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Diffuse reflection FTIR spectral database of dyes and pigments

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Anal Bioanal Chem (2006) 386:2183–2191
DOI 10.1007/s00216-006-0865-8
ORIGINAL PAPER
Diffuse reflection FTIR spectral database
of dyes and pigments
Carlos Eduardo Silva & Luciana P. Silva &
Howell G. M. Edwards & Luiz Fernando C. de Oliveira
Received: 13 June 2006 / Revised: 12 September 2006 / Accepted: 15 September 2006 / Published online: 7 November 2006
# Springer-Verlag 2006
Abstract 24 pigments commonly used in art have been
characterized by diffuse reflection infrared spectroscopy
(DR). All of the compounds have also been characterized
by means of infrared absorption spectroscopy to demon-
strate the reliability of the DR technique. This is the first
record of the use of this technique as an analytical tool in
conservation science, and the results appear to be promising
for the identification of unknown pigments used on
historical and artwork artifacts. Although the DR technique
used here is not nondestructive, it can still be usefully
applied to the analysis of artwork since it requires only a
very small quantity of sample for analysis.
Keywords Pigments . DR spectra . Infrared spectra
Introduction
The identification of pigments and dyes is one of the most
important targets aimed for in the scientific examination of
paintings, textiles, illuminated manuscripts and other
historic and archaeological materials. Several analytical
techniques have been used for this purpose, for example gas
chromatography/mass spectrometry [1], UV–visible spec-
C. E. Silva : L. P. Silva : L. F. C. de Oliveira (*)
Núcleo de Espectroscopia e Estrutura Molecular,
Departamento de Química, Instituto de Ciências Exatas,
Universidade Federal de Juiz de Fora,
Juiz de Fora, MG 36036-900, Brazil
e-mail: luiz.oliveira@ufjf.edu.br
H. G. M. Edwards
Chemical and Forensic Sciences, School of Pharmacy,
University of Bradford,
Bradford, West Yorkshire BD7 1DP, UK
trophotometry [2], thin-layer chromatography [3, 4], high-
performance liquid chromatography [5–7], reversed phase
liquid chromatography and capillary electrophoresis with
electrospray mass spectrometric detection [8, 9], FT–IR
spectroscopy [10, 11] and Raman spectroscopy [12–17].
The problem with most analytical techniques is that they
necessitate sample destruction during analysis; however,
several have the advantage of also being quantitative.
Molecular vibrational spectroscopy offers the possibility
of both qualitative and quantitative analysis; furthermore,
Raman spectroscopy is now being advocated as the
technique of choice, since it does not destroy the specimen
and Raman spectra also cover a wide range of wave-
numbers, so that both organic and inorganic components in
heterogeneous samples can be detected [18]; this is
particularly valuable for the identification of mineral pig-
ments alone or in admixture, since metal oxide or sulfide
vibrational modes generally occur below 400 cm−1. An
increasing number of applications of Raman spectroscopy
to art work characterization have been described in recent
years, and some of these have described databases of
Raman spectra of pigments and dyes [19–21]. However, on
occasion the acquisition of Raman spectra from pigments or
dyes in art work specimens has been compromised by
significant fluorescence emission, which swamps the
Raman spectral signatures; this emission can arise from
organic binders, resins and varnishes associated with
mineral pigments or, in the case of organic dyestuffs, from
the presence of functional groups with low-lying electronic
states. In these cases, the analytical provision of a
complementary technique such as infrared spectroscopy is
desirable; however, unless an FTIR microscope is used for
the analysis, the preparation of specimens for infrared
transmission analysis requires the consumption of the
2184
sample, which makes the technique difficult to apply when
only very small amounts or none of the sample can be
consumed.
Diffuse reflection infrared spectroscopy (DR) is a very
rapid and powerful alternative infrared vibrational technique
which can be applied to the analysis of solid samples in most
situations, and is especially appropriate for powders. The
standard problem with infrared spectroscopy—the limitated
wavenumber range—still applies, and the presence of
hydroxyl groups can be expected to interfere with the
analytical capabilities of the method, especially in the low
wavenumber region. However, the advantage that vibra-
tional information can be accessed which may not otherwise
be available from highly fluorescent specimens that do not
prove to be tractable for Raman spectroscopic analysis
means that the technique deserves further investigation. One
relatively common effect in DR spectra are the so-called
reststrahlen bands [22] caused by specular reflection, which
depend on the particle size and on sample packing and
concentration; this effect is enhanced significantly with
strongly absorbing samples, and the most intense vibra-
tional bands can exhibit bandshape distortion and wave-
number shift.
In this work we report on the DR spectra of a range of 24
