Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
Concern over the magnitude of discarded waste in the U . S. has in recent years
stimulated a great deal of research in the area of degradable plastics (1,2).
Several approaches have been developed to either render conventional plastics
degradable after disposal, or to produce inherently degradable materials. In
particular, starch, because of its abundance and low cost, has received much
attention as a raw material in both of these approaches to degradability. Other
advantages to the use of starch as a raw material are the fact that it is a renewable
resource, its potential for replacing nonrenewable petroleum or natural gas
feedstocks, and potential economic benefits to the agricultural industry by
providing new markets for agricultural products (3).
The use of starch in plastics has progressed through several stages. Early
attempts include efforts to polymerize allyl starch (4), the use of amylose to
produce films (5-7), and studies of amylose acetate and starch acetate as
competitors to cellulose acetate (8). Efforts in the early to mid 1970s focused on
using granular starch as a filler in rubbers, PVC, and polyolefins (9-15). Granular
starch formulations were generally limited to starch contents of approximately
10% by weight or less, due to the general deterioration of mechanical properties
seen in filled materials (16). Blends of gelatinized starch with water soluble or
water dispersible polymers were developed in the late 1970s and early 1980s
(17-19). These materials had the advantage of starch contents up to 50-60% with
good properties, but used relatively high cost raw materials. Another avenue of
starch incorporation in plastics is via graft polymerization (20-22). Grafting of
unsaturated monomers (e.g. methyl acrylate) onto the starch molecule backbone
Downloaded by IMPERIAL COLLEGE LONDON on February 18, 2015 | http://pubs.acs.org
yields materials with starch contents of up to 60%. These graft copolymers can
be injection molded or extruded into films with properties similar to low density
polyethylene (23).
The extrusion of starch offers a route to materials with high starch content,
Publication Date: May 5, 1994 | doi: 10.1021/bk-1994-0575.ch003
relatively low raw materials cost, and inherent degradability. Although the food
industry has been extruding starch for many years (24), only recently has extruded
starch been considered as a thermoplastic material (25-27). The rheology of starch
melts has therefore received little consideration from the polymer processing point
of view.
Starch is a polysaccharide of repeating glucose units. It is a mixture of two
polymers, amylose and amylopectin (7,28). Amylose is a predominantly linear,
lightly branched polymer, comprised of (1- > 4) α-D linkages with number average
molecular weights in the range of several hundred thousand. Amylopectin is
highly branched, with intermittent (l->6) links; its molecular weight is typically
several million, and can be as great as 50 million. Corn starch typically contains
amylopectin and amylose at a ratio of approximately 3:1; genotypes with higher
amylose contents (up to 70%) or virtually no amylose (waxy maize starch) are
available commercially. Native corn starch granules have an average diameter of
approximately 10 microns.
The structural differences in the two forms of starch have a considerable
effect on the properties of starch materials. Because of its branched structure,
amylopectin generally has inferior mechanical properties relative to amylose.
Wolff et al (6) showed that increasing the amylopectin content in
amylose/amylopectin films decreased the tensile strength and the elongation.
Similar behavior has been observed with synthetic polymers such as polystyrene
(29,30). Data of Lai and Kokini (31) show that at constant temperature, moisture
content, and shear rate, high amylose starch melts have a higher viscosity than
waxy maize starch melts. Similar branching effects have been observed for
polyethylene (32) and polystyrene (29) melts. The shear strength of expanded
starch products decreases with increasing amylopectin content (33).
Extrusion of Starch
The three hydroxyl groups on each monomer of the starch molecule lead to
significant hydrogen bonding between adjacent molecules. Penetrant molecules
which can disrupt this hydrogen bonding are able to disperse starch into solution;
this process is generally referred to as gelatinization. The melting point of starch
at atmospheric pressure and low moisture content, like that of cellulose (a (1- > 4)
β-Ό glucose polymer), exceeds its decomposition temperature. In closed systems
in the presence of water, the melting point of starch decreases with increasing
moisture content in a manner described by the Flory model of diluent effects (34).
