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Invited Paper

Mid-infrared hyperspectral imaging of painting materials


Francesca Rosi*a,b, Roland Harigc, Costanza Miliania,b, Ren Braunc, Diego Salid, Alessia Daverie,
Brunetto G. Brunettia,b, Antonio Sgamellottia,b
a
CNR-ISTM c/o Chemistry Department, Via Elce di sotto, 9 Perugia 06123 (Italy)
b
SMAArt Chemistry Department University of Perugia, Via Elce di sotto, 9 Perugia 06123 (Italy)
c
Bruker Optik GmbH, Rudolf-Plank-Strae 27 76275 Ettlingen (Germany)
d
Bruker Italia S.r.l. uni personale, Viale Vincenzo Lancetti 43 20158 Milan (Italy)
e
Associazione laboratorio di Diagnostica per i Beni Culturali, Piazza Campello 2, 06049 Spoleto
Perugia (Italy)
*Francesca.rosi@cnr.it; phone/fax 0039 075 5855638

ABSTRACT

A novel hyperspectral imaging system (HI90, Bruker Optics), working in the mid-infrared range and recently developed
for the remote identification and mapping of hazardous compounds, has here been optimized for investigating painting
surfaces. The painting Sestante 10 (1982) by Alberto Burri has been spectrally and spatially investigated with the HI90
system revealing the distribution of inorganic materials constituting the artworks. In order to validate the results
obtainable by the imager for the pigment identification previous tests on laboratory models were performed. Yellow,
white and blue pigments painted with different binders (namely egg, alkyd, acrylic and vinyl) were investigated by the
HI90. Afterwards, the polychrome painting Sestante 10 was investigated focusing the attention on the inorganic material
distribution revealing the presence of different extenders (kaolin, BaSO4, CaSO4) mixed with the various silica-based
pigments present in the painting. The brightness temperature spectra collected by HI90 have also been compared to
single point reflection spectra acquired by a conventional portable FTIR spectrometer (Alpha-R by Bruker Optics)
highlighting the good spectral quality of the imaging system. This comparison permitted also to evaluate the spectral
response and the diagnostic strengths of the spectral range available by the HI90 imaging (1300-860 cm-1), validating the
reliability of the obtained chemical images. This study clearly highlights the high potential of the new hyperspectral
imaging system and opens up new perspectives in the current scientific interest devoted to the application of mapping
and imaging methods for the study of painting surfaces.

Keywords: mid-FTIR, pigments, hyperspectral imaging, non invasive methods, portable techniques, pigments

1. INTRODUCTION
Imaging techniques have been widely applied in the cultural heritage science offering an alternative view of the artwork
through the visualization of underlying or surface layers otherwise not perceptible to the naked eye. They were employed
to art objects since the 20s when E.W. Forbes for the first time experimented the X-ray radiography to see and image
through the paintings revealing inner structures, metal elements and materials with different compositions. Since then,
many improvements have been made in the imaging technologies evolving from the concept of basic imaging towards
the necessity of correlating the images with the material characterization achievable through the modern spectral, multi
and hyperspectral imaging systems.
At this regard, the research trend turned towards the exploitation of the different spectral ranges and the optimization of
the spectral resolution in terms of number of acquirable bands/spectra to increase the specificity of the imaging
technique. As an example, the use of a portable scanning macro X-ray fluorescence system recently allowed for imaging
not only the elemental pigment distribution but to reveal the artists modus operandi visualizing changes made during the
painting creation and in some cases discovering hidden paintings from later overpainting1. Molecular imaging
investigations in the visible (VIS: 400-750 nm) and near infrared (NIR: 750-2500 nm) ranges have been exploited for the
pigment characterization and localization investigating both the electronic levels and the combination and overtone
vibrational modes of the infrared range2. More recently, Delaney et al.3 demonstrated the effectiveness of a spectral

Optics for Arts, Architecture, and Archaeology IV, edited by Luca Pezzati,
Piotr Targowski, Proc. of SPIE Vol. 8790, 87900Q 2013 SPIE
CCC code: 0277-786X/13/$18 doi: 10.1117/12.2020477