different dyes and pigments commonly used in painting and
art work, and for comparison we also describe the infrared
absorption spectra of each sample. The main purpose of this
study is to provide a preliminary database of DR spectra
from which the potential for applications can be assessed,
and to inform the selection of several suitable test cases for
future work to demonstrate the viability of the technique for
problem specimens in the art analysis field.
Experimental
All samples have commercial provenance, from Kremer
Pigments (Aichstetten, Germany; all samples excluding
sample 23) or BASF (Ludwigshafen, Germany; sample 23).
DR spectra were obtained using a Bomem MB102 FT-IR
spectrometer (ABB, Zurich, Switzerland) with a diffuse
reflection attachment from Spectra-Tech, Inc. (Shelton, CT,
USA) in the range between 4000 and 400 cm−1, at a spectral
resolution of 4 cm−1 with an average of 128 spectral scans
accumulated; KBr powder (Aldrich, St. Louis, MO, USA)
was used as both a diluent and for the background spectra.
All samples were dispersed in KBr at ratios of between 5 and
10%, using the 3 mm microsample cup (supporting around
15 mg of KBr), which requires about 1–2 mg of sample;
each sample was ground together with the appropriate
quantity of KBr in the same way for both techniques (DR
and transmission spectra). In this respect, it would be
incorrect to term the DR technique as being nondestructive
Anal Bioanal Chem (2006) 386:2183–2191
in terms of the sample; however, the actual consumption of
specimen is small, and is comparable with GCMS, for
example. For comparison purposes, the conventional infrared
absorption spectra from the materials in the KBr pellet were
also obtained for all samples, using the same experimental
conditions (4 cm−1 spectral resolution and 128 scans).
Several of these absorption spectra were later observed to
have baseline problems; see for instance the spectra depicted
in Figs. 1 and 3. This observation can be understood in terms
of the sample characteristics, since several of the oxide
specimens in particular have a wide range of particle sizes,
so they scatter the infrared radiation instead of absorbing it.
This problem can be solved making use of the DR accessory,
as can be seen in Figs. 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13,
14, 15, 16, 17, 18, 19, 20, 21, 22, 23 and 24, present units of
transmittance in the left axis and Kubelka-Munk units at the
right axis for the diffuse reflection spectra.
Results and discussion
A total of 24 pigments were investigated by means of diffuse
reflection infrared spectroscopy, and the absorption infrared
spectra from these pigments were also obtained for compar-
ison purposes. All spectra are depicted from Figs. 1, 2, 3, 4, 5,
6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23
and 24, and are divided up by colour: Figs. 1, 2, 3, 4, 5 and 6
comprise blue pigments, Figs. 7, 8, 9, 10, 11 and 12 are green
pigments, Figs. 13, 14, 15 and 16 are yellow pigments,
Figs. 17 and 18 are orange and red pigments, Figs. 19 and 20
are violet pigments, and Figs. 21, 22, 23 and 24 are white
pigments. The main vibrational wavenumbers observed in all
of these spectra are described in Tables 1, 2, 3, 4, 5 and 6,
together with some comments on the molecular formulae of
the specimens and their origin or use.
In practice, it proved very difficult to obtain the DR
spectra of some pigments; for instance the oxides, where
Fig. 1 Transmittance (upper) and diffuse reflection infrared (DR,„
lower) spectra of cerulean blue (sample 1)
Fig. 2 Transmittance (upper) and diffuse reflection infrared (DR, lower)
spectra of ultramarine blue (sample 2)
Fig. 3 Transmittance (upper) and diffuse reflection infrared (DR,
lower) spectra of cyan blue (sample 3)
Fig. 4 Transmittance (upper) and diffuse reflection infrared (DR,
lower) spectra of azurite (sample 4)
Fig. 5 Transmittance (upper) and diffuse reflection infrared (DR,
lower) spectra of Prussian blue (sample 5)
Fig. 6 Transmittance (upper) and diffuse reflection infrared (DR,
lower) spectra of phtalocyanin blue (sample 6)
Fig. 7 Transmittance (upper) and diffuse reflection infrared (DR,
lower) spectra of green malachite (sample 7)
Fig. 8 Transmittance (upper) and diffuse reflection infrared (DR,
lower) spectra of dark green (sample 8)
Anal Bioanal Chem (2006) 386:2183–2191 2185
2186
some of the most prominent vibrational bands are expected
below 400 cm−1, which is the lower optical limit of the
instrument and is a limit also imposed by the use of KBr as
the dispersion matrix component. However, in most cases
the direct comparison of DR with the absorption spectra
shows the potential of the technique, since in most of the
cases very high quality DR spectra were obtained.
Figure 1 depicts the DR spectrum of cerulean blue, a
mixture of cobalt and tin oxides; vibrational bands can be
seen at 649, 591, 533 and 449 cm−1. Blue ultramarine
pigment (Fig. 2) shows very specific vibrational bands that
can be used as markers related to the silicate group. The
observed band at 1010 cm−1 is assigned to the (Si–O–Si)
antisymmetric stretching mode, whereas the band at
449 cm−1 is related to the (O–Si–O) deformation mode
[23, 24]. Azurite (Fig. 4) presents one band at 3618 cm−1,
