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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.)
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.
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
Professor, Department of Prosthodontics. Professor, Department of Prosthodontics.
204 THE JOURNAL OF PROSTHETIC DENTISTRY
Norfolk.J. The colors were vaguely identified as white. Of the 5 pigments. MacBeth. Inc. Atlas Electronics) and direct outside exposure.15 evaluated the effects of 11 additive UV light absorbers and one antioxidant in nonpigmented polyurethane elastomers (Calthane ND2300. dark buff. Haug et al. Cincinnati. All specimens demonstrated a color change (∆E) greater than or close to 1. After reviewing the dental literature. Ariz.Y.16 tested 11 dry mineral earth pigments (Artskin Products. Before and after accelerated aging from a 2500-W xenon light source (Model 25WR. Some pigments 205 . when mixed or ground in a liquid vehicle. Inc.). Normal concentration of this benzotriazole compound in industrial use range from 0. Daro Products).) for a 900-hour testing period. does not dissolve but remains dispersed in the liquid.18 evaluated the color change in 6 nonpigmented elastomers. black. and a* and b* indicate 2 AUGUST 1998 color axes. which was considered a visually detectable color change. Calif. 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. but this finding did not adequately explain the degree of color degradation that is seen clinically. Visual and spectrophotometric observations revealed no statistically significant differences for any of the color systems before and after aging.). Spectrophotometric analyses (Color Eye 7000. Color was evaluated with artificial weathering that used a xenon light source (Ci35.17 evaluated the color stability of isophorone polyurethane. all materials were evaluated with a spectrophotometer (ACTA CIII.. and burnt sienna in an oil base medium.).). In the L*a*b* system to measure color. The chemical pureness of a pigment varies.0% by weight. The UV light absorber used in this study did not protect the samples from change.. The silicones (Silastic 4-4210. Va. whereas longer-term color shifts may be caused by color changes within the elastomer. Beatty et al. 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. Specimens were subjected to natural weathering. By using a twin-lamp carbon arc weathering chamber (Model HVDL-X. N. Inc. cadmium red. and artificial aging caused a greater change than outdoor aging. 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. kaolin with dry earth pigments.21 evaluated the effectiveness of an additive intrinsic UV light absorber. Minolta Co. medium brown. dry earth pigments (Artskin Products. Lakeside.). Ohio). yellow. Chu et al. value is L*. During the outdoor exposure. Turner et al. the variety of testing methods and the paucity of information on pigments makes it difficult to compare one study with another. in this study.) were performed to assess color changes.. showed more changes in color than the silicone A-102 (Factor II. red. Beckman Instruments). Lemon et al.). Dyes are colored substances that dissolve and give their color effects to materials by staining. The combined pigments tested were yellow ochre. Cal Polymer Co. red brown.” Changes in color were measured with a reflectance spectrophotometer (CM2002. on the color stability of a pigmented room temperature-vulcanized (RTV) silicone elastomer (mixture of MDX4-4210 and type A medical adhesive. No other description of the pigments were given.). McLaren21 described a dry pigment as a finely divided colored substance that. the samples were left uncovered and exposed. Very small changes in color were detected. Dow Corning Co. light brown.). and cosmetic yellow ochre. they found that the UV light absorbers made from the benzotriazole or amine group were most effective in reducing visible yellowing of the elastomer. Atlas Electric Devices). Beckman Instruments.19 evaluated 5 dry pigments (Factor II) and 1 maxillofacial elastomer (A-2186.5% to 1. mars violet. Dow Corning Co. although Silastic 44210 elastomer appeared to have the best overall properties.20 The authors concluded that early color changes in a prosthesis may be the result of degradation of certain UV light-susceptible 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. Ramsey. Four color systems were evaluated: artist’s oil pigments (Permanent Pigments. Color change (∆E) was calculated from the mean ∆L∆a∆b values for each group from before and after treatment values with the formula: ∆E = (∆L*2 +∆a*2 +∆b*2)1⁄2. N. Irvine. and Daro skin pigments (Daro Products. The authors concluded that slight color changes did occur. and polyurethane (Epithane-3. Samples were placed in a weathering chamber (model 18 wt. The samples were placed in a weathering chamber with a 2500-W xenon light source. Newburgh.GARY AND SMITH THE JOURNAL OF PROSTHETIC DENTISTRY rials were evaluated with a spectrophotometer (Acta CIII. All silicone elastomers showed good color stability.. Koran et al.). Inc.25% by weight to some samples. cosmetic red. Inc. Atlas Electronic Co. with a* the red/green axis and b* the yellow/blue axis. Silastic 4-4515. this UV light absorber was added up to 0. The 5 pigments tested were identified as titanium white. light orange. Medical Adhesive type A. Atlas Electric Devices) as the UV source..) with Silastic 44210 material (Dow Corning Co. blue. cadmium yellow medium. and orange yellow. which was described as exposing the specimens to outdoor Indianapolis weather for 6 months. a benzotriazole compound. Calif.
