SPECTROCHIMICA

ACTA
PART A
Spectrochimica Acta Part A 53 (1997) 2159-2179
Raman spectroscopic library of natural and synthetic pigments
(P
re- N 1850 AD)
Ian M. Bell, Robin J.H. Clark *, Peter J. Gibbs
Christopher Ingold Laboratories, UniversitJj College London, 20 Gordon Street, London WClH OAJ, UK
Received 24 April 1997; accepted 24 May 1997
Abstract
To assist in the greatly increasing number of applications of Raman microscopy as a tool for non-intrusive, in situ
archaeometric analysis, the Raman spectra of over 60 pigments, both natural and synthetic, known to have been in
use before - 1850 AD, have been studied by Raman microscopy. Fifty-six pigments have yielded high quality spectra
which have been arranged, by colour, into a spectroscopic library for reference purposes. The spectroscopic files may
be downloaded from http://www.ucl.ac.uk/chem/resources/raman/s~clib.html 0 1997 Elsevier Science B.V.
Keywords: Raman microscopy; Pigment; Dye; Archaeometry; Conservation science
1. Introduction
Raman microscopy is now established as the
analytical technique which is the most specific,
sensitive, spatially refined and immune to interfer-
ence for the in situ, non-intrusive analysis of
historical artefacts [l]. Interest in its use for ar-
chaeometric analysis has increased very signifi-
cantly over the last 5 years. With the recent
development of robust, compact Raman micro-
scopes, such as the Renishaw Ramascope and the
Dilor Labram systems, involving notch filters,
air-cooled lasers and charge coupled device
(CCD) detectors, the accessibility of the technique
to conservation scientists has increased greatly.
Although it is possible to envisage many areas
* Corresponding author.
of conservation science where the technique of
Raman microscopy may be of use (for example,
the study of paint binders and extenders or of
degradation and corrosion products) research to
date has concentrated on the identification and
study of pigments used on illuminated manu-
scripts [ l-101 and ceramics [ 1 1 - 131. The examina-
tion of pigments will continue to be an important
application of this technique, and it is for this
reason that a spectroscopic library has been com-
piled. The library, which consists of the spectra
obtained by Raman microscopy of pigments ar-
ranged by colour, will allow easy identification of
any pigment on a historical sample. It contains as
many common pigments [14-181, both mineral
and synthetic, as it was possible to obtain, al-
though the authors welcome suggestions for possi-
ble future additions. The library has been
restricted to pigments in use before the isolation,
1386-1425/97/$17.00 0 1997 Elsevier Science B.V. All rights reserved.
PIIS1386-1425(97)00140-6
by Perkin (1856 AD), of the first synthetic organic
dye, mauveine [19,20]; since then, many hundreds
of pigments and dyes, principally organic, have
been synthesized. By limiting the library to pig-
ments in use before b 1850 AD, a database of the
Raman spectra of < 70 pigments is sufficient as a
reference for thousands of years of pigment use.
2. Experimental
The Raman microscopes used in this study are
two modern instruments of the type that will be
of most use to conservation scientists. The first
was a Dilor Labram, supplied generously by In-
struments SA (UK) and configured with an inter-
nal Olympus BX-40 confocal microscope, an
air-cooled Instruments SA 20 mW helium-neon
laser light source (632.8 nm), and an air-cooled
CCD detector operating at - 70 C. The second
was a Renishaw Raman System 1000, supplied
generously by Renishaw PLC, configured with an
external Olympus BH-2 confocal microscope, an
air-cooled Spectraphysics 21 mW argon-ion laser
light source (514.5 nm), and an air-cooled CCD
detector operating at - 70 C. With both instru-
ments, neutral density filters were used to set the
laser power at the sample surface to a value
between 0.5 and 6.0 mW.
Each instrument is fitted with a notch filter
assembly to remove light at the excitation fre-
quency with the consequence that little spectro-
scopic information could be obtained from either
within 100 cm- of the laser line. The notch
filters also affect significantly the spectral response
of each instrument between 100-200 cm - from
the excitation line; as a consequence, the Raman
bands in this region appear less intense than they
At wavenumbers greater than 200 cm - i from the laser line
the spectral response functions of these instruments are domi-
nated by the grating and CCD efficiencies, In the region
200--3000 cm - the spectral response of the Renishaw Ra-
mascope (514.5 nm excitation) was found to increase, almost
linearly. by a factor of approximately two. Over the same
range, the measured spectral response of the Dilor Labram
(632.8 nm excitation) varies by approximately 25%, showing
maxima at 1000 and 2700 cm - and a minimum at 2100
cm-
1800 1600 1400 1200 1000 800
Wavenumber I cm
Fig. 1. Ivory black, 1, = 632.8 nm, 6 mW.
