Starch-Polyacrylonitrile Copolymers.
Properties of Hydrogels’
E. B. Bagley* and N. W. Taylor
Northern Regional Research Laboratory, Agricultural Research Service, U . S. Department of Agr!culture, Peor!a. lllinofs 6 7604
Gel sheets prepared from high-viscosity aqueous dispersions of hydrolyzed starch-polyacrylonitrile graft
copolymers absorb several hundred times their own weight in water. Viscosity of the dispersions can be
reduced to low levels by mechanical shear before t h e films are cast to give solutions which yield water-
soluble films. These soluble films can b e readily cross-linked to again form highly swellable but nonso-
luble gel sheets by: (a) heating, (b) irradiating with ~OCO,and ( c ) aging at high relative humidity.
One class of thickening agent (a combination of both
natural and synthetic polymers) is represented by hydro-
lyzed starch-polyacrylonitrile graft copolymers
(H-SPAN). These are made by converting the polyacrylo-
nitrile (PAN) graft in a starch-polyacrylonitrile (S-PAN)
graft copolymer to the polyelectrolyte form, containing
both carboxy and carboxamide groups, by hydrolysis with
alkali. It was discovered earlier (Weaver et al., 1974) that
these H-SPAN materials form dry, self-supporting films
which rapidly imbibe several hundred times their own
weight in water while still retaining their gross shape. The
gel sheet also retains its integrity over wide ranges of tem-
perature and pH.
Taylor and Bagley (1974) have shown that the typical
H-SPAN dispersions used in preparing these gel sheets
consist of two major components. In ultracentrifugal stud-
ies a sedimenting boundary is observed a t low (2000) rpm
(290g). This boundary is arbitrarily attributed to “gel”
material. Another sedimenting boundary is observed a t
40000 rpm (1.16 x 105g). This boundary is attributed to a
soluble fraction. For H-SPAN dispersions having high vis-
cosity a t low concentrations (about 1% H-SPAN by
weight), 80% or more of the material is gel; less than 20%
is soluble, by definition.
Weaver et al. (1974) noted that mechanical treatment
(Waring blending or sonification) reduced the viscosity of
a n H-SPAN dispersion, but that gel sheets cast from such
mechanically modified material still had high water sorp-
tive capacity while retaining film integrity. Taylor and
Bagley (1974), however, by more extensive mechanical
treatment than that used by Weaver et al. actually re-
duced viscosity levels of a 1%dispersion by three decades,
from 30,000 CPto 30 cP. At the lowest viscosity level the
material displayed Newtonian behavior and was invariant
under further mechanical action. Ultracentrifugal studies
then established that in this low-viscosity material, me-
chanically modified, there is no gel (i.e., no material sedi-
ments a t 2000 rprn); 100% of this modified H-SPAN dis-
persion sediments a t 40,000 rpm. Films cast from these
H-SPAN solutions are themselves soluble, in contrast to
the highly water swellable, but insoluble, films cast from
H-SPAN dispersions.
These soluble H-SPAN films can be readily modified in
several different ways to regain the gel sheet characteris-