Starch can be gelatinized in the high temperature, high shear, and high
pressure conditions found in extruders. The result is a melt of interspersed
amylopectin and amylose molecules and destruction of the granule structure. The
effects of extrusion conditions and various additives on starch as a food product
have received considerable attention (35-47).
The melt viscosity of starch can be described by equations of the form
Downloaded by IMPERIAL COLLEGE LONDON on February 18, 2015 | http://pubs.acs.org
(1)
Publication Date: May 5, 1994 | doi: 10.1021/bk-1994-0575.ch003
activation energy, R is the gas constant, and a is the moisture content coefficient.
This relationship was first suggested by Harper (48,49), and has been verified by
several groups. Various modifications to this equation have been added to account
for the effects of screw speed in twin screw extrusion (50), specific mechanical
energy input (51), residence time on degradation kinetics (31), and the degree of
cooking or starch conversion (31).
The effects of additives on starch melt viscosity have also been examined.
Amylose in solution forms helical inclusion complexes with linear fatty acids and
esters, as well as monoglycerides and some diglycerides. These materials form
complexes with starch during extrusion (37,39,42), but little is known of the
stability of the complexes during extrusion. Triglycerides and fats which do not
complex with starch influence the rheology of molten starch by reducing the
degree of molecular weight degradation (37,39). Most of the work in this area has
focused on the influence of additives on extrudate properties such as water
solubility and water absorption rather than Theological effects.
Various workers have shown that considerable molecular weight degradation
occurs during the extrusion of starch (36,39,52-54). Size exclusion
chromatography shows that the amylopectin undergoes more chain scission than
amylose. Little if any low molecular weight oligosaccharides are formed during
extrusion, suggesting that shear forces encountered during extrusion are more
important than thermally controlled bond scission. Theories of mechanical
degradation of polymers (55) predict that in the presence of shear, the largest
molecules are the most likely to degrade, while few of the lower molecular weight
chains will do so. The degradation of amylopectin observed during extrusion is
consistent with this prediction.
The purpose of this paper is to describe the effects of temperature, moisture
content, additives, and molecular weight on the melt viscosity of thermoplastic
starch. The starch was pelletized prior to the viscosity measurements. This
technique allowed the moisture content to be changed before the measurement step
to elucidate the MC effects during pelletizing on viscosity. Formation and thermal
Experimental Details
Buffalo 3401 unmodified cornstarch from CPC International was used. Urea (EM
Science), lecithin (Fisher Scientific), triethylene glycol (TEG, Fisher Scientific),
glycerol monostearate (GMS, Kemester 5500, Witco), and polyoxyethylene
stéarate (POES, ICI Americas) were used as received. Stardri 1, a waxy maize
derived dextrin (A. E. Staley), was used as a low molecular weight starch analog.
Distilled water was used for all formulations.
Downloaded by IMPERIAL COLLEGE LONDON on February 18, 2015 | http://pubs.acs.org
extruded through a 17-hole strand die (1.6 mm diameter holes) and air cooled.
The temperature profile during pelletizing was 140/160/160/130°C (feed zone to
die). The die zone temperature was reduced to 100°C when pelletizing starch at
30% MC to prevent foaming by steam expansion.
Viscosity measurements were performed with a 25/1 L/D, 19 mm diameter
screw with a 3/1 compression ratio. Capillary dies were 2 mm in diameter, with
length/radius (L/R) ratios 20/1, 30/1, and 40/1. Die temperatures for the
starch/water compounds ranged from 110°C to 180°C. All additive formulations
were pelletized with 20% MC and equilibrated to 15% MC for viscosity
measurements. Additive/starch viscosities were measured with a temperature
profile of 150/155/160/160°C. Melt temperature and pressure were measured
with a combination thermocouple/transducer unit (Dynisco) in contact with the
melt just prior to the die entrance.
Shear rates were determined using the Rabinowitch correction (56,57):
Ύβ
(2)
4b
(3)
where y is the corrected shear rate, 7, is the apparent shear rate, and b is the
c
slope of the plot of log(shear stress) versus log(7,). Q is the volumetric output,
and R is the capillary radius. Values for the power law index m and consistency
Κ were determined by linear regression of log(q) versus l o g ^ J plots.
