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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 processing. 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 implantretained 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 environmental exposure to ultraviolet (UV) light, air pollution, and changes in humidity and temperature. Handling the prosthesis during cleaning and the application of adhesives 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 patients give for disliking their prostheses. Objective investigations 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 Prosthodontics bMaxillofacial Prosthodontist, Section of Oncologic Dentistry and Prosthodontic. CMaxillofacial Prosthodontist, Private Practice, Kansas City, Kansas. dprofessor, Department of Basic Sciences, and Director, Biomaterials Research Center, University of Texas-Houston Health Science Center, Dental Branch. Copyright 9 1995 by the Editorial Council of THE JOURNALOF

Investigations into whether an additive UV light absorber 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 sunscreen 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 compatibility, 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 DraizeShelanski Insult Patch Test. 13 This investigation assessed the efficacy ofa UV light absorber on the color stability of a facial elastomer. Color was evaluated before and after artificial weathering and direct outdoor exposure. Spectrophotometric analysis was performed to assess color changes and to determine the effects of artificial weathering and outdoor weathering on color stability.

0022-3913/95/$5.00 + 0. 10/1/67769

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





Table I. P a r a m e t e r s in experimental design

Aging conditions Formulations (% of UV-5411) Exposure energy (kJ/m2) Repetitions Measurement Artificial aging Outdoor weathering 0.0 0.1 0.25 150 300 450 6 samples for each formulation and aging condition Color (CIE L*a*b* and AE*) by ASTM D22442~ using a reflectance spectrophotometer

Table II. E v a l u a t i o n of weathering by test specification

SAE J196014 Light source Controlled-irradiance xenon arc filtered through high borate borosilicate inner and outer glass filters. 0.55 W/m2/nm at 340 nm for test intervals of 150, 300, and 450 kJ/m 2 40 minutes light only 20 minutes light plus front spray 60 minutes light only 60 minutes dark plus back spray 70 3~ C light/38 + 3~ C dark 47 2~ C light/38 _+4~ C dark 50 5 light/95 _+5 dark

Irradiance level

Test cycle

Black panel temperature Dry bulb temperature Relative humidity (%)

and the flasks were allowed to cool. Eighteen flasks yielded a total of 18 samples. A 3:1 ratio of type A medical adhesive to MDX4-4210 elastomer by volume was used to prepare 54 samples. The kaolin was added at 10% by volume. The UV light absorber UV-5411 was also added at 0.0%, 0.1%, and 0.25% by weight. P r e l i m i n a r y mixing trials determined that 240 cc of material was needed for each of 18 samples. Thus a 180-cc mix of MDX4-4210, pigments, a n d kaolin was first made to ensure consistency of samples. A tuberculin syringe was used to add 0.05 cc of yellow ochre, cadmium red, and b u r n t s i e n n a oil-base pigments (M. Grumbacher, Inc., Cranbury, N. J.) to each sample and produced a common Caucasian base color. The mixture was then apportioned 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 A adhesive was t h e n combined with each pigznented portion up to 240 cc (total weight 290 gm). Finally, UV-5411 was incorporated into two of the mixtures at 0.1% (0.29 gin) and 0.25% (0.73 gm), respectively. Individual mixtures were spatulated by h a n d until the colors were evenly distributed. Then mixtures were poured into the flask with no separating medium. The flasks were placed into a standard, tightened flask press. The material was allowed to set at room temperature for 24 hours. After 24 hours the flasks were placed in circulating hot air at 80 ~ C for 30 minutes. The samples were removed and placed into a n oven for 30 m i n u t e s to ensure complete curing. The samples were inspected for voids, bubbles, and contamin a n t s , and the 12 best samples i n each 18-sample group were selected for a total of 36 samples.

