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. 2014 Apr 2;14(4):6338-55.
doi: 10.3390/s140406338.

Time-resolved photoluminescence spectroscopy and imaging: new approaches to the analysis of cultural heritage and its degradation

Austin Nevin  1 , Anna Cesaratto  2 , Sara Bellei  3 , Cosimo D'Andrea  4 , Lucia Toniolo  5 , Gianluca Valentini  6 , Daniela Comelli  7
Affiliations

Time-resolved photoluminescence spectroscopy and imaging: new approaches to the analysis of cultural heritage and its degradation

Austin Nevin et al. Sensors (Basel). .

Abstract

Applications of time-resolved photoluminescence spectroscopy (TRPL) and fluorescence lifetime imaging (FLIM) to the analysis of cultural heritage are presented. Examples range from historic wall paintings and stone sculptures to 20th century iconic design objects. A detailed description of the instrumentation developed and employed for analysis in the laboratory or in situ is given. Both instruments rely on a pulsed laser source coupled to a gated detection system, but differ in the type of information they provide. Applications of FLIM to the analysis of model samples and for the in-situ monitoring of works of art range from the analysis of organic materials and pigments in wall paintings, the detection of trace organic substances on stone sculptures, to the mapping of luminescence in late 19th century paintings. TRPL and FLIM are employed as sensors for the detection of the degradation of design objects made in plastic. Applications and avenues for future research are suggested.

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Figures

Figure 1.
Figure 1.
A timing diagram showing pulsed laser excitation, luminescent emission, and operation of the intensifier gate. The acquisition of luminescent images at different delays with respect to the laser pulse (purple). The intensity of the luminescence (red) decreases in time. The images recorded highlight the presence of a long-lived emission (>1,000 ns). Intensity in insets has been rescaled to fill the dynamic range of each image.
Figure 2.
Figure 2.
The TRPL setup. ND: neutral density attenuator; PD: photodiode; FI: Faraday isolator; PCF: photonic crystal fiber; FM flipping mirror; BBO: type I β-barium borate crystal; F1: low pass filter; DM: dichroic mirror; Obj.: microscope objective; F2: high pass filter.
Figure 3.
Figure 3.
Fluorescence lifetime of (a) egg white; (b) collagen-based glue; (c) egg yolk.
Figure 4.
Figure 4.
FLIM analysis (shown in false colour in circular insets) from a model sample painted in different mixtures of pigments in an egg yolk + linseed oil binder applied either to dry plaster (secco) or to fresh plaster (fresco).
Figure 5.
Figure 5.
FLIM analysis of the wall painting of the Life of John the Baptist (Colleggiata, Castiglione Olona, Varese, Italy) by Masolino: the fluorescence lifetime maps taken from the figure of Salome were superimposed on the color image. In the ovals of the headdress (a) and in the vest (b) areas with different lifetimes can be discriminated, which are related to a different content of red lake.
Figure 6.
Figure 6.
TRPL analysis of a yellow ((Zn,Cd)S) sample: gated PL spectra (a) in the 0–7 ps and 8–36 ps temporal windows; (b) decay kinetic from the band edge (475–505 nm); (c) gated PL spectra in the 0–3 μs and 10–12.5 μs temporal windows; (d) decay kinetic from the first trap state (640–740 nm).
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References

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