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Preparation and performance of thermoplastic starch and

microcrystalline cellulose for packaging composites: Extrusion
and hot pressing

Jie Chen, Xia Wang, Zhu Long, Shuangfei Wang, Jingxian Zhang,
Lei Wang

PII: S0141-8130(20)34748-6
DOI: https://doi.org/10.1016/j.ijbiomac.2020.10.117
Reference: BIOMAC 17007

To appear in: International Journal of Biological Macromolecules

Received date: 27 June 2020

Revised date: 25 September 2020
Accepted date: 14 October 2020

Please cite this article as: J. Chen, X. Wang, Z. Long, et al., Preparation and performance
of thermoplastic starch and microcrystalline cellulose for packaging composites: Extrusion
and hot pressing, International Journal of Biological Macromolecules (2020),
https://doi.org/10.1016/j.ijbiomac.2020.10.117

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© 2020 Published by Elsevier.

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Preparation and performance of thermoplastic starch and microcrystalline cellulose for

packaging composites: extrusion and hot pressing
Jie Chen 1, 2, 3, Xia Wang 2, Zhu Long 1, 3, *, Shuangfei Wang 1, *, Jingxian Zhang 3, Lei Wang 2
1
Guangxi Key Laboratory of Clean Pulp & Paper making and Pollution Control, Nanning 530004, China
2
Binjiang College, Nanjiang University of Information Science & Technology, Wuxi 214105, China
3
Key Laboratory of Eco-textiles, Ministry of Education, Jiangnan University, Wuxi 214122, China
Corresponding Author:
longzhu@jiangnan.edu.cn (Zhu. Long)
wangsf@gxu.edu.cn (Shuangfei Wang).
Abstract
The microcrystalline cellulose (MCC) used as the fillers, were incorporated into the starch matrix to prepared

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MCC/thermoplastic starch (TPS) granules by extrusion method blending with glycerol plasticizers. Then the

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MCC/TPS composite films were produced by the hot-pressing method, which were characterized by XRD, FTIR,

SEM, DSC, TGA, tensile test, water vapor permeation and water contact angle. When the loading of MCC was not

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more than 6wt. %, MCC were well dispersed in composite films seen from SEM images. XRD results show that the
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crystallinity of TPS in the presence of MCC was improved. The FTIR curves indicate that the interaction between

MCC and starch formed more hydrogen bonds, so the tensile strength and water vapor permeation of 6wt.%
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MCC/TPS composite films were better than those of other films. Besides, the water contact angle of MCC/TPS

composite films decreased gradually with the content of MCC increased.

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Keywords: Thermoplastic starch; Microcrystalline cellulose; Extrusion and hot pressing; Water vapor permeation
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1. Introduction

In recent years, many scholars have conducted extensive research on the use of biodegradable materials to develop
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environmentally friendly packaging materials [1, 2]. Bio-based polymers are considered to be the best candidate

materials for this application to replace the petroleum-based materials, which could not only effectively alleviate the

problem of white trash pollution, but also make the best of biological resources because of the advantages from

using the abundant and renewable resources in nature that are biodegradable [3, 4]. Therefore, bio-based and

biodegradable starch-based products have driven attention in bioplastic materials. Starch, as the abundant and

renewable resources in nature, is non-toxic and low-cost, thus its utilization has become the focus of research in the

field of truly biodegradable material science. At the molecular level, starch is a heterogeneous material with two

architectures [5]. Starch is not really a thermoplastic but can be converted to a continuous entangled polymeric

phase under heat and shear in the presence of water or a non-aqueous plasticizer such as glycerol, urea, glucose,
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sorbitol and so on [6]. Plasticizers could destroy the crystal structure of native starch [7], and incorporated into

starch macromolecular chains to prepare a material that have similar behavior to that of thermoplastic. The better

plasticizing effect, the more free hydroxyls of thermoplastic starch (TPS) there are [8, 9]. Thermoplastic starch is an

appropriate material for various applications, like packaging and coating and it is a suitable alternative solution for

the traditional petroleum polymers [6].

