Cross-Sections and Chemical Analysis of Paint Samples

Author(s): Joyce Plesters

Source: Studies in Conservation, Vol. 2, No. 3, (Apr., 1956), pp. 110-157
Published by: International Institute for Conservation of Historic and Artistic Works
Stable URL: http://www.jstor.org/stable/1505000
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JOYCE PLESTERS

Cross-sections and Chemical Analysis

of Paint Samples
Received 30/I/56
INTRODUCTION AND SURVEY OF PREVIOUS WORK

IT has now becomequiteusual for conservators and restorersto regard a painting

as a stratifiedstructure,so that methods
have been developedfor studying the internallayersof a painting.Examplesof such
methods are X-ray and infra-redphotography.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 paintingin cross-section.Thisis often
difficultto do in situ on the pictureeven
with a good travellingmicroscope,sinceeven
when cracksexistwhoseedgesmaybe examto the
ined,the edgesarenearlyperpendicular
focalplaneof the microscope,so that,at best,
only an obliqueandratherout-of-focusview
canbe obtained.It is usuallymoreconvenient
to detacha minutefragmentof paintfromthe
pictureand look at it separatelyunder the
microscope.Even then, in order to see the
separatelayers,the paint fragmentmust be
stood on one edge, and for a propermicroscopicalexaminationthe sampleneedsto be
mountedin a suitablemountingmediumand
to have an edge ground or cut smooth in
order to give a plane surfacefor focusing
underthe microscope.
This is the raisond'etrefor all methodsof
preparingpaint cross-sections.As a further
scientificmethodof pictureexaminationthe
techniqueis complementaryto radiography
and infra-redphotography,in that the paint
sectiongives a largeamountof preciseinformationover a very smallareaof the picture,
whereasthe radiographor infra-redphotographgives rathermore generalinformation
over a largeareaof the picture.
IIO

The preparationof paint cross-sectionswas

begun more than forty years ago. Pioneer
work was done by Laurie [i] as early as I914.
The scope of the method was extended and
the technique improved at the Fogg Art
Museum, Cambridge, Massachusetts,in the
I930's [2]. At this time waxes were used as
mounting media for the paint sections,which
were cut with a microtome. The friabilityof
most old paint films makes this a difficult
operation,and since then the processhas been
simplified by using modern synthetic resinsas
mounting mediaand by grindingand polishing
the sections. It must be pointed out here that
what is requiredis not a transparentsection,to
be viewed by transmittedlight, as is necessary
in the case of many mineral sections, but an
opaque section, the surface only of which is
examined by reflectedlight, which makes the
preparationfairly simple. Such paint crosssections are now made in many museum
laboratories. These include the Laboratoire
Central des Musees 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 [5 and 6]. In the National
Gallery, the resin used for mounting paint
sections is a cold-setting polyester resin.
THE ADVANTAGES AND LIMITATIONS OF THE
METHOD

Advantages
The two main advantagesare:
(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

and ChemicalAnalysisof Paint Samples

Cross-sections

11

III

ii-

i'V

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..I

..... -...
:.

'"::,
.
'[;*X;.._~~.i,:?'

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':-;;,i"'

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a ...

AX:

FIG. 2.-Panel
Painting.
N.G. No. 2475. Holbein.

FIG. i.-Fresco
Painting
Roman fresco, c. 200 A.D.

(i) Wall plastermixed with coarse marble dust.

(ii) Coarse green-blue pigment.
(iii) Blue pigment.

Christinaof Denmark, Duchess of Milan

(i) Wood of panel (oak).
(ii) White gesso (calcium carbonateand 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. II4.)

11-

,.iV'

--iii

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.
(Magnificationof all photomicrographsshown is X 75)

112

Joyce Plesters

andthe sizesof
thicknesses
may be measured,
and
pigmentparticles, pigmentand medium
analysedchemically,usinga squaremillimetre
or so of paint.
(b) By detachinga smallfragmentof paint
from the pictureit is possibleto carryout
on it whichit wouldbe inadvisable
operations
or evendangerousto carryout on the picture
itself.This is especiallyvaluablewherea safe
but efficientsolventmixturehas to be found
for the removal of overpaint.Tests with
strongreagentsmaybe carriedout safelyaway
fromthe pictureuntiltheireffecton the paint
is known. It would not be possibleto carry
out testson sucha smallscaleon the picture
surfaceeven under a binocularmicroscope,
and exceedinglydifficultto restrictthe area
of the pictureaffectedby the reagent.
Limitations

(a) In order that its appearancemay not

be damaged,only minute samplesof paint
can be removedfrom a picture,so that the
amountof materialavailableto work on is
verysmall.Thisadvantageis, however,somewhat offsetby the specialmethodsused.
(b)Long-termstudyof theartist'stechnique
or of paint structureby this methodwould
requirenumeroussamples,andthe sourcesfor
suchsamplesareratherlimited.IntheNational
Gallery,for example,specimenshave, up to
the present,beentakenonly frompicturesin
courseof treatment,and then usuallyonly
when some informationmight be obtained
whichwouldbe of useto therestorerworking
on the picture.
(c) Thereis what might be calleda statisticalhazard,in thatit cannotbe certainthata
squaremillimetreor lessof paintis representative of the areaunderstudy,which may be
asmuchasa hundredsquarecentimetres,
even
to
the
the
area
be
uniform
though
eye
may
in colour and texture. However, in cases
whereit hasbeenpossibleto makesectionsof
adjacentand similarareasof paint (e.g. in
work on 'guineapigs'-aestheticallyworthless,buthistoricallysoundpictures)the results

have been very consistent. Nevertheless,

accident,artistictemperament,and the artist's
cleaning his brush on the edge of the picture
have all to be reckonedwith.
PROCEDURE IN 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 preparedin order to solve
ad hoc problems of the restorer. Hence the
examples from National Gallery pictures
quoted are practically all from pictures restoredwithin the past five years during which
work on paint sections has been carriedout.
This is the reason for what would otherwise
seem a somewhat illogical and heterogeneous
selection 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 samplesof paint from picturesin
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-pointedknife. 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
magnificationprovided by a binocularloupe
or a travelling binocular microscope. It is
preferable that the picture should be lying
flat, so that any scatteredparticles,however
small, may be saved. The knife tip may be
moistened with saliva to assistthe paint fragment to adhereto it. The use of canadabalsam
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
microscopeslide. Otherwisesuch samplesmay
conveniently be stored in the small gelatin

Cross-sections
and Chemicali Analysisof Paint Samples

capsules used for pharmaceuticalpurposes.

They are carefullylabelled,and if there is any
doubt as to whether the exact spot from which
the sample was taken could be found again,
the co-ordinatesof the spot on the picture are
measured.It must be admittedthat 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
sharpenedhypodermic needle, but as pressure
is needed this tends to shatterthe brittle paint
and also there is the difficulty of getting the
specimen out of the hollow of the needle
intact. Gettens [7] constructeda more promising but rather complex instrument for this
purpose.
The sample of paint is removed to the
laboratoryand viewed under a microscope at
low power (30 X to I50 x usually proves a

suitable range). Requirements as far as the

microscopeis concernedarenot very exacting.
They are set out in a paper by Gettens 8
and a furtherpaper by Gettens and Stout 9
(thesealso list useful tools and equipment). In
addition to an ordinary microscope (or a
chemicalone for choice) a stereoscopicbinocular microscope is often useful. A microscope with polarizing and analysing Nicol
prisms is also valuable if much pigment
identificationis to be carriedout. 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 estimationof colour
at low magnifications.
The appearanceof the upper and lower
surfacesof the paint is noted and the largest
fragment is used to preparea 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
measuredusing 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 considerablybefore 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 replacedby a new
set mounted by more modern methods such
as those describedby Charlett [Io]. After the
optical examination has been completed the
paint section may be subjectedto a series of
solvent tests, stainingtests and other chemical
tests, which will be described later in this
article. Furtherchemical 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 techniquesused in handling these
small amounts of materialsare fully described
in Chamot and Mason's manual [II].

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-sectionswill be discussed,
together with the conclusions drawn from
them, and the results of paint analysis. The
chemical testsfor 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 sequenceof
layers present. It is often stated that the four
main strataof any pictureare 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

II4

Joyce Plesters

the picture. It is desirableto include at least

partof the thicknessof the ground or priming,
if only to make sure that all the paint layers
presentin the picturearerepresented.The first
three examples illustrated do, however, include the supportsin order to show the scale
of the layers and the general relationshipof
the differentcomponents of the picture:

examplesin whichthe studyof cross-sections

hasprovedof valueto the restorers:

Fig. I. Fresco Painting (Roman, c. 200 A.D.)

the picture had shown that as well as wear in the

face there were also damages in other parts of the
picture,including the darkblue background.A cleaning
test on the background showed that under the top
varnish layers was a dark blue repaint, and, beneath
this again, what appearedto 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 disappearsaltogether in the centre of the cross-section.It
is composed of azurite in a medium of oil.
vi. A thick layer of granulargrey-green paint, with
a few deep blue and some whitish particles visible.
The medium is an oil-and-resinvarnish which has discoloured and become opaque. On dissolving out this
medium, blue crystalsof azurite can be seen.
vii. A thin deep blue paint layer, which is a mixture
of azurite,prussianblue, and lead white in an oil resin
medium.
The discontinuity of layer (v) must representa 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. On dissolving out the medium it
was found to be pigmented with the same brilliant
blue crystallinepigment, 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 opaqueand 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

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 crystallinecalcium carbonate.There is no
varnish. A coarse structure is fairly typical of wall
paintings.
Fig. 2. Panel Painting (N.G. No. 2475, Hans

HOLBEIN

the Younger). Christina of Denmark, 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 thicknessof the paint layers (Dutch seventeenth centurypanelsare 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 photograph. The medium of
the paint layer is oil.
Fig. 3. Canvas painting (English School, seventeenth
century).
Here the canvas appearsas one warp thread running
the length of the section and weft threads spaced
at intervals perpendicularto the plane of the paper.
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 discussedhere

further, after this brief comparison.The rest
of the discussionwill deal solely with paintings
on canvasand panel.
PAINT SECTIONS AS AN AID TO PICTURE
RESTORATION

It has already been mentioned that the

primaryreasonfor taking paint samplesfrom
pictures in the National Gallery has been to
provide informationfor the restorerworking
on the picture. The following are a few

N.G. No. 2475, Hans HOLBEIN, the Younger, Christina of

Denmark,Duchessof Milan
Cleaning tests were made on this picturewith a view
to its being exhibited at the Royal Academy Winter
Exhibition of 'Works by Holbein and other Masters'
held in I950-5I. Radiographs covering the whole of

Cross-sections
and ChemicalAnalysisof Paint Samples
used by Holbein.Unfortunately,afterthese tests the
cleaningof the picturewas temporarilypostponedin
view of the lengthof timeit wouldtaketo removethe
repaintsand restorethe damagedareas,and also in
view of the ratherpoor state of preservationof the
face. It was interestingto note that at the Holbein
Exhibitiontwo contemporary
versionsof this picture
wereexhibited(in the catalogueof thatexhibition[I2]
No. 22, Studioof HansHolbeinthe younger,andNo.
23, After Holbein).In both these picturesthe backgroundto thefigurewasquitea bright,slightlygreenish
blue very like the backgroundof the Holbeinportrait
miniatures,and the effect of the figure againstthis
backgroundis much more telling. In the National
Gallerypicture,in additionto the changeof colour,the
repainthasbeencarriedover the edgesof the figurein
someplaces,especiallyaroundtheproperrightshoulder
andsideof the head.
N.G. No.

