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Cross-sections and Chemical Analysis

of Paint Samples
Received 30/I/56

INTRODUCTION AND SURVEY OF PREVIOUS WORK The preparationof paint cross-sectionswas

IT has now becomequiteusual for conser- begun more than forty years ago. Pioneer
work was done by Laurie [i] as early as I914.
vators and restorersto regard a painting
The scope of the method was extended and
as a stratifiedstructure,so that methods
the technique improved at the Fogg Art
have been developedfor studying the in-
ternallayersof a painting.Examplesof such Museum, Cambridge, Massachusetts,in the
methods are X-ray and infra-redphoto- I930's [2]. At this time waxes were used as
mounting media for the paint sections,which
graphy.Here,however,superimposed images were cut with a microtome. The friabilityof
of the layers are obtained (except,in the
case of X-rays, in very special circum- most old paint films makes this a difficult
operation,and since then the processhas been
stances).A more direct method is to look
at the paintingin cross-section.Thisis often simplified by using modern synthetic resinsas
difficultto do in situ on the pictureeven mounting mediaand by grindingand polishing
the sections. It must be pointed out here that
with a good travellingmicroscope,sinceeven
when cracksexistwhoseedgesmaybe exam- what is requiredis not a transparentsection,to
be viewed by transmittedlight, as is necessary
ined,the edgesarenearlyperpendicular to the
in the case of many mineral sections, but an
focalplaneof the microscope,so that,at best,
opaque section, the surface only of which is
only an obliqueandratherout-of-focusview examined by reflectedlight, which makes the
canbe obtained.It is usuallymoreconvenient
to detacha minutefragmentof paintfromthe preparationfairly simple. Such paint cross-
sections are now made in many museum
pictureand look at it separatelyunder the laboratories. These include the Laboratoire
microscope.Even then, in order to see the Central des Musees de Belge [3], where
separatelayers,the paint fragmentmust be
stood on one edge, and for a propermicro- methacrylate resins are used as the embed-
ding media, the Courtauld Institute of Art,
scopicalexaminationthe sampleneedsto be
mountedin a suitablemountingmediumand University of London [4], and the National
to have an edge ground or cut smooth in Gallery,London [5 and 6]. In the National
order to give a plane surfacefor focusing Gallery, the resin used for mounting paint
sections is a cold-setting polyester resin.
underthe microscope.
This is the raisond'etrefor all methodsof
preparingpaint cross-sections.As a further METHOD
scientificmethodof pictureexaminationthe
techniqueis complementaryto radiography Advantages
and infra-redphotography,in that the paint The two main advantagesare:
sectiongives a largeamountof preciseinfor- (a) A great deal of information can be
mationover a very smallareaof the picture, gained from a very small amount of material.
whereasthe radiographor infra-redphoto- At one and the same time the sequence of
graphgives rathermore generalinformation paint layers in the picture may be noted,
over a largeareaof the picture. together with their colour and texture, their
and ChemicalAnalysisof Paint Samples
Cross-sections III

11 ii-


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

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


... E"-- E,: _

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


FIG. i.-Fresco FIG. 2.-Panel 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'


