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Journal of Cereal Science 49 (2009) 371377

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Journal of Cereal Science


journal homepage: www.elsevier.com/locate/jcs

Rheological properties of starches with different amylose/amylopectin ratios


Fengwei Xie a, Long Yu a, b, *, Bing Su a, Peng Liu a, Jun Wang a, Hongshen Liu a, b, Ling Chen a
a
b

Centre for Polymers from Renewable Resources, ERCPSP, School of Light Industry and Food Science, SCUT, Guangzhou, China
CSIRO, Materials Science and Engineering, Melbourne, Vic 3168, Australia

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 2 October 2008
Received in revised form
3 January 2009
Accepted 5 January 2009

The rheological properties of corn starches with different amylose/amylopectin ratios (80/20, 50/50, 23/
77, and 0/100) were systematically studied by Haake rheometry. The starches were initially pre-compounded with water to designated moisture content levels using a twin-screw extruder. A single-screw
extruder with a slit capillary die was then used to characterize the shear stress and melt viscosity
characteristics of sample pellets, as a function of both moisture content (1927%) and extrusion
temperature (110140  C). The melts exhibited shear thinning behavior under all conditions, with the
power law index (0 < n < 1) increasing with increasing temperature and moisture content in the majority
of cases. The higher the amylose content, the higher is the viscosity (for example, h increases from
277 Pa s to 1254 Pa s when amylose content increases from 0% to 80% under a certain condition), which is
opposite to the sequence of molecular weight; amylopectin-rich starches exhibited increased Newtonian
behavior. These rheological behaviors are attributed to the higher gelatinization temperature of amyloserich starches, and in particular the multiphase transitions that occur in these starches at higher
temperatures, and the gel-ball structure of gelatinized amylopectin.
2009 Elsevier Ltd. All rights reserved.

Keywords:
Starch
Rheometry
Rheological
Amylose/amylopectin
Extrusion

1. Introduction
Extrusion cooking has been practiced for more than 50 years,
with early developments focused on the preparation of ready-toeat cereals (Harper, 1989). Some researchers have investigated the
effects of amylose content in starch or dough on the physical and
functional properties of their extruded products (Guha et al., 2003;
Matthey and Hanna, 1997). Others have analyzed viscoelastic
characterization of different biopolymers and their mixtures with
additives (Bhattacharya and Padmanabhan, 1992; Bhattacharya
et al., 1988; Seethamaju and Bhattacharya, 1994). More recently,
Chanvrier et al. (2007) investigated the effects of starch and protein
on the rheological properties of wheat our dough during processing at low hydration. Different viscosity models have been
proposed to describe the rheological properties of dough based on
the traditional power law function. For example, Jao et al. (1978)
derived a regression model for the die viscosity of soy dough by
considering the effects of temperature, shear rate and moisture
content; Bhattacharya and Hanna (1986, 1987) and Harper (1981)

* Corresponding author. Commonwealth Scientic and Industrial Research


Organization, Materials Science and Engineering, Gate 4, Normanby Rd, Clayton
South, Melbourne, Vic 3168, Australia. Tel.: 61 3 9545 2777; fax: 61 3 9544 1128.
E-mail address: long.yu@csiro.au (L. Yu).
0733-5210/$ see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jcs.2009.01.002

presented examples of viscosity models applied to cooked dough;


and Tomas et al. (1997) derived a regression viscosity model for
extruding rice our using a stepwise model starting from a power
law equation.
Due to environmental considerations and the shortage of oil,
starches are now attracting increased attention as raw materials in
the production of biodegradable plastics (Arvanitoyannis, 1999;
Signori et al., 2005; Soderqvist Lindblad et al., 2005). In addition,
the water requirements during the thermal processing of these
materials are normally lower than for conventional additives. There
are many reported investigations of the effects of starch type or
amylose/amylopectin ratio on the nal properties of starch-based
materials, including:
 Foams (Babin et al., 2007; Chinnaswamy and Hanna, 1988;
Della Valle et al., 1997; Fang and Hanna, 2001a,b; Guan et al.,
2005; Suknark et al., 1997).
 Sheets or lms (Fishman et al., 2006; Yu and Christie, 2005; Yu
et al., 2006).
 Lightweight concrete (Glenn et al., 1999).
 Injection-molded products (Funke et al., 1998; de Graaf et al.,
2003).
The melt rheology of starch-based materials has both scientic
and industrial importance, and thus it has been widely