X-ray diffraction patterns were obtained using a Phillips PW 1820
diffractometer with a slit opening of 0.20 mm. Readings were taken at intervals
of 0.05 20 units at a rate of 4 scans per second.
Melting curves of starch/additive extrudates were obtained on a Perkin-Elmer
Series 7 Thermal Analysis System. The scan rate was 10°C/minute over the range
5°C to 220°C. Sample weight was approximately 30 mg, and the moisture
content was 15%.
Results
at 120°C., and 0.40 (± 0.03) at 130°C. m values for starch pelletized with 30%
MC and tested at 30% MC increased from 0.31 ( ± 0.03) at 110°C to 0.37 ( ±
0.03) at 130°C. These results are consistent with those of Lai and Kokini (31),
who studied the melt viscosity of waxy maize starch and high amylose starch.
Publication Date: May 5, 1994 | doi: 10.1021/bk-1994-0575.ch003
loo' 1 ι
10 100 1000
1
SHEAR RATE (sec" )
Figure 1. Effect of temperature on starch viscosity. Starch pelletized at
20% MC; viscosity measured at 30% M C .
10 ι 1 ' 1
1 10 100 1000
1
SHEAR RATE (sec" )
Figure 2. Effect of moisture content on starch at 160°C. Starch pelletized
at 15% MC.
100 · 1 1 1
1 10 100 1000
1
SHEAR RATE (sec"" )
10000 ,
Ο STARCH
• 1X LECITHIN
1000
Ο
ο
(Λ
100' « -«
10 100 1000
1
SHEAR RATE (sec" )
Figure 4. Viscosity of thermoplastic starch with 1% lecithin.
POES overlubricated the melts to the extent that continuous extrusion was not
possible due to excessive slip. The amount of scatter in Figure 4 suggests that
even 1% lecithin is approaching the limit of overlubrication.
The effects of urea and TEG on starch melt viscosity are shown in Figures
Publication Date: May 5, 1994 | doi: 10.1021/bk-1994-0575.ch003
6 and 7. These additives also reduce the melt viscosity, but not as effectively as
lecithin and POES. A comparison of Figures 5 and 7 indicates that 5% TEG is
needed to reduce the viscosity as effectively as 1 % POES. The scatter in the 5%
TEG data suggest this formulation is approaching overlubrication; formulations
with more than 5% TEG could not be continuously extruded.
Urea is similar to TEG in ability to reduce starch viscosity at a 2% level.
When the urea is increased to 5%, a reduction in viscosity is seen, but it is not as
great as might be expected in comparison to TEG. The effectiveness of urea as
a plasticizer may be diminished if it is partially hydrolyzed to C 0 and N H during
2 3
10 100 1000
1
SHEAR RATE (sec" )
10 100 1000
1
SHEAR RATE (sec" )
10 100 1000
1
SHEAR RATE (sec" )
φ STARCH
V 2X GMS
Ο Ο 5X GMS
10 100 1000
1
SHEAR RATE (sec" )
100'
10 100 1000
Δ 100 c
V no c
1000
• 120 Ο
100
10 Ι 00 1000
The power law index increases from 0.78 at 100°C to 0.86 at 110°C. Increasing
the temperature to 120°C increases m to 0.88.
Higher moisture contents reduce the viscosity of the dextrin, as shown in
Figures 10a and 10b. The melts are also more Newtonian, as evidenced by an
increase in m with moisture content at both temperatures.
