Cross-Sections and Chemical Analysis of Paint Samples

Joyce Plesters
Studies in Conservation, Vol. 2, No. 3. (Apr., 1956), pp. 110-157.
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JOYCE PLESTERS

Cross-sections and Chemical Analysis

of Paint Samples
Received 3011 156
INTRODUCTION AND SURVEY OF PREVIOUS WORK

IT has now become quite usual for conservators and restorers to regard a painting
as a stratified structure, so that methods
have been developed for studying the internal layers of a painting. Examples of such
methods are X-ray and infra-red photography. Here, however, superimposed images
of the layers are obtained (except, in the
case of X-rays, in very special circumstances). A more direct method is to look
at the painting in cross-section. This is often
difficult to do in situ on the picture even
with a good travelling microscope, since even
when cracks exist whose edges may be examined, the edges are nearly perpendicular to the
focal plane of the microscope, so that, at best,
only an oblique and rather out-of-focus view
can be obtained. It is usually more convenient
to detach a minute fragment of paint from the
picture and look at it separately under the
microscope. Even then, in order to see the
separate layers, the paint fragment must be
stood on one edge, and for a proper microscopical examination the sample needs to be
mounted in a suitable mounting medium and
to have an edge g o u n d or cut smooth in
order to give a plane surface for focusing
under the microscope.
This is the raison d'itre for all methods of
preparing paint cross-sections. As a further
scientific method of picture examination the
technique is compleAentary to radiography
and infra-red photography, in that the paint
section gives a large amount of precise information over a very small area of the picture,
whereas the radiograph or infra-red photograph gives rather more general information
over a large area of the picture.

The preparation of paint cross-sections was

begun more than forty years ago. Pioneer
work was done by Laurie [ I ] as early as 1914.
The scope of the method was extended and
the technique improved at the Fogg Art
Museum, Cambridge, Massachusetts, in the
1930's [ 2 ] . At this time waxes were used as
mounting media for the paint sections, which
were cut with a microtome. The friability of
most old paint films makes this a difficult
operation, and since then the process has been
simplified by using modern synthetic resins as
mounting media and by grinding and polishing
the sections. It must be pointed out here that
what is required is not a transparent section, to
be viewed by transmitted light, as is necessary
in the case of many mineral sections, but an
opaque section, the surface only of which is
examined by reflected light, which makes the
preparation fairly simple. Such paint crosssections are now made in many museum
laboratories. These include the Laboratoire
Central des MusCes de Belge [3], where
methacrylate resins are used as the embedding media, the Courtauld Institute of Art,
University of London [4], and the National
Gallery, London [j and 61. In the National
Gallery, the resin used for mounting paint
sections is a cold-setting polyester resin.
THE ADVANTAGES AND LIMITATIONS OF THE

METHOD

Advanfagex
The two main advantages are:
(a) A great deal of information can be
gained from a very small amount of material.
At one and the same time the sequence of
paint layers in the picture may be noted,
together with their colour and texture, their
I10

Cross-sections and Chemical Analysis ?fPaint Samples

FIG. I .-Fresco Painting

Roman fresco, c. zoo A.D.
(i) Wall plaster mixed with coarse marble dust.
(ii) Coarse green-blue pigment.
(iii) Blue pigment.

111

FIG. 2.-Panel Painting.

N.G. No. 2475. Holbein.
Christina of Denmark, Duchess of Mian
(i) Wood of panel (oak).
(ii) White gesso (calcium carbonate and glue).
(iii) Pale fawn gesso (as (ii), but of a higher proportion of glue.
(iv) White underpaint (lead white in oil medium.)
(v) Original blue paint layer.
(vi) Grey-green repaint (at one time blue).
(vii) Second repaint, blue.
(Layers v-viii incl. are discussed more fully
on p. 114.)

FIG. 3 .-Canvas Painting.

English School, seventeenth century
(i) Threads of canvas.
(ii) Traces of whitish priming (lead white in
oil medium).
(iii) Blue paint layer (smalt mixed with lead
white in oil).
(iv) Discoloured varnish.
(Magnification of all photomicrographs shown is x 75)

Plesters

thicknesses may be measured, and the sizes of

pigment particles, and pigment and medium
analysed chemically, using a square millimetre
or so of paint.
(b) By detaching a small fragment of paint
from the picture it is possible to carry out
operations on it which it would be inadvisable
or even dangerous to carry out on the picture
itself. This is especially valuable where a safe
bm efficient solvent mixture has to be found
for the removal of overpaint. Tests with
strong reagents may be carried out safely away
from the picture until their effect on the paint
is known. It would not be possible to carry
out tests on such a small scale on the picture
surface even under a binocular microscope,
and exceedingly difficult to restrict the area
of the picture affected by the reagent.

Limitatiorts
(a) In order that its appearance may not
be damaged, only minute samples of paint
can be removed from a picture, so that the
amount of material available to work on is
very small. This advantage is, however, somewhat offset by the special methods used.
(b) Long-term study of the artist's technique
or of paint structure by this method would
require numerous samples, and the sources for
such samples are rather limited. In the National
Gallery, for example, specimens have, up to
the present, been taken only from pictures in
course of treatment, and then usually only
when some information might be obtained
which would be of use to the restorer working
on the picture.
(c) There is what might be called a statistical hazard, in that it cannot be certain that a
square millimetre or less of paint is representative of the area under study, which may be
as much as a hundred square centimetres, even
though to the eye the area may be uniform
in colour and texture. However, in cases
where it has been possible to make sections of
adjacent and similar areas of paint (e.g. in
work on 'guinea pigs'-aesthetically worthless, but hstorically sound pictures) the results

have been very consistent. Nevertheless,

accident, artistic temperament, and the artist's
cleaning his brush on the edge of the picture
have all to be reckoned with.
PROCEDURE I N THE NATIONAL GALLERY

It must be pointed out that in the National

Gallery the collection of paint sections from
pictures (those of permanent interest now
number over two hundred) has grown primarily out of those prepared in order to solve
ad hoc problems of the restorer. Hence the
examples from National Gallery pictures
quoted are practically all from pictures restored within the past five years during which
work on paint sections has been carried out.
This is the reason for what would otherwise
seem a somewhat illogical and heterogeneous
selectioil of illustrations. It is fortunate that
examples cover such a wide range of time
and most European Schools. In addition,
gratitude must be expressed to friends who
have given samples of paint from pictures in
other collections which have widened considerably the scope of study.
A sample of paint is removed from the
picture by the restorer. This is done with a
small, sharp-pointed knife. The knife is inserted into a crack, for preference, in the
paint and then a small piece is levered up,
the operation being carried out under low
magnification provided by a binocular loupe
or a travelling binocular microscope. It is
preferable that the picture should be lying
flat, so that any scattered particles, however
small, may be saved. The knife tip may be
moistened with saliva to assist the paint fragment to adhere to it. The use of canada balsam
or varnish is avoided if possible, because of
the difficulty they cause during chemical
analysis. The main sample and any grains of
paint which have fallen from it are picked up
with a slightly damp camel hair brush, and if
required for use immediately, placed on a
microscope slide. Otherwise such samples may
conveniently be stored in the small gelatin

Cross-sectiotzs atzd Chemica Analysis of Paittt Samples

11

capsules used for pharmaceutical purposes.

They are carefully labelled, and if there is any
doubt as to whether the exact spot from which
the sample was taken could be found again,
the co-ordinates of the spot on the picture are
measured. It must be admitted that the method
of removing the sample from the picture is
somewhat crude, and not wholly satisfactory.
In the past several attempts have been made
to devise a suitable instrument for this purpose. Laurie [I] had the idea of using a
sharpened hypodermic needle, but as pressure
is needed this tends to shatter the brittle paint
and also there is the difficulty of getting the
specimen out of the hollow of the needle
intact. Gettens [7]constructed a more promising but rather complex instrument for this
purpose.
The sample of paint is removed to the
laboratory and viewed under a microscope at
low power (30 x to 150 x usually proves a
suitable range). Requirements as far as the
microscope is concerned are not very exacting.
They are set out in a paper by Gettens [8]
and a further paper by Gettens and Stout [g]
(these also list useful tools and equipment). In
addition to an ordinary microscope (or a
chemical one for choice) a stereoscopic binocular microscope is often useful. A microscope with polarizing and analysing Nicol
prisms is also valuable if much pigment
identification is to be carried out. A powerful
light source such as a 'Pointolite' is essential,
as well as a white light source. For the latter
the National Gallery laboratory possesses a
small daylight fluorescent-tube microscope
lamp; it is useful for the estimation of colour
at low magnifications.
The appearance of the upper and lower
surfaces of the paint is noted and the largest
fragment is used to prepare a cross-section.
The rest is set aside for chemical analysis.
The polished section is then examined under
the microscope at a suitable magnification.
The thickness of the paint layers and the
particle sizes of the coarser pigments can be
measured using an eyepiece with a calibrated

113

scale. Moreover, by noting the colour, particle

size and shape, opacity or transparency,
crystallinity, etc., of the pigments it is possible
to narrow down the range of possible pigments present very considerably before proceeding to chemical analysis. An invaluable
aid at this stage is as complete a collection as
possible of known pigments mounted on
slides for comparison. Those used at present
in the National Gallery are mounted in
canada balsam, but it is intended that in the
near future they should be replaced by a new
set mounted by more modern methods such
as those described by Charlett [IO]. After the
optical examination has been completed the
paint section may be subjected to a series of
solvent tests, staining tests and other chemical
tests, which will be described later in this
article. Further chemical tests are then made
on the remainder of the sample which was
left unmounted. A series of solvent tests is
included in an attempt to identify the media
present in the sample, each reagent being
evaporated or removed by means of filter
paper or capillary tubes before the next is
added. Such techniques used in handling these
small amounts of materials are fully described
in Chamot and Mason's manual [I I].
The above, then, is the general scheme of
examination. Its application and results will
now be examined in detail. The observations
made on the cross-sections will be discussed,
together with the conclusions drawn from
them, and the results of paint analysis. The
chemical tests for pigments and media will be
given in detail at the end of this article.
THE LAYER STRUCTURE OF A PICTURE

The first and most obvious feature to be

observed in a paint section is the sequence of
layers present. It is often stated that the four
main strata of any picture are support, ground,
paint, and surface coating. It is possible to
make a section to show all of these layers, but
in practice the support is often omitted since
it can usually be examined from the back of

the picture. It is desirable to include at least

part of the thickness of the ground or priming,
if only to make sure that all the paint layers
present in the picture are represented. The first
three examples illustrated do, however, include the supports in order to show the scale
of the layers and the general relatioilship of
the different components of the picture:
Fiy. I. Fresco Paintiny (Rorizarz, c. 200 A.D.)
The plaster of the wall is exceedingly rough and is
mixed with coarse marble dust. The blue pigment particles are also very coarse. They were found to be surrounded by crystalline calcium carbonate. There is no
varnish. A coarse structure is fairly typical of wall
paintings.

Fig. 2. Pmel Painting (N.G. No. 2475, Hans

HOLBEIN

the Yourger). Christitra of Detrrizark, Duchess of

Milan. Blue paint from background
The wood fibres of the oak panel can be seen. There
are two layers of calcium carbonate and glue gesso.
Panels almost always have a gesso layer thick compared to the thickness of the paint layers (Dutch seventeenth century panels are one notable exception). Above
the gesso is an underpaint of lead white. Two of the
three layers of paint shown were proved to be repaints.
Traces of varnish were present, but not in the part of
the section shown in the photogr.~ph.The medium of
the paint layer is oil.

Fig. 3. Cnnvas painting (English School, seventeet~tlz

century).
Here the canvas appears as one warp thread running
the length of the section and weft threads spaced
at intervals vervendicular
to the vlane of the Ivaver.
I
I
I

This painting is rather atypical in having so scanty a

priming layer. The single paint layer consists of lead
white and a blue pigment, smalt, in an oil medium.

