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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 conser-
vators and restorersto regard a painting
as a stratifiedstructure,so that methods
have been developedfor studying the in-
ternallayersof a painting.Examplesof such
methods are X-ray and infra-redphoto-
graphy.Here,however,superimposed images
of the layers are obtained (except,in the
case of X-rays, in very special circum-
stances).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 exam-
ined,the edgesarenearlyperpendicular to the
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 propermicro-
scopicalexaminationthe 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 preciseinfor-
mationover a very smallareaof the picture,
whereasthe radiographor infra-redphoto-
graphgives 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 cross-
sections are now made in many museum
laboratories. These include the Laboratoire
Central des Musees de Belge [3], where
methacrylate resins are used as the embed-
ding 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 III

1
11 ii-

i'V

-11
..I :.
..... -...

a?
'"::, .
'[;*X;.._~~.i,:?' -c:....: _ ii

11

... E"-- E,: _

':-;;,i"' a ...

AX:

FIG. i.-Fresco FIG. 2.-Panel Painting.

Painting
Roman fresco, c. 200 A.D. N.G. No. 2475. Holbein.
Christinaof Denmark, Duchess of Milan
(i) Wall plastermixed with coarse marble dust.
(ii) Coarse green-blue pigment. (i) Wood of panel (oak).
(iii) Blue pigment. (ii) White gesso (calcium carbonateand glue).
(iii) Pale fawn gesso (as (ii), but of a higher propor-
tion 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
thicknessesmay be measured, andthe sizesof
and
pigmentparticles, pigmentand medium
analysedchemically,usinga squaremillimetre
or so of paint.
(b) By detachinga smallfragmentof paint
from the pictureit is possibleto carryout
operations on it whichit wouldbe inadvisable
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,some-
what 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 statis-
ticalhazard,in thatit cannotbe certainthata
squaremillimetreor lessof paintis representa-
tive of the areaunderstudy,which may be
asmuchasa hundredsquarecentimetres, even
though to the eye the areamay be uniform
in colour and texture. However, in cases
whereit hasbeenpossibleto makesectionsof
adjacentand similarareasof paint (e.g. in
work on 'guineapigs'-aestheticallyworth-
less,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 pri-
marily 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 re-
storedwithin 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 con-
siderably 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 in-
serted 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 frag-
ment 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 pur-
pose. 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 promis-
ing 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 stereoscopicbinoc-
ular microscope is often useful. A micro-
scope 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 pig-
ments present very considerablybefore pro-
ceeding 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, in-
clude the supportsin order to show the scale
of the layers and the general relationshipof
the differentcomponents of the picture:
Fig. I. Fresco Painting (Roman, c. 200 A.D.)
The plaster of the wall is exceedingly rough and is
mixed with coarse marble dust. The blue pigment par-
ticles are also very coarse. They were found to be sur-
rounded 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 com-
pared to the thicknessof the paint layers (Dutch seven-
teenth 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
examplesin whichthe studyof cross-sections
hasprovedof valueto the restorers:
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
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 grey-
green 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 ex-
amined and found to be:
v. A thin deep blue layer which tapers off and dis-
appearsaltogether 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 dis-
coloured 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
 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 back-
groundto 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
help of cross-sections.Firstof all, afterthe discoloured
varnishhad been removed with the usual type of
organicsolventmixture,it was foundthatthe picture
was stillcoveredwith a dull greyishfilm. It wasneces-
saryto 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 carefulexamina-
tion 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 grey-
nessand 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-sectionswere 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).
Unfortunatelyon otherpartsof the picturethe green
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 blistered-lookingsurfaceof somedark
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 sur-
face accurately described by the restorer as being
'crocodiled'. Both were found to be very insoluble oil-
resin 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 re-
paint, 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
II6 Joyce Plesters
obviously genuine. However, several retouchings on
the picture were also found to be copper greens of
the same type. The solubilities, appearance,and u.-v.
fluorescence of the paint from the green marbling,
original green paint and green repaintswere compared.
It was discovered that the green marbling bore rather
more similarity to the repaints than to the original
paint, but it was finally decided that the evidence was
not sufficiently conclusive to justify removal of the
green marbling.
N.G. No. 4, TITIAN, The Holy Family
A 'grey layer' of perished oil varnish such as that
found on N.G. No. 292 (Pollaiuolo) was found. The
layer, which was unpigmented, was shown to cover
light and darkareasof the picturefairly evenly, indicat-
ing that it could not consist of local glazes.
Repaints on Joseph's orange robe were also tested.
One darkrepaintwas found to consist of a conglomera-
tion of white, blue, crimson, and
orange particles.
One of the sections showed a crack in the original
bright orange paint, of which the pigment was realgar,
into which two brown iron oxide layers had pene-
trated.
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 red-
brown 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 penti-
mento 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
to be coveredwith an unevenbrownglazewhichwas
suspectednot to be original.A cross-sectionshowed
the glazeoverthe pinklayerasbeingrathercoarseand
crystalline;it was found to be an oil-resinglaze pig-
mentedwith a transparent red-brownironoxide.Two
stepsweretakento attemptto proveits authenticity or
otherwise.Firstly,its solubilitieswere comparedwith
a sampleof a genuinebrown glaze from the coat. It
was foundto be considerably moresoluble.Secondly,
a paintsectionwas takenfrom the blue inscriptionat
the top of the picture,sincethe art-historian working
on thepictureconceivedtheideathatif thebrownglaze
were originalandmeantto modifythe pinkcolourof
thebackground, it wouldmostlikelyhavebeenpainted
all over the backgroundbefore the inscriptionwas
added. If, on the otherhand,it was a repaint,it would
either over the blue inscriptionor roundit. The
go
section,in fact, showed the blue paintlayer directly
above the pink with the brown glazerunningoverthe
pink and up over the edge of the bluelettering.
Portraitof Eva Gonzales
N.G. No. 3259, MANET,
The design of this pictureis really oval in shape
althoughpaintedon a rectangular canvas.Thespandrels
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
paintmightbe a continuation of the underpaint on the
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
layerof the sectionfromthe mainbackground, beinga
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
Considerable discussion
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-

FIG. 4.-N.G. No. 3046. MASACCIO(1401-1428). FIG. 5.-N.G. No. 709. MEMLINC(active I405,
The Virgin and the Child (dated 1426) d. I494).
Gold background. The Virgin and Child Strip of green hanging.

/iv
/iii -iii
-11
--i -ii

FIG. 6.-N.G. No. 292. POLLAIUOLO (c. I432-I498). FIG. 7.-N.G. No. 292. POLLAIUOLO.
Martyrdom of S. Sebastian (dated I475). Green paint from near horse'shooves.
Blue sky showing the " grey layer " in a crack.

FIG. 8.-N.G. No. 772. Cosimo TURA(c. I43I-1495). FIG. 9.-N.G. No. 772. Cosinmo TURA.
The Virgin and Child Enthroned. Green column to right of throne.
Q Pink column to left of throne.
 /V
-iv
\111
\ii
\i

FIG. io.-N.G. No. 1045. FIG. ii.-N.G. No. 592.

Gerard DAVID (active 1492, d. 1523). BOTTICELLI (C. I445-15IO).
Canon Bemardius and Three Saints. Adoration of the Kings.
Red robe from painting on reverseof panel. Sleeve of red doublet.

