Gelatinization Mechanism of

STARCH GRANULES
RICHARD S . BEAR1 AND EDWARD G. SAMSA
Iowa State College, Ames, Iowa

The true nature of the gelatinization mech-
anism of starch granules is disclosed by
observations on certain gas bubbles which
develop in granules enlarging under the
influence of concentrated electrolyte swell-
ing agents. These bubbles change in vol-
ume remarkably, rising from zero volume
to maximum size and then disappearing.
In initial stages tangential enlargement of
the expanding granule layers takes place
more rapidly than fluid can penetrate
through them, with the result that low-
pressure cavities are developed in the inte-
rior. In time the infiltering water weakens
the swelling layers, which are then on the
periphery to form the sac wall and eventu-
ally present the familiar appearance of col-
lapsed balloons. The increase in area of
the swelling layers is very great, and this
change is exceedingly vigorous ; therefore
it seems likely that actual contraction and
thickening of radially oriented SIarch mole-
cules is responsible for the dilatation,
rather than that the phenomenon is
caused by ordinary osmotic or hydration
effects alone.

T H E remarkable swelling power of starch granules is of

considerable importance industrially, but probably
few chemists have a clear conception of what occurs
in each granule when starch is gelatinized. During a study
The words gelatinization and swelling have taken on spe-
cial significance in starch chemistry, and in the interest of clarity
their usage in this paper will be explained. Ordinarily the former
term is applied t o proc-
esses in which granules
of the swelling of individual starch granules, as induced by undergo many fold en-
chemical agents and observed microscopically, it was no- largements under the
influence of appropri-
ticed that a gas bubble frequently formed within a granule ate temperature or
and changed remarkably in size during the granule dilatation. chemical conditions;
This paper describes quantitative observations which use the latter word is
such bubbles as indicators of changing conditions within the often reserved for !he
granules. smaller volume In-
creases observed when
Undoubtedly the bubbles have been observed many times dry granules are sub-
in expanding starch granules. As early as 1849 Schleiden jected to polar sol-
(IS) noted them under certain conditions. Many years vents at relatively
later Zwikker (16) cited their appearance as an argument for a lowtemperatures. This
article does not dis-
theory that the individual concentric layers of a granule en- cuss the collective ac-
large primarily in a tangential direction, radial increase of tion of a ,number of
the whole granule being only a secondary result (Figure 1). granules In forming
The gas bubbles should not be confused with the nuclear a gel or viscous paste,
but rather the events
spaces (in which the bubbles swim) developed in dilating
granules. These spaces, frequently illustrated in the litera-
ture, are normally occupied by fluid, but the cause for their
development is probably the same one that gives rise to bubble Figure 1. Difference be-
formation. tween Concepts of Radial
The fact that starch granules enlarge by tangential ex- and Tangential Swelling
of Starch Granules
pansion, and not by development of internal radially di- A i s the original unswollen
rected pressure, has been known by various investigators for granule, with layered struc-
ture.
more than half a century. Recent reviews by Alsberg ( 1 ) and B is an early stage of a
Badenhuizen ( 2 ) discuss the evidence and accept the concep- granule supposed to be enlarg-
ing either by develo ment of
tion of tangential swelling. However, it is doubtful whether internal pressure Posmotic),
directedasshownbythearrow
the full significance of this view has yet been felt. This or by thickening of each layer:
paper confirms the tangential nature of the swelling and also C is a granule whose layers
have increased i n surface area
presents new ideas regarding the molecular alterations re- through extension i n tangen-
sponsible. tial directions, as shown by the
arrows, with consequent de-
velopment of a central space,
1 Present address, Massachusetts Institute of Technology, Cambridge, 8 , which amounts for moat of
Mass. the volume increase.
721
722 INDUSTRIAL AND ENGINEERING CHEMISTRY
Figure 2. Potato Starch Granules Swell-
ing in 0.5 M Sodium Hydroxide Solution,
with Relatively Large Bubbles Developing
The particularly large granule in the center shows
the phenomenon beet. The large black boundaries
divide solution from air spaces, into which the solu-
tion was allowed to penetrate slowly to permit ob-
servation soon after contact of granule and fluid.
happening within individual granules during gelatinization. Be-
cause swelling is particularly convenient and suitable for the
description of single-granule dilatation, it has seemed desirable
to use this word here in the more general sense as denoting any
type of granule enlargement whatever. Careful distinction be-
tween gelatinization and swelling becomes necessary, how-
ever, in referring to special expressions such as heat of gelatini-
zation which is very different from the more common heat of
swelling.
