Accepted Manuscript

Title: EFFECTS OF HYDROPHOBIZED STARCHES ON

THERMOPLASTIC STARCH FOAMS MADE FROM
POTATO STARCH

Authors: Bruno Felipe Bergel, Samara Dias Osorio, Luana

Machado da Luz, Ruth Marlene Campomanes Santana

PII: S0144-8617(18)30838-5
DOI: https://doi.org/10.1016/j.carbpol.2018.07.047
Reference: CARP 13847

To appear in:

Received date: 14-3-2018

Revised date: 28-6-2018
Accepted date: 15-7-2018

Please cite this article as: Bergel BF, Dias Osorio S, da Luz LM, Santana
RMC, EFFECTS OF HYDROPHOBIZED STARCHES ON THERMOPLASTIC
STARCH FOAMS MADE FROM POTATO STARCH, Carbohydrate Polymers (2018),
https://doi.org/10.1016/j.carbpol.2018.07.047

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EFFECTS OF HYDROPHOBIZED STARCHES ON THERMOPLASTIC
STARCH FOAMS MADE FROM POTATO STARCH
Bruno Felipe Bergel, Samara Dias Osorio, Luana Machado da Luz, Ruth Marlene
Campomanes Santana
Polymeric Materials Lab, Materials Engineering Department, Federal University
of Rio Grande do Sul, Av. Bento Gonçalves, 9500, P.O. Box 15090, ZC 91501-
970 Porto Alegre, RS, Brazil
Highlights
 Article: “Effects of hydrophobized starches on thermoplastic starch foams made from
potato starch”

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 Bruno Felipe Bergel, Samara Dias Osorio, Luana Machado da Luz, Ruth Marlene

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Campomanes Santana
 - Starch biodegradable foams with different amounts of modified starch were studied.
 - Two modifications were studied: acetylation and esterification with maleic anhydride.

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 - Samples with 6.67% and 13.34% of modified starch improved the foams properties.


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- Foams with 26.67% of modified starch showed irregular structures and weak properties.

E-mail address: bruno-bergel@hotmail.com

Abstract
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Single use food packaging made from expanded polystyrene (EPS) is generally
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discarded after use and, since it is a difficult material to recycle, generates a large
amount of waste. The EPS can be replaced by thermoplastic starch (TPS) foams,
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which are made from renewable sources and are biodegradable. However, TPS
foams are hydrophilic and absorb large amounts of water, which makes it difficult
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to use. An alternative to this problem is to chemically modify the starch to make

it more hydrophobic. Two modifications for potato starch were evaluated:
acetylation and esterification with maleic anhydride. Foams with 6.67%, 13.34%,
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20% and 26.67% (modified starch weight/ total starch paste mass) of modified
starch were prepared. While TPS foams without modified starch absorbed 75g
water /100g solids, foams with 13% acetylated starch and 20% esterified starch
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presented lower absorption results (42g and 45g water/100g solids, respectively),
which represents an improvement in water resistance.

Keywords: TPS foam; acetylated starch; esterified starch

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1. Introduction
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Starch is one of the most abundant natural polymers and is the main form of
storage of carbohydrates in plants. It is used in the food industry, where it has
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several applications, such as in the manufacture of cakes, breads and biscuits. It

also has applications in the cosmetics, pharmaceutical and textile industries.
Recently, starch has been widely used in the production of environmentally
correct materials, such bags, cups, cutlery and food packaging (López, Castillo,
Garcia, Villar, & Barbosa, 2015; Masina et al., 2017; Soykeabkaew, Thanomsilp,

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& Suwantong, 2015; Yates & Barlow, 2013). The starch can be plasticized with
different low molecular weight organic compounds (glycerol, sorbitol, polyvinyl
alcohol) to produce various materials, such as films, foams and plastic parts (Bie
et al., 2013; Glenn & Orts, 2001; Lu, Xiao, & Xu, 2009; Soykeabkaew et al., 2015;
Zhou et al., 2009). Foams based on thermoplastic starch attract special attention
because they can replace single-use packages made with EPS, which are largely
irregularly discarded and are not biodegradable (plastic from petrochemical
source) (Soykeabkaew et al., 2015).

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TPS foams are easily produced by compressing a mass of starch, water and

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plasticizer in a closed mold and heated for a few minutes. This method favors the

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production of foams in various forms such as cups and trays, as the material
gains the shape of the mold. Due to the easily production these materials can be

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used in a variety of applications. However, these foams suffer from a lack of
resistance to moisture. Starch has a high affinity with the water due to its

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numerous free hydroxyl groups present in the α-glucose monomer, the unit of the
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starch molecule, which form hydrogen bonds with the surrounding moisture,
resulting in a hygroscopic nature. Due to this hydrophilicity, the material may
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collapse, disintegrate when in contact with water, or lose mechanical strength in

