Investigation of the

Gelatinization and Extrusion

Processes of Corn Starch
ROBERTA C. R. SOUZA, CRISTINA T. ANDRADE
Instituto de Macromoléculas Professora Eloisa Mano, Universidade Federal do Rio de Janeiro,
P.O. Box 68525, 21945-970 Rio de Janeiro, RJ, Brazil
Received: July 19, 2001
Accepted: October 9, 2001

ABSTRACT: The gelatinization and extrusion processes of corn starch were

studied. Differential scanning calorimetry was used to determine the
gelatinization temperature as a function of the water content. Plasticized corn
starch was processed in single- and twin-screw extruders to produce
thermoplastic materials. The mechanical properties of the films obtained in the
twin-screw extruder with the addition of different quantities of water were
evaluated. Dynamic mechanical analysis applied to thermoplastic starch samples
obtained with 33% (w/w) total plasticizers showed two transitions, attributed to
the presence of two phases in the starch–glycerol–water system. ° C 2002 John

Wiley & Sons, Inc. Adv Polym Techn 21: 17–24, 2002; DOI 10.1002/adv.10007

KEY WORDS: gels, extrusion

ronmental concerns have arisen from their dis-

Introduction posal in nature. As a response, the development of
biodegradable materials that could substitute syn-

T raditional plastic artefacts, produced from

synthetic polymers, are known for their in-
ertness to the immediate attack by microorgan-
isms. Although this characteristic is associated with
their multipurpose applications, increasing envi-
Correspondence to: Cristina T. Andrade; e-mail: ctandrade@
ima.ufrj.br.
Contract grant sponsor: Conselho Nacional de Desenvolvi-
mento Cientı́fico e Tecnológico (CNPq).
Originally published in Polı́meros: Ciéncia e Tecnologia,
2000, 10, 24–30.
thetic polymers, at least in some of their applica-
tions, has been encouraged. Starch is one of the most
promising materials to achieve this objective. It is
produced worldwide from several crops, and is con-
sidered truly biodegradable.1–3 Much of the research
efforts on the subject is focused on the development
of thermoplastic materials composed essentially of
starch.4–7 The applications of these materials are
varied, ranging from the packaging to agricultural
fields. Starch-based composites, reinforced with hy-
droxylapatite, were injection-molded and exhibited

Advances in Polymer Technology, Vol. 21, No. 1, 17–24 (2002)

