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Thermal, rheological, and structural behaviors of natural and modified

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Article  in  Journal of Thermal Analysis and Calorimetry · March 2013

DOI: 10.1007/s10973-012-2592-z

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J Therm Anal Calorim (2013) 111:2217–2222
DOI 10.1007/s10973-012-2592-z
Thermal, rheological, and structural behaviors of natural
and modified cassava starch granules, with sodium hypochlorite
solutions
Cleoci Beninca • Tiago André Denck Colman • Luiz Gustavo Lacerda
Marco Aurélio da Silva Carvalho Filho • Ivo Mottin Demiate •
Gilbert Bannach • Egon Schnitzler
Received: 12 April 2012 / Accepted: 9 July 2012 / Published online: 21 August 2012
Ó Akadémiai Kiadó, Budapest, Hungary 2012
Abstract The use of chemically modified starches is
widely accepted in various industries, with several appli-
cations. In this research, natural cassava starch granules
were treated with standard sodium hypochlorite solution at
0.8, 2.0, and 5.0 g Cl/100 g starch. The native and modi-
fied starch samples were investigated by means of the
following techniques: simultaneous thermogravimetry–
differential thermal analysis, which allowed us to verify the
thermal decomposition associated with endothermic or
exothermic phenomena; and differential scanning calo-
rimetry that was used to determine gelatinization enthalpy
as well as the rapid viscoamylographic analysis that pro-
vided the pasting temperature and viscosity. By means of
non-contact-atomic force microscopy method and X-ray
powder patterns diffractometry, it was possible to observe
the surface morphology, topography of starch granules, and
alterations in the granules’ crystallinity.
Keywords Cassava starch
Thermal analysis

Gelatinization
Enthalpy
Oxidized starch
C. Beninca
T. A. D. Colman
I. M. Demiate

E. Schnitzler (&)
UEPG-Universidade Estadual de Ponta Grossa, Av. Carlos
Cavalvanti, 4748, Ponta Grossa, PR 84030-900, Brazil
e-mail: egons@uepg.br
L. G. Lacerda
M. A. da Silva Carvalho Filho
UP-Universidade Positivo, Rua Prof. Pedro Viriato Parigot de
Souza, 5300, Curitiba, PR 81280-330, Brazil
G. Bannach
Faculdade de Ciências, UNESP-Universidade Estadual Paulista,
Bauru, SP 17033-260, Brazil
•
Introduction
Tropical roots and tubers are rich sources of starches,
vitamins, and minerals (traces), and they serve as either
subsidiary or subsistence food in parts of the tropical belt.
These roots and tubers crops contain 70–80 % water,
16–24 % starch, and small quantities (\4 %) of proteins
and lipids and other substances [1–4].
Cassava (Manihot esculenta, Crantz) is an important
vegetable crop in tropical regions, where on a food energy
production basis; it ranks fourth after rice, wheat, and corn
as a source of complex carbohydrates [5, 6].
Starch is a raw material of different botanical origins,
and it is the most important storage reserve carbohy-
drate in plants; it is used by the food, paper, chemical,
pharmaceutical, and textile industries, among many
others [6–8].
Starch, a semi-crystalline polymer, is composed of two
polysaccharides: amylose and amylopectin. Amylose, mostly
a linear chain, typically consists of up to 3,000 glucose
molecules interconnected primarily by a-1,4 glycosidic
linkages, and it is reported to contain a few branched net-
works. Amylopectin is a large branched polymer with link-
ages of a-1,4 that serve as the backbone and a-1,6 bridges
at the branching points. Unprocessed native starches are
structurally too weak and functionally too restricted for
application in today’s advanced technologies; processing is
necessary to engender a range of functionality [7, 8].
Modified starch production is an alternative that is in
continuous development to overcome one or more of the
limitations of native starches and thus to increase the utility
of this polymer for industrial applications. The starch
market has been growing steadily over the past few years,
leading to the search for products with specific character-
istics that support the requirements of the industry [7–9].
123
2218 C. Beninca et al.