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an environment with high relative humidity. In addition, these foams have poor
mechanical properties and great fragility. As a consequence of these facts, TPS
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foams have limited use (Shogren et al., 1998a; Shogren et al., 1998b; Shogren
et al., 2002).
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One solution to overcome the low water resistance of TPS foam is to chemically
modify the starch, converting its hydroxyl groups into larger and less polar
clusters, such as acetyl groups. Acetylating the starch makes it more
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hydrophobic, making it difficult for water to enter the material (Chi, Xu, Wu, Chen,
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& Xue, 2008; Larotonda, Matsui, Soldi, & Laurindo, 2004; López, Zaritzky,
Grossmann, & García, 2013; Volkert, Lehmann, Greco, & Nejad, 2010). Xu,
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Dzenis, & Hanna (2005), produced and studied the properties of extruded foams
containing acetylated starch and reported that the more acetylated the starch the
lower the water absorption by the material. Another possible chemical
modification is esterification with maleic anhydride. The maleic anhydride reacts
with the hydroxyl groups and because it is a more spacious grouping tends to
improve the thermoplastic and hydrophobic characteristics of the starch (Zuo et

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al., 2013, 2014). There have been several researches in which hydrophobicized
starches made using these techniques have been used (Raquez et al., 2008; R.
L. Shogren et al., 2002; Zuo et al., 2014). Despite being conventional techniques,
there are no studies (to our knowledge) that evaluate the effects of the amount of
starch hydrophobized by these techniques on starch foams made by the
compression method. The novelty of this work is precisely to obtain TPS foams
with these modified starches by the compression method and to explain the
changes in the properties of the foams caused by the addition of hydrophobic

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starch.

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In this way, the objective of this work was to analyze and compare TPS foams

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produced with different proportions of hydrophobized potato starch. Two
modification forms were used: acetylation with acetic anhydride and esterification

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with maleic anhydride. All foams were produced by the baking/compression
method. The formation of the starch acetate and the starch maleate was

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confirmed by Fourier transform infrared spectroscopy (FT-IR) while the
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morphology of the samples was evaluated on scanning electron microscopy
(SEM).
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2. Materials and preparation

2.1 Materials
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Potato starch (Giro Verde®) was purchased at a local market in Porto Alegre,
Brazil. The acetylation of the starch was carried out using acetic anhydride
(Neon®) and sodium hydroxide (Neon®). The esterification was carried out with
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maleic anhydride (Dinamica®). Polyvinyl alcohol (PVOH) (Neon®) was used as

plasticizer in the preparation of the starch paste.
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2.2 Modification of starch

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For the acetylation of the starch, 50 g of starch and 168 g of acetic anhydride
were placed in a glass reactor with magnetic stirrer and reflux condenser. Then,
9.2 g of a 50% sodium hydroxide solution was added dropwise. The reactor was
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placed in a silicone oil bath at a temperature of 115 ° C for 5 hours with constant
stirring. Thereafter, the resulting product was precipitated and washed several
times with distilled water and then dried in an oven at 60 °C (Volkert et al., 2010).
For the esterification of the starch using maleic anhydride, 12.5 g of maleic
anhydride were weighted and ground into fine powder in a pestle. Then, the

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maleic anhydride was mixed to 50 g of dry starch inside a glass reactor. The
reactor was placed in a silicone oil bath at 100 °C and the mixture was shaken
with a glass rod intermittently for 5 hours. After the reaction time, the product was
cooled and acetone was added. The material was then filtered and washed
several times with acetone. After, the material was dried in an oven at 60 °C (Zuo
et al., 2013).
2.3 Foam preparation
The starch pastes were obtained from four-component mixture (PVA, water and

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starch in two forms, gelatinized and dried). A portion of the starch is gelatinized

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to aid dispersion of the components of the formulation, maintaining the solid

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components in the mass, forming a homogeneous paste and a suitable viscosity
(Carr, Parra, Ponce, Lugão, & Buchler, 2006). To obtain the gelatinized starch,

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20 g of starch were added to 100 mL of water at 70 °C. After the gel was cooled,
the dry starch and the PVOH plasticiser diluted in distilled water were added. The

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mixtures were made by mechanical stirring until complete homogenization. The
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obtained paste was placed in a preheated mold at 180°C and then compressed
in a 2.5 tons hydraulic press for 240 seconds. The mold used has the dimensions
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of 150 mm in length, 150 mm in width and 3 mm in thickness. All foams filled the
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molds. The resulting foams were kept at room temperature in a desiccator. The
analyzed foams have the formulation indicated in Table 1. The modified starch
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replaces the dried starch in the four component mixture. The proportion of
modified starch was calculated from the paste weight (with all the components
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added) before the foam manufacturing process.

