Starch/Stärke 2015, 67, 213–224 DOI 10.1002/star.

201400201 213

REVIEW

Gelatinization and rheological properties of starch

Yongfeng Ai 1 and Jay-lin Jane 2

1
Department of Food Science and Human Nutrition, Michigan State University, East Lansing, MI, USA
2
Department of Food Science and Human Nutrition, Iowa State University, Ames, IA, USA

Native and modified starches are important raw materials used in the industry. Gelatinization Received: October 10, 2014
and rheological properties of starch are primary physicochemical properties to determine its Revised: November 17, 2014
applications. Starch gelatinization refers to a process that starch loses the native order and crystalline Accepted: November 19, 2014
structure of the granules and becomes amorphous. Key rheological properties of starch include
pasting property, viscosity of starch paste, and rheological features of starch gel. In this review,
gelatinization and rheological properties of native starches from different botanical sources are
compared and impacts of other ingredients, including sugars, salts, and lipids, on the properties are
summarized. The review also covers current understandings of the gelatinization and rheological
properties of modified starches with different structures. The information provided will be useful
for the applications of starch in the industry as well as fundamental research in this field.

Keywords:
Starch / Gelatinization property / Pasting property / Viscosity / Starch gel

1 Introduction packed in a monoclinic unit cell, and the B-type starch,

Starch, the major form of carbohydrate storage in green
plants, is mainly found in seeds, roots, tubers, stems, leaves,
and fruits. Starch is synthesized in amyloplasts as granules
with different shapes and sizes in different plants and
organs [1]. Starch is composed of two major glucans: amylose
and amylopectin. Amylose is an essentially linear polymer,
consisting of a 1–4 linked D-glucopyranose with a few a 1–6
branch linkages [2], whereas amylopectin is a highly
branched polymer, consisting of about 5% a 1–6 branch
linkages [3]. The amylose content of starch varies: waxy,
normal, and high-amylose starch consist of 0–8%, 20–30%,
and more than 40% amylose, respectively [4, 5]. Branch
chains of amylopectin form double helices and contribute to
the crystalline structure of the granules, whereas amylose is
amorphous and interspersed among amylopectin mole-
cules [6]. Depending on the branch-chain length (BCL) of
amylopectin, native starch granules display different X-ray
diffraction patterns: A-, B-, or C-type [3, 7]. The A-type
polymorphic starch, consisting of more short branch-chains
(A and B1 chains) in the amylopectin, has the double helices
Correspondence: Dr. Yongfeng Ai, Department of Food Science
and Human Nutrition, Michigan State University, East Lansing, MI
48824, USA
E-mail: yongfengai@gmail.com
consisting of more long branch-chains (B2, B3, and B4
chains), packed in a hexagonal unit cell [8]. The C-type is a
mixture of the A- and B-type polymorphs [8, 9]. Starches from
some mutants, such as maize ae mutant, also have
intermediate components (IC). The IC have molecular
weights similar to amylose but have branched structures,
with BCL longer than amylopectin. High-amylose maize
starch can have up to 52% IC [5]. Besides the glucan
molecules, lipids (<1.5%) and proteins (<0.5%) are also
found in starch granules as minor components [10, 11].
Starch is an important raw material used in the food and
other industries and is commonly modified to improve its
functional properties. Native and modified starches have
wide applications [12–14]: As a gelling agent, a thickener, an
emulsifier, and an encapsulating agent in food products; as a
flocculation and retention aid, a sizing agent, a coating agent,
and an adhesive in the paper industry; as a printing thickener
and a warp sizing agent in the textile industry; and as a fluid
loss control additive in subterranean drilling. Starches are
chosen for different applications on the basis of their
functional properties. Gelatinization and rheological proper-
ties are the major functional properties of starch to
determine its applications. Gelatinization is a process that
Colour online: See the article online to view Figure 1 in colour.