Starches may be oxidized by different chemicals such as
bromine [10], potassium and ammonia persulphates [11],
potassium permanganate [12–14], hydrogen peroxide [6, 15],
and sodium hypochlorite [16, 20].
In the production of oxidized starch with sodium
hypochlorite in alkaline medium, two important modifica-
tions occur: the relatively bulky carboxyl (–COOH) and
carbonyl (=C=O) groups are introduced, together with
partial depolymerization of the starch chains. Oxidized
starches exhibit a significantly reduced hot viscosity
because of the breakdown of the starch granules beyond its
gelatinization temperature and increasing clarity [17].
For several years, many studies have been made with
starches [1–3], flour starches [4, 5], modified starches
[6–24], and starches grafted with synthetic polymeric
compounds [25], using thermoanalytic techniques, espe-
cially (differential scanning calorimetry) DSC, and many
others [25–28].
In this present study, natural cassava starch granules
were treated with standard sodium hypochlorite solutions
at 0.8, 2.0, and 5.0 g Cl/100 g starch. The thermal behav-
ior, pasting properties, and structural changes were studied
using the following techniques: TG–DTA, DSC, RVA,
XRD, and NC-AFM.
Experimental
Materials
All chemical products used in this study were of analytic
grade.
Modified starches with sodium hypochlorite solutions
were produced in the laboratory following the procedure
described in the literature [16]: a dispersion of starch at
40 % (m/v) in water was heated at 30 °C and stirred, and
pH was adjusted to 9.5 with NaOH 0.1 mol L-1. Standard
solution of sodium hypochlorite was added to this sus-
pension, until the chlorine mass/starch mass ratio was
adjusted to 0.8 %, and then maintained by stirring for
50 min. Afterward, the pH was adjusted to 7.0 with HCl
0.1 mol L-1, the suspension was filtered, and then washed
with distilled water until the ClO- ions are completely
eliminated; this solution was then dried at room tempera-
ture and kept in a desiccator over anhydrous calcium
chloride until constant mass. The same procedure was
adopted to produce starch modifications with NaClO at
2.0 % and at 5.0 %.
Methods
TG and DTA curves were recorded using a simultaneous
TG 60 system (Shimadzu) under an air flow at
100 mL min-1 and at a heating rate of 10 °C min-1. The
initial mass sample was about 9 mg. Alumina crucibles
were used for the TG and DTA experiments.
The DSC curves were recorded using a DSC 60 (Shima-
dzu) under an air flow at 100 mL min-1, and heating rate of
5 °C min-1. A 4:1 (water:starch w/w) mixture was prepared
and left for 2 h to equilibrate the moisture content; 10.0 lL
of each suspension was transferred to aluminum crucibles
which were sealed, and tests were carried out to study
gelatinization. The instrument was calibrated with Indium
99.99 % purity, m.p. = 156.6 °C, DH = 28.71 J g-1.
The pasting properties of the starch samples [16, 17]
were determined using RVA-4 (Newport Scientific Pvt.
Ltd., Australia). A suspension of 2.5 g (8 % moisture)
starch in 28 g of distilled water underwent a controlled

Fig. 1 TG-DTA curves: 40

100
120

a untreated cassava starch,

100
(a) 30 (b) 100
20 80
b cassava starch treated with 80 80
Mass loss/%

Mass loss/%

10 60
NaClO at 0.8 %, c cassava
DTA /μV
DTA /μV

60 60
0 40
starch treated with NaClO at 40 –10 40 20
2.0 %, and d cassava starch –20
20 0
treated with NaClO at 5.0 % –30
20
–20
0 Exo up –40 Exo up
0 –40
0 150 300 450 600 0 150 300 450 600

Temperature/ °C Temperature/ °C

250
100
(c) 200
100
(d) 250

80 80 200
Mass loss/%

Mass loss/%

150
150
DTA /μV
DTA /μV

60 60
100
100
40 40
50 50
20 20
0 0
0 0
Exo up Exo up
–50 –50
0 150 300 450 600 0 150 300 450 600