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 have been very consistent. Nevertheless,
pigmentparticles, pigmentand medium accident,artistictemperament,and the artist's
analysedchemically,usinga squaremillimetre cleaning his brush on the edge of the picture
or so of paint. have all to be reckonedwith.
(b) By detachinga smallfragmentof paint
from the pictureit is possibleto carryout PROCEDURE IN THE NATIONAL GALLERY
operations on it whichit wouldbe inadvisable
or evendangerousto carryout on the picture It must be pointed out that in the National
itself.This is especiallyvaluablewherea safe Gallery the collection of paint sections from
but efficientsolventmixturehas to be found pictures (those of permanent interest now
for the removal of overpaint.Tests with number over two hundred) has grown pri-
strongreagentsmaybe carriedout safelyaway marily out of those preparedin order to solve
fromthe pictureuntiltheireffecton the paint ad hoc problems of the restorer. Hence the
is known. It would not be possibleto carry examples from National Gallery pictures
out testson sucha smallscaleon the picture quoted are practically all from pictures re-
surfaceeven under a binocularmicroscope, storedwithin the past five years during which
and exceedinglydifficultto restrictthe area work on paint sections has been carriedout.
of the pictureaffectedby the reagent. This is the reason for what would otherwise
seem a somewhat illogical and heterogeneous
Limitations selection of illustrations. It is fortunate that
(a) In order that its appearancemay not examples cover such a wide range of time
be damaged,only minute samplesof paint and most European Schools. In addition,
can be removedfrom a picture,so that the gratitude must be expressed to friends who
amountof materialavailableto work on is have given samplesof paint from picturesin
verysmall.Thisadvantageis, however,some- other collections which have widened con-
what offsetby the specialmethodsused. siderably the scope of study.
(b)Long-termstudyof theartist'stechnique A sample of paint is removed from the
or of paint structureby this methodwould picture by the restorer.This is done with a
requirenumeroussamples,andthe sourcesfor small, sharp-pointedknife. The knife is in-
suchsamplesareratherlimited.IntheNational serted into a crack, for preference, in the
Gallery,for example,specimenshave, up to paint and then a small piece is levered up,
the present,beentakenonly frompicturesin the operation being carried out under low
courseof treatment,and then usuallyonly magnificationprovided by a binocularloupe
when some informationmight be obtained or a travelling binocular microscope. It is
whichwouldbe of useto therestorerworking preferable that the picture should be lying
on the picture. flat, so that any scatteredparticles,however
(c) Thereis what might be calleda statis- small, may be saved. The knife tip may be
ticalhazard,in thatit cannotbe certainthata moistened with saliva to assistthe paint frag-
squaremillimetreor lessof paintis representa- ment to adhereto it. The use of canadabalsam
tive of the areaunderstudy,which may be or varnish is avoided if possible, because of
asmuchasa hundredsquarecentimetres, even the difficulty they cause during chemical
though to the eye the areamay be uniform analysis.The main sample and any grains of
in colour and texture. However, in cases paint which have fallen from it are picked up
whereit hasbeenpossibleto makesectionsof with a slightly damp camel hair brush, and if
adjacentand similarareasof paint (e.g. in required for use immediately, placed on a
work on 'guineapigs'-aestheticallyworth- microscopeslide. Otherwisesuch samplesmay
less,buthistoricallysoundpictures)the results conveniently be stored in the small gelatin
and Chemicali Analysisof Paint Samples 113
capsules used for pharmaceuticalpurposes. scale.Moreover, by noting the colour, particle
They are carefullylabelled,and if there is any size and shape, opacity or transparency,
doubt as to whether the exact spot from which crystallinity,etc., of the pigments it is possible
the sample was taken could be found again, to narrow down the range of possible pig-
the co-ordinatesof the spot on the picture are ments present very considerablybefore pro-
measured.It must be admittedthat the method ceeding to chemical analysis. An invaluable
of removing the sample from the picture is aid at this stage is as complete a collection as
somewhat crude, and not wholly satisfactory. possible of known pigments mounted on
In the past several attempts have been made slides for comparison. Those used at present
to devise a suitable instrument for this pur- in the National Gallery are mounted in
pose. Laurie [I] had the idea of using a canada balsam, but it is intended that in the
sharpenedhypodermic needle, but as pressure near future they should be replacedby a new
is needed this tends to shatterthe brittle paint set mounted by more modern methods such
and also there is the difficulty of getting the as those describedby Charlett [Io]. After the
specimen out of the hollow of the needle optical examination has been completed the
intact. Gettens [7] constructeda more promis- paint section may be subjectedto a series of
ing but rather complex instrument for this solvent tests, stainingtests and other chemical
purpose. tests, which will be described later in this
The sample of paint is removed to the article. Furtherchemical tests are then made
laboratoryand viewed under a microscope at on the remainder of the sample which was
low power (30 X to I50 x usually proves a left unmounted. A series of solvent tests is
suitable range). Requirements as far as the included in an attempt to identify the media
microscopeis concernedarenot very exacting. present in the sample, each reagent being
They are set out in a paper by Gettens 8 evaporated or removed by means of filter
and a furtherpaper by Gettens and Stout 9 paper or capillary tubes before the next is
(thesealso list useful tools and equipment). In added. Such techniquesused in handling these
addition to an ordinary microscope (or a small amounts of materialsare fully described
chemicalone for choice) a stereoscopicbinoc- in Chamot and Mason's manual [II].
ular microscope is often useful. A micro- The above, then, is the general scheme of
scope with polarizing and analysing Nicol examination. Its application and results will
prisms is also valuable if much pigment now be examined in detail. The observations
identificationis to be carriedout. A powerful made on the cross-sectionswill be discussed,
light source such as a 'Pointolite' is essential, together with the conclusions drawn from
as well as a white light source. For the latter them, and the results of paint analysis. The
the National Gallery laboratory possesses a chemical testsfor pigments and media will be
small daylight fluorescent-tube microscope given in detail at the end of this article.
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 The first and most obvious feature to be
fragment is used to preparea cross-section. observed in a paint section is the sequenceof
The rest is set aside for chemical analysis. layers present. It is often stated that the four
The polished section is then examined under main strataof any pictureare support,ground,
the microscope at a suitable magnification. paint, and surface coating. It is possible to
The thickness of the paint layers and the make a section to show all of these layers, but
particle sizes of the coarser pigments can be in practice the support is often omitted since
measuredusing an eyepiece with a calibrated it can usually be examined from the back of
II4 Joyce Plesters
the picture. It is desirableto include at least examplesin whichthe studyof cross-sections
partof the thicknessof the ground or priming, hasprovedof valueto the restorers:
if only to make sure that all the paint layers
presentin the picturearerepresented.The first N.G. No. 2475, Hans HOLBEIN, the Younger, Christina of
three examples illustrated do, however, in- Denmark,Duchessof Milan
clude the supportsin order to show the scale Cleaning tests were made on this picturewith a view
to its being exhibited at the Royal Academy Winter
of the layers and the general relationshipof Exhibition of 'Works by Holbein and other Masters'
the differentcomponents of the picture: held in I950-5I. Radiographs covering the whole of
the picture had shown that as well as wear in the
Fig. I. Fresco Painting (Roman, c. 200 A.D.)
The plaster of the wall is exceedingly rough and is face there were also damages in other parts of the
mixed with coarse marble dust. The blue pigment par- picture,including the darkblue background.A cleaning
ticles are also very coarse. They were found to be sur- test on the background showed that under the top
rounded by crystallinecalcium carbonate.There is no varnish layers was a dark blue repaint, and, beneath
varnish. A coarse structure is fairly typical of wall this again, what appearedto be a thick layer of grey-
paintings. 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
Fig. 2. Panel Painting (N.G. No. 2475, Hans HOLBEIN
were analysed. The cross-section is shown in Fig. 2.
the Younger). Christina of Denmark, Duchess of
Milan. Blue paint from background Its layers have already been briefly described in the
The wood fibres of the oak panel can be seen. There previous paragraph. Three blue paint layers were
are two layers of calcium carbonate and glue gesso. present, layers v, vi, and vii in Fig. 2. They were ex-
amined and found to be:
Panels almost always have a gesso layer thick com-
v. A thin deep blue layer which tapers off and dis-
pared to the thicknessof the paint layers (Dutch seven-
teenth centurypanelsare one notable exception). Above appearsaltogether in the centre of the cross-section.It
the gesso is an underpaint of lead white. Two of the is composed of azurite in a medium of oil.
three layers of paint shown were proved to be repaints. vi. A thick layer of granulargrey-green paint, with
Traces of varnish were present, but not in the part of a few deep blue and some whitish particles visible.
the section shown in the photograph. The medium of The medium is an oil-and-resinvarnish which has dis-
the paint layer is oil. 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
Fig. 3. Canvas painting (English School, seventeenth of azurite,prussianblue, and lead white in an oil resin
century). medium.
Here the canvas appearsas one warp thread running
the length of the section and weft threads spaced The discontinuity of layer (v) must representa loss
at intervals perpendicularto the plane of the paper. in Holbein's original paint. This original blue paint
This painting is rather atypical in having so scanty a layer has kept its bright blue colour, for the oil medium
was sparingly used and does not seem to have become
priming layer. The single paint layer consists of lead discoloured.Layer(vi) goes over the loss in layer (v) and
white and a blue pigment, smalt, in an oil medium.
is therefore a repaint. On dissolving out the medium it
Wall paintings will not be discussedhere was found to be pigmented with the same brilliant
blue crystallinepigment, azurite, as the original paint,
further, after this brief comparison.The rest but the medium used was a mixture of oil and resin in
