Jean-Philippe Echard

The nature of the extraordinary finish of Stradivari's instruments.

What is Stradivaris “secret”? The composition of the mythical varnish that coats Stradivaris violins has raised controversial assumptions for the past two centuries. By using a complementary array of analytical tools, the chemical microstratigraphy of these varnishes has been established. The results provide information on the materials and techniques that were used by the Master, with a detailed characterization of the varnish.

Structural and optical properties of wood and wood finishes studied using optical coherence tomography: application to an 18th century Italian violin

Optical coherence tomography (OCT) is especially attractive for the study of cultural heritage artifacts because it is noninvasive and nondestructive. We have developed an original full-field time-domain OCT system dedicated to the investigation of varnished and painted artifacts: an interferometric Mirau objective allows one to perform the scan without moving the works of art. The axial and transverse high resolution (respectively, 1.5 and 1 microm) are well adapted to the detection of the investigated structures (pigment grains, wood fibers, etc.). The illumination spectrum is in the visible range (centered at 630 nm, 150 nm wide) to potentially allow us to perform spectroscopic OCT on pigment particles. The examination of wood samples coated with a traditional finish, demonstrates the ability of the system to detect particles, characterize layers thickness, and image the three-dimensional wood structures below the varnishes. OCT has finally been applied to study in situ the coated wood surface of an 18th century Italian violin and provides important information for its conservation treatment.

In situ 3D characterization of historical coatings and wood using multimodal nonlinear optical microscopy.

We demonstrate multimodal nonlinear optical imaging of historical artifacts by combining Second Harmonic Generation (SHG) and Two-Photon Excited Fluorescence (2PEF) microscopies. We first identify the nonlinear optical response of materials commonly encountered in coatings of cultural heritage artifacts by analyzing one- and multi-layered model samples. We observe 2PEF signals from cochineal lake and sandarac and show that pigments and varnish films can be discriminated by exploiting their different emission spectral ranges as in luminescence linear spectroscopy. We then demonstrate SHG imaging of a filler, plaster, composed of bassanite particles which exhibit a non centrosymmetric crystal structure. We also show that SHG/2PEF imaging enables the visualization of wood microstructure through typically 60 µm-thick coatings by revealing crystalline cellulose (SHG signal) and lignin (2PEF signal) in the wood cell walls. Finally, in situ multimodal nonlinear imaging is demonstrated in a historical violin. SHG/2PEF imaging thus appears as a promising non-destructive and contactless tool for in situ 3D investigation of historical coatings and more generally for wood characterization and coating analysis at micrometer scale.

Identification of the finishing technique of an early eighteenth century musical instrument using FTIR spectromicroscopy.

AbstractThe study of varnishes from musical instruments presents the difficulty of analysing very thin layers of heterogeneous materials on samples most of which are generally brittle and difficult to prepare. Such study is crucial to the understanding of historical musical instrument varnishing practices since written sources before 1800 are very rare and not precise. Fourier-transform infrared (FTIR) spectroscopy and imaging methods were applied to identify the major chemical components within the build-up of the varnish layers on a cello made by one of the most prominent French violin-makers of the eighteenth century (Jacques Boquay, ca. 1680–1730). Two types of FTIR imaging methods were used: scanning with a synchrotron-based microscope and full-field imaging using a 2D imager with a conventional source. An interpretation of the results obtained from these studies on the Boquay cello is that the maker first applied a proteinaceous layer, probably gelatine-based animal glue. He later applied a second layer based on a mixture of a drying oil and diterpenic resin from Pinaceae sp. From an historical perspective, the results complement previous studies by describing a second technique used for musical instrument finishes at the beginning of the eighteenth century in Europe. FigureFTIR spectromicroscopy study of a cello made by the luthier Jacques Boquay (Paris, ca. 1680-1729) shows that the maker first applied a proteinaceous layer, probably gelatine-based animal glue.

Excitation emission and time-resolved fluorescence spectroscopy of selected varnishes used in historical musical instruments.