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214 Y. Ai and J.-L Jane
starch transforms from ordered semicrystalline granules to
an amorphous state and loses the Maltese cross. Starch
gelatinization is normally achieved by heating starch with
water. After gelatinization, the amorphous starch readily
absorbs water and develops viscosity to form a paste. Upon
cooling, some starch pastes can develop gels. The difference
between starch paste and gel lies in that starch paste has
certain fluidity but starch gel has a defined shape without
fluidity [15]. Depending on the structure, starch exhibits
different deformation and flow behaviors responding to an
applied stress, which are known as the rheological properties
of starch [15]. The key rheological properties of starch
include the pasting property, the viscosity of starch paste, and
the rheological characteristics of starch gel.
This review aimed to summarize current understandings
of the gelatinization and rheological properties of native and
modified starches. Relationships between functional properties
and chemical structures of starch are discussed. The informa-
tion covered in this paper will be useful for various industrial
applications of starch as well as future research in this area.
2 Gelatinization property of starch
During gelatinization, crystalline double-helices of starch
chains dissociate and the granules lose the Maltese cross and
become amorphous. Starch gelatinization can be achieved by
heating starch in the presence of water or other plasticizers
(e.g., glycerol, ethylene glycol, and 1, 4-butanediol) [16–18],
or using alkaline solutions (e.g., NaOH and KOH) [19],
neutral salt solutions (e.g., CaCl2 and LiCl) [20], and solvents
like dimethyl sulfoxide (DMSO) [21]. In this review, we
mainly focus on the heating process.
2.1 Methods for the analysis of starch gelatinization
property
Many techniques are used to determine the gelatinization
temperature of starch, such as differential scanning
calorimetry (DSC) [22], polarized light microscopy equipped
with a hot stage [23], thermomechanical analysis [24], and
nuclear magnetic resonance spectroscopy [25], and other
methods for the degree of starch gelatinization, such as X-ray
scattering [17, 26] and Fourier transform infrared spectro-
scopy [27]. Among all these methods, DSC is the most
commonly used. Starch is heated with an adequate amount
of water in a DSC pan at a selected heating rate to accurately
measure both the gelatinization temperature and enthalpy
change (DH). Starch gelatinization DH reflects the energy
intake for the dissociation of crystalline double-helices in the
granules. To obtain consistent results of starch gelatinization
temperature and DH, the starch sample must contain at least
two times (w/w) of water. Without a sufficient amount of
water, the starch gelatinization peak broadens and shifts to a
ß 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Starch/Stärke 2015, 67, 213–224
higher temperature [28]. Without the presence of water or
other plasticizers, starch cannot be gelatinized and is
thermally decomposed at a temperature above 250 °C [29].
2.2 Factors influencing the gelatinization property of
native starch
Gelatinization properties of selected native starches of
different polymorphs have been reported, and the data are
shown in Table 1 [7]. A positive correlation between the
gelatinization temperature of starch and the BCL of
amylopectin reflects that long branch-chains of amylopectin
form thermally stable crystallites [7]. Although the amylo-
pectin of potato starch (B-type polymorph) has substantially
longer BCL than that of the A-type starches, the potato starch
exhibits a lower gelatinization temperature (To of 58.2 °C)
than most A-type starches. This is mainly attributed to the
fact that potato starch has phosphate-monoester derivatives
(0.09%) carrying negative charges. The negative charges of
the phosphate groups repel one another and destabilize the
double-helical structure of starch. The high-amylose
starches, Amylomaize V and Amylomaize VII (apparent
amylose-content of 52.0% and 68.0%, respectively), show
much higher conclusion gelatinization-temperatures (Tc of
112.6 °C and 129.4 °C, respectively) than the other starches
(Table 1), resulting from the presence of long-chain double-
helical crystallites of amylose and IC [30].
Effects of sugars, salts, and lipids on the gelatinization
property of native starch have been studied and reported. The
presence of simple sugars (e.g., sucrose, glucose, fructose,
and maltose) and maltodextrins (e.g., maltotetraose and
maltoheptaose) increases the gelatinization temperature and
DH of starch because the sugars bind with water and reduce
its availability for starch gelatinization [31–33]. It is
interesting to note that the presence of glycerol elevates
the gelatinization temperature and DH of starch for the same
mechanism [17]. When glycerol, ethylene glycol, or 1, 4-
butanediol is used as the sole plasticizer (100% concen-
tration in the added solution) for starch gelatinization, the
gelatinization temperature and DH of starch are substan-
tially larger than that with water [17, 18]. The results indicate
that glycerol, ethylene glycol, and 1, 4-butanediol are less
effective plasticizers than water, which are attributed to two
factors [17]: (1) the higher viscosity of those three
compounds, resulting from the larger molecular-weights,
retard their penetration into the starch granules; (2) their
molecules have weaker H-bonding capability than water.
Na2SO4 has been used as a stabilizer to control the
swelling of starch granules during chemical modifica-
tion [34]. The stabilization is attributed to the concept that
the sulfate ion (SO42
), having a high negative charge-
density, stimulates H-bond formation between water
molecules (structure-making effect) and repels hydroxyl
groups of starch to increase the gelatinization
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Starch/Stärke 2015, 67, 213–224 215

Table 1. Gelatinization properties of native starches with different polymorphic structures determined by differential scanning
calorimetry [7]

Type To (°C)a) Tp (°C) Tc (°C) Range (°C) DH (J/g)

