Composites: Part A 42 (2011) 1534–1541

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Composites: Part A
journal homepage: www.elsevier.com/locate/compositesa

Synthesis and characterization of organically modified clay/castor oil based

chain extended polyurethane nanocomposites
Anupama Kaushik a,⇑, Dheeraj Ahuja a, Vipin Salwani b
a
University Institute of Chemical Engineering and Technology (Formerly known as Department of Chemical Engineering and Technology), Panjab University,
Chandigarh 160 014, India
b
Centre for Emerging Areas in Science & Technology, Panjab University, Chandigarh, India

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

Article history: A series of 1,4-butane diol chain extended polyurethane nanocomposites based on castor oil, and
Received 1 January 2011 4,40 -diphenylmethane diisocyanate (MDI) were synthesized with modified clay (Cloisite 30B) as filler.
Received in revised form 12 April 2011 The synthesis was carried out in bulk and without catalyst via a two-step polymerization. The clay per-
Accepted 7 July 2011
centage was varied from 0% to 5% by weight of the nanocomposite. The prepared nanocomposites were
Available online 4 August 2011
characterized using TEM, SEM, WAXD, FTIR, Thermogravimetric Analysis (TGA), mechanical properties
and Moisture absorption behavior. TEM and XRD results confirmed successful exfoliation of clay in the
Keywords:
polyurethane matrix. Thermogravimetric Analysis (TGA) results showed that the thermal stability of
A. Polymer-matrix composites (PMCs)
B. Mechanical properties
nanocomposites improved with increased percentage of clay. Moreover, char percent also increased from
B. Thermal properties 5.6% to 12% as clay percent increased from 0% to 5%. The Young’s modulus improved more than 300% with
Transmission Electron Microscopy (TEM) addition of 5% clay filler. These nanocomposites exhibited lower water absorption and diffusivity values
as compared to neat polyurethane.
Ó 2011 Elsevier Ltd. All rights reserved.

1. Introduction crosslinking density, and position of fatty acid chain. Among all
these oils, castor oil is the most popular due to inherent hydroxyl
Polyurethanes have been extensively used due to their excellent group. Commercially castor oil consists of triglycerides that con-
physical properties (e.g. high tensile strength, abrasion and tear tain 90% ricinoleic acid residues and 10% non-functional acid resi-
resistance, oil and solvent resistance, low flexibility, etc.) and high dues, so that castor oil has effective hydroxyl functionality of 2.7
versatility in chemical structures. The properties of various types of [8]. The long pendant chains of fatty acids impart flexibility and
urethane polymers are dependent upon molecular weight, degree hydrolytic resistance to the network, whereas double bond present
of cross-linking, effective intermolecular forces, stiffness of chain in castor oil serves as grafting centers.
segments and crystallinity. Due to many structural variations that The disadvantage of castor oil include: low hydroxyl number
are possible in their formation, urethanes may be considered the leading to low modulus material; sluggish rate of curing of second-
most versatile polymers. ary hydroxyl groups [2] and structural irregularity due to steric
Although there are host of raw materials used for making poly- hindrances offered by the long pendant fatty acid chains during
urethanes, continuous depletion of natural resources has made it polyurethane formation, resulting in low tear strength. These disad-
imperative to identify alternate resources that are renewable or vantages can be offset in numerous ways: (a) making polyurethane
have plant origin [1]. Polyurethane based on polyols derived from interpenetrating network with various polymers like polystyrene
different vegetable oils, like castor [2–4], linseed [5], soybean [6], [9], poly methyl methacrylate [10], polyacrylonitrile and organic sil-
rice bran and coffee meal oil [7] with or without modifications icons [11], (b) castor oil can be transesterified or alcoholyzed with
are being used these days due to their excellent properties derived polyhydroxy alcohols, most commonly by glycerol and trimethylol
from hydrophobic nature of triglycerides. If the triglyceride struc- propane [12], (c) adding nano-reinforcement like exfoliated clay,
ture can be preserved, thermosetting polyurethane networks can carbon nanotubes, carbon nanofibers, exfoliated graphite (graph-
be obtained, whose network properties depend upon on the ene), nanocrystalline metals and a host of additional nanoscale inor-
ganic filler to pristine polymers to prepare nanocomposite that have
improved properties.
⇑ Corresponding author. Tel.: +91 172 2534925, +91 9815177772; fax: +91 172
2779173.
Among nano-reinforcements, clay has generated much interest
E-mail addresses: [email protected], [email protected] (A. due to its high aspect ratio and available surface area which results
Kaushik). in enhancement of mechanical properties, thermal stability, flame