-iii
-iv
-ni
-ii

)i
J

-i

FIG. I2.-N.G. No. 599. FIG. I3.-N.G. No. 812.

Giovanni BELLINI (c. 1459-1516). Ascribed to Giovanni BELLINI.
The Madonna of the Meadow. Blue sky. The Assassinationof S. Peter Martyr. Blue Sky.

vii
viii-
/vi
iii-
11-
ii/ iv
1V

i-

FIG. I4.-ENGLISH SCHOOL (I530-35). FIG. 5.-N.G. No. 635. TITIAN(1480-I576).

Panel Paintings in Chichester Cathedral. Virgin and Child with SS. John and Catherine.
Bishop's Gold Mitre. Virgin's blue dress : deep blue shadow.
 iv .-
..-

iii

ii

FIG. I6.-N.G. No. 1324. VERONESE(1528-88). FIG. I7.-N.G. No. 1122. EL GRECO (1545-I614).
Scorn. S. Jerome as Cardinal (dated 1566).
Orange drapery. Dark crimson shadow on sleeve.

( ToNlil _ .IiiflM hI -iv

lt if
iii
ii
-'i

FIG. i8.-N.G. No. 1195. RUBENS(I577-I646). FIG. I9.-N.G. No. 1172. Van DYCK (1599-1641).
Birth of Venus (sketch for a silver dish). CharlesI on Horseback (dated c. 1636).
Gold leaf beneath glazes. Blue sky.

-
111- -,_W. 7 = _... "-Ae
ii

FIG. 2o.-N.G. No. I383. VERMEER(I632-75). FIG. 21.-N.G. No. 4453. CANALETTO
(1697-1768).
Lady Standing at the Virginals. Bucentaurat Piazzetta.
Blue-grey background. Pale blue sky.
 120 Joyce Plesters
vulnerableto cleaningsolvents.Cross-sectionsshowed
thatthe bluesandpinks,at any rate,were mixedwith
leadwhite to form a very solidpaint.The leadwhite
has helped to dry the oil and will have combined
chemicallywith it. Tests carriedout on samplesof
paintunderthe microscopeshowedthatthe paintwas
unaffectedby prolongedimmersionin far stronger
solventmixturesthanthatrequiredto removethe soft-
resin varnish,and even withstood pure acetone.A
sectionshowingwhite priming,two blue paintlayers,
anda pink one, is shownin Fig. 23. The thickimpasto in minute spots of damage.
is evident.
One furtherexampleof overpaintingrevealedby
cross-sectionsis shown in Fig. 14. Paintsampleswere
examinedfroma seriesof panelpaintingsin Chichester
Cathedralwhich datedfrom c. 1530-35but had been
much damagedand repainted.Fig. 14 shows a cross-
sectionfrom a bishop'smitre which was gold em-
bellishedwith blue pearlsthe size of sixpences.The
sectionshows the followinglayers:(i) the gesso; (ii)
a reddishunderpaint;(iii) a whitishpaintlayer; (iv)
gold leaf; (v) a blackishlayer,probablydirt and dirty
varnish; (vi) white overpaint(in an oil medium,
whereasthe originalpaintis in a glue medium);(vii)
a secondlayerof gold leaf;and(viii)overtheleft-hand
sideof the sectiononly, blueoil paintfromthe 'pearls'
on the mitre.It seemsthatthe originalgold leaf must
have acquireda coat of dirtor varnish,andinsteadof
the restorercleaningthis off he overpaintedit with
white lead paint,regildedit, and, for extrameasure,
added the blue jewels. Since this investigationthe
pictureshave been cleanedand restoredand the gold
mitre is seen with its originalgold leaf and without
the bluejewels which had neverformeda partof the
originaldesign.
CROSS-SECTIONS AND THE DISCOVERY OF
ALTERATIONS BY THE ARTIST
As well as discovering overpaintings, cross-
sections from pictures have on occasions re-
vealed, 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.
Cross-sectionsshow (Figs.8 and9) thatoriginallyboth
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
from red to green,from one sideof the pictureto the
other.
N.G. No. 635, TITIAN, The Virgin and Child with SS.
John and Catherine
St. Catherine'sdress, now pale yellow, was shown
by cross-sectionsto have been rose pink originally. It
has been painted over, first with a white layer and then
with a pale yellow layer of lead monoxide. On close
inspection of the picture, the pink layer could be seen
N.G. No. 1195, RUBENS, The Birth of Venus
This is a grisaille sketch for an oval silver dish. A
cross-section from an area of greenish grey glaze
revealed some way below the paint surface a layer of
gold leaf (see Fig. I8). An X-radiograph revealed,
however, that the design had not been gilded entirely,
but small parts of the design reinforced with gold,
particularlysome scroll-like motifs.
GIORGIONE, The Woman Taken in Adultery (Glasgow
Art Gallery)
The bright orange and yellow satin doublet of the
man in the foreground was found to have been bright
green originally, a brighter and bluer green than the
landscapebackground. This was first painted out with
a layer of white lead before the orange paint (orpiment
and realgar)was applied.
N.G. No. 654, van derWEYDEN,The Magdalen
Cross-sections revealed that above the white gesso
there is in many parts of the picture (e.g. parts of the
green dress, the landscapethrough the window, newly
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 under-
paint. 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,West-
ern art continued through what are usually
 and ChemicalAnalysisof Paint Samples
Cross-sections
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 manu-
script 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,methodi-
cally 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
121
iii
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 super-
imposed semi-transparentlayers. Oil paint
seems to have been first introduced as glazes
for temperabody colours. In Fig. ii, a cross-
section 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 Renais-
sance painterstended to use pure pigments in
I22 Joyce Plesters

.x,

111 -111

-ii 11
i

-1

FIG. 24.-N.G. No. 1675. REMBRANDT. FIG. 25.-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).
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 mas-
sicot in an oil-resin medium.

IV
-iii

FIG. 26.-REMBRANDT.
Late self-portrait. (Private collection).
Black coat.
(i) Orange-red priming (ochre in oil).
(ii) Black underpaint (going all over the picture).
(iii) Pale greyish-white granularpaint (covering all
the picture but varying in thickness) ; lead
white, carbon black and yellow ochre in oil.
(iv) Blackish-brownopaque body colour.
(v) Translucentpale brownish oil-resin glaze.
THREE EXAMPLES OF PAINT STRUCTURE OF LATE REMBRANDT PORTRAITS
 : .

and ChemicalAnalysisof Paint Samples

Cross-sections 123

.I., I
:
..". * S.
.
. ."
..: .. .-::,K
:,:::'~ ...
*: -
*~ ..::
.
..:,
?
'" ':;..-:
.
s~":~
.. ..

:....
w^
..'. (Picture in private . .
collection.) ^
:
:. ... ..:-
'
... :, ...2: *
.,~:.
A. . :: i.'. ' .: :. . v.: ?&':
': i .
*?'::'.::;. . . ii: * ..
blue background of" a Holbein portrait. :-^.:."- ! ':'~ '*
,,~.' . . :::
:
,,,a
*~i~ii~!~!;~;~
,:;::, ,: .,...,,': .....
',,.w,?.i, ,.:.'E..
_is$..."
~ :~::'.
' ...... : : ..:.........i:
...''....
; .

