Maney Publishing

Spherical Copper Resinate on Coromandel Objects: Analysis and Conservation of Matt Green
Paint
Author(s): Lucia Burgio, Shayne Rivers, Catherine Higgitt, Marika Spring and Ming Wilson
Source: Studies in Conservation, Vol. 52, No. 4 (2007), pp. 241-254
Published by: Maney Publishing on behalf of the International Institute for Conservation of
Historic and Artistic Works
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 241

Spherical Copper Res?nate on

Coromandel Objects: Analysis and
Conservation of Matt Green Paint
Lucia Burgio, Shayne Rivers, Catherine Higgitt, Marika Spring andMing Wilson

An unusual green pigment was found on a seventeenth-century kuan cai (Coromandel) lacquer
screen at theVictoria and Albert
are roe.
Museum, London.The particles perfectly spherical and translucent, with the appearance ofgreen fish Analysis revealed
that thepigment is a copper res?nate, produced by reacting a copper salt with a resin, probably onefrom a Pinus species. The
binding medium for thepigment isproteinaceous. The unusual spherical morphology of theparticles resultsfrom themethod of
same was also on two other Coromandel same
manufacture. A pigment with the microscopic appearance found objectsfrom the
collection. In light or olive green areas, where thepigment ismixed with lead white, thepaint isglossy and well preserved. In

contrast, in the dark green areas where thepigment was used alone, thepaint ismatt and powdery and there is significant paint
loss and abrasion. The problem of consolidation of thepowdery paint, while still preserving the matt appearance of the surface,was
resolved by the use of immiscible solvents and consolidant.

INTRODUCTION morphology, which was used extensively on the screen.

2 and 3 show details of areas of decoration from
Figures
Following extensive renovation, the Victoria and Albert
the screen this pigment. In Figure 2 there
containing
(V&A) Museum's British Galleries opened to the public
are several shades of light green paint, all of which are
in late 2001. These galleries illustrate the historical
hard and glossy, and which survive in good condition.
of British art and
progression design, showcasing In contrast, the dark green paint of the underside of
significant influences along with examples from the most
the bladed leaves where this pigment was used alone
important designers and manufacturers. A small display
is powdery and matt, presenting particular in
problems
sets out examples of objects from China, Japan and
the conservation treatment. minor losses are
Although
India alongside their British-derived counterparts, with
apparent in the areas illustrated, some other dark green
Chinese a twelve-fold kuan cai
lacquer represented by areas have suffered more extensive loss (Figure 3). This
screen
(Coromandel) lacquer (Figure 1). Conservation of
describes the identification of the pigment and
paper
the screen was a
challenging undertaking because of its
the paint binding medium, as well as the method used to
size and condition, and because little detailed technical
consolidate the matt green paint.
information on kuan cai was available. The V&A initiated
a technical to
study of the object, both inform the
conservation treatment and to increase
Historical context
understanding
of this decorative form of Chinese lacquer. One of
The of kuan cat ('cut colour') was
technique lacquer
the most results of the examination was
interesting to China and involved into a
unique incising designs
the discovery of a previously unknown translucent
lacquer surface and then decorating the resulting lacunae
green copper resinate pigment with a
striking spherical with terms used
polychrome paint. Historical European
to describe this include 'Bantam work' in
technique
ReceivedOctober2006 late seventeenth-century England and 'Coromandel' in

STUDIES IN CONSERVATION 52 (2007) PAGES 241-254

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242 L. BURGIO, S. RIVERS, C. HIGGITT, M. SPRING AND M. WILSON

; ^. ?

>?H?

Figure 1 Coromandel screen, V&A accession number 130-1885.

early eighteenth-century France

[1, 2]. The front of the while the more brightly coloured glossy areas, such
as
kuan cai screen examined in this study is decorated with the deer and flowers, advance into the foreground.
a scene of animals and birds among trees and A limited range of pigmented was
pastoral lacquer produced
flowers alongside waves to the nineteenth
topped with spindrift, while the prior century, typically black, brown,
is characterized are two reasons for this limited
back by incised fan-shaped and square red and yellow [3].There
cartouches inscribed with extracts from the works of First, the drying of lacquer occurs
palette. through
well-known poets, an allusion to the screen-owner's a combination of oxidation and enzyme-catalysed
Both front and back are bordered (therefore pH-specific) and many pigments
literary knowledge. cross-linking
with the 'hundred antiques' design depicting flower disrupt the curing process [4]. Second, pigments used in
vases, urns and animals such as combination with must have the ability to mask
terrapins, dragons
dogs, lacquer
and phoenix. the natural dark brown colour of this binding medium,
The artistic quality of kuan cai can be judged by the
so it is not
possible to make white lacquer, for example.
intricacy and conception of the overall design, while A wider range of colours, including the greens, whites,
craft skill is evident in the execution of the decoration. are
and blues typical of kuan cai polychromy, possible if
Fine-lined and curves are the most other are used.
smooth-flowing binding media
difficult incised decoration to Texts on Chinese historical
technically produce. lacquer, documentary
The areas over to the depiction of fine sources and contemporary conservation literature give
large given
bundles of coniferous needles and waves are testament little information on kuan cai, while the materials and
to the of this screen. The used to create it rarely warrant more than a
exceptionally high quality techniques
decoration utilizes a wide range of colours sentence (see for
polychrome single example [5]).Typical descriptions
in combination with delicate are used for refer to the use of oil as
glazes, which of the polychromy technique
both detail and Matt the binding medium, or for certain colours,
pictorial graduated shadowing. lacquer
and are to create an impression two authors refer to the use of water-based
gloss paint juxtaposed although
of three-dimensionality in the design. The combination colours [6,7].
of fine line incised work with matt muted colour in The sixteenth-century Chinese lacquerist Huang
the coniferous needle bundles, for example, causes the listed kuan cai along with 90 other
Cheng lacquering
overhanging
tree greenery to recede within the design, techniques inXiu Shi Lu (The Lacquering Handbook)

