International Biodeterioration & Biodegradation 117 (2017) 278e288

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International Biodeterioration & Biodegradation

journal homepage: www.elsevier.com/locate/ibiod

Evaluation of biodegradability of green polyurethane/nanosilica

composite synthesized from transesterified castor oil and palm oil
based isocyanate
Sonalee Das*, Priyanka Pandey, Smita Mohanty, Sanjay Kumar Nayak
Laboratory for Advanced Research in Polymeric Materials, Central Institute of Plastics Engineering and Technology, Bhubaneshwar, Odisha 751024, India

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

Article history: This paper aims to assess the biodegradability of neat polyurethane and polyurethane/nanosilica com-
Received 20 July 2016 posite based on transesterified castor oil and isocyanate derived from palm oil under composting con-
Received in revised form dition for an exposure period of 90 days. Fungal and bacterial colonies have been isolated and identified
11 December 2016
from the surface of the degraded sample. The biodegradation of the films have been investigated in terms
Accepted 2 January 2017
of change in structural, morphological, weight loss and thermal properties. The FTIR results indicated
Available online 12 January 2017
noticeable changes between the spectra of unexposed and exposed samples, with respect to decrease in
the intensity of absorption bands corresponding to ester and urethane linkages suggesting the occur-
Keywords:
Transesterified castor oil
rence of biodegradation. The biodegradation has been also confirmed using SEM studies through the
Palm oil based isocyanate appearance of corrosive structures, cracks and surface pitting. However, faster rate of degradation has
Polyurethane been observed in case of polyurethane/nanosilica composite owing to its surface hydrophobicity, lower
Nanosilica crystallinity and presence of surface hydroxyl groups that facilitates attack of microorganisms.
Composting © 2017 Elsevier Ltd. All rights reserved.
Biodegradation
Crystallinity

1. Introduction
Over the past decade polyurethane (PUs) the 6th most used
class of heteropolymer has gained enormous attention in various
applications like coatings, adhesives, furniture and foams owing to
their exceptional mechanical properties and impeccable chemical
resistance and abrasion resistance (Gite et al., 2004; Zhang et al.,
2012). Due to its extensive applications the biodegradability of PU
has become an important factor in deciding its future market value
and prospects (Krasowska et al., 2012) in terms of eco friendly
nature. However, these polymers exhibit lack of biodegradability
and impose environmental hazards since, they are derived from
conventional petrobased isocyanate and synthetic polyol (Cangemi
et al., 2006; Hojabri et al., 2009). Hence, stringent efforts are being
undertaken worldwide for the development of biodegradable PU
which can undergo degradation in natural environment (Gloves,
1993). In this context “going green” by using renewable materials
like vegetable oils for synthesizing PU can be an important prop-
osition to design biodegradable materials.
* Corresponding author.
E-mail address: das.sonalee31@gmail.com (S. Das).
Amidst, all the non edible natural vegetable oil, Castor oil (CO) a
trifunctional polyester polyol with inherent hydroxyl group has
gained huge attention over the petro-based polyol for the synthesis
of biodegradable PUs (Cangemi et al., 2006; Kunduru et al., 2015;
Yeganeh et al., 2007). Isocyanate derived from palm oil may be an
efficient alternative to the petrobased isocyanate, owing to their
comparable reactivity and isocyanate content (Das et al., 2016).
Moreover, the properties of PUs derived from vegetable oil based
polyol and isocyanate can be tailored incorporating inorganic
nanofillers that can pave a way for designing prospective materials
with high end applications (Das et al., 2016). In recent years
nanosilica (NS) has been extensively used as a reinforcement to
enhance the mechanical, chemical, thermal and biodegradable
properties of PUs (Das et al., 2016: Jia-Hu et al., 2015: Han et al.,
2014). Biodegradation is a phenomenon of intentional chemical
degradation of polymeric chains provoked by microorganisms
present in the compost with the resultant disintegration of the
polymer segments (Nakkabi et al., 2015a,b, Oprea and Doroftei,
2011). Various literature reports have been published regarding
the degradation of PUs through composting which is a natural self-
heating process resulting higher rate of degradation accompanied
with an increase in temperature due to microbial growth and
respiration, as organic substrates are utilized (Kim and Kim, 1998,

