Accepted Manuscript

Title: Thermoplastic blends of chitosan: A method for the

preparation of high thermally stable blends with polyesters

Authors: Rafael Grande, Luiz Antonio Pessan, Antonio J.F.

Carvalho

PII: S0144-8617(18)30255-8
DOI: https://doi.org/10.1016/j.carbpol.2018.02.087
Reference: CARP 13349

To appear in:

Received date: 15-12-2017

Revised date: 2-2-2018
Accepted date: 28-2-2018

Please cite this article as: Grande, Rafael., Pessan, Luiz Antonio., & Carvalho,
Antonio J.F., Thermoplastic blends of chitosan: A method for the preparation
of high thermally stable blends with polyesters.Carbohydrate Polymers
https://doi.org/10.1016/j.carbpol.2018.02.087

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 Thermoplastic blends of chitosan: A method for the
preparation of high thermally stable blends with polyesters

Rafael Grande*1, Luiz Antonio Pessan2, Antonio J. F. Carvalho1

1Department of Materials Engineering, Engineering School of São Carlos, University of São Paulo. Av. João Dagnone, 1100 13563-

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120, São Carlos, SP, Brazil

2 Department of Materials Engineering, Federal University of São Carlos, São Carlos, SP, Brazil

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* Corresponding author: rafaelgrande@usp.br

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Highlights

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 Thermoplastic chitosan blends were prepared.

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Miscible thermoplastic poly(vinyl alcohol)/chitosan blends dispersed in poly(lactic acid).
 Poly(vinyl alcohol)/chitosan blends prepared by freeze- or spray-drying techniques.
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 Thermal stable PVA/chitosan/PLA blends were prepared and characteized.

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Abstract
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Chitosan is high potential material for new applications due to its properties, especially its microbial activity, and
because it is one of the most abundant natural polymers. However, chitosan can be processed only from solution
limiting its applications. Methods for processing chitosan in molten have been a subject of recent interest. One
method, involves thermoplastic its blends with poly(vinyl alcohol), however these blends undergo degradation due to
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acid residues from previous processing steps. Here we described a process to produce thermoplastic blends of
poly(vinyl alcohol)-chitosan in a poly(lactic acid) matrix by avoiding degradation even at higher chitosan contents. The
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process involves the use of spray- and freeze-drying techniques to produce acid free blends of PVA/chitosan, then
incorporated in PLA matrix by extrusion. These findings are expected to contribute to increasing and extending the
applications of polysaccharides, such as chitosan, in new applications such as textiles, medical and food packing.
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Keywords: extrusion, chitosan, natural polymers, thermoplastic blends, spray-drying, freeze-drying.

1. Introduction
 Polymer blends are one of the most relevant methods to produce new polymeric
materials with new properties from existing materials and has been applied in several fields.
Despite the potential use of biopolymers such as polysaccharides its applications are very
limited since in general these materials do not exhibit melting temperature. In this way, the
development of polymer blends containing polysaccharides and other natural polymers which
can be processed as thermoplastics is very attractive. One of these polymers which attract
interest is chitosan, a functional material with proved antimicrobial action.

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The development of new materials based on polymers from renewable resources has
been stimulated by a complex scenario involving policy, legislation, and international

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agreements (Philp, Bartsev, Ritchie, Baucher, & Guy, 2013). Polymers from renewable sources,

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sometimes referred to as bio-polymers or natural polymers, are attractive to industry as they
offer a raw material with low cost, non-toxicity, large availability, and the opportunity to

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produce plastic products from natural/sustainable resources. As already mentioned, the main
challenge in efficiently producing polymers based on renewable sources is that the material