Expansion of Granules
Under appropriate conditions, starch granules in the act of
gelatinization develop bubbles of gaseous composition within
their interiors. That these bubbles are not liquid phases is
readily discerned under the microscope because of the marked
refraction effects a t their surfaces. Their location within
the granules is easily demonstrated through determination of
their depths with respect to granule walls by focusing. Their
internal position is also indicated by the observations that
such bubbles are only associated with granules and never
appear outside them, and that in many instances collapse of
a granule wall during swelling results in a movement of the
bubble within the granule without escape. Except in rare
instances only one bubble is formed per granule, though all
granules do not develop them.
The experiments were performed chiefly with potato starch
granules because of their large size and the ease and frequency
with which bubble formation could be induced in the samples
available. The phenomena to be described can, however,
be observed with other granule types, such as the cereal
starches. The following procedure was typical of the way
the experiments were carried out: Granules sprinkled on a
microscope slide were treated with approximately 2.0 M cal-
cium nitrate solution, a cover slip was applied, and as quickly
as possible the granules were brought into focus by observa-
tion through the side telescope of a camera attached to the
microscope. Pictures were registered from time to time on
roll film as swelling proceeded. Individual views were pro-
jected on a screen and the granules measured. Since potato
granules are not spherical, major and minor diameters were
recorded as well as diameters for the bubbles, which were
usually round. On each roll of film the scale of a stage mi-
crometer was photographed for calibration purposes.
Observation of the granules between crossed Nicol prisms
was done visually, since photographic registration with the
Vol. 35, No. 6
reduced light available is too slow. Kith the same starch
sample, observations of bubble formation are apt to vary
somewhat from day to day, probably because of tempera-
ture and humidity inconstancy. Furthermore, small gran-
ules resist swelling agents to a greater degree than large ones.
Using typical commercial potato starch samples, the concen-
tration relations are a p t to be as follows: Dilatation proceeds
smoothly without bubble formation in 1.5 M calcium nitrate
and in 0.1 M sodium hydroxide. I n 2.0 M calcium nitrate the
expansion is accompanied by the formation of small bubbles;
in 0.5 M sodium hydroxide relatively enormous cavities filling
much of the entire granule interiors are observable (Figure 2 ) .
For the quantitative experiments described below the
choice of swelling agent was 2.0 M calcium nitrate, since in
this solution expansion proceeds a t a manageable rate and the
bubbles are not se large as to be unspherical and distorted as
they often are in sodium hydroxide swelling. The latter
reagent was, however, useful in some of the polarized light
experiments.
Origin of Bubbles
Pictures of the same field of view a t different swelling times
are presented in Figure 3. Figure 4 is a typical graph of the
changes in volume with time, both for a whole granule and
its included bubble. I n calculating granule volume, the
potato granules were taken to be prolate spheroids with a
volume of (4/3) 7r ab2, where a and b are major and minor
semiaxes, respectively. I n Figure 4 ordinates for granule
volume are given in units 100 times as large as those for the
bubble volume.
The consecutive pictures and the graph show clearly that
the gas bubbles undergo remarkable alterations in volume
during the gelatinization process. With proper interpreta-
tion of their origin, their behavior should furnish valuable
clues to conditions existing within the granules a t various mo-
ments during dilatation.
The several possible interpretations regarding the bubbles
can be divided into two groups on the basis of what is as-
sumed concerning the ability of the granule wall to shield the
interior from the constant exterior pressure of one atmosphere.
If the wall is strong and compact during initial stages of
granule expansion, the size of the bubble will be a function of
amount of gas available and the pressure in the interior. If
the wall is permeable or weak, the bubble volume will depend
only on the quantity of gas, since the pressure within the
granule 15 ill remain essentially constant a t one atmosphere.
Sources for gas (at atmospheric pressure) are (a) air en-
trapped in fissures or other interstices of the original unswollen
granule, or (b) gases dissolved in the solution and liberated
as it passes into the granule. It is clear from Figure 4 that,
in the case of this typical granule which underwent only
moderately extensive bubble formation, the initial bubble
volume is negligible compared to that developed as swelling
progresses. Therefore, assuming atmospheric pressure a t all
times, one mould be compelled to look for considerable evolu-
tion of gas during the process of enlargement.
