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Stradivari's varnish: A chemical analysis

Article  in  Strad · April 2010

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 THESTRAD/VOL.121 NO.1440/APRIL2010 CONTENTS

6 NEWS Longtime Guarneri Quartet cellist

David Soyer dies; plus events, people, competitions,
analysis, new products and Letter from Cape Town

19 NORMAN LEBRECHT Has the global

recession caused a cash crisis for classical music?

22 Ic.vw"ilo);ij! ARTEMIS QUARTET

The German foursome on getting intimate with
Beethoven and the pleasures of playing standing

26 LEONID KOGAN
The focus and intensity of the great violinist

28 YCATAT25
A quarter-century of supporting young players

33 VIOLINS IN CRIME NOVELS

Why is the string world such a ripe subject for
tales of madness, mayhem and murder?

38 PROKOFIEV AND ROSTROPOVICH

We examine what influence the Russian cellist
may have had on Prokofiev's Symphony-Concerto

44 SUMMER FESTIVALS
Top events around the world for string lovers

48 STRADIVARI'S VARNISH
We reveal the results of a seven-year Parisian
There can be few things in life as satisfying as playing a study into the master's instrument coatings
Beethoven quartet. For an amateur like me it's the ultimate
musical soul food. So I envy the players of the Artemis
52 IN FOCUS A 1913 cello by Celeste Farotti
~ Quartet (page 22). They are a quarter of the way through
;:: a two-season Beethoven cycle. What must it be like to 54 TRADE SECRETS A new way to set a neck
~ spend two years focusing on Beethoven? Eckart Runge tells us, 'We feel as
59 MY SPACE Anna Katharina Luhmann
~ if we are living with him. Playing his complete works is like looking into
g~ his soul, and he allows us to do it, almost as a reward for our hard work: 61 HEALTH MATTERS Peter Buckoke
~~ Hard work was in evidence during a recent visit by young Austrian
~!i musicians to Cape Town's Hout Bay Music Project (page 17). Together with
62 MASTERCLASS Strauss's Don Quixote

~ ~@ their South African counterparts they had only a few days to put together
!~~ a programme of Britten, Corelli and Xhosa music. One Austrian teenager's
§ ~~
I aG:i
response: 'It was the greatest experience I've ever had in my life!' No one's
~ ~~ ever too young to discover the transformative powers of music and work.
8 ~~ Ariane Todes, Editor

ETIENNE ABELIN (Letter JEAN-PHILIPPE ECHARD ALEXANDER IVASHKIN

from Cape Town. page 17)
is a violinist and conductor.
and artist in residence
and music curator at the
Festspielhaus in St Polten.
Austria. He also plays with
the Orchestra Mozart
Bologna and the Lucerne
Festival Orchestra
and BALTHAZAR SOULIER
(Stradivari's varnish, page
48) are conservators based
in Paris. Jean-Philippe
Echard is a scientist at
the Musee de la Musique,
and Balthazar Soulier
trained as a violin maker
in Mittenwald
(Prokofievand
Rostropovich, page 38) is
a cellist, conductor and Online at www.thestrad.com
professor of music at
DOWNLOADSProfile of Rostropovich Trade
Goldsmiths, University of
London. He has recorded Secrets article on neck fitting Don Quixote
Prokofiev's complete cello complete annotated viola solos
music and published a
PLUSThe latest news stories Blogs
book on Rostropovich
Summerplus, Directory and Degrees databases
Competitions Your comments on our stories
 Stradivari's varnish:
a chemical analysis
JEAN-PHILIPPE ECHARD and BALTHAZAR SOULIER reveal the results
of their seven-year research into Stradivari's varnish, using five of
the master's instruments from Paris's Musee de la Musique

