) between 60 and 80 ml/min. The samples were
exposed to microbial activity by putting in compost that
is derived from municipal solid waste. The cumulative
amount of CO2 produced from the sample was meas-
ured by acid-base titration method. The CO2 evolved was
absorbed in 0.024 N Ba(OH)2 solution, and the amount of
CO2 was determined by titrating the solution with 0.05 N
HCl (at an interval of 5 days). The schematic diagram of
aerobic biodegradability testing apparatus is shown in
Figure 1. The percent of biodegradation was calculated
with the help of Eq. (3). The theoretical mass of carbon
dioxide (CO2th) was determined from the carbon present
in the sample by using total organic carbon (TOC) ana-
lyzer, TOC-VCPH (solid module) from Shimadzu, Kyoto,
Japan. The TOC-VCPH analyzer utilizes 900°C heat. The
carbon dioxide is detected by a non-dispersive infrared
(NDIR) gas analyzer. The NDIR outputs an analog detec-
tion signal that forms a peak; the peak area is measured
by the TOC-Control V software.
CO2 t − CO2 b
Biodegradation (%) = × 100 (3)
CO2 th

where CO2t is the mass of CO2 evolved from each test
sample containing compost reactor in grams, and CO2b
is the mass of CO2 evolved from the blank reactor in
grams.
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 D.K. Mandal et al.: Biodegradable PP/PLA blends and their properties      5

4 R
 esults and discussion chosen as an optimum blend due to good tensile strength
and relatively low proportion of expensive compatibilizer.
The effects of pro-oxidant (0.2  wt%) on the tensile
4.1 Tensile properties
properties of PP and PP85PL15MA4 are shown in Table
2. Tensile strength of PP100CaSt0.2 and PP100CoSt0.2 is
Table 2 summarizes the tensile properties (tensile strength
35 MPa, which is lower than 39 MPa of PP. Tensile strengths
at yield and breaking elongation) of the PLA filled PP of
of PP85PL15MA4CaSt0.2 and PP85PL15MA4CoSt0.2 are 29
different compositions in the absence/presence of com-
and 28 MPa, respectively, which are similar to 30 MPa of
patibilizer and pro-oxidant. Tensile strength of PP/PLA
PP85PL15MA4.
blends decreases with increase in PLA content due to
After examining the tensile properties of all the blends,
immiscibility of these two polymers. In an ideal and
we selected PP100CaSt0.2, PP100CoSt0.2, PP85PL15,
highly compatible polymer blend, the blends are expected
PP85PL15MA4, PP85PL15MA4CaSt0.2 and PP85PL15MA-
to have strength higher than or at least between that of the
4CoSt0.2 for further studies, characterized and compared
pure polymers [9]. Tensile strength of PP/PLA (85/15) blend
with the neat PP.
was 28 MPa as against 39 MPa of PP, which may be due to
the less interaction and chain entanglement of polar PLA
with nonpolar PP during blending by internal mixing. But
4.2 Differential scanning calorimetry
further increase in PLA content beyond 15  wt% reduced
the tensile strength drastically up to 13  MPa. Therefore,
DSC analyses were carried out for virgin PP, PLA and PP/
PP85PL15 was chosen as optimum composition due to the
PLA blends with and without compatibilizer and pro-
better retention of tensile properties as well as the rela-
oxidant. The DSC curves of all the samples are shown in
tively low proportion of expensive material. Percentage
Figure 2. The melting temperature (Tm), crystallization tem-
elongation at break of PP/PLA (80/20) blend was 1.9 as
perature (Tc) and enthalpy of melting(ΔHm) values of the
against 3.6 of PP, which may be due to the change from
samples, obtained from DSC curves in Figure 2, are listed
ductile to brittle deformation. This is due to the fact that
in Table 3. The crystallinity of the samples is calculated
PLA has a low percentage elongation compared to PP and
from heat of melting by using Eq. (1). Crystallinity and Tm
the incompatibility between PP and PLA.
of the PP85PLA15 decreased due to immiscibility between
The effects of compatibilizer (2–8 phr) on the tensile
the crystalline/amorphous blending materials. The pres-
properties of PP/PLA (85/15) blend are shown in Table 2.
ence of separate domains of PLA (amorphous component)
The compatibilizer increased the tensile strength of blend
in the molten PP (crystalline component) decreases the
due to the fine bonding and better interaction between PP
possibility of an ordered structure [36]. The Tc of blends
and PLA molecules upto 6 phr. After which, tensile strength
is almost similar to pure components due to the presence
decreased due to increase in the heterogeneity of the blend
of different phases. Addition of compatibilizer PP-g-MA in
resulting in phase separation. The PP85PL15MA4  was
PP85PL15MA4  shows Tc 118°C, which is constant regard-
less of the addition of PP-g-MA [17]. The crystallinity of
Table 2: Tensile properties of different film samples.
PP85PL15MA4 blend is enhanced due to the modification
of interface between PP and PLA by the compatibilizer. In
Sample   Polymer/blend code   Tensile  Elongation
no. strength at at break the case of pro-oxidant filled compatibilized PP/PLA blend
yield (MPa) (%) and pro-oxidant filled PP, the Tm decreases due to increase
in thermal degradation with addition of pro-oxidant [37].
1   PP   39 ± 2  3.6 ± 0.2
2   PP95PL5   37 ± 2  3.1 ± 0.2 It is observed that the crystallinity of pro-oxidant filled PP
3   PP90PL10   35 ± 2  2.1 ± 0.1 and PP/PLA blends are lower than pure PP due to the inser-
4   PP85PL15   28 ± 2  2.0 ± 0.1 tion of the side and/or functional groups [28]. Pro-oxidant
5   PP80PL20   13 ± 1  1.9 ± 0.1 reduces the crystallinity and makes pro-oxidant filled PP
6   PP85PL15MA2   28 ± 2  1.7 ± 0.1
more susceptible to microbial attacks [37].
7   PP85PL15MA4   30 ± 2  1.7 ± 0.1
8   PP85PL15MA6   31 ± 2  1.8 ± 0.1
9   PP85PL15MA8   18 ± 1  1.5 ± 0.1
10   PP85PL15MA4CaSt0.2   29 ± 1  1.6 ± 0.1 4.3 X-ray diffraction
11   PP85PL15MA4CoSt0.2   28 ± 1  2.2 ± 0.1
12   PP100CaSt0.2   35 ± 2  3.3 ± 0.1 The XRD patterns of all the samples are shown in Figure 3.
13   PP100CoSt0.2   35 ± 2  3.4 ± 0.1
The diffraction peaks of the PP shown at 2θ = 14.1°, 16.9°,