1800 1600 1400 1200 1000 800
Wavenumber I cm
Fig. 2. Lamp black, 1, = 632.8 nm, 6 mW.
1600 1350 1100 850 600 350 100
Wavonumber / cm-
Fig. 3. Azurite, A0 = 514.5 nm, 2 mW.
I.M. Bell et al. /Spectrochimica Acta Part A 53 (1997) 2159-2179 2161
800 700 600 500 400
Wavenumber I cm
300 200
Fig. 4. Cerulean blue, R, = 514.5 mu, 4 mW. Fig. 7. Lazurite, A,, = 514.5 nm, 4 mW
600 500 400 300 200 100
Wavenumber I cm-
Fig. 5. Cobalt blue, 1, = 514.5 nm, 4 mW.
1100 900 700 500 300 100
Wavenumber I cm-'
1300 1100 900 700 500 300 100
Wavenumber I cm"
1100 900 700 500
Wavenumber I cm-'
300 100
Fig. 8. Posnjakite, 1, = 632.8 mu, 3 mW.
f
2100 1700 1300 900 500 100
Wavenumber I cm"
Fig. 6. Egyptian blue, 1, = 514.5 nm, 4 mW. Fig. 9. Prussian blue, A, = 514.5 nm, 2 mW.
I.M. Bell et ui. : Spertrochin~iea Acta Part A 53 (1997) 2159-2179
900 700 500 300 100
800 700 600 500 400 300 200
Wavenumber / cm-
Wavenumber! cm-
Fig. 10. Smalt, /i,, = 514.5 nm, 2 mW.
Fig. 13. Cobalt green, %, = 514.5 nm, 4 mW.
c
1
1100 900 700 500 300 100
Wavenumber I cm
3100 2350 1600 850 100
Wavenumber I cm-
Fig. 11. Atacamite*, 1, = 514.5 nm, 4 mW.
F ig. 14. Emerald green*, lo = 514.5 nm, 0.5 mW
500 400 300
Wavenumber I cm
1500 1300 1100 900 700 500 300 100
Wavenumber I cm
Fig. 12. Chromium(II1) oxide, R. = 514.5 nm, 4 mW. Fig. 15. Malachite, 1, = 514 nm, 1 mW.
I.M. Bell et al. /Spectrochimica Acta Part A 53 (1997) 2159-2179 2163
900 700 500 300 100
Wavenumber I cm
3600 3100 2600 2100 1600 1100 600 100
Wavenumber I cm-
Fig. 16. Scheeles green, 1, = 514.5 nm, 2 mW. Fig. 19. Verdigris (l), A,, = 514.5 nm, 1 mW.
1100 900 700 500 300
Wavenumber I cm-
Fig. 17. Terre verte, 1, = 514.5 nm, 1 mW.
3600 3100 2600 2100 1600 1100 600 100
Wavenumber I cm-
3600 3100 2600 2100 1600 1100 600 100
Wavenumber I cm
Fig. 20. Verdigris (2), ,I0 = 514.5 nm. 1 mW.
600 500 400 300
Wavenumber I cm
200 100
Fig. 18. Raw verdigris, A0 = 514.5 nm, 1 mW.
Fig. 21. Viridian, 1, = 514.5 nm, 4 mW.
2164 I.M. Bell et rd. !Spectrochimica Acta Parr A 53 (1997) 2159-2179
600 500 400 300
Wavenumber I cm-
200
Fig. 22. Mars orange, & = 632.8 nm, 3 mW
400 300 200 100
Wavenumber I cm
1500 1300 1100
Wavenumber I cm
900
Fig. 23. Litharge, 1, = 632.8 nm, 6 mW.
Fig. 25. Purpurin*, 1, = 632.8 nm, 1.5 mW
400 300 200
Wavenumber I cm
100
Fig. 26. Realgar, 1, = 632.8 mn, 0.6 mW.
700 600 500 400 300 200 100
Wavenumber I cm
500 400 300 200 100
Wavenumber / cm-
Fig. 24. Mars red, &, = 632.8 nm, 3 mW. Fig. 27. Red ochre, /2, = 632.8 mn, 3 mW.
