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Acknowledgement
The authors are indebted to Dr. L. Degras from CRAAG (I. N. R. A.,
Guadeloupe, French West Indies) who furnished the tubers.
Bibliography
[ l ] Banks, S. W., and C. T. Greenwood: Starch and its components.
Edinbourgh University Press, Edinburgh 1975.
[2] Robyt, J. E , and W.J. Whelan: In Starch and its derivatives,4th
ed., Chapman and Hall, London 1968.
[3] Mercier, C.: In Hydrolases et dCpolymCrases, Gauthier Villars.
Paris 1985.
[4] Delpeuch, E , and J. C. Favier: Ann. tech. agric. 29 (1980), 53.
[5] Gallant, D. J., H. Bewa, Q. H. Buy, B. Bouchet, 0. Szylit, and L.
Sealy.: Starkelstarch 34 (1982). 255.
[6] Rasper, V., G. Perry, and C. L. Dutschaever: Can. Inst. Food Sci.
Technol. J. 7 (1974). 166.
* The mention of firm names or trade products does not imply that they are endorsed or recommended by the U. S. Department of
Agriculture
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0038-9056/93/0808-0276$05.00+.25/0
1 Introduction
1.IThe development of starch-plastic composites
In recent years, most countries of the world have recognized the
need to reduce the amount of plastic waste discarded in
landfills. Although improved efforts to recycle discarded plastics would help accomplish this goal, recyclingwould be neither
practical nor economical for certain end-use applications such
as agricultural mulch films, planting pots and garbage bags. For
applicationssuch as these, plastics are needed that will fragment
or degrade into benign by-products under composting conditions. The maritime industry also requires degradable plastics in
order to comply with the MARPOL treaty, which prohibits the
dumping of non-degradable articles into the sea after January 1,
1994.
The incorporation of starch into plastics to enhance their
fragmentation and degradability in the environment has generated considerable interest [l]. Starch is inexpensive (about 10
cents per pound). is totally biodegradable and is available in
large quantities from certain crops (i. e. corn and wheat) produced in abundance beyond available markets. Replacement of
petroleum based plastics with starch is also attractive from the
standpoint of conserving our petrochemical resources. This
publication will center on starch-containingplastics prepared by
extrusion processing.
Use of granular starch as a filler in plastics began with the work
of Griffin [2-41 in the 1970s. Starch-containing polyethylene
films and other consumer items based on this technology are
currently being marketed. Since whole starch granules are used
in this technology, the level of starch addition is generally
limited to about 10% or less, by weight. Starch is dried to < 1%
moisture to inhibit steam formation during extrusion processing, and starch granules have also been surface-treated (for
example with silanes) to increase the compatibilityof hydrophilic starch with the hydrophobic plastic matrix. Pro-oxidants can
also be added to promote degradation of the synthetic polymer.
At about the same time period as Griffins research, Otey and
coworkers at the National Center for Agricultural Utilization
Research (NCAUR) were studying starch-plastic systems in
which the starch granule structure was totally disrupted [5-lo].
For example, a process was developed to extrusion-blow films
from mixtures of starch and poly (ethylene-co-acrylic acid
(EAA) in the presence of aqueous ammonium hydroxide and
urea [lo]. Polyethylene could be incorporated into these formulations as a partial replacement for EAA in order to reduce raw
material costs and in some instances improve film properties. In
these systems, starch can form a continuous phase rather than
merely being present as a particulate filler. Starch loadings as
high as 50% by weight can thus be obtained in these composites
and still obtain acceptable properties. The Ferruzzi Group of
Italy (Novamont) [ll-131 is marketing composites of this
general type. In these materials, starch is alloyed with various
low molecular weight hydrophilic polymers, such as vinyl
alcohol-containingcopolymersand the EAA polymer first used
by Otey et al. in starch based plastics.
Starch-thermoplastic polymer composites have also been prepared by graft polymerization [14]. Treatment of starch with
ceric ammonium nitrate in water yields free radical sites on the
starch backbone that can act as macroinitiators in the presence
of various monomers to yield polymer grafts of high molecular
weight. Extensive research has been carried out at NCAUR on
polymers of this type, particularly starch-g-poly(methyl acrylate) (S-g-PMA) [lS, 161. Graft copolymers have been prepared
from both granular and cooked starch, and extruded plastics
with good properties are obtained from S-g-PMA containing
starchlstiirke 45 (1993) Nr. 8. S. 276-280
230-250C. Peak B was presumed to be due to starch decomposition. Microscopic examination of starches at different stages of the heating process showed the disappearance of granule
birefringence along with cohesion of individual starch granules
at the temperature of Peak A. At the endpoint of Peak A,
granules were completely fused. Since there was insufficient
water present to cause granules to hydrate and swell, loss of
birefringence and granule fusion were assumed to be due to
granule melting. Peak A occurred at a different temperature
with each starch variety examined. Although this endotherm
shifted to higher temperatures with decreasing moisture content, the position of the decomposition peak B was relatively
moisture-independent.
