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International Biodeterioration & Biodegradation 117 (2017) 278e288

Contents lists available at ScienceDirect

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 Amidst, all the non edible natural vegetable oil, Castor oil (CO) a
trifunctional polyester polyol with inherent hydroxyl group has
Over the past decade polyurethane (PUs) the 6th most used gained huge attention over the petro-based polyol for the synthesis
class of heteropolymer has gained enormous attention in various of biodegradable PUs (Cangemi et al., 2006; Kunduru et al., 2015;
applications like coatings, adhesives, furniture and foams owing to Yeganeh et al., 2007). Isocyanate derived from palm oil may be an
their exceptional mechanical properties and impeccable chemical efficient alternative to the petrobased isocyanate, owing to their
resistance and abrasion resistance (Gite et al., 2004; Zhang et al., comparable reactivity and isocyanate content (Das et al., 2016).
2012). Due to its extensive applications the biodegradability of PU Moreover, the properties of PUs derived from vegetable oil based
has become an important factor in deciding its future market value polyol and isocyanate can be tailored incorporating inorganic
and prospects (Krasowska et al., 2012) in terms of eco friendly nanofillers that can pave a way for designing prospective materials
nature. However, these polymers exhibit lack of biodegradability with high end applications (Das et al., 2016). In recent years
and impose environmental hazards since, they are derived from nanosilica (NS) has been extensively used as a reinforcement to
conventional petrobased isocyanate and synthetic polyol (Cangemi enhance the mechanical, chemical, thermal and biodegradable
et al., 2006; Hojabri et al., 2009). Hence, stringent efforts are being properties of PUs (Das et al., 2016: Jia-Hu et al., 2015: Han et al.,
undertaken worldwide for the development of biodegradable PU 2014). Biodegradation is a phenomenon of intentional chemical
which can undergo degradation in natural environment (Gloves, degradation of polymeric chains provoked by microorganisms
1993). In this context “going green” by using renewable materials present in the compost with the resultant disintegration of the
like vegetable oils for synthesizing PU can be an important prop- polymer segments (Nakkabi et al., 2015a,b, Oprea and Doroftei,
osition to design biodegradable materials. 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
* Corresponding author. with an increase in temperature due to microbial growth and
E-mail address: das.sonalee31@gmail.com (S. Das). 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 279