A-type starch
Normal maize 64.1  0.2 69.4  0.1 74.9  0.6 10.8 12.3  0.0
Waxy maize 64.2  0.2 69.2  0.0 74.6  0.4 10.4 15.4  0.0
du Waxy maize 66.1  0.5 74.2  0.4 80.5  0.2 14.4 15.6  0.2
Normal rice 70.3  0.2 76.2  0.0 80.2  0.0 9.9 13.2  0.6
Waxy rice 56.9  0.3 63.2  0.3 70.3  0.7 13.4 15.4  0.2
Sweet rice 58.6  0.2 64.7  0.0 71.4  0.5 12.8 13.4  0.6
Wheat 57.1  0.3 61.6  0.2 66.2  0.3 9.1 10.7  0.2
Barley 56.3  0.0 59.5  0.0 62.9  0.1 6.6 10.0  0.3
Waxy amaranth 66.7  0.2 70.2  0.2 75.2  0.4 8.5 16.3  0.2
Cattail millet 67.1  0.0 71.7  0.0 75.6  0.0 8.5 14.4  0.3
Mung bean 60.0  0.4 65.3  0.4 71.5  0.4 11.5 11.4  0.5
Chinese taro 67.3  0.1 72.9  0.1 79.8  0.2 12.5 15.0  0.5
Tapioca 64.3  0.1 68.3  0.2 74.4  0.1 10.1 14.7  0.7
B-type starch
ae Waxy maize 71.5  0.2 81.0  1.7 97.2  0.8 25.7 22.0  0.3
Amylomaize V 71.0  0.4 81.3  0.4 112.6  1.2 41.6 19.5  1.5
Amylomaize VII 70.6  0.3 N.D.b) 129.4  2.0 58.8 16.2  0.8
Potato 58.2  0.1 62.6  0.1 67.7  0.1 9.5 15.8  1.2
Green leaf canna 59.3  0.3 65.4  0.4 80.3  0.3 21.0 15.5  0.4
C-type starch
Lotus root 60.6  0.0 66.2  0.0 71.1  0.2 10.5 13.5  0.1
Green banana 68.6  0.2 72.0  0.2 76.1  0.4 7.5 17.2  0.1
Water chestnut 58.7  0.5 70.1  0.1 82.8  0.2 24.1 13.6  0.5

a) To: onset temperature; Tp: peak temperature; Tc: conclusion temperature; range of gelatinization: Tc
To; DH: enthalpy change.
b) N.D.: Not detectable.

temperature [20, 35]. Anions with a hydrophobic moiety and
small charge-densities (e.g., SCN
and I3
), however, can
break H-bonds to increase free water (structure-breaking
effect) and also form helical complexes with starch chains to
reduce the gelatinization temperature and DH of starch [20].
Cations with large charge-densities, such as Liþ, Ca2þ, and
Mg2þ, also have structure-making effects on water. There-
fore, at a low concentration, their chloride salts increase the
gelatinization temperature and DH of starch [20, 36]. At a
higher concentration, however, those cations interact with
the hydroxyl groups of starch and release heat, which
destabilize the crystalline structure of starch and decrease
the gelatinization temperature and DH [20]. Saturated
solutions of LiCl and CaCl2 have been used for the surface
gelatinization of starch granules [37].
DSC thermograms of normal cereal starches (e.g., maize
and wheat) show another endothermic peak at a temperature
above 90 °C, which corresponds to the dissociation of
amylose-lipid complex (ALC) [38]. Addition of lipids to
normal and high-amylose starch results in a larger ALC peak,
but this phenomenon is not observed for waxy starch [38, 39].
The dissociation temperature of ALC generally increases
with the chain length of the fatty acid, but decreases with the
number of double bonds of the fatty acid [38].
2.3 Gelatinization property of modified starch
Native starch is commonly modified to achieve desirable
functional properties for specific industrial applications.
Modified starch can be produced using chemical, physical, or
enzymatic methods. Gelatinization properties of represen-
tative chemically- and physically-modified starches in
comparison with their respective control starches are shown
in Table 2. For practical use, starch generally undergoes mild
acid-hydrolysis to obtain acid-thinned starch with a targeted
viscosity. Compared with that of the control starch, the
gelatinization properties of acid-thinned starch do not show a
clear trend of changes (Table 2) [40–42], which is attributed to
different hydrolysis conditions (e.g., acid concentration,
incubation temperature and time) and various types of starch
used in the studies.
Gelatinization properties of oxidized and cross-linked
starch depend on the level of modification (Table 2). At a low
oxidation level (e.g., 3% active chlorine concentration), the
gelatinization properties of oxidized starch show incon-
sistent changes compared with that of the control starch [43–
45]. At a high oxidation level (e.g., 5% active chlorine
concentration), the oxidized starch loses some crystalline
structure and possesses carboxyl groups repelling one