292, POLLAIUOLO,Martyrdom of S.

Sebastian

This picturepresentedmany complex problemsto

the restorer,a few of which were resolvedwith the
Firstof all, afterthe discoloured
help of cross-sections.
varnishhad been removed with the usual type of
organicsolventmixture,it was foundthatthe picture
was stillcoveredwith a dull greyishfilm. It wasnecessaryto makecertainthatthis was a lateraccretionon
the pictureandnot an originalglazebeforeits removal
fromthe picturecouldbe contemplated.
Cross-sections
were madefrom variousareasof the picture.One of
these,from the pale blue sky, happenedto show the
'grey layer'going over and into a crackin the blue
paintlayer.This is shown in Fig. 6. The photograph
has been takenwith the illuminationexaggeratingthe
darknessof the 'greylayer'to show it up moreclearly.
It wasalsofoundbothby therestorer's
carefulexamination of the surfaceof the picture,and by the studyof
the sections,thatalthoughthe thicknessof the layerdid
vary slightlyover differentareasof the picture,it did
not do so in any logicalway as, say, a glaze usedfor
modellingmight be expectedto do. Fragmentsof the
'greylayer'itselfwere examinedunderthe microscope
and subjectedto solventtests.It was discoveredto be
a filmof driedoil, withthepossibilityof a smalladdition
of resin.It was not deliberatelypigmented,although
scattereddust particleshad become embeddedin it
hereand there,probablyduringits drying.The greynessand opalescenteffectof the film on the pictureis
probablydue to the scatteringof light on the surface
becauseof the fine crazingand disintegrationof the
film which couldclearlybe seenunderthemicroscope.
It was decidedto remove the 'grey layer' from the
pictureusinga mild alkalinesolvent.
Cross-sections
were also takenfrom differentareas
of green and brown foliage in order to discoverits
stateof preservation.
A few areasare a comparatively

I1S

bright green.A sectionof one of these is shown in

Fig. 7. The layersto be seenare: (i) a thickgessoof
gypsumandglue;(ii) a thinbrownlineof gluepriming;
(iii) a yellow-brown underpaintconsistingof lead
white andbrownandyellow ochrein an oil medium;
(iv) the main body colour which is pale green and
containsleadwhite, probablymixedwith yellow lead
monoxide,colouredgreen with copper resinateand
containingnumerousdarkgreencrystalsof verdigris,
someverylarge;(v) tracesof a brownedcopperresinate
glaze(not easilyseenin the photograph).
on otherpartsof the picturethe green
Unfortunately
colourwas producedonly by a thick layer of copper
resinateover a yellow or light brownunderpaint,
and
whenthe glazebecamediscoloured
the greencolourno
longerremained.In somecasesthe onlyvisibletraceof
greenis anoccasional
crystalof verdigrisembeddedwell
down in the brownedcopperresinate.Nevertheless,
thehighconcentration
of copperionsandtheabsenceof
any otherbrownpigmentshowsthesedecayedbrown
layersto havebeenoriginallythe greenresinate.
Theunpleasant
surfaceof somedark
blistered-looking
areasof the picturewas provedto be due to the use of
a bituminouspigmentfor the shadowsand this had
sunk into the paintbeneath,thus ruiningit.
N.G. No. 1330, DUCCIO, The Transfiguration

A cross-sectionof paint from the edge of a puttying

on St. James'sblue robe showed that beneathwere 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 alkalinepreparation.
N.G. No. 772, CosimoTURA, Virginand Child Enthroned
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 uncertainwhether or not this was original.
It was analysed and no modern pigment was found,
the paint being a copper resinate green such as was
presentin several other partsof the picture which were

Joyce Plesters
to be coveredwith an unevenbrownglazewhichwas
obviously genuine. However, several retouchings on
the picture were also found to be copper greens of
suspectednot to be original.A cross-sectionshowed
the same type. The solubilities, appearance,and u.-v.
the glazeoverthe pinklayerasbeingrathercoarseand
fluorescence of the paint from the green marbling,
crystalline;it was found to be an oil-resinglaze pigred-brownironoxide.Two
mentedwith a transparent
original green paint and green repaintswere compared.
or
It was discovered that the green marbling bore rather
stepsweretakento attemptto proveits authenticity
otherwise.Firstly,its solubilitieswere comparedwith
more similarity to the repaints than to the original
a sampleof a genuinebrown glaze from the coat. It
paint, but it was finally decided that the evidence was
moresoluble.Secondly,
not sufficiently conclusive to justify removal of the
was foundto be considerably
a paintsectionwas takenfrom the blue inscriptionat
green marbling.
the top of the picture,sincethe art-historian
working
on thepictureconceivedtheideathatif thebrownglaze
N.G. No. 4, TITIAN, The Holy Family
were originalandmeantto modifythe pinkcolourof
A 'grey layer' of perished oil varnish such as that
it wouldmostlikelyhavebeenpainted
thebackground,
found on N.G. No. 292 (Pollaiuolo) was found. The
the
all
over
backgroundbefore the inscriptionwas
layer, which was unpigmented, was shown to cover
otherhand,it was a repaint,it would
on
the
added.
If,
light and darkareasof the picturefairly evenly, indicatblue inscriptionor roundit. The
the
over
either
go
ing that it could not consist of local glazes.
the blue paintlayer directly
showed
in
fact,
section,
Repaints on Joseph's orange robe were also tested.
brown
with
the
the
above
glazerunningoverthe
pink
One darkrepaintwas found to consist of a conglomerabluelettering.
of
the
the
over
and
edge
up
pink
tion of white, blue, crimson, and
II6

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 undeterioratedgreen, but in practically
all areas the green colour had been produced by a
single layer of copper resinate,mixed with crystalline
verdigris in some parts, and the green colour was
almost completely lost.
N.G. No. 1675, REMBRANDT,Portrait of Margaretha Trip

Cross-sectionsshowed first of all that above the redbrown priming (which was evident along edges and
in damages) a coarse, granulargrey priming seemed to
cover the whole of the picturesurfacebeneaththe local
colours.
Sections from the black dress and the dark brown
background showed that both these areas had, in
addition to the opaque body colour, dark translucent
glazes which seemed 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) translucentblackishglaze.
One section taken from an area where a pentimento of the hand was faintly seen showed a dense
flesh-coloured layer beneaththe semi-transparentdark
layers.
N.G. No. I938,

DURER,

The Painter's Father

After the removal by the restorer of the yellowed

varnish, the pink background of the picture was seen

Portraitof Eva Gonzales

N.G. No. 3259, MANET,

The design of this pictureis really oval in shape

canvas.Thespandrels
althoughpaintedon a rectangular
at eachcornercanbe seencut off by the outlineof this
oval, and the two upperones are paintedblue-grey,
somewhatthe colourof the mainbackgroundof the
upperpart of the picture.Since they seemedto be
only thinly painted,the restorerthought that this
on the
of the underpaint
paintmightbe a continuation
partof the backgroundwithinthe oval, in which case
it could be consideredthat Manetmight have begun
paintingthe picture,andonly laterdecidedon the oval
shape.A sectionof the paintfrom within the oval is
shown in Fig. 22. It consistsof severalsuperimposed
layersof blue-greypaintinterposedwith thin layers
of white. A cross-sectionfrom within the spandrel
showed only a singlelayer of blue grey paint above
the white priming.It did not resemblethe lowest
beinga
layerof the sectionfromthe mainbackground,
much darkershade.It was most like the uppermost
but one layer, a thick darklayer in the photograph,
beforethis receivedits final thin pale scumble.This
seemsto suggestthatManetdidnot paintthe spandrels
of the picturewhen he firstbeganit, but left them as

white priming.

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

took placebeforethispicture
discussion
Considerable
was cleanedas it was one of the most recentlypainted
picturesin the collection.One authorityexpresseda
fearthatif the paintwererichin medium,the pigment
mighthavesunkto the bottomof the layer,leavinga
'pellicule'of unpigmentedand not very old linoxyn
film on the surfaceof the picturewhich might be

iii\
11ii/

iv

i1

111-

11
i-

No. 3046. MASACCIO(1401-1428).

FIG. 4.-N.G.
The Virgin and the Child (dated 1426)

Gold background.

FIG. 5.-N.G.

No.

709. MEMLINC(active
d. I494).

I405,

The Virgin and Child Strip of green hanging.

/iv

-iii

/iii

-11

-ii

--i

No. 292. POLLAIUOLO

(c. I432-I498).
Martyrdom of S. Sebastian (dated I475).

FIG. 6.-N.G.

Blue sky showing the " grey layer " in a crack.

FIG. 8.-N.G.

No. 772. Cosimo TURA(c. I43I-1495).

The Virgin and Child Enthroned.

Pink column to left of throne.

FIG. 7.-N.G.

No. 292.

POLLAIUOLO.

Green paint from near horse'shooves.

FIG. 9.-N.G.
No. 772. Cosinmo TURA.
Green column to right of throne.

/V

-iv
\111

\ii
\i

FIG. ii.-N.G.
No. 592.
BOTTICELLI
(C. I445-15IO).

FIG. io.-N.G.
No. 1045.
Gerard DAVID (active 1492, d. 1523).

Adoration of the Kings.

Sleeve of red doublet.

Canon Bemardius and Three Saints.

Red robe from painting on reverseof panel.

-iii
-iv
-ni

-ii
)i

J
-i

FIG. I3.-N.G.
No. 812.
Ascribed to Giovanni BELLINI.

FIG. I2.-N.G.
No. 599.
Giovanni BELLINI (c. 1459-1516).

The Assassinationof S. Peter Martyr. Blue Sky.

The Madonna of the Meadow. Blue sky.

vii

viiiiii-

/vi

11-

ii/

iv
1V

i-

FIG. I4.-ENGLISH

SCHOOL (I530-35).

Panel Paintings in Chichester Cathedral.

Bishop's Gold Mitre.

FIG. 5.-N.G.

No. 635.

TITIAN(1480-I576).

Virgin and Child with SS. John and Catherine.

Virgin's blue dress : deep blue shadow.

iv

.-

..-

iii

ii

No. 1324.

FIG. I6.-N.G.

VERONESE(1528-88).

Scorn.
Orange drapery.

FIG. I7.-N.G.

No.

1122.

EL GRECO (1545-I614).

S. Jerome as Cardinal (dated 1566).

Dark crimson shadow on sleeve.

hI

.IiiflM

( ToNlil

-iv

lt if
iii

ii
-'i

No. 1195.

FIG. i8.-N.G.

RUBENS(I577-I646).

Birth of Venus (sketch for a silver dish).

Gold leaf beneath glazes.

111-

FIG. I9.-N.G.

No. 1172.

Van DYCK (1599-1641).

CharlesI on Horseback (dated c. 1636).

Blue sky.

-,_W.

FIG. 2o.-N.G.

No.

_...

"-Ae

ii

I383.

VERMEER(I632-75).

Lady Standing at the Virginals.

Blue-grey background.

FIG. 21.-N.G.

No. 4453.

CANALETTO
(1697-1768).

Bucentaurat Piazzetta.
Pale blue sky.

