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A G~EAT deal of effort goes into attempts to improve the properties of the
cotton fibre by various chemical finishing processes. Since reactions designed
to introduce crosslinking agents into cellulose proceed via swelling of the
cotton, an understanding of the swelling mechanism of the cotton fibre is
of great importance to anyone engaged in this field of research. Swelling
is intimately connected with the fine structure of the fibre; hence a study
of the cotton in the swollen state should shed light on its fine structure.
Although in the past the cotton fibre has been the subject of many
studies, it is only recently that the advent of modern microtomes has
facilitated a more direct study of its fine structure. Of particular value is
the availability of diamond knives with which tough materials like mature
cotton fibres can be cut into sections only a hundred or so Angstr6m units
thick. As shown by Rollins, Moore and Tripp 1, not only can the fine
structure of unmodified cotton fibre be studied, but it is also possible by
suitable techniques to observe the effect of crosslinking reactions.
This paper presents results of the examination of sections of cotton
fibre. It will be shown that if fibres are first swollen in water, and then
after a suitable solvent exchange embedded in methacrylates, an enormous
additional swelling is obtained.
EXPERIMENTAL
Cotton cloth that had been desized, pressure boiled, bleached in sodium
hypochlorite and acid washed was cut into small pieces approximately
5 mm × 5 mm. Prior to being embedded, some of the pieces were dried in
an oven at 100°C while others were soaked in water at room temperature.
The methacrylate embedding was carried out as follows. The monomers,
supplied by Imperial Chemical Industries Ltd, were freed from inhibitor
by washing in dilute alkali, washing in distilled water, and drying with
427
J. DLUGOSZ
(2) (a) The cellulose was dissolved from the section, leaving the emlze2ding
medium intact, by floating the grid, section downwards, on the surface of a
solution of cuprammonium hydroxide (supplied by the British Drug
Heuses Ltd to the British Cotton Industry Research Association's specifi-
cationS). The sections were rinsed first in ammonia, then in a solution of
Rochelle salt, and finally in distilled water.
(b) Another way of dissolving the cellulose was by floating the grids on
the surface of 72 per cent sulphuric acid, and rinsing in distilled water.
(3) Some sections were stained by floating the grids on the surface of
five per cent phosphotungstic acid.
RESULTS
Figure 1 shows a shadowed cross section of the oven-dried fibre embedded
in methacrylates. Apart from general contours very little of the fibre
structure can be seen in such a section.
However, a cross section of an originally water-swollen fibre embedded
in methacrylates after solvent replacement contains a wealth of detail.
Figure 2 shows that the wall of the fibre has separated into concentric
layers, or lamellae, of remarkably uniform thickness. The lamellae are
seen in the micrograph as discontinuous rings; evidently they are split up.
In Figure 2 the darker areas correspond to the cellulose and the lighter
ones to the embedding medium. That this is so can be proved by treating
a ~ W
b
the sections with solvents. If a section is treated with a solvent for the
embedding medium, Figure 3 results, showing the cotton cellulose. If,
however, a solvent for cellulose is used, the resulting electron micrograph
(Figure 4) shows the embedding medium with many holes; each of these
originally contained cellulose. Kling ~ and co-workers published electron
micrographs similar to Figure 2, but they mistakenly interpreted the light
areas as corresponding to swollen lamellae and the dark areas as repre-
senting some noncellulosic interlammellar substances of unspecified chemical
composition; hence most of their conclusions are perforce wrong.
Staining the cross sections with phosphotungstic acid reveals that the
fibre wall is composed of very thin fibrils which will be called microfibrils.
These can be seen in Figure 5, which is a micrograph, taken at higher
magnification, of such a stained cross section; it shows parts of two
lamellae. The thickness of the microfibrils has been estimated to be about
80 A, although microfibrils having thickness of about 40 A have also been
observed. It is not yet known whether the 80 A microfibrils eventually split
into the thinner 40 A micro fibrils.
Figure 6 shows a shadowed longitudinal section from which the embedding
medium has been dissolved. It illustrates how in some regions the dispersion
DISCUSSION
It is well known that the bulk polymerization of methyl methacrylate
proceeds initially as a first-order reaction; at about 25 per cent conversion,
when the viscosity of the system increases markedly, the reaction acceler-
ates. The auto-acceleration is believed to be brought about by a decrease
in the termination rate caused by the rise in the viscosity of the polymerizing
medium. This explanation is supported by the finding of Trommsdorff et a U
that the polymerization is hastened if the viscosity of the monomer is
increased by the dissolution in it of its (or other) polymer.
Similar conditions exist in the medium permeating the cotton fibre; the
presence of cellulose, while not appreciably affecting the reactions of
initiation and propagation, impedes chain termination. Movement and
growth of a macroradical are restricted to the spaces that were originally
accessible to water and are now filled with monomer. A macroradical in
the fibre is to some extent isolated from other macroradicals by cellulose;
the probability of its colliding and reacting with another macroradical is
reduced and hence its lifetime is increased, during which it continues to
add on monomer molecules and so grows longer. Thus the rate of poly-
merization is higher and auto-acceleration occurs earlier than in the
external medium.
In a system comprising a cotton fibre impregnated with catalysed methyl
methacrylate monomer and immersed in it, the external medium is in
communication with the m e d i u m in the fibre; during polymerization,
therefore, a gradient of concentration of monomer is developed across the
boundary of the fibre. Monomer tends to diffuse through the outermost
lamella into the medium in the first interlamellar space and to dilute it.
