Color stability of facial prostheses

J a m e s C. L e m o n , D D S , a M a r k S. C h a m b e r s , D M D , b
M i c h a e l L. J a c o b s e n , D D S , c a n d J o h n M. P o w e r s , P h D d
The University of Texas, M. D. Anderson Cancer Center, Houston, Tex.

The limited service of facial prostheses is the result of degradation of the elastomer
and color instability. Deterioration m a y be caused by m a n y factors, w h i c h include
e n v i r o n m e n t a l exposure and changes in humidity. This investigation assessed the
efficacy of an additive, intrinsic, broad-spectrum ultraviolet light absorber on the
color stability of a p i g m e n t e d facial elastomer. Samples were w e a t h e r e d artificially
and outdoors at exposure levels of radiant energy of 150 to 450 kJ/m 2. The samples
changed color slightly but perceptibly. Artificial aging caused a greater change than
outdoor aging. The ultraviolet light absorber UV-5411 did not protect the samples from
color changes. (J PROSTHETDENT 1995;74:613-8.)

M a x i l l o f a c i a l prosthetic treatment allows many
patients with orofacial defects to return to an active role in
public.1 The results of prosthetic treatment are influenced
by the nature of the defect, the skill of the prosthodontist,
and the properties of the materials used. The most critical
properties are esthetics, durability, and accuracy of pro-
cessing. 2 Patients are concerned with the durability and
esthetics of the prosthesis. A prosthesis must be durable,
esthetic, and color stable, 3 and with the advent of implant-
retained facial prostheses, color stability is of particular
concern.
The limited service of facial prostheses is a result of the
rapid degradation of the elastomer and its color instability.
The wearing time for facial prostheses averages from 3
months to I year. Deterioration is mainly caused by envi-
ronmental exposure to ultraviolet (UV) light, air pollution,
and changes in humidity and temperature. Handling the
prosthesis during cleaning and the application of adhe-
sives and cosmetic additives may also alter the physical
properties and color stability of the material. 3-6 Surveys
have reported color fading as the most frequent reason pa-
tients give for disliking their prostheses. Objective inves-
tigations of color stability in facial elastomers have used
artificial light sources, artificial weathering chambers, and
reflection spectrophotometry. 2, 7-10
aAssociate Professor, Section of Oncologic Dentistry and Prostho-
dontics
bMaxillofacial Prosthodontist, Section of Oncologic Dentistry and
Prosthodontic.
CMaxillofacial Prosthodontist, Private Practice, Kansas City, Kan-
sas.
dprofessor, Department of Basic Sciences, and Director, Biomate-
rials Research Center, University of Texas-Houston Health
Science Center, Dental Branch.
Copyright 9 1995 by the Editorial Council of THE JOURNALOF
PROSTHETIC DENTISTRY.
0022-3913/95/$5.00 + 0. 10/1/67769
Investigations into whether an additive UV light ab-
sorber would improve color stability of facial elastomers
are limited. Adding an over-the-counter sunscreen product
to a facial elastomer m a y interfere with the polymerization
and properties of the elastomer because of the presence of
propylene, glyceryl, stearates, and mineral oils in the sun-
screen t h a t may inhibit total curing. 6, 11 Nevertheless, Chu
and Fischer TMevaluated the efficiency of additive UV light
absorbers and antioxidants in polyurethane elastomers by
exposing 11 types of UV light absorbers coupled with one
antioxidant to UV light in an aging chamber. They found
that yellowing was significantly lessened and that UV light
absorbers made from benzotriazole or amine groups were
the most effective compounds.
The plastics and cosmetics industries have addressed
problems of color stability by using chemical additives in
formulations. Spectra-sorb UV-5411 (American Cyanamid
Co., Wayne, N. J.), an off-white free-flowing powder, is a
benzotriazole compound with durability, broad-range (260
to 390 nm) UV-absorption properties, low color, good com-
patibility, a virtually unlimited shelf life, and reasonable
cost. Normal concentrations in industrial use range from
0.5% to 1.0% by weight. It is relatively nontoxic, as
evidenced by lack of skin irritation or allergic sensitization
in 100 h u m a n subjects tested with the Modified Draize-
Shelanski Insult Patch Test. 13
This investigation assessed the efficacy ofa UV light ab-
sorber on the color stability of a facial elastomer. Color was
evaluated before and after artificial weathering and direct
outdoor exposure. Spectrophotometric analysis was per-
formed to assess color changes and to determine the effects
of artificial weathering and outdoor weathering on color
stability.
METHODS AND MATERIAL
The study consisted of three groups of 12 samples each
that represented three different formulations. The base
elastomer material tested was a mixture of RTV silicones

