You are on page 1of 6

Gelatinization Mechanism of

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

The true nature of the gelatinization mech- rior. In time the infiltering water weakens
anism of starch granules is disclosed by the swelling layers, which are then on the
observations on certain gas bubbles which periphery to form the sac wall and eventu-
develop in granules enlarging under the ally present the familiar appearance of col-
influence of concentrated electrolyte swell- lapsed balloons. The increase in area of
ing agents. These bubbles change in vol- the swelling layers is very great, and this
ume remarkably, rising from zero volume change is exceedingly vigorous ; therefore
to maximum size and then disappearing. it seems likely that actual contraction and
In initial stages tangential enlargement of thickening of radially oriented SIarch mole-
the expanding granule layers takes place cules is responsible for the dilatation,
more rapidly than fluid can penetrate rather than that the phenomenon is
through them, with the result that low- caused by ordinary osmotic or hydration
pressure cavities are developed in the inte- 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 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
Figure 2. Potato Starch Granules Swell- reagent was, however, useful in some of the polarized light
ing in 0.5 M Sodium Hydroxide Solution, experiments.
with Relatively Large Bubbles Developing
The particularly large granule in the center shows Origin of Bubbles
the phenomenon beet. The large black boundaries
divide solution from air spaces, into which the solu- Pictures of the same field of view a t different swelling times
tion was allowed to penetrate slowly to permit ob-
servation soon after contact of granule and fluid. 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
happening within individual granules during gelatinization. Be- potato granules were taken to be prolate spheroids with a
cause swelling is particularly convenient and suitable for the volume of (4/3) 7r ab2, where a and b are major and minor
description of single-granule dilatation, it has seemed desirable semiaxes, respectively. I n Figure 4 ordinates for granule
to use this word here in the more general sense as denoting any volume are given in units 100 times as large as those for the
type of granule enlargement whatever. Careful distinction be- bubble volume.
tween gelatinization and swelling becomes necessary, how-
ever, in referring to special expressions such as heat of gelatini- The consecutive pictures and the graph show clearly that
zation which is very different from the more common heat of the gas bubbles undergo remarkable alterations in volume
swelling. during the gelatinization process. With proper interpreta-
tion of their origin, their behavior should furnish valuable
Expansion of Granules clues to conditions existing within the granules a t various mo-
Under appropriate conditions, starch granules in the act of ments during dilatation.
gelatinization develop bubbles of gaseous composition within The several possible interpretations regarding the bubbles
their interiors. That these bubbles are not liquid phases is can be divided into two groups on the basis of what is as-
readily discerned under the microscope because of the marked sumed concerning the ability of the granule wall to shield the
refraction effects a t their surfaces. Their location within interior from the constant exterior pressure of one atmosphere.
the granules is easily demonstrated through determination of If the wall is strong and compact during initial stages of
their depths with respect to granule walls by focusing. Their granule expansion, the size of the bubble will be a function of
internal position is also indicated by the observations that amount of gas available and the pressure in the interior. If
such bubbles are only associated with granules and never the wall is permeable or weak, the bubble volume will depend
appear outside them, and that in many instances collapse of only on the quantity of gas, since the pressure within the
a granule wall during swelling results in a movement of the granule 15 ill remain essentially constant a t one atmosphere.
bubble within the granule without escape. Except in rare Sources for gas (at atmospheric pressure) are (a) air en-
instances only one bubble is formed per granule, though all trapped in fissures or other interstices of the original unswollen
granules do not develop them. granule, or (b) gases dissolved in the solution and liberated
The experiments were performed chiefly with potato starch as it passes into the granule. It is clear from Figure 4 that,
granules because of their large size and the ease and frequency in the case of this typical granule which underwent only
with which bubble formation could be induced in the samples moderately extensive bubble formation, the initial bubble
available. The phenomena to be described can, however, volume is negligible compared to that developed as swelling
be observed with other granule types, such as the cereal progresses. Therefore, assuming atmospheric pressure a t all
starches. The following procedure was typical of the way times, one mould be compelled to look for considerable evolu-
the experiments were carried out: Granules sprinkled on a tion of gas during the process of enlargement.