of the discussionwill deal solely with paintings a high proportion to pigment. With time this medium
on canvasand panel. had yellowed, become opaqueand disintegrated,coating
the blue pigment crystals with a practically opaque
PAINT SECTIONS AS AN AID TO PICTURE yellow-brown layer so that the paint as a whole appears
RESTORATION grey-green in colour. After this change in the repaint
had taken place the colour of the background of the
It has already been mentioned that the picture must have been very dull indeed. A second
primaryreasonfor taking paint samplesfrom repainting was therefore carried out, represented by
layer (vii). It was found that although this final layer
pictures in the National Gallery has been to contained the same pigment, azurite, as the original
provide informationfor the restorerworking paint, it also contained much prussian blue, which
on the picture. The following are a few since it was invented as late as 1704 could not have been
and ChemicalAnalysisof Paint Samples I1S
used by Holbein.Unfortunately,afterthese tests the bright green.A sectionof one of these is shown in
cleaningof the picturewas temporarilypostponedin Fig. 7. The layersto be seenare: (i) a thickgessoof
view of the lengthof timeit wouldtaketo removethe gypsumandglue;(ii) a thinbrownlineof gluepriming;
repaintsand restorethe damagedareas,and also in (iii) a yellow-brown underpaintconsistingof lead
view of the ratherpoor state of preservationof the white andbrownandyellow ochrein an oil medium;
face. It was interestingto note that at the Holbein (iv) the main body colour which is pale green and
Exhibitiontwo contemporary versionsof this picture containsleadwhite, probablymixedwith yellow lead
wereexhibited(in the catalogueof thatexhibition[I2] monoxide,colouredgreen with copper resinateand
No. 22, Studioof HansHolbeinthe younger,andNo. containingnumerousdarkgreencrystalsof verdigris,
23, After Holbein).In both these picturesthe back- someverylarge;(v) tracesof a brownedcopperresinate
groundto thefigurewasquitea bright,slightlygreenish glaze(not easilyseenin the photograph).
blue very like the backgroundof the Holbeinportrait Unfortunatelyon otherpartsof the picturethe green
miniatures,and the effect of the figure againstthis colourwas producedonly by a thick layer of copper
backgroundis much more telling. In the National resinateover a yellow or light brownunderpaint, and
Gallerypicture,in additionto the changeof colour,the whenthe glazebecamediscoloured the greencolourno
repainthasbeencarriedover the edgesof the figurein longerremained.In somecasesthe onlyvisibletraceof
someplaces,especiallyaroundtheproperrightshoulder greenis anoccasional crystalof verdigrisembeddedwell
andsideof the head. down in the brownedcopperresinate.Nevertheless,
thehighconcentration of copperionsandtheabsenceof
N.G. No. 292, POLLAIUOLO,Martyrdom of S. Sebastian any otherbrownpigmentshowsthesedecayedbrown
This picturepresentedmany complex problemsto layersto havebeenoriginallythe greenresinate.
the restorer,a few of which were resolvedwith the Theunpleasant blistered-lookingsurfaceof somedark
help of cross-sections.Firstof all, afterthe discoloured areasof the picturewas provedto be due to the use of
varnishhad been removed with the usual type of a bituminouspigmentfor the shadowsand this had
organicsolventmixture,it was foundthatthe picture sunk into the paintbeneath,thus ruiningit.
was stillcoveredwith a dull greyishfilm. It wasneces-
saryto makecertainthatthis was a lateraccretionon N.G. No. 1330, DUCCIO, The Transfiguration
the pictureandnot an originalglazebeforeits removal A cross-sectionof paint from the edge of a puttying
fromthe picturecouldbe contemplated. Cross-sections on St. James'sblue robe showed that beneathwere two
were madefrom variousareasof the picture.One of
layers of varnish and a layer of the original blue paint
these,from the pale blue sky, happenedto show the
(the putty itself had a blue retouching on top). The
'grey layer'going over and into a crackin the blue varnish nearer the original blue paint was thin, still
paintlayer.This is shown in Fig. 6. The photograph transparent,but a deep yellow in colour. The upper
has been takenwith the illuminationexaggeratingthe
darknessof the 'greylayer'to show it up moreclearly. layer of varnish was very thick indeed, not very
It wasalsofoundbothby therestorer's carefulexamina- yellow, but disintegrated and perished, having a sur-
face accurately described by the restorer as being
tion of the surfaceof the picture,and by the studyof 'crocodiled'. Both were found to be very insoluble oil-
the sections,thatalthoughthe thicknessof the layerdid resin varnishes. Their insolubility in organic solvents
vary slightlyover differentareasof the picture,it did was such as to lead to the belief that a hard resin like
not do so in any logicalway as, say, a glaze usedfor
copal must have been present. Solubility tests were
modellingmight be expectedto do. Fragmentsof the carried out under the microscope to help in finding a
'greylayer'itselfwere examinedunderthe microscope suitable solvent for their removal. This was finally
and subjectedto solventtests.It was discoveredto be
a filmof driedoil, withthepossibilityof a smalladdition performed with a mild alkalinepreparation.
of resin.It was not deliberatelypigmented,although
scattereddust particleshad become embeddedin it N.G. No. 772, CosimoTURA, Virginand Child Enthroned
hereand there,probablyduringits drying.The grey- A blue glaze, suspected by the restorer to be a re-
nessand opalescenteffectof the film on the pictureis paint, on the blue background behind the throne was
probablydue to the scatteringof light on the surface found to contain prussian blue (invented 1704) and
becauseof the fine crazingand disintegrationof the was therefore removed.
film which couldclearlybe seenunderthemicroscope. A curious problem, yet unsolved, was the presence
It was decidedto remove the 'grey layer' from the of rather crude green marbling on the steps of the
pictureusinga mild alkalinesolvent. throne. It was uncertainwhether or not this was original.
Cross-sectionswere also takenfrom differentareas It was analysed and no modern pigment was found,
of green and brown foliage in order to discoverits the paint being a copper resinate green such as was
stateof preservation. A few areasare a comparatively presentin several other partsof the picture which were
II6 Joyce Plesters
obviously genuine. However, several retouchings on to be coveredwith an unevenbrownglazewhichwas
the picture were also found to be copper greens of suspectednot to be original.A cross-sectionshowed
the same type. The solubilities, appearance,and u.-v. the glazeoverthe pinklayerasbeingrathercoarseand
fluorescence of the paint from the green marbling, crystalline;it was found to be an oil-resinglaze pig-
original green paint and green repaintswere compared. mentedwith a transparent red-brownironoxide.Two
It was discovered that the green marbling bore rather stepsweretakento attemptto proveits authenticity or
more similarity to the repaints than to the original otherwise.Firstly,its solubilitieswere comparedwith
paint, but it was finally decided that the evidence was a sampleof a genuinebrown glaze from the coat. It
not sufficiently conclusive to justify removal of the was foundto be considerably moresoluble.Secondly,
green marbling. a paintsectionwas takenfrom the blue inscriptionat
the top of the picture,sincethe art-historian working
N.G. No. 4, TITIAN, The Holy Family on thepictureconceivedtheideathatif thebrownglaze
A 'grey layer' of perished oil varnish such as that were originalandmeantto modifythe pinkcolourof
found on N.G. No. 292 (Pollaiuolo) was found. The thebackground, it wouldmostlikelyhavebeenpainted
layer, which was unpigmented, was shown to cover
all over the backgroundbefore the inscriptionwas
added. If, on the otherhand,it was a repaint,it would
light and darkareasof the picturefairly evenly, indicat- either over the blue inscriptionor roundit. The
ing that it could not consist of local glazes. go
section,in fact, showed the blue paintlayer directly
Repaints on Joseph's orange robe were also tested.
One darkrepaintwas found to consist of a conglomera- above the pink with the brown glazerunningoverthe
tion of white, blue, crimson, and pink and up over the edge of the bluelettering.
orange particles.
One of the sections showed a crack in the original
bright orange paint, of which the pigment was realgar, Portraitof Eva Gonzales
N.G. No. 3259, MANET,
into which two brown iron oxide layers had pene- The design of this pictureis really oval in shape
trated. althoughpaintedon a rectangular canvas.Thespandrels
A number of sections were made to investigate the at eachcornercanbe seencut off by the outlineof this
condition of the browned foliage on this picture, to oval, and the two upperones are paintedblue-grey,
discover whether removal of the top brown surface somewhatthe colourof the mainbackgroundof the
might reveal undeterioratedgreen, but in practically upperpart of the picture.Since they seemedto be
all areas the green colour had been produced by a only thinly painted,the restorerthought that this
single layer of copper resinate,mixed with crystalline paintmightbe a continuation of the underpaint on the
verdigris in some parts, and the green colour was partof the backgroundwithinthe oval, in which case
almost completely lost. it could be consideredthat Manetmight have begun
paintingthe picture,andonly laterdecidedon the oval
N.G. No. 1675, REMBRANDT,Portrait of Margaretha Trip shape.A sectionof the paintfrom within the oval is
Cross-sectionsshowed first of all that above the red- shown in Fig. 22. It consistsof severalsuperimposed
brown priming (which was evident along edges and layersof blue-greypaintinterposedwith thin layers
in damages) a coarse, granulargrey priming seemed to of white. A cross-sectionfrom within the spandrel
cover the whole of the picturesurfacebeneaththe local showed only a singlelayer of blue grey paint above
colours. the white priming.It did not resemblethe lowest
Sections from the black dress and the dark brown layerof the sectionfromthe mainbackground, beinga
background showed that both these areas had, in
much darkershade.It was most like the uppermost
addition to the opaque body colour, dark translucent but one layer, a thick darklayer in the photograph,
glazes which seemed to contain resin. A section from
beforethis receivedits final thin pale scumble.This
the black dress is shown in Fig. 24. The layers are: seemsto suggestthatManetdidnot paintthe spandrels
(i) orange-red priming; (ii) granular grey priming
of the picturewhen he firstbeganit, but left them as
white priming.
showing coarse grains of white lead; (iii) black body
colour; (iv) translucentblackishglaze.
One section taken from an area where a penti- N.G. No. 3268, RENOIR, Les Parapluies
mento of the hand was faintly seen showed a dense took placebeforethispicture
Considerable discussion
flesh-coloured layer beneaththe semi-transparentdark
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
N.G. No. I938, DURER, The Painter's Father
After the removal by the restorer of the yellowed 'pellicule'of unpigmentedand not very old linoxyn
varnish, the pink background of the picture was seen film on the surfaceof the picturewhich might be
11ii/ iv