Wall paintings will not be discussed here

further, after this brief comparisoi~.The rest
of the discussion will deal solely with paintings
on canvas and panel.
PAINT SECTIONS AS AN AID TO PICTURE
RESTORATION

It has already been mentioned that the

primary reason for taking paint samples from
pictures in the National Gallery has been to
provide information for the restorer working
on the picture. The following are a few

examples in which the study of cross-sections

has proved of value to the restorers:
N.G. No.2475, Hms HOLBEIN,
tile Yolrr;yer, Ciiristir~aif
Det~rnark,Duchess qf Milarr
Cleaning tests were made on this picture with a view
to its being exhibited at the Royal Academy Winter
Exhibition of 'Works by Holbein and other Masters'
held in 1950-51. Radiographs covering the whole of
the oicture had shown that as well as wear in the
face there were also damages in other parts of the
picture, including the dark blue background. A cleaning
test on the background showed that under the top
varnish layers was a dark blue repaint, and, beneath
this again, what appeared to be a thick layer of greygreen tinted varnish. A cross-section was made in
order to elucidate these layers, and the pigments in the
various paint layers and also from the cleaning swabs
were analysed. The cross-section is shown in Fig. 2.
Its layers have already been briefly described in the
previous paragraph. Three blue paint layers were
present, layers v, vi, and vii in Fig. 2. They were examined and found to be:
v. A thin deep blue layer which tapers off and disappears altogether in the centre of the cross-section. It
is comvosed
of azurite in a medium of oil.
I

vi. A thick layer of granular grey-green paint, with

a few deep blue and some whitish particles visible.
The medium is an oil-and-resin varnish which has discoloured and become opaque. O n dissolving out this
medium, blue crystals of azurite can be seen.
vii. A thin deep blue paint layer, which is a mixture
of azurite, prussian blue, and lead white in an oil resin
medium.
The discontinuity of layer (v) must represent a loss
in Holbein's original paint. This original blue paint
layer has kept its bright blue colour, for the oil medium
was sparingly used and does not seem to have become
discoloured. Layer (vi) goes over the loss in layer (v) and
is therefore a repaint. O n dissolving out the medium it
was found to be pigmented with the same brilliant
blue crystalline pigment, azurite, as the original paint,
but the medium used was a mixture of oil and resin in
a high proportion to pigment. With time this medium
had yellowed, become opaque and disintegrated, coating
the blue pigment crystals with a practically opaque
yellow-brown layer so that the paint as a whole appears
grey-green in colour. After this change in the repaint
had taken place the colour of the background of the
picture must have been very dull indeed. A second
repainting was therefore carried out, represented by
layer (vii). It was found that although this final layer
contained the same pigment, azurite, as the original
paint, it also contained much prussian blue, which
since it was invented as late as 1704 could not have been

Cross-sections and Chernicnl Atzalysis

used by Holbein. Unfortunately, after these tests the
cleaning of the picture was ten~porarilypostponed in
view of the length of time it would take to remove the
repaints and restore the damaged areas, and also in
view of the rather poor state of preservation of the
face. It was interesting to note that at the Holbein
Exhibition two contemDorarv
versions of this I~ i
c t u r e
I
i
were exhibited (in the catalogue of that exhibition [IZ]
No. 22, Studio of Hans Holbein the younger, and No.
23, After Holbein). In both these pictures the background to the figure was quite a bright, slightly greenish
blue very like the background of the Holbein portrait
miniatures, and the effect of the figure against this
background is much more telling. In the National
Gallerv ~icture.
in addition to the change of colour. the
l
repaint has been carried over the edges of the figure in
some places, especially around the proper right shoulder
and side of the head.
0

7
'

N.G. No. 292,

POLLAIUOLO,

Martyrdonz o f S. Sebastian

This picture presented many complex problems to

the restorer, a few of which were resolved with the
help of cross-sections. First of all, after the discoloured
varnish had been removed with the usual type of
organic solvent mixture, it was found that the picture
was still covered with a dull greyish film. It was necessarv to make certain that this was a later accretion on
the picture and not an original glaze before its removal
from the picture could be contemplated. Cross-sections
were made frorn various areas of the picture. One of
these, from the pale blue sky, happened to show the
'grey layer' going over and into a crack in the blue
paint layer. This is shown in Fig. 6. The photograph
has been taken with the illumination exaggerating the
darkness of the 'grey layer' to show it up more clearly.
It was also found both by the restorer's careful examination of the surface of the picture, and by the study of
the sections, that although the thickness of the layer did
vary slightly over different areas of the picture, it did
not do so in any logical way as, say, a glaze used for
modelling might be expected to do. Fragments of the
'grey layer' itself were examined under the microscope
and subjected to solvent tests. It was discovered to be
a film of dried oil. with the oossibilitv of a small addition
of resin. It was not delibirately pigmented, although
scattered dust particles had become embedded in it
here and there, probably during its drying. The greyness and opalescent effect of the film on the picture is
probably due to the scattering of light on the surface
because of the fine crazing and disintegration of the
film which could clearly be seen under the microscope.
It was decided to remove the 'grey layer' from the
picture using a mild alkaline solvent.
Cross-sections were also taken from different areas
of green and brown foliage in order to discover its
state of preservation. A few areas are a comparatively

4' Paint Samples

115

bright green. A section of one of these is shown in

Fig. 7. The layers to be seen are : (i) a thick gesso of
gypsum and glue; (ii) a thin brown line ofglue priming;
(iii) a yellow-brown underpaint consisting of lead
white and brown and yellow ochre in an oil medium;
(iv) the main body colour which is pale green and
contains lead white.' ~robablv
mixed with vellow lead
I
monoxide, coloured green with copper resinate and
containing numerous dark green crystals of verdigris,
some very large; (v) traces of a browned copper resinate
glaze (not easily seen in the photograph).
Unfortunately on other parts of the picture the green
colour was produced only by a thick layer of copper
resinate over a ello ow or light brown underpaint, and
when the glaze became discoloured the green colour no
longer reAined. In some cases the onlyvisible trace of
green is an occasional crystal of verdigris ernbedded well
down in the browned copper resinate. Nevertheless,
the high concentration of copper ions and the absence of
any other brown pigment shows these decayed brown
layers to have been originally the green resinate.
The unpleasant blistered-looking surface ofsorne dark
areas of the picture was proved to be due to the use of
a bituminous pigment for the shadows and this had
sunk into the paint beneath, thus ruining it.

N.G. No. 1330, DUCCIO, The Trat?$girration

A cross-section of paint frorn the edge of a puttying
on St. James's blue robe showed that beneath were two
layers of varnish and a layer of the original blue paint
(the putty itself had a blue retouching on top). The
varnish nearer the original blue paint was thin, still
transparent, but a deep yellow in colour. The upper
layer of varnish was very thick indeed, not very
yellow, but disintegrated and perished, having a surface accurately described by the restorer as being
'crocodiled'. Both were found to be very insoluble oilresin varnishes. Their insolubility in organic solvents
was such as to lead to the belief that a hard resin like
copal must have been present. Solubility tests were
carried out under the microscope to help in finding a
suitable solvent for their removal. This was finally
performed with a mild alkaline preparation.

N.G. No. 772, Cosinzo TURA, Virgin and Child Eiztlrroiied

A blue glaze, suspected by the restorer to be a repaint, on the blue background behind the throne was
found to contain prussian blue (invented 1704) and
was therefore removed.
A curious problem, yet unsolved, was the presence
of rather crude green marbling on the steps of the
throne. It was uncertain whether or not this was original.
It was analysed and no modern pigment was found,
the paint being a copper resinate green such as was
present in several other parts of the picture which were

obviously genuine. However, several retouchings on

the picture were also found to be copper greens of
the same type. The solubilities, appearance, and u.-v.
fluorescence of the paint frorn the green marbling,
original green paint and green repaints were compared.
It was discovered that the green marbling bore rather
more similarity to the repaints than to the original
paint, but it was finally decided that the evidence was
not sufficiently conclusive to justify removal of the
green marbling.

N.G. No. 4,

TITIAN,

The Holy Fanzily

A 'grey layer' of perished oil varnish such as that

found on N.G. No. 292 (Pollaiuolo) was found. The
layer, which was unpigmented, was shown to cover
light and dark areas of the picture fairly evenly, indicating that it could not consist of local glazes.
Repaints on Joseph's orange robe were also tested.
One dark repaint was found to consist of a conglomeration of white, blue, crimson, and orange particles.
One of the sections showed a crack in the original
bright orange paint, of which the pigment was realgar,
into which two brown iron oxide layers had penetrated.
A number of sections were made to investigate the
condition of the browned foliage on this picture, to
discover whether removal of the top brown surface
might reveal undeteriorated green, but in practically
all areas the green colour had been produced by a
single layer of copper resinate, mixed with crystalline
veldigris in some parts, and the green colour was
almost completely lost.

N.G. No. 1675, REMBRANDT, Portrait o- f Marqarehra

Trip
Cross-sections showed first of all that above the redbrown priming (which was evident along edges and
in damages) a coarse, granular grey priming seemed to
cover the whole of the picture surface beneath the local
colours.
Sections from the black dress and the dark brown
background showed that both these areas had, in
addition to the opa ue body colour, dark translucent
glazes which seeme to contain resin,. A section from
the black dress is shown in Fig. 24. The layers are:
(i) orange-red priming; (ii) granular grey priming
showing coarse grains of white lead; (iii) black body
colour; (iv) translucent blackish glaze.
One section taken frorn an area where a per~titrrerzto of the hand was faintly seen showed a dense
flesh-coloured layer beneath the semi-transparent dark
layers.

N.G. No. 1938,

D ~ R E R ,The

Paitzter's Fatlrer

After the removal by the restorer of the yellowed

varnish, the pink background of the picture was seen

to be covered with an uneven brown glaze which was

suspected not to be original. A cross-section showed
the glaze over the pink layer as being rather coarse and
crystalline; it was found to be an oil-resin glaze pigmented with a transparent red-brown iron oxide. Two
steps were taken to attempt to prove its authenticity or
otherwise. Firstly, its solubilities were compared with
a sample of a genuine brown glaze from the coat. It
was found to be considerably more soluble. Secondly,
a paint section was taken frorn the blue inscription at
the top of the picture, since the art-historian working
on the picture conceived the idea that if the brown glaze
were original and meant to modify the pink colour of
the background, it would most likely have been painted
all over the background before the inscription was
added. If, on the other hand, it was a repaint, it would
either go over the blue inscription or round it. The
section, in fact, showed the blue paint layer directly
above the pink with the brown glaze running over the
pink and up over the edge of the blue lettering.

N.G. No. 3259, MANET, Portrait ofEva Gorzzales

The design of this picture is really oval in shape
although painted on a rectangular canvas. The spandrels
at each corner can be seen cut off by the outline of this
oval, and the two upper ones are painted blue-grey,
somewhat the colour of the main background of the
upper part of the picture. Since they seemed to be
only thinly painted, the restorer thought that this
paint might be a continuation of the underpaint on the
part of the background within the oval, in which case
it could be considered that Manet might have begun
painting the picture, and only later decided on the oval
shape. A section of the paint from within the oval is
shown in Fig. 22. It consists of several superi~liposed
layers of blue-grey paint interposed with thin layers
of white. A cross-section from within the spandrel
showed only a single layer of blue grey paint above
the white priming. It did not resemble the lowest
layer of the section from the main background, being a
much darker shade. It was most like the uppermost
but one layer, a thick dark layer in the photograph,
before this received its fmal thin pale scun~ble. This
seems to suggest that Manet did not paint the spandrels
of the picture when he first began it, but left them as
white priming.

N.G. No. 3268, RENOIR, Les Parapluies

Considerable discussion took place before this picture
was cleaned as it was one of the most recently painted
pictures in the collection. One authority expressed a
fear that if the paint were rich in medium, the pi,Ument
might have sunk to the bottom of the layer, leaving a
'pellicule' of unpigmented and not very old linoxyn
film on the surface of the picture which might be

FIG. 4.-N.G.
No. 3046. MASACCIO (1401-1428).
The Virgin and the Child (dated 1426)
Gold background.

FIG. 6.-N.G. No. 292. POLLAIUOLO (c. 1432-1498).

Martyrdom of S. Sebastian (dated 1475).
Blue sky showing the " grey layer " in a crack.

FIG.

8.-N.G. No. 772. Cosimo TURA (c. 1431-1495).

The Virgin and Child Enthroned.
Pink column to left of throne.

FIG. 5.-N.G.

No. 709. MEMLINC (active 1405,

d. 1494).
The Virgin and Child Strip of green hanging.

7.-N.G. No. 292. POLLAIUOLO.

Green paint from near horse's hooves.

FIG.

FIG. 9.-N.G. No. 772. Cosimo TURA.

Green column to right of throne.

FIG. 10.-N.G. NO. 1045.

Gerard DAVID (active 1492, d. 1523).
Canon Bernardius and Three Saints.
Red robe from painting on reverse of panel.

FIG. 12.-N.G. NO. 599.

Giovanni BEUINI (c. 1459-15 16).
The Madonna of the Meadow. Blue sky.

FIG. 11.-N.G.
BOTTICELLI (c.

NO. 592.
1445-15 10).
Adoration of the Kings.
Sleeve of red doublet.

FIG. 13.-N.G.
No. 812.
Ascribed to Giovanni BELLINI.
The Assassination of S. Peter Martyr. Blue Sky.
'"**

FIG. 14.-ENGLISH SCHOOL (1530-3 5).

Panel Paintings in Chichester Cathedral.
Bishop's Gold Mitre.

IS.-N.G.
NO. 635. TITIAN (1480-1576).
Virgin and Child with SS. John and Catherine.
Virgin's blue dress : deep blue shadow.