The analysis of various varnishes from different origins, which are commonly found on historical musical instruments was carried out for the first time with both fluorescence excitation emission spectroscopy and laser-induced time-resolved fluorescence spectroscopy. Samples studied include varnishes prepared using shellac, and selected diterpenoid and triterpenoid resins from plants, and mixtures of these materials. Fluorescence excitation emission spectra have been collected from films of naturally aged varnishes. In parallel, time-resolved fluorescence spectroscopy of varnishes provides means for discriminating between short- (less than 2.0 ns) and long-lived (greater than 7.5 ns) fluorescence emissions in each of these complex materials. Results suggest that complementary use of the two non destructive techniques allows a better understanding of the main fluorophores responsible for the emission in shellac, and further provides means for distinguishing the main classes of other varnishes based on differences in fluorescence lifetime behaviour. Spectrofluorimetric data and time resolved spectra presented here may form the basis for the interpretation of results from future in situ fluorescence examination and time resolved fluorescence imaging of varnished musical instruments.

Study of varnish layers with optical coherence tomography in both visible and infrared domains

Optical Coherence Tomography (OCT) is an attractive technique to study works of art because it allows non-destructive and contactless analysis. In the case of musical instruments, the study of wood finishes could give interesting information as the thicknesses of the layers, the number of layers and the presence of fillers. A time-domain full-field OCT, achieving high resolution, is used in both visible and near infrared ranges to characterize semi-transparent layers containing scattering particles as charged varnish layers. We present OCT measurements on wood varnished with different coatings. We show that the detection of pigment particles is dependent of the spectral range and that both spectral domains allow to reach micrometer-scale spatial resolutions.

Implementation of a neural network for multispectral luminescence imaging of lake pigment paints.

Luminescence multispectral imaging is a developing and promising technique in the fields of conservation science and cultural heritage studies. In this article, we present a new methodology for recording the spatially resolved luminescence properties of objects. This methodology relies on the development of a lab-made multispectral camera setup optimized to collect low-yield luminescence images. In addition to a classic data preprocessing procedure to reduce noise on the data, we present an innovative method, based on a neural network algorithm, that allows us to obtain radiometrically calibrated luminescence spectra with increased spectral resolution from the low-spectral resolution acquisitions. After preliminary corrections, a neural network is trained using the 15-band multispectral luminescence acquisitions and corresponding spot spectroscopy luminescence data. This neural network is then used to retrieve a megapixel multispectral cube between 460 and 710 nm with a 5 nm resolution from a low-spectral-resolution multispectral acquisition. The resulting data are independent from the detection chain of the imaging system (filter transmittance, spectral sensitivity of the lens and optics, etc.). As a result, the image cube provides radiometrically calibrated emission spectra with increased spectral resolution. For each pixel, we can thus retrieve a spectrum comparable to those obtained with conventional luminescence spectroscopy. We apply this method to a panel of lake pigment paints and discuss the pertinence and perspectives of this new approach.

Multiphoton microscopy: an efficient tool for in-situ study of cultural heritage artifacts

We present multimodal nonlinear optical imaging of historical artifacts by combining Two-Photon Excited Fluorescence (2PEF) and Second Harmonic Generation (SHG) microscopies. Three-dimensional (3D) non-contact laser-scanning imaging with micrometer resolution is performed without any preparation of the objects under study. 2PEF signals are emitted by a wide range of fluorophores such as pigments and binder, which can be discriminated thanks to their different emission spectral bands by using suitable spectral filters in the detection channel. SHG signals are specific for dense non-centrosymmetric organizations such as the crystalline cellulose within the wood cell walls. We also show that plaster particles exhibit SHG signals. These particles are bassanite crystals with a non-centrosymmetric crystalline structure, while the other types of calcium sulphates exhibit a centrosymmetric crystalline structure with no SHG signal. In our study, we first characterize model single-layered samples: wood, gelatin-based films containing plaster or cochineal lake and sandarac film containing cochineal lake. We then study multilayered coating systems on wood and show that multimodal nonlinear microscopy successfully reveals the 3D distribution of all components within the stratified sample. We also show that the fine structure of the wood can be assessed, even through a thick multilayered varnish coating. Finally, in situ multimodal nonlinear imaging is demonstrated in a historical violin. SHG/2PEF imaging thus appears as an efficient non-destructive and contactless 3D imaging technique for in situ investigation of historical coatings and more generally for wood characterization and coating analysis at micrometer scale.

La tomographie optique cohérente pour l'étude des instruments de musique vernis

La technique d’imagerie a trois dimensions qu’est la tomographie par coherence optique (OCT) est reconnue dans le domaine biomedical, mais elle presente egalement de nombreux interets pour l’etude des objets du patrimoine : cette methode d’analyse sans prelevement ni contact appliquee au vernis des instruments de musique permet d’obtenir des coupes virtuelles et apporte ainsi des informations precieuses pour mieux comprendre les anciennes techniques de vernissage.