Temperature/ °C Temperature/ °C

123
Thermal, rheological, and structural behaviors 2219

heating and cooling cycle under constant stirring when it The non-contact-atomic force microscopy (NC-AFM)
was held at 50 °C for one min; heated from 50 to 95 °C at method was used to observe the surface of the starch
6 °C min-1, and held at 95 °C for 5 min; cooled to 50 at granules. This method according to the literature [26, 27]
6 °C min-1, and held at 50 °C for 2 min. allowed us to obtain micro-images with high resolution of
each sample, and the average roughness and particle size
Table 1 TG and DTA results: (a) untreated cassava starch, (b) cas- were determined. X-ray diffraction (XRD) powder patterns
sava starch oxidized with NaClO at 0.8 %, (c) cassava starch oxidized were obtained using Ultim 4 X-ray diffractometer (Riga-
with NaClO at 2 %, and (d) cassava starch oxidized with NaClO at ku), with parameters: Cu Ka radiation, k = 1.544 Å, with
5%
settings of 40 kV and 20 mA, and the relative crystallinity
Samples TG results DTA results was calculated [28].
Step Dm/% DT/°C Tp/°C

(a) 1st 12.3 30–137 98 (endo) Table 2 DSC results: (a) untreated cassava starch, (b) cassava starch
Stability – 137–279 – oxidized with NaClO at 0.8 %, (c) cassava starch oxidized with
NaClO at 2 %, and (d) cassava starch oxidized with NaClO at 5 %
2nd 68.4 279–347 309 (endo), 380 (exo)
3rd 19.2 347–532 525 (exo) Samples To/°C Tp/°C Tc/°C DHgel/J g-1
(b) 1st 7.2 30–128 100 (endo) (a) 55.8 65.1 76.4 13.3
Stability – 128–251 – (b) 60.9 67.6 77.8 16.2
2nd 67.4 251–379 312 (endo), 378 (exo) (c) 59.5 66.5 75.9 17.0
3rd 25.3 379–517 507 (exo) (d) 49.7 58.9 70.9 22.4
(c) 1st 8.8 30–129 98 (endo)
To ‘‘Onset’’ initial temperature, Tp peak temperature, Tc ‘‘endset’’ final
Stability – 129–227 –
temperature, DHgel gelatinization enthalpy
2nd 58.9 227–379 361 (exo)
3rd 32.2 379–455 444 (exo)
(d) 1st 7.9 30–135 101 (endo)
100
Stability – 135–204 – (a)
2000
2nd 58.1 204–339 337 (shoulder-exo)
90
3rd 33.9 339–424 (not determ.-exo)
1500 (b)

Temperature/°C
Viscosity/cP

Dm Mass loss (%), DT temperature range, Tp peak temperature 80

1000
70

500
60
(c)
(a) 0
(d) (e) 50
0 300 600 900 1200 1500
Time/sec
(b)
Fig. 3 RVA curves: a untreated cassava starch, b cassava starch
Heat flow/mW

treated with NaClO at 0.8 %, c cassava starch treated with NaClO at

2.0 %, d cassava starch treated with NaClO at 5.0 %, and e temperature
(c)
Table 3 RVA results: (a) untreated cassava starch, (b) cassava
starch oxidized with NaClO at 0.8 %, (c) cassava starch oxidized with
(d) NaClO at 2 %, and (d) cassava starch oxidized with NaClO at 5 %
Samples Pasting Viscosity Peak Setback/ Break/ Final
temperature/ peak/cP time/ cP cP viscosity/
0.5 °C sec cP
Exo up

40 50 60 70 80 90 100 (a) 67.2 2,118 360 696 1,335 1,479

Temperature/ °C (b) 73.3 1,502 552 384 495 1,391
(c) 66.4 243 328 – 243 0
Fig. 2 DSC curves: a untreated cassava starch, b cassava starch (d) 56.7 29 184 – 29 0
treated with NaClO at 0.8 %, c cassava starch treated with NaClO at
2.0 %, and d cassava starch treated with NaClO at 5.0 % cP Centipoises, sec seconds

123
2220 C. Beninca et al.