FIG.

FIG. 16.-N.G.

No. 1324. VERONESE (1528-88).

Scorn.
Orange drapery.

FIG. 17.-N.G. No. 1122. EL GREcO (1545-1614).

S. Jerome as Cardinal (dated 1566).
Dark crimson shadow on sleeve.

Goldleaf

FIG. 18.-N.G. No. 1195. RUBENS (1577-1646).

Birth of Venus (sketch for a silver dish).
Gold leaf beneath glazes.

FIG. 19.-N.G. No. 1172. Van DYCK (1599-1641).

Charles I on Horseback (dated c. 1636).
Blue sky.

iii-

FIG.20.-N.G. NO. 1383. VERMEER (1632-75).

Lady Standing at the Virginals.
Blue-grey background.

FIG.21.-N.G.

No. 4453. CANALETTO (1697-1768).

Bucentaur at Piazzetta.
Pale blue sky.

Plesters
vulnerable to cleaning solvents. Cross-sections showed
that the blues and pinks, at any rate, were mixed with
lead white to form a very solid paint. The lead white
has helped to dry the oil and will have combined
chemically with it. Tests carried out on samples of
paint under the microscope showed that the paint was
unaffected by prolonged immersion in far stronger
solvent mixtures than that required to remove the softresin varnish, and even withstood pure acetone. A
section showing white priming, two blue paint layers,
and a pink one, is shown in Fig. 23. The thick irnpasto
is evident.
One further example of overpainting revealed by
cross-sections is shown in Fig. 14. Paint samples were
examined from a series of panel paintings in Chichester
Cathedral which dated from c. 1530-35 but had been
much damaged and repainted. Fig. 14 shows a crosssection from a bishop's mitre which was gold embellished with blue pearls the size of sixpences. The
section shows the following layers: (i) the gesso; (ii)
a reddish underpaint; (iii) a whitish paint layer; (iv)
gold leaf; (v) a blackish layer, probably dirt and dirty
varnish; (vi) white overpaint (in an oil medium,
whereas the original paint is in a glue medium); (vii)
a second layer of gold leaf; and (viii) over the left-hand
side of the section only, blue oil paint from the 'pearls'
on the mitre. It seems that the original gold leaf must
have acquired a coat of dirt or varnish, and instead of
the restorer cleaning this off he overpainted it with
white lead paint, regilded it, and, for extra measure,
added the blue jewels. Since this investigation the
pictures have been cleaned and restored and the gold
mitre is seen with its original gold leaf and without
the blue jewels which had never formed a part of the
original design.
CROSS-SECTIONS AND THE DISCOVERY OF
ALTERATIONS BY THE ARTIST

As well as discovering overpaintings, crosssections from pictures have on occasions revealed, albeit often accidentally, changes made
in the picture by the artist himself. A few
examples are given below:
N.G. No. 772, Cosinzo TURA, Virgin and Child Enthroned
Two pillars support the arch over the throne, the
one on the left being pink, the one on the right, green.
Cross-sections show (Figs. 8 and 9) that originally both
columns were pink, but that the right-hand one was
repainted with two layers of green paint which is
identical with green paint found elsewhere in the
picture. This is probably in accordance with Tura's
curious colour scheme for the picture. The colours of
the robes of the pairs of angels also alternate, this time

from red to green, from one side of the picture to the

other.

N.G. hro. 635, TITIAN, The Virgin arid Child with SS.
Johtz and Catherine
St. Catherine's dress, now pale yellow, was shown
by cross-sections to have been rose pink originally. It
has been painted over, first with a white layer and then
with a pale yellow layer of lead monoxide. O n close
inspection of the picture, the pink layer could be seen
in minute spots of damage.
N.G. No. 1195, RUBENS, The Birth o f Vetxns
This is a grisaille sketch for an oval silver dish. A
cross-section from an area of greenish grey glaze
revealed some way below the paint surface a layer of
gold leaf (see Fig. 18). An X-radiograph revealed,
however, that the design had not been gilded entirely,
but small parts of the design reinforced with gold,
particularly some scroll-like motifs.
The Wonzan Taken in Adultery (Gkasgow
Art Gallery)
The bright orange and yellow satin doublet of the
man in the foreground was found to have been bright
green originally, a brighter and bluer green than the
landscape background. This was first painted out with
a layer of white lead before the orange paint (orpiment
and realgar) was applied.
GIORGIONE,

N.G. No. 654, van der WEYDEN, The Magdaletl

Cross-sections revealed that above the white gesso
there is in many parts of the picture (e.g. parts of the
green dress, the landscape through the window, newly
revealed by recent cleaning) a very pale pink priming.
This was at first thought by the restorer to be traces of
pink putty in small damages. Under other areas there
is a thin layer of a pale blue-grey paint. Above these
rather perplexing layers the painting is built up in a
very logical way. One cross-section also shows the
fine muslin-like canvas which is embedded in the gesso.
N G., No. 592, BOTTICELLI, The Adorntioil ofthe Kirgs
Fig. 11 shows a cross-section from a red sleeve. The
gesso layer is not shown. The first layer is a white underpaint. Then follows what is virtually a single layer of
blue-green verdigris crystals. This green layer has been
painted out with another layer of lead white, and the
top paint layer is now a dark red glaze.
THE STUDY OF ARTISTS' TECHNIQUE BY MEANS
OF PAINT CROSS-SECTIONS

After the decline of Roman painting, Western art continued through what are usually

Cross-sections and Chemica1 Analysis ofpaint Samples

FIG. 22.VN.G. NO. 3259. MANET (1832-83)Portrait of Eva Gonzales.

Blue-grey background within outline of oval,
top right comer.

121

FIG. 23.-N.G.

termed the Dark Ages, not in the form of

wall or easel painting but rather in the applied
arts of metalwork, ivory carving and manuscript illumination. As late as the thirteenth
and fourteenth centuries, painted altarpieces
were more the work of the gilder and carver
than of the painter. Painting was one craft of
many and the painter had not yet achieved his
renaissance status of 'artist'. Painting tended
therefore to be carried out as a craft, methodically and according to traditional rules. This
attitude shows itself in the very regular and
logical construction seen in cross-sections of
early pictures. Fig. 4 shows a section of the
gold background of N.G. No. 3046, MASACCIO,
TheVirginand Child. The traditional methods
of gilding and tooling are used, although in
this same picture Masaccio has introduced
real perspective and modelling. The section
consists of three layers: layer (i) is a thick layer
of white gesso of a fine crystalline texture.
It is more than a millimetre thick (the full
depth is not seen in the photograph). The
surface has been carefully smoothed and upon
it has been applied layer (ii), which is a thin
coating of bole, the red clay used in gilding.
Layer (iii), the gold leaf itself, is laid with great
precision. Its thickness is only 9-18 p. The

NO. 3268. RENOIR (1841-1919).

Les Parapluies.
Blue paint with pink scumble over a white
priming.

nature of the egg-tempera used as a medium

in early Italian paintings also contributed to
this tendency for the pictures to be built up
in t h regular paint layers. Egg-tempera
paint dries rapidly and with a hard outline so
that subtleties of modelling and shading were
in many cases produced by the effect of superimposed semi-transparent layers. Oil paint
seems to have been first introduced as glazes
for tempera body colours. In Fig. 11, a crosssection from a picture by Botticelli, a crimson
oil glaze has been used over white tempera
paint. Oil paint, even when used for all the
paint layers of a picture, tended for a long
time to be used rather cautiously in thin
regular layers in the same way as tempera
paint. This can be seen especially in Figs. 5-14
inclusive (Figs. 4-23 inclusive are arranged
more or less in chronological order of artists).
Full use was not really made of the rheological
properties of oil paint until the time of
Rembrandt who used it as thick impasto,
thin glazes, dry granular paint, rich oily
enamel-like paint, and with every possible
permutation. During the early Renaissance
such effects were perhaps not desired. It will
be stated later on that the medieval and Renaissance painters tended to use pure pigments in

Joyce Plesters

122

FIG.2 4 . - N . G . NO. 1 6 7 5 . REMBRANDT.

Portrait of Margaretha Trip. Black dress.
(i) Orange-red priming (ochre in oil).
(ii) Coarse granular priming of lead white and
carbon black.
(iii) Blackest body colour (carbon black and
brown ochre in oil).
(iv) Translucent brownish glaze (oil resin
medium).

(i)
(ii)
(iii)
(iv)
(v)

FIG.25.-REMBRANDT.
Late Portrait Group. (Private collection.)
Red dress with yellow scurnble.
(i) Orange-red priming.
(ii) Opaque scarlet body colour (vermilion).
(iii) Thin dark line of black pigment mixed with
iron oxide red pigment.
(iv) Thick ale yellow scumble of yellow massicot in an oil-resin medium.

FIG. 26.-REMBRANDT.
Late self-portrait. (Private collection).
Black coat.
Orange-red priming (ochre in oil).
Black underpaint (going all over the picture).
Pale greyish-white granular paint (covering all
the picture but varying in thickness) ; lead
white, carbon black and yellow ochre in oil.
Blackish-brown opaque body colour.
Translucent pale brownish oil-resin glaze.

THREE EXAMPLES OF PAINT STRUCTURE OF LATE REMBRANDT PORTRAITS

Cross-sections and Chemical Analysis $Paint Samples

123

FIG. 28.
Sample of Modem Cobalt Blue.

FIG. 27.-Particles of Azurite from the

blue background of a Holbein portrait.
(Picture in private collection.)

FIG. 29.-N.G.

No. 5283.
(c. 1512-71).
Landscape with Eurydice and Aristaeus.
Cross-section from grass in foreground, showing a
dark green and a light green paint layer both
containing large crystals of verdigris.
NICCOLO DELL' ABBATE

EXAMPLES OF RELATIVELY COARSE PARTICLE SUE OF PIGMENTS FOUND IN EARLIER PICTURES

their painting rather than obtaining a desired

shade by mixing together different coloured
pigments. Modifications of colour were produced by the use of translucent glazes. A good
example is seen in Fig. 10. This is a section of
paint from a red robe. Above the gesso,
layer (i), is a bright red body colour, this is
heightened by a thin semi-opaque pink
scumble, and finally the colour is enriched by
layer (iv), a translucent deep red madder glaze.

Slowly oil paint began to be used in a freer

way and the regularity of the layer structure
is to be less evident. Paint layers also tended
to become thicker, and impasto and the effects
of raised brush strokes were discovered. The
development can be seen through Fig. 16
(Veronese) to Fig. 26 (Rembrandt).
Of the illustrated examples, space will only
permit the mention of a few noteworthy
points. Fig. 5 (MEMLINC) shows the complex

12.4

Joyce Plesters

structure of green paint in Flemish primitives

and this will be more fully discussed under
copper greens. Figs. 12 and 13 are of gesso
from two different panel pictures by Giovanni
Bellini. In both cases the gesso is seen to be
built up in numerous layers. Although this
process is described by Cennino Cennini, in
practice a single layer of gesso seems more
common. An odd feature is that in Fig. 12
(from the Giovanni BELLINI,
N.G. No. 599,
Madonna of the Meadow), what might be
considered as the fine pure white gesso sottile
is at the bottom, near the panel, whereas a
coarse brownish gesso is nearest the paint
layer. In Fig. 13 (from N.G. No. 812, assigned
to BELLINI,Death of St. Peter Martyr) the
lowest gesso layers are palest in colour.
Perhaps this is an early example of the use of
a coloured gound. Fig. 15 shows a section
from a Titian. The layers are fairly regular
and the total paint thickness comparatively
small. There are two very similar Titians in the
National Gallery (No. 4, The Holy Family,
and No. 635, The Virgin and Child with SS.
John and Catherine). Sections and pigment
analyses of each showed coilsiderable resemblance in both layer structure and pigments
and medium used. The only considerable
difference was that whereas in the case of
N.G. No. 4, the canvas was merely primed
with lead white in oil, the canvas of N.G.
No. 635 has first a layer of calcium sulphate
gesso below the thin lead white priming.
Fig. 17 shows the use made by El Greco of
deeply coloured transparent glazes over a
thick white body colour. This gives his
painting great luminosity. Fig. 16 shows the
coarse canvas and rather dry crumbly oil
paint used by Veronese (and other later
Venetians). Here the priming (layer (ii) in the
diagram) is a cool pale brown in colour and
is thinly spread. The orange colours found in
layers (iv) and (v) of this section were shown
to be massicot and red lead. Fig. 18 shows a
section from a Rubens grisaille sketch. The
priming is a light red brown on which is
superimposed a series of red, brown, and