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must be compatible with the common industrial processing methods, such as extrusion,
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injection molding and blow film extrusion. However, most abundant polymers from renewable
sources, such as chitin, cellulose, and starch, cannot be directly manufactured by melt
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processing since they do not melt.
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Chitosan stands out as an attractive material for compound functional blends with synthetic
polymers and has potential applications in food packaging (Leceta, Guerrero, & de la Caba,
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2013; van den Broek, Knoop, Kappen, & Boeriu, 2015) due its low-toxicity, biodegradability,
(Bagheri-Khoulenjani, Taghizadeh, & Mirzadeh, 2009; Kean & Thanou, 2010) and antimicrobial
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activity (Cruz-Romero, Murphy, Morris, Cummins, & Kerry, 2013; Hosseinnejad & Jafari, 2016;
Verlee, Mincke, & Stevens, 2017; Zheng & Zhu, 2003). Chitosan is also widely studied as a
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functional polymer for pharmacological/medical purposes (Dash, Chiellini, Ottenbrite, &

Chiellini, 2011; Jayakumar, Menon, Manzoor, Nair, & Tamura, 2010; Muxika, Etxabide, Uranga,
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Guerrero, & de la Caba, 2017) due its excellent biocompatibility (Busilacchi, Gigante, Mattioli-
Belmonte, Manzotti, & Muzzarelli, 2013; Muzzarelli, 2009, 2010). A major challenge in
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producing new chitosan-based materials is that chitosan cannot be directly melted and has
usually been incorporated as a solid particulate material in a polymer matrix (Bonilla, Fortunati,
Vargas, Chiralt, & Kenny, 2013; Correlo et al., 2005, 2009). Such behavior means that the
common methods of large-scale processing are not suitable for this material. In a previous
study (Grande and Carvalho, 2015), it was developed a new method for producing extruded
blends based on chitosan, in which a thermoplastic blend of chitosan and poly (vinyl alcohol)
 (PVA) was produced by solution blending then blended into PLA in the presence of glycerol.
When PVA is solution processed with chitosan it acts as a thermoplastic substract that later
can be dispersed in a PLA matrix by extrusion were PVA acts as an agent to increase the
compatibility between PLA and chitosan (Grande and Carvalho, 2011). Despite promising
results, the technique showed limited success in practice due to the presence of residual
solvents, which are very hard to be removed. The acid is necessary to promote the solubility
of chitosan and its residues caused severe degradation of chitosan and of PLA leading to
decrease in the mechanical properties and strong darkening during processing and even when

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the PVA-chitosan blend is dried at mild temperatures (<50 °C). Thus, the extraction of acid

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residues proved to be an obstacle to be overcome. More recently, some studies used
“thermoplastic chitosan”, chitosan plasticized with a high content of polyols, water, and acetic

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acid (Epure, Griffon, Pollet, & Avérous, 2011; Matet, Heuzey, Pollet, Ajji, & Avérous, 2013), as

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an alternative to produce thermo-mechanically mixed blends based on chitosan (Dang &
Yoksan, 2015; Matet, Heuzey, Ajji, & Sarazin, 2015; Mendes et al., 2016). Although this

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approach reduced the size of the dispersed chitosan phase to a few microns, the irregular
geometry of the dispersed phase indicated that the chitosan was not effectively melted during
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thermo-mechanical mixing. In addition, the darkening of the blends with increasing chitosan
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content is a common observation in these works and may indicate that the acetic acid residues
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degrade the blends.

Here we describe a method for effectively producing thermoplastic PVA/chitosan blends

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that can be melted and dispersed by extrusion without the negative effects of acid acetic
residues into a polyester matrix such as poly(lactic acid). PLA/chitosan blends were obtained
by solution processing which was dried by the conventional oven drying method and using new
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approaches such as freeze- and spray drying. The main goal was to demonstrate that chitosan
can be effectively melted and incorporated in a thermoplastic polyester matrix such PLA using
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this both freeze- and spray drying methods, opening new and widening the range of
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applications for chitosan.