Joyce Plesters
showed
from red to green,from one sideof the pictureto the
vulnerableto cleaningsolvents.Cross-sections
thatthe bluesandpinks,at any rate,were mixedwith
other.
leadwhite to form a very solidpaint.The leadwhite
has helped to dry the oil and will have combined
N.G. No. 635, TITIAN, The Virgin and Child with SS.
chemicallywith it. Tests carriedout on samplesof
John and Catherine
St. Catherine'sdress, now pale yellow, was shown
paintunderthe microscopeshowedthatthe paintwas
unaffectedby prolongedimmersionin far stronger
by cross-sectionsto have been rose pink originally. It
solventmixturesthanthatrequiredto removethe softhas been painted over, first with a white layer and then
resin varnish,and even withstood pure acetone.A
with a pale yellow layer of lead monoxide. On close
sectionshowingwhite priming,two blue paintlayers,
inspection of the picture, the pink layer could be seen
anda pink one, is shownin Fig. 23. The thickimpasto in minute spots of damage.
is evident.
One furtherexampleof overpaintingrevealedby
N.G. No. 1195, RUBENS, The Birth of Venus
is shown in Fig. 14. Paintsampleswere
cross-sections
This is a grisaille sketch for an oval silver dish. A
examinedfroma seriesof panelpaintingsin Chichester
cross-section from an area of greenish grey glaze
Cathedralwhich datedfrom c. 1530-35but had been
revealed some way below the paint surface a layer of
much damagedand repainted.Fig. 14 shows a crossgold leaf (see Fig. I8). An X-radiograph revealed,
sectionfrom a bishop'smitre which was gold emhowever, that the design had not been gilded entirely,
bellishedwith blue pearlsthe size of sixpences.The
but small parts of the design reinforced with gold,
sectionshows the followinglayers:(i) the gesso; (ii)
particularlysome scroll-like motifs.
a reddishunderpaint;(iii) a whitishpaintlayer; (iv)
and
dirty
gold leaf; (v) a blackishlayer,probablydirt
GIORGIONE, The Woman Taken in Adultery (Glasgow
varnish; (vi) white overpaint(in an oil medium,
Art Gallery)
whereasthe originalpaintis in a glue medium);(vii)
The
bright orange and yellow satin doublet of the
a secondlayerof gold leaf;and(viii)overtheleft-hand
man
in
the foreground was found to have been bright
sideof the sectiononly, blueoil paintfromthe 'pearls'
green originally, a brighter and bluer green than the
on the mitre.It seemsthatthe originalgold leaf must
landscapebackground. This was first painted out with
have acquireda coat of dirtor varnish,andinsteadof
a layer of white lead before the orange paint (orpiment
the restorercleaningthis off he overpaintedit with
and
realgar)was applied.
white lead paint,regildedit, and, for extrameasure,
added the blue jewels. Since this investigationthe
N.G. No. 654, van derWEYDEN,The Magdalen
pictureshave been cleanedand restoredand the gold
Cross-sections revealed that above the white gesso
mitre is seen with its originalgold leaf and without
there is in many parts of the picture (e.g. parts of the
the bluejewels which had neverformeda partof the
green dress, the landscapethrough the window, newly
originaldesign.
120

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, CosimoTURA, Virginand ChildEnthroned

Two pillarssupportthe arch over the throne,the

one on the left beingpink,the one on the right,green.
show (Figs.8 and9) thatoriginallyboth
Cross-sections
columnswere pink, but that the right-handone was
repaintedwith two layers of green paint which is
identicalwith green paint found elsewherein the
picture.This is probablyin accordancewith Tura's
curiouscolourschemefor the picture.The coloursof
the robesof the pairsof angelsalsoalternate,thistime

revealed by recent cleaning) a very pale pink priming.

This was at first thought by the restorerto be tracesof
pink putty in small damages. Under other areasthere
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 canvaswhich is embeddedin the gesso.
N G., No. 592, BOTTICELLI,The Adorationof the Kings
Fig. ii shows a cross-sectionfrom a red sleeve. The
gesso layer is not shown. The firstlayer 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 Romanpainting,Western art continued through what are usually

and ChemicalAnalysisof Paint Samples

Cross-sections

121

iii

FIG.

22.-N.G.

No.

3259.

MANET (I832-83)-

Portrait of Eva Gonzales.

Blue-grey background within outline of oval,

top right comer.

termed the Dark Ages, not in the form of

wall or easelpaintingbut ratherin 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.Paintingwas one craft of
many and the painterhad not yet achievedhis
renaissancestatus of 'artist'. Painting tended
thereforeto be carriedout as a craft,methodically and according to traditionalrules. This
attitude shows itself in the very regular and
logical construction seen in cross-sectionsof
early pictures. Fig. 4 shows a section of the

gold background of N.G. No. 3046, MASACCIO,

TheVirginand Child. The traditionalmethods

of gilding and tooling are used, although in
this same picture Masaccio has introduced
real perspective and modelling. The section
consistsof threelayers: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
surfacehas been carefullysmoothed 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-I8 ,/. The

FIG.

23.-N.G.

No. 3268.
RENOIR (1841-1919).
Les Parapluies.

Blue paint with pink scumble over a white

priming.

natureof the egg-temperausedas a medium

in early Italian paintings also contributed to
this tendency for the pictures to be built up
in thin regular paint layers. Egg-tempera
paint dries rapidlyand with a hard outline so
that subtletiesof modelling and shadingwere
in many casesproducedby the effect of superimposed semi-transparentlayers. Oil paint
seems to have been first introduced as glazes
for temperabody colours. In Fig. ii, a crosssection from a pictureby 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 especiallyin Figs. 5-I4
inclusive (Figs. 4-23 inclusive are arranged

more or less in chronologicalorder of artists).

Full use was not reallymade 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 effectswere perhaps not desired.It will
be statedlateron that the medievaland Renaissance painterstended to use pure pigments in

Joyce Plesters

I22

.x,
111

-111

-ii

11

-1

FIG. 24.-N.G.

No.

1675.

REMBRANDT.

Portraitof MargarethaTrip. 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).

FIG.

25.-REMBRANDT.

Late PortraitGroup. (Privatecollection.)

Red dresswith yellow scumble.
(i) Orange-redpriming.
(ii) Opaque scarletbody colour (vermilion).
(iii) Thin dark line of black pigment mixed with
iron oxide red pigment.
(iv) Thick pale yellow scumble of yellow massicot in an oil-resin medium.

V
IV

-iii

FIG. 26.-REMBRANDT.

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

Late self-portrait. (Private collection).

Black coat.
Orange-red priming (ochre in oil).
Black underpaint (going all over the picture).
Pale greyish-white granularpaint (covering all
the picture but varying in thickness) ; lead
white, carbon black and yellow ochre in oil.
Blackish-brownopaque body colour.
Translucentpale brownish oil-resin glaze.

THREE EXAMPLES

OF PAINT

STRUCTURE

OF LATE REMBRANDT

PORTRAITS

Cross-sections
and ChemicalAnalysisof Paint Samples
.I., I
:
..".

*:

123

..: .. .-::,K
. ."

S.

:,:::'~ ...
-

*~

..::
..:,
?

'"

':;..-:
.

s~":~

.. ..

:....

w^
..'.

(Picture

in

private

A.

collection.)

:
:.
.,~:.

:.

:-^.:."
:::

'
*

...2:

... :,

:: i.'. '
.:
*?'::'.::;. .

of" a Holbein portrait.

blue background
.
,,~.'
.

..:-

...

v.: ?&':
': i
ii:
* ..

.
.

! ':'~

'*

,,,a
~ :~::'.
*~i~ii~!~!;~;~
,:;::, ,: .,...,,': .....
...''....
; .
',,.w,?.i,
' ...... : : ..:.........i:
_is$..."
,.:.'E..

FIG.28.
CobaltBlue.
Sampleof Modemrn

of Azurite
Azurite from
from the
the
FIG.
FIG. 27.-Particles
27.--Particlesof
blue background
of a Holbeinportrait.
(Picturein privatecollection.)

FIG. 29.-N.G.
NICCOLO

No. 5283.

DELL' ABBATE

(c.

1512-7I).

Landscapewith Eurydice and Aristaeus.

Cross-section from grassin foreground, showing a
dark green and a light green paint layer both
containing large crystalsof verdigris.
EXAMPLES

OF RELATIVELY COARSE PARTICLE SIZE OF PIGMENTS

theirpaintingratherthanobtaininga desired
shadeby mixing togetherdifferentcoloured

pigments. Modifications of colour were pro-

ducedby the useof translucent

glazes.A good
in
is a sectionof
is
seen
io.
This
example
Fig.
from
a
red
robe.
Above
the gesso,
paint

layer (i), is a bright red body colour, this is

heightened by a thin semi-opaque pink

scumble,andfinallythe colouris enrichedby

layer (iv), a translucentdeep red madderglaze.

FOUND

IN EARLIER PICTURES

Slowly oil paintbeganto be usedin a freer

way and the regularityof the layerstructure
is to be less evident.Paintlayersalso tended
to become thicker,and impastoand the effects

of raisedbrushstrokeswere discovered.The
development can be seen through Fig. 16
(Veronese)to Fig. 26 (Rembrandt).

Of the illustratedexamples,spacewill only

permit the mention of a few noteworthy

points. Fig. 5

(MEMLINC)

shows the complex

Joyce Plesters

I24

structureof green paint in Flemishprimitives

and this will be more fully discussedunder
copper greens. Figs.

12

and 13 are of gesso

from two differentpanel picturesby 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

consideredas 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.

Perhapsthis is an early example of the use of
a coloured ground. Fig. 15 shows a section
from a Titian. The layers are fairly regular
and the total paint thickness comparatively
small.There aretwo very similarTitiansin the
National Gallery (No. 4, The Holy Family,
and No. 635, The Virgin and Child with SS.
John and Catherine). Sections and pigment
analysesof each showed considerableresemblance 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. I6 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 sectionwere shown
to be massicotand red lead. Fig. I8 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. I9 shows a section of

blue paint from Van Dyck's Portrait of
CharlesI 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 structureof 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 backgroundof a picture
by Vermeer.There are two priming layerson
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-grainedred-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
meansbecauseof a greaternumber of samples
available.This was so in the case of N.G. No.
783 (follower of van der WEYDEN). A detail

of the centralportion of this picture is illustrated (Fig. 30). The most interestingfeature
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-sectionsagreedvery well with
the observations on the technique made by
Mr. H. Ruhemannfrom his detailedtechnical
examinationof the picture.
Figs. 24, 25, and 26 show cross-sections

from portraitspaintedby Rembrandttowards

the end of his life. All have thick, coarseredbrown primings. In Figs. 24 and 26 this red

and ChemicalAnalysisof Paint Samples

Cross-sections

priming is separatedfrom the local colouring

by a second priming, a coarsegrey and white
granularlayer containing numerous lumps of
unmixed lead white (in addition a blackish
layer appearsbetween these two in Fig. 26).
Fig. 25 is a section from the latest of these
three pictures and shows a very irregular
layer structurewith, on top, an exceptionally
thick irregularyellow scumble.
PIGMENTS OF THE OLD MASTERS: FINDINGS
FROM PAINT ANALYSES

One of the most striking featuresof early

picturesis 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 restorerhas
added small amounts of first one pigment and
then another to match the surroundingarea.
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 mixed
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 scarletred.
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 deliberatelychosen in order to retain
the utmost colour of the crystallinepigments,
for much of it would be lost by light scatter
through fine grinding. Fig. 27 shows a sample
of azurite from the backgroundof a portrait
by Holbein (privatecollection). 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
R

I25

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

No. 5283,

NICCOLO DELL ABBATE.