DECEMBER 1995 613

T H E J O U R N A L OF P R O S T H E T I C D E N T I S T R Y L E M O N E T AL

Table I. P a r a m e t e r s in experimental design and the flasks were allowed to cool. Eighteen flasks yielded
a total of 18 samples.
Aging conditions Artificial aging
Outdoor weathering A 3:1 ratio of type A medical adhesive to MDX4-4210
Formulations (% of 0.0 elastomer by volume was used to prepare 54 samples. The
UV-5411) 0.1 kaolin was added at 10% by volume. The UV light absorber
0.25 UV-5411 was also added at 0.0%, 0.1%, and 0.25% by
Exposure energy 150 weight. P r e l i m i n a r y mixing trials determined that 240 cc
(kJ/m2) 300 of material was needed for each of 18 samples. Thus a
450 180-cc mix of MDX4-4210, pigments, a n d kaolin was first
Repetitions 6 samples for each formulation made to ensure consistency of samples. A tuberculin
and aging condition syringe was used to add 0.05 cc of yellow ochre, cadmium
Measurement Color (CIE L*a*b* and AE*) by
red, and b u r n t s i e n n a oil-base pigments (M. Grumbacher,
ASTM D22442~ using a
Inc., Cranbury, N. J.) to each sample and produced a com-
reflectance spectrophotometer
mon Caucasian base color. The mixture was then appor-
tioned into three 60 cc parts, each weighing 74 gm. To each
60 cc (74 gm) part, 24 cc (13 gin) of kaolin was added. Type
Table II. E v a l u a t i o n of weathering by test specification A adhesive was t h e n combined with each pigznented por-
SAE J196014 tion up to 240 cc (total weight 290 gm). Finally, UV-5411
Light source Controlled-irradiance xenon was incorporated into two of the mixtures at 0.1% (0.29 gin)
arc filtered through high and 0.25% (0.73 gm), respectively.
borate borosilicate inner Individual mixtures were spatulated by h a n d until the
and outer glass filters. colors were evenly distributed. Then mixtures were poured
Irradiance level 0.55 W/m2/nm at 340 nm for into the flask with no separating medium. The flasks were
test intervals of 150, 300, placed into a standard, tightened flask press. The material
and 450 kJ/m 2
was allowed to set at room temperature for 24 hours. After
Test cycle 40 minutes light only
24 hours the flasks were placed in circulating hot air at 80 ~
20 minutes light plus front
C for 30 minutes. The samples were removed and placed
spray
60 minutes light only into a n oven for 30 m i n u t e s to ensure complete curing. The
60 minutes dark plus back samples were inspected for voids, bubbles, and contami-
spray n a n t s , and the 12 best samples i n each 18-sample group
Black panel 70 • 3~ C light/38 + 3~ C were selected for a total of 36 samples.
temperature dark
Dry bulb temperature 47 • 2~ C light/38 _+4~ C S a m p l e e x p o s u r e s a n d e v a l u a t i o n o f color
dark Two groups of 18 samples were exposed to two different
Relative humidity (%) 50 • 5 light/95 _+5 dark conditions, artificial aging and direct outdoor weathering.
Specification SAEJ 1960 was used for the artificial aging
parameters. 14 Samples were placed in a n aging chamber
(MDX4-4210 and type A medical adhesive, Dow Coming, (Ci35 Weather-Ometer, Atlas Electronics, Chicago, Ill.)
Midland, Mich.), oil-base pigments, and kaolin (Factor II, and subjected to light exposure, water spray, temperature,
Georgia Silica, Lakeside, Ariz.). A UV light absorber UV- and h u m i d i t y (Table II). Light from the xenon arc light
5411 (Spectra-sorb UV-5411; American Cyanamid Co.) source was filtered through high borate borosilicate i n n e r
was added in the formulations of the three groups (0.0%, and outer filters to better simulate the spectral power dis-
control; 0.1% and 0.25% by weight) of 12 samples each. Six tribution of sunlight. 15 The test was r u n at a n irradiance
samples from each group were subjected to artificial aging, level of 0.55 W/m2/nm at 340 n m for increments of 150,300,
a n d six were exposed to outdoor weathering. The experi- and 450 kJ/m 2 of total r a d i a n t energy. 16
m e n t a l design is summarized in Table I. The outdoor samples were mounted on a n untreated,
plywood-backed exposure rack (ASTM G7) and were ex-
Sample preparation and materials posed according to the ASTM E782 variable angle sched-
manipulation ule. 17 ' 18 During the outdoor exposure the samples were left
The samples, 2.4 m m x 6 cm x 4.5 cm sheets, were made uncovered and exposed to the environment. The exposure
by investing two layers ofbaseplate wax (Truwax, Dentsply rack was adjusted to a n angle close to perpendicular to the
International, York, Pa.) in a polyvinyl chloride flask with direct beam of solar radiation to maximize the a m o u n t of
vacuum-mixed stone (Die-Keen; Miles Inc. Dental Prod- sunlight on the samples. Peak radiation levels in Florida
ucts, South Bend, Ind.). A tinfoil substitute was used to fa- d u r i n g the s u m m e r m o n t h s can reach 1.0 W/m2/nm at 340
cilitate separation of the flasks. The wax was boiled out, nm.15