i1 111-


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.

/iii -iii
--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.

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.




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.

ii/ iv


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 .-



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

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

FIG. 2o.-N.G. No. I383. VERMEER(I632-75). FIG. 21.-N.G. No. 4453. CANALETTO
Lady Standing at the Virginals. Bucentaurat Piazzetta.
Blue-grey background. Pale blue sky.
120 Joyce Plesters
vulnerableto cleaningsolvents.Cross-sectionsshowed from red to green,from one sideof the pictureto the
thatthe bluesandpinks,at any rate,were mixedwith other.
leadwhite to form a very solidpaint.The leadwhite
has helped to dry the oil and will have combined N.G. No. 635, TITIAN, The Virgin and Child with SS.
chemicallywith it. Tests carriedout on samplesof John and Catherine
paintunderthe microscopeshowedthatthe paintwas St. Catherine'sdress, now pale yellow, was shown
unaffectedby prolongedimmersionin far stronger by cross-sectionsto have been rose pink originally. It
solventmixturesthanthatrequiredto removethe soft- has been painted over, first with a white layer and then
resin varnish,and even withstood pure acetone.A with a pale yellow layer of lead monoxide. On close
sectionshowingwhite priming,two blue paintlayers, inspection of the picture, the pink layer could be seen
anda pink one, is shownin Fig. 23. The thickimpasto in minute spots of damage.
is evident.
One furtherexampleof overpaintingrevealedby N.G. No. 1195, RUBENS, The Birth of Venus
cross-sectionsis shown in Fig. 14. Paintsampleswere This is a grisaille sketch for an oval silver dish. A
examinedfroma seriesof panelpaintingsin Chichester cross-section from an area of greenish grey glaze
Cathedralwhich datedfrom c. 1530-35but had been revealed some way below the paint surface a layer of
much damagedand repainted.Fig. 14 shows a cross-
sectionfrom a bishop'smitre which was gold em- gold leaf (see Fig. I8). An X-radiograph revealed,
however, that the design had not been gilded entirely,
bellishedwith blue pearlsthe size of sixpences.The but small parts of the design reinforced with gold,
sectionshows the followinglayers:(i) the gesso; (ii)
a reddishunderpaint;(iii) a whitishpaintlayer; (iv) particularlysome scroll-like motifs.
gold leaf; (v) a blackishlayer,probablydirt and dirty GIORGIONE, The Woman Taken in Adultery (Glasgow
varnish; (vi) white overpaint(in an oil medium, Art Gallery)
whereasthe originalpaintis in a glue medium);(vii)
a secondlayerof gold leaf;and(viii)overtheleft-hand The bright orange and yellow satin doublet of the
sideof the sectiononly, blueoil paintfromthe 'pearls' man in the foreground was found to have been bright
on the mitre.It seemsthatthe originalgold leaf must green originally, a brighter and bluer green than the
have acquireda coat of dirtor varnish,andinsteadof landscapebackground. This was first painted out with
the restorercleaningthis off he overpaintedit with a layer of white lead before the orange paint (orpiment
white lead paint,regildedit, and, for extrameasure, and realgar)was applied.
added the blue jewels. Since this investigationthe
N.G. No. 654, van derWEYDEN,The Magdalen
pictureshave been cleanedand restoredand the gold
mitre is seen with its originalgold leaf and without Cross-sections revealed that above the white gesso
the bluejewels which had neverformeda partof the there is in many parts of the picture (e.g. parts of the
originaldesign. 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
CROSS-SECTIONS AND THE DISCOVERY OF pink putty in small damages. Under other areasthere
ALTERATIONS BY THE ARTIST is a thin layer of a pale blue-grey paint. Above these
rather perplexing layers the painting is built up in a
As well as discovering overpaintings, cross- very logical way. One cross-section also shows the
sections from pictures have on occasions re- fine muslin-like canvaswhich is embeddedin the gesso.
vealed, albeit often accidentally, changes made
N G., No. 592, BOTTICELLI,The Adorationof the Kings
in the picture by the artist himself. A few
Fig. ii shows a cross-sectionfrom a red sleeve. The
examples are given below: gesso layer is not shown. The firstlayer is a white under-
N.G. No. 772, CosimoTURA, Virginand ChildEnthroned paint. Then follows what is virtually a single layer of
Two pillarssupportthe arch over the throne,the blue-green verdigris crystals.This green layer has been
one on the left beingpink,the one on the right,green. painted out with another layer of lead white, and the
Cross-sectionsshow (Figs.8 and9) thatoriginallyboth top paint layer is now a dark red glaze.
columnswere pink, but that the right-handone was
repaintedwith two layers of green paint which is THE STUDY OF ARTISTS' TECHNIQUE BY MEANS
identicalwith green paint found elsewherein the OF PAINT CROSS-SECTIONS
picture.This is probablyin accordancewith Tura's After the decline of Romanpainting,West-
curiouscolourschemefor the picture.The coloursof
the robesof the pairsof angelsalsoalternate,thistime ern art continued through what are usually
and ChemicalAnalysisof Paint Samples
Cross-sections 121


