Pigments and their application in maxillofacial elastomers: A literature review

John J. Gary, DDS,a and Charles T. Smith, DDSb University of Tennessee at Memphis, Memphis, Tenn. Purpose. This literature review provides information about pigments used for facial and somatoprostheses. Material. This information includes common pigment and index names and numbers, lightfastness categories, chemical type and class, and the chemical formulas of the common pigments used in maxillofacial prosthetics. Conclusion. It can be deduced from this review that the pigments used with silicone elastomers do exhibit a color change, and that a color change is to be expected. (J Prosthet Dent 1998;80:204-8.)

CLINICAL IMPLICATIONS
Color changes are to be expected when pigments are used with silicone elastomers.

xtraoral maxillofacial prostheses can be a valuable treatment option for patients with orofacial defects. Materials used in the fabrication of these facial prostheses can be silicones that are tinted externally and internally to match the color of the surrounding facial structures. Lewis et al.1 stated that the ideal color properties required in a maxillofacial prosthetic material must accept and retain intrinsic and extrinsic coloration, and that the appearance and mechanical strength of the prosthesis must not be changed by sunlight or other environmental factors. Unfortunately, facial prostheses do not have longevity. Color instability of the prosthesis may be attributed to ultraviolet (UV) light exposure, air pollution, cosmetics, and the use of strong solvents to clean the prosthesis, such as benzene and xylene.2-4 In an article on 20 patients treated with implant-retained auricular prostheses fabricated with Cosmesil silicone (Cosmedica, Cardiff, Wales) tinted with unspecified pigments, 7 patients complained of loss of color, principally after exposure to the sun and sea water, necessitating replacement of the prostheses in 9 occasions; the average period of color stability was 21 months.5 A recent article stated that facial prostheses last approximately 1 to 3 years under normal use, and one of the reasons for adjustment, repair, or replacement was color change.6 There are few scientific investigations reported in the dental literature regarding pigments and maxillofacial materials, although there are several articles on the application of internal and external color to prostheses.7-11 The purpose of this review of the current dental literature and art textbooks on materials is to stimuaAssistant

late scientific experimentation toward theories for improving color stability in facial prostheses. It is important that the effects of individual environmental effects on pigments be better understood to fabricate an improved color-stable prosthesis.

LITERATURE REVIEW
In 1969, Cantor et al.12 reported on methods to objectively evaluate prosthetic maxillofacial materials. One property evaluated was esthetics or color matching. Reflectance spectrophotometry was used to evaluate, measure, and record the amount of light reflected in the visible spectrum for each wavelength, and made it possible to characterize quantitatively the pigments contributing to a certain color. The authors suggested that by using spectrophotometric analysis, the development of isomerically matched facial materials with skin appeared to be possible. In 1972, Sweeney et al.13 reported on the use of an accelerated aging chamber in the evaluation of the color stability of maxillofacial materials. A weatherometer or weathering chamber (Model 25WR, Atlas Electric Devices, Chicago, Ill.) used in the study was a device where specimens can be exposed to conditions similar to outdoor atmosphere, radiation, temperature, and humidity. Differences could be measured with a colorimeter by comparison of exposed and nonexposed specimens. The authors recommended 2000 hours of exposure to evaluate maxillofacial materials. Craig et al.14 later tested the color stability of a nonpigmented polyvinyl chloride (Prototype III, Sartomer Industries, Essington, Pa.), a polyurethane (Epithane, Daro Products, Butler, Wis.), and 4 silicones (Silastic 382, Silastic 399, Silastic 44210, Silastic 44515, Dow Corning, Midland, Mich.). Before and after accelerated aging (Model 25WR, Atlas Electric Devices), all mateVOLUME 80 NUMBER 2

bAssociate

Professor, Department of Prosthodontics. Professor, Department of Prosthodontics.