°
C 2002 by John Wiley & Sons, Inc.
GELATINIZATION AND EXTRUSION OF CORN STARCH
properties that might be useful in biomedical
applications.8 Systematic studies on the starch
characteristic properties and its behavior during
processing have shown significant importance on
the development of thermoplastic starches.9–11
Starch is produced by nearly all green plants to
store energy. It occurs as granules in grains, roots,
and tubercules. Starch is composed of a mixture of
amylose and amylopectin macromolecules, both of
high molar masses and consisting of (1 → 4)-a-D -
glucopyranose repeating units. While amylose is
essentially linear, amylopectin is highly branched
via additional (1 → 6)-a linkages, with a cluster
type structure.12 When observed under polarized
light, the starch granules show birefringence, which
indicates a certain degree of molecular organization.
X-ray scattering has shown that granular starch
has an overall crystallinity of about 20–45%. The
amorphous regions are formed by amylose and the
residues around the branch points of amylopectin.
The linear segments of amylopectin are present in
the form of double helices crystallized into thin
lamellar domains.13–15
Almost any application of starch involves pro-
cesses that lead to the disruption of the molecular
order within the granules. This may be achieved by
heating a starch suspension in water above a tem-
perature denoted gelatinization temperature, T(G).
Gelatinization, which is influenced by the presence
of other solutes, is preceded by swelling and pro-
vides irreversible changes in properties.16,17 When
the disruption of the crystalline regions is reached in
the presence of a low content of water, the process is
denominated as melting.18 Industrially, thermal and
mechanical energy input associated with the addi-
tion of plasticizers, such as water and glycerol, are
necessary to transform granular starch into a homo-
geneous matrix.
The aim of the present work was to determine the
better conditions for processing corn starch by ex-
trusion. Differential scanning calorimetry (DSC) and
optical microscopy were used to determine the T(G)
of corn starch in the presence of differing contents of
plasticizers.
Experimental
MATERIALS
Food grade corn starch (CS) was supplied by Re-
finações de Milho Brasil Ltda., São Paulo, SP, Brazil.
18
Glycerol P.A. was supplied by Vetec Quı́mica Fina
Ltda., Rio de Janeiro, RJ, Brazil, and was used as
received.
METHODS
Purification of Corn Starch
CS was dispersed in distilled and deionized water
under vigorous stirring for 4 h. The dispersion was
filtered and the recovered solid was dried in an oven
at 50◦ C to constant weight (40 h). The product was
milled and kept at ambient conditions.
Ash Content
The ash contents of the commercial and washed
samples of CS were determined after incineration
under oxidant flame and heating in a furnace at
650◦ C for 24 h.
Gelatinization Temperature T (G)
A small sample of CS was spread on a glass lam-
ina. Water was dropped to attain a 5 g l−1 dispersion.
The dispersion was analyzed in an Olympus BX50
Optical microscope (Shibuya-ku, Tokyo, Japan),
equipped with a Linkan THM5600 heating plate
(Waterfield, Surrey, UK), from 25 to 90◦ C.
Determination of T (G) as a Function
of the Moisture Content
DSC measurements on granular starch were
performed with a Perkin Elmer DSC-7 calorimeter
(Norwalk, Conn., USA) at a heating rate of 10◦ C
min−1 from 30 to 270◦ C. The instrument calibration
was done with indium and zinc. Dispersions con-
taining ca. 20 mg CS and the required amounts of
water were placed into stainless steel pans, which
were hermetically sealed. An empty pan was used
as reference.
Processing in a Single-Screw Extruder
CS (300 g) was mixed with 9% water (35.5 g) and
15% glycerol (59.2 g) under stirring at room tem-
perature. This mixture was processed into monofil-
ament threads, using a PlastiCorder Brabender
model GNF106/2 (South Hackensack, NJ, USA)
single-screw extruder, provided with four electri-
cally heated modules and cooled by a refrigeration
system. The screw rotation speed was maintained
at 20–40 rpm. The temperature profile along the
VOL. 21, NO. 1
 GELATINIZATION AND EXTRUSION OF CORN STARCH

FIGURE 1. Optical micrographs of corn starch granules at 5 g l−1 concentration in water and 25◦ C; (a) polarized light,
(b) ordinary light.

extruder was 70, 80, 95 and 115◦ C from feed zone to
die. Films were obtained by pressing the extruded
filaments at 110◦ C under 0.92 × 102 kPa for 15 min
followed by cooling to 25◦ C under pressure. Films of
1 mm thickness were obtained.
Processing in a Twin-Screw Extruder
CS (300 g) was mixed with 18% water (80.6
g) and 15% (67.2 g) glycerol and processed into
nonexpanded ribbons, using a Haake Rheocord

FIGURE 2. Optical micrographs of corn starch granules at 5 g l−1 concentration in water; (a) at 40◦ C and (b) 60◦ C,
under ordinary light.