FIG. 22.-N.G. No. 3259. MANET (I832-83)- FIG. 23.-N.G. No. 3268. RENOIR (1841-1919).
Portrait of Eva Gonzales. Les Parapluies.
Blue-grey background within outline of oval, Blue paint with pink scumble over a white
top right comer. priming.
termed the Dark Ages, not in the form of natureof the egg-temperausedas a medium
wall or easelpaintingbut ratherin the applied in early Italian paintings also contributed to
arts of metalwork, ivory carving and manu- this tendency for the pictures to be built up
script illumination. As late as the thirteenth in thin regular paint layers. Egg-tempera
and fourteenth centuries, painted altarpieces paint dries rapidlyand with a hard outline so
were more the work of the gilder and carver that subtletiesof modelling and shadingwere
than of the painter.Paintingwas one craft of in many casesproducedby the effect of super-
many and the painterhad not yet achievedhis imposed semi-transparentlayers. Oil paint
renaissancestatus of 'artist'. Painting tended seems to have been first introduced as glazes
thereforeto be carriedout as a craft,methodi- for temperabody colours. In Fig. ii, a cross-
cally and according to traditionalrules. This section from a pictureby Botticelli, a crimson
attitude shows itself in the very regular and oil glaze has been used over white tempera
logical construction seen in cross-sectionsof paint. Oil paint, even when used for all the
early pictures. Fig. 4 shows a section of the paint layers of a picture, tended for a long
gold background of N.G. No. 3046, MASACCIO, time to be used rather cautiously in thin
TheVirginand Child. The traditionalmethods regular layers in the same way as tempera
of gilding and tooling are used, although in paint. This can be seen especiallyin Figs. 5-I4
this same picture Masaccio has introduced inclusive (Figs. 4-23 inclusive are arranged
real perspective and modelling. The section more or less in chronologicalorder of artists).
consistsof threelayers:layer (i) is a thick layer Full use was not reallymade of the rheological
of white gesso of a fine crystalline texture. properties of oil paint until the time of
It is more than a millimetre thick (the full Rembrandt who used it as thick impasto,
depth is not seen in the photograph). The thin glazes, dry granular paint, rich oily
surfacehas been carefullysmoothed and upon enamel-like paint, and with every possible
it has been applied layer (ii), which is a thin permutation. During the early Renaissance
coating of bole, the red clay used in gilding. such effectswere perhaps not desired.It will
Layer (iii), the gold leaf itself,is laid with great be statedlateron that the medievaland Renais-
precision. Its thickness is only 9-I8 ,/. The sance painterstended to use pure pigments in
I22 Joyce Plesters


111 -111

-ii 11


FIG. 24.-N.G. No. 1675. REMBRANDT. FIG. 25.-REMBRANDT.

Portraitof MargarethaTrip. Black dress. Late PortraitGroup. (Privatecollection.)
(i) Orange-red priming (ochre in oil). Red dresswith yellow scumble.
(ii) Coarse granular priming of lead white and (i) Orange-redpriming.
carbon black. (ii) Opaque scarletbody colour (vermilion).
(iii) Blackest body colour (carbon black and (iii) Thin dark line of black pigment mixed with
brown ochre in oil). iron oxide red pigment.
(iv) Translucent brownish glaze (oil resin (iv) Thick pale yellow scumble of yellow mas-
medium). sicot in an oil-resin medium.


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.
: .

and ChemicalAnalysisof Paint Samples

Cross-sections 123

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

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

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

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 greenish glazes. Fig. I9 shows a section of
and this will be more fully discussedunder blue paint from Van Dyck's Portrait of
copper greens. Figs. 12 and 13 are of gesso CharlesI on Horseback.The holes in the red-
from two differentpanel picturesby Giovanni brown priming, layer (i), are those made by
Bellini. In both cases the gesso is seen to be the shape of the canvas threads. A layer of
built up in numerous layers. Although this lead white (ii) was applied before the blue
process is described by Cennino Cennini, in paint. The structureof the blue paint reminds
practice a single layer of gesso seems more us that lapis lazuli was still an expensive com-
common. An odd feature is that in Fig. 12 modity in Van Dyck's time, for he has
(from the Giovanni BELLINI,N.G. No. 599, followed the medieval practice of having an
Madonna of the Meadow), what might be underpaint,layer (iii), of the less expensive
consideredas the fine pure white gesso sottile azurite, followed by (iv) a mixture of ultra-
is at the bottom, near the panel, whereas a marine and lead white, and finally (v) a glaze
coarse brownish gesso is nearest the paint of pure ultramarine.Fig. 20 shows a section
layer. In Fig. 13 (from N.G. No. 812, assigned from the blue-grey backgroundof a picture
to BELLINI, Death of St. Peter Martyr) the by Vermeer.There are two priming layerson
lowest gesso layers are palest in colour. this picture. Layer (i) is pale grey in colour,
Perhapsthis is an early example of the use of and is composed of lead white and carbon
a coloured ground. Fig. 15 shows a section black in an oil medium. Layer (ii) is pale
from a Titian. The layers are fairly regular pinkish-brown, and consists of lead white
and the total paint thickness comparatively mixed with a little red-brown ochre. There
small.There aretwo very similarTitiansin the is a single blue-grey paint layer (iii). Fig. 21
National Gallery (No. 4, The Holy Family, shows a section from blue sky on a picture
and No. 635, The Virgin and Child with SS. by Canaletto and has a surprisingly thick
John and Catherine). Sections and pigment coarse-grainedred-brown priming composed
analysesof each showed considerableresemb- of brown and red ochres, lead white and an
lance in both layer structure and pigments oil medium.
and medium used. The only considerable For some pictures it has been possible to
difference was that whereas in the case of study technique very thoroughly by this
N.G. No. 4, the canvas was merely primed meansbecauseof a greaternumber of samples
with lead white in oil, the canvas of N.G. available.This was so in the case of N.G. No.
No. 635 has first a layer of calcium sulphate 783 (follower of van der WEYDEN). A detail
gesso below the thin lead white priming. of the centralportion of this picture is illus-
Fig. 17 shows the use made by El Greco of trated (Fig. 30). The most interestingfeature
deeply coloured transparent glazes over a was the variety of methods used to paint the
thick white body colour. This gives his flesh. In some parts there is strong black
painting great luminosity. Fig. I6 shows the underdrawing, and in others softer brown
coarse canvas and rather dry crumbly oil undermodelling. Many very thin red glazes
paint used by Veronese (and other later were also found. The information obtained
Venetians).Here the priming (layer (ii) in the from the cross-sectionsagreedvery well with
diagram) is a cool pale brown in colour and the observations on the technique made by
is thinly spread.The orange colours found in Mr. H. Ruhemannfrom his detailedtechnical
layers (iv) and (v) of this sectionwere shown examinationof the picture.
to be massicotand red lead. Fig. I8 shows a Figs. 24, 25, and 26 show cross-sections
section from a Rubens grisaille sketch. The from portraitspaintedby Rembrandttowards
priming is a light red brown on which is the end of his life. All have thick, coarsered-
superimposed a series of red, brown, and brown primings. In Figs. 24 and 26 this red
and ChemicalAnalysisof Paint Samples
Cross-sections I25