372

F. Xie et al. / Journal of Cereal Science 49 (2009) 371377

investigated. For example, Llo et al. (1996) studied the effects of


extrusion conditions on the apparent viscosity of maize grits,
including the effects of melt temperature, shear rate, material
composition, and extrusion processing history. Willett et al. (1997)
reported that waxy corn starch exhibited shear thinning behavior,
becoming more Newtonian as either temperature or moisture
content was increased. Gonzalez et al. (2006) investigated the
effects of several factors including screw speed, die restriction (l/r)
and moisture content, together with corn endosperm hardness and
rice amylose content, on apparent melt viscosity using a Brabender
single-screw extruder. Recently, Thuwall et al. (2006) studied the
effects of amylose content, moisture content and starch/glycerol
ratio on the apparent viscosity of potato starch. The effects of
amylose content on reactive extrusion have also been studied
(Wing and Willett, 1997).
Corn starches have attracted particular scientic interests,
because different amylose/amylopectin content materials can be
obtained from natural, renewable resources, and they exhibit
multiphase transitions during thermal processing (Chen et al.,
2006, 2007; Liu et al., 2006). Previous studies have shown that
higher amylose-content starches exhibit superior strength and
toughness in the preparation of starch-based materials and in
producing modied starches by reactive extrusion (Cha et al., 2001;
Dean et al., 2007; Guan and Hanna, 2004; Guan and Hanna, 2006;
Miladinov and Hanna, 2000, 2001; Nabar et al., 2006; van Soest and
Borger, 1997; Yu and Christie, 2005; Yu et al., 2006; Zhou and
Hanna, 2004). However the extrusion of high-amylose starches is
more difcult than that of normal starches, partly due to the higher
die pressure and torque requirements due to the higher melting
temperature and viscosity of these starches (Liu et al., 2006;
Shogren, 1992; Shogren and Jasberg, 1994). In this work, the rheological properties of corn starches with different amylose/amylopectin ratios (80/20, 50/50, 23/77 and 0/100) were systematically
studied as functions of moisture content and extrusion temperature
using a Haake rheometer. The effects of different amylose/amylopectin ratios on the rheological behaviors will be discussed based
on their microstructures and gelatinization behaviors.
2. Experimental work
2.1. Materials
Four commercially available corn starches with different
amylose/amylopectin ratios were used in this experimental work:
 Gelose 80 (G80, 80/20), supplied by Penford (Australia).
 Gelose 50 (G50, 50/50), supplied by Penford (Australia).
 A normal corn starch (NC, 23/77), supplied by Huanglong Food
Industry Co. Ltd (P.R. China).
 A waxy corn starch (WC, 0/100), supplied by Shanxi Jinli
Industry Group Co. Ltd (P.R. China).
An infra-red heating balance (Model DHS-20) was used to
measure the moisture contents of the original starches during
heating to 110  C for 20 min. All formulations were prepared on
a dry weight basis.
2.2. Sample preparation
Starches were rstly premixed with water to achieve designated
moisture contents. A Haake parallel, co-rotating twin-screw
extruder (Rheomex PTW 24/40p, 30) with a rod die (nozzle L/
D 3, diameter 3 mm) was used to produce gelatinized starch
pellets at a screw speed of 90 rpm. The extruder heating barrel
comprises 10 sections. The highest temperature used during

compounding was 160  C, and the die temperature was kept at


105  C to avoid foaming. A gravimetric feeder was used to deliver
the materials into the extruder.
The moisture contents in the compounded pellets were
measured after heating the samples overnight at 130  C in
a vacuum oven.
2.3. Rheological measurements
Compounded pellets were used to study the rheological properties of various samples. A Haake Rheocord Polylab RC500p
incorporating a single-screw extruder (Rheomex 252p, 19, screw
2:1, L/D 25) with a slit capillary die (20  1 mm) was used to
measure the shear stress and apparent viscosity of samples under
different shear rates at specic temperatures. The screw speed was
varied between 30 and 180 min1, and normally six points were
recorded for each sample using the cutting and manual entry
measurement mode.
Apparent shear rates were calculated by:

6Q
WH 2

(1)

where g is the shear rate, Q is the volumetric ow rate (in cm3/s), W


is the slit width, and H is the slit height. Shear stress values were
calculated using the following equation:

H$DP
2L

(2)

in which s is the shear stress, DP is the pressure drop over the


capillary, and L is the slit length.
2.4. Differential scanning calorimetry
A PerkinElmer Diamond-I differential scanning calorimeter
(DSC) with an internal coolant (Intercooler 1P), nitrogen purge gas,
and stainless steel sample pans, was used to study the thermal
properties of samples with high moisture content over a high
temperature range (up to 350  C). The melting point and enthalpy
of indium were used for temperature and heat capacity calibrations,
respectively. The detailed methodology and a discussion of some
critical issues are presented elsewhere (Liu et al., 2006; Yu and
Christie, 2001).
3. Results and discussions
3.1. Effects of moisture content
Fig. 1 shows the results for shear stress and melt viscosity as
a function of shear rate for the various corn starches (G80, G50, NC,
and WC) with different moisture contents at an extrusion
temperature of 130  C. It can be seen that, for all moisture contents,
the apparent viscosity decreased with increasing shear rate, and
that, in general, it also decreased with increasing moisture content
in the range studied (1927%). Similar patterns have been observed
at different extrusion temperatures.
A strong power law dependence of apparent viscosity on shear
rate was observed for all the starch samples and measurement
conditions studied, and this dependence was linear on doublelogarithmic plots, indicating that the power law model of Bird et al.
(1960) could be used to describe the rheological behaviors of
starch-based materials:

h K gn1

(3)

F. Xie et al. / Journal of Cereal Science 49 (2009) 371377

10000

(27% mc)
(19% mc)

100000

1000

(23% mc)
(27% mc)

G80

10000

10

100

100
1000

(23% mc)
(27% mc)
(19% mc)

100000

(27% mc)
G50

10000

10

100

1000

(23% mc)
(27% mc)

NC
10

100

1000

Shear stress (Pa)

(19% mc)

100

10000

(19% mc)
(23% mc)
(27% mc)
(19% mc)

100000

1000

(23% mc)
(27% mc)

WC

10000

10

100

Shear rate (-s)

1000

Viscosity (Pas)

(27% mc)

1000000

Viscosity (Pas)

Shear stress (Pa)

10000

(23% mc)

10000

100
1000

Shear rate (-s)

(19% mc)

100000

1000

(23% mc)

Shear rate (-s)


1000000

10000

(19% mc)

Viscosity (Pas)

(23% mc)

1000000

Shear stress (Pa)

(19% mc)

Viscosity (Pas)

Shear stress (Pa)

1000000

373

100

Shear rate (-s)

Fig. 1. Effect of moisture content on shear stress and melt viscosity of various starches (extrusion temperature 130  C).

where h is the melt viscosity, K is the consistency, g is the shear rate,


and n is the pseudoplastic index. The corresponding consistency
and pseudoplastic index can be determined individually from the
intercept and the slope of each single straight line in the double-log
plots. For starch-based materials in this study, values of n are
between 0 and 1, and when n < 1, the apparent viscosity will
decrease with increasing shear rate and the materials will undergo
shear thinning (Tanner, 2000).

a function of shear rate. It can be seen that the apparent viscosity


generally decreased with increasing temperature from 110 to
140  C. A strong power law dependence of apparent viscosity on
shear rate is observed. For all the starch samples and measurement
conditions studied, the dependence of apparent viscosity on the
shear rate was linear on double-logarithmic plots, again indicating
that the power law model could describe the rheological behaviors
of the molten starches.

3.2. Effects of extrusion temperature

3.3. Effects of amylose content

Fig. 2 shows the effect of temperature on the rheological properties of the different starches at 23% moisture content, as

Fig. 3 shows the effect of amylose content on the shear stress


and melt viscosity of various samples at a moisture content of 23%

1000

1000000

100000

G80

10000

100

100
1000

10000

10

100

Shear rate (-s)

10

Shear stress (Pa)

Shear stress (Pa)

10000

110C
120 C
130 C
140 C
110C
120 C
130 C
140 C

100000

1000

WC

100

Shear rate (-s)

100
1000

10000

10

100

Shear rate (-s)

Fig. 2. Effect of temperature on shear stress and melt viscosity of various starches (moisture content 23%).