Evolution of gas might be brought about either by actual
chemical production (from impurities) of a gas such as car-
bon dioxide or ammonia, or by decrease of solubility of oxy-
gen or nitrogen in the swelling solution, caused by local tem-
perature elevations due to heat liberated during the granule
hydration or swelling process. Under the conditions of the
present experiments the chemical evolution is improbable,
since the effects were essentially the same either in the acid
solution of calcium nitrate or in the basic solution of sodium
hydroxide, and the bubbles always finally disappeared into
the same solution in which they were produced.
According to Mullen and Pacsu (11) the gelatinization of
various starches in water and in aqueous pyridine solutions
June, 1943 INDUSTRIAL AND ENGINEERING CHEMISTRY
is a n endothermic process; this might be expected from the
facts that most hydrated carbohydrates exhibit negative
heats of solution, that gelatinization is greatly favored by
increase of temperature, and that retrogradation (essentially
the reverse of gelatinization) is brought about by decrease of
temperature. Under conditions of swelling in calcium ni-
trate and sodium hydroxide solutions, however, qualitative
tests have shown that moderate heat is produced, so that the
possibility of gas evolution due to this cause has to be con-
sidered.
It seems unlikely that the heating explanation is valid for
the following reasons: Calculation indicates that the total
amount of air dissolved in a volume of water equal to t h a t of
the granule a t the time of maximum bubble development is
not quite sufficient to account for bubble volume in the case of
moderate development illustrated in Figure 4. The diffi-
culty is even greater when relatively large bubbles are pro-
duced by concentrated swelling agents. I n addition, un-
doubtedly less gas is dissolved in the concentrated solutions
employed, the temperature required t o release all the gas
would seem difficult t o secure and maintain locally for the
appreciable times observed, and it is difficult to understand
why the bubble should disappear during the period of maxi-
mum swelling rate. Finally, it has been found that well-
aerated calcium nitrate solutions and solutions which have
been boiled to remove dissolved gases do not differ appre-
ciably in their ability to induce bubble formation.
If we assume a definite lowering of internal pressure, the
phenomenon is more easily understood. The increase in
bubble size is so great that, even before the most rapid rise
(Figure 4) in bubble volume sets in, the pressure has un-
Figure 3. Stages i n Granules Swelling, Included in Constant Field of View, with 2.0 M Calcium Nitrate Solution
Time progresses from a tof, with 30-second intervals between each.
723
doubtedly been lowered to equal the aqueous tension of the
solution. After this occurs, the increase in volume proceeds
with water vaporizing to fill the cavity developed by the tan-
gentially swelling granule.
At first it may appear unbelievable t h a t an expandjng
starch granule can develop and maintain for appreciable
periods a pressure difference equal t o most of a n atmosphere
between its interior and exterior. When it is noted that the
phenomenon of limited swelling (dry granules in cold water)
can develop pressures of the order of thousands of atmos-
pheres ( l a ) , and that increase in bubble volume occurs only
during early stages of granule dilatation (at 5 fold granule
volume increase or a t 1.7 fold development of granule radius
the bubble of Figure 4 reached a maximum size), the phenom-
enon does not seem too strange. Actually, in many instances
while expansion is still progressing rapidly, the granule wall
becomes weak a t local regions and proceeds to bend inward
visibly, whereupon the bubble fades and disappears com-
pletely. The observation of wall collapse with accompanying
bubble disappearance and the fact that bubbles always even-
tually vanish constitute the best direct evidence for the exist-
ence of internal low pressure and the supposition that most
of the bubble content consists of water vapor.
With the conception that the bubbles are low-pressure
cavities, the volume of the bubble is most simply regarded as
a measure of the lag of internal adjustments behind the es-
sential enlargement process. The bubble volume is equal
to the difference between the space enclosed by the tangen-
tially expanding starch layers and the volume occupied by
the fluid which has been able to filter from the outside
through the developing layers.
Small black circles are gas bubbles; gray crements show regions of collapse.
724 INDUSTRIAL AND ENGINEERING CHEMISTRY
Events during Granule Dilatation
With the bubbles interpreted as indicating lag of internal
pressure adjustments, the stages occurring during chemically
induced gelatinixation of starch can be cited. These state-
ments summarize the observations of a large number of gran-
ules during enlargement, both from photographs and by
visual study between crossed Nicol prisms. Reference to
Figure 3 can be made for such phenomena as are readily re-
produced:
1. At the outset the granule has the typical appearance:
striations are frequently visible about the hilum as an eccentric
center, the hilum often being marked by slight irregularities in
its neighborhood. The polarization cross (positive) has its cen-
ter at the hilum.
