Research Article

pubs.acs.org/journal/ascecg

Value-Added Biopolymer Nanocomposites from Waste Eggshell-

Based CaCO3 Nanoparticles as Fillers
Tarig A. Hassan, Vijaya K. Rangari,* and Shaik Jeelani
Department of Materials Science and Engineering, Tuskegee University, Tuskegee, Alabama 36088, United States

ABSTRACT: Waste eggshells were used as a raw material to

produce high surface area biocalcium carbonate nanoparticles
using a combination of mechanochemical and ultrasonic
irradiation techniques. High resolution transmission electron
microscopy (HR-TEM) and X-ray analysis showed that the
synthesis process was effective and yields only CaCO3
nanoparticles with high porosity. The bionanocomposites
were prepared by infusing three different weight percentages
(1%, 2%, and 3%) of the calcium carbonate nanoparticles
(CaCO3) in Bioplast GS 2189 thermoplastic polymer.
Thermal analyses indicated that the 2% bionanocomposites
are thermally more stable (by 15 °C) than the corresponding
neat systems. Mechanical test results of 2% bionanocomposite
showed an approximately 35.3% and 30.5% increase in the flexural strength and modulus, respectively, over the pristine Bioplast
GS 2189 polymer.
KEYWORDS: Biodegradable polymers, Renewable materials, Mechanical properties, Calcium carbonate, Nanocomposites

■ INTRODUCTION
Sustainable biobased polymer composites have been the subject
nanoparticles is their use as nanofillers to enhance the
properties of pristine thermoset and thermoplastic polymeric
of intense research in recent years. Currently, there is a serious materials. Finding renewable resources for the development of
demand for new green materials and composites in all new environmentally friendly and biobased fillers are also
applications. This growing demand is derived from the essential and has attracted substantial global interest. Lin and
implementation of new environmental regulations around the co-workers have reported the preparation of a shell/β-
world. Moreover, petroleum-based resources are getting more polypropylene biocomposite. Incorporation of the biobased
expensive and are being depleted at a very high rate in addition micrometer-sized shell powder derived from fisheries waste
to their destructive impact on the environment. On the other have substantially improved the impact strength of the resultant
hand, biobased polymer composites are developed from biocomposite by 240% compared to the neat polypropylene.17
renewable resources so they are environmentally friendly and Eggshell represents a great source of biobased calcium
do not contribute to the depletion of energy resources, offering carbonate that can be efficiently used as biofiller in polymer
great energy and greenhouse gas emission savings.1,2 nanocomposites.18−22 This natural bioceramic composite is
Many natural and biobased materials like soy bean oil have abundantly available and has an exceptional chemical
been utilized in the creation of different biopolymers and composition that consists of high inorganic content (∼95%
composites.3−6 Various biodegradable thermoplastic polymers of calcium carbonate) and about 4% organic components.23−25
are developed from plant-based materials such as different types The mechanical properties of the eggshells are influenced by
of starches and sugars along with polylactic acid (PLA).7,8 the interaction between these organic and inorganic constitu-
These materials are employed in a wide range of engineering ents making it suitable for use as fillers.26,27 Takamine at el.
applications due to their economical and environmental studied the effect of eggshell on the properties of corn starch
advantages compared to petroleum-based materials and have extrudates. They reported that the addition of up to 10%
comparable properties. Biobased polymer nanocomposite eggshell has increased the shear strength of extrudates.28 Xu
materials have been extensively studied due to their remarkable and Hanna studied the use of micrometer-sized eggshell
combinations of properties.9−12 Also, a number of United particles as a nucleating agent in a composite foam material
States patents in biobased polymers have been issued.13−16 derived from corn starch that was used for food packaging
One of the most important means to alter the mechanical application. The composite foam was prepared by extrusion
and thermal properties of polymers is through the use of
various kinds of soft/hard fillers. Current research efforts focus Received: October 4, 2013
on the use of filler materials in the nanometer scale to improve Revised: January 12, 2014
different properties of polymers. A major application of Published: January 23, 2014

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and characterized to investigate the effects of eggshell on the technique for synthesis of nanoparticles; one of the important
structure, morphology, and physical and mechanical properties, parameters is the liquid vapor pressure.36 There is a direct effect of
as well as the thermal stability of the foam. The foam properties the solvent used during sonication and the reaction outcome.
were significantly enhanced and foam thermal transition and Nanostructured materials can be prepared by the sonochemical
route in low volatility solvents that have relatively low vapor pressures.
stability increased with the addition of 6% loading of the Solvents with low vapor pressures are expected to have better
eggshell.29 Bootklad and Kaewtatip investigated the use of sonochemical effects and lead to better reaction results.36 The
eggshells as filler in a biodegradable thermoplastic starch sonochemical effect of DMF is more pronounced, and the particles
composite prepared using compression molding. The effect of were irregular platelets of ∼10 nm. The BET surface area (43.687 m 2/
incorporation of the micrometer-sized eggshell powder on the g) of these nanoparticles is much higher than that of nanoparticles
properties of thermoplastic starch was compared with the effect from other solvents such as decaline and THF (R). The excellent
of commercial calcium carbonate particles. The eggshell/ sonication effect of DMF was also confirmed by the studies of other
thermoplastic starch composite achieved better adhesion researchers.37,38 During the sonochemical step, eggshell particles were
between the filler powder and the matrix and improved water irradiated with a high intensity ultrasonic horn (Ti-horn, 20 kHz, and
100 W/cm2) in the presence of dimethylformamide (DMF) for 5 h.
resistance and thermal stability compared to commercial
The synthesis process is described in detail in our previous paper.39
calcium carbonate/thermoplastic starch composites that were The as-prepared bio-CaCO3 nanoparticles were used as reinforcing
more rapidly degraded.30 filler in Bioplast GS 2189 thermoplastic polymer. Bio-CaCO3/Bioplast
These studies have described the use of micrometer-sized GS 2189 nanocomposites were fabricated using a Wayne Yellow Label
eggshell particles in polymeric composites as reinforcement table top single screw melt extruder. One of the big challenges in the
fillers at relatively high loadings.18−21,29,30 The objective of this fabrication of bio-CaCO3/Bioplast GS 2189 nanocomposites was the
research is to study the effect of infusion of small amounts (1%, initial mixing of the bio-CaCO3 nanoparticles and the 3 mm polymer
2%, and 3% by weight) of high surface area nano-sized pellets. To incorporate the nanofiller in the polymer matrix and
biocalcium carbonate particles derived from eggshells in achieve a good dispersion of the bio-CaCO3 nanoparticles in the
biobased biodegradable thermoplastic polymer on the thermal Bioplast GS 2189 polymer, a solution mixing process was used. In this
process, Bioplast GS2189 polymer was completely dissolved in
and mechanical properties of the resultant bionanocomposites.

