Hydrolysis of this portion is different according t o the a-amylase used: bacterial amylase causes the fragmentation of the

granule while outer resistant layers remain after hydrolysis by

pancreatic a-amylase. In this case, the filamentous thin and long
structures observed here are very different from the structures
already described elsewhere for potato as well as the other
starches [8, 121.
These results confirm the need of direct electron diffraction on
thin cross section of starch granules as already carried out for
spherolytes by Helberr et al. [19].

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.

[7] Leach, H. W., and T. J . Schoch: Cereal Chem. 38 (1961), 34.

[8] Guilbot, A., and C. Mercier: In The polysaccharides Vol. 3,
Academic Press, New York 1984.
[9] Fuwa, H,, M.Nakajima, and A . Hamada: Cereal Chem. 54 (1977).
230.
[ 101 Fuwa, H., Y. Sujimoto, and T. Tanaku: Carb. Hydr. Res. 70 (1979).
233.
[ 111 Gallant, D. J., C. Mercier, and A . Guilbot: Cereal Chem. 49 (1972),
354.
1121 Gallant, D. J., A. Derrien, A . Aumaitre, and A. Guilbot: Starch/
Starke 25 (1973), 56.
[13] Tollier, M. T., and J. P. Robin: Ann. Technol. Agric. 28 (1979),
1.
[14] AOAC Officials Methods of Analysis. Association of Official
Analyticals Chemists: Washington, DC, 1984.
1151 Thivend,P., C. Mercier, and A. Guilbot: Determination of starch
with glucoamylase. In:Methods in Carbohydrate Chemistry, Vol.
VI, Academic Press, New York 1975.
[16] Larson, B. L., K. A. Cilles, andS. R. Jenes:Anal. Chem. 25 (1953),
802.
[17] Gallant, D. J., and A . Guilbot: StarchlStarke 21 (1969). 156.
[lS] Svensson,B.: FEBS Letts. 230,(1988), 72.
[19] Helberr, W., H. Chanzy, V. Planchot, A. BulCon, and P. Colonna:
Carbohydr. Polymers, accepted (1992).
Address of authors: Jean-Claude Valerudie*), Paul Colonnu**), Brigitte Boucher, and Daniel J. Gallant*).Institut National de la Recherche
Agronomique. BP 527 - 44026 Cedex 03 (France).
*) Laboratoire de Technologie Appliquee i la Nutrition.
**) Laboratoire de Biochimie et Technologie des Glucides.

(Received: March 16, 1993).

Development of Starch Based Plastics A Reexamination of Selected Polymer

Systems in Historical Perspective
Randal L. Shogren, George F. Fanta, and
William M. Doane, Peoria, IL (U.S.A.)
Recent patents in the starch-based plastics area have claimed melted
or destructurized starch as a new type of material. The term destructurized starch has apparently been coined after the physically
modified state of starch obtained by the disruption of the granular
state, resulting in the loss of order and crystallinity. A brief literature
review is presented which shows that, in the 1970s, starch containing
low (10-30%) water contents was extruded at elevated temperatures
to give a thermoplastic melt exhibiting no residual starch crystallinity.
Differential scanning calorimetry studies of starch-g-polymethyl acrylate and blends of starch with poly (ethylene-co-acrylic acid) are also
presented. These data indicate that these materials, prepared in the
1970s. also contain starch which was partially or completely destructurized. Thus, although ideas and uses for destructurized starch
in plastic items have proliferated in recent years, completely melted
or destructurized starch had been conceived and used much earlier.

Die Entwicklung von auf Stiirke basierenden Kunststoffen. Eine

Uberpriifung ausgewahlter Polyrnersysterne aus historischer
Perspektive. Neuere Patente auf dem Gebiet der starkebasierenden
Kunststoffe erforderten geschmolzene oder ,,destrukturierte Starke
als neues Material. Der Begriff ,,destrukturierte Starke wurde offenbar gepragt nach dem physikalisch modifizierten Status von Stake,
die nach dem ZerreiBen des kornigen Zustandes erhalten wurde
unter Verlust der Ordnung und der Kristallinitat. Ein kurzer Literaturuberblick wird aufgezeigt, welcher darlegt, daR in den 1970er Jahren Starke mit geringem Wassergehalt (10-30%) bei erhohten Temperaturen extrudiert wurde, um eine thermoplastische Schmelze zu
ergeben. die keine restliche Kristallinitat enthielt. Differential-Raster-Kalorimetrie-Untersuchungen von Stake-g-Polymethylacrylat
und Mischungen von Starke mit Poly(ethy1en-co-Acrylsaure)werden
ebenfalls aufgezeigt. Diese Daten zeigen, daR diese in den 1970er
Jahren hergestellten Materialien ebenfalls teilweise oder vollstlndig
destrukturierte St2rke enthielten. Somit haben sich in den vergangenen Jahren Vorstellungen und Verwendungen fiir destrukturierte
Starke in plastischen Artikeln entwickelt, obwohl vollstandig gescbmolzene oder .,destrukturierte Starke schon vie1 fruher verwendet worden waren.

