Fred W. Billmeyer, Jr.
*
Yuan Chent
Department of Chemistry
Rensselaer Polytechnic Institute
Troy, New York 12180-3590
On the Measurement of Haze
Possible pitfalls and errors in the measurement of haze by
ASTM Method D 1003 are pointed out and discussed. This
propert?, is an important measure of the optical clarity of
plastic $films and sheets. Although special hazemeters are
usually used for the measurement, it is demonstrated that
accurate haze measurements can be performed by using
widely available integrating-sphere spectrophotometers.
Additional advantages of obtaining both spectrophotometric
and goniophotometric data for the characterization and
interpretation of haze are pointed out.
Introduction
In the plastics industry, haze is a term used to describe the
slightly cloudy appearance of film or sheet material resulting
from the forward scattering of light. Haze may arise from
internal causes, such as dirt, poorly dispersed pgments, or
other small particles within the specimen, or from external
causes, such as surfaces with a very fine roughness. In the
1940s, when plastic sheets were first used in optical appli-
cations. such as aircraft canopies, it because desirable to
have an objective measure of haze, correlating with its visual
perception, for quality-control purposes. A method was de-
vised using a simple integrating-sphere photometer to mea-
sure the forward-scattered light when the specimen was
placed flush against the entrance port of the sphere. The
method was adopted by the ASTM’ and has been practiced
ever since.
Much of the development work on the haze method was
carried out by using the integrating-sphere recording spec-
trophotometer then commercially available, based on the
Hardy design and marketed by the General Electric Com-
pany. Subsequently special hazemeters were designed and
*Present address: 2121 Union Street, Schenectady, New York 12309.
fPermanent address: Xian Institute of Optics and Precision Mechanics,
Xian, People’s Republic of China.
0 1985 by John Wiley & Sons. Inc.
Volume 10, Number 4, Winter 1985
were made commercially available.* The original ASTM
haze method incorporated provision for the use of either
type of instrument, designating the spectrophotometric method
as the referee technique. That method is now being revised,?
and it was ascertained that the spectrophotometric method
is no longer used to an appreciable extent. The question
arose whether it should be retained in the method.
It was our opinion, based on almost 40 years of experience
in the study of the optical properties of plastics, that the
availability of spectrophotometric data is advantageous in
the diagnosis of the causes of haze and in determining how
to minimize or avoid it. We therefore undertook to ascertain,
for the benefit of the ASTM task force carrying out the
revision of the haze method, whether it was still possible
to make accurate haze measurements by spectrophotometry
using modem instruments. We define accuracy in this case
as agreement with the results now obtained, several decades
after the original test development, by using the haze stand-
ards available for the calibration of commercial hazemeters.
Because there are several critical geometric conditions writ-
ten into the haze method, it was not clear that this would
be the case.
In the course of the work, we explored the effects of a
number of parameters on the results of the haze measure-
ment, some of them not widely appreciated. We also made
both spectrophotometric and goniophotometric measure-
ments of a variety of samples. In this article we discuss our
results, pointing out some of the pitfalls to be avoided if
accurate haze measurements are to be obtained and some
of the advantages of more detailed studies of haze than can
be obtained by the usual test methods.
Definition of Haze
ASTM Method D 1003’ defines haze as “that percentage of
transmitted light which in passing through the specimen
*Gamer-NeotecInstrument Division, Pacific Scientific CO., Silver Spring,
MD; Hunter Associates Laboratory, Reston, VA.
tASTM Committee D 20 on Plastics, Subcommittee D 20.40 on Optical
Properties, Task Force X-40-6, J . H. Cain, chairman, Dow Chemical
Company, Freeport, TX.
CCC 0361-2317185104 219-06$04.00 219
deviates from the incident beam by forward scattering. For
the purposes of this method only light flux deviating more
than 2.5 deg on the average is considered to be haze."
It is necessary to translate this definition into the instru-
ment geometries and measurement steps required for the
determination of haze. Figure 1 shows a schematic of an
integrating sphere such as is used in hazemeters and spec-
trophotometers. (Although the latter instruments often uti-
lize the double-beam configuration, the figure shows a sin-
gle-beam sphere for simplicity.) The specimen can be placed
at point A, and must be set flush against the entrance port