microscope slide were treated with approximately 2.0 M cal- Evolution of gas might be brought about either by actual
cium nitrate solution, a cover slip was applied, and as quickly chemical production (from impurities) of a gas such as car-
as possible the granules were brought into focus by observa- bon dioxide or ammonia, or by decrease of solubility of oxy-
tion through the side telescope of a camera attached to the gen or nitrogen in the swelling solution, caused by local tem-
microscope. Pictures were registered from time to time on perature elevations due to heat liberated during the granule
roll film as swelling proceeded. Individual views were pro- hydration or swelling process. Under the conditions of the
jected on a screen and the granules measured. Since potato present experiments the chemical evolution is improbable,
granules are not spherical, major and minor diameters were since the effects were essentially the same either in the acid
recorded as well as diameters for the bubbles, which were solution of calcium nitrate or in the basic solution of sodium
usually round. On each roll of film the scale of a stage mi- hydroxide, and the bubbles always finally disappeared into
crometer was photographed for calibration purposes. the same solution in which they were produced.
Observation of the granules between crossed Nicol prisms According to Mullen and Pacsu (11) the gelatinization of
was done visually, since photographic registration with the various starches in water and in aqueous pyridine solutions
June, 1943 INDUSTRIAL AND ENGINEERING CHEMISTRY 723

is a n endothermic process; this might be expected from the doubtedly been lowered to equal the aqueous tension of the
facts that most hydrated carbohydrates exhibit negative solution. After this occurs, the increase in volume proceeds
heats of solution, that gelatinization is greatly favored by with water vaporizing to fill the cavity developed by the tan-
increase of temperature, and that retrogradation (essentially gentially swelling granule.
the reverse of gelatinization) is brought about by decrease of At first it may appear unbelievable t h a t an expandjng
temperature. Under conditions of swelling in calcium ni- starch granule can develop and maintain for appreciable
trate and sodium hydroxide solutions, however, qualitative periods a pressure difference equal t o most of a n atmosphere
tests have shown that moderate heat is produced, so that the between its interior and exterior. When it is noted that the
possibility of gas evolution due to this cause has to be con- phenomenon of limited swelling (dry granules in cold water)
sidered. can develop pressures of the order of thousands of atmos-
It seems unlikely that the heating explanation is valid for pheres ( l a ) , and that increase in bubble volume occurs only
the following reasons: Calculation indicates that the total during early stages of granule dilatation (at 5 fold granule
amount of air dissolved in a volume of water equal to t h a t of volume increase or a t 1.7 fold development of granule radius
the granule a t the time of maximum bubble development is the bubble of Figure 4 reached a maximum size), the phenom-
not quite sufficient to account for bubble volume in the case of enon does not seem too strange. Actually, in many instances
moderate development illustrated in Figure 4. The diffi- while expansion is still progressing rapidly, the granule wall
culty is even greater when relatively large bubbles are pro- becomes weak a t local regions and proceeds to bend inward
duced by concentrated swelling agents. I n addition, un- visibly, whereupon the bubble fades and disappears com-
doubtedly less gas is dissolved in the concentrated solutions pletely. The observation of wall collapse with accompanying
employed, the temperature required t o release all the gas bubble disappearance and the fact that bubbles always even-
would seem difficult t o secure and maintain locally for the tually vanish constitute the best direct evidence for the exist-
appreciable times observed, and it is difficult to understand ence of internal low pressure and the supposition that most
why the bubble should disappear during the period of maxi- of the bubble content consists of water vapor.
mum swelling rate. Finally, it has been found that well- With the conception that the bubbles are low-pressure
aerated calcium nitrate solutions and solutions which have cavities, the volume of the bubble is most simply regarded as
been boiled to remove dissolved gases do not differ appre- a measure of the lag of internal adjustments behind the es-
ciably in their ability to induce bubble formation. sential enlargement process. The bubble volume is equal
If we assume a definite lowering of internal pressure, the to the difference between the space enclosed by the tangen-
phenomenon is more easily understood. The increase in tially expanding starch layers and the volume occupied by
bubble size is so great that, even before the most rapid rise the fluid which has been able to filter from the outside
(Figure 4) in bubble volume sets in, the pressure has un- through the developing layers.

