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Composition and Properties

of Commercial Native Starches


By J. J. M. Swinkels, Veendam
(The Netherlands)

The physico-chemical properties of starches depend upon the botan- Zusammensetzung und Eigenschaften der nativen Starken des
ical source from which they are isolated. Important differences Handels. Die physikalisch-chemischen Eigenschaften der Starken
between potato, maize, wheat, tapioca and waxy maize starch are sind abhangig von den Pflanzen, aus denen sie isoliert werden. Es
reviewed. Special attention is given to production and applications; wird eine Ubersicht uber einige wichtige Unterschiede zwischen
to composition and properties of the starch granules ;to amylose and Kartoffel-, Mais-, Weizen-, Tapioka- und wachsiger Maisstarke
amylopectin; to gelatinization characteristics; and to the properties gegeben. Besondere Berucksichtigung finden: Produktion und An-
of starch pastes and starch films. wendungen ; Zusammensetzung und Eigenschaften der Starkekor-
ner ; Amylose und Amylopektin ; Verkleisterungseigenschaften ; die
Eigenschaften von Starkepasten und Starkefilmen.

1 Introduction Table 1.
Production and Uses of Commercial Starches.
Starch occurs in the form of tiny white granules in various Production and Potato Maize Wheat Tapioca Waxy
sites of plants, for example in cereal grains (maize, rice, IJses starch starch starch starch maize
wheat, barley, oat, sorghum), in roots (sweet potatoes, cassa- starch
ve, arrowroots, yam), in tubers (potatoes), in stems (sago
palm) and in legume seeds (peas, beans). The main sources of World production
commercial starch are maize, potatoes, wheat, cassave and (million t ) 2 13 0.8 0.7 0.2
waxy maize. I n addition, starch is also commercially isolated Percent of raw
from sweet potatoes, rice, sorghum, arrowroots, mung bean material used
and sago. for starch produc-
The properties of starches prepared from different sources tion (world) 3 5 0.2 3 100
vary considerable. The chemical composition and the physi- Main production
cal characteristics are essentially typical to the biological countries Holland USA Austra- Thai- USA
origin of the starch. In this survey the differences between the Sovjet- Japan lia land
Union Sovjet- USA Brazil
main starches of commerce are reviewed with respect to
Poland Union Japan
production and applications, properties and composition of
Main commercial
starch granules, amylose and amylopectin, gelatinization
uses Food Sugars Bakery Food Food
characteristics, properties of starch pastes and properties of Paper Paper Adhe- Adhe- Adhe-
starch films. Adhe- Corru- sives sives sives
For some important commercial starches the following syn- sives gated Sugars
onyms are used: board
maize starch corn starch; regular corn starch; dent
corn starch, ca. About 70% of the world production of maize starch is
potato starch farina, converted into corn syrup, isoglucose or dextrose.
tapioca starch cassave starch; manioc starch,
waxy maize starch waxy corn starch; amioca. 3 Starch Granule Properties
By chemical and/or physical modification, the properties of
the native starches may be altered. The relative differences Various properties of starch granules can be seen from Table
between the native starches are however more or less retained
2 [2-91.
in the corresponding modified starches. The properties of the Starches may be classified into three groups. The first group
parent starch greatly affect the characteristics of the modified comprises the common cereal starches (maize, wheat, sor-
starches. ghum, rice). The second group comprises the tuber (potato)
and root (tapioca, arrowroot, sweet potato) starches. The
2 Production and Uses composition and properties of these two groups of starches
are distinctly different from each other. The third group
Table 1 shows the annual world production (estimated) and comprises the waxy starches (waxy maize, waxy sorghum,
the most important industrial uses of various commercial waxy rice). These starches are isolated from cereals but the
starches [ I , 21 (Table 1). rheological properties of the waxy starches resembles most
The total annual world production of commercial starches is closely t o those of tapioca starch.
about 17 million. Only about 1.5% of the annual world crop Figure 1 shows schematically the appearance of various
of starch containing raw materials (cereals, tubers, roots) is starches.
used for the industrial production of starch. About 50% of Potato starch has relatively large oval granules in contrast t o
the maize starch are produced in the United States ofAmeri- the smaller round or polygonal granules of maize starch.