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216 Y. Ai and J.-L Jane Starch/Stärke 2015, 67, 213–224

Table 2. Gelatinization properties of selected modified starches in comparison with the control starch

Starch gelatinization property

Type Toa) Tp Tc DH References

Chemically-modified starch
Acid-thinned —b) — — — [40–42]
Oxidized
Low level — — — — [43–45]
High level #c) # # # [44, 46]
Cross-linked
Low level # # # # [47, 48]
High level "c) " " — [34, 47, 48]
Acetylated (DSd) <0.2e)) # # # # [49]
Cationic # # # # [50]
Hydroxypropylated (MSf) <0.17e)) # # # # [51]
Phosphorylated # # # # [52]
Carboxymethylated # # # # [53]
Octenyl succinic (DSd) <0.058e)) # # # # [54]
Physically-modified starch
Annealed " " " — [55]
Heat-moisture treated " " " — [56]
High hydrostatic-pressure treated — — — # [57–59]
Radiation treated — — — # [60–63]

a) To: onset temperature; Tp: peak temperature; Tc: conclusion temperature; DH: enthalpy change.
b) Discrepant results are shown in the literature.
c) #: A smaller value compared with that of the control starch; ": A larger value compared with that of the control starch.
d) DS: degree of substitution.
e) Representative values found in the literature.
f) Molar substitution.

another and, thus, displays a lower gelatinization temper-
ature and DH [44, 46]. Lightly cross-linked starch exhibits a
slightly lower gelatinization temperature and DH than the
control starch, whereas highly cross-linked starch displays a
higher gelatinization temperature [34, 47, 48].
Starch substituted with chemical derivatives, including
acetyl [49], cationic [50], hydroxypropyl [51], phosphate
(monoester) [52], carboxymethyl [53], and octenyl succinic
groups [54], displays a lower gelatinization temperature and
DH than the control starch (Table 2) because the
incorporations of the chemical derivatives destabilize the
crystalline structure of starch granules.
Starch modified using hydrothermal treatments, includ-
ing annealing and heat-moisture treatment (HMT), displays
an increased gelatinization temperature (Table 2) [55, 56].
Compared with that of the control starch, the gelatinization
temperature range of annealed starch is narrower, whereas
that of the HM-treated starch is broader. Annealed or HM-
treated starch, in general, exhibits an increased gelatiniza-
tion DH [55, 56]. But if the incubation temperature is above
starch gelatinization temperature during the treatment, it
can cause partial gelatinization of starch and decrease the
gelatinization DH [55, 56]. Starch subjected to high hydro-
static-pressure treatment (HHPT) is partially or fully
gelatinized and, thus, the treated starch displays a reduced
gelatinization DH (Table 2) [57–59]. The gelatinization
temperatures of HHP-treated starch show inconsistent
changes [57–59]. Starch subjected to gamma radiation [60],
electron beam [61], UV light [62], or microwave [63] treat-
ment exhibits a smaller gelatinization DH than the control
starch, indicating that the radiation treatments damage the
crystalline structure of starch granules. The gelatinization
temperatures of radiation-treated starch vary, depending on
the radiation dosage and starch source (Table 2) [60–63].
Unlike chemically- and physically-modified starch,
enzymatically-modified starch is much less studied.
Starches subjected to different enzyme treatments possess
different gelatinization properties. Normal maize starch
hydrolyzed by porcine pancreatic a-amylase (PPA) with up
to 27% hydrolysis displays a similar gelatinization temper-
ature and DH to the control starch, which is attributed to
PPA simultaneously hydrolyzing the crystalline and
amorphous structures of starch granules [64, 65]. With
further hydrolysis, the starch exhibits a reduced gelatiniza-
tion DH but varied gelatinization temperatures [64, 66].
Starches treated with other enzymes, including a-amylase
from Rhizomucor sp. [64] and Bacillus licheniformis [67], a-1,
4-glucanotransferase from Thermotoga maritima [68], and a
bacterial glucoamylase [69], exhibit increased gelatinization
temperatures but decreased DH, resulting from the fact that