614 VOLUME ~ NUMBER6

LEMON ET AL THE JOURNAL OF PROSTHETIC DENTISTRY

Table III. The effect of artificial aging on CIE color parameters

UV-absorber concentration
Energy
(k J i m 2) Parameter 0.0% 0.1% 0.25%

0 L* 74.33 (0.24)* 74.64 (0.10) 73.67 (0.20)

a* 10.16 (0.05) 9.30 (0.10) 9.39 (0.11)
b* 16.31 (0.21) 16.04 (0.21) 15.63 (0.11)
150 L* 74.82 (0.17) 75.50 (0.08) 74.75 (0.15)
a* 9.25 (0.06) 8.56 (0.10) 8.80 (0.12)
b 16.59 (0.10) 16.81 (0.15) 16.63 (0.12)
AE* 1.08 (0.08) 1.37 (0.10) 1.58 (0.09)
300 L* 74.48 (0.19) 75.26 (0.08) 74.49 (0.12)
a* 9.13 (0.06) 8.36 (0.11) 8.51 (0.10)
b* 16.93 (0.10) 17.32 (0.13) 17.10 (0.16)
AE* 1.21 (0.07) 1.70 (0.15) 1.90 (0.10)
450 L* 74.40 (0.18) 75.21 (0.06) 74.28 (0.23)
a* 8.94 (0.08) 8.20 (0.12) 8.34 (0.14)
b* 16.96 (0.08) 17.49 (0.12) 17.23 (0.23)
hE* 1.39 (0.07) 1.91 (0.12) 2.01 (0.16)
*Mean w i t h s t a n d a r d deviation in p a r e n t h e s e s . The T u k e y - K r a m e r interval for comparisons of m e a n s of AE* a m o n g concentrations at the 0.05 significance
level w a s 0.15. Differences between m e a n s g r e a t e r t h a n the T u k e y - K r a m e r interval were considered statistically significant.