which can be assigned to the O–H stretching mode, and
bands at 1435 and 874 cm−1 that can be assigned to
carbonate stretching [2], whereas Prussian blue (Fig. 5)
presents one band at 2085 cm−1 that is very characteristic of
CN stretching [25]; two other important vibrational modes
can also be observed at 591 and 501 cm−1 (medium and
strong intensities, respectively), assigned to MC stretching
and MCN deformation [26]. Figure 6 presents the DR
spectrum of phthalocyanin blue, an organic pigment with
several characteristic bands in the 1500–1000 cm−1 range.
It is worthy of mention here that some bands assigned to
the presence of hydroxyl and water molecules in the
structure of the pigment can be affected in terms of the
wavenumber positions of the DR bands, as in the case of
the azurite DR spectra (Fig. 4). As pointed out by Weckler
and Lutz [27], the presence of different quantities of KBr
can induce a shift of more than 20 cm−1 in the case of
several iron hydroxides investigated by those authors.
Another interesting feature in the DR spectrum of sample
4 is the presence of a strong bands at 1032, 1011 and
909 cm−1, which, together with the bands in the hydroxyl
region, could indicate the presence of kaolinite or a related
material in the chemical composition of azurite. Kaolinite
shows bands at 910, 1000 and 1024 cm−1, and the last two
bands are of high intensity [28]. However, azurite is a very
well-known mineral, and the presence of kaolinite as a
whitening agent in the mixtures of pigments cannot be
ruled out.
The use of a spectral library database for the identifica-
tion of pigments and dyes has a problem in that the
common name of the pigment is not sufficient to specify
the specimen composition, as described in several articles
in the literature [19, 20]. In this sense, the nomenclature of
some of the samples analyzed here, for instance the organic
pigment cyan blue (Fig. 3), seems to be related only to the
colour of the specimen, and not to a specific chemical
composition; our spectroscopic analysis shows that this
Anal Bioanal Chem (2006) 386:2183–2191
Fig. 9 Transmittance (upper) and diffuse reflection infrared (DR, lower)„
spectra of viridian (sample 9)
Fig. 10 Transmittance (upper) and diffuse reflection infrared (DR, lower)
spectra of emerald green (sample 10)
Fig. 11 Transmittance (upper) and diffuse reflection infrared (DR, lower)
spectra of verdigris (sample 11)
Fig. 12 Transmittance (upper) and diffuse reflection infrared (DR, lower)
spectra of phtalocyanin green (sample 12)
Fig. 13 Transmittance (upper) and diffuse reflection infrared (DR, lower)
spectra of Naples yellow (sample 13)
Fig. 14 Transmittance (upper) and diffuse reflection infrared (DR, lower)
spectra of yellow iron oxide (sample 14)
Fig. 15 Transmittance (upper) and diffuse reflection infrared (DR, lower)
spectra of goethite (sample 15)
Fig. 16 Transmittance (upper) and diffuse reflection infrared (DR, lower)
spectra of yellow avane (sample 16)
pigment has almost identical bands to those observed in the
DR spectrum of cerulean blue, which is a mixture of cobalt
and tin oxides. Clearly, the labelling of some pigments in
current use has no relation at all to their chemical
composition.
The green pigment called malachite (Fig. 7) shows bands
at 3412 and 3328 cm−1 assigned to O–H stretching; the
most prominent bands at 1508 and 1396 cm−1 can be
assigned to the antisymmetric CO32 stretching modes,
whereas the band at 1100 cm−1 can be assigned to the
symmetric carbonate mode. In the dark green pigment
spectrum (Fig. 8), a band at 2029 cm−1 can be observed,
which is assigned to CN stretching, whereas bands at 894
and 797 cm−1 are assigned to the vibrational modes of
goethite. With these bands present in the green dark
pigment, it can be concluded this pigment is a synthetic
composite of a mixture of Prussian blue, goethite and
carbonate. Figure 9 shows the spectrum of viridian green, a
hydrated chromium(III) oxide, with no Raman signal
obtained previously; the DR spectrum presents several
bands, and the prominent features are those at 565 and
488 cm−1. However, the presence of vibrational bands in
the 3000 cm−1 region, as well bands in the 1300–
1000 cm−1 region, is an indication of organic components
or functionality present in the pigment mixture. Figure 10
displays the DR spectrum of emerald green, which is a
inorganic pigment described by Burgio and Clark [19] as
copper(II) acetate/tri-copper(II) arsenate, with no detectable
Raman signal when excited using the near-infrared
1064 nm laser line. The DR spectrum obtained shows only
two bands, at 604 and 432 cm−1, very characteristic of
metal oxides. Comparison with the mineralogical literature
reveals that emerald green is also the common name for
beryl, whose general formula is Be3Al2(SiO3)6; the result
presented here indicates that the sample labelled as emerald
green is actually an alumino-silicate species. Verdigris
pigment (Fig. 11) presents bands at 1602 and 1441 cm−1
that are related to the symmetric and antisymmetric (COO−)
stretching modes [23] of a carboxylate ion. Figure 12
Anal Bioanal Chem (2006) 386:2183–2191 2187
2188 Anal Bioanal Chem (2006) 386:2183–2191
 Anal Bioanal Chem (2006) 386:2183–2191 2189