T
he exact composition of Cremonese varnish
- and that used by Stradivari in particular - has
been discussed many times, often in these pages.
But despite the increasing fondness of scientists for
the subject, and the publication of a small number of analytical
surveys in the past 60 years, no clarification has been achieved;
if anything, the reverse is true.
We began our research in 2003 at the instigation of
Stephane Vaiedelich, head of the laboratory at the Musee
de la Musique in Paris, and from the outset it was clear to
us that a multi-approach method, inspired by those used in
archaeology and conservation science, could shed new light
on the historical techniques and materials used by instrument
makers. We were especially fortunate that the Musee de la
Musique's instruments are freed from market considerations,
and the museum's protocols allowed us to conduct and publish
our research freely.
Here we will outline the specifics of our approach, discuss
its impact and limitations, and provide a new perspective on
Stradivari's varnishing techniques.
AS STEWART POLLENS REITERATED in the May 2009 issue of
The Strad, to date only a very limited number of instruments
- mostly unidentified - have been studied. In particular, the
sampling and authentication procedure, which is crucial to
assessing how relevant and significant any eventual results are,
seems not to have been sufficiently considered. Taking a sample
of varnish from a genuine Stradivari instrument, from under
the fingerboard for instance, does not mean that that varnish is
genuine or original. The absolute transparency of the research
and the traceability of each step of the process are crucial,
and only by analysing varnish samples from multiple genuine
instruments can meaningful results be achieved.
In the past few years, we have regularly published analytical
results, in an attempt to identify the ingredients and the
structure of the varnishes of ancient musical instruments.
Recently, we have focused our research on five Stradivari
instruments spanning more than 30 years of the master's
career (see table below).
We were again fortunate that these instruments have been
recognised as representative of Stradivari's work by eminent
experts since the end of the 19th century - Charles-Nicolas-
Eugene Gand, the Hills, Emile Fran<;:ais, Etienne Vatelot and
Charles Beare among them. Furthermore, they have rarely
been played or handled since they were added to the collection.
Perhaps most notably, the head of the viola d'amore given
by Vuillaume in June 1873 to the Musee Instrumental du
Conservatoire de Paris has one of the best-preserved of all
Stradivari varnishes.
THE INDISPENSABLE FIRST STEP, before any sampling and
in-depth analysis, is to authenticate the sampling area with
the greatest possible certainty. Until now, varnish has only
been identified from its visual aspect, which requires great
experience. That is why we have carried out our research by
applying knowledge of historical restoration practices and
by comparing the varnish in question with that of many
other Cremonese instruments or comparable instruments
from outside the Musee. We have coupled this approach
with complementary in situ observations (light microscopy,
UV- Vis), X-ray radiographies and spectrometric analyses
(X-ray fluorescence, UV- Vis fluorescence, Fourier- Transform

Instrument type Date Designation (last owner) Entry date into the collection Inventory number

Violin c.1692 Queux de Saint-Hilaire (long pattern) 1890 E1375

Violin 1708 Davidoff 1887 E1111

Violin 1716 Provigny 1909 E1730.1

Head of a viola d'amore 1720(7) Vuillaume 1873 E484

Violin 1724 Sarasate 1909 El729

48 THE STRAD APRIL 2010

Five Stradivari instruments from the Musee de la Musique in Paris: (from left to right) the 'Davidoff (1708),
the 'Tua' (1708), a long-pattern violin ((.1692), the 'Provigny' (1716) and the 'Sarasate' (1724)

InfraRed, or FTIR). The sampling limited if the fingerboard is not

process always involves a compromise
To our knowledge, removed; and the back, since it can
between obtaining the information our study is the first to be considered as the most aesthetic
expected and respect for the and visible part of the instrument,
instrument's integrity, both aesthetic employ a large number has been avoided.
and material.
of complementary, The area under the tailpiece
We have avoided analysing original has often proved in our case to
but non-representative sections of state-of-the-art be quite adequate - generally it is
the instrument, such as glued areas representative, is easily accessible
(purfling, joints, cracks and other
analytical techniques and viewable, and is relatively well
alterations). Indeed, the original glue to study a large group obscured in playing conditions.
may have impregnated the wood cells Original varnish that demonstrates
by capillarity, before the instrument of well-identified little wear is also often to be found on
was varnished. If this were the case, the C sections of the ribs. Where we
analysing genuine varnish taken
instruments have studied these sections, we have
from the fluting, edges or original preferred to take a sample from the
joints would lead to the detection of proteinaceous materials edge blocks area - after checking that glue has not penetrated
and to the - possibly improper - conclusion that the ground the whole thickness of the rib - in order not to weaken the
layer contains proteins. We have also carefully identified (and stability of the rib.
stayed away from) areas that have been repaired or retouched. We have opted for samples containing both varnish and wood
X-ray radiography and endoscopy allow us to detect patches of between 0.5 and 1mm2 and to a depth of O.5mm to enable
where glue may have contaminated the wood. A clean and us to obtain information about the full layer structure and
large enough surface of visual reference is needed to discern composition all together, using specially adapted micro-tools to
the original layers and, for this reason, we have sometimes take samples. Despite this meticulous approach, there is always a
had to clean dirt locally, using non-polar volatile solvents. possibility that the samples will contain more recent exogenous
Although each instrument is unique, we have noted a few dirt, polish or retouching material. This is another reason why
general observations for sampling areas: the fingerboard area we have used specific high-resolution techniques to map and
is often covered with dirt and rosin; access and visibility are characterise precisely the chemical compounds in the varnish ~