greenish glazes. Fig. 19 shows a section of

blue paint from Van Dyck's Portrait of
Charles I on Horseback. The holes in the redbrown priming, layer (i), are those made by
the shape of the canvas threads. A layer of
lead white (ii) was applied before the blue
paint. The structure of the blue paint reminds
us that lapis lazuli was still an expensive commodity in Van Dyck's time, for he has
followed the medieval practice of having an
underpaint, layer (iii), of the less expensive
azurite, followed by (iv) a mixture of ultramarine and lead white, and finally (v) a glaze
of pure ultramarine. Fig. 20 shows a section
from the blue-grey background of a picture
by Vermeer. There are two priming layers on
this picture. Layer (i) is pale grey in colour,
and is composed of lead white and carbon
black in an oil medium. Layer (ii) is pale
pinkish-brown, and consists of lead white
mixed with a little red-brown ochre. There
is a single blue-!grey paint layer (iii). Fig. 21
shows a section from blue sky on a picture
by Canaletto and has a surprisingly thick
coarse-gained red-brown priming composed
of brown and red ochres, lead white and an
oil medium.
For some pictures it has been possible to
study technique very thoroughly by this
means because of a greater number of samples
available. This was so in the case of N.G. No.
783 (follower of van der WEYDEN).
A detail
of the central portion of this picture is illustrated (Fig. 30). The most interesting feature
was the variety of methods used to paint the
flesh. In some parts there is strong black
underdrawing, and in others softer brown
undermodelling. Many very thin red glazes
were also found. The information obtained
from the cross-sections agreed very well with
the observations on the technique made by
Mr. H. Ruhemann from his detailed technical
examination of the picture.
Figs. 24, 25, and 26 show cross-sections
from portraits painted by Rembrandt towards
the end of his life. All have thick, coarse redbrown primings. In Figs. 24 and 26 this red

priming is separated from the local colouring

by a second priming, a coarse grey and white
granular layer containing numerous lunlps of
unmixed lead white (in addition a blackish
layer appears between these two in Fig. 26).
Fig. 25 is a section from the latest of these
three pictures and shows a very irregular
layer structure with, on top, an exceptionally
thick irregular yellow scuinble.
PIGMENTS OF THE OLD MASTERS: FINDINGS
FROM PAINT ANALYSES

One of the most striking features of early

pictures is the fact that all the pigments seem
to be used in the brightest, purest form without much mixing together, except with white,
and usually without admixture of brown or
black. If paint is found on a picture which is,
say, a grey colour composed of red, blue, and
yellow pigments mixed, it is most often found
to be a retouching in which the restorer has
added small amounts of first one pigment and
then another to match the surrounding area.
The blue robes of Christ or the Virgin in pictures by Duccio, Bellini, Titian, or Giorgione
are almost sure to be painted in lapis lazuli
ultramarine, used alone for shadows, or inixed
with white for highlights. Shadows and
modelling might be augmented by a dark
underpaint. Vermilion is used constantly as
the pure pigment, but is often glazed with a
crimson lake to give a less scarlet red.
Many of the pigments are very coarsely
ground, compared with modern pigments.
This may be because methods of grinding
were primitive, but in some cases, especially
that of the blue pigments, the coarse particle
size was deliberately chosen in order to retain
the utmost colour of the crystalline pigments,
for much of it would be lost by light scatter
through fine grinding. Fig. 27 shows a sample
of azurite from the background of a portrait
by Holbein (private collection). Fig. 28 shows
a sample of modern cobalt blue pigment at
the same magnification. Fig. 29 shows very
large particles of verdigris in a cross-section
It

having two layers of green paint, froin N.G.

NO. 5283, NICCOLO DELL'ABBATE.
With this obvious desire for brilliant colour
it is a shock to find so many brown colours in
pictures where greens would be expected.
This is because there was not until the end of
the eighteenth century a permailent bright
green pigment. The early painters lacked a
natural grass-green pigment. Terre verte was
rather a dull grey-green, malachite b l ~ e - ~ r e e i l
and rather weak in colour, while verdigris was
more peacock-blue than green. Moreover, a
pure green could not be made by mixing
blue or blue-green with yellow since the only
bright yellow was orpiment which, being a
sulphide, was incompatible with the copper
greens or blues. A solution was found, however. It was discovered that verdigris or malachite would partly dissolve if warmed in a
resinous material such as Venice turpentine,
producing a beautiful clear green varnish.
This preparation was used in various waysas a glaze with or without the addition of
further solid verdigris or mixed with lead
white or massicot to give opaque greens.
The colour was extensively used and its results
have been calamitous. The copper green is
often browned completely by the atmosphere.
Its worst effects can be seen in the small
POLLAIUOLO N.G. No. 928, Apollo and
Daphne. Its deterioration has also been mentioned in connection with another picture
by Pollaiuolo and two pictures by Titian,
where its condition is only a little better. This
colour has been prepared in the National
Gallery laboratory. O n exposure to u.-v. it
was found that specimens painted out turned
brown in a matter of a few months. Where
the resin was mixed with lead white in oil the
change was rather slower. Mr. J. S. Mills
(Nuflield Scholar at the National Gallery)
carried out chromatographic tests on copper
resinate and came to the conclusion that the
substance was simply a copper salt of the
resin acids. He also succeeded in preparing a
similar product from copper oxide and pure
abietic acid (which is isolated from rosin).

This means that when the resin component

oxidizes and decays with time, as it is bound
to do, the compound will break up and its
colour will be lost. Possibilities of its regeneration seem rather remote. Since this
colour has been used also by the Flemish
painters a question which might properly be
asked is why the green colours in such
pictures as, for example, those of Van Eyck
remain so well preserved. In the examples
examined it seems that it is firstly a matter
of careful building up of the layers. In Fig. 5
is shown a cross-section from a green curtain
in a picture by MEMLINC (N.G. No. 709, The
Virgin and Child). Here (above the gesso (i)
and a layer of white underpaint (ii)) are three
green layers, the first (iii) a dark opaque
green composed of copper resinate, verdigris,
lead white and yellow lead monoxide. The
second layer (iv) contains the same components but is lighter in colour. The third
layer (v) is a clear green copper resinate glaze
(difficult to see in the photograph). Near the
top surface it is beginning to brown. This does
not matter, however, since the green underpaint can still be seen through it, perhaps a
trifle warmer in colour than originally. The
same kind of building-up was seen in the
green of the Magdalen's robe in N.G. No. 654,
Van der WEYDEN. Here, however, only faint
traces of the browned glaze remained although
the opaque green below had kept its
brilliant colour. The second factor in the preservation seems to be that the colour is protected by being locked up, as it were, in a
lead white oil paint.
An example of an Itahan picture where the
green colour is perfectly preserved is N.G. No.
772, TURA (see Fig. 9). Here both the above
conditions are fulfilled.
Violet was another colour for which there
was not a single pigment, although some of
the red vegetable dyestuffs were of a purplish
tinge. In pictures by both Botticelli and
Bellini a clear violet was found to be produced
by an opaque pink made from lead white and
a crimson lake, glazed with ultramarine. The

curious deep purple seen in the bands of the

altar cloth in N.G. No. 783 (follower of Van
der WEYDEN)
(see Fig. 30 below) is, on the other

hand, produced by a body colour of deep

ultramarine, unmixed with white, glazed with
what appears to be burnt madder (there is
little reason to suppose it was originally
crimson since crimson glazes in other parts
of the picture have not browned).
A few pigments found but rarely in
pictures include smalt, which had a very
limited period of use between about the
middle of the sixteenth century until it was
superseded by the invention of cobalt blue in
1802. It has been found in the National
Gallery Laboratory in only four of the paint
samples investigated, viz. a Veronese, a seventeenth-century English painting, a picture by
Rembrandt and a mural by Thornlull. A
curious pigment is the red resin dragon's
blood, which seems to have been used only
for toning gold leaf. It has been identified in
The
this capacity in N.G. No. 13 3 I, FUNGAI,
Virgin and Child surrounded by Cherubim.

Cross-sections and Chemical Analysis $Paint Samples

Of the lake pigments, an unusual purplish one
has been found in N.G. No. 1122, School of
EL GRECO,
St. Jerome as Cardinal. It has a
very strong colour but is unusual in that its
colour is entirely destroyed by alkali. One
other odd discovery was the identification
of the silver of the armour of St. George in
N.G. No. 776, PISANELLO,
as tin leaf.
A last example is the only exception so
far found to the rule that Italian painters used
calcium sulphate for their gesso, and northern
painters calcium carbonate. The gesso of N.G.
No. 194, RUBENS,
The Judgement of Paris,
was found to be gypsum.
THE MEDIA OF THE OLD MASTERS

Little can be said on this subject, for the

only means of identification are the rather
rough tests given later in this article, together
with comparison with samples of paint of
known media. The following summarizes the
findings :
(i) Ghe Mediutii: One picture only in the National
Gallery, No. 664, Dieric BOUTS,
The Entombment, was
found to be painted in a glue medium, together with
one other example, the series of sixteenth-century
panels in Chichester Cathedral (see Fig, 14).
(ii) Egg Tenipera: Of all the pictures so far examined
it can only be stated with any confidence that the
following are in this medium:
N.G. No. 1330, DUCCIO,
The Transfiguration;
N.G. No. 1331, FUNGAI, Virgin and Child with
Cherubim;
Adoration of the Kings;
N.G. No. 592, BOTTICELLI,
Portrait of a Lady.
N.G. No. 758, BALDOVINETTI,
(iii) Oil Medium: The vast majority of the pictures
examined were in this rather loose category, which
should be taken to mean 'a medium predominantly of
oil'. They include pictures by artists as diverse as
Bellini, Titian, Claude, Van Goyen and Renoir.
(iv) Oil-resin tnedititn: This is very difficult to assess.
One of the more certain examples is that of the glazes
in some of Rembrandt's pictures.
PIGMENT ANALYSIS

The identification of pigments can be

carried out with far greater certainty than
that of the medium, and is also more likely
to prove useful in establishing the age or

127
authenticity of a picture. The method used in
the National Gallery will therefore be given
in detail, for although it includes much work
which has appeared elsewhere, it does bring
together into a schematic whole a number of
scattered sources of information as well as
adding a few techniques and tests not hitherto
applied to paint analysis of pictures.
There is a fair amount of published work
on pigment analysis, as distinct from work on
properties of pigments in general. One of the
earliest references to chemical analysis of
pigments is a paper by Chaptal [13] in 1809
on pigments found at Pompeii. In 1903
Wright [14] published a book on simple
methods for testing painters' materials which
included rather crude qualitative and quantitative analysis designed mainly for dry pigments. Raehlmann in 1910 [IS] was the first
chemist to use microscopic investigation in
the examination of paint from pictures.
Another early treatise was by Weber [16] in
1923. This gives a series of simple tests for all
artists' pigments available at the time, using a
limited range of common reagents. It was,
however, designed primarily for the use of
artists so that they might ascertain that the
pigment they were buying was what it claimed
to be.
Hetterich [17] in 1930 and 1931 investigated micro-chemical methods of pigment
identification for pictures and painted statues.
Scheffer 1181 was also applying simple microchemical tests for pigments, and his pupil de
Wild wrote a treatise on the scientific examination of pictures with tests for pigments
based mainly on standard micro-chemical
crystallizations [ ~ g ] Laurie
[20] was at the
.
same time evolving microchemical tests for
pigments and these were carried further by
Gettens [8] and Gettens and Stout [g] in
the 193os, the latter working out tables for
identification of white, green, and blue pigments. Eibner, in a posthumous paper published 1932 [21], developed microchemical
analysis of paintings much farther than any
other worker in this sphere, and his tests