priming is separatedfrom the local colouring having two layers of green paint, from N.G.
by a second priming, a coarsegrey and white No. 5283, NICCOLO DELL ABBATE.
granularlayer containing numerous lumps of With this obvious desirefor brilliantcolour
unmixed lead white (in addition a blackish it is a shock to find so many brown coloursin
layer appearsbetween these two in Fig. 26). pictures where greens would be expected.
Fig. 25 is a section from the latest of these This is becausethere was not until the end of
three pictures and shows a very irregular the eighteenth century a permanent bright
layer structurewith, on top, an exceptionally green pigment. The early painters lacked a
thick irregularyellow scumble. 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
One of the most striking featuresof early blue or blue-greenwith yellow since the only
picturesis the fact that all the pigments seem bright yellow was orpiment which, being a
to be used in the brightest,purest form with- sulphide, was incompatible with the copper
out much mixing together, except with white, greens or blues. A solution was found, how-
and usually without admixture of brown or ever. It was discoveredthat verdigrisor mala-
black. If paint is found on a picture which is, chite would partly dissolve if warmed in a
say, a grey colour composed of red, blue, and resinous material such as Venice turpentine,
yellow pigments mixed, it is most often found producing a beautiful clear green varnish.
to be a retouching in which the restorerhas This preparationwas used in various ways-
added small amounts of first one pigment and as a glaze with or without the addition of
then another to match the surroundingarea. further solid verdigris or mixed with lead
The blue robes of Christ or the Virgin in pic- white or massicot to give opaque greens.
tures by Duccio, Bellini, Titian, or Giorgione The colour was extensivelyused and its results
are almost sure to be painted in lapis lazuli have been calamitous. The copper green is
ultramarine,used alone for shadows,or mixed often browned completely by the atmosphere.
with white for highlights. Shadows and Its worst effects can be seen in the small
modelling might be augmented by a dark POLLAIUOLO N.G. No. 928, Apollo and
underpaint. Vermilion is used constantly as Daphne. Its deteriorationhas also been men-
the pure pigment, but is often glazed with a tioned in connection with another picture
crimson lake to give a less scarletred. by Pollaiuolo and two pictures by Titian,
Many of the pigments are very coarsely where its condition is only a little better. This
ground, compared with modern pigments. colour has been prepared in the National
This may be because methods of grinding Gallery laboratory. On exposure to u.-v. it
were primitive, but in some cases, especially was found that specimenspainted out turned
that of the blue pigments, the coarse particle brown in a matter of a few months. Where
size was deliberatelychosen in order to retain the resinwas mixed with lead white in oil the
the utmost colour of the crystallinepigments, change was rather slower. Mr. J. S. Mills
for much of it would be lost by light scatter (Nuffield Scholar at the National Gallery)
through fine grinding. Fig. 27 shows a sample carried out chromatographictests on copper
of azurite from the backgroundof a portrait resinateand came to the conclusion that the
by Holbein (privatecollection). Fig. 28 shows substance was simply a copper salt of the
a sample of modern cobalt blue pigment at resin acids. He also succeededin preparinga
the same magnification. Fig. 29 shows very similar product from copper oxide and pure
large particles of verdigris in a cross-section 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
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.
and ChemicalAnalysisof Paint Samples 127
Of thelakepigments,an unusualpurplishone authenticityof a picture.The methodusedin
has been found in N.G. No. 1122, School of the NationalGallerywill thereforebe given
EL GRECO, St. Jerome as Cardinal. It has a in detail,for althoughit includesmuchwork
very strong colour but is unusual in that its which has appearedelsewhere,it does bring
colour is entirely destroyed by alkali. One togetherinto a schematicwhole a numberof
other odd discovery was the identification scatteredsourcesof informationas well as
of the silver of the armour of St. George in addinga few techniquesandtestsnot hitherto
N.G. No. 776, PISANELLO, as tin leaf appliedto paintanalysisof pictures.
A last example is the only exception so Thereis a fair amountof publishedwork
far found to the rule that Italianpaintersused on pigmentanalysis,as distinctfromwork on
calcium sulphatefor their gesso, and northern propertiesof pigmentsin general.One of the
painterscalciumcarbonate.The gesso of N.G. earliest referencesto chemical analysisof
No. 194, RUBENS, The Judgement of Paris, pigmentsis a paperby Chaptal[I3] in 1809
was found to be gypsum. on pigments found at Pompeii. In 1903
Wright [14] publisheda book on simple
THE MEDIA OF THE OLD MASTERS methodsfor testingpainters'materialswhich
Little can be said on this subject, for the includedrathercrudequalitativeand quanti-
only means of identification are the rather
tative analysisdesignedmainlyfor dry pig-
rough tests given later in this article,together
ments.Raehlmannin 191o [I5] was the first
with comparison with samples of paint of chemistto use microscopicinvestigationin
known media. The following summarizesthe the examinationof paint from pictures.
findings: Anotherearlytreatisewas by Weber [i6] in
(i) GlueMedium:One pictureonly in the National 1923. This gives a seriesof simple tests for all
Gallery, No. 664, Dieric BOUTS,The Entombment, was artists'pigmentsavailableat the time, usinga
found to be paintedin a glue medium,togetherwith limited range of common reagents.It was,
one other example, the series of sixteenth-century however, designedprimarilyfor the use of
panelsin ChichesterCathedral(seeFig. I4). artistsso that they might ascertainthat the
Of all the picturesso farexamined
(ii) Egg Tempera:
it can only be statedwith any confidencethat the pigmenttheywerebuyingwaswhatit claimed
followingarein this medium: to be.
N.G. No. 1330, DUCCIO,
The Transfiguration; Hetterich [I7] in 1930 and 1931 investi-
N.G. No. 1331, FUNGAI, Virgin and Child with gated micro-chemicalmethods of pigment
Cherubim; identification
for picturesandpaintedstatues.
N.G. No. 592, BOTTICELLI,Adoration of the Kings; Scheffer[I8] wasalsoapplyingsimplemicro-
N.G. No. 758, BALDOVINETTI,Portrait of a Lady. chemicaltestsfor pigments,and his pupil de
(iii) Oil Medium:The vast majority of the pictures Wild wrote a treatiseon the scientificex-
examined were in this rather loose category, which amination of pictureswith tests for pigments
should be taken to mean 'a medium predominantlyof based mainly on standardmicro-chemical
oil'. They include pictures by artists as diverse as
Bellini, Titian, Claude, Van Goyen and Renoir. crystallizations[19]. Laurie [20] was at the
(iv) Oil-resinmedium:This is very difficult to assess.
same time evolving microchemicaltests for
One of the more certain examples is that of the glazes pigmentsand thesewere carriedfurtherby
in some of Rembrandt'spictures. Gettens [8] and Gettensand Stout [9] in
the I930s,the latterworkingout tablesfor
identificationof white, green,and blue pig-
The identification of pigments can be ments.Eibner,in a posthumouspaperpub-
carried out with far greater certainty than lished 1932 [21], developed microchemical
that of the medium, and is also more likely analysisof paintingsmuch fartherthan any
to prove useful in establishing the age or other worker in this sphere,and his tests
I28 Joyce Plesters
includethe use of manyorganicreagentsfor tests on filter paper or on a spot plate. The
metals, then newly developed. The most reagents used are extraordinarily sensitive
recentadditionsto the literaturearea contri- under these conditions. Thus a fraction of a
butionby Whitehead[22] on the application millimetre of paint dissolved in a drop or
of chemicalreagentsto paintcross-sections in two of acid will furnish enough solution for
industrialresearch,anda manual by Stock [23] several differenttests.
on the chemicalanalysisof pigments,whichis In some cases chemical tests can be carried
of great value becauseit includestests for out on the paint cross-sections. The poly-
almost all artists'pigmentsup to the most ester resin used for embedding the samples
recent,includingphthalocyanine blue, titan- penetrates the paint and to some extent
ium white and monolitered. protects it from chemical attack. Reactions
The table given below combinesmicro- only proceed on the surface exposed by
scopicaland chemicalexamination.In most grinding and even then quite slowly. For
casesa descriptionof the crystallineformand example, if a paint section is treated with a
figures for the refractiveindex is omitted drop of dilute nitric acid followed by a drop
sincethesecanbe foundin the tablegivenby of potassium iodide and excess reagent then
Gettensand Stout in their Encyclopaedia of washed off with water, all layers containing
PaintingMaterials[24]. Photomicrographsof lead white or lead oxide pigments will be
pigmentsare to be foundin De Wild [I9] seen to have become bright yellow owing to
and in Mattiello [25]. The necessitycannot be the formation of yellow lead iodide. This
too stronglyemphasized, however,of having principle can be followed for a number of
aswide a rangeof mountedcomparison slides tests including some organic reagents for
of pigmentsas possible.A rangeof refractive metals which produce coloured complexes.
indexliquidsis alsouseful. Unfortunately its application is restrictedto
The chemicaltestson pigmentsareusually those pigments which are somewhat soluble
carriedout afterthose on media. Some can in moderately dilute acids.
runconcurrently; thus,treatmentwith sodium Solubility tests with organic reagents,
hydroxide,with concentrated nitricacid,and acids and alkalisare carriedout in the case of
alsothe effectof heaton the sampleappearin every paint sample,becauseby the time these
both the table for the identificationof pig- have been worked through, all the medium is
ments and the tests for the identificationof usually extracted or destroyed and in many
media. One test only need be made on the cases the pigment itself has also been dis-
paintsampleand the effecton both medium solved. In the confirmatorytests it has been
and pigment observed at the same time. the aim to find two or more differenttestsfor
Thereare also variousways of economizing each pigment. The samplesbeing so small, the
with the amountof the sampleavailable,e.g. tests have to be simple in application,conse-
after solvent treatmentfor identificationof quently even very sensitive tests have been
mediahas been carriedout and the medium excluded if these require specially controlled
extractedor destroyed,the residuecanbe used conditions or are liable to interferencein the
for pigmenttests;afterignitionof partof the presenceof other metal ions (in paint samples
sample the residue from the combustion, impurities are often encountered; certainly
which may containmetaloxides,can be re- iron and lead are present in almost every
dissolvedand testedfor metal ions. Perhaps paint sample).
the most valuableeconomyis in the use of For the purpose of the tables the pigments
spot tests.When the samplehas passedinto are grouped into various colours since this is
solution minute drops can be removedby how they are first distinguished.By looking at
meansof a capillarytube and used for spot the sample under a low power microscope
and ChemicalAnalysisof Paint Samples
Cross-sections I29

