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 cate-
gories, 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 exhib-
it 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.

E xtraoral maxillofacial prostheses can be a valuable

treatment option for patients with orofacial defects.
late scientific experimentation toward theories for
improving color stability in facial prostheses. It is
Materials used in the fabrication of these facial prosthe- important that the effects of individual environmental
ses can be silicones that are tinted externally and inter- effects on pigments be better understood to fabricate
nally to match the color of the surrounding facial struc- an improved color-stable prosthesis.
tures.
LITERATURE REVIEW
Lewis et al.1 stated that the ideal color properties
required in a maxillofacial prosthetic material must In 1969, Cantor et al.12 reported on methods to
accept and retain intrinsic and extrinsic coloration, and objectively evaluate prosthetic maxillofacial materials.
that the appearance and mechanical strength of the One property evaluated was esthetics or color match-
prosthesis must not be changed by sunlight or other ing. Reflectance spectrophotometry was used to evalu-
environmental factors. ate, measure, and record the amount of light reflected
Unfortunately, facial prostheses do not have longevi- in the visible spectrum for each wavelength, and made
ty. Color instability of the prosthesis may be attributed it possible to characterize quantitatively the pigments
to ultraviolet (UV) light exposure, air pollution, cos- contributing to a certain color. The authors suggested
metics, and the use of strong solvents to clean the pros- that by using spectrophotometric analysis, the develop-
thesis, such as benzene and xylene.2-4 In an article on ment of isomerically matched facial materials with skin
20 patients treated with implant-retained auricular appeared to be possible.
prostheses fabricated with Cosmesil silicone (Cosmed- In 1972, Sweeney et al.13 reported on the use of an
ica, Cardiff, Wales) tinted with unspecified pigments, 7 accelerated aging chamber in the evaluation of the
patients complained of loss of color, principally after color stability of maxillofacial materials. A weather-
exposure to the sun and sea water, necessitating ometer or weathering chamber (Model 25WR, Atlas
replacement of the prostheses in 9 occasions; the aver- Electric Devices, Chicago, Ill.) used in the study was a
age period of color stability was 21 months.5 A recent device where specimens can be exposed to conditions
article stated that facial prostheses last approximately 1 similar to outdoor atmosphere, radiation, temperature,
to 3 years under normal use, and one of the reasons for and humidity. Differences could be measured with a
adjustment, repair, or replacement was color change.6 colorimeter by comparison of exposed and nonexposed
There are few scientific investigations reported in specimens. The authors recommended 2000 hours of
the dental literature regarding pigments and maxillofa- exposure to evaluate maxillofacial materials.
cial materials, although there are several articles on the Craig et al.14 later tested the color stability of a non-
application of internal and external color to prosthe- pigmented polyvinyl chloride (Prototype III, Sartomer
ses.7-11 The purpose of this review of the current den- Industries, Essington, Pa.), a polyurethane (Epithane,
tal literature and art textbooks on materials is to stimu- Daro Products, Butler, Wis.), and 4 silicones (Silastic
382, Silastic 399, Silastic 44210, Silastic 44515, Dow
aAssistant Professor, Department of Prosthodontics. Corning, Midland, Mich.). Before and after accelerated
bAssociate Professor, Department of Prosthodontics. aging (Model 25WR, Atlas Electric Devices), all mate-

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GARY AND SMITH THE JOURNAL OF PROSTHETIC DENTISTRY

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

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Table I. Partial list of pigments used in maxillofacial prosthetics

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

Ivory black Pigment black 9 (PBk9) I Inorganic synthetic C.xCaPO4

77267 Carbon black Calcined animal bones
Cobalt blue Pigment blue 28 (PB28) I Inorganic synthetic CoAl2O4
77346 Mixed metal oxide Calcined cobalt oxide/aluminum oxide
Raw sienna Pigment brown 7 (PBr7) I Inorganic Fe2O3
77491 or 77492 Iron oxide Ferric oxide produced from ores
Burnt sienna Pigment brown 7 (PBr7) I Inorganic Fe2O3
77491 or 77492 Iron oxide Calcined ferric oxide
Raw umber Pigment brown 7 (PBr7) I Inorganic Fe2O3⋅xMnO2
77491 or 77492 Iron oxide Ferric oxide with manganese
Burnt umber Pigment brown 7 (PBr7) I Inorganic Fe2O3⋅xMnO2
77491 or 77492 Iron oxide Calcined ferric oxide with manganese
Green earth Pigment green 23 (PG23) I Inorganic
77009 Ferrous silicates, aluminum, and magnesium
Alizarin crimson Pigment Red 83 (PR83) III Organic synthetic C14H8O4
58000.1 Anthraquinone Calcium salt of anthraquinone dye
Cobalt yellow Pigment yellow 40 (PY40) II Inorganic synthetic CoK3N6O12
77357 Potassium nitrite/cobalt salt solutions
Mars violet Pigment red 101 (PR101) I Inorganic synthetic Fe2O3
77491 Iron oxide Ferric oxide produced chemically
Cadmium-barium Pigment red 108:1 (PR108.1) I Inorganic synthetic CdS⋅xCdSe⋅yBaSo4
red (medium) 77202.1 Cadmium Cadmium seleno-sulfide precipitate w/BaSO4
Titanium white Pigment white 6 (PW6) I Inorganic synthetic TiO2
77891 Opaque white Titanium dioxide with zinc oxide
Yellow ochre Pigment yellow 43 (PY43) I Inorganic Fe2O3⋅H2O
77492 Colored oxide of iron Hydrated ferric oxide from limonite ore