Plesters
include the use of many organic reagents for
metals, then newly developed. The most
recent additions to the literature are a contribution by Whitehead [22] on the application
of chemical reagents to paint cross-sections in
industrial research, and a manual by Stock [23]
on the chemical analysis of pigments, which is
of great value because it includes tests for
almost all artists' pigments up to the most
recent, including phthal~c~anine
blue, titanium white and monolite red.
The table given below combines microscopical and chemical examination. In most
cases a description of the crystalline form and
figures for the refractive index is omitted
since these can be found in the table given by
Gettens and Stout in their Encyclopaedia of
Painting Materials [24]. Photomicrographs of
pigments are to be found in De Wild [ ~ g ]
and in Mattiello [ z ~ ]The
.
necessity cannot be
too strongly emphasized, however, of having
as wide a range of mounted comparison slides
of pigments as possible. A range of refractive
index liquids is also useful.
The chemical tests on pigments are usually
carried out after those on media. Some can
run concurrently; thus, treatment with sodium
hydroxide, with concentrated nitric acid, and
also the effect of heat on the sample appear in
both the table for the identification of pigments and the tests for the identification of
media. One test only need be made on the
paint sample and the effect on both medium
and pigment observed at the same time.
There are also various ways of econonlizing
with the amount of the sample available, e.g.
after solvent treatment for identification of
media has been carried out and the medium
extracted or destroyed, the residue can be used
for pigment tests; after ignition of part of the
sample the residue from the combustion,
which may contain metal oxides, can be redissolved and tested for metal ions. Perhaps
the most valuable economy is in the use of
spot tests. When the sample has passed into
solution minute drops can be removed by
means of a capillary tube and used for spot

tests on filter paper or on a spot plate. The

reagents used are extraordinarily sensitive
under these conditions. Thus a fraction of a
millimetre of paint dissolved in a drop or
two of acid will furnish enough solution for
several different tests.
In some cases chemical tests can be carried
out on the paint cross-sections. The polyester resin used for embedding the samples
penetrates the paint and to some extent
protects it from chemical attack. Reactions
only proceed on the surface exposed by
grinding and even then quite slowly. For
example, if a paint section is treated with a
drop of dilute nitric acid followed by a drop
of potassium iodide and excess reagent then
washed off with water, all layers containing
lead white or lead oxide pigments will be
seen to have become bright yellow owing to
the formation of yellow lead iodide. This
principle can be followed for a number of
tests including some organic reagents for
metals which produce coloured complexes.
Unfortunately its application is restricted to
those pigments which are somewhat soluble
in moderately dilute acids.
Solubility tests with organic reagents,
acids and alkalis are carried out in the case of
every paint sample, because by the time these
have been worked through, all the medium is
usually extracted or destroyed and in many
cases the pigment itself has also been dissolved. In the confirmatory tests it has been
the aim to find two or more different tests for
each pigment. The samples being so small, the
tests have to be simple in application, consequently even very sensitive tests have been
excluded if these require specially colltrolled
conditions or are liable to interference in the
presence of other metal ions (in paint samples
impurities are often encountered; certainly
iron and lead are present in almost every
paint sample).
For the purpose of the tables the pigments
are grouped into various colours since this is
how they are first distinguished. By looking at
the sample under a low power microscope

Cross-scctiofzs and Chcmic

and noting its colour and physical appearance

it is usually possible to narrow down the
range of possible pigments to as few as two
or three. This limits the number of chemical
tests required. For example, if the only pigment visible in the sample were red it would
be pointless to test for copper. On the other
hand, if the pigment were bright blue it
would be usual to test for copper and cobalt
ions and for ultramarine.
All pigments commonly used in panel and
canvas paintings up to the end of the nineteenth century are included in the table; at the
present time there are no twentieth-century
pictures in the National Gallery.
The identification of organic pigments
other than madder, alizarin, and indigo is not
attempted since the subject is somewhat
controversial and not much is known of the
identity of these pigments nor of the physical
and chemical changes which they undergo
with ageing.
It should be noted that all spot tests and
tests involving the use of organic reagents
for metals are taken from Feigl's book [ 2 6 ] .
In order to try to ascertain the date of some
paint samples, especially where the examination of repaints is concerned, it is necessary
to know the dates of introduction of the
various pigments. Many of the dates are shown
in the following table (pp. 1 3 3 E ) , but more
detailed chronological tables are given by
Eibner [27] and by Heaton [28].
EXAMINATION OF MEDIA

The term 'analysis' can hardly be applied

to the rather rough and ready tests which are
available. The most that can be done is to
attempt to classify the medium as glue, egg
tempera, oil, or oillresin mixture. Very little
work has been done in the past on this
problem compared with the amount done on
pigment analysis. An early pioneer was
Ostwald [ 3 3 ] who in 1905 was developing
microscopic tests for the identification of
media and had also done some work on the

staiiliilg of media with biological

stains, a technique which has recently been
resuined at the National Gallery. Eibner [34]
also tackled the problem, testing the solubility
of media and also attempting to identify
protein media by the presence of nitrogen,
phosphorus, and sulphur. In more recent
times an extensive investigation into the
techniques of the Flemish Primitives has been
proceeding at the Laboratoire Central des
Musees de Belge under the direction of Dr.
Paul Coremans, and a useful table of tests for
media has been published in a previous number
of this journal, in an article by Coremans,
Thissen, and Gettens [35].
Micro tests for nitrogen, such as the
Lassaigile test, have recently been carried out
by Miss Margaret Hey (Nuaeld Scholar at
the National Gallery) who has found that
many of the paint samples tested which were
certainly oil paint gave a positive test for
nitrogen. This may be because of small
amounts of impurities in the original paint,
but it seems even more likely that at some
time the paint has become contaminated with
gelatin during blister laying or relining.
Until a test specifically distinguishing between
egg and glue protein can be devised, tests
for nitrogen, etc., do not seem to be very
useful. Such a test might be possible by
modern techniques such as chromatography,
but even so it is doubtful whether much
success could be hoped for with as small a
quantity of starting material as the medium
contained in a square millimetre of paint.
In the case of mixtures of oils and resins the
position is very complicated. The effect of
adding resins to linseed oil films is not fully
understood, and of course the effects of adding
a soft resin such as mastic are likely to be very
different from those produced by adding a
hard resin such as copal. There are several
useful colour tests for resins such as the
Storch-Morawski test (Kraus [36] g'ives a
modification of this test suitable for paint
and varnish samples) but unfortunately aged
resins tend to give a uniform dull brown

130

Joyce

colour with this test instead of the characteristic colour given by the fresh resin. What
is worse is that linseed oil gives the same
brownish colour. Ultra-violet microscopy is
some help in distinguishing differences in
media by their different fluorescence, but such
fluorescence is not characteristic of any particular components.
In the National Gallery laboratory tests for
media begin with a series of solvent tests on
the paint sample. This is treated with cold
water, hot water, acetone, chloroform, 0.88
ammonia, sodium hydroxide and alcoholic
sodium hydroxide solutions in turn. If
possible a further sample is used for staining tests. Two stains have been found particularly effective for distinguishing between oily
and proteinous media. These are nile blue,
which stains oils and fats, and acid fuchsin,
w h c h stains protein. The sample can be
treated with a mixture of the two stains and
after a few minutes washed with water. The
stain which is specific for that type of medium
remains. This technique has not been used
for very long, but it has proved to be fairly
consistent in a series of tests on known aged
media. A combustion of a small sample of the
paint is usually done (for this is used as a test
for pigment also) and the effect of heating is
noted. The effect of concentrated nitric acid
on the medium as well as on the pigment is
observed. The reactions of the various media
to these tests are listed below.

Soluble in hot water with disintegration of

the paint fragment and formation of a ring
of clear material after evaporation of the
drop; stained red by acid fuchsin. O n heating,
ammoniacal fumes are given off (smell of
'burnt feathers') which turn universal indicator
blue.

Egg Ternpeva
Unaffected by water, dilute acids or alkalis
(except by prolonged treatment). O n dissolving out the pigment the medium is some-

times seen as membrane-like flakes, and concentrated nitric acid often yellows these
without disintegrating them. The paint sample
is readily stained by acid fuchsin. O n heating
it behaves in the same way as glue.

Dryirzg Oils
Unaffected by water or by dilute acids, but
aqueous ammonia and sodium hydroxide
rapidly dissolve out the oil, sometimes as a
yellowish solution, and the pigment particles
flow out from the specimen. The film is
strongly stained by nile blue. Subjected to the
Storch-Morawski test for resins, it gives only
a dull brown spot. O n heating, the paint
usually first melts, then gives off an odour of
burnt oil: charring occurs and white fumes
are produced which are usually acid to
universal indicator paper. Concentrated nitric
acid often turns oil films red brown in colour.

Oil arzd Rexiti Mixtures

These behave in practically all respects like
drying oils. Often, however, part of the
resinous material may be extracted by treatment with organic solvents such as acetone
or chloroform without disintegration of the
paint film; the ring of transparent material
left after evaporation of the solvent usually
fluoresces under u.-v. Oil-resin films are often
more readily soluble in alcoholic solutions of
ammonia or sodium hydroxide and in morpholine than in aqueous alkalis. Gentle warining usually produces an odour of the resin. The
Storch-Morawski test usually gives only a
brown colour with aged films, but sometimes
a transient pink or purple colour due to the
resin is produced, turning brown almost at
once.
ACKNOWLEDGMENTS

The author would like to thank members

of the Conservation Department at the
National Gallery for their coiltinuous cooperation; Mr. H. Ruhemann, for the benefit
of his very extensive knowledge of artists'

Cross-sections and Chernical Analysis of Paifzt Samples

techniques; Dr. A. E. A. Werner of the

British Museum Research Laboratory for his
help and encouragement throughout the
work; Mrs. V. Wilson and members of the
Photographc Department at the National
Gallery for the photographs.
The work here described is part of a research
programme in progress in the Scientific

131

Department of the National Gallery under the

general direction of Mr. F. I. G. Rawlins.
JOYCE

PLESTERS

T h e National Gallery,
London.

A. P. LAURIE,
'The Pigments and mediums of the Old Masters' (London 1914).
R. J. GETTENS,
'The Cross-Sectioning of Paint Films', in Technical Studies in the
Field ofthe Fine Arts, v (1936), p. 18.
3 R. LEFBVRE
and R. SNEYERS,
.Vededelityen

vat1 de Vlaanue Chewiische Gereintmng, XII

(1950), p. 99.

R.E. STRAUB
and S. REESJONES,'Mikroskopische

Querschnitte von Gemalden',

in .Waltechnik, IV (1955), p. 119.

J. PLESTERS,
'The Preparation and Study of Paint Cross-Sections', Museums
Journal, Vol. 54 (1954)~No. 4.
F. I. G. RAWLINS
and A. E. A. WERNER,
'Some scientific investigations at the
National Gallery, London', in Et~deavour,xIn (1954), No. 51, p. 140.
R. J. GETTENS,
'A Microsectioner for Paint Films', in Techtlical Studies in the Field
of the Fine Arts, I ( r g p ) , 20.
R. J. GETTENS,
'An Equipment for the Microchemical Examination of Paintings',
in Techtlical Studies in the Field ofthe Fine Arts, 11 (1934), p. 185.
and G. L. STOUT,
'The Stage Microscope in the Routine ExaminaR. J. GETTENS
tion of Paintings', in Technical Studies in the Field of the Fine Arts, IV (1936),
p. 207.
S. M. CHARLETT,
'Reference microscopical preparations', in Paint, O i l and Colour
Jorirnal (1955), 128, No. 2961, p. 144.
E. M. CHAMOT
and C. W . MASON,'Handbook of Chemical Microscopy' (2nd
edn., New York 1939).
Catalogue of the Exhibition of Works by Holbein and Other Masters of the
sixteenth and seventeenth centuries. Royal Academy of Arts (London
1950-51), p. 22.
M. CHAPTAL,
'Sur quelques couleurs trouvtes B Pompeia', in Antlales de Chimie,
LXX (1809), p. 22.
A. C. WRIGHT,'Simple Methods for Testing Painters' Materials' (London
1903).
E. RAEHLMANN,
' ~ b e die
r Maltechruk der Alten' ( B e r h 1910).
F. W . WEBER,
'Artists' Pigments' (New York 1923).
H. HETTERICH,
' ~ b e die
r Anwendung mikrochemischen Methoden bei pigmentuntersuchung von Gemalden', in Mikrochenlie, Emich Festschrift (1930),
p. 152; ' ~ b e Mikrochemische
r
Bilduntersuchung', in Mikrocheniie, x (1931),
p 27.
F. E. SCHEFFER,
'L'Examin Chimique des Tableaux', in Mouseion, XIII-XIV
(1931), P. 93.
19 A. M. de WILD,'The Scientific Examination of Pictures' (London 1929).
I

l oyce Plesters
20

21

22

23
24
25

26
27
28
29
30
31
32
33
34

35
36

A. P. LAURIE,'The Identification of Pigments used in Painting at different

Periods, with a Brief Account of Other Methods of Examining Pictures', in
T h e Analyst, LV (1930)~p. 162; 'Methods of Testing Minute Quantities of
Materials from Pictures and Works of Art', in T h e Atralyst, LVIII (1g33),
p. 468.
A. EIBNER(posthumous), 'L'Analyse Microchimique des Couleurs', in Mouseion,
XXIX-XXX (1935), p. 113.
A. D. WHITEHEAD,
'The Micrography of Paint Films', in Journal of the O i l and
Colour Cketr~ist,XXII (1939), p. 139.
E. STOCK,'Analyse der Korperfarben' (Stuttgart 1953).
R. J. GETTENS
and G. L. STOUT,'Painting Materials, a Short Encyclopaedia' (New
York 1942).
J. J. MATTIELLO
(Editor), Protective and Decorative Coatings, Vol. 11 (New York
1941).
F. FEIGL,Spot Tests, Vol. I , 4th edn. (Amsterdam and New York 1954).
A. EIBNER,Etztlvincklut~und Werkstofe der Wandtzzalerei (Munich 1926), p. 549.
N. HEATON,
'The Permanence of Artists' Materials', in]ourtzal ofthe Royal Society
of Arts (London), LXXX (1932), p. 415.
R. M. BARRER
and J. S. RAITT,'Ion Exchange in Ultramarine', in Journal of the
Chetuical Society (December 1954)~p. 4641.
A. E. CHURCH,T h e Chemistry of Paints aud Paitztitzg (3rd edn. London 1901).
A. ROBERTSON,
W . B. WHALLEY
(et alii), 'The Pigments of "Dragon's Blood"
Resin', in Journals of the Chetnical Society, in six parts, beginning Part I,
1.C.S. ( I ~ s o )p.
, 1876.
D. V. THOMPSON,
T h e Materials qf Medieval Paitztitg (London 1936), p. 124.
W . OSTWALII(trans.), 'Microscopic Identification of Hon~ogeneousBinding
Mediums', in Technical Studies in the Field o f t h e Fitze Arts, IV (1936).
A. EIBNER,'L'Examen Microchemique des Agglutinants', in Mousciotr, x x
(1932), p. 5; Zuni gegenwartigen Stand des naturwissenschaftlichen Bildin Angewandte Chernie, XLV (1932), p. 301.
unters~chun~',
1.' COREMANS,
R. J. GETTENS
and J. THISSEN,'La Technique des "Primitifs
Flamands" ', in Strrdics itz Cotzscrvatiorl, Vol. I , No. I (October 1952), p. 20.
A. KRAUS,'Uber eine Modifikation der Storch-Morawskischcn Harzreaktion',
in Forhetz-Zeiturg, xxxv111 (1932), p. 322.