Table IV. Analysis of variance of the effects of energy levels of artificial aging and UV absorber concentration on color
change (AE*)
Source df Sum of squares Mean square F value p Value

Concentration 2 3.470 1.735 57.8 0.0001

Sample 15 0.450 0.030
Energy 2 1.631 0.815 347 0.0001
Energy*conc. 4 0.107 0.027 11.4 0.0001
Energy*sample 30 0.070 0.002

Color was determined from spectral reflectance mea-
surements in the visible range of 400 to 700 n m with a
double-beam, UV-visible spectrophotometer and integrat-
ing sphere (MacBeth Color Eye 7000, Newburgh, N.Y.)
with specular reflectance component included. The spec-
trophotometer was calibrated with a zero cone and a pri-
mary white porcelain s t a n d a r d of known absolute reflec-
tance value.
Reflectance m e a s u r e m e n t s were made for each sample
at the intervals of interest. Before the samples were mea-
sured, they were cleaned by wiping with gauze soaked in
distilled water. The position of the samples was the same
for each data-recording interval. CIELAB L*a*b* color
data were computed (Version 1.2KA, MacBeth Optiview,
Newburgh, N. Y.) based on the CIE chromaticity diagram
1931 and source A. 19 The values of L*, a*, and b* were en-
tered on a spreadsheet program (Microsoft Excel, Red-
mond, Wash.) for calculation of AE* as follows.
AE* = [(AL*)2 + (Aa*) 2 + (Ab*)2]1/2, where AL*, ha*, and
hb* are changes in L*, a*, and b* between the interval of
interest and baseline, a n d hE* is the color difference. 2~L*,
a*, b*, and AE* are dimensionless.
Means and s t a n d a r d deviations of L*, a*, b*, and AE*
were calculated. A two-way analysis of variance (ANOVA)
with repeated-measures (SuperANOVA, Abacus Concepts,
Berkeley, Calif.) was performed for the color difference
(AE*) with the factors of exposure energy (repeated mea-
sure at 150,300, or 450 kJ/m 2) and concentration of the UV
absorber (0.0%, 0.1%, or 0.25%). I n the second experiment
a two-way ANOVA of AE* was used with factors of condi-
tion (artificial or outdoor exposure) and concentration
(0.0%, 0.1%, or 0.25%) of the UV absorber. Means were
compared by T u k e y - K r a m e r intervals (SuperANOVA) cal-
culated at the 0.05 significance level. Differences between
m e a n s greater t h a n the Tukey-Kramer interval were con-
sidered statistically significant. Values of L*, a*, and b* are
reported but were not analyzed statistically.
RESULTS
Effects of artificial aging
The samples were examined initially for color uniformity
and were assessed to be uniform. A sample from each UV-
5411 concentration group was tested in 10 different orien-
tations on the spectrophotometer. The means and stan-

DECEMBER 1995 615

THE JOURNAL OF PROSTHETIC DENTISTRY LEMON ET AL

Table V. Effects of artificial versus outdoor aging a n d UV-absorber concentration on AE*

UV-absorber Concentration
Mode of Energy
exposure (k J i m 2) Parameter 0.0% 0.1% 0.25%