100
1000

Viscosity (Pas)

Viscosity (Pas)

1000

1000000

NC

10000

100
1000

Shear rate (-s)


10000

110C
120 C
130 C
140 C
110C
120 C
130 C
140 C

100000

1000

G50

10

1000000

10000

110C
120 C
130 C
140 C
110C
120 C
130 C
140 C

Viscosity (Pas)

100000

Shear stress (Pa)

10000

110C
120 C
130 C
140 C
110C
120 C
130 C
140 C

Viscosity (Pas)

Shear stress (Pa)

1000000

374

F. Xie et al. / Journal of Cereal Science 49 (2009) 371377

10000
G80
G50
NC
WS
G80
G50
NC
WS

100000

10000

1000

10

Viscosity (Pas)

Shear stress (Pa)

1000000

100
1000

100

Shear rate (-s)


Fig. 3. Effect of amylose content on shear stress and melt viscosity of various starches
(moisture content 23%; extrusion temperature 130  C).

and extrusion temperature of 130  C, as a function of shear rate. It


was found that higher amylose content resulted in a higher
apparent viscosity over the same shear rate range. For example, at
a shear rate of 100 S1, h is 277, 635, 1008, and 1254 Pa s for WC, NC,
G50, and G80 respectively under the condition of 23% moisture
content and 130  C extrusion temperature.
3.4. Power law parameters
Table 1 lists the detailed parameters of regression power law for
the different samples and extrusion conditions investigated. It can
be seen that, in most cases, n was higher when the moisture
content was higher, which is to be expected, since increased water
content in starches could make them more Newtonian. This
corresponds with most previous studies (Della Valle et al., 1996a;
Gonzalez et al., 2006; Kokini et al., 1992; Lai and Kokini, 1990),
although Willett et al. (1997) reported that the effect of moisture on
n was not clear in their study of waxy corn starch. The results in this
experimental work show that there are only a few conditions (e.g.

Table 1
Power law parameters of the various starches.
Starch

Extrusion conditions


Power law index (n)

K (h at 1 s1)

Correlation coefcient (R2)

Temperature ( C)

% MC

110
110
110
120
120
130
130
130
140
140

19
23
27
23
27
19
23
27
23
27

0.161
0.197
0.206
0.284
0.031
0.259
0.386
0.316
0.431

97,500
65,300
65,500
300
201,000
38,000
14,400
22,800
8510

0.9670
0.9800
0.9805
0.9823
0.9950
0.9768
0.9677
0.9898
0.9734

G50

110
110
110
120
120
130
130
130
140
140
140

19
23
27
23
27
19
23
27
19
23
27

0.102
0.243
0.217
0.263
0.154
0.266
0.345
0.562
0.322
0.400

119,000
28,300
50,200
19,500
59,400
29,600
10,400
3660
17,400
5480

0.9897
0.9961
0.9932
0.9956
0.9633
0.9916
0.9959
0.8273
0.9975
0.9990

NC

110
110
110
120
120
120
130
130
130
140
140
140

19
23
27
19
23
27
19
23
27
19
23
27

0.289
0.331
0.351
0.383
0.434
0.475
0.411
0.435
0.589
0.535
0.494
0.571

43,900
25,300
15,900
20,400
10,900
5970
13,800
8560
2390
5570
5590
2260

0.9654
0.9768
0.9938
0.9819
0.9963
0.9590
0.9963
0.9399
0.9599
0.9736
0.9889
0.9856

WC

110
110
110
120
120
120
130
130
130
140
140
140

19
23
27
19
23
27
19
23
27
19
23
27

0.477
0.455
0.458
0.549
0.658
0.492
0.780
0.741
0.504
0.825
0.847
0.680

14,000
8020
7400
5950
2060
4290
1260
913
2800
710
366
835

0.9503
0.9564
0.9715
0.9296
0.9196
0.9930
0.9551
0.9503
0.9479
0.8592
0.9618
0.9701

G80

F. Xie et al. / Journal of Cereal Science 49 (2009) 371377

Heat Flow Endo Up (mW)

WC

NC

G50
1
M2
G

0
50

G80
M

100

150

Temperature (C)
Fig. 4. Gelatinization endotherms of different starches.