I.M. Bell et al. /Spectrochimiea Acta Part A 53 (1997) 2159-2179 2165
600 500 400 300
Wavenumber I cm
200 100
Fig. 28. Red lead, 1, = 632.8 nm, 3 mW. Fig. 31. Bone white, A0 = 514.5 nm, 4 mW
T
z
.Z
r
2
E
400 300 200
Wavenumber I cm-
100 900 700 500
Wavenumber I cm-
Fig. 29. Vermilion, A,, = 632.8 mn, 6 mW Fig. 32. Chalk, 1, = 514.5 nm, 4 mW.
900 700 500 300
Wavenumber I cm
Fig. 30. Barytes, 1, = 514.5 nm, 4 mW. Fig. 33. Gypsum, 1, = 514.5 nm, 4 mW
4
1200 1000 600 600 400
Wavenumber I cm
T
5
.%
f
5
900 700 500
Wavenumber I cm
I.&f. Bell et ul. 1 Spectrorhin~ica .4cta Part A 53 (1997) 21.59-2179
T
5
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f
E
1100 900 700 500 300 100
Wavenumber / cm-
Fig. 34. Lithopone, 1, = 514.5 nm, 4 mW.
1200 1000 800 600 400
Wavenumber I cm-
Fig. 35. Lead white, 1, = 514.5 nm, 4 mW. Fig. 38. Berberine*, 1, = 632.8 nm, 3 mW
600 500 400 300 200
Wavenumber I cm-
II
J,k ,
900 700 500 300 100
Wavenumber I cm-
Fig. 37. Barium yellow, 1, = 514.5, 4 mW.
1800 1600 1400 1200 1000
Wavenumber I cm
500 400 300
Wavenumber J cm-
Fig. 36. Zinc white, A0 = 514.5 nm, 4 mW. Fig. 39. Cadmium yellow*, A,, = 514.5 nm, 4 mW
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I.M. Bell et al. /Spectrochimica Acta Part A 53 (1997) 2159-2179 3169
would using, for example, a triple grating spec-
trometer. However, the spectra have not been
corrected for the spectral response of the instru-
ments as it is anticipated that this spectroscopic
library will be of use principally to conservation
scientists using this new generation of Raman
microscope, all of which use notch filters, and the
spectra obtained here are illustrative of the spec-
tra to be expected from such an instrument.
References have been included if the Raman
spectrum of a particular pigment has previously
been studied in detail and the bands assigned.
Wavenumber I cm-
Fig. 52. Pararealgar, 632.8 nm, 1.5 mW.
Wavenumber calibration was achieved by su-
perposition of neon emission lines on the spec-
trum recorded for each pigment (in the case of
excitation at 514.5, the 546.1 nm mercury emis-
2000 1800 1600 1400 1200 1000
Wavenumber I cm
Fig. 53. Saffron*, 1, = 514.5 nm, 1 mW.
900 700 500 300 100
Wavenumber I cm
E Gg. 55. Yellow ochre, A, = 632.8 nm, 1.5 mW.
Wavenumber I cm-
700 500 300 100
Wavenumber I cm-
Fig. 54. Strontium yellow, i., = 514.5 nm, 4 mW. Fig. 56. Zinc yellow, 1, = 632.8 nm, 6 mW.
Table I
Black pigments
Name Composition Band wavenumbers (crn~~ ) Excitation
and relative intensiti& wavelength
(nm)
Notes and date
Ivory black Carbon 961 m ( = \,,(a,) PO:-); 632.8 Antiquity. Also contains cal- I
- 1325 vs(br): - 1580 vs(br) cium phosphate
Lamp black Carbon - 1325 vs(br); - 1580 vs(br) 632.8 Antiquity 2
_.
a Approximate centres of broad bands in the laser fluorescence spectrum.
b s, strong; m, medium; v. very; br, broad.
The pigment is either specified to be a mineral or the date of its first manufacture is listed.
sion line was also used). Following routine cali-
bration of each instrument, linear interpolation
was found to be adequate, and gave a typical
root-mean-square deviation of 0.3 cm - for the
fitted neon lines. After the corrected Raman
wavenumbers were rounded to integers, and al-
lowing for regions of the spectrum in which cali-
bration lines are sparse, it is expected that all
quoted wavenumbers are accurate to -t 1 cm- r.
Exceptions to this level of accuracy occur in the
case of bands described as broad (br) or shoulders
(sh) in the peak tables.
Data were collected via a PC, and the spectra
analyzed and the peak positions picked using the
GRAMS/32 software package. The baseline of
eight spectra, principally those of the organic
pigments, were corrected and these are indicated
by an asterisk (*) after the pigment name in the
figure caption.