* The mention of firm names or trade products does not imply that they are endorsed or recommended by the U. S. Department of

Agriculture

over other firms or similar products not mentioned.

276

starch/stirke 45 (1993) Nr. 8, S. 276-280

8 VCH Verlagsgesellschaft mbH. D-69451 Weinheim, 1993

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

40-60% PMA by weight. A study of granular S-g-PMAshowed

that PMA is the continuous phase when extrusions are carried
out under low moisture conditions [16]. Phase reversal can take
place if the level of PMA in the polymer is sufficiently low and if
there is sufficient water present to yield a starch melt during
extrusion. Extruded S-g-PMA ribbons showed only small starch
melting peaks when examined by differential scanning calorimetry (DSC), and these were only for samples extruded at the
lowest moisture content. Areas of crystallinity were therefore
largely disrupted during extrusion.
Since starch will biodegrade to carbon dioxide and water in a
relatively short time compared with most synthetic polymers,
much of the research in recent years has centered on increasing
the amount of starch in starch-plastic composites to the highest
possible level. The ultimate goal of these research efforts is to
prepare consumer items for one-time use from substantially
pure starch and to exclude synthetic polymers from the formulation. For materials such as these, starch must contain enough
water so that it will melt below its decomposition temperature
and yield a final product in which the polysaccharide forms a
continuous polymeric phase. Wiedmann and Sfrobel[171 refer
to starch in this form as thermoplastic starch and discuss the
conditions necessary to form and process this type of material in
a twin screw extruder. A good example of the commercial
potential of these extruded starch plastics is the starch based
expanded packaging material recently patented by National
Starch and Chemical Corp. and now marketed as a biodegradable replacement for Styrofoam [18].
Another example of the preparation of single-use items from a
starch melt is the Novon technology patented by Warner
Lambert Co. [19-201. Starch, containing 5-30% water, is
processed at elevated temperatures in an extruder or injection
molder to form a melt in which the molecular structure of starch
is completely disordered. Evidence for disordering suggested in
these patents is the disappearance in the DSC thermogram of a
high temperature endotherm attributable to starch melting [21].
For potato starch, the endotherm was observed at moisture
contents of 12-40% in the range of 190-160C. This so-called
destructurized starch is claimed as a new material. substantially comparable to melts formed from well-known hydrophobic thermoplastics. To modify and improve its physical properties, destructurized starch has also been compounded with a
variety of different polymers that are sufficiently hydrophilic to
afford some degree of compatibility with the aqueous starch
system.

1.2 Thermal transitions in starch

Thermal analysis of native starch granules using DSC and
differential thermal analysis (DTA) has provided some insight
into the behavior of starch when it is heated in the presence of
limited amounts of water. DSC showed a single endotherm at
66C for potato starch containing a volume fraction of water
greater than 0.7 [22].At lower water levels, a second higher
temperature endotherm developed, which was attributed to the
melting of starch crystallites. This endotherm became the only
one observed with volume fractions of water less than 0.45. As
the water concentration decreased, this endotherm shifted to
higher temperatures and also decreased in size. When a cooled
sample was reheated (in both the presence and absence of
added water), DSC showed no endothermic transitions, indicating that crystallinity had been lost.
Takahashi et al. [23] used differential thermal analysis (DTA)
to study thermal transitions in corn, waxy corn, wheat, kuzu and
potato starches at low moisture contents. For moisture contents
of 0.7-12 wt%. two strong endothems were observed, one at
about 190-230C (Peak A) and the other (Peak B) at
277

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.