■
chloroform, and the bio-CaCO3 nanoparticles were further dispersed
in the polymer/chloroform solution by ultrasonic irradiation. Chloro-
MATERIALS AND METHODS form was used as a solvent because of high polymer solubility at room
Materials. In this study, we have used biobased materials that have temperature. In addition, it can be easily removed from the polymer/
been acquired from renewable resources. The primary source of our nanoparticles mixture after the process. In a typical experiment, 100 g
biobased nanofiller is waste eggshells that were obtained from of Bioplast GS 2189 polymer pellets were dissolved in 600 g of
American Dehydrated Foods, Inc. (Social Circle, GA), a local food chloroform in a glass beaker, and known weight percentages bio-
processing company. These waste eggshells were used as raw material CaCO3 nanoparticles were added to the polymer/chloroform solution.
for the synthesis of bio-CaCO3 nanoparticles. Commercially available Three different weight percentages of the bio-CaCO3 nanoparticles
Bioplast GS 2189 was used as the polymeric matrix. Bioplast GS 2189 were used (1%, 2%, and 3%). The mixture of polymer/chloroform
is a completely biodegradable thermoplastic polymer in the form of solution and bio-CaCO3 nanoparticles was stirred for 24 h using a
small, white, spherical-like pellets of 3 mm in size and was purchased magnetic stirrer to ensure that the polymer has completely dissolved
from Biotec Distribution (The Netherlands). Chloroform was used as into the chloroform; when the bio-CaCO3 nanoparticles are infused in
a solvent in the solution mixing process, and it was purchased from the mixture, an absolutely homogeneous solution will result. In the
Sigma-Aldrich (St. Louis, MO). next step, the polymer/chloroform solution containing the bio-CaCO3
Processing and Fabrication of Bio-CaCO3/Bioplast GS 2189 nanoparticles was irradiated with high intensity ultrasonic horn (Ti-
Bionanocomposites. Bio-CaCO3 nanoparticles used in this horn, 20 kHz, 100 W/cm2) at 50% amplitude for 30 min at room
investigation were derived from chicken eggshells. The nanoparticles temperature. The sonochemical technique is efficient in producing
have been synthesized via a top-down approach for producing high quality monodispersed nanocomposites.40 To control the process
nanostructured materials. The first step was cleaning and drying of the temperature and avoid heating of the contents and solvent
eggshells. The shells were then ground with a grinder to produce fine evaporation, the beaker was immersed in a coolant, and the coolant
powder that was then subjected to further size reduction via a temperature was controlled by a thermostatted bath at 5 °C. After the
mechanical attrition method. After that, the particle sizes were ultrasonic irradiation step, the polymer/bio-CaCO3 nanoparticles
standardized by passing through a set of standard stainless steel sieves composite mixture was precipitated by addition of excess amounts of
95 and 20 μm in size using a Retsch high speed shaker. Further size methyl alcohol. This uniform mixture of Bioplast GS 2189 polymer
reduction was carried out using a sonochemical method to produce and bio-CaCO3 nanoparticles was then collected in the form of
bio-CaCO3 nanoparticles of size less than or equal to approximately 10 powder and dried under vacuum in a conventional oven at 65 °C for
nm with a BET surface area of approximately 44 m2/g.27 The 48 h to ensure complete removal of the solvent and methanol residues
sonochemical technique is extensively reported in the literature for size from the composite mixture. The solution mixing method was
reduction of different bulk materials to nanoscale materials.31,32 The followed for the preparation and dispersion of all weight fractions of
sonochemical processing is considered to be one of the most efficient the nanoparticles in the Bioplast GS 2189 polymer including 1%, 2%,
techniques for generating novel materials with remarkable properties. and 3% loadings. Neat polymer pellets were also converted into
Sonochemistry arises from the acoustic cavitation phenomenon, that polymer powder using the same procedure for comparison.
is, the formation, growth, and implosive collapse of bubbles in a liquid The Bioplast GS 2189 polymer and bio-CaCO3 nanoparticles
medium.31 The extremely high temperatures (>5000 K), pressures powder mixture was then extruded using a Wayne Yellow Label table
(>20 MPa), and very high cooling rates (>107 K s−1)32 attained during top single screw extruder. The extruder has a 19 mm diameter screw,
cavity collapse lead to many unique properties in the irradiated which is driven by a 2 HP motor via a toothed timing belt for smooth
solution. Using these extreme conditions, researchers have been able speed variations. Thermostatically controlled five heating zones were
to synthesize several materials; this technique has proven to be a used to melt the mixture prior to extrusion, three of which were
unique method for size reduction. Franco et al. stated that sonication is occupied by the barrel zone and the other two by the die zone. The
an effective tool for reducing the particle size of different inorganic heaters inside the barrel zone were set at temperatures above the
materials, while the crystalline structure is retained.33−35 During the melting temperature of the Bioplast GS 2189 polymer. Table 1 shows
sonochemical irradiation phase, three different organic solvents were the temperatures of the heating zones of the extruder along with die
used. There are a number of parameters affecting the sonochemical zones 1 and 2.