FIG. 27.--Particlesof
FIG. 27.-Particles Azurite from
of Azurite the
from the FIG.28.
blue background of a Holbeinportrait. Sampleof ModemrnCobaltBlue.
(Picturein privatecollection.)

FIG. 29.-N.G. No. 5283.

NICCOLO 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 FOUND IN EARLIER PICTURES

theirpaintingratherthanobtaininga desired Slowly oil paintbeganto be usedin a freer

shadeby mixing togetherdifferentcoloured way and the regularityof the layerstructure
pigments. Modifications of colour were pro- is to be less evident.Paintlayersalso tended
ducedby the useof translucent glazes.A good to become thicker,and impastoand the effects
example is seenin Fig. io. Thisis a sectionof of raisedbrushstrokeswere discovered.The
paint from a red robe. Above the gesso, development can be seen through Fig. 16
layer (i), is a bright red body colour, this is (Veronese)to Fig. 26 (Rembrandt).
heightened by a thin semi-opaque pink Of the illustratedexamples,spacewill only
scumble,andfinallythe colouris enrichedby permit the mention of a few noteworthy
layer (iv), a translucentdeep red madderglaze. points. Fig. 5 (MEMLINC) shows the complex
I24 Joyce Plesters
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 considerableresemb-
lance 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 red-
brown 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 com-
modity 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 ultra-
marine 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 illus-
trated (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, coarsered-
brown 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 with-
out 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 pic-
tures 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, how-
ever. It was discoveredthat verdigrisor mala-
chite would partly dissolve if warmed in a
resinous material such as Venice turpentine,
producing a beautiful clear green varnish.
This preparationwas used in various ways-
as 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 men-
tioned 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 curiousdeep purpleseenin the bandsof the
oxidizes and decays with time, as it is bound altarcloth in N.G. No. 783 (follower of Van
to do, the compound will break up and its (see Fig. 30 below) is, on the other
der WEYDEN)
colour will be lost. Possibilities of its re-
generation 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 com-
ponents 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 under-
paint can still be seen through it, perhaps a
trifle warmer in colour than originally. The hand, producedby a body colour of deep
same kind of building-up was seen in the ultramarine,unmixedwith white,glazedwith
green of the Magdalen'srobe in N.G. No. 654, what appearsto be burnt madder(thereis
Van der WEYDEN. Here, however, only faint little reason to suppose it was originally
tracesof the browned glaze remainedalthough crimsonsince crimsonglazesin other parts
the opaque green below had kept its of the picturehavenot browned).
brilliantcolour. The second factor in the pre- A few pigments found but rarely in
servation seems to be that the colour is pro- picturesinclude smalt, which had a very
tected by being locked up, as it were, in a limited period of use between about the
lead white oil paint. middleof the sixteenthcenturyuntil it was
An example of an Italianpicture where the superseded by the inventionof cobaltbluein
green colour is perfectlypreservedis N.G. No. I802. It has been found in the National
772, TURA (see Fig. 9). Here both the above Gallery Laboratoryin only four of the paint
conditions are fulfilled. samplesinvestigated,viz. a Veronese,a seven-
Violet was another colour for which there
teenth-centuryEnglish painting, a picture by
was not a single pigment, although some of Rembrandt and a mural by Thornhill. A
the red vegetable dyestuffswere of a purplish curious pigment is the red resin dragon's
tinge. In pictures by both Botticelli and blood, which seems to have been used only
Bellini a clearviolet was found to be produced for toning gold leaf. It has been identified in
by an opaque pink made from lead white and this capacity in N.G. No. 1331, FUNGAI, The
a crimson lake, glazed with ultramarine.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 quanti-
tative analysisdesignedmainlyfor dry pig-
ments.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] wasalsoapplyingsimplemicro-
chemicaltestsfor pigments,and his pupil de
Wild wrote a treatiseon the scientificex-
amination 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 pig-
ments.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 contri-
butionby Whitehead[22] on the application
of chemicalreagentsto paintcross-sections in
industrialresearch,anda manual by Stock [23]
on the chemicalanalysisof pigments,whichis
of great value becauseit includestests for
almost all artists'pigmentsup to the most
recent,includingphthalocyanine blue, titan-
ium white and monolitered.
The table given below combinesmicro-
scopicaland 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
runconcurrently; thus,treatmentwith sodium
hydroxide,with concentrated nitricacid,and
alsothe effectof heaton the sampleappearin
both the table for the identificationof pig-
ments 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 re-
dissolvedand 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 poly-
ester 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 dis-
solved. 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,conse-
quently 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 pig-
ment 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 nine-
teenthcenturyareincludedin 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
controversial and not much is known of the
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].
the dateof some
In orderto try to ascertain
paintsamples,especially where the examina-
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 character-
istic 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 par-
ticularcomponents.
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 stain-
ing tests.Two stainshave been found particu-
larly 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 dis-
solving out the pigment the medium is some-
timesseenas membrane-like flakes,and con-
centratednitric acid often yellows these
withoutdisintegratingthem.Thepaintsample
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 treat-
ment 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 mor-
pholine than in aqueousalkalis.Gentlewarm-
ing 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 co-
operation;Mr. H. Ruhemann,for the benefit
of his very extensive knowledge of artists'
 and ChemicalAnalysisof Paint Samples
Cross-sections I 3I

techniques; Dr. A. E. A. Werner of the Departmentof the National Galleryunderthe

British Museum ResearchLaboratoryfor his general direction of Mr. F. I. G. Rawlins.
help and encouragement throughout the
work; Mrs. V. Wilson and members of the JOYCEPLESTERS
Photographic Department at the National
Gallery for the photographs. TheNational
Gallery,
The work here describedis partof a research London.
programme in progress in the Scientific