2. Initial expansion takes place tangentially rather than
radially at all points in the granule. This condition tends to in-
crease the periphery before fluid has been able to penetrate into
the hilum or center. Pregumably small amounts of gas (air) or
water vapor may be present in fissures of the granule, and these
serve as nuclei for the development of the bubble observed.
Swelling may proceed noticeably, however, before the bubble
appears, and it is always found initially in the region of the hilum.
3. As dilatation progresses, the peripheral area is increased
still further while the structure remains sufficiently intact to
impede the flow of fluid to the interior from outside. Conse-
quently the bubble continues to grom in volume, expanding at
constant pressure equal to the aqueous vapor tension. During
this period the birefringence of the thick peripheral swelling re-
gion is slowly reduced but remains readily visible; this confirms
the fact that oriented structure persists. That the structure a t
this stage still possesses considerable strength is shown by its
ability to resist collapse under a considerable pressure difference
between the exterior and the interior of the granule (almost a
whole atmosphere).
4. In time the water beinq forced inward through the ex-
panding peripheral layers weakens them by dissolving or maxi-
mally smelling their constituents. Influx of fluid now becomes
more rapid than the enlargement demands. The bubble is then
free to contract and proceeds to diminish in size until it disap-
pears completely. During this period the double refraction be-
comes vanishingly small but never becomes negative, as it might
be expected to do if the volume increase were caused purely by
typical osmotic forces acting to distend a membrane. (The ten-
sion would produce double-r efraction positive with respect to the
direction of tension, but negative with respect to granule radius.)
Neither the swelling nor the final weakening of the swelling layers
occurs, in general, uniformly throughout. In many instances
the low internal pressure causes collapse of the wall at localized
regions where weakening is evidenced by disappearance of
double refraction, while vigorous expansion is yet in progress
in other places whose birefringence is still visible. Concomitant
n ith the caving in of the wall, the bubble rapidly fades away.
5 . Under the conditions of these experiments the granule con-
tinues to swell, though less rapidly, even after the bubble dis-
appears. There is no need to regard this stage as any different
from preceding ones, since it represents a situation in which iii-
flux of water keeps pace with granule enlargement. The final
completely quiescent granule presents the familiar picture of a
wrinkled sack or a deflated balloon; according to the present
view, this appearance results from localized collapse of the wall
to relieve internal low pressure, rather than from shriveling
brought about by loss of dissolved material from the granule.
The final boundary material of a swollen granule should not be
regarded as a true osmotic membrane. I t would seem to be a
porous network of the more insoluble material drawn from the
complete original granule rather than from any particular re-
gion, such as the external surface.
In addition to the above observations the following are also
of interest:
6 . In many instances the accidental movement of a granule
during swelling results in a displacement of the position of the
bubble. This displacement happens in particular when a por-
tion of the granule wall invaginates near the bubble. In such
cases the bubble appears to move freely about within the granule;
thus the central region, which appears isotropic in polarized light,
is clearly a fluid.
7 . A granule swelling in sodium hydroxide often presents
particularly well the phenomena under investigation, though
photographic registration is difficult. Thus, even in 0.1 M sodium
Vol. 35, No. 6
hydroxide, while a bubble is not developed, there is slight but
sufficient difference between the refractive indices of the swelling
layers and of the isotropic ctnter to distinguish visually the
smooth boundary separating these two regions. Betwecn crossed
Xicol prisms the swelling layers light up while the center remains
dark. The slow decrease in double refraction can be followed to
very small values by a technique found useful with weakly bi-
refringent biological tissues (5)-namely, to insert in t,he tube slot
of the microscope a Kohler l / ? ~wave-length rotating mica com-
pensator. When the compensator is turned slightly either way
from the dark-ficld position, alternate quadrants of the granule
wall are, respectively, brighter or darker than the field; thus ob-
servation of sign and approximate magnitude of retardation is
possible long after observation of a distinct polarization cross be-
comes difficult.