The crystallinity of starch granules disappears during the above-mentioned process and an amorphous material is

ultimately obtained. Compared to common thermoplastic polymers, TPS has three main disadvantages, including

poor mechanical properties, low thermal stability, and water sensibility. To overcome these shortcomings, TPS must

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be reinforced to achieve satisfactory packaging materials. Various methods have been used to reinforce TPS can be

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reduced to three main categories: (1) chemical treatment of starch molecule [10], (2) mixing TPS with other natural

or synthetic[11], and (3) using various natural and mineral reinforces [12]. Natural reinforces such as plant fibers

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from different sources, cellulose microfibers, cellulose whiskers, microcrystalline Cellulose (MCC) were usually
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used to as fillers added into the thermoplastic starch matrix [13]. Because microcrystalline cellulose has excellent

properties such as high purity, high crystallinity, high strength, high transparency, low thermal expansion coefficient,
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biodegradability and no environmental pollution after disposal. Therefore, MCC is often used as a filler in

composite materials [14]. Area [15] processed green biocomposites based on corn starch plasticized with isosorbide
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and glycerol and filled with microcrystalline cellulose (MCC). An isosorbide content of 35% and the addition of

MCC filler enhanced in a greater extent these properties with a complete biodegradability in 7 month. Othman S H
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[16] developed biodegradable films from biopolymer that is sustainable and environmentally friendly particularly
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tapioca starch (TPS) films. It was found that 3 wt.% MCC was the ideal concentration of filler that resulted to the

highest performance of the films in terms of mechanical and barrier properties. Thermal properties of the films were

also improved with the addition of MCC into the films. Tabassi N [17] prepared TPS-based green composites

containing various amounts of high-stiff cellulose nanocrystals (CNCs), 0-9 wt% in an internal mixer to modify the

abovementioned drawbacks. Adding CNC level from 0 to 9wt% considerably increased the tensile strength of the

TPS from 3.1 to 11.1 MPa (358 %), Young's modulus from 237.3 MPa to 4.2 GPa, and the glass transition

temperature (T-g) from 69.2 to 90.7 degrees C. The relatively good interfacial interaction between CNC and TPS

matrix caused a remarkable improvement of these mechanical properties. The most conventional method used to

prepare the MCC/TPS composite films by solution casting of a dilute slurry of thermoplastic starch solutions and

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MCC fillers. For large scale production, the solution casting method is low in efficiency, high in cost and manpower.

Extrusion and hot pressing are the most interesting methods for the industrial process because of the easy scale-up

and the possibility of further molding of the materials. Thus, the main goal of this paper was to study the extrusion

and hot pressing to produce MCC/TPS composite films. The TPS composite films were characterized by Fourier-

transform infrared spectroscopy (FT-IR) and X-ray diffraction (XRD). Then, the effects of the addition of MCC and

its concentration on the performance of MCC/TPS composite films were researched to investigate the interaction

between thermoplastic starch and microcrystalline cellulose and the crystallinity of composites. Scanning electron

microscopy (SEM), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), Universal material

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testing machine, water vapor permeation and water contact angle was used to analyze the morphology,

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thermostability, mechanical properties and water resistance of TPS composite films, respectively.

2. Materials and methods

2.1 Materials
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Food-grade corn starch (contains 25% amylose) was purchased from Quan Wang Biological Technology Co., Ltd.

(Shanghai, China). Microcrystalline cellulose (MCC, molecular weight: 31439.64; pH of 10% aqueous suspension:
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7; particle size: 20 ~ 100μm) was supplied by Tianjin Institute of Refractories and Fine Chemicals (Tianjin, China).

glycerol and other chemicals were provided by Sinopharm Chemical Reagent Co., Ltd. (Shanghai, China). All
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chemicals are of analytical grade.

