2016 RRP Violin Varnishes
2016 RRP Violin Varnishes
2016 RRP Violin Varnishes
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Ion Sandu
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1. INTRODUCTION
different that the ones used today [1–2]. In the case of wooden musical
instruments, especially stringed ones, the practice of varnish techniques has had its
golden age within the mid-16th century Italian lutes, the varnish recipes of this
period being considered to have not only a protective and aesthetical role, but
acoustical one as well [3] with sound quality as a result of both the construction
technique and combination of materials used [4]. Taking into consideration the
scientific studies [5–8] carried within the latest decades on the characteristics of
coatings materials applied on historical musical instruments’ surfaces, classical
varnishes appear in most of the analyzed cases as complex mixtures of organic
layers, occasionally blended with inorganic compounds that interact, age and
degrade in a strong heterogeneous matrix [9]. In order to improve the diagnostic
research – stratigraphic and micro-chemical analysis of the layers, morphology of
the interfaces, functional or molecular composition of organic products, mineral
composition and particles distribution in the binder, etc, and nevertheless their
statistic relevance [3–4] while still preserving the integrity of the instrument when
studying authentic original artworks, a non-invasive approach is required – with
test copies reproducing the presumed materials used within the original instrument
[4]. In the context of a combined based analytical methodology that could provide
extensive information on the above mentioned areas of interest, Attenuated Total
Reflectance (ATR) Fourier Transform Infrared Spectroscopy and its derivative
techniques [6], can be considered as a powerful method when analyzing and
mapping organic species of heterogeneous stratigraphic materials [10]. Focused on
a 1712 Stradivari violin copy manufactured during 1963 in Reghin (Romania), the
present paper is intended to be an analytical and technical study of wooden musical
instrument varnishes as well as an insight into the potential of IR spectroscopic
techniques as a discrimination tool when dealing with complex organic materials.
The object of this work deals with the varnish of a violin instrument
manufactured in the early 1960s in Reghin after an 18th century Stradivari model;
belonging to Victor Brauner School of Fine Arts (Piatra Neamt, Romania) the
violin was played until 2003, when after an incident the arm and sound cavity were
fractured. For the study, a number of three micro-samples were collected with the
use of a scalpel from areas that showed no evidence of retouching or repairs.
Optical microscopy analysis was performed with the use of a Carl Zeiss Axio
Imager A1m having an Axiocam camera attached. Images at variable
magnification were captured. For morphological and elemental mapping SEM
investigations were carried via a Tescan Vega LSH scanning electron microscope
coupled with a Quantax QX2 X-ray spectrometer. Secondary electron images were
3 Characterization of historical violin varnishes 617
taken at an operating voltage of 30 kV; samples were gold coated. Further, for
molecular characterization ATR-FTIR analysis was performed using a PerkinElmer
Spectrum Two FITR spectrometer, equipped with a PIKE Technologies ATR
accessory with a monolithic diamond crystal. Spectra were collected in the mid
infrared range 4,000–450 cm–1 at a spectral resolution of 4 cm–1 by averaging 16
scans, with automatic background subtraction; no special sampling preparation was
required. Multiple measurements were carried both on micro-samples as well as in
situ, by direct contact of the artwork with the crystal surface. Excellent technique
when studying thin surface layers, its applications sets certain care as damage of
fragile materials can occur due to the high pressure exerted by the ATR crystal on
the analyzed sample; the relative positioning of the specimen in relation with the
ATR crystal is also particularly important as the achieved optical contact is directly
related with the data quality obtained [6]. Taking into consideration these technical
aspects for in situ measurements minimum pressure was applied, while in the case
of varnish micro-samples spectra were recorded under higher force. In terms of
data processing, all spectral data presented here was baseline corrected and a
smooth factor applied.
Fig. 1 – Violin fragment, back plate, with details under optical microscope examination
(A – 100× / B – 200×); due to aging factors, environmental and inadequate storage conditions
the varnish film is visibly degraded and quite extensive areas can be characterized by a gloss loss,
a mat finish with visible scratches, craquelure and exfoliations, and a general poor adherence
onto the wood substrate; at higher magnifications crystalline particles can be clearly observed
apparently concentrated in the lower part, above the wood surface.