1359-835X/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compositesa.2011.07.009
 A. Kaushik et al. / Composites: Part A 42 (2011) 1534–1541 1535

redundancy, and barrier properties of the matrix polymers [13]. drop of a dilute suspension of clay in pre-polymer matrix (before
Since natural clay is hydrophilic and lacks affinity with hydropho- addition of BDO) was deposited on the carbon-coated grids and
bic organic polymers, it needs to be modified by introducing organ- allowed to dry at room temperature.
ic cationic molecules. Organic modifiers can impart hydrophilicity SEM model JSM JEOL-6100 was used to study the morphology
to clay, thereby improving compatibility of clay with polymers. of polyurethane clay nanocomposites. Thin films of nanocompos-
Since pioneering work in the area of polyurethane/clay nanocom- ite were surface coated with platinum in order to make surface
posites by Wang et al. [14] numerous studies have been reported conducting. For analyzing the cross section, specimens were
[15–20]. But none of these studies have focused on castor oil based frozen under liquid nitrogen, then fractured, mounted and
polyurethanes. observed. Particle size distribution of polyurethane in SEM
The objective of this work was to synthesize and characterize a images was undertaken using a UTHSCSA Image Tool image ana-
series of chain extended polyurethane nanocomposites based on lyzer program (IT version 3). The images were loaded into the
biobased polyol i.e. castor oil and commercially available organi- software and particle size measured using a two point measur-
cally modified clay, Cloisite 30B. The soft segment was castor oil ing analysis. The scale of the software was calibrated using the
and the hard segment structure was 1,4-butanediol (BD) chain ex- scale bars on each SEM image (given below each SEM image).
tender. Synthesis was carried out in bulk and without catalyst via a Approximately, 300 measurements were taken to obtain the
two-step polymerization varying the amount of clay and keeping distribution.
hard segment ratio constant. Nanocomposites synthesized were FTIR analysis of clay nanocomposites was done on Perkin Elmer
characterized using Fourier Transform Infrared Spectroscopy RX infrared spectrophotometer. Thin film of nanocomposite (after
(FTIR), Differential Scanning Calorimetry (DSC), Thermogravimetric addition of BDO) was spread on KBr pallet and reaction was al-
Analysis (TGA), Transmission Electron Microscopy (TEM), Scanning lowed to complete. FTIR spectra were recorded in a spectral range
Electron Microscopy (SEM) and Wide angle X-Ray diffraction of 4000–450 cm1 with a resolution of 2 cm1 taking two scans for
(WAXD). each sample.
Tensile testing of the nanocomposites was carried out using
universal tensile testing machine Instron 4466 with a load cell of
2. Experimental
10 kN and following ASTM D 638. The crosshead speed was set
to 2 mm/min. Samples were cut in a dumbbell shape with an ASTM
2.1. Material used
D 638 (type V). Four to five specimens were tested for each sample
and average value taken.
Castor oil was commercial grade and was purchased from the
Thermal stability of polyurethane nanocomposites was deter-
local market. It was dehydrated at 105 °C in nitrogen atmosphere
mined using a Thermogravimetric Analyzer (TGA) of type Perkin
and characterized for hydroxyl value (148), acid value (2) and
Elmer STA-6000. It has weighing capacity of 1500 mg with resolu-
moisture content (0.379%). Modified montmorillonite clay Cloisite
tion around 0.1 lg. Samples were taken in a very small quantity (in
30B was procured from Southern Clay Products, USA with methyl,
milligram) in sample cup made of alumina and having maximum
tallow, bis-2-hydroxyethyl, quaternary ammonium (MT2EtOH) as
capacity around 180 ll. All the tests were performed in nitrogen
modifier, modifier concentration of 90 meq/100 g clay and mois-
environment and at heating rate of 10 °C/min.
ture content <2%. Chain extender, 1,4-butane diol was procured
Moisture absorption measurements were performed under 98%
from Himedia, India. 4,40 -Diphenyl methane diisocyanate (MDI)
RH (K2SO4) and water at 25 °C according to ASTM D570. All speci-
was supplied gratis by Bayer Polymers, India (Mondur M, Melting
mens for moisture absorption experiments with dimensions of
point 40 °C, Isocyanate content 33.5%).
30 mm  10 mm  2 mm were cut from composite sheets. Prior
to absorption experiments, all specimens were vacuum dried until
2.2. Synthesis of polyurethane nanocomposites a constant weight was attained. At predetermined intervals, spec-
imens were taken out from the chambers and weighed using a
Nanocomposites were synthesized by in situ polymerization in Sartorius model analytical balance (with a precision of 0.1 mg).
presence of clay. Clay was first dispersed in dehydrated castor oil The moisture uptake at any point of time was determined by
using sonication for 5 h (Branson ultrasonic bath 2510 E-DTH with equation:
frequency 40 kHz, 220 V) followed by mixing with Fluko FA25 high
shear homogenizer (10,000 rpm) for 20 min. The mixture was then
reacted with 4,40 -diphenylmethane diisocyanate (MDI) with con-
tinuous stirring in a glass reactor under nitrogen atmosphere.
The pre polymer so obtained was reacted with 1,4-butane diol
(BDO). The amount of castor oil, BDO and MDI was adjusted to
keep NCO:OH ratio 1. When the mixture became viscous, it was
poured in a stainless steel mold and kept for 24 h to complete
the reaction. Clay percentage was varied from 0% to 5%.

