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European Polymer Journal 76 (2016) 266–277

Contents lists available at ScienceDirect

European Polymer Journal


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

Morphological characteristics of stearic acid-grafted starch-


compatibilized linear low density polyethylene/thermoplastic
starch blown film
Nattaporn Khanoonkon a, Rangrong Yoksan a,b,⇑, Amod A. Ogale c
a
Department of Packaging and Materials Technology, Faculty of Agro-Industry, Kasetsart University, Bangkok 10900, Thailand
b
Center for Advanced Studies for Agriculture and Food, Kasetsart University, Bangkok 10900, Thailand
c
Chemical and Biomolecular Engineering and Center for Advanced Engineering Fibers and Films, Clemson University, Clemson, SC 29634-0909, USA

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

Article history: The objective of the present work is to verify the possibility of using stearic acid-grafted
Received 23 November 2015 starch (ST-SA) as a novel compatibilizer for a blend system consisting of linear low density
Received in revised form 26 January 2016 polyethylene (LLDPE) and thermoplastic starch (TPS). ST-SA was successfully synthesized,
Accepted 1 February 2016
as confirmed by FTIR and 1H NMR techniques. The obtained ST-SA was compounded with
Available online 1 February 2016
LLDPE and TPS in a twin-screw extruder. A weight ratio of LLDPE:TPS was fixed at 60:40,
while ST-SA concentrations were varied from 1% to 5%. The blends were further converted
Keywords:
into films by blown film extrusion. Incorporation of ST-SA improved the extrusion process-
Polyethylene
Thermoplastic starch
ability and melt flowability of the LLDPE/TPS blends. In addition, the blends became com-
Stearic acid-grafted starch patible and homogeneous when ST-SA was loaded due to the increased interfacial adhesion
Blend between LLDPE and TPS phases. The results suggest that ST-SA, particularly at a content of
Morphological characteristics 1%, could serve as an effective compatibilizer for the immiscible LLDPE/TPS blend system.
Microstructure Ó 2016 Elsevier Ltd. All rights reserved.

1. Introduction

Polyethylene (PE) is one of the most important thermoplastics used nowadays due to its low price, light weight, durabil-
ity, chemical inertness, and ease of converting into plastic products of various shapes and sizes. PE films have been utilized in
various areas including packaging (e.g. plastic bags, wrap films, labels) and agricultural applications (e.g. mulch film). How-
ever, PE is a petroleum-based plastic that is non-biodegradable under normal composting conditions [1], which contributes
to the adverse impact of plastic waste on the environment.
Recently, biodegradable plastics have gained considerable interest because they can be degraded by the action of
microorganisms found in nature. Thermoplastic starch, or TPS, which is derived from cheap, renewable, biodegradable
[2], compostable [3] and non-toxic raw materials, is considered to be one of the cheapest biodegradable plastics with short
composting time [3]. TPS has been used as a replacement or substitute for non-biodegradable petroleum-based plastics,
including PE, in order to reduce the use of PE and to lower the cost of the final products. However, the hydrophilicity of
TPS restricts its compatibility with hydrophobic PE [4,5].
Several studies have reported that incorporation of compatibilizers – e.g. maleic anhydride-grafted polyethylene [6–10],
polyethylene-co-vinyl alcohol [11], polyethylene–maleic anhydride terpolymers containing elastomeric segments [8] and

⇑ Corresponding author at: Department of Packaging and Materials Technology, Faculty of Agro-Industry, Kasetsart University, Bangkok 10900, Thailand.
E-mail address: rangrong.y@ku.ac.th (R. Yoksan).

http://dx.doi.org/10.1016/j.eurpolymj.2016.02.001
0014-3057/Ó 2016 Elsevier Ltd. All rights reserved.
N. Khanoonkon et al. / European Polymer Journal 76 (2016) 266–277 267

stearic acid-grafted starch [12] – could improve the compatibility between PE and TPS phases and enhance the properties of
the blends. To our knowledge, a starch-based compatibilizer for a PE/TPS blend system has rarely been utilized [12], although
it is of interest because it is produced mainly from environmentally friendly and renewable materials, which could result in
reduced use of PE in the future, and it is applicable for either bio-based or biodegradable polymeric blend systems. A series of
modified granular starch, such as octanoated starch [13], epichlorohydrin cross-linked starch [14], adipate starch [15] and
acetylated starch [15], has been blended with PE to overcome the restricted interfacial adhesion between PE and starch gran-
ules [15] and to improve the blend properties. However, the amount of the modified starch loaded was rather high, depend-
ing on the required weight fraction of starch, resulting in increased cost. Rivero et al. found that octenyl succinylated starch
with a content of 10 wt% of starch could act as a compatibilizing agent for the blends of PE and native cassava starch gran-
ules; the interfacial adhesion with PE occurred only at the surface of starch granules [16]. Blending PE with TPS was thus
expected to offer the interfacial attraction force between PE and starch at the molecular level, as the starch granules are
destroyed during the plasticization, resulting in much improved compatibility. Recently, we reported that stearic acid-
grafted starch (ST-SA) could improve the tensile strength, secant modulus, extensibility, and UV absorption of the LLDPE/
TPS blend, as well as promote diminished water vapor and oxygen permeabilities [12]; however its morphological charac-
teristics and microstructures have not yet been revealed.
Therefore, the present article focuses on the role of stearic acid-grafted starch (ST-SA) as a compatibilizer for a PE/TPS
blend system. ST-SA was synthesized and characterized using FTIR and 1H NMR techniques. The effects of ST-SA on extrusion
processability, melt flowability, morphological properties, chemical interaction, and crystallinity of the PE/TPS blend resins
and films were also investigated.

