Fibers and Polymers 2018, Vol.19, No.

9, 1970-1979 ISSN 1229-9197 (print version)

DOI 10.1007/s12221-018-8023-4 ISSN 1875-0052 (electronic version)

Properties of Thermoplastic Corn Starch Based Green Composites Reinforced

with Barley (Hordeum vulgare L.) Straw Particles Obtained by
Thermal Compression
José Antonio Silva-Guzmán, Raúl Rodríguez Anda, Francisco Javier Fuentes-Talavera,
Ricardo Manríquez-González, and María Guadalupe Lomelí-Ramírez*
Department of Wood, Cellulose and Paper, University Center for Exact Sciences and Engineering, University of Guadalajara,
Jalisco 45020, México
(Received January 16, 2018; Revised July 5, 2018; Accepted July 11, 2018)

Abstract: Currently, greater environmental awareness promotes research and development advances in biodegradable
materials; they represent an alternative that decreases the environmental impact caused by traditional synthetic plastics. This
study consists of the development and characterization of thermoplastic corn starch-based composites, reinforced with barley
straw particles made by thermal compression. The study materials were prepared by using three particle concentrations (5,
10, and 15 %), while the matrix (0 %) was used as a reference. A mechanical evaluation of all samples was carried out, as
well as that of their water absorption properties. They were also characterized by scanning electron microscopy (SEM),
infrared spectroscopy (FTIR), X-ray diffraction (XRD), and flammability tests. The inclusion of straw in the thermoplastic
matrix increased water absorption and quickened carbon formation, although it also increased its tensile strength (7 MPa) and
the Young’s modulus of activity (MOE) (420 MPa) with a 15 % reinforcement. The FTIR analysis highlights the presence of
a carbonyl signal (1720 cm-1) caused by a thermal breakdown (caramelization) linked to barley particles. Moreover, X-ray
diffraction demonstrated a VA-type crystallinity pattern (anhydrous) within the biocomposites and an increase of the
crystallinity index, through incorporating barley particles in the thermoplastic corn starch-based matrix.
Keywords: Thermoplastic starch, Barley straw, Green composites, Thermal compression

Introduction plastic through temperature change and shearing. A partial

substitution of the original hydrogen bonds between amylose
Synthetic polymers have been widely used in the and amylopectin macromolecules with other hydrogen
application of human products, the petroleum-derived bonds and the plasticizer is needed [4]. Thermoplastic starch
plastics representing around a fifth of household waste in materials (TPSs) may be reinforced with lignocellulosic
cities. During the last few decades, the plastic volume and fibers to produce biocomposites or “green” composites, a
related issues about its disposal and prolonged degradation special class of composite materials that are currently quite
time have caused several environmental problems [1]. relevant. As every component is biologically- or naturally-
Conversely, the increasing demand for technologies (and derived, it is considered completely biodegradable. Generally,
products that cause less environmental impact) has driven all composite materials made from thermoplastic starch
ecologic awareness and an interest in studying and applying display low mechanical properties. As such, the inclusion of
biodegradable and renewable raw materials. Research in the lignocellulosic fibers has been proposed, as they may
material engineering field has developed easily degradable improve its mechanical performance [5]. There is no limitation
packaging materials that are less harmful to the environment regarding the use of natural fibers as a reinforcement for a
[2]. The adaptation of composite materials, classified in the thermoplastic starch matrix, including non-timber fibers
scope of sustainable development and included in ecological (kenaf, jute, sisal, coconut, banana, sugarcane bagasse, etc.)
projects, is a philosophy being applied in both technology and wood particles (hard and soft woods). All vegetable
and new materials development. resources may be used directly from the production process
Starch is the second most abundant polymer in the world or in the form of residues from a number of agricultural
after cellulose, and it is obtained from renewable resources activities.
[3]. Plants synthesize and store starch within their seeds Several studies have demonstrated improved properties of
(corn grain, wheat, rice, sorghum, barley, and beans) as well thermoplastic starch [6-8] by including several types, along
as within their tubercles and roots (potato, cassava, yucca), with lignocellulosic fiber materials. The use of natural fibers
used as an energy reserve by the plant. Starch is considered a is considered to be renewable, biodegradable, and less of a
promising candidate for sustainable materials development, pollutant on the environment, and may be obtained from
as it (i) is a natural occurring polymer, (ii) economical, (iii) several plant species. The use of vegetable fibers as composite
abundant, and (iv) biodegradable. It can be turned into reinforcement has the following advantages: abundance, low
cost, low density, lack of toxicity, non-abrasive, biodegradable,
*Corresponding author: [email protected] anisotropic, viscoelastic, reactive, renewable, recyclable,