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Starch/Stärke 2015, 67, 213–224
these enzymes prefer to hydrolyze starch crystallites of less
thermal-stability or with shorter branch-chains [70].
3 Rheological property of starch
Rheological property of a material is defined as the
deformation and flow behaviors responding to a stress [15].
In the characterization of rheological property of starch,
viscosity is an important parameter because starch is often
utilized as a thickener in different applications. Viscosity
measures the resistance of a fluid or semifluid to flow when a
shear stress is applied [15]. A native-starch suspension, even
at a high concentration (35–40%, w/w), displays a low
viscosity at the ambient temperature. After heating to above
the gelatinization temperature, starch granules lose crystal-
line structure, absorb water, swell, some disperse, and
develop significant viscosity. This process of viscosity
development is known as starch pasting. The viscosity of
the resultant starch paste determines the thickening power
of starch for various applications. After cooling and storage,
some starch pastes (e.g., normal wheat and maize) at an
adequate concentration (6%, w/w) can form gels with a
defined shape without fluidity, reflecting the concept that
starch molecules within granules form networks to
immobilize water and exhibit a viscoelastic property. Some
starch pastes (e.g., waxy maize, tapioca, and potato), however,
remain as pastes or form rather weak gels at a higher
concentration. Rheological characteristics of starch paste and
gel depend on many factors, including the chemical
structure of starch, starch concentration, pasting conditions
(e.g., temperature, shear rate, and heating rate), and storage
conditions (temperature and time).
3.1 Pasting property of native starch
Pasting properties of starch can be measured using an
amylograph, such as Brabender Amylograph and Rapid
Visco-Analyzer (RVA) [71], or using a dynamic rheometer in
a flow temperature ramp mode [72, 73]. Pasting properties of
selected native starches determined using an RVA are shown
in Table 3 and Fig. 1 [7]. Waxy maize and waxy rice starches
display lower pasting-temperatures (69.5 and 64.1 °C,
respectively) but higher peak-viscosities [205 and 205 Rapid
Viscosity Unit (RVU), respectively] than the normal maize
and rice starches (82.0 and 79.9 °C, 152 and 113 RVU,
respectively). Amylopectin is the primary component of
starch responsible for the swelling power and viscosity
development of starch during cooking, whereas amylose,
particularly with the presence of lipids, tends to intertwine
with amylopectin and restrict the swelling of starch granules.
A negative correlation between the peak viscosity and the
amylose content of starch has been reported [74, 75]. During
cooling, amylose interacts with other starch molecules and
ß 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
217
forms networks, which substantially contributes to the
setback viscosity. Consequently, normal maize and rice
starches exhibit greater setback-viscosities (74 and 64 RVU,
respectively) than their waxy counterparts (16 and 16 RVU,
respectively).
Minor components of starch granules, such as lipids and
phosphate-monoester derivatives, remarkably affect the
pasting property. ALC formed in starch during cooking
renders entanglements with amylopectin molecules and
restricts the swelling of granules, which results in a higher
pasting-temperature and a lower peak-viscosity. Wheat and
barley starches consist of larger amounts of phospholipids,
which readily complex with amylose [7]. Consequently, these
two starches exhibit higher pasting-temperatures and lower
peak-viscosities than the other normal cereal starches
(Table 3 and Fig. 1). When the endogenous lipids of wheat
starch are removed using a detergent (e.g., sodium dodecyl
sulfate), the starch displays a pasting temperature and peak
viscosity similar to tapioca and waxy maize starch [10, 38]. In
contrast, the phosphate-monoester derivatives of potato
starch carry negative charges, repel one another, and
enhance the swelling of starch granules, which result in a
substantially lower pasting-temperature (63.5 °C) and higher
peak-viscosity (702 RVU) (Table 3 and Fig. 1). The
remarkably great peak-viscosity of potato starch is also
contributed by its large granule sizes (diameter up to 75 mm).
Addition of sugars, including sucrose, glucose, fructose,
maltose, galactose, and lactose, increases the viscosity of
starch, which is attributed to the water-binding ability of the
sugars [76–78]. At a low concentration (<1.0%, w/w), salts
display minimal effects on the pasting property of most
native starch except potato starch [54, 79, 80]. Salts
substantially decrease the viscosity of potato starch because
the cations of salts mask the negative charges of the
phosphate-monoester derivatives and reduce the charge
repulsion [80]. Addition of lipids reduces the viscosity of
normal starch and produces a short paste because of the ALC
formation as discussed earlier, but little effect is observed for
waxy starch because of lacking amylose [38].
3.2 Viscosity of native starch paste
Viscosity of a starch paste can be measured using a
viscometer, including capillary flow, orifice, falling ball,
and rotational type, or using an amylograph [81]. Viscosity of
a starch paste usually displays a non-Newtonian feature: the
shear stress does not increase linearly with the increase in
shear rate. The shear stress of starch paste can be expressed
as a function of shear rate by fitting them into different
models, such as power law, Herschel–Bulkley, and Bingham
model [82]. Viscosity of a starch paste is also thixotropic
(shear thinning): It exhibits a decreased viscosity with
respect to shear rate and time [83]. Also, viscosity of a starch
paste increases with starch concentration but decreases
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218 Y. Ai and J.-L Jane Starch/Stärke 2015, 67, 213–224