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imaging system which working in the 1000-2500 nm (10000-4000 cm-1) range with a spectral resolution of 4.4 nm
consents the visualization of the combination and overtone vibrational modes for the characterization and localization of
organic materials.
From a diagnostic point of view the mid-infrared range, investigating the vibrational energies, provides for a detailed
study of the materials assessing their molecular composition and thus the identification. Although later with respect to
other non-invasive and portable techniques, point reflection mid-FTIR spectroscopy has been proved to be a valuable
tool for both pigments, binders, and surface contaminants identification in complex and heterogeneous paint matrices4-8.
In the specific case of pigment identification, successful results have been obtained on case studies ranging from wall
paintings to manuscripts and from ancient to modern art9-10. Despite these positive results, the use of the mid-FTIR as
imaging technique for spatially resolved spectral information is until now only explored in a single case study recently
published11 and focused on the binder identification and localization on a painting surface.
This paper proves the feasibility of stand-off mid-FTIR hyperspectral imaging to investigate both spatially and spectrally
the pigment composition on the surface of artworks. The chosen measurement set-up combines the use of the
hyperspectral imager HI90, developed for the remote identification and mapping of hazardous compounds12-13, with an
infrared radiation source. As the signals are small the use of a highly sensitive measuring device is crucial. The chosen
hyperspectral imager HI9014-15 combines a plane mirror interferometer with a detector array thus providing both the
highest throughput of radiation and high spatial resolution at the same time. The design of the actively aligned plane
mirror interferometer allows an extremely high signal-to-noise ratio that is essential for this measurement technique.
The opportunity to have access to a modern painting by Alberto Burri, Sestante 10, allowed us to test and evaluate the
performances, both in terms of spectral quality, diagnostic strengths, imaging power as well as portability and in situ
accessibility, of the HI90 device for the pigment identification and localization.
In order to train the non invasive and in situ imaging measurements, previous tests have been carried out with the same
set up on a laboratory model simulating a modern painting. Several imaging experiments have been conducted in the
different pigments evaluating their identification opportunity varying the nature of the binding medium.

2. EXPERIMENTAL
2.1 Mid-Infrared Hyperspectral Imager
The hyperspectral imager HI90 is based on the combination of a Michelson interferometer with a focal plane array (FPA)
MCT detector. The plane mirror interferometer is actively aligned. The maximum lateral resolution is 256x256 pixels
and cooling is performed by a Stirling cooler. The configuration applied in this study operates in the spectral range 1300-
860 cm-1. A spectral resolution of 4 cm-1 and a lateral resolution of 128x128 pixels were chosen. The hyperspectral
imager measures the emitted and reflected radiation of the painting from a distance of app. 1 m. The field of view of each
pixel is 0.69 mrad, investigating a total area of 8.8x8.8 cm2. The data acquisition time for 32 scans with these parameters
is app. 80 s. The radiometric calibration is automatically performed by an internal active calibration system. This enables
the calculation of brightness temperature (K) spectra. The measurements are performed illuminating the sample with an
infrared radiation source. The source is controlled via USB allowing the user to control the radiant power. To minimize
the exposure time of the analyzed painting, the source is equipped with an iris shutter which opens only during the data
acquisition. During the data acquisition time of c. 80s the measured heating of the painting surface was 4-5 C.
The user can choose between various forms of displaying the measurement results. Among others there is the display of
the measured brightness temperature at a chosen frequency or the difference between the brightness temperatures at two
different frequencies. Furthermore the correlation between the measured spectra and reference data and the results of the
automatic identification routines can be displayed. In this work, the hyperspectral images were processed using a linear
filter with a Gau kernel of 3x3 pixels with a width of 3 pixels14.
The HI90 has overall dimensions of 550x455x210 mm, and a mass of 33 kg. The device is mounted on a tripod and can
be positioned with a motorized and automatically controlled pan-tilt head. In figure 1 the HI90 system is reported
working on the Burris painting Sestante 10 during the in situ measurements at the Ex-Seccatoi del Tabacco (Perugia,
Italy).