Artificial 0 L* 73.33 (0.24)* 74.64 (0.10) 73.67 (0.20)

a* 10.16 (0.05) 9.30 (0.10) 9.39 (0.11)
b* 16.31 (0.21) 16.04 (0.21) 15.63 (0.11)
150 L* 74.82 (0.17) 75.50 (0.08) 74.75 (0.15)
a* 9.25 (0.06) 8.56 (0.10) 8.80 (0.12)
b* 16.59 (0.10) 16.81 (0.15) 16.63 (0.12)
AE* 1.08 (0.08) 1.37 (0.10) 1.58 (0.09)
Outdoor 0 L* 74.30 (0.15) 74.37 (0.14) 73.57 (0.18)
a* 10.16 (0.09) 9.33 (0.06) 9.27 (0.12)
b* 16.28 (0.22) 15.97 (0.10) 15.57 (0.25)
150 L* 73.77 (0.16) 74.23 (0.16) 73.59 (0.13)
a* 9.65 (0.11) 8.76 (0.30) 9.07 (0.08)
b* 16.50 (0.19) 16.78 (0.28) 16.55 (0.25)
hE* 0.78 (0.09) 1.04 (0.38) 1.01 (0.14)
*Mean w i t h s t a n d a r d deviation in p a r e n t h e s e s . T u k e y - K r a m e r intervals for comparisons of m e a n s of hE* between a g i n g conditions a n d a m o n g concentrations
a t t h e 0.05 significance level w e r e 0.12 a n d 0.18. Differences between m e a n s g r e a t e r t h a n the a p p r o p r i a t e T u k e y - K r a m e r interval were considered statistically
significant.

Table VI. Analysis of variance of effects of aging condition and UV absorber concentration on color change (hE*)
Source df Stun of squares Mean square F value p Value

Condition 1 1.480 1.480 45.6 0.0001

Concentration 2 0.876 0.438 13.5 0.0001
Cond.*conc. 2 0.135 0.067 2.07 0.14
Residual 30 0.974 0.032

d a r d deviations were very similar, a n d the coefficients of
v a r i a t i o n were low.
The m e a n s and s t a n d a r d deviations for values of L*, a*,
b*, a n d AE* of the artificially aged samples are presented
in Table III. The analysis of variance of AE* (Table IV) re-
vealed t h a t significant differences were found, because en-
ergy h a d a g r e a t e r influence on AE* t h a n did UV-absorber
concentration. The interaction of energy and concentration
was significant b u t h a d less of a n effect t h a n the m a i n fac-
tors. The T u k e y - K r a m e r interval for comparisons of m e a n s
of AE* a m o n g concentrations at the 0.05 significance level
w a s 0.15.
Values of L* for the 0.0 a n d 0.25 concentrations in-
creased at 150 k J / m 2, t h e n decreased with increasing en-
ergy. F o r all concentrations tested a* decreased, whereas
b* increased with increasing energy. Values of AE* in-
creased w i t h increasing energy for all concentrations.
E f f e c t s o f artificial v e r s u s o u t d o o r a g i n g
The m e a n s and s t a n d a r d deviations for AE* of the sam-
ples aged artificially a n d outdoors are presented in Table
V. The ANOVA (Table VI) revealed significant differences
between condition of exposure a n d UV absorber concen-
t r a t i o n (p < 0.05). T u k e y - K r a m e r intervals at the 0.05 sig-
nificance level were 0.12 for condition of exposure and 0.18
for concentration.
Values of L* at all UV absorber concentrations increased
with artificial aging b u t decreased with outdoor exposure.
For both aging conditions a* decreased, whereas b* in-
creased with increasing energy for all concentration. A t
each concentration values of hE* were greater for artificial
aging t h a n for outdoor exposure.
DISCUSSION
The CIELAB system uses t h r e e p a r a m e t e r s (L*, a*, b*)
to define color (Fig. 1). L* is lightness, whereas a* and b*
are chromatic components. Red h a s a positive a* value,
whereas green has a negative a* value. Yellow h a s a pos-
itive b* value, whereas blue h a s a negative b* value. Two
objects with a AE* of a p p r o x i m a t e l y one unit were judged
to be a color m a t c h 50% of the time by h u m a n observers. 2~
All artificially aged samples a t 0.0% a n d 0.25% concen-
trations of UV absorber became lighter when exposed to
150 k J / m 2 of energy, and t h e n t h e y g r a d u a l l y d a r k e n e d as
exposure increased to 450 k J / m 2 of energy. The outdoor-
aged samples became d a r k e r w h e n exposed to 150 k J / m 2.