2. Materials and methods

2.1. Materials

Linear low density polyethylene (LL 1001KW), with a density of 0.918 g/cm3 and a melt flow index (MFI) of 1.0 g/10 min
(190 °C/2.16 kg; ASTM D1238), was purchased from ExxonMobil (Irving, TX, USA). Cassava starch (99% purity and 11.6% of
moisture content) was supplied by Tong Chan Registered Ordinary Partnership (Bangkok, Thailand). Stearic acid and potas-
sium persulfate were products of Ajax Finechem (New South Wales, Australia). Dimethyl sulfoxide (DMSO) was obtained
from RCI Labscan (Bangkok, Thailand). Ethanol was purchased from Merck (Darmstadt, Germany). Lugol’s solution (1.8%
of I2) was a product of Fisher Science Education (Hanover Park, IL, USA). Glycerol used was a commercial-grade product.

2.2. Synthesis and characterization of stearic acid-grafted starch

Stearic acid-grafted starch (ST-SA) was synthesized according to a method modified from the one reported by Simi and
Emilia Abraham [17]. Briefly, cassava starch was dissolved in DMSO (10% w/v) at 100 °C under reduced pressure for 24 h.
Stearic acid (3 mol equivalent to the pyranose ring) and potassium persulfate (1.0% w/w of starch) were subsequently added
to the starch solution. The reaction was performed with agitation under reduced pressure at 100 °C for 6 h. The obtained
homogeneous mixture was precipitated in ethanol. The precipitate was then collected by centrifugation at 8000 rpm for
10 min at 25 °C; afterward it was washed several times with ethanol and dried at 45 °C in a vacuum oven (model VD53; Bin-
der, Tuttlingen, Germany) to provide ST-SA in the form of a yellowish powder.
Fourier transform infrared (FTIR) and proton nuclear magnetic resonance (1H NMR) techniques were applied to charac-
terize the chemical structure of the obtained ST-SA. For FTIR characterization, a sample was ground with potassium bromide
(KBr) into a homogeneous fine powder and then hydraulically pressed to form a pellet. The FTIR measurement was per-
formed in a transmission mode by a Bruker Tensor 27 FTIR spectrometer (Bruker, Billerica, MA, USA) over a wavenumber
range of 400–4000 cm1 with 16 scans at a resolution of 4 cm1. For 1H NMR analysis, a sample was dissolved in deuterated
dimethyl sulfoxide (DMSO-d6). The measurement was carried out at 80 °C by a 400 MHz spectrometer (JNM-ECS series; JEOL,
Tokyo, Japan).

2.3. Preparation of LLDPE/TPS blend films containing ST-SA

Cassava starch was premixed with glycerol and ST-SA in a kitchen mixer (model HW-3083S; House Worth, Thailand). The
weight ratio of starch to glycerol was fixed at 100:40.5, while the contents of ST-SA were varied as 0, 2.5, 7.2 and 11.6 wt%.
The mixture was fed into an LTE 20-40 twin-screw extruder with an L/D ratio of 40 (Labtech Engineering, Samut Prakan,
Thailand) through an LSF 20-10 twin-screw side feeder (Labtech Engineering). The extrusion was carried out using a barrel
temperature profile in a range of 80–150 °C, a screw speed of 180 rpm and a material feed rate of 18 rpm. The extrudate of
thermoplastic starch (TPS) was cut into 2.5-mm-long plastic resins using an LZ 120 pelletizer (Labtech Engineering). Four
types of TPS resins, containing ST-SA with different contents of 0, 2.5, 7.2 and 11.6 wt%, were produced.
The as-prepared TPS resins were subsequently compounded with LLDPE in a twin-screw extruder using a barrel temper-
ature profile ranging from 80 °C to 155 °C, a screw speed of 180 rpm and a material feed rate of 18 rpm. The weight ratio of
LLDPE to TPS was fixed at 60:40. TPS resins containing ST-SA with contents of 0, 2.5, 7.2 and 11.6 wt% were used to prepare
268 N. Khanoonkon et al. / European Polymer Journal 76 (2016) 266–277

LLDPE/TPS blends with ST-SA contents of 0, 1, 3 and 5 wt%, respectively. After pelletizing, the 2.5-mm-long LLDPE/TPS blend
resins were dried at 50 °C overnight in a Binder FD53 hot-air oven and then converted into films using an LE 25-30/C single-
screw extruder with an L/D ratio of 30 connected to an LF 400 film-blowing attachment (Labtech Engineering). Blown film
extrusion was carried out at a temperature range of 130–150 °C, a screw speed range of 30–50 rpm and a take-off speed of
2.6 m/min.