http://dx.doi.org/10.1016/j.ibiod.2017.01.015
0964-8305/© 2017 Elsevier Ltd. All rights reserved.
 S. Das et al. / International Biodeterioration & Biodegradation 117 (2017) 278e288
Nakajima-Kambe et al., 1999, Oprea and Doroftei, 2011). The com-
posting technique presents a faster as well as cost effective eco-
friendly strategy to evaluate the biodegradability of PUs (Kim and
Kim, 1998, Sza
raz and Beczner, 2003, Muenmee et al., 2015). It
has been reported that microorganisms i.e. bacteria and fungi
present in the compost use PU as a source of nitrogen and carbon
for metabolism (Oceguera-Cervantes et al., 2007, Glass and Swift,
1989). These omnipresent microorganisms are liable for the
biodegradation of PU through colonization by producing enzymes
that can hydrolyse the methyl ester and urethane linkages (Oprea
and Doroftei, 2011, Cosgrove et al., 2007). However, till date liter-
ature reports regarding the degradation of in-situ synthesized
green PU/NS composite via composting are scanty.
Thus, the present study attempts to estimate the degradability
of in-situ synthesized PU/NS composite derived from trans-
esterified castor oil and palm oil based isocyanate via composting.
To the best of our information this is a distinctive approach towards
the synthesis and development of biodegradable green PU/NS
composites based on complete natural resources. For a better un-
derstanding, about the biodegradation rate, a comparative study
has been carried out in between neat PU and PU/NS composite. The
rate of biodegradation has been analysed by investigating the
morphological, chemical and thermal properties using scanning
electron microscopy (SEM), Fourier transform infrared analysis
(FTIR) and Differential scanning calorimetry (DSC).
2. Materials and method
The aliphatic isocyanate derived from palm oil (PoIs) was kindly
supplied by M/s. Vencorex Chemical, France. Castor oil (CO) polyol
was purchased from M/s.SD Fine chemicals (Kolkata, India). Chain
extender 1, 4 Butanediol (1, 4 BD), Pentaerythritol (PE) and litharge
catalyst (PbO) were purchased from M/s Himedia, India. The
dibutyltin dilaurate catalyst (DBTDL) and modified nanosilica par-
ticle (NS) with 99.9% purity were procured from M/s. Sigma Aldrich,
Germany and was used as received.
2.1. Transesterification of castor oil
The modification of CO using pentaerythritol (PE) at the opti-
mized molar ratio (PE/CO) of 0.2 in presence of 0.05% PbO by
transesterification process has been well documented in our earlier
literature reports (Das et al., 2015a,b). The obtained transesterified
castor oil was named as MCO. The hydroxyl value of MCO as
determined through ASTM D-1957 was found to be 234 mgKOH/g.
In addition, the complete information regarding the reaction
mechanism, including the physical properties of MCO has been
elaborated in our earlier publication (Das et al., 2015a,b).
2.1.1. Synthesis of neat polyurethane and polyurethane nanosilica
composite
The synthesis of neat PU utilizing MCO, PoIs and 1, 4 BD at an
optimized NCO: OH molar ratio of 1.4:1 has been carried out using a
well established method and was named as MBPU (Das et al., 2016).
The in-situ preparation of PU/NS composite has been also car-
ried out at the optimized NCO: OH molar ratio of 1.4:1 using MCO,
PoIs, 1, 4 BD with 2.5 wt (%) of NS particle as illustrated in our recent
publication (Das et al., 2016) and was named as MBPU/NS. The
detailed report about the physical properties of MBPU and MBPU/
NS has been well elaborated in our previous publications (Das et al.,
2015a,b, 2016). The reaction parameter and actual composition of
the reactants have been summarized in Table 1.
279
2.2. Biodegradability analysis of MBPU and MBPU/NS via.
Composting technique
The biodegradation of MBPU and MBPU/NS film samples with
dimension (2
2) cm2 was carried through composting technique
for 90 days as per BS standard EN ISO 846. The compost prepared
under natural environment and consisted of food waste, cow dung,
dried leaves, straw and waste papers. Red worms like Eisenia foetida
present in compost, actively convert the decaying matter into
product called worm castings which are rich in organic nutrients
(Cooperband, 2002, Gu et al., 1994). Biodegradation via. composting
provides a conducive environment for co-metabolism with rich
organic matrix and elevated temperature that can assist in
biodegradation (Williams et al., 1992, Kastner and Mahro, 1996,
Tuomela et al., 2000). It has been reported that the distinctive
features of compost such as dry solid content, ash content, C/N ratio
and pH have considerable influence on the growth of micro-
organisms (Krasowska et al., 2012). Hence, these parameters were
monitored prior to the degradation process and the values obtained
are summarized in Table 2.
For the bio-degradation study 5 test specimens of MBPU and
MBPU/NS respectively were buried in the compost taken in sepa-
rate 100 ml beaker. The respective beakers were kept in a well
ventilated place with average temperature being maintained at
30  C during the test period. The moisture content of the compost
in the beakers was maintained at approximately 30% throughout
the test. Respective film samples were removed at regular interval
of 30, 45, 60, 75 and 90 days washed with deionised water to