616 VOLUME 74 NUMBER 6

LEMON ET AL
L*
+a
rec
ClELAB and Munsell Color Space Arrangement
Fig. 1. CIE L*a*b* and Munsell color arrangements (adapted from Seghi RR, Johnston
WM, O'Brien WJ. Spectrophotometric analysis of color differences between porcelain sys-
tems. J PROSTHETDENT 1986;56:35-40).
The increase in L* for the artificially aged samples may
have resulted from fading of the surface. The darkening of
L* in the outdoor-aged samples is attributed to the
impregnation of dirt into the porous surface of the elas-
tomer.
The decrease in a* for both modes of exposure relates to
the fading of red in the samples, which was more pro-
nounced with artificial aging. The negative change in a*
suggests a change in the red (cadmium red) and reddish
brown (burnt sienna) off-base pigments.
The b* value increased for both the artificially and out-
door-aged samples, and the samples became yellower. This
process may have occurred as a result of the fading of the
red pigments with the emerging dominance of the yellow
(yellow ochre) oil-base pigments. Another cause could be
the yellowing of the linseed oil within the base pigment.
The change in b* became greater with the addition of the
UV light absorber. The initial decrease in b* with the ad-
dition of the UV light absorber may be due to its off-white
color. The UV light absorber also ma.y have blocked the re-
flection of red in favor of yellow and thus may have made
the samples appear yellower.
The artificially aged samples showed an increase in the
AE* values at each aging level for all UV absorber concen-
trations. These values of AE*, which ranged from 1.08 to
DECEMBER 1995
THE J O U R N A L OF PROSTHETIC DENTISTRY
eft
b*
Ilow
2.01, were considered minor changes, although they were
visually perceptible. The changes in AE* were greater for
the artificially aged than for the outdoor-aged samples.
The aging chamber is an intense, accelerated source of
many weathering factors. The addition of the UV light ab-
sorber did not protect the samples from change.
The intent of exposing samples to artificial and outdoor
weathering was to assess the color stability of a pigmented,
silicone elastomer with and without a UV light absorber.
The combination of pigments yielded a common base shade
for white people. The samples were made 2.4 mm thick to
approximate the usual thickness of a prosthesis. The effect
of thickness on the wavelength sensitivity of a material
demonstrated that the screening requirements of a UV
light absorber for a thin sample or for the surface layers of
a thicker sample are different from those for the bulk of the
material. 21
The conditions and energy of exposure along with the
presence of a UV light absorber affected the color stability
of the elastomer and allowed the effectiveness of the UV
light absorber to be observed. Although this study was
limited to one UVlight absorber, future studies should deal
with several different types of UV light absorbers to deter-
mine whether a suitable product exists.
The test samples changed color as determined by spec-
617
THE J O U R N A L OF PROSTHETIC DENTISTRY
trophotometric analysis. Although the changes were per-
ceptible, they did not represent the level of color degrada-
tion that is observed clinically. The major changes in ap-
pearance of maxillofacial prostheses result from staining
that is caused by environmental factors such as stains,
fungal accumulation, handling, body oil accumulation, or
cosmetics applied by the patient.
CONCLUSIONS
The effect of a UV light absorber on the color stability of
a facial elastomer was evaluated by using reflection spec-
trophotometry. The samples were weathered artificially
and outdoors at exposure levels of 150 kJ/m 2 up to 450
kJ/m 2 radiant energy. Color changes were evaluated with
the CIELAB system. Changes occurred in the color of the
samples, with artificial aging causing a greater change
than outdoor aging. The UV light absorber UV-5411 did
not protect the samples from color changes.
We appreciate the assistance of Mr. J u d e Richard for his edito-
rial expertise a n d continued s u p p o r t to o u r d e p a r t m e n t .
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