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ACS Sustainable Chemistry & Engineering Research Article

Table 1. Temperature Settings of the Extrusion Process on a copper grid (carbon-coated copper grid, 200 mesh), then dried in
air, and used for TEM analysis. The 2% bio-CaCO3 nanoparticles-
temperature (°C) infused Bioplast GS 2189 bionanocomposites samples were sliced to
zone 1 zone 2 zone 3 die zone 1 die zone 2 approximately 100 nm using a diamond blade attached to a Leica EM
UC6 microtome.
148.9 151.7 154.4 160.0 162.2
To study the thermal stability of the neat Bioplast GS 2189 polymer
and bio-CaCO3/Bioplast GS 2189 nanocomposite systems prepared in
The purpose of these three heating zones is to maintain a gradually this investigation, thermogravimetric analysis (TGA) of all samples
increasing temperature in the molten polymer. The process began by was carried out under a nitrogen gas atmosphere on a Mettler Toledo
pouring the polymer/nanoparticles mixed powder through the feed TGA/SDTA 851e apparatus. The samples were precisely cut into
hopper. As the mixture reached the barrel zone, the polymer started small pieces (∼10−20 mg) and kept in an aluminum oxide sample
melting due to high barrel temperature. The outer surface of the pan. TGA measurements were carried out from 30 to 800 °C at a
extruder screw is designed to maintain a close fit with the barrel’s inner heating rate of 10 °C/min. Real time characteristic curves were
surface. As a result, the molten mass cannot escape from the screw generated by a Mettler data acquisition system. These analyses were
surface. As the extruder screw rotates, the molten matrix was further carried out according to ASTM Standard E1131-03. DSC experiments
mixed with the bio-CaCO3 nanoparticles, conveyed in a spiral pattern, were also carried out using a Mettler Toledo DSC 822e. DSC
and then reached the screw end, which is located right before the die experiments were conducted from room temperature to 500 °C at a
zone. The screw end is shaped in a way that allows the flowing mass to heating rate of 10 °C/min under a nitrogen gas atmosphere. The
escape through a narrow opening at high velocity. The die zone samples were precisely cut into small pieces of 10−20 mg, kept in an
consists of two parts; one is the die itself and the other part is a aluminum sample pan, and used for DSC analysis. These tests were
rectangular stainless steel sample mold. The stainless steel sample carried out using ASTM Standard E1356-03.
mold was attached to the extruder and has the shape and dimensions Dynamic mechanical analysis (DMA) of various specimens was
of a flexural sample so that the extruded nanocomposite samples take carried out on a TA Instruments dynamic mechanical analyzer DMA
the shape of a flexure test specimen according to ASTM D790-02. The Q800. The samples were cut into small pieces using a diamond cutter
stainless steel sample mold is composed of two stainless steel parts that and machined using a mechanical grinder to maintain the specified
attached to each other by 10 screws with a sample mold trapped in sample dimensions. The width of the samples was 12 mm, and the
between. Before the mold was attached to the extruder, it was cleaned, span length to thickness ratio was 10. The test was carried out
sprayed with freekote (releasing agent for easy removal of the sample according to ASTM D4065-01. DMA tests were run on a double
after the process), then assembled, and attached to the extruder die cantilever beam mode with a frequency of 1 Hz and amplitude of 15
end. Eight steel bars were inserted into four holes in each stainless μm. The temperature was ramped from room temperature to 180 °C,
steel part to heat up the mold. A thermocouple was attached to the and the heating rate was maintained at 5 °C/min throughout the test
bottom of the lower part of the mold to measure the mold runs so that there was a minimum temperature lag between the sample
temperature (die zone 2). The mold is equipped with a circular and the furnace environment. From the test data, storage modulus,
cooling system. The two heaters in the die zone were set at a loss modulus, and tan δ were determined.
temperature of 162.2 °C to maintain constant temperature of the Thermo-mechanical analysis (TMA) experiments of the neat
flowing mass. One of the heaters was placed after the circular plate, Bioplast GS 2189 polymer and bio-CaCO3 reinforced Bioplast GS
and the other one was the steel bars inserted into the sample mold. As 2189 polymer nanocomposites were carried out on a TA Instruments
the bulk materials passed through the plate, they were diverted into thermomechanical analyzer TMA Q400. The samples were cut into
several branches and then combined again. This ensured a distributive small pieces of dimensions 5 mm × 5 mm × 5 mm using a diamond
mixing of the nanofillers with polymer.41 The polymer melt and cutter and machined using a mechanical grinder to maintain the
bionanoparticles mixture passed through the 100 mm long steel tube specified sample dimensions according to standard ASTM E 831-06.
and approached the die area. As the liquid Bioplast GS 2189 polymer Dimensional changes were measured in the thickness direction, and
containing the bio-CaCO3 nanoparticles arrived at the die area, the the temperature was ramped from room temperature to 180 °C.
molten masses were extruded and pushed into the sample mold. The Flexural tests under a three-point bend (TPB) configuration were
extruded sample filled the mold, and the excess amount of the sample performed according to ASTM D790-02. Test specimens length and
was dispensed out of the sample mold through two small holes in the width are 100 and 13 mm, respectively. The span length is 80 mm, and
bottom of the mold. Subsequently, the screw and die zone heaters average sample thickness is 4.8 mm. The tests were conducted in a 2.5
were turned off, and the water cooling system was turned on for 15 kN Zwick Roell Z 2.5 testing machine equipped with TestXpert data-
min to cool the sample mold to room temperature. The sample was acquisition system. The machine was operated under displacement
left in the mold for 12 h to completely solidify and was then removed control mode at a crosshead speed of 2.0 mm/min, and all the tests
and used for later characterizations. The extrusion process was were performed at room temperature. Stress−strain data for each
conducted for neat Bioplast GS 2189 polymer as well as for all bio- sample was collected. Flexural strength and modulus were calculated
CaCO3/Bioplast GS 2189 nanocomposites. from the slope of the stress−strain plot. Five samples were tested from
Characterization. X-ray diffraction measurements were conducted each material, and the average values of flexural strength and modulus
using a Rigaku D/MAX 2200 X-ray diffractometer to investigate the were determined. Scanning electron microscopy (SEM) analysis was
structure of bio-CaCO3 nanoparticles. XRD measurements were also carried out using a JEOL JSM 5800 scanning electron microscope to
used to study the exfoliation of bio-CaCO3 in as-prepared study the fracture surface of samples in response to flexural load at the
bionanocomposites. The XRD samples were prepared by uniformly microscopic level. The failed samples of the neat Bioplast GS 2189
spreading the bio-CaCO3 nanoparticles on a quartz sample holder, polymer and bio-CaCO3/Bioplast GS 2189 nanocomposites were cut
whereas the as-prepared neat polymers and bionanocomposites cured into small pieces and placed on a double-sided adhesive conductive
samples were cut precisely into small specimens and mounted in an carbon tape and coated with a thin layer of a gold/palladium mixture
aluminum sample holder for measurement. XRD tests were conducted (Au/Pd) using a sputter coater Hummer 6.2 to prevent charge buildup
at room temperature from 10° to 80° of 2θ. The pattern peaks by the electron absorbed by the specimen.
resulting from the diffraction were analyzed using Jade 9 software.
High-resolution transmission electron microscopy (HR-TEM) has
been performed on as-prepared bio-CaCO3 nanoparticles and the 2 wt
% bio-CaCO3 nanoparticles-infused Bioplast GS 2189 polymer, using a
■ RESULTS AND DISCUSSION
XRD analysis was carried out to investigate the crystal structure
JEOL-2010 transmission electron microscope. TEM samples were of the bio-CaCO3 nanoparticles derived from eggshells. The
prepared by dispersion of nanoparticles in ethanol using a sonication XRD pattern of bio-CaCO3 nanoparticles is presented in Figure
bath for 5 min at room temperature, and a drop of solution was placed 1a.
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Figure 1. XRD pattern of bio-CaCO3/Bioplast GS 2189 nanocomposites.