This results in a swelling pressure which causes the outermost lamella to
expand and to separate from the rest of the fibre. The tension in the
expanding lamella splits it up. The now open structure of the outermost
lamella facilitates the diffusion of monomer. Consequently, a concentration
gradient is set up across the second lamella, which, in its turn, expands
and splits up. In this way the dispersion of cellulose is propagated, layer by
layer, towards the lumen.
Monomer must evidently be driven into the fibre under the influence
of a considerable concentration gradient to account for the rapidity with
which polymerization swelling is propagated. Continuous removal, by
polymerization, of molecules from the diffusing monomer tends to maintain
the gradient and swelling of the polymer so generated continues to expand
the fibre. The following factors are thought to contribute to this state of
affairs.
(1) The medium within the expanding part of the fibre, containing
polymer of higher molecular weight and hence being more viscous, poly-
merizes faster than the external medium.
(2) The restricted mobility of the polymer molecules confined to grow
in the spaces that have been opened by swelling the fibre in water may
result in the existence of long-lived macroradicals. On being brought into
contact with the diffusing monomer, these trapped radicals would resume
their polymerization.
(3) The viscoelastic flow of cellulose during polymerization swelling
involves first the breaking of van der Waals and hydrogen bonds and, as
stress concentrations exceed chemical bond strength, probably the scission
of cellulose chains. Now the breaking of primary valence bonds results
in the production of free radicals. This additional source of initiation, by
further increasing the rate of polymerization, would tend to increase the
concentration gradient; the grafted polymer chains, though attached at
one end to cellulose, can still participate in the swelling phenomena.
The polymerization swelling occurs some hours after the polymerization
reaction has started. Evidently it is only after auto-acceleration has begun
in the medium permeating the fibre but before it has done so in the
external medium that the concentration gradient, and hence the swelling
pressure, may become high enough to disrupt the fibre. The polymerization
swelling ceases when, with the onset of auto-acceleration in the external
medium, the monomer concentrations within and without the fibre equalize.
It is thus seen that the polymerization swelling is likely to be a complex
phenomenon involving diffusion, polymerization, and viscoelastic flow,
which taking place simultaneously, determine its progress. For instance,
when a piece of cotton fabric rather than a single fibre is embedded, the
polymerization swelling is not uniform throughout the sample; only the
fibres lying along the edge of the fabric tend to be swollen along their
entire length, while in those disposed at right angles to the edge the
swelling decreases away from the edge. This is readily explained: just as
the presence of cellulose hastens the polymerization in the medium within
the fibre, so the presence of the fabric hastens, though to a less extent, the
oolymerization of the part of the medium that fills inter-fibre spaces.
Thus, except at the edges of the fabric, the time is reduced during which
the concentrations of monomer in the medium within and without the
fibres may differ appreciably.
434
THE FINE STRUCTURE OF COTTON FIBRE
CONCLUSIONS
it has long been known that biological specimens, when embedded in
methacrylates, may suffer serious distortion, which has been called 'poly-
merization damage' or 'polymerization explosion' because it results in the
separation of cells or even in the disruption of the contents of a single
cellL Cotton fibres, being so susceptible to this damage and showing it
readily, are suitable specimens with which to study the methacrylate
embedding method, should such a study be undertaken in an effort to
find how to eliminate this damage.
This disruptive tendency of the methacrylate embedding medium is
nevertheless found useful in structural studies of materials lacking inherent
contrast. The methacrylate embedding technique disperses the structural
building units of cellulose to a considerable extent, without at the same
time altering their relative positions, and thus provides an exploded view
of the fibre, so that its architecture can be studied. In particular, the
technique sheds light on the problem of water accessibility; it shows where
in the fibre the imbibed water goes. At the same time it reveals the shape
and the size of the cellulose crystallites. It is generally understood that the
water swelling of cellulose is intercrystalline; the crystalline regions are
impermeable to water on account of the very regular van der Waals and
hydrogen bonding that arises from the regular arrangement of the mole-
cules. Evidently the microfibrils, the thinnest supermolecular building units
into which the fibre splits during polymerization swelling, may be identified
as the crystalline regions of cotton cellulose.
The structure of the cotton fibre may therefore be pictured as an array
of elastic crystalline microfibrils held together principally by hydrogen bonds
formed between the hydroxyl groups residing on the surfaces of microfibrils.
This bonding is weak since it is irregular, depending on the degree of
perfection with which the microfibrils are aligned with respect to one
another; a whole range of bond strengths is thus thought to exist in the
inler-microfibrillar spaces. This variable bonding probably accounts for
the properties of cotton fibre that are usually ascribed to the so-called
amorphous regions of cellulose.
The very strong lateral cohesive forces operating within a microfibril
may be either entirely of the secondary type or may, in part at least, be
due to primary chemical bonds, i.e. either the cellulose chains are parallel
to each other and to the axis of the microfibril, or they form regular folds
or spirals. It may prove possible to decide with the aid of the electron
microscope which type of molecular arrangements does in fact obtain.
Since polymerization swelling is bound to result in the breaking of some
of the microfibrils, the examination of the broken ends at sufficiently high
magnification may give the answer to this question.
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Blackwell: Oxford, 1961
a KRANITZ, M. and SEAL, M. Fifth Internat. Congr. Electron Microscopy, Philadel-
phia, FF7 (1962)
4 CLIBBENS, D. A. and LITTLE, A. H. J. Text. Inst. 1936, 27, T285
•5 KLING, W., LANGNER-IRLE, C. and NEME'~SCHEK, T. Melliand Textilber. 1958, 39, 879
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