2.2 Preparation of TPS and MCC/TPS composite films

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TPS films and MCC/TPS composite films, shown in Scheme 1, were prepared by extrusion and hot-pressing method
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with the ratio of starch: glycerol: water of 55:30:15 (wt.%). After this preliminary step, the glycerol and water were

dissolved at 40°C. Next, the starch, which was previously dried for 6h at 100 oC, was gradually added and

thoroughly mixed for 2 h at 800 rpm with an overhead stirrer. Then the wet modified starch mixture was sealed in a

plastic bag for 48 h to balance water and increase the fluidity of starch. Afterward, the resulting blend was extruded

through a corotating twin-screw extruder (Shanghai Xinshuo Precision Machinery Co., Ltd., China). The screw

speed was adjusted to 100 rpm and the feeder-to-nozzle temperature ware set to 140 °C and 140 °C. Subsequently,

the obtained linear materials were air-cooled and granulated using a blade grinder equipped with a nominal 2-mm

internal diameter. Finally, the plasticized starch granules were equilibrated for one week and then thermo-pressed for

15 min at 140 °C under a load of 5 MPa/m2 in order to produce TPS composite films with the approximate thickness

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of 0.3 mm. The MCC/TPS composite films were prepared in the same method, in which MCC was added to the

mixed starch in different proportions.

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Scheme 1. The preparation process of MCC/TPS composite films

2.3 Film Characterization -p

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2.3.1 X-Ray diffraction (XRD)
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XRD was used to test the crystalline structure of the composite films. The X’ Pert PRO MPD X-ray diffractometer

(Panalytical, Poland) with Cu radiation exhibiting a wavelength of 1.5418 Å was used to record the scanned 2θ
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range 5~50° at the rate of 4°/min with a step size of 0.05° (2θ). The XRD was performed at 40 kV and 30 mA. An

adjustable sample holder was used to analyze the 50mm×15mm TPS films and MCC/TPS composite films.
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2.3.2 Fourier transform infrared spectroscopy (FTIR)

Fourier Transform-Infrared Spectroscopy (FTIR) spectrum of all thermoplastic starch films was obtained using
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Nicolet Nexus spectrophotometer (Thermo Electron Corporation, Waltham, MA, USA). The transmission sampling

approach was implemented. The measurement was recorded between 4000-500 cm-1 with the resolution of 4 cm-1.

All tests were carried out in triplicated.

2.3.3 Scanning electron microscopy (SEM) of the composite flims

Samples of all composite films were frozen and fractured under liquid nitrogen to study their morphology. A SU

1510 scanning electron microscope (SEM, Hitachi, Japan) was used to analyze the surfaces of films. For analyses,

films were mounted on bronze stubs and sputter-coated with a thin layer of gold for 35s and observed with an

accelerating voltage of 15kV and magnification 5k×.

2.3.4 Differential Scanning calorimetry (DSC)

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The DSC thermograms were acquired by a DSC-Q200 (American TA Instrument Co., Ltd.) equipment and were

done to determine glass transition temperature (T g) of the samples by DSC measurements. Before an examination,

an empty aluminum pan was taken as a reference test. Film samples weighing about 5mg were placed individually in

other aluminum pans and hermetically sealed. All the samples were scanned at a rate of 10 °C /min from 40°C to

240°C under a nitrogen atmosphere to remove previous thermal history and moisture. Two samples of each film

system were tested to ensure repeatability.

2.3.5 Thermogravimetric Analysis (TGA)

Thermogravimetric analyzer (TGA/TA-Q500, Newcastle, UK) was employed to test samples under the protection of

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N2, with the temperature ranging from 30~600℃ and the heating rate at 10℃/min.