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. Small black circles are gas bubbles; gray crements show regions of collapse.
724 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 35, No. 6
Events during Granule Dilatation hydroxide, while a bubble is not developed, there is slight but
sufficient difference between the refractive indices of the swelling
With the bubbles interpreted as indicating lag of internal layers and of the isotropic ctnter to distinguish visually the
pressure adjustments, the stages occurring during chemically smooth boundary separating these two regions. Betwecn crossed
Xicol prisms the swelling layers light up while the center remains
induced gelatinixation of starch can be cited. These state- dark. The slow decrease in double refraction can be followed to
ments summarize the observations of a large number of gran- very small values by a technique found useful with weakly bi-
ules during enlargement, both from photographs and by refringent biological tissues (5)-namely, to insert in t,he tube slot
visual study between crossed Nicol prisms. Reference to of the microscope a Kohler l / ? ~wave-length rotating mica com-
pensator. When the compensator is turned slightly either way
Figure 3 can be made for such phenomena as are readily re- from the dark-ficld position, alternate quadrants of the granule
produced: wall are, respectively, brighter or darker than the field; thus ob-
servation of sign and approximate magnitude of retardation is
1. At the outset the granule has the typical appearance: possible long after observation of a distinct polarization cross be-
striations are frequently visible about the hilum as an eccentric comes difficult.
center, the hilum often being marked by slight irregularities in 8. When swelling becomes too rapid, as in 0.5 J4 sodium hy-
its neighborhood. The polarization cross (positive) has its cen- droxide, a bubble may become very large (Figure 2) and some-
ter at the hilum. times irregular in shape, and may fill t,he central cavity of the
2. Initial expansion takes place tangentially rather than granule almost completely. In such instances the swelling
radially at all points in the granule. This condition tends to in- layers seem to pass fluid to the interior only reluctantly; and the
crease the periphery before fluid has been able to penetrate into bubble may remain for long periods, even after penetration of the
the hilum or center. Pregumably small amounts of gas (air) or granule by fluid has reduced its refractive index nearly t,o thc
water vapor may be present in fissures of the granule, and these point of invisibility. The apparently isolated bubble of this t,ype
serve as nuclei for the development of the bubble observed. then slowly but completely vanishes.
Swelling may proceed noticeably, however, before the bubble
appears, and it is always found initially in the region of the hilum. Interpretation in Terms of Granule Structure
3. As dilatation progresses, the peripheral area is increased
still further while the structure remains sufficiently intact to The experiments leave little room for doubt of the essential
impede the flow of fluid to the interior from outside. Conse-
quently the bubble continues to grom in volume, expanding at correctness of the tangential nature of starch granule swelling.
constant pressure equal to the aqueous vapor tension. During Alsberg ( 1 ) favored this description, and the present observa-
this period the birefringence of the thick peripheral swelling re- tions support his general point of view. Since Alsberg dis-
gion is slowly reduced but remains readily visible; this confirms cussed the question a t some length, we need only emphasize
the fact that oriented structure persists. That the structure a t
this stage still possesses considerable strength is shown by its that his statements regarding radially oriented starch chains
ability to resist collapse under a considerable pressure difference (or micelles), tangential thickening of these chains during
between the exterior and the interior of the granule (almost a swelling, the origin of the swollen granule sacks, and the
whole atmosphere). absence of a preformed membrane, seem essentially correct.