Table 1 - Formulation of the analyzed foams.
Gel.
Dry Acetylated Esterified Water Proportion of modifie
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Sample Starch PVOH (g)

Starch (g) Starch (g) Starch (g) (mL) starch in paste (%)
(g)
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TPS 47 0 0 47 6 50 0
TPS Ac.10 37 10 0 47 6 50 6.67
TPS Ac.20 27 20 0 47 6 50 13.34
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TPS Ac.30 17 30 0 47 6 50 20
TPS Ac.40 7 40 0 47 6 50 26.67
TPS Es.10 37 0 10 47 6 50 6.67
TPS Es.20 27 0 20 47 6 50 13.34
TPS Es.30 17 0 30 47 6 50 20
TPS Es.40 7 0 40 47 6 50 26.67

2.4 Characterization of the modified starches

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2.4.1 Infrared Spectroscopy and Determination of degree of substitution
To evaluate the chemical structure of natural starch and modified starches,
Fourier transform infrared spectroscopy (Perkin-Elmer frontier equipment) was
used. The analyses were done by transmittance in the range of 4000-650 cm-1,
30 scans, at room temperature, according to ASTM E 1252.
For modified starches, the degree of substitution (DS) was determined using the
method described by Volkert et al. (2010). 150 mg of modified starch were placed

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in 10 mL of water-acetone solution (1:1 by volume). After 24 hours at rest for the

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starch to swell, 5 mL of a sodium hydroxide solution (1 mol / L) was added to

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deacetylate or de-esterify the starch. 24 hours later, the excess sodium hydroxide
was titrated with hydrochloric acid solution (0.5 mol / L) until reaching pH 7. The

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consumption of hydrochloric acid was noted and the degree of substitution was
calculated using the following equations:

%𝑆𝑢𝑏 = 𝐸 U
(𝐵𝑉−𝑉𝐻𝐶𝑙 ) 𝑥 𝑀𝑆𝑢𝑏 𝑥 𝐶𝐻𝐶𝑙 𝑥 100%
(1)
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162 x %Sub
DS = (2)
MSub x (1+MSub ) x %Sub
M

Where BV is the blank value (mL), VHCl is the volume of spent hydrochloric acid
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(mL), E is the weight of esterified starch (mg), CHCl is the molarity of hydrochloric
acid (mol/L) and MSub is the molar mass of the substituent (g/mol).
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2.4.2 Moisture Absorption

The natural and modified starches were oven dried at 60 ° C for three days to
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eliminate moisture from the grains. Afterwards, 1 g of each type of starch was
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weighed and placed in an environment with 90% relative humidity for 24 h. After
this time, the samples were weighed again. The amount of moisture absorbed
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was calculated gravimetrically.

2.5 Characterization of the foams

2.5.1 Density
The foams density were calculated by foam weight (g)/ foam volume (cm 3) in
triplicate, following methodology from Shogren et al., (1998a). The

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measurements of length, width and thickness of specimen test of foam were
made in triplicate for each sample.

2.5.2 Scanning electron microscopy (SEM)

Images of surfaces and fracture surfaces of the samples were studied using a
JEOL JSM 6060 Scanning Electron Microscope (SEM) operating at 5 kV voltage
acceleration. The samples were gold metalized. The cross-section of the foams
was evaluated for average cell size and cell density (number of cells per volume

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unit). The software used to measure cell size was ImageJ. The cell density was

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calculated using the following equation:
3⁄2

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𝑛𝑀2 1
𝑁𝑓 = ( ) . (1−𝑉𝑓) (3)
𝐴

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Where Vf is the void content, Nf is the cell density (cells/cm³), n is the number of

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cells in the micrograph, A is the area of the micrograph (cm²) and M is the
magnification of the micrograph.
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2.5.3 Water absorption
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Samples of 4 cm x 2 cm were weighed and placed in distilled water for 5 min.

The samples were then weighed again after removing the excess water using a
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tissue paper. The amount of water absorbed was calculated gravimetrically, and
the analysis was done in triplicate for each formulation. (Vercelheze et al., 2012)
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2.5.4 Moisture content

Pre-dried samples measuring 4 cm in length and 3 cm in width were weighed and
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placed in sealed containers with 90% relative humidity (RH) and then placed in
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an oven at 25 ° C. The humidity was guaranteed by sulfuric acid solution with

20% w / w. Absorbed moisture was calculated by the difference in weight of
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samples before and after exposure to the humid environment for 24, 48, 72, 96
and 120 hours.(Bénézet, Stanojlovic-Davidovic, Bergeret, Ferry, & Crespy, 2012;
Glenn, Orts, & Nobes, 2001). The obtained data were adjusted according to the
mathematical model proposed by Peleg, presented in Equation 3. The model
allows an analysis of the absorption kinetics of the samples.

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 𝑡
𝑀(𝑡) = 𝑀0 + ((𝐾 ) (4)
1 + 𝐾2 𝑡)

Where M(t) is the moisture in time, M0 is the initial moisture, t is the time, K1 is the
Peleg flux constant (h/(w water /w solids)), while K2 is Peleg capacity constant (w
solids /w water). The statistical program used was Statistic Statsoft for Windows
10 software. The assay was done in triplicate for each sample.