at 140  C) that produce abnormal effects of moisture content on the


power law index n. One explanation could relate to the slight
expansion at the higher temperature and the enhancement of
moisture evaporation during measurement. Variations of volume
or mass at higher temperatures will affect the shear rate, which will
in turn affect the exponent n (see Eqs. (1) and (3)).
Increasing temperature will increase the power law index n and
thus make the starch melt less pseudoplastic and more Newtonian.
Similar results have been reported for both waxy corn starch (Della
Valle et al., 1996b; Willett et al., 1997) and normal corn starch
(Willett et al., 1994, 1995). An increase in n with increasing
temperature has also been observed with waxy corn starch during
rst-pass twin-screw extrusion (Della Valle et al., 1996b; Lai and
Kokini, 1990).
It is important to note that n became higher with decreasing
amylose content for the studied corn starches, clearly indicating
that lower amylose-content corn starch has a more Newtonian
behavior in its melting state. Similar results have been observed in
previous studies (Della Valle et al., 1996b; Lai and Kokini, 1990). The
decrease in the power law index with increasing amylose content
was generally attributed to an increase in entanglements between
amylose chains, since the highly branched amylopectin was not
expected to form effective entanglements (Willett et al., 1997; Yu
and Christie, 2005).
Table 1 also shows that the power law consistency value K
decreased with increasing moisture content and extrusion
temperature. Since the K value has a direct relationship with
viscosity (see Eq. (3)), it can be used to represent the viscosity
characteristics of a material under certain conditions. The K results
are as expected, since both water (as plasticizer) and temperature
will normally decrease the viscosity of a polymeric material. By
plotting the effects of amylose content and temperature on K

375

(gure not shown here), it can be seen that higher amylose content
resulted in a higher K value. For example, K increased from 103 for
WC to 105 for G80 at the highest temperature investigated (140  C).
However, all starches recorded a lower K value with increasing
temperature, although the decrease in K was not linear for starches
with different amylose/amylopectin ratios. It should be pointed out
that there were a few anomalies for the waxy starch at higher
temperature, which could be explained by the expansion of the
material during extrusion, as discussed earlier.
Gelatinization during thermal processing is one of the unique
characteristics of starch-based materials, and Fig. 4 shows the
gelatinization endotherms of the various starches as measured by
DSC. It can be seen that for the waxy and normal corn starches,
a large gelatinization endotherm, G, appeared at about 70  C. A
second endotherm, M2, was detected for NC at about 90  C, which
was considered to be a phase transition within an amyloselipid
on, 1999; Liu
complex (Biliaderis et al., 1985; Jovanovich and An
et al., 2006; Raphaelides and Karkalas, 1988). A very broad endotherm was observed in the temperature range of 65115  C for both
high amylose-content starches (G50 and G80), which represents
a composite of gelatinization endotherm G and a phase transition
within the amyloselipid complex M2. For G80, a small endotherm,
M, was also detected at about 155  C, which was considered to be
amylose melting (Liu et al., 2006). The higher temperature detected
for the amylose-rich starches can be used to explain their higher
viscosity and less Newtonian behavior.
It is has been noticed that the higher the amylose content, the
higher the viscosity, which is opposite to the sequence of molecular
weight (see Fig. 3) (Liu et al., 2006). The unique microstructure and
phase transition can be used to explain this phenomenon. Fig. 5
shows a schematic representation of the microstructure and phase
transition of starch during gelatinization, in which the double
helical, crystalline structure formed by the short branched chains in
amylopectin are torn apart. However, these short branched chains
remain in a regular pattern by retaining a certain memory. French
(1984) reported that the thickness of crystalline lamellae in native
amylopectin and recrystallized amylopectin is the same (about
50 ), which supports the memory theory. In a previous study, Yu
and Christie (2005) indicated that these short branched chains
form gel-balls that are comprised mainly of chains from the same
sub-main chain. In addition, one amylopectin molecule may form
a relatively separate super-globe. The molecular entanglements
between gel-balls and super-globes are much less than those
between linear polymer chains, due to their size and the length of
the chains (only 46 glucose).
These gel-balls require less energy to move than long linear
chains, especially when they are lubricated by a plasticizer (water).
Because of the highly branched microstructure of starch, and the
formation of gel-balls and super-globes after gelatinization, the
entanglement of polymer chains in amylopectin-rich starch is
much less than that in amylose-rich linear starch. This could
explain why amylopectin-rich materials initially have lower

Fig. 5. Schematic representation of microstructure and phase transition of starch during gelatinization.