It is observed from the pattern that all the peaks matched

very well with calcium carbonate CaCO3 JCPDS card No. 47-
1743 of calcite. Also, the pattern does not show any peaks of
impurities in the sample, which clearly suggests the high purity
of inorganic calcium carbonate in the bioinspired nanoparticles.
The XRD pattern of the neat Bioplast GS 2189 polymer is
presented in Figure 1b and shows crystalline peaks at 17°, 19°,
and 30° of 2θ. These results are consistent with the polymer
data sheet.
The characteristic peaks in XRD patterns of Figure 1(a−e)
also match with the CaCO3 JCPDS card No. 47-1743. An
additional wide peak at approximately 18° of 2θ is noticeable in
all bio-CaCO3/Bioplast GS2189 nanocomposites. This distinct
wide peak corresponds to the polymer. XRD data show a
significant decrease in the intensities of the characteristic
CaCO3 peaks between the XRD pattern of pure bio-CaCO3
nanoparticles and the XRD patterns for the as-prepared
Bioplast GS 2189 polymer nanocomposites. Reduction in the
peak intensities indicate that the bio-CaCO3 nanoparticles are
highly exfoliated in the polymer matrix, and this may be the
result of good dispersion of the bio-CaCO3 nanoparticles in
Bioplast GS 2189 polymer.40 Good dispersion was achieved by
the efficient solution mixing procedure and proper extrusion
temperatures used in the fabrication process.
TEM was used to determine the characteristics of as-
prepared bio-CaCO3 nanoparticles. A TEM micrograph of bio-
CaCO3 nanoparticles is presented in Figure 2a. TEM results
show that all bio-CaCO3 nanoparticles are uniform in particle
sizes less than 10 nm. The TEM image also indicates that the
bio-CaCO3 nanoparticles demonstrate highly crystalline
structures along with irregular shapes that justify the high
surface area of these nanoparticles.
Transmission electron microscopy was also used to
investigate the dispersion of bio-CaCO3 nanoparticles in the
Bioplast GS 2189 polymer, and the results showed that the as-
prepared bio-CaCO3 nanoparticles are superbly dispersed in
the polymer matrix. Figures 2b and c show TEM micrographs
of the 2% bio-CaCO3/Bioplast GS 2189 nanocomposite. The Figure 2. TEM micrographs of (a) bio-CaCO3 nanoparticles and (b,
TEM micrograph in Figure 2b indicates good dispersion of the c) 2% bio-CaCO3/Bioplast GS 2189 nanocomposite.
bionanoparticles over the entire volume of the polymer, and
Figure 2c displays a very good dispersion also and clearly shows
that there is no agglomeration of bio-CaCO3 nanoparticles in small volume of polymer even at a relatively high magnification.
the polymer with a relatively high number of particles in a given Furthermore, these TEM results illustrate the highly crystalline
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Figure 3. TGA results for neat Bioplast GS 2189 and bio-CaCO3/Bioplast GS 2189 nanocomposites.

Table 2. TGA Results for Neat Bioplast GS 2189 Polymer and Bio-CaCO3/Bioplast GS 2189 Nanocomposites
no. sample decomposition temperature Td (°C) degrees increased 50% weight loss temperature (°C) degrees increased
1 neat Bioplast GS 2189 342.2 ± 1.1 − 361.4 ± 2.2 −
2 1% bio-CaCO3/Bioplast GS 2189 nanocomposite 349.0 ± 1.7 06.8 367.2 ± 1.6 05.8
3 2% bio-CaCO3/Bioplast GS 2189 nanocomposite 357.8 ± 2.1 15.6 371.7 ± 1.4 10.3
4 3% bio-CaCO3/Bioplast GS 2189 nanocomposite 345.3 ± 0.9 03.1 369.5 ± 1.2 08.1

