NOTES

The Effect of Particle Size on the Haze of Polymer Films

Haze in thin polymer films is of significant commercial importance. I t arises from the scattering
of light by the film, either due to surface effects or internal structure effects. The understanding
of these effects can lead to control of the film’s clarity.
Surface effects are extremely important factors contributing to polymer haze, as pointed out by
Stehling e t a1.l Analysis of the internal structure of the polymer is also necessary to understand
the causes of haze. Debye and Bueche2 and others3s4have shown, for internal structures composed
of isotropic, random inhomogeneities, that the scattered light represented by the Rayleigh factor
R ( H ) is given by
R ( H ) = 4a3Fa3(1+ cos28)/c2X4(l+ a2H2)2 (1)
where H is the magnitude of the scattering vector, H = (4a/X)sin1/2), X is the wavelength of the
light in the medium, 0 is the polar scattering angle in the medium, q2 is the mean-square fluctuation
in the dielectric constant, a is the correlation length (a measure of the average size of the inhomo-
geneities), and c is the average dielectric constant of the medium.
Equation (1)describes the scattering of unpolarized, monochromatic light by a medium containing
isotropic, random inhomogeneities. If the inhomogeneities are anisotropic (as polymer crystals
or spherulites), one must consider the scattering from orientation fluctuations as well as density
fluctuation^.^ We shall consider only isotropic inhomogeneities in this discussion.
The turbidity 7 arising from the internal structure is calculated by integrating eq. (1)over all
scattering angles:

The turbidity is defined by the relation

It = I0 exp(-rd) (3)
where It is the intensity transmitted by a sample of thickness d when the incident intensity is Zo.
Integration of eq. (2) leads to an expression relating the turbidity to the average size of the inho-
mogeneities and the radiation wavelength3:
(b + 2)* 2(b + 2) + 1)) (4)

where b = (16a2/X2)a2. Equation (4) predicts that, for a given wavelength of light, the turbidity
will increase as the average size of the inhomogeneities increases.
In practical polymer film usage, the light scattered a t very small angles, as well as the transmitted
light, contributes to clarity. This very small-angle scattering should not be included in the “turbidity”
when analyzing the effects of internal structure on polymer clarity. Hazemeters, often used to assess
polymer clarity, do not include in the measured haze the light scattered a t 0‘ < 2.5’, where 8’ is the
polar scattering angle in ail.6 (8’ is related to 0 by Snell’s law, n sin0 = sin8’, where n is the refractive
index of the medium; n2 = c). Standard light transmission tests also include some small-angle
scattering in the measurement of “transmission.”
Let us define turbidity 7 as the amount of light that is scattered, a t any angle. The incident and
transmitted intensities are then related as in eq. (3). Haze is here defined as being that portion of
the scattered light intensity which does not contribute to clarity. Haze [7’(Omin)] is calculated by
excluding the very small angles from the integration of eq. (2):

where Omin is the minimum angle of the scattered light to be included in the haze. In practice, Omin
is dependent upon the distance between the light source and the film and the distance between the
observer and the film. Effectively, Bmjn tends to decrease as either of these distances is decreased.

Journal of Polymer Science: Polymer Physics Edition, Vol. 21,831-833 (1983)

01983 John Wiley & Sons, Inc. CCC 0098- 1273/83/050831-03$01.30
832 J. POLYM. SCI.: POLYM. PHYS. ED. VOL. 21 (1983)

POLYMER FILM HAZE

100.01
1 9,,.,in=0.500
80

60,

40.

20.

0. I
0.0 5.0 10.0 15.0 20.0 25.0
A (MICRONS)
Fig. 1. Haze as a function of inhomogeneity size a, for various values of Omin; A’ = 0.6328 pm, n
= 1.5.

Integration of eq. (5) yields

where F = 1 + ‘/zb(l - cosOmin). Equation (6) leads to eq. (4) in the case of Omin = 0.
For a given Omin > 0 and a given wavelength of light, eq. (6) predicts that, as a function of the in-
homogeneity size a, 7’(Bmin) reaches a maximum a t a critical value of a(a = uc). For Bmin = 1.67O
(&,in = 2.5’, refractive index 1.5) and A’ = 0.6328 (A’ is the wavelength in air), a, = 2.3 pm. For
reasonably small minimum angles (Omin < 7O), the critical inhomogeneity size is related to the min-
imum angle according to

UcHmin = 1.0 (7)

where Hmin= (4n/A)sin(Omin/2). Figure 1 shows the effect of the inhomogeneity size on 7’(Omin)
for various values of Omin.
The analysis of haze arising from the internal structure of polymer films can be made using eqs.
(6) and (7). These equations indicate that haze is not necessarily reduced by reducing the size of
the inhomogeneities in the polymer film, but that there is a critical size when the haze is a maximum.
This phenomenon is dependent upon the exclusion of some small-angle scattering from the mea-
surement of haze. Since larger particles scatter more a t small angles, the choice of a nonzero Omin
will tend to exclude some of the scattering due to large particles from the measurement of haze. It
is this exclusion which leads to the critical-size phenomenon. It is therefore important to define
Omin when comparing transmission, haze, and visual clarity measurements.
Since eqs. (6) and (7) are derived for a fixed wavelength of light, haze from “white light” can be
determined by integrating the haze as given in eq. (6) over the visible spectrum. One must also assess
surface effects when evaluating haze from polymer films. In order to separate surface and internal
effects, one can eliminate the surface effects by performing the scattering experiments using a
matching refractive index immersion fluid on the surface of the film.

The authors acknowledge the support of the National Science Foundation and the Materials
Research Laboratory of the University of Massachusetts for these studies.
References
1. F. C.Stehling, C. S. Speed, and L. Westerman, Macromolecules, 14,698 (1981).
2. P. Debye and A. M. Bueche, J . Appl. Phys., 20,518 (1949).
 NOTES 833

3. P. Dehye, H. R. Anderson, and H. Brumberger, J. Appl. Phys., 28,679 (1957).

4. J. R. Koherstein and R. S. Stein, J. Polym. Sci. Polym. Phys. Ed., 18,199 (1980).
5. R. S. Stein and P. R. Wilson, J . Appl. Phys., 33,1914 (1962).
6. “Standard Test Method for Haze and Luminous Transmission of Transparent Plastics,” ASTM
D1003, in 1980 Annual Book of A S T M Standards, Part 35, American Society for Testing and Ma-
terials, Easton, MD, 1980.
7. “Standard Test Method for Transparency of Plastic Sheeting,” ASTM D1746, in 1980Annual
Book of A S T M Standards, Part 35, American Society for Testing and Materials, Easton, MD,
1980.
R. J. TABAR
C. T. MURRAY
R. S. STEIN
Polymer Research Institute
University of Massachusetts
Amherst, Massachusetts 01003
Received August 9,1982
Accepted December 17,1982