andnotingits colourandphysicalappearance preferentialstaining of media with biological

it is usually possibleto narrow down the stains, a technique which has recently been
rangeof possiblepigmentsto as few as two resumed at the National Gallery. Eibner [34]
or three.This limitsthe numberof chemical also tackledthe problem, testing the solubility
tests required.For example,if the only pig- of media and also attempting to identify
ment visiblein the samplewere red it would protein media by the presence of nitrogen,
be pointlessto test for copper.On the other phosphorus, and sulphur. In more recent
hand, if the pigment were bright blue it times an extensive investigation into the
would be usualto test for copperand cobalt techniquesof the FlemishPrimitiveshas been
ions and for ultramarine. proceeding at the Laboratoire Central des
All pigmentscommonlyusedin paneland Musees de Belge under the direction of Dr.
canvaspaintingsup to the end of the nine- Paul Coremans,and a useful table of tests for
teenthcenturyareincludedin the table;at the mediahas beenpublishedin a previousnumber
presenttime there are no twentieth-century of this journal, in an article by Coremans,
picturesin the NationalGallery. Thissen,and Gettens[35].
The identificationof organic pigments Micro tests for nitrogen, such as the
otherthanmadder,alizarin,andindigois not Lassaignetest, have recently been carriedout
attempted since the subject is somewhat by Miss Margaret Hey (Nuffield Scholar at
controversial and not much is known of the the National Gallery) who has found that
identityof thesepigmentsnor of the physical many of the paint samplestested which were
and chemicalchangeswhich they undergo certainly oil paint gave a positive test for
with ageing. nitrogen. This may be because of small
It shouldbe noted that all spot tests and amounts of impurities in the original paint,
tests involving the use of organic reagents but it seems even more likely that at some
for metalsare takenfrom Feigl'sbook [26]. time the paint has become contaminatedwith
the dateof some
In orderto try to ascertain gelatin during blister laying or relining.
paintsamples,especially where the examina- Until a test specificallydistinguishingbetween
tion of repaintsis concerned,it is necessary egg and glue protein can be devised, tests
to know the dates of introductionof the for nitrogen, etc., do not seem to be very
variouspigments.Manyof thedatesareshown useful. Such a test might be possible by
in the followingtable (pp. 133ff.), but more modern techniques such as chromatography,
detailed chronologicaltables are given by but even so it is doubtful whether much
Eibner [27] and by Heaton [28]. 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
The term 'analysis'can hardlybe applied position is very complicated. The effect of
to the ratherroughandreadytestswhichare adding resins to linseed oil films is not fully
available.The most that can be done is to understood,and of coursethe effectsof adding
attemptto classifythe mediumas glue, egg a soft resinsuch as masticare likely to be very
tempera,oil, or oil/resinmixture.Very little different from those produced by adding a
work has been done in the past on this hard resin such as copal. There are several
problemcomparedwith the amountdone on useful colour tests for resins such as the
pigment analysis. An early pioneer was Storch-Morawski test (Kraus [36] gives a
Ostwald [33] who in 1905 was developing modification of this test suitable for paint
microscopictests for the identificationof and varnish samples) but unfortunatelyaged
mediaand had also done some work on the resins tend to give a uniform dull brown
I30 Joyce Plesters
colour with this test instead of the character- timesseenas membrane-like flakes,and con-
istic colour given by the fresh resin. What centratednitric acid often yellows these
is worse is that linseed oil gives the same withoutdisintegratingthem.Thepaintsample
brownish colour. Ultra-violet microscopy is is readilystainedby acidfuchsin.On heating
some help in distinguishing differences in it behavesin the sameway as glue.
media by their differentfluorescence,but such
fluorescenceis not characteristicof any par- Drying Oils
ticularcomponents. Unaffectedby water or by dilute acids, but
In the National Gallerylaboratorytests for
aqueous ammonia and sodium hydroxide
media begin with a series of solvent tests on
rapidly dissolve out the oil, sometimes as a
the paint sample. This is treated with cold
yellowish solution, and the pigment particles
water, hot water, acetone, chloroform, 0o88 flow out from the specimen. The film is
ammonia, sodium hydroxide and alcoholic strongly stainedby nile blue. Subjectedto the
sodium hydroxide solutions in turn. If Storch-Morawskitest for resins,it gives only
possible a further sample is used for stain- a dull brown spot. On heating, the paint
ing tests.Two stainshave been found particu- usually first melts, then gives off an odour of
larly effective for distinguishingbetween oily burnt oil: charring occurs and white fumes
and proteinous media. These are nile blue, are produced which are usually acid to
which stains oils and fats, and acid fuchsin, universalindicatorpaper. Concentratednitric
which stains protein. The sample can be acid often turnsoil films red brown in colour.
treated with a mixture of the two stains and
after a few minutes washed with water. The
stainwhich is specificfor that type of medium Oil and Resin Mixtures
remains. This technique has not been used These behave in practicallyall respectslike
for very long, but it has proved to be fairly drying oils. Often, however, part of the
consistentin a series of tests on known aged resinous material may be extracted by treat-
media. A combustionof a small sampleof the ment with organic solvents such as acetone
or chloroform without disintegrationof the
paint is usually done (for this is used as a test
for pigment also) and the effect of heating is paint film; the ring of transparentmaterial
noted. The effect of concentratednitric acid left after evaporationof the solvent usually
on the medium as well as on the pigment is fluorescesunder u.-v. Oil-resin films are often
observed. The reactionsof the various media more readily soluble in alcoholic solutions of
to these tests are listed below. ammonia or sodium hydroxide and in mor-
pholine than in aqueousalkalis.Gentlewarm-
Animal Glue ing usuallyproducesan odour of the resin.The
Soluble in hot water with disintegrationof Storch-Morawski test usually gives only a
the paint fragment and formation of a ring brown colour with aged films, but sometimes
of clear material after evaporation of the a transientpink or purple colour due to the
resin is produced, turning brown almost at
drop; stainedred by acid fuchsin. On heating, once.
ammoniacal fumes are given off (smell of
'burntfeathers')which turnuniversalindicator
The author would like to thank members
Egg Tempera of the Conservation Department at the
Unaffectedby water, dilute acids or alkalis National Gallery for their continuous co-
(except by prolonged treatment). On dis- operation;Mr. H. Ruhemann,for the benefit
solving out the pigment the medium is some- 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
The work here describedis partof a research London.
programme in progress in the Scientific