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6      D.K. Mandal et al.: Biodegradable PP/PLA blends and their properties

18.6°, 21.1° and 21.9° correspond to the α-monoclinic form

of PP. Addition of pro-oxidant in PP decreased the inten-
sity of these peaks, indicating the reduction of crystal-
linity. After addition of PLA in PP (PP85PL15 blend), the
intensity of the peaks decreased, but addition of compati-
bilizer in the PP85PL15MA4 did not have much effect on
the intensity of the peaks.
The percentage crystallinity of different samples is
calculated from Eq. (2) and is shown in Table 4. The per-
centage crystallinity of PP and PLA are 57% and 10%,
respectively. The addition of PLA into PP decreases crys-
tallinity from 57% to 47%; compatibilized blend has
almost the same crystallinity as that of PP85PL15. Addi-
tion of prooxidant also decreases the crystallinity as com-
pared to pure PP.

4.4 Rheology

It is well known that the structure of polymer blends influ-

Figure 2: DSC curves. (A) Melting behavior (heating curves) and (B)
crystallization (cooling curves) of PP, PLA and blend samples.
ences the rheological properties of the blends. The LVE
behavior of polymeric blends, especially in the melt state,
is a key factor to understand the processing structure-
property relationship of materials. In rheological property
measurements, first dynamic shear strain sweep test was
applied to characterize the viscoelastic region. The storage
modulus (G′) is taken as a measure of the energy stored in
the materials. It is dependent on what rearrangements can
take place within the period of oscillation, which is used
to estimate the elastic behaviors of the materials. On the
other hand, the loss modulus (G″) measures the energy
squandered or lost per capita of sinusoidal deforma-
tion, and it is characteristic of the viscous behaviors. The
storage modulus is a more sensitive rheological function
than the loss modulus to structural changes of the polymer
blends. Rheological studies of all the samples are shown
in Figure 4. The dependence of storage modulus (G′) and
loss modulus (G″) on the shear strain for all modified PP
samples are presented in Figure 4A and B. All blended

Table 3: Thermal properties and crystallinity of different samples (determined from DSC data).

Polymer/blend code   Tg (°C)   Tm (°C)   Tc (°C)   ΔHm (J/g)   Crystallinity (%)

PP   –   166   117   104   63

PLA   66   171   –   34   Negligible (amorphous)
PP85PL15   –   162   118   78   48
PP85PL15MA4   –   162   118   95   58
PP85PL15MA4CaSt0.2  –   162   123   90   55
PP85PL15MA4CoSt0.2  –   158   119   77   47
PP100CaSt0.2   –   164   122   78   48
PP100CoSt0.2   –   145   114   78   48