With this obvious desirefor brilliantcolour

it is a shock to find so many brown coloursin
pictures where greens would be expected.
This is becausethere was not until the end of
the eighteenth century a permanent bright
green pigment. The early painters lacked a
natural grass-greenpigment. Terre verte was
rathera dull grey-green, malachiteblue-green
and ratherweak in colour, while verdigriswas
more peacock-blue than green. Moreover, a
pure green could not be made by mixing
blue or blue-greenwith 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 discoveredthat verdigrisor malachite would partly dissolve if warmed in a
resinous material such as Venice turpentine,
producing a beautiful clear green varnish.
This preparationwas 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 extensivelyused 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 deteriorationhas 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. On exposure to u.-v. it
was found that specimenspainted out turned
brown in a matter of a few months. Where
the resinwas mixed with lead white in oil the
change was rather slower. Mr. J. S. Mills
(Nuffield Scholar at the National Gallery)
carried out chromatographictests on copper
resinateand came to the conclusion that the
substance was simply a copper salt of the
resin acids. He also succeededin preparinga
similar product from copper oxide and pure
abietic acid (which is isolated from rosin).

I26

Joyce Plesters

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
paintersa 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 carefulbuilding up of the layers. In Fig. 5
is shown a cross-sectionfrom 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 resinateglaze
(difficultto see in the photograph). Near the
top surfaceit 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'srobe in N.G. No. 654,
Van der WEYDEN. Here, however, only faint

tracesof the browned glaze remainedalthough

the opaque green below had kept its
brilliantcolour. 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 Italianpicture where the
green colour is perfectlypreservedis 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 dyestuffswere of a purplish
tinge. In pictures by both Botticelli and
Bellini a clearviolet was found to be produced
by an opaque pink made from lead white and
a crimson lake, glazed with ultramarine.The

curiousdeep purpleseenin the bandsof the

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

hand, producedby a body colour of deep

unmixedwith white,glazedwith
ultramarine,
what appearsto be burnt madder(thereis
little reason to suppose it was originally
crimsonsince crimsonglazesin other parts
of the picturehavenot browned).
A few pigments found but rarely in
picturesinclude smalt, which had a very
limited period of use between about the
middleof the sixteenthcenturyuntil it was
superseded
by the inventionof cobaltbluein
I802.

It has been found in the National

Gallery Laboratoryin only four of the paint

samplesinvestigated,viz. a Veronese,a seventeenth-centuryEnglish painting, a picture by
Rembrandt and a mural by Thornhill. 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
this capacity in N.G. No. 1331, FUNGAI, The
Virgin and Child surroundedby Cherubim.

Cross-sections
and ChemicalAnalysisof Paint Samples

Of thelakepigments,an unusualpurplishone

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 Italianpaintersused
calcium sulphatefor their gesso, and northern
painterscalciumcarbonate.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 summarizesthe
findings:
(i) GlueMedium:One pictureonly in the National

Gallery, No. 664, Dieric BOUTS,The Entombment, was

found to be paintedin a glue medium,togetherwith

one other example, the series of sixteenth-century
panelsin ChichesterCathedral(seeFig. I4).
Of all the picturesso farexamined
(ii) Egg Tempera:
it can only be statedwith any confidencethat the
followingarein this medium:
N.G. No. 1330, DUCCIO,
The Transfiguration;
N.G.

No.

1331, FUNGAI, Virgin and Child with

Cherubim;
N.G. No. 592, BOTTICELLI,Adoration of the Kings;
N.G. No. 758, BALDOVINETTI,Portrait of a Lady.

(iii) Oil Medium:The vast majority of the pictures

examined were in this rather loose category, which
should be taken to mean 'a medium predominantlyof
oil'. They include pictures by artists as diverse as
Bellini, Titian, Claude, Van Goyen and Renoir.
(iv) Oil-resinmedium:This is very difficult to assess.
One of the more certain examples is that of the glazes
in some of Rembrandt'spictures.
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

authenticityof a picture.The methodusedin

the NationalGallerywill thereforebe given
in detail,for althoughit includesmuchwork
which has appearedelsewhere,it does bring
togetherinto a schematicwhole a numberof
scatteredsourcesof informationas well as
addinga few techniquesandtestsnot hitherto
appliedto paintanalysisof pictures.
Thereis a fair amountof publishedwork
on pigmentanalysis,as distinctfromwork on
propertiesof pigmentsin general.One of the
earliest referencesto chemical analysisof
pigmentsis a paperby Chaptal[I3] in 1809
on pigments found at Pompeii. In 1903
Wright [14] publisheda book on simple
methodsfor testingpainters'materialswhich
includedrathercrudequalitativeand quantitative analysisdesignedmainlyfor dry pigments.Raehlmannin 191o [I5] was the first
chemistto use microscopicinvestigationin
the examinationof paint from pictures.
Anotherearlytreatisewas by Weber [i6] in
1923. This gives a seriesof simple tests for all

artists'pigmentsavailableat the time, usinga

limited range of common reagents.It was,
however, designedprimarilyfor the use of
artistsso that they might ascertainthat the
pigmenttheywerebuyingwaswhatit claimed
to be.
Hetterich [I7] in 1930 and 1931 investi-

gated micro-chemicalmethods of pigment

identification
for picturesandpaintedstatues.
Scheffer[I8] wasalsoapplyingsimplemicrochemicaltestsfor pigments,and his pupil de
Wild wrote a treatiseon the scientificexamination of pictureswith tests for pigments

based mainly on standardmicro-chemical

crystallizations[19]. Laurie [20] was at the

same time evolving microchemicaltests for

pigmentsand thesewere carriedfurtherby
Gettens [8] and Gettensand Stout [9] in
the I930s,the latterworkingout tablesfor
identificationof white, green,and blue pigments.Eibner,in a posthumouspaperpub-

lished 1932

[21],

developed microchemical

analysisof paintingsmuch fartherthan any

other worker in this sphere,and his tests

I28

Joyce Plesters

includethe use of manyorganicreagentsfor

metals, then newly developed. The most
recentadditionsto the literaturearea contributionby Whitehead[22] on the application
of chemicalreagentsto paintcross-sections
in
industrial
and
a
manual
Stock
research,
[23]
by
on the chemicalanalysisof pigments,whichis
of great value becauseit includestests for
almost all artists'pigmentsup to the most
recent,includingphthalocyanine
blue, titanium white and monolitered.
The table given below combinesmicroscopicaland chemicalexamination.In most
casesa descriptionof the crystallineformand
figures for the refractiveindex is omitted
sincethesecanbe foundin the tablegivenby
Gettensand Stout in their Encyclopaedia
of

PaintingMaterials[24]. Photomicrographsof

pigmentsare to be foundin De Wild [I9]

and in Mattiello [25]. The necessitycannot be

too stronglyemphasized,
however,of having
aswide a rangeof mountedcomparison
slides
of pigmentsas possible.A rangeof refractive
indexliquidsis alsouseful.
The chemicaltestson pigmentsareusually
carriedout afterthose on media. Some can
with sodium
runconcurrently;
thus,treatment
nitricacid,and
hydroxide,with concentrated
alsothe effectof heaton the sampleappearin
both the table for the identificationof pigments and the tests for the identificationof
media. One test only need be made on the
paintsampleand the effecton both medium
and pigment observed at the same time.
Thereare also variousways of economizing
with the amountof the sampleavailable,e.g.
after solvent treatmentfor identificationof
mediahas been carriedout and the medium
extractedor destroyed,the residuecanbe used
for pigmenttests;afterignitionof partof the
sample the residue from the combustion,
which may containmetaloxides,can be redissolvedand testedfor metal ions. Perhaps
the most valuableeconomyis in the use of
spot tests.When the samplehas passedinto
solution minute drops can be removedby
meansof a capillarytube 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 differenttests.
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 restrictedto
those pigments which are somewhat soluble
in moderately dilute acids.
Solubility tests with organic reagents,
acids and alkalisare carriedout in the case of
every paint sample,becauseby 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 confirmatorytests it has been
the aim to find two or more differenttestsfor
each pigment. The samplesbeing so small, the
tests have to be simple in application,consequently even very sensitive tests have been
excluded if these require specially controlled
conditions or are liable to interferencein the
presenceof 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

and ChemicalAnalysisof Paint Samples

Cross-sections

andnotingits colourandphysicalappearance
it is usually possibleto narrow down the
rangeof possiblepigmentsto as few as two
or three.This limitsthe numberof chemical
tests required.For example,if the only pigment visiblein the samplewere red it would
be pointlessto test for copper.On the other
hand, if the pigment were bright blue it
would be usualto test for copperand cobalt
ions and for ultramarine.
All pigmentscommonlyusedin paneland
canvaspaintingsup to the end of the nineteenthcenturyareincludedin the table;at the
presenttime there are no twentieth-century
picturesin the NationalGallery.
The identificationof organic pigments
otherthanmadder,alizarin,andindigois not
attempted since the subject is somewhat
and not much is known of the
controversial
identityof thesepigmentsnor of the physical
and chemicalchangeswhich they undergo
with ageing.
It shouldbe noted that all spot tests and
tests involving the use of organic reagents
for metalsare takenfrom Feigl'sbook [26].
In orderto try to ascertain
the dateof some
the examinawhere
paintsamples,especially
tion of repaintsis concerned,it is necessary
to know the dates of introductionof the
variouspigments.Manyof thedatesareshown
in the followingtable (pp. 133ff.), but more
detailed chronologicaltables are given by
Eibner [27] and by Heaton [28].
EXAMINATION OF MEDIA

The term 'analysis'can hardlybe applied

to the ratherroughandreadytestswhichare
available.The most that can be done is to
attemptto classifythe mediumas glue, egg
tempera,oil, or oil/resinmixture.Very little
work has been done in the past on this
problemcomparedwith the amountdone on
pigment analysis. An early pioneer was
Ostwald [33] who in 1905 was developing
microscopictests for the identificationof
mediaand had also done some work on the

I29

preferentialstaining of media with biological

stains, a technique which has recently been
resumed at the National Gallery. Eibner [34]
also tackledthe 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
techniquesof the FlemishPrimitiveshas been
proceeding at the Laboratoire Central des
Musees de Belge under the direction of Dr.
Paul Coremans,and a useful table of tests for
mediahas beenpublishedin a previousnumber
of this journal, in an article by Coremans,

Thissen,and Gettens[35].