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 SPHERICAL COPPER RES?NATEON COROMANDELOBJECTS 243

written between 1567 and 1572.1 Although this suggests

that incised was
polychrome lacquer already being
made in the latter half of the sixteenth century, if not
earlier, kuan cai objects are attributed to the
generally

' Kangxi period (1622-1722). Describing polychrome

?1*?' .< decoration, Huang Cheng

states: 'Kuan cai, some
colours are with some with oil.
compatible lacquer,
Those compatible with lacquer should be applied using
the drymethod, those compatible with oil should be
applied with lead powder. Some add gold and silver
^ ^
to the palette,
129]. Huang
which

goes
makes it more[8,
on
the
beautiful'
to describe
paragraph Cheng
in which was brushed onto an
'dry method', lacquer
intaglio area, followed by the application of powdered
on top. In the 'wet method', were
pigments pigments
mixed with oil and brushed onto the surface.
directly
The handbook, under the heading
of'oil', explains that
such as
several colours sky blue, white and peach pink
cannot be obtained the pigment with
by mixing lacquer
and therefore have to be mixed with oil. 'Oil' refers to

paulownia from the seeds of the paulownia

oil, obtained
tree [8, 16 and 97]. Water-based media are
paragraphs
not referred to in this text. Glues derived from cowhide,
are mentioned,
staghorn and fish bladder though only in
reference to or bamboo to
joining wood pieces together
form the substrate [8, paragraph 41].
While there is a substantial body of literature dealing
with general principles of the conservation of lacquer

[3,9-11], there are very few references dealing with the

conservation of kuan cai (Coromandel) lacquer. Passing
reference to the restoration of kuan cai screens is made
Figure 2 Glossy green paint on theCoromandel screen. Thematt green
can be seen insome of the long thinleaves (note thepaintbsses in their by Sk?lov? [12] and Piert-Borgers [13]. Bresinsky gives
a historical overview of the use of Coromandel and
centre).
Japanese lacquer in eighteenth-century French furniture
but does not address conservation issues [14]. Piert
Borgers undertook the examination and limited analysis
of several Coromandel objects, including three screens
examined a screen
[7]. Breidenstein gilded Chinese
and information on the materials and
incorporated
techniques in the foundation layers [15],which may be
similar to those found on Coromandel screens.

OPTICAL MICROSCOPY

Samples taken from the glossy green areas on the screen

revealed that the uppermost layer contained lead white

'/? i 625 the lacqueristYang Ming wrote commentaries toHuang's

Figure 3 Matt dark green leaves on theCoromandel screen, showing
extensive damage. A fewpaler glossy leaves, stillinperfect condition,can text, and further annotations to both texts were made byWang
also be seen and are marked with arrows. Shixiang [8].

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244 L. BURGIO, S. RIVERS, C. HIGGITT, M. SPRING AND M. WILSON

mixed with a translucent dark green pigment malachite, and is more frequently observed when
spherical
(see the Appendix and Figure 4). The spheres ranged preparing dispersions of copper-containing glaze paint
from approximately 2 to 100 um in diameter. In the sam where verdigris has reacted with oil. In addition, emerald
areas a thick layer composed yield distinctive Raman
ples from the matt of the green and spherical malachite
same translucent green spheres was always present, used spectra, unlike the green pigment from the Coromandel
alone rather than with lead white, giving the appearance screen (only fluorescence was observed with 514.5 and
under the microscope of green fish roe. The pigment in 632.8 nm excitation).
areas was and there were voids occurrences of a green described
these very leanly bound Other pigment
between the In a few areas there as fish roe have been on Chinese
spherical particles. resembling reported
was a over the the but the pigment is either not discussed in
layer of malachite layer containing objects,
on its
translucent green spherical pigment, and in these places detail [20], or it is described, based microscopic
the matt green paint is in better condition rather than on results, as a
(Figure 5). appearance analytical synthetic
The and colour of the translucent form of malachite, a white centre surrounded
appearance 'showing
green pigment
was
typical of a copper-containing by a shellof green' [21].
at first have
material. The shape of the particles might
that the could be either emerald
suggested pigment SCANNING ELECTRON MICROSCOPY AND
acetoarsenite, the particles of which are
green (copper ENERGY DISPERSIVE X-RAY ANALYSIS
a
usually characterized by spherical shape) [16] or so
or
called spherical malachite(either synthetic naturally The flawless geometrical shape of the particles and the

[17-19]. However, the green pigment smoothness and perfection of their surface could be
precipitated)
found on the Coromandel screen was darker and more appreciated fully only with the aid of a scanning electron
translucent than either of these
pigments, and was microscope (Figure 6). Cross-sections of samples from

isotropic when viewed in transmitted light between the screen, from both matt and glossy green areas, were
crossed polars. analysed by energy-dispersive X-ray analysis (EDX) in
The green seemed to partially dissolve the scanning electron microscope (SEM). Unmounted
spheres
to be as were a
when heated in Cargille Meltmount viewed samples also imaged with tabletop scanning
a at higher
temperatures, and electron under conditions suited to the
dispersion, particularly microscope
was no examination of the and
their morphology longer visible (dispersions topography pigment particle
were made in the temperature range 65?95?C). This (see the Appendix). Perfect dark grey spheres of
shape
is not typical of emerald green or spherical are visible in the SEM
behaviour variable diameter images, which

Figure 4 Photomicrograph of a cross-sectbn of a sample froma pale, Figure 5 Photomicrographof a cross-section of a sample froma matt
glossy green area on theCoromandel screen, showing translucent,
dark green area on theCoromandel screen showing a layerofmalachite on top
green spheres of variable size embedded ina lead whitematrix. of a layerof translucent,
dark green spheres.

