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JOURNAL OF POLYMER SCIENCE: PART A-2 VOL.

7, 983-992 (1969)

Birefringence of Native Cellulosic Fibers. Part 11.
Spiral Structure of Cotton

li. R. IiRISHNA IYER, P. NEELATiAKTAS, and T.
R ADH A N <TSH NAK The A hmedabad Textile In dust ry ' s Reseawh
Iridia
A ssociation, Atrm~~llabarl,

Synopsis
Interferometric studies have been made on cotton fibers as well as on twisted nylon
filaments. The results so obtained provide strong evidence that the fibrils in the cotton
fiber become less inclined to the fiber axis as one proceeds from the surface to the core.
Also, studies on twisted nylon filaments by the fiber refractometer and Becke line tech-
niques indicate that the latter, as practiced in this laboratory, does give values of refrac-
tive index which are heavily weighted towards the fiber periphery.

INTRODUCTION
The well-known fiber refractometer of Freeman and Preston' has been
improved in the authors' laboratory so that its scope can be extended to
cover variable natural fibers such as cotton.2 By using this improved in-
strument, i t becomes possible to measure the mean value of each refractive
index in a parallel pad of fibers. An estimate can also be made of the
variability in the refractive index among fibers or length elements within
fibre^.^ The results obtained on cotton differed in two respects from
those obtained by earlier workers who used the Becke line m e t h ~ d . ~ . ~
The extraordinary refractive index n and consequently the birefringence
A n were higher; the variability in refractive index also appeared to be more
than could be surmised from B e c k line results which indicate next to no
variability. By following the a r g ~ m e n t ~ofs Preston et al.,6J these differ-
ences were tentatively attributed to the differences between the surface
and the interior of the fiber. The Beckr line method gives an estimate of
the refractive index near the fiber surface, while the refractometer result
represents some sort of average through all the layers of the fiber. Since
cotton has a spiral s t r u c t ~ r eand
~ * ~the fibrils in the inner layers may be
more oriented than those along the surface, the refractometer value for the
extraordinary refractive index could be higher than the Becke line result.
The higher variability of refractive index could likewise be due to vari-
ations among individual fibers in the spiral arrangement of fibrils from the
surface to the core, to which the refractometer is sensitive. However, these
explanations are questionable in the light of other earlier work. li'aust1°
has adduced reasons to believe that the Becke line refractive indices are
983
984 KRISHNA, IYER, NEELAKANTAN, RADHAKRISHNAN

not superficial. This belief is strengthened by certain interferometric
observations of McLean." There is also a view that the fibrils in different
layers of cotton may be deposited in spirals of equal angle12 rather than
equal pitch.13 I n the present paper, a critical analysis of the situation is
attempted with the help of data gathered in three ways: (1) with the im-
proved fiber refractometer, (2) by the Becke line method, and (S) by inter-
ferometry of single fibers.

EXPERIMENTAL
Samples
The fibers studied were ramie, cotton, and filaments of viscose and nylon.
Eight varieties of cotton were chosen on the basis of x-ray angle to repre-
sent a large spread in orientation. The viscose and nylon filaments were
included since they were fibers with no spiral structure, lumen, etc. How-
ever, certain experiments were conducted with nylon filaments twisted so
as to simulate a spiral structure. Full particulars of the method and the
extent of twisting will be given later.
Measurements by the Refractometer
The details of measurement are fully described in earlier papers2s3
and will not be repeated here. It will only be remarked that the samples
were in the form of a pad of highly parallelized fibers immersed in a "match-
ing" liquid and illuminated by polarized, collimated white light. The
irradiated portion consisted of about 1 cm length of the pad consisting of
a few thousand fibers. Prior to immersion, the samples were conditioned
a t 65% R H and during measurement, the temperature was controlled
within 30 f 0.1"C.
Measurements by the Becke Line Method
Contrary to the usual practice, as many as a hundred fibers were ex-
amined by this method. A somewhat elaborate procedure3 was used to
estimate not only the mean, but the coefficient of variation (CV) of the
refractive index. Fibers used for this measurement were also conditioned
a t 65% R H and tested a t 30°C.