Micro tests for nitrogen, such as the

Lassaignetest, have recently been carriedout
by Miss Margaret Hey (Nuffield Scholar at
the National Gallery) who has found that
many of the paint samplestested 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 contaminatedwith
gelatin during blister laying or relining.
Until a test specificallydistinguishingbetween
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 mixturesof oils and resinsthe
position is very complicated. The effect of
adding resins to linseed oil films is not fully
understood,and of coursethe effectsof adding
a soft resinsuch as masticare 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] gives a
modification of this test suitable for paint
and varnish samples) but unfortunatelyaged
resins tend to give a uniform dull brown

I30

Joyce Plesters

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 differentfluorescence,but such
fluorescenceis not characteristicof any particularcomponents.
In the National Gallerylaboratorytests for
media begin with a series of solvent tests on
the paint sample. This is treated with cold
water, hot water, acetone, chloroform, 0o88
ammonia, sodium hydroxide and alcoholic
sodium hydroxide solutions in turn. If
possible a further sample is used for staining tests.Two stainshave been found particularly effective for distinguishingbetween oily
and proteinous media. These are nile blue,
which stains oils and fats, and acid fuchsin,
which stains protein. The sample can be
treated with a mixture of the two stains and
after a few minutes washed with water. The
stainwhich is specificfor that type of medium
remains. This technique has not been used
for very long, but it has proved to be fairly
consistentin a series of tests on known aged
media. A combustionof a small sampleof 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 concentratednitric acid
on the medium as well as on the pigment is
observed. The reactionsof the various media
to these tests are listed below.
Animal Glue

Soluble in hot water with disintegrationof

the paint fragment and formation of a ring
of clear material after evaporation of the
drop; stainedred by acid fuchsin. On heating,
ammoniacal fumes are given off (smell of
'burntfeathers')which turnuniversalindicator
blue.
Egg Tempera

Unaffectedby water, dilute acids or alkalis

(except by prolonged treatment). On dissolving out the pigment the medium is some-

timesseenas membrane-like
flakes,and concentratednitric acid often yellows these
them.Thepaintsample
withoutdisintegrating
is readilystainedby acidfuchsin.On heating
it behavesin the sameway as glue.
Drying Oils

Unaffectedby 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 stainedby nile blue. Subjectedto the
Storch-Morawskitest for resins,it gives only
a dull brown spot. On 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
universalindicatorpaper. Concentratednitric
acid often turnsoil films red brown in colour.
Oil and Resin Mixtures

These behave in practicallyall respectslike

drying oils. Often, however, part of the
resinous material may be extracted by treatment with organic solvents such as acetone
or chloroform without disintegrationof the
paint film; the ring of transparentmaterial
left after evaporationof the solvent usually
fluorescesunder u.-v. Oil-resin films are often
more readily soluble in alcoholic solutions of
ammonia or sodium hydroxide and in morpholine than in aqueousalkalis.Gentlewarming usuallyproducesan odour of the resin.The
Storch-Morawski test usually gives only a
brown colour with aged films, but sometimes
a transientpink 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 continuous cooperation;Mr. H. Ruhemann,for the benefit
of his very extensive knowledge of artists'

and ChemicalAnalysisof Paint Samples

Cross-sections

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

British Museum ResearchLaboratoryfor his
help and encouragement throughout the
work; Mrs. V. Wilson and members of the
Photographic Department at the National
Gallery for the photographs.
The work here describedis partof a research
programme in progress in the Scientific

I 3I

Departmentof the National Galleryunderthe

general direction of Mr. F. I. G. Rawlins.
JOYCEPLESTERS
TheNational
Gallery,
London.

References
'The Pigments and mediums of the Old Masters'(London I914).
I A. P. LAURIE,
'The Cross-Sectioningof Paint Films', in TechnicalStudiesin the
2 R. J. GETTENS,
Fieldof the Fine Arts,v (1936), p. I8.
van de VlaamseChemischeGereinung,xii
and R. SNEYERS,
Mededelingen
3 R. LEFEVRE
4

(I950), p. 99.
R. E. STRAUBand S. REESJONES,'Mikroskopische Querschnitte von Gemalden',

in Maltechnik,Iv (1955), p. II9.

'The Preparation and Study of Paint Cross-Sections', Museums
5 J. PLESTERS,

Journal,Vol. 54 (I954),No. 4.

F. I. G. RAWLINSand A. E. A. WERNER,'Some scientific investigations at the

National Gallery,London', in Endeavour, III(1954), No. 51, p. 140.

'A Microsectionerfor Paint Films', in TechnicalStudiesin theField
7 R. J. GETTENS,
of the Fine Arts,I (1932), 20.
8 R.J. GETTENS,
'An Equipmentfor the MicrochemicalExaminationof Paintings',
in TechnicalStudiesin the Field of the Fine Arts, i (1934), P. i85.
'The Stage Microscopein the Routine Examinaand G. L. STOUT,
9 R. J. GETTENS
tion of Paintings',in TechnicalStudiesin theField of theFine Arts, Iv (1936),
10

p. 207.

'Reference microscopical preparations', in Paint, Oil and Colour

S. M. CHARLETT,

Journal(I955), 128, No. 2961, p. I44.

and C. W. MASON,'Handbook of Chemical Microscopy' (2nd
11 E. M. CHAMOT
edn., New York I939).
12 Catalogue of the Exhibition of Works by Holbein and Other Masters of the
sixteenth and seventeenth centuries. Royal Academy of Arts (London
I950-51), p. 22.

'Sur quelques couleurs trouvees a Pompeia', in Annalesde Chimie,

13 M. CHAPTAL,
LXX (I809), p. 22.
14 A. C. WRIGHT, 'Simple Methods for Testing Painters' Materials' (London
I903).
I5

'Uber die Maltechnik der Alten' (Berlin I9IO).

E. RAEHLMANN,

'Artists'Pigments' (New York I923).

I6 F. W. WEBER,
'Ober die Anwendung mikrochemischenMethoden bei pigmenI7 H. HETTERICH,
Emich Festschrift (1930),
tuntersuchungvon Gemalden', in Mikrochemie,
x (1931),
p. 152; 'Uber MikrochemischeBilduntersuchung',in Mikrochemie,
p. 27.

'L'Examin Chimique des Tableaux', in Mouseion,xmI-xIV

I8 F. E. SCHEFFER,
(1931), p. 93.
19 A. M. de WILD,'The Scientific Examination of Pictures' (London I929).

I32

Joyce Plesters
20 A. P. LAURIE,'The Identification of Pigments used in Painting at different
Periods,with a Brief Account of Other Methods of Examining Pictures',in
The Analyst,LV (I930), p. 162; 'Methods of Testing Minute Quantities of
Materialsfrom Pictures and Works of Art', in The Analyst, LVIII (1933),
p. 468.
21 A. EIBNER (posthumous), 'L'AnalyseMicrochimique des Couleurs',in Mouseion,
XXIX-XXX(1935), P. 13.

22
23
24

A. D. WHITEHEAD, 'The Micrography of Paint Films', in Journalof the Oil and

ColourChemist,xxI (1939), p. I39.
E. STOCK, 'Analyse der Korperfarben'(Stuttgart I953).
R. J. GETTENSand G. L. STOUT, 'PaintingMaterials,a ShortEncyclopaedia'(New

York 1942).
25 J. J. MATTIELLO
(Editor), Protectiveand DecorativeCoatings,Vol. ni (New York
26
27
28
29

30
31
32
33
34
35
36

I94I).
F. FEIGL,
Spot Tests,Vol. I, 4th edn. (Amsterdamand New York I954).
A. EIBNER,Entwincklung
und Werkstoffe
der Wandmalerei
(Munich 1926), p. 549.
N. HEATON,'The Permanenceof Artists'Materials',inJournalof theRoyal Society
of Arts (London), LXXX(1932), p. 415.
R. M. BARRERandJ. S. RAITT,'Ion Exchange in Ultramarine',in Journalof the
ChemicalSociety(December 1954), p. 4641.
A. E. CHURCH,The Chemistryof PaintsandPainting(3rd edn. London I90I).
A. ROBERTSON,
W. B. WHALLEY(et alii), 'The Pigments of "Dragon's Blood"
Resin', in Journalsof the ChemicalSociety,in six parts, beginning Part I,
J.C.S. (1950), p. 1876.
D. V. THOMPSON,
The Materialsof MedievalPainting(London 1936), p. 124.
W. OSTWALD(trans.), 'Microscopic Identification of Homogeneous Binding
Mediums', in TechnicalStudiesin the Fieldof the Fine Arts, Iv (1936).
A. EIBNER,'L'Examen Microchemique des Agglutinants', in Mouseion, xx
(1932), p. 5; 'Zum gegenwartigen Stand des naturwissenschaftlichenBildChemie,XLV (1932), p. 301.
untersuchung',in Angewvandte
P. COREMANS,R. J. GETTENSand J. THISSEN,'La Technique des "Primitifs
Flamands"', in Studiesin Conservation,
Vol. I, No. i (October I952), p. 20.
A. KRAUS,'Liber eine Modifikation der Storch-MorawskischenHarzreaktion',
in Farben-Zeitung,
xxxvIII (1932), p. 322.
The illustrationon the cover,whichalso appearson p. 126,
is reproduced
by permissionof the Trusteesof the National
Gallery, London.

TABLES FOR IDENTIFICATION

OF PIGMENTS Pages I34-I55

N.B. A dash'-' undersolubilitiesindicatesthatthereis no visibleeffect

aftera few minutes'immersionin the reagent.

BLUE PIGMENTS(Contd.)

Solubilities
Pigment

Azurite
(mountain
blue, blue
verditer).

Chemical
Origin,or date Appearanceunder
Composition of invention low magnification

Basic copper
carbonate,
2CuCO3,

Cu(OH)2.

Natural
mineral
known from
very early
times.

Bright, slightly
greenishblue
crystalline fragments, often irregularin size
and shape.

Effectof heat
3N HCI
Very soluble,
with effervescence
of CO2 to give a
green solution.

4N NaOH
Slow hydrolysis takes
place with
formation of
black CuO on
the surface of
the pigment
particles.

HNO3
(concentrated)

Black residueof
Very soluble,
(
with efferam
copper oxide
vesence of CO2 CuO.
blu
to give a pale
mo
blue solution.
(
sod
ate
I
pig
is d
and
sma
oadd
is fo
(Pb
tur
by
add
the
it am
(
ru
ox
A
of t
filte
mon
rub
add
a gr
pre
the
pec
add
gre
Cu+
an o

Blue bice

Basic copper
carbonate,
2CuCO3.
Cu(OH)2

An artificially Usually more

preparedsub- rounded and
stitutefor Azu- finer particles
thanthose of
rite; recipes
for its manu- Azurite.
factureare

As above.

As above.

As above.

As above.

As

given from

medieval
times onwards.

Ultramarine,
natural.

A complex
compound
of sodium
aluminium

silicateand
sulphur,of
somewhat
variablecomposition, but
approximating

to 3Na2 0.
3A12036 SiO2.
2Na2S.

From the blue

mineral Lapis
Lazuliin
which it occurs
with calcspar
and iron
pyrites.

Clear, often
slightly purplish
blue crystalline
particlesof irregular size and
shape. A few
orange-redparticles of iron
pyrites are often
seen, and white
crystalline
material,which
viewed between
crossedNicol
prismsproves to
be the doubly
refractingcalcite.

Becomes white
and an effervescence of H2S is
produced (this
can often be detected by smell).

Reacts quite
slowly, the
colour changing
to pale yellow.

Te
evol
hydr
(i)
agen
A
adde
lowe
azid
sodi
iodid
iodin
Bub
surf
of th
is pr
abse
(ii
may
blac
sodi
or of
ping
actio
cups
cove
the H

BLUE PIGMENTS(Contd.)

I
Solubilities
Pigment

Chemical
Origin, or date Appearanceunder
Composition of invention low magnification

Effectof heat
3N HC1

Ultramarine
artificial.