are almost pure, simple compounds. Other pigments tional information provided in a list of ASTM-approved
are of a high purity, but contain minor elements either pigments are lightfastness category, chemical type and
as natural impurities or as a result of ingredients added class, chemical formula and description, vehicle com-
during manufacturing to modify the color. For exam- patibility, toxicity, common names, and representative
ple, raw sienna is a native clay that contains iron oxide; spectral curves.
the composition of raw umber is similar to raw sienna Mayer22 stated that pigments can be classified
but it contains manganese. according to their color and origin. Pigments are nor-
Mayer22 stated that the nomenclature of pigments mally classified according to their major component
can be confusing. A single color can be known by many element. The term “organic” can be applied to pig-
names or 2 entirely different colors can be known by ments of an animal, vegetable, or synthetic origin.
the same name. Titanium white can be known as tita- Organic pigments are those that are carbon hydrogen
nium dioxide, anatase, or rutile. A system of color derivatives. Inorganic pigments are not formed from
names is needed to eliminate the confusion of the vari- carbon and hydrogen; they contain metal atoms. The
ous color names that appear in research. A list of pig- term inorganic can be applied to pigments of mineral
ments has been developed according to the color index origin. Inorganic pigments can be native earths (ochre,
names by the ASTM.22,23 The ASTM created standards raw umber), calcined native earths (burnt umber, burnt
intended to identify materials and their degree of puri- sienna) or synthetic origin (cadmium yellow, zinc
ty and permanence. This list can correspond to outdat- oxide).
ed color names and common names for ASTM One can infer that organic pigments have a limited
approved pigments. life span and are more subject to decay on aging and
The pigments that have been approved by the exposure to adverse environmental conditions. This
ASTM are followed by an abbreviation of the color view may have some merit. From a list22 of 109 ASTM-
index name and number. In Table I, the common name approved pigments, 46 pigments have an inorganic ori-
of a pigment, raw umber, is followed by the color index gin. From that list of inorganic pigments, 45 pigments
name and number, Pigment Brown 7 or PBr 7. Addi- have an ASTM lightfastness category of I and 1 pig-