nature of the bio-CaCO3 nanoparticles with very distinguished nanoparticles and the thermoplastic polymer, which stabilizes
lattice planes presented in the TEM micrographs. the bionanocomposite against thermal decomposition.45 The
The thermal stability of the as-fabricated neat Bioplast GS decomposition temperatures for the neat Bioplast GS 2189
2189 polymer and bio-CaCO3/Bioplast GS 2189 nano- polymer and bio-CaCO3/Bioplast GS 2189 nanocomposites are
composites were characterized by TGA. In the present TGA presented in Table 2 along with the 50% weight loss
studies, the peak of the derivative curve was considered as a temperature. From these TGA data, it is evident that the
marker for structural decomposition of the samples.42,43 Figure 50% weight loss temperatures of bio-CaCO3/Bioplast GS 2189
3 shows the TGA graphs for the neat Bioplast GS 2189 nanocomposites have been enhanced considerably over the
polymer and bio-CaCO3/Bioplast GS 2189 nanocomposites. As 50% weight loss temperature of the neat Bioplast GS 2189
shown in Figure 3a, the decomposition temperature of neat polymer. When compared to the 50% weight loss temperature
Bioplast GS 2189 is measured at 342 °C. This temperature is of the neat Bioplast GS 2189 polymer measured from Figure
assigned to the decomposition of polylactic acid (PLA) in the 3(a) at 361 °C, the 50% weight loss temperatures have been
Bioplast GS 2189 polymer, while it is measured at 349 °C for increased by 5.8, 10.3, and 8.1 °C for 1%, 2%, and 3% bio-
bio-CaCO3/Bioplast GS 2189 nanocomposites loaded with 1 CaCO3/Bioplast GS 2189 nanocomposite, respectively.
wt % of the nanofiller as shown in Figure 3b.44 The highest TGA graphs also show that all tested samples have
decomposition temperatures among all tested samples was experienced three separate weight loss events at higher
measured at 358 °C for 2 wt % of bio-CaCO3/Bioplast GS temperatures. These weight loss events may correspond to
2189 as presented in Figure 3c. Figure 3d shows the the decomposition of certain additives and plasticizers in the
decomposition temperature of the 3% bio-CaCO3/Bioplast commercial Bioplast GS 2189 polymer. It is very much evident
GS 2189 nanocomposite at 345 °C. These results clearly show from the TGA graphs that all these weight losses temperatures
there is a significant increase in the decomposition temper- have been shifted toward higher temperatures by several
atures of nanophased Bioplast GS 2189 due to the infusion of degrees. This also confirms that bio-CaCO3/Bioplast GS 2189
as-prepared bio-CaCO3 nanoparticles compared to the neat nanocomposites are thermally more stable as compared to the
polymer. The improved thermal stability of the bionanocom- neat Bioplast GS 2189 polymer because of the presence of bio-
posite is attributed to the strong adhesion between bio-CaCO3 CaCO3 nanoparticles.
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ACS Sustainable Chemistry & Engineering Research Article

Figure 4. DSC results for neat Bioplast GS 2189 and bio-CaCO3/Bioplast GS 2189 nanocomposites: (a) heating curves, (b) cooling curves.

Table 3. DSC Results for Neat Bioplast GS 2189 and Bio-CaCO3/Bioplast GS 2189 Nanocomposites
glass transition degrees melting temperature degrees crystallization degrees
no. sample temperature Tg (°C) increased Tm (°C) increased temperature Tc (°C) increased
1 neat Bioplast GS 2189 56.2 ± 1.2 − 141.1 ± 0.9 − 60.0 ± 1.0 −
2 1% bio-CaCO3\Bioplast GS 2189 57.4 ± 0.8 1.2 147.2 ± 1.2 06.1 70.6 ± 0.7 10.6
nanocomposite
3 2% bio-CaCO3\Bioplast GS 2189 60.2 ± 1.0 4.0 154.0 ± 1.1 12.9 67.8 ± 1.3 07.8
nanocomposite
4 3% bio-CaCO3\Bioplast GS 2189 56.4 ± 0.7 0.2 151.0 ± 1.8 02.9 73.76 ± 1.1 13.8
nanocomposite

DSC experiments were carried out to estimate the glass Interestingly, each sample exhibits an exothermic peak at a
transition temperature (Tg), melting temperature (Tm), and temperature range of 100−110 °C. These exothermic peaks are
crystallization temperature of neat Bioplast GS 2189 and bio- noticed prior to samples melting, and they correspond to cold
CaCO3/Bioplast GS 2189 nanocomposites. The DSC results crystallization of the samples due to the reorganization of
are shown in Figure 4a for the heating cycle and Figure 4b for amorphous into crystalline domains on account of the
the cooling cycle, and the results are summarized in Table 3. As increased macromolecular flexibility and mobility upon
shown in Figure 4a, all tested samples experience three increasing temperature.46 The samples then approach the
distinctive thermal events. All samples show glass transition as a melting region, which is represented as a wide endothermic
peak at 140−155 °C. The melting point of neat Bioplast GS
wide baseline shift at temperatures in the range of 50−60 °C.
2189 polymer is at 141.1 °C. Bio-CaCO3/Bioplast GS 2189
Neat Bioplast GS 2189 shows Tg at approximately 56 °C, while nanocomposites showed a significant increase in the melting
1% bio-CaCO3/Bioplast GS 2189 show glass transition at temperature by 6.1 °C for 1% bio-CaCO3/Bioplast GS 2189
approximately 58 °C. The Tg values for 2% and 3% bio- (147.2 °C), by 12.9 °C for 2% bio-CaCO3/Bioplast GS 2189
CaCO3/Bioplast GS 2189 nanocomposites are obtained at ∼60 (154 °C), and by 2.9 °C for 3% bio-CaCO3/Bioplast GS 2189
°C and ∼56 °C, respectively. It is clear that all bio-CaCO3/ (151 °C). As observed from Figure 4a, all bionanocomposite
Bioplast GS 2189 nanocomposites have increased the glass samples showed higher heat of fusion compared to the neat
transition temperatures due to the incorporation of the bio- Bioplast polymer, which also indicates better interfacial
CaCO3 nanoparticles. properties between bio-CaCO3 nanoparticles and the polymer.
711 dx.doi.org/10.1021/sc400405v | ACS Sustainable Chem. Eng. 2014, 2, 706−717
ACS Sustainable Chemistry & Engineering Research Article