Results and discussion
The TG–DTA curves are shown in Fig. 1. All the TG
curves show mass losses in three stages: the first is due to
dehydration, with a corresponding endothermic peak in the
DTA curve.
The second and third mass losses are attributed to the
decomposition of organic matter with the corresponding
exothermic peaks (DTA) and the formation of final resi-
dues (ash). The untreated cassava starch (Fig. 1a) and the
one treated with NaClO at 0.8 % (Fig. 1b) showed a small
endotherm at the beginning of the second mass loss,
attributed to the low decompositions of amylose and
amylopectin—which did not occur with those treated with
NaClO at 2.0 and 5.0 % (Fig. 1c, d), because of the
reduction in the decomposition temperature.
The profiles of the TG curves of the third mass loss that
occurred are shown in Fig. 1c, d; this third mass loss is
attributed to the heat of the oven and the heat generated
by the burning of the sample (dynamic atmosphere of
synthetic air), as observed by the exothermic peaks in the
DTA curves. At this stage, two exothermic peaks
(Fig. 1a–c) are observed, which are superposed (Fig. 1d),
with shoulder at 337 °C. The TG–DTA results are shown
in Table 1.
Starch, when heated in the presence of excess water,
undergoes an order-to-disorder phase transition known as
‘‘gelatinization’’ over a temperature range characteristic of
the starch source or treatment. This phase transition is
associated with diffusion of water into the granule, water
uptake by the amorphous background region, hydration
and radial swellings of the starch granules, loss of bire-
fringence, loss of crystalline order, uptake of heat,
uncoiling and dissociation of double helices in the crys-
talline regions, and amylose leaching. The gelatinization
process, which is a function of the starch:water ratio, can
be studied by DSC [19].
A 4:1 (water:starch, w/w) mixture was prepared and
maintained for 50 min to equilibrate the moisture content.
The experiments were carried out in duplicate.
The DSC curves are shown in Fig. 2, and the main
objective is to observe the gelatinization process and cal-
culate the enthalpy for the untreated and treated samples.
The onset initial and endset or conclusion temperatures
(To and Tc), as well as the peak temperature (Tp), and gela-
tinization enthalpy (DHgel) are calculated and are shown in
Table 2.
The gelatinization enthalpy was lower for the untreated
sample (a) and increased gradually according to how the
samples were treated with NaClO solutions; samples (b),
(c), and (d).
The pasting properties of the samples were determined
by RVA analysis, and the corresponding curves are shown
in Fig. 3, with the main results being shown in Table 3.
The pasting temperature (RVA) was 67.2 °C for
untreated cassava starch, increased initially to 73.3 °C, and
then decreased gradually with higher concentrations of
NaClO. The higher viscosity peak was observed for the
untreated cassava starch which decreased with increases in
the concentration of NaClO. The behaviors of the samples
were similar to those at the peak temperature (Tp) in the
DSC curves.

Fig. 4 NC-AFM images: (a) (b)

a untreated cassava starch,
height difference height
difference 3.36 lm; b cassava
starch treated with NaClO at 3.36/ 2.51/
μm μm
0.8 %, height difference
2.51 lm; c cassava starch 0.00 0.00
treated with NaClO at 2.0 %,
5.00 15.00 5.00 15.00
height difference 3.20 lm; and
d cassava starch treated with 10.00 10.00 10.00 10.00

NaClO at 5.0 %, height 15.00 5.00 15.00 5.00

difference 3.40 lm
0.00 0.00

(c) (d)