ADVANCES IN POLYMER TECHNOLOGY 19

GELATINIZATION AND EXTRUSION OF CORN STARCH
90 system (Dallas, TX, USA) equipped with a
twin-screw extruder provided with four electrically
heated modules and fitted with a slit die of 25-mm
width and 1-mm thickness. The mixtures were man-
ually fed into the extruder and the screw rotation
speed was maintained at 40–50 rpm. The extrusion
temperature profile was 90–100, 110–120, 120–130,
and 90◦ C. Films of uniform thickness were formed
by passing the blends through a calender.
Optical Microscopy
The surface of the films obtained by processing in
the single- and twin-screw extruders were analyzed
by optical microscopy, using a Stereo Olympus Mi-
croscope SZH10 (Shibuya-ku, Tokyo, Japan).
Scanning Electron Microscopy (SEM)
Samples of CS and thermoplastic CS obtained
by processing in the twin-screw extruder were ob-
served by SEM in a Jeol microscope model JSM5300
(Peabody, MA, USA). CS granules were spread on
a support, coated with gold/palladium alloy by va-
por deposition and analyzed at 5 kV. The extruded
films were dried, fractured in liquid nitrogen, stuck
to aluminum stubs, and coated as explained before.
The fracture and extruded surfaces were analyzed at
20 kV.
Conditioning
Samples of thermoplastic CS obtained by pro-
cessing in the twin-screw extruder were dried in an
oven at 50◦ C to constant weight and conditioned at
25◦ C at different relative humidities for 96 h. The
water content after conditioning was determined
by difference.
Tensile Tests
Tensile properties were evaluated according to
ASTM D882-75b method on rectangular specimens
(100 × 8 mm), after equilibration at 8, 12, and 18%
water contents, using an Instron Universal Testing
Machine model 4204 (Canton, MA, USA) at a rate
of 5 mm min−1 . At least five bars were measured for
each sample and the median values were considered.
Dynamic Mechanical Analysis (DMA)
Dynamic mechanical properties were evaluated
with a DMTA MkIII unit (Rheometrics, Epsom,
Surrey, UK) operating in the bending mode. This
20
setup provides the storage (E 0 ) and loss (E 00 ) moduli
and the internal friction (tan δ = E 0 /E 00 ) as a function
of the temperature, for several frequencies. Samples
obtained by processing in the twin-screw extruder
were compression molded into 150 × 150 × 3 mm
sheets at 120◦ C and 6.2 × 10 kPa for 10 min. After
conditioning to 18% water content, rectangular spec-
imens of 8 × 25 × 3 mm were submitted to a sinu-
soidal strain of 10%. The temperature was increased
at the rate of 2◦ C min−1 from −80 to 150◦ C, at a fre-
quency of 1 rad s−1 .
Results and Discussion
The starting food grade starch had a low ash con-
tent (0.14%) and the washing procedure was effica-
cious to eliminate at least part of the soluble inor-
ganic material present; after washing, a 0.10% ash
content was found and the product was visually
clearer.
The gelatinization process of a starch dispersion at
5 g l−1 in water was observed by optical microscopy.
Figure 1 shows micrographs of starch granules ob-
tained at 25◦ C with an amplification of 100 times
under ordinary and polarized light. Maltese crosses,
which reveal the radial order, may be seen under po-
larized light. In Figs. 2a and 2b, the same dispersion
was observed at 40 and 60◦ C, respectively. The in-
crease in the diameter of some granules are clearly
seen in Fig. 2b, due to swelling. The dark artefacts
result from water condensation at the laminula sur-
face. At 70◦ C (Fig. 3a), most granules (∼70%) are dis-
rupted. This temperature may be taken as the T(G)
for this sample, at this water content. At 75◦ C, no
birefringence is observed for the same dispersion un-
der polarized light (Fig. 3b). Some authors showed
TABLE I
Melting Temperature (Tmax ) of Corn Starch as a Func-
tion of Water Content Expressed as the Peak Temper-
ature of the DSC Melting Endotherm
Water Content (%) Tmax (◦ C)
0 168
10 126
20 123
30 120
40 109
50 108
60 72
VOL. 21, NO. 1
 GELATINIZATION AND EXTRUSION OF CORN STARCH

FIGURE 3. Optical micrographs of corn starch dispersions at 5 g l−1 concentration in water at 75◦ C and different
amplifications; (a) and (c) ordinary light, (b) polarized light.

that crystallinity still decreased after all the granules In the present work, DSC was used to evaluate
had lost birefringence, which means that birefrin- the melting of corn starch at varying water con-
gence measurements provide only an approximation tents. Table I shows values of the peak temperatures
of the final melting point of the ordered regions.19 observed for the melting endotherm. For dispersions

FIGURE 4. Optical micrograph of the external surface FIGURE 5. Optical micrograph of the external surface
of a thermoplastic starch film obtained in a single-screw of a thermoplastic starch film obtained in a twin-screw
extruder. extruder.