Inorganic pigments can be native earths (ochre. The term “organic” can be applied to pigments of an animal. vegetable. is followed by the color index name and number. toxicity. The pigments that have been approved by the ASTM are followed by an abbreviation of the color index name and number. A list of pigments has been developed according to the color index names by the ASTM. 45 pigments have an ASTM lightfastness category of I and 1 pigVOLUME 80 NUMBER 2 . 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. Mayer22 stated that the nomenclature of pigments can be confusing. Organic pigments are those that are carbon hydrogen derivatives. From that list of inorganic pigments. the common name of a pigment. For example. The term inorganic can be applied to pigments of mineral origin.23 The ASTM created standards intended to identify materials and their degree of purity and permanence. or rutile.1 Pigment yellow 40 (PY40) 77357 Pigment red 101 (PR101) 77491 Pigment red 108:1 (PR108. or synthetic origin. chemical formula and description. Pigment Brown 7 or PBr 7. Addi206 tional information provided in a list of ASTM-approved pigments are lightfastness category.THE JOURNAL OF PROSTHETIC DENTISTRY GARY AND SMITH Table I. chemical type and class. In Table I. simple compounds. Pigments are normally classified according to their major component element.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. anatase. A system of color names is needed to eliminate the confusion of the various color names that appear in research. and representative spectral curves.22. calcined native earths (burnt umber. and magnesium C14H8O4 Calcium salt of anthraquinone dye CoK3N6O12 Potassium nitrite/cobalt salt solutions Fe2O3 Ferric oxide produced chemically CdS⋅xCdSe⋅yBaSo4 Cadmium seleno-sulfide precipitate w/BaSO4 TiO2 Titanium dioxide with zinc oxide Fe2O3⋅H2O Hydrated ferric oxide from limonite ore are almost pure.xCaPO4 Calcined animal bones CoAl2O4 Calcined cobalt oxide/aluminum oxide Fe2O3 Ferric oxide produced from ores Fe2O3 Calcined ferric oxide Fe2O3⋅xMnO2 Ferric oxide with manganese Fe2O3⋅xMnO2 Calcined ferric oxide with manganese Ferrous silicates. the composition of raw umber is similar to raw sienna but it contains manganese. they contain metal atoms. raw umber). 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. 46 pigments have an inorganic origin. burnt sienna) or synthetic origin (cadmium yellow. common names. From a list22 of 109 ASTMapproved pigments. This view may have some merit. but contain minor elements either as natural impurities or as a result of ingredients added during manufacturing to modify the color. Mayer22 stated that pigments can be classified according to their color and origin. This list can correspond to outdated color names and common names for ASTM approved pigments. Other pigments are of a high purity. vehicle compatibility.1) 77202. raw umber. zinc oxide). raw sienna is a native clay that contains iron oxide. Inorganic pigments are not formed from carbon and hydrogen. aluminum. 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.