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
Two groups of 18 samples were exposed to two different 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 (Ci35 Weather-Ometer, Atlas Electronics, Chicago, Ill.) and subjected to light exposure, water spray, temperature, and h u m i d i t y (Table II). Light from the xenon arc light source was filtered through high borate borosilicate i n n e r and outer filters to better simulate the spectral power distribution of sunlight. 15 The test was r u n at a n irradiance level of 0.55 W/m2/nm at 340 n m for increments of 150,300, and 450 kJ/m 2 of total r a d i a n t energy. 16 The outdoor samples were mounted on a n untreated, plywood-backed exposure rack (ASTM G7) and were exposed according to the ASTM E782 variable angle schedule. 17 ' 18 During the outdoor exposure the samples were left uncovered and exposed to the environment. The exposure rack was adjusted to a n angle close to perpendicular to the direct beam of solar radiation to maximize the a m o u n t of sunlight on the samples. Peak radiation levels in Florida 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 nm.15

(MDX4-4210 and type A medical adhesive, Dow Coming, Midland, Mich.), oil-base pigments, and kaolin (Factor II, Georgia Silica, Lakeside, Ariz.). A UV light absorber UV5411 (Spectra-sorb UV-5411; American Cyanamid Co.) was added in the formulations of the three groups (0.0%, control; 0.1% and 0.25% by weight) of 12 samples each. Six samples from each group were subjected to artificial aging, a n d six were exposed to outdoor weathering. The experim e n t a l design is summarized in Table I.

Sample preparation and materials manipulation

The samples, 2.4 m m x 6 cm x 4.5 cm sheets, were made by investing two layers ofbaseplate wax (Truwax, Dentsply International, York, Pa.) in a polyvinyl chloride flask with vacuum-mixed stone (Die-Keen; Miles Inc. Dental Products, South Bend, Ind.). A tinfoil substitute was used to facilitate separation of the flasks. The wax was boiled out,






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%




L* a* b* L* a* b AE* L* a* b* AE* L* a* b* hE*

74.33 (0.24)* 10.16 (0.05) 16.31 (0.21) 74.82 (0.17) 9.25 (0.06) 16.59 (0.10) 1.08 (0.08) 74.48 (0.19) 9.13 (0.06) 16.93 (0.10) 1.21 (0.07) 74.40 (0.18) 8.94 (0.08) 16.96 (0.08) 1.39 (0.07)

74.64 (0.10) 9.30 (0.10) 16.04 (0.21) 75.50 (0.08) 8.56 (0.10) 16.81 (0.15) 1.37 (0.10) 75.26 (0.08) 8.36 (0.11) 17.32 (0.13) 1.70 (0.15) 75.21 (0.06) 8.20 (0.12) 17.49 (0.12) 1.91 (0.12)

73.67 (0.20) 9.39 (0.11) 15.63 (0.11) 74.75 (0.15) 8.80 (0.12) 16.63 (0.12) 1.58 (0.09) 74.49 (0.12) 8.51 (0.10) 17.10 (0.16) 1.90 (0.10) 74.28 (0.23) 8.34 (0.14) 17.23 (0.23) 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 Sample Energy Energy*conc. Energy*sample

2 15 2 4 30

3.470 0.450 1.631 0.107 0.070

1.735 0.030 0.815 0.027 0.002

57.8 347 11.4

0.0001 0.0001 0.0001

Color was determined from spectral reflectance measurements in the visible range of 400 to 700 n m with a double-beam, UV-visible spectrophotometer and integrating sphere (MacBeth Color Eye 7000, Newburgh, N.Y.) with specular reflectance component included. The spectrophotometer was calibrated with a zero cone and a primary white porcelain s t a n d a r d of known absolute reflectance 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 measured, 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 entered on a spreadsheet program (Microsoft Excel, Redmond, 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 measure 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 condition (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) calculated at the 0.05 significance level. Differences between m e a n s greater t h a n the Tukey-Kramer interval were considered 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 UV5411 concentration group was tested in 10 different orientations on the spectrophotometer. The means and stan-





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

UV-absorber Concentration
Mode of exposure Energy (k J i m 2)









L* a* b* L* a* b* AE* L* a* b* L* a* b* hE*

73.33 (0.24)* 10.16 (0.05) 16.31 (0.21) 74.82 (0.17) 9.25 (0.06) 16.59 (0.10) 1.08 (0.08) 74.30 (0.15) 10.16 (0.09) 16.28 (0.22) 73.77 (0.16) 9.65 (0.11) 16.50 (0.19) 0.78 (0.09)

74.64 (0.10) 9.30 (0.10) 16.04 (0.21) 75.50 (0.08) 8.56 (0.10) 16.81 (0.15) 1.37 (0.10) 74.37 (0.14) 9.33 (0.06) 15.97 (0.10) 74.23 (0.16) 8.76 (0.30) 16.78 (0.28) 1.04 (0.38)