1970
Corn TPS-Barley Straw Composites by Thermal Compression Fibers and Polymers 2018, Vol.19, No.9 1971

and compostable: their handling is also safer in comparison mixtures were transferred to a stainless steel mold (170 mm
with synthetic fibers. High-resistance products are obtained ×170 mm×3 mm) to process composite. A hydraulic press
with a highly specific modulus, as well as suitable thermal (Smart Steel model HI-TR2014) with a heating system and
stability, high electric resistance, and good acoustic properties controlled cooling was used to obtain the laminates of both
[9]. Barley is an agricultural waste that is increasingly the thermoplastic starch (TPS) matrix and composites. The
produced in large amounts, but has no intended use. According processing conditions used were: temperature 160 oC with
to reports by the Food and Agriculture Organization (FAO) applied pressure 100-150 bar and pressurization time of
in 2014, it is the fourth most harvested cereal worldwide, 50 min. From the resulted laminated biocomposites were
with approximately 145.5 million tons produced [10]. obtained the specimens for mechanical testing, water
Barley straw represents an important source of lignocelluose absorption, X-ray diffraction, behavior to the flame and
material that may be used as raw material in several industrial chemical characterization by FTIR.
processes or as a reinforcement of polymeric matrices
[11,12]. Water Absorption Test
Thermoplastic starch (TPS) is a sustainable component The percentage of water absorption was evaluated
that incorporates reinforcements of natural origin to form following the EN 317 standard (EN 317-1993) [13]. For this
biocomposites that are completely biodegradable. Most of test, specimens measuring 30×30×3 mm cut from the
them are obtained following a typical injection-extrusion laminates plaques were first dried in an air-circulating oven
process of several steps; every step involves time and energy at 60 oC and then immersed in water at room temperature
consumption. On the other hand, biocomposites prepared by (23 oC) for 2 and 24 h respectively. To determine the
thermal compression offer several advantages in comparison percentage of water absorption, the samples were weighed
to the traditional injection-extrusion process: (i) the process before and after immersion.
is relatively new, (ii) fibers are used as a reinforcement to be The water absorption (WA) of the laminates was
better distributed in the matrix, (iii) they are economically calculated using the following equation:
profitable, since the complete process of plasticization takes
% WA = [(M1 – M0/M0) × 100] (1)
place in one step, saving energy and preparation time.
Thus, this study aims to develop biocomposites from where, M0 and M1 are the masses of the sample before and
thermoplastic corn starch by incorporating barley straw after immersion in water.
particles to act as a reinforcement by thermal compression
(within the scope of producing environment-friendly Tensile Strength
materials). Mechanical, structural, and chemical evaluations of Tensile samples of the matrix and the composites were cut
the matrix and biocomposites (related to different amounts of from respective laminates (plaques) using a laser cutting
barley straw) assess tensile strength, water absorption, and machine (Guian Modelo GN 600 LS). The samples obtained
use a flammability test (knowing the combustible properties were tested in a universal testing machine (Instron model
of biocomposites are an important parameter), optical 4411), following ASTM standard D 638M [14] (specimen
microscopy, scanning electron microscopy (SEM), X-ray type 1). All the specimens were tested after of thermal
diffraction (XRD) and infrared spectroscopy (FTIR). treatment of which consisted of placing them in a drying
oven at 50 oC for 5 hours. Seven specimens were tested for
Experimental each sample and the average values of the tensile strength,
Young’s modulus and percentage of elongation were
Materials recorded.
Native corn starch was supplied by Indumex, Monterrey
N.L., barley straw (Financiera Cebaderos S.A de C.V del Flammability Test
Valle de Apan, Hidalgo, Mexico) and glycerol reactive The behavior to the composite specimens to flame was
degree (Golden Bell) were used for preparing the TPS made based on the ASTM D-635 [15]. For this assay, the
matrix and the composites. samples are approached to a flame of a Bunsen burner for 10
seconds to start burning. The parameters that were measured
Samples Preparation were the amount and color of smoke, the color of the flame,
The barley straw was dried, milled and sieved to obtain the kind of combustion, the odor, if fire is self- extinguished,
particles of length of mostly 425 µc. The cornstarch was the possible deformation of the test and combustion rate
mixed thoroughly with 30 wt. % glycerol in a plastic bag (mm/s).
until attaining a homogeneous mixture. Then, the particles
of barley straw were added in different proportions to Infrared Spectroscopy with Attenuated Total Reflectance
prepare the composites with 5, 10 and 15 %, they were (ATR)
compared with the thermoplastic matrix (0 %). These The FTIR analyses of the native starch and the bio-
1972 Fibers and Polymers 2018, Vol.19, No.9 José Antonio Silva-Guzmán et al.