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 SPHERICAL COPPER RES?NATEON COROMANDELOBJECTS 245

are clear in the glossy green areas because of such as malachite. In the
particularly copper-containing pigments
the strong contrast with the lead white inwhich are backscattered some
they images of of the cross-sections there
embedded (Figures7 and 8). is a more highly scattering feature in the centre of the
The EDX spectra confirm some was
that the spherical green largest spheres (Figure 9), in which chlorine

pigment contains copper, at a low detected in association with copper.

although relatively
level compared to the which is more
background,
typical of copper salts of organic acids than other

TM-1000 I I I I I I I I I I I
200 (im L 50 ?im

Figure 6 Tabletop electronmicroscope backscattered electron images of an unmounted sample froma matt green area on theCoromandel screen, at
twodifferent
magnifications.

'?h^
V?h***

K 3J?* t&
^..?fc??...1
TM-1000 L ?ufim

Figure 7 SEM backscattered electron image of a cross-section of a Figure 8 Tabletop electronmicroscope backscattered electron image
sample froma pale, glossy green area on theCoromandel screen. of an unmounted sample froma glossy green area on theCoromandel
screen.

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246 L. BURGIO, S. RIVERS, C. HIGGITT, M. SPRING AND M. WILSON

on a seventeenth-century Coromandel cabinet in the

Museum furOstasiatische Kunst, Berlin [7].

A from a dark green area only
sample containing
the resinate was gas
copper pigment analysed by
chromatography-mass spectrometry (GC-MS) (see
the Appendix). The content of the sample
diterpenoid
suggests that a conifer resin is present, probably
from a Pinus (the diterpenoid region of
species
the chromatogram is shown in Figure 11 and the

components identified are listed in Table 1). It is not

to determine if the pine resin has a European
possible
or Asian but the absence of the methyl esters
origin,
of lambertianic (mass spectrum with base peak, B+ 121
and molecular ion, M+
330) or merkusic (B+ 121, M+
acids rules out certain East Asian Pinus species
364)
such as P. armandii, P. wallichiana, P. koraiensis and P. sibirica
or P. merkusii [27, pp. 100-101]. The unusual degree of
Figure 9 SEM backscattered electron image ofdark green spheres of the resin components is undoubtedly
preservation
fromtheCoromandel screen. Two of theparticles show thepresence of a
related to the presence of copper in the pigment, which
nucleus, marked with arrows.
acts as an antioxidant. A sesquiterpene was
component
also detected (B+ 161,M+ 204) but its identitycannot
as a number of sesquiterpenes show
readily be assigned,
FOURIER TRANSFORM INFRARED MICROSCOPY similar mass spectral patterns. The sesquiterpene could

AND GAS CHROMATOGRAPHY-MASS be a component of the Pinus resin used in the copper

SPECTROMETRY ANALYSES resinate, or could represent the residues of some form of

oil of turpentine or other essential oil.
The Fourier transform infrared (FTIR) spectra obtained GC-MS also some indication of the
analysis gave
from a
sample of the matt green paint from the screen The of saturated
identity of the paint medium. absence
(Figure 10) indicated the presence of a true copper the
in the chromatograms
fatty acids argues against
resinate [22, 23] and were in good agreement with or a number
use of an binder of oils. The
egg-based
as
those obtained from standard samples [24], as well oil mentioned as a binder in the historic
paulownia
at the National Gallery by heating
samples produced literature contains low levels of saturated fatty
only
verdigris with pine resin (based on a recipe in the De
in a leanly
acids, which could be almost undetectable
see at 1696 and
Mayerne manuscript, [25]). The bands
bound but there was also no indication of the
paint,
1242 cm"1 are characteristic of resin acids, and the band
at 1607 cm"1 is characteristic of the copper-resin acid
interaction (asymmetric copper
carboxylate stretching
the green were in
frequency) [26].When particles placed
a diamond micro-compression cell, a few deeper blue

green particles could be seen within the compressed

green matrix. These are the residues of the

presumably
copper salt used to prepare the copper resinate (possibly

copper chloride, based on results), but attempts

the EDX
to characterize this material
by infrared microscopy
failed. Examination of a sample from a glossy pale green
area confirmed the presence of the same green copper
lead white. no
resinate pigment, mixed with Although
3150 2650 2150
information is given about the particle morphology, wavenumber/cm1
a
light green translucent pigment which gave a good
match with copper resinate reference spectra when
Figure 10 FTIR spectrum of a sample froma matt green area on the
examined IR spectroscopy has also been reported
by Coromandel screen.

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 SPHERICAL COPPER RESINATEON COROMANDELOBJECTS 247

Table 1 Results of theanalysis of a green sample fromtheCoromandel screen by GC-MS

Retention time (minutes) Component m/z [M+,B*]