to the sphere. At B is placed either a white standard, as
discussed in detail later, or a black trap to absorb the light
beam. Four measurements are required, as indicated in Ta-
ble I.
Although it is not essential, it is customary to calculate
the total luminous transmittance of the specimen, T,, as well
as the haze, H . The approximate equations most often used'
are:
T , = (T2/T,) x 100, % (1)
H = ((T4/T2) - (T3/T')] X 100, % (2)
The second term in the brackets in eq. (2) is particularly
important when specimens with low transmittance are being
measured.
The quantitative definition of haze is empirical, based on
an arbitrary angular specification of deviation of rays in a
collimated beam. In practice the definition specifies the an-
gle of an annulus formed by the difference in radii between
that of the beam and that of the exit port (B) of the sphere
subtended at the entrance port (A). The ASTM method
specifies that the beam shall be circular in cross section and
concentric with the port, leaving an annulus of 1.3 ? 0.1
deg subtended at the entrance port. This specification ap-
pears to have been selected as a matter of convenience with
the apparatus at hand in the early days of the development
of the test method.
A further point that is not always appreciated by the user
of the method is the need for care in the selection of the
white standard used in measurements T , and T2. In steps TI
and T 2 ,light flux from the source falls on the white standard
and is reduced by a factor equal to its reflectance factor,
which can vary, among the standards in common use, from
nearly 100% to around 75%. Subsequently, the reflected
flux falls on the internal walls of the sphere, from which it
is further diffusely reflected and ultimately detected, the
Chtrctor
Sourcr
AuB
FIG. 1. Sketch of the geometry of the integrating sphere
used in haze measurement.
220
TABLE I. Instrument arrangements used in the
measurement of total luminous transmittance and haze.
Measurement Position A Position B
11 No specimen White standard
T2 Specimen White standard
T3 No specimen Light trap
T4 Specimen Light trap
detector viewing the sphere wall but not either port at A or
B . However, in steps T3 and T 4 , scattered flux falls directly
on the sphere wall without the intermediate step of reflection
from a white standard. Analysis shows that the two mea-
surements are consistent only if the white standard has the
same reflectance factor as the sphere wall. This is the case
in commercial hazemeters, as is discussed below, but is
unlikely to be true in spectrophotometers unless special care
is taken.
Apparatus
Hazemeters
Two types of hazemeter are or have recently been com-
mercially available. One type is known as a pivotable-sphere
instrument (Gardner, Hunter). Here it is possible to rotate
the integrating sphere about point A so that the flux falls
either on a light trap permanently mounted at B or on the
wall of the sphere adjacent to B . Thus the sphere wall
automatically serves as the white standard. In a second type
of hazemeter (Gardner), a similar result is obtained by mov-
ing a white disk into place to cover the light trap for the
measurement of TI and T2. If the disk and the sphere wall
initially had the same reflectance and are properly main-
tained, the error associated with the white standard is avoided.
Hazemeters of the types just described are invariably sin-
gle-beam instruments, for reasons of simplicity and econ-
omy. This introduces the possibility of another error, the
so-called single-beam integrating-sphere error. ' The effi-
ciency of the sphere in reflecting flux internally depends on
the reflectances and areas of not only the internal sphere
wall, but also all of the ports (of which A, B, and the port
with the detector behind it are shown in Fig. I ) . If, in the
rearrangement of components to make the measurements,
the reflectance of any port is changed, the sphere efficiency
is changed, and in single-beam instruments an error is in-
troduced that can be as large as 5%. This source of error is
eliminated by using a double-beam optical system.
In the pivotable-sphere type of instrument, the reflectance
of the ports is not changed in the measurements; the light
beam is merely moved with respect to port 9.Thus there
is no error if the reflectance of the sphere wall is uniform
over its surface. In the second type of hazemeter, the light
trap is replaced with a white standard and an error is created.
The manufacturers of these instruments compensate for the
error by placing a black disk, presumably identical in size
and reflectance to the light trap, behind the white disk when
COLOR research and application
that disk is not in the light beam. Moving the white disk to TABLE II. Effect of reflectance factor R of white standard
cover the light trap uncovers the equivalent black disk and on indicated haze of glass and plastic haze standards.
~~