starch/starke 37 (1985) Nr. 1, S. 1 - 5 0VCH Verlagsgesellschaft mbH, D-6940 Weinheim 1985 0038-9056/85/0101-0001$02.50/0 1
Table 3.
Composition of Starch Granules (Average Values)

Starch Components Potato Maize Wheat Tapioca Waxy


starch starch starch starch maize
starch

Moisture at 6570
Pofafo Sfarch Maize Sfarch Wheaf sfarch
RH and 20°C. 19 13 13 13 13
Lipids (YOon dry
substance) 0.05 0.7 0.8 0.1 0.1 5
Proteins
(YOon d.s.) 0.06 0.35 0.4 0.1 0.25
Ash (YOon d.s.) 0.4 0.1 0.2 0.2 0.1
Phosphorus
I
7apioca sfarch
I
Waxy maize Sfarch
I ( % on d.s.) 0.08 0.02 0.06 0.01 0.01
Amount of taste
Figure 1 . Micrcscopic appearance of commercial starches (enlar-
and odour
gement 500 x ).
substances low high high low medium
relative relative
Table 2.
Starch Granule Properties (Average Values).

Starch granule Potato Maize Wheat Tapioca Waxy compared with potato (0.05%)and tapioca starch (0.1%).
properties starch starch starch starch maize The fatty substances (lipids) in the cereal starches are predo-
starch minantly lysophospholipids (in wheat starch) or free fatty
acids (in maize and waxy maize starch). In maize and wheat
Type of starch tuber cereal cereal root cereal
starch granules at least a part of the amylose and the lipids
Shape oval, round, round, trun- round, exist as an amylose-lipid inclusion complex.
spheri- POIY- lenti- cated, POlY-
cal gonal cular round, gonal
The high amount of lipids in the common cereal starches has
oval the following unfavourable effects:
Diameter, range a ) Lipids reduce the water-binding capacity, the swelling and
(w) 5-100 2-30 1-45 4-35 2-30 the solubilization of starches;
Diameter, number b ) The oxidation of lipids results in the formation of unde-
average (pm) 21 10 8 15 10 sirable flavours;
Diameter, weight c) In starch pastes and starch films the lipids are present in
average (pm) 40 15 25 25 15 the form of an “inert” complex with the amylose molecu-
Number of granules les. This complex does not contribute to the thickening
p c v g starch x lo6 60 1300 2 600 500 1300 power or binding force of the gelatinized starch;
Average number d ) The presence of amylose-lipid inclusion compounds
of starch makes starch pastes and starch films opaque or cloudy.
molecules in one
granule x 10” 50 10 5 4 0.01 The cereal starches (maize, wheat, waxy maize) contain a
considerable amount of proteins (0.25 - 0.5 YO)compared
Specific area
with potato (0.06%) and tapioca starch 0.1 YO). The amount
m2/w 100 300 500 200 300
of proteins is calculated as N x 6.25 and includes the real
proteins, peptides, amides, amino acids, enzymes and nucleic
”heat starch posesscs a bimodal particle-size distribution. acids. The high content of proteins in the cereal starches may
The subdistribution of small granules ranges in size from less have the following undesirable effects: formation of mealy
than 0.5 pm to about 10 pm with a weight average diameter flavours ; foam building and colour formation in hydro-
of about 6 pm. The subdistribution of large granules ranges 1ysates.
from about 10 pm. to 45 pm with a weight average diameter The ash content can be determined as the residue after
of about 24 pm. The larger granules in wheat starch represent ignition of the starch at a specified temperature. Potato
only about 20% of the total number but account for about starch has a relatively high ash-content because of the pre-
90% of the weight. sence of phosphate groups. As metals, the ash of native
starches contains mainly calcium, potassium, magnesium
and sodium.
4 Composition of Starch Granules Potato starch is the only commercial starch which contains
an appreciable amount of covalently bonded phosphate
Table 3 shows the chemical composition (average values) of monoester groups (0.06 - 0.10% calculated as P). The nega-
various native starches [2, 5, 6 , 7 , 10, 11, 12, 131. tively charged phosphate groups are linked exclusively to the
The amount of water absorbed by starch granules is depen- potato amylopectin molecules (about 1 phosphate mono-
dent on the relative humidity (RH) and the temperature of ester group per 300 glucose units).
the atmosphere in which they have been stored. Most com- Although the ionic charge is not high, in aqueous solutions
mercial native starches contain 10 t o 20% moisture under the repulsion of like charges very likely helps t o untangle the
normal atmospheric conditions. individual polymer molecules and extends there sphere of
The common cereal starches (maize, wheat, rice, sorghum) influence. This extension or uncoiling of the branches of the
contain a high percentage of fatty substances (0.6- 1 .O%) anionic potato starch amylopectin increases the viscosity and