1 22.50 methylseco-dehydroabietate type (bicyclic) 376, 284, 146, 101

2 22.71 methylseco-dehydroabietate type (monocyclic) 316, 284,146
3 23.51 methylpimarate 376,121
4 23.68 methylsandaracopimarate 376,121
5 24.04 methylpalustrate 376,301,241,105,91
6 24.11 methyl isopimarate 376,241,121, 105,91
7 24.41 methyldehydroabietate 374, 299, 239
8 24.96 methylabietate 376,256,241,121,105
9 25.42 methyl3- or 7-hydroxydehydroabietate(?) 330,312,237
10 25.53 methylneoabietate 376,135
11 26.12 methyl3- or 7-hydroxydehydroabietate(?)a 330,312,237(344,329)
12 26.54 (?)
methyl 15-hydroxydehydroabietate 330,315,312,255,237
13 27.20 methyl7-oxodehydroabietate 328, 253
14 27.53 unassigned 345(7), 342(7), 330, 270, 253, 235, 149,121
15 27.60 unassignedb 358, 340, 283, 265, 225
16 28.13 unassigned 340, 280, 265, 227
17 30.06 unassigned 358,313,253
18 30.20 methyl7-oxo-15-hydroxydehydroabietate(and dehydrated 344,329(326,251)
species)0
19 30.24 unassigned 360(7), 358, 313, 253
20 30.68 unassigned 370, 355
21 31.49 unassignedd 356, 341, 338, 281, 278, 263, 238, 225, 197
The use of TMTFTH (3-(trifluoromethyl)phenyltrimethylammonium hydroxide)as thederivatizingreagentnormallyyields a single derivative foreach
component and these are reported in the table.However, theresultsobtained here suggest thatminor quantities of some additional components are being
formed, much as are seen with themore alkaline reagent, tetramethylammonium hydroxide(TMAH). Inaddition,a fewcomponents show signs of some
dehydrationoccurringduring therunand co-elution:perhaps reflection problems with the injectorsystem or theGC column [28].
a Two butmight be a methoxy
species appear tobe co-eluting. Theminor component elutes too early tobe themethyl 7-oxo-15-hydroxydehydroabietate
versionofmethyl 15-hydroxydehydroabietate [29].
bThis
may be themethylated enol-formofmethyl 7-oxo-15-hydroxydehydroabietate [29].
0Two
species appear tobe co-eluting.Theminor component appears tobe thedehydrated formofmethyl 7-oxo-15-hydroxydehydroabietate.
dTwo
species are possibly co-elutinghere. One species may yield356/341 and theother338/225/263.

or is
38]. A proteinaceous polysaccharide-based binder
therefore more likely,
a conclusion
supported by the fact
that the green spheres have not 'dissolved' and lost their
distinctive as have been in
morphology might expected
a resin-, oil- or binder.
lacquer-based
No bands to a polysaccharide binder
assignable
could be seen by FTIR microscopy. Where the pigment
was used alone, the very strong bands associated with
the copper resinate pigment masked the regions of
the where absorbances associated with a
spectrum
proteinaceous binder would be expected, although
shoulders at around 1650 and 1550 cm"1 in the spectrum
for the sample containing the green pigment mixed
with lead white were of a protein binder.
suggestive
Figure 11 Chromatogram of a sample froma matt green area on the remove a
To the pigment interference, sample of the
Coromandel Screen.
matt green was extracted with hot water and the
paint
dried extract examined. The IR spectrum (not shown)
presence of unsaturated fatty acids in which paulownia confirmed the use of a protein-based binding medium
[30, p. 234] and other drying oils
are rich (no residual (probablyanimal glue).
unsaturated fatty acids and no oxidative degradation No descriptions of the manufacture of a pigment such

products such as azelaic acid were detected) [29, pp. 36? as that on the screen have been found in accounts of

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 248 L. BURGIO, S. RIVERS, C. HIGGiTT, M. SPRING AND M. WILSON

term
Coromandel craftsmanship. The 'copper resinate' is brush marks. White accretions along the edges of many
more encountered in the context ofWestern incised areas were identified as wax
commonly paraffin [34]. The
easel painting, where it has traditionally been varnished surface had a autofluorescence
European greenish-white
used for green translucent copper-containing glazes, under ultraviolet (UV) illumination, which is consistent
recent work has shown that these glazes in with several Western natural resin varnishes. contrast,
although By
fact generally consist of verdigris which has wholly or black oriental
photo-degraded lacquer frequently
in the oil binding medium. a muted
partially reacted and dissolved exhibits orange autofluorescence [35]. These
A small amount of varnish was sometimes added to these factors, combined with the solubility characteristics,

glazes,
so that some
'copper resinate' can be present, but suggested the presence of a wax-resin varnish.
formed through reaction with the resin on ageing of the Although alcohols and ketones would usually be used
to remove this type of varnish, contact with
paint rather than by deliberate reaction [22, 23, 31]. such solvents
The unusual of the copper resinate often causes in oriental
morphology blanching photo-degraded
on the Coromandel screen suggests that it did more
particles lacquer. The light-damaged the lacquer and the
not a copper to these solvents, the more
simply result from the reaction of pigment longer it is exposed likely it
with an
organic binding medium but is a deliberately is that significant blanching will occur [36]. Solvent tests
manufactured copper resinate pigment. It seems likely
on the varnish demonstrated that aromatic hydrocarbon
that the molten copper resinate mix was solvents caused sufficient to allow removal of
quenched swelling
in water and that the green then the varnish from the a combination of
spherical particles lacquer using
out of the
emulsion as the copper resinate solvent and mechanical action.
separated
cooled and solidified. Such a method of production tests on the matt green copper resinate
Solubility
would account for the shape and the variable size of were undertaken small viewed
paint using samples
resinate has under 100?200x The was
the pigment particles. Where the copper magnification. pigment
not been mixed with lead white, the lean proteinaceous in ethanol and acetone and insoluble in
readily soluble
binder does not fill the voids between the large pigment deionized water, aliphatic and aromatic hydrocarbon
particles, explaining why the paint appears rather matt solvents. The overlapping solubility parameters of
and is very powdery and brittle. The lighter green
areas
pigment and varnish combined with the friabilityof the
the same pigment and also have a proteinaceous that no attempt was made to remove
contain paint layer meant
but contain lead white, which fills the theWestern varnish from the matt paint. However, itwas
binding medium,
voids between the green particles a more still necessary to consolidate the matt paint decoration
giving glossier,
durable paint. without further altering its appearance.
The aims of the consolidation treatment for the
matt on the screen were to introduce
CONSERVATION paint enough
consolidant to prevent further loss of pigment, ideally
In contrast to the areas, which were without altering the appearance of the paint, and to allow
gloss painted largely
intact, areas of matt painted decoration were for the possibility of future re-treatment without damage
powdery
and friable and had suffered significant losses, as is to the paint or adjacent lacquer. Common approaches
typical ofmatt paintswith theirhigh ratio of pigment for the consolidation of matt paint include reducing the
volume to binder volume [32, p. xxxix]. Adhesive failure concentration of consolidant, using multiple applications
is of very dilute consolidant solutions less than
had occurred both within the paint layer, which (sometimes
0.5-1.5 mm thick, and at the interface with the white 1%) or using a nebulizer [37] or ultrasonicmister [38];
that this paint had of consolidant into the paint layer
preparation layer. SEM images showed increasing penetration
a was means of a slow-evaporating solvent [39] or a vapour
rough surface, poorly bound and contained large by
voids. This a since saturated atmosphere [40] ; the
use of additives such as
paint presented particular challenge,
any conservation treatment that alters these properties matting agents in the consolidant and experimentation
will causea marked in the appearance of such with traditional materials in new ways, for example
change
a reduction an in Japanese conservation
paint, due to in the diffuse reflection of light funori, alginate used [37, 41,
from the surface of the paint [33, p. 164]. 42]. Several methods and materials were tested, including
Both the front and rear of the screen had been Paraloid B72 in dilute solutions and in the slow