the error can be compensated. Haze (%) with white standard of R (“10)
The spectral response of commercial hazemeters is by Calib.
Standard 98.5 91.3 87.7 84.8 79.8 value
convention adjusted to provide luminous quantities weighted -
for CIE standard illuminant C and the CIE 1931 standard 1% Plastic 0.52 0.54 0.56 0.59 0.64 0.4
colorimetric observer. 5% Plastic 3.58 3.85 4.00 4.11 4.41 4.0
10% Plastic 9.84 10.56 10.86 1 1.28 11.a9 10.8
15% Plastic 13.93 14.83 15.30 15.78 16.62 15.3
20% Plastic 18.02 19.05 19.61 20.27 21.35 19.8
30% Plastic 32.79 34.51 35.19 36.10 37.58 35.8
Spectrophotometer Glass A 7.36 7.93 8.13 8.40 8.97 7.9
Glass 6 13.47 14.47 14.73 15.35 16.10 14.5
The spectrophotometer used in the experiments to be de- Glass C 19.49 20.95 21.25 21.97 22.92 21.6
scribed was a General Electric (Hardy-type) instrument, no
longer commercially available but identical in geometry with
the spectrophotometers available when the haze method was Instrument Variables
developed. It is a double-beam integrating-sphere instru-
ment in which the specimen can be placed flush against the Effect of White Standard
entrance port to the sphere. It was necessary to study the
effect of the reflectance of the white standard for the ex- Table 11 illustrates the effect on indicated haze when the
periments, as described below, since there is no easy way reflectance factor of the white standard is changed, as mea-
to use the wall of the sphere as the standard. sured on the spectrophotometer in our laboratory. The col-
From the spectral curves obtained with this instrument, umn labeled Calibration value lists the average of the haze
we calculated the appropriate luminous values for illuminant readings relative to those obtained at the National Bureau
C and the 1931 standard observer by the selected-ordinate of Standards for these plastic haze standards and glasses as
method. measured on either two or three commercial hazemeters. *
It can be seen that by the appropriate selection of a white
standard, presumably one with a reflectance factor matching
that of the sphere wall, it is possible to adjust the haze
Goniophotometry
readings to approximate the calibration values closely.
Goniophotometric measurements, characterizing the rel-
ative amounts of light scattered at various angles from sam-
EfSect of Size of Port and Beam
ples and standards exhibiting haze, were carried out on a
Hunter Associates Laboratory D 10 recording goniophoto- In our spectrophotometer, it was possible to adjust the
meter. * size of the exit port (B) of the sphere to the correct value
by means of a suitable mask, and to adjust the size of the
beam at that port by means of an iris diaphragm suitably
located. We were thus able to explore the effect of the size
Haze Standarch
of the annulus between the beam and port by varying the
Because of the specific geometric conditions required for beam size. It should be noted that this adjustment is valid
accurate haze measurement, it has been necessary to devise only if the beam at port B is of uniform intensity across its
working standards for the calibration and performance area, as was the case in our instrument. In an article de-
checking of haze-measuring instruments. Haze standards scribing the reference hazemeter at National Bureau of Stan-
currently commercially available consist of plastic chips, dards, Weidner and Hsia3 gave similar results.
50 mm square, very lightly pigmented with a white pigment The important fact to note is that, as is detailed in the
such as titanium dioxide. They cover a range of 1 to 30 % next section, the behavior of the plastic and glass standards
haze. The standards with lowest haze are susceptible to is quite different in their sensitivity to the size of the annulus,
significant change in measured haze if the surface is scratched the indicated haze of the plastic standards being almost
or marred. There is an unfulfilled need for additional haze insensitive to this variable, but the readings for the glasses
standards with different geometric scattering properties, as depending markedly on it. Table 111 presents our results for
is discussed below. In the experiments described in this one glass standard. At the beam size corresponding to the
article, we used a set of rough-surface (acid-etched) glass defined annulus of 1.3 deg, the standard has an indicated
specimens as temporary uncalibrated standards to meet this haze close to its calibration value, 21.6%. At annuli 0.1
need. deg above and below the specified value, corresponding to
the tolerance on the annulus in the ASTM method, the