ƒFig. 17 Transmittance (upper) and diffuse reflection
lower) spectra of cadmium orange (sample 17)
Fig. 18 Transmittance (upper) and diffuse reflection
lower) spectra of red iron oxide (sample 18)
Fig. 19 Transmittance (upper) and diffuse reflection
lower) spectra of cobalt violet (sample 19)
Fig. 20 Transmittance (upper) and diffuse reflection
lower) spectra of cobalt violet light (sample 20)
Fig. 21 Transmittance (upper) and diffuse reflection
lower) spectra of titanium dioxide (sample 21)
Fig. 22 Transmittance (upper) and diffuse reflection
lower) spectra of zinc white (sample 22)
Fig. 23 Transmittance (upper) and diffuse reflection
lower) spectra of titanium white (sample 23)
Fig. 24 Transmittance (upper) and diffuse reflection
lower) spectra of talc (sample 24)
infrared (DR, shows the DR spectrum of phthalocyanin green, with
several bands in the region between 1600 and 1000 cm−1
infrared (DR, characteristic of the organic aromatic group.
DR spectra from yellow pigments can be seen in
infrared (DR,
Figs. 13, 14, 15 and 16. Figure 13 shows the spectrum of
infrared (DR, Naples yellow, a mixed oxide of lead and antimony, with
characteristic bands in the wavenumber region below
infrared (DR, 700 cm−1. Figures 14 and 15 show the spectra of two iron
oxide samples, one named yellow iron oxide and the other
infrared (DR, goethite. Clearly, both spectra are very similar in intensity
and band wavenumber, especially with regards to the major
infrared (DR, features at 900 and 797 cm−1, suggesting strongly that the
yellow iron oxide sample is actually goethite; the small
infrared (DR,
wavenumber shifts observed in both spectra can be
explained in terms of the environmental effects of water
molecules present in the specimens. Figure 16 presents the