2.3. Characterization of nanocomposites

WAXD of nanocomposite film was conducted by subjecting the

films to X-ray radiation at room temperature. The films were ana-
lyzed using a Philips X’Pert Pro R-ray diffractometer system. The
radiation was Cu Ka (k = 1.54060 Å) with 40 kV voltage and
40 mA intensity.
Dispersion of clay was determined using TEM model Hitachi-
2100. Images were taken at 80 kV accelerating voltage. Samples
for TEM were prepared by drying diluted suspension on a gold grid Fig. 1. WAXRD of castor oil based clay nanocomposites with varying percentages of
plated with a thin layer of carbon (thickness around 200 nm). A clay.
1536 A. Kaushik et al. / Composites: Part A 42 (2011) 1534–1541

Wh  Wo spacing of 1.85 nm, while there is a complete absence of this peak

Percentage moisture uptake ¼  100 ð1Þ
Wo for nanocomposite samples. This disappearance could be explained
either by the exfoliation of the silicate or by a high disorder of the
where Wh and Wo denote the weight of humid specimens and the
clay. If the silicate layers were exfoliated, the d-spacing would be-
original dry value (initial weight of materials prior to exposure to
come too high and may not be detected by the XRD methods, and if
moisture absorption), respectively. Data was collected till no suc-
the clays were not well ordered, it would fail to produce a Bragg
cessive change in weight was observed. An average of three
diffraction peak. The results suggest that the processing method
repeated tests was taken.
used for the study i.e. sonication followed by high shear mixing,
is effective in dispersion of clay platelets.
3. Results and discussion Absence of Bragg diffraction peaks in the XRD patterns cannot
be used as the sole evidence for the formation of an exfoliated
3.1. Morphology and dispersion of polyurethane nanocomposites structure. Several factors such as clay dilution, peak broadening
and preferred orientation make XRD characterization of polymer
XRD is commonly used for characterization of the structure of nanocomposites susceptible to errors. To corroborate the results
nanocomposites. For an intercalated structure, the (0 0 1) charac- obtained by XRD, TEM investigations were performed.
teristic peak tends to shift to lower angle regime due to expansion Direct evidences of the formation of a true nanocomposite were
of the basal spacing [21]. Although the layer spacing increases, provided by TEM investigation. TEM images of polyurethane nano-
there still exists an attractive force between the silicate layers to composite containing 5% clay are shown in Fig. 2a. The nanocom-
stack them in an ordered structure. In contrast, no peaks are posites were subjected to sonication and high shear mixing. The
observed in the XRD pattern of exfoliated polymer nanocomposites sonication helps in breaking the clay aggregate into fine clay parti-
due to loss of structural registry of the layers. Fig. 1 shows the XRD cles. High shear homogenization helps to disperse the clay plate-
pattern for chain extended polyurethane and its polyurethane clay lets homogenously throughout the matrix. White lines (similar to
nanocomposites with varying clay content. For Cloisite 30B, the TEM images of thermoplastic clay nanocomposites as reported by
(0 0 1) diffraction peak is visible at 4.85°, referring to a basal Chavarria and Paul [22]) in Fig. 2a represent random orientation