Lightfastness III—pigments that exhibit a mean color change of more than 8. Lightfastness IV—pigments that exhibit a mean color change of more than 16. the specimen should be placed 3 inches from the plane of the lamps.GARY AND SMITH THE JOURNAL OF PROSTHETIC DENTISTRY ment (pigment yellow 40 or cobalt yellow) has a lightfastness category of II. Besides applying UV protection internally to the silicone prosthesis. Lightfastness II—pigments that exhibit a mean color change of more than 4.0 but not more than 16.26 In the L*a*b* system. ASTM uses 3 test methods that involve exposure of the pigment under glass to the sun. a ∆E of 1 is considered visually detectable. exposure to irradiance from artificial daylight fluorescent lamps.) Mayer22 stated that the fading of a pigment or dye on exposure to daylight is not an evanescence. The ambient room temperature should be maintained at 24° ± 3°C. and pigment red 146 or naphthol carmine FBB). different varieties of a pigment from company to company.29 There can be variations in the test results from differences in pigment manufactured from time to time within a company. whereby the effect of months of exposure to direct sunlight is duplicated in a relatively short time. (Written communication: Schoenherr WJ. 11 have a lightfastness category of II.0 but not more than 8. 1996. pigment red 17 or naphthol red. Lightfastness categories for pigments are assigned values based on the color difference units calculated by the CIE 1976 L*a*b* color difference equation. Allowance for these variables is made by requiring more than 1 test and by establishing lightfastness categories that include a range of color differences. The pigments change to a colorless or less highly colored compound. this can be accomplished with a weathering chamber. To evaluate the lightfastness of pigments. specimen preparation. From those 63 pigments.25 used RTV silicone elastomers in facial prostheses.0. Unless otherwise specified. Healthcare Industries. different instruments and instrumental readings. Dow Corning Corp. Lightfastness V—pigments that exhibit a mean color change of more than 24.26 The tests consist of exposing the pigment used in artists’ paints to light (natural sunlight or simulated sunlight) filtered through glass. Relative humidity in the test chamber should be 55% ± 5% and a black panel temperature of 63° ± 2°C. Much of the research conducted to date has involved the use of weathering chambers. and 4 have a lightfastness category of III (pigment green 8 or Hooker’s green.27 In the ASTM test method. Research may need to be directed toward minimizing the degree of color change. The ASTM has developed standard test methods for determining the lightfastness of pigments used in artists’ paints. Lightfastness is described as the ability of a material to withstand color change on exposure to light. This test method takes approximately 9 months to complete. external protection from a spray with a UV inhibitor should be investigated.0 but not more than 24. 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. and the conditions of exposure. it was deduced that RTV silicone elastomers and pigments do exhibit a color change and that a color change is to be expected.0 ∆E*ab. 48 pigments have a lightfastness category of I.26 In the ASTM test method in which the specimen is exposed to simulated daylight (xenon-arc type).24 The majority of the respondents from a survey by Andres et al. because there would be less chance that the pigments would be dissolved during cleaning the prosthesis. The test specimens should be exposed continuously to a total radiant dose of 1260 MJ/m2. but is actually the result of a chemical change.. Internal pigments may result in less loss of color. The possibility of using UV absorbers may be a partial solution regarding pigment stability of facial prostheses. or the disappearance of the substance itself into thin air. sometimes with the combination of air and or moisture. Silicones as a class of materials are transparent to UV radiation and are highly permeable to moisture vapor and many gases verses organic elastomers. variations in the surface of the specimen. The UV wavelengths in the light react with the pigment or trigger a reaction. 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. and exposure to a xenon-arc lightfastness apparatus. November 18. pigment red 83 or alizarin crimson. Pigments are tested for resistance to fading by subjecting them to concentrated UV light with a laboratory apparatus.24 CONCLUSIONS From the literature review. For tests in southern Florida below 27 degrees latitude. 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.0.28 AUGUST 1998 In the ASTM test method in which the specimen is exposed to simulated daylight (fluorescent lamb light). 207 .18 The interpretation of the results are placed in the following categories: Lightfastness I—pigments that exhibit a mean color change of 4 or less ∆E*ab. in which the specimen is exposed to the sun. The remaining 63 pigments have an organic origin. the exposed pigments should be tested during the months of October through May.