Tire ilhrstratiotz on the cover, lvhrch also appears on p. 126,

i~ rcprodrrced by pcrrtzissrori of the Trustees elf the Natiotzal
Gallery, Lotzdort.

TABLES FOR IDENTIFICATION OF PIGMENTS Pages 134-15 5

h!B.

A dash '-' under solubilities indicates that there is no visible effect

after a few minutes' immersion in the reagent.

Solnbilities
Pigment

Chen~ical
Cotnposition

Origin, or date
ofirzverztion

Appearance trnder
low magtzification
1 N HCl

Azurite
(mountain
blue, blue
verditer).

Basic copper
carbonate,
2CuCC,.
Cu(OH),.

Natural
mineral
known from
very early
times.

Bright, slightly
greenish blue
crystalline f r a g
ments, often irregular in size
aud s h a ~ e .

-.

q N NaOH

Slow hydroVery soluble,

with effervescence lysis takcs
of CO, to give a place with
formation of
green solution.
black C u O on
the surface of
the piginent
particles.

HNO,
(concentrated)
Vcry solublc,
with effervesence of CO,
to give a pale
blue solution.

Effect of heat

SpeciJic tests

(i) Dissolves in exccss

Black residue of
annnonia produciug a deep
copper oxidc
blue solution of coppcr amCuO.
illotlia conlplex.
(ii) Tcst for Cu++ with
sodium dicthyl-dithiocarbouate:
I drop of the solution of
pigmcnt in HCl or HNO,
is droppcd on to filter papcr
aud held ovcr ammonia. A
sn~alldrop of the reagent (a
0-1 % solution in water) is
added. An orangc-brown spot
is fornlcd if Cu-i--i-is present.
(Pb .produces only a white
turbidity, and intcrfereuce
can be prcvcnted by
by R+++
adding citric acid sol~~tion
to
the test drop before rcnderirig
it anlmoniacal.)
(iii) Tcst for Cub-+with
rubeanic acid (dithiooxamide):
A drop of the acid solution
of the pigrrlcrit is placed on
filter paper and held ovcr amrnonia. A drop of reageut (1%
rubeauic acid in cthanol) is
added. In thc prcscncc of&++
a grecuish black coloration or
precipitate is produccd. (If
the presence of Co++ is suspected, acetic acid is first
added whcn thc central
greenish-black spot due to
Cu++ will bc surrounded by
an orange zone duc to C o ++.)

23

Ultramarine,
natural.

Basic copper
carbonate.

An artificially
prepared substitute for Azu
rite; recipes
for its manufacture are
given from
medieval
tinies onwards.

Usually more
rounded and
finer particles
than those of
Azurite.

A complex
compound
of sodium
aluminium
silicate and
sulphur, of
somewhat
variable composition, but
approximating
to gNa, 0 .
3Al,03 6 SiO,
zNa,S.

From the blue

mineral Lapis
Lazuli in
which it occurs
with calcspar
and iron
pyrites.

Clear, often
slightly purplish
blue crystalline
particles of irregular size and
shape. A few
orange-red particles of iron
pyrites are often
seen, and white
crystalline
material, which
viewed between
crossed Nicol
prisms proves to
be the doubly
refracting calcite.

Becomes white
and an effervescence of H,S is
produced (this
can often be detected by smell).

Reacts quite
slowly, the
colour changing
to pale yellow.

Tests for hydrogen sulphide

evolved on treatment with
hydrochloric acid:
(i) Sodiun~i-azideliodinereagent:
A drop of dilute acid is
added to the pigment followed bv a drow ofthe sodium
azide/iodine reagent (I g.
sodium azide, I g. potassium
iodide and a small crystal of
iodine in 3 ml. of water).
Bubbles of uitrogen rise to the
surface and the orange colour
of the reagent fades if sulphide
is wresent (it remains in the
absence of'sulphide).
(ii) The presence of H,S
may be ascertained by the
blackening of lead acetate or
sodium plulnbite papers,
or of a bright silver wire dipping into the drop. The reaction is best carried out in a
cupslide covered with a glass
coverslip to prevent escape of
the H,S.

Zs
o

sE'
ri

2
2.

&.

'%

$
5

3s

b
%

BLUEPIGMENTS(Contd.)
Solubilities
Pigrnent

Cltemical

Composition

Origin, or date
of invention

Appearance under
low magnijication
3 N HCI

Ultramarine
artificial.

As above but
approximate
formula
Na,-,,, Al,
Si, O,, S2-4.
(See BARRER
and RAITT[zg
for modern
views on
structure.)

Manufacture
first discoverec
by Guinet in
1828.

Smalt

A potassium
silicate glass
coloured blue
with cobalt
oxide.

Manufactured. Uy transmitted
Eibner [27]
light, usually a
reports it to be rather pale blue.
mentioned
Very characteris.
tic glassy fragfirst in 1584.
ments, often ver]
coarse.

Usually smaller
and more
rounded piglnen
grains than those
of lapis ultramarine. Moreover, there are
few colourless
particles and no
doubly refractin!
calcite crystals,
or particles of
iron pyrites.

4N NaOH

As above.

As above.

Effect of hear
HNO,
(concentrated)
In samples
examined in thl
National Gallery, artificial
ultramarine
seems to be
attacked more
rapidly. This
does not seem
to be wholly
due to particle
size. Most
samples of the
artificial pigment had become wholly
pale yellow in
less than half ar
hour, but the
lapis variety wa:
still blue after
2 hours.

Specific Tests

As above.

I
Melts at high
temperatures.

The pigment can be got

into solution by heating in a
platinum spoon with sodium
fluoride and a drop of concentrated sulphuric acid. The
residue dissolved in a drop of
watcr usually gives a fairly
pink solution. This solution
may be used for tests for Co++:
(i) Tcst for Co++ with crnitroso-p-naphthol:
(Rcagcnt solution is I gm.
of solid in 50 ml. glacial acetic
acid diluted to IOO ml. with
watcr.) I drop oftest solution
(neutral or weakly acid) is
spotted onto filter paper and I
drop of reagcnt added. The
reagent alone gives a yellow
spot, but if Co++ is present a

138

Joyce Plesters

U "

2.&&

S&

12.2

x
2207

=
,m 0.2'c
"3
.
0 .s2 2
*"u
42

" t i ti
W

0
nekati
& , M G L ~ ~

(b) A drop of the acid test

solution 1s placed on a spot
plate lined with paraffin wax.
The yellow Fe+++solution is
dccolorized by adding a crystal or two of potassium
fluoride (Fe ' -> K, Fe F,).
A drop of cr-a'-dipyridyl rcagent (z % in ethanol is added).
Fcf produces a pink coloration.
++

.-

A basic copper
carbonate,
CuCO, .
Cu(OH),.

Malachite
(mountain
green).

Crystalline fragments, a rather

pale, blue-green
in colour.

Soluble with effervcrscncc of C O z

giving a green
solution.

Unaffected in
the cold, but
on warnling,
the particles
partially dissolve giving a
pale blue solu-
tion and they
becorne coated
with black
CuO.

Soluble with
effervescence of
CO,, giving a
blue solution.

The solution in acid rnay be

Black residue of
used for the tests for copper
CuO.
described under 'Azurite'
(see 'filue Pigments').

2
(0

m
r-7

z.
0

2
B
--

. --

.-

Usually the
dibasic copper
acetate,
Cu(CH,COO),.
zCu (OH),.

Verdigris

Known from
earliest times
as a natural
mineral; often
occurs in conjunction with
azurite, q.v.

Prepared from
ancient times
by corroding
copper with
vinegar.

Clear blue-green
crystals, somctiines pointed
needles. Colour
ofien very
strong.

Soluble giving a
green solution.

Soluble, giving Soluble giving Gives off a

apalc bluepptt. a green solution. smell of acetic
acid on wannof copper hying (vapour
droxide which
turns Universal
turns black on
Indicator paper
boiling.
red). Further
heating converts into black
CuO.

(i)
The tests for Cu++ described under 'Azurite' may
be carried out on the solution
of the pigment in dil. HC1,
or HNO,.
(ii) Tests for acetate:
(a) Warnling with dil.
H,SO, usually yields a smell
of acetic acid.
(6) Addition of silver nitrate solution to a solution of
the pigment in H N O , produccs a white pptt. of silver
acctatc.

;
i

9
2.
r-7

-k
n

2.
%

%t

.
-

Trarlsparerlt
copper green.

Not strictly a
pigment. A
transparent
green varnish
is formed if a
copper salt is
dissolved in a
resin such as
Venice turpentine, when the
Cu 1 ion
forms a salt
with the resin
acids, c.g. copper abictatc.
+

Laurie [I]
claimed to
have found
this type of
paint on illuminated inanuscripts dating
from the 8th
century.

Partly soluble
Clear rather
grass-green when giving a solution
freshly prepared of CuC1,.
or in good prcservation; when
decayed becomes
brown. O n pictures it is somctimes mixed with
lead white or
:
litharge to givc
an opaque
yellow-~reen.

Disintegrated,
the resinous
component
being dissolved, and
pale blue
copper hydroxide being
precipitated.

Soluble, giving
a brown solution.

The resin usually gives off a

characteristic
resinous smell
on warming,
then the resinatc
melts and bccomes brown.
Finally an incombustible
black residue of
CuO remains.

Tlle solutio~~
in acid usually
contains sufficient Cu++ for
the tests listed under
'Azurite' ('Blue Pigments')
to be carried out.

(0

CI

\D
--

Chernical

Cornposition

Orcqitl, or date
c ~ f invetttion

Appearance under
lolo m<qnification

Effect cf heat
3 N HCl

Cobalt Green
(Rinmanu's
green, zinc
green).

Chronliunl
Oxidc Grccn,
opaque.

A co~npound
of cobalt oxide
and zinc oxide
of rathcr iudcfiuitc proportion~.l'robably there is
a small proportion of
COO to ZnO.

Anhydrous
Cllronlic
Oxidc,
Cr,O,.

A synthetic
pignlent discovcrcd by
Rinrnann in
1780, but not
u ~ c da5 a pignlcnt until thc
ni~~ctccnth
century.

Vauquclin, the
di~covcrcrof
chromium,
suggc~tedthe
use of Cr,O,
in ceramic
glazes in r809,
but it probably did uot
appear as an
artist's pigment until
some years
later. [See
Lamic (I).]

Fine regular
rounded particle~,rathcr blucgrccn by rcflcctcd light, but
pure green by
transmitted light.

Rather dull olivc

grccn opaque
granules, usually
rathcr coarse;
high refractive
index.

Slightly soluble
on heating, and
more so with
conc. H C l giving
a pale piuk solution.

qN NaOH

Specijc tests

HNO,
(corlcentrated)
Slowly solublc
wit11 heating to
give a pale
bluc solution.

(i) T c ~ t sfor C o + ~listed

+
under 'Smalt' ('Bluc Pigments') may be made on the
solution of the pigmcnt in
nitric acid.
(ii) Test for Zn-'--Iwith
dithizonc:
T drop of the t c ~ ~olution
t
on a spot plate i~ made alkaline with 2N NaOH, a few
drops of dithizonc solutio~l
(10 nlg. in roo rill. of carbon
tctrachloridc) arc added. The
solution is stirred and the CCI,
evaporated by blowiug. A
ra~pberryred solution (iudependint of precipitates precnt) indicates Zn (the tcst is
spccific for Zn in alkaline
solution).