4. In time the water beinq forced inward through the ex-
panding peripheral layers weakens them by dissolving or maxi- The exact nature of the thickening process remains to be
mally smelling their constituents. Influx of fluid now becomes determined.
more rapid than the enlargement demands. The bubble is then Recent discussions of granule structure have tended to
free to contract and proceeds to diminish in size until it disap- emphasize either t'he starch chain as the important unit ( 1 , 7 )
pears completely. During this period the double refraction be-
comes vanishingly small but never becomes negative, as it might or the knitting of these chains into interlocked micelles ( I O ) .
be expected to do if the volume increase were caused purely by While all have reached similar structural conclusioiis in spite
typical osmotic forces acting to distend a membrane. (The ten- of different emphasis, the view of Meyer and Bernfeld ( I O )
sion would produce double-r efraction positive with respect to the seems to neglect the t'angential type of smelling. A swollen
direction of tension, but negative with respect to granule radius.)
Neither the swelling nor the final weakening of the swelling layers granule is not a net'work of interlocked resistant' material
occurs, in general, uniformly throughout. In many instances except in the wall regions resulting from the tangential swell-
the low internal pressure causes collapse of the wall at localized ing. Ordinary osmotic effects through a semipermeable
regions where weakening is evidenced by disappearance of membrane are secondary to the aspiration effects which follow
double refraction, while vigorous expansion is yet in progress
in other places whose birefringence is still visible. Concomitant tangential expansion and cause fluid to enter the granule.
n ith the caving in of the wall, the bubble rapidly fades away. The recognition of the true nature of starch gelatinization
5 . Under the conditions of these experiments the granule con- leads to a realization that the final volume attained by each
tinues to swell, though less rapidly, even after the bubble dis- granule is very dependent on swelling conditions. Thus, if
appears. There is no need to regard this stage as any different
from preceding ones, since it represents a situation in which iii- a considerable portion of the relief of the internal reduced
flux of water keeps pace with granule enlargement. The final pressure is accomplished by caving in of the walls, the total
completely quiescent granule presents the familiar picture of a fluid taken up will be sharply reduced. Slow swelling, which
wrinkled sack or a deflated balloon; according to the present allows fluid to enter wit,hout much interior pressure reduction,
view, this appearance results from localized collapse of the wall
to relieve internal low pressure, rather than from shriveling will permit a maximum of fluid entry. A more constant re-
brought about by loss of dissolved material from the granule. sult of complete granule swelling should be t'he surface de-
The final boundary material of a swollen granule should not be veloped.
regarded as a true osmotic membrane. I t would seem to be a Estimates of the surface areas of a number of the granules
porous network of the more insoluble material drawn from the
complete original granule rather than from any particular re- measured during swelling in the above experiments indicat'e
gion, such as the external surface. that the surface increases ten to sixteen fold. This is a con-
servative estimate of the power of potato starch granules to
In addition to the above observations the following are also expand, as Furry's results (8) show for the same granules
of interest: thermally enlarged. However, the rigid structure capable of
withstanding almost an atmosphere of pressure difference
6 . In many instances the accidental movement of a granule between exterior and interior is maintained only up to about
during swelling results in a displacement of the position of the a twofold area increase (the point a t which the bubble begins
bubble. This displacement happens in particular when a por-
tion of the granule wall invaginates near the bubble. In such to fade) under the conditions of the swelling in 2.0 A4 cal-
cases the bubble appears to move freely about within the granule; cium nitrate; i t may perhaps he maintained farther in so-
thus the central region, which appears isotropic in polarized light, dium hydroxide.
is clearly a fluid. The detailed description of a structure which is capable of
7 . A granule swelling in sodium hydroxide often presents
particularly well the phenomena under investigation, though such extensive lateral swelling requires a certain amount of
photographic registration is difficult. Thus, even in 0.1 M sodium 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 Figure 4. Typical Graph of Volume Changes in a
during tangential expansion and the decrease of double re- Potato Starch Granule and Its Included Bubble
fraction are in agreement with it, these observations could during Swelling in 2.0 M Calcium Nitrate
have other explanations, such as a deterioration in amount Solid circles apply to granule volumes, with the ordinate i n
oubic centimeters X 107% open circles apply to bubble volume,
and organization of the starch brought about by the rush of with the ordinate in cubic centimeters X 10'.