tics typical of films formed from H-SPAN dispersions.
Products with widely differing degrees of water sorptive
capacity can readily be prepared. Factors that influence
’ Presented at the 168th National Meeting of the American Chemical
Society, Division of Organic Coatings and Plastics Chemistry, Atlantic
City, N.J.. Sept 8-13, 1974.
the water-absorbing properties of H-SPAN films include
aging a t high relative humidity, heat, and radiation.
Experimental Section
A pilot-plant lot of H-SPAN, manufactured by General
Mills and designated as SGP-502, was stored as a dry
powder in the acid form prior to use. Dispersions were ti-
trated to pH 7.6 with NaOH before use. Viscosity was
measured a t 23°C in a cone and plate rheometer (Rheom-
etrics Mechanical Spectrometer) of 72 mm diameter and
cone angle of 0.04 radian.
Ultracentrifugation was carried out as described earlier
by Taylor and Bagley in a Spinco ultracentrifuge. Soluble
fraction by centrifugation was defined as the fraction of
material appearing as a sedimenting boundary a t 40,000
rpm. Gel was defined as material sedimenting a t 2000
rpm.
Radiation cross-linking was carried out in a Gammacell
200 unit (Atomic Energy of Canada, Ltd.) cobalt-60
source.
Sonification of dispersions was carried out on 20-ml
samples with a Branson (Stamford, Conn.) sonifier. Ex-
tent of treatment given to different samples is described
arbitrarily by the length of time the sample is sonified at
a given instrument setting.
Gel swelling a t room temperature was determined by
the following method. A small weight of dry film, (0.02 g
moisture-free basis), is put in a weighed vial with an ex-
cess of deionized HzO, about 20 ml. The vial has a cap
with a bolting cloth insert (approximately 100-p hole
size). The mixture is gently stirred until swelling is com-
plete; 1 hr is normally adequate. Then the vial, cap end
down, is inserted into a larger plastic centrifuge tube. The
vial cap is held away from the bottom of the centrifuge
tube by a plastic cylinder. The assembly is centrifuged in
a Serval1 angle centrifuge a t 1400 rpm (130g) for 5 min.
After centrifuging, the filtrate that passed through the
cloth was washed from the centrifuge tube, dried, and
weighed to determine soluble fraction by filtration. The
gel retained on the cloth is briefly centrifuged to the bot-
tom of the vial and weighed. Results are reported as the
ratio of the weight of swollen gel to the weight of initial
sample (moisture-free basis), unless otherwise noted, and
this ratio describes a lower swelling limit for the gel.
Because the test depends on time and speed of centrifu-
gation, those chosen are reasonable compromises for our
preliminary study. By keeping test conditions constant,
we can compare materials and treatments with adequate
precision. The results are only semiquantitative.
Water absorption isotherms at partial pressures less than
unity were determined by equilibrating samples over satu-
rated salt solutions giving known relative humidities.
Ind. Eng. Chem., Prod. Res. Dev., Vol. 14, No. 2, 1975 105
Table I. Blending and Sonifying Affect Viscosity and Soluble Fraction of 1% H-SPAN=Suspensions