References
I A. P. LAURIE, 'The Pigments and mediums of the Old Masters'(London I914).
2 R. J. GETTENS, 'The Cross-Sectioningof Paint Films', in TechnicalStudiesin the
Fieldof the Fine Arts,v (1936), p. I8.
3 R. LEFEVRE and R. SNEYERS, Mededelingen van de VlaamseChemischeGereinung,xii
(I950), p. 99.
4 R. E. STRAUBand S. REESJONES,'Mikroskopische Querschnitte von Gemalden',
in Maltechnik,Iv (1955), p. II9.
5 J. PLESTERS,'The Preparation and Study of Paint Cross-Sections', Museums
Journal,Vol. 54 (I954),No. 4.
6 F. I. G. RAWLINSand A. E. A. WERNER,'Some scientific investigations at the
National Gallery,London', in Endeavour, III(1954), No. 51, p. 140.
7 R. J. GETTENS, 'A Microsectionerfor Paint Films', in TechnicalStudiesin theField
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.
9 R. J. GETTENS and G. L. STOUT, 'The Stage Microscopein the Routine Examina-
tion of Paintings',in TechnicalStudiesin theField of theFine Arts, Iv (1936),
p. 207.
10 'Reference microscopical preparations', in Paint, Oil and Colour
S. M. CHARLETT,
Journal(I955), 128, No. 2961, p. I44.
11 E. M. CHAMOT and C. W. MASON,'Handbook of Chemical Microscopy' (2nd
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.
13 M. CHAPTAL, 'Sur quelques couleurs trouvees a Pompeia', in Annalesde Chimie,
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,
I6 F. W. WEBER, 'Artists'Pigments' (New York I923).
I7 H. HETTERICH, 'Ober die Anwendung mikrochemischenMethoden bei pigmen-
tuntersuchungvon Gemalden', in Mikrochemie, Emich Festschrift (1930),
p. 152; 'Uber MikrochemischeBilduntersuchung',in Mikrochemie,
x (1931),
p. 27.
I8 F. E. SCHEFFER, 'L'Examin Chimique des Tableaux', in Mouseion,xmI-xIV
(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 A. D. WHITEHEAD, 'The Micrography of Paint Films', in Journalof the Oil and
ColourChemist,xxI (1939), p. I39.
23 E. STOCK, 'Analyse der Korperfarben'(Stuttgart I953).
24 R. J. GETTENSand G. L. STOUT, 'PaintingMaterials,a ShortEncyclopaedia'(New
York 1942).
25 J. J. MATTIELLO (Editor), Protectiveand DecorativeCoatings,Vol. ni (New York
I94I).
26 F. FEIGL, Spot Tests,Vol. I, 4th edn. (Amsterdamand New York I954).
27 A. EIBNER,Entwincklung und Werkstoffe der Wandmalerei (Munich 1926), p. 549.
28 N. HEATON,'The Permanenceof Artists'Materials',inJournalof theRoyal Society
of Arts (London), LXXX(1932), p. 415.
29 R. M. BARRERandJ. S. RAITT,'Ion Exchange in Ultramarine',in Journalof the
ChemicalSociety(December 1954), p. 4641.
30 A. E. CHURCH,The Chemistryof PaintsandPainting(3rd edn. London I90I).
31 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.
32 D. V. THOMPSON, The Materialsof MedievalPainting(London 1936), p. 124.
33 W. OSTWALD(trans.), 'Microscopic Identification of Homogeneous Binding
Mediums', in TechnicalStudiesin the Fieldof the Fine Arts, Iv (1936).
34 A. EIBNER,'L'Examen Microchemique des Agglutinants', in Mouseion, xx
(1932), p. 5; 'Zum gegenwartigen Stand des naturwissenschaftlichenBild-
untersuchung',in Angewvandte Chemie,XLV (1932), p. 301.
35 P. COREMANS,R. J. GETTENSand J. THISSEN,'La Technique des "Primitifs
Flamands"', in Studiesin Conservation, Vol. I, No. i (October I952), p. 20.
36 A. KRAUS,'Liber eine Modifikation der Storch-MorawskischenHarzreaktion',
in Farben-Zeitung, xxxvIII (1932), p. 322.

The illustrationon the cover,whichalso appearson p. 126,

is reproducedby 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.

s
BLUE PIGMENTS(Contd.)

Solubilities
Pigment
Chemical Origin,or date Appearanceunder Effectof heat
Composition of invention low magnification HNO3
3N HCI 4N NaOH
(concentrated)

Azurite Basic copper Natural Bright, slightly Very soluble, Slow hydro- Very soluble, Black residueof (
(mountain carbonate, mineral greenishblue with effervescence lysis takes with effer- copper oxide am
blue, blue 2CuCO3, known from crystalline frag- of CO2 to give a place with vesence of CO2 CuO. blu
verditer). Cu(OH)2. very early ments, often ir- green solution. formation of to give a pale mo
times. regularin size black CuO on blue solution. (
and shape. the surface of sod
the pigment ate
particles. I
pig
is d
and
sma
o-
add
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 An artificially Usually more As above. As above. As above. As above. As
carbonate, preparedsub- rounded and
2CuCO3. stitutefor Azu- finer particles
Cu(OH)2 rite; recipes thanthose of
for its manu- Azurite.
factureare
given from
medieval
times onwards.

Ultramarine, A complex From the blue Clear, often Becomes white Reacts quite Te
natural. compound mineral Lapis slightly purplish and an efferves- slowly, the evol
of sodium Lazuliin blue crystalline cence of H2S is colour changing hydr
aluminium which it occurs particlesof irreg- produced (this to pale yellow. (i)
silicateand with calcspar ular size and can often be de- agen
sulphur,of and iron shape. A few tected by smell). A
somewhat pyrites. orange-redpar- adde
variablecom- ticles of iron lowe
position, but pyrites are often azid
approximating seen, and white sodi
to 3Na2 0. crystalline iodid
3A12036 SiO2. material,which iodin
2Na2S. viewed between Bub
crossedNicol surf
prismsproves to of th
be the doubly is pr
refractingcalcite. abse
(ii
may
blac
sodi
or of
ping
actio
cups
cove
the H
BLUE PIGMENTS(Contd.)
I
Solubilities
Chemical Origin, or date Appearanceunder
Pigment
Composition of invention low magnification Effectof heat
HNO3
3N HC1 4N NaOH
(concentrated)

Ultramarine As above but Manufacture Usually smaller As above. As above. In samples A

artificial. approximate first discovered and more examined in the
formula by Guinet in rounded pigment National Gal-
Na8_l1, A16 1828. grainsthan those lery, artificial
Si6 024 S2-4. of lapis ultra- ultramarine
(See BARRER marine. More- seems to be
and RAITT[29] over, there are attackedmore
for modern few colourless rapidly. This
views on particlesand no does not seem
structure.) doubly refracting to be wholly
calcite crystals, due to particle
or particlesof size. Most
iron pyrites. samples of the
artificialpig-
ment had be-
come wholly
pale yellow in
less than half an
hour, but the
lapisvariety was
still blue after
2 hours.

Smalt A potassium Manufactured. By transmitted Melts at high T

silicateglass Eibner [27] light, usually a temperatures. into
coloured blue reportsit to be ratherpale blue. plat
with cobalt mentioned Very characteris- fluo
oxide. first in 1584. tic glassy frag- trat
ments, often very resi
coarse. 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 The pure syn-A blue dye Very dark blue, Slowly turns Slowly turns Decomposes to With gentle (
theticproductfrom a plant. and of very fine brown on pro- brown on pro- a darkbrown heat sublimes giv
andthe prin- The plant con- particlesize. The longedimmersion, longed immer- precipitate. with a purple and
cipal constit-
tains a gluco- dyestuffseemsto and partly dis- sion and partly vapour, then spir
uent of the side which on stain oil films. solves. dissolves. decomposes solu
naturaldye is:
hydrolysiswith giving a brown (
C O- co OC \ acidsgives the distillate,dark hyp
Il I I blue dyestuff fumes and a
\/\ \\ and glucose. characteristic
The synthesis smell.
of indigo was
discovered in
1880by Baeyer

PrussianBlue FerricFerro- A synthetic Very dark blue Goes into solu- Changes to a (i)
(BerlinBlue, cyanide pigment in- and of very fine tion with pre- golden brown pre
ParisBlue, Fe4[Fe(CN)6]3 vented by particlesize. By cipitation iron oxide still afte
Antwerp Blue, (or a closely Diesbach in transmittedlight of orange- keeping its NaO
Chinese Blue). relatedcom- I704. it is green-blue. brown ferric finely powdered hyd
pound). hydroxide. form. (
hyd
me
diss
pre
by
am
tion
duc
be
dro
to t
solv
Th
out
BLUE PIGMENTS(Contd.)
I
Solubilities
Chemical Origin, or date Appearancetinder Effect of heat
Pigment
Composition of invention low magnification HNO3
3N HC1 4N NaOH
(concentrated)