composites samples were performed in a Perkin-Elmer Table 1. Water absorption in matrix (0 %) and the biocomposites
(model Spectrum GX) spectrophotometer by means of ATR Water absortion
(Attenuated Total Reflectance) technique. All IR spectra Material
2 hr (%) 24 hr (%)
were the average of 64 scans with a resolution of 4 cm-1
0% 41.6 (4.9) 95.1 (9.0)
within a frequency of 4000-700 cm-1.
5% 48.3 (3.4) 105.0 (5.6)
Optical Microscopy 10 % 86.3 (4.2) 113.9 (5.1)
A Motic stereoscope microscope (model K-400L) 15 % 100.6 (4.5) 116.9 (6.4)
equipped with a Moticam camera was used to observe the
transparency obtained in the composites, porosity and the
distribution of the particles of barley straw in the matrix of different amounts of particles of barley. After 2 h, the TPS
thermoplastic starch. The composites were observed with no matrix showed 41.6 % of water uptake, while incorporation
previous preparation. of barley straw increased this amount up to 100 %, in the
composite with 15 %. Incorporation of barley particles in the
Scanning Electron Microscopy (SEM) starch matrix with water uptake was more evident after 24 h.
Through a Hitachi (model TM 1000) scanning electron The thermoplastic starch matrix absorbed water up to
microscope was observed the fracture surface of the 95.1 %, while all composites (5, 10, and 15 % barley straw)
specimens used in the tensile strength test, without gold showed water absorption above 100 %. Increased incorporation
addition. of barley straw particles in the starch matrix also increases
water uptake. This may be because barley straw has a great
X-ray Diffraction (XRD) deal of parenchyma, and a hydrophilic character. Saetun et
X-ray diffraction (XRD) studies were carried out using a al. [6] reported an increase of water absorption with 12 wt%
Shimadzu diffractometer (Model XRD 7000), with mono- rubber wood sawdust in TPS composites. However, several
chromatic Cu Kα radiation (k=1.5418 Å), at operation authors report a less hydrophilic nature of composites when
conditions of 40 KeV and 20 mA to determine the lignocellulosic fibers are included in the matrix, as
crystallinity of the materials. All samples were dried at 60 oC biocomposite water absorption decreases when cellulose
during 8 h, composites specimen used had dimensions of fiber is added with its crystalline features [18].
40×20×0.3 mm, while the starch sample was in the powder
form. The analysis was carried out in the 2θ angle range of Tensile Strength
2.5o to 60 o with a scanning speed of 1 o/min. The relative Figure 1 shows the matrix tensile strength (0 % particles),
crystallinity of starch and composites was calculated as well as that displayed by biocomposites containing 5, 10,
according to equation (1) [16], based on the deconvolution and 15 % barley particles. It is noticeable that only 10 and
calculus of amorphous and crystalline areas calculated with 15 % concentrations show significant differences for
the aid of the computer program ORIGIN 8.5. increased tensile strength by including a reinforcement.
Shah et al. [21] and Müller et al. [22] point out that the
IRC = (AC/AC + AA) (2)
where, RC is the index relative crystallinity, AC is the
crystalline area and AA is the amorphous area in the XRD
pattern obtained.