3.40/
3.20/ μm
μm
0.00
0.00

5.00 15.00
5.00 15.00

10.00 10.00 10.00 10.00

15.00 5.00 15.00 5.00

0.00 0.00

123
Thermal, rheological, and structural behaviors 2221

By means of the NC-AFM technique, it was possible to
observe the action of NaClO in different concentrations on
the surface granules, Fig. 4. The untreated sample showed
few bulges and relatively smooth surface; with NaClO
treatment, absorption followed by rupture occurs. The
average size of the granules, as well as the average
roughness, was calculated, and the respective values are
shown in Table 4.
The XRD powder patterns of each sample are depicted
in Fig. 5.
According to the literature [28], using XRD technique, it
was possible to calculate the relative crystallinities of each
sample, which were (a) 22.63 %, (b) 24.70 %, (c) 25.20 %,
and (d) 20.42 %. These results are in agreement with those
Table 4 NC-AFM results: (a) untreated cassava starch, (b) cassava
starch oxidized with NaClO at 0.8 %, (c) cassava starch oxidized with
NaClO at 2 %, and (d) cassava starch oxidized with NaClO at 5 %
Sample Da/lm
(a) 8.26
(b) 7.62
(c) 8.41
(d) 11.62
Da Average diameter, Ra average roughness
in the literature [16], indicating no changes in the bire-
fringence of oxidized starch granules and the occurrence of
oxidation mainly in the amorphous region. These results
were in agreement with those of NC-AFM, Fig. 4 and the
average roughness (Tables 4, 5).
Conclusions
The study of thermal properties (TG–DTA, DSC) as well
as pasting properties (RVA), microscopy (NC-AFM), and
XRD powder patterns allowed us to delineate the behaviors
of the untreated cassava starches and under the action of
sodium hypochlorite with different concentrations.
Appreciable thermal stability was observed in the
untreated cassava starch, which decreased with higher
NaClO concentrations. The same behavior was observed in
the paste viscosity. The pasting temperature was directly
proportional to the peak temperature observed in the DSC
Ra/lm curves. The maximum viscosity (peak viscosity—RVA)
433.994 was inversely proportional to the gelatinization enthalpy
348.892 (DSC).
379.645
Acknowledgements The financial resources for this study were
582.803 provided by the Fundação Araucária-PR-Brazil, the FINEP-Brazil,
the CAPES-Brazil, and the CNPq-Brazil, which the authors gratefully
acknowledge.

(a)
References
(b)
Intensity/cps

1. Moorthy SN. Physicochemical and functional properties of

(c) tropical tuber starches: a review. Starch/Stärke. 2002;54:559–92.
2. Hoover R. Composition, molecular structure and physicochemi-
cal properties of tuber and root starches: a review. Carbohydr
(d) Polym. 2001;45:253–67.
3. Schuttleworth PS, Budarin V, Clark JH. Thermal investigation of
‘molten starch’. J Therm Anal Calorim. 2011;105:577–81.
10 20 30 40 50 60 70 4. Leivas CL, Costa FJOG, Almeida RR, Freitas RJS, Stertz SC,
2θ / ° Schnitzler E. Structural characteristics, physico-chemical, ther-
mal and pasting properties of potato (Solanum tuberosum, L.)
Fig. 5 XRD results: a untreated cassava starch, b cassava starch flour: study of different cultivars and granulometries. J Therm
treated with NaClO at 0.8 %, c cassava starch treated with NaClO at Anal Calorim. 2012. doi:10.1007/s10973-012-2395-2.
2.0 %, and d cassava starch treated with NaClO at 5.0 % 5. Haynes L, Schuenzel M. Flour starch thermal characteristics.
Modulated scanning calorimetric studies. J Therm Anal Calorim.
2011;106:261–6.
Table 5 Degree of relative crystallinity results: (a) untreated cassava 6. Costa FJOG, Almeida RR, Lacerda LG, Filho MASC, Bannach
starch, (b) cassava starch oxidized with NaClO at 0.8 %, (c) cassava G, Schnitzler E. Thermoanalytical study of native cassava starch
starch oxidized with NaClO at 2 %, and (d) cassava starch oxidized and treated with hydrogen peroxide. Alim Nutr. 2011;22:7–15.
with NaClO at 5 % 7. Beninca C, Demiate IM, Lacerda LG, Filho MASC, Ionashiro M,
Schnitzler E. Thermal behavior of corn starch granules modified
Sample Degree of crystallinity/%* by acid treatment at 30 and 50 °C. Ecl Quim. 2008;33:13–8.
8. Lacerda LG, Filho MASC, Demiate IM, Bannach G, Ionashiro M,
(a) 22.63
Schnitzler E. Thermal behaviour of corn starch granules under
(b) 24.70 action of fungal a-amylase. J Therm Anal Calorim. 2008;93:
(c) 25.20 445–9.
(d) 20.42 9. Rudnik E, Matuschek G, Milanov N, Kettrup A. Thermal stability
and degradation of starch derivatives. J Therm Anal Calorim.
* The degree of crystallinity was calculated as percentage 2006;85:267–70.