2 starch/stirke 37 (1985) Nr. 1, S. 1 - 5


the thickening power of potato starch pastes. The phos- Table 4.
phorus in the cereal starches is mainly present as lysophos- Amylose and Amylopectin (Average Values).
pholipids.
The light flavour of raw cereal of maize and wheat starch Content; DP; Potato Maize Wheat Tapioca Waxy
products results from their high content of lipids and pro- numbers starch starch starch starch maize
starch
teins. Potato and tapioca starch generally exhibit much less
of the undesirable starchy flavours (low content of lipids and Amylose content
proteins). Waxy maize starch has less off-flavours than maize (% on d.s.) 21 28 28 17 0
starch but somewhat more than tapioca or potato starch. Amylopectin
content 79 72 72 83 100
5 Amylose and Amylopectin Amylose, Degree
of Polyme-
Table 4 lists some data relating to amylose and amylopectin risation (DP) 3000 800 800 3000 -
[2, 3, 7, 12, 13, 14, 15, 161. Amylopectin,
Nearly all kinds of starch contain two types of glucose Degree of Polyme-
polymers : an essentially linear molecule termed amylose and risation x lo6 2 2 2 2 2
a highly branched polymer termed amylopectin. Potato Number of amy-
(21 YO) and tapioca starch (17%) have a much lower amylose lose molecules
per g starch x 10’’ 30 130 130 20 0
content as compared to 28% for maize and wheat starch. The
linear starch chains (amylose) have an increased tendency to Number of amylo-
pectin molecules
line up into bundles or micelles (retrogradation).
per g starch x lo” 150 130 130 150 190
The amylopectin content is calculated from : amylose con-
+
tent amylopectin content = 100%. Waxy maize starch is
Ratio number of
molecules amylose :
different from the other 4 starches in that is consists solely of amylopectin 200 1 000 1000 150 0
amylopectin. The degree of polymerisation (DP) of amylose Average degree of
depends upon the source of the starch. Potato and tapioca polymerisation of
starch contain amylose molecules which have a substantially starch molecules 14000 3 000 3000 18000 2000000
higher degree of polymerisation than the amylose molecules ~