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2. Materials and Methods

2.1. Materials
Chitosan with ~85% deacetylation and a viscometric molecular weight (Mw) of 60,100 g.mol−1
was used. PVA purchased from Sigma Aldrich (CAS 9002-89-5), 80% hydrolyzed with a Mw of
9000–10,000 g.mol−1, was used in the blends. Bi-distilled glycerol and reagent grade acetic acid
were used as received. The PLA used in this work was a thermoplastic resin from Natureworks
(extrusion grade - INGEO 2003d), melt flow rate 6 g/10 min (210°C, 2.16 kg) and molecular Mw
≈ 150,000 g/mol.

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2.2. PVA/chitosan solution

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The blends of PVA and chitosan were prepared by mixing PVA, solubilized in water, and

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chitosan, solubilized in 1% acetic acid solution, both at a concentration of 1 wt%. Then, the
PVA/chitosan solutions were mixed at 90/10 and 75/25 wt% proportions. The PVA/chitosan

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solutions were then dried by different methods, as described below.

2.2.1. Drying

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The PVA/chitosan solutions were poured onto Teflon plates and dried in a forced air oven
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at 38°C for 72 h then dried in a vacuum oven for 24 h at 50 °C. The PVA/chitosan blend was
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cryogenically ground and sifted. The resulting powder was then dried under vacuum for 24 h
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at 50 °C to remove moisture adsorbed during the cryo-grinding process.

To perform the freeze-drying method, the PVA/chitosan solutions were frozen dryed at -90 °C
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and then placed in a Liotop® K 105 freeze dryer. The applied vacuum was 0.14 mmHg and the
drying process took 72 h.
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Last, PVA/chitosan blends were spray-dried using a Niro Atomizer 2052 spray dryer, a
concurrent system equipped with a rotary atomizer were used to perform the PVA/chitosan
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blends drying. The rotation speed of the atomizer was approximately 32,500 rpm, while the
inlet and outlet temperatures were 180 °C and 70 °C respectively.
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2.3. PVA/chitosan extrusion in PLA

PVA/chitosan 90/10 and 75/25 wt% blends dried using the three different methods were
mixed with PLA at the ratio of 75;25 wt% of PLA/PVA/ chitosan by extrusion. The mixtures were
extruded in an AX Plásticos LAB 16 mm single-screw extruder with a length-to-diameter ratio
(L/D) of 16. The temperature profile from feed, screw and die was 140, 150, 155 ⁰C and the
screw speed was 35 rpm.
 2.4. Characterization

2.4.1. Scanning electron microscopy (SEM)

The phase morphologies of the PVA/ chitosan samples processed using different drying
methods and PLA/(PVA/ chitosan) blends were examined using SEM. The images were
obtained using a FEI Inspect F50 electron microscope. PLA/(PVA/ chitosan) pellets were hot
pressed at 140 °C in rectangular aluminum molds (20 x 10 x 2 mm) and then fractured in liquid

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nitrogen before microscopy. The PVA/chitosan solution blends dried using the different

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methods were examined by SEM without any pre-treatment. However, the PLA/(PVA/

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chitosan) extruded blends were submitted to phase extraction in hot water for 24 h to remove
PVA/ chitosan dispersed phase in order to facilitate observation of the morphology. All

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samples were sputter coated with platinum prior to SEM.

2.4.2. Thermogravimetric analysis (TGA) U

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TGA was used to determine the residual solvent content and thermal degradation behavior of
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the PVA/ chitosan blends. TGA thermograms were obtained using a PerkinElmer Pyris 1
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instrument. Each sample (10–20 mg) was placed in a platinum crucible and heated from 25 °C
to 800 °C at a heating rate of 10 °C/min under a nitrogen atmosphere.
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2.4.3. Fourier transform infrared spectroscopy (FTIR)