Agglomerated clay
Delaminated & platelets/tactoids
exfoliated clay
platelets in
polyurethane matrix.

Fig. 2a. TEM images of dilute suspension of clay (5% Cloisite 30B) dispersed in polyurethane prepolymer before addition of butanediol chain extender.

70

60
Percentage in range

50

40

30

20

10

0
0-1 1-2 2-3 3-4 4-5
Particle size (µ
µm)

Fig. 2b. Scanning Electron Micrographs (SEM) of castor oil based polyurethane nanocomposites containing 5% Cloisite 30B showing homogenous distribution of clay in the
matrix.
 A. Kaushik et al. / Composites: Part A 42 (2011) 1534–1541 1537

Fig. 3. FTIR spectra of various nanocomposite samples with varying amount of organoclay: (a) wavelength range 2000–4000 cm1 and (b) wavelength range 400–2000 cm1.

of platelets of Cloisite 30B, the thickness of which ranges from 2 to parallel to the surface are visible in size range 1–3 lm. The size
10 nm. Single platelets as well as stacks of few platelets are visible greater than 1 lm can be explained on the basis of platelet stacking
in the Fig. 2a. The spaces between the platelets represent the inter- as shown in Fig. 2b. The particle stacking is not ordered but stack-
layer spaces. The black cloud represent tactoids consisting of few ing particles slip over each other giving an appearance that particle
platelets. Dispersion of platelets in the matrix are an evidence that size is more than 1 lm. The size distribution shows that 65% of the
the clay is exfoliated in polyurethane matrix. particles lie in 1–2 lm range and 18% lie in range 2–3 lm. Approx-
Scanning Electron Micrographs of fractured surfaces of polyure- imately 12% of the particles have size >3 lm.
thane nanocomposites with 5% clay are given in Fig. 2b. It is evi-
dent that the clay particles are homogenously distributed in the 3.2. FTIR of polyurethane nanocomposites
matrix with minimum agglomeration. Since SEM cannot be per-
formed at very high resolution, very small particles in nanometer Fig. 3 shows the FTIR spectra of Closite 30B, neat polyurethane
range cannot be seen in the images. However, we can observe clay and nanocomposites with different percentages of clay. Cloisite
particles oriented in direction parallel to the surface being frac- clays are derivates of montmorillonite (MMT) and have the charac-
tured. It is known fact that Cloisite is a modified form of MMT clay, teristic peaks of MMT i.e. 1048 cm1 which corresponds to stretch-
and except for the modifiers, the structure of Cloisite is same as ing vibrations of SiAOASi, 525 and 462 cm1 corresponding to
that of MMT. The single platelet in MMT has a thickness approxi- AlAO and SiAO bending vibrations, respectively. The absorption
mately of 1 nm and width of 1 lm. Hence, the particles oriented bands at 3633.1 cm1 and 3394 cm1 are ascribed to the free
1538 A. Kaushik et al. / Composites: Part A 42 (2011) 1534–1541

Fig. 4. Thermograms of castor oil based chain extended polyurethane and polyurethane clay nanocomposites with varying percentages of clay.