The pigmcnt can be got

into solution by fu$ng with a
lnixturc of ~odiunlcarbonate
and sodiurn peroxide on a
platinu111spoon a i d di~~olving
the inelt iu 2 drops of conc.
H,SO,. The chron~iu~n
goes
into ~olutionas sodium chroinatc. T a t s for chronlium as
chromate may be made on this
solution:
t G O , - - with
(i) T e ~ for
diphcnylcarbazide:
T o a drop of t c ~ solution
t
on a spot platc arc added 1-2
drops of the reagent ( I %
diphcnylcarbazidc in ethanol).
A violet colour i~formed in
the prcscncc of chronlatc.

REDAND VIOLET
PIGMENTS
(Contd.)

Pigment

Chemical
composition

Orkin, or date Appearance under

of invention low magnijicatiorz

Solubilities

Effect qf heat

Specijic t e w

Dragon's blood A natural

From a tree
resin (for
in East Asia;
chemical com- known in
position see
medieval
Robertson and times. (See
W ~ ~ [311)
C Y Thompson
1321).

Dark red by reflected light but

clear orange-red
by transmitted
light.

Partly soluble,
giving a yellow
solution.

Partially dissolves to an
orange-red
turbid solu-

Disintegrates
Melts then
to a dark brown evolves
mass.
benzoic acid
(characteristic
smell). See
Gettens and
Stout [z6].

Madder Lake
(Crimson
madder).

A mixture of
two hydroxyanthraquinonc
dyestuffs, alizarin and purpurin, mordanted on to a
base which is
usually
AI(OH),.

Extracted
from the root
of the madder
plant.

Usually a very
fine powder,
crimson red in
colour. In oil
films the separate particles cannot be seen owing to the transparency of the
Al(OH),.

The Al(OH),
partly dissolves
and the colour of
the pigment becomes more
orange.

Soluble, giving a purplish

solution.

Decomposes
to a dark bro
solution.

Colour change
to purple
brown, then
black and
finally only a
pale grey ash a
A1,0, remains.

(i) Tests for the dyestuff:

(a) O n addition of excess
dil. H,SO, the Al(OH), base
is dissolved and a flocculent
pptt. of the dyestuff formed,
orange in colour.
(b) Natural madder lakes
often fluoresce whitish in u.v.
owing to the presence of purpurin.
(ii) 'Test for Al(OH),, with
Morin reagent:
'The paint fragment is
treated with NaOH which
dissolves out the medium
and the Al(OH),. I drop of
the Morin reagent (satd. solution in methanol) is placed on
filter paper and dried. I drop
of the test solution is added
and the paper again dried. O n
addition of a drop of dil. HCl
the spot fluoresces yellowgreen in u.-v. (A blank test
should be doue with the reagents.)

Alizarin
crimson.

A single
hydroxyanthraquinone
dyestuff, alizarin. on a basc
of Al(OH),.

Synthesized
for the first
time in 1868
by Graebe and
Lieberrrian.

As above.

As above.

As above.

As above.

As above.

As above, except that in the

case of tcst (i) (b), the absence
of purpurin means that there
is no fluorescence undcr U.V.
light.

Soluble in alcohol, benzene

and chloroform to give bright
red solutions.

Brown Madder Madder or

(burnt madder). alizarin
charred by
heating.

See above.

As above, but a
dull brownish or
purplish red.

Cobalt Violet,
dark.

Preparation
described in
1859 by
Salvttat.

Irregular particles, redviolet in transmitted light and

highly rcfract-

Cobalt Violet,
light.

Manganese
Violet (Niirnberg Violet,
Permanent
Violet).

Anhydrous
cobalt phosphate
Co,(PO,),.

Anhydrous
cobalt
arsenate.

Appeared
about 1880
(see Eibner

Fusion product Prepared first

of manganese by E. Leykauf
dioxide and
in 1868.
ammonium
phosphate.

As above.

As above.

See above.

As above.

Somewhat
soluble.

(i) Tests for Co listed

under 'Smalt' (see 'Blue
Pigments') can be made on
the solution in aqua regia.
(ii) Tests for Phosphate:
A few grains of pigment
arc placed on filter paper,
moistened with a drop of
ammonium molybdate solution and warmed over a flame.
A drop of benzidinc solution
(0.05 g. base or chloride in
10 ml. conc. acetic acid, then
diluted with watcr to loo ml.)
is added and the moist fleck
held over NH,. A brilliant
blue colour forms around the
sample.

As above

Rounded granules of rather

irregular size,
bright red-violet
by reflected light,
but pale transparent mauve by
transmitted light.

See above.

Tests for Co++:

(i) As above.
lii) Test for Arsenate: see
tesis Lnder Scheelc's Green
('Green Pigments').
O n heating gradually turns black
with evolution of
Cl,.

Black pptt.
of MnO,.

Greyish
residue.

Test for Mn:

The sample of pigment is
mixed with solid Na,CO, and
potassium nitrite (KNO,) and
fused on platinum foil. A
green mass of alkali manganate is formed. This is
soluble in watcr, and on
standing is oxidized to purple
alkali permangatlate.

$)
2

2$
4a
0

s+
?
,

EL
3

Z.
w

%
b

r,

2p
w

Solubilities
Orisin, or date
oj'irrverrtion

Appearance urrder
low mqnjfcation

Effcct ofhent

Specific

fests

3N HCl

Yellow Ochre Hydrated iron

(Golden Ochre, oxide, Fc,O,.
Mars Yellow). H,O. The
natural ochres
may contain
aluminium
silicate and
other impurities

Massicot and
Litharge.

Principally lead
mo~loxide
PbO, but
lithargc usually contains a
littlc red lead,
Pb,O,.

Orpinlent
Yellow
(King's Yellou arsenic
sulphidc,
As,S,.

Natural
~nincralsarc
widely distributcd, but
an artificial
variety (Mars
yellow) is also

made.

Usually very
small regular
grains, a rathcr
dull golden
yellow by reflected light.

Some samples arc

slightly soluble,
giving a yellow
solution of FeCl,.

Manufactured
pigments
known froln
antiquity.
Massicot is
the unfused
o x ~ d emade b
roasting lcad
white; litllargc is the
fused oxide
~nadcby
oxidation of
~noltcnlead.
(See Gettens
and Stout [z4]

Usually of fine
allnost amorphous texture
like lead white.
Massicot is pale
yellow, lithargc
a little more
orange, owing
to the presence
of red Pb,O,.

Soluble with
pptn. of white
PbCI,.

Solublc on
heating, as
sodium
plumbite.

Natural
mineral, used
from
antiquity.

Bright goldcn
yellow; occurs
in small flakes
or in fibrous
masses, has a
glossy or waxy
looking surface.

O n heating goes
into solution witk
evolution of
H,S.

Solublc giving Soluble (desodium arsen- composes to

ate and sulph- give As and
arscnitcs.
H,SO,).

Partly soluble,
givinz a ycllow
solution.

Turns brownred on loss of

colnbincd
water.

Soluble in hot concentrated

H C l giving a yellow solution
of FcCl,. The terts for iron
given under 'Grecn Earth'

(see 'Grccn Pigments') may

be carried out on thir solution.

Readily soluble.

Unaffected at
moderate tetnperatures.
Changes to
red Pb,O, if
heated above
400' c.

The solution in acids may

be used to carry out any of
the tests for lcad given under
'Iled Lead' (see 'Ilcd Pigmerits').

Sublillles, then
(i) Tests for As listed under
becomes colour. 'Schcclc's Grccn' (see 'Grccn
less owing to
Pigments') may be carried out
oxidation to
011 the solution in alkali.
(ii) Test for Sulphide:
the trioxidc
As,O,.
The sodiurri azidcjiodine
tcst given for Vermilion (see
'Ilcd Pigment$') nlay be made
on the solid pigment.

5n

Realgar.

Orangc-red
arsenic sulphide As,S,.

Natural
n~incraloften
occurring
with Orpiment.

Similar to above, As above.

but more orange
By transmitted
light, orangcrcd. It has a
slightly lower
R.I. than Orpi-

ment.

Solublc.

As abovc.

Melts at 310C.

Naples Yellow
(Antimony
Yellow).

Lcad antimonatc,
Pb (SbO,),.

Manufactured
pigment whos
history is
obscure. (Scc
Gettcns and
Stout [24].)

Very fine granPartially sol. with

ulcs, like Massi- whitc PbCI,
ppttd.
cot in appcarancc. It is dificult to see a crystalline form.
Colour varics
from Icn~onycllow to orangcycllow.

Partially sol.

Soluble.

Sublimes with
an orangcyellow vapour.

Chrome
Yellow.

Lead chromatc Preparation

Pb CrO,.
described by
Vauquclin in
1809.

Brilliant
ycllow; particle size varies;
usually very finc
crystals; rather

Soluble, with
pptn. of white
PbC1, and an
orangc solution
of chromic acid.

Sol~~blc
giving a yellow
solution of
alkali chromate.

Soluble giving
a yellow solution.

(i) Tcsts for Pb++:

Those listed under Red
Lead (see 'Red Pigments')
may be employed with the
solution of the pigment in
acid.
(ii) Tests for Cr0,--:
These rnay be found under
'Chron~iumOxide Green,
Opaque' (see 'Green Pigments') and may be carried
out on the solution of the
pigment in acid.

Barium
Ycllow.

Barium
chromate,
BaCrO,.

By reflected
light, bright
Icnlon ycllow;
by transmitted
light, nearly
colourless ; finc
xn. structure.

Soluble, giving a
ycllow solution.

Soluble, giving a ycllow

solution.

Soluble, giving
a yellow solution.

(i) Tcsts for Ba++:

(a) T o a solution of pigment
in HCI or H N O , is added
H,SO.,; a whitc pptt. of
insoluble BaSO, is formed.
(b) Flame tcst gives a pale
green flame.
(ii) Tests for G O 4 - - , see
'Chrome Yellow', above.

As abovc.

As abovc.

(i) Test for Antimony:

drop of the solutiotl of the
piglncnt in H C l is treated
with I drop of conc. H,SO,
on platinuru foil and a zinc
filing added, and allowed to
stand for 5-30 min. with the
Zn and Pt in contact. The
platinutn darkens when Sb is
present, and the elcll~cnt
separates on the platinum in
black plates. (As gives mainly
gaseous h~dride,Sn gives a
grey deposit only.)
(ii) Tests for Pb: under
'Red Lcad' (see 'Red Pig~nents').
I

YELLOWAND ORANGE
PIGMENTS
(Contd.)

Solubilities
Pigment

Chemical
Composition

Origin, or date Appearanre under

low magniJication
ofinvention
3 N HCI

Strontiuni
Ycllow
(Lenion
Ycllow).

Strontiunl
chromate,
Sr CrO,.

As abovc.

A littlc stronecr
yellow than
BaCrO,.
Finely dividcd
crystalline mass
consisting of
nccdlcs.

As abovc.

4N NaoH

As above.

Efect of heat

(i) Tcsts for Sr++:

( a ) Addition of H,S04 to
thc acid tcst drop givcs a white
pptt. of insol. SrSO,.
(b) Flanlc tcst givcs a
crinlson flanlc.
(ii) Tcsts for CrO,--: see
'Chromc Ycllow'.
(iii) Tcst with Sodium
Rhodizonatc for distinguishing betwccn Barium and
Strontium in lemon yellows:
I drop of the neutral test
solution is spotted on filter
paper and I drop of the
reagent (0.2 % aq.) added.
Ba++ and Sr++ both give a
red-brown spot, but the
colour due to Sr++ disappears
with I drop of dil. (I in 20)
HCI, the Ba++ cmpd. rcrnaining as a bright red spot.

As abovc.
I

I
Cobalt Ycllow
(Aurcolin).

Potassiunl
cobaltinitritc,
CoK3. (NO,),
H,O.

Discovered by
N. W . Fisher
in 1848.

Snlall crystals
and clustcrs of
crystals, ycllow
by transniittcd
light.

Slightly soluble
giving a yellow
solution.

Colour varies
from lcnlon yellow to orangc,
probably accord
ing to particlc
size, thc orangc
usually bcing
coarser. All
types arc, howcvcr, comparativcly fincly
divided.

Insoluble in thc
cold; partly soluble on hcating,
with evolution of
H,S.

Slightly solublc.

SpeciJic tests

HNO,

(concentrated)

Soluble, giving
an orange
solution.

Whcn hcatcd
strongly, givcs
black C o o ,
and oxides of
nitrogcn.

Thc rcsiduc froni cornbustion can bc dissolvcd in dil.

HCI or HNO, and thc solution uscd for tcsts for Co++
listcd undcr 'Snlalt' (sce 'Blue
Pigmcnts ').

Solublc, with
evolution of
H,S.

At high temperatures
brown CdO is
produccd.