Table 1 Blue pigments

Pigment Molecular Vibrational wavenumbers (cm−1) General comments Figure

formula

Cerulean CoO.n SnO2 649 m; 591 s; 533 s; 449 s Synthesized 1860 1

blue
Ultramarine Na8 1010 vs; 694 w; 668 w; 578 vw; 449 vs Mineral: lapis lazuli; XIth 2
blue [Al6Si6O24]Sn century; synthesized 1828
Cyan blue Probably 674 s; 591 s; 481 s; 425 s 3
CoO.SnO2
Azurite 2CuCO3. 3695 m; 3618 m; 1435 m; 1106 m; 1029 vs; 1010 vs; Mineral: azurite , Middle Ages; 4
Cu(OH)2 913 s; 874 m; 533 vs; 468 vs; 424 vs synthesized XIX century
Prussian blue Fe4 [Fe(CN)6]3. 2085 vs; 971 vw; 816 w; 591 m; 501 s Oldest synthetic pigment: 5
14–16 H2O year 1704
Phtalocyanin Cu(C32H16N8) 1499 w; 1415 w; 1338 m; 1287 m; 1166 w; 1120 m; Synthesized 1933 6
blue 1090 m; 1067 w; 900 w; 877 vw; 778 w; 748 w; 730 vs

Table 2 Green pigments

Pigment Molecular formula Vibrational wavenumbers (cm−1) General comments Figure

Green CuCO3.Cu(OH)2 3412 s; 3328 ms; 1635 w; 1508 s; 1431 sh; 1396 vs; 1100 w; Mineral malachite; 7
malachite 1052 m; 883 wm; 820 m; 752 wm; 580 w; 525 wm; 506 w ancient pigment;
synthetic; XVIIIth
century
Dark green Fe4 [Fe(CN) 6]3 . 3399 m; 3135 m; 2029 s; 1615vw; 1422 m; Synthetic; 1850 8
14–16 H2O + 1100 vs; 894 m; 797 m; 662 vw; 623 w
α −FeO.OH
Viridian Cr2O3.2H2O 3109 m; 2819 m; 1248 vw; 1286 w; 1061 w; Synthetic; 1838 9
790 w; 629 m; 565 vs; 488 vs
Emerald Be3Al2 (SiO3)6 604 s; 432 s Synthetic; 1814 10
green
Verdigris Cu(CH3COO) 2.Cu(OH) 2 3470 w; 3373 w; 3270 w; 1602 vs; 1441 vs; 1351 vw; Synthetic; XIXth 11
1048 vw; 1022 vw; 694 s; 623 m; 530 w century
Phtalocyanin Cu(C32H1–2Cl14–15N8) 1562 w; 1499 vw; 1392 s; 1305 vs; 1321 m; 1278 s; Synthetic; 1933 12
green 1211 vs; 1153vs; 1095 m; 948 m; 778 w; 749 w; 510 w
2190 Anal Bioanal Chem (2006) 386:2183–2191

Table 3 Yellow pigments Table 5 Violet pigments

Pigment Molecular Vibrational General Figure Pigment Molecular Vibrational General Figure
formula wavenumbers comments formula wavenumbers comments
(cm−1) (cm−1)