AOH stretching and the hydrogen-bonded AOH stretching respec- given in Fig. 4. As evident, TGA thermograms of the nanocompos-
tively. The 1658 cm1 band for Cloisite 30B is caused by the free- ites were shifted toward high temperatures as compared to PU,
of-hydrogen-bonding carbonyl, and the bands at 1472 and indicating that addition of clay improved the thermal stability of
1379 cm1 are associated with the ACH3 group in MT2EtOH. Some the system. The increase in thermal stability is attributed to the
bands in the region located at 2930, 2856 and 1472 cm1 are good thermal stability of the well-dispersed and exfoliated silicate
attributed to the ACH2 asymmetric and symmetric stretching layers. Nanocomposites show the same TGA and DTG profiles as
and bending vibrations respectively, due to the presence of meth- neat polyurethane but displaced to a temperature 10 °C higher
ylene group. than that in the case of the neat PU. This may be attributed to
FTIR spectra of chain extended polyurethane and its clay nano- strong interaction between the organic clay and PU matrix. The
composites show a small broad band in the range 4000–3500 cm1 can also be explained on the basis of labyrinth (barrier) effect gen-
which is related to OAH stretching vibrations from either water or erated by highly anisotropic clay platelets which delays the escape
hydroxyl terminated compounds and silicates & NAH stretching of volatile degradation products from the nanocomposites [28].
vibrations from either urea or amine group [23,24]. Characteristic The polymer–clay nanocomposites exhibit extremely large inter-
peaks of hydrogen bonded ANH groups of urethane linkages were face polymers due to the confinement of polymer chains within
observed at 3333.2–3392.4 cm1 and a small shoulder, seen at the galleries of clay platelets of large surface area per unit volume.
3420 cm1 is characteristic of stretching of free ANH groups. It is considered that the confinement of polymer–clay interactions
The free urethane carbonyl (C@O) is seen at 1728.0–1735 cm1 would affect the local chain dynamics to a certain extent. Since
while the peak at 1715–1725 cm1 is due to hydrogen bonded car- several chemical and physical interactions are governed by sur-
bonyl. The peaks at 2264.4–2262.2 cm1 correspond to the ANCO faces, polymer–clay nanocomposites can have substantially differ-
stretching. A reduction in this peak is observed from 2270 cm1 ent properties from conventional polymer microcomposites.
which confirms the polymer clay interaction and formation of The percent residue increases from 5.65% to 12.05% at 600 °C as
polyurethane [25]. Small bands at 2962.4–2964.4 cm1 and the clay contents increased from 0 wt.% to 5 wt.%. The curves dis-
2854.8–2856.6 cm1 correspond to the ACH2 asymmetric and play three weight loss stages (DTG maxima around 320 °C, 380 °C
symmetric stretching vibrations respectively. The moderate inten- and 470 °C, respectively) that lead to the formation of a small high
sity peaks at 1598.4–1652.9 cm1 contribute to the urea C@O temperature residue (5–12 wt.%). The first DTG peak can be related
stretching vibrations [26]. Bands at 1531.9 and 1538.8 cm1 corre- to the overlapping of urethane bond scission (degradation) and
spond to the combination of NAH out of plane bending and CN char-forming secondary reactions (e.g. dimerisation, trimerisation,
stretching [27]. Low intensity bands at 1417.0–1412.1 cm1 relate cross-linking). At this temperature, breaking of low energy ure-
to the isocyanurates. Small bands at 1094.2–1097.9 cm1 could be thane bonding (AHNACOAOA) releases CO, CO2, amines, and alde-
attributed to CO stretching vibrations of an ether group [24]. Small hydes whereas the second and third peaks at around 380 and
bands at 1028.1–1022.2 cm1 relate to the stretching vibrations of 470 °C correspond to decomposition of the stabilised urea/isocyan-
SiAOASi from silicates seen only in case of PU/clay nanocomposite urate structures i.e. they are related to the breaking of high energy
[23]. The bands at 512.4–514.8 cm1 correspond to the AlAOASi bonds, such as CAC, CAO, CAH, C@C, and C@O [29]. The intimate
deformation [23]. contact between clay layers and polyurethane matrix seems to
have favored the reaction occurring in polyurethane degradation.
3.3. Themal properties of polyurethane clay nanocomposites
3.4. Mechanical properties of polyurethane clay nanocomposites
The thermal stability of castor oil based polyurethane and poly-
urethane clay nanocomposites were investigated by TGA. The ther- The Young’s modulus, tensile strength and elongation at break
mograms of nanocomposites with varying percentages of clay are for polyurethane and its clay nanocomposites are shown in
 A. Kaushik et al. / Composites: Part A 42 (2011) 1534–1541 1539