Results and Discussion

Water Absorption
Water sensitivity is an important criterion for many
practical applications of starch-based thermoplastic products:
their water absorption in high humidity or in direct contact
with water is very important, because it determines their
integrity and performance under adverse conditions [17,18].
Thermoplastic starch composites have a hydrophilic character
due to their chemical composition of starch (amylopectin
and amylose), and the hydroxyl groups and oxygen form
hydrogen bonds with water [18]. In addition, a plasticizer
increases the affinity to moisture [19]. Table 1 shows the Figure 1. Results of tensile strength of matrix (0 % barley straw
percentage of water uptake by the composites containing particles) and the biocomposites (5-15 %).
Corn TPS-Barley Straw Composites by Thermal Compression Fibers and Polymers 2018, Vol.19, No.9 1973

enhanced mechanical properties (e.g., tensile strength) of

starch-based composite materials compared to those of the
matrix (0 %) confirm the interfacial attachment and improved
interactions between the matrix and lignocellulosic fibers.
These results are favored by chemical similarities between
starch and cellulose fibers. In addition to the type and
amount of reinforcement, the starch type (native or
modified) used, the amount and type of plasticizer, and the
thermoplastic starch processing method also impacts the
resistance properties. For instance, with the tensile strength,
Müller et al. [23] reported values ranging between 1.59 and
26.6 MPa by using cellulose fibers (eucalyptus) with the
casting method. Guimarães et al. [24] found 1.73-4.34 MPa
by using sugarcane bagasse with the thermal conformation
method, and Texeira et al. [25] reported 1.6-4.6 MPa by
using cellulose nanofibers by Haake’s rheometer; Corradini Figure 2. Tensile modulus of the matrix (0 %) and the
et al. [26] used coconut fibers to reinforce a starch matrix biocomposites (with 5, 10 and 15 % barley straw particles).
processed with Haake’s rheometer and reported a 4.45 MPa
value, whereas Ma et al. [18] found values between 5 and
15 MPa using cotton textile fibers in biocomposites, improves the mechanical properties.
processed by extrusion. The results obtained for tensile Figure 2 shows the modulus of elasticity (MOE) of the
strength, caused by the inclusion of barley particles, are study materials. All composite MOEs exhibited statistical
within the expected range for thermoplastic starch-based differences with a 95 % confidence level. Elasticity modulus
composites by other authors. Prachayawarakorn et al. [27] concomitantly increased with the barley particle percentage.
reported lower values of 3, 4, and 5 MPa for tensile strength It is well known that the fiber/particle geometry, orientation,
by studying 5, 10, and 15 % jute and kapoc reinforcements. volume and density are factors that greatly impact on the
Saetun et al. [6] found tension values of 1.2 MPa for mechanical properties [22]. The elasticity or Young’s modulus
thermoplastic starch biocomposites, containing 12 % wood is a parameter that defines the tenacity and rigidity of a given
sawdust and 0.7 MPa when a 12 % reinforcement with material. Müller et al. [23] reported values ranging from 11-
thermal compression of commercially available cellulose 1047 MPa for the elasticity modulus, Guimarães et al. [24]
was used. Previously, Lomelí et al. [8] evaluated the tensile obtained 24.6-484.0 MPa, Texeira et al. [25] reported 16.8-
strength of composites made from cassava starch, reinforced 84.3 MPa, Corradini et al. [26] observed 331 MPa, and Ma
with different concentrations of green coconut fiber. The et al. [18] reported values ranging from 40 to 140 MPa. The
tensile strength values were 3.5, 5.8, 7.9, and 9 for MOE values here were higher compared to those obtained
biocomposites with 0, 5, 10, and 15 % reinforcements, by Kaushik et al. [28], using thermoplastic starch bio-
respectively. These are slightly higher than in the present composites reinforced with barley straw nanofibers. The
study associated with mechanical properties of coconut observed values were 76, 107, 175, and 224 MPa for the
fibers used as reinforcement. matrix and a concentration of 5, 10, and 15 % nanofibers,
Sarsari et al. [9] examined walnut shell composites through respectively. Wattanakornsiri et al. [29] reported a 17 MPa
three compatibilization processes: (i) haake rheometer, (ii) MOE by using a cellulose reinforcement obtained from
extrusion, and (iii) pellets processed by injection, as well as recycled paper.
by powdered maleated anhydride grafted polypropylene Lopez-Gil et al. [7] also assessed the properties of
(MAPP) as a coupling agent to improve the interface biocomposites, based on thermoplastic starch and barley
between components. Although the process involved shear straw fibers with plasticizers at high temperatures and shear
and chemical compatibilization, the tensile strength obtained forces applied by extrusion. The results obtained showed
with 0 and 30 % reinforcement was not in accordance with that tensile strength values are comparable to those obtained
the values of 5 and 6 MPa, respectively. Recently, Guleria et in this work; however, the MOE values are at the same
al. [10] evaluated the properties of thermoplastic starch concentrations: 0 % (90 MPa), 5 % (150 MPa), 10 % (250
crosslinked with urea formaldehyde and reinforced with MPa), and 15 % (310 MPa), and are much lower than those
okra cellulosic fiber through thermocompression. The values obtained by thermal compression.
of tensile strength reported were 11.2, 12.1, 14.8, and Sarsari et al. [9] report MOE results for composites with
17.7 MPa with 0, 5, 10, and 15 % reinforcement, respectively. corn thermoplastic starch of 1 GPa with 0 % and 1.2 GPa
These results are higher due to the type of reinforcement with 30 % of walnut shells. However, the authors did not
used, as well as the crosslinking of the starch, which explain the direct contribution of the 3 stages and the
1974 Fibers and Polymers 2018, Vol.19, No.9 José Antonio Silva-Guzmán et al.