376

F. Xie et al. / Journal of Cereal Science 49 (2009) 371377

modulus and higher elongation, and lower viscosity during extrusion (Yu and Christie, 2005). It could also explain why amylopectinrich starches exhibit increased Newtonian behavior.
4. Conclusions
In this work, the rheological properties of various corn starches
with different amylose/amylopectin ratios (0/100, 23/77, 50/50, and
80/20) were rstly systematically studied using a Haake rheometer.
A single-screw extruder with a slit capillary die was used to characterize shear stress and apparent melt viscosity as functions of
moisture content (1927  C) and extrusion temperature (110
140  C). The melts exhibited shear thinning behavior under all
conditions, with the power law index n (0 < n < 1) increasing with
increasing temperature and moisture content in most cases; and it
decreased as amylose content increased. The K value decreased
with increasing moisture content and extrusion temperature; and
it increased with increasing amylose content (for example, K
increased from 103 for WC to 105 for G80 at 140  C). The amyloserich corn starches showed higher viscosity and less Newtonian
behavior, which can be explained by its higher gelatinization
temperature (and in particular multiphase transition at higher
temperature), greater molecular entanglements between linear
polymer chains, and less gel-balls and super-globes that are much
easier to move than long linear chains. The results of this work have
conrmed some previously reported results, and have addressed
some earlier confusion.
Acknowledgement
The authors from SCUT, China, would like to acknowledge the
research funds NRDPHT (863) (2007AA10Z312, 2007AA100407),
GNSF (05200617) and ETRFNK (2006C40038).
References
Arvanitoyannis, I.S., 1999. Totally-and-partially biodegradable polymer blends
based on natural and synthetic macromolecules: preparation and physical
properties and potential as food packaging materials. Journal of Macromolecular Science Reviews in Macromolecular Chemistry and Physics 39, 205271.
Babin, P., Della Valle, G., Dendievel, R., Lourdin, D., Salvo, L., 2007. X-ray tomography
study of the cellular structure of extruded starches and its relations with
expansion phenomenon and foam mechanical properties. Carbohydrate Polymers 68, 329340.
Bhattacharya, M., Hanna, M.A., 1986. Viscosity modelling of dough in extrusion.
Journal of Food Technology 21, 167174.
Bhattacharya, M., Hanna, M.A., 1987. Inuence of process and product variables on
extrusion energy and pressure requirements. Journal of Food Engineering 6,
153163.
Bhattacharya, M., Hanna, M.A., Kaufman, R.E., 1988. Viscoelastic properties of
extrusion-cooked plant protein mixtures. Journal of Food Engineering 7, 518.
Bhattacharya, M., Padmanabhan, M., 1992. On-line rheological measurements of
food dough during extrusion cooking. In: Kokini, J.L., Ho, C., Karwe, M.V. (Eds.),
Food Extrusion Science and Technology. Marcel Dekker, New York, pp. 213231.
Biliaderis, C.G., Page, C.M., Slade, L., Sirett, R.R., 1985. Thermal behavior of amylose
lipid complexes. Carbohydrate Polymers 5, 367389.
Bird, R.B., Stewart, W.E., Lightfoot, E.N., 1960. Transport Phenomena. Wiley, New
York.
Cha, J.Y., Chung, D.S., Seib, P.A., Flores, R.A., Hanna, M.A., 2001. Physical properties of
starch-based foams as affected by extrusion temperature and moisture content.
Industrial Crops and Products 14, 2330.
Chanvrier, H., Uthayakumaran, S., Lillford, P., 2007. Rheological properties of wheat
our processed at low levels of hydration: inuence of starch and gluten.
Journal of Cereal Science 45, 263274.
Chen, P., Yu, L., Chen, L., Li, X., 2006. Morphologies and microstructure of cornstarch
with different amylose/amylopectin content. Starch/Starke 58, 611615.
Chen, P., Yu, L., Kealy, T., Chen, L., Li, L., 2007. Phase transition of cornstarch under
shearless and shear stress conditions. Carbohydrate Polymers 68, 495501.
Chinnaswamy, R., Hanna, M.A., 1988. Relationship between amylose content and
extrusion-expansion properties of corn starches. Cereal Chemistry 65, 138143.
Dean, K., Yu, L., Wu, D.Y., 2007. Preparation and characterization of melt-extruded
thermoplastic starch/clay nanocomposites. Composites Science and Technology
67, 413421.