(i) Tcst for Cd++ with dip-nitrophenylcarbazide:

A drop of the test solution
is mixed on a spot plate with
a drop of NaOH (10 %)and of
K C N (10 %), a drop of rcagent (0.1 % alcoholic solution of di-p-nitrophcnylcarbazide) and two drops of
forn~aldehydc(40 %). In
the presence of Cd++ a blucgreen pptt. or colour is
formed. The reagcnt alonc

Cadnliu~n
Ycllow.

Cadmium
A synthetic
Sulphidc, CdS pigment preparcd by pptn.
(a mineral
form cxists
but thcrc is no
rccord of its
cvcr having
bccn uscd as a
pigtncnt). First
obscrvcd by
Stronieyer in
1817.

rn

5Z

givcs a violet colour with

fornialdchyde. The colour
should be cotnparcd with a
blank using thc rcagents only.
(ii) Test for Sulphidc: The
sodium azideliodine test described undcr 'Vcrmilion'
(see 'Red Pigments') can be
uscd with the solid pigment.

BROWNAND BLACKPIGMENTS.
Raw Sienna

Burnt Sienna.

Raw Utnber.

Hydrated
ferric oxide,
Fe,03. H,O.

Anhydrous
Ferric Oxide,
Fe,O,.

Natural
mineral.

Prepared by
calcining Raw
Sienna.

Hydrated
Natural
Ferric Oxide
mineral.
Fe,O, . H,O
with a proportion of Manganese dioxide
MnO,. (from
8-16 %.)

1
'

By reflected
light, a goldenbrown; by transmitted light, a
mixture of transparent yellow,
red-brown and
colourless particles can be seen,
as well as opaque
brown ones.

Slightly soluble,
especially on heating. (Usually
sufficient to give
a blue colour with
K,Fe(CN),.)

Most of the
grains are reddish brown. N o
visible crvstal'
line form.

As above.

Fine darkish
yellow-brown
grams tnainly,
but some orange
yellow and
colourless par-

2X

Partly soluble.

Colour changes
to the darkcr
warnicr brown
of Burnt Sicnna
(see below), the
anhydrous
oxide.

The pigment will dissolve

in hot concentd. HCl giving
a ycllow solution. The tests for
iron may be carried out on
this solution which are listed
undcr 'Green Earth' (see
'Green Pigments').

8.
2

3a
r)

R
2.
&.
-

As above.

As above.

I
As above.

As above.

Loses water to
become the
anhydrous
oxide Burnt
Umbcr (see
bclow) which is
a darker,
redder brown.

(i) Tests for Fe+++ as for

Raw Sicnna.
(ii) Tcsts for Mn:
(a) Catalytic oxidation to
permanganate:
A little of the pigment or a
drop of its solution in HNO,
(Cl- must be absent) is mixed
with a drop of conc. H,SO, in
a platinum spoon. A drop of
AgNO, solution (0.1 %) is
stirrcd in, followed by a milligram or two of arntnonium
pcrsulphate. The mixture is
gently hcated. In the presence
of M n a red-violet colour due
to thcpcrmanganate is formed.

ft

2.
$

'",
2

BROWNAND BLACKPIGMENTS
(Contd.)

w
3

Chemical
composition

Origin, or date
of invention

Burnt Umber. Anhydrous

Prepared by
ferric oxide
gently heating
Fe,O,, with a Raw Umber.
proportion of
manganese
dioxide, MnO,

Bitumen
(asphaltum,
mummy,
bistre).

Van Dyck
Brown (Cassell
Earth, Cologne
Earth).

Appearance under
low mqnification

As above, but
a little darker,
redder brown in
colour, and
slightly more
transparent.

A mixture of Bitumen or
hydrocarbons asphaltum
occurs as a
with organic
and inorganic semi-liquid
impurities and mineral deposit. Mummy
of variable
is a pigment
composition.
made from
(See Church
the asphaltum
[301 2nd
used to emGettens and
balm Egyptian
Stout [24])
mummies.
Bistre is a
tarry material
from burned

Dark brown
amorphous
solid, semitransparent and
orange-brown
by transmitted
light. It is partially soluble in
oil media giving
a translucent
brown film.

Consists of as A mineral
much as 90 % deposit similar
to Lignite.
of organic
matter (hydrocarbons similar
to those of
Bitumen), together with
iron oxide,
alumina,
silica, etc.

As above, but
of a more
heterogeneous
appearance, and
with granules of
inorganic brown
pigment.

Solubilities

3.

Hcl

As above.

4N

Soluble, giving an orangebrown solution.

As above.

Efect of heat

SpeciJic tests

(i) Tests for Fe+++, as for

Raw Sienna.
(ii) Tests for Mn, as above.

(coE22ed)
As above.

Soluble, giving
a red-brown
solution.

As above.

At first melts
to a black tarry
liquid. Dense
yellow-brown
fumes are then
produced, with
a pungent, tarry
odour, and a
brown distillate collects
at the mouth of
the ignition
tube.
Finally only a
very small residue of incombustible inorganic matter
remains.
As above, but
leaves rather
more incombustible residue

(i) At least part of the

material is soluble in benzene,
petroleum ethers and other
organic solvents.
(ii) The incombustible
residue usually gives a positive
Y
test for iron (see tests for
Fe+++ under 'Green Earth',
4
'Green Pigments').

As above.

METALS
USED

AS

PIGMENTS
(Contd.)

Chemical
cumporition

Origin, or date
of invention

Appearance under
low magnijcation
3N HCl

Silver.

Metallic element, Ag.

Known from
antiquity.

When untarnished has a

white metallic
sheen, but
rapidly discolours in an
itilpure atmosphere, owing to
the fortnation of
a film of black
sulphide.

Very slight solvent action.

qN NaOH

HNO,
(corrcentrated)
Dissolves with
evolution of
nitrogen oxides
(brown fumes
with characteristic odour).

(i) T o the solution in HNO,

is added dil. HCl. A white
ppt. of AgCI, is formed,
darkening on exposure to
light and soluble in excess
NH,.
(ii) Addition of K,CrO, to
the tcst solution produces a
pptt. of brick-red silver
chromate. Ag,CrO,. (The reaction is best seen on a spot
plate.)
(iii) Test with p-diniethylamino benzylidene rhodamine:
A drop of the neutralized
test solution is stirred on a
spot plate with a drop of KCN
solution (10 % aq.);A.drop
of the reagent (003 /o In
ethanol) is added followed by
dil. HNO, until the mixture
is acid. A pink colour indicates Ag. (Under these conditions Au does not give a
coloured compound.)

'7

2
2
"

'"
T

Tin.

Metallic eletnent, Sn.

Known fro111
antiquity and
sonictimcs
used on pictures in the
Middle A ~ c s .

Lustrous white
metal, untarnished by air
and water.

Dissolves rather
slowly in the
diluted acid.

I
I

Dissolves very
slowly on
heating forniing sodiutn
stannate,
Na,SnO,.

A filtn of hydrated stannic

oxide becotncs
fortned on the
surface of the
metal, and the
action slows
down and stops.

i
-

The nietal dissolves quite

rapidly in conc. HCl, forniing
stannous chloride. This sohtion can be uscd for the following tcsts for Sn:
(i) With atnri~oniutnphosphornolybdate:
Filter paper itnpregnated
with a solution of phosphotnolybdic acid is held over
NH, until yellow anitnonium
phosphotnolybdate is formed
and thcn dricd. A drop of the
test solution produces a blue
spot if Sn is present.
(ii) Test with Cacotheline:
Filter paper is impregnated
with a satd. aq. solution of the
reagent. A drop of the test
solution is added before the
paper is quitc dry. According
to the atnount of Sn a red
circle or ring is formed on the
paper coloured yellow by the
reagent, surrounded by a
colourless zone.

$
rn
c-,

2.
2

2a
C)

2.
r'

E..

-.
'-r

Joyce Plesters
I
COUPES TRANSVERSALES E T ANALYSE CHIMIQUE D'&CHANTILLONS

DE PEINTURE

Rhsunze'
Le but de la prkparatioil et de l'ktude des
coupes de peintures est discutt et la base des
mtthodes pratiques est dtcrite.
Un bref rtsumt historique des travaux antirieurs sur le sujet est donnt.
Les avantages et limitations de cette mtthode
d'ttude de la construction picturale sont
tnumkrts, pour arriver B la conclusion que la
mtthode est conlplkmentaire B d'autres mkthodes comme la photographie en rayons X et
infra-rouges.
Suit une description -de la mtthode employke au laboratoire de la National Gallery.
Les kcllantillons sont prtlevts par le restaurateur au moyen d'une lame pointue bien aiguiste, ce travail se fait sous un microscope binoculaire B faible grossissement. Une partie de
l'tchantillon est montte en coupe, l'autre sert
B l'analyse de la matikre picturale. Une rtsine
polyester durcissable B froid sert de milieu de
montage pour les coupes.
A la National Gallery les coupes de peinture
ne sont faites en premikre instance que dans le
cas oil elles pourraient fournir des informations
d'ordre pratique au restaurateur. La plupart
des exemples donnts se rapportent donc B des
peintures, restaurtes au cours des cinq dernikres anntes. U n certain nombre d'exemples
mettent en lvidence l'apport des coupes et de
l'analyse des peintures B la solution de problkmes de restauration-dttection
des surpeints ou des vernis anciens, ttat de prtservation de la peinture originale . . . O n donne
aussi quelques exemples d'altkations et de
surpeiilts effectuts par le maftre original.
L'article discute ensuite l'ktude de la technique picturale. Les peintres du moyen-ige et
du debut de la Renaissance construisaient leurs
peintures en superposant de fines couches
rtgulihes. Ceci ttait d'une part dii B une conception mtthodique et artisanale du travail et

d'autre part aux proprittts de la dktrempe B

l'oeuf.
I1 semble bien, qu'i l'origine, la peinture B
l'huile s'appliquait en couches minces et rtgulikres, tout comme la dktrempe.
Ce n'est qu'avec Rembrandt que toutes les
proprittts rhtologiques de la peinture B
l'huile furent exploittes. U n certain nombre
d'exemples de coupes de peintures depuis
Masaccio jusqu'i Renoir sont illustrts et discutts du point de vue de la technique. Dans
quelques cas il fut possible d'ttudier des
kchantillons de peinture de plusieurs oeuvres
d'un m t m e maftre (par exemple: tableaux de
Giovanni Bellini et de Rembrandt).
L'analyse des pigments conduit B la conclusion que jusqu'en pleine Renaissance les
peintres ont rechercht l'emploi de pigments
aussi purs et brillants que possible. I1 est rare
de trouver une couleur composte d'un
mtlange de plusieurs pigments, bien que tous
les pigments fussent mtlangtj avec du blanc
pour produire les zones trks tclairtes. Les
gradations subtiles des tons sont le plus souvent
obtenues par des glacis translucides appliquts
sur des couleurs opaques. Les dimensions
grossikres des grains de quelques uns des pigments, compartes B celles des pigments modernes, est trks perceptible. Ceci vaut surtout
pour les pigments bleus et verts. Des exemples
sont donnts.
Les informations concernant les liants utilisks par les maftres ancienssontbeaucoup illoins
prtcises. Quelques tableaux oh l'identification
du liant semble presque certaine, sont repris
dans une liste.
U n aperqu de l'histoire de l'analyse des
pigments sert d'introduction B une strie de
tableaux d'analyse pour l'identification des
pigments. Ces derniers sont classes en groupes,
suivant leur couleur. Quelques rtactions

Cross-sections and Chemical Analysis of Paint Samples

simples ainsi qu' une ou deux rtactions de

confirmation basCes sur les 'Spot Tests' de
Feigl, sont donntes pour chaque pigment. La
plupart des pigments, ordinairement retrouvts
dans la peinture sur panneau ou sur toile
jusqu'i lafin du dix-neuvieme sickle, sont
mentionnts.
Suit un sommaire de rtactions pour liants.
Bien que leur identification prtcise soit im-

1.57

possible, ils peuvent gtntralement ttre classts

en de larges groupes. Quelques-unes des rtactions utilistes figurent tgalement dans les
tables d'identification des pigments et dans ce
cas, un seul essai, effectut sur l'tchantillon de
peinture, permet &observer simultantment
l'effet sur le pigment et sur le liant.

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Cross-Sections and Chemical Analysis of Paint Samples
Joyce Plesters
Studies in Conservation, Vol. 2, No. 3. (Apr., 1956), pp. 110-157.
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References
35

La technique des "Primitifs flamands"

P. Coremans; R. J. Gettens; J. Thissen
Studies in Conservation, Vol. 1, No. 1. (Oct., 1952), pp. 1-29.
Stable URL:
http://links.jstor.org/sici?sici=0039-3630%28195210%291%3A1%3C1%3ALTD%22F%3E2.0.CO%3B2-4

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