2.4. Characterization and properties testing of LLDPE/TPS blends containing ST-SA

2.4.1. Melt flow index measurement


Resins were dried at 40 °C overnight prior to melt flow index (MFI) measurement. The measurement was performed
according to ASTM D1238 using an MFI2-203 melt flow indexer (Custom Scientific Instruments, Newark, NJ, USA). A temper-
ature of 190 °C, a load cell of 2.16 kg and a preheating time of 6 min were employed. The MFI of the sample was determined
as an extrudate weight (g) per 10 min. The mean ± SD of 10 determinations was reported for each sample.

2.4.2. Morphological study by optical microscopy


Each film sample was dipped in Lugol’s solution for 20 min and then thoroughly washed with distilled water several
times before drying at ambient temperature under reduced pressure. The film was cut into a rectangular shape with dimen-
sions of 1 cm  5 cm prior to immobilizing on a glass slide. Surface morphology of the stained film was observed using an
Olympus BX60 optical microscope (Tokyo, Japan).

2.4.3. Morphological study by scanning electron microscopy


A small piece of each film sample was mounted on a stub using two-sided carbon tape and then coated with a thin layer of
gold. The surface morphology of the film was characterized by a JEOL JSM-6610LV scanning electron microscope at an oper-
ating voltage of 20 kV. TPS phase size in the film sample was also investigated by SEM. The sample was immersed in an aque-
ous solution of HCl (6 N) at room temperature for 48 h to extract a TPS phase. The extracted film was thoroughly washed
with distilled water several times before dipping in liquid N2, followed by breaking and mounting on a stub using two-
sided carbon tape. The fracture surface of the film sample was then coated with a thin layer of gold and observed by SEM
at an operating voltage of 20 kV.

2.4.4. Determination of chemical interaction


Temperature-dependent FTIR measurement was performed at a temperature range of 30–150 °C in an attenuated total
reflection (ATR) mode using a Bruker Tensor 27 FTIR spectrometer over a wavenumber range of 550–4000 cm1 with 32
scans at a resolution of 4 cm1. The film sample was dried at 40 °C under reduced pressure for 5 h prior to measurement.

2.4.5. Morphological study by X-ray diffractometry


XRD measurement was performed over a 2h range of 5–40° using a Philips X’Pert X-ray diffractometer (PANalytical,
Almelo, Netherlands) with an accelerating voltage of 40 kV and a scan rate of 0.04°/sec. The crystallite size of LLDPE in
the film sample was determined using the Scherrer equation, Eq. (1) [18,19]:
Dp ¼ 0:89k=b cos h ð1Þ

where Dp is the average size of the crystalline region, b is the full width at half maximum (FWHM, in radians) of the crys-
talline peak, h is the Bragg’s angle and k is the wavelength of a Cu Ka source (0.154 nm). The FWHM of the (1 1 0) crystal plane
at 2h of 21.4° of orthorhombic LLDPE was used to determine the crystallite size of LLDPE in the sample. Crystallinity of the
film sample was calculated as the ratio of the area under the crystalline peaks and the total area under all peaks.

2.5. Statistical analysis

Mean values and standard deviations (SD) were calculated and compared by a one-way analysis of variance (ANOVA),
with the value of statistical significance at p < 0.05. Multiple comparisons of group means were made using Duncan’s mul-
tiple range test (DMRT). All data were analyzed with the SPSS statistical software package.

3. Results and discussion

3.1. Chemical structure of ST-SA

ST-SA was synthesized via a condensation reaction of starch hydroxyl groups and stearic acid carboxyl groups in DMSO at
100 °C under reduced pressure for 6 h in the presence of potassium persulfate as a catalyst. The successful preparation of ST-
SA was confirmed by FTIR and 1H NMR techniques. Starch showed characteristic peaks at 3418 cm1 (–OH stretching),
2932 cm1 (–CH– stretching), 1643 cm1 (–OH bending), 1016 cm1 and 929 cm1 (–CO stretching) (Fig. 1a) [17,20,21],
while stearic acid exhibited characteristic bands at 2917 cm1 and 2849 cm1 belonging to –CH– stretching and
N. Khanoonkon et al. / European Polymer Journal 76 (2016) 266–277 269

1016

949
2916
2849
3294 ↓


↓ 1701

(c)

2917
2849

Intensity
↓ 1703

(b)

1016
3418 ↓

2932

929
↓ 1643
(a) ↓ ↓

4000 3400 2800 2200 1600 1000 400


-1
Wavenumber (cm )

Fig. 1. FTIR spectra of (a) starch, (b) stearic acid and (c) ST-SA.