Measurements by the Interferometer
Multiple-beam interferometry, employing fringes of equal chromatic
order,14was adopted in the present investigation. Since earlier ~ o r k e r s ~ ~ ~ ~ ~
have fully described the method, only a few aspects will be mentioned here.
The interferometer plates were thin glass pieces, each about 2 cm in di-
ameter and cut from a good photographic plate. These plates were coated
with aluminum so that each allowed a transmission of about 10%. The
plates were mounted (with their reflecting surfaces facing each other)
on a metal jig provided with three tilting screws which could be adjusted
C I<I, L LJ LOSI C F I B Ell S 985

to bring the plates into parallelism. The interferometer was held with the
plates vertical and illuminated a t normal incidence by a parallel beam of
white light from a tungsten filament lamp. A microscope objective com-
bined with a projection eyepiece cast a magrufied image of the fiber, which
was immersed in the liquid in the interferometer gap. The image was re-
ceived on the slit of a prism spectrograph. The fiber was so mounted that
the fiber axis was perpendicular to the length of the slit. The entire op-
tical system was mounted on a precision optical bench. Strips of metal
foil were placed between the interferometer plates to prevent any jamming
of the fiber while adjusting the tilting screws. No auxiliary temperature
control for the int,erferomet,er was incorporat>ed,as the purpose of the ex-
periment was to det,ect local variat8ionsin the refractive index of the fiber
rather than to det,ermine its absolute value. The sufficient requirement
was the constancy of temperat,ure of the fiber and the ambient liquid (mix-
ture of a-bromonaphthalene arid liquid paraffin) during the photography
of the fringe pat,t,ern. This could be achieved by controlling the room
temperature.

Preparation of Twisted Filaments
Filaments were twisted individually on a yarn twisting machine. The
number of turns per unit length N and the radius R of the twisted filament
were measured on the machine. The nominal surface angle 8, was cal-
culated from the well-known equation

tane, = 2aNR (1)
For refractometric measurements, the twisted filaments were wound on a
thin metal frame, forming a uniform pad of parallel filaments. For Becke
line measurements, the twisted filaments were held across a number of
microscope slides arranged side by side. The filaments were fixed to the
edges of each slide with a good cement. After the cement dried, the fila-
ments were suitably cut and the slides separated. For interferometric
work, the twisted filament was glued to the metal frame holding one of the
silvered plates. Throughout the sample preparation, the twisted filaments
were handled with meticulous care to ensure complete retention of the im-
parted twist.

RESULTS AND DISCUSSION
Discrepancies in Refractive Index
The refractive indices of a number of fibers, as measured by the fiber
refractometer and by the Becke line method, are given in Table I. Both
methods give the same results for viscose, nylon, and ramie. However, the
refractometer gives higher values of n,ll and of birefringence for all cottons,
and also high estimates of CV of refractive index. (The CV of the Becke
line results on individual fibers is below 0.1% for all the samples.) We have
\D
P
n

TABLE I
Results of Refractive Index Measurements (58'33 .k)
CV, yo of n by
Becke line Refractometer refractometer
__ -
Sample ni I An 4n
Viscose 1 .d.i2 1 ,512 0.040 1.S.il 1 ..ill 0.040 0.1 0.1
Nylon 1 ..i86 1 . ,527 0.0.i9 1 ,586 1 . ,726 0 060 0.2 0.1
Ramie 1 . XI9 1 .,729 0.070 1 . .509 1 .329 0.070 0.2 0 .1
Cottons
Hopi Acala 1 .5x2 1,529 0.053 1.588 1 .-5% 0 ,031 0.4 0.3
Jarila 1 . .%3 1.530 0.053 1.588 1 .529 0.0.59 0.5 0.4
Deltapine 1 -579 1.530 0.049 1 .,585 1 ,530 0.055 0 ..5 0.3
Giza-45 1 ,583 1.532 0,051 1 ,586 1 . .532 0 .0.2 0.6 0.4
Bobshaw 1 . .i77 1.532 0.045 1.582 1 ..5:30 0.05'2 0.7 0.4
Acala P18C 1 .57.5 1.533 0.042 1 ,584 1. ,533 0.0.51 0.7 0.4
Watson Mebane 1 .,573 1.533 0.040 1 ,581 I ,532 0,049 0.8 0.5
Swollen cottons
Jarila NaOH 1.562 1 ,524 0,038 1.564 1 ,522 0.042 0.4 0.3
Swollen slack
Jarila EI)A 1 ,573 1 .52.i 0.048 1 ,377 1 ,523 0.054 0.5 0.4
Swollen slack
CET,LULOSIC FIBERS 987

attributed these differences to the pronounced and variable spiral structure
of the cotton fiber.3 There may also be other possible contributions to
optical variability, arising from convolutions, irregular size and shape of the
fiber cross section, the lumen, and structural reversals. All effects but the
last are known to decrease markedly when the fiber is highly swollen, yet
the CV of lzl, shows only a slight decrease when cotton is swollen in alkali
(Table I). Thus, these effects seem to exert only a marginal influence on
optical variability. Reversals can also be dismissed since they account for
so lithle of the fiber length.17 We are therefore left with the need for n
deeper examination of the optical effects of spiral structure, which can be
experimentally just, discerned in ramie, which has a spiral angle less than
60.18