Two recent articles in The Strad have revealed analyses
of Stradivari's varnish using contrasting methods
STEWART POLLENS (MAY 2009)
• Research carried out into the varnish of five Stradivari instruments
using techniques such as Raman microscopy
• Samples taken from high up under fingerboard or more exposed
areas of the instruments
• Substances such as charcoal, pine resin and shellac indicated
• No obscure ingredients identified
• Stradivari's varnish bears a close relation to vernice comune
and to assessments made by the Hillsand Charles Reade
STEFAN-PETER GREINER (JUNE 2009)
• Optical and chemical analyses carried out on the varnish
of 80 Stradivari instruments
• Stradivari used natural cinnabar in his varnish to achieve the
dual effects of luminosity and cloudiness when seen at an
angle that characterise the appearance of his instruments
• The theory of a connection between the varnish and the
sound of Stradivari's instruments is untenable
cross-section. The sampled areas were documented before
and after the sampling operations, and were not retouched.
The stratigraphy is resolved by observing non-embedded,
microtomed thin sections (l micrometre thick) and polished,
embedded cross-sections of different samples, using
light microscopy in reflection mode and epifluorescence
filters (different UV and blue excitation wavelengths)
and in transmission mode using polarisation contrast to
characterise the distribution and morphology of particles.
FOR EACH OF THE INSTRUMENTS, we have distinguished
only two separate layers. The underlying layer, which can be
considered a ground layer of varnish, fills the upper wood cells
and barely rises above the surface of the wood. Depending on
the orientation of the wood, the material penetrates to a depth
of between about 30 micrometres to 0.6mm.
No mineral particle has
been observed in the ground
layer, using light and scanning
electron microscopy (SEM).
For confirmation, no inorganic
elements have been detected with
X-ray analysis (SEM/EDX).
The surface layer, the coloured
varnish, is 10 to 50 micrometres
thick on all of the instruments. Two
types of intense and finely divided
red particles dispersed in the binding
medium of this layer have been
observed on all of the instruments,
except for the 'Queux de Saint-Hilaire'.
The characterisation of pigments was performed using light
microscopy, Raman microspectrometry (two-micrometres spot
analysis of individual particles) and SEM/EDX analyses.
Some particles have exhibited Raman spectra of iron oxides,
mostly hematite. The SEM/EDX spectra have confirmed that
these particles are iron- and oxygen-rich. Other particles have
exhibited typical Raman-spectra of anthraquinonic materials.
Among our reference materials, carminic acid is the most
probable candidate, indicating an insect dye. At the beginning
of the 18th century, the most frequently used insect dye was
central American cochineal. SEM/EDX analyses have shown
that the particles were aluminium- and oxygen-rich, indicating
the use of a lake pigment, the dye being precipitated with alum.
A few years ago, we identified vermilion (mercury sulphide) in
the 'Sarasate' instrument's varnish.
With UV-excitation, the ground layer has quite an intense
whitish fluorescence, and the surface layer fluoresces orange-
yeUow. The characterisation of the organic nature of each of the
layers has been performed using, first, FTIR (Fourier-Transform
InfraRed) spectromicroscopy using the infrared light produced
at a synchrotron facility (SR-FTIR), and then, pyrolysis gas
chromatography coupled with mass spectrometry (Py-GC/MS).
Briefly, SR-FTIR is a unique technique that enables us to
perform spot analyses with a very bright infrared beam no
wider than six micrometres. This yields information about the
main mineral and organic chemical families without damaging
the sample. The beam size is smaller than the thickness of the
layers, enabling each layer to be analysed separately.
With this technique we have been able to rule out certain
ingredients as the main constituents of each of the varnish
layers: protein materials (such as egg, casein and animal glue),
gums and waxes. (On other samples from non-Stradivari
instruments, however, we have detected very thin, protein-
based ground layers using this technique.)
SR-FTIR indicates that both layers are based on a drying
oil. To further specify the nature of each layer, we have used
Py-GC/MS on minute fragments of the separated layers.
A protocol dedicated to the fine molecular characterisation
of oils, resins and waxes has been used. The typical biomarkers
of an aged drying oil have been detected in the ground
layer. For the surface layer, in addition to the aged drying oil
markers, oxidised diterpenic acids (abietane skeleton) have
been identified. These indicate the presence of a resinous
material coming from a species of
the Pinaceae family, mixed with the
drying oil, and exclude the presence
of sandarac, mastic, elemi, shellac
or other resins as main compounds.
THIS IS THE FIRST TIME that
chemical analysis has allowed the
specific organic composition of
each layer of violin varnish to be
described. Sadly, the results do not
alJow us to distinguish the main
drying oils (linseed, walnut and
poppy seed all contain basically
 Above left: cross-section of the varnish of the 'Davidoff' Stradivari (1708) under epifluorescence (UV excitation at 36Snm). The red rectangle
is the area represented in the picture above right, under visible transmitted light, which shows the various pigment particles