analyse the structural changes, weight loss, surface morphology
and thermal properties after degradation.
2.3. Isolation and identification of polyurethane degrading
microorganisms
The microorganisms responsible for degradtion were isolated
from the compost present on the surface of the degraded PU
sample using a clean cotton swap to avoid contamination. Spread
plate technique was utilized for identifying and quantifying the
microorganisms present in the degraded sample surface. The
compost collected from the degraded sample was diluted through
the serial dilution technique in phosphate buffer saline (PBS) and a
small amount of this highly diluted solution was placed on steril-
ized dry agar plate and potato dextrose agar (PDA) plate for iden-
tifying the bacterial and fungal colonies respectively (Crabbe et al.,
1994). The dry agar plate and PDA plate were kept in dark at room
temperature for incubation of colonies. After incubation the bac-
terial and fungal colonies were observed through microscope and
depicted in Fig. 1. The identification of bacterial and fungal colonies
was carried out through gram staining which gave an idea about
the shape, colony morphology and cell arrangement etc. The
quantification of these bacterial and fungal colonies was done
through spread plate technique and represented in terms of colony
forming unit (CFU).
2.4. Residual weight loss measurement
The residual weight loss of degraded MBPU and MBPU/NS film
Table 1
Details regarding the synthesis parameter and reactant composition.
Code NCO:OH MCO PoIs 1,4 BD NS (wt. %)
MBPU 1.4:1 30 49.7 10 e
MBPU/NS 1.4:1 30 49.7 10 2.5
280 S. Das et al. / International Biodeterioration & Biodegradation 117 (2017) 278e288
Table 2
Characteristics of compost.
Compost characteristics Value
Dry solid content 51.24
Ash content 31.32
C/N ratio 28
pH 7.5e8.2
was determined using equation (1) to give an indication regarding
microbial degradation and to determine the amount of residual
polymer left after composting. The respective exposed film samples
were isolated from the compost, cleaned thoroughly with deion-
ised water and dried at ambient temperature to attain constant
weight (Wt). The residual weight loss was then calculated using the
weight after incubation (Wt) and weight before incubation (W1) i.e.
W1 ðW1  Wt Þ
Residual Weight loss ¼
100
where W1 is the initial weight of the sample prior to exposure (t ¼ 0
day) and, Wt is the final weight of sample obtained after t days
(where, t ¼ 30, 45, 60, 75 and 90 days).
2.5. Differential scanning calorimetry (DSC) analysis
The change in the physical structure and the variation in glass
transition temperature (Tg) of the exposed MBPU and MBPU/NS
film samples was investigated by using DSC analysis (Q 20, M/s. TA
instruments, USA) at a scanning rate of 10  C/min under N2 flow
within a temperature range of 70  C to 100  C.
2.6. Wide angled X-Ray diffraction analysis (WAXD) analysis
WAXD analysis was carried out using (M/s. Shimadzu XRD-700L,
X-Pert MPD, Japan) equipped with Cu Ka radiation source and
monochromatic graphite operated at 40 kV and 30 mA to charac-
terize the crystallinity of neat MBPU and MBPU/NS films. The
scanning 2q angle ranged from 2 to 70 with a test speed of 5 /min.
Fig. 1. Plates with isolated (a) Bacterial colonies and (b) Fungal colonies.
2.7. Fourier transform infrared spectroscopy (FTIR) analysis
FTIR analysis of unexposed and exposed MBPU and MBPU/NS
film samples were analysed using M/s. Nicolet 6700, Thermo Sci-
entific equipped with omnic software for analysis and data
collection in the frequency range of 4000e400 cm1 to detect the
changes in surface functional groups on account of composting.
2.8. Scanning electron microscopy (SEM) analysis
SEM micrographs were recorded using (M/s. EVO MA 15, Carl
Zeiss, Germany) instrument to assess the change in surface
morphology of the exposed samples by comparing with the mi-
crographs of the control one. The respective degraded MBPU and
MBPU/NS film samples taken out at regular interval from the
compost were cleaned with distilled water and sputter coated with
Au/Pd mixture to make the surface conductive prior to the SEM
(1)
analysis.
3. Results
3.1. Identification and analysis of the microbial community
It was revealed from the spread plate technique that 1 gm of
compost sample contains 2.4
105 CFU/gm of bacteria and
2.4
101 CFU/gm of fungi. This indicates that the bacterial species
were predominant as compared to the fungal ones in the compost
sample collected from the surface of the PU sample. The isolated
bacterial and fungal colonies were identified through gram staining
technique and their microscopic images are depicted in Fig. 2(aeb).
Both gram negative and gram positive bacteria were found to be
present in the compost material isolated from the surface of the
sample. The bacterial isolates were found to be Bacillus sp. i.e.
gram þ ve and Cocco Bacillus sp. i.e. gram -ve. On the other hand,
the fungal isolates were identified as Aspergillus sp., Penicillium sp.
and Mucor sp. Similar fungal and bacterial colonies were also
identified from the isolates recovered from compost and PU surface
by (Zafar et al., 2014, Cangemi et al., 2008, Shah et al., 2008,
Cosgrove et al., 2007).
 S. Das et al. / International Biodeterioration & Biodegradation 117 (2017) 278e288 281