1703 cm1 attributed to C@O stretching (Fig. 1b) [17,22]. It was clearly observed that the product obtained after the reaction
of starch and stearic acid presented both characteristic peaks of starch and stearic acid, i.e. glucose ring at 949 cm1, –CH–
stretching at 2916 cm1 and 2849 cm1, and C@O stretching at 1701 cm1 (Fig. 1c). The appearance of C@O stretching
belonging to the ester bond and the increased intensity of –CH– stretching peaks confirmed the achievement of ST-SA.
The chemical structure of ST-SA was also verified by 1H NMR technique. Native cassava starch showed proton signals in
the range of 3.3–5.6 ppm, attributed to methine and methylene protons of the pyranose ring (Fig. 2a) [20], whereas stearic
acid exhibited bands of methylene protons in a chemical shift range of 1.1–2.2 ppm and methyl protons at a chemical shift of
0.8 ppm (Fig. 2b). As compared with starch, ST-SA showed methylene and methyl proton signals in a chemical shift range of
0.8–1.2 ppm, ascribed to the protons of stearic acid. This result also confirmed the grafting of stearic acid onto starch
molecules.
The degree of substitution (DS) of stearyl chains onto starch molecules was calculated based on the information obtained
from 1H NMR spectra, as the peak integral ratio of stearic acid protons to starch protons, i.e. DS = (I0.8–1.1/31)/(I3.3–5.6/7). The
DS of the synthesized ST-SA was 0.01, implying that every 100 pyranose rings of starch bear only 1 stearyl chain.

3.2. Extrusion processability of LLDPE/TPS blend films containing ST-SA

The obtained ST-SA was mixed with LLDPE/TPS blend in a twin-screw extruder to produce four formulations of LLDPE/TPS
blends possessing ST-SA with different contents, i.e. 0%, 1%, 3% and 5%. Incorporation of ST-SA could improve the extrusion
processability of LLDPE/TPS blends, as evidenced from the continuity of the process. This might be a result of the increased
intermolecular interaction between LLDPE and TPS via ST-SA, causing enhanced melt strength.
The melt flow index (MFI) was measured at 190 °C with an applied load of 2.16 kg. LLDPE showed an MFI of 0.95 g/10 min,
while LLDPE/TPS blends exhibited decreased MFI to 0.84 g/10 min, suggesting that the material became more viscous when
it was blended with TPS. This could be explained by the relatively high viscosity of TPS, which is a material consisting of large
starch molecules with branched amylopectin causing limited starch chain mobility [23]. Wang et al. also reported that high
viscosity of glycerol-plasticized TPS and poor dispersion between glycerol-plasticized TPS and polylactic acid (PLA) reduced
the flowability of TPS/PLA blend compared with that of pure PLA [24].
In comparison with LLDPE/TPS blend, the blends containing ST-SA with contents of 1%, 3% and 5% possessed higher MFI,
i.e. 1.92, 1.49 and 1.03 g/10 min, respectively. The results showed that melt flowability of the blend increased by adding ST-
SA due to the better interfacial adhesion between LLDPE and TPS phases, since both LLDPE and TPS could interact with ST-SA
270 N. Khanoonkon et al. / European Polymer Journal 76 (2016) 266–277

DMS0-d6
3’ 5’ 7’ 9’ 11’ 13’ 15’ 17’
1’
2’ 4’ 6’ 8’ 10’ 12’ 14’ 16’ 18’
4 6
5

DMS0-d6
2 1
3

H5, H3, H6
m

H2,H4
n H1 4’-17’
18’
(c)
4’-17’

O
3’ 5’ 7’ 9’ 11’ 13’ 15’ 17’
HO 1’
2’ 4’ 6’ 8’ 10’ 12’ 14’ 16’ 18’

DMS0-d6
2’ 18’
3’ (b)
DMS0-d6
6
4 5

2 1
H5,H3,H6

3
n
H2,H4

H1
DMS0-d6

(a)

10 9 8 7 6 5 4 3 2 1 0
Chemical shift (ppm)

Fig. 2. 1H NMR spectra of (a) starch, (b) stearic acid and (c) ST-SA.