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11

Figure 1. Picture of the HI90 imaging device and Alpha-R portable spectrometer working in situ on the Burris painting Sestante 10 at
the Ex-Seccatori del Tabacco (Perugia, Italy).
2.2 Portable Alpha-R spectrometer
The portable infrared spectrophotometer ALPHA-R Bruker Optics is equipped with a Globar radiation source, a
modified Michelson interferometer to work in all spatial conditions (RockSolidTM) and a DLaTGS detector. The working
optical layout for reflection measurements is 22/22. Its weight is about 7 kg and its dimensions are 20x30x12 cm3. 200
interferograms in the spectral range 7500-375 cm-1 with a spectral resolution of 2 cm-1 were acquired. The sampling area
was 28 mm2. Reflection spectra were directly compared with the brightness temperature spectra collected by the HI90. A
background correction using a reference spectrum from a gold flat mirror was applied for representing the reflectance
profile (R) expressed in the graphs as pseudo absorbance, log (1/R).

2.3 Laboratory model

For the preparation of the laboratory model a cotton canvas primed with calcium carbonate and an acrylic medium has
been purchased by Zecchi. Different pigments in combination with four organic binders (whole egg, acrylic resin -CTS,
vinyl resin- CTS and alkyd resin- Gamblin) have been painted in separate square sectors (ca. 2x2 cm2). Three different
types of yellow, white and blue pigments have been considered on the basis of their infrared vibrational properties and
their occurrence on work of arts. The following pigments have been applied: lead chromate (Sigma-Aldrich), yellow
ochre (Zecchi) and PY173 (Kremer) for the yellow sectors, barium white (Zecchi), gypsum (Carlo Erba) and lead white
(Sigma Aldrich) as white pigments and ultramarine blue (Zecchi), azurite (Zecchi) and phtalocyanine blue (Kremer) as
the blue ones.

3. RESULTS
3.1 Laboratory models
Figure 2a depicts the mid-FTIR spectra recorded by the portable mid-FTIR spectrometer Alpha-R from the yellow, white
and blue pigments painted with egg tempera in the laboratory model. The spectral range achievable by this device (7000-
400 cm-1) allows the visualization of both the fundamental, combination, and overtone modes of the investigated
pigments9. The non invasive identification of the painting materials by single point infrared reflection spectroscopy is
generally achieved by combining all these spectral data observable in the wide range4,10.
In figure 2a, the black rectangle highlights the spectral range accessible by the HI90 imaging device, namely 1300-860
cm-1. In this range, most of investigated pigments show a number of infrared bands, some of which are very intense as

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the strong reststrahlen 3 modes of sulfate in barium white and gypsum (w1 and w2)9,16 or of the chromate moiety in
yellow lead chromate17 (y1). Inverted reststrahlen bands are also observed for the silicate-containing pigments for which
is possible to clearly identify the presence of kaolin due to the typical shape of the a (Si-O) appearing as a doublet9 in
the yellow ochre (y2) and absent in ultramarine blue (b1) where the silicate component shows a broad inverted band at
about 1000 cm-1. Other pigments show weaker absorptions in this spectral range, like the derivative-shaped bands of the
organic yellow PY173 and phtalocyanine blue (y3 and b3). Also the carbonate-based pigments (azurite and lead white)
show in the range 1300-800 cm-1 derivative bands associated with the 1 (CO3-2) (w3 and b2)9.
In order to test the feasibility of the hyperspectral imaging system to identify and visualize different pigments,
measurements have been carried out on the different pigment-binder combinations of the laboratory model. In the part b
of figure 2, the spectra recorded by the Alpha-R (shown in reflection mode without any background correction), are
compared with the brightness temperature profiles acquired by the imaging HI90 system. The similarity of the profiles
clearly underlines the good spectral quality of the data acquired by the hyperspectral imager.

a) yellow

y2
uh
y1
m

wightness t :emperatun
!.
(1 /R)