As above but
approximate
formula

Smalt

A potassium
silicateglass
coloured blue
with cobalt
oxide.

Manufacture Usually smaller As above.

first discovered and more
by Guinet in rounded pigment
1828.
Na8_l1, A16
grainsthan those
of lapis ultraSi6 024 S2-4.
marine. More(See BARRER
and RAITT[29]
over, there are
for modern
few colourless
views on
particlesand no
structure.)
doubly refracting
calcite crystals,
or particlesof
iron pyrites.

Manufactured.
Eibner [27]
reportsit to be
mentioned
first in 1584.

By transmitted
light, usually a
ratherpale blue.
Very characteristic glassy fragments, often very
coarse.

4N NaOH
As above.

HNO3

(concentrated)
In samples
examined in the
National Gallery, artificial
ultramarine
seems to be
attackedmore
rapidly. This
does not seem
to be wholly
due to particle
size. Most
samples of the
artificialpigment had become wholly
pale yellow in
less than half an
hour, but the
lapisvariety was
still blue after
2 hours.

Melts at high
temperatures.

T
into
plat
fluo
trat
resi
wat
pink
may
(i
nitr
(R
of so
acid
wate
(neu
spot
drop
reag
spot

dee
in t
of
dro
tris
be
ppt
not
(
rub
A
on
am
rea
add
an
for
pre
bla
ora
Indigo

C O- co
Il
\/\

PrussianBlue
(BerlinBlue,
ParisBlue,
Antwerp Blue,
Chinese Blue).

The pure syntheticproduct

andthe principal constituent of the
naturaldye is:

OC
\\

A blue dye
from a plant.
The plant contains a glucoside which on
hydrolysiswith
\ acidsgives the
I I blue dyestuff
and glucose.
The synthesis
of indigo was
discovered in
1880by Baeyer

FerricFerrocyanide
Fe4[Fe(CN)6]3
(or a closely
relatedcompound).

A synthetic
pigment invented by
Diesbach in
I704.

Very dark blue, Slowly turns

Slowly turns Decomposes to
and of very fine brown on probrown on pro- a darkbrown
particlesize. The longedimmersion, longed immer- precipitate.
sion and partly
dyestuffseemsto and partly disstain oil films.
solves.
dissolves.

With gentle
heat sublimes
with a purple
vapour, then
decomposes
giving a brown
distillate,dark
fumes and a
characteristic
smell.

(
giv
and
spir
solu
(
hyp

Very dark blue

and of very fine
particlesize. By
transmittedlight
it is green-blue.

Changes to a
golden brown
iron oxide still
keeping its
finely powdered

(i)
pre
afte
NaO
hyd
(
hyd
me
diss
pre
by
am
tion
duc
be
dro
to t
solv
Th
out

Goes into solution with precipitation

of orangebrown ferric
hydroxide.

form.

BLUE PIGMENTS(Contd.)

I
Solubilities
Pigment

Cobalt Blue
(Thenard's
Blue).

Chemical
Origin, or date Appearancetinder
Composition of invention low magnification

Cobalt aluminate,
CoO. A12 03

A synthetic
pigment discovered by
Th6nardin
I802.

CeruleanBlue.

Cobaltous
stannate,
CoO. nSnO2.

Effect of heat

3N HC1

4N NaOH

HNO3
(concentrated)

Th
into
platin
sodiu
ture
sodiu
extra
acid
given
carri
Al++
A1(O
by a
drox

Pure blue
rounded particles, moderately fine and of
irregular size.
Bright blue by
transmittedlight.

A synthetic
pigment

Green-blue,
finely divided,
rounded
known as a
chemicalcom- particles.
pound in the
Igth century
but not introduced as a pigment until
I860.

Sufficiently
soluble, with
heating, to give
a pale blue solution.

Th
tione
appl
nitri
is no
the
fusio
und

Soluble, giving
a reddish solution.

(i)
Gradually turns
of F
golden brown.
on th
ment
(a)
Prus
(b
thioc
(ii
prese
(a
Fe (
ment
oxid
brow
of a
oxide

GREEN PIGMENTS.

GreenEarth
(terreverte).

Variable in
composition;
a complex
hydrosilicate
of Fe, Mg, Al
and K.
The green
colour is
caused by a
small amount
of Fe++.

Known from
earliest times
as a natural
mineral.

Usually coarse
crystalline particles of a rather
blue-green, some
tinged with
brown. Colourless particles are
usually present
also.

Partially soluble
to give a pale
greenishsolution.

Partially soluble to give a

greenish grey
ppt. of
Fe(OH)2
which becomes brown
on standing.

sol
pla
Th
de
sta
flu
A
ag
Fe
tio

Malachite
(mountain
green).

Verdigris

Transparent
copper green.

Soluble with
effervescenceof
CO2, giving a
blue solution.

T
Black residueof
use
CuO.
de
(se

A basiccopper
carbonate,
CuCO3 .
Cu(OH)2.

Known from
earliesttimes
as a natural
mineral;often
occursin conjunction with
azurite,q.v.

Crystallinefrag- Soluble with efferments, a rather versenceofCO2

pale, blue-green giving a green
solution.
in colour.

Unaffected in
the cold, but
on warming,
the particles
partially dissolve giving a
pale blue solution and they
become coated
with black
CuO.

Usually the
dibasiccopper
acetate,
Cu(CH3COO)2.
2Cu (OH)2.

Preparedfrom
ancient times
by corroding
copper with
vinegar.

Clearblue-green Soluble giving a

green solution.
crystals,sometimes pointed
needles. Colour
often very
strong.

Soluble, giving Soluble giving

apalebluepptt. a green solution.
of copper hydroxide which
turns black on
boiling.

Gives off a
smell of acetic
acid on warming (vapour
turns Universal
Indicatorpaper
red). Further
heating converts into black
CuO.

(
scr
be
of
or
(
(
H2
of
(
tra
the
du
ace

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++ ion
forms a salt
with the resin
acids,e.g. copperabietate.

Laurie [I]
claimed to
have found
this type of
painton illuminatedmanuscriptsdating
from the 8th
century.

Clear rather
Partly soluble
grass-greenwhen giving a solution
freshly prepared of CuCl12
or in good preservation;when
decayed becomes
brown. On pictures it is sometimes mixed with
lead white or
litharge to give
an opaque
yellow-green.

Disintegrated, Soluble, giving

a brown soluthe resinous
tion.
component
being dissolved, and
pale blue
copperhydroxide being
precipitated.

The resinusually gives off a

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

T
con
the
'Az
to

GREENPIGMENTS
(Contd.)
Solubilities
Pigment

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

Chemical
Composition

A compound
of cobalt oxide
and zinc oxide
of rather indefinite proportions. Probably there is
a small proportion of
CoO to ZnO.

Origin, or date Appearanceunder

of invention low magnification

A synthetic
pigment discovered by
Rinmann in
I780, but not
used as a pigment until the
nineteenth
century.

Fine regular
rounded particles,ratherbluegreen by reflected light, but
pure green by
transmittedlight.

Effect of heat

3N HC1
Slightly soluble
on heating, and
more so with
cone. HC 1 giving
a pale pink solution.

4N NaOH

HNO3
(concentrated)
Slowly soluble
with heating to
give a pale
blue solution.

(
und
me
solu

nitr

(
dith
I
on
line
dro
(io

tetr
solu
eva
ras
pen
ent
spe
solu
Chromium
Oxide Green,
opaque.

Anhydrous
Chromic
Oxide,
Cr2O,.

Vauquelin,the
discovererof
chromium,
suggestedthe
use of Cr20O
in ceramic

glazes in I809,
but it probably did not
appear as an
artist'spigment until
some years
later. [See
Laurie (I).]

Ratherdull olive
green opaque
granules,usually
rathercoarse;
high refractive
index.

T
into
mix
and
pla
the
H2
into
ma
chr
solu
(
dip
T
on
dro
dip
Av
the

-3

(
Ag
tion
pap
of s
(
giv
PbC
Viridian
(Guignet's
green).

Transparent
hydrousoxide
of Chromium
CraO. 2H20.

Chrome Green A mixture of

Prussianblue,
(Cinnabar
Green).
Fe4[Fe(CN)6]3
with chrome
yellow, i.e.
lead chromate
Pb CrO4.

Syntheticpigment firstprepared by
Pannetierin
1838. [See
Church (30).]

Brilliant somewhat blue-green

colour; particles
usually large, irregular, slightly
rounded, and exceptionallytransparent. Refractive index is lower
than that of the
opaque oxide,

Chrome
Yellow was
describedby
Vauquelin in
I809, so that
the first manufactureof
chrome green
must be after
this date.

Colour varies
from grassgreen
to blue-green.
(The latter
known as Cinnabar green.) The
blue and yellow
particlesare
often not distinguishablesince
the Prussianblue
seems to coat the
yellow particles.

The lead chromate is dissolved

with pptn. of
white lead chloride. The Prussian
blue is unchanged,
so that the
colour of the
sample changes
from green to
blue.

The Prussian
blue is dissolved with
pptn. of
orange-brown
ferrichydroxide, so that
the colour of
the sample
changes from
green to
brownish
yellow.

Partly soluble;
the lead chromate dissolves
to give a yellow
solution, the
Prussianblue
remainsunchanged.

Turns yellowbrown owing

to the formation of ferric
oxide.

(
und
gre
on t
acid
(i
mad
tion
und
'Wh
(
('Bl
for

GREENPIGMENTS
(Contd.)
Solubilities
Pigment

Scheele's
Green.

EmeraldGreen.
(Schweinfurt
Green,Paris
Green,Veronese
Green.)

Chemical
Origin, or date Appearanceunder
Composition of invention low magnification

A synthetic
Copperhydroarsenite, pigment inCuHAsO3(but vented by
Scheelein
composition
varies with
I778.
mode of
preparation).

Copper acetoarsenate.
Cu(CH3
COO)2
3Cu(AsO2)2

Effectof heat
3N HC1

Soluble giving a
Bright limegreen irregularly green solution.
shapedflakesof

varying size.

Ratheropaque.

A synthetic
Distinctive
pigment first brilliant bluishmade at
green, small
Schweinfurt, rounded grains,
some with the
Germany,in
I8I4.
appearanceof
being trefoil or
quatrefoilin
shape, probably
owing to a depressionin their
centres.

As above, but an
almost colourless
solution.

4N NaOH

HNO3
(Concentrated)

Soluble with
formationof a
paleblue pptt.
of Cu(OH)2.

Soluble giving
a blue solution.

Black residueof
(
un
CuO.
Pig
the
(
(
sol
dro
sta
add
wa
ate
(th
les
not
(
tio
me
cru
of
per
aci
I-2
(i
pp
for
(Si
the
Gr
bef

As above.

As above.

As above.

RED AND VIOLET PIGMENTS

Vermilion
(Cinnabar).

Red mercuric Occurs as a

Very deep red
naturalmineral by transmitted
sulphide,
cinnabar,but light. Pigment
HgS.
has been syn- size and crystalthesizedfrom linity vary;
naturaland synearly times.
thetic varieties
are not distinguishable.

Iron oxide reds

(Red ochre,
Indianred,
Venetianred,
light red,
haematite,Mars
red, etc.).

Iron oxide,
either anhydrous,Fe2Oa
or hydrated
Fe23O. nH2O.

Red lead
(minium).