Figure 3. Percentage of elongation at break of matrix and the Figure 4. Stress-strain curves compared the matrix (0 %) and the
biocomposites. biocomposites (5, 10 and 15 %).

coupling agent in the process over enhanced mechanical the stress-strain.

properties of biocomposites. Guleria et al. [10] also reported
high values of MOEs in biocomposites reinforced with 0 % Flammability Test
(0.5 GPa), 5 % (1.1 GPa), 10 % (1.2 GPa), and 15 % (2.5 There are few studies on the behavior of biocomposites
GPa) of okra fiber by crosslinking. exposed to fire. Some, however, have established that certain
Figure 3 presents the results for the deformation percentage combinations of matrix and fiber may reduce flammability,
with different concentrations of reinforcement barley straw while others state that the incorporation of fiber increases the
particles: increasing the number of particles within the combustibility of composite material [30,31]. In general,
matrix causes an elongation decrease. Fibers restrict the incorporating lignocellulosic fibers into thermoplastic starch
thermoplastic corn starch-based matrix elongation during matrix improves its properties, but in the case of flammable
the tension test. Saetun et al. [6] reported deformation behavior, it can be a drawback: vegetable fibers have little
percentage values for thermoplastic starch biocomposites of fire resistance. Thus, the flammability of a composite
20 % with wood sawdust and 30 % with a commercially material depends not only on the polymer matrix and fiber
available cellulose reinforcement. Shah et al. [21] showed type, but also on the interaction between them [32].
that the waste cellulose fiber of biodegradable composites Table 2 shows the flammability test of the matrix and
include thermoplastic starch (containing waste cellulose biocomposites. During this process, carbon appeared in most
fiber), which increased the composite’s stiffness, thereby of the composites, although no leak was observed for the
increasing its tensile strength, although its elongations were thermoplastic starch matrix. It has been found that these
reduced. Müller et al. [23] reported elongation values materials produced scarce but clear-colored smoke, with an
ranging from 13-101 %, Guimarães et al. [24] observed 1.2- orange flame and slightly sweet odor during combustion.
75.5 %, Texeira et al. [25] obtained 29.8-92.4 %, Corradini The matrix tends to self-extinguish while the composites do
et al. [26] found 2.2 %, whereas Ma et al. [18] reported not. The test specimens are not deformed, as they only
values between 20 and 115 %. Guleria et al. [10] reported burned, in turn forming carbon (Figure 5). The carbonized
that the elongation percentage decreased according to the layer created during combustion is an important criterion in
amount of okra fiber added in the thermoplastic starch assessing a polymer’s flammability, as the produced carbon
matrix. All results shown here are in agreement with earlier may serve as a barrier between the ignition source and
reports on starch composites with different reinforcements. internal unburned polymer layers. A carbon-forming polymer
Figure 4 shows typical stress vs strain curves in this study may possess low flammability, which is a desirable quality
for tensile strength tests of matrix (0 % fiber) and bio- for a polymeric matrix [32].
composites with 5, 10, and 30 % barley straw particles. The TPS exhibits a low burning time and high burning rate due
curves of the matrix with and without reinforcement show to its flammable nature, although combustion is very slow
differences: typical curves of ductile material reveal large [31]. The progressive increase of barley particles in the