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
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
I5 'Uber die Maltechnik der Alten' (Berlin I9IO).
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
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.
N.B. A dash'-' undersolubilitiesindicatesthatthereis no visibleeffect
aftera few minutes'immersionin the reagent.


Chemical Origin,or date Appearanceunder Effectof heat
Composition of invention low magnification HNO3

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
is d
is fo
it am
of t
a gr
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.
given from
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
or of
the H
Chemical Origin, or date Appearanceunder
Composition of invention low magnification Effectof heat
3N HC1 4N NaOH

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
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
of so
in t

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. (
to t
Chemical Origin, or date Appearancetinder Effect of heat
Composition of invention low magnification HNO3
3N HC1 4N NaOH

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
by a

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


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 (
of a

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

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. (

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-

Chemical Origin, or date Appearanceunder Effect of heat
Composition of invention low magnification

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

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
-3 (
of s

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-
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

Chemical Origin, or date Appearanceunder
Pigment Composition of invention low magnification Effectof heat
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

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
shape, probably
owing to a de-
pressionin their

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

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
ties from the

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

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

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
the M
of th
and t
the s

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.

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
A d
Io m
is ad

Cobalt Violet, Anhydrous Appeared As above. - -Tests

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

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

Chemical Origin, or date Appearanceunder Effectof heat
Pigment composition of invention low magnification
3N HC1 4N NaOH

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.

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
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-

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

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.
out o

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

Chemical Origin, or date Appearanceunder Efect of heat
Pigment Composition of invention low magnification

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. (

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

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



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
of M
to th

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

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

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,
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


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
of g

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

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

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

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
in a


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
in Io
of b
the b

Chemical Origin, or date Appearanceunder
Pigment composition of invention low magnification Effectof heat

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
of th
is ac
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
to th
I56 Joyce Plesters

Le but de la preparationet de l'etude des d'autrepartaux proprietesde la detrempea
coupesde peinturesest discut6et la basedes l'oeuf.
methodespratiquesest decrite. I1semblebien, qu'al'origine,la peinturea
Un brefresumehistoriquedestravauxante- l'huiles'appliquait
en couchesminceset regu-
rieurssurle sujetest donne. lieres,tout commela detrempe.
Lesavantageset limitationsde cette methode Ce n'estqu'avecRembrandtque toutesles
d'etude de la construction picturale sont proprietesrheologiquesde la peinture a
enumeres,pour arrivera la conclusion que la l'huilefurentexploit6es.Un certainnombre
methode est complementairea d'autresmeth- d'exemplesde coupes de peinturesdepuis
odes comme la photographieen rayons X et Masacciojusqu'aRenoirsont illustreset dis-
infra-rouges. cut6sdu point de vue de la technique.Dans
Suit une description-de la methode em- quelques cas il fut possible d'etudier des
ployee au laboratoirede la National Gallery. echantillonsde peinturede plusieursoeuvres
Les echantillonssont preleves par le restaura- d'unmeme maitre(parexemple:tableauxde
teur au moyen d'une lame pointue bien aigui- GiovanniBelliniet de Rembrandt).
see, ce travailse fait sous un microscopebino- L'analysedes pigmentsconduit a la con-
culaire a faible grossissement.Une partie de clusion que jusqu'enpleine Renaissanceles
l'echantillonest montee en coupe, l'autre sert peintresont recherchel'emploide pigments
a l'analysede la matiere picturale.Une resine aussipurset brillantsque possible.I1est rare
polyester durcissablea froid sert de milieu de de trouver une couleur composee d'un
montage pour les coupes. melangede plusieurspigments,bienque tous
A la National Galleryles coupes de peinture les pigmentsfussentmelangesavec du blanc
ne sont faites en premiereinstanceque dansle pour produire les zones tres eclairees. Les
cas oil ellespourraientfournirdesinformations gradationssubtilesdes tons sont le plus souvent
d'ordre pratique au restaurateur.La plupart obtenues par des glacis translucidesappliques
des exemples donnes se rapportentdonc a des sur des couleurs opaques. Les dimensions
peintures, restaureesau cours des cinq der- grossieresdes grains de quelquesuns des pig-
nieres annees. Un certainnombre d'exemples ments, compareesa celles des pigments mod-
mettent en evidence l'apportdes coupes et de ernes, est tres perceptible. Ceci vaut surtout
l'analyse des peintures a la solution de pro- pour les pigments bleus et verts. Des exemples
blemes de restauration-detection des sur- sont donnes.
peints ou des vernis anciens,etat de preserva- Les informationsconcernantles liants util-
tion de la peinture originale . . . On donne isesparles maitresancienssontbeaucoupmoins
aussi quelques exemples d'alterations et de precises.Quelques tableauxoZul'identification
surpeintseffectuespar le maitre original. du liant semble presque certaine, sont repris
L'articlediscute ensuite l'etude de la tech- dans une liste.
nique picturale.Les peintresdu moyen-age et Un apergu de l'histoire de l'analyse des
du debut de la Renaissanceconstruisaientleurs pigments sert d'introduction a une serie de
peintures en superposant de fines couches tableaux d'analyse pour l'identification des
regulieres.Ceci etait d'une part du a une con- pigments. Ces dernierssont classesen groupes,
ception methodique et artisanaledu travail et suivant leur couleur. Quelques reactions
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