Fig. 5. Tensile strength (MPa), Young’s modulus (MPa) and elongation at break (%) for various polyurethane clay nanocomposites.

Fig. 5. The Young’s modulus increases from 51.52 MPa to

198.35 MPa while elongation at break increases from 99% to
124% with increase in clay content from 0% to 5%. The enhance-
ment of Young’s modulus is directly attributed to the reinforce-
ment provided by the dispersed silicate layers in polyurethane
matrix. Young’s modulus can also be affected by the interfacial
interaction between silicate layers and polyurethane matrix [17].
There are two strong interactions between polyurethane matrix
and layered silicates such as the hydrogen bonding and the chem-
ical bonding (as evident in FTIR analysis from peak at 3333.2–
3392.4 cm1 and the peak at 1715–1725 cm1), hence the tensile
strength and elongation at break increased with exfoliation of clay.
Similar trend has been reported by many authors [30–33]. The in-
crease in elongation at break with clay content is attributed to the
chain interconnectivity generated by clay platelets and to the
strong interactions between polyurethane matrix and layered sili-
cates. An increase in clay content is associated with an increase of
interfacial area between organoclay and polyurethane matrix. As a
consequence, the elongation of polyurethane clay nanocomposite Fig. 6a. Moisture absorption curves of castor oil based polyurethanes and its
is significantly higher than that of neat polyurethane. The clay nanocomposites in 98% relative humidity at 25 °C.
platelets also act as crosslinks for the anchored polyurethane
chains on their surfaces. The interfacial area between organoclay
and polyurethane matrix became larger as the clay is exfoliated
in the matrix by sonication and high shear mixing.

3.5. Moisture absorption behavior of polyurethane clay

nanocomposites

The mass transport mechanism of gasses permeating a nano-

platelet reinforced polymer is similar to that in a semicrystalline
polymer. In most theoretical treatises, nanocomposite is consid-
ered to consist of a permeable phase (polymer matrix) in which
non-permeable nanoplatelets are dispersed. There are three main
factors that influence the permeability of a nanocomposite: the
volume fraction of the nanoplatelets; their orientation relative to
the diffusion direction; and their aspect ratio. Presence of clay lay-
ers are like aligned impermeable flakes, acting as barriers, increas-
ing tortuosity of the diffusion path and decreasing water vapor and
gas permeation through the polymeric membranes. Extent of tor-
tuosity is a function of clay content and degree of exfoliation. Fig. 6b. Moisture absorption curves of castor oil based polyurethanes and its
Therefore, to determine how the content of clay in a hybrid nanocomposites in water at 25 °C.
1540 A. Kaushik et al. / Composites: Part A 42 (2011) 1534–1541

Table 1
Barrier properties of castor oil based polyurethane clay nanocomposites under 98% relative humidity and water at 25 °C.