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2.5.5 Impact Test

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The foams density were calculated by foam weight (g)/ foam volume (cm 3) in
triplicate, following methodology from Shogren et al., (1998a). The

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measurements of length, width and thickness of specimen test of foam were
made in triplicate for each sample.

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Impact IZOD strength test was carried out with ASTM D256 on IMPACTOR II,
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using a 0,5J hammer. The samples dimensions were 60 mm x 12 mm x 3 mm.
The results were obtained from the mean of the measurements of 7 samples
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analyzed independently. The analysis took place at room temperature (25 °C)
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and relative humidity of 40-60%.

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3. Results and Discussion

3.1 Characterization of modified starches
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The FT-IR spectrum of the thermoplastic starch (TPS), acetylated starch (TPS
Ac.) and esterified starch with maleic anhydride (TPS Es.) are presented in Fig.
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1. The TPS spectrum shows the characteristic bands of d-anhydroglucose units:

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a large band in the range of 3400–3200 cm-1 attributed to the stretching of O-H
bonds; a band in 2925 cm-1 corresponding to the elongation of C-H bonds; a band
between 1644-1625 cm-1 attributed to the angular deformation of O-H bonds; a
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band between 1400-1300 cm-1 assigned to the symmetrical and asymmetric

vibrations of C-H. The bands in the range of 1200-1000 cm-1 correspond to the
elongation and vibration of C-O-C bonds and the elongation and vibration of
hydroxyl-linked C-O bonds. Since starch has three hydroxyl groups and one C-
O-C bond per repeating unit, the major starch-related bands are those found

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between 3400-3200 cm-1 and between 1200-1000 cm-1 (Lima et al., 2012;
Wokadala, Emmambux, & Ray, 2014). The spectrum of the starch esterified with
maleic anhydride (TPS Es.) shows the characteristic peaks of the starch reported
above, but also showed some differences. A band arose in 1750 cm-1, due to the
elongation of C=O bonds. As the unreacted maleic anhydride was removed by
the various washes made with acetone, it can be concluded that these C=O
bonds came from the modified starch. It may also be noted that the intensity of
the O-H band has decreased, which indicates the decrease of hydroxyls in the

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starch chain. Between 1675-1645 cm-1 a band associated with the C=C bond was

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supposed to appear, which is present in the esterified starch with maleic

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anhydride. However, this does not appear to be present, possibly due to the
coupling between this band and the band corresponding to the vibration of O-H

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bonds (1625 cm-1) (Dias, Souza, & Andrade, 2011; Raquez et al., 2008; Zuo et
al., 2013; Zuo, Gu, Yang, Qiao, & Zhang, 2016). This assumption is best explored

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and explained in the work of Zuo et al., 2013. Between 845-820 cm-1 there was
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the appearance of a small band, which may be associated with the butyl group
formed in the starch through the ring opening of the maleic anhydride in the
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esterification reaction (Zuo et al., 2013). The IR spectrum of acetylated starch

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(TPS Ac.) also shows different bands relative to the normal TPS spectrum. An
intense band can be seen in 1736 cm-1, referring to the C=O bonds of the acetyl
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groups which replaced the hydroxyl groups in the starch chain.

A pronounced reduction of the O-H band (3500-3000 cm-1) is also observed
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when compared to the normal TPS spectrum, indicating that a large part of the
hydroxyl groups has been substituted. The bands at 1366 cm -1 and 1220 cm-1
are attributed to symmetrical deformation vibration of CH3 and the stretching
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vibration of C-O bonds in esters, respectively (Diop, Li, Xie, & Shi, 2011; Randal
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L Shogren & Biswas, 2006).

The analysis of the degree of substitution (DS) of the modified starches was
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carried out by titration with HCl (Volkert et al., 2010). The TPS-Es presented DS
of 0.45 while the TPS-Ac presented DS of 2.60. These results were already
expected, as the esterification with maleic anhydride adds more spacious groups
to the starch chain. The acetylation adds less spacious groups and consequently
these settle more stable in the starch chain. Another factor that may have been
important for these results was the fact that the esterification with maleic

8
anhydride was carried out by dry method, which has little efficiency compared to
the solvent method (Volkert et al., 2010; Zuo et al., 2013).

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Fig. 1. Infrared spectrum of the: (a) TPS, (b) TPS Es. and (c) TPS Ac.
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3.2 Moisture absorption of the modified starches

The results of the moisture absorption analysis of the natural and modified starch
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are shown in Fig. 2. The results of the moisture absorption analysis of the natural
and modified starch are shown in Fig. 2. It can be noted that both starches that
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underwent chemical reactions absorbed less moisture than the natural starch in
24h. While the natural starch absorbed on average 15.99% of its weight in water,
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the acetylated starch absorbed only 8.24% and the esterified starch absorbed
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11.61%. As the FTIR results show, hydroxyl groups have been replaced by ester
groups which show more hydrophobicity. The increase of the ester groups and
the decrease of the hydroxyl groups tends to increase the resistance to water
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absorption of materials made with starch (Zuo et al., 2013).