via hydrophobic interaction and hydrogen bonding, respectively. Consequently, the chain entanglement of each polymer was
reduced. Ren et al. revealed that maleic anhydride-compatibilized blend systems of PLA/TPS and PLA/PBAT/TPS had much
higher MFI values than the non-compatibilized ones; this was due to the better interfacial interaction between polyesters
and starch, since the anhydride groups of the compatibilizer could react with the hydroxyl groups of starch to provide more
hydrophobicity to starch granules [25]. However, increasing ST-SA content reduced the melt flowability or increased the vis-
cosity of the LLDPE/TPS blends; as a result the poor dispersion of TPS phase in the blend was observed. This indicated the less
compatibilizing effect which in turn caused phase separation (as discussed later).
The as-prepared LLDPE/TPS blend resins without and with incorporation of ST-SA were then converted into films by
blown film extrusion. All formulations could be successfully blown into films. However, the addition of ST-SA facilitated film
blowing processability, as seen from the reduction of induced pressure (180–240 Pa vs. 200–300 Pa) and torque (56–60 Nm
vs. 60–65 Nm), better bubble stability during the process, and decreased film thickness. In addition, the blend films contain-
ing ST-SA exhibited better surface homogeneity and became more yellowish than the film without ST-SA.
Blow-up ratio (BUR) and take-up ratio (TUR) are the two important process parameters affecting the geometry, molecular
orientation and properties of the final products. High TUR implies a good molecular orientation of the polymer melt in the
stretching or machine direction (MD), while BUR controls the orientation of polymer molecules in the cross-machine direc-
tion (CD) [26]. Table 1 shows that BUR and TUR of LLDPE film were 2.9 and 2.6, respectively, whereas those of LLDPE/TPS
N. Khanoonkon et al. / European Polymer Journal 76 (2016) 266–277 271

Table 1
Blow-up ratio (BUR), take-up ratio (TUR) and forming ratio of LLDPE film and LLDPE/TPS blend films containing different ST-SA contents.

Sample ST-SA content (%) BURa TURb Forming ratioc


LLDPE film – 2.9 2.6 0.9
LLDPE/TPS blend films 0 2.4 1.7 0.7
1 2.8 3.0 1.1
3 2.8 2.6 0.9
5 2.6 2.2 0.8
a
Blow-up ratio (BUR) = bubble diameter above the frost line/die diameter [26].
b
Take-up ratio (TUR) = die gap/(BUR  film thickness) [27].
c
Forming ratio = TUR/BUR [26].

blend film were 2.4 and 1.7, respectively. These results indicated that the inflation in CD and stretching in MD of LLDPE/TPS
blend film were limited as compared with those of LLDPE due to the lower melt strength of the blend, corresponding to the
poor extrusion processability as mentioned above. Introduction of ST-SA could facilitate the processability of the LLDPE/TPS
blend, as evidenced from the higher BUR and TUR (Table 1). It should be pointed out that BUR and TUR of the blends
decreased with increasing ST-SA content.
The forming ratio, a ratio of TUR/BUR, is a parameter used to indicate the degree of isotropy in biaxially oriented blown
film. The degree of isotropy increases when the forming ratio approaches 1. LLDPE film had a forming ratio of 0.9, while
LLDPE/TPS blend film possessed a lower forming ratio, i.e. 0.7 (Table 1), indicating that LLDPE/TPS blend film was more ani-
sotropic than LLDPE film. Isotropy of the blend was improved by incorporating ST-SA, as confirmed by less deviation of the
forming ratio from 1 (Table 1). However, the LLDPE/TPS blend film containing ST-SA with a content of 1% had a higher molec-
ular orientation in MD than CD, and vice versa for the blend films containing ST-SA with a content of 3% and 5%.