Maxillofacial prostheses: reproducible fabrication. Stroud L. Dick K. Jacobsen ML. 1991. 20. Yu R. Munoz CA. Reprint requests to: DR. J Prosthet Dent 1969. Arlington: ABI Professional Publications. Int J Oral Maxillofac Implants 1995. Color characterizing silicone rubber facial prostheses. 15. 161-7. 9. Bristol: Adam Hilger Ltd. Cantor R. 4. Fundamentals of facial prosthetics.22:271-5. Philadelphia: American Society for Testing and Materials. 30. 27. REFERENCES 1. reapproved 1994). Andres CJ. p. Standard test method for calculation of color differences from instrumentally measured color coordinates. Haug SP. Spencer J. (ASTM D4302-96a). 193-9. 0022-3913/98/$5. 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. Chu CC.24:198-202. Color stability of elastomers for maxillofacial appliances. Evaluation of sunlight stability of polyurethane elastomers for maxillofacial use. Mayer R. resin-oil. clean the prosthesis. 18. The artist’s handbook of materials and techniques.00 + 0. 16. Patients should avoid smoking. Standard practice for conducting exposures to daylight filtered through glass.10:445-9. Blomfield JV. I.39:643-9. (ASTM G26-95). 5th ed. Coward TJ. 13. p. 21. 1995. 24. Chambers MS. Drane JB. Powers JM. (ASTM D4303-93a). Karl L. 26. Castleberry DJ. 1986. (ASTM D2244-93).43:426-32. Commercial cosmetics and their role in the coloring of facial prostheses. Koran A. 22. 6. Firtell DN.27:297305. Arlington: ABI Professional Publications.68:820-3. J Prosthet Dent 1969. Andres CJ.. the repeated washing may dissolve and remove some pigments on the external surface. 17. J Prosthet Dent 1980. Janus CE. Patients should not use any solvents such as isopropyl alcohol to clean the prosthesis. 23. J Prosthet Dent 1995. West Conshohocken (PA): American Society for Testing and Materials. J Prosthet Dent 1978. even if a waterbased makeup is used. Sweeney WT. 1995.46:538-44. Webber RL. 10. Forman GH. Arlington: ABI Professional Publications.21:324-32. which could cause dissolution of the pigments. Ouellette JE. patients must be instructed thoroughly on the care of their facial prostheses to prolong the longevity of the prosthesis. Beatty MW. Cowperthwaite GF. New York: Viking Penguin. Udagama A. Color changes in dry-pigmented maxillofacial elastomer resulting from ultraviolet light exposure. McKinstry RE. Part II: color stability. Standard specification for artists’ oil.58:1450-4. Spray coloring of silicone elastomer maxillofacial prostheses. 14. Craig RG.22:247-52. Mahanna GK. J Prosthet Dent 1981. and alkyd paints. Color stability of facial prostheses.74:613-8. Color stability of a pigmented elastomer for maxillofacial appliances. Schaaf NG. McKinstry RE.THE JOURNAL OF PROSTHETIC DENTISTRY GARY AND SMITH In the meantime. J Prosthet Dent 1978. Proper daily care and maintenance of the facial prosthesis has been specified in the literature. Lemon JC. 3. Fischer TE. Jia W. J Dent Res 1979. 1995. The colour science of dyes and pigments. McLaren K. J Dent Res 1978. Bernal G. Watson RM. J Prosthet Dent 1969. Fundamentals of facial prostheses.39:546-50. Haug SP. J Prosthet Dent 1992. New method for coloring facial prostheses. 25.74:493-8. Hanson MD. J Prosthet Dent 1992. J Biomed Mater Res 1978. Results of treatment of 20 patients with implant-retained auricular prostheses. Lemons JE. J Prosthet Dent 1984. 2. An evaluation of facial prostheses. Turner GE. Methods for evaluating prosthetic facial materials. (ASTM G24 -87. 28. 10/1/91415 208 VOLUME 80 NUMBER 2 . J Prosthet Dent 1995. 19. 7. Intrinsic color of isophorone polyurethane for maxillofacial prosthetics. Standard practice for operating light-exposure apparatus (xenon-arc type) with and without water for exposure of nonmetallic materials. West Conshohocken (PA): American Society for Testing and Materials. Shipman B. Fine L. J Prosthet Dent 1972.51:673-5. JOHN J. Patients should be encouraged to avoid prolonged exposure to sunlight and to use brimmed hats and sunglasses. Ryge G. Robinson JE. Philadelphia: American Society for Testing and Materials. Bartlett SO.12:347-59. which could stain a nasal prosthesis. Barnhart GW. (ASTM E 284-96c). Yu R.57:866-71. Lewis DH.68:519-22. Effects of environmental factors on maxillofacial elastomers: part IV– optical properties. and store the prosthesis. Fischer TE. 11. Castleberry DJ. Jani RM. 29. West Conshohocken (PA): American Society for Testing and Materials. 12. 2nd ed. McKinstry RE. Effects of environmental factors on maxillofacial elastomers: part II – report of survey. Fundamentals of facial prosthetics. J Prosthet Dent 1970.30 Explicit written and verbal instructions should be provided to patients on how to position and remove the prosthesis. Evaluation of facial prostheses for head and neck cancer patients. Powers JM. 8. Fischer TE. Craig RG. West Conshohocken (PA): American Society for Testing and Materials. 5. An assessment of recent advances in external maxillofacial materials. Bernal G. 198. Standard terminology of appearance.50:818-20. They should avoid using cosmetics on the prosthesis. Chen M. Castleberry DJ. Evaluation of improved maxillofacial prosthetic materials. p. Koran A. Brown DT. J Prosthet Dent 1983. Standard test methods for lightfastness of pigments used in artists’ paints. Schaaf NG.
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