3.2. Wide angled X-ray diffraction (WAXD) analysis Moreover, clear growth of bacterial and fungal colonies could be
seen on the surface of MBPU and MBPU/NS samples buried in the
Broad diffraction halo nearly at 2q ¼ 20 , was observed for both compost. Similar observation have been reported by (Nakkabi et al.,
MBPU and MBPU/NS film associated with the amorphous phase of 2015a,b, Malik and Grohmann, 2011). Further, Robert et al. (1998)
PUs (Fig. 3). This broad peak is due to the long aliphatic hydrocar- and Shah et al. (2008) have also reported about the adherence of
bon chain in MCO which remains as a pendant group, and hinders Bacillus sp. on the surface of PU which is in good agreement to the
the close packing increasing the flexibility and amorphous content
(Bao et al., 2006, Bhunia et al., 1998). However, with the inclusion of
NS, the peak intensity of composite is lowered, which suggests that
there is a homogenous dispersion of NS resulting in a strong
interfacial interaction within MBPU and NS particle in the nano-
structured film (Zhang et al., 2011).

3.3. Visual inspection

It was mandatory to investigate the visible changes on the

surface of exposed MBPU and MBPU/NS film since, the degradation
owing to bacterial and fungal attack initiates at the outer surface
(Oprea and Doroftei, 2011). Fig. 4 represents the visual images
regarding the degradation of MBPU and MBPU/NS before and after
90 days of exposure to confirm the biodegradability behaviour of
the samples. It can be clearly observed, that the surface of the
control sample is rather smooth while, the exposed sample became
rougher after exposure to microorganisms in compost indicating
considerable level of surface degradation (Nakkabi et al., 2015a,b).
Both exposed MBPU and MBPU/NS films showed noticeable surface
deformation with colour change from white to brown and whit-
ening indicating surface degradation (Persenaire et al., 2001).
Fig. 3. WAXD pattern of (a) MBPU and (b) MBPU/NS film.