Cobalt Blue Cobalt alu- A synthetic Pure blue Th

(Thenard's minate, pigment dis- rounded par- into
Blue). CoO. A12 03 covered by ticles, moder- platin
Th6nardin ately fine and of sodiu
I802. irregular size. ture
Bright blue by sodiu
transmittedlight. extra
acid
given
carri
Al++
A1(O
by a
drox

CeruleanBlue. Cobaltous A synthetic Green-blue, Sufficiently Th

stannate, pigment finely divided, soluble, with tione
CoO. nSnO2. known as a rounded heating, to give appl
chemicalcom- particles. a pale blue solu- nitri
pound in the tion. is no
Igth century the
but not intro- fusio
duced as a pig- und
ment until
I860.

GREEN PIGMENTS.

GreenEarth Variable in Known from Usually coarse Partially soluble Partially sol- Soluble, giving Gradually turns (i)
(terreverte). composition; earliest times crystalline par- to give a pale uble to give a a reddish solu- golden brown. of F
a complex as a natural ticles of a rather greenishsolution. greenish grey tion. on th
hydrosilicate mineral. blue-green, some ppt. of ment
of Fe, Mg, Al tinged with Fe(OH)2 (a)
and K. brown. Colour- which be- Prus
The green less particles are comes brown (b
colour is usually present on standing. thioc
caused by a also. (ii
small amount prese
of Fe++. (a
Fe (
ment
oxid
brow
of a
oxide
 sol
pla
Th
de
sta
flu
A
ag
Fe
tio

Malachite A basiccopper Known from Crystallinefrag- Soluble with effer- Unaffected in Soluble with Black residueof T
(mountain carbonate, earliesttimes ments, a rather versenceofCO2 the cold, but effervescenceof CuO. use
green). CuCO3 . as a natural pale, blue-green giving a green on warming, CO2, giving a de
Cu(OH)2. mineral;often in colour. solution. the particles blue solution. (se
occursin con- partially dis-
junction with solve giving a
azurite,q.v. pale blue solu-
tion and they
become coated
with black
CuO.

Verdigris Usually the Preparedfrom Clearblue-green Soluble giving a Soluble, giving Soluble giving Gives off a (
dibasiccopper ancient times crystals,some- green solution. apalebluepptt. a green solution. smell of acetic scr
acetate, by corroding times pointed of copper hy- acid on warm- be
Cu(CH3COO)2. copper with needles. Colour droxide which ing (vapour of
2Cu (OH)2. vinegar. often very turns black on turns Universal or
strong. boiling. Indicatorpaper (
red). Further (
heating con- H2
verts into black of
CuO. (
tra
the
du
ace

Transparent Not strictly a Laurie [I] Clear rather Partly soluble Disintegrated, Soluble, giving The resinusu- T
copper green. pigment. A claimed to grass-greenwhen giving a solution the resinous a brown solu- ally gives off a con
transparent have found freshly prepared of CuCl12 component tion. characteristic the
green varnish this type of or in good pre- being dis- resinous smell 'Az
is formed if a painton illu- servation;when solved, and on warming, to
copper salt is minatedmanu- decayed becomes pale blue then the resinate
dissolved in a scriptsdating brown. On pic- copperhy- melts and be-
resin such as from the 8th tures it is some- droxide being comes brown.
Venice turpen- century. times mixed with precipitated. Finally an in-
tine, when the lead white or combustible
Cu++ ion litharge to give black residue of
forms a salt an opaque CuO remains.
with the resin yellow-green.
acids,e.g. cop-
perabietate.
GREENPIGMENTS
(Contd.)

Solubilities
Pigment
Chemical Origin, or date Appearanceunder Effect of heat
Composition of invention low magnification
3N HC1 4N NaOH HNO3
(concentrated)

Cobalt Green A compound A synthetic Fine regular Slightly soluble Slowly soluble (
(Rinmann's of cobalt oxide pigment dis- rounded par- on heating, and with heating to und
green, zinc and zinc oxide covered by ticles,ratherblue- more so with give a pale me
green). of rather in- Rinmann in green by re- cone. HC 1 giving blue solution. solu
definite pro- I780, but not flected light, but a pale pink solu- nitr
portions. Pro- used as a pig- pure green by tion. (
bably there is ment until the transmittedlight. dith
a small pro- nineteenth I
portion of century. on
CoO to ZnO. line
dro
(io
tetr
solu
eva
ras
pen
ent
spe
solu

Chromium Anhydrous Vauquelin,the Ratherdull olive T

Oxide Green, Chromic discovererof green opaque into
opaque. Oxide, chromium, granules,usually mix
Cr2O,. suggestedthe rathercoarse; and
use of Cr20O high refractive pla
in ceramic index. the
glazes in I809, H2
but it prob- into
ably did not ma
appear as an chr
artist'spig- solu
ment until (
some years dip
later. [See T
Laurie (I).] on
dro
dip
Av
the
-3 (
Ag
tion
pap
of s
(
giv
PbC

Viridian Transparent Syntheticpig- Brilliant some- A

(Guignet's hydrousoxide ment firstpre- what blue-green
green). of Chromium pared by colour; particles
CraO. 2H20. Pannetierin usually large, ir-
1838. [See regular, slightly
Church (30).] rounded, and ex-
ceptionallytrans-
parent. Refract-
ive index is lower
than that of the
opaque oxide,

Chrome Green A mixture of Chrome Colour varies The lead chrom- The Prussian Turns yellow-
Partly soluble; (
(Cinnabar Prussianblue, Yellow was from grassgreen ate is dissolved blue is dis- the lead chro- brown owing und
Green). Fe4[Fe(CN)6]3 describedby to blue-green. with pptn. of solved with mate dissolves to the forma-
with chrome gre
Vauquelin in (The latter white lead chlo- pptn. of to give a yellow tion of ferric on t
yellow, i.e. I809, so that known as Cinna- ride. The Prussian orange-brown solution, the oxide. acid
lead chromate the first manu- bar green.) The blue is unchanged, ferrichydrox- Prussianblue (i
Pb CrO4. factureof blue and yellow so that the ide, so that remainsun- mad
chrome green particlesare colour of the the colour of changed. tion
must be after often not distin- sample changes the sample und
this date. guishablesince from green to changes from 'Wh
the Prussianblue blue. green to (
seems to coat the brownish ('Bl
yellow particles. yellow. for
GREENPIGMENTS
(Contd.)