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2.3.6 Mechanical properties

Samples were pre-conditioned at 23 ± 2 °C and relative humidity of 53 ± 2%. The mechanical properties of films

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were determined from samples cut in 50mm long × 15mm wide. Film samples were investigated using a Universal
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Testing Machine (KDⅡ-0.05, Shenzhen KQL Test Instrument Co., Ltd, China) at room temperature, recording

tensile strength (TS) and percentage elongation at break (E). The crosshead speed was set at 10.0 mm/min and the
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width and thickness of each sample were measured before testing. The measurement was repeated three times for

each sample, and the results were averaged.

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2.3.7 Water Vapor Permeation

10-gram dry calcium chloride were placed in each weighing bottles, which were sealed by composite films after
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being placed in a 59% relative humidity (RH) environment (25℃) for48 hours to balance the moisture content. The
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effective area of each membrane sample was 19.625 cm2. The accuracy was 0.0001 grams for the weight of sealed

bottles. The weighing bottles were placed in two different desiccators containing saturated sodium chloride (75%

RH) and saturated potassium nitrate (95% RH), respectively. Weighing bottles were weighed every 12 hours until

their weight was stable. The water vapor transmittance and water vapor permeation of composite films were

calculated by the following formulas [18]. During the test, each sample was tested three times to calculate its

average value and error.

(1)

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In the formula, WVT represents the water vapor transmission (g/m2/s); t represents the time interval between two

mass increments (s); △m represents the mass increment during the period of t (g), and A refers to the area of

samples permeated by water vapor (m2).

(2)

In formula, WVP represents the water vapor permeability (g/m2/s/Pa); d represents the sample depth (m); P refers to

the saturation pressure of water vapor at a temperature of 25 oC (Pa); R1 refers to the relative humidity of the test

environment (%); and R2 refers to the relative humidity of the inner environment of weighing bottles (%).

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2.3.8 Water contact angle

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The hydrophilic/hydrophobic of the composites was evaluated using the sessile drop method at ambient temperature

(CAM 200, KSV Instruments LTD, Helsinki, Finland). The experiments were conducted depositing the ultrapure

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water (72.1 mN m−1) on the surface of sample films using an automatic microsyringe (5 μL). For all samples, the
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average was calculated on five measurements and the standard deviation was determined, too.

3. Results and discussion

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3.1 XRD of composite films

The X-ray patterns of natural corn starch, pure TPS film, and MCC/TPS composite films are shown in Fig.1 to
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investigate the crystallinity of the composite films. Glycerol and MCC were added to the starch matrix as

plasticizers and fillers, respectively. The XRD curves were used to verify whether the plasticization of the starch was
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fully plasticized, whether the crystal structure of the native starch was destroyed, and analyze the interaction of the
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MCC with the starch matrix.

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Fig.1 XRD of composite films: (a) corn starch; (b) MCC; (c) TPS; (d) 1wt.% MCC/TPS; (e) 3wt.% MCC/TPS; (f)
6wt.% MCC/TPS; (g) 9wt.% MCC/TPS

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Natural corn starch has a type A crystal structure with characteristic peaks of 2θ = 15.3°, 17.3°, 18.2°, and 23.1° [19].

The XRD pattern of corn starch has some low-intensity diffraction peaks and semi-crystalline polymer with a large
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amorphous and typical low crystallinity, which can be distinguished from TPS after hot melt processing.
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TPS films show a little characteristic peak of native starch in its XRD pattern, indicating that the crystal structure of

native starch was almost destroyed during hot melt processing. Thermoplastic starch exhibits process-induced
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crystallinity by hot-processing process, which was due to the crystallinity of the starch chain compounded with

plasticizer and water into a single helix structure. This degree of crystallinity was induced by hot-processing,
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attributing to a strong interaction among the hydroxyl groups of the starch molecular chain, which was replaced by a
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hydrogen bond formed between the starch and the plasticizer. TPS films plasticized with glycerol and water show a

derivative peak at 2θ = 13.1°, 18.3°, 19.8° and 22.5°, which has the characteristic of degraded corn starch and

corresponded to a semi-crystalline structure [20]. The new peak of TPS at 2θ = 19.8o is related to a processing-

induced crystallinity Vh-type, and the crystallinity of TPS is lower than that of native starch. This is because that

natural crystals were destroyed in the hot-processing, but only a small amount of crystals were formed in the hot-

processing process.