3.3. Morphological properties of LLDPE/TPS blend films containing ST-SA

Surface morphology of the films was characterized by SEM, as presented in Fig. 3 (left). LLDPE film showed a smooth sur-
face (Fig. 3a), whereas the surface of LLDPE/TPS blend film was rough (Fig. 3b), indicating incompatibility between LLDPE and
TPS phases. As compared with the naked blend, the addition of ST-SA with contents of 1% and 3% led to smoother surfaces
(Fig. 3c and d), while the film surface of the blend became rough when 5% of ST-SA was loaded (Fig. 3e). The results suggested
that ST-SA with the concentration below 3% could enhance the compatibility of LLDPE/TPS blend.
In addition, the distribution of the TPS phase in the blends was investigated by staining the films with iodine (I2) and
observing their surface morphologies using an optical (light) microscope. It should be noted that the color of the samples
containing starch would be changed to purple or blue after staining with I2 due to amylose–I2 complex formation [28].
Fig. 3 (right) illustrated optical micrographs of the films after I2 staining. LLDPE film possessed a smooth and homogeneous
surface without change in color (Fig. 3a). In contrast, LLDPE/TPS blend films exhibited color change (Fig. 3b–e). Without the
addition of ST-SA, the surface of LLDPE/TPS blend film was intermittent and streaky (Fig. 3b), implying phase separation
between LLDPE and TPS. In addition, the alignment of polymers was markedly observed, indicating anisotropic film. The sur-
face morphology of the LLDPE/TPS blend film was altered by incorporating ST-SA and its concentration. The film containing
ST-SA with a content of 1% presented a smooth and homogeneous surface, with purple coloration throughout the film matrix
(Fig. 3c), indicating that the TPS phase was well dispersed in the LLDPE matrix. This film became isotropic. However, when
too high concentrations of ST-SA, i.e. 3% and 5%, were loaded (Fig. 3d and e), the blend films demonstrated phase separation
and were less isotropic. This evidence supported the information obtained from SEM (Fig. 3, left) and the forming ratio
(Table 1). Although the surface morphologies of the blends containing ST-SA with contents of 1% and 3% were similarly
homogeneous when observed by SEM, optical micrographs showed that the blend containing 1% of ST-SA was more compat-
ible than that containing 3.
TPS phase size in the LLDPE/TPS blend films was analyzed by extracting the film with 6 N of HCl solution for 48 h to
remove TPS, followed by observation of their fracture surface morphologies by SEM. LLDPE film showed a smooth fracture
surface (Fig. 4a), while the fracture surfaces of LLDPE/TPS blend films became porous due to etching of the TPS phase
(Fig. 4b–e). This result confirmed that LLDPE was a continuous phase whereas TPS was a dispersed phase in the film. Without
adding ST-SA, LLDPE/TPS blend film possessed large-sized TPS phase dispersed throughout the film matrix and broad size
distribution (Fig. 4b), reflecting an incompatible blend. The incompatibility of LLDPE and TPS could be explained by the poor
interfacial adhesion between non-polar LLDPE and highly polar starch [7], or by the difference in their viscosity [5]. A reduc-
tion of TPS phase size and size distribution as well as thickness of the blend films was observed when ST-SA was incorpo-
rated (Fig. 4c–e), indicating that ST-SA could act as a compatibilizer for LLDPE/TPS blend. Bikiaris and Panayiotou also
reported that the phase size reduction of plasticized starch (PLST) in a LDPE/PLST blend system which resulted from
incorporating a PE-g-MA copolymer was due to its compatibilizing effect [6].
In the present work, TPS phase size and size distribution were affected by the concentration of ST-SA. The blend film
containing ST-SA with a content of 1% exhibited the smallest TPS phase size and a narrow size distribution of the TPS phase,
implying the most effective compatibilizing effect and lowest thickness (25 lm), reflecting the improved extrusion
272 N. Khanoonkon et al. / European Polymer Journal 76 (2016) 266–277

Fig. 3. SEM micrographs at the film surface (left) and optical micrographs at the film surface after staining with I2 (right) of (a) LLDPE film and (b–e) LLDPE/
TPS blend films containing ST-SA with different contents: (b) 0%, (c) 1%, (d) 3% and (e) 5%.
N. Khanoonkon et al. / European Polymer Journal 76 (2016) 266–277 273

Fig. 4. SEM micrographs at the fracture surface after acid hydrolysis of (a) LLDPE film and (b–e) LLDPE/TPS blend films containing ST-SA with different
contents: (b) 0%, (c) 1%, (d) 3% and (e) 5%. Magnification of 1000 (left) and 2000 (right).
274 N. Khanoonkon et al. / European Polymer Journal 76 (2016) 266–277

processability (Fig. 4c). However, TPS phase size and size distribution as well as film thickness increased with increasing ST-
SA content (Fig. 4d and e), indicating less compatibilizing effect. This corresponded to the surface morphological results.
Although the blend films containing ST-SA with contents of 3% and 5% displayed less compatibilizing effect than the film
containing ST-SA with a content of 1%, all three films had higher homogeneity and compatibility than the naked blend film.
The less compatibility of LLDPE/TPS blends containing too high concentrations of ST-SA, i.e. 3% and 5%, might be attributed to
the agglomeration of ST-SA, causing less effective compatibilizing behavior and not facilitating interfacial tension reduction
of the dispersed phase; therefore phase separation of the blends occurred eventually as clearly evidenced in Fig. 3d and e
(right).
The reduction of TPS phase size and the better TPS phase distribution of the LLDPE/TPS blends resulted from the incor-
poration of ST-SA leaded to improved tensile properties as well as water vapor and oxygen barrier properties of the blend
films as discussed in our previous work [12].

3.4. Chemical interaction of components in LLDPE/TPS blend films containing ST-SA

The interaction of starch and ST-SA was expected to be via H-bonds formed between hydroxyl groups of starch and those
of ST-SA. Temperature-dependent FTIR spectroscopy is a useful technique for studying the different types of H-bond asso-
ciation, the strength of H-bonds, as well as the dissociation and redistribution of H-bonds [29–32]. Here, this technique
was applied to confirm the interaction between starch and ST-SA; the measurement was performed at a temperature range
from 30 °C to 150 °C. The insets of Fig. 5 show that hydroxyl bands of LLDPE/TPS blend films, both without and with the addi-
tion of ST-SA, shifted to a higher wavenumber (blueshift) and became broader with lower intensity when temperature was
increased, reflecting the temperature dependence variation in the H-bond structure of the blends. The blueshift of the hydro-
xyl band with increased temperature indicated weakened inter- and intramolecular H-bonds. It should be pointed out that
the blends containing ST-SA exhibited less broadening of the OH peak upon heating (Fig. 5b–d, insets) as compared with the
naked blend (Fig. 5a, insets). It is possible that the distances or strengths of all H-bonds formed in the blends containing ST-
SA were nearly the same due to the consistent dispersion of the two domains throughout the film matrices; as a result, there
was less variation or narrow distribution of OH species. In contrast, the uncompatibilized blend might have a higher distri-
bution of OH species with different distances or different strengths, causing overlapping of each OH band.
LLDPE/TPS blend showed three transition ranges of blueshift (Fig. 5a). At a low temperature range (30–80 °C), the
increased blueshift as a function of temperature was related to the dissociation of intermolecular H-bonds formed between