1.3 Extrusion processing of starch in foods

As correctly stated by Wiedmann and Strobe1 (17), Technologically, starch extrusion know-how for the extrusion cooking of
food complements that for compounding plastics. Furthermore, this know-how, which was largely obtained in the 1970sand
1980sseems to form the basis for much of the new technology
now being reported for starch-based plastics.
Food extruders can be regarded as high temperature, short time
reactors, in which granular starch having a moisture content of
roughly 10-25% ist first compressed into a dense, compact
solid and is then converted into a molten, amorphous mass by
the high pressure, heat and mechanical shear forces encountered during processing. Excellent reviews on the subject of starch
extrusion related to food processing have been published by
Mercier and coworkers [26-281, by Lai and Kokini [29], and by
Harper [30].
The transformations of starch that occur during extrusion are
influenced by extruder geometry as well as by processing
variables such as extrusion temperature, screw speed, feed rate
and moisture content of the starch. Temperature and moisture
content have been cited as the two most important variables
affecting physical properties of the extruded starch [29].
Chemical modifications of starch during extrusion processing
are minimal, although degradation into lower molecular weight
components has been demonstrated using gel permeation chromatography and intrinsic viscosity measurements [29]. Degradation increases as extrusion temperature is increased and as
the moisture level in starch is reduced [30].
Extruded starches absorb water at room temperature to form
pastes composed of soluble starch and swollen gel particles. The
absence of ethanol-soluble material in extruded cornstarch
indicated that there is little degradation to maltodextrins [27]. In
contrast to cereal starch, potato starch yields a fraction soluble
in 80% ethanol, suggesting the formation of oligosaccharides
having a molecular weight iower than about 2000 [26].
Starch extrudates tend to expand upon exiting the extruder die,
and this phenomenon has resulted in the widespread use of
extrusion for the preparation of snack foods [27,30]. Expansion
of starch extrudates is caused not only by flash-off of internal
moisture but also by die swell,due to the elastic character of the
molten extrudate (i. e. the Barus effect [31]). The observance of
die swell provides evidence that the granular structure has been
278

destroyed and that a polysaccharide melt, analogous to a

conventional polymer melt, has indeed been produced. The
destruction of native starch granules in molten extrudates has
also been confirmed by scanning electron microscopy [27]. As
expected, expansion at the die is reduced when extrusion
temperatures are not high enough to convert starch granules
into a continuous melt.
Starch extrudates are largely amorphous glasses at room temperature, and polymer chains are thus frozen in a random
configuration; a small amount of crystalline amylose-lipid
complexes is also present [26]. Water acts as a plasticizer to
depress the glass transition temperature (Tg); slow reassociation of polysaccharide chains, increased hydrogen bonding and
recrystallization (i. e. annealing) are observed above Tg [28].
Cornstarch extruded at a number of different temperatures and
moisture contents showed no endothermic transitions when
examined by DSC [32, 331, indicating the loss of crystallinity
during the extrusion process. It thus appears that starch crystallites have been totally disrupted by melting, as in the destructurized starch claimed at a later date in the patent literature
~91.
Structural changes that occur in starch during extrusion processing have also been studied by X-ray diffraction [26]. Native
cereal starches exhibit the A-type diffraction pattern, whereas
potato starch exhibits the B-type. These diffraction patterns are
either partially or completely destroyed during extrusion, depending on the moisture in the starch as well as the temperature
and the amount of shear used during processing.
Extrusion of cornstarch at 135C and a moisture content of 22%
produces a V-type diffraction pattern due to complex formation
between amylose and the small amount of lipid present in the
native starch [27]. When extrusion is carried out at 185,200 and
225C, a final water content of only 13% is obtained, and a new
structure called the extruded or E-type is observed. This
structure is characterized by three diffraction peaks slightly
displaced from those of the V-structure and is transformed back
into the stable V-type, if the starch extrudate is conditioned to a
water content of 30%. Similar behavior has been observed with
wheat, rice and amylomaize starches containing 55 and 70%
amylose. It has been proposed that the E-type structure is
helical and, like the V-structure, has six glucose residues per
turn. Differences between the two structures have been attributed to different interaxial distances between helices.
The V-type and E-type structures have not been observed with
potato starch (which is lipid free) or with waxy maize starch
(which contains no amylose) [28]. With these two starches,
X-ray diffraction patterns showed reduced crystallinity at extrusion temperatures as low as 70C. At higher temperatures, the
crystalline structure was completely destroyed, and the X-ray
diffraction pattern was typical of an amorphous state [27].
The literature published on starch extrusion over roughly the
last two decades (mainly in relation to food processing) clearly
shows that a melt is formed under high temperature, low
moisture conditions and that none of the original starch crystallinity remains after processing. From the data presented, it is
difficult to see how the physical state of starch in these extrudates is substantially different from that in the so-called destructurized starch claimed in recent patents.
Since research at NCAUR over the last 20 years has dealt with
the preparation and extrusion processing of starch-polymer
composites. we wished to determine whether the original
crystalline structure of starch in some of our previously prepared products was completely lost during processing. Products
chosen for this study were extruded starch, polymer composites
containing starch and EAA and, finally, a graft copolymer
prepared from granular starch and methyl acrylate (S-g-PMA).
DSC was used to study phase transitions in these materials.
starchlstarke 45 (1993) Nr. 8, S . 276-280