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GARY AND SMITH THE JOURNAL OF PROSTHETIC DENTISTRY

ment (pigment yellow 40 or cobalt yellow) has a light- In the ASTM test method in which the specimen is
fastness category of II. The remaining 63 pigments exposed to simulated daylight (fluorescent lamb light),
have an organic origin. From those 63 pigments, 48 the specimen should be placed 3 inches from the plane
pigments have a lightfastness category of I, 11 have a of the lamps. Unless otherwise specified, the specimen
lightfastness category of II, and 4 have a lightfastness should be exposed to a cycle of 8 hours light followed
category of III (pigment green 8 or Hooker’s green, by 4 hours dark until the specimen has been exposed to
pigment red 17 or naphthol red, pigment red 83 or a total radiant dose of 1260 MJ/m2. The ambient
alizarin crimson, and pigment red 146 or naphthol room temperature should be maintained at 24° ± 3°C.
carmine FBB). Lightfastness is described as the ability This test method takes approximately 9 months to
of a material to withstand color change on exposure to complete.26
light.24 In the ASTM test method in which the specimen is
The majority of the respondents from a survey by exposed to simulated daylight (xenon-arc type), this
Andres et al.25 used RTV silicone elastomers in facial can be accomplished with a weathering chamber. The
prostheses. Silicones as a class of materials are transpar- test specimens should be exposed continuously to a
ent to UV radiation and are highly permeable to mois- total radiant dose of 1260 MJ/m2. Relative humidity
ture vapor and many gases verses organic elastomers. in the test chamber should be 55% ± 5% and a black
Any pigment that is sensitive to this type of exposure panel temperature of 63° ± 2°C.29
would degrade regardless of whether they were incor- There can be variations in the test results from dif-
porated into the silicone or applied to the exterior sur- ferences in pigment manufactured from time to time
face. (Written communication: Schoenherr WJ, within a company, different varieties of a pigment from
Healthcare Industries, Dow Corning Corp., November company to company, specimen preparation, different
18, 1996.) instruments and instrumental readings, variations in
Mayer22 stated that the fading of a pigment or dye the surface of the specimen, and the conditions of
on exposure to daylight is not an evanescence, or the exposure. Allowance for these variables is made by
disappearance of the substance itself into thin air, but is requiring more than 1 test and by establishing light-
actually the result of a chemical change. The UV wave- fastness categories that include a range of color differ-
lengths in the light react with the pigment or trigger a ences.26 In the L*a*b* system, a ∆E of 1 is considered
reaction, sometimes with the combination of air and or visually detectable.18
moisture. The pigments change to a colorless or less The interpretation of the results are placed in the
highly colored compound. following categories:
Pigments are tested for resistance to fading by sub- Lightfastness I—pigments that exhibit a mean color
jecting them to concentrated UV light with a laborato- change of 4 or less ∆E*ab.
ry apparatus, whereby the effect of months of exposure Lightfastness II—pigments that exhibit a mean color
to direct sunlight is duplicated in a relatively short time. change of more than 4.0 but not more than 8.0 ∆E*ab.
Much of the research conducted to date has involved Lightfastness III—pigments that exhibit a mean
the use of weathering chambers. The ASTM has devel- color change of more than 8.0 but not more than 16.0.
oped standard test methods for determining the light- Lightfastness IV—pigments that exhibit a mean
fastness of pigments used in artists’ paints.26 The tests color change of more than 16.0 but not more than
consist of exposing the pigment used in artists’ paints 24.0.
to light (natural sunlight or simulated sunlight) filtered Lightfastness V—pigments that exhibit a mean color
through glass. change of more than 24.24
To evaluate the lightfastness of pigments, ASTM
CONCLUSIONS
uses 3 test methods that involve exposure of the pig-
ment under glass to the sun, exposure to irradiance From the literature review, it was deduced that
from artificial daylight fluorescent lamps, and exposure RTV silicone elastomers and pigments do exhibit a
to a xenon-arc lightfastness apparatus. Lightfastness color change and that a color change is to be expect-
categories for pigments are assigned values based on ed. Internal pigments may result in less loss of color,
the color difference units calculated by the CIE 1976 because there would be less chance that the pigments
L*a*b* color difference equation.27 would be dissolved during cleaning the prosthesis.
In the ASTM test method, in which the specimen is Research may need to be directed toward minimizing
exposed to the sun, it is recommended that the speci- the degree of color change. The possibility of using
men has an exposure angle of 45 degrees to the verti- UV absorbers may be a partial solution regarding pig-
cal for a total radiation dose of 1260 MJ/m2. For tests ment stability of facial prostheses. Besides applying
in southern Florida below 27 degrees latitude, the UV protection internally to the silicone prosthesis,
exposed pigments should be tested during the months external protection from a spray with a UV inhibitor
of October through May.28 should be investigated.

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THE JOURNAL OF PROSTHETIC DENTISTRY GARY AND SMITH

In the meantime, patients must be instructed thor- 14. Craig RG, Koran A, Yu R, Spencer J. Color stability of elastomers for max-
illofacial appliances. J Dent Res 1978;57:866-71.
oughly on the care of their facial prostheses to prolong 15. Chu CC, Fischer TE. Evaluation of sunlight stability of polyurethane elas-
the longevity of the prosthesis. Patients should be tomers for maxillofacial use. I. J Biomed Mater Res 1978;12:347-59.
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tomer for maxillofacial appliances. J Dent Res 1979;58:1450-4.
and to use brimmed hats and sunglasses. They should 17. Turner GE, Fischer TE, Castleberry DJ, Lemons JE. Intrinsic color of
avoid using cosmetics on the prosthesis; even if a water- isophorone polyurethane for maxillofacial prosthetics. Part II: color sta-
based makeup is used, the repeated washing may dis- bility. J Prosthet Dent 1984;51:673-5.
18. Haug SP, Andres CJ, Munoz CA, Bernal G. Effects of environmental fac-
solve and remove some pigments on the external sur- tors on maxillofacial elastomers: part IV– optical properties. J Prosthet
face. Patients should not use any solvents such as iso- Dent 1992;68:820-3.
propyl alcohol to clean the prosthesis, which could 19. Beatty MW, Mahanna GK, Dick K, Jia W. Color changes in dry-pigment-
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cause dissolution of the pigments. Patients should thet Dent 1995;74:493-8.
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21. Lemon JC, Chambers MS, Jacobsen ML, Powers JM. Color stability of
thesis has been specified in the literature.30 Explicit facial prostheses. J Prosthet Dent 1995;74:613-8.
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23. Standard specification for artists’ oil, resin-oil, and alkyd paints. (ASTM
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Materials.
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305. 0022-3913/98/$5.00 + 0. 10/1/91415

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