Fig. 2. Identified (a) Bacterial genus and (b) Fungal genus in polyurethane surface.
282 S. Das et al. / International Biodeterioration & Biodegradation 117 (2017) 278e288
present observation. Further, quantitative tests were also per-
formed in order to confirm the degradation of exposed MBPU and
MBPU/NS samples through weight loss, morphological and chem-
ical changes.
3.4. Polyurethane structural characterization
FTIR spectroscopy has been utilized to analyse the structural
changes in MBPU and MBPU/NS during composting on account of
biodegradation. Fig. 5 and Fig. 6 represents the spectra of MBPU and
MBPU/NS before and after composting. Much attention has been
paid to the labile vulnerable linkages i.e. ester, urethane and amide
since, they are reported to be responsible for biodegrading poly-
ester PU (Oprea and Doroftei, 2011, Howard and Hilliard, 1999,
Akutsu et al., 1998). Scheme 1 represents the degradation reac-
tion mechanism of MBPU under fungal and bacterial attack. The
spectra of unexposed film samples of MBPU and MBPU/NS have
been taken as a benchmark, from which the change in band pattern
can be investigated in the respective exposed samples. The most
important characteristic bands observed for unexposed MBPU and
MBPU/NS samples were located at 2972-2853 cm1 for asymmetric
and symmetric eCH2 stretching vibration, 3300 to 3600 cm1 for
eNH stretching vibration and 1740 to 1685 cm1 for urethane
carbonyl stretching vibration. Moreover, other characteristic bands
were also observed between 1540 and 1500 cm1 related to d-NH þ
d-CN þ d-C-C, 1300-1200 cm1 for d-NH bending þ d-CN þ d-C-C and at
1042 cm1 for of ester eC]O axial deformation stretching vibra-
tions. The additional bands at 1181-1101 cm1 corresponding to
SieOeSi asymmetric stretching vibration and at 772 cm1 for
OeSieO linkage in MBPU/NS composite were also observed (Das
Fig. 4. Visual inspection of MBPU and MBPU/NS samples in compost after 0 days and 90 days.
et al., 2015a,b).
FTIR analysis of exposed MBPU and MBPU/NS film samples
indicated that with gradual increase in degradation time peak at
2972 cm1 and 2853 cm1 shifts to lower wavenumber that is
attributed to the cleavage of eCH bonds in PUs (Shah et al., 2008).
The band corresponding to eNH stretching vibration at 3288 cm1
for MBPU and 3277 cm1 for MBPU/NS indicated an increase in
intensity and broadening upon increment in exposure time due to
the formation of eOH groups (Oprea and Doroftei, 2011). This
observation was further supported through the formation of glyc-
erol (see Scheme 1) as a by-product formed during the composting
process. Chow et al. (2014) has also mentioned about the formation
of glycerol and free fatty acid intermediates due to the action of
microbial lipase enzyme in fungi and bacteria as a carbon source for
metabolism. In addition, carbon dioxide and water were also
observed to be formed as by-products during this biodegradation
process as reported by Kim and Kim (1998) (see Scheme 1). The
decrease in intensity of the urethane carbonyl peak at 1714 cm1 for
MBPU and 1685 cm1 for MBPU/NS with increase in exposure time
might be due to the chain scission of urethane group (-ROe
COeNH2) due to fungal attack resulting in free amine (Oprea and
Doroftei, 2011) (see Scheme 1). Thus, the decrease in intensity of
urethane carbonyl peak confirms the occurrence of biodegradation
through the dissociation of ester linkages (Fukushima et al., 2010:
Filip et al., 2008). Further, in both the cases the peak located at
1042 cm1 for ester C]O also diminished in intensity after expo-
sure, confirming structural change in the urethane and ester link-
ages (Oprea and Doroftei, 2011, Silverstein and Webster, 2000,
Albertsson and Karlsson, 1993). Moreover, the band intensity of
SieOeSi linkage and OeSieO linkage in MBPU/NS also decreased
 S. Das et al. / International Biodeterioration & Biodegradation 117 (2017) 278e288 283

Fig. 5. Comparison of FTIR spectrum of unexposed and exposed MBPU composite film.