Solubilities
Chemical Origin, or date Appearanceunder
Pigment Composition of invention low magnification Effectof heat
4N NaOH HNO3
3N HC1 (Concentrated)

Scheele's Copper- A synthetic Bright lime- Soluble giving a Soluble with Soluble giving Black residueof (
Green. hydroarsenite, pigment in- green irregularly green solution. formationof a a blue solution. CuO. un
CuHAsO3(but vented by shapedflakesof paleblue pptt. Pig
composition Scheelein varying size. of Cu(OH)2. the
varies with I778. Ratheropaque. (
mode of (
preparation). sol
dro
sta
add
wa
ate
(th
les
not
(
tio
me
cru
of
per
aci
I-2
(i
pp
for
(Si
the
Gr
bef

EmeraldGreen. Copper aceto- A synthetic Distinctive As above, but an As above. As above. As above. A
(Schweinfurt arsenate. pigment first brilliant bluish- almost colourless
Green,Paris Cu(CH3 made at green, small solution.
Green,Veronese COO)2 Schweinfurt, rounded grains,
Green.) 3Cu(AsO2)2 Germany,in some with the
I8I4. appearanceof
being trefoil or
quatrefoilin
shape, probably
owing to a de-
pressionin their
centres.
RED AND VIOLET PIGMENTS

Vermilion Red mercuric Occurs as a Very deep red Very slightly No change at (
(Cinnabar). sulphide, naturalmineral by transmitted soluble. moderate tem- T
HgS. cinnabar,but light. Pigment peraturesbut sol
has been syn- size and crystal- sublimesat rep
thesizedfrom linity vary; 580?C. HC
early times. naturaland syn- sol
thetic varieties Id
are not distin- pla
guishable. pre
par
age
vio
Hg
(
O
pla
azi
Bu
rise
is
col

Iron oxide reds Iron oxide, Occur widely Some varieties Some specimens - Partly soluble. -The
(Red ochre, either anhy- as natural (e.g. haematite) are slightly sol- con
Indianred, drous,Fe2Oa minerals, also are transparent uble. yel
Venetianred, or hydrated made artifi- and red by T
light red, Fe23O. nH2O. cially (the transmitted (
haematite,Mars Mars colours. light. Others are giv
red, etc.). quite opaque. (
It is difficultto giv
distinguishthe
artificialvarie-
ties from the
natural.

Red lead Leadtetroxide, Orange-red, Artificallymade, Dissolves with - A brown pptt. - T

(minium). Pb304. finely divided, but known from pptn. of white of lead dioxide HN
may be cry- antiquity. PbCl2. is formed. (
stallineor Id
amorphous. yel
afte
gol
(
Id
giv
PbC
RED AND VIOLETPIGMENTS(Contd.)

Solubilities
Pigment Chemical Origin, or date Appearanceunder Efect of heat
composition of invention low magnification HN03
3N HCl 4N NaOH (co
(concentrated)

Dragon'sblood. A natural From a tree Dark red by re- Partly soluble, Partiallydis- Disintegrates Melts then So
resin (for in East Asia; flected light but giving a yellow solves to an to a darkbrown evolves and
chemicalcom- known in clear orange-red solution. orange-red mass. benzoic acid red
position see medieval by transmitted turbid solu- (characteristic
Robertsonand times. (See light. tion. smell). See
Whalley [3I]). Thompson Gettens and
[32]). Stout [26].

MadderLake A mixture of Extracted Usually a very The AI(OH)3 Soluble, giv- Decomposes Colour changes (i
(Crimson two hydroxy- from the root fine powder, partly dissolves ing a purplish to a darkbrown to purple (a
madder). anthraquinone of the madder crimson red in and the colour of solution. solution. brown, then dil. H
dyestuffs,ali- plant. colour. In oil the pigment be- black and is di
zarin and pur- films the separ- comes more finally only a pptt
purin, mor- ate particlescan- orange. pale grey ash of oran
dantedon to a not be seen ow- A1203 remains. (b
base which is ing to the trans- often
usually parencyof the owin
A1(OH)3. Al(OH),. puri
(ii
Mor
Th
trea
disso
and
the M
tion
filter
of th
and t
addi
the s
gree
shou
agen

Alizarin A single Synthesized As above. As above. As above. As above. As above. As

crimson. hydroxy- for the first case o
anthraquinone time in I868 of pu
dyestuff,ali- by Graebeand is no
zarin,on a base Lieberman. light
of Al(OH)2.
Brown Madder Madderor See above. As above, but a As above. As above. See above. As above. S
(burntmadder). alizarin dull brownish or
charredby purplishred.
heating.

Cobalt Violet, Anhydrous Preparation Irregularpar- Somewhat (

dark. cobalt phos- describedin ticles, red- soluble. und
phate i859 by violet in trans- Pig
Co3(PO4)2, Salvetat. mitted light and the
highly refract- (
ing. A
are
moi
amm
tion
A d
(0o
Io m
dilu
is ad
held
blue
sam

Cobalt Violet, Anhydrous Appeared As above. - -Tests

light. cobalt about I88o (i
arsenate, (see Eibner (i
Co3(AsO4)2. [27]). tests
('Gr

Manganese Fusionproduct Preparedfirst Rounded gran- On heating grad- Black pptt. - Greyish T
Violet (Nirn- of manganese by E. Leykauf ules of rather ually turns black of MnO2. residue. T
berg Violet, dioxide and in I868. irregular size, with evolution of mix
Permanent ammonium bright red-violet C12. pota
Violet). phosphate. by reflectedlight, fuse
but pale trans- gree
parentmauve by gan
transmittedlight. solu
stan
alka
YELLOW AND ORANGE PIGMENTS

Solubilities
Chemical Origin, or date Appearanceunder Effectof heat
Pigment composition of invention low magnification
HNO3
3N HC1 4N NaOH
(concentrated)

Yellow Ochre Hydratediron Natural Usually very Some samplesare Partly soluble, Turns brown- So
(GoldenOchre, oxide, Fe203. mineralsare small regular slightly soluble, giving a yellow red on loss of HC1
MarsYellow). H20. The widely dis- grains, a rather giving a yellow solution. combined of F
naturalochres tributed,but dull golden solution of FeCl3. water. given
may contain an artificial yellow by re- (see
aluminium variety (Mars flected light. be ca
silicateand yellow) is also
other impuri- made.
ties

Massicotand Principallylead Manufactured Usually of fine Soluble with Soluble on Readilysoluble. Unaffected at Th
Litharge. monoxide pigments almost amor- pptn. of white heating, as moderatetem- be u
PbO, but known from phous texture PbC12. sodium peratures. the t
lithargeusu- antiquity. like lead white. plumbite. Changes to 'Red
ally containsa Massicot is Massicotis pale red Pb3O4if men
little red lead, the unfused yellow, litharge heated above
Pb3O4. oxide made by a little more 400? C.
roasting lead orange, owing
white; lith- to the presence
arge is the of red Pb304.
fused oxide
made by
oxidation of
molten lead.
(See Gettens
and Stout [24].)

Orpiment Yellow Natural Bright golden On heating goes Soluble giving Soluble (de- Sublimes, then (i)
(King'sYellow) arsenic mineral,used yellow; occurs into solution with sodium arsen- composes to becomes colour- 'Sche
sulphide, from in small flakes evolution of ate and sulph- give As and less owing to Pigm
As2S3. antiquity. or in fibrous H2S. arsenites. H2SO4). oxidation to on th
masses,has a the trioxide (ii
glossy or waxy As203. Th
looking surface. test g
'Red
on th
Realgar. Orange-red Natural Similarto above, As above. Soluble. As above. Melts at 31o?C. A
arsenicsul- mineral often but more orange.
phide As2S2. occurring By transmitted
with Orpi- light, orange-
ment. red. It has a
slightly lower
R.I. than Orpi-
ment.