8. When swelling becomes too rapid, as in 0.5 J4 sodium hy-
droxide, a bubble may become very large (Figure 2) and some-
times irregular in shape, and may fill t,he central cavity of the
granule almost completely. In such instances the swelling
layers seem to pass fluid to the interior only reluctantly; and the
bubble may remain for long periods, even after penetration of the
granule by fluid has reduced its refractive index nearly t,o thc
point of invisibility. The apparently isolated bubble of this t,ype
then slowly but completely vanishes.
Interpretation in Terms of Granule Structure
The experiments leave little room for doubt of the essential
correctness of the tangential nature of starch granule swelling.
Alsberg ( 1 ) favored this description, and the present observa-
tions support his general point of view. Since Alsberg dis-
cussed the question a t some length, we need only emphasize
that his statements regarding radially oriented starch chains
(or micelles), tangential thickening of these chains during
swelling, the origin of the swollen granule sacks, and the
absence of a preformed membrane, seem essentially correct.
The exact nature of the thickening process remains to be
determined.
Recent discussions of granule structure have tended to
emphasize either t'he starch chain as the important unit ( 1 , 7 )
or the knitting of these chains into interlocked micelles ( I O ) .
While all have reached similar structural conclusioiis in spite
of different emphasis, the view of Meyer and Bernfeld ( I O )
seems to neglect the t'angential type of smelling. A swollen
granule is not a net'work of interlocked resistant' material
except in the wall regions resulting from the tangential swell-
ing. Ordinary osmotic effects through a semipermeable
membrane are secondary to the aspiration effects which follow
tangential expansion and cause fluid to enter the granule.
The recognition of the true nature of starch gelatinization
leads to a realization that the final volume attained by each
granule is very dependent on swelling conditions. Thus, if
a considerable portion of the relief of the internal reduced
pressure is accomplished by caving in of the walls, the total
fluid taken up will be sharply reduced. Slow swelling, which
allows fluid to enter wit,hout much interior pressure reduction,
will permit a maximum of fluid entry. A more constant re-
sult of complete granule swelling should be t'he surface de-
veloped.
Estimates of the surface areas of a number of the granules
measured during swelling in the above experiments indicat'e
that the surface increases ten to sixteen fold. This is a con-
servative estimate of the power of potato starch granules to
expand, as Furry's results (8) show for the same granules
thermally enlarged. However, the rigid structure capable of
withstanding almost an atmosphere of pressure difference
between exterior and interior is maintained only up to about
a twofold area increase (the point a t which the bubble begins
to fade) under the conditions of the swelling in 2.0 A4 cal-
cium nitrate; i t may perhaps he maintained farther in so-
dium hydroxide.
The detailed description of a structure which is capable of
such extensive lateral swelling requires a certain amount of
imagination a t present. One might suppose, with Meyer and
June, 1943 INDUSTRIAL AND ENGINEERING CHEMISTRY 725

Bernfeld (IO), that small pockets within the swelling layers

become filled with starch solution and are distended osmoti-
caliy ; expansion thus occurs most easily in tangential direc-
tions because of the radial orientation of fissures developed
between chains or micelles. It is difficult t o believe that the
relatively dilute solutions of starch of high molecular weight
could successfully compete with the concentrated calcium
nitrate solution to secure water rapidly enough for the vigor-
ous expansion observed.
If, as Alsberg ( 1 ) supposed, chains or micelles of more or less
cylindrical shape take upon their surfaces sufficient water to
cause a t least ten to twenty fold increases in cross-sectional
area, then one must imagine greater than three to four fold
increases in their diameters. One is tempted to conclude that
the striking swelling manifestations of starch granules are a
result of an active tendency of starch chains to coil or other-
wise contract, and thus shorten in a radial direction and ex-
pand tangentially as they are placed in the granule. Only in
such fashion is it easy to visualize the remarkable increases
in cross-sectional area.
Alsberg came to somewhat opposite conclusions. He re-
garded hydrated chains as fully extended and dehydrated ones
as contracted, t o the extent allowed by granule structure, in
order to explain the remarkable contraction of the diameters
of dried granules which may amount to over 15 per cent. It
would seem possible to suppose that in either extreme-of
dehydration or of chemical or temperature swelling-the
chains are more or less free to indulge in a natural tendency
to shorten because certain critical cross linkages (hydrogen I

bridges?) have been broken.

Precise evaluation of this hypothesis is difficult a t present.