Discussion
The starch melts in this study exhibited power law behavior. In a power law
fluid, the shear stress r is dependent on the shear rate in the following manner
Downloaded by IMPERIAL COLLEGE LONDON on February 18, 2015 | http://pubs.acs.org
(56,57):
m 4
x=Ky (>
Publication Date: May 5, 1994 | doi: 10.1021/bk-1994-0575.ch003
where m and Κ have the same definitions as in Equation 1. Substituting the above
relationship into the Newtonian definition of the viscosity η = τ/*γ, one has for a
power law fluid
1
η^γ*" (5)
For shear thinning melts such as thermoplastics, 0 < m < 1. The smaller the
value of m, the more shear thinning the melt. Conversely, as m approaches 1, the
melt becomes more Newtonian and exhibits less shear thinning. Values of the
power law index for thermoplastic starch melts in this study ranged from 0.31 to
0.50, depending on the moisture content and temperature. When the molecular
weight is significantly reduced, the melts exhibit an increasing degree of
Newtonian behavior, indicated by m values greater than 0.80 for the dextrin.
The m values of thermoplastic starch are similar to those of polyethylene,
polystyrene, and poly (methyl methacrylate) (56,57). Thermoplastic starch melts
are therefore similar in character to synthetic polymer melts with regards to shear
thinning. Changes in the power law index of thermoplastic starch with
temperature are similar to those observed for synthetic thermoplastics (57).
Thermoplastic starch melts are similar to melts of synthetic polymers with
low glass transition temperatures. A measure of the temperature sensitivity of a
melt is given by the relative change in viscosity with temperature (56):
-ι -ι ( η - η σ , ) ) ( 6 )
where T is the reference temperature. Typical values of this parameter for the
r
starch melts in this study range from 0.026 to 0.033. By comparison, values for
polyethylene, polyamide-6, polyamide-6,6, polypropylene, and poly(ethylene
terephthalate) are in the range of 0.02 to 0.03. Polymers with higher T s such as
g
a
Publication Date: May 5, 1994 | doi: 10.1021/bk-1994-0575.ch003
10 100 1000
1
SHEAR RATE (secf )
101 • «
10 100 1000
1
SHEAR RATE (sec" )
Figure 10. Effect of MC on dextrin viscosity: (a) 110°C.; (b) 120°C.
content from the slope of ln(K) versus 1/T plots, where Τ is in Kelvins. Values
for the thermoplastic starch melts in this study are 9950, 8500, and 8500 Kelvins
at moisture contents of 15 %, 20%, and 30% respectively. These value are higher
than those reported by others (51), and lower than the value reported for potato
starch (25).
Activation energies for the dextrins are much higher than those of
thermoplastic starch. At 15% MC, E /R is 23,300 Kelvins, decreasing to 13,300
a
at 20% MC. The activation energy for dextrin is not simply a measure of flow
activation, but also reflects the changes in power law index with temperature.
Downloaded by IMPERIAL COLLEGE LONDON on February 18, 2015 | http://pubs.acs.org
(Pa*secT)
Control 38,900 (3,800) 0.43 (0.03)
TEG 2 21,400 (1,500) 0.48 (0.02)
TEG 5 14,100 (3,600) 0.48 (0.04)
Publication Date: May 5, 1994 | doi: 10.1021/bk-1994-0575.ch003
12
0 5 10 15 20 25 30
SCATTERING ANGLE 2*THETA
Figure 11. X-ray diffraction patterns of native starch and extruded starch
with and without additives: (1) native starch; (2) extruded with 20% MC;
(3) 1% lecithin; (4) 1% POES; (5) 2% GMS.
The fact that levels of POES or lecithin above approximately 1% do not extrude
well due to overlubrication suggests that complexes of these additives with
amylose are not stable during extrusion. Therefore, the viscosity and DSC data
Publication Date: May 5, 1994 | doi: 10.1021/bk-1994-0575.ch003
Conclusions
1
100 ι '
Publication Date: May 5, 1994 | doi: 10.1021/bk-1994-0575.ch003
10 100 1000
1
SHEAR RATE (sec"" )
Acknowledgements
Literature Cited
42. Launay, B.; Lisch, J.M. Twin-screw Extrusion Cooking of Starches: Flow
Behavior of Starch Pastes, Expansion and Mechanical Properties of
Extradates In: Extrusion Cooking Technology; Jowitt, R., Ed.; Elsevier
Applied Science: London, 1983; 159-180.
Publication Date: May 5, 1994 | doi: 10.1021/bk-1994-0575.ch003