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 20
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16 24 h

Moisture Absorpion (wt%)

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12
10
8
6
4

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2

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0
Natural Starch Acetylated Starch Esterified Starch

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Fig. 2 - Moisture absorption of the modified starches

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3.3 Density of the foams
The density of the analyzed foams is shown in Table 2. Values ranged from
0.1428 to 0.1983 g/cm³. In general the addition of modified starches increased
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the density of the foams compared to the natural starch TPS foam. However,
when the concentration of modified starch increased to 26.67%, the density of
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the foams decreased. Shogren et al. (2002) explains that foams made with
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modified starch have lower densities than normal foams mainly due to the rapid
gelatinization of the modified starches. Maybe this effect is not seen in the other
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foams due to the lower concentration of acetylated starch present in these foams.
These values are higher than those found for EPS (0.06 g / cm³) , but are lower
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than those found in other recent studies (Mello & Mali, 2014; Pornsuksomboon,
Holló, Szécsényi, & Kaewtatip, 2016; Uslu & Polat, 2012; Vercelheze et al.,
2012).
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Table 2 – Density, cell area and cell density of the analyzed foams.

Average cell area

Samples Density (g/cm³) Cell density (cell/cm³)
A

(mm²)

TPS 0.1428 ± 0,0051 0.2687 4.19x108

TPS Ac.10 0.1616 ± 0,0045 0.2352 4.86x108
TPS Ac.20 0.1983 ± 0,0032 0.2349 4.21x108
TPS Ac.30 0.1622 ± 0,0096 0.3276 3.96x108
TPS Ac.40 0.1564 ± 0,0145 0.3505 2.48x108
TPS Es.10 0.1700 ± 0,0062 0.2439 4.91x108

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TPS Es.20 0.1971 ± 0,0073 0.2365 4.49x108
TPS Es.30 0.1950 ± 0,0102 0.2358 5.08x108
TPS Es.40 0.1589 ± 0,0111 0.3267 3.76x108

3.4 Morphology of TPS foams

The SEM micrographs of cross-sections of the TPS, TPS-Ac and TPS-Es foams
are shown in Fig. 3. It can be observed that all the analyzed foams have a

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sandwich-type structure, which has two layers. The outer layers of the sandwich

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have a denser structure, smaller cell size and therefore less voids. The interior of

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the sandwich has much larger cells and an expanded structure. This type of
structure is characteristic in TPS foams produced by the mold compression

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process or baking process. The cells are formed by the water vapor that expands
the material and tend to be larger in the center and smaller in the ends, where

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the dense layer is formed (Cinelli et al., 2006; Matsuda et al., 2013; Shogren et
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al., 1998a; Vercelheze et al., 2012). Despite the same type of structure, the foams
presented significant differences in both the outer and inner layers. The SEM
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micrographs of the cross sections of the TPS-Ac 10 and TPS Ac 20 foam show
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a denser outer layer and a more compact cellular structure compared to pure
TPS foam. However, the TPS-Ac 30 and TPS-Ac 40 foams seem to have a
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thinner and less dense outer layer. Furthermore, the internal structure of the TPS-
AC 40 foam indicates a high foam expansion, which is characterized by a thinner
outer layer and larger cells. These differences could be explained by the
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decrease in the viscosity of the pastes with increasing the proportion of acetylated
starch. This reduction of viscosity with the highest amount of acetylated starch
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may have occurred due to the reduction of the intermolecular bonds with
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molecules of water and unmodified starch due to the hydrophobicity of the acetyl
groups (Ačkar et al., 2015; Berski et al., 2011; Huang & Voragen, 2007;
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Muhamedbegović et al., 2012; Saartrat, Puttanlek, Rungsardthong, & Uttapap,

2005). When in the baking process, less viscous pastes can not hold vapor
bubbles as effectively as more viscous pastes. Consequently, the lower the
viscosity of the paste, the greater the paste expansion, which generates foams
with a thinner outer layer and large inner cells (Pornsuksomboon et al., 2016;
Shogren et al., 1998a; Shogren, 1996). These effects are not seen in the TPS-

11
Ac 10 and TPS-Ac 20 foams possibly because the amount of acetylated starch
present is lower than in the other foams.
The TPS-Es 10, TPS-Es 20 and TPS-Es 30 foams have similarities to each other,
such as a well defined outer layer and a compact inner layer with medium cells.
The TPS-Es 40 presents an inner layer with larger cells, showing that this foam
had a larger expansion compared to the other TPS-Es foams. This larger
expansion of the TPS-Es 40 foam can be explained by the lower viscosity of the
paste that generated this foam compared to the other pastes that generated the

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other TPS-Es foams. This drop in viscosity has an explanation similar to that

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found for the TPS-Ac pastes, as the modified starch with maleic anhydride also

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acquires hydrophobic properties, although this drop in viscosity has been noted
only with higher proportions of maleated starch, which may be due to the lower

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degree of substitution of the maleated starch (Dias et al., 2011; Raquez et al.,
2008; Zuo et al., 2013, 2016).