Viscosity, 17, Non-Newtonianism O/o

Sample Treatment cP, at 10 sec'' -(d log q/d log +) Solubleb

1 None 14,400 0.65 18

2 Sonify 4' at lC 2,530
3 Blend 3'd 1,250
4 Blend 13'd
5 Sonify 4' at 3"
6 Sonify 5' at 7
with coolingC
7 Sonify 5' at 7
no coolingC
8 Resuspended film
from 7
9 Dextran T-250
a H-SPAN = starch-polyacrylonitrile graft copolymers. Soluble fraction was determined by the ultracentrifuge method. Sonification
described by Branson sonifier setting and treatment time. d Dispersion treated in Waring Blendor for different times. e Viscosity was
extrapolated from values a t higher shear rates.
Each sample was started from a dry state and no desorp-
tion experiments were carried out.
Results a n d Discussion
Solubilization of H-SPAN Dispersions. Mechanical
action affects the rheological properties of H-SPAN in
water (Table I). For sample 1 (a dispersion untreated by
mechanical action) the viscosity, 7, was high, being 14 x
lo3 CPa t a shear rate, +, of 10 sec-l. The original disper-
sion was also highly non-Newtonian, t h e slope d log V/d
+
log being -0.65. In ultracentrifugal experiments 82% of
the product sedimented a t 2000 rpm while the remaining
18% was soluble, sedimenting a t 40,000 rpm.
Succeeding samples 2-7 were subjected to varying de-
grees of mechanical working, either sonification (samples
2, 5 , 6, 7 ) or Waring blending (samples 3 and 4). The
more mechanical shear imposed on the initial dispersion
the lower the viscosity falls, reaching a final level of only
about 26 cP. This drop in viscosity is accompanied by a
decrease in the degree of non-Newtonianism so that a t the
lowest viscosity levels the H-SPAN-water mixture has a
viscosity which is almost Newtonian, i.e., independent of
shear rate. Simultaneously, the percentage of soluble ma-
terial rises from 18% for sample l to more than 90% for
sample 7.
The actual flow curves for samples 1 through 8 (Table I)
are shown in Figure 1, which brings out some significant
points of rheological detail. Note that for sample 1 there is
no evidence of any approach to Newtonian behavior as
shear rate, +, decreases. This is contrary to the behavior
that would be expected for a polymer solution. For sample
5, however, it is evident that as the shear rate decreases,
the viscosity is becoming less and less non-Newtonian,
consistent with the large percentage of soluble polymeric
material in this sample. Comparison of the curves 3, 4,
and 5 (having within experimental error the same amount
*
of soluble material, 52 2%) indicates that there are sig-
nificant rheological differences in these samples. Samples
3 and 4 were treated in a Waring Blendor while sample 5
was sonified. Thus the type of mechanical action imposed
on the sample has an influence on the detailed rheological
properties even when the measured parameter (% sol-
ubles) is essentially the same.
Similar differences between samples of ostensibly the
same percent solubles level (curves 6, 8, and 7 ) are ob-
served even though the samples show essentially Newto-
nian behavior. In these cases, viscosity is probably quite
sensitive to differences in percent solubles level. The
method we use for determining the percent solubles is
0.42 33
0.34 50
730 0.34 54
420 0.30 52
50" 0.11 91
26e < 0.01 >90
32e 0.03 > 90
93.2
It I
Shear Rate. Y , sec-I
Figure 1. Viscosity vs. shear rate curves for samples 1 through 8
of Table I. Appropriate sample number and percent solubles are
appended to each curve.
probably too imprecise to expect good correlations with
viscosity, but we cannot at this time differentiate between
that possibility and the possible differences in rheological
behavior arising from differences in the actual mechanical
history of samples 6, 7 , and 8.
The experimental measurement is not highly precise,
and a reported value of solubles of greater than 90%
implies complete solubility. This view is supported by our
measurement of the percent solubles on a product regard-
ed as being completely soluble; namely, Dextran T-250,
sample 9 of Table I. Our measurement of solubles on
T-250 is only 93% instead of loo%, a difference which is
indicative of the procedural experimental error and which
supports the contention that samples 6 and 7 are essen-
tially completely soluble.
Films cast from sample 7 and dried in a forced air oven
a t 30°C redissolve readily in deionized water. The resul-
tant solution, sample 8, is within experimental error iden-
tical with sample 7 . Recall that films cast from the un-
treated original sample 1 would not redissolve but would
form the gel sheets previously reported by Weaver et al.
(1974).
Effect of Heat on Cross-Linking of Soluble Film.
Samples of initially soluble film prepared as described
were placed in a vacuum oven at 165°C. Even after 30 min
under these conditions the film became essentially insolu-
ble and regained the rapid and large swelling capacity of
films cast from an untreated dispersion (Table 11). The
measurements given in Table I1 are not highly precise

106 Ind. Eng. Chem., Prod. Res. Dev., Vol. 14, No. 2, 1975
Table 11. Effect of Time (at 165°C in Vacuum Oven) on Table IV. A 2-Week Incubation at Different Relative
Water Sorptive Capacity of an Initially Soluble Humidities Changes Water Swelling of Initially
H-SPAN Film Soluble H-SPAN Film
Water uptake Water uptake
Time, min g of water/ g of sample Relative Water uptake, of gel fraction,
0 PJ (soluble) humidity, g of H,O/g % g of HzO/g
30 1800 % of d r y film Soluble of gel (calcd)
60 1400
120 450 97 210 67 640
150 230 92 470 7 5 00
75 600 20 750
Table 111. Effect ofRadiation Cross-Linking on Water 44 Soluble 93 Soluble
Sorptive Capacity of an Initially Soluble H-SPAN Film
Water uptake, g of H20/g of film
Radiation NaCl
dose, Deionized
Mrads water 0.0019 M 0.0086 M 0.086 M
0 Soluble
1 570 400 210 60
2 250 200 130 55
3 160 140 100 47
4 125 110 87 43