the same fatty acids) nor the natural and semi-transformed as we have explained, this procedure can yield objective and
resinous materials from the Pinaceae species. These natural significant results, and, at the same time, is compatible with
materials have complex chemical signatures, which evolve deontological principles.
with ageing and the resulting oxidation and degradation Our results seem to confirm accepted opinion, as well as
processes. In particular, it is seldom possible to distinguish shedding new light on some aspects of Stradivari's varnishing
between the aged resinous products from fir, pine, spruce technique, even if the number of instruments studied is limited.
and larch or to tell, for instance, if the original ingredient While the stratigraphy and the binding media materials did
used was in a semi-liquid form (turpentines, balsams) or not seem to change, his colouring system seems to have evolved
a solid form (such as rosin). throughout his long career. The results tally with common
It should be noted that the interpretation of analytical observations on Stradivari's production: most instruments from
results always has its limitations. First, and quite obviously, it before 1700 are very slightly coloured - this is backed up by the
is impossible to trace the volatile parts (such as spirits, volatile absence of pigments on the 'Queux de Saint-Hilaire'. These kinds
bases or acids), though they might be of varnishes are described as the vernice
crucial in the elaboration and application COl1lllne in historic painting treatises.
of the varnish. Only matter that is still During the so-called golden period,
in the varnish can be analysed! Second, Stradivari employed highly coloured
each analytical technique has its intrinsic • While the stratigraphy and lake pigments, probably the extremely
detection limits: if a compound is binding materials of Stradivari's costly cochineal lake, which he finely
present in a quantity or percentage varnish did not change during mixed with hematite.
lower than the detection limit for a the course of his career, his The mix of these two pigments
certain compound by a certain analytical colouring system did with remote refractive indexes may
procedure, it will not be detected. In • Before 1700, Stradivari's varnishes be responsible for the unique and
particular, some ground layers could are consistent with descriptions recognisable visual aspect of these red
still contain a minimal quantity of of vemice comune in historic glazes. From the 1720s onwards, the
proteins. We are of course aware of the painting treatises varnish (on the 'Sarasate', for example)
limited insights provided by analytical • The golden-period varnishes appears pinker and less transparent.
chemistry in describing the full and exact contain highly coloured lake This could be linked to Stadivari's
re-creation process of the Cremonese pigments, probably cochineal use of vermilion in his final years.
violin makers. However, our main goal, lake mixed with hematite It should also be noted that binding
as any museum's, is to achieve a greater • From the 1720s, the varnish media oxidise over time and lake
understanding of the materials for the appears pinker and less pigments fade, factors that will have
care and documentation of cultural transparent. This could be linked combined to reduce the visual differences
heri tage artefacts. to Stradivari's use of vermilion that would have been more striking
To our knowledge, our study is in his final years originally. Scientific examination
the first to employ a large number of • Protein materials, gums and of antique varnishes may thus also
complementary, state-of-the-art analytical waxes can be ruled out as main help to describe and understand the
techniques in the study of a large group constituents of the varnish original and irrecoverable appearance
of well-identified instruments and, of historical instruments._

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