Sample K2SO4 Water

6 8
M1 Diffusivity (10 ) Sorption Permeability (10 ) M1 Diffusivity (106) Sorption Permeability (108)
(%) (mm2 s1) (mm2 s1) (%) (mm2 s1) (mm2 s1)
Neat 2.125 27.82 0.0184 513.36 6.494 43.585 0.021 910.53
1% 1.541 3.398 0.0242 82.21 4.230 3.345 0.024 79.72
2% 1.436 2.447 0.0244 59.76 3.701 2.807 0.026 73.56
3% 1.353 0.281 0.0339 9.55 3.215 0.712 0.026 18.68
4% 1.152 0.199 0.3787 7.54 2.785 0.111 0.028 3.17
5% 1.092 0.0147 0.0454 0.67 1.860 0.048 0.035 1.70

composite would affect the sorption and diffusion of the nanocom- about 27.82  106 mm2 s1 in 98% RH and 49.59  106 mm2 s1
posites, transport properties were investigated for all the samples in water. It can be found from Table 1 that the values of D and P
prepared using water vapor. In this study moisture absorption decrease gradually with increasing clay loading. It is hypothesized
behavior of nanocomposites was studied at 25 °C for 98% RH using that the improved resistance to water absorption for polyurethane
saturated solution of K2SO4. Liquid water sorption experiments clay nanocomposites can be attributed to following aspects. Firstly,
were performed in addition to water vapor sorption ones. Samples the lower values of D, P, and M1 of the nanocomposites can be ex-
were dried before being damped in water at 25 °C and periodically plained by the impermeable character of the lamellar inorganic
removed and weighed. Theoretically, moisture absorption pro- layers dispersed in the polyurethane matrix that induces a tortuos-
cesses in polymer composites, mostly from conventional non-bio- ity effect. This tortuosity effect depends highly on the filler content
degradable composites, can be described by Fick’s second law of and on the clay dispersion state.
diffusion [34]. General series solution of Fick’s second law for plane Secondly, the decreased M1, P, and D are related to the presence
sheet geometry with the assumptions of molecular migration by of strong hydrogen bonding interactions between polyurethane
diffusion, negligible shrinkage besides constant diffusion and tem- and modifier on clay platelets. Hence hydrogen bonding interac-
perature is given by Eq. (2) [35]: tions in the composites tend to stabilize the nanocomposites when
" ! # subjected to highly moist atmosphere.
Mt 8 X1 1 Dð2n þ 1Þ2 t 2
¼1 2 exp  p ð2Þ
M1 p n¼0
ð2n þ 1Þ2 h
2
4. Conclusions
where Mt and M1 are the moisture contents at time t and at equi-
librium, respectively. D is the diffusion coefficient and h is the sam- Castor oil based chain extended polyurethane nanocomposites
ple thickness. At short times, i.e., the initial absorption (initial linear were synthesized with organoclay, Cloisite 30B as filler. The syn-
portion of the curve), (Mt/M1 6 0.5), Eq. (2) reduces to thesized nanocomposites were characterized using TEM, SEM,
  1=2 WAXD, FTIR, TGA, mechanical and barrier properties. XRD and
Mt 4 D TEM confirmed exfoliation of clay platelets in the polyurethane
¼ t 1=2 ð3Þ
M1 h p matrix. The results of TGA and FTIR experiments indicated an inter-
action between the clay and polymer improving thermal stability.
Eq. (3) can be rewritten as
A reduction in water sorption compared to the pure matrix con-
1=2
M t ¼ kt ð4Þ firmed increasing the tortuosity of the diffusion path. Mechanical
1/2
properties including the Young’s modulus and tensile strength re-
where k is the slope of Mt vs. t curve flected marked improvement with addition of clay. Thus it can be
  1=2 concluded that addition of clay to biobased polyurethane results in
4M 1 D
k¼ ð5Þ overall improvement of physical, mechanical and thermal
h p
properties.
Hence D can be calculated from the slope of Mt vs. t1/2 curve for
known thickness of the sample. The sorption coefficient S is given Acknowledgements
by following equation:
m1 We gratefully acknowledge financial support rendered by All
S¼ ð6Þ
mp India Council of Technical Education (AICTE), India and University
Grants Commission (UGC), India for the research work.
where m1 represents mass of the solvent taken up at the equilib-
rium and mp represents initial mass of the sample. The permeability
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