deformation and low stress strain. In contrast, biocomposites starch matrix causes a faster ignition. The combustion rate
show typical curves of ductile materials with less deformation. (mm/s) was 0.20, 0.24, 0.34, and 0.81 for the matrix and
Increasing the reinforcement in the samples also increases composites of barley particles, at a concentration of 5 %,
Corn TPS-Barley Straw Composites by Thermal Compression Fibers and Polymers 2018, Vol.19, No.9 1975

Table 2. Flammability test of the different materials evaluated

Deformation of
Smoke Flame Self-extinguish Carbon Burning speed
Material the specimen
hue formation (mm/s)
Amount Color Yes/Not Yes/Not
0% * Orange Yes * 0.20
5% * ** 0.24
White Not
10 % ** Blue/orange Not ** 0.34
15 % *** *** 0.81

Figure 6. FTIR-ATR spectra of corn starch, matrix (0 %) and

biocomposites (with 5, 10 and 15 % of barley straw particles).
Figure 5. Behavior evaluation by flame test of matrix and
biocomposites.
spectrum. In the signal of 1720 cm-1, this can be attributed to
10 %, and 15 %, respectively. This agrees with data reported C=O stretching vibrations of carbonyl groups such as
by Bocz et al. [30], having identified that the natural fiber aldehydes, ketones, and carboxylic acids formed by starch
inclusion in the thermoplastic starch matrix increases decomposition in the thermal treatment of TPS lamination.
flammability. Thus, a retardant was needed to decrease On the other hand, the signal of 1240 cm-1 is associated with
combustion. CH-OH groups from glycerol in the TPS matrix. We
previously reported those signals in similar TPS biocomposites
FTIR Analysis [9]. Furthermore, the intensity of those signals increased
The chemical composition and differences of thermoplastic when the amount of barley straw increased in the TPS
biocomposites, prepared with native and modified starch, matrix. In the carbonyl signal (1720 cm-1), it increased as a
have been extensively measured by FTIR spectroscopy consequence of thermal decomposition in the biomaterials,
[7,18,33-36]. Figure 6 shows the FTIR spectra of the corn associated with the amount of barley straw particles. However,
starch samples, TPS, and biocomposites of 5, 10, and 15 % this thermal decomposition (known as caramelization) only
barley straw particles with an average size of 425 µ. All occurs on the surface of samples without affecting their
samples depict a similar spectroscopic pattern of signals, mechanical properties, as we earlier reported [8]. This can be
with a broad signal of around 3300 cm-1 originating from explained by the molecular organization of the starch and the
OH groups in the hydrogen bond system and stretching glycerol changes when the barley straw particles are added
vibrations of 2970 and 2850 cm-1 of C-H aliphatic chains; to the matrix, thus exposing more OH groups to thermal
this includes the water signal of 1650 cm-1, since signals oxidation. In addition, the molecular organization of OH
between 1500 to 900 cm-1 are attributed to C-H bending as groups is also observed in the glycerol signal (1240 cm-1),
well as C-C and C-O stretching vibrations. These signals which increased according to the barley straw particles in the
also corroborate alcohol, ether, and aliphatic composition biocomposite; this is due to the hydrogen bond system in the
from the starch and glycerol matrix (TPS) of biomaterials. TPS being disturbed.
Spectroscopic changes are observed in samples of TPS with
5, 10, and 15 % of barley straw with signals of 1720 cm-1 Optical Microscopy
and 1240 cm-1-which are not appreciated in the corn starch Figure 7(a, b, and c) shows photographs of corn starch-
1976 Fibers and Polymers 2018, Vol.19, No.9 José Antonio Silva-Guzmán et al.