Naples Yellow Lead anti- Manufactured Very fine gran- Partiallysol. with Partiallysol. Soluble. Sublimeswith (i)
(Antimony monate, pigment whose ules, like Massi- white PbC12 an orange- Id
Yellow). Pb(SbO4)2. history is cot in appear- ppttd. yellow vapour. pigm
obscure. (See ance. It is diffi- with
Gettensand cult to see a cry- on p
Stout [24].) stallineform. filing
Colour varies stan
from lemon- Zn a
yellow to orange- plati
yellow. pres
sepa
blac
gase
grey
(ii
'Red
men

Chrome Leadchromate Preparation Brilliant Soluble, with Soluble giv- Soluble giving - (i)
Yellow. Pb CrO4. describedby yellow; par- pptn. of white ing a yellow a yellow solu- Th
Vauquelin in tide size varies; PbC12and an solution of tion. Lead
I809. usually very fine orange solution alkali chro- may
crystals;rather of chromic acid. mate. solut
opaque. acid.
(ii
Th
'Chr
Opa
ment
out o
pigm

Barium Barium As above. By reflected Soluble, giving a Soluble, giv- Soluble, giving -(i) T
Yellow. chromate, light, bright yellow solution. ing a yellow a yellow solu- (a
BaCrO4. lemon yellow; solution. tion. in H
by transmitted H2S
light, nearly inso
colourless; fine (b
xn. structure. gree
(ii
'Chr
 ANDORANGE
YELLOW PIGMENTS
(Contd.)

Solubilities
HNOa
Chemical Origin, or date Appearanceunder Efect of heat
Pigment Composition of invention low magnification
3N HC1 4N NaOH HNO3
(concentrated)

Strontium Strontium As above. A little stronger As above. As above. As above. (

Yellow chromate, yellow than (
(Lemon Sr CrO4. BaCrO4. the
Yellow). Finely divided ppt
crystallinemass (
consistingof crim
needles. (
'Ch
(
Rho
ing
Str
I
solu
pap
rea
Ba+
red
colo
wit
HC
ing

Cobalt Yellow Potassium Discovered by Small crystals Slightly soluble Slightly sol- Soluble,giving When heated T
(Aureolin). cobaltinitrite, N. W. Fisher and clustersof giving a yellow uble. an orange strongly, gives tion
CoK3. (NO2)6. in 1848. crystals,yellow solution. solution. black CoO, HC
H20. by transmitted and oxides of tion
light. nitrogen. liste
Pig

Cadmium Cadmium A synthetic Colour varies Insolublein the Soluble, with At high tem- (
Yellow. Sulphide,CdS. pigment pre- from lemon yel- cold; partly sol- evolution of peratures p-n
paredby pptn. low to orange, uble on heating, H2S. brown CdO is A
(a mineral probably accord- with evolution of produced. is m
form exists ing to particle H2S. a dr
but there is no size, the orange KC
record of its usuallybeing age
ever having coarser.All tion
been used as a types are, how- baz
pigment). First ever, compara- form
observedby tively finely the
Stromeyerin divided. gre
1817. form
 giv
fo
sh
bla

so
scr
(se
us

BROWN AND BLACK PIGMENTS.

Raw Sienna Hydrated Natural By reflected Slightly soluble, Partly soluble. Colour changes T
ferricoxide, mineral. light, a golden- especiallyon heat- to the darker in h
Fe203 . H20. brown; by trans- ing. (Usually warmer brown ay
mitted light, a sufficientto give of Burnt Sienna iro
mixture of trans- a blue colour with (see below), the thi
parent yellow, K4Fe(CN)6.) anhydrous un
red-brown and oxide. 'Gr
colourless par-
ticles can be seen,
as well as opaque
brown ones.

Burnt Sienna. Anhydrous Preparedby Most of the As above. As

FerricOxide, calciningRaw grains are red-
Fe2o3. Sienna. dish brown. No
visible crystal-
line form.

Raw Umber. Hydrated Natural Fine darkish As above. As above. Loses water to (
FerricOxide mineral. yellow-brown become the Raw
Fe2O3. H20 grains mainly, anhydrous (
with a propor- but some orange, oxide Burnt (
tion of Man- yellow and Umber (see per
ganesedioxide colourlesspar- below) which is A
MnO2. (from ticles. a darker, dro
8-I6 %.) redderbrown. (C1
wit
ap
AgN
stir
gra
per
gen
of M
to th
BROWN AND BLACKPIGMENTS(Contd.)

Solubilities
Pigment Chemical under
Origin, or date Appearance Effectof heat
composition of invention low magnification HNO
3N HC1 4N NaOH (co
(concentrated)

Burnt Umber. Anhydrous Preparedby As above, but As above. - As above. -(i)

ferricoxide gently heating a little darker, Raw
Fe2O3,with a Raw Umber. redderbrown in (
proportion of colour, and
manganese slightly more
dioxide, MnO2 transparent.

Bitumen A mixture of Bitumen or Dark brown -Soluble, giv- Soluble, giving At first melts (
(asphaltum, hydrocarbons asphaltum amorphous ing an orange- a red-brown to a black tarry ma
mummy, with organic occurs as a solid, semitrans- brown solu- solution. liquid. Dense pet
bistre). and inorganic semi-liquid parentand tion. yellow-brown org
impuritiesand mineralde- orange-brown fumes are then (
of variable posit. Mummy by transmitted produced,with resi
composition. is a pigment light. It is par- a pungent, tarry test
(See Church made from tially solublein odour, and a Fe+
[30] and the asphaltum oil media giving brown distil- 'Gr
Gettens and used to em- a translucent late collects
Stout [24]) balmEgyptian brown film. at the mouth of
mummies. the ignition
Bistre is a tube.
tarry material Finally only a
from burned very smallresi-
wood. due of incom-
bustible inor-
ganic matter
remains.

Van Dyck Consistsof as A mineral As above, but -As above. As above. As above, but A
Brown (Cassell much as 9go% deposit similar of a more leaves rather
Earth,Cologne of organic to Lignite. heterogeneous more incom-
Earth). matter (hydro- appearance,and bustible residue.
carbonssimilar with granulesof
to those of inorganicbrown
Bitumen), to- pigment.
gether with
iron oxide,
alumina,
silica,etc.
 CarbonBlack Consists pri- Except for Except for Can be almost N
(Charcoalblack, marily of car- graphite, graphite,which completely
lamp black, bon asthe free which is a is in the form of burnt in air
vine black, element. Im- natural flaky grey-black (except for
graphite). puritiesvary mineral (but crystals,all these minute amounts
as to sources, can also be pigments are of inorganic
e.g. lamp preparedarti- black or blackish impurities).
blackcontains ficially), car- brown opaque
hydrocarbons. bon blacks are amorphousma-
all produced terials.The par-
by the partial ticle size varies
combustion of greatly; lamp
organic blackis very fine,
materials whereascharcoal
such as wood is often seen as
and oil. Most rathercoarse
forms were jagged chips;yet
known from other forms are
earliesttimes. granular.