uopo: Tg
;.,,

5000 4000 3000 2000 1000 1200 1050 900


wavenumber/cm' wavenumber/cm'
Figure 2. a) infrared reflection spectra acquired by the Alpha-R system in the entire accessible spectral range from the yellow (y1-lead
chromate, y2-ochre, y3-PY173), white (w1-barium white, w2-gypsum, w3-lead white) and blue (b1-ultramarine, b2-azurite, b3-
phtalocyanine) pigments painted with egg (the rectangle highlight the portion of the range available by the HI90). b) Comparison of
the spectral profiles obtained by the HI90 (thick lines) and the Alpha-R system (thin lines) for the yellow, white and blue pigments of
the laboratory model.
In figure 3, the visible photo (a) is compared with the corresponding brightness temperature difference images (figure
3b-d) measured for different spectral ranges on the basis of the profiles recorded by the HI90. The distribution of lead
chromate is clearly visualized in the sectors painted with egg, acrylic and vinyl binders considering difference between
the average brightness temperature in the range 1225 and 1098 cm-1 and the average brightness temperature between 925
and 950 cm-1 (figure 3f). The contrast of the reflected radiation is due to the strong band of the chromate antisymmetric
stretching at about 930 cm-1 17. In the same range, the brightness temperature profile does not show higher variability thus
not permitting the imaging of lead chromate when mixed with the alkyd resin (figure 3e,f, profile Y1d). The ochre
pigments, as discussed before, contains kaolin which causes the contrast of the brightness temperature (figure 3c) in the
sectors painted with egg, acryl and vinyl binders. In fact, the false color image (figure 3c) shows the difference between
the average of brightness temperature between 1025 and 1040 cm-1 and the average brightness temperature between 1045
and 1050 cm-1, thus including the kaolin Si-O stretching signal at 1030 cm-1 (figure 3g). Once again, the pigment painted
with alkyd is not detected and localized by the HI90.
In figure 3c, it can be noted that in the sectors painted with a vinyl binder and the three different yellow pigments (figure
3f sectors Y1c, Y2c, Y3c), the spectral range selected to image the distribution of yellow ochre is not specific as a weak

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brightness difference is measurable also in the sector containing lead chromate (Y1c) and the organic yellow (Y3c). This
is due to the fact that the vinyl binder presents a derivative bands at about 1020 cm-1 that is overlapping with the kaolin
signals and it is weakly contributing to the contrast of the brightness temperature. The detection of the organic yellow
PY173 resulted unsatisfactory for all the binders, some efforts have been made by considering the weak derivative band
at about 1300 cm-1 (figure 2a, line y3 marked with an arrow, figure 3h) but low brightness temperature variations have
been recorded resulting in a poor contrasted false color image (figure 3d). In addition, the selected peak is too much
close to the margin of the achievable range and above 1300 cm-1 the humidity signals start appearing and covering those
of the sample. The impossibility to detect none of the yellow pigments in the sectors with the alkyd medium (last row of
the model, figure 3e) may be related to a not optimal arrangement of the device with respect to the painting model, either
in term of illumination or detection set up. This consideration is supported by the fact that the brightness temperature
profiles in correspondence of the yellow alkyd-treated sectors (excluding the previous discussed organic yellow) show a
low variation not in agreement with the strong signals arising from both lead chromate and ochre that should be
highlighted in the spectral profile similarly to what observed with the other binder-treated sectors (figure 3 f-g).

a) b) c) d)

o 7 o 1.8 o i

g) h)

Via Y2a Y3a

Y1b Y2b Y3b

Y3c

Y1c Y2c Y3c


.Y Yld Y3d

Yid II'2c II''3d 1200 900 1200 900 1200 900

wavenumber/cm1 wavenumber/cm-' wavenumber/cm'

Figure 3. a) Visible image of the laboratory model in correspondence of the yellow pigments (imaged area dimensions ca. 12x6 cm2).
False color representation of the difference between: b) the mean brightness temperature (K) between 1225 and 1098 cm-1 and the
mean brightness temperature (K) between 925 and 950 cm-1, c) the mean brightness temperature (K) between 1025 and 1040 cm-1 and
the mean brightness temperature (K) between 1045 and 1050 cm-1, d) the mean brightness temperature (K) between 1303 and 1306
cm-1 and the mean brightness temperature (K) between 1309 and 1312 cm-1, e) representation of the model, labels indicate the pigment
and binder combination. Brightness temperature profiles from f) lead chromate, g) ochre, h) PY173; (the rectangle highlights the
spectral region considered for calculating the mean brightness temperature difference).
Figure 4b-d reports the chemical images representing the distribution of the white pigments (namely barium sulfate,
gypsum and lead white) mixed with the different binders in comparison with the corresponding visible photo of the
laboratory model (figure 4a). For sake of clarity, the brightness temperature spectra for each sector are also presented
(figure 4 f-h). Regarding the detection of BaSO4, it resulted reliably distributed (figure 4b) when considering the