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As shown in Table 2, most of the analyzed foams had a average cell area
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between 0.23 and 0.27 as well as cell density between 4 and 5x108 cells/cm³. The
only foams whose results were different from this average were the TPS-Ac 30,
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TPS-Ac 40 and TPS-Es 40 foams, which presented higher average cell area
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(0.3276, 0.3505 and 0.3267 mm², respectively). Furthermore cell density of these
samples decreased (3.96, 2.48 and 3.76x108 cells/cm³, respectively). These
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results confirm what was seen in the MEV images of Fig. As these foams
expanded further, it formed larger cells. These larger cells have become so large
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that absorbed the minors (Rizvi, Park, & Guo, 2008). Consequently the larger cell
size decreased the amount of cells present in the foam, causing the decrease in
cell density.
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A

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 TPS

TPS-Ac 10 TPS-Ac 20

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TPS-Ac 30

U TPS-Ac 40
N
A
M
ED

TPS-Es 10 TPS-Es 20
E PT
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TPS-Es 30 TPS-Es 40
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Fig. 3 - SEM micrographs of cross-sectional surface of TPS foam, TPS-Ac and TPS-Es foams.

13
Fig. 4 shows the SEM micrographs of the surface of the TPS, TPS-Ac 30, TPS-
Ac 40 and TPS-Es 40. It can be seen from the images that the surface of the TPS
foam without modified starch is smooth, with no major imperfections. However,
the foams with higher amounts of acetylated starch (TPS-Ac 30 and TPS-Ac 40)
presented a high porosity surface. This information corroborates with the
previous images of the transverse surface of these foams, which show that the

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outer layer of these foams is thinner and more irregular. The TPS-Es 40 foam

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also exhibits porosity, although apparently less than the foams with acetylated
starch. It is also noted that this foam has more relief and roughness.

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N
A
M
ED
E PT

Fig. 4. SEM Micrographs of the surface of TPS foams.

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3.5 Water Absorption of TPS foams

Fig. 5 shows the results for water absorption of TPS foams. This property of the
foams has great importance for the future use of these materials, because the
water absorption influences the mechanical properties and the dimensional
stability of these materials.

14
The results show that TPS without modified starch absorbed 75 g water/100 g
solids in 5 minutes, while the TPS-Ac 10, TPS-Ac 20, TPS-Ac 30 and TPS-Ac 40
foams absorbed 52, 42, 79 and 95 g water/100 g solids respectively in the same
time period. It can be seen that the amount of acetylated starch caused
differences in the absorption of the foams. With 6.67% and 13.34% of acetylated
starch, TPS foams exhibited a tendency to absorb less water, which was
expected due to the hydrophobic nature of the acetyl groups, which tend to repel
water. However, when the amount of acetylated starch increased to 30g and 40g,

T
an opposite effect was observed as the foams absorbed more water. This could

IP
be explained by the morphology of these foams, because as seen before these

R
foams presented a very thin and irregular outer layer, as well as an inner layer
with large cells. These characteristics increase failures and porosity, resulting in

SC
foams that absorb more water (Sjoqvist, Boldizar, & Rigdahl, 2010). According to
Vercelheze et al. (2012), a porous surface provides a large capacity for water

U
absorption. In a study on extruded foams of acetylated starch made by Xu et al.,
N
(2005), when the acetylated starch was extruded with ethanol, the resulting foams
also showed cells with thin, fragile walls and consequently absorbed more water
A

than foams without acetylated starch.

M

The TPS-Es foams presented a similar trend. The TPS-Es 10, TPS-Es 20, TPS-
Es 30 and TPS-Es 40 absorbed 60, 51, 45 and 59 g water/100 g solids. While
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the foams with 6.67%, 13.34% and 20% of esterified starch showed a gradual
decrease in water absorption, the absorption increased in the foams with 26.67%
PT

of esterified starch. The decrease in absorption is due to the hydrophobic nature

of the esterified starch (Xu et al., 2005; Zuo et al., 2013, 2016). The tendency
would be that the absorption would decrease further in the TPS-Es 40 foam, but
E

the structure of this foam (larger cells and thinner and irregular outer layer)
CC

facilitated the absorption of water, as explained before (Bergel, da Luz, &

Santana, 2017; Shogren et al., 1998a; Vercelheze et al., 2012). For comparison
A

purposes, the average water absorption of EPS was 3.76 g water/100 g solid in
5 min. Although the absorption values were high in relation to the EPS, the
modified starch foams presented greater resistance to water when compared to
other attempts to make water resistant starch foams reported in the literature
(Cinelli et al., 2006; Matsuda et al., 2013; Vercelheze et al., 2012).