The low loading of MCC does not affect the crystallinity of the films seen from the figure. However, the MCC/TPS

composite films (contains 9wt.%MCC) have a higher crystallinity than other films due to the crystalline property of

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the MCC [21]. With the increase loading of MCC, MCC filler play an important role in improving the crystallinity

of MCC/TPS composite films.

3.2 FTIR of composite films

The interactions between MCC fillers and the starch matrix in the composite films were identified by ATR-FTIR

spectroscopy through some subtle changes occurring in the spectra. ATR-FTIR spectra curves show absorbance

peaks attributed to the different functional group structure. The obtained spectra curve of neat TPS film and

MCC/TPS composite films are shown in Fig. 2. As shown in figure, the characteristic peak in 3296 cm-1 corresponds

to the O-H stretch band attributed to vibrations of the hydrogen bonded hydroxyl (O-H) [22]. The peaks at 2928 cm-1

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is due to the aliphatic saturated C-H stretching vibration of CH2 of starch. The peak at 1647 cm-1 may be due to the

O-H bending of the absorbed water and free water [23]. The peak at 1367 cm-1 is attributed to C-H deformation

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(asymmetric) and represents the crystalline nature of cellulose. The peak at 1367cm-1 represents CH2 wagging

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vibration in cellulose. The peak at 1149 cm-1 is due to C-O-C asymmetric stretch vibration in cellulose and peak at

669 cm-1 is for C-O-H out-of-plane bending mode in cellulose [24]. By the addition of MCC, the MCC/TPS
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composite films show almost the same FTIR spectra as the TPS films, except the peak at 3296 cm-1 which is the O-
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H stretching of associated hydrogen bonds. It is observed that the peak of 3296 cm-1 become wider and its intensity

increase in the composite films with the increase of MCC loading, suggesting the formation of much more hydrogen
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bond interactions between MCC and starch [25].

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Fig.2 FTIR of composite films

3.3 Morphological characteristics of composite films (SEM)

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Fig.3 shows surface morphological of glycerol plasticized starch films and glycerol plasticized thermoplastic starch

(TPS) with different microcrystalline cellulose. The figures were observed by scanning electronic microscopy to

analyze the MCC dispersion in these thermoplastic starch matrixes and to confirm the whole thermo-plasticization

of starch. All the neat TPS film has shown a smooth surface without the presence of any starch granules indicating

the complete thermo-plasticization with the glycerol and water, and furthermore illustrate that glycerol molecular

could adequately get into the thermoplastic starch under the thermos-press processing conditions used in the

experiment. Compared with a neat starch film, although the MCC/TPS composite films also have a smooth

morphology with quite well dispersed MCC particles, the morphology of the existence of the microcrystalline

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cellulose in the glycerol plasticized starch matrix can be easily observed in the composite films. The lower loading

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of microcrystalline cellulose incorporated in thermoplastic starch matrix seems to be slightly more homogeneous

than higher loading. Some fillers appear as white domains at the surface of composite films. With the increase of the

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loading of microcrystalline cellulose, large agglomerates of the fillers are observed. Hydrogen-bonding interactions,
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between the hydroxyl groups of MCC fillers and the thermoplastic starch matrix, influences the physical and

mechanical properties of the materials[26]. Besides, good adhesion between MCC filler and the TPS matrix leads to
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no cracks on the surface of composite films. This is because of the chemical structure similarity between

thermoplastic starch and microcrystalline cellulose [27], due to their similar components which are formed by
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glucose molecules and the possibility of hydrogen bond interactions among them [28].
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Fig.3 SEM of composite files