Fig. 6. Comparison of FTIR spectrum of unexposed and exposed MBPU/NS composite film.

with exposure time which can be attributed to the surface reor-
ganization of the NS particles (Raghunath et al., 2008). The prob-
able reason behind the above observations has been elucidated
below.
In general, the degradation mechanism of MBPU and MBPU/NS
follows two stages i.e. (a) hydrophobic adsorption of
microorganism onto the surface of PU followed by (b) hydrolysis of
the ester bonds in PU breaking them to smaller molecular units
resulting surface erosion with further hydrolysis process (Kim and
Kim, 1998:Akutsu et al., 1998). This results in chain scission of PU
due to the hydrolysis process by extracellular enzymes secreted by
the microorganisms for metabolism (Kim and Kim, 1998: Zanetti-
284 S. Das et al. / International Biodeterioration & Biodegradation 117 (2017) 278e288

Scheme 1. Biodegradation reaction mechanism of MBPU film during composting.

Ramos et al., 2005). Protease, urease and esterase are the extra-
cellular enzymes secreted by fungi and bacteria which are reported
to be responsible for the degradation of polyester PU (Nakajima
Kambe et al., 1999, Howard, 2002). In addition, Rowe and Howard
(2002), Tokiwa and Suzuki (1974) and Pathirana and Seal (1985a)
have mentioned about the secretion of esterolytic enzyme like
lipase and esterase secreted by Bacillus sp. and fungal community. It
is likely that the above mentioned extracellular enzymes owing to
their enzymatic behaviour adhere onto the PU surface. As a
consequence, the bacterial and fungal species stick to the PU sur-
face thereby hydrolyzing the PU substrate to metabolites (Shah
et al., 2008). Thus, it was assumed that these enzymes have a
catalytic domain and a hydrophobic PU surface binding domain
wherein, the later was associated for degrading PU (Nakajima-
Kambe et al., 1999). Further, the results also support the fact that
the soft segment region is more biodegradable as compared to the
hard segment region (Kim and Kim, 1998).
However, from the figures it can be observed that MBPU/NS
reveal pronounced decrease in the intensity of the above
mentioned peaks as compared to MBPU indicating higher vulner-
ability of former to microbial attack. Reports by Kim and Kim (1998)
mentioned that the degradation rate of polymer depends upon the
ease of surface adhesion and subsequent colonization of microor-
ganisms on its surface. Thus, we can assume that the degradation of
 S. Das et al. / International Biodeterioration & Biodegradation 117 (2017) 278e288 285

MBPU and MBPU/NS proceeds through an inhomogeneous mech-

anism due to differential rate of adsorption of microorganisms onto
the sample surface resulting different extent of microbial growth as
reported by Fukushima et al. (2010). This might be due to the higher
surface hydrophobicity of MBPU/NS composite film as revealed
from our recent studies (Das et al., 2015a,b) which favour prefer-
ential adhesion of microorganisms onto its surface resulting faster
rate of degradation as compared to MBPU (Kim and Kim, 1998).
Similar observation has been reported by Pringle and Fletcher
(1983) and Bitritto et al. (1979) for bacterial and fungal colonies.
Moreover, the silanol groups on the surface of NS alongwith its
lower crystallinity creates a synergistic effect for preferential mi-
crobial interaction during composting (Han et al., 2008). This im-
plies that the presence of NS particles can increase the
susceptibility of MBPU surface to microbial attack resulting frag-
mentation of polymer chain and higher degradation of functional
groups in composite.