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brightness temperature difference in range corresponding to the strong antisymmetric stretching at about 1070 cm-1
(figure 4f). However, the resulting false color image (figure 4b) indicates the presence of some barium white also on the
border of the lead white sector. This false positive result is due to the alkyd medium, which having bands in the range
selected to image barium sulfate (figure 4h line W3d), contributes to some extent to the image contrast. The color
representation of the brightness temperature difference in the range 1045 and 1165 cm-1 visualizes the CaSO4 in the
gypsum-painted sectors (figure 4c, 4g), regardless to the binder, whose spectral features are covered. The contrast in the
brightness temperature spectrum is related by the 3(SO4-2) band. The color representation of gypsum highlights the
detection of the Ca-sulphate pigment also in one of the lead white sectors (figure 4c). In this case, the false positive peak
is generated by the acrylic medium (see figure 4 h, profile W3b) which contributes to the selected spectral range for the
gypsum detection. The evident bands in the range 11501176 cm-1 due to CC(=O)O asymmetric stretching of the
acrylic18 are masked by the strong sulfate bands in gypsum (figure 4g) but not in the lead white sector thus contributing
to the image contrast.The white lead carbonate compound shows the comparatively weak 1 (CO3-2) mode at about 1050
cm-1 9. Although this signal is rather small its sharp change in the brightness temperature profile allows the correct
visualization of lead white in the sectors treated with egg, acrylic and vinyl binders (figure 4d, h). No spectral features
are observed for the alkyd medium sector.

a) b) c) d)

e)

W1a W2a W3a


I

L6

g)
S

h)
0
w2a-7/
ro Wla vv-'
W1b W2b W3b
W24
W lb

W1c W2c W3c w. W2

Wia W21

W1d W2d II W3d


1200 900 1200 900 900
wavenumber/cm ' wavenumber/cm l wavenumber/cm I

Figure 4. a) Visible image of the laboratory model in correspondence of the white pigments (imaged area dimensions ca. 12 x 6 cm2).
False color representation of the difference between: b) the brightness temperature (K) at 1065 cm-1 and the mean brightness
temperature (K) between 1035 and 1110 cm-1, c) the mean brightness temperature (K) between 1045 and 1165 cm-1 and the mean
brightness temperature (K) between 1056 and 1070 cm-1, d) the brightness temperature (K) at 1360 cm-1 and the brightness
temperature (K) at 870 cm-1, e) representation of the model, labels indicate the pigment and binder combination. Brightness
temperature profiles from f) barium white, g) gypsum, h) lead white; (the rectangle highlights spectral region considered for
calculating the mean brightness temperature difference).
The case study related to blue pigments revealed positive results for the identification and localization of ultramarine
blue whilst not reliable data have been recorded for azurite and phtalocyanine blue. In figure 5a and b the visible and the

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brightness temperature images for the blue sectors are reported. The silicate-base blue pigment is localized in the
ultramarine-treated sectors by considering the brightness temperature difference in correspondence of the a (Si-O) of
ultramarine at about 1000 cm-1 (figure 5 c). No evident signals of the different binders are present in this range allowing
a consistent imaging of the blue pigment. Differently for both azurite and phtalocyanine blue the absence of vibrational
patterns in the range achieved by the HI90 does not allow for any pigment discrimination. The temperature brightness
profiles of the two blues mainly show the signals related to the organic binders (figure 5 e-f, asterisks)

a) b C

MIR III
MEIN
MUM o 2
1200
wavenumber/cm-1
900

d) e)

b2a
B1a 1 B2:31 F31111

61b12b 63b1
I _J
Bic] 62c B3-c ,
-.MN I.-

b3d
b2d
63d
B1dir62d
l J 1200
wavenumber/cm-I
900 1200
wavenumber/cm-I
900

Figure 5. a) Visible image of the laboratory model in correspondence of the blue pigments (imaged area dimensions ca. 12 x 6 cm2)
false color representation of the difference between the brightness temperature (K) at 975 cm-1 and the brightness temperature (K) at
1050 cm-1, c) brightness temperature profiles from ultramarine blue (the rectangle highlights the limits considered for calculating the
mean brightness temperature difference), d) representation of the model, labels indicate the pigment and binder combination.
Brightness temperature profiles from e) azurite and f) phtalocyanine blue. Asterisks indicate the spectral features of the acrylic-b,
vinyl-c and alkyd-d binders.