Della Valle, G., Boche, Y., Colonna, P., Vergnes, B., 1996a. The extrusion behaviour of
potato starch. Carbohydrate Polymers 28, 255264.
Della Valle, G., Colonna, P., Patria, A., Vergnes, B., 1996b. Inuence of amylose
content on the viscous behavior of low hydrated molten starches. Journal of
Rheology 40, 347362.
Della Valle, G., Vergnes, B., Colonna, P., Patria, A., 1997. Relations between rheological properties of molten starches and their expansion behaviour in extrusion. Journal of Food Engineering 31, 277296.
Fang, Q., Hanna, M.A., 2001a. Characteristics of biodegradable mater-bi-starch
based foams as affected by ingredient formulations. Industrial Crops and
Products 13, 219227.
Fang, Q., Hanna, M.A., 2001b. Preparation and characterization of biodegradable
copolyesterstarch based foams. Bioresource Technology 78, 115122.
Fishman, M.L., Cofn, D.R., Onwulata, C.I., Willett, J.L., 2006. Two stage extrusion of
plasticized pectin/poly(vinyl alcohol) blends. Carbohydrate Polymers 65, 421429.
French, D., 1984. Organization of starch granules. In: Whistler, R., Bemiller, J.,
Paschall, E. (Eds.), Starch: Chemistry and Technology. Academic Press, Orlando.
Funke, U., Bergthaller, W., Lindhauer, M.G., 1998. Processing and characterization of biodegradable products based on starch. Polymer Degradation and Stability 59, 293296.
de Graaf, R.A., Karman, A.P., Janssen, L.P.B.M., 2003. Material properties and glass
transition temperatures of different thermoplastic starches after extrusion
processing. Starch/Starke 55, 8086.
Glenn, G.M., Gray, G.M., Orts, W.J., Wood, D.W., 1999. Starch-based lightweight
concrete: effect of starch source, processing method, and aggregate geometry.
Industrial Crops and Products 9, 133144.
Gonzalez, R.J., Torres, R.L., de Greef, D.M., Guadalupe, B.A., 2006. Effects of extrusion
conditions and structural characteristics on melt viscosity of starchy materials.
Journal of Food Engineering 74, 96107.
Guan, J., Eskridge, K.M., Hanna, M.A., 2005. Acetylated starchpolylactic acid loosell packaging materials. Industrial Crops and Products 22, 109123.
Guan, J., Hanna, M.A., 2004. Functional properties of extruded foam composites of
starch acetate and corn cob ber. Industrial Crops and Products 19, 255269.
Guan, J., Hanna, M.A., 2006. Selected morphological and functional properties of
extruded acetylated starchcellulose foams. Bioresource Technology 97,17161726.
Guha, M., Ali, S.Z., Bhattacharya, S., 2003. Screening of variables for extrusion of rice our
employing a PlackettBurman design. Journal of Food Engineering 57, 135144.
Harper, J.M., 1981. Extrusion of Food. CRC Press, Boca Raton.
Harper, J., 1989. Food extruders and their applications. In: Mercier, C., Linko, P.,
Harper, J. (Eds.), Extrusion Cooking. American Association of Cereal Chemists,
St. Paul, pp. 115.
Jao, Y.C., Chen, A.H., Lewandowski, D., Irwin, W.R., 1978. Engineering analysis of soy
dough rheology in extrusion. Journal of Food Process Engineering 2, 97112.
on, M.C., 1999. Amyloselipid complex dissociation: a study of the
Jovanovich, G., An
kinetic parameters. Biopolymers 49, 8189.
Kokini, J.L., Chang, C.N., Lai, L.S., 1992. The role of rheological properties on extrudate expansion. In: Kokini, J.L., Ho, C.T., Karwe, M.V. (Eds.), Food Extrusion
Science and Technology. Marcel Dekker, New York, pp. 631652.
Lai, L.S., Kokini, J.L., 1990. The effect of extrusion operating conditions on the on-line
apparent viscosity of 98% amylopectin (amioca) and 70% amylose (hylon 7) corn
starches during extrusion. Journal of Rheology 8, 12451266.
Liu, H., Yu, L., Xie, F., Chen, L., 2006. Gelatinization of cornstarch with different
amylase/amylopectin content. Carbohydrate Polymers 65, 357363.
Llo, S., Tomschik, U., Berghofer, E., Mundigler, N., 1996. The effect of extrusion
operating conditions on the apparent viscosity and the properties of extrudates
in twin-screw extrusion cooking of maize grits. Lebensmittel-Wissenschaft und
Technologie 29, 593598.
Matthey, F.P., Hanna, M.A., 1997. Physical and functional properties of twin-screw
extruded whey protein concentratecorn starch blends. Lebensmittel-Wissenschaft und Technologie 30, 359366.
Miladinov, V.D., Hanna, M.A., 2000. Starch esterication by reactive extrusion.
Industrial Crops and Products 11, 5157.
Miladinov, V.D., Hanna, M.A., 2001. Temperatures and ethanol effects on the properties
of extruded modied starch. Industrial Crops and Products 13, 2128.
Nabar, Y.U., Draybuck, D., Narayan, R., 2006. Physicomechanical and hydrophobic
properties of starch foams extruded with different biodegradable polymers.
Journal of Applied Polymer Science 102, 5868.
Raphaelides, S., Karkalas, J., 1988. Thermal dissociation of amylosefatty acid
complexes. Carbohydrate Research 172, 6582.
Seethamaju, K., Bhattacharya, M., 1994. Effect of ingredients on the rheological
properties of extruded corn meal. Journal of Rheology 38, 10291044.
Shogren, R.L., 1992. Effect of moisture content on the melting and subsequent
physical aging of cornstarch. Carbohydrate Polymers 19, 8390.
Shogren, R.L., Jasberg, B.K., 1994. Aging properties of extruded high-amylose starch.
Journal of Environmental Polymer Degradation 2, 99109.
Signori, F., Chiellini, F., Solaro, R., 2005. New self-assembling biocompatible
biodegradable amphiphilic block copolymers. Polymer 46, 96429652.
Soderqvist Lindblad, M.S., Albertsson, A.-C., Ranucci, E., Laus, M., Giani, E., 2005.
Biodegradable polymers from renewable sources: rheological characterization
of hemicellulose-based hydrogels. Biomacromolecules 6, 684690.
Suknark, K., Phillips, R.D., Chinnan, M.S., 1997. Physical properties of directly
expanded extrudates formulated from partially defatted peanut our and
different types of starch. Food Research International 30, 575583.
van Soest, J.J.G., Borger, D.B., 1997. Structure and properties of compression-molded
thermoplastic starch materials from normal and high-amylose maize starches.
Journal of Applied Polymer Science 64, 631644.

