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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)
372
6Q
WH 2
(1)
H$DP
2L
(2)
h K gn1
(3)
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
(19% mc)
100
10000
(19% mc)
(23% mc)
(27% mc)
(19% mc)
100000
1000
(23% mc)
(27% mc)
WC
10000
10
100
1000
Viscosity (Pas)
(27% mc)
1000000
Viscosity (Pas)
10000
(23% mc)
10000
100
1000
(19% mc)
100000
1000
(23% mc)
10000
(19% mc)
Viscosity (Pas)
(23% mc)
1000000
(19% mc)
Viscosity (Pas)
1000000
373
100
Fig. 1. Effect of moisture content on shear stress and melt viscosity of various starches (extrusion temperature 130 C).
Fig. 2 shows the effect of temperature on the rheological properties of the different starches at 23% moisture content, as
1000
1000000
100000
G80
10000
100
100
1000
10000
10
100
10
10000
110C
120 C
130 C
140 C
110C
120 C
130 C
140 C
100000
1000
WC
100
100
1000
10000
10
100
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
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
10000
110C
120 C
130 C
140 C
110C
120 C
130 C
140 C
Viscosity (Pas)
1000000
374
10000
G80
G50
NC
WS
G80
G50
NC
WS
100000
10000
1000
10
Viscosity (Pas)
1000000
100
1000
100
Table 1
Power law parameters of the various starches.
Starch
Extrusion conditions
K (h at 1 s1)
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
WC
NC
G50
1
M2
G
0
50
G80
M
100
150
Temperature (C)
Fig. 4. Gelatinization endotherms of different starches.
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
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).
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