150 °C (a) 150 °C (b) 150 °C (c) 150 °C (d)

30 °C 30 °C 30 °C
30 °C

3800 3400 3000 3800 3400 3000 3800 3400 3000 3800 3400 3000
-1
Wavenumber (cm )
-1
Wavenumber (cm ) Wavenumber (cm-1) Wavenumber (cm-1)
180
(d)
Wavenumber shift of OH band (cm )
-1

150
(c)

(b)
120

90
(a)

60

30

0
30 60 90 120 150
Temperature (°C)

Fig. 5. Wavenumber shift of the OH band as a function of temperature of LLDPE/TPS blend films containing ST-SA with different contents: (a) 0%, (b) 1%, (c)
3% and (d) 5%. The results shown in the insets represent FTIR spectra upon heating from 30 °C to 150 °C.
N. Khanoonkon et al. / European Polymer Journal 76 (2016) 266–277 275

hydroxyl groups of starch–glycerol and starch–starch; at these temperatures the mobility of starch main chains was
restricted due to some residual intermolecular H-bonds. All intermolecular H-bonds were destroyed at 80 °C, which cor-
respond to the a-relaxation or glass transition temperature of TPS as confirmed from DMTA [12] and DSC techniques (in
the Supplementary data, Fig. S1). At the temperature above 80 °C, a constant blueshift was observed, indicating that there
was no further destruction of intermolecular H-bonds. The augmentation of blueshift regained at temperatures above
130 °C, which can be attributed to the dissociation of intramolecular H-bonds among the hydroxyl groups in the side chains
of starch. It is interesting to point out that the increased blueshift in the second transition region (80–120 °C) of the blends
containing ST-SA (Fig. 5b–d) might be related to the dissociation of intermolecular H-bonds formed between the hydroxyl
groups of starch and ST-SA. In addition, the blends containing ST-SA tended to have higher blueshifts (Fig. 5b–d) than the
neat blend (Fig. 5a). The weaker H-bond strength of the compatibilized blends upon heating might arise from the longer dis-
tance between hydroxyl groups among starch molecules due to the interference of LLDPE induced by ST-SA.
In order to confirm the interaction between hydroxyl groups of starch in TPS and those in ST-SA, the temperature-
dependent FTIR measurement of TPS and TPS containing ST-SA (2.5%) was performed and the results were shown in the Sup-
plementary data (Fig. S4). It was clearly seen that as compared with TPS (Fig. S4Aa), TPS containing ST-SA exhibited increased
wavenumber shift of OH-band (Fig. S4Ab). The result implied that the distance between hydroxyl groups of starch molecules
in TPS containing ST-SA was longer than that of TPS without ST-SA. This might be a result of the H-bond formation between
starch hydroxyl groups in ST-SA and those in TPS.
As hydrogen bonding is reversible, the temperature-dependent FTIR on cooling and reheating were also measured. Upon
cooling from 150 °C, both TPS and TPS containing ST-SA showed the shift of OH band to lower wavenumber or redshift as a
function of temperature (Fig. S4Ba and b), implying H-bond formation. The OH band shift of TPS containing ST-SA was more
pronounced than that of TPS, suggesting the increased H-bond strength. The stronger H-bonds might come from the addi-
tional interaction between hydroxyl groups of starch and those of ST-SA. During reheating, H-bond dissociation behavior of
TPS and TPS containing ST-SA (Fig. S4Ca and b) was similar to that found in the first heating (Fig. S4Aa and b).
As compared to TPS (Fig. S4a and b), LLDPE/TPS blends showed the same behavior of H-bond dissociation and association
during heating and cooling, respectively (Fig. S4c and d). However, the blends possessed higher blueshift and redshift of OH
band, reflecting that LLDPE/TPS blend became weaker upon heating, but stronger upon cooling than TPS. The result sug-
gested that LLDPE affected the destruction and formation of H-bond of starch hydroxyl groups during heating and cooling,
respectively. It is important to point out that during cooling LLDPE/TPS blend containing ST-SA showed higher redshift than
the neat blend, corresponding to stronger H-bond formation, which resulted in improved tensile properties [12].