Model of Spiral Structure
That there is a spiral organization of fibrils in cotton has been known for
a long t,ime.8a9 There are, however, two views as to the nature of the spiral
angle. Duckett and TrippIg have recently tried to explain the azimuthal
intensity distribution of the (002) x-ray diffraction from cotton on the
basis that all fibrils are inclined to the fiber axis a t essentially the same angle,
which is perturbed only by a random wander. This view is shared by earlier
workers, such as Rebenfeld12 and Hearle.20 On the other hand, War-
wicker13 sees in the (002) x-ray diffraction arc, evidence of a spiral angle
which progressively decreases towards the core of the fiber. Strong con-
firmatory evidence is provided by x-ray work in this laboratory on the
much more informative (040) profile.21 Berkley,22 Meredith,4 and Orr
et al.9 also provide arguments in favor of a decrease in spiral angle towards
the interior of the fiber. The optical data presented in Table I can be
meaningfully interpreted in terms of a decrease in spiral angle from the
periphery to the core of the fiber. It is assumed, following Preston et
aL6J (and despite possible c r i t i ~ i s m ~that
~.~~ the) Becke line value of nII
represents a result which is weighted towards the surface of the fiber and is
therefore low because the surface fibrils show maximum tilt to the fiber
axis. On the other hand, the refractometer result depends on Rayleigh-
Gans scattering of light24and would be affected by an integrated phase dif-
erence through the fiber cross section. If the spiral angle decreases towards
the core of the fiber, the refractometer should give higher values of ?)11, as
has been found only in the case of cotton. The high CV of refractive
index would be due to variations in spiral arrangement among diff erent
fibers or segments of the same fiber.
Results on Twisted Nylon Filaments
The effects found in cotton can be simulated by twisted nylon filaments.
The results are shown in Table 11. The refractive indices obtained with
the refractomet,er and with the Becke line method are identical for the un-
twisted filaments. When enough twist is inserted to correspond to a surface
helix angle of 37.5" [eq. (1)], there is a marked drop in nil and in birefrin-
\D
P
P

TABLE I1
Results of Observations on Untwisted and Twisted Nylon Filaments
Twist
angle Surface
on the refractive Becke Line Refractometer C.V., yo of
surface index rill by
(02) hl) n1 I ni An nI I ni An refractometer
0 1.586 1.586 1.527 0.059 1.586 1.526 0.060 0.2
37.5 1.564 1.568 1.530 0.038 1.577 1.527 0.050 0.4
CELLULOSIC FIRERS 989

gence as measured by both methods. However, the drop is greater by the
Becke line technique. The difference in measurements by the two methods
is of the same kind as in cotton, but greater in magnitude. These results can
be understood in terms of a structural model consisting of a number of ele-
ments which are twisted together in accord with the “spinner’s rule” em-
bodied in eq. (l),whereby the optical properties would become similar to
those observed in cotton. A quantitative verification of the model is
afforded by the Becke line value of nil for the twisted filament. Assuming
that this is the value of rill a t the surface of the filament, the latter can be
calculated from the refractive index ellipsoid of a uniaxial ~ r y s t a l : ~ , ~ ~
1 cos2 6, sin2 BS
-
nt l 2 nc2 +n,Z
where the values of nr and n, are taken as nil and nl, respectively for the
untwisted filament. This calculation yields a result which is in reasonable
agreement with the Becke line value of nil for the twisted filament (Table
11). Therefore the Becke line result does seem to be weighted towards the
surface of the fiber, as Preston et a1.6J originally postulated. The refrac-
tometric value of rill is considerably higher, in accord with the “equal pitch”
model of spiral structure. The refractometric estimate of enhanced CV of
nll on twisting the filament can be easily explained. When a long filament is
held a t one end and twisted a t the other, it is difficult to achieve constancy
of twist over all segments. These twist variations will in turn cause vari-
ability in the measured value of rill. It was verified that when filaments
having different values of inserted twist were mixed together in the re-
fractometer, the CV increased from 0.4 to 0.53%. There is an obvious
similarity between this situation and the case of cotton fibers.