Naples Pb2Sb2O7 674 s; 527 s; Synthetic; 13 Cobalt Co3 3450 w; 1042 s; Synthetic; 19
yellow 410 s XVIIth violet (PO4)2 984 m; 849 w; 1859
century 597 m; 565 m
Yellow FeO.OH 900 s; 797 s; Mineral 14 Cobalt Co3 1147 m; 1102 s; Synthetic; 20
iron 617 m; 655 m; violet (AsO4)2 1061 s; 978 s; 1859
oxide 426 vs; 413 vs light 580 m; 548 m;
Goethite α-FeO. 894 s; 790 s; Mineral 15 517 m; 472 m
OH 623 m; 662 m;
457 vs; 418 vs
Yellow SiO4 + 3620 w; 1101 s; Mineral 16
avane α-FeO. 1032 vs; 913 w;
The DR spectra of white pigments can be seen in
OH 800 vw; 534 m; Figs. 21, 22, 23 and 24. Figure 21 shows the spectrum of
471 s; 424 m titanium dioxide; the strong bands at 674 and 452 cm−1 are
very characteristic of rutile. The DR band at 1422 may refer
to a carbonate stretching mode, suggesting that the
spectrum of yellow avane, with a very strong band at specimen is a mixture of carbonate and TiO2. However,
1032 cm−1 related to (Si–O–Si) antisymmetric stretching the type of carbonate cannot be described exactly, due to
and another band at 913 cm−1 assigned to the symmetric the small spectral differences between the different types of
stretching mode; the band at 800 cm−1 is assignable to inorganic natural carbonates, calcite or aragonite. Figure 22
goethite, which leads to the conclusion that this pigment is presents the spectrum for zinc white, and the most
a really a mixture of silicate and α-FeO.OH. prominent bands are related to the zinc oxide species.
In Fig. 17 the DR spectrum of cadmium orange, the Figure 23 refers to the DR spectrum of titanium white, a
common name of CdS (cadmium sulfide), can be seen. The common name for titanium dioxide. Several pigment
most intense band at 1106 cm−1 can be assigned to sulfate dealers present titanium white as pure titanium dioxide,
stretching; suggesting that the pigment has suffered however, some of them present as a mixture involving other
oxidation or has been diluted with sulfate ion. Red iron components. In the case of sample 23, the spectrum shows
oxide (Fig. 18) presents bands at 572 and 475 cm−1, clearly the presence of the main vibrational bands of
characteristic of the mineral haematite [29, 30]. This titanium dioxide, but the presence of a very intense band
spectrum is similar to the one discussed by Weckler and in the region of C–H stretching suggest the presence of
Lutz [27] for the δ FeO(OH) polymorph, where the use of
the DR technique was able to discriminate several different
iron hydroxide polymorphs. Figures 19 and 20 present the Table 6 White pigments
spectra from cobalt violet and cobalt violet light, the
inorganic cobalt salts of phosphate and arsenate, respec- Pigment Molecular Vibrational General Figure
formula wavenumbers comments
tively. From the DR spectra it is possible to discriminate
(cm−1)
between these two cobalt pigments, since the presence of
the characteristic bands of phosphate or arsenate are very Titanium TiO2 3431 w; 1628 vw; Synthetic; 21
clear in the spectra. dioxide 1422 w; 122 9w; 1918
1074 w; 674 s;
552 s; 421 m
Zinc ZnO 501 s; 475 s; 450 s Mineral 22
Table 4 Red and orange pigments
white and
Pigment Molecular Vibrational General Figure synthetic
formula wavenumbers comments Titanium TiO2 2923 vs; 2845 s; Synthetic 23
(cm−1) white 1531 vs; 1461 m;
1402 m; 739 vs;
Cadmium CdS 1106 vs; 990 vw; Synthetic 17 713 vs; 681 s;
orange 900 w; 816 vw; 552 s
636 w; 617 w Talc Mg3Si4O10 1119 w; 1055 vs; Mineral 24
Red iron Fe2O3 572 s; 475 m; Mineral 18 (OH)2 945 m; 739 w;
oxide 443 m 533 vs; 415 vs
Anal Bioanal Chem (2006) 386:2183–2191
organic compounds in the mixture. Other bands observed in
the spectrum can also be assigned to the presence of
organic compounds, mainly elastomer, since titanium white
is also the common name for the pigment base often used in
the paint industry. In talc (Fig. 24), the observed bands at
1055 and 945 cm−1 are very characteristic of symmetric and
antisymmetric (Si–O–Si) stretching modes, obviously
referring to a silicate material. The natural mineral talc
with the general formula Mg3Si4O10(OH)2 contains a
silicate group, thus strongly suggesting that sample 24
really is composed of the mineral talc. However, talc is a
very common generic designation, and the DR spectra do
not permit us to describe this sample in any more detail
without performing a more extensive study.
Conclusions
DR spectra of 24 common pigments have been recorded in the
range 4000–400 cm−1. Most of the main bands of the
pigments could be identified, mainly the ones below
1000 cm−1 in the case of inorganic compounds. Another
great advantage of the method that should be highlighted is
the baseline quality of the DR spectra from the oxides, since
the infrared spectra obtained for most of them were very
affected by particle size, and the absorption of infrared light
is dependent on the wavenumber, however, as can be seen in
Figs. 1 and 3, the DR spectra do not show this effect.
This is the first attempt to use the technique as a tool in
conservation science, and the results seem to be promising
for the identification of unknown pigments used on
historical and art work artifacts. Although the DR technique
used in this report is not nondestructive, it is a very low
impact method since only a very small quantity of sample is
needed. Several works have been performed that have used
the Raman effect as a tool for the identification and
characterization of pigments, and this is a nondestructive
technique; however, laboratories around the world do not
always have the equipment or lasers to prevent fluorescence
effects from occurring during the analysis. Therefore, the
complementary and combined use of Raman and DR could
lead to more detailed analyses of such samples.
Acknowledgments The authors are grateful to CNPq and FAPE-
MIG for financial support and to Mrs. Yara Ligia Mello Moreira
Petrella from Museu Paulista of the Universidade de São Paulo for
supplying the samples.
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2191
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