Table 3. Pasting properties of native starches analyzed using a Rapid Visco-Analyzer (RVA) with 8% (dry starch basis) starch content [7]

Viscosity (RVU)a)

Starch Pasting temperature (°C) Peak Hot paste Final Setback

Normal maize 82.0 152 95 169 74

Waxy maize 69.5 205 84 100 16
du Waxy maize 75.7 109 77 99 22
ae Waxy maize 83.2 162 150 190 40
Normal rice 79.9 113 96 160 64
Waxy rice 64.1 205 84 100 16
Sweet rice 64.6 219 100 128 28
Wheat 88.6 104 75 154 79
Barley 91.2 88 58 116 58
Waxy amaranth 70.2 125 75 86 11
Cattail millet 74.2 201 80 208 128
Chinese taro 73.1 171 88 161 73
Tapioca 67.6 173 61 107 46
Lotus root 67.4 307 84 138 54
Potato 63.5 702 165 231 66
Mung bean 73.8 186 161 363 202
Green banana 74.0 250 194 272 78
Water chestnut 74.3 61 16 27 11

a) RVU: Rapid Viscosity Unit.

with starch amylose content and determination temper- rates. A dynamic rheometer can evaluate the storage
ature [83–85]. modulus (G0 ), the loss modulus (G00 ), and the loss tangent
(tan d ¼ G00/G0 ) of a starch gel. G0 measures the deformation
3.3 Gel formation of native starch energy recovered per cycle of deformation, representing the
elastic behavior of the gel; G00 measures the energy dissipated
Different methods have been used to characterize the as heat per cycle of deformation, representing the viscous
rheological property of a starch gel. The most frequently used behavior. A small tan d (G0 is much larger than G00 ) indicates
methods include: (1) determination of starch gel strength that the deformation is essentially recoverable and the starch
using a texture analyzer, which provides a “single-point” gel is stiff, behaving more like a solid; whereas a large tan d
measurement; (2) dynamic modulus analysis of starch gel (G0 is much smaller than G00 ) reflects that the energy used to
using a dynamic rheometer, which allows continuous deform the gel is dissipated viscously and the starch gel is
assessment of starch gel at various temperatures and shear less stiff, behaving more like a liquid [15, 86].

250 100 100

A 700 B
200 80 600 80
Temperature (°C)

500
Temperature (°C)
Viscosity (RVU)

Viscosity (RVU)

150 60 60
400

100 40 300 40

200
50 20 20
100

0 0 0 0
0 4 8 12 16 20 0 4 8 12 16 20
Time (min) Time (min)
Normal maize Waxy maize Normal rice Chinese taro Tapioca Lotus root
Waxy rice Wheat Barley
Amylomaize V Amylomaize VII Temp. Potato Temp.

Figure 1. Pasting properties of native starches analyzed using a Rapid Visco-Analyzer (RVA) with 8% (dry starch basis) starch content [7]. A:
representative cereal starches; B: representative root and tuber starches. RVU: Rapid Viscosity Unit.