of corn and wheat starch. Potato and tapioca amylose have a


DP-range of about 1000 t o 6000 glucose-units (average 6 Gelatinization characteristics
about 3000). Corn and wheat amylose have a degree of
polymerisation ranging from 200 to 1 200 glucose-units (aver- The gelatinization characteristics of various native starches
age about 800). The long amylose molecules d o not readely are summarized in Table 5 [ 2 , 5 , 10, 14, 17, IS].
move into tight association with other chains (low rate of A well-known method for following the viscosity changes
retrogradation). The small amylose molecules are more pro- during cooking of a starch paste, is with the Brabender visco-
ne to quick association (high rate of retrogradation). Amy- amylograph. This apparatus measures the viscosity (in Bra-
lose with a high DP has a higher binding force compared to bender units) of starch-water dispersions that are stirred and
amylose with a low DP. heated at a rate of 1.5”C.per min, held at 95°C. for 60 min,
Apparently, there are n o substantial differences between the and then cooled to 50°C. Brabender viscosity curves are
average molecular weight ( = D P x 162) of the amylopectin characteristic for each type of starch as shown in Figure 2 .
molecules of various kinds of starch. The average degree of
The pasting temperature is the temperature at which the
polymerisation (DP)of amylopectin is about 2 million (mole-
viscosity of the stirred starch suspension begins to rise (Fig.
cular weight about 400 million). The molecular weight of
2). Maize and wheat starch have a substantial higher pasting
amylopectin is about 1000 times as high as the molecular
weight of amylose. Amylopectin has only a very low rate of
retrogradation owing to its highly branched structure. Table 5.
Table 4 shows the numbers of amylose and amylopectin Gelatinization Characteristics of Native Starches.
molecules per g of starch. These numbers can be calculated
from the content and the molecular weight (DP x 162) of Characteristics Potato Maize Wheat Tapioca Waxy
starch starch starch starch maize
amylose and amylopectin. Table 4 also gives the ratios starch
between the number of amylose molecules and the number of
amylopectin molecules for each individual starch type. It Pasting tempera-
appears that the number of amylose molecules (per g of ture (“C) 60-65 75-80 80-85 65-70 65-70
starch) in maize and wheat starch is about 5 times as high as Peak viscosity,
the number of amylose molecules in potato and tapioca range (Brabender
starch. All these starches contain 100 - 1 000 times as much units; 5 % starch
amylose molecules as amylopectin molecules. concentration) 1000- 300- 200- 500- 600-
Table 4 further shows the average degree of polymerisation 5000 1000 500 1500 1000
(DP) of various native starches. These figures can be calcu- Peak viscosity,
lated from the ratio between the numbers of amylose and average (Brabender
units; 5% starch
amylopectin molecules and the average D P of amylose and concentration) 3000 600 300 1000 800
amylopectin. The average molecular weight of the various
Swelling power
native starches can be calculated as D P x 162. Potato and at 95°C 1153 24 21 71 64
tapioca starch have a substantial higher average degree of
Solubility (YO)
polymerisation as compared with maize and wheat starch. at 95°C 82 25 41 48 23
Waxy maize starch has the very high D P of amylopectin

starch/starke 37 (1985) Nr. 1, S . 1 - 5 3


300
2500

2000
___* Time
0 30

Potato
60 90 120 150

5% starch
by weight
180rnin
Table 6.
Properties of Starch Pastes.
Properties Potato
starch
Maize
starch
Wheat
starch