618 Ioana Maria Cortea, Raluca Cristache, I. Sandu 4
Fig. 2 – ATR-FTIR spectra obtained on analyzed varnish micro-samples (a) compared to in situ
measurements (b); good correlation in respect to specific IR absorption bands can be seen, with only
minor variations in band intensities due to experimental factors – such as applied force, quality of the
achieved optical contact, depth of penetration, etc., and/or local material characteristics.
5 Characterization of historical violin varnishes 619
Taking into consideration the overall weaker resin signal when compared to
a fresh varnish [11], we assume the existence within the analyzed samples of
various levels of degradation that generates IR results mixing molecular fingerprint
of both fresh as aged resins. Under these aspects, the global decrease of the C-H
band around 2919, 2853 cm-1 and of the C=C absorption band at 1650 cm-1, and on
the other hand the increased absorbance observed in the 3200–3400 cm-1 region,
could be explained by undergoing natural ageing process, with autoxidation and
crosslinking reactions affecting the polymeric fraction. Moreover, with interactions
and/or ageing products that may be present within the matrix [15–16], an exact
attribution of absorption bands has clear limitations, recent studies [11] on regard
molecular characterization of aged mixtures of natural resins and oils suggesting
that the identification by specific absorption bands is only possible in unknown
sample by determination of the resin type via combination of specific and non-
specific band, with no precise identification possible in the case of triterpenic reins
that exceeded a certain degradation stage without advanced multivariate analysis
[11, 17].
In terms of the oil medium, the shifting and broadening of the carbonyl band
due, as previous stated [18], to the formation of carboxylic acids – as one of the
most pronounced effects observed in the infrared spectra of oil-based varnishes and
paints, affects significantly the identification of characteristic peaks that may
discriminate between the various drying oils that may have been used within the
varnish formulation (linseed oil, walnut oil, castor oil), as the relative proportion
of saturated and unsaturated fatty acids can be considered the only major factor that
differentiates these oils [19].
On another aproach focused on morfological and elemental characterisation,
SEM/EDX analysis allowed the identification of a series of inorganic substances
present within the varnish layer, among the major components being found silicon,
aluminum, sodium and magnesium, followed in smaller amounts by sulfur,
calcium, potassium and chlorine, trace elements that may point towards various
inorganic compounds that may have been added as fillers [5] – quartz or glass,
potassium feldspar, gypsum, clay or other calcium sulphates; or may be present as
impurities either as part of the original materials or embedded later, via
contamination of the varnish film. For the elemental distribution within the
analysed samples some aspectes need though to be clarified as the investigations
were carried through the varnish layer and thus absorbtion of elements in the
uppermost layers may be disproportionaly over-represented in the spectra, in
contrast to those found in deeper regions due to soft X-rays attenuation [20]. With
this aspects taken into account we can only assume based on the occurrence of
detected elemets and FTIR results, the presence of manganese based earths added
as a pigment along with a series of inorganic fillers difussed within the matrix,
while the identfied trace elements can be explained as contaminants asigned to
human sweat [21] or, to a lesser extent, to the inorganic portion of wood bellow the
620 Ioana Maria Cortea, Raluca Cristache, I. Sandu 6
varnish, calcium and potassium being among the most abundant inorganic elements
found in wood species.
Fig. 3 – FTIR results (1) on wood – clean, back area of the analyzed violin fragment (a),
compared to impregnated wood (b) (top of the fragment, varnish exfoliated area), and back side
of a varnish micro-sample (c); SEM image (2) revealing the heterogeneous nature of the coating
characterized near the surface by an amorphous fracture and a high concentration of solid particles
dispersed within an insoluble dense organic binder; EDX spectrum (3) and recorded microanalysis
data (K series).
4. CONCLUSIONS
Acknowledgments. The presented activities are part of the National Project PN 09-27 02 03
contract 27N /27.02.2009.
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