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

DSC thermograms of granular, unprocessed cornstarch at 11

and 20% moisture (A and B respectively) are shown in Fig. 1.
Peak numbers 2 and 4 correspond to the melting of amylopectin

c,"
I

50

100

150

200

2 I0

Temperature ('C)

Figure 2. DSC thennograms of granular S-g-PMA, 55% PMA (A),

S-g-PMA extruded at 110C and 10% moisture (based on starch
content) (B). and S-g-PMA extruded at 110C and 30% moisture (C).
AU samples were adjusted to 20/0 moisture based on starch content for
DSC runs.

44i
42

40-

ii
c
mP)

while peak 5 corresponds to the melting of amylose 1341. The

second, sharper melting endotherm (#4) for amylopectin is
only seen at moisture contents of 16-30% [34]. This is apparently the sharp endotherm referred to in the Warner-Lambert
patents [20, 211 and in earlier work [24, 251 (i.e. the Z endothem). The melting temperature of endotherm #4 in Fig. 1 B is
165C similar to that found for waxy maize starch (170C) [24]
and potato starch (179C) [25] at 20% moisture. Its origins are
unclear, although it may represent the melting of larger crystallites of amylopectin formed by annealing during the heating
cycle.
Figure 1 also shows thermograms of starch processed by extrusion at 175C (C) and starch solubilized by jet cooking and then
drum dried (D). These two samples were also equilibrated to a
moisture content of 20%. The disappearance of peaks 2 and 4
indicates that the native crystalline structure of starch has been
destroyed or melted by each of these treatments. The small
melting endotherms corresponding to amylose suggest that
amylose, which is known to be in an amorphous state in the
starch granule, has partially crystallized during the heating
process. X-ray diffraction studies have shown that extruded
starch usually contains amylose-lipid V-type complexes [32,36].
These complexes likely melt and then recrystallize into the
crystalline B-form during heating in the DSC. Peak 1 corresponds to enthalpy relaxation (physical aging) of amorphous
starch [34].
Figure 2 shows similar DSC thermograms for (A) granular
S-g-PMA, (B) S-g-PMA extruded at 110C with 10% moisture

27-

3 Results and Discussion

F
E

~~

50

100

150

250

Temperature ('C)

Figure 1. DSC thermogramsof granular cornstarch at 11% moisture

(A), granular cornstarch at 20% moisture (B). extruded cornstarch at
20% moisture (C) and jet cooked and drum dried cornstarch at 20%
moisture (D).

(based on starch) and (C) S-g-PMA extruded at 110Cwith 30%

moisture. Samples were adjusted to 9.5% moisture (20% water
based on starch) for the DSC runs. These thermograms indicate
that about 30% of the starch has been melted after extrusion at
10% moisture, while essentially all the starch has been melted at
30% moisture. These results suggest that the S-g-PMA samples
generated previously in the examples of Bugley et al. [15] also
contained partially or completely melted (or "destructurized"
starch.
Figure 3 shows thermograms for starch EAA films prepared by
methods a. b and c, as described in the Experimental Section.
All three thermograms are similar with melting peaks for EAA
at 40-100C and exothenns in the 150-180C region. No
melting peaks for starch are evident, indicating that the starch
component of these materials is completely melted and that all

starch/starke 45 (1993) Nr. 8.S. 276-280

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.

structure and crystallinity originally present in starch has been

lost during processing. The exotherms may be due to the heat
released during the hydration of the carboxyl groups of
EAA.

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.

[5] Westhoff, R. P., F. H. Otey, C. L. Mehltrerter, and C. R. Russell: Ind.