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. extensive contraction under the influence of temperature
The ability of the layers to remain intact during these altera- increase or chemical treatment, much as do starch chains.
tions undoubtedly arises from the ramifications and inter- Kuntzel and Prakke ( 9 ) concluded that the thermal and
lacings of starch chains so frequently cited by Meyer and chemical shortening of tendon is not a hydration phenomenon,
others. Acid solubilization destroys these links, and swelling as visible appearances suggest, but rather depends primarily
phenomena are then abolished. on an initial dehydration. Their paper contains arguments
While the suggestion of actively contracting starch chains which might well be transferred to the case of starch gelatini-
indicates that starch molecules in freshly prepared solutions zation.
are in a contracted state, as viscosity studies (14) show they The reader is also referred to a recent paper (3)describing
may be, it is not necessary to conclude that this is the equi- relations between current concepts of contracted or helical
librium state under ordinary conditions. It is possible that at models for starch chains, the iodine-staining ability of starch,
room temperature starch chains dissolved in nonswelling the production of Schardinger dextrins, and the crystalline
aqueous solutions may slowly become maximally extended V (alcohol-precipitated) modification of starch. All of these
(though perhaps never so fully as in cellulose, 6); the fullest relations add considerable credence to the view that the gela-
possible hydration is thus possible. Recent x-ray diffraction tinization process involves primarily a vigorous contraction
studies (4) suggest that starch granules contain an organiza- of chains which in the granule were originally extended, and
tion of chains into crystalline regions whose structural re- that retrogradation is a reversal of this change.
peating units (unit cells) resemble in dimensions those of While the experiments described in this paper bring little
cellulose and maltose; hence they do not call to mind a con- or no direct light to the amylose-amylopectin conception of
tracted configuration. Identical crystalline modifications starch, it has been suggested t o the writers by Eugene Pacsu,
are readily obtained by retrogradation from aqueous starch of Princeton University, that the straight-chain retrogradable
solutions at ordinary temperatures, and the reversion from amylose is probably the primary fraction involved in the mo-
the contracted state to an extended one may be an important lecular contraction process; the latter process is here postu-
phase of the retrogradation process. lated as chiefly responsible for gelatinization, and its reversal
The picture of the molecular mechanism of swelling here constitutes retrogradation. The nonretrogradable amylo-
presented is in some respects a denial that hydration of starch pectin fraction has been widely considered the chief constitu-
is the essential process in gelatinization, although consider- ent of the final insoluble residue forming the deflated sacs of
able rearrangement and hydration of starch chains may take the completely swollen granules; its branched-chain struc-
place. It is worth noting that the protein collagen in fibrous ture is not so suitable for extensive changes in molecular
form (animal connective tissue, tendon, etc.) undergoes shape, except in so far as longer branches may be involved.
726 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 35, No. 6
The heats of gelatinization measured in Pacsus laboratory (3) Bear, R. S.,J . Am. Chem. Soc., 64,1388 (1942).
(11) are also of interest in connection with the present hypoth- (4) Bear, R. S.,and French, D., Ibid., 63, 2298 (1941).
(5) Bear, R. S.,and Schmitt, F. O., J . CelZular Comp. Physiol., 9,
esis. Since they are negative and of a magnitude consistent 289 (1937).
with the breaking of one or two hydrogen bridges per glucose (6) Caesar, G. V., and Gushing, M. L., J . Phys. Chem., 45, 776
residue, these measurements can be considered to agree with (1941).
the conception that hydration is not the significant process (7) Frey-Wyssling, A., Naturwissenschuften, 28, 78 (1940).