While the progressive radial thinning of the swelling layers
during tangential expansion and the decrease of double re-
fraction are in agreement with it, these observations could
have other explanations, such as a deterioration in amount
and organization of the starch brought about by the rush of
water through the layer. It should be emphasized that the
thinness of the final sack wall is not produced by pressure
within the granule, but that the motivating forces come from
within the original peripheral swelling layers themselves.
The ability of the layers to remain intact during these altera-
tions undoubtedly arises from the ramifications and inter-
lacings of starch chains so frequently cited by Meyer and
others. Acid solubilization destroys these links, and swelling
phenomena are then abolished.
While the suggestion of actively contracting starch chains
indicates that starch molecules in freshly prepared solutions
are in a contracted state, as viscosity studies (14) show they
may be, it is not necessary to conclude that this is the equi-
librium state under ordinary conditions. It is possible that at
room temperature starch chains dissolved in nonswelling
aqueous solutions may slowly become maximally extended
(though perhaps never so fully as in cellulose, 6); the fullest
possible hydration is thus possible. Recent x-ray diffraction
studies (4) suggest that starch granules contain an organiza-
tion of chains into crystalline regions whose structural re-
peating units (unit cells) resemble in dimensions those of
cellulose and maltose; hence they do not call to mind a con-
tracted configuration. Identical crystalline modifications
are readily obtained by retrogradation from aqueous starch
solutions at ordinary temperatures, and the reversion from
the contracted state to an extended one may be an important
phase of the retrogradation process.
The picture of the molecular mechanism of swelling here
presented is in some respects a denial that hydration of starch
is the essential process in gelatinization, although consider-
able rearrangement and hydration of starch chains may take
place. It is worth noting that the protein collagen in fibrous
form (animal connective tissue, tendon, etc.) undergoes
Figure 4. Typical Graph of Volume Changes in a
Potato Starch Granule and Its Included Bubble
during Swelling in 2.0 M Calcium Nitrate
Solid circles apply to granule volumes, with the ordinate i n
oubic centimeters X 107% open circles apply to bubble volume,
with the ordinate in cubic centimeters X 10'.
extensive contraction under the influence of temperature
increase or chemical treatment, much as do starch chains.
Kuntzel and Prakke ( 9 ) concluded that the thermal and
chemical shortening of tendon is not a hydration phenomenon,
as visible appearances suggest, but rather depends primarily
on an initial dehydration. Their paper contains arguments
which might well be transferred to the case of starch gelatini-
zation.
The reader is also referred to a recent paper (3)describing
relations between current concepts of contracted or helical
models for starch chains, the iodine-staining ability of starch,
the production of Schardinger dextrins, and the crystalline
V (alcohol-precipitated) modification of starch. All of these
relations add considerable credence to the view that the gela-
tinization process involves primarily a vigorous contraction
of chains which in the granule were originally extended, and
that retrogradation is a reversal of this change.
While the experiments described in this paper bring little
or no direct light to the amylose-amylopectin conception of
starch, it has been suggested t o the writers by Eugene Pacsu,
of Princeton University, that the straight-chain retrogradable
amylose is probably the primary fraction involved in the mo-
lecular contraction process; the latter process is here postu-
lated as chiefly responsible for gelatinization, and its reversal
constitutes retrogradation. The nonretrogradable amylo-
pectin fraction has been widely considered the chief constitu-
ent of the final insoluble residue forming the deflated sacs of
the completely swollen granules; its branched-chain struc-
ture is not so suitable for extensive changes in molecular
shape, except in so far as longer branches may be involved.
 726 INDUSTRIAL AND ENGINEERING CHEMISTRY
The heats of gelatinization measured in Pacsus laboratory
(11) are also of interest in connection with the present hypoth-
esis. Since they are negative and of a magnitude consistent
with the breaking of one or two hydrogen bridges per glucose
residue, these measurements can be considered to agree with
the conception that hydration is not the significant process
in gelatinization; if it were, heat should be evolved. The
problem is, however, not simple, since it is possible that the
observed heat of gelatinization is the net effect of endother-
mic and exothermic processes involving the disruption and
reconstitution of more than two hydrogen bridges per residue.
Even if as many of these bridges exist after gelatinization as
before, there may yet be differences in heat content arising
from the nonequivalence of the hydroxyl groups involved.
Literature Cited
(1) Alsherg, C. L., Plant Physio., 13, 295 (1938).
(2) Badenhuiaen, N. P., Rec. trav. botan. nEerZancl., 35,559 (1938).