varnished in the past, probably in an attempt to unify the aromatic solvent a range of
evaporating diethylbenzene,
of wax ethers, and the use of fumed silica as a matting
appearance repairs and the adjacent lacquer. The cellulose

agent. All were

semi-matt varnish was characterized uneven unsuccessful, either insufficient
by thick, providing

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 SPHERICAL COPPER RES?NATE ON COROMANDEL OBJECTS 249

adhesion or the matt green paint. However, a coherent film on top of the pigment
darkening forming particles.
during informal discussions of this consolidation problem, By the time the white spirit has evaporated, the isinglass
from the V&A conservation studio has gelled below the surface. The low concentration of
colleagues sculpture
referred to their use of immiscible solvents to prevent the sufficient adhesion within the paint
isinglass provides
filling the voids and darkening the paint.
penetration of aqueous cleaning agents into uncoated layer without
surfaces Consolidation of the friable matt paint using
porous plaster during cleaning [43]. Typically
the plaster surface was wetted with a immiscible solvents facilitated the rapid treatment of
hydrocarbon
solvent (white spirit) which acted as a barrier to prevent substantial areas of matt on the Coromandel
paint
water-soluble dirt being carried further into the porous, screen. These vertical surfaces have suffered no further
water sensitive as the surface was cleaned loss in the years since the screen was at the
plaster surface redisplayed
with a swab. The use of immiscible solvent V&A in a gallery where relative humidity ranges from
dampened
combinations has been for aqueous 32 to 57%. Two other matt a small
reported cleaning painted objects,
of paintings solvent Chinese polychrome sculpture and
(hydrocarbon layer/ammonium eighteenth-century
a also
hydroxide-water solution [44]) and paper objects with nineteenth-century Japanese ceiling panel, have
water-sensitive media barrier layer [45]). been treated successfully using this method.
(cyclododecane
There is only a anecdotal reference to the use
single
of immiscible solvents for consolidation of matt
paint CONCLUSION
as Futernick, communication):
(footnoted personal
adhered The areas of the Coromandel screen contain
'sensitive flaking paint has been successfully green
with emulsions while the was saturated a translucent dark green with an unusual
acrylic paint pigment
with toluene... the toluene was allowed to form. It was using FTIR
identified
dry, leaving spherical particle
the flaking paints still porous but adhered' and GC-MS as copper resinate, which had
[32, p. lvi]. microscopy
These with materials been deliberately as a resin that
experiences porous prompted prepared pigment using
consolidation tests following a similar was
probably from a species of pine. This is the first
approach.
An acrylic dispersion, Primal WS24 (5% solids), time to the authors'
knowledge that a pigment of this

and 5% w/v were tested. First, drops of a which was used in the green
isinglass description, extensively
were to the areas on the screen, has been
hydrocarbon solvent (white spirit) applied reported. A pigment with
friable paint from a
pipette, followed by application of the same microscopic appearance has also been found on
the consolidant, drawn off by capillary action from a two other Coromandel a casket and a cabinet
objects,
to the surface. Once from late seventeenth century, which were
fine sable brush touched dry, the dating the
treatment was evaluated
by brushing lightly
over the
sampled for comparison (Figure 12). It seems likely that
surface with a dry sable brush while the effect further of Coromandel will uncover
observing analysis objects
under low magnification. No loose pigment more of its use.
particles examples
were was used, but 5% Primal was
observed when isinglass The paint glossy, hard and well preserved where
WS24 was insufficient to secure the pigment. In both the spherical green pigment was used in admixture with

cases, the appearance of the surface was unchanged. lead white, and matt and porous where itwas not. The
further was selected was identified as proteinaceous in both
After successful trials, isinglass binding medium
as the consolidant for the matt areas of the cases, which contradicts historical sources that document
painted
Coromandel screen. Some adhesives the materials and techniques used to create Coromandel
collagen-derived
can offer
stability if natural contaminants are
lacquer. Consolidation of the matt paint was achieved
long-term
minimized, relative fluctuations limited and without the appearance of the a
humidity altering paint using
high light levels avoided [33,p. 165]. combination of the immiscible materials white spirit and
The most for the effectiveness of isinglass.
likely explanation
the treatment on
is simple displacement. Isinglass used
its own as a consolidant forms a thin layer on the surface
APPENDIX - EXPERIMENTAL
that saturates and darkens matt paint. Pre-wetting the
surface with a solvent such as white
hydrophobic spirit
Optical microscopy
prevents the isinglass is applied,
this.As the white spirit is
and forms a at the surface of the paint, on Samples
were embedded in clear casting polyester
displaced layer
top of the isinglass. The white spirit layer resin, polished and examined under visible and UV
hydrophobic
acts as a barrier that repels the isinglass and prevents it illumination with a Leica Aristomet and a
microscope