The pigments used were genuine artists pig-
ments from Winsor and Newton, Cornelissen, and
Kremer. Most were purchased from the specialist
pigment suppliers L. Cornelissen and A.P. Fitz-
patrick (both London, UK) and some were do-
nated by the National Gallery, London and the
British Museum Department of Scientific Re-
search.
3. Results and discussion
A total of 64 pigments were studied using 514.5 First, the common name of a pigment may not
and 632.8 nm laser excitation lines. High quality be sufficient to specify the composition or struc-
Raman spectra were obtained for 56 of the pig- ture. The term chalk, for example, is interpreted
ments, with only eight of those selected failing to
give an adequate spectrum with either of the
excitation lines. The spectra obtained are illus-
trated in Figs. l-56 and are arranged by pigment
colour: Figs. 1 and 2, black; Figs. 3- 10, blue;
Figs. 11-21, green; Fig. 22, orange; Figs. 23-29,
red; Figs. 30-36, white; and Figs. 37-56, yellow.
The calibrated wavenumbers (Raman shift-cm - )
and relative intensities (uncorrected for spectral
response) are listed in Tables l-7. Those pig-
ments that failed to give adequate Raman spectra
with the excitation lines and instrumentation de-
scribed are listed in Table 8; some of these, nota-
bly the fluorescent pigments/dyes, are known to
give Raman spectra by FT-NIR Raman spec-
troscopy (2, = 1064 nm). The tables are arranged
alphabetically by pigment colour (Table 1, black;
Table 2, blue; Table 3, green; Table 4, orange;
Table 5, red; Table 6, white; and Table 7, yellow),
and they also indicate the laser excitation wave-
length used, whether the pigment is a mineral or,
if synthetic, the date of its earliest known use, and
references to its Raman spectrum if the bands
have been assigned in the literature [Zl-431.
The spectroscopic library is intended to allow
rapid identification of a pigment; however, there
are a number of factors that may result in spectra
obtained from a historical artefact, and even from
a standard pigment of different origin, differing
somewhat from those of the standard samples
reported here.
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I

I.M. Bell et al. /Spectrochimica Acta Part A 53 (1997) 2159-2179
2173
Table 4
Orange pigment
Name Composition Band wavenumbers (cm-) and
relative intensities
Excitation
wavelength
(nm)
Notes and date Spectrum illus-
trated in figure
Mars orange Synthetic iron(II1) 224 vs; 291 vs; 407 m; 494 w; 608 632.8 Middle 19th C 22
oxide, FezOX m
as being calcium carbonate; however, there are
five known polymorphs of calcium carbonate:
aragonite, vaterite and three forms of calcite [21].
In each case the principal band of interest arises
from v,(a;) CO:-: for calcite, as studied here, this
band is at 1088 cm- (see Fig. 32 and Table 7),
but for aragonite it has been reported to occur at
1085 cm- * [21]. There is little chance of such a
small variation causing confusion with other car-
bonates, such as basic lead(I1) carbonate (lead
white-2PbC0,. Pb(OH),) for which vl(aJ CO: -
is at approximately 1050 cm- , but careful cali-
bration will be required to determine the exact
identity of any polymorph of chalk. For the
same reason, the spectra of only three types of
verdigris have been illustrated (Figs. 18-20) al-
though this pigment occurs in many possible hy-
drated and basic forms, each of which will have a
different Raman spectrum.
Second, the degree of hydration of a pigment
will also affect the wavenumbers of the Raman
bands. For example, the well known mineral gyp-
sum is a dihydrate, CaS0,.2H20, for which vl(al)
SO:- is approximately 1007 cm- (see Fig. 33
and Table 7); however, the important rock-form-
ing mineral anhydrite (CaSO,) is often found with
gypsum, and a study of the Raman spectrum of
the former has shown that the band attributed to
the vibration v,(a,) SO:- is at approximately
1016 cm- [22].
Third, the earth pigments, such as red earth
(Fig. 27 and Table 5) and green earth (terre
verte-Fig. 17 and Table 3) encompass pigments
from many possible sources, obtained, as their
names suggest, from the soil. Red earths have the
same chromophore, iron(II1) oxide (Fe,O,), which
has a characteristic spectrum (Fig. 27). However,
due to the source of the pigment, it is not incon-
ceivable that a particular red earth may contain
components that result in the Raman spectrum
differing slightly from that illustrated here. This is
especially likely for green earths (Fig. 17) since
these are complex pigments of general formula
K[(Al, Fe)(Fe, Mg)], (AlSi,, Si4)010(OH)2.