3.5. Residual weight loss measurement

The residual weight loss curves of MBPU and MBPU/NS as a Fig. 7. Residual Weight loss curve of MBPU and MBPU/NS as a function of degradation
function of time (t) is depicted in Fig. 7 to examine the intensity of time.
fungal and bacterial degradation. It can be seen that both MBPU and
MBPU/NS exhibited a significant decrease in their physical weight
MBPU and MBPU/NS before and after exposure to the microbial
to about 0.3 g and 0.5 g respectively, as compared to the initial one,
community in compost. It can be clearly observed, that the surface
after 30 days of exposure. The weight loss of the exposed samples is
of the controlled samples is rather smooth and continuous. In
presumable due to the fungal and bacterial degradation which
addition, it can be clearly seen from Fig. 8 (a) that the NS particles
disintegrate the fatty acid of MCO into smaller units for cell meta-
are dispersed uniformly within the MBPU matrix devoid of any
bolism (Fukushima et al., 2011, Chow et al., 2014). From the residual
agglomeration (Das et al., 2016). After microbial exposure consid-
weight loss curve it is also clear that this biodegradation process
erable damage was observed through increase in roughness and
during composting is autocatalytic in nature wherein, there is
inhomogeneous morphology which indicated surface degradation
significant weight loss with increase in exposure time. Earlier
(Nakkabi et al., 2015a,b). The increase in roughness of the exposed
report by Khan and Khan (2012) suggests that this autocatalytic
samples was due to the impregnation of microorganisms which use
behaviour is due to the cleavage of ester linkage in the PU backbone
PU as a resource of carbon and nitrogen for metabolic growth
at the initial stage to produce carboxyl end group. This further leads
(Akutsu et al., 1998, Starnecker and Menner, 1996). Further damage
to the autocatalysis and hydrolysis of the remaining ester linkages
to the PU surface was observed through the appearance of large
at the later stage of biodegradation. However, after certain time it
porous structure with fungal mycelia, bacterial colonies, deep pits,
was noticed that there was no further reduction in the physical
cracks, and erosion regions like webs which became more promi-
weight which can be attributed to the decrease in the hydrolysis
nent with increase in exposure time (Oprea, 2010). This might be
rate by microorganisms owing to the heavy consumption of ester
due to the hydrolytic degradation process (Krasowska et al., 2012,
linkages in PU (Azevedo and Reis Rui, 2005, Rutkowska et al., 2002).
Pinchuk et al., 2004, Nakkabi et al., 2015a,b) as discussed in
Thus, the results obtained are consistent to the FTIR observation
earlier section by the enzymes secreted by the bacterial and fungal
confirming the disintegration of ester linkages by the identified
community. Moreover, the presence of pores in exposed MBPU and
bacterial and fungal community in the compost.
MBPU/NS surface are the focal point of microorganism invasion
Furthermore, it was observed that MBPU/NS exhibits relatively
resulting peeling off of polymer layers (i.e. delamination) which
higher weight loss as compared to MBPU over the entire test
aids in degradation increasing the surface roughness as well as
duration revealing faster rate of degradation. This variation in the
non-homogeneity of the surface (Pramanik et al., 2013). Oprea
rate of degradation within MBPU and MBPU/NS indicates the role of
(2010) has also found similar fungal colonies colonized on the
NS which can be explained on the basis of an analogous mechanism
PUA/ESO blend film after 130 days of exposure. Motta et al. (2009)
as reported by Dutta et al. (2009) wherein, the presence of hydroxyl
reported that for biodegradation of polymers such colonization by
groups in NS surface enhance the susceptibility to microbial attack
microbes is a basic requirement. Thus, taking into consideration the
resulting in heterogeneous hydrolysis (Fukushima et al., 2011).
above facts and figures it is confirmed that MCO based MBPU and
Moreover, the relatively lower crystallinity of MBPU/NS composite
MBPU/NS are biodegradable by the identified fungal and bacterial
film as signified through WAXD studies might be another probable
communities present in the compost.
reason behind its faster continued rate of weight loss as compared
However, it is clear from the SEM micrographs that the most
to MBPU film (Han et al., 2008). Thus, the results obtained confirms
distorted surface morphology was observed in MBPU/NS as
that the inclusion of NS particles within the MBPU matrix provides
compared to MBPU. The presence of holes on the degraded surface
active sites for microbial attack and interaction that in turn leads to
of MBPU/NS reveals a significant amount of surface erosion due to
improved degradability of MBPU/NS.
chain scission and pitting which initiates from the surface to the
interior (Wu et al., 1992, Christenson et al., 2004; Oprea, 2010).
3.6. Scanning electron microscopy (SEM) analysis
According to Fukushima et al. (2011) since, the degradation initiate
from sample surface to its interior it can be suggested that the NS
The surface morphological change of MBPU and MBPU/NS was
particle cannot serve as a barrier to the microbial attack or to the
investigated through SEM in order to confirm the occurrence of
diffusion of water. This phenomenon is due to the presence of
biodegradation. Fig. 8 and Fig. 9 represent the SEM micrographs of
286 S. Das et al. / International Biodeterioration & Biodegradation 117 (2017) 278e288

Fig. 8. SEM micrographs of MBPU for (a) 0 days (b) 30 days (c) 45 days (d) 60 days (e) 75 days and (f) 90 days.