3.4 Thermostability of composite films

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Fig. 4(a) and (b) shows the DSC curves of all the original materials and the DSC curves of the MCC/TPS composite

films, respectively. The glass transition temperature (T g) of all samples was determined during the heating run. It can

be observed from Fig. 4(a) that the Tg of TPS is lower than the Tg of corn starch. This phenomenon could be

explained by the fact that the structure of the starch granules was destroyed by the plasticizer during the high

temperature extrusion process, but the hydrogen bonding force of the starch and the plasticizer is much lower than

that of the starch molecules [29]. It is observed from Fig. 4(b) that the addition of MCC increases the Tg of the TPS-

based composite film due to the interaction between MCC and the starch matrix, which also proves that the mobility

of the TPS molecular chain is affected by the MCC content. However, when the loading amount of MCC was

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increased to 9 wt. %, the Tg of the composite film was lowered due to agglomeration between a large amount of

MCC. The Tg of the pure TPS film was about 116.59oC. When the MCC content was increased to 6wt. %, the T g

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also increased to a maximum value of about 133.00 oC, which was higher than other composite films.

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(a) (b)
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Fig.4 DSC of original materials and composite films

Decomposition of glycerol occurs in an unique step due to their evaporation with the maximum degradation at about

120℃, and few residue of films are left at 600℃ (showed in Fig.5). The native starch granules show two degradation

steps, one initial step is related to the water evaporation, and a main step with a maximum degradation is related to a

molecular dehydration to form glucose at about 336℃. The final residue is lower than 10% at 600℃ attributed to the

partial carbonization of starch [30].

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Fig.5 TGA of composite films

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The degradation curves of the neat TPS films and the MCC/TPS composite films have two main steps. The initial

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step occurs from 30 ℃ until 120℃ and this is because of the evaporation of water firstly and of plasticizer rich

phases secondly, which are partially overlapped. The main step of degradation, mostly occurs at 335℃, mainly
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corresponds with the thermal decomposition of starch-rich phase overlapped to the MCC degradation [31]. There is
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a shoulder seam at 305℃, which was due to the degradation of MCC. A residue about 10% is left after 600 ℃ for all

TPS composites. The degradation temperature of MCC in the composite film is 173℃, 182℃ and 193℃, respectively,
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which is attributed to the increase of the hydrogen bonds formed by MCC molecules and starch molecules as the

content of MCC increases. When the content of MCC is 9wt.%, the flocculation of much MCC decreased its
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degradation temperature.
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3.5 Mechanical properties of composite films

The mechanical properties, such as tensile strength and elongation at break of glycerol thermoplastic starch films

(TPS films) and their composite films (1wt.%MCC/TPS, 3wt.%MCC/TPS, 6wt.%MCC/TPS and 9wt.%MCC/TPS

composite films) analyzed at room temperature, are shown in Fig. 6. With increasing the MCC content, the tensile

strength increases significantly from 7.63 MPa for neat TPS film to 12.47 MPa for composite films containing

6wt.% MCC, whereas the elongation at break decreases from 52% to 15% for composite films containing 6wt.%

MCC. The results indicates the compatibility between starch matrix and MCC filler. The increasement in the tensile

strength of the TPS film reinforced with the microcrystalline cellulose can be attributed to the formation of a more

hydrogen bonded cellulose network [32]. Also, incorporating microcrystalline cellulose into a starch matrix to form

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hydrogen bonding leading to strong interactions between microcrystalline cellulose and thermoplastic starch,

thereby restricting the chain motion of thermoplastic starch. However, when the microcrystalline cellulose content

exceeds 6wt.% (9wt.%MCC/TPS), the tensile strength of the composite film is significantly decreased. This is due

to the uneven dispersion of MCC in the starch matrix or the aggregation of MCC [33]. Furthermore, the elongation

at break of the TPS composite films with the MCC is rapidly lower than the neat TPS film, which could be due to

the rigidity and less flexibility of MCC.