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rials were evaluated with a spectrophotometer (Acta CIII, Beckman Instruments, Irvine, Calif.). The samples were placed in a weathering chamber with a 2500-W xenon light source. All silicone elastomers showed good color stability, although Silastic 44210 elastomer appeared to have the best overall properties. The authors suggested that the color stability of pigments and the stain resistance of the elastomers may be partly responsible for the color degradation experienced in clinical situations. Chu et al.15 evaluated the effects of 11 additive UV light absorbers and one antioxidant in nonpigmented polyurethane elastomers (Calthane ND2300, Cal Polymer Co., Calif.). By using a twin-lamp carbon arc weathering chamber (Model HVDL-X, Atlas Electric Devices) as the UV source, they found that the UV light absorbers made from the benzotriazole or amine group were most effective in reducing visible yellowing of the elastomer. Koran et al.16 tested 11 dry mineral earth pigments (Artskin Products, Inc., Norfolk, Va.) with Silastic 44210 material (Dow Corning Co.). The colors were vaguely identified as white, yellow, dark buff, medium brown, light brown, red brown, black, red, blue, light orange, and orange yellow. Before and after accelerated aging from a 2500-W xenon light source (Model 25WR, Atlas Electric Devices), all materials were evaluated with a spectrophotometer (ACTA CIII, Beckman Instruments). Very small changes in color were detected, but this finding did not adequately explain the degree of color degradation that is seen clinically. Turner et al.17 evaluated the color stability of isophorone polyurethane. Four color systems were evaluated: artists oil pigments (Permanent Pigments, Inc., Cincinnati, Ohio), dry earth pigments (Artskin Products, Inc.), kaolin with dry earth pigments, and Daro skin pigments (Daro Products, Inc.). No other description of the pigments were given. Samples were placed in a weathering chamber (model 18 wt, Atlas Electronic Co.) for a 900-hour testing period. Visual and spectrophotometric observations revealed no statistically significant differences for any of the color systems before and after aging. Haug et al.18 evaluated the color change in 6 nonpigmented elastomers. Specimens were subjected to natural weathering, which was described as exposing the specimens to outdoor Indianapolis weather for 6 months. The silicones (Silastic 4-4210, Silastic 4-4515, Medical Adhesive type A, Dow Corning Co.), and polyurethane (Epithane-3, Daro Products), showed more changes in color than the silicone A-102 (Factor II, Inc., Lakeside, Ariz.). Color change (E) was calculated from the mean Lab values for each group from before and after treatment values with the formula: E = (L*2 +a*2 +b*2)12. In the L*a*b* system to measure color, value is L*, and a* and b* indicate 2
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color axes, with a* the red/green axis and b* the yellow/blue axis. All specimens demonstrated a color change (E) greater than or close to 1, which was considered a visually detectable color change. Beatty et al.19 evaluated 5 dry pigments (Factor II) and 1 maxillofacial elastomer (A-2186, Factor II) for color changes resulting from exposure up to 1800 hours from UV-A and UV-B emitted from a four bulb light fixture. Changes in color were measured with a reflectance spectrophotometer (CM2002, Minolta Co., Ramsey, N.J.). The 5 pigments tested were identified as titanium white, cadmium yellow medium, mars violet, cosmetic red, and cosmetic yellow ochre. Of the 5 pigments, cosmetic red and cosmetic yellow ochre were 2 common color names that cannot be crossreferenced to the American Society for Testing and Materials (ASTM) approved list of pigments.20 The authors concluded that early color changes in a prosthesis may be the result of degradation of certain UV light-susceptible pigments, whereas longer-term color shifts may be caused by color changes within the elastomer. Lemon et al.21 evaluated the effectiveness of an additive intrinsic UV light absorber, a benzotriazole compound, on the color stability of a pigmented room temperature-vulcanized (RTV) silicone elastomer (mixture of MDX4-4210 and type A medical adhesive, Dow Corning Co.). Normal concentration of this benzotriazole compound in industrial use range from 0.5% to 1.0% by weight; in this study, this UV light absorber was added up to 0.25% by weight to some samples. The combined pigments tested were yellow ochre, cadmium red, and burnt sienna in an oil base medium. Color was evaluated with artificial weathering that used a xenon light source (Ci35, Atlas Electronics) and direct outside exposure. During the outdoor exposure, the samples were left uncovered and exposed. Spectrophotometric analyses (Color Eye 7000, MacBeth, Newburgh, N.Y.) were performed to assess color changes. The authors concluded that slight color changes did occur, and artificial aging caused a greater change than outdoor aging. The UV light absorber used in this study did not protect the samples from change. After reviewing the dental literature, the variety of testing methods and the paucity of information on pigments makes it difficult to compare one study with another. A review of art textbooks on materials can provide additional information on pigments that may explain the observed differences in the color stability of pigments. McLaren21 described a dry pigment as a finely divided colored substance that, when mixed or ground in a liquid vehicle, does not dissolve but remains dispersed in the liquid. Dyes are colored substances that dissolve and give their color effects to materials by staining. The chemical pureness of a pigment varies. Some pigments
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Table I. Partial list of pigments used in maxillofacial prosthetics