3.2 In situ hyperspectral mid-FTIR imaging of Sestante 10


Non invasive and in situ measurements by the HI90 have been carried out from an area of dimension c. 9 x 9cm2 of the
painting Sestante 10 with the aim to spatially and spectrally detect the inorganic components. In figure 6a the visible
image of the investigated portion of the painting is reported along with the corresponding false color images (figure 6 b-
e) resulting from the brightness temperature spectra and highlighting four different spectral profiles (figure 6 f). In this
case the false color images represent the coefficient of correlation calculated for each pixel between the measurement
data of the HI 90 and the spectra acquired by the Alpha-R FTIR device recorded in the analogous colored sectors (figure
6 g).

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The light green area shows a brightness temperature spectrum (figure 6f) indicating the presence of barium sulfate
identified through the typical three bands profile in the range 1040-1180cm-1 9. The white pigment is probably mixed
with the green pigment to light the hue and it is not observed in the other green sector where only a silicate component is
underlined by a signal at about 1000 cm-1 (figure 6f). Although also the blue sector is composed of a silica-based
pigment (i.e ultramarine blue), the imaging results differentiate it from the dark green since the contribution in the
brightness temperature profile of the signals from the vinyl binder at about 1200 cm-1 11 (figure 6f). In addition to a
silicate component, the purple area shows also a brightness temperature profile with a band at about 1150 cm-1 (SO4=
antisymmetric) (figure 6f) which may indicate the use of calcium sulfate16.

The overall results have been confirmed by point measurements by the Alpha-R (figure 6g) which indicate clearly the
presence of kaolin in the blue, purple and green sectors (all of them having a brightness temperature profile with a band
at 1000cm-1, figure 6f). The point investigation confirms also the presence of gypsum in the purple whilst indicates the
presence of the calcium sulfate also in the dark green not highlighted by the imaging since the overlapping with the vinyl
binder.

Fe?,'";;!..

0.85 1 0.83 1 0.85 1

o
kaolin gypsum

' \ CaCO3 1
"VI
l'green ,' l

ff
.

1300 1200 1100 1000 900 3500 2800 2100 400 700
0.8 I
1 wavenumber./cm wavenumber/crri 1

Figure 6. a) Color image of a portion of the Burris painting Sestante 10, the black rectangle highlights the area investigated by the
HI90 system. Correlation images with reference spectra collected from: b) light green; c) green; d) blue; and e) purple areas, f)
brightness temperature profiles for each colored sector, g) infrared reflection spectra acquired by the Alpha-R system with the spectral
assignment from each colored sector (the rectangle highlight the portion of the range available by the HI90). Figure adapted from Ref
11.

4. CONCLUSIONS
The study here presented highlights the potential of the mid-FTIR range to create molecular image of the distribution of
pigments on painting surfaces through the use of a the novel hyperspectral imaging system HI90 based on a Michelson
interferometer equipped with a focal plane array MCT detector.

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The imaging device has been adapted for reflection FTIR measurements on paintings starting from another instrument
previously designed and set-up for gas detection. The dimension, the easy to hand set up of the system, and the fast
acquisition time, make it very suitable for in situ measurements of paintings.

Preliminary tests on a laboratory model mimicking a modern art painting, demonstrated the feasibility of spectrally and
spatially discriminate among sulfate-, silicate-, and carbonate-based pigments also when worked with different binders.
Overall, the comparison among the brightness temperature spectra recorded by the HI90 and the reflection profiles
acquired from the same model by a portable point-analysis FTIR spectrometer demonstrated that data produced by the
imaging device are highly reliable in term of both position and profile of the infrared bands. Difficulties aroused only for
organic yellow, phtalocyanine blue and azurite, since the weak/absent infrared signals in the range accessible by the
HI90, did not allow for their positive identification. In some cases, false positive results were observed, mainly due to the
contribution of signals from the organic binders overlapping with the pigment bands.

All these shortcomings are related to the current limitation of the spectral range available (1300-860 cm-1) which was
selected for the optimal detection of gaseous compounds. On the basis of the results obtained during this feasibility study
and also considering the previous knowledge about the response of painting materials in the mid-infrared range in
reflection model, an extension of the current spectral range will be considered. The use of appropriate optics and detector
will enable to investigate wider and different spectral ranges.

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