Bone black Containsas Obtainedby The carbonseems -- - A white residue (

(Ivory black, little as Io % charring to be mixed in of calcium salts (
Animal black). carbon,the animal bones a very fine state remainsafter resi
remainderbe- (or tusks) in with the cal- combustion. flam
ing mainly a restricted cium phosphate, (
calcium phos- air supply. and the general due
phate appearanceis of but
Ca3(PO4)2 translucent exc
with a little blackishbrown is fo
calcium grainsof rather (
carbonate. irregularshape, T
but with no dat
separateblack 'Co
and white 'Re
particles. may
bus

WHITE PIGMENTS AND INERTS.

Chalk (Whit- Calcium car- Natural de- Fine white or Dissolves with -Dissolves with None until (i
ing, Lime- bonate CaCO3 posit. whitish powder: effervescenceof effervescence very high tem- H2S
white). Low R.I. CO.2 of CO2. temperatures dry
when CaO the
formed. give
shea
of g
(i
bril
Ca.
WHITE PIGMENTS AND INERTS(Contd.)

Solubilities
Chemical Origin, or date Appearanceunder
Pigment of invention Effectof heat
composition (if after 1700) low magnification HNO3
3N HC1 4N NaOH
(concentrated)

Gypsum. Calcium sul- Natural Usually fine Moderately Moderately At IIo? C. (

phate dihyd- deposit. granularcry- soluble. soluble. loses water of HC
rate, CaSO4. stallinemass. crystallization lize
2H2O. (giving plaster she
of Paris).Water for
vapour conden- (
ses at the top of (
the tube. the
filte
tion
inso
form

Anhydrous CaSO4. Preparedby Fine white Moderatelysol- Moderatelysol- No effect; with (

Calcium Sul- calcining powder. uble, but less so uble. a dry sample no (
phate (anhy- gypsum. than gypsum. water vapour is gyp
drite). given off on form
heating. bili
two
pla
Na2
wit
the
wir
solu
drit
(
iner
cry

Lead white. Basic lead car- Artificially Fine white Soluble, giving a Partiallysol- Soluble. Turns yellow T
bonate, 2Pb preparedfrom powder (indivi- white pptt. of uble as sodium owing to the und
CO3, Pb(OH)2 very early dualgrainsand PbCl2, soluble on plumbite. formation of Pig
times. crystallinityonly heating. Massicot (ead out
seen at very high monoxide, pigm
power). PbO).
Zinc white Zinc oxide, Artificially Very finely Completely sol- Soluble as Completely Turnsyellow on (i
(Chinese white) ZnO. prepared. divided white uble, with no sodium soluble with no heating but be- sinc
The use of powder. effervescence. zincate. effervescence. comes white (i
ZnO as a pig- again on cool- dith
ment was first ing. I
suggestedin NaO
1782. plat
dith
dith
The
stirr
colo
Zn.
in a

METALS USED AS PIGMENTS.

Gold. Metallic ele- Known from Colour varies, So

ment, Au. antiquity. with the degree conc
of purity being and
sometimes reag
pinkish and T
sometimes mad
yellowish. (i
Bright metallic dine
sheen which A
does not tarnish. and
Used as thinly agen
beaten sheets or acid
'leaves' laid pap
down on the a blu
picture surface, (i
or as a powder Rho
like an ordinary I
pigment. regi
with
in Io
tion
of b
the b
red-
min
u.-v.
METALSUSED AS PIGMENTS(Contd.)

Solubilities
Chemical Origin, or date Appearanceunder
Pigment composition of invention low magnification Effectof heat
3N HC1 4N NaOH HNO3
(concentrated)

Silver. Metallic ele- Known from When untar- Very slight sol- Dissolves with (i
ment, Ag. antiquity. nished has a vent action. evolution of is ad
white metallic nitrogen oxides ppt
sheen, but (brown fumes dar
rapidlydis- with character- ligh
colours in an istic odour). NH
impure atmos- (i
phere, owing to the
the formationof ppt
a film of black chr
sulphide. acti
plat
(i
ami
mine
A
test
spo
solu
of th
etha
dil.
is ac
cate
tion
colo
Tin. Metallicele- Known from Lustrouswhite Dissolves rather Dissolves very A film of hy- Th
ment, Sn. antiquity and metal, untar- slowly in the slowly on dratedstannic rapi
sometimes nished by air diluted acid. heating form- oxide becomes stan
used on pic- and water. ing sodium formed on the tion
turesin the stannate, surfaceof the ing t
Middle Ages. Na2SnO3. metal, and the (i
action slows phom
down and stops. Fi
with
moly
NH3
phos
and
test
spot
(ii
Fi
with
reag
solu
pape
to th
circl
pape
reag
colo
I56 Joyce Plesters
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 brefresumehistoriquedestravauxante-
rieurssurle sujetest donne.
Lesavantageset limitationsde cette methode
d'etude de la construction picturale sont
enumeres,pour arrivera la conclusion que la
methode est complementairea d'autresmeth-
odes comme la photographieen rayons X et
infra-rouges.
Suit une description-de la methode em-
ployee au laboratoirede la National Gallery.
Les echantillonssont preleves par le restaura-
teur au moyen d'une lame pointue bien aigui-
see, ce travailse fait sous un microscopebino-
culaire 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 der-
nieres annees. Un certainnombre d'exemples
mettent en evidence l'apportdes coupes et de
l'analyse des peintures a la solution de pro-
blemes de restauration-detection des sur-
peints ou des vernis anciens,etat de preserva-
tion de la peinture originale . . . On donne
aussi quelques exemples d'alterations et de
surpeintseffectuespar le maitre original.
L'articlediscute ensuite l'etude de la tech-
nique 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 con-
ception methodique et artisanaledu travail et
d'autrepartaux proprietesde la detrempea
l'oeuf.
I1semblebien, qu'al'origine,la peinturea
l'huiles'appliquait
en couchesminceset regu-
lieres,tout commela detrempe.
Ce n'estqu'avecRembrandtque toutesles
proprietesrheologiquesde la peinture a
l'huilefurentexploit6es.Un certainnombre
d'exemplesde coupes de peinturesdepuis
Masacciojusqu'aRenoirsont illustreset dis-
cut6sdu 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 con-
clusion 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 pig-
ments, compareesa celles des pigments mod-
ernes, est tres perceptible. Ceci vaut surtout
pour les pigments bleus et verts. Des exemples
sont donnes.
Les informationsconcernantles liants util-
isesparles 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 I57

simples ainsi qu' une ou deux reactions de possible,ils peuventgeneralementetreclasses

confirmation basees sur les 'Spot Tests' de en de largesgroupes.Quelques-unesdes re-
Feigl, sont donnees pour chaque pigment. La actionsutiliseesfigurentegalementdans les
plupartdes pigments, ordinairementretrouves tablesd'identification des pigmentset dansce
dans la peinture sur panneau ou sur toile cas, un seul essai,effectue sur l'echantillonde
jusqu'a lafin du dix-neuvieme siecle, sont peinture,permet d'observer simultanement
mentionnes. l'effetsur le pigment et sur le liant.
Suit un sommaire de reactionspour liants.
Bien que leur identification precise soit im- J. P