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 D.K. Mandal et al.: Biodegradable PP/PLA blends and their properties      7
Figure 3: XRD results of PP and pro-oxidant filled PP/PLA blends.
Table 4: Crystallinity of different samples as determined by XRD
analysis.
Sample no. Polymer/blendcode Crystallinity (%)
1 PP
2 PLA
3 PP85PL15
4 PP85PL15MA4
5 PP85PL15MA4CaSt0.2
6 PP85PL15MA4CoSt0.2
7 PP100CaSt0.2
8 PP100CoSt0.2
samples have shown a linear region (Newtonian plateau)
at lower shear strain and a nonlinear region at higher
shear strain. The storage modulus and loss modulus of the
blended samples are lower than those of PP.
The viscosity parameter is a measure of the resistance
to flow, specially the complex viscosity (η*). The complex
viscosity (η*) versus angular frequency (ω) curves for the
modified PP blends are given in Figure 4C. The complex
viscosity decreases monotonically with an increase in
angular frequency (shear thinning) for all the samples.
The decrease in η* with increase in ω indicates the
pseudo-plastic behavior of all the blends. With an increase
in shear rate, the viscosity has decreased for all the blends
as expected. The results suggested that addition of PLA
in PP (PP85PL15) decreases the viscosity of the blend due
to less entanglement and weak interaction between two
different polymers. However, the addition of compatibi-
lizer PP-g-MA (4 phr) in PP85PL15MA4 blend increases the
complex viscosity due to increase in the interaction and
compatibility between two different polymers. Compat-
ibility increases due to the increase in mobility of chains
at the interface caused by a chemical reaction between the
end group of PLA and MA group of PP-g-MA. Addition of
pro-oxidant in PP blends (PP100CoSt0.2, PP100CaSt0.2,
PP85PL15MA4CoSt0.2 and PP85PL15MA4CaSt0.2) also
decreases the complex viscosity but less significantly due
to the better mixing of pro-oxidant.
The elastic and viscous characteristics of the polymer
blends are well reflected in Figure 4D and E depicting
the storage modulus versus the angular frequency and
loss modulus versus angular frequency. The dependence
of G′ and G″ on the ω measures the relative motion of all
molecules in the bulk and can give important information
about the flow behavior of the melts [11]. Storage modulus
of PLA at low frequencies is extremely smaller than PP,
but it sharply increases with the enhancement of fre-
quency. Storage modulus of all blends increases monot-
onically with increase in frequency. The elasticity of the
blends is higher than PLA due to the strong segmental
interaction and chain entanglement. Addition of compati-
bizer in the PP85PLA15MA4 blend enhances the storage
modulus at all frequencies than that in PP85PL15 blend
57 due to the enhancement of chain entanglement between
10
PP and PLA. The loss modulus results are very similar to
47
51
the storage modulus outcome.
46 The dependence of the loss angle (tan δ) on frequency
44 of two different polymer blends with or without compat-
42 ibilizer and pro-oxidant is shown in Figure 4F. The loss
41 angle, which is expressed as the ratio of the loss to the
storage moduli, exhibits the viscoelastic damping behav-
ior of a polymer system. As seen for the blends, the tan δ
decreases with increase in frequency. A positive slope in
the tan δ curve shows the elastic response of the viscoe-
lastic samples. It can be observed from Figure 4F that the
slope of the tan δ curve is negative for all the samples,
showing that the blends behave as viscoelastic.
4.5 Scanning electron microscopy
Morphology of PP, PP100CaSt0.2, PP100CoSt0.2,
PP85PL15, PP85PL15MA4, PP85PL15MA4CaSt0.2, PP85PL-
15MA4CoSt0.2 and PLA studied by SEM are shown in
Figure 5. These SEM micrographs were taken on the cry-
ofractured surface of all the samples. The surfaces of PP
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8      D.K. Mandal et al.: Biodegradable PP/PLA blends and their properties

Figure 4: Rheology studies. (A) Storage modulus (G′) versus shear strain (γ), (B) loss modulus (G″) versus shear strain (γ), (C) complex
viscosity (η*) versus angular frequency (ω), (D) storage modulus (G′) versus angular frequency (ω), (E) loss modulus (G″) versus angular
frequency (ω), and (F) tan (δ) versus angular frequency (ω) of PP, PLA and blend samples.