ADVANCES IN POLYMER TECHNOLOGY 21

GELATINIZATION AND EXTRUSION OF CORN STARCH

FIGURE 6. SEM micrographs of (a) corn starch granules (5 kV), (b) cryofractured and (c) external surfaces (25 kV) of a
thermoplastic starch film obtained in the twin-screw extruder.

with water contents in the range 0–50%, melting oc- of the extruded film, respectively. In both micro-
curred at much more elevated temperatures than for graphs, the appearance of intact or fragmented gran-
those at 60% water content. These results are useful ules is rare, which reveals that the processing condi-
for an estimation of the thermal conditions necessary tions used were adequate to produce a homogeneous
for processing starch, without degradation. Since the polymer matrix.
loss of crystallinity during extrusion is caused by the The tensile properties of thermoplastic starches
action of heat and intense shear forces in the pres- are dependent on the water content. Samples
ence of plasticizers, milder thermal conditions could conditioned] at different relative humidities had
be used. their water contents determined as 8, 12, and 18%.
The extrudates obtained from processing in
the single-screw extruder were clear, flexible, and
apparently homogeneous. However, optical micro-
graphs (Fig. 4) taken from compression molded films
prepared with the extrudate revealed the presence
of heterogeneities, which may be attributed to un-
melt, partially melted, or fragmented starch gran-
ules. No such heterogeneities were observed in films
obtained by processing in the twin-screw extruder.
Figure 5 shows an optical micrograph taken from
the surface of one of those films.
During processing in the twin-screw extruder,
when the screw speed was maintained at 40 rev
min−1 , the torque developed was around 20 N m.
This high value was expected, since the moisture
content was low. On increasing the screw speed from
40 to 50 rev min−1 , torque was decreased to 10 N m.
Scanning electron microscopy was used to an-
alyze the thermoplastic starch films obtained in
the twin-screw extruder (Fig. 6). For comparison,
Figure 6a shows a micrograph obtained from corn
starch granules, which appear as spherical or polyg-
onal shaped nodules with diameters in the range FIGURE 7. Stress-strain curves for corn starch
5–15 mm. Figures 6b and 6c show the micrographs extrudates at 15% glycerol and different water contents;
of a cryofractured surface and of an external surface I (¤) –8%; II (◦) –12%, III (M) –18%.

22 VOL. 21, NO. 1

 GELATINIZATION AND EXTRUSION OF CORN STARCH
FIGURE 8. Temperature dependence of the storage modulus ( E 0 ) and of the loss tangent (tan δ) measured at 10 Hz for
a thermoplastic starch sample obtained with 33% (w/w) total plasticizers.
Typical stress–strain curves are shown in Fig. 7. The
sample with 8% water content presented a brittle
fracture, characterized by the rapid decrease in stress
at a low strain value. For the sample with 18% water
content, a maximum value (∼70%) of strain (ε) was
observed.
Dynamic mechanical properties are reported in
Fig. 8 for a thermoplastic starch sample with 15%
glycerol and 18% water, in terms of the tempera-
ture dependence of the storage modulus (E 0 ) and
loss tangent (tan δ). Two distinct transitions are ob-
served in the tan δ vs. T curve. Previous studies
based on the glass transition temperatures and on the
corresponding heat capacity increments determined
for barley starch–glycerol–water mixtures charac-
terized the system as either monophasic or bipha-
sic, depending on the total content of plasticizers.
At intermediate plasticizer levels (between 20 and
35% total contents of water and glycerol), two glass
transitions were observed and phase separation was
suggested to occur. DMA carried out for such mix-
tures showed two loss peaks, attributed to the tran-
sitions of a starch-poor phase (lower temperature)
and of a starch-rich phase (higher temperature).20 In
the present work, the first transition has a maximum
at around −55◦ C and the second transition at around
40◦ C.
ADVANCES IN POLYMER TECHNOLOGY
Conclusions
The gelatinization process of corn starch was fol-
lowed by optical microscopy in excess water and by
DSC, as a function of the water content. Processing
of starch–water–glycerol mixtures in a single-screw
extruder produced films that, although clear, flexi-
ble, and apparently homogeneous, showed hetero-
geneities, probably resulting from incomplete melt-
ing of starch granules. Transparent, flexible, and ho-
mogeneous films were obtained by extrusion in a
twin-screw extruder. The mechanical properties of
these films varied with the water content. At 8% wa-
ter content, the material is brittle and at 18% water
content, although not elastic, the material reaches a
maximum value of strain. Two transitions were ob-
served by DMA, probably due to the presence of two
phases in the starch–glycerol–water system.
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