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250 L. BURGIO, S. RIVERS, C. HIGGITT, M. SPRING AND M. WILSON

.* -
?B:--1-'1'
**.W
*?*

1
*

*V

F/gi/re 72 Photomicrograph of a cross-section of a sample froma matt green area on theCoromandel cabinet (V&Aaccession numberFE.39-1981)
showing a layerofgreen spheres. Imagewidth: approximately0.8 mm.

Leica Laborlux 12 ME microscope. Dispersions

were GC-MS
using Cargille Meltmount
(refractive index:
prepared reac
The were in 1 mL
as the medium and a hotplate, the paint samples placed tapered
1.662) dispersing
tion vials and treated with microlitre quantities of 5%
temperature of which was set between 65 and 95?C.
methanolic TMTFTH (3-(trifluoromethyl)phenyltri
(The pigment discoloured slightlywhen heated at The vials were sealed
100?C in water.) methylammonium hydroxide).
and heated at ~70?C for about five hours. Each sample
was before 1 uL of the supernatant was
centrifuged
SEM-EDX was
injected. Thermolytic methylation accomplished,
under moderate conditions, upon injection into the
Polished carbon-coated cross-sections were examined
at 25 kV a Instruments S200 SEM
GC injection port at a temperature of 270?C. Analysis
using Cambridge
was carried out on a Trio 2000 quadrupole
mass
with a backscattered electron detector and
equipped
spectrometer to a Hewlett-Packard 5890 Series
Instruments coupled
energy dispersive X-ray analyser (Oxford
II gas Chromatograph. 30 m x 0.32 mm bore BPX5
INCA 300 EDX system).An Hitachi tabletop scanning
coated silica column with 1 jam film thickness
electron TM-1000 at 15 kV was capillary
microscope operating
to produce (5% phenyl (equiv.) polysilphenylene-siloxane stationary
also used backscattered electron images of
injector temperature 250?C, helium carrier,
unmounted of the spherical phase),
samples green pigment
column head pressure 48 kPa, splitless mode, column
(working distance ~5 mm, chamber pressure ~50 Pa).
70?C one minute) and then ramp at
programme: (for
10?C perminute to 300?C (held for 105 minutes), line
FTIR microscopy 290?C. Mass conditions: 70 eV
temperature spectrometer
electron source 210?C, scan range
were a Nicolet 710 Series FTIR impact, temperature
Spectra acquired using
40-600 Daltons, scan time 1 s, interscan time 0.1 s.
with a NicPlan infrared microscope, fitted
spectrometer
with a (MCT) Type A
mercury-cadmium-telluride
detector (cooled with liquid nitrogen). Measurements ACKNOWLEDGEMENTS
were made in transmission mode, a
using Spectra-Tech
Reflachromat xl5 128 scans The authors are to Dr Daffydd Griffiths,
Cassegrain objective. grateful
were made at a resolutionof 4 cm"1 with Happ-Genzel Institute of Archaeology, UCL for providing access to

Both spectrometer and microscope were SEM-EDX facilities at the early stages of this research
apodization.
with water- and air. were in 2001; to Hitachi Corporation for
purged C02-free Samples High-Technologies
between the windows of a Spectra-Tech micro kindly making available instrument time on aTM-1000
placed
diamond cell. to Julie Arslanoglu, Sarah Medlam
compression tabletop microscope;

STUDIES IN CONSERVATION 52 (2007) PAGES 241-254

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 SPHERICAL COPPER RESINATE ON COROMANDEL OBJECTS 251

and Julia Hutt for discussions on Coromandel to 12November 1993, ed. K. Nishikawa,Tokyo National Research
lacquer;
Barbara Schertel and Nanke Schellmann Institute of Cultural Properties, Tokyo (1993) 49-62.
Edgar Mantz,
texts. Rian 13 Piert-Borgers, B.,'Aspects and problems of the application of
for assistance with German Kanduth and
Urushi in the restoration of objects from European collections',
Alice contributed to the conservation of the
Kleyboldt in International Symposium on theConservation and Restoration of
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Cultural Property:Conservation ofUrushi Objects, 10?12 November
1993, ed. K. Nishikawa, Tokyo National Research Institute of
Cultural Properties,Tokyo (1993) 147-165.
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14 Bresinsky, H., 'Montierter Lack' (Mounted oriental lacquer:
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16 Fiedler, I., and Bayard, M.A., 'Emerald green and Scheele's
Cargille Meltmount: McCrone Ltd,. McCrone House, 155a
London NW5 green', in Artists' Pigments: A Handbook of theirHistory and
Leighton Road, 2RD, UK.
CharacteristicsVol. 3, ed. E. West Fitzhugh, National Gallery of

Art,Washington (1997) 219-293.