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For FTIR analysis, samples of PVA/chitosan blends were hot pressed at 140 °C to produce films
with an average thickness of 50 μm. The FTIR spectra of PVA/ chitosan blends were acquired
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using a Perkin-Elmer Spectrum 100 FT-IR spectrometer equipped with a single horizontal
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Golden Gate ATR cell. The spectra were recorded over a wavenumber range from 500 cm-1 to
4000 cm-1 with 32 accumulation scans and a spectral resolution of 4 cm−1.
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2.5. PVA/CHITOSAN dispersion in PLA by extrusion

PVA/chitosan 90/10 and 75/25 samples were incorporated into a PLA matrix by extrusion. The
composition of the extruded materials was kept constant, where the PLA matrix corresponded
to 75 wt% and the PVA/chitosan dispersed phase was 25 wt%. Both, PVA/ chitosan blends
 obtained by oven and freeze-drying were ground in a cryogenic mill for easier incorporation
into the PLA as a powder. Thermo-mechanical mixing was performed using a single-screw
bench extruder (AX Plastics LAB-16) equipped with a mixing element maddock. The
temperature profile was 140, 150, 155 ° C and a screw rotation speed of 35 rpm was used. The
material obtained was directly pelletized by an automatic picker. The pellets of
PLA/(PVA/chitosan) blends were then hot pressed to obtain 0.2-mm-thick films for observation
of the visual appearance and 3-mm-thick specimens were prepared for SEM analysis. The
pressing conditions were the same for all blends (press temperature of 145 °C and a load of

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500 kg for 1 min). The thicker specimens were cryo-fractured in liquid nitrogen after 5 min of

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immersion. Extraction of the dispersed PVA/chitosan was also required to observe the
PVA/chitosan blend dispersion in the PLA matrix; extraction was performed by immersing the

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specimen in a 1% acetic acid solution at 60 °C for 24 h. Thus, the SEM images of

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PLA/PVA/chitosan are from the fractured and transversal section of the samples where the
voids corresponded to the extracted dispersed phase of PVA/chitosan.

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3. Results and discussion
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3.1. (PVA/chitosan) blends obtained using different drying methods
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3.1.1. Thermal stability

The TGA thermograms are shown in Fig. 1., revealing that the weight loss of the PVA/chitosan
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blends plasticized with glycerol occurs in a four-stage process. The first stage at 25–150 ˚C was
related to the loss of bound and adsorbed water in addition to the residual acetic acid (Bonilla
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et al., 2013; Chen, Wang, Mao, Liao, & Hsieh, 2008). The second weight loss at 150-250 ˚C was
associated with the weight loss of glycerol (Dou, Dupont, Williams, Chen, & Ding, 2009). The
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third (250–450 ˚C) and fourth (450–700 ˚C) stages, referred respectively to degradation of the
PVA/chitosan blend components (Lewandowska, 2009; Tripathi, Mehrotra, & Dutta, 2009) and
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degradation of by-products from PVA (Holland & Hay, 2001).

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a) b)
100
100 100

WEIGHT LOSS (%)

100
98

WEIGHT LOSS (%)

98 96
96 94
80 80 92
WEIGHT LOSS (%)

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WEIGHT LOSS (%)

90
92 88
90 86
60 60 25 50 75 100 125 150 175
88
25 50 75 100 125 150 175 TEMPERATURE (°C)
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TEMPERATURE C
40 40

20 20
90-10 OVEN 75-25 OVEN
90-10 FREEZE 75-25 FREEZE
90-10 SPRAY 75-25 SPRAY
0 0

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100 200 300 400 500 600 700 800 100 200 300 400 500 600 700 800
TEMPERATURE (°C) TEMPERATURE (°C)

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Fig. 1 Thermograms of mass loss versus temperature of a) 90/10 PVA/chitosan blends and b)
75/25 PVA/chitosan for oven, freeze and spray-drying.