(8) Furry, M . S.,U. S.Dept. Agr., Tech. Bull. 284 (1932).
in gelatinization; if it were, heat should be evolved. The (9) Kuntael, A., and Prakke, F., Biochem. Z . , 267, 243 (1933).
problem is, however, not simple, since it is possible that the (10) hleyer, K. H., and Bernfeld, P., Helv. Chim. Acta, 23, 890
observed heat of gelatinization is the net effect of endother- (1940).
mic and exothermic processes involving the disruption and (11) Mullen, J. W., and Pacsu, Eugene, IKD,ENG.CHEX., 34, 807
(1942).
reconstitution of more than two hydrogen bridges per residue. (12) Samec, M.,Kolloidchemie der StBrke, p . 131, Dresden, Theo-
Even if as many of these bridges exist after gelatinization as dor Steinkopff, 1927.
before, there may yet be differences in heat content arising (13) Schleiden, J. M., Principles of Scientific Botany, t r . by
from the nonequivalence of the hydroxyl groups involved. Lankester, p. 12, London, Longmans, Green and Co., 1849.
(14) Staudinger, H., and Eilers, H., Ber., A69, 819 (1936).
(15) Zwikker, J. J. L., Rec. trav. botan. nderland., 18, 1 (1921).
Literature Cited
(1) Alsherg, C. L., Plant Physio., 13, 295 (1938). JOURNALPaper 5-921, Iowa Agricultural Experiment Station. Project 638.
(2) Badenhuiaen, N. P., Rec. trav. botan. nEerZancl., 35,559 (1938). supported in part by a grant from Corn Industries Research Foundation.

Water Adsor tion By


Animal Glue
CHARLES ill. MASON1 AND HERBERT E. SILCOX
University of New Hampshire, Durham, N. H.

ADSORPTIOR OV T H I h FILMS
The adsorption of water on thin films of
five animal glues and one gelatin have been One bone glue, four hide glues, and a gelatin were chosen
investigated, the glues covering the range of which seemed to cover the range of known physical prop-
erties of glues. The glues were obtained through the
physical properties commonly employed. courtesy of a large industrial user who selected those most
Both adsorption and equilibrium moisture characteristic of available commercial glues. The gelatin
content have been studied. The former was a sample sold as suitable for bacteriological work and was
obeys Freundlichs law, and the latter is therefore supposed to be of unusual purity. No attempt
found to be greater than represented by the was made to purify the samples further because this would
have vitiated the results from a practical viewpoint. Table
moisture adsorbed on the surface. I gives physical characteristics as determined b y the firm
It is proposed that water is held by glue in which supplied the glues.
two forms-by true adsorption on the glue
surface and by some other mechanism in HTJ?IIDITY CoxDIrIoxs. The basic problem involved in the
the voids of the glue itself. 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

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
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
and incomplete. Wilson and Fuwa (11) give some data on 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
glue as part of an extensive study of many materials. Katz hours. Water was then added t o the swollen product and the
(4) and Sheppard, Houck, and Dittmar (7) studied gelatin, mixture heated t o 40 C. on the steam bath. When liquefied,
a similar material. the glue was drawn into films by the method of Kallender (S),
The present investigation was undertaken to supply data for using moistureproof regenerated cellulose (cellophane) as a sup-
porting medium. The films were then allomed to cool and dry
glues covering as wide a range of physical properties as partially in the air. The glue n a s peeled from the support and
possible. A t the same time a n investigation has been made cut into strips 1 inch vide and 15 or 18 inches long. They were
of the adsorption of water on glue in relation to Freundlichs rolled into loose cylinders and placed edgehise in glass weighing
law. 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
1 Present address, Tennessee Valley Authurity. Wilson Dam, Ala. glass cloth instead of moistureproof regenerated cellulose. This