17 Gettens, R.J., andWest Fitzhugh, E., 'Malachite and green
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27 Mills, J.S., andWhite, R., The Organic Chemistry ofMuseum 41 Michel, F., Geiger, T., Reichlin, A., and Teoh-Sapkota, G.,
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resins: In situ derivatization procedures using quaternary 257-275 [inGerman].
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257-272. JunFunori used to consolidate matt paint', Studies inConservation
29 van den Berg, K.J., Boon, J.J.,Pastorova, I., and Spetter, L.F.M., 50 (2005) 193-204.
'Mass spectrometric methodology for the analysis of highly 43 Hubbard, C, and Kosinova, A., Victoria and Albert Museum,

diterpenoid acids in Old Master paintings', Journal of

oxidized personal communication (1997).
Mass Spectrometry35 (2000) 512-533. 44 Hook, J., 'The use of immiscible solvent combinations for
30 Hilditch, T.P., andWilliams, P.N., The Chemical Constitution of the cleaning of paintings', Journal of theAmerican Institutefor
Natural Fats, 4th edn, Chapman and Hall, London (1964). Conservation 27 (1988) 100-104.
31 Spring, M., and Higgitt, C, 'Analyses reconsidered: The 45 Briickle, I., Thornton, J., Nichols, K., and Strickler, G.,
importance of the pigment content of paint in the interpretation 'Cyclododecane: Technical note on some uses in paper
of the results of examination of binding media', inMedieval and objects conservation', Journal of theAmerican Institutefor

Painting inNorthern Europe, ed. J.Nadolny, K. Kollandsrud, Conservation 38 (1999) 162-175.

M.L. Sauerberg and T. Froysaker, Archetype, London (2006)
223-229.
32 Hansen, E.F., Walston, S., and Bishop, M.H., Matte Paint: Its AUTHORS
History and Technology, Analysis, Properties and Conservation
Lucia Burgio in chemistry from the
Treatment, with Special Emphasis on Ethnographic Objects: A graduated
a
Bibliographic Supplement to theArt and Archaeology Technical University of Palermo, Italy, in 1996. She completed
Abstracts (AATA) 30 (1993). PhD in at University College London
degree chemistry
33 Hansen, E.F., Sadoff, E.T., and Lowinger, R., 'A review of in 2000 with a thesis on the analysis of pigments
on ethno
problems encountered in the consolidation of paint on art
objects using Raman microscopy and other
graphic wood objects and potential remedies', in ICOM a few months at ENEA
techniques. After working
Committee for Conservation, 9th Triennial Meeting, Dresden, ed.
(New Technologies, Energy and Environment Agency)
K. Grimstad, ICOM Committee for Conservation/Getty
in Italy, she joined the Science Section, Conservation
Conservation Institute,Los Angeles (1990) Vol. I 163-168.
at the Victoria and Albert Museum in
34 Russell, J.,Analysis ofAccretionsfrom a Coromandel Screen,V8cA Department,
2000. Her research interests include the analysis of
Conservation Science Report 01/70/JER (2001).
35 Rivers, S., and Umney, N., Conservation ofFurniture,Butterworth pigments and other artists' materials (including lacquer)
on museum and the application of scientific
Heinemann, Oxford (2003) 761. objects,
36 Rivers, S., 'Removal of varnish from japanned and lacquered to art and cultural heritage issues. She is
techniques
surfaces:Principles and practice', in The Meeting ofEast andWest senior scientist at the Victoria
currently object analysis
in the Furniture Trade, Sixth International Symposium onWood and Albert Museum as well as research fellow
honorary
and Furniture Conservation, Stichting Ebenist: Postprints, ed. P. at University London. Address: Science
College Section,
van Duin and H. Piena, Rijksmuseum, Amsterdam (2002) Conservation Department, Victoria and Albert Museum, South
52-58.
37 Grantham, S., Byobu and Fusuma: Developing an Approach to the Kensington,London SW7 2RL, UK andChristopherIngold
Laboratories, University College London, 20 Gordon Street,
Conservation ofJapanese Screens throughTechnical Study and an
London WCiH OAf UK. Email: [email protected]
Investigation ofCurrent Practices,unpublished PhD thesis,Royal
College of Art/Victoria and Albert Museum Conservation
Shayne Rivers from the Royal College of
Programme (1998). graduated
38 Michalski, S., Dignard, C, van Handel, L., and Arnold, D., 'The Art/V&A Conservation Programme in 1998 with an
ultrasonic mister: Applications in the consolidation of powdery MA in furniture and decorative surfaces conservation.
matte paint on wooden artifacts', in PaintedWood: Conservation Since 1999 she has been a senior conservator at the
andHistory, ed.V Dorge and EC. Howlett, Getty Conservation Victoria and Albert London. She is co-editor
Museum,
Institute,Los Angeles (1998) 498-513. and a contributor to the Conservation
principal of
39 Welsh, E.C., 'A consolidation treatment for powdery matte
Furniture, in 2003 as part of the Butterworth
published
paint', in Preprints of Papers Presented at the Eighth Annual Heinemann Series. In recent her
Museology years
Meeting of theAmerican Institutefor Conservation ofHistoric and
primary research interest has been the conservation of
ArtisticWorks, American Institute for Conservation (AIC), San
oriental Address: Furniture Conservation, Victoria
Francisco (1981) 141-150. lacquer.
and Albert Museum, South Kensington, London SW7 2RL
40 Hansen, E.F., Lowinger, R., and Sadoff, E., 'Consolidation of
UK. Email: s. rivers@vam .ac.uk
porous paints in a vapour saturated atmosphere', Journal of the
American Institutefor Conservation 32 (1993) 1-14.