Paste viscosity very high medium medium- high


low
Tapioca Waxy
starch maize
starch
medium-
high
Water-binding
capacity (in
parts of water
-% 1500
per part of dry
‘D native starch
h 1000
to give the
c
.-
v)
same hot visco-
0, sity after
5 cooking) 24 15 13 20 22
500
Paste texture long short short long long
Paste clarity very opaque cloudy quite fairly
clear clear clear
50 95 95 95 50 50 50°C Resistance to medium medium medium low low
1 Heat 1 Hold I Cool 1 Hold 1 shear -low
Rate of retro- medium high high low very-
__* Temperature gradation -low low
Figuce 2. brabender viscosity curves of commercial native
starches.
starch have a much lower paste viscosity than tapioca and
temperature than potato, tapioca and waxy maize starch. waxy maize starch (compared at the same conditions).
As the temperature is increased, the starch granules swell and The water-binding capacity of various starches may be ex-
increase the viscosity of the starch paste until the peak pressed in parts of water per part of dry starch t o give about
viscosity is reached (Fig. 2). Potato starch shows the highest the same hot viscosity after cooking (Table 6). In order t o
peak viscosity. Wheat and maize starch have a low peak obtain a starch paste with a given viscosity. a lower amount
viscosity, because the granules are only moderately swollen. of a high-viscous type of starch is needed than with a low-
A higher peak viscosity corresponds with a higher thickening viscous type of starch.
power of a starch. The texture of potato starch pastes can be described as
The swelling power of various starches can be determined by stringy, cohesive, long-bodied, visco-elastic and fluid. The
suspending a weighed dry starch sample in water, heating the paste character of tapioca and waxy maize starch is similar to
mixture at 95°C for 30min and centrifuging the swollen that of potato starch, but generally less stringy and less
sediment from the supernatant solution. The weight of the cohesive. The texture of pastes of maize and wheat starch is
swollen sediment is determined. The swelling power is de- short, soft, heavy-bodied and non-cohesive.
fined as the swollen sediment weight (8) per g of dry starch. The clarity of starch pastes is dependent upon the kind of
Potato starch has an exceptionally high swelling power. This starch. The pastes of potato, tapioca, and waxy maize starch
may be due to the presence of negatively charged phosphate are transludent, clear and transparant. Maize and wheat
groups which assist in swelling of the potato starch granules. starch give pastes which are described as flat, dull, cloudy
The relative low swelling power of maize and wheat starch is and opaque.
partly due to the presence of amylose-lipid complexes. Mechanical shear generally reduces the viscosity of starch
The solubility can be determined by evaporation to dryness pastes. Pastes of native starches vary in their ability to
of the supernatant solution above-mentioned. The solubility withstand shearing or mixing. Waxy maize and tapioca
is expressed as the percentage (by weight) of the starch starch are considerable less stable than maize and wheat
sample that is dessolved molecularly after heating in water at starch. Potato starch pastes are intermediate in resistance t o
95‘C. during 30 min. Potato and tapioca starch show the shear. Cross-linking greatly increases the resistance of
highest solubilization. The lipids in the cereal starches reduce starches t o mechanical breakdown.
the solubilization. Retrogradation (set-back ; congealing) of starch pastes may
On heating in water, the granules of potato, tapioca and have the following physical effects:
waxy maize starch desintegrate more rapidly than the gran- a ) The tendency of starch pastes to thicken and t o increase in
ules of maize and wheat starch and consequently they more viscosity on cooling and aging;
quickly reach the homogeneous condition necessary for ma- b) the development of turbidity and opacity;
ny uses. c) the tendency t o form stiff gels;
d ) the formation of “skins” on hot pastes;
e ) the formation of insoluble aggregates which may actually
precipitate ;
7 Properties of Starch P a s t e s f ) syneresis (weeping) of water from the paste.
Different starches retrogradate at different rates, as shown in
Table 6 shows the properties of starch pastes obtained from Table 7 [19].
commercial native starches [2, 3, 4, 5 , 14, 19, 20, 211. It appears that maize and wheat starch retrogradate more
The very high paste viscosity of potato starch may be explain- quickly than potato or tapioca starch. Waxy maize starch
ed by the influence of phosphate groups. Maize and wheat shows the lowest rate of retrogradation, due to the absence of

4 starchjstarke 37 (1985) Nr. 1, S. 1 - 5


Table 7. In the manufacture of gummed papers, gummed tape, sized
Rate of Retrogradation of Native Starches, Given in % by Weight of yarns, sized paper and adhesive bonds, starch pastes are
Starch that is Precipitated (as Insoluble Aggregates) from a 2 % applicated to a solid surlace followed by drying of the starch
Aqueous Starch Solution During 0-30 Days Preservation at 0 film. Table 8 shows the more favourable properties of starch
-2°C.
films obtained from potato, tapioca and waxy maize starch
% precipitated after as compared with starch films obtained from maize and
Native starch wheat starch. The films of maize and wheat starch have a
5 days 10 days 30 days tendency t o become brittle when dried.