Common name Color index name/ number Lightfastness ASTM D4302 Chemical type/class Chemical formula description

Ivory black Cobalt blue Raw sienna Burnt sienna Raw umber Burnt umber Green earth Alizarin crimson Cobalt yellow Mars violet Cadmium-barium red (medium) Titanium white Yellow ochre

Pigment black 9 (PBk9) 77267 Pigment blue 28 (PB28) 77346 Pigment brown 7 (PBr7) 77491 or 77492 Pigment brown 7 (PBr7) 77491 or 77492 Pigment brown 7 (PBr7) 77491 or 77492 Pigment brown 7 (PBr7) 77491 or 77492 Pigment green 23 (PG23) 77009 Pigment Red 83 (PR83) 58000.1 Pigment yellow 40 (PY40) 77357 Pigment red 101 (PR101) 77491 Pigment red 108:1 (PR108.1) 77202.1 Pigment white 6 (PW6) 77891 Pigment yellow 43 (PY43) 77492

I I I I I I I III II I I I I

Inorganic synthetic Carbon black Inorganic synthetic Mixed metal oxide Inorganic Iron oxide Inorganic Iron oxide Inorganic Iron oxide Inorganic Iron oxide Inorganic Organic synthetic Anthraquinone Inorganic synthetic Inorganic synthetic Iron oxide Inorganic synthetic Cadmium Inorganic synthetic Opaque white Inorganic Colored oxide of iron

C.xCaPO4 Calcined animal bones CoAl2O4 Calcined cobalt oxide/aluminum oxide Fe2O3 Ferric oxide produced from ores Fe2O3 Calcined ferric oxide Fe2O3xMnO2 Ferric oxide with manganese Fe2O3xMnO2 Calcined ferric oxide with manganese Ferrous silicates, aluminum, and magnesium C14H8O4 Calcium salt of anthraquinone dye CoK3N6O12 Potassium nitrite/cobalt salt solutions Fe2O3 Ferric oxide produced chemically CdSxCdSeyBaSo4 Cadmium seleno-sulfide precipitate w/BaSO4 TiO2 Titanium dioxide with zinc oxide Fe2O3H2O Hydrated ferric oxide from limonite ore

are almost pure, simple compounds. Other pigments are of a high purity, but contain minor elements either as natural impurities or as a result of ingredients added during manufacturing to modify the color. For example, raw sienna is a native clay that contains iron oxide; the composition of raw umber is similar to raw sienna but it contains manganese. Mayer22 stated that the nomenclature of pigments can be confusing. A single color can be known by many names or 2 entirely different colors can be known by the same name. Titanium white can be known as titanium dioxide, anatase, or rutile. A system of color names is needed to eliminate the confusion of the various color names that appear in research. A list of pigments has been developed according to the color index names by the ASTM.22,23 The ASTM created standards intended to identify materials and their degree of purity and permanence. This list can correspond to outdated color names and common names for ASTM approved pigments. The pigments that have been approved by the ASTM are followed by an abbreviation of the color index name and number. In Table I, the common name of a pigment, raw umber, is followed by the color index name and number, Pigment Brown 7 or PBr 7. Addi206