*We thank The Munsell Color Science Laboratory, Rochester Institute *We thank Harry K. Hammond, 111, Gardner-Neotec Instrument Divi-
of Technology, for making the Hunter goniophotometer available for these sion, Pacific Scientific Co., for the loan and calibration of the plastic and
measurements. glass haze standards.

Volume 10, Number 4, Winter 1985 221

 IC
TABLE Ill. Effect of annulus size on indicated haze (YO)
of glass standard C.
Annulus Haze
("/.I
0.4 17.7
0.7 18.6
1.o 19.7
1.2 20.6
1.3 21.2
1.4 21.8
1.6 22.6

change in indicated haze is 0.6%. The current method rec-

ommends that haze be reported to the nearest 0. I %. Clearly,
it is necessary to control the annulus size much more closely 5 0 5
than the present method specifies if adequate accuracy is to Angle, deg
be achieved for samples with the sensitivity to beam di-
vergence characteristic of the glasses. FIG. 3. Goniophotometric curve of the nominal 20% haze
plastic standard.

Goniophotometry of Standards and Typical Samples

The cause and importance of the difference in behavior of
Figure 2 shows the goniophotometric curve of glass haze
the plastic and glass haze standards is elucidated by means
standard C, with an ASTM haze of 21.6%. Three decades
of their goniophotometric characteristics, as shown in Figs.
of transmitted light flux are shown to illustrate the behavior
2-4. In these figures, obtained with the Hunterlab D10 in-
of the scattering over a wide range of intensities and angles;
strument, the abscissa is angle, in degrees, from the direc-
subsequent figures are limited to two decades of flux cen-
tion of the light beam, and the ordinate is the logarithm of
tering on the range of interest in haze measurement.
the relative transmitted light flux, normalized to 100 at 0
For comparison, the curve for the nominal 20% plastic
deg. The resolution of the instrument without sample is haze standard, with actual haze 19.8%, is shown in Fig. 3.
about ? 0.4 deg at two decades below the peak beam in-
The difference in the characteristics of these two "standard"
tensity, that is, at the point labeled 1.0.
materials should now become clear: A larger fraction of the
scattered flux from the plastic standard is diverted through
wider angles. The material of the glass standards is known
as a narrow-angle scatterer, and that of the plastic standards

0
Angle, deg
Angle, deg
FIG. 4. Goniophotometric curve of a polyethylene plastic
FIG. 2. Goniophotometric curve of Glass C. film.

222 COLOR research and application

as a wide-angle scatterer. From the results given above and
in the Weidner and Hsia paper' it is seen that it is the narrow-
angle-scattering materials that are most sensitive to the size
of the annulus in the haze measurement.
Which type of material is most suitable as a haze standard?
That depends on the scattering characteristics of the spec-
imens to be measured. In the intercomparison associated
with the revision of the ASTM method, the first (and only
to the date of this writing) sample to be selected as typical
for the use of hazemeters was a polyethylene plastic film
with about 25% haze. The goniophotometric curve of a
specimen of this material is shown in Fig. 4. By comparing
it to the curve of glass standard C in Fig. 2 and to the curve
of the 20%-haze plastic standard in Fig. 3 , it is seen that
the industrial film is a narrow-angle scatterer with charac-
teristics almost identical to those of glass C and quite dif-
ferent from those of the plastic haze standards. Use of a
hazemeter with the wrong size annulus but calibrated with
plastic haze standards would lead to erroneous results when
this type of sample is measured.

Advantages of Spectrophotometric Haze Data

Our final experiments were designed to illustrate the ad-
vantages of obtaining and examining the spectrophotometric
curve of the haze of a colored specimen. Such a study allows
useful information on the probable sources of the haze to
be obtained, information for which there is often no other
easy source. We selected for the specimens to study a rather
old series of acrylic plastic chips colored with a phthalo-
cyanine blue pigment, a common colorant for transparent
plastics and coatings because of its very small particle size
and low refractive index relative to that of the plastic, the
combination usually leading to low scattering from the pig-
ment particles and thus low haze.
Figure 5 illustrates the spectral curves of total and diffuse
transmittance for one of these plastic chips, obtained with
the General Electric spectrophotometer. For the diffuse-
transmittance recording a 5 x magnification was used. It can
be seen that the diffuse-transmittance curve mirrors to some
extent, but not completely, the total-transmittance curve that
is characteristic of the phthalocyanine colorant. This is strong
evidence that part, but not all, of the scattering leading to
haze arises from poorly dispersed pigment, and the re-
mainder from other causes not associated with the pigment.
Because of the age of the specimens (over 35 years), we
speculate that the remaining haze arose largely from dete-
rioration of the surfaces of the specimens.
For this colorant further analysis can be made. The re-
fractive index of phthalocyanine blue as a function of wave-
length was published by B r a ~ nThat . ~ of the resin was de-
termined by one of us (F.W.B.) and published in trade
literature of the Du Pont Company in the late 1940s. Com-
parison of these results show that the two refractive indices
are equal at two wavelengths in the visible range, approx-
imately 5 15 and 602.5 nm. lnspection of the diffuse-trans-
mittance curve in Fig. 5 shows minima at nearly these wave-
'' 460 40 WAVELENGTH
5hO &O WM) 6b0 SAO 7<
FIG. 5. Spectral curve of the total transmittance (top) and
the diffuse transmittance (bottom, 5 x magnified) of an acrylic
chip pigmented with phthalocyanine blue.
lengths; scattering theory states that there should be no
scattering from the pigment at these wavelengths. Thus some
estimate could be made of the relative importance of pigment
scattering and other causes of haze, but we did not pursue
the matter.
Other Spectrophotometers
We have carried out preliminary tests of haze measure-
ment with two current commercially available spectropho-
tometers. * The Diano-Bausch and Lomb Match-Scan has
the correct integrating-sphere geometry for haze measure-
ment, but the transmission compartment is too small to hold
the available 50 mm-square standards easily. In addition,
the beam is not centered on the center of such a specimen,
so that in the case of a nonuniform material such as the
available glasses, calibration of the specific measured area
of the standards would be required. Tests with the Match-
Scan did show that, as expected from the Helmholtz reci-
procity relation in optics, essentially the same haze readings
were obtained with normal illumination of the specimen and
diffuse detection, as illustrated in Fig. I , and with the re-
verse system of diffuse illumination and normal detection.
*We thank the Munsell Color Science Laboratory for making the modem
spectrophotometers available for these tests.