Maurice et al. [24] and Russell [25] have published DSC studies
of waxy maize starch at various moisture levels. They found
three distinct endotherms which were referred to as G (gelatinization) and M1 and Z (melting). The G endotherm was
observed only at 50% moisture and above while the Z endotherm, a sharp peak appearing at temperatures slightly higher
than the M1 endotherm. was observed at 20-50% moisture.
The origin of the Z endotherm is uncertain although it was
suggested that it resulted from annealing of the amylopectin
crystallites during heating.
2 Experimental
2.1 Sample preparation
Cornstarch was Buffalo 3401 from CPC International Inc.
Cornstarch, adjusted to 25% water content, was extruded into a
ribbon at 175C as described earlier [34]. Starch was also
dissolved by passing 20% aqueous suspensions of cornstarch
through a steam-jet cooker (Penick & Ford, Cedar Rapids, IA)
at 140C [35]and the resulting solution was dried on a steamheated. double-drum drier heated to 150C.
Granular starch containing 55% (by weight) grafted PMA was
synthesized according to Bugley et al. [15] as modified by
Trimmell et al. [16]. Starch-g-PMA, containing 30% water
based on starch. was extruded at 110C following example 11 B
of Bugley et al. 1151.
Starch-EAA films. containing 50% starch, were prepared by
Orev and coworkers using the following three techniques: a)
heating starch with an aqueous suspension of the ammonium
salt of E A A (20% total solids) in a flask at 80C and casting a
film onto a heated plate [6,7], b) by pasting starch, EAA and
ammonia at 50% solids in a Readco mixer followed by multiple-pass extrusion film blowing at 120- 130C to reduce water
content to 5-10% [8, 91 and c) by multiple-pass extrusion of
starch and E A A with 15% urea and 20% water at 8O-ll0"C
Wl.
2.2 DSC Analyses
Prior to DSC analysis, the above samples were pulverized by
shaking in a stainless steel vial with two steel balls at liquid
nitrogen temperature. The starch-EAA film prepared by the
above method (c) was extracted with water before pulverizing
to remove urea. Samples (29-30mg) were adjusted to the
desired moisture level by placing them in a desiccator containing water, and samples were then sealed in stainless steel,
high-pressure DSC pans (Perkin-Elmer Corp., Norwalk, CT).
DSC analyses were carried out using a Perkin-Elmer DSC7.
Samples were heated from 2 to 220C at a rate of 10"C/min.
347
331
zE
ii
c
m
29-
28-
-'
250
26
c,"
I
50
100
150
200
2 I0
Temperature ('C)
44i
42
40-
ii
c
mP)
27-
F
E
~~
50
100
150
250
Temperature ('C)
279
F
E
ii
c
3:
P
I
50
100
150
200
250
Temperature (C)
Figure 3. DSC thermograms of starcNEAA films containing approximately 50% starch prepared by procedures a (A), b (B) and c (C) as
described in the experimental section. All samples were adjusted to
20% moisture based on the starch content for DSC runs.
4 Conclusions
Although recent research on starch-based plastics has provided
new information on the behavior of starch during extrusion and
injection molding, a major criticism of some of this work is the
terminology used to describe physical changes that occur within
the starch granule during processing. New terms, such as
destructurized starch have been coined to describe physical
states that are already well-known in the literature under other
names, such as melted starch, molecularly dispersed or disrupted starch, etc. Over the past two decades, scientists studying the
processing of starch-containing foods have been major contributors to research related to starch extrusion and have published a body of literature that encompasses many of the so-called
new principles set forth in publications related to starch-based
plastics.
DSC studies of extruded starch, starch-EAA composites and
S-g-PMA graft copolymers prepared in the 1970s and 1980s at
.NCAUR show that the original crystalline structure of the
starch component has been lost through processing. It thus
appears that the physical state of starch in these systems is
substantially the same as that of destructurized starch. This
leads one to conclude that destructurized starch is not a new or
novel entity but is merely another term used to describe the
well-known disordering of starch chains and the melting of
crystallites that takes place when starch is heated in the presence of limited amounts of water.
Bibliography
[l] Doane, W. M., C. L. Swanson, and G. F. Fanta: In Emerging
Technologies for Materials and Chemicals from Biomass, ACS
Symp. Ser. No. 476. (Eds. R. M. Rowell, T. P. Schultz and R.
Narayan), American Chemical Society (1992), p. 197.
[2] Grvfin, G. J. L.: U. S . Patent 4,016,177 (1977).
[3] Griffin, G. J. L.: U. S. Patent 4,021,388 (1977).
[4] Griffin, G. J. L.: U. S. Patent 4,125,495 (1978).
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