Figure 7. Images of the biocomposites with 5 % (a), 10 % (b) and 15 % (c) of barley particles.

glycerol biocomposites with 5, 10, and 15 % barley particles barley straw. The uniform and homogenous distribution of
observed under a stereomicroscope. When the original semi- particles within the matrix is also observed. Vallejos et al.
crystalline structure of the starch granule is completely [38] reported poor dispersion of fibers during preparation of
disorganized by heat, shearing, and pressure, it becomes a thermoplasticized cassava starch composites with 10 %
thermoplastic starch characterized by amorphousness, sugarcane bagasse, processed in a rheometer (Haake).
transparency, and low crystallinity. A main feature of Oniszczuk and Janssen [39] point out that the size of the
amorphous polymers is their transparency [37], especially in fiber or particle is a limiting factor for extrusion and
the polymeric phase (TPS matrix in Figure 7), allowing for injection methods. Very long fibers or those in high amounts
observation of the parenchymal tissue characteristic of the may cause an excessive increase in viscosity that induces

Figure 8. SEM micrographs of barley straw (a), and composites 5 % (b), 10 % (c), 15 % (d).
Corn TPS-Barley Straw Composites by Thermal Compression Fibers and Polymers 2018, Vol.19, No.9 1977

aggregation and may increase mechanical energy during

processing. Small-sized fibrous materials are used for these
processes, with images showing no air bubbles or
unplasticized parts during the thermal plasticizing process.