Leadtetroxide, Orange-red, Artificallymade, Dissolves with

Pb304.
finely divided, but known from pptn. of white
PbCl2.
may be cryantiquity.
stallineor
amorphous.

Occur widely
as natural
minerals, also
made artificially (the
Mars colours.

Some varieties
Some specimens
(e.g. haematite) are slightly solare transparent uble.
and red by
transmitted
light. Others are
quite opaque.
It is difficultto
distinguishthe
artificialvarieties from the
natural.

Very slightly
soluble.

No change at
moderate temperaturesbut
sublimesat
580?C.

Partly soluble.

-The

A brown pptt.
of lead dioxide
is formed.

(
T
sol
rep
HC
sol
Id
pla
pre
par
age
vio
Hg
(
O
pla
azi
Bu
rise
is
col

con
yel
T
(
giv
(
giv

HN

(
Id
yel
afte
gol
(
Id
giv
PbC

RED AND VIOLETPIGMENTS(Contd.)

Solubilities
Pigment

Chemical
Origin, or date Appearanceunder
composition of invention low magnification

Efect of heat
3N HCl

4N NaOH

HN03
(co
(concentrated)

Dragon'sblood. A natural
resin (for
chemicalcomposition see
Robertsonand
Whalley [3I]).

From a tree
in East Asia;
known in
medieval
times. (See
Thompson
[32]).

Dark red by re- Partly soluble,

flected light but giving a yellow
clear orange-red solution.
by transmitted
light.

Partiallydissolves to an
orange-red
turbid solution.

MadderLake
(Crimson
madder).

A mixture of
two hydroxyanthraquinone
dyestuffs,alizarin and purpurin, mordantedon to a
base which is
usually
A1(OH)3.

Extracted
from the root
of the madder
plant.

Usually a very
fine powder,
crimson red in
colour. In oil
films the separate particlescannot be seen owing to the transparencyof the
Al(OH),.

The AI(OH)3
partly dissolves
and the colour of
the pigment becomes more
orange.

Colour changes
Soluble, giv(i
Decomposes
(a
ing a purplish to a darkbrown to purple
solution.
solution.
dil. H
brown, then
is di
black and
finally only a
pptt
pale grey ash of oran
A1203 remains.
(b
often
owin
puri
(ii
Mor
Th
trea
disso
and
the M
tion
filter
of th
and t
addi
the s
gree
shou
agen

Alizarin
crimson.

A single
hydroxyanthraquinone
dyestuff,alizarin,on a base
of Al(OH)2.

As above.
Synthesized
for the first
time in I868
by Graebeand
Lieberman.

As above.

As above.

Melts then
Disintegrates
to a darkbrown evolves
mass.
benzoic acid
(characteristic
smell). See
Gettens and
Stout [26].

As above.

As above.

So
and
red

As
case o
of pu
is no
light

Brown Madder Madderor

(burntmadder). alizarin
charredby
heating.

See above.

As above, but a As above.

dull brownish or
purplishred.

Cobalt Violet,
dark.

Anhydrous
cobalt phosphate
Co3(PO4)2,

Preparation
describedin
i859 by
Salvetat.

Irregularparticles, redviolet in transmitted light and

highly refracting.

Cobalt Violet,
light.

Anhydrous
cobalt
arsenate,
Co3(AsO4)2.

Appeared
about I88o
(see Eibner
[27]).

As above.

Manganese
Violet (Nirnberg Violet,
Permanent
Violet).

Fusionproduct Preparedfirst
of manganese by E. Leykauf
dioxide and
in I868.
ammonium
phosphate.

As above.

See above.

As above.

Somewhat
soluble.

(
und
Pig
the
(
A
are
moi
amm
tion
A d
(0o
Io m
dilu
is ad
held
blue
sam

-Tests

(i
(i
tests
('Gr
Rounded granules of rather
irregular size,
bright red-violet
by reflectedlight,
but pale transparentmauve by
transmittedlight.

On heating grad- Black pptt.

ually turns black of MnO2.
with evolution of
C12.

Greyish
residue.

T
T
mix
pota
fuse
gree
gan
solu
stan
alka

YELLOW AND ORANGE PIGMENTS

Solubilities
Pigment

Chemical
Origin, or date Appearanceunder
of invention low magnification
composition

Yellow Ochre Hydratediron

(GoldenOchre, oxide, Fe203.
MarsYellow). H20. The
naturalochres
may contain
aluminium
silicateand
other impurities

Natural
mineralsare
widely distributed,but
an artificial
variety (Mars
yellow) is also
made.

Principallylead
monoxide
PbO, but
lithargeusually containsa
little red lead,
Pb3O4.

Manufactured
pigments
known from
antiquity.

Massicotand
Litharge.

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

3N HC1

4N NaOH

Some samplesare
slightly soluble,
giving a yellow
solution of FeCl3.

HNO3
(concentrated)
Partly soluble,
giving a yellow
solution.

Effectof heat

Turns brownred on loss of

combined
water.

So
HC1
of F
given
(see
be ca

Th
be u
the t
'Red
men

Usually of fine
almost amorphous texture
like lead white.
Massicot is
Massicotis pale
the unfused
yellow, litharge
oxide made by a little more
lead
roasting
orange, owing
to the presence
white; lithof red Pb304.
is
the
arge
fused oxide
made by
oxidation of
molten lead.
(See Gettens

Soluble with
pptn. of white
PbC12.

Soluble on
heating, as
sodium
plumbite.

Readilysoluble. Unaffected at
moderatetemperatures.
Changes to
red Pb3O4if
heated above
400? C.

Natural
mineral,used
from
antiquity.

On heating goes
into solution with
evolution of
H2S.

Soluble giving
sodium arsenate and sulpharsenites.

Soluble (decomposes to
give As and
H2SO4).

and Stout [24].)

Yellow
Orpiment
(King'sYellow) arsenic
sulphide,
As2S3.

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

Sublimes, then
(i)
becomes colour- 'Sche
less owing to
Pigm
on th
oxidation to
the trioxide
(ii
Th
As203.
test g
'Red
on th

Melts at 31o?C.

Very fine gran- Partiallysol. with Partiallysol.

ules, like Massi- white PbC12
cot in appearppttd.
ance. It is difficult to see a crystallineform.
Colour varies
from lemonyellow to orangeyellow.

Soluble.

Sublimeswith
(i)
Id
an orangeyellow vapour. pigm
with
on p
filing
stan
Zn a
plati
pres
sepa
blac
gase
grey
(ii
'Red
men

Brilliant
yellow; partide size varies;
usually very fine
crystals;rather
opaque.

Soluble, with
pptn. of white
PbC12and an
orange solution
of chromic acid.

Soluble giving a yellow

solution of
alkali chromate.

Soluble giving
a yellow solution.

(i)
Th
Lead
may
solut
acid.
(ii
Th
'Chr
Opa
ment
out o
pigm

By reflected
light, bright
lemon yellow;
by transmitted
light, nearly
colourless; fine
xn. structure.

Soluble, giving a
yellow solution.

Soluble, giving a yellow

solution.

Soluble, giving
a yellow solution.

-(i)

T
(a
in H
H2S
inso
(b
gree
(ii
'Chr

Orange-red
arsenicsulphide As2S2.

Natural
mineral often
occurring
with Orpiment.

Similarto above, As above.

but more orange.
By transmitted
light, orangered. It has a
slightly lower
R.I. than Orpiment.

Naples Yellow
(Antimony
Yellow).

Lead antimonate,
Pb(SbO4)2.

Manufactured
pigment whose
history is
obscure. (See
Gettensand
Stout [24].)

Chrome
Yellow.

Leadchromate Preparation
Pb CrO4.
describedby
Vauquelin in
I809.

Barium
Yellow.

Barium
chromate,
BaCrO4.

As above.

As above.

Realgar.

Soluble.

ANDORANGE
YELLOW
PIGMENTS
(Contd.)
Solubilities
Pigment

Strontium
Yellow
(Lemon
Yellow).

Cobalt Yellow
(Aureolin).

Cadmium
Yellow.

Chemical
Origin, or date Appearanceunder
Composition of invention low magnification

Strontium
chromate,
Sr CrO4.

As above.

A little stronger As above.

yellow than

4N NaOH

Efect of heat

HNO3
(concentrated)

As above.

As above.

Slightly soluble.

Soluble,giving
an orange
solution.

When heated
strongly, gives
black CoO,
and oxides of
nitrogen.

T
tion
HC
tion
liste
Pig

Soluble, with
evolution of

At high temperatures
brown CdO is
produced.

(
p-n
A
is m
a dr
KC
age
tion
baz
form
the
gre
form

(
(
the
ppt
(
crim
(
'Ch
(
Rho
ing
Str
I
solu
pap
rea
Ba+
red
colo
wit
HC
ing

BaCrO4.

Finely divided
crystallinemass
consistingof
needles.

Discovered by Small crystals

Potassium
cobaltinitrite, N. W. Fisher and clustersof
CoK3. (NO2)6. in 1848.
crystals,yellow
H20.
by transmitted
light.

A synthetic
Cadmium
Sulphide,CdS. pigment preparedby pptn.
(a mineral
form exists
but there is no
record of its
ever having
been used as a
pigment). First
observedby
Stromeyerin
1817.

3N HC1

HNOa

Colour varies
from lemon yellow to orange,
probably according to particle
size, the orange
usuallybeing
coarser.All
types are, however, comparatively finely
divided.

Slightly soluble
giving a yellow
solution.

Insolublein the
cold; partly soluble on heating,
with evolution of
H2S.

H2S.

giv
fo
sh
bla

so
scr
(se
us

BROWN AND BLACK PIGMENTS.

Raw Sienna

Hydrated
ferricoxide,
Fe203 . H20.

Natural
mineral.

Burnt Sienna.

Anhydrous
FerricOxide,
Fe2o3.

Most of the
Preparedby
calciningRaw grains are redSienna.
dish brown. No
visible crystalline form.

Raw Umber.

Natural
Hydrated
FerricOxide
mineral.
Fe2O3. H20
with a proportion of Manganesedioxide
MnO2. (from
8-I6 %.)

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,
especiallyon heating. (Usually
sufficientto give
a blue colour with
K4Fe(CN)6.)

Partly soluble.

Colour changes
to the darker
warmer brown
of Burnt Sienna
(see below), the
anhydrous
oxide.

As

As above.

Fine darkish
As above.
yellow-brown
grains mainly,
but some orange,
yellow and
colourlessparticles.

T
in h
ay
iro
thi
un
'Gr

As above.

Loses water to
become the
anhydrous
oxide Burnt
Umber (see
below) which is
a darker,
redderbrown.

(
Raw
(
(
per
A
dro
(C1
wit
ap
AgN
stir
gra
per
gen
of M
to th

BROWN AND BLACKPIGMENTS(Contd.)

Solubilities
Pigment

Burnt Umber.

under
Origin, or date Appearance
Chemical
composition
of invention low magnification

Anhydrous
Preparedby
ferricoxide
gently heating
Fe2O3,with a Raw Umber.
of
proportion
manganese
dioxide, MnO2

3N HC1

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

Bitumen
(asphaltum,
mummy,
bistre).

A mixture of
hydrocarbons
with organic
and inorganic
impuritiesand
of variable
composition.
(See Church
[30] and
Gettens and
Stout [24])

Bitumen or
asphaltum
occurs as a
semi-liquid
mineraldeposit. Mummy
is a pigment
made from
the asphaltum
used to embalmEgyptian
mummies.
Bistre is a
tarry material
from burned
wood.