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The thermograms shows that PVA/chitosan blends obtained by oven drying had a continuous
mass loss over the entire measured temperature range, indicating constant degradation of the
components catalyzed by the presence of the residual solvents. On the other hand, the
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samples obtained from spray and freeze-drying techniques resulted in more stable materials
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showing weight loss plateaus within the measured temperature range. In addition, significant
changes due the different drying methods were observed, in particular in the first and second
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stages. The blends obtained from oven drying showed higher overall weight loss when
compared with that of blends obtained from spray and freeze drying. For example, the 75/25
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oven-dried sample showed 15% weight loss, while the same blends obtained from spray and
freeze-drying showed weight losses of 2% and 1% wt, respectively, over the same temperature
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range. At the second stage, oven- and freeze-dried samples was close to 10 wt% of weight loss,
indicating complete preservation of the glycerol additive. However, the blends obtained by
spray drying showed a 6 wt% weight loss over the same temperature range. Thus, spray drying
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resulted in the evaporation of a fraction of the glycerol. This may have occurred due to the
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high contact surface generated during spraying of the material, making the transfer of heat
much more efficient compared to oven drying for example. Therefore, the higher efficiency of
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extracting solvent residues in both the spray- and freeze-drying techniques resulted in
PVA/chitosan blends with better thermal stability and less thermal degradation. The weight
loss values for the specific temperature ranges are shown in Table 1.

Table 1: PVA-chitosan weight loss values over different temperature ranges

WEIGHT LOSS (%)

 25–150 150–250 250–450 450–700
Temperature range
(˚C) (˚C) (˚C) (˚C)
90/10 oven-dried 8 11 65 16
90/10 spray-dried 2 6 76 16
compositions
PVA-chitosan
90/10 freeze-dried 1 11 72 16
75/25 oven-dried 15 11 54 20
blend

75/25 spray-dried 2 7 73 17
75/25 freeze-dried 1 11 72 16

3.1.2. Chemical interaction (FTIR)

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FTIR spectroscopy was used to assess the chemical groups of the polymers. Fig. 2 shows the

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FTIR spectra of PVA, chitosan, and PVA/chitosan blends. The interactions between chitosan

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and PVA were expected to be observed by strong hydrogen bonding, that could be detected
by changes at 1400 cm−1 peak, related to vibrations of OH in the CH ring and the broad band

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between 3450 and 3200 cm−1 associated with the O-H stretch from hydroxyls (Pawlak &
Mucha, 2003). However, FTIR spectra of the PVA/chitosan blends resulted in a typical

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combination of the characteristic peaks of the components. It was not observed any change in
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the FTIR pattern due to the methods used to prepare the PVA/chitosan blends.
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chitosan chitosan
PVA PVA
90-10 Freeze-dried 75-25 freeze-dried
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90-10 Spray-dried
75-25 spray-dryed
90-10 Oven-dried
75-25 oven-dried
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FTIR - ATR
FTIR-ATR

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800 1200 1600 1000 2000 3000 4000

-1 -1
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Wavenumber (cm ) Wavenumber (cm )

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Fig. 2: FTIR spectra from PVA/chitosan blends 90/10 and 75/25

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Fig. 3 shows the FTIR spectra of the PLA(PVA/chitosan) blends in which it is possible to observe
two changes attributed to the interactions of the components. The broad absorption band at
3450 cm−1, due mainly to hydroxyl groups in PVA, chitosan and glycerol, is less intense in the
blends, which was attributed to specific interactions of the OH groups only when the three
components (PVA, PLA and chitosan) are present. The absorption at 1760 cm−1 from carbonyl
group of PVA shift to higher wavenumber indicating specific interactions between the
 components PLA/PVA since this shifting was not observed in PVA/chitosan blends. These
results agree with previous studies (R. Grande & Carvalho, 2011; Rafael Grande, Pessan, &
Carvalho, 2015).

chitosan chitosan
PVA PVA
PLA PLA
PLA(75-25) frezee PLA(90-10) frezee
PLA(75-25) spray PLA(90-10) spray
PLA(75-25) Oven PLA(75-25) oven
FTIR - ATR

FTIR-ATR

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1000 2000 3000 4000 1000 2000 3000 4000

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-1 -1
Wavenumber (cm ) Wavenumber (cm )

Fig. 3: FTIR spectra from PLA(PVA/chitosan) of the blends 90/10 and 75/25 processed by oven,
spray- and freeze-drying.