since the measurements of water uptake of such magni-

0' ' " " L
tude is difficult because the swollen film is so susceptible 20 40 60
~

to damage. Nevertheless, the semiquantitative data indi-
cate clearly that a t 165°C under vacudm some cross-link-
ing occurs in the initially soluble H-SPAN film. Although
the extent of cross-linking is small, i t is sufficient to con-
vert the film from a soluble material to a largely insoluble
swellable product.
Radiation Cross-Linking of Soluble Film. Soluble
H-SPAN films prepared from mechanically treated dis-
persions, such as sample 7 of Table I, also regained their
swellable gel sheet characteristics after irradiation with a
6OCo source (Table 111). Also indicated in the table is the
effect that ionic strength of the swelling medium has on
water sorptive capacity of these polyelectrolyte films. In a
subjective sense these radiation cross-linked films appear
to be of better quality than the films of Table I1 cross-
linked in the vacuum oven.
Spontaneous Cross-Linking a t Different Relative
Humidities. Initially soluble film becomes insoluble, but
capable of absorbing large quantities of water, when left
in the laboratory under ambient conditions. Typical water
uptake data of film maintained for 2 weeks at four differ-
ent relative humidities (RH) are tabulated in Table IV.
At the lowest RH, the film essentially was unchanged
during this period and remained essentially soluble. At
the three higher RH levels, slight cross-linking, and thus
insolubilization of the film, occurred. The second column
of Table IV shows the ratio of grams of water absorbed to
grams of initial film. However, the cross-linking has inso-
lubilized only a portion of the material, as indicated by
column three of Table IV, where the percent soluble prod-
uct of the partially cross-linked film is given. Surprising-
ly, cross-linking was most effective a t an RH of 92%.
Higher or lower RH gives a lower percentage of gel mate-
rial. The final column of Table IV gives the water absorp-
tion of the cross-linked gel product, the absorbency being
a measure of cross-link density.
Figure 2 shows the water absorption isotherm for a film
cast from sonified material. This film is soluble in water
but its behavior a t RH below about 95% appears rather
typical of polymer-solvent sorption. No effort was made to
determine the extent of hysteresis that might occur on
sorption cycling of this product, but our expectation
80 IO
Relative Humidity, %
Figure 2. Water sorption isotherm measured at 23°C for a film
cast from sonified hydrolyzed starch-polyacrylonitrile film. The
film is soluble in water.
would be that the major effects would be observed in the
90-100% region. This prediction is based on the fact that
exposure of these films to water vapor results eventually
in their insolubilization.
Summary a n d Conclusions
H-SPAN gel sheet films exhibiting a wide range of
water absorbency characteristics can be readily prepared.
The initial high viscosity dispersions form highly swellable
film. Mechanical treatment of the film dispersion can re-
duce viscosity to low levels, and films cast from these so-
lutions are soluble.
These soluble films can be readily cross-linked by: (a)
heating under vacuum, (b) irradiating with W o , and (c)
aging under appropriate relative humidity conditions. The
water absorbing characteristics of these films vary tre-
mendously, the films taking up from perhaps 100 (or less)
times their own weight in water to nearly 2000 times their
own weight depending on treatment.
The practical significance of being able to produce
highly absorbent gel from low viscosity solutions should be
emphasized. In application to porous substrates, for ex-
ample, use of a high-viscosity, high-elasticity casting dis-
persion may not be feasible since penetration into the po-
rous substrate is not possible. Such penetration would be
readily achieved with the low viscosity H-SPAN solution.
The cross-linking mechanism has not been established.
Literature Cited
Taylor, N . W., Bagley, E. B . , J. Appl. Polym. Sci., 18, 2747 (1974).
Weaver, M. O.,Bagley. E. B., Fanta, G. F., Doane, W. M., Appl. Poiym.
Symp., No. 25, 25 (1974).
Received for review October 31,1974
Accepted January 29, 1975
The mention of firm names or trade products does not constitute
an endorsement by the U.S. Department of Agriculture over other
products or firm names not mentioned.

Ind. Eng. Chem., Prod. Res. Dev., Vol. 14, No. 2, 1975 107