Eng. Chem. Prod. Res. Dev. 13 (1974) 123.
[6] Otey, F. H., R. P. Westhofj and C. R. Russell: Ind. Eng. Chem. Prod.
Res. Dev. 16 (1977), 305.
[7] Otey, F. H., and R. P. Westhoff: U. S . Patent 4,133,784 (1979).
[8] Otey, F. H., R. P. Westhofj and W. M . Doane: Ind. Eng. Chem.
Prod. Res. Dev. 19 (1980), 592.
[9] Otey, F. H., and R. P. Westhog: U. S . Patent 4,337,181 (1982).
[lo] Otey, F. H., R. P. Westhoff, and W. M. Doane: Ind. Eng. Chem. Res.
26 (1987), 1659.
[ll]Bastioli, C., V. Bellotti, L. Del Giudice, G. Del Tredici, R. Lombi,
and A . Rallis: PCT Int. Patent Appl. WO 90/10671, September 20,
(1990).
[12] Durkin, H. L.: Proceedings of Corn Utilization Conference 111,
National Corn Growers Assn., Session IV (1990).
[13] Bastioli, C., and E. Tinello: Proceedings of Corn Utilization Conference IV, National Corn Growers A m . , Session I (1992).
[14] Fanta, G. F., and W. M. Doane: In Modified Starches: Properties
and Uses (Ed. 0. B. Wurzburg), CRC Press, Boca Raton, FL,
1986, p. 149.
[15] Bagley, E. B.,G . F. Fanta, W. M . Doane, L. A. Gugliemelli, and C.
R. Russell: U. S . Patent 4,026,849 (1977).
[16] Trimnell, D., C. L. Swanson, R. L. Shogren, and G. F. Fanta: J.
Appl. Polym. Sci. 48 (1993), 1665.
[17] Wiedmann, W., and E. Strobel: StarchIStarke 43 (1991), 138.
[18] Lacourse, N . L., and P. A . Altieri: U. S . Patent 4,863,655 (1989).
[19] Wittwer, F., and I. Tomka: U. S . Patent 4,673,438 (1987).
[20] Lay, G., J. Rehm, R. F. Stepto, M. Thom, J.-P. Sachetto, D. J. Lenrz,
and J. Silbiger: U. S . Patent 5,095,054 (1992).
[21] Stepto, R., and B. Dobler: EP Appl. 0326517 (1989).
[22] Donovan, J. W.: Biopolymers 18 (1979), 263.
[23] Takahashi, K., K . Shirai, and K. Wada: Agric. Biol. Chem. 46
(1982), 2505.
[24] Maurice, T. J., L. Slade, R. R. Sirett, and C. M . Page: In Properties
of Water in Foods (Eds. D. Simatos and S . L. Multon), Martinus
Nijhoff, Dordrecht, The Netherlands, 1985, p. 211.
[25] Russell, P.J.: J. Cereal Sci. 6 (1987), 133.
[26] Mercier, C., R. CharbonniPre, D. Gallant, and A . Guilbot: In
Polysaccharides in Food (Eds. J. M. V. Blanshard and J. R.
Mitchell), Butterworths, London 1979, p. 153.
[27] Mercier, C.: In Food Processing Engineering vol. 1 (Food Processing Systems), (Eds. P. Linko, Y. Malkki and J. Olkku), Applied
Science Publishers, Ltd., London 1980, p. 795.
[28] Colonna, P., J. Tayeb, and C. Mercier: In Extrusion Cooking
(Eds. C. Mercier, P. Linko and J. M. Harper), American Association of Cereal Chemists, St. Paul, MN, USA, 1989, p. 247.
[29] Lai, L . S.,and J. L. Kokini: Biotechnol. Prog. 7 (1991), 251.
[30] Harper, J. M.: In Developments in Carbohydrate Chemistry
(Eds. R. J. Alexander and H. F. Zobel), American Association of
Cereal Chemists, St. Paul, MN, USA, 1992, p. 37.
[31] Mendelson, R. A., E L. Finger, and E. B. Bagley: J. Polym. Sci. C,
No. 35 (1971), 177.
[32] Chinnaswamy, R., M. A . Hanna, and H. F. Zobel: Cereal Foods
World 34 (1989), 415.
[33] Gomet, M . H., and J. M. Aguilera: J. Food Sci. 49 (1984), 40.
[34] Shogren, R. L.: Carbohyd. Polym. 19 (1992). 83.
[35] Christianson, D. D., G. F. Fanta, and E. B. Bagley: Carbohyd.
Polym. 17 (1992), 221.
[36] Mercier, C.,R. CharbonniPre,J. Grebaut, and J . F. de La GueriviPre:
Cereal Chem. 57 (1980), 4.

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).

280

Address of authors: R. L. Shogren, G. F. Fanta, and W. M . Doane,

Research Chemists, Plant Polymer Research, National Center for

Agricultural Utilization Research, Agricultural Research Service, U. S.
Department of Agriculture, 1815 N. University St., Peoria, IL 61604,
(U. S. A.).
(Received: May 15, 1993).

starch/st&rke45 (1993) Nr. 8,S . 276-280