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3.1.1. Visual aspect / Morphology
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3.1.2. A color change in the PVA/chitosan blends was observed after the different drying
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methods, as shown in Fig. 4 The PVA/chitosan blends obtained by oven drying

showed a brownish color (Fig. 4 a, d), while the PVA/chitosan blends obtained by
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spray- (Fig. 4 b, e) and freeze-drying (Fig. 4 c, f) were lighter, with only a slightly
yellow tone. In addition, previous work reported that PVA/chitosan blends became
increasingly darker as they underwent subsequent heating cycles at 50 °C during
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oven drying(Grande, Pessan, & Carvalho, 2015); this effect was not observed when
using spray- and freeze-drying methods. This darkening was even more notable for
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PVA/chitosan -75/25 blends obtained by oven drying due to the higher amount of
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acetic acid residues (Fig. 4 d).

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Fig. 4. Photographs of 90/10 and 75/25 PVA/chitosan obtained from (a, d) oven-dried, (b,e)
spray-dried, and (c, f) freeze-dried. SEM images of PVA/chitosan 90/10 and 75/25 (a1, d1)
oven-dried, (b1, e1) spray-dried, and (c1, f1) freeze-dried.
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The PVA/chitosan samples, in both compositions, dried by spray or freeze-drying (Fig. 4 b, c,

e, f) showed a similar visual appearance and were much lighter in color than the oven dried
sample (Fig. 4 a, d). SEM analysis showed that the microstructures of the samples were also
dependent on the different drying techniques (Fig. 4 g, h, i). The PVA/chitosan membranes
obtained after oven drying were ground and sifted, resulting in particles with a wide size
distribution and irregular geometry. The particles with

dimensions ranging from 30–300 μm, as observed in Fig. 4 a1, d1. On the other hand, spray
drying directly produced a fine powder with predominantly spherical particles with diameters
of 1–5 μm (Fig. 4 b1-e1). Thus, the homogeneous spray-dried particles with dimensions up to
100 times smaller than those produced after oven drying are expected to result in easier
incorporation of the PVA/chitosan into PLA during extrusion. Freeze-drying of the

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PVA/chitosan blends resulted in a low-density material with a morphology composed of
porous layers, as can be seen in Fig. 4 c1-f1.

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PLA/chitosan blends were also hot-pressed at 150 °C, giving rise to membranes witch 0.2 mm

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thickness. Fig. 5 shows the obtained membranes in which spray- and freeze-drying methods

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resulted in more transparent and homogeneous membranes for both compositions also,
confirming the increasing in PVA/chitosan thermoplasticity.

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Fig. 5. PVA/chitosan blends obtained from different drying methods hot pressed.
 3.2. Dispersion of PVA/chitosan in PLA

The PVA/chitosan obtained from oven, spray and freeze-drying were then mixed with PLA
powder and extruded. Fig. 6 shows the as-extruded pellets and hot-pressed films resulting from
extrusion-blending of the PLA with PVA/chitosan obtained from oven, spray, and freeze drying.

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Fig. 6. Photographs of PLA/(75/25) obtained from dispersing 25% PVA/chitosan after (a, a1)
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oven drying, (b, b1) spray drying, and (c,c1) freeze-drying in 75% PLA.
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Extruded PLA/PVA/chitosan pellets containing spray- or freeze-dried PVA/chitosan (Fig. 6 b, c

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respectively) had a similar visual appearance; both drying techniques resulted in extruded
blends that were significantly lighter compared to the oven-dried sample (Fig. 6. a). This result
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agrees well with the TGA analysis that identified the highest residual solvent content in the
oven-dried blends. The hot-pressed films (Fig. 6. b1, c1) revealed that the PLA/(PVA/chitosan)
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blends with spray- and freeze-dried PVA/chitosan were more homogeneous and did not
contain any evident disperse domains compared with the oven-dried PLA/(PVA/chitosan) (Fig.
6. a1). This may have been due to the reduced size and homogeneity of the PVA/chitosan
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particles produced during the spray drying process. Obtaining particles with a controlled
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geometry and reduced size could greatly affect the mixing dynamics in the molten state during
extrusion. Dispersing larger particles requires a higher shear rate for melting and breaking up
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the domains during extrusion.