tional information provided in a list of ASTM-approved pigments are lightfastness category, chemical type and class, chemical formula and description, vehicle compatibility, toxicity, common names, and representative spectral curves. Mayer22 stated that pigments can be classified according to their color and origin. Pigments are normally classified according to their major component element. The term organic can be applied to pigments of an animal, vegetable, or synthetic origin. Organic pigments are those that are carbon hydrogen derivatives. Inorganic pigments are not formed from carbon and hydrogen; they contain metal atoms. The term inorganic can be applied to pigments of mineral origin. Inorganic pigments can be native earths (ochre, raw umber), calcined native earths (burnt umber, burnt sienna) or synthetic origin (cadmium yellow, zinc oxide). One can infer that organic pigments have a limited life span and are more subject to decay on aging and exposure to adverse environmental conditions. This view may have some merit. From a list22 of 109 ASTMapproved pigments, 46 pigments have an inorganic origin. From that list of inorganic pigments, 45 pigments have an ASTM lightfastness category of I and 1 pigVOLUME 80 NUMBER 2

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ment (pigment yellow 40 or cobalt yellow) has a lightfastness category of II. The remaining 63 pigments have an organic origin. From those 63 pigments, 48 pigments have a lightfastness category of I, 11 have a lightfastness category of II, and 4 have a lightfastness category of III (pigment green 8 or Hookers green, pigment red 17 or naphthol red, pigment red 83 or alizarin crimson, and pigment red 146 or naphthol carmine FBB). Lightfastness is described as the ability of a material to withstand color change on exposure to light.24 The majority of the respondents from a survey by Andres et al.25 used RTV silicone elastomers in facial prostheses. Silicones as a class of materials are transparent to UV radiation and are highly permeable to moisture vapor and many gases verses organic elastomers. Any pigment that is sensitive to this type of exposure would degrade regardless of whether they were incorporated into the silicone or applied to the exterior surface. (Written communication: Schoenherr WJ, Healthcare Industries, Dow Corning Corp., November 18, 1996.) Mayer22 stated that the fading of a pigment or dye on exposure to daylight is not an evanescence, or the disappearance of the substance itself into thin air, but is actually the result of a chemical change. The UV wavelengths in the light react with the pigment or trigger a reaction, sometimes with the combination of air and or moisture. The pigments change to a colorless or less highly colored compound. Pigments are tested for resistance to fading by subjecting them to concentrated UV light with a laboratory apparatus, whereby the effect of months of exposure to direct sunlight is duplicated in a relatively short time. Much of the research conducted to date has involved the use of weathering chambers. The ASTM has developed standard test methods for determining the lightfastness of pigments used in artists paints.26 The tests consist of exposing the pigment used in artists paints to light (natural sunlight or simulated sunlight) filtered through glass. To evaluate the lightfastness of pigments, ASTM uses 3 test methods that involve exposure of the pigment under glass to the sun, exposure to irradiance from artificial daylight fluorescent lamps, and exposure to a xenon-arc lightfastness apparatus. Lightfastness categories for pigments are assigned values based on the color difference units calculated by the CIE 1976 L*a*b* color difference equation.27 In the ASTM test method, in which the specimen is exposed to the sun, it is recommended that the specimen has an exposure angle of 45 degrees to the vertical for a total radiation dose of 1260 MJ/m2. For tests in southern Florida below 27 degrees latitude, the exposed pigments should be tested during the months of October through May.28
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In the ASTM test method in which the specimen is exposed to simulated daylight (fluorescent lamb light), the specimen should be placed 3 inches from the plane of the lamps. Unless otherwise specified, the specimen should be exposed to a cycle of 8 hours light followed by 4 hours dark until the specimen has been exposed to a total radiant dose of 1260 MJ/m2. The ambient room temperature should be maintained at 24 3C. This test method takes approximately 9 months to complete.26 In the ASTM test method in which the specimen is exposed to simulated daylight (xenon-arc type), this can be accomplished with a weathering chamber. The test specimens should be exposed continuously to a total radiant dose of 1260 MJ/m2. Relative humidity in the test chamber should be 55% 5% and a black panel temperature of 63 2C.29 There can be variations in the test results from differences in pigment manufactured from time to time within a company, different varieties of a pigment from company to company, specimen preparation, different instruments and instrumental readings, variations in the surface of the specimen, and the conditions of exposure. Allowance for these variables is made by requiring more than 1 test and by establishing lightfastness categories that include a range of color differences.26 In the L*a*b* system, a E of 1 is considered visually detectable.18 The interpretation of the results are placed in the following categories: Lightfastness Ipigments that exhibit a mean color change of 4 or less E*ab. Lightfastness IIpigments that exhibit a mean color change of more than 4.0 but not more than 8.0 E*ab. Lightfastness IIIpigments that exhibit a mean color change of more than 8.0 but not more than 16.0. Lightfastness IVpigments that exhibit a mean color change of more than 16.0 but not more than 24.0. Lightfastness Vpigments that exhibit a mean color change of more than 24.24