Scanning Electron Microscopy

Figure 8(a) shows a SEM micrograph of barley straw.
Stomata arranged in rows (straw veins) can be observed, as
well as wax accumulation on the barley straws. The presence
of epicuticular waxes is common in monocotyledonous
plants, which appear as rods, granules, clusters, scales, and
several other forms that may reach 3.9 mm [40,41].
Wisniewska et al. [42] similarly found various granules of
wax, with an approximate 5 mm diameter in the barley
straw.
Figure 8(b-d) shows the surface of the studied cylinders, Figure 9. X-ray diffractograms of native starch, matrix (0 %) and
evaluated by traction of composites containing 5 %, 10 %, biocomposites.
and 15 % of barley particles, respectively. The images show
an interaction between barley particles and the thermoplastic
matrix during tensile stress. Some barley particles are starch granule (semi-crystalline structure) during the
separated during the mechanical test, although there are plasticizing process, as the interaction between the hydroxyl
other particles that remain well attached to the thermoplastic groups in amylose and amylopectin are modified, with new
starch matrix, demonstrating the effect of the reinforcement. interactions occurring between the plasticizing agent
The composites containing 15 % of barley particles were (glycerin) and the starch chains. Furthermore, the combined
deformed during the stress as a function of the tension test. action of temperature, time, and applied pressure must be
The reinforcement theory establishes that its effect is taken into account [48]. The type-A crystallinity of corn
reflected when a suitable interface (optimal attachment) starch disappeared and a VA polymorphic was formed. The
occurs during the mechanical test, as the tensile stress is identification of the peaks on the diffractogram was based on
transferred to the matrix with an increased tensile resistance the data reported by Van Soest et al. [49], Teixeira et al. [24],
[39]. Figure 8(c,d) shows wax granules on the barley particle and Corradini et al. [26]. At 2θ ~13.5 o, a strong signal is
during the thermal compression process. observed, whereas at 2θ ~17.5 o the signal is intermediate,
and at 2θ ~20.9 o a very pronounced peak occurs for both the
X-ray Diffraction matrix and composites. According to Van Soest et al. [49],
The crystallinity of corn starch was calculated according these peaks match type-VA crystallinity (anhydrous). Lu et
to equation (2) at 33 %. Srichuwong et al. [43] reported a al. [2] reported that the content of the plasticizer agent, the
31-37 value for corn, whereas Avérous and Halley [44] temperature, and the processing method, including the
observed it at 39 %. Figure 9 shows the X-ray diffractograms residence time and cooling rate, are factors impacting the
for native starch, the matrix, and biocomposites. The material’s final crystallographic pattern. The VA lattice has
particular type-A crystallinity pattern of most cereals (corn, more contracted amylose helices and less water than the VH
rice, wheat, and oat) is observed on the diffractograms. It has lattice [49]. Dai et al. [50] also found a VA-type crystallinity
previously been described as amylopectin chains of the type- for thermoplastic corn starch at the same angles as seen in
A structure, and 23-29 glucose-units long, forming a highly this study. The crystallinity index is an important parameter,
condensed and crystalline monocyclic cell unit that harbors as it impacts physical, mechanical, chemical, and technological
4 water molecules between its helixes [45,46]. Native corn properties of materials. The crystallinity index observed for
starch displayed particular diffraction peaks at 2θ 15 o, a the matrix was 0.56, whereas the values for 5 %, 10 %, and
doublet at 18 o, along with an additional peak at 23 o [25,47]. 15 % composites were 0.63, 0.68, and 0.74, respectively.
Figure 9 shows the diffractograms of the TPS matrix and its These values are higher in comparison to those we reported
composites. The direct plasticization process in the press, previously [9].
and the combined action of temperature, pressure, and the
plasticizer caused granular disruption, leading to a change in Conclusion
the characteristic profile of native starch from type-A to type
VA. However, a change is observed when diffractogram It is possible to prepare thermoplastic corn starch-based
profiles of the studied materials are compared to those of composites with the thermal compression method, reinforced
granular starch. This is caused by disorganization of the with 5 to 15 % of particles from barley straw residues. The
1978 Fibers and Polymers 2018, Vol.19, No.9 José Antonio Silva-Guzmán et al.

materials had optimal transparency, enabling the observation 14. ASTM D 638-10. Book of Standards, 08.01. West
of homogeneous distribution of barley particles in the Conshohocken, PA, USA, p.16, 2010.
thermoplastic matrix. The inclusion of barley particles 15. ASTM D 635-03. Book of Standards, 08.02. West
quickened combustion and carbon formation, as well as Conshohocken, PA, USA, p.7, 2003.
water absorption. Although barley straw is a material 16. K. Frost, D. Kaminski, G. KIrwan, E. Lascaris, and R.
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the thermoplastic starch matrix increased mechanical 17. U. Funke, W. Bergthaller, and M. G. Lindhauer, Polym.
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effect. The infrared analysis exhibited a carbonyl signal 19. S. Kuciel, P. Kuźniar, and A. Liber-Kneć, Arch. Foundry
(1720 cm-1) caused by thermal decomposition (caramelization) Eng., 10, 53 (2010).
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