123
2222
10. Muhrbeck P, Eliasson AC, Salomonsson A-C. Physical charac-
terization of bromine oxidized potato starch. Starch/Stärke.
1990;42:418–20.
11. Harmon RE, Gupta SK, Johnson J. Oxidation of starch catalyzed
by persulfate. Starch/Stärke. 2006;23:197–9.
12. Takizawa FF, Silva GO, Konkel FE, Demiate IM. Characteriza-
tion of tropical starches modified with potassium permanganate
and lactic acid. Braz Arch Biol Technol. 2004;47:921–31.
13. Wurzburg OB. Modified starches: properties and uses. Boca
Raton: CRC; 1989.
14. Silva RM, Ferreira GF, Shirai MA, Haas A, Scherer ML, Franco
CML, Demiate IM. Caracterı́sticas fı́sico-quı́micas de amidos
modificados com permanganato de potássio/ácido lático e hipo-
clorito de sódio/ácido lático. Ciênc Tecnol Aliment. 2008;28:
66–77.
15. Zhang Y-R, Wang X-L, Zhao G-M, Wang Y-Z. Preparation and
properties of oxidized starch with high degree of oxidation.
Carbohydr Polym. 2012;87:2554–62.
16. Kuakpetoon D, Wang Y-J. Characterization of different starches
oxidized by hypochlorite. Starch/Stärke. 2001;53:211–8.
17. BeMiller J, Wistler R. Starch—chemistry and technology. 3rd ed.
Amsterdam: Elsevier; 2009.
18. Bicudo SCW, Demiate IM, Bannach G, Lacerda LG, Filho
MASC, Ionashiro M, Schnitzler E. Thermoanalytical study and
characterization of native starches of Paraná pine seeds (Arau-
caria angustiofolia, Bert O. Ktze) and European chestnut seeds
(Castanea sativa, Mill). Ecl Quı́m 2009;34:7–12.
19. Aggarwal P, Dollimore D. A comparative study of the degrada-
tion of different starches using thermal analysis. Talanta. 1996;
43:1527–30.
123
View publication stats
C. Beninca et al.
20. Soliman AAA, El-Shinnavy N, Mobarak F. Thermal behavior of
oxidized starch. Thermochim Acta. 1997;296:149–53.
21. Aggarwal P, Dollimore D. The effect of chemical modification on
starch studied using thermal analysis. Thermochim Acta. 1998;
324:1–8.
22. Aggarwal P, Dollimore D. Degradation of starchy food material
by thermal analysis. Thermochim Acta. 2000;357–8:57–63.
23. Aggarwal P, Dollimore D. A thermal analysis investigation of
partially hydrolyzed starch. Thermochim Acta. 1998;329:17–25.
24. Aggarwal P, Dollimore D, Heon K. Comparative thermal analysis
of two biopolymers, starch and cellulose. J Therm Anal. 1997;
50:7–17.
25. Kewtatip K, Tanrattanakul V, Mézaros K, Pavličević J, Budinski-
Simendić J. Thermal properties and morphology of cassava starch
grafted with different content of polystyrene. J Therm Anal
Calorim. 2010;102:1035–41.
26. Juszczak L, Fortuna T, Krok F. Non-contact atomic force
microscopy of starch granules surface. Part I. Potato and tapioca
starches. Starch/Stärke. 2008;55:1–7.
27. Juszczak L, Fortuna T, Krok F. Non-contact atomic force
microscopy of starch granules surface. Part II. Selected cereal
starches. Starch/Stärke. 2008;55:8–18.
28. Zhang L, Xie W, Zhao X, Liu Y, Gao W. Study on the mor-
phology, crystalline structure and thermal properties of yellow
ginger starch acetates with different degrees of substitution.
Thermochim Acta. 2009;495:57–62.