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Starch/Stärke 2015, 67, 213–224
The formation of a starch gel from a paste is a result of the
interactions between amylose and amylopectin molecules in
the granules and the formation of networks to hold water in
the swollen granules [87, 88]. The short-term development of
starch gel strength or stiffness after cooking is primarily a
result of amylose gelation [89, 90]. Native starch with a
greater amylose-content tends to develop a stronger gel at a
faster rate [91–93]. The strength or stiffness of a starch gel
continues to increase during storage, which is a result of the
recrystallization of amylopectin [89, 94, 95].
Swollen starch granules with integrity, which can fill up a
container, are essential for the formation of a strong gel [38, 88,
94, 96]. Normal maize and pea starches can form a strong gel at
6–8% (w/w) concentration, whereas waxy maize, tapioca, and
potato starches fail to form a gel at the same concentration [38,
85, 88]. The differences can be ascribed to the fact that the
granules of waxy maize, tapioca, and potato starch readily swell
and disperse during cooking because of lacking ALC formation
to maintain the integrity of swollen granules (Table 3 and
Fig. 1). Addition of soy lecithin, oleic acid, or linoleic acid (10%,
w/w, dry starch basis) to tapioca starch before cooking
facilitates the gel formation at 8% (w/w) starch concentration
because the formed ALC leads to controlled swelling of the
starch granules and maintains the integrity [38].
Addition of sugars, including sucrose, glucose, fructose,
and maltose, in general, reduces the gel strength and G0 of
sago starch (6% starch, w/v) [97]. The effects can be
attributed to restricted granule swelling resulting from water
binding with the sugars. Salt solutions (0.5 M) that increase
the gelatinization temperature and DH of starch, including
Na2SO4, MgCl2, CaCl2, NaCl, and KCl, increase the gel
strength of sago starch (6% starch, w/v). Salt solutions that
decrease the gelatinization temperature and DH of starch,
including NaI, NaSCN, KI, and KSCN, however, decrease the
gel strength of sago starch (6% starch, w/v) [35]. As discussed
earlier (Section 2.2.), Na2SO4, MgCl2, CaCl2, NaCl, and KCl
increase the water structure and stabilize the starch granules
at a low concentration (e.g., 0.5 M) [20], which favors the
formation of a strong gel; whereas NaI, NaSCN, KI, and
KSCN break the water structure, destabilize starch granules,
and cause dispersion of starch granules [20], which impedes
the gel formation.
3.4 Rheological property of modified starch
Rheological properties of representative chemically- and
physically-modified starches in comparison with their
respective control starches are summarized in Table 4.
Acid-thinned starch exhibits a reduced viscosity because of
the depolymerization of starch molecules (Table 4) [98–100].
Acid-thinned starch prepared using very mild acid-hydrolysis
displays increased gel strength or stiffness, which is ascribed
to the feature that limited acid-hydrolysis releases more
linear starch molecules for the gelation process [98–100].
ß 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
219
Starch obtained after prolonged acid-hydrolysis produces a
weak gel because of reduced molecular-weights [98–100].
Rheological properties of oxidized and cross-linked starch
depend on the level of modification (Table 4). Lightly
oxidized starch (e.g., <2% active chlorine concentration)
shows an increase in the peak viscosity (except potato starch),
which is attributed to the repulsion between the introduced
carboxyl groups and the cross-linking with the aldehyde
groups [43, 101]. Highly oxidized starch (e.g., 2–5% active
chlorine concentration) displays a decreased viscosity
because of the depolymerization of starch molecules [43,
45, 101, 102]. Oxidized cassava and barley starches display
lower gel-strength than the respective control starches,
resulting from the depolymerization of starch molecules and
charge repulsion [45, 103].
Lightly cross-linked starch displays an increased peak-
viscosity because of increased starch molecular-weights
(Table 4) [48, 104, 105]. Highly cross-linked starch, however,
shows an increased pasting-temperature and a decreased
viscosity because the extensive cross-linking inhibits the
swelling of starch granules [48, 104]. The paste of cross-linked
starch has improved stability towards thermal and mechanical
processing [106]. Therefore, cross-linked starch is a preferred
choice of thickeners and stabilizers used in food systems.
Cross-linked potato starch (using 80–500 ppm POCl3) forms a
gel with a larger G0 and a smaller tan d than the control starch,
suggesting improved gelling-ability of the modified starch [47].
But the gel-strength results of other starches cross-linked by
using 100 ppm POCl3 show inconsistent trends compared
with that of the control starch [107]. The discrepant results
suggest that different starches need different levels of cross-
linking for optimal functions.
Substitution of starch with chemical derivatives, in
general, renders the swelling of starch granules. Conse-
quently, the substituted starch displays a lower pasting-
temperature and a higher peak-viscosity than the control
starch, and the difference is more significant for the
chemical derivatives with charges [e.g., cationic, phosphate
(monoester), carboxymethyl, and octenyl succinic groups]
(Table 4) [49–52, 54]. If the derivatization reaction causes
severe disruption of starch granules and/or the derivatized
chemical groups carry charges, the modified starch can
develop viscosity in cold water. For example, carboxymethy-
lated starch with a high degree of substitution (DS) readily
develops viscosity in cold water and forms a clear solution [53,
108]. Other substituted starches, however, show the opposite
pasting profile. For example, acetylated starch with a DS
greater than 0.7 displays a much lower peak-viscosity than
the control starch, which is attributed to two factors: (1) the
loss of granular structure after the high DS modification; (2)
the esterification with acetyl groups increases the hydro-
phobicity of the starch and reduces the hydration
capacity [109]. Compared with the control starch, substi-
tuted-starch pastes display inconsistent changes in the
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220 Y. Ai and J.-L Jane Starch/Stärke 2015, 67, 213–224

Table 4. Rheological properties of selected modified starches in comparison with the control starch

Starch pasting property

Type Pasting Temperature Peak viscosity Hot paste viscosity Final viscosity Starch Starch gel References
paste strength or
viscosity stiffness