15
The mixtures between acetylated starch/natural starch and esterified
starch/natural starch tend to lower the viscosity of the starch pastes, which
modifies foam formation (Ačkar et al., 2015; Biswas, Shogren, Kim, & Willett,
2006; Saartrat et al., 2005). Less viscous pastes form more porous foams and
porous foams tend to absorb water more easily (Vercelheze et al., 2012). In the
TPS-Ac 10 and TPS-Ac 20 foams, the viscosity of the pastes was high enough
to form foams with less irregularities. Consequently, having a cohesive, more
regular structure and greater amount of acetylated starch (compared to TPS-Ac

T
10 foam) the TPS-Ac 20 foam presented lower water absorption. The same

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occurred with the esterified starch foams.

R
Although the degree of acetylation was greater than the degree of esterification
which in theory should hydrophobize more acetylated starch foams, the foams

SC
exhibited similar water absorption results up to the modified 20% starch ratio
when the foams with acetylated starch absorbed much more water than the

U
foams with esterified starch. This can be explained by the size of the groups in
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the starch chains. The maleic anhydride esterification substituents are more
voluminous and take up more space than the acetyl groups. These groups may
A

have moved away the water molecules as much as the acetyl groups and
M

compensated for the lower degree of substitution (Zuo et al., 2013, 2016).
Another explanation may be related to the unsaturation present in the maleated
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starch, which forms cross-linked bonds that may increase the hydrophobicity of
the material (Tay, Pang, & Chin, 2012).
E PT
CC
A

16
 100

80
Water Absorption (wt%)

60

40

T
TPS-Ac

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TPS-Es
20

R
SC
0
0 5 10 15 20 25 30 35 40 45 50
Amount of modified starch (g)

U
Fig. 5 - Water absorption of the TPS foams.
N
A
M

3.6 Moisture absorption of TPS foams

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Moisture absorption is also an important property of TPS foams because when

the foam absorbs a lot of moisture it tends to wither and lose its mechanical
resistance. Soykeabkaew et al. (2015) states that the mechanical properties of
PT

TPS foams reach their maximum with a moisture content of 0.075 g water / g
solids and above this value tend to decrease. The moisture absorption over time
E

of the TPS-Ac foams at 90% RH (ambient relative humidity) is shown in Fig. 6A.
CC

The equilibrium moisture content of the TPS foam at 120 h was 0.2317 g water/g
solids, while for the TPS-Ac 10, TPS-Ac 20, TPS-Ac 30 and TPS-AC 40 was
A

0.2041, 0.1631, 0.2177 and 0.2489 g water/g solids, respectively. These results
show that the increase in the amount of acetylated starch lowered the absorption
of moisture to a certain extent, since the TPS-Ac 40 foam absorbed more
moisture than the normal TPS. The increase in the amount of acetylated starch
makes the foam more hydrophobic, making it difficult for moisture to enter the

17
foam (Miladinov & Hanna, 1999, 2000; Xu et al., 2005), but the outer layer and
porosity of the TPS-Ac 30 and TPS-Ac 40 foams make moisture entry easier.
Fig. 6B shows the moisture absorption of TPS-Es foams. In 120h, the TPS-Es 10
foam absorbed 0.2057 g water/ g solids, while the TPS-Es 20, TPS-Es 30 and
TPS-Es 40 foams absorbed 0.2009, 0.1815 and 0.2204 g water/g solids,
respectively. As the amount of starch esterified with maleic anhydride increased,
there was a decrease in the moisture absorption of the foams because of the
hydrophobicity of the esterified starch (Zuo et al., 2016). The exception was the

T
TPS-Es 40 foam due to its irregular outer structure and the higher surface

IP
porosity.

R
For a better understanding of the absorption kinetics of TPS-Ac and TPS-Es
foams, the results obtained through the experiment were analyzed using a

SC
mathematical model to analyze the kinetics of food moisture absorption, the
Peleg model (Mello & Mali, 2014; Paquet-Durand, Zettel, & Hitzmann, 2015;

U
Peleg, 1988). The Peleg constants K1 and K2 for the analyzed foams are
N
presented in Table 3. K1 represents mass transfer. The lower K1 is, the higher
the initial absorption rate of the foam. K2 represents the maximum absorption
A

capacity. Likewise, the lower K2 is, the greater the foam absorption capacity. It
M

can be seen that TPS-Ac 10, TPS Ac-20 and TPS-Ac 30 had higher K1 and K2
constants compared to normal TPS, indicating that these foams had lower initial
ED

absorption and lower total absorption capacity. Note that the parameters
increased from TPS-Ac 10 to TPS-Ac 20 (where K1 and K2 reached their
PT

maximum value) and decreased again from TPS-Ac 30. It is also noted that the
K1 from TPS-Ac 40 was lower than the K1 of normal TPS, which indicates that
the initial absorption rate is higher than TPS. Sjoqvist et al. (2010) and Vercelheze
E

et al. (2012) states that the increase of water absorption in the initial times is
CC

related to porosity of the foam.