73.67 (0.20) 9.39 (0.11) 15.63 (0.11) 74.75 (0.15) 8.80 (0.12) 16.63 (0.12) 1.58 (0.09) 73.57 (0.18) 9.27 (0.12) 15.57 (0.25) 73.59 (0.13) 9.07 (0.08) 16.55 (0.25) 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*)
df Stun of squares Mean square F value p Value

Condition Concentration Cond.*conc. Residual

1 2 2 30

1.480 0.876 0.135 0.974

1.480 0.438 0.067 0.032

45.6 13.5 2.07

0.0001 0.0001 0.14

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) revealed t h a t significant differences were found, because energy 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 factors. 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 increased at 150 k J / m 2, t h e n decreased with increasing energy. F o r all concentrations tested a* decreased, whereas b* increased with increasing energy. Values of AE* increased w i t h increasing energy for all concentrations.

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 significance 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* increased 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 positive 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% concentrations 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 outdooraged samples became d a r k e r w h e n exposed to 150 k J / m 2.

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 samples 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-









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 systems. 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 elastomer. The decrease in a* for both modes of exposure relates to the fading of red in the samples, which was more pronounced 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 outdoor-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 addition of the UV light absorber may be due to its off-white color. The UV light absorber also ma.y have blocked the reflection 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 concentrations. These values of AE*, which ranged from 1.08 to 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 absorber 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 determine whether a suitable product exists. The test samples changed color as determined by spec-





trophotometric analysis. Although the changes were perceptible, they did not represent the level of color degradation that is observed clinically. The major changes in appearance 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.

The effect of a UV light absorber on the color stability of a facial elastomer was evaluated by using reflection spectrophotometry. 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 editorial 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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8. Goldberg AJ, Craig RG, Fillisko FE. Ultraviolet light stability of external maxillofacial prosthetic materials [Abstract]. International Association for Dental Research Program and Abstracts of Papers. 1976;55: B138. 9. Koran A, Yu R, Powers JM, Craig RG. Color stability of a pigmented elastomer for maxillofacial appliances. J Dent Res 1979;58:1450-4. 10. Weins JP. A comparative study of selected elastomers subjected to artificial and outdoor weathering. Masters thesis. University of Minnesota, 1980. 11. Lewis DH, Castleberry DJ. An assessment of recent advances in external maxillofacial materials. J PROSTHETDENT 1980;43:426-32. 12. Chu CC, Fischer TE. Evaluation of sunlight stability of polyurethane elastomers for maxillofacial use. I. J Biomed Mater Res 1978;12:34759. 13. Spectra-sorb UV 5411 ultraviolet light absorber, specification and toxicity summary, Wayne, New Jersey: American Cyanamid Co, 1991. 14. Society of Automotive Engineers. Accelerated exposure of automotive exterior materials using a controlled irradiance water-cooled xenon arc apparatus. Specification SAEJ 1960, June 1989. 15. Crewsdon L. Correlation of outdoor and laboratory accelerated weathering tests at currently used and higher irradiance levels. Part I. Atlas Sun Spots 1991:21. 16. Lane S. A guide to product durability testing and research. Miami, Florida, South Florida Test Service, 1989. 17. Standard practice for atmospheric environmental exposure testing of non-metallic materials (ASTM G7-83). In Annual Book of ASTM Standards 1989:2740-8. 18. Standard practice for: exposure of cover materials for solar collectors to natural weathering under conditions simulating operational mode (ASTM E782-81). Annual Book of ASTM Standards 1989:4264-70. 19. Judd DB, Wyszecki G. Color in business, science, and industry. New York: Wiley and Sons, Inc, 1975:533. 20. Standard method for calculation of color differences from instrumentally measured color coordinates (ASTM D2244-85). Annual Book of ASTM Standards 1989:213-8. 21. Searle NZ. Analytical photochemistry and photochemical analysis of solids, solutions, and polymers. In: Fitzgerald JM, editor. Marcel Dekker, Inc, 1971. Reprint requests to: DR. MARKS. CHAMBERS SECTIONOF ONCOLOGICDENTISTRYAND PROSTHODONTICS,BOX 69 THE UNnrERSI~ OF TEXAS M. D. ANDERSONCANCERCENTER 1515 HOLCOMBEBLVD. HOUSTON,TX 77030