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Fig.6 Mechanical properties of composite films

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3.6 Water Vapor Permeation of composite films

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In order to minimize the effect of water vapor, the packaging materials must prevent, or at least decrease, moisture

exchange with the environment. The WVP values of the neat TPS film and MCC/TPS composite films were
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investigated and the results are presented in Fig. 7. It could be found that the WVP values of MCC/TPS composite

films are lower than the neat TPS films with the addition of the MCC. This is attributed to that MCC filler is less

hydrophilic than the TPS matrix [34]. On the other hand, the addition of MCC to the thermoplastic starch matrix

could lead to denser and less porous composites [35]. Furthermore, good interfacial adhesion between the MCC

fillers and starch matrix can probably introduce a tortuous path for water molecules to restrict the moisture diffusion

rate in the MCC/TPS composite films compared with the neat TPS films [36]. So, the addition of MCC could

significantly improve the barrier properties of the neat TPS film. However, 9.wt% TPS/MCC composite films show

WVP values higher than those of 6.wt% MCC/TPS films due to the flocculationa of large amount MCC. After 24h,

the water vapor transmission rate of films is slightly lower than the value of 12h, which was due to that the starch
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absorbed water and swelled, reducing the distance among molecules in the films, thereby reducing the water vapor

transmission rate of the film [37].

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Fig. 7 Water vapor permeation of composite films
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3.7 Water contact angle of composite films

The hydrophilic properties of the pure TPS film and the MCC/TPS composite film were evaluated by measuring
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their water contact angle data on the surface of the films. The measurement of the water contact angle was carried

out by dropping a drop of water on the upper surface of the films as Fig.8 shown. It has been observed that the water
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contact angle of the composite films increased with the addition of MCC in the thermoplastic starch matrix due to
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the hydrophilicity of the MCC filler compared to starch [38]. The pure TPS film has the lowest water contact angle

(57.24°) due to the number of hydroxyl groups from the native. All MCC/TPS composite films show higher contact
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angles than pure TPS films, from 63.02o through 67.23o, to 72.79o, respectively, 1wt.%, 3wt.% and 6wt.%,

indicating MCC can increase the properties of the hydrophilic MCC/TPS composite films. This phenomenon was

because the incorporation of differently loading of MCC was also a polysaccharide, and could easily interact with

starch to form a network between the starch polymer chains, so that the surface of the composite film effectively

prevented water from entering the composite films [39]. However, when the content of MCC was increased to

9wt.%, too much MCC particles aggregated to form large particles by themselves, which weakened the interaction

between starch and microcrystalline cellulose, and also increased the porosity of the films to promote the penetration

of moisture into the interior of the composite films [40], resulting in a decrease in the water contact angle of the 9

wt. % MCC/TPS composite film (69.81o).

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Fig. 8 Water contact angle of composite films

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4. Conclusion
The prepared MCC/TPS composite films were characterized by various test instruments. XRD results show that the

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crystallinity of TPS film is lower than corn starch after melt extrusion and hot-pressing process, but those of

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composite films, containing MCC, are improved compared to neat TPS films. The FTIR curves indicate that the
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interaction between MCC and starch may form much more hydrogen bonds. When the loading of MCC is not more

than 6wt.%, MCC is well dispersed in MCC/TPS composite films. The T g of MCC/TPS composite films is increased
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form 119.80oC to 133.00oC with the increase of MCC content. Due to the formation of strong hydrogen bonds

between microcrystalline cellulose and starch molecules, so the tensile strength and water vapor transmission rate of
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6wt.%MCC/TPS composite films are better than those of other composite films. Besides, the water contact angle of

MCC/TPS composite films decreased gradually with the content of MCC increased, due to that the hydrophilicity of
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microcrystalline cellulose is lower than that of starch.

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Acknowledgments

This Project was supported by the Foundation [No.2019KF03] of Guangxi Key Laboratory of Clean Pulp &

Papermaking and Pollution Control, College of Light Industry and Food Engineering, Guangxi University and the

National Natural Science Foundation [No.31270633] of China.

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