(f)

(e)

(d)
Intensity

24
19.6 ↓ (c)
18.2 24

21.4
↓ (b)
13.1

9.5 29.5
↓ 23.6 28.3 36.1
↓↓ ↓ (a)

5 10 15 20 25 30 35 40
2θ (Degree)

Fig. 6. XRD patterns of (a) LLDPE film, (b) TPS film and (c–f) LLDPE/TPS blend films containing ST-SA with different contents: (c) 0%, (d) 1%, (e) 3% and (f) 5%.
276 N. Khanoonkon et al. / European Polymer Journal 76 (2016) 266–277

Table 2
Full width at half maximum (FWHM), crystallite size and crystallinity (vc) of LLDPE film and LLDPE in LLDPE/TPS blend films containing different ST-SA
contents, based on XRD data.

Sample ST-SA content (%) Peak angle (°) FWHM (°) Crystallite sizea (nm) vc (%)
LLDPE – 21.4 0.6 13.3 36.4
LLDPE/TPS 0 21.5 0.7 12.1 31.2
1 21.8 1.1 7.5 26.2
3 21.6 1.0 8.1 26.4
5 21.6 0.9 9.1 22.2
a
Calculated from Eq. (1).

3.5. Crystallinity of LLDPE in LLDPE/TPS blend films containing ST-SA

Crystallinity of the films was determined by XRD technique. LLDPE exhibited diffraction peaks at 2h of 9.5°, 21.4°, 23.6°,
28.3°, 29.5° and 36.1° (Fig. 6a) [33,34], while TPS showed diffraction peaks at 2h of 13.1° and 19.6° (ascribed to V-type crys-
tal) as well as 18.2° and 24° (belonging to B-type crystal) [35–37]; these were formed after the extrusion process and during
storage, respectively (Fig. 6b). It should be noted that blending LLDPE with 40% w/w of TPS caused little change in the XRD
diffractogram (Fig. 6c). This might be due to the relatively higher crystallinity of LLDPE as compared to that of TPS. Therefore,
the crystallinity evaluated from XRD diffractograms belonged to LLDPE in the blends. Table 2 shows that FWHM and average
crystallite size of LLDPE in the naked LLDPE/TPS blend was very close to those of LLDPE, indicating that TPS had little effect
on the crystal arrangement of LLDPE – or in other words, the interaction between TPS and LLDPE was negligible. After incor-
porating ST-SA, diffraction peaks of LLDPE in the blends became broader with lower intensity (Fig. 6d–f), corresponding to
higher values of FWHM and smaller average crystallite sizes of LLDPE in the blends (Table 2). This result suggested that ST-SA
could hinder LLDPE chain arrangement and cause imperfect crystal lattices. It is possible that LLDPE formed hydrophobic
interaction with stearyl chains of ST-SA, resulting in reduced chain mobility. However, a reduction of FWHM and an increase
of average crystallite size of LLDPE in the blends containing 3% and 5% of ST-SA was observed (Table 2), implying phase sep-
aration between LLDPE and TPS. This might be explained by the poor dispersion of ST-SA, resulting in less interaction with
LLDPE or the reduced compatibilizing effect.
In addition, Table 2 shows that the crystallinity of LLDPE film was 36.4%, while those of LLDPE/TPS blend films were in the
range of 22.2–31.2%, indicating that the packing structure of LLDPE was impeded by TPS. This result was in agreement with
the crystallinity determined by DSC technique [12]. Crystallinity of LLDPE in the blends containing ST-SA tended to decrease
with increasing ST-SA content, confirming that stearyl chains of ST-SA might form hydrophobic interaction with LLDPE. The
results from microscopy, FTIR and XRD techniques verified that ST-SA could serve as a compatibilizer for the LLDPE/TPS
blend system.

4. Conclusions

Incorporating ST-SA could improve the extrusion processability and homogeneity of the LLDPE/TPS blends as well as pro-
vide compatibility to the blends due to the enhanced interfacial adhesion between the LLDPE and TPS phases. Temperature-
dependent FTIR and XRD results confirmed that ST-SA interact with TPS via H-bond formation and with LLDPE through
hydrophobic interaction. The amount of ST-SA recommended in the present work as an effective compatibilizer for the
LLDPE/TPS blend is 1% because it gave the smallest size and the best dispersion of the TPS phase in the LLDPE matrix.

Acknowledgements

The authors thank the Thailand Research Fund (TRF), Thailand for the Royal Golden Jubilee Ph.D. Program (Grant No.
PHD/0290/2552); and the Commission on Higher Education, Ministry of Education, Thailand (National Research Universities
initiative) for financial support. Appreciation is also expressed to the Union J. Plus (Thailand) Co., Ltd., for providing PE resins.

Appendix A. Supplementary material

Supplementary data associated with this article can be found, in the online version, at http://dx.doi.org/10.1016/j.eur-
polymj.2016.02.001.

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