In the cooling curves presented in Figure 4b, it is observed

that all loadings of bio-CaCO3 nanoparticles caused an increase
in the crystallization temperature (Tc) compared to the neat
Bioplast GS 2189. The crystallization temperature for the neat
Bioplast GS 2189 is approximately 60 °C, and it is
approximately 70, 67, and 74 °C for 1%, 2%, and 3% bio-
CaCO3/Bioplast GS 2189 nanocomposites, respectively. The
increase in the crystallization temperature of the nanophased
polymer nanocomposite systems is attributed to the infusion of
the bio-CaCO3 nanoparticles. These nanofillers act as
nucleating agents in the polymer melts; hence, when the
polymers melt and recrystallize, faster nucleation takes place at
the site where these nucleating agents are more available,
causing a higher crystallization than that of the neat Bioplast GS
2189 polymer. This effect is more significant in the case of the
3% of bio-CaCO3/Bioplast GS 2189 composite, which resulted
in a too oblique cooling curve than the pristine polymer.
Furthermore, the presence of the bio-CaCO3 nanoparticles
cause crystallization to start earlier and at higher temperatures. Figure 5. Storage modulus for neat Bioplast GS 2189 and bio-CaCO3/
As shown in the DSC curves, the broader exothermic peaks of Bioplast GS 2189 nanocomposites.
the bio-CaCO3/Bioplast GS 2189 nanocomposites compared
to the sharp exothermic peak of the neat Bioplast GS 2189 temperature, and the results are shown in Table 5. As shown
polymer indicate that crystallization of the bionanocomposites in Figure 5, all the curves show a characteristic peak between
is slower than the crystallization of the pristine polymer. The temperatures of 65−70 °C; these peaks correspond to the glass
combination of a larger number of nucleation sites and limited transition. The glass transition temperatures (Tg) are usually
crystal growth produces crystals that have fine grain sizes, which interpreted as the peak of either the tan δ or the loss modulus
will lead to a material with enhanced thermal and mechanical curves obtained during the dynamic mechanical test; in this
properties. Similar results were also observed by other study, the peaks of tan δ curves were used to determine the
researchers.46,47 glass transition temperatures (Tg) of the neat Bioplast GS 2189
The dynamic mechanical analysis (DMA) reveals informa- and bio-CaCO3/Bioplast GS 2189 nanocomposites.49
tion about the amount of energy stored in the nanocomposites As shown in Figure 6, there is an improvement in the loss
as elastic energy and the amount of energy dissipated during modulus of the 1% bio-CaCO3/Bioplast GS 2189 nano-
mechanical strain, which strongly depends on the geometrical composite at 30 °C (47 MPa) compared to neat Bioplast GS
characteristic and the level of dispersion of the reinforcing fillers 2189 polymer (32.7 MPa), 2% bio-CaCO3/Bioplast GS 2189
in the matrix. It also depends on the degree of interaction nanocomposite (28.6 MPa), and 1% bio-CaCO3/Bioplast GS
between the matrix and filler surface.48 DMA was performed to 2189 nanocomposite at 30 °C (34.1 MPa). At 60 °C, the loss
study how the properties of the neat Bioplast GS 2189 polymer modulus has improved for all bio-CaCO3/Bioplast GS 2189
and bio-CaCO3/Bioplast GS 2189 nanocomposites are affected nanocomposites compared to the neat polymer, and as the
by the increase in temperature. Storage modulus, loss modulus, temperature increased past the softening temperature, loss
and phase lag (tan δ) for neat and nanophased polymers were modulus has diminished for all samples. Moreover, it is
measured. The values of storage modulus (E′) for the neat noticeable from Figure 6 that the loss modulus peak values
Bioplast GS 2189 polymer and bio-CaCO3/Bioplast GS 2189 increase as an effect of the addition of bio-CaCO3 nanoparticles
nanocomposites with different weight fractions are presented in in Bioplast GS 2189 polymer. The reason for this might be the
Figure 5, and the results are compared in Table 4 for three limitation in the molecular mobility induced by the
different temperatures. It is shown in Figure 5 that the neat bionanoparticles.
Bioplast GS 2189 polymer has a much lower storage modulus Figure 7 shows the variation of tan δ with temperature for
(796.9 MPa) than the bio-CaCO3/Bioplast GS 2189 samples neat Bioplast GS 2189 and bio-CaCO3/Bioplast GS 2189
(941.6, 968.2, and 892.6 MPa for 1%, 2%, and 3% bio-CaCO3/ nanocomposites. As shown in the figure, all the curves are
Bioplast GS 2189 nanocomposite, respectively) at room closely packed and overlaid; however, several observations are
temperature. When the temperature was increased to 60 °C, noticed. The peak heights of tan δ curves for the bio-CaCO3/
the storage modulus for all samples decreased. The Bioplast GS Bioplast GS 2189 nanocomposites have been reduced with the
2189 nanocomposite sample with 2% bio-CaCO3 nanoparticles introduction of bio-CaCO3 nanoparticles compared to the
loading has the highest storage modulus value at this height of the neat Bioplast GS 2189 polymer curve. All peaks
temperature (800.1 MPa) compared to neat Bioplast GS are lowered with the increase in the loading of bio-CaCO3
2189 (679.9 MPa), 1% bio-CaCO3/Bioplast GS 2189 (743.1 nanoparticles. The reason may be due to the restriction of the
MPa), and 3% bio-CaCO3/Bioplast GS 2189 (713.9 MPa). At mobility of the polymer chains by the bio-CaCO3 nanoparticles.
higher temperature (100 °C), all the samples passed the The other prominent effect is a broadening of the transition
softening stage, and the storage modulus values dropped as region. This may be due to the inhibition of the relaxation
listed in Table 4. The improvement in the storage modulus of process within the bionanocomposites upon incorporation of
bionanocomposites is due to the presence of highly exfoliated the bio-CaCO3 nanoparticles.50 Glass transition temperatures
bio-CaCO3 nanoparticles in the polymer matrix. Figure 5 shows obtained from the peaks of tan δ curves are presented in Table
the variation of the loss modulus of the neat Bioplast GS 2189 6. The bio-CaCO3/Bioplast GS 2189 nanocomposite with 2%
and bio-CaCO3/Bioplast GS 2189 nanocomposites with loading of the particles have the highest Tg (76.1 °C) compared
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ACS Sustainable Chemistry & Engineering Research Article

Table 4. Storage Modulus for Neat Bioplast GS 2189 and Bio-CaCO3/Bioplast GS 2189 Nanocomposites
storage modulus (MPa)
no. sample at 30 °C at 60 °C at 100 °C
1 neat Bioplast GS 2189 796.9 ± 11.2 679.9 ± 10.0 2.6 ± 0.4
2 1% bio-CaCO3/Bioplast GS 2189 nanocomposite 941.6 ± 13.4 743.1 ± 14.5 2.0 ± 0.1
3 2% bio-CaCO3/Bioplast GS 2189 nanocomposite 968.2 ± 09.6 800.1 ± 11.7 2.3 ± 0.3
4 3% bio-CaCO3/Bioplast GS 2189 nanocomposite 892.6 ± 12.1 713.9 ± 12.9 4.9 ± 1.7