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 SPHERICAL COPPER RESINATE ON COROMANDEL OBJECTS 253

Catherine Higgitt graduated in chemistry from the InstituteinCambridge in 1991. She joined the Scientific
University ofYork in 1994 and completed a PhD degree Department in the National Gallery in 1991. Her
in chemistry at the same institution in 1998. After one interests are the of historical
principal study painting
year working for the Historic Scotland Conservation technique and materials, particularly pigments, and
Centre in Edinburgh, she joined the Scientific research into the mechanisms of their deterioration.
at the National in London in 1999, She is currently senior scientific officer at the National
Department Gallery
working with Raymond White. Here she specialized Gallery. Scientific Department, The National Gallery,
in the study of natural organic materials in old master Trafalgar Square, London WC2N 5DN, UK. Email: marika.

paintings using spectroscopic, Chromatographie and [email protected]. uk

methods. The study described in this
spectrometric
Ming an MA
she was Wilson, Chinese by birth, has degree from
paper was undertaken while senior organic
the School of Oriental and African Studies, London
at the National of 2007
analyst Gallery. At the beginning
University. She joined the Victoria and Albert Museum
Catherine moved to the British Museum to take up the
in 1994 and is now a senior curator in the Asian
post of head of the Science Group. Address: Department
Department, where she is responsible for the collection
of Conservation, Documentation and Science, The British
of Chinese decorative arts. Her recent publications
Museum, Great Russell Street, London WC?B 3DG, UK.
Rare Marks on Chinese Ceramics
Email: uk
include (1998), Souvenir
[email protected].
fromCanton,ChineseExportPaintingsfrom the V&A (2003)
Marika Spring graduated in natural sciences, specializing and Chinese Jades (2004). Address: Asian Department,
in chemistry, from the University of Cambridge in Victoria and Albert Museum, South Kensington, London

1988, and completed a in the SW1 2RL, UK Email:

postgraduate diploma [email protected]
conservation of easel paintings at the Hamilton Kerr

?
R?sum? Un pigment vert inhabituel a ?t? trouv? dans un paravent laqu? kuan cai (Coromandel) du XVIIe si?cle du
Victoria and Albert Museum, ? Londres. Les particules sont parfaitement sph?riques et translucides et ont Vapparence d' ufs de
un resinate de cuivre avec une r?sine,
poisson. Les analyses ont montr? que lepigment est produit par la r?action d'un sel de cuivre
de Pinus. Le liant pour ce est La inhabituelle des est
probablement Vesp?ce pigment prot?inique. morphologie sph?rique particules
due ? la m?thode defabrication. Un pigment d'apparence semblable a aussi ?t? trouv? sur deux autres objets Coromandel de la
m?me collection. Dans les zones vert clair ou vert olive, o? lepigment est m?lang? avec du blanc de plomb, la peinture est brillante
et bien conserv?e. En revanche, dans les zones vert sombre, o? lepigment est utilis? seul, la peinture est mate et pulv?rulente et
on observe des lacunes et des zones d'abrasion. de solvants non miscibles entre eux et d'un consolidant a permis de
L'emploi
consolider la peinture pulv?rulente tout en mat de la surface.
pr?servant l'aspect

Zusammenfassung ?Auf cai (Coromandel) Lacktafel des 17. Jahrhunderts aus dem Besitz des Victoria
einer kuan
and Albert Museum, ein ungew?hnliches Gr?npigment gefunden. Die Partikel sind perfekt sph?risch und
London wurde
durchscheinend und haben das Aussehen von konnte das Pigment als Kupferresinat bestimmt
gr?nen Fischrogen. Analytisch
?
werden, das durch Reaktion eines Kupfersalzes mit einem Harz, wahrscheinlich aus einer Pinus Species, entstanden ist.
Das Bindemittel des Pigmentes istproteinisch. Die ungew?hnliche sph?rische Morphologie des Pigmentes istErgebnis des

Herstellungsprozesses. Ein Pigment des gleichen mikroskopischen Aussehens wurde auf zwei anderen Coromandel
Objekten
wo das
derselben Sammlung gefunden. In den hellgr?nen bzw. olivgr?nen Bereichen, Pigment mit Bleiwei? ausgemischt ist, ist
Im Gegensatz dazu sinddie dunkelgr?nen
dieMalschichtgl?nzend undgut erhalten. Bereiche,indenendas Pigmentalleine
verwendet wurde, matt und abgepudert und einMalschichtverlu?t sowie Abrieb istfeststellbar. Das Problem derKonsolidierung
der pudernden Malerei unter gleichzeitigem Erhalt des matten Oberfl?chencharakters wurde durch die Verwendung von
unmischbaren L?sungs- und Konsolidierungsmitteln.

?
Resumen Un pigmento verde inusual fue identificado en un panel de laca kuan cai (Coromandel), del siglo XVII,
al Victoria and Albert Museum, Londres. Las son con la
perteneciente part?culas perfectamente esf?ricas y transl?cidas, apariencia
de huevos de pescado verdes. Los an?lisis revelaron que el pigmento es un resinato de cobre producido por la reacci?n de la sal

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254 L. BURGIO, S. RIVERS, C. HIGGITT, M. SPRING AND M. WILSON

de cobre con una resina, probablemente una de la

especie Pinus. El aglutinante para este
pigmento es prote?nico. La inusual
de las es del proceso de elaboraci?n. Un con la misma se detect? en
morfolog?a part?culas fruto pigmento apariencia microsc?pica
otros dos objetos Coromandel de la misma colecci?n. En las ?reas claras o de color verde oliva, donde el est? mezclado
pigmento
con blanco de es brillante y est? bien Por el contrario, en las zonas de verde oscuro, donde el
plomo, la pintura presentada.
se ha se presenta mate y con abundantes
pigmento empleado puro, la pintura pulverulenta p?rdidas y abrasi?n. El problema de
la consolidaci?n de la pintura manteniendo la apariencia mate se resolvi? con el uso de disolventes inmiscibles y de
pulverulenta
consolidante.

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