Dark brown
amorphous
solid, semitransparentand
orange-brown
by transmitted
light. It is partially solublein
oil media giving
a translucent
brown film.

-Soluble,

Van Dyck
Brown (Cassell
Earth,Cologne
Earth).

Consistsof as A mineral
much as 9go% deposit similar
of organic
to Lignite.
matter (hydrocarbonssimilar
to those of
Bitumen), together with
iron oxide,
alumina,
silica,etc.

As above, but
of a more
heterogeneous
appearance,and
with granulesof
inorganicbrown
pigment.

-As

4N NaOH
-

HNO
(co
(concentrated)
As above.

Soluble, giving
giving an orange- a red-brown
brown solusolution.
tion.

above.

As above.

Effectof heat

-(i)

Raw
(

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 smallresidue of incombustible inorganic matter
remains.

(
ma
pet
org
(
resi
test
Fe+
'Gr

As above, but
leaves rather
more incombustible residue.

CarbonBlack
(Charcoalblack,
lamp black,
vine black,
graphite).

Consists primarily of carbon asthe free

element. Impuritiesvary
as to sources,
e.g. lamp
blackcontains
hydrocarbons.

Bone black
Containsas
little as Io %
(Ivory black,
Animal black). carbon,the
remainderbeing mainly
calcium phosphate
Ca3(PO4)2
with a little
calcium
carbonate.

Except for
graphite,
which is a
natural
mineral (but
can also be
preparedartificially), carbon blacks are
all produced
by the partial
combustion of
organic
materials
such as wood
and oil. Most
forms were
known from
earliesttimes.

Except for
graphite,which
is in the form of
flaky grey-black
crystals,all these
pigments are
black or blackish
brown opaque
amorphousmaterials.The particle size varies
greatly; lamp
blackis very fine,
whereascharcoal
is often seen as
rathercoarse
jagged chips;yet
other forms are
granular.

Obtainedby
charring
animal bones
(or tusks) in
a restricted
air supply.

The carbonseems
to be mixed in
a very fine state
with the calcium phosphate,
and the general
appearanceis of
translucent
blackishbrown
grainsof rather
irregularshape,
but with no
separateblack
and white
particles.

Can be almost
completely
burnt in air
(except for
minute amounts
of inorganic
impurities).

--

A white residue
(
of calcium salts
(
remainsafter
resi
flam
combustion.
(
due
but
exc
is fo
(
T
dat
'Co
'Re
may
bus

WHITE PIGMENTS AND INERTS.

Chalk (Whiting, Limewhite).

Calcium car- Natural debonate CaCO3 posit.

Fine white or
Dissolves with
whitish powder: effervescenceof
Low R.I.
CO.2

-Dissolves

with
effervescence
of CO2.

None until
very high temtemperatures
when CaO
formed.

(i
H2S
dry
the
give
shea
of g
(i
bril
Ca.

WHITE PIGMENTS AND INERTS(Contd.)

Pigment

Origin, or date Appearance

under
Chemical
of invention
composition (if after 1700) low magnification

Solubilities
3N HC1

4N NaOH

HNO3
(concentrated)

Effectof heat

At IIo? C.
loses water of
crystallization
(giving plaster
of Paris).Water
vapour condenses at the top of
the tube.

Calcium sulphate dihydrate, CaSO4.

2H2O.

Natural
deposit.

Usually fine
granularcrystallinemass.

Moderately
soluble.

Moderately
soluble.

Anhydrous
Calcium Sulphate (anhydrite).

CaSO4.

Preparedby
calcining
gypsum.

Fine white
powder.

Moderatelysoluble, but less so

than gypsum.

(
Moderatelysol- No effect; with
a dry sample no
uble.
(
water vapour is gyp
form
given off on
bili
heating.
two
pla
Na2
wit
the
wir
solu
drit
(
iner
cry

Lead white.

Fine white
Basic lead car- Artificially
bonate, 2Pb
preparedfrom powder (individualgrainsand
CO3, Pb(OH)2 very early
times.
crystallinityonly
seen at very high
power).

Gypsum.

Soluble, giving a
white pptt. of
PbCl2, soluble on
heating.

Soluble.
Partiallysoluble as sodium
plumbite.

Turns yellow
owing to the
formation of
Massicot (ead
monoxide,
PbO).

(
HC
lize
she
for
(
(
the
filte
tion
inso
form

T
und
Pig
out
pigm

Zinc white
Zinc oxide,
(Chinese white) ZnO.

Artificially
prepared.
The use of
ZnO as a pigment was first
suggestedin

Very finely
divided white
powder.

1782.

Completely soluble, with no

effervescence.

Soluble as
sodium
zincate.

Turnsyellow on
(i
Completely
soluble with no heating but be- sinc
effervescence. comes white
(i
again on cool- dith
I
ing.
NaO
plat
dith
dith
The
stirr
colo
Zn.
in a

METALS USED AS PIGMENTS.

Gold.

Metallic element, Au.

Known from
antiquity.

Colour varies,
with the degree
of purity being
sometimes
pinkish and
sometimes
yellowish.
Bright metallic
sheen which
does not tarnish.
Used as thinly
beaten sheets or
'leaves' laid
down on the
picture surface,
or as a powder
like an ordinary
pigment.

So
conc
and
reag
T
mad
(i
dine
A
and
agen
acid
pap
a blu
(i
Rho
I
regi
with
in Io
tion
of b
the b
redmin
u.-v.

METALSUSED AS PIGMENTS(Contd.)

Solubilities
Pigment

Silver.

Chemical
Origin, or date Appearanceunder
composition
of invention low magnification

Metallic element, Ag.

Known from
antiquity.

Effectof heat
3N HC1

When untarVery slight solnished has a

vent action.
white metallic
sheen, but
rapidlydiscolours in an
impure atmosphere, owing to
the formationof
a film of black
sulphide.

4N NaOH

HNO3
(concentrated)
Dissolves with
evolution of
nitrogen oxides
(brown fumes
with characteristic odour).

(i
is ad
ppt
dar
ligh
NH
(i
the
ppt
chr
acti
plat
(i
ami

mine

A
test
spo
solu
of th
etha
dil.
is ac
cate
tion
colo

Tin.

Metallicelement, Sn.

Known from
antiquity and
sometimes
used on picturesin the
Middle Ages.

Lustrouswhite
metal, untarnished by air
and water.

Dissolves rather
slowly in the
diluted acid.

Dissolves very A film of hydratedstannic

slowly on
heating form- oxide becomes
formed on the
ing sodium
surfaceof the
stannate,
metal, and the
Na2SnO3.
action slows
down and stops.

Th
rapi
stan
tion
ing t
(i
phom
Fi
with
moly
NH3
phos
and
test
spot
(ii
Fi
with
reag
solu
pape
to th
circl
pape
reag
colo

Joyce Plesters

I56

I
COUPES TRANSVERSALES ET ANALYSE CHIMIQUE D'tCHANTILLONS
DE PEINTURE
Resume

Le but de la preparationet de l'etude des

coupesde peinturesest discut6et la basedes
methodespratiquesest decrite.
Un brefresumehistoriquedestravauxanterieurssurle sujetest donne.
Lesavantageset limitationsde cette methode
d'etude de la construction picturale sont
enumeres,pour arrivera la conclusion que la
methode est complementairea d'autresmethodes comme la photographieen rayons X et
infra-rouges.

Suit une description-de la methode employee au laboratoirede la National Gallery.

Les echantillonssont preleves par le restaurateur au moyen d'une lame pointue bien aiguisee, ce travailse fait sous un microscopebinoculaire a faible grossissement.Une partie de
l'echantillonest montee en coupe, l'autre sert
a l'analysede la matiere picturale.Une resine
polyester durcissablea froid sert de milieu de
montage pour les coupes.
A la National Galleryles coupes de peinture
ne sont faites en premiereinstanceque dansle
cas oil ellespourraientfournirdesinformations
d'ordre pratique au restaurateur.La plupart
des exemples donnes se rapportentdonc a des
peintures, restaureesau cours des cinq dernieres annees. Un certainnombre d'exemples
mettent en evidence l'apportdes coupes et de
l'analyse des peintures a la solution de problemes de restauration-detection des surpeints ou des vernis anciens,etat de preservation de la peinture originale . . . On donne

aussi quelques exemples d'alterations et de

surpeintseffectuespar le maitre original.
L'articlediscute ensuite l'etude de la technique picturale.Les peintresdu moyen-age et
du debut de la Renaissanceconstruisaientleurs
peintures en superposant de fines couches
regulieres.Ceci etait d'une part du a une conception methodique et artisanaledu travail et

d'autrepartaux proprietesde la detrempea

l'oeuf.
I1semblebien, qu'al'origine,la peinturea
l'huiles'appliquait
en couchesminceset regulieres,tout commela detrempe.
Ce n'estqu'avecRembrandtque toutesles
proprietesrheologiquesde la peinture a
l'huilefurentexploit6es.Un certainnombre
d'exemplesde coupes de peinturesdepuis
Masacciojusqu'aRenoirsont illustreset discut6sdu point de vue de la technique.Dans
quelques cas il fut possible d'etudier des
echantillonsde peinturede plusieursoeuvres
d'unmeme maitre(parexemple:tableauxde
GiovanniBelliniet de Rembrandt).
L'analysedes pigmentsconduit a la conclusion que jusqu'enpleine Renaissanceles
peintresont recherchel'emploide pigments
aussipurset brillantsque possible.I1est rare
de trouver une couleur composee d'un
melangede plusieurspigments,bienque tous
les pigmentsfussentmelangesavec du blanc
pour produire les zones tres eclairees. Les
gradationssubtilesdes tons sont le plus souvent
obtenues par des glacis translucidesappliques
sur des couleurs opaques. Les dimensions
grossieresdes grains de quelquesuns des pigments, compareesa celles des pigments modernes, est tres perceptible. Ceci vaut surtout
pour les pigments bleus et verts. Des exemples
sont donnes.
Les informationsconcernantles liants utilisesparles maitresancienssontbeaucoupmoins
precises.Quelques tableauxoZul'identification
du liant semble presque certaine, sont repris
dans une liste.
Un apergu de l'histoire de l'analyse des
pigments sert d'introduction a une serie de
tableaux d'analyse pour l'identification des
pigments. Ces dernierssont classesen groupes,
suivant leur couleur. Quelques reactions

Cross-sections
and ChemicalAnalysisof Paint Samples

simples ainsi qu' une ou deux reactions de

confirmation basees sur les 'Spot Tests' de
Feigl, sont donnees pour chaque pigment. La
plupartdes pigments, ordinairementretrouves
dans la peinture sur panneau ou sur toile
jusqu'a lafin du dix-neuvieme siecle, sont
mentionnes.
Suit un sommaire de reactionspour liants.
Bien que leur identification precise soit im-

I57

possible,ils peuventgeneralementetreclasses
en de largesgroupes.Quelques-unesdes reactionsutiliseesfigurentegalementdans les
tablesd'identification
des pigmentset dansce
un
seul
effectue
sur l'echantillonde
essai,
cas,
simultanement
d'observer
peinture,permet
liant.
et
sur
le
sur
le
pigment
l'effet

J. P