CONCLUSIONS
From the literature review, it was deduced that RTV silicone elastomers and pigments do exhibit a color change and that a color change is to be expected. Internal pigments may result in less loss of color, because there would be less chance that the pigments would be dissolved during cleaning the prosthesis. Research may need to be directed toward minimizing the degree of color change. The possibility of using UV absorbers may be a partial solution regarding pigment stability of facial prostheses. Besides applying UV protection internally to the silicone prosthesis, external protection from a spray with a UV inhibitor should be investigated.
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In the meantime, patients must be instructed thoroughly on the care of their facial prostheses to prolong the longevity of the prosthesis. Patients should be encouraged to avoid prolonged exposure to sunlight and to use brimmed hats and sunglasses. They should avoid using cosmetics on the prosthesis; even if a waterbased makeup is used, the repeated washing may dissolve and remove some pigments on the external surface. Patients should not use any solvents such as isopropyl alcohol to clean the prosthesis, which could cause dissolution of the pigments. Patients should avoid smoking, which could stain a nasal prosthesis. Proper daily care and maintenance of the facial prosthesis has been specified in the literature.30 Explicit written and verbal instructions should be provided to patients on how to position and remove the prosthesis, clean the prosthesis, and store the prosthesis.
REFERENCES
1. Lewis DH, Castleberry DJ. An assessment of recent advances in external maxillofacial materials. J Prosthet Dent 1980;43:426-32. 2. Chen M, Udagama A, Drane JB. Evaluation of facial prostheses for head and neck cancer patients. J Prosthet Dent 1981;46:538-44. 3. Jani RM, Schaaf NG. An evaluation of facial prostheses. J Prosthet Dent 1978;39:546-50. 4. Hanson MD, Shipman B, Blomfield JV, Janus CE. Commercial cosmetics and their role in the coloring of facial prostheses. J Prosthet Dent 1983;50:818-20. 5. Watson RM, Coward TJ, Forman GH. Results of treatment of 20 patients with implant-retained auricular prostheses. Int J Oral Maxillofac Implants 1995;10:445-9. 6. McKinstry RE. Fundamentals of facial prostheses. Arlington: ABI Professional Publications; 1995. p. 198. 7. Firtell DN, Bartlett SO. Maxillofacial prostheses: reproducible fabrication. J Prosthet Dent 1969;22:247-52. 8. Ouellette JE. Spray coloring of silicone elastomer maxillofacial prostheses. J Prosthet Dent 1969;22:271-5. 9. Schaaf NG. Color characterizing silicone rubber facial prostheses. J Prosthet Dent 1970;24:198-202. 10. McKinstry RE. Fundamentals of facial prosthetics. Arlington: ABI Professional Publications; 1995. p. 161-7. 11. Fine L, Robinson JE, Barnhart GW, Karl L. New method for coloring facial prostheses. J Prosthet Dent 1978;39:643-9. 12. Cantor R, Webber RL, Stroud L, Ryge G. Methods for evaluating prosthetic facial materials. J Prosthet Dent 1969;21:324-32. 13. Sweeney WT, Fischer TE, Castleberry DJ, Cowperthwaite GF. Evaluation of improved maxillofacial prosthetic materials. J Prosthet Dent 1972;27:297305.