Nakajima-Kambe et al., 1999, Oprea and Doroftei, 2011). The com- 2.2. Biodegradability analysis of MBPU and MBPU/NS via.
posting technique presents a faster as well as cost effective eco- Composting technique
friendly strategy to evaluate the biodegradability of PUs (Kim and
Kim, 1998, Sza raz and Beczner, 2003, Muenmee et al., 2015). It The biodegradation of MBPU and MBPU/NS film samples with
has been reported that microorganisms i.e. bacteria and fungi dimension (2  2) cm2 was carried through composting technique
present in the compost use PU as a source of nitrogen and carbon for 90 days as per BS standard EN ISO 846. The compost prepared
for metabolism (Oceguera-Cervantes et al., 2007, Glass and Swift, under natural environment and consisted of food waste, cow dung,
1989). These omnipresent microorganisms are liable for the dried leaves, straw and waste papers. Red worms like Eisenia foetida
biodegradation of PU through colonization by producing enzymes present in compost, actively convert the decaying matter into
that can hydrolyse the methyl ester and urethane linkages (Oprea product called worm castings which are rich in organic nutrients
and Doroftei, 2011, Cosgrove et al., 2007). However, till date liter- (Cooperband, 2002, Gu et al., 1994). Biodegradation via. composting
ature reports regarding the degradation of in-situ synthesized provides a conducive environment for co-metabolism with rich
green PU/NS composite via composting are scanty. organic matrix and elevated temperature that can assist in
Thus, the present study attempts to estimate the degradability biodegradation (Williams et al., 1992, Kastner and Mahro, 1996,
of in-situ synthesized PU/NS composite derived from trans- Tuomela et al., 2000). It has been reported that the distinctive
esterified castor oil and palm oil based isocyanate via composting. features of compost such as dry solid content, ash content, C/N ratio
To the best of our information this is a distinctive approach towards and pH have considerable influence on the growth of micro-
the synthesis and development of biodegradable green PU/NS organisms (Krasowska et al., 2012). Hence, these parameters were
composites based on complete natural resources. For a better un- monitored prior to the degradation process and the values obtained
derstanding, about the biodegradation rate, a comparative study are summarized in Table 2.
has been carried out in between neat PU and PU/NS composite. The For the bio-degradation study 5 test specimens of MBPU and
rate of biodegradation has been analysed by investigating the MBPU/NS respectively were buried in the compost taken in sepa-
morphological, chemical and thermal properties using scanning rate 100 ml beaker. The respective beakers were kept in a well
electron microscopy (SEM), Fourier transform infrared analysis ventilated place with average temperature being maintained at
(FTIR) and Differential scanning calorimetry (DSC). 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
2. Materials and method of 30, 45, 60, 75 and 90 days washed with deionised water to
analyse the structural changes, weight loss, surface morphology
The aliphatic isocyanate derived from palm oil (PoIs) was kindly and thermal properties after degradation.
supplied by M/s. Vencorex Chemical, France. Castor oil (CO) polyol
was purchased from M/s.SD Fine chemicals (Kolkata, India). Chain 2.3. Isolation and identification of polyurethane degrading
extender 1, 4 Butanediol (1, 4 BD), Pentaerythritol (PE) and litharge microorganisms
catalyst (PbO) were purchased from M/s Himedia, India. The
dibutyltin dilaurate catalyst (DBTDL) and modified nanosilica par- The microorganisms responsible for degradtion were isolated
ticle (NS) with 99.9% purity were procured from M/s. Sigma Aldrich, from the compost present on the surface of the degraded PU
Germany and was used as received. 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
2.1. Transesterification of castor oil compost collected from the degraded sample was diluted through
the serial dilution technique in phosphate buffer saline (PBS) and a
The modification of CO using pentaerythritol (PE) at the opti- small amount of this highly diluted solution was placed on steril-
mized molar ratio (PE/CO) of 0.2 in presence of 0.05% PbO by ized dry agar plate and potato dextrose agar (PDA) plate for iden-
transesterification process has been well documented in our earlier tifying the bacterial and fungal colonies respectively (Crabbe et al.,
literature reports (Das et al., 2015a,b). The obtained transesterified 1994). The dry agar plate and PDA plate were kept in dark at room
castor oil was named as MCO. The hydroxyl value of MCO as temperature for incubation of colonies. After incubation the bac-
determined through ASTM D-1957 was found to be 234 mgKOH/g. terial and fungal colonies were observed through microscope and
In addition, the complete information regarding the reaction depicted in Fig. 1. The identification of bacterial and fungal colonies
mechanism, including the physical properties of MCO has been was carried out through gram staining which gave an idea about
elaborated in our earlier publication (Das et al., 2015a,b). 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
2.1.1. Synthesis of neat polyurethane and polyurethane nanosilica forming unit (CFU).
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 2.4. Residual weight loss measurement
well established method and was named as MBPU (Das et al., 2016).
The in-situ preparation of PU/NS composite has been also car- The residual weight loss of degraded MBPU and MBPU/NS film
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 Table 1
publication (Das et al., 2016) and was named as MBPU/NS. The Details regarding the synthesis parameter and reactant composition.
detailed report about the physical properties of MBPU and MBPU/
Code NCO:OH MCO PoIs 1,4 BD NS (wt. %)
NS has been well elaborated in our previous publications (Das et al.,
2015a,b, 2016). The reaction parameter and actual composition of MBPU 1.4:1 30 49.7 10 e
MBPU/NS 1.4:1 30 49.7 10 2.5
the reactants have been summarized in Table 1.
280 S. Das et al. / International Biodeterioration & Biodegradation 117 (2017) 278e288

Table 2 2.7. Fourier transform infrared spectroscopy (FTIR) analysis


Characteristics of compost.

Compost characteristics Value FTIR analysis of unexposed and exposed MBPU and MBPU/NS
Dry solid content 51.24
film samples were analysed using M/s. Nicolet 6700, Thermo Sci-
Ash content 31.32 entific equipped with omnic software for analysis and data
C/N ratio 28 collection in the frequency range of 4000e400 cm1 to detect the
pH 7.5e8.2 changes in surface functional groups on account of composting.

was determined using equation (1) to give an indication regarding 2.8. Scanning electron microscopy (SEM) analysis
microbial degradation and to determine the amount of residual
polymer left after composting. The respective exposed film samples SEM micrographs were recorded using (M/s. EVO MA 15, Carl
were isolated from the compost, cleaned thoroughly with deion- Zeiss, Germany) instrument to assess the change in surface
ised water and dried at ambient temperature to attain constant morphology of the exposed samples by comparing with the mi-
weight (Wt). The residual weight loss was then calculated using the crographs of the control one. The respective degraded MBPU and
weight after incubation (Wt) and weight before incubation (W1) i.e. MBPU/NS film samples taken out at regular interval from the
compost were cleaned with distilled water and sputter coated with
W1 ðW1  Wt Þ Au/Pd mixture to make the surface conductive prior to the SEM
Residual Weight loss ¼ (1)
100 analysis.