Water Adsor tion By
Animal Glue
CHARLES ill. MASON1 AND HERBERT E. SILCOX
University of New Hampshire, Durham, N. H.
The adsorption of water on thin films of
five animal glues and one gelatin have been
investigated, the glues covering the range of
physical properties commonly employed.
Both adsorption and equilibrium moisture
content have been studied. The former
obeys Freundlichs law, and the latter is
found to be greater than represented by the
moisture adsorbed on the surface.
It is proposed that water is held by glue in
two forms-by true adsorption on the glue
surface and by some other mechanism in
the voids of the glue itself.
A S I D E from general interest in the field of colloidal science
a knowledge of the water adsorption of animal glue is
of great interest to all who use this material in manu-
facturing processes. Previous publications have been scanty
and incomplete. Wilson and Fuwa (11) give some data on
glue as part of an extensive study of many materials. Katz
(4) and Sheppard, Houck, and Dittmar (7) studied gelatin,
a similar material.
The present investigation was undertaken to supply data for
glues covering as wide a range of physical properties as
possible. A t the same time a n investigation has been made
of the adsorption of water on glue in relation to Freundlichs
law.
1 Present address, Tennessee Valley Authurity. Wilson Dam, Ala.
Vol. 35, No. 6
(3) Bear, R. S.,J . Am. Chem. Soc., 64,1388 (1942).
(4) Bear, R. S.,and French, D., Ibid., 63, 2298 (1941).
(5) Bear, R. S.,and Schmitt, F. O., J . CelZular Comp. Physiol., 9,
289 (1937).
(6) Caesar, G. V., and Gushing, M. L., J . Phys. Chem., 45, 776
(1941).
(7) Frey-Wyssling, A., Naturwissenschuften, 28, 78 (1940).
(8) Furry, M . S.,U. S.Dept. Agr., Tech. Bull. 284 (1932).
(9) Kuntael, A., and Prakke, F., Biochem. Z . , 267, 243 (1933).
(10) hleyer, K. H., and Bernfeld, P., Helv. Chim. Acta, 23, 890
(1940).
(11) Mullen, J. W., and Pacsu, Eugene, IKD,ENG.CHEX., 34, 807
(1942).
(12) Samec, M.,Kolloidchemie der StBrke, p . 131, Dresden, Theo-
dor Steinkopff, 1927.
(13) Schleiden, J. M., Principles of Scientific Botany, t r . by
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JOURNALPaper 5-921, Iowa Agricultural Experiment Station. Project 638.
supported in part by a grant from Corn Industries Research Foundation.
ADSORPTIOR OV T H I h FILMS
One bone glue, four hide glues, and a gelatin were chosen
which seemed to cover the range of known physical prop-
erties of glues. The glues were obtained through the
courtesy of a large industrial user who selected those most
characteristic of available commercial glues. The gelatin
was a sample sold as suitable for bacteriological work and was
therefore supposed to be of unusual purity. No attempt
was made to purify the samples further because this would
have vitiated the results from a practical viewpoint. Table
I gives physical characteristics as determined b y the firm
which supplied the glues.
HTJ?IIDITY CoxDIrIoxs. The basic problem involved in the
pxperimental technique is tu obtain reproducible and controllable
humidity and temperatures over long periods. Air was passed
over saturated salt solutions in saturators of the type designed by
Bichowsky and Storch ( 1 ) and then through a chamber contain-
ing the glue samples. The whole train was immersed in a water
thermostat regulated t o 25 * 0.02 C. The humidity produced
by these salt solutions had previously been determined by ex-
tensive calibration at 25 C.
The exposure of the glue samples to the humidity conditions
was carried out in the form of thin films 0.008 t o 0.01 inch (0.2 to
0.25 mm.) thick. The films were prepared by first mixing equal
parts of glue and water and alloving the mixture to stand for 2
hours. Water was then added t o the swollen product and the
mixture heated t o 40 C. on the steam bath. When liquefied,
the glue was drawn into films by the method of Kallender (S),
using moistureproof regenerated cellulose (cellophane) as a sup-
porting medium. The films were then allomed to cool and dry
partially in the air. The glue n a s peeled from the support and
cut into strips 1 inch vide and 15 or 18 inches long. They were
rolled into loose cylinders and placed edgehise in glass weighing
bottles, In the case of the glues of lomcr gel strength, which
tended to melt down at high humidities, the films w-ere drawn on
glass cloth instead of moistureproof regenerated cellulose. This