Table 5. Loss Modulus for Neat Bioplast GS 2189 and Bio-CaCO3/Bioplast GS 2189 Nanocomposites
loss modulus (MPa)
no. sample at 30 °C at 60 °C at 100 °C
1 neat Bioplast GS 2189 32.7 ± 3.1 103.2 ± 4.8 0.96 ± 0.2
2 1% bio-CaCO3/Bioplast GS 2189 nanocomposite 47.0 ± 3.2 140.6 ± 3.4 1.17 ± 0.1
3 2% bio-CaCO3/Bioplast GS 2189 nanocomposite 28.6 ± 1.5 138.5 ± 2.7 1.22 ± 0.1
4 3% bio-CaCO3/Bioplast GS 2189 nanocomposite 34.1 ± 1.1 118.2 ± 2.5 1.35 ± 0.1

Table 6. Glass Transition Temperatures for Neat Bioplast

GS 2189 and Bio-CaCO3/Bioplast GS 2189 nanocomposites
measured by DMA
no. sample Tg°C
1 neat Bioplast GS 2189 72.9 ± 1.5
2 1% bio-CaCO3/Bioplast GS 2189 nanocomposite 75.6 ± 0.9
3 2% bio-CaCO3/Bioplast GS 2189 nanocomposite 76.1 ± 1.2
4 3% bio-CaCO3/Bioplast GS 2189 nanocomposite 73.7 ± 2.1

to the addition of bio-CaCO3 nanoparticles. These results show

that the bio-CaCO3/Bioplast GS 2189 nanocomposite are more
thermally stable compared to the neat Bioplast GS 2189
polymer, and they are inconsistent with the TGA and DSC
results.
Thermomechanical analysis (TMA) measurements were
carried out to obtain information on the dimensional stability
of as-prepared bionanocomposites under variation of temper-
Figure 6. Loss modulus for neat Bioplast GS 2189 and bio-CaCO3/ ature. The TMA curves for neat Bioplast GS 2189 and bio-
Bioplast GS 2189 nanocomposite. CaCO3/Bioplast GS 2189 nanocomposites are presented in
Figure 8.
As shown in Figure 8, tested samples show a rather uniform
expansion to about 55 °C. Above this temperature, the samples
experience a huge extension that takes place due to plastic flow
and softening of the polymer, which is followed by melting of
the samples at higher temperatures. Bio-CaCO3/Bioplast GS

Figure 7. Tan (δ) for neat Bioplast GS 2189 and bio-CaCO3/Bioplast

GS 2189 nanocomposites.

to neat Bioplast GS 2189 and the 1% and 3% bio-CaCO3/

Bioplast GS 2189 nanocomposites (72.9,, 75.6, and 73.7 °C,
respectively). The shifting of Tg to higher temperatures can be Figure 8. Dimensional change vs temperature plot for neat Bioplast
associated with the decreased mobility of the matrix chains due GS 2189 and bio-CaCO3/Bioplast GS 2189 nanocomposites.

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ACS Sustainable Chemistry & Engineering Research Article

Table 7. CTE Results for Neat Bioplast GS 2189 and Bio-CaCO3/ Bioplast GS 2189 Nanocomposites
CTE (μm/m °C)
no. sample below Tg (40−50 °C) above Tg (75−85 °C)
1 neat Bioplast GS 2189 142.8 ± 3.4 4203.9 ± 32.6
2 1% bio-CaCO3/Bioplast GS 2189 nanocomposite 139.1 ± 1.2 3944.7 ± 52.7
3 2% bio-CaCO3/Bioplast GS 2189 nanocomposite 136.3 ± 2.2 3889.5 ± 36.2
4 2% bio-CaCO3/Bioplast GS 2189 nanocomposite 140.6 ± 1.3 4021.8 ± 42.4

2189 nanocomposites show better dimensional stability in the GS2189 with loadings of 2% and 3% bio-CaCO3 nanoparticles
softening region between temperatures of (55−75 °C) and also exhibited an increase in the flexure modulus by 30.5% and
below about 90 °C. The CTE values acquired from the test 6.9%, respectively.
results are presented in Table 7, and they clearly indicate the A common trend in nanoparticles-reinforced polymer tested
improved thermal stability of the bionanocomposites compared in flexure configuration is the increase in strength and modulus,
to the neat polymer but on the other hand, nanofiller reinforcements may have a
Flexure tests were carried out to investigate the effect of bio- detrimental effect on the flexural strain to break.51 Many
CaCO3 nanoparticles on the mechanical properties of the neat researchers have reported a decrease in the failure strains of
Bioplast GS 2189 thermoplastic polymer and bio-CaCO3/ different polymers upon the addition of reinforcing fillers as the
Bioplast GS2189 nanocomposites as well. Stress−strain curves resultant composite become more brittle.52−55 Interestingly, in
of tested specimens are presented in Figure 9, and the results this investigation, bio-CaCO3/Bioplast GS2189 nanocompo-
sites exhibited a significant increase in the strain-to-failure
compared to the neat Bioplast GS2189 polymer. The strain-to-
failure for the neat polymer was 3.8%, while it was 4.75% and
6.8% for 1% and 3% bio-CaCO3/Bioplast GS2189 nano-
composites, respectively. The addition of bio-CaCO3 nano-
particles results in a maximal increase of 8.39% of strain-to-
failure at 2% loading. The bio-CaCO3/Bioplast GS2189
nanocomposite sample with 2% loading was very ductile and
never failed with the increase in flexure loading; however, some
cracks appeared in the tested samples.
The enhancement in the mechanical properties of bio-
CaCO3/Bioplast GS2189 nanocomposites is due to the
presence of well-dispersed highly porous bio-CaCO3 nano-
particles. In addition to good bionanoparticles dispersion, some
important characteristics of the as-prepared bionanocomposites
have to be considered such as the quality of the interface in as-
prepared bionanocomposites and the interfacial stiffness that
plays an important role in the materials’ capability to transfer
load and stresses between matrix and the nanofillers, allowing
the rigid nanoparticles to efficiently contribute in carrying the
load and enhancing the mechanical properties.56
Figure 9. Stress−strain curve of flexure test for neat Bioplast GS 2189 The morphology of the fracture surfaces of neat Bioplast GS
and bio-CaCO3/Bioplast GS 2189 nanocomposites. 2189 and the bio-CaCO3/Bioplast GS 2189 nanocomposite
was investigated by SEM, and the fractographs are presented in
Figure 10. Figure 10a shows that the fracture surface of neat
are listed in Table 8. The flexure strength for neat Bioplast GS Bioplast GS 2189 is relatively smooth, while it is rough and
2189 is 29.23 MPa, and as the bio-CaCO3 nanoparticles loading uneven for the 1% bio-CaCO3/Bioplast GS 2189 nano-
increases, the flexure strength remarkably increases by 25.24% composite and 3% bio-CaCO3/Bioplast GS 2189 nano-
for the 1% samples, 35.3% for the 2% samples, and 11.77% for composite as illustrated in Figure 10b and c, respectively. For
the 3% samples. A similar trend was observed for the flexural the 2% bio-CaCO3/Bioplast GS 2189 nanocomposite sample,
modulus. The flexure modulus for the neat Bioplast GS 2189 the fracture surface was not examined by SEM as the samples
polymer was 5.8 MPa, whereas for the 1% bio-CaCO3/Bioplast did not fail during the flexure test. Figure 11 shows optical
GS2189 nanocomposite, the flexure modulus increased micrographs of the sample. As shown in Figure 11a, the sample
significantly by 57.2% (9.1 MPa). Nanophased Bioplast has cracked on the tensile stress zone and the crack propagated