Potato starch 10 15 20
Maize starch 37 48 62 Bibliography
Wheat starch 45 48 52
Tapioca starch 11 12 13
[l] Berkhout, F.: in “Starch Production Technology”, ed. by J . A .
Waxy maize starch 0.2 0.5 1 Radley, p. 109, Applied Science Publishers, London 1976.
[2] Glicksrnan, M . : in “Gum Technology in the Food Industry”, p.
amylose. Important factors which promote the retrograda- 274, Academic Press, New York 1969.
tion of maize and wheat starch pastes are the following: [3] Schoch, T. J . : Wallerstein Laboratorium Communications 32
a) The high a’mylose content of maize and wheat starch (1969), 149.
[4] Rutenberg, M . W . :in “Handbook of Water-soluble Gums and
(about 28%); Resins”, ed. by R. L . Dauidson, p. 22, Mr. Graw Hill Book
b ) the small molecular size of maize and wheat amylose Company, New York 1980.
molecules (DP 200 - 1 200); [5] Knight, J . W.: in “The Starch Industry”, Pergamon Press,
c) the high amount of lipids in maize and wheat starch (0.6 Oxford 1969.
- 1 .OYO). [6] Kerr, R. W.:in “Chemistry and Industry of Starch”, Academic
The amylose fraction in maize and wheat starch pastes is at Press, New York 1950.
least partially present as an associated amylose-lipid com- [7] Greenwood, C. T., and J . 7hornpson:J. Chem. SOC.(1962), 222.
plex with a reduced hydration capacity. This starch portion is [8] van Lonkhuysen, H., and J . Blonkestijn: Starch/Stiirke 26
relatively inert and does not contribute to the thickening (1974), 337.
[9] Yamusaki. W . T., and J . T. Wilson: Methods Carbohydr.
power or the binding force of maize and wheat starch pastes. Chem. 4 (1964), 20.
[lo] Fleche, G.: Industries Alimentaires et Agricoles 96 (1979), 585.
[Ill Davies, 7., D.C. Miller and A . A . Procter: StarchjStiirke 32
8 Properties of Starch Films (1980), 149.
[12) Melvin, M . A , : J . Sci. Food Agric. 30 (1979), 731.
The properties of dried starch films obtained from various [13] Morrison, W . R. and T. P . Milligan: in “Maize,Recent Progress
cooked native starches are listed in Table 8 [2, 3, 61. in Chemistry and Technology”. p. 1, ed. by G . E. Inglett,
Academic Press, New York 1982.
Table 8. [14] Wurzburg, 0.B . : in “Handbook of Food Additives”, p. 361, ed.
Properties of Starch Films. by 1. E. Furia, CRC-Press, Cleveland 1972.
[15] Banks, W . , and C. 7. Greenwood: in “Starch and its Compo-
Properties Potato Maize Wheat Tapioca Waxy nents”, Edingburg University Press 1975.
starch starch starch starch maize [16] Greenwood, C. 7.:in “Advances in Cereal Science and Techno-
starch logy”, p. 119, American Association of Cereal Chemists, Min-
nesota 1976.
Clarity; gloss; [I71 Leach, H . W., L. D. M c . Cowun and 7. J . Schoch: Cereal
transparency high low low high high Chemistry 36 (1959), 534.
Smoothness; conti- [18] Leach, H . W . : in “Starch, Chemistry and Technology”, Vol. 1.
nuity high low low high high p. 289, e. d. by R. L. Whistler and E. F. Paschal/, Academic
Press, New York 1965.
Flexibility; plasticity, [19] Collison, R.: in “Starch and its Derivatives”, p. 194, e. d. by J .
toughness ; folding A . Radley, Chapman and Hall Ltd., London 1968.
endurance high low low high high [20] Howling, D.: Food Chemistry 6 (1980), 51.
Internal strength; [21] Jarowenko, W . : in “Handbook of Adhesives”, p. 192, ed. by I .
tensile strength; Skeist, Van Nostrand Reinhold Company, New York 1977.
film strength high low low high high
Film solubility; Address of author: Ir. J . J . M . Swinkels, Auebe B. A . , K1. Nieboer-
susceptability to weg 12, 9607 PN Foxhol (Holland).
rewetting high low low high high
(Received : December 16, 1983)

~ ~~

starch/starke 37 (1985) Nr. 1, S. 1 - 5 5