Chemically-modified starch
Acid-thinned —a) #b) # # # — [98–100]
Oxidized
Low level — "b) — — # # [43, 45, 101, 103]
High level — # # # # # [43, 45, 101–103]
Cross-linked
Low level — " — " N. A.c) — [47, 48, 104, 105, 107]
High level " # # # N. A.c) — [47, 48, 104, 107]
Acetylated (DSe) <0.2f)) # " — — — # [49, 110, 111]
Cationic # " — — N. A.c) — [50]
Hydroxypropylated (MSg) <0.17f)) # " — — " # [51, 112]
Phosphorylated # " — — N. A.c) # [52]
Carboxymethylated N. A.d) N. A.d) N. A.d) N. A.d) # # [53, 108]
Octenyl succinic (DSe) <0.058f)) # " " " N. A.c) — [54, 113]
Physically-modified starch
Annealed " # — — — " [114, 115, 117, 118]
Heat-moisture treated " # — — — — [115, 116–120]
High hydrostatic-pressure treated — — — — N. A.c) # [57, 58, 121]
Radiation treated — # # # # — [60–63, 122]

a) Discrepant results are shown in the literature.

b) #: A smaller value compared with that of the control starch; ": A larger value compared with that of the control starch.
c) N. A.: Not available because no data are found in the literature.
d) N. A.: Not available because carboxymethylated starch can be readily solubilized in cold water.

viscosity, depending on the modification method, DS, and
starch origin [108, 110–112].
Because chemical derivatization reactions disrupt the
granular structure of starch and cause great granular
swelling, and the derivatives interfere with the network
formation between starch chains, the substituted starch
usually forms a weaker gel than the control starch
(Table 4) [49–52, 108, 113]. Liu et al., however, report that
the gel strength of cationic high-amylose maize starch
increases with an increased DS because the modified starch
has a decreased gelatinization temperature and can be
gelatinized and swell at the boiling-water temperature, which
is favorable for the gel formation [50].
Annealed or HM-treated starch shows an increased
pasting-temperature and a decreased peak- and breakdown-
viscosity because annealing and HMT enhance associations
between starch molecules (Table 4) [114–116]. Annealed or
HM-treated starches show varied paste viscosities compared
with the control starch [117]. Because annealing and HMT
enhance molecular associations and restrict the swelling of
starch granules, the modified starch tends to preserve the
integrity of swollen granules after cooking. Consequently,
annealed or HM-treated starch generally forms a firmer gel
than the control starch, and the increasing effect appears to
be more obvious for native starch having a large swelling-
capacity, such as potato starch [114, 115, 118, 119]. But HMT
has also been reported to impede the gel formation of rice
and sweet potato starch [116, 120].
HHP-treated starches do not show a clear trend of changes
in the pasting properties compared with the control starch, and
the results are dependent on the starch source and treatment
condition (Table 4) [57, 58, 121]. HHP-treated (8.6% starch
suspension, 600 MPa, 15 min, 20–25 °C) normal wheat, maize,
and pea starches form weaker gels than the control starch,
resulting from the fact that the HHPT destroys the granular
integrity and reduces the swelling of starch [58].
Similar to acid-thinned starch, gamma radiation [60],
electron beam [61], UV light [62], or microwave [63] treated
starch displays a decreased viscosity of the paste because of
the depolymerization of starch molecules (Table 4). Pimpa
et al. report that sago starch treated with 10 or 15 kGy electron
beam radiation forms a firmer gel than the control starch,
but that treated with 20–30 kGy dosage produces a weaker
gel [122]. These results reflect the depolymerization and
cross-linking effects of radiation treatment on starch
granules [60].
Starches hydrolyzed by a-amylase from Bacillus amylo-
liquefaciens [123], b-amylase from Bacillus cereus [73], or

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Starch/Stärke 2015, 67, 213–224
isoamylase from Pseudomonas amyloderamosa [72] exhibit
decreased viscosities in comparison with the control starch.
The results are consistent with that of the acid-thinned and
radiation-treated starch as shown in Table 4. Normal rice
starch hydrolyzed by a-amylase from Bacillus licheniformis
fails to form a gel because of the depolymerization of starch
molecules [124].
4 Summary
In the past decades, tremendous research has been
conducted to advance our understandings of the gelatiniza-
tion and rheological properties of native starches and those
modified using chemical, physical, and enzymatic methods.
This review provides a summary of gelatinization and
rheological properties of native and modified starches with
different structures. In the industry, starch may be subjected
to a combination of different modifications to achieve
desirable functional properties. Physically- and enzymati-
cally-modified starches will attract more attention in the
future because the modification processes are chemical-free
or environment-friendly and the modified starches possess
unique properties.
The authors have declared no conflict of interest.
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