POLYMER LETTERS VOL. 9, PP.

595-598 (1971)

ORIGIN OF POLYETHYLENE TRANSPARENCY

A number of publications have appeared recently (1,2) describing proce-

dures for preparing polyethylene of high optical clarity. These have usually
involved crystallization under conditions leading to orientation. It has been
indicated (2) that “the smaller crystallites . . . may account for the transpar-
ency of the film in visible light.”
We contend that the transparency of such polyethylene films is not pri-
marily related to crystallite size but rather to the kind of morphology and
size of superstructures much bigger than the crystallites themselves. Polyeth-
ylene, as normally crystallized, is not transparent because of the scattering of
light. It has been demoilstrated that such scattering primarily arises from
fluctuations of orientation of anisotropic volume elements rather than from
fluctuations in average refractive index from place to place as might be ex-
pected from scattering which would arise from crystals embedded in an
amorphous matrix of different refractive index.
Evidence for this origin of scattering comes from photographic light scat-
tering patterns of the sort shown in Figure 1. Patterns obtained with paral-
lel polarizers (V,) are comparable in intensity with those obtained with
crossed polarizers (H,). The latter pattern is a consequence of the anisotropy
of scattering elements, whereas the former may have contributions from aver-
age refractive index values.
Patterns of the type shown in Figure 1 may be accounted for by theories
based upon scattering from anisotropic spheres (3) which correspond to
spherulitic aggregates of crystals observed microscopically in such polymers.
For commonly observed ranges of spherulite sizes between 2 and 20 1.1, most
scattering occurs at angles less than 10” from the incident beam. Scattering
at larger angles may arise from disordered orientation of crystals within such
spherulites (4), but the total amount of scattered energy arising from such
disorder is usually much less than that which would be found from an as-
sembly of perfectly ordered spherulites.
A spherulite-type H, pattern is characterized by intensity maxima occur-
ring at a distance from the center of the pattern inversely related to the
size of the spherulite. The scattering at the center of an H, pattern from
an ordered spherulite should be zero, as a consequence of its spherical sym-
metry. In practice, a finite intensity is found which is a consequence of
disorder (4). Such disorder may lead to the tennis-racquet type H, pattern
described by Kawai et al. (5). The pattern of Figure 1 (a) exhibits some
intensity at 6 = 0” indicating some disorder. The position of the maximum at
6 = 2” 44’indicates an average spherulite size of 5.8 1.1.
These patterns may be contrasted with those obtained from films of
quenched-rolled Phillips Marlex 6002 linear polyethylene kindly furnished by
Dr. T. T. Wang, which he prepared according to the procedures described in
595
0 1971 by John Wiley & Sons, Inc.
596 POLYMER LETTERS

(b)
Fig. 1. Light scattering patterns found for a sample of convential com-
pression-molded film of Phillips Marlex 6002 linear polyethylene with (a)
H, polarization and (b) V, polarization-(1/50 sec exposure time).

his article (2). The scattering patterns are of lower intensity so that longer
exposure times'were required to obtain a picture, It is noted that the H,
scattering pattern is most intense at the center and that the intensity mono-
tonically decreased with increasing scattering angle. The four arms of the
pattern are not at 45" but are bent away from the machine direction. This
POLYMER LETTERS 597

(C)

Fig. 2. Light scattering patterns found for a sample of quench-rolled

film of Phillips Marlex linear polyethylene with (a) Hv polarization (1/10
sec exposure time, stretching direction horizontal), (b) V, and (c) Hh
polarization (1/25 sec exposure time).

pattern is like that expected for rod-like structures with the long axis hav-
ing some preferential orientation parallel to the machine direction (6). The
V, and Hh patterns show no clear-cut structure, with most scattering occur-
ring at very small angles.
It is evident that there is no spherulite structure in the quenched rolled
sample. The rod-like morphology might be identified with lamellar struc-
ture where the orientation is correlated over distances larger than the wave-
length of light. Such a structure is less heterogeneous optically than a
spherulitic structure. Consequently there is less light scattering. A simpli-
fied model based upon the random orientation correlation model (7) led to
the prediction that scattering decreases as the orientation of anisotropic scat-
tering elements increases and as the distance over which such orientations
are correlated increases (8).
598 POLYMER LETTERS

The increased clarity of the quench-rolled sample is thus a consequence

of the difference in organization of the crystalline superstructure. It is like-
ly that crystallization of the sample under the high shear and compression
of the quench-roll process leads to high nucleation rates and to crystalliza-
tion in an oriented matrix. It is probable that the crystalline morphology
produced in this manner may be locally like the “shish-kebab” structure (9).
This would be consistant with the light scattering patterns shown in Figure
2.

This work was supported in part by a contract with the Office of Naval
Research and in part by a grant from the Petroleum Research Fund of the
American Chemical Society.

References

(1) J. H. Southern and R. S. Porter, J. Macromol. Sci.-Phys., B4,(3),

541 (1970); J. Appl. Polymer Sci., 1_4, 2305 (1970).
(2) T. T. Wang, H. S. Chen, and T. K. Kwei, J. Polymer Sci., B, S , 505
(1970).
(3) R. S. Stein and M. B. Rhodes, J. Appl. Phys., 2, 1873 (1960).
(4) R. S. Stein and W. Chu, J. Polymer Sci., A-2, 8, 1137 (1970).
(5) M. Motegi, T. Oda, M. Moritani, and H. Kawai, Polymer Journal
(Japan), 1,209 (1970).
(6) M. B. Rhodes and R. S. Stein, J. Polymer Sci., A-2, 1,1539 (1969).
(7) R. S. Stein and P. R. Wilson, J. Appl. Phys., 33, 1914 (1962).
(8) R. S. Stein and J. J. Keane, F. H. Norris, F. A. Bettelheim, and
P. R. Wilson, AM. N.Y. Acad. Sci., 83, 37 (1959).
(9) A. Keller and M. J. Machin, J. Macromol. Sci., B1(1),41 (1967).

Richard S. Stein
Robert Prud’homme

Polymer Research Institute and

Dept. of Chemistry
University of Massachusetts
Amherst, Massachusetts 01002

Received April 28, 1971