Fig. 9. SEM micrographs of MBPU/NS for (a) 0 days (b) 30 days (c) 45 days (d) 60 days (e) 75 days and (f) 90 days.
 S. Das et al. / International Biodeterioration & Biodegradation 117 (2017) 278e288
surface silanol group in NS and to due to its low aspect ratio which
leads to the scission of the ester and urethane linkage and marginal
acceleration of the degradation process in MBPU/NS.
Thus, the SEM observation also corroborates with the FTIR and
residual weight loss confirming higher biodegradability of MBPU/
NS composite film owing to its chemical structure and composition.
3.7. Differential scanning calorimetry (DSC) analysis
The DSC thermogram of unexposed and exposed MBPU and
MBPU/NS film were intended to confirm the polymer chain scission
observation obtained in the earlier sections and results are sum-
marized in Table 3. Both MBPU and MBPU/NS films exhibited two
glass transition temperatures as depicted in table, the first transi-
tion observed at negative temperature corresponds to the soft
segment (Tgss) i.e. polyol while, the second transition observed at
positive temperature corresponds to the hard segment (Tghs) i.e.
isocyanate and chain extender (Das et al., 2015a,b). It was observed
that both the exposed PU samples indicated substantial reduction
in the temperature corresponding to Tgss and Tghs with respect to
their initial values revealing microbial degradation (Fukushima
et al., 2011). The reduction in Tgss of the exposed MBPU and
MBPU/NS film might be due to the increased flexibility associated
with the amorphous soft segment (Zafar et al., 2014) This is due to
chain scission of the ester groups in MCO as observed in FTIR
analysis (Krasowska et al., 2012). On the other hand, the reduction
in Tghs of the exposed MBPU and MBPU/NS film is due to the
decrease in the physical crosslinks of the hard segment (Zafar et al.,
2014). This is probably due to the scission of the urethane groups
and polymer segment thereby increasing the plasticizing effect and
reducing the crosslinking density of the polymer chain (Fukushima
et al., 2009). Thus, the synergistic influence of change in hard
segment and soft segment explains the decrease in Tgss as well as
Tghs of MBPU and MBPU/NS respectively, during composting (Zafar
et al., 2014). However, MBPU/NS composite films exhibits signifi-
cant reduction in Tgss and Tghs values as compared to the corre-
sponding MBPU film which might be due to the previously
suggested factors as discussed earlier.
Thus, the DSC results also corroborates with the above findings
confirming higher degradability in MBPU/NS as compared to neat
MBPU.
4. Conclusion
The rate of biodegradation of MBPU and MBPU/NS synthesized
from transesterified castor oil, palm oil isocyanate and nanosilica as
a reinforcing filler was determined through weight loss, FTIR, SEM
and DSC. Gram staining technique indicated the presence of bac-
terial and fungal colonies in the compost. The hydrolysis of ester
and urethane linkages in MBPU and MBPU/NS by the extracellular
enzymes was indicated through FTIR spectra. Residual weight loss
curve revealed decrease in physical weight of MBPU and MBPU/NS
after exposure to compost. SEM micrograph study indicated surface
Table 3
DSC data of unexposed and exposed MBPU and MBPU/NS.
Days MBPU MBPU/NS
Tgss ( C) Tghs( C) Tgss( C)
0 26.06 72.6 21.6
30 30 70.2 26.5
45 34.5 68.6 30.1
60 36.7 65.3 33.2
75 39.1 62.9 36.1
90 39.6 62 36.8
287
whitening and deformation in the form of cracks, pits and pores
confirming the chain scission and microbial degradation of MBPU
and MBPU/NS. Further, DSC thermogram revealed reduction in Tgss
and Tghs of MBPU and MBPU/NS due to plasticizing effect. Thus, the
above findings imply that MBPU and MBPU/NS synthesized from
transesterified castor oil and palm oil based isocyanate can be easily
degraded by the identified bacterial and fungal community in the
compost. However, it was found that MBPU/NS exhibit higher
biodegradation rate as compared to MBPU due to its structural
organization and composition. Thus, the green MBPU/NS composite
represent a useful biodegradable material with promising appli-
cation to design eco-friendly products in future.
Acknowledgement
The authors thank Department of Chemicals and Petrochemi-
cals, Government of India (No.15012/1/2013-PC-I) for the financial
support.
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