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 3. Results
(where, t ¼ 30, 45, 60, 75 and 90 days).
3.1. Identification and analysis of the microbial community

2.5. Differential scanning calorimetry (DSC) analysis It was revealed from the spread plate technique that 1 gm of
compost sample contains 2.4  105 CFU/gm of bacteria and
The change in the physical structure and the variation in glass 2.4  101 CFU/gm of fungi. This indicates that the bacterial species
transition temperature (Tg) of the exposed MBPU and MBPU/NS were predominant as compared to the fungal ones in the compost
film samples was investigated by using DSC analysis (Q 20, M/s. TA sample collected from the surface of the PU sample. The isolated
instruments, USA) at a scanning rate of 10  C/min under N2 flow bacterial and fungal colonies were identified through gram staining
within a temperature range of 70  C to 100  C. 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
2.6. Wide angled X-Ray diffraction analysis (WAXD) analysis 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,
WAXD analysis was carried out using (M/s. Shimadzu XRD-700L, the fungal isolates were identified as Aspergillus sp., Penicillium sp.
X-Pert MPD, Japan) equipped with Cu Ka radiation source and and Mucor sp. Similar fungal and bacterial colonies were also
monochromatic graphite operated at 40 kV and 30 mA to charac- identified from the isolates recovered from compost and PU surface
terize the crystallinity of neat MBPU and MBPU/NS films. The by (Zafar et al., 2014, Cangemi et al., 2008, Shah et al., 2008,
scanning 2q angle ranged from 2 to 70 with a test speed of 5 /min. Cosgrove et al., 2007).

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

Fig. 4. Visual inspection of MBPU and MBPU/NS samples in compost after 0 days and 90 days.
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- microorganism onto the surface of PU followed by (b) hydrolysis of
ganization of the NS particles (Raghunath et al., 2008). The prob- the ester bonds in PU breaking them to smaller molecular units
able reason behind the above observations has been elucidated resulting surface erosion with further hydrolysis process (Kim and
below. Kim, 1998:Akutsu et al., 1998). This results in chain scission of PU
In general, the degradation mechanism of MBPU and MBPU/NS due to the hydrolysis process by extracellular enzymes secreted by
follows two stages i.e. (a) hydrophobic adsorption of 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- catalytic domain and a hydrophobic PU surface binding domain
cellular enzymes secreted by fungi and bacteria which are reported wherein, the later was associated for degrading PU (Nakajima-
to be responsible for the degradation of polyester PU (Nakajima Kambe et al., 1999). Further, the results also support the fact that
Kambe et al., 1999, Howard, 2002). In addition, Rowe and Howard the soft segment region is more biodegradable as compared to the
(2002), Tokiwa and Suzuki (1974) and Pathirana and Seal (1985a) hard segment region (Kim and Kim, 1998).
have mentioned about the secretion of esterolytic enzyme like However, from the figures it can be observed that MBPU/NS
lipase and esterase secreted by Bacillus sp. and fungal community. It reveal pronounced decrease in the intensity of the above
is likely that the above mentioned extracellular enzymes owing to mentioned peaks as compared to MBPU indicating higher vulner-
their enzymatic behaviour adhere onto the PU surface. As a ability of former to microbial attack. Reports by Kim and Kim (1998)
consequence, the bacterial and fungal species stick to the PU sur- mentioned that the degradation rate of polymer depends upon the
face thereby hydrolyzing the PU substrate to metabolites (Shah ease of surface adhesion and subsequent colonization of microor-
et al., 2008). Thus, it was assumed that these enzymes have a 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 287

surface silanol group in NS and to due to its low aspect ratio which whitening and deformation in the form of cracks, pits and pores
leads to the scission of the ester and urethane linkage and marginal confirming the chain scission and microbial degradation of MBPU
acceleration of the degradation process in MBPU/NS. and MBPU/NS. Further, DSC thermogram revealed reduction in Tgss
Thus, the SEM observation also corroborates with the FTIR and and Tghs of MBPU and MBPU/NS due to plasticizing effect. Thus, the
residual weight loss confirming higher biodegradability of MBPU/ above findings imply that MBPU and MBPU/NS synthesized from
NS composite film owing to its chemical structure and composition. transesterified castor oil and palm oil based isocyanate can be easily
degraded by the identified bacterial and fungal community in the
3.7. Differential scanning calorimetry (DSC) analysis compost. However, it was found that MBPU/NS exhibit higher
biodegradation rate as compared to MBPU due to its structural
The DSC thermogram of unexposed and exposed MBPU and organization and composition. Thus, the green MBPU/NS composite
MBPU/NS film were intended to confirm the polymer chain scission represent a useful biodegradable material with promising appli-
observation obtained in the earlier sections and results are sum- cation to design eco-friendly products in future.
marized in Table 3. Both MBPU and MBPU/NS films exhibited two
glass transition temperatures as depicted in table, the first transi- Acknowledgement
tion observed at negative temperature corresponds to the soft
segment (Tgss) i.e. polyol while, the second transition observed at The authors thank Department of Chemicals and Petrochemi-
positive temperature corresponds to the hard segment (Tghs) i.e. cals, Government of India (No.15012/1/2013-PC-I) for the financial
isocyanate and chain extender (Das et al., 2015a,b). It was observed support.
that both the exposed PU samples indicated substantial reduction
in the temperature corresponding to Tgss and Tghs with respect to
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