Table 8. Flexure Test Results for Neat Bioplast GS 2189 and Bio-CaCO3/Bioplast GS 2189 Nanocomposites

flexural strength increase flexural modulus increase strain at max increase

no. sample (MPa) (%) (GPa) (%) strength (%)
1 neat Bioplast GS 2189 29.2 ± 2.7 − 5.8 ± 1.3 − 6.3 ± 0.7 −
2 1% bio-CaCO3/Bioplast GS 2189 nanocomposite 36.6 ± 1.4 25.2 9.1 ± 0.9 56.9 4.8 ± 0.5 −24.6
3 2% bio-CaCO3/Bioplast GS 2189 nanocomposite 39.6 ± 1.7 35.3 7.6 ± 1.1 30.5 8.4 ± 1.0 33.3
4 3% bio-CaCO3/Bioplast GS 2189 nanocomposite 32.7 ± 2.1 11.8 6.2 ± 1.5 06.9 6.8 ± 0.8 07.9

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ACS Sustainable Chemistry & Engineering Research Article

Figure 10. Fracture surfaces for (a) neat and bio-CaCO3/Bioplast GS 2189 (b, c) 1% and 3% bio-CaCO3/Bioplast GS 2189 nanocomposites,
respectively.

Figure 11. Optical microscope micrographs of 2% bio-CaCO3/Bioplast GS 2189 nanocomposite sample.

through the sample. In Figure 11b, the lower side of the sample analysis results have shown that the as-fabricated bionanocom-
is shown, and it is clear from the image that increasing the load posites are thermally more stable than their pristine counter-
during the test has created several cracks within the tensile parts. The mechanical properties of as-prepared bionanocom-
stress side of the sample. These images suggest that the crack posites have increased substantially. The 2% bio-CaCO3/
growth was difficult and did not propagate to cause failure due Bioplast GS 2189 nanocomposite exhibited a 35.3% and 30.5%
to the enhanced mechanical properties of the sample. The increase in the flexural strength and modulus, respectively,
fracture surface studies for neat Bioplast GS 2189 and the bio- when compared to pristine Bioplast GS 2189 polymer.
CaCO3/Bioplast GS 2189 nanocomposite are in agreement Moreover, the 2% bio-CaCO3/Bioplast GS 2189 nano-
with the flexure test results. composite demonstrated a significant increase by 33.3% in

■ CONCLUSIONS
This investigation has successfully demonstrated the fabrication
the strain-to-failure compared to the neat Bioplast GS 2189
polymer. The fracture surfaces investigations were in agreement
with the mechanical test results.
of bionanocomposite materials derived from renewable Dynamic mechanical analysis proved that as-prepared
resources with enhanced thermal and mechanical properties. bionanocomposites have demonstrated a considerable enhance-
Novel bionanocomposites were produced via the incorporation ment in the storage modulus, loss modulus, and tan δ when
of bio-CaCO3 nanoparticles derived from eggshells as nano- compared to the neat Bioplast GS 2189 polymer. Equally
fillers in Bioplast GS 2189 thermoplastic biopolymer. The bio- important, thermo-mechanical analyses showed a significant
CaCO3 nanoparticles were efficiently dispersed and highly decrease in the coefficients of thermal expansion of all loadings
exfoliated in the polymer matrix via the solution mixing process, of bio-CaCO3 in Bioplast GS 2189 compared to the coefficient
which was confirmed by XRD and TEM studies. Thermal of thermal expansion of pristine Bioplast GS 2189 before and
715 dx.doi.org/10.1021/sc400405v | ACS Sustainable Chem. Eng. 2014, 2, 706−717
ACS Sustainable Chemistry & Engineering Research Article

after the glass transition temperature. This important increase (17) Lin, Z.; Guan, Z.; Chen, C.; Cao, L.; Wang, Y.; Gao, S.; Xu, B.;
in the materials properties at low loadings of the nanofillers Li, W. Preparation, structures and properties of shell/polypropylene
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for food packaging applications that demonstrate excellent
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properties and eliminate the environmental issues of disposal.

■
Eggshell, a new biofiller for polypropylene composites. Mater. Lett.
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The authors declare no competing financial interest.

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1383−1388.
(22) Kang, D.; Pal, K.; Park, S.; Bang, D.; Kim, J. Effect of eggshell
ACKNOWLEDGMENTS and silk fibroinon styrene−ethylene/butylene−styrene as bio-filler.
The financial support of the NSF-CREST #1137681, Alabama Mater. Des. 2010, 31 (4), 2216−2219.
(23) Tsai, W.; Yang, J.; Hsu, H.; Lin, C.; Lin, K.; Chiu, C.
EPSCoR #1158862, and The Alabama Commission on Higher
Development and characterization of mesoporosity in eggshell ground
Education is gratefully acknowledged.

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