F. Xie et al. / Journal of Cereal Science 49 (2009) 371377


Tanner, R.I., 2000. Engineering Rheology. Oxford University Press, Oxford.
Thuwall, M., Boldizar, A., Rigdahl, M., 2006. Extrusion processing of high amylose
potato starch materials. Carbohydrate Polymers 65, 441446.
Tomas, R.L., Oliveira, J.C., McCarthy, K.L., 1997. Rheological modelling of
enzymatic extrusion of rice starch. Journal of Food Engineering 32, 167
177.
Willett, J.L., Jasberg, B.K., Swanson, C.L., 1994. In: Fishman, M.L., Friedman, R.B.,
Huang, S.J. (Eds.), Polymers from Agricultural Coproducts. American Chemical
Society, Washington, D.C., pp. 5068.
Willett, J.L., Jasberg, B.K., Swanson, C.L., 1995. Rheology of thermoplastics starch:
effects of temperature, moisture content, and additives on melt viscosity.
Polymer Engineering and Science 35, 202210.

377

Willett, J.L., Millardt, M.M., Jasberg, B.K., 1997. Extrusion of waxy maize starch: melt
rheology and molecular weight degradation of amylopectin. Polymer 38, 59835989.
Wing, R.E., Willett, J.L., 1997. Water soluble oxidized starches by peroxide reactive
extrusion. Industrial Crops and Products 7, 4552.
Yu, L., Christie, G., 2001. Measurement of starch thermal transition using differential
scanning calorimetry. Carbohydrate Polymers 46, 179184.
Yu, L., Christie, G., 2005. Microstructure and mechanical properties of orientated
thermoplastic starches. Journal of Materials Science 40, 111116.
Yu, L., Dean, K., Li, L., 2006. Polymer blends and composites from renewable
resources. Progress in Polymer Science 31, 576602.
Zhou, J., Hanna, M.A., 2004. Extrusion of starch acetate with mixed blowing agents.
Starch/Starke 56, 484494.