TPS-Es foams exhibited a behavior similar to that found by TPS-Ac foams. The
A

TPS-Es 30 obtained the highest constant K2, which shows that this foam has a
lower moisture absorption capacity than the other evaluated foams. The TPS-Es
40 presented a higher initial absorption rate (K1 lower) and lower absorption
capacity (K2 higher) than TPS foam, which also indicates the influence of porosity
and irregular outer layer on the absorption of moisture in the initial times.

18
 A

T
R IP
SC
B

U
N
A
M
ED
PT

Fig. 6 - Moisture absorption of TPS foam, TPS-Ac and TPS-Es foams at 90% RH.
E
CC

Table 3 - Peleg constants K1 and K2 of all analyzed TPS foams.

Samples K1 K2
TPS 86.69 5.89
TPS Ac.10 187.75 6.17
A

TPS Ac.20 342.11 6.75

TPS Ac.30 127.96 6.22
TPS Ac.40 81.34 5.59
TPS Es.10 122.46 6.57
TPS Es.20 170.01 6.47
TPS Es.30 156.14 7.36
TPS Es.40 85.67 6.38

19
3.5 Impact energy of the TPS foams
Fig. 7A shows the property of the impact resistance of the TPS-Ac foams,
correlating this with the foam density, which has already been presented
previously (Table 2). Density and impact strength are properties that have
correlation, since a foam with more density tends to have a more stable and
compact internal structure and a more dense outer structure. Consequently,
these characteristics make the foam more impact resistant. The results show that

T
both the density and the impact resistance increased with the amount of 6.67%

IP
and 13.34% of acetylated starch in the TPS foams. As shown in Fig. 3, the TPS-

R
Ac 10 and TPS-Ac 20 foams have a denser outer layer and a more compact inner
layer, which makes them denser. Consequently, this more compact structure

SC
makes these foams more resistant to impact (Bergel et al., 2018; Martins and
Santana, 2016). Foams with 20% of acetylated starch have similar impact

U
strength to that found for TPS foam. However, in the proportion of 26.67% of
N
acetylated starch there was a decrease in the impact strength compared to
normal TPS. This result is in agreement with the structure of this material seen in
A

Fig. 3, because the foam presents thin and fragile outer layer (Guan, Fang, &
M

Hanna, 2004; Guan and Hanna, 2006).

The density and impact resistance of the TPS-Es foams are shown in Fig. 7B. It
ED

could be seen that all TPS-Es foams analyzed had higher impact strength
compared to TPS foams. The TPS-Es 20 and TPS-Es 30 presented the highest
PT

impact strengths, 16.98 and 16.86 J/m respectively. Zuo et al. (2016) states that
the presence of modified starch decreases the crystallinity of extruded starch
foams, which results in more flexible foams. More flexible foams tend to have
E

greater impact strength (Bergel et al., 2018; Martins & Santana, 2016). TPS-Es
CC

40 showed a decrease in its impact resistance compared to other TPS-Es foams,

probably due to its more irregular structure explained previously. The densities of
A

the TPS-Es 10, TPS-Es 20 and TPS-30 foams were also increased in relation to
the TPS. This is probably due to the more compact inner layer of these foams
(Guan et al., 2004). The TPS-Es 40 foam had a density similar to normal TPS.

20
 A

T
R IP
SC
B

U
N
A
M
ED
PT

Fig. 7 - The impact energy (gray bars) and the density (black line) TPS foam, TPS-Ac and TPS-
Es foams.
E
CC

4. Conclusions
In this paper the effect of acetylated starch and esterified starch on TPS foams
was studied. TPS foams with 6.67% and 13.34% w/w of acetylated starch and
A

TPS foams containing 6.67%, 13.34% and 20% w/w of starch esterified with
maleic anhydride presented lower water absorption, lower moisture absorption,
higher density and greater impact resistance. This improvement in the properties
of the foams without having to use a second processing (such as the use of
coating) constitutes an advantage of this material. However, foams with more

21
acetylated starch (20% and 26.67% w/w) and more esterified starch (26.67%
w/w) showed irregular structures (more porous) and thinner outer layer.
Consequently, these foams presented higher water absorption and lower impact
resistance. The most satisfactory results were obtained by the TPS-Ac 20
(13.34% w/w of acetylated starch) and TPS-Es 30 (20% w/w of esterified starch),
as they showed stable structures, good impact resistance and were the two
foams that less absorbed water and moisture. Although the inclusion of modified
starches in these proportions has improved some properties of the foams, the

T
water absorption of these foams still is high in comparison to EPS. Therefore

IP
these materials still do not meet the requirements needed to be used as packages

R
for moist food. Further studies should be done to improve these parameters.

SC
Acknowledgments
The authors thank the National Council for Scientific and Technological

U
Development (CNPQ), the Laboratory of Polymeric Materials (LAPOL), the post
N
graduated program of Materials Engineering (PPGEM) and the Federal
University of Rio Grande do Sul (UFRGS) for the support. The authors also thank
A

Carlos Avelleda and the Federal Institute of Education, Science and Technology
M

of Rio Grande do Sul (IF-RS), for assistance with the FTIR spectra.
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