Finally, it is often possible to purchase pig-
ments, especially the more modern ones, in vari-
ous shades. The colour of a pigment arises as a
consequence of absorption (via. ligand-field.
charge-transfer, or intervalence charge-transfer
bands) and specular reflectance, and it is affected
by the absorption coefficient and band width of
electronic bands in the visible region [3]. The
colour of a pigment can be modified by mixing
with another lighter or darker pigment, or by
alteration of the particle size, as is well known for
CuSO,. 5H,O, since this affects the relative im-
portance of diffuse and specular reflectance
[23,24]. In certain cases, however, different shades
of a pigment have significantly different Raman
spectra. To illustrate this, the Raman spectra of
three shades of chrome yellow (lead(I1) chromate,
PbCrO,) have been included here: chrome yellow
(Fig. 40), chrome yellow deep (dark yellow--Fig.
41) and chrome yellow-orange (Fig. 42). The Ra-
man spectra of chrome yellow (Fig. 40) and
chrome yellow deep (Fig. 41) are very similar, but
the wavenumber of the strongest band [$!,(a,)
CrOz -1 shifts from 841 cm - for the standard
yellow, to 838 cm- for the deeper shade; that of
chrome yellow-orange is significantly different
from the others, and the wavenumber of the
strongest band shifts to 828 cm - . In this case,
the depth of colour is dependent on the propor-
tion of PbO present with PbCrO, in the lattice,
and this affects both the wavenumber and the
shape of the Raman bands. Comparison with a
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I.M. Bell et al. /Spectrochimica Acta Part A 53 (2997) 2359-2179
217X
Table 8
I.M. Bell et 01. Spectrochivlicrr Actu Part A 53 (1997) 2159%.?I 79
Pigments with no detectable Raman signal using either 514.5 or 632.8 nm excitation
Colour Name Composition Notes, date and literature references
Black Magnetite Iron(H) di-iron(III) oxide. Fe,O, Mineral. Transforms rapidly to Fe,O, in the laser beam 1371.
[431
Mars black Synthetic iron(I1) di-iron(II1) Middle 19h C. Transforms rapidly to Fe,O, in the laser beam
oxide, Fe,O,
[421, [431
Blue Indigo Indigotin. C,,H,,N,O, Plant leaf (BC)
Brown Van Dyck brown Humic acids, allomelanins Lignite containing iron (16th C?)
Purple Tyrian purple 6,6-dibromo-indigotin Marine mollusc (1400 BC)
Cd-IdrJW2
Red Carmine Carminic acid, C22HZ,,0,3 Scale insect, cochineal (Aztec)
kermesic acid, Ci6Hi00s Scale insect, kermes (antiquity)
Alizarin
CJW4
Secondary component (after purpurin) of the madder root dye
(3000 BC)
Yellow Quercitron
CdboO,~
A flavonoid dye from the inner bark of the Quercus oak
(antiquity)
a The pigment is either specified to be a mineral or the estimated date of its first use is listed.
study of the similar MnO; ion [25], indicates
that the presence of PbO increases the lattice
size, which reduces the constraints on the CrO$ -
ion and results in a lower wavenumber for its
v,(a,) mode.
This library is comprehensive, encompassing
all common pigments in use pre- - 1850 AD, but
it is not exhaustive: as mentioned above there are
many types of red and green earths that could
have been examined individually, different poly-
morphs of pigments that could have been in-
cluded, and many shades of the more modern
pigments that could have been studied. However,
the extra space required to illustrate the Raman
spectra of these many possible inclusions is not
justifiable as the spectra would differ only
slightly, if at all, from those included in this
work.
4. Conclusions
The Raman spectra of 56 common pigments in
use before - 1850 AD have been recorded by
Raman microscopy and compiled into a spectro-
scopic library. The library will enable conserva-
tion scientists rapidly to identify unknown
pigments on historical artefacts.
Acknowledgements
We are indebted to the Leverhulme Trust for
the award of a fellowship (PJG), to the EPSRC
and ULIRS for financial support, to Instruments
SA (UK) Ltd. for the loan of the Dilor Labram,
to Renishaw PLC for the loan of the Renishaw
Raman System 1000, and to the National Gallery,
the British Museum Scientific Research Depart-
ment, and A.P. Fitzpatrick for the donation of
pigments.
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