Volume 10, Number 4, Winter 1985 223

 Tests with the Applied Color Systems Spectro-Sensor,
that uses the diffuse-illumination system, suggested that it
should be possible to obtain accurate haze measurements
with this instrument (and also with the similar Hunterlab D
54P and the LabScan I1 with sphere head5) if the transmit-
tance sample holder is removed and the specimen is placed
flush against the transmission port. The difficulty here, and
with all instruments using only diffuse illumination, lies in
checking the size and centering of the annulus formed by
the sphere reflectance port and, in this case, the area viewed
by the detector, which is difficult to evaluate precisely.
The Gardner-Neotec Spectrogard has been shown* to
give correct haze readings with plastic haze standards, but
at this writing has not been tested with the narrow-angle
scatterers.
The Macbeth 1500 and related instruments are not suitable
for haze measurement because the specimen cannot be placed
flush against the sphere port in the transmission compart-
ment.
Conclusions
This article has discussed several possible errors that can
be encountered in the measurement of haze by ASTM Method
D 1003, either by using commercially available hazemeters
or by using integrating-sphere spectrophotometers; the latter
instruments have not found great use for haze measurement
in recent years but offer the advantage of providing infor-
mation on the wavelength dependence of haze.
Our data show that it is still possible to utilize integrating-
sphere spectrophotometers that allow the specimen to be
placed flush against the entrance port of the sphere to obtain
haze measurements in good agreement with those made by
using hazemeters. With spectrophotometers, it is necessary
to take care that the reflectance factor of the white standard
*Thomas J. Keane, Gardner-Neotec lnstrument Division, Pacific Sci-
entific Co., private communication, 1984.
224
used is the same as that of the internal wall of the integrating
sphere. Most hazemeters are constructed so that this is au-
tomatically the case.
With both hazemeters and spectrophotometers, the size
of the annulus between the light beam and the exit port of
the sphere is very important. A simple way to determine
that the annulus is correct is to utilize calibrated haze stand-
ards that exhibit narrow-angle scattering, such as certain
acid-etched glasses. Unfortunately, these are not commer-
cially available; the plastic wide-angle-scattering haze
standards that are commercially available are not sensitive
enough to annulus size to allow accurate calibration for the
measurement of typical plastic film specimens, that exhibit
narrow-angle scattering. These results are illustrated by gon-
iophotometric and spectrophotometric data. The merits of
studying the goniophotometric properties of specimens of
interest cannot be overlooked. However, suitable equipment
for such studies is not widely available.
Obtaining spectrophotometric data serves a very useful
purpose in the study of haze, since it allows the possible
determination of the origin of the haze, information that is
not usually readily available in other ways.
This is Contribution No. 13 1 from The Rensselaer Color
Measurement Laboratory.
1. Standard Test Method,for Haze and Luttiinous Transrriittancc of Trans-
parent P lustics. ASTM Designation: D 1003-61, American Society for
Testing and Materials, Philadelphia, PA.
2. David G. Goebel. Generalized integrating sphere theory. Appl. Opt.
6 , 125-128 (1967).
3. Victor K. Weidner and Jach 1. Hsia. NRS reference hazenietcr: its
development and testing. Appl. Opt. 18, 1619-1626 (1979).
4. Juergen H. Braun, Bron~ingof phthalocyanine pigments. off Dig.
Fed. Soc. Pain! Technul. 37, 1623-1640 (1965).
5. John S. Christie, Jr., Hunter Associates Laboratory, private cornmu-
nication. 1984.
Received October 5 , 1984; accepted November 7, 1984
COLOR research and application