14. Craig RG, Koran A, Yu R, Spencer J. Color stability of elastomers for maxillofacial appliances. J Dent Res 1978;57:866-71. 15. Chu CC, Fischer TE. Evaluation of sunlight stability of polyurethane elastomers for maxillofacial use. I. J Biomed Mater Res 1978;12:347-59. 16. Koran A, Yu R, Powers JM, Craig RG. Color stability of a pigmented elastomer for maxillofacial appliances. J Dent Res 1979;58:1450-4. 17. Turner GE, Fischer TE, Castleberry DJ, Lemons JE. Intrinsic color of isophorone polyurethane for maxillofacial prosthetics. Part II: color stability. J Prosthet Dent 1984;51:673-5. 18. Haug SP, Andres CJ, Munoz CA, Bernal G. Effects of environmental factors on maxillofacial elastomers: part IV optical properties. J Prosthet Dent 1992;68:820-3. 19. Beatty MW, Mahanna GK, Dick K, Jia W. Color changes in dry-pigmented maxillofacial elastomer resulting from ultraviolet light exposure. J Prosthet Dent 1995;74:493-8. 20. McLaren K. The colour science of dyes and pigments. 2nd ed. Bristol: Adam Hilger Ltd.; 1986. 21. Lemon JC, Chambers MS, Jacobsen ML, Powers JM. Color stability of facial prostheses. J Prosthet Dent 1995;74:613-8. 22. Mayer R. The artists handbook of materials and techniques. 5th ed. New York: Viking Penguin; 1991. 23. Standard specification for artists oil, resin-oil, and alkyd paints. (ASTM D4302-96a). West Conshohocken (PA): American Society for Testing and Materials. 24. Standard terminology of appearance. (ASTM E 284-96c). West Conshohocken (PA): American Society for Testing and Materials. 25. Andres CJ, Haug SP, Brown DT, Bernal G. Effects of environmental factors on maxillofacial elastomers: part II report of survey. J Prosthet Dent 1992;68:519-22. 26. Standard test methods for lightfastness of pigments used in artists paints. (ASTM D4303-93a). Philadelphia: American Society for Testing and Materials. 27. Standard test method for calculation of color differences from instrumentally measured color coordinates. (ASTM D2244-93). West Conshohocken (PA): American Society for Testing and Materials. 28. Standard practice for conducting exposures to daylight filtered through glass. (ASTM G24 -87, reapproved 1994). Philadelphia: American Society for Testing and Materials. 29. Standard practice for operating light-exposure apparatus (xenon-arc type) with and without water for exposure of nonmetallic materials. (ASTM G26-95). West Conshohocken (PA): American Society for Testing and Materials. 30. McKinstry RE. Fundamentals of facial prosthetics. Arlington: ABI Professional Publications; 1995. p. 193-9.

Reprint requests to: DR. JOHN J. GARY THE UNIVERSITY OF TENNESSEE AT MEMPHIS COLLEGE OF DENTISTRY 875 UNION AVE MEMPHIS TN 38163
Copyright 1998 by The Editorial Council of The Journal of Prosthetic Dentistry. 0022-3913/98/$5.00 + 0. 10/1/91415

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