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 D.K. Mandal et al.: Biodegradable PP/PLA blends and their properties      9
A B
C D
E F
G H
Figure 5: SEM images of (A) PP, (B) PP100CoSt0.2, (C) PP100CaSt0.2, (D) PP85PL15, (E) PP85PL15MA4, (F) PP85PL15MA4CoSt0.2,
(G) ­PP85PL15MA4CaSt0.2 and (H) PLA.
(Figure 5A) and PLA (Figure 5H) seem to look smoother
than other samples. More voids and roughness are present
in the PP85PL15 (Figure 5D) blend than PP and PLA indicat-
ing the presence of immiscibility in the blend due to phase
separation. This immiscibility is due to the brittle nature of
the PLA; this behavior is confirmed by the lowest storage
modulus. The blend PP85PL15MA4 (Figure 5E) containing
4 phr compatibilizer is showing much smoother surface
and co-continuous phase compared to blend PP85PL15.
The co-continuous phase of PP85PL15MA4 blend might
be the result of better compatibility and improved facial
adhesion between two different phases because of com-
patibilizerPP-g-MA. In contrast, further addition of pro-
oxidant in blends PP85PL15MA4CoSt0.2 (Figure 5F) and
PP85PL15MA4CaSt0.2 (Figure 5G) has reduced the inter-
face interaction, and several holes and pits were also
observed. Addition of calcium stearate and cobalt stearate
did not significantly change the morphology of the PP in
PP100CoSt0.2 (Figure 5B) and PP100CaSt0.2 (Figure 5C)
blends.
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10      D.K. Mandal et al.: Biodegradable PP/PLA blends and their properties
4.6 Biodegradation
Biodegradation test was conducted using biodegradation
testing apparatus under the controlled conditions. The
test apparatus was fabricated as per guideline of ASTM
standard D5338-11. In the biodegradation test, cellulose
was used as a positive reference and PP as negative ref-
erence. Figure  6 shows the biodegradability of all the
samples, which was calculated according to Eq. (3) in
45 days. The percentage biodegradability of all the samples
was as follows: cellulose (76%) > PP85PL15MA4CoSt0.2
(8.96%) > PP85PL15MA4CaSt0.2 (8.25%) > PP100CoSt0.2
(8.34%) > PP100CaSt0.2 (7.65%) > PP85PL15MA4 (3.48%) >  to increase in the functional groups, amorphous nature
A ceptible to attack of microorganisms [37]. Microorganisms
B further studies: PP100CaSt0.2, PP100CoSt0.2, PP85PL15,
Figure 6: Biodegradability of (A) cellulose and (B) PP and pro-oxi-
dant filled PP and PP/PLA blends.
PP85PL15 (3.2%). PP has not shown any biodegradability
due to their hydrophobic nature and unavailability of the
functional groups. But PLA is a biodegradable polymer.
Addition of PLA in PP85PLA15 blend reduces the crys-
tallinity of blend and is helpful for the microbial attack.
Microorganisms easily assimilate the amorphous part of
the polymer than the crystalline part. Addition of com-
patibilizer enhances the compatibility in PP85PLA15MA4
blend, but it also enhances the biodegradation of the
blend up to some extent. Addition of pro-oxidant (cobalt
stearate/calcium stearate) enhances the biodegradability
of PP and PP/PLA. Biodegradability enhancement is due
and a weak linkage in the blends. The more amorphous
nature of the pro-oxidant filled blends makes them sus-
consume them as an energy source and release CO2, H2O
and biomass as by-products [38]. Cobalt stearate filled PP
and PP/PLA blends have shown higher biodegradability
than calcium stearate filled PP. Higher biodegradability is
due to the susceptibility towards the thermal degradation
and availability of low molecular weight products for the
microbial attacks.
5 Conclusions
Pro-oxidant (calcium stearate/cobalt stearate) filled PP/
PLA blends and pro-oxidant filled PP blends have been
successfully formed in the internal mixer and moulded in
hot moulding press. The following blends were chosen for
PP85PL15MA4, PP85PL15MA4CaSt0.2 and PP85PL15MA-
4CoSt0.2 on the bases of tensile properties. DSC studies
revealed that addition of PLA leads to decrease in the Tm
and crystallinity of PP85PL15 blend. Addition of pro-oxi-
dant also decreases the crystallinity of the blends. The LVE
results have confirmed the enhancement of the complex
viscosity and storage modulus in PP85PL15MA4 blend.
But the addition of pro-oxidant reduces the complex vis-
cosity and storage modulus. The shear thinning behavior
is observed for PP and all PP/PLA blends. Morphology
analysis confirmed the increase in the void and rough-
ness on the addition of PLA in PP. The addition of com-
patibilizer reduces it, but further addition of pro-oxidant
(beyond 0.2 wt%) increases the void and roughness in the
blend. Biodegradability studies have confirmed that the
addition of pro-oxidant in the PP/PLA blend enhances the
biodegradability up to 8.96% for PP85PL15MA4CoSt0.2
blend.
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 D.K. Mandal et al.: Biodegradable PP/PLA blends and their properties      11
Acknowledgements: The authors gratefully acknowledge
the financial support from the Department of Atomic
Energy-Board of Research in Nuclear Sciences (DAE-
BRNS), Bhabha Atomic Research Centre, Govt. of India
through sanction no. 35/14/08/2014-BRNS. Special thanks
go to Dr. Debaprasad Mandal, Assistant Professor, Depart-
ment of Chemistry, IIT Ropar, Punjab, for helping with the
DSC experiments.
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