3.2.1. PLA/(PVA/chitosan) morphology

The morphology of the PLA/PVA/chitosan (75/25) samples is shown in Fig. 7. Scattered

disperse domains with dimensions as large as 250 μm are observed in Fig. 7. a (oven-dried
PVA/chitosan). (Rafael Grande et al., 2015) showed that the blend of PVA/chitosan plasticized
with glycerol could not be easily melt processed when the chitosan content was higher than
10%, even using extruders with a high shear rate. By using spray- (Fig. 7. b) and freeze-drying
techniques (Fig. 7. c) a significant improvement in PVA-chitosan dispersion in PLA was
achieved. It was also observed better dispersion and particle size distribution (Fig. 7. b1, c1)
and a reduction in the dispersed particle reaching 0.5–5 μm. A dominance of spherical particles
in the dispersed phase was observed, indicating that the PVA/chitosan actually melted during
the thermo-mechanical mixing process. The same behavior as described for the 75/25 blends

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was observed for the 90/10 blends, as can be seen in Fig. 8.

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Fig. 7. SEM images of PLA/(PVA/chitosan) 75/25. (a, a1) oven drying, (b, b1) spray drying, and
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(c, c1) freeze drying.

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Fig. 8. SEM images of PLA/(PVA/chitosan) 90/10. (a, a1) oven drying, (b, b1) spray drying, and
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(c, c1) freeze drying.

4. Conclusions

The present study successfully demonstrated an innovative approach for processing a

carbohydrate, in this case chitosan, as a thermoplastic. These results are unprecedented in the
 literature and demonstrate the viability of this new method to melt process polymers of high
polarity into thermoplastic matrices. The methods used here also overcame the limitation
previously described in the literature regarding the presence of residual solvents by using two
different drying techniques, spray and freeze drying. Both these methods were shown to be
effective in producing PVA- chitosan blends with low residual solvent contents and good
processability, even for a composition that could not previously be melt processed
(75/25%wt). The main difference between the PVA- chitosan blends obtained by these
techniques and standard oven drying was the morphology. Spray drying is considered

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advantageous due to the direct production of a suitable blend powder, eliminating the need

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for a grinding step that can result in moisture adsorption and degradation (especially in
polyester matrices). In addition, there is the potential for applying this technology to biological

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applications as cell growth scaffolds in PVA- chitosan blends obtained using freeze-drying due

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to the layered porous morphology, biocompatibility, and low toxicity of PVA and chitosan.

5. Acknowledgements U
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R. G. thanks São Paulo research found (FAPESP) for a postdoctoral grant (2015/07744-0) and
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National Council for Scientific and Technological Development (CNPq) for financial support,
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project CNPq 476709/2013-0. We would like to thank also Liobras by allowing us to obtain the
freeze-drying materials on their facilities.
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6. References
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Bonilla, J., Fortunati, E., Vargas, M., Chiralt, A., & Kenny, J. M. (2013). Effects of chitosan on the
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physicochemical and antimicrobial properties of PLA films. Journal of Food Engineering,

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Busilacchi, A., Gigante, A., Mattioli-Belmonte, M., Manzotti, S., & Muzzarelli, R. A. A. (2013).
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Chen, C.-H., Wang, F.-Y., Mao, C.-F., Liao, W.-T., & Hsieh, C.-D. (2008). Studies of chitosan: II.
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