Results of Interferometry
As described earlier, transmission interference fringes of equal chromatic
order14were obtained by passing collimated, polarized white light through
slightly transmitting glass plates between which the fiber and a matching
liquid were sandwiched. Photographs of these fringes are shown in Figures
1 and 2 . I n the case of glass and nylon, t,he fringes are exactly similar to
those described by earlier w ~ r k e r s . ~ The
~ J ~ fringes inside the fiber are
straight and continuous with those inside the liquid in the region of the
matching wavelength (marked B). Thus the refractive index is homo-
geneous across the fiber. On either side of this wavelength, the fringes
bulge towards the middle of the fiber on account of increased path length.
The situation changes slightly with ramie and markedly with cotton and
twisted nylon. The shape of the fringe can be explained in terms of optical
heterogeneity of the fiber from the surface to the core. Figure 3 shows a
heterogeneous fiber with a n idealized circular cross section. It is assumed
that the refractive index of a fiber element increases progressively from the
edge to the center. Different segments of the fiber, such as K , L, M in
99 0 KRISHNA. IYER. NEELAKAhTAN. RADHAKRISHNAN

Fig. 1. Fringes of equal chromatic order formed by ( a ) glass, ( b ) nylon, and ( c ) ramie, for
light vibrating parallel to the fiber axis (positive print).

Fig. 2 . Fringes of equal chromatic order formed by ( a ) twisted nylon and ( b ) and (c)
cotton, for light vibrating parallel to the fiber axis (negative print).
CELLULOSIC FIBERS 991

(b)
4 Fibre region

+Red cb-b Violet-

Fig. 3. Schematic diagrams of ( a ) an idealized circrilar C I ’ U S ~section of an optically
heterogeneous fiber and ( b ) fringes of equal chromatic order i i i such a fiber having
refractive index increasing towards the axis.

Figure 3, will introduce a total path retardation (or advance) given by
J[n(z,y) - 1211dz for each y, where n.(z,y) is the refractive index of the
fiber a t the point (ZJ) on the cross section, and nl that of the liquid, for the
same wavelength. Since the liquid has a steeper dispersion curve than the
fiber,1.3 the fiber will show a lower refractive index than the liquid on
the ‘blue’ or low wavelength side of matching. The decrement in refractive
index is greatest a t the edges of the fiber, in segments such as K . However,
there is little path retardation because the fiber thickness is small a t the
edges. At interior segments such as, L and ill, the geometrical path
difference increases, but the average value of decrement in refractive index
drops. Thus the fringes in the fiber show a displacement which rapidly
increases to a maximum as one goes away from the edge and then falls back
towards the middle. Figures 1 and 2 show that this is the shape of the
fringes obtained in cotton, twisted nylon and, to a just discernible extent, in
ramie. Such fringe shapes are not obtained on the higher or “red” side
of matching, because the changes in geometric path and in refractive index
do not oppose each other. The resulting fringes are similar to those ob-
tained with optically homogeneous fibers.
The foregoing explanation is very sinipliiied and does not, take into ac-
count the complicated tilt of the index ellipsoid in different regions of the
fiber. However, it appears unlikely that a more sophisticated theory mill
alter the nature of the argument. One coriditioii of the argument is that
there should be a steep fall in the path through the fiber from the middle
992 KHISHNA, IYEH, NEELAKANTAN, HADHAKHISHNAN

towards the edges. This condition will not be fulfilled by typical cotton
cross sections, which approximate to hollow fiattened ellipses. A mature
and nearly circular fiber from a coarse species, such as Bengals, shows the
effect best.
CONCLUSIONS
The difference between Becke line measurements and refractometric
measurements of the extraordinary refractive index of cotton can be ex-
plained on the basis that the fibrils in cotton are more inclined towards the
fiber axis as one goes away from the core of the fiber. Interferometric
studies of the fiber are also in full agreement with this hypothesis. The
optical effects of spiral structure in cotton can be well simulated by a twisted
nylon filament.
The authors thank the Director of ATIltA for permission to publish this paper.

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Received November 18, 1968